CA1240994A - Benzofuran and benzothiophene sulfonamides - Google Patents

Abstract

Title BENZOFURAN AND BENZOTHIOPHENE SULFONAMIDES
Abstract of the Disclosure Benzofuran and benzothiophene sulfonamides show utility as herbicides and plant growth regulants.

Description

~Z~t)994 Title BA-8466-A
BENZOFURAN AND BENZOTHIOPHENE SULFONAMIDES
Back~round of the Invention This invention relates to benzofuran and benzo-thiophene sulfonamides which are novel. The compoundsof this invention and their agriculturally suitable salts, are useful as agricultural chemicals, e.g., plant growth regulants and herbicides. The invention also includes intermediates useful for making these compounds.
Netherlands Patent 121,788, published Septem-~er 15, 1966, diâcloses the preparation of compounds of the following Formula and their use as general or selective herbicides:
Cl R 4~5 02NHCN ~ N ( i ) wherein R1 and R2 may independently be alkyl of 1-4 carbon atoms; and R3 and R4 may independently be hydrogen, chlorine or alkyl of 1-4 carbon atoms.
U.S. Patent 3,637,366 discloses compounds having the formula:

HN ~502-NHR2 wherein R1 is hydrogen or lower saturated aliphatic acyl and R2 is hydrogen, 2-pyrimidinyl, pyridyl, amidino, acetyl or carbamoyl.
The disclosed compounds are said to provide control of crabgrass, cress, endive, clover and Poa annua.

~2~Q994 French Patent No. 1,468,747 discloses the fol-lowing para-substituted phenylsulfonamides as being useful 2S antldiabetic agents:
s ~ ~so2 NH c NH ~/ 3 wherein R = H, halogen, CF3 or alkyl.
Logemann et al., Chem. Ab., 53, 18052g (1959), disclose a number of sulfonamides, including uracil derivatives and those having the formula:

r~~~ G
H3C ~ S02NHCNHR
wherein N
R is butyl, phenyl or ~ / ~ ; and N
R
Rl is hydrogen or methyl.
When tested for hypoglycemic effect in rats (oral doses of 25 mg/100 9), the compounds in which R is butyl and phenyl were most potent. The others were of low potency or inactive.
Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem. Ab., 59 1633 e] describes the synthesis of N-~(2,6-dimethoxypyrimidin-4-yl)aminocar-bonyl]-4-methylbenzenesulfonamide:

3 ~ O ~ OCH3 ~2 ~O 9g4 3 U.S. Patent 4,127,405 teaches compounds which are useful for controlling weeds in wheat having the formula W
Rl-so2-NH-c-NH-R
wherein R is X
N__~ N ~
or ~/ N
N ~ N

Rl is ~ ~ R

R9 Rlo X
R3 and R6 are independently hydrogen, fluorine, chlorine, bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms, nitro, trifluoromethyl, cyano, CH3S(O)n-or CH3CH25(0)n ;
R4 is hydrogen, fluorine, chlorine, bromine or methyl;
R5 is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;
R7 is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atoms or alkoxy of 1-2 carbon atom;

`s R8 is hydrogen, methyl, chlorine or bromine;
Rg and Rlo are independently hydrogen, methyl, chlorine or bromine;
W and Q are independently oxygen or sulfur;
n is 0, 1 or 2;
X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbon atoms, trifluoro-methyl, CI13S- or CH3OCH2-; and z is methyl or methoxy;
or their agriculturally suitable salts;
provided that:
(a) when R5 is other than hydrogen, at least one of R3, R4, R6 and R7 is otner than hydrogen and at least two of R3, R4, R6 and R7 must be hydrogen;
(b) when R5 is hydrogen and all of R3, R4, R6 and R7 are other than hydrogen, then all of 3, R4, R6 and R7 must be either chlorine or methyl; and (c) when R3 and R7 are both hydro-gen, at least one of R4, R5 or R6 must be hydrogen.' In addition, copending Canadian application No. 372 369 filed 03-05-81 teaches _-alkylsulfonylbenzene-sulfonylureas which are useful as herbicides.
In copending Canadian application No. 382 415 filed 07~23-81, there is a disclosure of herbicidal benzo[b]thiophene- and benzofuransulfonylureas in which the sul~onylureido group is bonded to the hetero-cyclic ring.

lhe presence of undesired vegeta-tion causes sub-stantial damage to useful crops, especially agricul-tural products that satisfy man's basic food and fiber needs, such as cotton, rice, corn, wheat, and the like. The current population explosion and concomi-tant world food and fiber shortage demand improvements in the efficiency of producing these crops. Preven-tion or minimizing the loss of a portion of such valu-able crops by killing, or inhibiting the gro~th of undesired vegetation is one way of improving this efficiency. A wide variety of materials useful for killing, or inhibiting (controlling) the growth of undesired vegetation is available; such materials are commonly referred to as herbicides. The need still exists however, for more effective herbicides.

c~6 Summar~ of the Invention This invention relates to compounds of Formula I, Formula I' and Formula II and their agriculturally suitable salts, suitable agricultural compositions containing them7 and their use as preemergence and/or postemergence herbicides.

R~Rl ~R

I I' II
wherein Q is 0, S, SO or S02;
Ql is O, S or S02;
W
L is S02NHCNA
R

Rl is H or C1-C3 alkyl;
R2 is H or CH3;
R3 is H or CH3;

R4 is H, C1, CH3~ CF3, OCH3 or Br;
R5 is H, CH3, OCH3 9 Cl ~ Br, N02, C02R7 ~ 502R~ 9 OS02Rg or 52 lORll;
R6 is H, Cl, Br or Cl-C3 alkyl;
R6 is H, CH3, Cl or Br;
R7 is Cl-C3 alkyl, CH2CH=CH2, C 2C 20CH3 or CH2CH2Cl;
R8 is Cl-C3 alkyl;
Rg is Cl-C3 alkyl or CF3;
Rlo and Rl1 are independently Cl-C2 alkyl;
R12 is H or CH3;

g~

is O or S;
A is N ~ N Xl N X

~N

~ NO

X is H, CH3, OCH3 or Cl;
s ~H3, OCH3, 0C2H5, CH20CH3, NH2, NHCH3~ N(CH3)2~ CH(CH3)2' ~0~
CjHo J 9 C2H5, CF3, SCH3, CH2=CHCH20, HC--CCH20 or CF3CH20;
Z is CH, N, CCH3, CC2H5, CCl or C8r;
G is O or CH2; and Xl is CH3, OCH3 or OC2H5;
X2 is CH3, C2H5 or CH2CF3; and Y2 is C2H5, CH3, OCH3, OC2H5, SCH3 or SC2H5;
provided that l) In Formulae I and I', when Q is O and R5 is other than H, Cl, Br or N02, then at least one of Rl and R2 is alkyl; and when Q is S, then R5 cannot be N02;

2) In Formula II9 when R5 i.s N02 or 2NRloRll, then R~ is Cl-C
alkyl and R6 is CH3;

3) when X is Cl, then Z is CH and `~ is OCH3, NH2, NHCH3 or N(CH3)2;

4) when Q is SO, then W is O; and

5) when R4 is other than H, then R5 is H.

Preferred for reasons of their higher herbicidal activity or more favorable ease of synthesis are:
1) Compounds of the generic scope of Formula I.
2) Compounds of Preferred 1 where W is O and R12 is H.
3) Compounds of Preferred 2 where R5 is H, 10Cl, CH3, OCH3, C02R7 or 52R8 4) Compounds of Preferred 3 where R4 and R5 are H and Rl and R2 are independently H
or CH3.
5) Compounds of Preferred 4 where A is X
N_~
~OZ i N ~

20Z is CH or N; and X is CH3, OCH3 or Cl.

6) Compounds of Preferred 5 where Y is CH3, OCH3, CH20CH3 or N(CH3)2.

7) Compounds of the generic scope of Formula I'.
258) Compounds of Preferred 7 where W is O and R12 is H.
9) Compounds of Preferred 8 where R5 is H, Cl, CH3, OCH3, C02R7 or S02R8.
10) Compounds of Preferred 9 where R5 is H and 30Rl and R2 are independently H or CH3.
11) Compounds of Preferred 10 where A is N ~
~OZ i N ~
Y

Z, is CH or N; and X is CH3, OCH3 or Cl.
12) Compounds of Preferred_ll where Y is CH3, OCH3, CH20CH3 or N(CH3)2 13) Compounds of the generic scope of Formula II.
14) Compounds of Preferred 13 where W is O and R12 is H.
15) Compounds of Preferred 14 where R5 is H, Cl, CH3, OCH3, C02R7 or S2R8 and where L is at the 7-position.
16) Compounds of Preferred 15 where R5 is H
and R6 is H or CH3.
173 Compounds of Preferred 16 where A is X
N ~

Z is CH or N; and X is CH3, OCH3 or Cl.
18) Compounds of Preferred 17 where Y is CH3, 0C~3, CH2CH3 OT N(C~1})2-Specifically Preferred are:
25 0 N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, l,l-dioxide;
o N-[(4-methoxy-6-methylpyrimidin-2-yl)aminGcarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, l~l-dioxide;
o N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, l,l-dioxide;
o N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, l,l-dioxide;

o N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino-carbonyl]-2~3-dihydro-2-methyl-7-benzothiophene-sulfonamide, l,l-dioxide;
o N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, l,l-dioxide;
2,3-dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]-2-methylbenzofuran-7-sulfonamide;
o N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methylbenzofuran 7-sulfonamide;
o N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydrobenzo[b]thiophene-7-sulfonamide, l,l-dioxide;
and e 2,3-dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)-aminocarbonyl]benzo[b]thiophene-7-sulfonamide, 1,1-dioxide.
This invention also relates to compounds of For-mula III' which are useful intermediates for the pre-paration of the herbicidal compounds of Formula I

~ R~

so2Nco III' where Q is 0, S or Sû2;
Rl is H or Cl-C3 alkyl;
R2 is H or CH3; and R3 is H or CH3.

99~

Detailed Description of the Invention Synthesis As shown in Equations l and 2, the compounds Formulae (I), (I') and (II) can be prepared by react-ing sulfonylisocyanates or isothiocyanates of Formulae (III) and (IV), respectively, with an appropriate amine of Formula (V) J wherein Rl to R6' 3 Rl2, A, Ql~
Q and W are as previously defined.
Equation 1 SO NHCN A

15~ 502NC`~ ~HN- --~~ R512 (III) (V)(.I') R
(III) t (V) -~3 R ~ R4 (I) Rl2 Equation 2 R ~ 502NCW t HN-A--~~ S2NHCN-A

35(IV) (V) (II) ~ 3~3~ 12 The reactions of Equations 1 and 2 are best car-ried out in inert aprctic organic solvents e.g.
methylene ehloride, tetrahydrofuran or acetonitrile at amhient pressure and temperature. The mode of addi-tion is not critical; however, it is often convenientto add the sulfonylisocyanate or isothiocyanate to a stirred suspension of amine V. The reactions are generally exothermic. In some cases the desired product is insoluble in the warm reaction medium and crystallizes from it in pure form. Products soluble in the reaction medium are isolated by evaporation of the solvent, trituration of the solid residue with solvents e.g. l-chlorobutane, ethyl ether, ethyl acetate or pentane, and filtration.
Alternatively, as shown in Equations 3 and 4, com?ounds I, I' and II, where R5 is other than C02R7 and W=0, can be prepared by reacting arylsulfonamides of Formulae (VI) and (VII), respectively, with an appropriate methyl carbamate of Formula (VIII), in the presence of an equimolar amount of trimethylaluminum.
E~uati?n 3 R

R~ ~ S02NH2 tCH30CN-A CH C31 3 R 12 25 to 40C

(VI) (VIII) Equation ~

R
O ~ 2 2 + CH30CN_A - 3)3 ~ (II) 12 25 to 40C
(VII) (VIII) wherein for Equations 3 and 4 Rl to R6', R12, A, Ql and Q are as previGusly defined, except R5 is other than C02R7.

The reactions of Equations 3 and 4 are best carried out in methylene chloride at about 25~ to 40C
for 10 to 96 hours under a nitrogen atmosphere. The product is isolated by addition of an aqueous acetic acid or hydrochloric acid solution followed by extrac-tion of the product into methylene chloride, or by direct filtration of a product of low solubility. The product is purified by trlturation with solvents e-g-l-chlorobutane, ethyl acetate or ethyl ether or subjected to chromatography procedures. Trimethyl-aluminum is commercially available. The reactions of Equations 3 and 4 are particularly useful for prepar-ing I, I' and II (W_0) where sulfonylisocyanates are difficult to prepare from the corresponding sulfon-amides VI and VII.
In addition, as shown in Equations 3a and 4a below, compounds of Formulae (I), (I') and (II) (where W=0) can be prepared by reacting sulfonyl-3C carbamates VI' and VII', respectively, with an appro-priate amine V.

14 ~ 3~4~
Equation 3a ~02NllCOC6H5 (VI' ) (~') (VI') ~ (V) ~
( I ) Equation 4a (VII) ~ C6H5CC6 5 ~ ~ S02NHCûC5H5 23 (VII') (VIII) t (Y) wherein for Equations 3a and 4a Rl to R6', R12, A, ~1 and Q are as previously defined. DMF is dimethylformamide.

The reactions are run at 50-100C in a solvent e.g. dioxane for 0.5 to 24 hours as taught in EP0 Publication No. 44807. The required carbamates VI' and VII' are prepared by reacting corresponding sul-fonamides _ and VII, respectively, with diphenylcar-bonate in the presence of a strong base.
The intermediate sulfonylisocyanates of Formu-lae (III) and (IV) (W=0) in Equations 1 and 2 can be prepared from sulfonamides by methods taught in U.S.

~2 ~9~ -4,238,~21. The method requires reacting sulfonamides wi~h phosgene, in the presence of n-butylisocyanate and a tertiary amine catalyst, at reflux in a solvent e-g- xylene cr chlorobenzene. A preferred cata-lyst is 1,4-diazabicyclo[2.2.2]octane (DAB00).
Alternatively, the sulfonylisocyanates can be prepared from sulfonamides by a two-step procedure.
This involves (a) reacting the sulfonamides with n-butylisocyanate and a bzse e.~. K2C03 at reflux in an inert solvent e.g. ~-butanone to rorm a n-butyl sulfonylurea; and (b) reacting this compound with phosgene and DABC0 catalyst at reflux in xylene or chlorobenzene solvent. The latter method is simi-lar to a procedure taught by Ulrich and Sayigh, N~w Methods of Preparative Organic ~hemistry, Vol. VI, p. 223-241, Academic Press, New York and London, W. Foerst Ed.
The intermediate sulfonylisothiocyanates of For-mulae (III) and (IV) (W=S) in Equations l and 2 can be prepared from sulfonamides by methods taught in H. Hartke, Arch. Pharm., 229, 174 (1966). The method requires (a) reacting an appropriate sulfonamide with an equivalent amount of carbon disulfide and two equivalents of potassium hydroxide in dimethylform-amide at room temperature for 1-8 hours to form the dipotassium salt of the sulfonyliminodithiocarbonate;
(b) diluting the suspension with ethyl acetate, ethyl ether or similar aprotic solvent to cause the salt to precipitate, (c) reacting the isolated, dried salt with phosgene in an inert solvent e.g. xylenes, ben7ene, carbon tetrachloride or methylene chloride at about room temperature for 1-3 hours; and (d) isolat-ing the sulfonylisothiocyanate, which is usually solu-ble in the solvent, by filtering off the insoluble potassium chloride and concentrating the filtrate. In ~ ~ 16 place of phosgene, a chloroformic ester (e.g., methyl chloroformate), phosphorus pentachloride, sulfuryl chlor de or thionyl chloride may be used.
The sulfonylisothiocyanates III and IV (W=5) may tend to be unstable and dimerize readily, as illus-trated below; however, the dimers can be used in the same manner as the parent isothiocyanates for the purposes of this invention.
S

~

J 52~5 J S02 N C
~ ..

where J is R ~ R ~

The intermediate sulfonamides of Formulae (VI) and (VII) in Equations 3 and 4 can be prepared by re-acting corresponding sulfonyl chlorides with ammonium hydroxide or ammonia in an inert solvent e.g.
tetrahydrofuran or methylene chloride at ambient tem-perature, according to procedures widely reported inthe literature for preparing other sulfonamides, e.g., Crossley et al., J. Am. Chem. _oc., 60, 2223 (1938) and Pailer, Mon , 92, 677 (1961).
Arylsulfonyl chlorides are ordinarily prepared from aromatic amines by diazotization with sodium nitrite in HCl, followed by reaction of the diazonium salt with sulfur dioxide and cupric chloride in ace-tic acid, according to the teachings of Yale and Sowinski, J. Org Chem., 25, 1824 (1960). As shown in Equations 5 and 6, however, sulfonyl chlorides (Y~I) and (XII) are preferably prepared by a modification of this procedure.

~ 17 Equa-tion 5 R~3 R5 R ~ ~ NH2 HONO, H2S04 (20 to 50%) l about 0 to 10C
R4 0.2 to l hour (IX) ~ ~5 S02, HCl, CuC12, R l( ~ N2~HSO~ CH3C02H, H20, cosolvent Rl Q ~ about 0 to 40C
R4 l to 24 hours (A) R ~ 52 (XI) L~rL
Equation 6 NH2 HONO, H2504 (20 to 50~) 6 ~ about 0 to 10C
0.2 to 1 hour (X) R ~ R5 52' HCl, CuC12, ~J ~ N2+HS04~ CH3C02H, H20, cosolvent R6 Q1'~` " ' about 0 to 40C
1 to 24 hours (~) R~502Cl I
(XII) The diazotization reactions of Equations 5 and 6 are best carried out with sodium nitrite in dilute sulfuric acid (about 20 to 5û%), at about 0 to 10C
for about 0.2 to l hour. This method for preparing diazonium salts from benzofuranamines and benzo[b]-thiopheneamines is widely reported in the literature, e.g., Bordwell and Stange, J. Am. Chem. Soc., 27, 5939 (1955); Arnold and McCool, ibid 64, 1315 (1942)9 Neth.
Appl. 6,6029601; and U.S. 4,032,649.
The sulfonyl chlorides in Equations 5 and 6 are prepared by reacting the diazonium salts with stirred suspensions containing sulfur dioxide, hydrochloric acid and cupric chloride. The reactions are prefer-ably carried out in a cosolvent mixture consisting of 19acetic acid-water (about 1:1) and an immiscible, inert solvent e.g. l-chlorobutane or methylene chloride, preferably l-chlorobutane. The reactions are run at about 0 to 40C, preFerably at 25 to 40C for 1 to about 24 hours. The mode of addition is not critical;
it is however, often convenient to add the diazonium salt to the suspension containing the sulfur dioxide.
The sulfonyl chlorides are isolated by addition of water, separation of the organic phase, washing the organic phase with saturated aqueous NaHC03 and water and evaporation of the solvent under reduced pressure at less than about 50C.
An alternate method for preparing some 2,3-dihy-dro-7-benzo[b]thiophenesulfonamides of Formula (VI) (Q=S) in Equation 3 above is shown in Equation 7 below.
Equation 7 2 ¦ ~ Li ¦ 8 >
50 2N C ( CH 3 ) - 2~ i C D
-2) Cl-C - C=CH-R3 ~ SC~ C-CH-R3 [ ~ 5 2 N H C ( C H 3 ) 3 E

3~
~ o b) E ~ ~ 5 ~ 2 A I Rl S02~HC(CH3)3 F

10 c) F 20~ to 50 ~~ ~ 32 ~ 0.5 to 24 hours 5 R

(VIa) wherein Rl is Cl-C3 alkyl;
R2 and R3 are as previously defined;
R1' is H or CH3; and Rl" is H, CH3 or C2H5; when Rl" is C2H5, P~l' is H-The reactions of Equation 7(a) are run in-situ as follows: The dilithium salt C is prepared by reacting t-butylbenzenesulfonamide with two equiva-lents of n-butyl lithium at 0 to 30DC in an inert solvent e.g. tetrahydrofuran for one to five hours, according to the teachings of Lombardino, J. Org.
Chem., 36, 1843 (1971). The N-t-butyl-2-propenylthio-benzenesulfonamide of Formula E is then prepared by (1) contacting this mixture containing C with elemen-tal sulfur at 0 and stirring at ambient temperature for one to five hours to form lithium thiolate D; (~) contacting this mixture with an appropriate allyl halide at 0 and stirring at arnbient temperature for about 24 hours to form E; and (3) isolating E by addi-tion of dilute hydrochloric acid to this mixture to decompose any salts present, followed by separation s and concentration of the organic phase. The reaction of organolithium reagents with sulfur to form lithium thiolates which may be alkylated in-situ is known in the art, e.g., Gschwend et al., "Organic Reactions", 25, Chapter 1, p. 83 (1979) and references cited 10 therein.
In Reaction 7(b) above, the N-t-butyl-2,3-dihy-dro-7-benzolb]thiophenesulfonamides of Formula F are prepared by heating E either neat or in an inert sol-vent e.g. quinoline or N,N-dimethylaniline at 150-300C for 0.25 to 2 hours to cause cyclization.
Compound F is isolated by addition of an inert solvent e.g. ethPr or methylene chloride, washing well with dilute hydrochloric acid and water, followed by sepa-ration and concentration of the organic phase. Com-pound F can be purified by column chromatography andrecrystallization procedures.
And in Reaction 7(c), the t-butylsulfonamides F
are dealkylated to form sulfonamides VIa by reacting F
with excess trifluoroacetic acid at 20 to 40C for about 10 to 30 hours. Compounds VIa are isolated and purified by concentration of the reaction mixture, addition of methylene chloride to the residue, washing the suspension with dilute aqueous NaHC03 and concen-tration of the organic phase. Alternatively, t-butyl-sulfonamides F may be converted to sulfonamides VIa byheating in methanol containing at least an equimolar quantity of hydrochloric acid, followed by concentra-tion of the reaction mixture and precipitation of the product with ether.

The amines of Formulae (IX) and (X) in Equations 5 and 6 above are important star-ting materials for the preparation of the compounds of this inven-tion, which can be prepared by the following general methods.
Several of the starting 4- and 7-amino-2,3-dihydrobenzofurans of Formula (IX) in Equation 5 are known. For lnstance, 4-amino-2,3-dihydro-2,2-dime-thylbenzofuran may be prepared by the procedure of 10 Cruickshank et al., J. Med. Chem., 13, 1110 (1970);
7-amino-2,3-dihydro-2,2-dimethylbenzofuran by the procedure of Netherlands 6,602,601 assigned to FMC
and published 1966 September 2; 7-amino-2,3-dihydro-2-methylbenzofuran by the procedure of Belgium 15 744,858 assigned to Bayer and published 1970 January 23; 4-amino-2,3-dihydrobenzofuran by the procedure of U.S. 3,963,717 to Cooke et al, issued 1976 June 15;
and 7-amino-2,3-dihydrobenzofuran by the procedure of U.S. 3,963,717.
The 7-amino-2,3-dihydrobenzofurans of Formula (IX) in Equation 5, where R5 is H, CH3, OCH3, Cl or Br, can be prepared by a procedure analogous to that taught in Netherlands 6,602,601. This pro-cedure is illustrated in Equation 8 below.
Equation 8 a) R

OH ,1 ,2 K2CO3 ~ R ~ OC~ C=CH-R
35 about 25 to 80C 2 R
1 to 10 hours ~' b) G M9C12 (catalyst) R~4 ~ ~ R
about 150 to 30ûC~ ~r 1 to 24 hours R ~ O ~ R

H

c) H reduction ~ 1 ~ R12 ~ NH2 (IXa) wherein Rl is Cl-C3 alkyl;
R2, R3 and R4 are as originally defined;
R5 is H, CH3, OCH3, Cl or Br;
Rl' is H or CH3; and Rl is H~ CH3 or C2H5; when Rl is C2 5' Rl is H-As shown in Equation 8, the preparation requires three steps: (1) reacting a 3- or 4-(substituted)-2-nitrophenol with an appropriately substituted allyl chloride to form intermediate G; (2) heating this com-pound at elevated temperatures 15û to 300C with a catalyst to cause cyclization to form H; and (3) re-ducing this compound to form IXa. The first reaction is run in a warm protic solvent e.g. ethanol in the presence of a weak base such as K2C03. The cycliza-tion step is normally run neat at elevated tempera-tures, in the range of 150 to 3ûOC for 1 to 24 ~ 24hours~ A Friedel-Crafts catalyst, such as magnesium chloride, is ordirlarily used to promote the cycliza-tion reaction and increase product yields. Interme-diate H may be purified by recrystallization or chroma-tography procedures. The reduction step can be car-ried out by any of several known methods for reducing nitro groups to amino groups. For examole, interme-diate H can be catalytically reduced with 5% palladium-on-charcoal in ethanol solvent at about 25 to 45C
and at 1 to 3 atmospheres of pressure. Alternatively, H can be heated with stannous chloride in concentrated hydrochloric acid at about 25 to 80C for 0.5 to 3 hours to form IXa.
Alternatively, the Claisen rearrangement-cycliza-tion reaction in Equation 8b above can be run stepwise as follows: (a) phenyl allyl ether G can be rearranged at about 150 to 200C for 0.5 to 10 hours either neat or in the presence of a suitable high boiling solvent e.s~ diethylaniline to yield the corresponding 4-or 5-(substituted)-6-nitro-2 allylphenol, according to the teachings in S. J. Rhoads and N. R. Raulins, Organîc Reactions, Vol. 22, p. 1-253, John Wiley and Sons, NPW York and London, W. G. Dauben, Ed.; and (b) this compound may be cyclized to dihydrobenzofuran H
by methods widely reported in the literature for analogous type reactions. For instance, heating the rearranged product with pyrimidine~HCl (R4 and R5 ~
OCH3), or with acidic reagents e.g. hydrogen bro-mide in acetic acid, or with a Friedel~Crafts catalyst such as magnesium chloride can yield H according ~o teachings of Claisen and Tietze, Ann, 449, 81 (1926), and 442, 235 (1925); Arnold and Mc Cool, J. Am Chem.
Soc., 64, 1315 (1942); J. Entel et al., ibid., 73, 2365 (1951); P. Cruickshank et al., J. Med. Chem., 13, 1110 (1970); and Q. Bartz et al., J. Am. Chem. Soc., 57, 371 (1935).

~z~
2~
The 7-amino-2,3-dihydrobenzofurans of Formula (IX) in Equation 5, where R5 is OS02Rg, 502R8 or CO~R7, can be prepared as shown in Equation 9 below.
Equation 9 C1 ~ R~ ~ ~ R

(XIII) (I) I reduction _~ R ~ 1 (IXb) wherein 23 Rl is Cl-C3 alkyl;
R~ and R3 are as originally defined; and R5 is OS02Rg, 502R8 or C02R7.

According to Equation 9, a 5-chloro-7-nitro-2,3-dihydrobenzofuran of Formula (XIII) is reacted with reagents as discussed below to form intermediate I
containing the desired R5 group. The nitro compound I is then reduced to form IXb. These reactions can be run by obvious methods oy one skilled in the art.
Intermediate (I), where R5 is OSû2CH3 for exam-ple, is prepared in two steps: (1) heating XIII with one equivalent of a strong base e.g. sodium or po-tassium hydroxide in dimethylformamide at 5û to 80C, for 1 to 8 hours, to form (I), where R5 is ûH; and (2) reacting the resulting phenol with methanesulfonyl chloride, in the presence of a base e.g. triethyl-amine, in an inert solvent such as tetrahydrofuran, at 253 to 70~C, for 1 to 24 hours, to form (I) where R5 is OS02CH3. Intermediate (I), where R5 is S02CH3 for example, is also prepared in two steps: (1) heat-ing XIII with one equivalent of sodium methylmercap-tide in dimethylformamide at 25 to 80, for 1 to 8 hours, to form (I), where R5 is SCH3; and (2) oxidiz-ing the resulting compound with 30% hydrogen peroxide in acetic acid solvent, at 0 to 60, for 1 to 8 hours, to form (I), where R5 is S02CH3. Intermediate (I), where R5 is C02CH~ for example, is prepared in three steps: (1) reacting XIII with one equivalent of potas-sium cyanide in dimethylformamide at 50 to 80C, for 1 to 24 hours, to form (I) where R5 is CN; (2) hydro-lyzing the cyano group to a carboxylic acid by any of several methods known in the art; fur example, (I) where R5 is CN can be refluxed with concentrated hydrochloric acid in acetic acid solvent to form (I) ~here R5 is C02H; and (3) converting the carboxylic acid to a carbonyl chloride which is then reacted with methanol to form (I) where R5 is C02CH3. The latter reactions can be run by known methods by one skille~
in the art.
In the final step of Equation 9, (I) can be re-duced to IXb by methods previously described in Equa-tion 8. The starting 6-chloro-7-nitro-2,3-dihydro-benzofurans of Formula (XIII) are also prepared by methods described above in Equation 8.
Similarly, the 4-amino-2,3-dihydrobenzofurans of Formula (IX) in Equation 5, where R5 is S02R8, OS02Rg or C02R79 Rl is Cl-C3 alkyl, and R2 and R3 are as originally defined, can be prepared by procedures described in Equation 9. Thus, by starting with an appropriate 5-chloro-4-nitro-2,3-dihydrobenzofuran, ~124~3~3~

and proceeding with the reactions described above in Equation 9, one skilled in the art can prepare the subiect 4-amino-2,3-dihydrobenzofurans of Formula (IX). The starting 5-chloro-4-nitro 2,3-dihydro-benzofurans are described below in Equation ll.
The 7-amino-2,3-dihydrobenzofurans of Formula (IX) in Equation 5, where R5 is N02 or 502NRloRll, can be prepared as shown in Equation 10.
Equation lO
R3 ~3 a) ~ 2 ~oa3ent ~ XR2 NHCCH3 " 3 (XIV) (Jl b) J R ~ R

(IXc) wherein-Rl, R2 and R3 are as originally defined; and R5 is N02 or 502NRloRll~

According to Equation lO, a 7-acetamido-2,3-dihydrobenzofuran XIV is reacted with reagents as de-scribed below to form intermediate J Then ~ is de-acetylated to form IXc.
Intermediate J, where R5 is N02, is preparedin two steps: (l) nitration of XIV with nitric acid in acetic acid solvent, at about 10 to 25~C, for 0.5 to 5 hours, to form a mixture containing in part J
where R5 is N02; and (2) separation of J from the mixture by recrystallization or chromatographic procedures.

:

~ 28 Intermediate Jl where R5 is S02NRloRll, is prepared in three steps: (1) chlorosulfonating XIV
with chlorosulfonic acid to form a mixture of products containing in part J, where R5 is SO~Cl; (2) reacting the resulting mixture with an appropriate dialkylamine in an inert solvent e.g. tetrahydrofuran, at about 10 to 60C, for 0.5 to 10 hours to form in part J

desired intermediate J-by recrystallization or chroma-tographic procedures. The chlorosulfonation step canbe run by reacting XIV with excess chlorosulfonic acid, i.e., about a three equivalent excess, at 25~ to 70C, in an inert solvent e.g. chloroform, for 0.5 to 8 hours.
Deacetylation of ~ to form IXc, can be carried out by saponification or acid hydrolysis procedures.
Thus, refluxing Jlin 90% ethanol with one equivalent of sodium hydroxide, for 0.25 to 3 hours, can provide IXc. Alternatively, heating Jl at 50 to 80C, with hydrochloric acid in acetic acid for 0.5 to 3 hours can also provide IXc. The starting compound XIV can be prepared by known methods, i.e., by heating, at 50 to 100C, an appropriate 7-amino-2,3-dihydrobenzofuran in acetic anhydride, with a catalytic amount of sul-furic acid, for 1 to 10 hours.
Similarly, the 4-amino-2,3-dihydrobenzufurans of Formula (IX) in Equation 5, where R5 is N02 or S02NRlûRll, can be prepared by procedures described in Equation 10 above. Thus, by starting with an appropriate 4-acetamido-2,3-dihydrobenzofuran, and proceeding with the appropriate reactions described above in Equation 10, the following compounds can be prepared: 4-amino-2,3-dihydro-5-nitrobenzofurans and 4-amino-5-(N,N-dialkylsulfonamido)-2,3-dihydrobenzo-furans of Formula (IX), where Rl to R3 are as defined 9~
29above. The starting 4-acetamido-2,3-dihydrobenzo-furans can be prepared from 4-amino-2,3-dihydrobenzo-furans by methods also described in Equation 10.
The 4-amino-2,3-dihydrobenzofurans of Formula (IX) in Equation 5, where R5 is H, OCH3, Cl, Br, CO2R7 or 0502R9, can be prepared as illustrated below in Equation 11.
Equation 11 - !1 2N~X R 2 1 ) d e a 9 e n t Z e ~ R 5~oS<3 R

(XV) (K) K reduction _~ 5 ~ O \3R

h (IXd) w ereln Rl is Cl-C3 alkyl;
R2 and R3 are as originally defined; and R5 is H, OCH3, Cl, Br, C02R7 or OS02Rg.

25 According to Equation 11, a 5-amino-2,3-dihydro-4-nitrobenzofuran of Formula (XV) is diazotized, then reacted with appropriate reagents to form intermediate K. Reduction of K can then provide IXd. The diazo-._ _ nium salt can be prepared with sodium nitrite in dilute sulfuric (20 to 50%) at about 0 to 10C by methods known in the art, e.g., Arnold and McCool , J .
Am. Chem. Soc., 64, 1315 (1942). Intermediate K9 where R5 is as defined above, can be prepared from the diazonium salt by methods also known in the art.

:: `
\

~L~ 30 Thus, intermediate K, where R5 is Cl or Br, can be prepared by heating the diazonium salt with cuprous chloride and hydrochloric acid or with cuprous bromide and hydrobromic acid, according to the Sand-meyer reaction, e.g., Powers, J. Med. Chem., 19, 57 (1976). Intermediate K, where R5 is OCH3, can be prepared in two steps: (1) intermediate K, where R5 is OH, is prepared by refluxing the diazonium salt with copper sulfate solution (50~), a procedure well-known in the art for preparing phenols From diazonium salts, e.g., Arnold and McCool, J. Am. Chem.
S _ , 64, 1315 (1342); and (2) the phenol can then be methylated by a variety of known methods to give K
where R5 is OCH3. For instance, heating the phenol with dimethylsulfate at about 25 to 60C in water in the presence of an equivalent of NaOH, gives K where R5 is OCH3.
Intermediate K, where R5 is 0502R9, can be prepared by reacting the phenol described above with an appropriate alkylsulfonyl chloride and a base e.g.
triethylamine in an inert solvent e.g. tetrany-drofuran at a temperature of about 0 to 60C.
Intermediate K, where R5 is C02R7, is pre-pared in the following manner: (1) intermediate K, where R5 is CN, is prepared by the Sandmeyer reac-tion. Thus, the diazonium salt is heated with cuprous cyanide according to methods well known in the art, e.g, Hansch and Schmidhalter, J. Org. Chem., 20, 1056 (1955); (2) intermediate K, where R5 is C02H, is then prepared by refluxing the cyano compound, with hydrochloric acid in acetic acid solvent for 1 to 10 hours; and (3) intermediate K, where R5 is C02R7, is prepared by converting the carboxylic acid to a carbonyl chloride which is then reacted with appro-priate alcohols to form K, where R5 is C02R7.

31Reaction (3), takes place according to methods known in the art.
Intermediate K, where R5 is H, is prepared by reac-ting the diazonium salt with 50% hypophosphorous 5 acid at 0 to 20C for 1 to 2~ hours, according to a procedure of ~3rodwell and Stange, J. Am. Chem. Soc., 77, 5939 (1955). The final step in Equation 11, the reduction of K to form IXd, is carried out by the methods described previously in Equation 9.
The starting compounds of Formula (XV) in Equa-tion 11 can be prepared according to the disclosure of Arnold and McCool, J. Am. Chem. Soc., 64, 1315 (1942).
Arnold and McCool teach the preparation of 5-amino-2, 3-dihydro-2-methyl-4-nitrobenzofuran by a multistep procedure starting with the reaction of 4-hydroxy-acetophenone with allylbromide. By reacting 4-hydro~yacetophenone with other appropriately substi-tuted allybromides, or allyl chlorides, and using the multistep reactions and conditions taught by Arnold and McCool, one skilled in the art can prepare the compounds of Formula (XV) in Equation 11.
The 4-amino-2,3-dihydrobenzofurans of Formula (IX) in Equation 5, where R5 is CH3, H, Cl or Br, can be prepared by a procedure analogous to that taught in Cruickshank, J. Med. Chem., 13, 1110 (1970). This procedure is illustra-ted in Equation 12 below.

39~
Equation 12 o NHCCH3 Cl-CH-C-CHR K2C03 OH about ~5 to 80C
(XVI) O
10NHCCH3 1 ) MgC12 ( catalyst) \5 1 about 150 to 300 , ~ ~ Rl R2 2 rdeacetylate >
OCH C=CHR3 (Ll) R 5 ~ 2 20 wherein (IXe) Rl ' is H, CH3 or C2H5;
Rl is Cl-C3 alkyl;
R2 and R3 are as originally defined; and R5 is H ~ CH3 ~ Cl or ~r-According to Equation 12, the preparation re-quires three steps: (1) reacting a 2-(substituted)-5-hydroxybenzacetamide of Formula (XVI) with an appro-priately substituted allyl chloride and potassium 30 carbonate at about 25 to 80C in an inert solvent e.g. acetone to form intermediate L1;(2) heating this compound at elevated temperatures, about 150 to 300C with a suitable Friedel-Crafts catalyst such as magnesium chloride to cause cyclization to form a 5-(substituted)-4-acetamido-2,3-dihydrobenzofuran; and (3) deacetylating this compound in the usual manner to ~ 33 form IXe. These reactions can be run using methods described previously in Equations 8 and 10. Thus, by starting with an appropriate 2-(substituted)-5-hy-droxybenzacetamide of Formula (XVI), and using the reactions and conditions described in steps (a) and (b) of Equation 8 and step (b) of Equation 10, one skilled in the art can prepare the compounds of Formula (IXe).
The 4- and 7-aminobenzofurans of Formula (X) in Equation 6, where R5 is H and R6 and R6' are H or CH3, can be prepared by known methods. Such methods are exemplified by Pene et al., Bull. Soc.
Chim. France, 586 (1966); Rodighiero et al., Gazz.
Chim. Ital., _, 90 (1961); Royer et al., Bull. Soc.
Chim. France, 1026 (1970); Kawase, Chem. Ind.
(London), 687 (1970); Belgium 744,859 published 1970 January 23; Kawase et al., Bull. Chem. Soc. Japan, 44, 749 (1971); Fr. Demande 2,338,041 to Turin and Guerret, published 1976 January 16; U.S. 3,577,441 to Kaminsky et al, issued 1971 May 4; and U.S.
3,452,033 to Mooradin et al, issued 1969 June 24.
The 7-aminobenzofurans of Formula (X) in Equation 6, where R5 is H, CH3, OCH3, Cl, Br, CO2R7, SO2R8, or OSO2Rg can be prepared as shown in Equation 13 below.
Equation 13 R2 - - ~ 2~ r (XVII) (M) C6H5N(C~3)2 ~ 6 35 M reflux R ~ ~ 6 (N) :`

`~34 N _ reduction ~ ~ R6s R ~ 5 (Xa) wherein R1, R2 and R3 are as originally defined, except at least one of Rl or R2 must be H;
R5 is H, OCH3, Cl, Br, C02R7,~S02R8 or OS02Rg;
R6' is H or CH3; and R6 is H or Cl-C3 alkyl-As shown in Equation 13, the 7-aminobenzofurans of Formula (Xa) can be prepared from corresponding 7-nitro-2,3-dihydrobenzofurans of Formula (XVII), where at least one of Rl or R~ is H. The prooedure 2û involves a dehydrogenation reaction followed by a reduction reaction. The dehydrogenation reaction may be carried out using a procedure of Geisman, J. Am.
Chem. Soc., 72, 4326 (1950) and Hurd J Am Ch~m S _ , 809 4711 (1958).
Thus, compound XVII is dehydrogenated by a two-step sequence: (1) 2,3-dihydrobenzofuran (XVII) is heated at 60 to 80C for l to 24 hours with N-bromo-succinimide (NBS) and benzoyl peroxide catalyst in an inert organic solvent e.y. benzene or carbon tetra-chloriàe thereby brominating the non-aromatic portion of the molecule to form intermediate M; (2) this in-termediate is heated with excess N,N-dimethylaniline, [C6H5N(CH3)2], either neat or in an inert aprotic solvent e.g. toluene for l to 24 hours; to cause dehydrobromination to form 7-nitrobenzofuran N. Re-~ 35duction o~ N td ~o~m~ aminobenzofuran Xa can be carried out by any of several methods known in the art for reducing nitrobenzofurans. For instance, cataly-tic reduction of N with Raney Nickel catalyst in an inert solvent e.g. lethanol at about 25 to 70C and i to 3 atmospheres of hydrogen can provide Xa, accord-ing to a procedure of aelgium 744,858. Many of the starting compounds XVII are described above in Equa~
tions 8 and 9.
Similarly, the 4-aminobenzofurans of Formula (X) in Equation 6, where R5 is H, OCH3, Cl 9 Br, C02R7, OS02Rg or 502R8 and R6 is H or Cl-C3 alkyl and R6' is H or CH3, can be prepared by procedures described in Equation 13. Thus, by starting with an appropriate 5-(substituted)-2,3-dihydro-4 nitrobenzofuran, and proceeding with the reactions described in Equation 13, one skilled in the art can prepare the subject 4-aminobenzofurans of Formula (X). The preparation o~
many of the starting 5-(substituted)-2,3-dihydro-4-nitrobenzofurans is described above, e.g. Equations 9and 11.
The 7-aminobenzofurans of Formula (X) in Equa-tion 6, where R5 is H, CH3, Cl, Br, OCH3 or S02R8, can be prepared as shown in Equation 14 below.

~2 ~ 36 Equation - -`

~ ClCH-C-R6', K~C03~ R, O
5 R ~ OH ~ -- ~ ~ OCH-C-R6' (XVIII) (O) O 1) cyclization ~ ~
2 reduction 5 ~ R6 ~H2 (Xb) wherein R5 is H, CH3, Cl, Br, OCH3 or S02R8;
R6 is H or Cl-C3 alkyl; and R6' is CH3.
According to Equation 14, the preparation re-quires three steps (1~ reacting a 3-(substituted)-2-nitrophenol with an a-chloroketone e.g. chloropro-panone for 1 to 8 hours at 30 to 80C in the presence of a base e.g. K2C03 in an inert solvent e.g.
acetone to form intermediate 0; (2) cyclizing O to form a 7-nitrobenzofuran; and (3) reducing this compound to form a 7 aminobenzofuran of Formula (Xb). The cycli-zation step is carried out in polyphosphoric acid at a temperature of about 100C for 0.5 to 24 hours. Other methods are known in the art for preparing benzofurans from phenoxypropanones e.g., Pene, ~ c Ch m France~ 586 (1966); Kawase, Chem. Ind. (London), 687 (1970) r an~ Kawase et al., Bull. Chem. Soc. Japan, 44, 749 (1971). The reduction step can be carried out by the methods described i.n Equation 13 above. Compound i 2~ 0 ~ g~ 37 Xb, where R5 is S02R8, is prepared by (a) oxidizing the intermediate 7-nitrobenzofuran, where R5 is SR8, with 30% peracetic acid in acetic acid at 0 to 60C
to form an intermediate 7 nitrobenzofuran, where R5 is S02R8, and (b) reducing this compound to form Xb where R5 is S02R8, by methods described in Equation 13 above.
The 7-aminobenzofurans of Formula (X) in Equa-, R5 is N02 or 502NRloRll and R6 is Cl-C3 alkyl and R6' is CH3, can be prepared as shown in Equation 15.
Equation 15 6 R ' 15~ 1) Reagent ~ ~ 6 0 R6 3) deaCetylate R ~ o R6 o 20(XIX) ~ (Xc) The reactions of Equation 15 can be carried out by procedures described previously in Equation 10.
Thus, by nitrating or chlorosulfonating an appropriate 7-acetamidobenzofuran XIX according to procedures described in Equation 10, one skilled in the art can prepare the subject compounds Xc.
Similarly, the 4-aminobenzo~urans of Formula (X) in Equation 6, where R5 is N02 or S02NRloRll~ R6 is 3~ Cl-C3 alkyl and R6' is CH3, can be prepared by procedures described in Equation 15 above. Thus, by starting with an appropriate 4-acetamidobenzofuran, and carrying out the reactions described in Equation 15, one skilled in the art can prepare the subject 35 4-aminobenzofurans of Formula (X).

~ 3~
The 4-aminobenzofurans of Formula (X) in Equa-tion 6, where R5 is CH3? Cl, Br or H, can be prepared by a procedure analogous to that taught by Kawase et al., Bull. Chem. Soc. Jap., 749, 44 (1971). This procedure is illustrated in Equation 16 below.
Equation 16 N02 ,6 " N02 5 ~ Cl-cH-c-R6~ K2C03 R ~
101 0 1 about 60 to 8 ~L O ~
'OH 1 to 8 hours ~ ûCH-C-R6' (XX) (P) NH R ' 1) cYclization \ ~ 2 / 6 i ~ o ~ R
(Xd) wh~rein R5 is H, Cl, Br or CH3;
R6' is CH3; and 6 is H or Cl C3 alkyl-According to Equation 16, the procedure requires three steps: (1) refluxing an appropriately substi-tuted 4-substituted-3-nitrophenol with an ~-chloroke-tone e.g. chloropropanone for 1 to 8 hours in the presence of a base, e.g., K2C03~ in a solvent, e.g., acetone, to form intermediate P; (2) cyclizing P to form a 4-nitrobenzofuran; and (3) reducing this com-pound to form a 4-aminobenzofuran of Formula (Xd).
The cyclization step can be carried out in polyphos-phoric acid at about 80 to 120C for û.5 to 24 hours.
The reduction step can be carried out by methods de-scribed in Equation 13 above.

The 4- and 7-amino-2,3-dihydrobenzo[b]thiophenes of Formula (IX) in Equation 5, where R4 and R5 are H
can be prepared by the Bucherer reaction, as shown in Equation 17 below.
Equation 17 ~ R2 ( H4)2503J N 3> ~ R2 HO- ~ I ~ about 140 to H N
~ S/ \ R 180C; 10 to 2 ~ /\
(XXI) (IXf) wherein Rl, R2 and R3 are as originally defined.
The reaction of Equation 17 can be carried out using conditions reported in the literature for Bucherer reactions, e.g., Boswell et al., J. Hetero-cyclic Chem., 5, 69 (1968). An appropriate 4- or 7-hydroxy-2,3-dihydrobenzo[b]thiophene of Formula (XXI) is heated with concentrated ammomium hydroxide, sulfur dioxide and water in an autoclave at about 140 to 180C for 10 to 30 hours to provide IXf. The starting compounds XXI can be prepared by known me-thods. Several such methods are exemplified by GerO
Offen. 2,252,335; Kilsheimer, J. A~r. Food Chem., 17, 91 (1969); U.S. 4,032,649; and Ger. Offen. 2,534,857.
The 7-amino-2,3-dihydrobenzo[b]thiophenes of Formula (IX) in Equation 5, where R5 is H, CH3, OCH3, Cl or Br, can be prepared as shown in Equation 18 below.

Eguation 18 a) R4 ~ SH tCl-C - C=CHR3 10 = R4 ~ R' R
25 to 80 1 ,1 ,2 1 to 10 hours R ~ ~ ~ S-C- C=CHR3 NH2 Rl Q

b) Ql ? to 300OC ~4~RR32 0.5 o 5 hours R~ ~ S R
N~2 (IXg) R

R 4~ R ~ '' wherein (R) Rl is Cl-C3 alkyl;
R2, R3 and R4 are as originally defined;
R5 is H, CH3, OCH3, Cl or Br;
35Rl' is H or CH3; and Rl" is H, CH3 or C2H5; when Rl is C2H5' Rl is H-According to ~q~ation 18, the preparation re-quires two steps: In Step 18(a) a 3- or 4-(substi-tuted)-2-aminothiophenol is reacted with an appropri-ately substituted allyl chloride, or allyl bro~ide, to form intermediate Ql. The reaction is run in a warm protic solvent e.g. ethanol in the presence of an equimolar amount of a base e.g. sodium hydroxide for 1 to 10 hours. After dilution with water, the product Ql is isolated by extraction with methylene chloride and concentration of the organic phase.
Compound Ql may be further purified by chromatography procedures.
And in step 18(b), Ql is heated neat at 200 to 300C for about 0.5 to 5 hours to cause cyclization to form (IXg). During the reaction, a thiochroman of Formula R may also form as a side-product. The de-sired product IXg can be separated from R and purified by high resolution distillation or chromatography procedures by one skilled in the art.
The 7-amino-2,3-dihydrobenzo[b]thiophenes of Formula (IX) in Equation 5, where R5 is H, CH3, OCH3, Cl or Br, can be prepared by a procedure analogous to that taught in Singerman, U.S. 4,032,649. The relevant portion of the procedure is illustrated in Equation 19 below.
Equation 19 .

R4 ~ R2 5-ste~s ~ R ~ R2 ~XXII) (IXh) wherein ~1 is Cl~C3 alkyl;
R2 and R4 are as originally defined;
R3 is H; and R5 is ~, CH3, OCH3, Cl or 8r.

U.S. 47032,649 teaches the preparation of 7-amino-2,3-dihydro-2,2-dimethylbenzo[b]thiophene by a six-step reaction sequence starting with 7-nitro-2,3-dihydro-2,2-dimethylbenzofuran. By starting with an appropriate 5- or 6-(substituted)-7-nitro-2,3-dihydrobenzofuran of Formula (XXII), and following the six reactions described in U.S. 4,032,649, one skilled in -the art can prepare the 5- or 6-(substi-tuted)-7-amino-2,3-dihydrobenzo[b]thiophenes of For-mula (IXh). The starting compound XXII can be pre-pared by methods described heretofore in Equation 8.
The six-step reaction sequence of Equation 19 involves (a) reacting XXII with potassium tert-butox-ide in dimethylsulfoxide at 0 to 60C For 0.5 to 10 hours to form a 6-nitro-4 or 5-(substituted)-2-vinylphenol, (b) reacting this compound with sodium hydride and dimethylthiocarbamoyl chloride in tetra-hydrofuran solvent at 0 to 60C for 1 to 10 hours to form a 0-[6-nitro-4 or 5-(substituted)-2-vinyl]-N,N-dimethylthiocarbamate, (c) heating this compound undernitrogen at 150 to 200C for 0.5 to 5 hours to form a S-[6-nitro-4 or 5-(substituted)-2-vinyl]-N,N-dime-thylthiocarbamate, (d) reducing this compound with iron powder in acetic acid at 25 to 90C for 0.5 to 3 hours to form a S-[6-amino-4 or 5-(substituted) 2-vinyl]-N,N-dimethylthiocarbamate, (e) reacting this compound with potassium hydroxide in water-methanol solvent at 40 to 8ûC for 1 to 24 hours to form a 6-amino-4 or 5-(substituted)-2-vinylthiophenol, and -(f) cyclizing this compound by heating under nitrogenat 150 to 250C for 0.5 to 6 hours to form IXh in Equation 19.

~24L~

The 7-amino-2,3-dihydrobenzo[b]thiophenes of Formula (IX) in Equation 5, where R5 is C02R7, QS02Rg or SO~R8, can be prepared as shown in Equation 20 below.
Equation 20 a~

~ ~ R2 Reagent ~~ ~ R2 (S) (T) b) . T Reduction _~R5 1 ~ R

(IXi) wherein Rl is Cl-C3 alkyl;
R2 is as originally defined;
R3 is H; and R5 is C02R7, 0502Rg or 502R8.

According to Equation 20, a 6-chloro(or bromo-)-7-nitro-2,3-dihydrobenzo[b]thiophene S is reacted with reagents described below to form intermediate T
containing the desired R5 group. The nitro- compound T is then reduced to form IXi. These reactions can be run by obvious methods.

Thus, com~ounnl T, ~here R5 is 0502Rg or C02R7, can be prepared by one skilled in the art using proce-dures similar to those described above in Equation 9 for preparing I, where R5 is OS02Rg or C02R7. Com-pound T, where R5 is S02R8, is prepared by reacting Swith an appropriate sulfinate salt, i.e., KS02R8, in an inert solvent e-g- dimethylformamide at about 40 to 100C for 1 to 8 hours. Nitro compound T is re-duced to amine IXi with iron powder and acetic acid in ethanol solvent at about 50 to 80C for 1 to 5 hours.
The starting compound S may be prepared by analogous procedures described above in Equation 19 and in U.S.
4,032,649 by one skilled in the art. Thus, an appro-priate S-[6-nitro-5 chloro(or bromo)-2-vinyl]-N,N-dimethylthiocarbamate may be reacted with potassiumhydroxide to form the corresponding 6-nitro-5~chloro-(or bromo)-2-vinylthiophenol. This compound may then be heated at elevated temperatures, i.e., 150 to 250C, to cause cyclization to form a mixture con-taining S and the corresponding 7-chloro(or bromo)-

8-nitrothiochroman. Compound S may be isolated and purified by high resolution distillation or chromato-graphy.
The 7-arnino-2,3-dihydrobenzo[b]thiophenes of Formula (IX) in Equation 5, ~here R5 is CH3, H, C1, Br, OCH3, C02R7, or OS02Rg, can be prepared as shown in Equation 21 below.
Equation 21 a) R6 R6, R4 ~ 30 22 I O I ~about 40 to 90C) I O ~ \ ~
R5 ~ S R60 5 to 3 hours R ~ S2 R6 (XXIII)(U) ~ 45 b) U 5% Pd/Charcoal R3R
about 253 to 45C ~ R ~ / 2 1 to 3 atm. R ~ OS ~ Rl (V) V Zn; HCl, CH3C02H R ~ ~ 3 1 to 3 hours R ~ S R

(IXj) wherein Rl to R4 are as originally defined, except at least one of Rl or R2 is H;
R5 is H, CH3, Cl, Br, OCH3, C02R7 or OS02Rg;
R6 is H or Cl-C3 alkyl; and R6' is H or CH3.

~ 46 The stepwise reduction of benzo[b]thiophenes to form 2,3-dihydrobenzo[b]thiophenes is known in the art, e.g., Bordwell and Stange, J. Am. Chem. Soc., 77, 5939 (1955) and Bordwell and McKellin9 ibid., 73, 2251 (1951). The reactions of Equation 21 can be carried out using prccedures disclosed in the cited refer-- ences. In the first step, a 7-nitrobenzo~b]thiophene of Formula (XXIII), is oxidized with 30% hydrogen peroxide in acetic acid at about 50 to 115aC for 0.5 to 2 hours to form benzo[b]thiophene-1,1-dioxide U.
Intermediate U is catalytically hydrogenated with 5%
palladium-on-charcoal at 1 to 3 atmospheres of pres-sure, at 25 to 45C, in ethanol so].vent to form 2,3-dihydrobenzo[b]thiophene-l,l-dioxide V. In the last step, V is refluxed with zinc and concentrated hydro-chloric acid in acetic acid solvent for 1 to 3 hours to produce IXj. Many of the starting 7-nitrobenzo-[b]thiophenes of Formula (XXIII) are described here-inafter.
The 4-amino-2,3-dihydrobenzo[b]thiophenes of Formula (IX) in Equation 5, where R5 is H, CH3, Cl, Br, OCH3, C02R7, OS02Rg or S02R8, can also be prepared using procedures described in Equations 20 and 21 above. Thus, by starting with an appropriate 5-chioro-4-nitro-2,3-dihydrobenzo[b~thiophene, and carrying out the appropriate reactions described in Equation 20 above, one skilled in the art can prepare the subject compounds, where R5 is S02R8. Similarly, by starting with an appropriate 5-(substituted)-4-nitrobenzo[b]-thiophene, and carrying out the appropriate reactionsdescribed in Equation 219 the subject compounds can be prepared, where R5 is H, CH3, OCH3, Cl, Br, C02R7 or OS02Rg. The required starting 5-(substituted)-4-nitro~
benzo[b]thiophenes are described hereinafter.

g~

The 4- and 7-amino 2,3-dihydrobenzo[b]thiophenes of Formula (IX) in Equation 5, where R5 is 502NRloRll, can be prepared by using methods described previously in Equation 10. By starting with an appropriate 4- or 7-acetamido-2,3-dihydrobenzo[b]thiophene, an~ carrying out the chlorosulfonation reactions described in Equa-tion 10, one skilled in the art can prepare the sub-ject 4- and 7-amino-2,3 dihydrobenzo[bjthiophenes of Formula (IX). The starting acetamides can be prepared by known methods, i.e., refluxing a 4- or 7-amino-2,3-dihydrobenzo[b]thiophene in acetic anhydride in the presence of sulfuric acid as catalyst. The latter amino co~pounds can be prepared by the 8ucherer reaction, as described above in Equation 17.
The 4- and 7-aminobenzo[b]thiophenes of Formula (X) in Equation 6, where R5 is H, R6 is H or Cl-C3 alkyl and R6' is H or CH3, can also be prepared by the Bucherer reaction. By starting with an appropriate 4- or 7-hydroxybenzo[b]thiophene, and carrying out the reaction described in Equation 17, one skilled in the art can prepare the subject 4- and 7-aminobenzo[b]-thiophenes of Formula (X). Many of the starting 4-and 7-hydroxybenzo[b]thiophenes are known in the literature.

9~
` 48 The 4-aminobenzo~b]thiophenes of ~ormula (X) in Equation ~, where R5 is H, OCH3, Cl, Cr, C02R7, or OSD~Rg, can be prepared as shown in Equation 22 below.
EquatiOn 2?

NO R ' N02 R,' 1 2 f 6 1) aiazotize~ R
H2N ~ ~ 2) Re ~ 5 ~ R6 (XXIV) (Wl) Wl SnCl2, HCl R N~12 R6 0.5 to 3 hours ~ 5 ~
25 to 90C ~ S ~ R6 (Xe) wherein R5 is H7 OCH3, Cl, Br, C02R7 or OS02R9;
R6 is H or Cl-C3 alkyl; and R6' is H or CH30 .

According to Equation 22, a 5-amino-4-nitroben-zo[b]thiophene of Formula tXXIV) is diazotized, then the diazonium salt is reacted with appropriate rea-gents to form intermediate W Reduction of W thenprovides Xe. The diazonium salt can be prepared with sodium nitrite in dilute sulfuric acid (20 to 50%) at 0 to lO~C, a method well-known in the art for diazo-tizing aminobenzo[b]thiophenes, e.g, Bordwell and Stange, J. Am. Chem. Soc., 77, 593~ (1955). Interme-diate Wl where R5 is as defined above, can be pre-pared from the diazonium salt using methods described heretofore in Equation ll by one skilled in the art.
The reduction step to form Xe from W can be carried out by any of several methods known in the art for reducing nitrobenzo~b]thiophenes to aminobenzo[b]thio-phenes, e.g., Bordwell and Albisetti, J. Am. Chem.
Soc., 70, 1955 (1~48); and Martin-Smith and Reid, J.
Chem. Soc., 938 (1960). Thus, refluxing Illwith stan-_ 5 nous chloride and hydrochloric acid in acetic acidsolvent for 0.5 to 3 hours can provide Xe. The starting 5-amino-4-nitrobenzo[b]thiophenes of Formula (XXIV) can be prepared by one skilled in the art ac-cording to the teachings of Bordwell and Stange, J.

10 Am. C_em. Soc., 77, 5939 (1955); Fries et al., Ann, 527, 83 (1936); and G. Karimov et al., Dokl. Akad.
Nauk. Tadzh. SSR, 13, 41 (1970), Chem. Abstr.
75:5605j.
The 7-aminobenzo[b]thiophenes of Formula (X) in 15 Equation 6, where R5 is H, CH3, OCH3, Cl or ar can be prepared as shown in Equation 23.

3û

`~ ~æ~9~4 Equation 23 R6 o ll ~ Cl-CH-C-R ', K CO
i ~ l 6 2 I U I acetone ~J R6 ~
5 R ~ SH about 25 to 60C R~ ~ ~SCH-C-R6' NO~ N02 ( XXV) ( x Xl polyphosphoric acid > ~ R6 1 to 24 nours ~
about 75 to 110C R, ~ S' NO~

Iyl) y1 _ t 23 hours- ~ R6' - l û r \~
25 to ~0C R ~ S ~R6 '70 NH2.

(X~) wherein R5 is H, CH3, OCH3, Cl or Br;
R6 is H or C1-C3 alkyl; and R~' is CH3.

~ 51 The procedure of Equation 23 involves three reaction steps: (1) refluxing an appropriate 3~(sub-stituted)-2-nitrothiophenol with an ~-chloroketone such as chloropropanone in the presence of a base e.g.
K2Cû3 in acetone solvent for 1 to 10 hours to form intermediate X ;cyclizing Xlin polyphosphoric acid at about 100 for 1 to 24 hours to form a 6-(substituted~-7-nitrobenzo[b]thiophene Yl;and reducing Y to form Xf. The reduction can be carried out by procedures described above in Equation 22. The cyclization of thiophenoxypropanones to form benzo-[b]thiophenes is known in the art, e.g., Karimov et al., Dokl. Akad. Nauk. Tadzh, USSR, 13, 41 (197û), Chem. Abstr. 75:56û5j; and Yasuo, Nippon Kaqaku Zassh 88, 758 (1967), Chem. Abstr 69:590189.
Also, by substituting chloroacetaldehyde diethyl acetal or 2-chloropropionaldehyde diethyl acetal for the ~-chloroketone in Equation 23 above, and carrying out the procedure described therein, one skilled in the art can prepare 7~aminoben~o[b~thiophenes Xf, where R5 is as defined above, R6 is H or CH3 and R6' is H.
The 4- and 7-aminobenzo~b]thiophenes of Formula (Xl)in Equation 6~ where R5 is S02R~, C02R7 or OSû2R~, -R6 is H or Cl-C3 alkyl and R6' is H or CH3, can be prepared by methods analogous to those described pre viously in Equation 9. Thus, by starting with an appropriate 6-chloro-7-nitrobenzo[b]thiophene or 5-chloro-4-nitrobenzo[b]thiophene, and carrying out the ~o appropriate reactions described in Equation 9, one skilled in the art can prepare the subject compounds of Formula (X )- The starting S-chloro~4-nitrobenzo-[b]thiophenes and 6-chloro-7-nitrobenzo[b]thiophenes are described above in Equations 22 and 23, respec-tively.

~æ~ 52 The 4- and 7-aminobenzo[b]thiophenes of Formula (Xl)in Equation 6, where R5 is N02 or 502NRloRll, R6 is Cl-C3 alkyl and R6' is CH3, can be prepared by methods described heretofore in Equation 10. Thus 7 by starting with an appropriate 4- or 7-acetamidobenzo[bi-thiophene, and carrying out the nitration procedures described in Equation 10, one skilled in the art can prepare the subject 4- or 7-aminobenzo[b]thiophene of Formula (X ) where R5 i5 N02. Similarly, by carrying out the chlorosulfonation reactions on an appropriate 4- or 7-acetamidobenzo[b]thiophene, one can prepare the subject 4- or 7-aminobenzo[b]thiophene of Formula (X ),where R5 is S02NR1oR11. The nitration o~ acet-amidobenzo[b]thiophenes is known in the art, e.g., Bordwell and Stange, ? . Am. Chem. Soc., 77, 5939 (1955). The chlorosulfonation of benzo[b]thiophenes is also known, e.3., Pailer, Monatsh 92, 677 (1961)~
The 4- and 7-aminobenzo[b~thiophene-1,1-dioxid~s of Formula (Xl) in Equation 6 (Ql=52)' where R5 is other then C02R7 or OS02Rg, can be prepared from cor-responding 4- and 7-aminobenzo~b]thicphenes. The pre-paration involves three steps: (1) acetylating the amine with acetic anhydride to form a 4- or 7-acetami-dobenzo[b]thiophene; (2) oxidizing this compound with 30% hydrogen peroxide to form a 4- or 7-acetamidoben-zo~b]thiophene-l,l-dioxide; and (3) deacetylating this compound to form a 4- or 7-aminobenzo[b]thiophene~rl,l-dioxide of Formula (X~ The acetylation step can be carried out in refluxing acetic anhydride with sul-furic acid catalyst by obvious methods. The oxidationstep can be carried out in acetic acid solvent at 50 to 115C for 0.5 to about 3 hours, according to the teachings of Bordwell and Stange, J. Am. Chem. Soc., - 77, 5939 (1955). The deacetylation step can be car-ried out by hydrolysis with hydrochloric acid or saponi~ication with sodium hydroxide by methods de-scribed heretofore in Equation lO.
Alternativelyy certain 4- and 7-aminobenzo[b]-thiophene-l,l-dioxides of Formula (X ) described below can be prepared from corresponding 4- and 7-nitroben-zo[b]thiophenes. This involves two steps: (l) oxi-dizing the nitro compound with 30% hydrogen peroxide by methods described above to form a 4- or 7-nitro-benzo[b]thiophene-l,l-dioxide; and (2) reducing this nitro compound to form a 4- or 7-aminobenzo~b]thio-phene-l,l-dioxide of Formula (X ). The reduction step can be carried out with warm stannous chloride and hydrochloric acid in ethanol solvent according to the teachings of Bordwell and Albisetti, J. Am. Chem.
Soc., 70, 1955 (1948) and Fries et al., Ann. 527 83 (1936). The starting 4- and 7-nitrobenzo[b]thiophenes have been described heretofore. 8y this method the 4- and 7-aminobenzo[b]thiophene-l,l-dioxides of Formula (X) can be prepared, where R5 is H; Cl, Br, OCH3, S02R8, C02R7 or OS02Rg.
The 4- and 7-amino-2,3-dihydrobenzo[b]thiophene-l,l-dioxides of Formula (IX) in Equation 5 (Q=S02), where R5 is other than C02R7, OS02Rg or N02, can be prepared from corresponding 4- and 7-aminobenzo[b]-thiophenes. The preparation involves four steps: (1)acetylating the amine with acetic anhydride to form a 4- or 7-acetamidobenzo~b]thiophene; (2) oxidizing this compound with 30~ hydrogen peroxide to ~orm a 4- or 7-acetamidobenzo[b]thiophene-l)l-dioxide; (3) reducing 3~ this compound catalytically ~ith 5% palladium-on-char-coal to form a 4- or 7-acetamido-2,3-dihydro-benzo[b]-thiophene-l,l-dioxide; and (4) deacetylating this com-pound to form a 4- or 7-amino-2,3-dihydrobenzo[b]thio-phene-171-dioxide of Formula (IX). The acetylationy oxidation and deacetylation steps can be carried out ~ ` 54 by methods described above for preparing 4 and 7-aminobenzo[b]thiophene~ dioxides. The reduction step is best carried out at 25 to 40C at 1 to 3 atmospheres of pressure in an inert solvent e-s-ethanol. The catalytic reduction of benzo[b]thiophene-l,1-dioxides to form 2,3-dihydrobenzo[b]thiophene-1,1-dioxides is known in the art, e.g., Bordwell and Stange, J. Am Chem. Soc., 77, 5939 (1955) and aordwell and McKellin, ibid, 7}, 2251 (1951).
Also, certain 4- and 7-amino-2,3-dihydrobenzo[b]-thiophene-l,l-dioxides of Formula (IX) described below can be prepared from corresponding 4- and 7-nitrobenzo-[b]thiophenes. By starting with an appropriate 5-(sub-stituted)-4-nitrobenzo[b]thiophene or 6-(substituted)-7-nitrobenzo[b~thiophene, and carrying out the reac-tions heretofore described in E~uations 21a and 21b, one skilled in the art can prepare 4- and 7-amino 2,3-dihydrobenzo[b~thiophene-l,l-dioxldes of Formula (IX), where Rs is H, Cl, ~r, CH3, OCH3, 502R8, C02R7 or OS02Rg. The starting 5-(substituted)-4-nitrobenzo-[b]thiophenes and 6-(substituted)-7-nitrobenzo[b~thio-phenes have been described heretofore.
In addition, the 4~ and 7-amino-2,3-dihydroben-zo[b]thiophene-l,l-dioxides of Formula (IX), where R5 is other than C02R7 or 0502Rg, can be prepared from corresponding 4- and 7~amino-2,3-dihydrobenzo[b~thio-phenes. The preparation involves three steps: (1) acetylating the amine with acetic anhydride to form a 4- or 7-acetamido-2,3-dihydrobenzo[b]thiophene; (2) oxidi~ing this compound with 30% hydrogen peroxide in acetic acid at 15 to 80C for 0.5 to about 5 hours to form a 4- or 7-acetamido-2,3-dihydrobenzo[b]thiophene~
l,l-dioxide; and ~3) deacetylating this compound to form the subject compounds of Formula (IX). The acetylation and deacetylation reactions can be run by methods described above for preparing 4- and 7-amino-benzo[b]thiophene-l 3 l-dioxides from corresponding amines.
Similarly, the 4- and 7-amino-2,3-dihydrobenzo-[b]thiophene-l-oxides of Formula (IX) in Equation 5 (Q=S0), where R5 is other than C02R7 or OS02Rg, can be prepared from corresponding 4- and 7-amino-2,3-di-hydroben~o[b]thiophenes. The preparation involves three steps: (1) acetylating the amine with acetic anhydride to form a 4- or 7-acetamido-2,3-dihydrobenzo-[b]thiophene; (2) oxidizing this compound with one mole equivalent of m-chloroperbenzoic acid to form a 4- or 7-acetamido-2,3-dihydrobenzo[b]thiophene-1-oxide; and (3) deacetylating this compound to form the subject compound of Formula IX. The oxidation step can be run in an inert solvent e.g. methylene chloride at about 0 to 10C for 1 to 16 hours, according to the teachings of Johnson and McCants, Jr J Am Chem Soc., 87, 1109 (1965). The acetyl-ation and deacetylation steps can be run by methodsdescribed above.
The 4- and 7-amino-benzofurans, -benzo[b]thio-phenes and -benzo[b]thiophene-l,l-dioxides of Formula (Xl)in Equation 6, where R6 or R6' is Cl or Br, can be prepared by halogenation reactions by obvious me-thods. Thus, the compounds are prepared by (a) heat ing an appropriate 4- or 7-acetamido-benzofuran, -ben-zo[b]thiophene or -benzo[b]thiophene-l,l-dioxide with chlorine or bromine at about 10 to 60C for 0.5 to 5 hours in an inert solvent e.g. chloroform or acetic acid, followed by (b) deacetylating the resulting halogenated product by one of the methods described previously in Equation 10.
It will also be apparent that the amines of For-mula (V) in Equations 1, 2, 3a and 4a are importantintermediates for preparing the compounds of this invention.

The pyrimidines and triazines of Formula (Va) -to (Vd) below are either known or can be prepared by obvious methods by one skilled in the art. For instance, the synthesis of pyrimidines and triazines of the general formula Va has been reviewed in "The Chemistry of Heterocyclic Compounds", a series pub-lished by Interscience Publishers, Inc., New York and London. 2-Aminopyrimidines are described by D. J.
Brown in "The Pyrimidines", Vol. 16 of this series.
2-Amino-1,3,5-triazines are reviewed by E. M. Smolin and L. Rapaport in "s-Triazines and Derivatives", Vol. 13 of the same series. The synthesis of tri-azines is also described by F. C. Schaefer, U.S.
3,154,547 and by K. R. Huffman and F. C. Schaefer, J. Org. Chem., 28, 1812 (1963). The synthesis of the bicyclic amines Vc and Vd are described in European Patent Application No. 803,005,05.7 to G. Levitt, published 1980 September 10 under Publication No.
15 683; and that of Vb in European Patent Publication No. 46,677 to Zimmerman, published 1982 March 3.
H2N~ 2~

(Va) (Vb) / Xl ~1 H2N ~ ~ ~ 2 ~ N~

(Vc) (Vd) wherein 35 G, X, Xl, Y and Z are as originally defined /o~
except Y ~ CH(OCH3)2 or C\H J

" ~

~æ~o~

Pyrimidines below o~ Formula (Ve), where Y is CH(OC2H5)2, are described by W. Braker et al., J. Am.
Chem. Soc.g 69, ~072 (1947). Using techniques taught by Braker, or suïtable modifîcations that would be obvious to one skilled in the art, t.he pyrimidines Ve can be prepared.

H~N ~\0 N
y (Ve) wherein X is CH~;, OCH 5 or Cl; and Y is CH(3CH3)2 or CH ~1 -O

Triazines of Formula (Vf) may be prepared accord-ing to the methcds outlined in Equations 24 and 25.
~g~
a) NH
Y-CN ~ Y-C-OCH3~HCl HCl ~XXVI) (XXVII)~HCl b) NCN
~û XXVII H2NCN Y-C-OCH3 pH 5.5 (XXVI I I ) NH , N
XXVIII t X-C-NH2 -~ 2 ~ O
N ~
X
(Vf) wherein X is CH3 or OCH3; and jo~
10Y is CH(OCH~)2 or CH- ~ .
o Equation 25 a) NH

(XXVII) 20 b~
NH
XXVII ~ Y-C-NH2~HCl (XXIX) c ) NCN

XXIX ~ Vf wherein X and Y are as defined in Equation 24.

The reaction of Equation 24a is carried out ac-cording to the teachings of J. M. McElYain and R. L.
Clarke, J. Amer. Chem. Soc., 69, 2657 (1947), in which che preparation of ethyl diethoxyiminoacetate is de-s9scribed. The intermediate N-cyanoimidate of Formula ~XXVIII) may be prepared according to the teaching o~
D. Lwowski in Synthesis, 1971, 263, by reacting XXVII
with cyanamide at pH 5.5, and this may be condensed according to reaction 24c with either acetamidine or O-methyl isourea in an alcoholic solvent at 25 to 80C
to provide the appropriate triazines. Alternatively, the reaction of Equation 25a, described for substi-tuted acetonitriles by F. C. Schaefer and G. A. Peters in J. Or~ Chem., 26, 412 (1961), may be used to con-vert nitrile of Formula XXVI to the corresponding iminoesterO The Free base may be carried on through reactions 25b and 25c, or, alternatively, converted to the amidinium hydrochloride salt (XXIX) as described in the aforementioned reFerence, and condensed with either methyl N-cyanoacetimidate or with dimethyl N-cyano imidocarbonate in the presence of one equivalent of sodium methoxide to provide the triazines of Formula (Vf).
Cyclic acetals of Formula (Vh) may also be pre-pared From compounds of Formula (Vg) according to Equa-tion 26 by acetal exchange.
Equation 26 X X
25N ~ N ~
H2N--<OZ _HOCH2CH23H ~, H2N--<OZ
N ~ H N ~ O
CH(OCH3)2 CH
30(Vg) (Vh~
wherein X is CH3 or OCH3; and Z is CH or N.

~2~a~
The reaction of Equation 26 is carried out by heatiny the acyclic acetal in an inert solvent in the presence of one equivalent ethylene glycol and slight-ly more than one equivalent o~ a strong acid, e.g.
p-toluenesulfonic acid with removal of the methanol or ethanol formed in the reaction by distillation. The product is isolated by treatment with aqueous base, and extraction with an organic solvent, and purified by crystallization or column chromatography.
Preparations of 3-amino-1,2,4-triazoles of For-mula (V) in Equations 1, 2, 3a and 4a are known in the art and 1,2,4-triazoles are reviewed in T_e Chemistry of Heterocyclic Compounds "Triazoles 1,2,4" (John Wiley and Sons, New York, 1981). Commonly used starting materials containing nitrogen are N-aminoguanidine, hydrazine, alkylhydrazines, cyanamide, ethyl cyano-acetimidate, dimethyl cyanodithioimidocarbonate, dimethyl cyanoimidocarbonate, ethoxymethylenecyan-amide, and acylhydrazines. Some literature synthesis are illustrated below. Using these techniques or suitable modi~ications that would be apparent to one skilled in the art, the 3-amino-1,2,4-triazole inter-mediates can be readily prepare~.
Heating equimolar amounts o~ ethyl propionimi-date hydrochloride and N-aminoguanidine nitrate in pyridine gives 3-amino-5-ethyltriazole; German Patent 1,073,499 (1960); Berichte, 96, 1064 (1963).

NH NH N ~H
30 H NCNHNH HN0 EtC-OCH2CH3 H2N ~' ~

Condensation of hydrazine with ethyl N-cyanoacetimi-date yields 3-amino-5-methyltriazole; Journal of Ornanic Chemistry, _ , 1816 (1963).

~ C;3 N_~N~H

U.S. Patent 2,835,581 (1958) teaches the preparation of 3-amino-5-(hydroxymethyl)triazole from N-amino-guanidine and glycolic acid and British Patent 736,568 (1955) describes the synthesis of 3-amino-5-mercapto-triazole.

HOCH2C02H > H2N ~' NH
H2NCNHNH2~\
2) OH N- N~H

Condensing hydrazine with dimethyl cyanodithioimido-carbonate in acetonitrile gives 3-amino-5-methylthio-1,2,4-triazole while reaction of hydrazine with di-methyl N-cyanoimidocarbonate produces 3-amino-5-me-thoxy-l 9 2,4-triazole; Journal of Or~anic Chemistry, 39, 1522 (1974).

`' ~L2~

NC-N=C

CH CN 3 ~ N ~ SCH
H2NNH2 ~ ~ OCH3 \ NC-N=C

CH3CN > N N~H
Reaction of substituted hydrazines with N-cyano-thioimidocarbonates (prepared according to the proce-dure given in D. M. Wieland, Ph.D. Thesis, 1971, pp.
123-124) yields disubstituted aminotriazoles as shown below.

X2NNH2 t 0 ~ ~H3CN RT> H2N N
20` 2 ( 2 - CH3 or C2H5~
Many of the aminoheterocyclic intermediates of Formula (V) where R12 is methyl may be prepared by a two-step procedure as described for Vi in Equation 27.

:~L2~

Equation 27 X X
N_< N_( N ~< ~ C 1--~/ Z

( X X X ) ( XX X I ) X

X X X I H 2N R 1 2 R 12 N H--</ Z
N :~<
y ( v wherein X, Y and Z are as originally defined and R12 is CH3.

A solution of the amine (XXX) in concentrated hydrochloric acid is treated with sodium nitrite solu-tion and the chloro compound (XXXI) is isolated in the usual manner by filtration of the acidic solution. A
representative procedure is described by Bee and Rose in ?. Chem. Soc. C, 2031 (1966), for the case in which Z = CH, and X = Y = OCH3. Displacement of the chlor-ine of (XXXI) may bs accomplished by heating with an excess of methylamine in water to obtain the methyl-amino heterocycle (Vi).
Equation 28 below illus-trates the preparation of the required methyl pyrimidinyl carbama-tes and methyl triazinyl carbamates of Formula (VIII) in Equations 3 and 4. By obvious modifications, other methyl car-bamates af Formula (VIII) may be prepared by this method.

~ 64 Equat~on ~8 X

N ~ 0 HN -~ O Z + (C 3 )2 25 to 70C ~ CH30CN ~ O Z
1 to 24 hours 12 (VIIIa) wherein X, Y, Z and R12 are as originally defined.

According to Equation 28, a heterocyclic amine is reacted with two equivalents of sodium hydride and excess dimethyl carbonate to form VIIIa. The reaction is run in an inert solvent e.g. tetrahydrofuran at 25C to reflux for 1 to 24 hours. The product is iso-lated by (a) adding about two equivalents of concen-trated hydrochloric acid under nitrogen at 0 to 30C;
(b) filtering; and tc) separating out the organic phase, then drying (sodium sulfate and/or magnesium sulfate) and concentrating to dryness in vacuo. The product VIIIa may be purified further by recrystalli-zation or chromatography procedures.
Agriculturally suitable salts of compounds of Formulae I, I' and II are also useful herbicides and can be prepared by a number of ways known to the art.
For example, metaL sa~ts can be made by treating com-pounds of Formulae I, I' or II with a solution of alkali or alkaline earth metal salt having a suffi-65ciently basic anion (e.g., hydroxide, alkoxide, car-bonate or hydride). Quaternary amine salts can be made by similar techniques.
Salts of compounds of Formulae I, I' and II can also be prepared by exchange of one cation to ano~
ther. Cationic exchange can be effected by direct treatment of an aqueous solution of a salt of a com-pound of Formulae I, I' or II (e.g., alkali metal or quaternary amine salt) with a solution containing the lû cation to be exchanged. This method is most effec-tive when the desired salt containing the exchanged cation is insoluble in water, e.g, a copper salt, and can be separated by filtration.
Exchange may also be effected by passing an aqueous solution of a salt of a compound of Formulae I, I' or II (e.g., an alkali metal or quaternary amine salt) through a column packed with a cation exchange resin containing the cation to be exchanged. In this method, the cation of the resin is exchanged for that of the original salt and the desired product is elute~
from the column. This method is particularly useful when the desired salt is water soluble, e.g., a potas-sium, sodium or calcium salt.
Acid addition salts, useful in this invention, can be obtained by reacting a compound of Formulae I, I' or II with a suitable acid, e.g, ~-toluenesulfonic acid, trichloroacetic acid or the like.

~%~

In the following examples all parts are by weight and temperature in C unless otherwise indicated.

Example_1 2,3-Dihydro-2,2-dimethyl-7-benzofuransulfonyl chloride A diazonium salt was prepared by adding 13.8 g of sodium nitrite to a suspension of 32.6 9 of 7-amino-2,3-dihydro-2,2-dimethylbenzofuran and 40 ml of con-centrated sulfuric acid in 200 ml water cooled 0 to 5C. After stirring for about 0.4 hour at 0 to 5C, the diazonium salt suspension was poured in one por-tion into a mixture consisting of 170 ml of acetic acid, 40 ml of concentrated hydrochloric acid, 17 g of cupric chloride dihydrate and 30 ml of sulfur dioxide and cooled at 10C by an ice-water bath. The mixture was stirred about 1 hour at 15 to 25C. Then 400 ml of l-chlorobutane and 200 ml of water was added and the mixt~lre was stirred and heated at 35C for 5 hours. After cooling to room temperature, the organic layer was separated, washed with saturated aqueous NaHC03 and water, and dried over sodium sulfate for 0.5 hour. The solvent was evaporated under reduced pressure at less than 45C to give 26 g of crude 2,3-dihydro-2,2-dimethyl-7-benzofuransulfonyl chloride as an oil.

Example 2 2,3-Dihydro-2,2-dimethyl-7-benzofuransulfonamide A solution of 26 9 of 2,3 dihydro-2,2-dimethyl-7-benzofuransulfonyl chloride prepared in Example l, 5 in 130 ml of tetrahydrofuran, was cooled in an ice-water bath while about 30 ml of concentrated aqueous ammonium hydroxide was added portionwise at 10 to 30C. The resulting suspension was stirred at room temperature for 3 hours, then the solvent was evapo-10 rated under reduced pressure. The residue was stirredin 150 ml of water for 0.5 hour, then filtered. The crude, wet solid was dissolved in chloroform and dried over sodium sulfate. The solvent was evaporated under reduced pressure to give a dry solid. The solid was 15 washed once with about 100 ml of hot toluene to give 20 9 of 2,3 dihydro-2,2-dimethyl-7-benzofuransulfon-amide, m.p. 163-165C.
Anal. Calcd. for CloH13N03S:
C, 52.8; H, 5.8; N, 6.2;
Found: C, 52.5; H, 5.7; N, 6.1.

~0~

Example 3 N-~autylaminocarbonyl)-2~3-dihydro-2~2-dimethyl-7-ben ofuransulfonamide _ _ _ A solution of 19 9 of 2,3-dihydro-2,2-dimethyl-7-benzofuransulfonamide prepared in Example 2 and 9.9 9 of n-butyl isocyanate in 200 ml of 2-butanone was re-fluxed with 11.5 9 of anhydrous potassium carbonate for 7 hours. The resulting mixture was concentrated to dryness in vacuo. The residue was taken up in 400 ml of water and extracted once with 100 ml of ethyl ether. The aqueous layer was acidified with 2N HCl and the resulting mixture was filtered and suction dried. The still slightly wet solid was washed once with lOû ml of hot acetonitrile, then suction dried an additional 8 hours to give 23 9 of N-(butylaminocar-bonyl)-2,3-dihydro-2,2-dimethyl-7-benzofuransulfon-amide, m.p. 20û-203C.
Anal. Calcd. for C15H22N204S:
C, 55.2; H, 6.8; N, 8.6;
Found: C, 54.8; H, 6.6; N, 8.5.

Example 4 2,3-Dihydro-2,2-dimethyl-7-benzofuransulfonyl isocVanate A suspension of 22 9 of the N-(n-butylaminocar-bonyl)-2,3-dihydro-2,2-dimethyl-7-benzofuransulfonamide prepared in Example 3, in 125 ml of xylene containing 0.3 9 of DABC0 was heated at 130-135C while 5.3 ml of phosgene was added portionwise at a rate to maintain a reflux temperature of 130-135C. The mixture was refluxed for an additional 1.5 hours, cooled under nitrogen, and concentrated to dryness in vacuo. A
sample of the crude oily product displayed a charac-teristic sulfonyl isocyanate band in the IR at 2200 cm~l.

Example 5 N-[(4,6-Dimethylpyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2,2~dimethyl-7-benzofuransulfonamide To a solution of 1.2 9 of 2-amino 4,6-dimethyl-pyrimidine in 25 ml of tetrahydrofuran was added 2.5 9of 2,3-dihydro-2,2-dimethyl-7-benzofuransulfonyl iso-cyanate prepared above. After a slight exotherm the solution was stirred at room temperature for 4 hours.
The solution was concentrated in vacuo to give a vis-cous oil that precipitated a solid from 10 ml of ace-tonitrile. The solid was recrystallized from aceto-nitrile to give 2 9 of N-[(4,6-dimethylpyrimidinr2-yl)aminocarbonyl]-2,3-dihydro-2,2-dimethyl-7-benzo-furansulfonamide, m.p. 203-206C. The IR spectrum showed a carbonyl absorption at 1680 cm 1 indicative of a sulfonylurea.
Anal. Calcd- for C17H20N4045:
C, 54.2; H, 5.4; N, 14.9;
Found: C, 54.3; H, 5.4; N, 15.2.
Example 6 ~ethyl (4-methoxy-6-methylpyrimidin-2-~l)carbamate To a suspension of 50 9 of 2-amino-4-methoxy-O-methylpyrimidine in 1000 ml of tetrahydrofuran was added portionwise, under a nitrogen atmosphere, 42.8 9 of 50~ sodium hydride while cooling the reaction flask in an ice-water bath. After stirring one hour at 25C, 58.5 9 of dimethylcarbonate was added dropwise at 5 to 25C. The suspension was stirred about 16 hourc at ambient temperature, then 80 ml of concen-trated hydrochloric acid was added dropwise while maintaining a reaction temperature of 20 to 25C with external ice-bath cooling. The suspension was stirred 0.5 hour, filtered, and the filtrate was dried over sodium sulfate and then concentrated in vacuo. The residue was recrystallized from hexane to yield 54 9 of the title compound, m.p. 89-92.5C.

`` ~,æ~6~3~

Example 7 7-Amino-2,3-dihydro-2-methylbenzo[b~thiophene t2-Aminophenyl)allylsulfide (80 g) was heated at 250-280C for 3 hours, cooled, then subjected to spinning band distiliation through a 20 cm column usin~ a 5:1 reflux ratio. The fraction distilling at 80-82 at û.25 mm of mercury was collected (18.0 g) and shown by NMR spectrum analysis to be the title compound in approximately 90% purity.
NMR (CDCl3)~: 7.0-6.3 (m, 3H, ArH);
3.9 (m, lH, CH);
3.5 (broad, 2H, NH2);
3.5-2.6 (m, 2H, CH2); and 1.35 (d, 3H, CH3).

ExamQle ~
7-Acetamido-2,3-dihy_ro-2-methylbenzo[b~thiophene To a solution of 18.0 g of 7-amino-2,3-dihydro-2-methylbenzoCb]thiophene (~xample 7) in 100 ml of l-chlorobutane was added a solution of 13.0 ml of acetic anhydride in 20 ml of l-chlorobutane. After the exothermic reaction subsided, the mixture ~as refluxed for 0.3 hour, cooled in an ice-bath and filtered. The isolated solid was washed with 1-chlorobutane to yield 15.2 g of the title compound;m.p. 125-127C.
NMR (CDC13)~: 7.8-6.7 (m, 4H, ArH ~ NH);
4.0 (m, lH, CH);
3.6-2.8 (m, 2H, CH2);
2.2 (s, 3H, CH3); and 1.4 (d, 3H, CH3).

Example 9 7-Acetamido-2,3-dihydro-2-methylbenzo[b]thiophene l,l-dioxide _ _ _ _ _ _ _ To a solution of 24.7 9 of 7-acetamido-2,3-di-hydro-2-methylbenzo[b]thiophene (Example 8) in 100 ml of glacial acetic acid was added dropwise 60 ml of a 30% aqueous solution of hydrogen peroxide. The reac-tion temperature rose to 65C during the addition.
The mixture was heated at 65-75C for one hour, cooled to 25C, diluted with water and extracted wi-th methyl-ene chloride. The extract was washed with water satur-ated with sodium bisulfite, dried over magnesium sul-fate and concentrated in vacuo. The oily residue was crystallized from l-chlorobutane to yield 14.3 9 of the title compound as light yellow crystals; m.p.
115-117C.
NMR (CDC13)~: 8.4-7.0 (m, 4H, ArH + NH)-;
3.8-2.7 (m9 3H, CH2 ~ CH);
2.2 (s, 3H, CH3); and 1.5 (d, 3H, CH7,).

Example 10 2,3-Dihydro-2-methyl 7-benzo[b]thiophenesulfonamide-1,l-dioxide A. A solution of 18.6 9 of 7-acetamido-2,3-dihy~ro-2-methylbenza[b]thiophene-1,1-dioxide (Example 9) in 100 ml of concentrated hydrochloric acid was refluxed For one hour to yield a suspension containing the hydrochloride salt of 7-amino-2,3-dihydro-2-methyl-benzo[b]thiophene~l,l-dioxide.
B. This suspension was diluted with 25 ml of glacial acetic acid, cooled to -5C and treated with a solution of 6.4 9 of sodium nitrite in 10 ml of water such that the temperature did not rise above 5C. The mixture was stirred for 0.5 hour at 0C, then added in one portion to a suspension cooled at -7C and con-taining 50 ml of concentrated hydrochloric acid, 50 ml of glacial acetic acid, 2.0 g cupric chloride dihydrate and 10 ml of liquified sulfur dioxide.
The mixture was stirred at 20C for two hours then diluted with excess water to yield a precipitate.
The mixture was filtered and the solid residue was washed with water to yield 2-methyl 2,3-dihydro~7-benzo[b~thiophenesulfonyl chloride l,l-dioxide as a crude solid.
C. This solid was dissolved in methylene chloride and contacted with 7 ml of liquified ammonia at -10C. The mixture was stirred at 20C for 16 hours, then filtered and the solids were washed with water and ether. The wet, solid residue was suspend-ed in benzene and refluxed under a dean-stark trap until no more water distilled from the suspension.
The suspension was cooled and filtered to yield 11.4 g of the title compound; m.p. 167-169C.
NMR (CDC13 + DMSO)~: 8.1-7.5 (m, 3H, Ar);
7.1 (broad, 2H, NH2);
3.8-2.5 (m, 3H, CH2 + CH);
and 1.5 (d, 3H, CH3).
IR (Nujol* mineral oil): 3300, 3200 cm 1 (NH2 ) .

*denotes trade mark.

', .

Example 11 N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl)-2,3-dihydro-2-methyl-7-benzo[b]thiophenesulfonamide-l,l=dioxide A suspension of 1.15 g 2,3-dihydro-2-methyl-7-benzo[b]thiophenesulfonamide-1,1-dioxide (Example 10) in 20 ml of dry methylene chloride was purged with nitrogen. To the slurry was added carefully 3.0 ml of a 20% toluene solution of trimethyl aluminum (Aldrich Chemicals) while cooling the flask at 10 to 30C. After stirring Eor 0.2 hour, 0.9 g of methyl (4-methoxy-6-methylpyrimidin-2-yl)carbamate (Example 6) was added in one portion, and the sus-pension was refluxed under nitrogen atmosphere for 24 hours. The suspension was cooled in an ice-water bath while 20 ml of lN hydrochloric acid was slowly added. After several minutes of stirring, the organic layer was separated, washed with water follow-ed by water saturated with sodium chloride (brine), then dried over magnesium sulfate and concentrated ln vacuo. The residue was triturated with chloroform and methylene chloride to yield 0.3 g of the title compound; m.p~ 224-226C.
NMR (CDC13 ~ D~SO)~: 10.3 (broad, lH, NH)i 8.2-7.6 (m, 3H, Ar);
6.3 (s, lH, CH);
4.0 (s, 3H, OCH3);
3.7-2.8 (m, 3H, CH2 -~ CH);
2.5 (s, 3H, CH3); and 1.5 (d, 3H, CH3)-IR (Nujol): 1700 cm 1 (c=o) . ~

~2~3~ 74 N-t-Butyl-2-(2-methyl-2-propenylthio)benzenesulfon-amide _ _ __ To an ice-cooled solution of 42.6 g of N-t butyl-benzenesulfonamide in 800 ml of dry tetrahydrofuran under a nitrogen atmosphere was added dropwise 262 ml of a 1.6M solution of n-butyl lithium in hexane. The mixture was stirred for 2 hours at 20C during which time a precipitate formed. The suspension was cooled lû to 0C and 6.4 9 of elemental sulfur was added in one portion. The mixture was warmed to 20C and stirred for one hour, then cooled at 0C while 20.5 ml of methallyl chloride was added slowly. The mixture was stirred at 20C for 16 hours, then 100 ml of 10~
hydrochloric acid was added. After stirring several minutes, the organic layer was separated, washed with water and brine, dried over magnesium sulfate and con centrated in vacuo. The residue was slurried in 20%
ether in hexane for several minutes and filtered to yield 47 g of the title compound; m.p. 104-107C.
NMR (CDC13)~: 8.2-7.2 (m, 4H, Ar);
5.6 (broad, lH9 NH);
4.9 (broad, 2H, vinyl);
3.7 (s, 2H, CH2);
1.9 (m, 3H, CH3); and 1.2 (s, 9H, t-butyl).

~2~

Example 13 N-_-Butyl-2,3-dihydro-2,2-dimethyl-7-benzo[b]thio-phenesulfonamide A solution of 37 g of N-t-butyl-2-(2-methyl-2-propenylthio)benzenesulfonamide (Example 12) in 40 ml of quinoline was heated at 220C for one hour, then cooled to 25C and diluted with ether. The ether suspension was washed well with 10% hydrochloric acid followed by water and brine, then dried over magnesium sulfate and concentrated ln vacuo. The oily residue was chromatographed on 300 g of silica gel, packed and eluted with 206 ether in hexane, to give a major band which was concentrated in vacuo to yield a solid. The solid was slurried in 20% ether in hexane and filtered to yield 14.2 g of the title compound; m.p. 103-105C.
NMR (CDC13)~: 7.9-7.0 (m, 3H, Ar);
5.0 (broad, lH, NH);
3.15 (s, 2H, CH2);
1.6 (m, 6H, CH3); and 1.2 (s, 9H, t-butyl).
IR (Nujol): 3200 cm 1 (N~I).

99~

Example 14 2 r 3-Dihydro-2,2-dimethyl-7-benzo[b]thiophenesulfonamide _ A solution of 17.2 g of N-_-butyl-2,3-dihydro-2,2-dimethyl-7-benzo[b]thiophenesulfonamide (Example 13) in 100 ml of trifluoroacetic acid was stirred at 20C for 16 hoursO The solution was con-centrated in vacuo, 100 ml of fresh trifluoroacetic acid was added and the mixture stirred at 20~C for four more hours. After concentrating the solution in vacuo, the residue was dissolved in methylene chloride and the solution was washed with saturated a~ueous sodium bicarbonate followed by brine, then dried over magnesium sulfate and concentra-ted in vacuo. The solid residue was slurried in 50% ether in hexane for several minutes then filtered to yield 8.4 g of the title compound; m~p. 102-104C.
NMR (CDC13)~: 8.9-7.0 (m, 3H, Ar);
5.1 (broad, 2H, NH2);
3.2 (s, 2H, CH2); and 1.6 ~s, 6H, CH3)-IR (Nujol): 3300 cm 1 (NH).

~$~ 77 Example 15 2,3-Dihydro-2,2-dimethyl-7-benzo[b]thiophenesulfonyl-isocyanate To a refluxlng solution of 8.6 g of 2,3-dihydro-2,2-dimethyl-7~benzo[b]thiophenesulfonamide (Example 14), 4.0 ml of n-bu-tylisocyanate and 0.1 g of DABCO in 100 ml of xylenes was added 3.0 ml of phosgene at such a rate that the reaction temperature did not drop below 135C. The mixture was refluxed for 1.5 hours, then the excess phosgene was purged with a stream of dry nitrogen. The mix-ture was cooled, filtered and concen-trated ln vacuo to yleld the title compound as an oil. The crude yield was assumed to be near quantitative. IR (nea-t) 2220 cm 1 (NCO).
The oil was dilu-ted to a volume of 88 ml with dry acetonitrile for use as a stock solution in subsequen-t reactions.
Example_16 N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2,2-dimethyl-7-benzo[b]thiophenesulfonamide To 22 ml of the sulfonylisocyanate stock solution prepared in -the previous Example (15) was added 0.78 g of 2-amino-4,6-dimethoxypyrimidine in one portion. The mix-ture was heated to reflux and stirred for 16 hours at 20C during which time a precipitate formed. The suspension was filtered and the solid washed with ether to yield 1.4 g of the title compound; m.p. 190-192C.
NMR (CDC13)~: 12.7 (broad, lH, NH), 8.0-7.0 (m, 4H, Ar -~ NH);
5.8 (s, lH, CH);
4.0 (s, 6H, OCH3);
3.15 (s, 2H, CH2); and 1.5 (s, 6H, CH3)-IR (Nujol): 1700 cm 1 (c=o).

Example 17 7-Ni-trobenzo[b]thiophene l,l-dioxide To a solution of 24.8 g of 7-nitrobenzo-[b]thiophene in 200 ml of glacial acetic acid pre-heated to 100C was added 90 ml of a 30% aqueoussolution of hydrogen peroxide at such a rate that the temperature remained between 100 to 105~C. The solution was refluxed for one hour, then 200 ml of water was added and the mixture was cooled in an ice-bath and filtered. The solid residue was washed sequentially with water, ethanol and ether to yield 20 g of the -title compound; m.p. 195-197C.
NMR (CDC13 + DMSO)~: 8.5 (m, lH, Ar);
8.0 (m, 2H, Ar);
7.6 (m, lH, Ar); and 7.2 (m, lH, Ar).
IR (Nujol): 1540 and 1300 cm 1.
Example 18 7-Amino-2,3-dihydrobenzo[b]thiophene l,l-dioxide 7-Nitrobenzo[b]thiophene-l,l-dioxide (19 g~
Example 17) was hydrogenated in 200 ml of ethyl ace-tate over 1.0 g o~ 10% palladium-on-charcoal catalyst at 500 pounds-per-square-inch of pressure and 100C
until no more hydrogen gas was absorbed. The mixture was filtered through celite, and the filtrate was concentrated in vacuo. The solid residue was recrystallized from l-chlorobutane to yield 13.2 g of the title compound; m.p. 117-119C.
NMR (CDC13 + DMSO)~: 7.3-6.7 (m, 3H, Ar);
5.1 (broad, 2H, NH2);
and 3.4 (m, 4H, CH2).
IR (Nujol): 3400, 3300, 1630 and 1590 cm 9~

Example 19 2,3-Dih~dro-7-benzo[b]thiophenesulfonamide l,l-dioxide A. A diazonium salt was prepared by adding a solution of 5.3 g of sodium nitrite in 10 ml of water to a suspension containing 12.8 g of 7-amino-2 J
3-dihydrobenzo[b]thiophene-1,1-dioxide (Example 18), 25 ml of glacial acetic acid and 75 ml of concentrated hydrochloric acid, cooled at -5 to 5C during the addition. After stirring for 0.5 hour at 0C, the diazonium salt suspension was added dropwise to a mixture consisting of 75 ml of concentrated hydro-chloric acid, 50 ml of glacial acetic acid, 1.0 g of cupric chloride dihydrate and 8.0 ml of liquified sulfur dioxide, cooled at -5C during the addition.
The mixture was stirred at 0C for one hour and at 20C for two hours, then diluted with excess water and stirred to yield a precipitate. The mixture was filtered and the solid residue was washed with water to yield ~rude 2,3-dihydro-7-benzo[b]thiophenesulfonyl chloride-l~l-dioxide.
B. The above sulfonyl chloride was dis-solved in methylene chloride and dried over magnesium sulfate. The dried solution was contacted with 5.0 ml of liquified ammonia at -7C, then stirred at 20C
for 18 hours. The suspension was concentrated in vacuo, and the residue was slurried in 100 ml of 10%
hydrochloric acid, then filtered. The solid residue was washed with water and ether to yield 11.5 g of the title compound; m.p. 215-217C.
NMR (CDC13 -~ DMSO)~: 8.1-7.6 (m, 3H, Ar);
7.0 (broad, 2H, NH2);
and 3.8-3.3 (m, 4EI, CH2).
IR (Nujol): 3300, 3200 and 1350 cm 1.

:~l2~
Example 20 N-[(4-Methoxy-6-methylpyrimidin-2-yl)aminocarbonyl-2,3-dihydro-7-benzo[b]thiophene l,l-dioxide A slurry of 1.0 g of 2,3-dihydro-7-benzo[b]thiophenesulfonamide l,l-dioxide (Example 19) in 20 ml of dry methylene chloride was treated with 2.5 ml of a 20~ solution of trimethylaluminum in toluene (Aldrich Chemicals) under a blanket of dry nitrogen. After stirring at 20C for 0.25 hour, 1.0 g of methyl (4-methoxy-6-methylpyrimidin-2-yl)carba-mate (Example 6) was added in one portion and the resulting solution was stirred at 20C for 60 hours followed by refluxing for 24 hours. The mixture was cooled in an lce-bath, then treated with 10 ml of 10% hydrochloric acid and filtered. The solid residue was heated in tetrahydrofuran and filtered hot to yield 0.45 g of the title compound; m.p.
227-229C.
NMR (CDC13 -~ DMSO)~: 13.7 (broad, lH, NH);
10.1 (broad, lH, NH);
8.2-7.7 (m, 3H, Ar);
6.3 (s, lH, CH);
4.0 (s, 3H, OCH3);
3.5 (m, 4H, CH2); and 2.4 (s, 3H, CH3)-IR (Nujol): 3200 (NH), 1710 (c=o) cm 1.

Using the techniques described in Equations 1-28 and Examples 4 and 15, or simple modifications thereof, the following compounds in Table I can be made by one skilled in the art.

9 ~ 81 Table I

R ~ 1 ~S02NCO

Rl R2 3 Q IR(c_ 1) H H H S

~ C3H7 H H 0 Using the techniques described in Equations 1-28 and Examples 5, 11, 16 and 20, or simple modifications thereof, the f`ollowing compounds in Tables II-Vd can be made by one skilled in the ar-t.

Table II

R3 ~Rl ~( W N
(O> S02NHCN~OZ
R12 N i R~l R5 Y

Rl R2 R3 R4 Rs R12 l~l Q X Y Z m.p.(C) _ ~ 3 H H H H O O Cl OCH3 CH

CH3 CH3 H H H H O O Cl OCH3 CH

C2H5 H H H H rl CH3 CH3 CH

C2H5 H H H H H O O Cl OCH3 CH

~æ~ 83 Table II (continued) Rl R2 R3 R4 Rs R12 W Q X Y Z m.p.(_C) _ H l1 H H H H O O OCH3 CH3 N

H H H H H H O O Cl OCH3 CH

CH3 H C~13 H H H O O OCH3 OCH3 N
CH3 H CH3 H H H O o OCH3 CH3 N

CH3 H CH3 H H H o O Cl OCH3 CH
n-c3H7 H H H H H OCH3 OCH3 CH
n-c3H7 H H H H H OCH3 CH3 CH
rl-C3H7 H H H H H CH3 CH3 C
n-c3H7 H H H H H O O OCH3 OCH3 n-c3H7 H H H H H O O OCH3 CH3 N
n C3H7 H H H H H O O Cl OCH3 CH

CH3 CH3 H H H CH3 0 0 OCH3 OCH3 N 151~152 CH3 H H H H H O S Cl OCH3 CH

~z4~'39~

Table II (con-tinued) Rl R2 R3 R4 Rs R12 W Q X Y Z m~p.(C) _ _ _ _ _ _ _ CH3 CH3 H H H H O S Cl OCH3 CH

n-c3H7 H H H H H O S OCH3 OCH3 CH
15 n-C3H7 H H H H H o S OCH3 CH3 N
CH3 H CH3 H H Ho S OCH3 OCH3 CH
C~13 H CH3 H H Ho S OCH3 CH3 CH

H H H H H H O S Cl OCH3 CH

CH3 H H H H H 52 CH3 OC~i3 CH 238-240 CH3 H H H H H O S02 Cl OCH3 CH 223-226 Table II (continucd) Rl R2 R3 R4 R5 R12 W Q X Y Z m.~.(C) CH3 CH3 H H H H 52 OCH3 OCH3 N 214-216o CH3 C~13 H H H H O S02 CH3 CH3 N 208 211 CH3 CH3 H H H H O S02 Cl OCH3 CH

C2H5 H H H H H 52 Cl OCH3 CH3 n C3H7 H H H H H O 52 OCH3 CCH3 CH
n-c3H7 H H H H H 52 OCH3 CH3 N
H H H H H H O S02 OCH3 OCH3 CH ~300 H H H H H H 52 Cl OCH3 CH

CH3 H C~13 H ~I H O S02 OCH3 OCH3 CH

C~13 H CH3 H H H 0 52 OCH3 CH3 N

~æ~ 86 Table II (continued) .

Rl R2 R3 R4 R5 Rl2 W Q X Y Z (C) CH3 CH3 H ar H H O O CH3 OCH3 N
CH3 H H Cl H 3 3 lO CH3 H H CF3 H H O O OCH3 OCH3 CH
CH3 H H OCH3 H H o o OC~13 CH3 CH

15 CH3 CH3 H H H H S o OCH3 CH3 N

CH3 CH3 H H Cl H O S OCH3 CH3 CH
CH3 H H H Br H o 3 OCH3 CH3 N
CH3 H H H No2 H O O OCH3 OCH3 CH

CH3 ~1 H H C02C2H5 H O S02 OCH3 OCH3 CH
CH3 H H H C02CH2CH2CH3 H O O nCH3 OCH3 CH
CH3 CH3 H H C02CH(CH3)2 H O S OCH3 OCH3 CH
CH3 H H H C02CH2CH=CH2 H O O OCH3 OCH3 CH
CH3 H H H C2CH2CH2CH3 1~ OCH3 OCH3 CH
CH3 H H H C2CH2CH2Cl H 0 0 OCH3 OCH3 CH

CH3 CH3 H H 502C2H5 H o o OC~13 CH3 CH

CH3 H H H 502CH(CH3)2 H O O OCH3 OCH3 CH

099~

Table II (continued) -Rl R2 R3 R4 R5 Rl2 W Q X Y Z m.p.(C) CH3 H H H 52CH2cH2cH3 H O O OC 3 3 CH
CH3 H H H OS02CH(CH3)2 H O S CH3 OCH3 CH

CH3 H H H 52N(C~l3)2 H O O CH3 CH3 CH
CH3 H H H S02N(CH3)C2H5 H O O OCH3 OCH3 CH
CH3 H H H H H O O CH3 CH3 CCl CH3 H H H H H O S H CH3 CCl CH3 H H H H H O O H CH3 CBr CH3 CH3 H H H H O S H OCH3 CCl 15 CH3 CH3 H H H H O O H OCH3 car CH3 CH3 H H H H O S02 C 3 3 CBr CH. H H H H H O O CH3 CH20CH3 CH

25 CH3 H H H H H O O OCH3 N(CH3)2 N
CH3 H H H H H O O OCH3 N(CH3)2 CH

CH3 CH3 H H H H O O CH3 OCH2CH=CH2 N

CH3 H H H H H O O Cl NH2 CH
35 CH3 H H H H H O O Cl NHCH3 CH

Table II (continued) R1 R2 R3 R4 Rs R12 W Q X Y Z m.p.(C) ~ _ _ _ _ _ _ 5 CH3 H H H H H O O Cl N(CH3)2 CH
CH3 CH3 H H H H O S OCH3 CH(OCH3)2 CH
CH3 H H H H H O O CH3 CH(OCH3)2 N
CH3 H H H H H O O CH3 CH(OCH3)2 CH

/o~
CH3 H H H H H O O CH3 CH ~ CH
CH3 H H H 11 H O S02 OCH3 CH(OCH3)2 CH 111-113 CH(CH3)2 H H H H H O O ~CH3 OCH3 CH

CH3 H H H H H O O OCH3 CH(OCH3)2 CH
2 0 H H H H H O O OCH3 CH ~ CH
/o~, CH3 CH3 H H H H O O O~H3 CH ~ CH

CH CH H H H H O O CH CH ~ CH
3 3 3 ~O

CH3 CH3 H H H H o o OC~13 SCH3 CH

~f~ 3~3~f~

Table 11 (~ontinued) . . .
P~l R2 R3 R4 R5 R12 W Q X Y 2m.p. (-~) 3 H H H H CH3 0 S02 CH3 O~H3 CH220 222 CH3 H H H CH3 0 S02 OCH3 OCH3 CH20~3 211 ~H3 H H H H CH3 SO~ CH3 OCH3 N175-180 CH3 ~ H H H H O S02 CH3 CH20CH3 CH203-206 CH3 H H H H H O S02 C~3 OC2H5 N178-180 CH3 ~ H H H H O S02 OC~3 N(CH3)2 N180-183 Table IIa R ~ R
~ ~ Q X
~ W N ~ .
< O >--502NHCN ~ 0 12 N ~ G

Rl R2 R3 R4 R5 R12 W Q G Xl m.p.(C) 20 n-C3H7 H H H H H C o CH3 n C3H7 H H H H H OCH3 CH3 H H H H H O O C~12 CH3 CH3 CH3 ~ H H H O O CH3 OC2H5 CH3 ~ H H H H O S CH3 so Table IIa (continued) Rl R2 R3 R4 R5 Rl2 W Q G Xl m.p.(C) C~13 CH3 H H H H 52 CH2 OCH3 Table IIb R ~ R
~ Q X
5 ~ W N

" ~~

Rl R2 R3 R4 R5 R12 W Q Xl m.p.(C) . CH3 H H H H H S CH3 CH3 H CH3 H H H c~3 ~Z~39~
Table IIc ~X X
1~ ~N~

Rl R2 R3 R4 R5 R12 W Q Xl m.p.(~C) C 3 C 3 H Cl H CH3 Table IId R~,><Rl O NHCN ~ ' Rl R2 R3 R4 R5 R12 W Q X2 ~2 m.p.(C) _ C2~15 H H .H H H CH3 OCH3 n C3H7 H H H H H CH3 OCH3 n-c3H7 H H H H H CH3 SCH3 9'~
Table IId (continu~d) Rl R2 R3 R4 R5 R12 W Q X2 Y2 m.p.(C) n-c3H7 H H H H H 52 CH3 OCH3 n-c3H7 H H H H H O 52C~13 SCH3 25 C~,3 CH3 H H H H O S CH3 SCH3 C~13 H H H H H O S CH3 SCH3 CH3 H CH3 H H H o S CH3 OCH3 ~æ~o~

Table IId (continued) Rl R2 R3 ~4 R5 R12 W Q X2 Y2 m.p.(C) ~ _ _ _ _ _ _ _ _ CH3 H H H Cl H O O CH3 OCH3 3g~

Table III

Rl R2 Q X~/ X
~( W Nl ~S02NHCN _~0 7 Rl R2 R3 R5 R12 W Q X Y Z m.p.(C) H H H H H o oOCH3 OCH3 CH 177-180 H H H H rl O 3 3 N

H H H H H o 5 OCH3 CH3 N

CH3 H CH3 H H o S02 OCH3 CH3 CH

H H H H H O O Cl OCH3 CH
H H H H H o o OCH3 CH20CH3 CH
H H H H H O O OCH3 N(CH3)2 CH

Table IIIa Q~ X
~( W N ~/
" ~0 Rl R2 R3 R5 R12 W Q G Xl m.p.(C) Table IIIb RQl~R3 X
~ W N
<O~SO2NHC~ O>_~

_ R2 R3 R5 R12 Q Xl W m.p.(C)_ _ _ _ 15 H H H H H O OC~13 0 CH3 H CH3 Cl H O OCH3 0 39~ 99 Table IIIc Q~ R3 X
W N
~ 502NHCN--<

Rl R2 R3 R5 R12 Q Xl W m.p.(C) H H CH3 Cl H S02 CH3 H

Table IIId Q >~

Rl R2 R3 R5 R12 W Q X2 Y2 m.p (C) H H H H H O O C~3 SC 3 H H CH3 Cl H 52 CH3 OCH3 Table IV

~ 1 X
W N
>- S02NHCN ~OZ

R~ Y

R5 R6 R6' R12 W Ql X Y Z m.p.(C) H CH3 H H O O OCH3OCH3 CH 18~-191 H~ CH3 CH3 OCH3 OCH3 C
H CH3 CH3 H o O OCH3 CH3 CH
H CH3 CH3 H O o CH3 CH3 CH

H H CH3 H O o OCH3 CH3 CH

H C 3 CH3 o S CH3 CH3 CH

H HCH3 H o S OCH3 OCH3 CH 216-218 9~

Table IV (continued) R5 R6 R6 Rl2 W Ql X Y Z m.p.(C) H H H H O S OC~13 OCH3 N
l H H H H O S OCH3 CH3 N

H H CH3 ~l O S02 OCH3 CH3 CH

H H H H O S CH3 CH3 CCl H CH3 CH3 H O O H CH3 CCl H H H H O S H CH3 CBr H CH3 CH3 H O O H OCH3 CCl H H 3 CH3 CH3 C3r H CH3 ~1 H O O CH3 NH2 CH

~æ~ D3 Table IV (continued) R5 R6 26' Rl2 W Ql X Y Z m.p.(C) H CH3 CH3 H O O CH3 N(CH3)2 CH
H CH3 H H O O H OCH3 CCr lO H CH3 H H O O CH3 CH20CH3 C
H CH3 CH3 H O O Cl OCH3 CH

Cl CH3 H H o o OCH3 CH3 N
15 Br CH3 CH3 H O S OCH3 OCH3 CH
NO2 CH3 CH3 H o O OCH3 OCH3 CH

C02CH(CH3)2 CH3 CH3 H o B OCH3 CH3 N

C2CH2CH CH2 CH3 CH3 H G o CH3 CH3 CH

C2CH2CH2Cl CH3 CH3 CH3 O O CH3 C 3 CH

SO2CH(CH3)2 CH3 CH3 H o o OCH3 CH3 N

OSO2CH(CH3)2 CH3 CH3 H o O OCH3 CH3 N
52CH2cH2cH3 CH3 CH3 3 3 CH

SO2N(CH3)2 CH3 CH3 H O S CH3 OCH3 CH
SO2N(CH3)CH2CH3 ~H3 CH3 H O O CH3 OCH3 N

S2C2~l5 CH3 CH3 H O O CH3 OCH3 CH

Table IV (continued) R5 R6 R6' R12 W Ql X Y Z m p.(C) H H H H o o CH3 CH3 CH
H H H H o o OCH3 OCH3 N
H C2H5 H H o o OCH3 OCH3 CH
H n-C3H7 H H O O OCH3 OCH3 CH
H CH(CH3)2 H H 3 O OCH3 OCH3 CH
H Cl CH3 H o 3 OCH3 OCH3 CH
H Br CH3 H o o OCH3 OCH3 CH
H CH3 Cl H O O OCH3 OCH3 CH
H CH3 Br H O O OC 3 OCH3 CH

H CH3 H H O O Cl OCH3 CH
H H H H O S02 Cl OCH3 CH
H CH3 CH3 H o S02 OCH3 CH(OCH3)2 N

H CH3 H H o o CH3 CF3 CH
H H H H O S CH3 CH2cH=cH2 N

/o~
35 H CH3 H H O O CH3 CH ~ CH

3~3~ 105 Table IV (continued) R5 R6 R~' R12 W Ql X Y Z m.p.(C~
5 H H H H O S Cl NH2 CH
H CH3 H H O O Cl NHCH3 CH
H CH3 CH3 H O S02 Cl N(CH3)2 CH
H CH3 H H S o OCH3 OCH3 CH

10 4~
5_ Cl H CH3 H O S CH3 CH3 CH 218-220 or 6 4- ~
5- Cl H CH3 H O S CH3 OCH3 CH 231-233 4~
5- ¦C1 H CH3 H O S OCH3 OCH3 CH 21~-221 or 6J
H CH3 H H o o OCH3 SCH3 N
20 H CH3 H . H o o ~CH3 SCH3 CH

Table IVa R~l~Ql X

~ W N

R5 R6 26' R12 W Ql G Xl m.p.(C) Cl CH3 H H O CH3 Table IVb ~ Ql X
)--( W N¦

~S02NHCN ~0 R5 R6 Rol R12 W Ql Xl m.p.(C) Cl CH3 H H CH3 Table IVc ~ Ql W N

~ ~12 N

R5 R6 R6' R12 W Ql Xl m.p.(C) H CH3 CH3 H 52 CH~

Cl CH3 H H CH3 9~

Table IVd R~ 12 2 R5 R6 R6 I R12 W Ql X2 Y2 m.p.(C) H CH3 CH3 H O SO2 CH3 OCH~

Cl CH3 H H CH3 OCH3 H CH3 CH3 H O SO2 C~13 OC2H

~L2~

Table V

~ SD2NHCN--<~

R5 R6 R6' R12 ~ Ql X Y Z m.p.(C) H H CH3 H O O OC~3 CH3 CH3 H o S02 OCH3 CH3 N

lll Table Va Ql~R6 X
~ W N ~
<~502NHCN ~b R5 R6 R6 R12 W Ql G Xl m.p.(C) CH3 H O OC~H5 Cl H CH3 H O CH3 Table Vb Ql~ 6 X
\I W N~
<~S02NHCN ~b R5 R6 R6' R12 W Ql Xl m.p.(C) H H CH3 H o S CH3 Cl H CH3 H CH3 H H CH3 H O S OCH}

Table Vc Ql~R6 X
~ ~ N ~

- R6 6 12 W 1 Xl m.p.(C) Cl H CH3 H CH3 .

T~ble Vd Ql~R6 502NHCN ~ - N 2 R5 R6 26' R12 W QlX2 Y2 m.p.(C) H CH3 CH3 H o S CH3 OCH3 Cl H CH3 ~ O O CH~ OCH3 Formulations Useful formulations of the compounds of Formulae I, I' and II can be prepared in conventional ways.
They include dusts, granules, pellets, solutions, sus-pensions, emulsions, wettable powders, emulsifiable concentrates and the like. Many of these may be ap-plied directly. Sprayable formulations can be exten-ded in suitable media and used at spray volumes of from a few liters to several hundred liters per hec-tare. High strength compositions are primarily usedas intermediates for further formulation. The formu-lations, broadly, contain about û.1% to 99% by weight of active in~redient(s) and at least nne of (a) about 0.1% to 20,~ surfactant(s) and (b) about 1% to 99.9~
solid or liquid diluent(s~. More specifically, they will contain these ingredients in the following approximate proportions:
Table VI

Weight Percent*
Active Ingredient Diluent(s) Surfactant(s) Wettable Powders 2û-90 0-74 1-10 Oil Suspensions, 3-50 40 95 0-15 Emulsions, Solutions, (including Emulsifiable Concentrates) Aqueous Suspension10-50 40-84 1-20 Dusts 1-25 70-99 0-5 Granules and Pellets 0.1-95 5-99.9 0-15 High Strength 90-99 0-10 0-2 Compositions * Active ingredient plus at least one of a Surfactant or a Diluent equals 100 weight percent.

~æ~

Lower or higher levels of active ingredient can, of course, be present depending on the intended use and the physical properties of the compound. Higher ratios of surfactant to active ingredient are some-times desirable, and are achieved by incorporationinto the formulation or by tank mixing.
Typical solid diluents are described in Watkins, et al., "Handbonk of Insecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books, Caldwell, New Jersey, but other solids, ei-ther mined or manufac-tured, may be used. The more absorptive diluents are preferred for wettable powders and the denser ones for dusts. Typical liquid diluents and solvents are de-scribed in Marsden, "Solvents Guide," 2nd Ed., Inter-science, New York, 1950. Solubility under 0.1% ispre~erred for suspension concentrates; solution con-centrates are preferably stable against phase separa-tion at 0C. "McCutcheon's Detergents and Emulsifiers Annual"9 MC Publishing Corp., Ridgewood, New Jersey, as well as Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc., New York, 1964, list surfactants and recommended uses.
All formulations can contain minor amounts of addi-tives to reduce foaming, caking, corrosion, microbio-logical growth, etc.
The methods of making such compositions are wellknown. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer or fluid energy mill. Suspensions are prepared by wet milling (see, for example, Littler, U.S. Patent 3,060,084). Granules and pellets may be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See J. E.
arowning~ "Agglomeration", Chemical Engineering, ~2~

December 4, 1967, pp. 147ff. and "Perry's Chemical Engineer~s Handbook", 5th Ed., McGraw-~lill) New York, 1973, pp. 8-57ff.
For further information regarding the art of formulation, see for example:
H. M. Loux, U.S. Patent 3,235,361, February 15, 1966, Col. 6, line 16 through Col. 77 line 19 and Examples 10 through 41;
R. W. Luckenbaugh, U.S. Patent 3,309,192, ~arch 14, 1967, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 165, 167 and 169-182;
H. Gysin and E. Knusli, U.S. Patent 2,891,855, June 23, 1959, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4;
G. C. Klingman7 "Weed Control as a Science", John Wiley ~ Sons, Inc., New York, 1961, pp. 81-96; and J. D. Fryer and S. A. Evans, "Weed Control Hand book", 5th Ed., Blackwell Scientific Publications, ûxford, 1968~ pp. 101-103.
In the following examples, all parts are by weight unless otherwise indicated.
Example 21 Wettable Powder 25 N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7 benzothiophenesulfonamide, l,l-dioxide 80%
sodium alkylnaphthalenesulfonate 2~
sodium ligninsulfonate 2%
syn-thetic amorphous silica 3%
kaolinite 13%
The ingredients are blended, hammer-milled until all the solids are essentially under 50 microns, re-blended, and packaged.

Example 22 Oil SusDension N-~(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7~benzothiophenesulfonamide, l,l-dioxide 25%
polyoxyethylene sorbitol hexaoleate 5%
highly aliphatic hydrocarbon oil 70%
The ingredients are ground together in a sand mill until the solid particles have been reduced to under about 5 microns. The resulting thick suspension may be applied directly, but preferably after being extended with oils or emulsified in water.
Example 23 Wettable Powder 15 N-[(4~6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2 dihydro-2-methyl-7-benzothiophenesùlfonamide, l,1-dioxide 20%
sodium alkylnaphthalenesulfonate 4%
sodium ligninsulfonate 4%
low viscosity methyl cellulose 3%
attapulgite 69%
The ingredients are thoroughly blended. After grinding in a hammer-mill to produce particles essen- .
tially all below 100 microns, the material is re-blended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) and packaged.

, _ ~æ~

Example 2 Lo~ Strength Granule N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl 7-benzothiophenesulfonamide, l,l-dioxide 0.1%
attapulgite granules 99.9%
(U.S.S. 20-40 mesh) The active ingredient is dissolved in a solvent and the solution is sprayed upon dedusted granules in a double-cone blender. After spraying of the solution has been completed, the material is warmed to evapor-ate the solvent. The material is allowed to cool and khen packaged.
Example 25 Granule N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocar-bonyl]-2,3-dihydro-2-methyl-7-benzofuransulfonamide l,l-dioxide ~0%
wetting agent lS
crude ligninsulfonate salt (containing 10%
5-20% of the natural sugars) attapulgite clay 9~
The ingredients are blended and milled to pass through a 100 mesh screen. This material is then added to a fluid bed granulator, the air flow is ad-justed to gently fluidize the material, and a fine spray of water is sprayed onto the fluidized ma-terial. The fluidization and spraying are continued until granules of the desired size range are made.
The spraying is stopped, but fluidization is con-tinued9 optionally with heat, until the water content is reduced to the desired level, generally less than 1%. The material is then discharged, screened to the desired size range, generally 14-100 mesh (1410-149 microns), and packaged for use.

~z~9~

Example 26 High Strength Concentrate -N-~(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide l,l-dioxide 99%
silica aerogel û.5%
synthetic amorphous silica 0.5%
The ingredients are blended and ground in a hammer-mill to produce a material essentially all passing a U.S.S. No. 50 screen (0.3 mm opening). The concentrate may be formulated further if necessary.

9~ -Utllit~
The compounds of -the present invention are ef-fective herbicides. They have utility for broad-spectrum pre- and/or post-emergence weed control in areas where complete con-trol of all vegetation is desired, such as around fuel storage tanks, ammunition depots, industrial storage areas, parking lots, drive-in theaters, around billboards, highway and railroad s-tructures, or on fallow land.
The rates of application for the compounds of the invention are determined by a number of factors, including the types of weeds to be controlled, weather and climate, formulations selected, mode of applica-tion, amount of foliage present, etc. In general terms, the subject compounds should be applied at levels of around 0.005 to 5 kg/ha, the lower rates being suggested for use on lighter soils and/or those having a low organic matter content, or for situations where only short-term persistence is required.
The compounds of the invention may be used in combination with any other commercial herbicide exam-ples of which are those of the triazine, triazole, uracil, urea, amide, diphenyletherl carbamateS ace-tanilide, bipyridylium, dinitroaniline and phenolic types.
The herbicidal properties of the subject com-pounds were discovered in a number of greenhouse tests. The test procedure and results follow.

. .

Test A
~, Seeds of crabgrass (Digitaria sp.), barnyard-grass (Echinochloa crus~lli), wild oats (Avena fatua) t sicklepod (Cassia obtusifolia), morningglory (~ sp.), cocklebur (Xanthium pensylvanicum), sorghum, corn, soybean, sugar beet, rice, wheat and purple nutsedge (Cyperus rotundus) tubers were planted and treated pre-emergence with the chemicals dissolved in a non-phytotoxic solvent. At the same time, these crop and weed species, along with cotton and bush bean, were treated with a soil/foliage application.
At the time of treatment, the plants ranged in height from 2 to 18 cm. Treated plants and controls were maintained in a greenhouse for sixteen days, after which all species were compared to controls and visually rated for response to treatment. The rat-ings, summarized in Table A, are based on a numerical scale extending from û = no injury, to 10 = complete kill. The accompanying descriptive symbols have the following~meanings:
A = growth acceleration;
C = chlorosis/necrosis;
D = defoliation;
E = emergence inhibi-tion;
G = growth retardation;
H = formative effects;
U = unusual pigmentation;
X = axillary stimulationi and 6Y = abscised buds or flowers.
It will be seen that the compounds have high pre-and post-emergence activity at the low rates of appli-cation selected for this evaluation. A few compounds, e.g., Compounds 26, 29, 46, 47 and 52, have low activ-ity at the very low rates of application selected for this test. It is reasonable to assume that these com-pounds would exhibit higher activity at higher use rates.

c~ 123 ~T _ e A Struotures Compound 1 O N
5 ~ 502-NH-C-NH ~ 0~
~ O CH3 Compound 2 OCH3 O N~
~S02-NH-C-NH--<0~

~ O OCH3 Compound 3 OCH

O N~
" ~0~
~ O CH3 Compound 4 OCH3 O N
52-NH-C-NH ~ O N

~ O CH3 Table A S-tructures (Continued) Compound 5 OCH3 O N ~
(~5 2 - N H - C - N H--<0~

Compound 6 CH3 O N ~
~;2-NH-C-NH ~0 N

~ O CH3 Compound 7 ~_S02-NH-C-NH--<~

Compound 8 S2-N~-C-NH ~

_ CH3 i~2~

Table A Structures (Continued) Compound 9 O N ~
~S02-NH-C-NH ~0~

~ 52 OCH3 Compound 10 O N ~
50 2 - N H- C -N H ~O N
~ S02 CH3 Compound 11 ` OCH3 502-NH-C-NH ~ ~

Compound 12 O N
502-NH-C-NH ~< 0 A N ~
~52 CH3 ~2~

Table A Structures (Continued) Compound 13 CH3 ~ SO2-NH-c-NH ~ ~

Cornpound 14 ~S02-NH-C-NH--<0~
~ SO2 OCH3 Compound 15 OCH3 SO2-NH-C-NH ~ ~ N

~ SO2 CH3 Compound 16 S02-NH-C-NH ~ ~

3~L 12 Table A Structures (Continued) Compound 17 CH3 ~ S02-NH-C-NH ~ ~
~ S02 N CH3 Compound 18 ~ S02-NH-C-NH--<~
~ S02 CH3 Compound_19 5 2 - N H - C - N H--(~

Compound 20 CH3 532-NH-c-NH ~ O N

S 2 ,, - -Table A Structures_(Continued) Cnmpound 21 ~ SO~-NH-C-NH ~ ~

Compound 22 ~ - 502-NH-C-NH ~ ~ N

Compound 23 O N ~
~0~

Compound 24 S02-NH-C-NH--<~

~2~(~9~

Tab1e A StrUCtUreS (COnt1nUed) COmPOUnd 25 ~ 5O2-NH-C-NH < ~

COmPOUnd 26 CH3 O N ~
~ S02-NH-C-NH--<ON
/~SO2 CH3 COmPOUnd 27 O N ~
502-NH-C-NH ~ O N

C mPOUnd 28 S2-NH-C-N~ 0 N

C~3 Table A Structures (Continued) .
Compound 29 O N
< ~ 502-NH-C-NH--<
~ N ~
CH3 ~ 502 CH3 Comoound 30 <~S02-NH-C-NH--<~

CH3 ~ S02 N CH3 ~Q~

Comeound 32 O N ~
30 ~ 502-NH-C-NH ~ O N
~ N ~
C 3 ~ 52 CH3 Table A Structures (Cont _ued) Compound 33 OCH3 ~ _ 502-NH- -NH ~ ~ N

Compound 34 OCH3 ~ S02-NH-C-NH--<~

~ S CH3 20 Compound 35 OCH3 50~-NH-C-NH ~ ~

~ S OCH3 Compound 36 o N ~
~S02-NH-C-NH~ON

~ S CH3 : 35 CH3 Table A Structures (Cont_nued) Compound 37 ~ 502-NH-C-NH ~ ~ N

Compound 38 ~ sO2-NH-C-NH ~ ~
~ S CH3 CH"'~CH

20 Compound 39 OCH3 ~502-NH-C-NH ~

Compound 40 CH3 ~502-NH-C-NH ~0 N
~ S OCH3 13~
Table A Structures (Continued) Compound 41 ~OCH3 O N-~
~ ~ 502-NH-C-NH ~ O N
~S N OCH3 Compound 42 O N ~
<~502-NH-c-NH~o~

Compound 43 OCH3 O N ~
52-NH-C-NH--~0~

Compound 44 OC~13 (:) N_~
<~ 5 2 - N H - C - N H ~0~

CH3 ~ S C~13 ~o~

Table A Structures (Continued) Compound 45 OCH3 ~ 5o2-NH-c-NH ~ ~

Compound 46 Cl CH3 \ O N
~ 02-NH-C-NH ~ 0~
CH ~ S CH3 Compound 47 Cl OCH3 ~ 532-NH-C-NH ~ O~

~ CH S CH3 Compound_48 OCH
Cl ~ 3 --S02-NH-C-NH--<
~ N ~
C ~ S OCH3 Table A Structures tContinued) Compound 49 ~ 5o2-NH-c-NH -< ~

Compound 50 2 NH-C-NH ~ ~
~ O N CH3 Compound 51 ON _ , ~S02-NH-C-NH~<

~ O OCH3 Compound 52 ~ O ~ N

N ~

~H3 Table A Structures (Continued) Compound 53 O N ~
~ SO2-NH-C-NH ~ ~ N

~0 CH 3 CH

Compound 54 ~ SO2-NH-C-NH-< O N

Compound 55 ~N~

)--~ N
~0 CH3 Compound 56 O N~
502-NH-C-NH ~0~
~0 CH3 Table A Structures (Continued) Compound 57 S02-NH-C-NH~

Compound 58 ~ N ~

O OC~13 -~ound ~9 ~2~0~

(~5 2 C \(~

C~r.DOUn~ 6C

~5 0 2 N H C N H~

ComDoun~ 61 c~3 CDmDound 62 r~

g~(S 2 N H C 7~ H -(~0~

C~m~ound 63 " /~3 CDmp~und 6~

[~`502NHCNH~
CH ( OC113 ) 2 C~mD~u~d 65 -Table A

Structure No.

Rate kg/ha û.05 0.05 0.05 POST-EMERGENCE
aush bean 3C,8G,6Y 6C,9G 6C,9G,6Y
Cotton 3C,3H,9G 6C,9G 6C,9H
Morningglory 2C,9G 3C,9H 6C,9G
Cocklebur 5G lOC 9C
Sicklepod lC,5G 6C,9G 4C,8H
Nutsedge 4G 6C,9G 2C,8G
Crabgrass 4G 6C,9G 2C,7G
Barnyardgrass 2C,9H lOC lOC
Wild Oats 2C,6G 7C,9G 5C,9G
~heat 2C,6G 2C,9G 6C,9G
15 Corn 2C,8H lOC 3U,9G
Soybean 3C,9G,5X 5C,9G 4C,9G
Rice 2C,9H 5C,9G 5C,9G
Sorghum 3C,9H 5C,9G 9G
Sugar beet PRE-EMERGENCE
Morningglory 2C,6H 8G 9G
20 Cocklebur 8H 9H 9H
Sicklepod 6G 7G 2C,7G
Nutsedge 3G lOE 2C,9G
Crabgrass lC 2C,6G 2C,8G
aarnyardgrass 4C,9H 5C,9H 6C,9H
Wild Oats 2C,9H 4C,9H 3C,9H
Wheat lC,9G 9H 9G
25 Corn 2C,7G lOH 5C,9H
Soybean 2C 9H 9H
Rice 2C lOE 5C,9H
Sorghum 2C,8H 5C,9G 4C,9H
Sugar beet Table A (continued) Structure No.

Rate kg/ha 0.05 0.05 0-05 POST-EMERGENCE
Bush bean 9C 9C 3C,9G,6Y
Cotton 6C,9G 9C 2C,5G
Morningglory lOC 9C 2C
10 Cocklebur 9C lOC 2C
Sicklepod 4C,7H 2C,8H 2A
Nutsedge 7X 3C,6G O
Crabgrass 3C,8G 2C,8G O
Barnyardgrass 9C 9C 2C,7H
Wild Oats 6C,9G 9C lC
Wheat 9C lOC O
15 Corn lOC lOC 2C,8H
Soybean 9C 9C 2C,5H
Rice 6C,9G 6C,9G 6G
Sorghum 9C lOC 2C,8H
Sugar beet .
PRE-EMERGENCE
Morningglory 9G 9G 2C,5H
20 Cocklebur 9H 9H 2C,9H
Sicklepod 5C,9G . 5C,9G lC
Nutsedge 5G 2C,7G O
Crabgrass 3C,6G 3C,7H O
Barnyardgrass 5C,9H 5C,9H 2C,7H
Wild Oats 4C99H 4C,9H 2C,8G
Wheat 2C,9G 2C,9G lC
25 Corn 5C,9G lOH 4C,7H
Soybean 9H 9H lH,lA
Rice lOE lOE 4C,7H
Sorghum 7C,9H 6C,9H 4C,8H
Sugar beet Table A (continued) Cmpd. 7 Compound 8 5 Rate kg/ha 0.05 0.4 0.05 POST-EMERGENCE
Bush bean 5C,9G,6Y 9C 9C
Co-tton 5C,9G 9C 9C
Morningglory 4C,9G lOC 9C
10 Cocklebur 3C,9G 9C lOC
Sicklepod 3C,8G lOC 9C
Nutsedge 9G 5C,9G 9G
Crabgrass 4C,9G 6C,9G 5C
Barnyardgrass 9C 9C 5C
Wild Oats 9C 6C,9G 6C
`~heat 9C 9C 6C
Corn 4U,9G 3U,9C 5U
15 Soybean 4C,9G 9C 9C
Rice 9C 5C,9G 5C
Sorghum 5C,9G . 5C,9G 4C
Sugar beet 9C - -PRE~EMERGENCE
Morni.ngglory 9G 9C 9G
20 Cocklebur 3C~8H 9H 9H
Sicklepod 3C,7G 9G 9G
Nutsedge 3C,8G lOE lOE
Crabgrass 3C,7G lOE 5C,9G
Barnyardgrass 3C,8H 9H,7C 6C,9H
Wild Oats . 5C,9G 6C,9H 6C,9H
Wheat 3C,9G lOE lOE
Corn 2C,9G lOH lOE
25 Soybean 3C,6H 9H 9H
Rice lOE lOE lOE
Sorghum 3C,9G lOE 6C,9H
Sugar beet 4C,9G lOE lOE

~2~

Table A (continued) Compound 9 Compound 10 5 Rate kg/ha 0.4 0.05 0.4 0-05 POST-EMERGENCE
aush bean 9C 6C,9G,6Y 9C 6C,9G,6Y
Cotton 9C lOC 4C,9G 5C,9G
Morningglory lOC lOC 4C,9G 3C,7H
Cocklebur 9C 9C 5C,9G 4C,8G
Sicklepod 9C 9C 5C,9G 3C,7G
Nutsedge 9C 9G 2C,8G O
Crabgrass 7C,9G 7C,9G 4C,9G 2C,8G
3arnyardgrass 9C 7C,9G 9C 4C,9H
Wild Oats 6C,9G 6C,9G 9C 6C,9G
Wheat 7C,9G 6C,9G 6C,9G 9C
Corn 9C 9C 7C,9G 4U,9G
Soybean 9C 9C 9C 3C,7G
Rice 6C,9G 5C,9G 5C,9G 4C,9G
Sorghum 9C 5C,9G 2C,9G 2C,9G
Sugar beet PRE-EMERGENCE
Morningglory 9H 5C,9G 9G 2C,5G
20 Cocklebur 9H 9H 9H 5H
Sicklepod 9G,4C 5C,9G 9G 7G
Nutsedge lOE lOE 2G lC,3G
Crabgrass 6C,9G 5C,9G 2C,6G 2G
Barnyardgrass 6C,9H 5C,8H 3C,9H 4G
Wild Oats 6C,9H 5C,9H 3C,8H 2C,6G
Wheat 6C,9H 5C,9H 5C,9H 9G
Corn lOE 5C,9G 5C,9H 2C,8G
25 Soybean 9H 9H 2C,8H lC,lH
Rice lOE lOE lOE lOE
Sorghum lOE 6C,9H lOH 9H
Sugar beet lOE lOE lOE 6G

g~

T _ e A (continued) Cmpd. 11 Cmpd. 12 Cmpd. 13 Cmpd.14 5 Rate kg/ha 0.4 0.05 0.05 0.05 POST-EMERGENCE
Bush bean 9C 9C 9C 9C
Cotton 4C,8G 5C,9G 6C,9G 5C,9G
Morningglory 9C 5C,9G 9C 9C
10 Cocklebur 4C,9G 9C 9C lOC
Sicklepod 5C,9G 4C,9G 9C 9C
Nutsedge 7G 4C,8G lOC 6C,9G
Crabgrass 4C,9G 5C,9G 9C 7C,9G
aarnyardgrass 4C,9H 5C,9H 6C,9H 9C
Wild Oats 6C,9G 9C 9C 9C
Wheat 4C,9G 9C 9C 9C
Corn 3C,9G 5U,9C lOC 9C
15 Soybean 9C 9C 9C 9C
Rice 5C,9G 5C,9G 6C,9G 6C,9G
Sorghum 2C,9G 5U,9C 9C 9C
Sugar beet - 9C 9C 9C
PRE-EMERGENCE
Morningglory 9G 9G 9C 9C
Cocklebur 9H 9H 9H 9H
~ Sicklepod 9G 5C,9G 2C,9G 9G
Nutsedge 5G lOE lOE lOE
Crabgrass 2C,6G 5C,9G 6C,9H 6C,9G
aarnyardgrass 3C,9H 4C,9H 6C,9H 6C,9H
Wild Oats 2C,8H 4C,8G 6C,9H 6C,9H
Wheat 9G 9H 9H 9H
Corn 2U,9G 5C,9H 9H 9H
Soybean 2C,8H 8H 9H 9H
Rice lOE lûE lOE lOE
Sorghum 4C,9H 5C,9H lOH 6C,9H
Sugar beet lOE lOE lOE lOE

~ ~2~

1~13 Table A (continued) Compound 15 Compound 16 Rate kg/ha 0.4 0.05 0.4 0.05 POST-EMERGENCE
Bush bean 9C 9C 9C 6C,9G,6Y
Cotton 4C,9G 5C,9G 4C ? 9G 4C,9G
Morningglory 9C 4C,8H 5C,9G 4C,9G
Cocklebur 9C 4C,9H 9C 5C,9G
Sicklepod 9C 5C,9G 9C 5C,9G
Nutsedge 3C,9G 3C,9G 9G 2C,8G
Crabgrass 9C 4C,8G 7C,9G 2C,8G
3arnyardgrass 9C 9C 9C 9C
Wild Oats 9C 9C 9C 9C
Wheat 9C 8U,9G 9C 9C
Corn lOC 9C 9C 7U,9C
Soybean 6C,9G 5C,9G 6C,9G 5C,9G
2ice 9C 9C 9C 9C
Sorghum 9C 6C,9G 9C 6C,9G
Sugar beet 9C 9C 9C 9C
PRE-EMERGENCE
Morningglory 9C 9G 9C 9G
Cocklebur 9H 9H 9H 2C,8H
20 Sicklepod 9G 9G 9C 9G
Nutsedge lOE 2G lOE 5C,9G
Crabgrass 5C,9G 7G 7C,9G 2C,6G
Barnyardgrass 6C,9H 3C,8G 6C,9H 5C,8G
Wild Oats 6C,9H 4C,9H 6C,9H. 5C,9H
Wheat lOE 5C,9H 6C,9H gH
Corn lOE 5C,9H lOH 5C,9H
25 Soybean 8H 8H 9H 8H
Rice lOE lOE lOE lOE
Sorghum 7C,9H 5C,9H 7C,9H 5C,9H
Sugar beet lOE lOE lOE lOE

Table A (continued) Cmpd. 17 Cmpd. 18 Cmpd. 19 Cmpd.20 5Rate kg/ha 0.05 0.05 0.05 0.05 POST-EMERGENCE
Bush bean lC lOD,9G,6Y 9D,9G,6Y O
Cotton lC,2H 4C,9G 4C,9G O
Morningglory 2C,3G 2C,8H 3C,9G O
Cocklebur 2G 2C,9H 5C,9G O
10 Sicklepod 2C,8H 6C,gG O
Nutsedge O ~ 2C,8G 9C O
Crabgrass 0 3C,9G 9C O
Barnyardgrass 3G 9C 9C O
Wild Oats 0 2C,9G 6C,9G O
Wheat O lOC 9C O
Corn 0 5U,9G lOC O
Soybean 0 3C,9G 5C,9G o Rice 5G 5C,9G 9C O
Sorghum lC 5C~9G lOC O
Sugar beet 2G 9C 9C O
PRE-EMERGENCE
Morningglory 0 9H 5C,9H O
Cocklebur 0 9H 9H O
20 Sicklepod 0 8G 9G O
Nutsedge 0 2C l.OE O
Crabgrass 0 2C,3H 2C,6G O
Barnyardgrass 0 5C,9H 5C,9H O
Wild Oats 0 5C,9G 5C,9G O
Wheat O lOC 6C,9H O
Corn 0 2C,9H 9C O
25 Soybean 0 3C,8H 9H O
Rice 0 5C,9H lOE O
Sorghum 0 5C,9H 5C,9H O
Sugar beet 2C 5C,9G 9C O

~L2~

Table A (contînued~

Cmpd. 21 Cmpd. 22 Compound 23 Rate kg/ha 0.05 0.05 2.0 0.05 POST-EMERGENCE
Bush bean 4C,9G,6Y 6C,8G,6Y 3C,5G,6Y O
Cotton 3C,4G 4C,8G 4C,8G O
Morningglory 5C,8H 4C,9H 4C,8G O
Cocklebur 5C,9H 4C,8H 4C,9G O
Sicklepod 2C,4H 3C,3H 3G O
Nutsedge 2C O 2G O
Crabgrass 2C,7G 2C,8G 2G O
Carnyardgrass 9C 9C O O
Wild Oats 8C 9C O O
Wheat 9C lOC 5G,5X O
Corn 7U,9C 9C 3H O
Soybean 4C,8G,5X 2C,9G lC,5G O
Rice 6C,9G 5C,9G 2C,5G O
Sorghum 5U,9C 9C 2C,7H O
Sugar beet 5C,9G 9C
PRE-EMERGENCE
Morningglory 3C,8H 9G 2H O
20 Cocklebur 9H 5C,9G 8H O
Sicklepod 2C,7G 2C,3H lC O
Nutsedge O O O
Crabgrass lH o O O
Barnyardgrass 2C,5G 6H 4G . O
Wild Oats 2C,9G 2C,9G 5G O
Wheat 2C,9G 2C,9G 4G o Corn 3C,9H 5C,9H 5C,8H 2G
25 Soybean 2C,3H lC,lH 2G O
Rice lOE lOE O O
Sorghum 5C,9G 5C,9H 2C,7G 2G
Sugar beet lC 4C,8G

Table A (continued~

Cmpd. 24 Cmpd. 25 Compound 26 5 Rate kg/ha 0.05 O.û5 2.0 0.05 POST-EMERGENCE
Bush bean 3C,9G,6Y 7C,9G,6Y O O
Cotton 3C,4H,9G 4C,4H,9G û O
Morningglory 3C,9G 3C,8G O O
Cocklebur 3C,9G 3C,9G 3 O
10 Sicklepod 2C,5G 3C,8H O O
Nutsedge 3G 3G O O
Crabgrass 0 2H O O
aarnyardgrass 2C,5H 6H O O
Wild Oats 2G O O O
Wheat 8G 4G O O
Corn 3C,9G 2C,9G 3 O
Soybean 3C,9G 3H39G O O
Rice 3C,9G 6C,9G O O
Sorghum 3C,9G 9G O O
Sugar beet - - - -PRE-EMERGENCE
Morningglory 2C,8H 2C,8G O O
Cocklebur 811 9H O O
20 Sicklepod 0 3C,8H o o Nutsedge 0 2C,6G 3 O
Crabgrass 2C,4G lC O 3G
aarnyardgrass 6H 2C,7H O 3G
Wild Oats 2G 2C,8H O o Wheat 7G 2C,9G O O
Corn 2C,9H 2C,8G O O
25 Soybean 2C,6G 2C,6H O o Rice 3C,7H 9H O O
Sorghum 4C,8H 3C,9G O O
Sugar beet Table A (continued) .

Compound 27 Compound 28 5 Rate kg/ha 0.4 0.05 2.0 O.û5 POST-EMERGENCE
Bush bean 5C,9G,6Y 2CJ2H 6C,9G,6Y lC,3G
Cotton 4C,8G lC 2C,3H,8G lC
Morningglory 3C lC 5C,9H lC
1 Cocklebur 2C,5H lC 2C,5H O
Sicklepod 3C lC 3C,4H lC
Nutsedge 2G O O ~ O
Crabgrass 2G O lC,3G O
Barnyardgrass 2C,7H O 5C,9H O
'l~ild Oats 9G,7X 4G,5X 5C,9G O
~heat lOC lC,5G 9C O
Corn 9C 2C,7H 6U,9C O
15 Soybean 2H,5G lC,lH 3C,5G O
Rice 9C 2U,9G 9C O
Sorghum 9C 2C,9H 2U,9G O
Sugar beet PRE-EMERGENCE
Morningglory 2C,4G O 8G O
~ Cocklebur lH O 8H 2G
20 Sicklepod O 0 8G 2G
Nutsedge O 0 8G 2G
Crabgrass O 0 2G 2G
Barnyardgrass 2G O 2C,8G 2G
Wild Oats 5H O 2C,8G O
Wheat 8G O 2C,9G O
Corn 3C,9G 2C,5G 2C,9G O
25 Soybean O lH lC,2H 2G
Rice 9G,9E 2G 5C,7G O
Sorghum 2C,9G lC,4G 3C,9G O
Sugar beet Table A (continued) .

Cmpd. 29 Cmpd. 30 Cmpd. 31 Cmpd.32 5 Rate kg/ha 0.4 0.4 0.4 0.4 POST-EMERGENCE
Bush bean lC 4C,9G,6Y 9D,9G,6Y O
Cotton lC 5C,9G 5C,9G O
Morningolory 0 4C98H 4C,6H O
Cocklebur lC 5C,9G 3C,9G O
10 Sicklepod 2C,3H 3C,8G o Nutsedge 0 2G 2G O
Crabgrass 2G 4G lC,3G O
aarnyardgrass lC 2C,8H lOC O
Wild Oats O 0 3G O
Wheat 0 3G 5G O
Corn 0 3C,7G 2C,9H 3 Soybean 0 4C,8G 5C,9G O
Rice 0 4C,9G 6C,1G O
Sorghum 2C 5C,9G 9G O
Sugar beet - - - -PRE-EMERGENCE
Morningglory 0 9G 9G O
Cocklebur - 9H 8H O
20 Sicklepod 0 2C,8G 9G O
Nutsedge lOE lOE lOE O
Crabgrass lC 2C 4G O
3arnyardgrass lC 2C,9H 5C,9H O
Wild Oats 2G 2C,6G 2C,6G O
Wheat 0 9G 9H O
Corn 2C,5G 2C,9G 2C,9G O
25 Soybean 0 2C,6H 9H O
Rice lC lOE lOE O
Sorghum 2C,3G 5C,9H lOH O
Sugar beet Table A (continued) Cmpd. 33 Cmpd. 34 Cmpd. 35 Cmpd.36 5 Rate kg/ha 0.4 0.05 0.05 0.05 POST-EMERGENCE
Bush bean 4C,9G,6Y 9C 9C 5C,9G,6Y
Cotton 5C,9G 4C,9G 4C,9G 4C,8G
Morningglory 2C 5C,9G 9C 4C,7G
10 Cocklebur 2C 9C lOC lOC
Sicklepod 2C 5C,9G 9C 4C,8G
Nutsedge 0 5C,9G 9C 2G
Crabgrass 2G 9C 6C,9G lC,3G
Barnyardgrass 2H 9C 9C 4C,9H
Wild Oats 3G 9C 9C 2C,8G
Wheat 2G 9C 9C 8G
Corn 4C,8H 9C 9C 5U,9G
Soybean 5C,6G 5C,9G 9C 5C,9G
Rice 3C,9G 9C 9C 6C,9G
Sorghum 2C,9G 9C 9C 3C,9G
Sugar beet - 9C 5C,9G 5C,9G
PRE-EMERGENCE
Morningglory 2G 9G lOC 9C
20 Cocklebur 9H 8H 9H 9H
Sicklepod 2C,6G 9C 3C,9G 8G
Nutsedge 0 9G lOE 2C
Crabgrass 2G 4C,8G 5C,9G 2C,4G
Barnyardgrass 2C,7G 9C 9H 3C,6H
Wild Oats 3C 4C,9G 5C,9G 2C,9G
Wheat 2C,9H 9C lOC 2C,8G
Corn 2C,9H 9C 5C99G 3C,9H
Soybean 2C,3H 4C,8H 3C,8H 2C,7H
Rice lOE lOE lOE lOE
Sorghum 5C,9G 9H 6C,9H 5C,9H
Sugar beet - 5C,9G 5C,9G lOC

Table A_(continued) Cmpd. 37 Cmpd. 38 Cmpd. 39 Cmpd.40 Rate kg/ha 0.05 0.05 0.05 0-05 POST-EMERGENCE
Bush bean 5C,9G,6Y 4C,6G,6Y 5C,9G,6Y 4C,8G,6Y
Cotton 4C,8H 4C,7H 4C,9G 4C,7H
Morningglory 3C,7G 4C 3C,8G 4C,9G
Cocklebur 9C 3C,8H 9C 3C,9H
Sicklepod 3C,8G 2C 4C,5H 2C
Nutsedge 3G 2G 4C,9G O
Crabgrass 3G lC 2C,8G lC
Barnyardgrass 3C,9H 4C,sH 9C 3C,9H
Wild Oats 3C,9G 2C,6G 9C lC,3G
Wheat 2C,9G,5X 2C,8G 9C lC,5G
Corn 3U,9G 2C,8H 4U,9C 2C,9G
Soybean 5C,9G 2C,8G 4C,9G 4C,9G
Rice 5C,9G 5C,9G 6C,9G 6C,9G
Sorghum 2C,9G 4C,9H 9C 2C,9G
Sugar beet 9C 4C,7G 9C 4C,8G
PRE-EMERGENCE
Morningglory 9G 2C,8H 9G 3C,8G
Cocklebur 9H - 9H 9H
Sicklepod 9G 4G 2C,4G 2C,5G
Nutsedge 2C 4G lOE O
Crabgrass lC,2G 2G 2G lC
Barnyardgrass 3C,8H 3C,9H 4C,9H 5C,8H
Wild Oats 2C,6G 2C,8G 2C,9G 3C,7G
Wheat lC,5G 2C,9G 2C,9H 7G
Corn 2C,9H 2C,9H 2C,9H 2C,9G
Soybean 2C,6G 2C,3H 2C,5H 3C,6H
Rice lOE 5C,9H lOE lOE
Sorghum 4C,9G 3C,9H 2C,9H 2C,9H
Sugar beet lOE 9G 4C,9G 4C,9G

Table A (continued) Cmpd. 41 Cmpd. 42 Cmpd. 43 Cmpd.44 Rate kg/ha 0.05 0.4 0.4 0.4 POST-EMERGENCE
Bush bean 4C,9G,6Y 5C,9G,6Y 9C 2C
Cotton 2C,2H 5C,9G 5C,9G 2C,2H
Morningglory 4C,8H lOC 4C,8G lC
Cocklebur 4C,9H lOC 9C 3C,7H
Sicklepod 2C,3H 9C 9C 2C
Nutsedge 0 9G 4C,9G 2G
Crabgrass 2C 5C,9G 5C,9G O
3arnyardgrass 4C,8H 5C,9H 9C O
Wild Oats 3C,9G 5C,9H 4C,9G O
'~Iheat 2C,5G 4C,9G lC,7G O
Corn lU,9G 3U,9G 4U,9G O
Soybean 3C,9G 9C 9C 2G
Rice 5C,9G 5C,9G 5C,9G O
Sorghum 2C,9G 2U,9G 3C,9G O
Sugar beet 3C,5H 9C 5C,9G
PRE-EMERGENCE
Morningglory 8G 9G 9G 8G
Cocklebur 8H 9H 9H 8H
20 Sicklepod 7G 9G 9G 5G
Nutsedge 2G lOE lOE 5G
Crabgrass lC lOE 5C,9G O
~arnyardgrass 4C,8H 5C,9H 5C,9H 3C
Wild Oats 2C,8G 5C,9H 4C,8G O
Wheat 2C,7G 9H 8G O
Corn 2C,9G 9H 3C,9G 3C
Soybean 2C,4H 9H 9H 2C
Rice lOE lOE lOE 2C,5G
Sorghum 2C,9H lOE 5C,9G lC
Sugar beet 3C,9G lOE lOE

~29L~

Table A (continued) Crnpd. 45 Cmpd. 46 Cmpd. 47 Cmpd.48 5 Rate kg/ha 0.4 0.4 0.4 0.4 POST-EMERGENCE
3ush bean 4C,4G,6Y O 0 6C,9G,6Y
Cotton 2C O lO lC
Morningglory O O O lC,2G
10 Cocklebur 3C,8G o o lC
Sicklepod 2C 3 O O
Nutsedge O O O
Crabgrass O 3 O O
Oarnyardgrass O O O O
Wild Oats O O O O
Wheat O
Corn O
15 Soybean 2C,4G O O lC,2H
Rice Sorghum O O
Sugar beet PRE-EMERGENCE
Morningglory 2G O O O
20 Cocklebur 8H O O O
Sicklepod SG O 8H O
Nutsedge O O
Crabgrass O O
aarnyardgrass 2C O O o Wild Oats O O O O
Wheat lC O O O
Corn 2C O O o 25 Soybean O O O lH
Rice 3C,8H O 2 O
Sorghum 3C,5H O O O
Sugar beet ~2~g~

Table A (continued) Cmpd. 49 Cmpd. 50 Cmpd. 51 Cmpd.52 Rate kg/ha 0.05 0.05 0.05 0.05 POST-EMERGENCE
8ush bean 5C,8G,6Y 9C 9C 4C,7G,6Y
Cotton 2C,5G 9C 9C lC
Morningylory lC,4G lC,4G 4C,8H lC
10 Cocklebur lC 2C,8H 9C lC
Sicklepod 0 4C,9G 9C O
Nutsedge lC,4G 3C,7G lOC 2G
Crabgrass 2G 3C,7G 2C,6G O
Barnyardgrass 2C,6H 5C,9H lOC O
Wild Oats 0 2C,9H 5G O
Wheat O lC,9G 5G O
Corn lC,4H 2C,8G 2C,9G O
Soybean 2C,4H 9C 9C 3C,3H
Rice 2C,4G 3C,9G 9G lC,4G
Sorghum 3C,8H 3C,9G 2C,9G IC,3G
Sugar beet lC,5G 4C,7G - 4C,9G
PRE-EMERGENCE
Morningglory 0 9G 9G lC
20 Cocklebur - - -Sicklepod 3H 9G 9G lC
Nutsedge. 9G lOE lOE O
Crabgrass 2G 5G 8G 2G
aarnyardgrass lC 5C,9H 9H lC
Wild Oats lC 3C,8H 3C,8G O
Wheat lC,5G 2C,9H 8G O
Corn lC,5G 9H 2C,9G O
25 Soybean 0 8H 7H O
Rice 2G lOE 9H O
Sorghum 3C,5G lOH 5C,9H 2G
Sugar beet 2G lOE - lC

Table A (continued) CmpdO 53 Cmpd. 54 Cmpd. 55 Cmpd.56 Rate kg/ha 0.05 0.05 0.05 0.05 POST-EMERGENCE
Bush bean 9C 9C 9C 9C
Cotton 2C,8G 9C 4C,8G 5C,9G
Morningglory 3C,6G 5C,9G 2C,8H 5C,9G
Cocklebur 3C,6G 9C 9C lOC
Sicklepod 5C,9G 5C,9G 5C,9G 9C
Nutsedge O lC,5G 4C,8G 9C
Crabgrass 2C,5G lC,4G 4C,9G gC
Barnyardgrass 2C,9H 3C,9H 9C 9C
Wild Oats O lC,5G 2C,9G 9C
'~heat 2G 4G 2C,9G 9C
Corn lU,9H lC,9G lOC lOC
Soybean 9C 9C 5C,9G 9C
Rice 5C,9G 5C,9G 5C,9G 9C
Sorghum lC,9G lC,9G 9C lOC
Sugar beet 2C,9G 3C,9G 2C,8H 9C
PRE-EMERGENCE
Morningglory 9G 9G lOC 9H
Cocklebur 9H 9H 9H 9H
Sicklepod 8G 9G 2C,9G 9G
Nutsedge 9G 8G lOE lOE
Crabgrass 2G O lC 8G
Barnyardgrass 3C 2C,7H 2C,9H 9H
Wild Oats 2C,4G 2C,6G 2C,9H 6C,9G
`~heat 6G 6G 5C,9H lOC
Ccrn lC 7 9G 2U,9G 5C,9H lOH
Soybean 7H 9H 2C,8H 9H
Rice lOE lOE lOE lOE
Sorghum 2C,8H ZC,9H 3C,9H 6C,9H
Sugar beet lOE lOE 9G lOE

~2~109~

Table A (continued) Cmpd. 57 Cmpd. 58 5 Rate kg/ha 0.05 0-4 POST-EMERGENCE
Bush bean 9C 5C,8G,6Y
Cotton 5C,9G 4C,3H,9G
Mornîngglory 4C,5G lC,2H
Cocklebur lOC 5G
10 Sicklepod 4C,8H 2C,8H
Nutsedge 9C 9G
Crabgrass 5C,9G O
Barnyardgrass 9C 2C,8H
Wild Oats 9C O
Wheat 9C O
Corn lOC 2C,6G
15 Soybean 9C 2C,9G
Rice 9C 6G
Sorghum lOC 2C,9H
Sugar beet 9C
PRE-EMERGENCE
Morningglory 8H 6G
Cocklebur 9H 8H
20 Sicklepod 9G 5G
Nutsedge lOE 2C,8G
Crabgrass 8G lC
Barnyardgrass 9H 3C,6H
Wild Oats 5C,9G 2C,6C
Wheat lOH O
Corn 5C,9H 2C,7G
25 Soybean 2C,8H 2H
Rice lOE 5G
Sorghum 9H 2C,5G
Sugar beet lOE

15iA
C~mpound 5~ ComDound 5 Rate (kg/ha) O.C5 0,05 ~IST, ~r~ER5ENCE
Bush bean 5C, 9G, 6Y 9C
Cctton 5C, 9G 5C, 9G
Scrahum 6C, gG 9C
C3rn 3U, 9G lOC
Soybean 5C, 9G 5C, 9G
k'he2t 2C, 9G 9C
h'ild Oats 2C, 9G 3C, 9G
Rice 4C, 9G 9C
Barnyardgrass 3C> 8H 9C
Crabgrass 2C, 9G 9C
Morninoglory 5C, gG 5C, 9G
Cocklebur 9C 10C
Sicklep~d 3C, BG 5C~ 9G
Nutsedg~ g~CC 9C

PREE~ERG'NCE
SDrohu~ 2C, 9H 5C~ 9H
Corn 2C, 6H 5C, 9G
Soybean lC 2C 8H
~ild Oats O 2C, 8G
Rice 8H lOE
Earnyardgr~ss lC 5C, 9G
Crabgrass O 2C, 9 M,orningglory 2C, ~H 8G
Cocklebur 8H ~H
SicklepDd 4G 5C, 9G
Nutsedge D 10E
5ugar beet 9G lOC

~2~
155~
Compound 61 ComDound 62 Rzte (kg/ha) O.O~ 0.05 POS~EMERGEN _ ~ush bean 2C, 2H 9D, 9G, 6Y

~'~ld Oats ~ 4C, 9G
~arnyardgrass O 2C. 9G
Crabgrass lC 3G
Morningglory O

Nutsed~e 5 Sugar beet O iC
PREEMERGENCE
Sorghum O 2C, 9H
Soybtan O 2C, 8G
~ild Oats O 9H
Barnyardgrass O
Cr~bgrass Morningglory O . v Cocklebur O 5G
Sicklepod O lC, Nutsed~e O 76 Sugar beet O

3~
155;C
Compound 6~ Compound 64 Rate (kg/ha) 0.05 0.05 POSTE~'iERCENCF
Bush bean 5C, 9G, 6Y 5C, 9G, 6Y
Co~ t or ?G __ Corn 5C, 9G 6C 9H
Soybean 5C, 9G -5C, 9H
h'itd Oats 5C, 9G 6C 9G

Crabor~ss ~C, 9G ~C, 9H
~ 1 ~C 9G 4C 9H

Sugar beet 2C 9G 4C 9H
PRrEr~,FRGE~CE
__ Corn lC 9G 3C, 7H
Soybean gH 3C 3H
~ 2C, 9G ~C gH
Barnyardgrass 5C, 9H lC
Crabgrass 5C 2G
~orninggtory ?G 3C, 7H
Sicktepod 8G 2C
5ugar beet 1gE6 3C, 7H

Compound 65 Rate (kg/ha) O.OS
POSTEMERG'#CE
Bush bean 9C
Cotton 4C, gG
50r~hum 5C, 9G
Corn 9C
Soybean 4C, 9G
~heat 9C
~ild ~ats 5C, 9G
Rice 6C, 9 Barnyardgrass 9C
Crabgrass 9C
~,orningglory 4C, 9G
Cocklebur lOC
Sieklepod 3C, 9G
Hutsedq~ 5C, 9G
Sugar beet 5C, 9G
PREEMERGENCE
S~rghum 5C, 9H
C~rn 3C, 9G
Soybean 3C, 7G
~heat 3C, 9H
~ild Oats 3C, 9H
Rice 10E
Barnyard~r~ss 2C, 9H
Crabgrass 5C, 9G
Morninqgl~ry 9 Cocklebur 9H
Sicklepod lC, 9G
~utsedge lOE
Sugar beet 5C, 9G

Test B
Two plastic bulb pans were filled with Ferti-lized and limed Woodstown sandy loam. One pan was planted with corn, sorghum, Kentucky bluegrass and several grassy weeds. The other pan was planted with cotton, soybeans, purple nutsedge (Cyperus rotundus), and several broadleaf weeds. The following grassy and broadleaf weeds were planted: crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avena fatua), johnsongrass (Sor~hum hale-pense), dallisgrass ( aspalum dilatatum), giant fox-tail (Setaria faberii), cheatgrass (Bromu_ secalinus), mustard (8rassica arvensis), cocl<lebur (Xanthium pensvlvanicum), pigweed (Amaranthus retroflexus), morningglory (Ipomoea spp.), sicklepod (Cassia obtu-sifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A
12.5 cm diameter plastic pot was also filled with pre-pared soil and planted with rice and wheat. Another 12.5 cm pot was planted with sugarbeets. The above four containers were treated pre-emergence with several test compounds within the scope of the invention.
Twenty-eight days after treatment, the plants were evaluated and visually rated for response to the chemical treatments utilizing the rating system de-scribed previously for Test A. The data are summar-ized in Table B. Note that the compounds are highly active when applied as a pre-emergence treatment at low rates of application to soil.

Table B

PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM

Compound 3 Compound 9 Rate kg/ha 0.03 0.120 0.25 0.06 Crabgrass 2G 6G,3H lOC lOC
Barnyardgrass 7G,3H 9G,5H lOC 9G,9C
Sorghum - - lOC lOC
Wild Oats 6G 7G 9G 9G
Johnsongrass 7G,3H 8G,3H 9G,9C 9G
Dallisgrass 7G,3H 8G,3H lOC lOC
15 Giant foxtail 3G 5G,3H lOC lOC
Ky. bluegrass 9Gt9C 8G,8C 9G,9C 9G,9C
Cheatgrass 7G 8G,8C lOC lOC
Sugar beets 0 5G lOC lOC
Corn 4G 6G,5H lOC lOC
Mustard 9G,8C 9G,9C lOC lOC
Cocklebur 4G 6G,3H 7G,5H 6G,3H
20 Pigweed 8G lOC
Nutsedge 3G 5G lOC lOC
Cotton 2H 6G,5H 8G 8G
Morningglory 3G 7G,5H 8G 8G
Sicklepod 3G 4G 9G,9C 8G,8C
Teaweed 0 5G 7G 5G
Velvetleaf 2G 6G,5H 9G,9C 8G
Jimsonweed 4G,3H 7G,5H lOC 9G
Soybean 4G,3H 6G,5H 9G 9G
Rice 7G 8G,5H lOC lOC
Wheat 4G 7G,3C lOC lOC

~L2~

Table 8 (continued) PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM

Compound 12 Compound 25 Rate kg/ha 0.015 0.06 0.125 0.03 Crabgrass 9G 9G,9C O O
Barnyardgrass 6G 9G,9C 5G,3H o Sorghum lOC lOC 9G,9C 4G,2H
Wild Oats 7G 9G 2G O
Johnsongrass 8G 9G 8G,5H 6G,3H
Dallisgrass lOC lOC 3H O
15 Giant foxtail 9G 9G,9C 2H O
Ky. bluegrass 9G 9G,9C 5G,3H 3G
Cheatgrass 9G lOC 7G,5H O
5ugar beets 9G lOC 6G,5H 2G
Corn 7G lOC 9G,9C 2G
Mustard 9G 9G,9C 8G,8C O
Cocklebur 6G 9G 7G O
Pigweed - - 9G,9C 2G
20 Nutsedge lOC lOC o o Cotton 5G 7G 5G,3H O
Morningglory 6G 7G 7G O
Sicklepod 9G 9G 6G O
Teaweed 2G 6G 5G 2G
Velvetleaf 3G 9G 5H,5G O
Jimsonweed 8G 9G,9C 5G O
25 Soybean 6G 8G,7H 3G O
Rice lOC lOC lOC 4G
Wheat 8G lOC 2G O

~2~ 3~

Table B (continued) PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM

Compound 31 Rate kg/ha 0.05 0.125 0.03 Crabgrass O O û
Barnyardgrass 6G 4G 2G
Sorghum 9G,9C 8G,8C 6G
Wild Oats O O
Johnsongrass 9G lOC 6G
Dallisgrass O O
15 Giant foxtail 4G 2G 2G
Ky. bluegrass 7G 5G 2G
Cheatgrass 2G O O
Sugar beets 9G,9C 8G 4G
Corn 8G,5H 4G . 2G
Mustard 8G 5G 3G
Cocklebur 7G,3C 5G O
20 Pigweed - - -Nutsedge 2G O O
Cotton 2G O O
Morningglory 4G O O
Sicklepod 8G,8C 5G O
Teaweed 9G 8G O
Velvetleaf - - -Jimsonweed 4G 2G O
25 Soybean 4G 4G 3G
Rice lOC lOC lOC
Wheat 3G O O

Table B (continued) PRE-EMERGENCE ON
WOODSTOWN SANDY LOAM

Compound 42 Compound 50 Rate kg/ha 0.125 0.03 0.125 0.03 Crabgrass 9G 8G 7G 2G
aarnyardgrass 9G 8G 9G,9C 8G
Sorghum lOC 9G lOC 9G,9C
Wild Oats 8G 6G 7G 7G
Johnsongrass 9G 8G 8G 8G
Dallisgrass 7G 5G 8G 5G
15 Giant foxtail 9G 5G 6G 2G
Ky. bluegrass 9G 8G 9G,9C 8G
Cheatgrass 9G 7G 9G,9C 9G
Sugar beets lOC lOC lOC 8G
Corn 9G 6G 9G,9C 7G,5H
Mustard 9G 9G lOC 9G,9C
Cocklebur 7G 6G
2 Pigweed Nutsedge 7G 4G lOC lOC
Co-tton 9G 6G 8G 7G
Morningglory 7G 4G 3G O
Sicklepod 9G 9G 9G 9G
Teaweed 9G 8G 8G 7G
Velvetleaf 9G 9G 9G 8G
Jimsonweed 9G 9G 9G 8G
Soybean 9G 8G 7G,7H 6G,5H
Rice lOC lOC lOC lOC
Wheat 7G 3G 7G 3G

2~

Test C
The test chemicals, dissolved in a non-phyto-toxic solvent, were applied in an overall spray to the foliage and surrounding soil of selected plant spe-cies. One day after treatment, plants were observedfor rapid burn injury. Approximately fourteen days after treatment, all species were visually compared to untreated controls and rated for response to treat-ment. The rating system was as described previously lû for Test A. The data are presented in Table C.
All plant species ~ere seeded in Woodstown sandy loam soil and grown in a greenhouse. The following species were grown in soil contained in plastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa, corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania (Sesbania exaltata), sicklepod (Cassia obtusifolia), morningglory (Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthium pensylvanicum), crabgrass (Digitaria sp.), nutsedge (Cyperus rotundus), barnyardgrass (Echino-chloa crusgalli), giant foxtail (Setaria faberii) and wild oats (Avena fatua). The following species were grown in soil in a paper cup (12 cm diameter by 13 cm deep): sunflower, sugarbeets, and mustard. All plants were sprayed approximately 14 days after planting. Additional plant species are sometimes added to this standard test in order to evaluate unusual selectivity.
The compounds tested by this procedure are highly active post-emergence herbicides when one considers the low rates of application selected for this test.

Table C

Overall Soil-Folia~e Treatments Compound 4 Rate kg/ha 0.06 0.015 0.004 Soybeans 9G,5C 9G,3C 8G,6C
Velvetleaf 9G,5C 9G 9G
Sesbania 9G,9C 9G lOG
10 Sicklepod 8G 7G 6G
Cotton 2C,9G 6G 5G
Morningglory 9G,5C 9G 9G,4C
Alfalfa 8G,8G 8G,6C 6G
Jimsonweed 5G,2C 5G,2C 3G
Cocklebur 8G 8G
Corn 8G,6U 8G,2H 8G,2U
15 Crabgrass 8G 2G o R.ice 8G,7C 8G,3C 5G,3C
Nutsedge O O n aarnyardgrass lOC 8G 8G
Wheat 8G 5G 2G
Giant foxtail 9G 3G O
Wild Oats 7G,2C 7G O
Sorghum 7G,2C 8G 8G
20 Sunflower lOC lOC lOC
Mustard 8G,8C 7G,4C 5G,4C
Johnsongrass 8G,8U 7G,3U 8G
Sugar beets 9G 9G 6G
Bindweed 7G O O

Table C (continued) Overall Soil-Foliage Treatments Compound 13 Rate kg/ha 0.06 0.015 0.004 Soybeans lOC 9G,8C 9G,8C
Velvetleaf lOC 9G 8G
Sesbania lOC 9G 8G
Sicklepod 7G 7G lOC
Cotton 8G lOC lOC
Morningglory lOC lOC 7G
Alf-alfa 7G 9G 4C,4G
Jimsonweed 8G 8G 8G
Cocklebur 9G 9G 5G
Corn lOC lOC lOC
15 Crabgrass 9G 9G
Rice 9G,4C 9G,7C 9G,8C
Nutsedge 8G 8G,9C 7G
Barnyardgrass lOC lOC 8C,9G
Wheat 9G,3C 9G,6C 9G,3C
Giant foxtail 8G 8G 9G
Wild Oats 9G,3C lOC 9G,3C
Sorghum 9G,4U 9G,2U 2G,2U
Sunflower lOC 9G 9G
Mustard 9G lOC lOC
Johnsongrass 9G~8U lOC lOC
Sugar beets 2indweed lOC 7G 5G

Table C (_ontinued) Overall Soil-Foliaqe Treatments Compound 27 Rate kg/ha 0.25 0.06 0.015 Soybeans lH,6G 4G O
Velvetleaf 6G lC O
Sesbania 5G O ` O
Cotton 75GG lG 2G
Alfalfa 87GG 2G O
Jimsonweed 5G 5G O
Cocklebur 4G lG
Crabgrass 84CGG,94G 6GG 2G
Nutsedge 3G O O
3arnyardgrass 3G lG O
~heat lG O O
Giant foxtail O O O
Wild Oats lG O O
Sorghum 8G 8G 4G
20 Sunflower 6G,2H 3G lG
Mustard 9G 8G 5G
Johnsongrass 8G 7G O
Sugar beets 5G,4C 4G O
Bindweed 7G,2C 5G 2G

Table C ~continued) Overall Soil-Folia~e Treatments Compound 30 Rate kg/ha 0.25 0.06 Soybeans 7G,8C 6G,6C
Velvetleaf 6C 6G
10 Sesbania 5G,5C 5G,5C
Sicklepod 2C 2C
Cotton 8G 7G
Morningglory 9G 8G
Alfalfa 8G,4C 8G,4C
Jimsonweed 2G 2G
Cocklebur lOG 9G
Corn lG,lH lH
15 Crabgrass O O
Rice 9C 9G
Nutsedge O O
Barnyardgrass O O
Wheat 2G O
Giant foxtail 4G O
Wild Oats O
Sorghum 9G 8G
20 Sunflower lOC lOC
Mustard 7G 2G
Johnsongrass lOU lH,9G
Sugar beets lOC 8G
8indweed 8G 4G

Test D
Plastic pots lined with polyethylene bags were filled with prepared Woodstown sandy loam soil. Seeds of kochia (Kochia scoparia), Russian thistle (Salsola kali), downy brome (Bromus tectorum) and green foxtail .
(Setaria lutescens) were planted. About 10 days later seeds of wheat (Triticum aestivum) and wild oats (Avena fatua) were added. After an additional 10 days, seeds of wheat, corn and sorghum were planted.
The compounds were then diluted with a non-phytotoxic solvent and sprayed over the pots. An untreated con-trol and a solvent-alone control were included for comparison. All treatmen-ts were maintained in a greenhouse for 19-22 days at which time the treatments were compared to the controls and the effects visually rated.
The data, presented in Table D, indicate that certain of the test compounds have utility for the control of undesirable vegetation on land which is kept in fallow between cereal crops.

167 ~2~
Table D

Co~pound Nos.

Rate, g/ha 16 4 16 4 16 4 POST-EMERGENCE
Russian thistle 5C O lOC lOC lOC 7C
Kochia 5G O lOC 9G lOC 2G
10 Downy brome 5G O - 8C 6G lOC 8C
Green foxtail 5G O ac 7C 9C 6C
Wild oats 5G O lOC 9C lOC 9C
Wheat 9C O lOC lOC lOC lOC
PRE-EMERGENCE
15 Wheat O 0 8G O 3C,8G 2G

Compound Nos.

20 Rate, g/ha 16 4 16 4 16 4 POST-EMERGENCE
Russian thistle lOC 5G lOC 3G lOC lOC
Kochia 9C,9G 4G 9G ~G lOC lOC
25 Downy brome lOC 5G9C 6G lOC lOC
Green foxtail 4G 2G5G 4G lOC 7C,9G
Wild oats lOC 5GlOC 4G lOC lOC
Wheat lOC 8GlOC 9G lOC lOC
PRE-EMERGENCE
30 Wheat 8G O 9C 3G lOE 9G

,

Claims (39)

WHAT IS CLAIMED IS:

1. A compound selected from:

I I' II
wherein Q is O, S, SO or SO2;
Q1 is O, S or 5°2;
L is R1 is H or C1-C3 alkyl;
R2 is H or CH3;
R3 is H or CH3;
R4 is H, C1, CH3, CF3, OCH3 or Br;
R5 is H, CH3, OCH3, C1, Br, NO2, CO2R7, SO2R8, OSO2R9 or SO2NR10R11;
R6 is H, C1, Br or C1-C3 alkyl;
R? is H, CH3, C1 or Br;
R7 is C1-C3 alkyl, CH2CH=CH2, CH2CH20CH3 or CH2CH2C1;
R8 is C1-C3 alkyl;
R9 is C1-C3 alkyl or CF3;
R10 and R11 are independently C1-C2 alkyl;
R12 is H or CH3;
W is O or S;

A is X is H, CH3, OCH3 or C1;
Y is CH3, OCH3, OC2Hs, CH20CH3, NH2, NHCH3, N(CH3)2, CH(OCH3)2, , C2H5, CF3, SCH3, CH2=CC2O, HC?CCH2O or CF3CH2O;
Z is CH, N, CCH3, CC2H5, CC1 or CBr, G is O or CH2; and X1 is CH3, OCH3 or OC2H5;
X2 is CH3, C2H5 or CH2CF3; and Y2 is C2H5, CH3, OCH3, OC2H5, SCH3 or SC2H5;
provided that l) In Formulae I and I', when Q is O and R5 is other than H, C1, Br or NO2, then at least one of Rl and R2 is alkyl; and when Q is S, then R5 cannot be NO2;
2) In Formula II, when R5 is NO2 or SO2NR1OR11, then R6 is C1-C3 alkyl and R? is CH3;
3) when X is C1, then Z is CH and Y is OCH3, NH2, NHCH3 or N(CH3)2;

4) when Q is SO, then W is O, and 5) when R4 is other than H, then R5 is H.

2. A compound of Claim l, Formula I.

3. A compound of Claim 2 where W is O and R12 is H.

4. A compound of Claim 3 where R5 is H, C1, CH3, OCH3, CO2R7 or SO2R8

5. A compound of Claim 4 where R4 and R5 are H and R1 and R2 are independently H or CH3.

6. A compound of Claim 5 where A is Z is CH or N; and X is CH3, OCH3 or C1.

7. A compound of Claim 6 where Y is CH3, OCH3, CH2OCH3 or N(CH3)2.

8. A compound of the Claim 19 Formula I'.

9. A compound of Claim 8 where W is O and R12 is H.

10. A compound of Claim 9 where R5 is H, C1, CH3, OCH3, CO2R7 or SO2R8

11. A compound of Claim 10 where R5 is H and R1 and R2 are independently H or CH3.

12. A compound of Claim 11 where A is Z is CH or N; and X is CH3, OCH3 or C1.

3. A compound of Claim 12 where Y is CH3, OCH3, CH2OCH3 or N(CH3)2.

14. A compound of Claim 1, Formula II.

15. A compound of Claim 14 where W is O and R12 is H.

16. A compound of Claim 15 where R5 is H, Cl, CH3, OCH3, CO2R7 or SO2R8 and where L is at the 7-position.

17. A compound of Claim 16 where R5 is H and R6 is H or CH3.

18. A compound of Claim 17 where A is ;

Z is CH or N; and X is CH3, OCH3 or Cl.

19. A compound of Claim 18 where Y is CH3, OCH3, CH2OCH3 or N(CH3)2.

20. The compound of Claim 1, N-[(4,6-dimethyl-pyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, 1,1-dioxide.

21. The compound of Claim 1, N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, 1,1-dioxide.

22. The compound of Claim 1, N-[(4,6-dimethoxy-pyrimidin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, 1,1-dioxide.

23. The compound of Claim 1, N-[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, 1,1-dioxide.

24. The compound of Claim 1, N-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, 1,1-dioxide.

25. The compound of Claim 1, N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-2,3-dihydro-2-methyl-7-benzothiophenesulfonamide, 1,1-dioxide.

26. The compound of Claim l, 2,3-dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-2-methylbenzofuran-7-sulfonamide.

27. The compound of Claim l, N-[(4,6-dime-thoxypyrimidin-2-yl)aminocarbonyl]-2,3 dihydro-2-methyl-benzofuran-7-sulfonamide.

28. The compound of Claim l, N-[(4,6-dime-thoxypyrimidin-2-yl)aminocarbonyl]-2,3-dihydrobenzo[b]
thiophene-7-sulfonamide, l,l-dioxide.

29. The compound of Claim l, 2,3-dihydro-N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]
benzo[b]-thiophene-7-sulfonamide, l,l-dioxide.

30. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim l.

31. A method for controlling the growth of undesired vegetation which comprises applying to -the locus to be protected an effective amount of a compound of Claim 2.

32. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 3.

33. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 4.

34. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 5.

35. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 6.

36. A method for controlling the growth of unde-sired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim 7.

37. A method for controlling the growth of unde-sired vegetation which comprises applying to the locus to be protected an effective amount of a compound of Claim 8.

38. A compound of the formula:

39. A compound of the formula:

wherein: Q is o, SO or SO2;
R2 is H or CH3;
X is CH3 or OCH3;
Y is CH3 or OCH3; and Z is CH or N.