CA1126971A - 2,4-disubstituted-5-thiazolecarboxylic acids and derivatives - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE This invention provides a method of reducing injury to sorghum or rice crop plants due to the application thereto of acetamide herbicides. The method is carried out by applying to the plant locus a safening effective amount of a compound having the formula wherein n is zero or one; X is selected from the group consist-ing of chloro, bromo, iodo, fluoro, lower alkoxy, phenoxy and phenoxy substituted by one or two groups independently selected from the group consisting of lower alkyl and halogen; R is alkyl having up to nine carbon atoms; when n is one, R' is selected from the group consisting of hydrogen, agriculturally acceptable cations, alkyl, lower alkenyl, lower alkynyl, alkoxyalkyl, halo-alkyl, benzyl, phenyl and phenyl substituted by one or two members selected from the group consisting of halogen, lower alkyl, trifluoromethyl and nitro; when n is zero, R' is selected from the group consisting of chloro, amino and mono- or dialkyl-amino.

Description

This application is a divisional of co-pending application serial number 327,554, filed May 14, 1979.
This invention relates to novel 2,4-disuhstituted-5-thiazolecarboxylic acids and derivatives thereof as well as their use in compositions and methods for redueing herbi-eidal injury. More speeifically, the invention relates to novel compositions and methods for reducing injury to crop plants by herbieides, such as acetamides, espeeially acetanilides, whieh eomprises treating the crop plant loeus or the seed of the crop plant with an effective amount of a

2,4-disubstituted-5-thiazolecarboxylie aeid or derivative thereof that will be described more fully below.
BACKGROUND_OF T}-3E INVENTION
Acetalnide herbiei(les are very useful for con-l.rol11ng cerlain weeds, especially grasses, in the preseneeoE ~rowing crops. l~owever, many of the acetamide herbicides injure eertain crop plants slowing growth and development at application rates necessary to stunt or kill the weeds.
Aeeordingly, some of the aeetamide herbieides eannot be used for controlling weeds in the presence of eertain erops.
obviously, a safc-niny agent consisting of a eomposition that coulcl be used to treat the seed of the erop plant, the erop plant ]oeus or 1:he erop plant itself, resulting in a reduetion of injury due to applieation of the herb;eJde ~ilhout a colm/s-pol-c3inc3 rcduction of h(rbicidal rlC'ti~Jn (.)n t.]~C~ weed, would be ~uite h(nefi(-ial.
DESCRI PTION OF THE INVENTION
In accordanee with the novel aspects of the present invention, injury to erop plants, such as eorn, riee and sorghum, clue to applieation thereto of aeetamide herbieides, espeelally aeetanilide herbieides such as 2~chloro-2',6'-diethyl--N-(methoxymetllyl)acetanilide (hereinafter referred to by its com~on name, alaehlor), 2-chloro-2',6'-diethyl-N-(butoxyrnethyl)aeetanilide (hereinafter referred to by its eommon name, butaeh]or), 2-ehloro-N-isopropylaeetanilide '(hereinafter referred to by its eommon name, propaehlor), , `` -2- AG-1152 .
2-chloro-N- (2-methoxy-l-methylethyl) -6 '-ethyl-o-acetotoluidide and 2-chloro-N-5 (ethoxy,nethyl)-6'-ethyl-c-acetotoluidide, may be reduced without a corresponding reduction in injury to the weeds by appl ication to the crop plant locu s or the seed of the crop plant prior to planting of an effective arnount of a safening agent cornprising a 2,4-disubstituted-5-thiazole-10 carboxylic acid or derivative thereof having the formula O
R - C = Cj - C - (O)nR ' N~ S
C
X
wherein n is zero or one; X is selected from the group con-sisting of chloro, brorno, iodo, lower alkoxy, phenoxy and phenoxy substituted by one or two groups inderendently 15 selected frorn the group consisting of lower alkyl and halogen; R is selected from the group consisting of alkyl having up to nine carbon atoms, haloalkyl and trialkoxy-methyl; when n is one, R ' is selected from the group con-sisting of hydrogen, agri.culturally acceptable cati.ons, 20 alkyl (1-10 carhon atomx bei.ng p:r( fe~ ed), low-.-r alkenyl, lower alkynyl., lower al}ioxy l.ow~.~ a1.kyl, hi~.loalkyl, ben~yl, phenyl and phenyl sul:stituted by one or two m-?.mbers selected from the group consisting of haloyen, ].ower alkyl, trifluoro-methyl and nitro; when n is zero, R' is selected rrom the 25 group consisting of chlo.ro, amino and rnono- or di-] ower a lkyl am ino .
All of the compounds of the above formula are believedl¦
to be novel except those in which R is alkyl.
As used herein, the terms "lower alkyl", "lower 30 alkenyl" and "lower alkynyl" are understood to include alkyl, alkenyl and alkynyl groups having up to five carbon atoms, inclusive .
The terms "alkyl", "alkenyl" and "alkynyl" are - ~

~3~ ~ 26971 AG-1152 understood to include branchcd and unbranch,ed groups. When R' is lower alkenyl, allyl is preferred. When R' is lower alXynyl, propargyl is preferred.
The term "haloalkyl" is understood to mean those 5 alkyl moieties having up to five carbon atoms wherein at least one hydrogen atom has been replaced by a halogen atom.
Specifically included are those alkyl moieties in which all of the hydrogen atoms have been replac ed by halogen atoms, suc h as trif1uoromethyl.
The term "agrieulturally acceptable cations" is understood to mean those eations that are comTnonly used to ¦
form the salt of the free aeid. Sueh eations inelude, but are not lunited to, alkali metal, alkaline earth, substituted amine and ammonium eations.
The amount of safen;ng agent e-mployed in the nethod and compositions of the invention will vary depending upon the particular herbicicle with which the agent is eJnployc-d, the rate of application of the herbicide, the crop to be protected as well as the manner of application of the 20 safening agent. In each instance, the amount e~nployed is a safening effeetive amount, i.e., the amount which reduces erop injury by the acetamide herbieide.
The safening agent may be applied to the plant loeus in a mi~ture with the herbieide sequentially or it 25 may be applied direetly to the .seed OL the erop plant. By app]ieation to the "plant locus" jS nl~ al~t "ppl.icclt .ion t:o the planl: ~rowing mcc~ium, sl~ch as th~ ;oil, as w~11 as the seeds, emergirlg seedlings, roots, st~sns, leaves, flowers, fruit s or other plant parts.
The amount of her~ieide employed is well within the skill of the art and is diselosed in various patents.
Propaehlor and its herbieidal use is diselosed in U.S. Patent 2,863,752 and Relssue,26,961. Alaehlor, butaehlor and 2-chloro-N-(ethoxymethyl)-6'-ethyl-_-acetotoluidide and their 35 herbieidal use are diselosed in U.S. Patents 3,442,945 and

3,547,620. U.S. Patent 3,937,730 diseloses and elaims 2-chloro-N-(2-methoxy-1-methylethyl)-6'-ethyl-o-acetotoluidide.

- -4- ~G-1152 ~ i971 To illustrate the effectiveness of the 2,4-disubstituted 5-thia~olecarboxylic acids and derivatives thereof, the following examples are presented. These examples are presented merely as being illustrative of the novel aspects of the invention and are not intended to be a limitation as to the scope thereof.
~~ample 1 A good grade of top soil is placed in a container and compacted to a depth of approx;mately ].27 cm. from the top of said container. A predetermined number of seeds of each of the crop species to be tested are placed on top of the soil. A (~uantity of soil sufficient to substantially fill the con~ainer is measured and placed in a second con-lainer. A Ineasured ~uantity of the safening agent dis-persed or dissolved in a suitable carrier is applied to the soil in the second container. A measured quantity of the acetamide herbicide dispersed or dissolved in a suitable carrier is then sprayed on the soil already treated with the safening agent. The soil containins the safeni,ng agent and herbicide is thoroughly mixed. This mixing is sometimes reerred to as incorporaticn of the herbicide and safening ayent into the soil. The mixiny or incorporation provides a s~bstantial:Ly uniform distr:iblltjon o lhe sclf~niny agent and hlrbicicle t}lroughout tlle sc)il. Th(~ cds .]re coveted with the soil containing the saf(nincl agent and acetamide herbicide and the pots are leveled. The pots are then placc~ on a sand bench in the greellhouse and watered from below as needed. The plants are obser~ed at the end of approxirnately 21 days and the results in terms of percent inhibition of each seed lot are recorded. For each test series, a pot is also prepared containing no acetamide herbicide and no safening agent as a control. Additionally, for each test, pots are prepared with soil covering the seed containing no acetamide herbicide and only the measured 'amount of safening agent being incorporated into the soil covering the seeds to ascertain any herbicidal effect or the . ~

safening agent alone. For each series of tests, the herbicidal effect of the acetamide herbicide is observed from pots treated with the same quantity of herbicide alone.
The safening effect' is determined by adding the herbicidal effect of the acetamide herbici.de when applied alone to the herbicidal effect of the safening agent when applied alone (in no instance, nowever, will this sum be greater than 100) and substracting from that the herbicidal effect obtained when both the herbicide and safening agent are incorporated into the soil as discussed above.
Table I summarizes the results obtained when the compounds of the invention were -tested in accordance with the procedure of Examp.le 1 utilizi.ng alachlor as the herbi-cide.
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t~ ~I h r-l ~ O tl~ U~
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~r o I o '~ u Q) I ~ ~ Q rl wO t~ I h h Q (~
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S ~ S ~C> ~l td ~ a) ~ I I s tn ~ ,,, # .

-1S- liZ6~37~ AG-1152 r~ ~1 a) a) Ln In Ln Ln In Ln o o Ln o ~ Cl~
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u~ ~

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U~ h h h h u~ u~ u2 U) h h h 5~ h h h h aJ
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a) ,Q ~ O r--l f~1 ~ O r-i fN ~ O r-l f~l ~ O r-l (N ~ O r-l r~l ~ O r~l f~l ~r ,_ d ah) ,!C
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:

-16- 1~26~71 AG-1152 ~1 ~
r~ ~ o O O L~ O O U~ O O G~ ~O ~7 0 0 0 0 d' ~
4~ cr~ O C~ r ~ # # ~ c~ c~ i~ ~ `I ~ ~ ~ t` ~ I~ ~ ~ * *
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O t~ _~ ~ ~ r u~ ,~ ~ cr u~ r Ln ,~ ~ ~r

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tn u~ U~ h ~ h h ra l ~ r1 ~D ~1 ~r o~ D ~ ~ 0 ~D ~ ~r co O O-- u~ ;r ~ r-l N ~r O .4 ~ o .~l ;r o r~ I ~r o r-l t ~l ~.~ O r~l (~
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S-l N ~I 11~ rl O (~
r~l rl r--I r-l S .t;
c,) ,~ S S

:.

'; ~' :

( -18- ~Z697~ AG-1152 Table II summarizes the results obtained when the compounds of the invention were tested in accordance with the procedure of Example 1 utilizing butachlor as the - herbicide.

19 ~2697~ 7`,G - 1 15 2 ., ~ c, aJ ~ o ~ o o In o c~o o o ~ o r~ o l_ r) o u ~ ~ ~ ~ ~ r ~D ~r ~r ~ ~ ~ n r~
u~ ~

s s ~. s c .c~ ~ .C .c~c 5~ u ~ ~s~ o C~ O r~l O r~/ O ~ O ~1 0 ~-1 0 r~ O ~1 O ~ ~ O r~
n h UJ h v~ S~ u~ ~ u~ ~ u~

ra C~ C~ ~ C~ C~ C~~ C~ ~ C~ C~ CO C~ C~ C~
O O~ ~ r ~r -;r ~r ~r~r -;r ~r ~ ;r ~r ~r ~r ~ r ~ r~ C
o .4 ~ ~r ~r ~r ~r r ~r e~ -r ~ r -~ ;r ~ ~r ~r ir ~J
~ a),.~

H S
~ t;~ X
.4 ~ ,_ ~~ o~ c~ c~ ~ G~ ~ G~ c~
~I) O r~
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O
aJ ~ r~ X
r-l O ~ O ~O i~ O (a h ~ I h ~ I h r~ I h ~h r~ h r~ r~~r ~ %
.1.) ~ Il )O >~r~lO :~ O >~ O ~5 `~ I U ~) o I ::~ x ~ x ~ x ~ x ~-1 xo a) ~1) auh r-~ r-l 0 ~1r-l O~~~ O r-l O ~1 0 h ~Q~ " Q~1 ~ ~ Q r~ Q O O
o ~ r~ rl h.a ~r~ h~ h ~ h h hr-l N U~
u~ h ~ d h tr1 --1 r-l (1) lJIJ U~) Ir~ U ~ C~
I ,~ I a)I '1I C)I aJ I a) ~r a)I r ~1er X~r ,-~ ~r ~~r X~~r r~l er r-l~r r-lI r-l (~ ~1 ~) _~IO I:'~ IOIO IO IO IO OO I U
C)O ,S ~ O X O NO ,~ O N O N O N h N r-1 n ~h h h 0 1~ dh h s~ a h ~d O ~ ~ I ~
~o ~ o R o 1-lo ~o r~O ri O r~ l 1~1C r-l 4~
U~r~l U r~l ~~ S~ Ur- l r r-/ Sr--l 1~ S S 11) ~I C.) s ~ r ~ r ~JS ~1)r ~r ~ r ~ U ~ s s u ,~ u u u I u ~ u I u I u I I I ~ ~
O I Q~ I L'~I OI L~ L~ ¦ Lnt~l L'') O O
(~1 N ~ I(~ N (~ J I ( N I
O r~ r-lr--l r--lr--l r--l O O
1 r~ N r--I ~r--I riI--I ~r~l :~ r-l ~ ~ ~ ~I h ~.c :~ ~ ~s~1 c~r ~s ~s ~ s s o .c ~ r~ ~ r ~ r ~ ~ ~ x o s ~ U ~ r~
n ~ ~ ~ E~~ Ln~ ~ ~ ~ o ~ ~ ~ ~1~ *

2 o ~Z6971 _ r~
a) 0~ 0~ 03 o o ~ ( ~ ~ 1` ~ 1~ r~
~Df~ 1/'1 * 1~ D ~D ~r) ~ * ~ ~ D U') ~) N
U~ rL1 Q ,C ,~: ,~ ,~ r ,~
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r--l r~ G~ ) r r o r~ c~ r~a~ cs; c/:~ co G':) c~ r co Q ~ ~ rl) rd r~ rd r~ rJ7 ~:
r~l (I) rd r ~ I; r~J
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a) OrlJ I rvO rl) E~ri rl) I O S~
O J~ I ~ I ~ I O ~J~ ~) O ~J ~~ ,D, r~,) h rd:>1 rdO rd ,~ h rdr-l rd S~ r~ rdI ~I rl) o r-l X r~~ r~ '1 rdO r-l~ ~ O h ~O rr~ 3 r.~r--l X~I X '~ X ~ L)~ X S~ X r--II X O rO rl) rLI ~ QJJ Q ;~ Qrl) rd~l~ Q~J O ~ ~ O r-l r-l R
tn ,1 ,10 ,r~ ~ I R ~ auI R ~ O
r~ h ~ r~ O ~ ~ O ~ N rn ~ rd ~ rd ~ rd ~ r~ \ rd I rd ~ rd ~ rd I r~ d tnI t)~ ~ ~ r--lI t ~O t.lI r~ O ~ ) r ~I r1 3 ~ rlJ I rV I O ::5 r~1~ a)5-1 ~V~ r~ r--l rv S
I r--I ~ ~~ r--I r--l XI r-lO r~l I X S l--~ r--r ~ r'1 O I O I O ~IJ O O Or--l O O O ~ ) O
Cl X N ~ N O N ~I Q~ N S N ~ QI N S IJ~ ~V
O rd X rd~ rd ~ S~ O rdo rd O ~ ~I rd~ I
rd r~ r-lO r-l O ~ ~1~ rdr -l r-lI r~r-1 rl~r-l rlJ r~l ~
rJ~rl) S S S r--i SI C~S St~l S S t.)r--l S O ~ ~V
'~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~~) ~V ~ ~S~ S
v Ic) I I ~ r Ir--I II r--l S I O .L) ~1 r ~ O O ~ ~r~1 Ir)r.~ O~ u~) r--l a) r.~l I ~N I ~ I N I ~ I N rv I 5 ~= r l r-l r-l r-lO rdr~ r--lO ~--1 r-l rd:~, r-l t.) O ~
1 r~-1 r-~~ r~ ~r~ ~I X r ~ rv ~1 S ~1 Sr~l S S S S S ~, N S O S ',1 0 ~1 S ~I S ~Ir--l ~I C I ~~) JJO ~) ~ U ~) -IJ
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t_)O r lO ~--1 0 rl O ~ O --~ O ~ O ~ O
tn s~tn htn ~ tn S~ tn ~ ~n ~ (n s ~ ~n tv rl r~ t~ ~~0 rl~ r~ r r~ t~t~l t~l t~ r~ t~ t ~J t~
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0 rl tv C t.J rxJ r~r rl~ r~ rr~ r.~ r~ r~ r~ t~O r r~ r~ r.~ t~o r~ tV tl) .q ~ 4 r~ rl ) rr~ t~
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~5 t~5 0 ~1 I tt5 tv r--l Sr~ r1 0 I tl) tv r-l ~ T50 r-l ~~ t~ ~-I E
-~JU_l ~r-l r-l ~1 ~O S~ r~5 0 0 ~) Ctt5 X 4~ X ~ C5 I X r-l~4 N tv tvJ-' Ott5 X~ O Otl) rl ~ O ._ O ~ Q
~D~ Q J_) 0r-1 R ~ tVE C)I .at~ tvrl r~I~ ~V S~l~r . ,Q ~ ~ r-l L)0 rt50 ~1 r1 ~-- ~) S tn ~ rt5tv ~~-1 tt5 4-1 rt5 LlS.j t5,Li 1~5r~l ~J tt5 ti I I t )R- tt5 h t~rl r-l 0 t.) 0 t IJ r-l t~5 1 3 C~ tl)I t~~ tv ~5 r~ r-I tVI ~1tn ul rlI r~l~r tl) I r-l~) Xr--l r~l,( I r~l ~ X I ~J
r O O I r-~~ O I O ~ ~ ~1t ) OI O tV r~~ ~ ~
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r~5 r-l r10 tt5 E~ ~r~ O tt5~) QI r~ O ~t5 E ~) ~
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tN 1/~tN I tN N~ r-ltv I~ N1~5 0 rt r l r~l I r~ 50 0 rl rit~5.~ '~5 C
~ r-l r-lr-l >1 r-l rl l- i Nl~1 ~1r-l ~1~) r-l tV
S R~'`1 >1>1 C >1S.C (~5 r s ~s ~ ~ rc5 ~
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(~ ~4 U) ~

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S N I N h 3 U ~t~l 0 0 .~
C I r~ r1 ~ t~) a) ~ 4_1 . r-l R
~ ~J O ~ 4-1 a) FC 4~ r~ ~ tn ~J~ O I.sJ U) h t~5 rd L~ r~r~ ~1 1 ~
r~ r-~ ~tn ~ ~ x JJ
~: ~J S r~J, .C ~ I O ~ r~
a) ~n ~ ,~ a) ~ rt 0 5~ aj 4~ a) ~,) .C al ~.) S-l .~1 4-1 rd a) F rd ~ ~ 115 0 (a 4-J
v~ ~ E~ O ~ t) a lu h rd ~0 ,1~ ~ r t~
r~ ~i ~ ~ N ~1 >1~4 XO ~ X ~a ~
S r1 0~ rl O r-l ~1 Cl o ~ ~ ,c r1 I rd ~n I ra IJ I u~
~,)H ~ 0 ` ~2~;;9'71 ( -23- .~G-1152 Exanple 2 : A good grade of top soil is placed in a p]astic pot. A measured quantity of the safening agent dispersed or dissolved in a suitable carrier is sprayed on the soil surface. A measured quantity of butachlor herbicide dissolved in a solvent is sprayed on the soil surface.
Pre-soaked rice is seeded into the pots that were pre-viously flooded with water. The pots are flooded at least up to the soil surface for the duration of the test. The plants are observed at the end of approximately 21 days and the results in terms of the percent inhibition of ricearerecorded. As in Example 1, for each test pots are prepared containing soil treated only with butachlor. For each test, pots are also prepared containing soil treated only with the safening agent. The safening e~fe~ct is deter~ni~ed in accord-!-lce with rx~lnp].e 1.
'rahle III sumrnarizes the results obtained when the compounds of the invention were tested in accordance with the procedure of Example 2.

~Z697~

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a u~

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O c~ _ ,~ u~ o ~1 ,~ o .~1 ,~ o ~ ,~ o ~ ,~ o ~ ,~ o ~
,~s .. ... ... ... ... ... ..
a) ~ ~ o o r~ o ,~ r~ o ,~ o c~ ,~ c~ o ,~ o o ,~
ta ::C~

H t~ ,Yr~ r.`1 ~9 ~D ~D~D ~D LD LD LD ~D U~ U~ LD ~ LD LD LD LD LD
H LL-I S `-- r-l r~ n un un r~ r~ un n ~n ~n ~n Ln ~n n n n n Ln un H O r-l - ........ .. - .. - .. - ... ...
~ ~-1r-l OOO OOO OOO OOO OOO ooo r~ ~ ~ t;l) a ,a a ~
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u~ o a o a o a h a I ~ a u h r~ r-l o r~ ao ~ 3 ,~ o ~ o ~ o ~
X ~ X ~ X ~ X O ~ X
r-l Q r~/ Or~l O ~I Q,r~ r_l~1 o Q
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c I ~1 1 0 1 0 1 0 0 0 1 ~ O t O X O N O N O N ~I Nr-l U~ X N a~
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I u~ I u~ I u~ t~l u~o a) I Ln r~ r~ t~ I r,~ I r~ t~
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S r~ ~ ~ X ~ ~ ~ tl) ~~ ~ S ~ a ~.c ~ U ~ s ~)I ,~ ~ aJ u

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r~
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( -27- AG-1152 As noted previously, the 2,4-disubstituted-5-thiazolecarboxylates may be used to protect cxops from the herbicidal activity of acetamide herbicides without a corresponding diminution in herbicidal activity to the weeds.
Examples 3-6 are illustrative of such activity.
Example 3 A good grade of top soil is placed in a plastic pot and compacted to a depth of approximately 1.27 cm. from the top of said pot. A predetermined number of crop seeds and weed seeds are placed on top of the soil. A cover layer, approximately 1.27 cm., is placed on top of said seeds. The soil is then treated with a mixture of the safening agent and alachlor dispersed or dissolved in a suitàble solvent.
For each test series, pots are treated with only t:he herbi-cide. ~dditionally, pol:s are treated with only the saEeningayent. 'rhe herbicidal effect is observed approximately 21 days after treatment.
Tables IV-IX summarize the results obtained when the compounds of the invention were tested in accordance with the procedure of Example 3. Each table represents the results of different tests using said procedure. Note that in each test a control is used in which the plants are treated wi-th various rates of the herbicide alone.

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( -36-- AG 1152 Example 4 The procedure of Example 3 is repeated wherein the herbicide used is butachlor. Table X summarizes results obtained in accordance with this procedure.

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l~Z6971 ( -38- AG-1152 Example 5 5.08 cm. of a good grade of top soil is placed in a 7.62 cm. deep plastic pot. A predetermined number of barnyard grass seeds are applied to the soil surface. A
measured quantity of the safening agent dispersed or dis-solved in a suitable carrier is sprayed on the soil surface.
A measured quantity of butachlor herbicide dissolved in a solvent is sprayed on the soil surface. Pre-soaked rice is seeded into the pots that were previously flooded with water. The pots are flooded just above the soil surface for the duration of the test. The plants are observed at the end of approximately 21 days and the results in terms of percent inhibition recorded. For each test, a pot is prepared containing soil treated only with butachlor. For each t:est, pots are prcpared containing soil trea-ted only with the safening agent. Tables XI, XII and XIII represent the results of three separate tests conducted in accordance with the procedure of Example 5.

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--42-- l:lZ697~ AG-1152 u~
u~

., O o O ~ oo u~ c~ o o ~ ~ o o r~ a~ o ~ 5~G~ G~ OG~ a~ o a~ a~ o cO ~ o ~1 rd~I r-l r-l r~l .,_ H

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t~O O Cl~ I~O O ~ ~ O U~ c~ CO O O O L~

d .~J _~
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r~ O ~ 5 0 S~ S O h ~ ~X ~ S~ 0 ~ ~
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td X r-~ ~.) r-l r~ N r-l r~ N r-l r~ N

U~ O ~ ~1 .C S~ rd S s~ rd ~ rd ~) r~ r~l ~ V ~ r~ t) ~1 r~ IJ r~
~ ~ O I I S I I S I I S

ra ~1 r-l O U^
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~ I O N r-l I O N r--l I N r--l I O N r-l (~ ~U ~ I O O r-¦ I O O r-¦ ¦ O O r--l ¦ O O r~l '~

. . .

3 ~L2697~ ~G-- 115 2 U~
U~
*,_ ~
rlr~IJ') O O O (~ O O
5-1cn o oc~ o o r-l r~ r~ri r-l ~ h r~(~5 m S~
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.

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Ir-l n, ~ I~ o s~
s~ IV h la .~ I O t) U) ~ ~ , ~ aJ a~
a) r--~I r-1 ~) rl r-l ~ O
~ ~1 ,a N C) rJ~ .~ ~ ~ r~
~ n, . r~ r~l a) ~ ' O
O o ^r- co ~I r~ 0 N
r1 .~O ~ r~lI O t~l r-~ r~
o .n ~. . .I ~a r ~ ~O O r~lI O O r~l a) td a) ~ :~
r~ ~ ~ *

;97~

Example 6 A good grade of top soil is placed in a container and compacted to a depth of approximately 1.27 cm. from the top of said container. A predeterrnined number of sorghum, green foxtail, crabgrass and barnyard grass were applied to the soil surface. The seeds were then covered with top soil and the surface was treated with a miX~IIre of the herbicide and safening agent. The plants are observed at the end of approxirnately 18 days and the results in terms of percent inhihition recorded. Table XIV surnmarizes the results of tests conducted in accordance with Example 6.

~ Z697i h ~ O O G~ ~ ~ O
u~ O O O ~ O o a~ O
_l h 0 O~ ~
,~I ~n v7 u~ ~ O o o o ~ a~ o ~ ~ o C~ o . ~~ ~ ~ G~ O ~ ~ O a~ ~ o a~c~ O
h '~ .-1 ~1 ~j ,_1 H C ) t;
~,~
O ~ a~ ~ o o o o 0~ ~ O o~ O r~o o a) ~ ' ' c~ ~ o a~a~ o ~ o o ha) X ~1 ~j ~ ~1 ~1 a)h O

o o In o InIn O O Ln O Lr h ,~

U~l C ' .~

O~rl l l I ~ ~ . . . . . . . . .
~ ~ I I I O O ~ o o o o o O
a) o H a~
X ~ cn ~

I
I rl I rl I -1 1 -1 1 h ~J h r~ h n5 JJ ~ r~
S:~ I .C I ~: I S I
a~
r; l l lo l~7 ~ o u~ ~ o u~ ~ o ~ ~
I I Ih 1 0 h 1 0 h 1 0 h 1 0 t~' I I IO r-l r--I ~O r -~( r- J ~O ~ O I--I r -l I l I--1 `'1 r ~ r'~ I r ~
~-1 ~ ~ C X ~ X ( ~ C rC X
s~ t) ~ O O ~J O tJ ;. O ~) IJ O
tv I tV R I 'V .Q I tV .Q I a),Q
'`~ E~ h ~N ~ h ~ P h 'N E3 h 0 0 0 0 0 0 t~ 0 0 U) r~l h ~ ~ r~l 5_~ t ~ r~ r-l h ~.) ~1 0 tV >1 0 t-V :~ O a~ ~, o a~
r~ C ~ r~ C ~ r~ ,C ~ r~
r-l O ~ r-l O -I.J r-l O .J ~ r~l O
~ ~-I N ~ ~ N l L1 ~I N ~ (~1 N
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1~1 rC r~l11 ) t~ I J I ~ ~ r~ t~ t~
t!J .~ ~ . . .I
h t~l o o ~1 I I I O O t~ O O t~ O O ('~1 0 a~ ~

tv r~ h S-l h ~I h ~ h h h h h 5-1 t~ r-l r-l r-l I I I r--lr--I r--/ r-l r-l r--I r~l --1 r-l ri C ~C C I I I rC rC rC ~C rCrC ~ rC
R t.) O o I I I C~ o U c~ O C) C~ C~ O
h 0 0 0 1 1 1 0 0 td td 0 0 0 td rd ~V ~ r r `` 112~97~ ~

,~
C~tJ~ O o~ ~ O ~ ~ O t~ O O
5 ul a~ ~ o tJ~ o . t~ t~ o ~ o o 5~ ~d ,~ ,~ ~1 ,~ ,~
~o a~ v ,~ I ~n ~ ,!2 U~ r- G~ O t,o a~ O 1-- t~ O tX~ tJ~ O
-,~ td rdtJ~ ~ o a~ G~ o c~ t~ o t~ a~ o ~ h h ,1 ,~ ~I r~l H r--l ,~
~J ,., td 1~ tx) a~ t~ o t a~ o t~o o o o a) ~ t~ t~ a~ o a~ a~ o a~ o o h X ,~ ,~ ,~ ,~
a) ~ o ~ V ~

S t~ o ~ o o o t.~o o In o o In h ,~~D t;o ~ ,~ ,~ ,~ ,~ ,~
U~
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~a I I I ~ ~ ~r w ~D ~ ~ ~r ~
4~ I I I ,~ ~ r~ 11') In U'l t~ t'~l t'~l O O r1 ~) r,~ III OOO OOO t'~lt~lt~l ,~ td X

a) ,~
~d h td 5~ rd ~d ~ .~ ~ r-l E~ ~ I S I S I S
~ ~ ~ ~ ~ ~r tr~ I I
I I IO Ul ~ O Ut ~ O L~l ~
I I Ih I ~d h I td h I td tJ I I IO ~ 1 o r~l ~1 0 r-l r-l ~ I I Ir l "'1 ~1 t~
r~ ,C ,C X ,C ~ ~ .C .t~
C o J_~ O t,) ~ O ~,) Jl Ql I O ~ I a) R I ~
r_ h '`I r; h N E~ h td O td O td o .a U~ r-l h U r-l h ~ ) r-l ,4 ~1 0 t~ ~ O ~ :~ O
r--l ~ 5 r~ I r~
~ r-l O ~I r-l O ~ r--l O
r~ ~ N r l (1-~ N ri ~ N
a r~
O ~) _ r1 L(~ N r~ U~ N r~l u) N r~l LO N
~r-I .C
o R ~ o o t`~ o o N O O N O O N
h tJ
td ~1) .Y
~
æ ~ I ~ rcl Z ~1 1 U rl ~ Z ~ ) rc5 Z ~ I t) rc~
a~ I I x I -- a ,~ I x I - a r~ I X I ~ td r1 I X I ~ t~ r~l r~ ~ O O r-l ~D I r~ O O r-~ ~D I ~ O t~ r--1 ~ I r~ O O r~l ~ I r~
r-l h rC ~1 1 O l~r~ I O l r~ h rC ~1 1 O ¦ r1 h ~ ~ I O l-r~
O O U .r~ O ~ 1 0 r~r--l O .LI r-l r~l r-l r-J a) ~ r--l r--l r-l r--l a) ~_) r--l r-l r-l r-l a) ~) r--l r--l r--l R C ~ O .~ 1) ~ ~ O ~ E~ a) ~ r~l O ~ ~1 0 ~--1 ~ rC ~) C~ C .~ ~ ~I t,~ r C ~S ~) (1~I N I ~J ~) O T N I ~J ~1 0T N r ~ ~) O I N I ~1 IJ O
5N ~ r--l O ~.) 1-- N ~ r-l C) ~ ~ N ~ r-l a) a) ~J N ~ r-l O a) ~) , ;, ' :~-( _47_ ~2697~ AG-1152 ~xa;nple _ A predetermined number of corn, sorglum and rice seeds were placed on top of a good grade of top soil. The cover layer was then treated with an apvropriate amount of safening ayent. A cover layer of soil treated with the appropriate herbicide was placed on top of the seeds. The plants were obse~ved at the end of approxi~nately 21 days and the results in terms of percent inhibition recorded.
Table XV summarizes the results of tests conducted in accordance with Example 7.

_4 ,,~ 3L2~i97l AG-1152 5 ~ 1 o U~ o o o o o o ~ CC) ~ o o O O r~ ~ . ~ 1~) ~ r-l ~1 rl { ) ~J
~ a) .,1 U Ct~ O O f~ O O LS~ O c~ ~ O u~ O
~5 ~1 C;l Ct) ~I C~ 0 Il O
r- ~ r~ r-l r-l r-l H

a~,~ a~ cn O ~cc> o u~ o u~ o ~-- o u~
Ut~ ct~c~ In r~7c,~ ~ Lr) c~ r--S~
O
P~ ,~

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I Ic~ c;~ c5~ 1 I c~ cr~ I I c;~ cr 0 -1 I I. .. II , . I
I IcO c~cc)l lcc) c ~ I I co co J ~IJ ~I) t~-r~

a) ~ o r-l r-l r-l l O l O l O
> r l N rl N rl N
X ~ 0 S ~ ~5 h rd ',5 ~ 5 ~r ~ ~ ~ ~r .
rd ''~I ' I u-) I IO u~ I I o u~
E-l I I S l I I I ~ I I 1 ~1 1 tJI ¦ ¦ O r-¦ : ~ ¦ ¦ O r~l ~ I I O r-l ..
rl ,5 ,5 ~ ~ .5 ~) ~ .5 JJ
~ o ~ rd U ~ rd U ~ rd '.1)I C) r~l I O r-l I rll r-l '~ ~ r~ ~ k ~ O X O X O X
U~ r~l h O ~ ~ ~ O ~ i O
~1 0 ,q . ~ ~ O ,Q r '1 0 ~
IJ ~-1 rd l~1 ra J l-l rd r l l~ U 1~ 0 r~l ~ u r~ll ,~
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~ rl SIr) ~ I r n ~ r~ r ~l cr~ U ~ ~r U7 ~I) rq ~
O ~ I O ~ r--lc~ r~l Cc) O ~J~
rd U x I I r U ~ ~ I X I - rd ,~
r5 ~ 1 0 0 0 0 0 0 r~ I r~
r-l O O O O r--l r-¦ r~l r~l r~ ~ C ~ ¦
U r~l r-l r-lr~l ,~ ,L~ 5 ,~ O .~
rl .~ ,5 ~ ~ U U U C.) r-l r~) ~ r-l r-l r~l R U O I U C) rd rd rd rr~ .5 f, r~ 0 ,,, ~ a I rd rd ~ ~ ~ ~ o I r_,5 .5 ~.) Cl r-¦ r~l I r-l r~ ) O
:~ ~s ~ m ~ m ~ a) rl) ~

.

Z~97~
` -49- AG-1152 As noted above, crop plants may be protected from herbicidal activity by treating the crop seed with the safening agent prior to planting. Example 8 illustrates such activity.
Example 8 -Sorghum seeds were treated with a solution of the appropriate safeing agent in dichloromethane. The solvent was evaporated which left only the safening agent on the seed. Untreated and treated sorghurn seeds were planted in pots. Selected weed species were planted in separate pots.
1.27 cm. deep soil cover layer was placed on the pre-seeded pots. The soil surface was then treated with the herbicide.
Approxirnately 21 days later, the results were observed and recorded. T~ble XVIsulnrnarizes t}-~e res-llts observed when tests were conducted in accordallce with Exdmple 8.

. .

?

Z6~

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O r--l r--l O r i r~l O r-l r--l r--l r--l r--l t~r-l ~`'1 ~ r--l ~ ~ r-l ~1 ~ ~ ~ >1 ~S S X .~ ~~ X S S X O .C X
r~ O ~) O ~U ~\ O : ~ O IJ O ~ - I ~) O
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r~ O O O O O O O O O O O O
O r--lr-l r--lr--l r--¦r--l r-l r~ r-l r~l r-lr--l r-l r-lr--l r~l r~ .C S S S .C S S S S S S S S S S S
~ ~ O U t~ U ~) O ~ ~ C,) O C) C) ~) O O
~1) r~lr-l r~l r~¦ r-l r-l r~l r-l r~lr~l r~lr~l r-l r_l r I r-l ' . ~ ' :

' ~ :

~126971 -~2- AG-1152 ~ 5 ~:
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O ~ O ~ ~ o I I I I o In oc~ o o o O co -,~ O ~ ~ a~ I I I I ~ ~ ~ ~ ~ ~ r~ U~
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a) >1 1 a) I I O ~ o ~d r--l tJ~X U~ ~ O ~ ~ r1 N ~r I r-l ~-1 C) ~:l ~ O
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r.~ ~ o ~ '1~ r~
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a) I
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I o ,~ ~ I o ,~ ~ I o ,~ ~ I o ~ ~r r~ -" ~ 5~ ~ ~ h S~ ~ ~ h r1 O O O O O O O O O O O O O O O O
U ._ S .C S ,C S S S C S S S C S S S
R u U u u U u u u u o u u u u u u ~ ~ (a~a ilZ~97~

,~ a o ~ U~ o ~ o ~ ~ ~ ~ o ~ o ~ ~ ~ o ~ ~ ~
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U~ O
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c~ .~ o o s o a~ N S-l ~ I E~ 1 ~ rd O l _ ~ O r-~ I -r-l I rl r-l Ir) 1_~ ~ h ~ S I
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r~ r) N S ~
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4~ O O ~ r-l O ~r~ O XX r~ r~
a~ '~ I QO ~ ~13 U~ S I O S ,1: 0 0N O ,SI ~J r-l r~l r~ t~ O
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N t~

~a r~
O t~ ~ I ~ N CO I C~ N r I CC~ N Cl~ N CO
r l . C I N r-l ~ I N r-~ ~ I N r JI ~! I N r-l . ~ ~ ~ I o ~ ~ I o ~ ~;r I o ~ c I o t a) 'd ~ h ~ ~I h ~ h ,~ O O O O O O O O O O O O O O O O
t ) r~l r-/ r-lr--l r-l r-l r~l r~ r-l r~ r~ r~ r-l r~ r~l r~
r~ S ~ rC ~ ~ S ~ S S S ~; S S ~C S
R O O U o ~ O C) C) C) C~ o O C) t) C) C
a) r~ ~-1 r~ 1 r-l r~ r~ 1 r-l r~ r~ r~l r~l : :
:

l~Z6971 -54- ~G-]l52 U~
a) ~ ~n C ~
O --~ ~ o co O ~ O O ~ tc::) O ~ ou~ o In ~ ~ ..
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t1' ~J X 1 1~ J ~ ~ X
~I) ~ ,-( a) o o I ~ I I (d ~ a) o ,~ ~ e ~ F ~ ~1o ,~ ,~ C ~ ~
R ~ s o s~ o ~: - ~d ~ o o ~
~ ~ _ ~ S X O rC X = _~ ~ td = =
E~ ,~ o o t) R ~ o ~ ~ o ~ o r~
~ o ~ ~1 1 a) R I a) .q o ~ a3 ~ ~ e ~
o~ o o ~ o ~ o~ o (~ r1 r~ N r~l 5-~

u~ S ~ ~0 ~ O ~U ~ O a.) ,~
rl ,1 ,.~ r~ 1 C) .l l r~
O~J 1'~ 0 1 1 .C
N ~ N

~a r~
o O _1 0 ~ C~ 1~0 ~ ~ I00 ~ ~ I CO
.,I ~ r~ ~ I ~r~ ~ I ~r~ ~ I ~ r~
a)~ I. . . I .. . I. . . I
IO ~1 ~ I Or~ ~ IOr~~r I o,~ ~r ~ds~s~ h ~,~ OO O O O O O O O O O O O O O O
~ ' r~ ~S S rC ~C _ S ~ S _ S S S S S S
rq UU ~ O O ~)C~)C)C) C)~) 1) 0C) ~) O
O~ ~I r~ ~ r~ r~r~r~r~ r~r~ r~r~r~ r~ r~ r~

. ` ~lZ6971 __ AG-1152 ~ a h u~
O ~ ~ O ~ C~ o U7 '~ o r-l '~IU~ ~
,~ ~
-ri ~ 1~5 S~
S~ o o o o O ' r~
r~
~ ~ ~1 0 ~
~ ~ 9 o o oo o o a) ,~
U~ ~ ~o U ~ r~
~, a) ~:
a) h o o o ~ r~
P~ E~ ~ c~

,~ U~ o -o o I
h U~ aJ
H ~ O I ~
~ ~ ~ ~,-1 x a) u~
1, Q) ~ I a) o , ~ ~ O ~
_ _ ~ ~ ~ a a) a) ,~ ~
O
~ O ' '~ ~
~ ~ rl L~

a U~--I c~
O ,LI ~ I ~ ,~
I o ~ ~r a~
5-1 h ~-1 u ~~
r~ ~c ~c ~ ~c ,q ~u ~U ~u ~u ~ r3 L2697~
( -56- AG-1152 As noted, selected weed species were planted as a control to determine the efficiency of the herbicide. At rates between 0.28 and 1.12 kilograms per hectare, weed inhibition ranged fLom 80 to 100 percent.

.

( --57~ ~697~ AG-1152 Exam~le g Two rows of each crop and weed were seeded at 1.~6 '.o 3.1 cm. depth in Ray silt loam soil. The soil is then trea.~d with the herbicide and safening agent. Approx-imately 19 days later, the plants were observed and theresults recorded. Table XVII s~nmarizes the results of tests conducted in accordance with Example 9 .

- ~126971 -~&- AG-ll52 I ~ o o o o o o X ~ o o o o o o O ~T5 ~ ~ rir-l 1~ ~

- ri O O O O O O
O O O O O O
r-lr-l r-lr-l r-l r-l O
U~
~ '1 ~ U~ O O O O O O
h h ~ o o o o o o /15 ~J ~ r-l r~l r-l r l r~l r-l ~q ~
~
- r~ r_ rl :^/
r~ C ~-1 ~ O t~l O n O
J ~-1 0U~ U~ G ~ ~D r~
r~ O r-l ~ X ~
~_~ r,-.
O
~~ u~ ~da~ o a~ c~
~ ~ a~ 00 a~
h o o o o o o o ,~ o o o o o o cr;r~l r-l r~ 1 r~l r-l ~ ~C r~
O r~
H U~ b' H
~ ~ ~ ~ ~ O
a) o~ r--l ~D N U
~ ~) E~ ,_ I~r I
~ I ~ I ~ I
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~Z6~7~

The above examples il1ustrate that the thiazole-carboxylates of the present invention are useful in reducing herbicidal injury to crop plants, especially sor-ghum and rice. The safening agents may be applied to the plant locus as a mixture, i.e., a mixture of a herbicidally effective amount of acetamide herbicide and a ~afening effective amount of safening agent, or sequentially, i.e., the plant locus may be treated with an effective amount of the herbicide followed by a treatment with the safening agent or vice versa. The ratlo of herbicide to safening agent may vary ~epending upon the crop to be protected, weeds to be inhibited, herbicide used, etc., but nor-mally a herbicide to safening agent ratio ranging from 1:25 to 25:1 (preferably 1:5 to 5:1) parts by weight may be em pl oy c ~d.
The herb;cide, saEen-ing agent or mixture thereof may be applied to the plant locus alone or the herbicide, safening agent or mix-ture thereof may be applied in con-junction with a material referred to in the art as an adjuvant in liquid or solid form. Mixtures containing the appropriate herbicide and safening agent usually are prepared by ad~ixing said herbic;de and safening agent with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particuJate so]ids, grallul(~s, pell(?ts, we-ttable powders, lusts, solu~iolll, arld aqu(-~ous di~persions or emulsion.s. Thus, the mixture may include an adjuvant such as a finely-divided particulate solid, a solvent liquid of organic origin, water, a wetting agent, dispersing agent, or emulsifying agent or any suit~ble combination of these.
When applying the herbicide, safening agent or mixture thereof to the plant locus, useful finely-divided solid carriers and exténders include, for example, the talcs, clays, pumice, silica, diatomaceous earth, quartz, Fullers earth, sulfur, powdered cork, powdered wood, walnut flour, chalk, tobacco dust, charcoal and the li~e. Typical liquid diluents useful include for example, St~dard solvent, acetone, alcohols, glycols, ethyl acetate, benzene and the --60- ~Z6971 AG-1152 ( like. Such compositions, particularly liquids and wettable powders, usually contain as a conditioning agent one or ~ore surface-açtive agents in amounts sufficient to render a given composition readily dispersi~le in water or in oil.
By the term "surface-active agent", it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein. Such surface-active agents are well known and referellce is made to U.S.
Patent No. 2,547,724, Columns 3 and 4, for detailed e~amples of the same.
Compositions of this invention generally contain from about 5 to 95 parts herbicide and safening agent, about 1 to 50 parts surface-active agent and about 4 to 94 parts solvent, all parts being by weight based on the total weight of the colnposition.
The application of the hl?rbicide, safening agent or mixture ther(-of in a liquid or particulate solid form can be carrie~ out by conventional techniques utilizlng, for example, spreaders, power dusters, boom and hand sprayers, spray dusters and granular applications. The com-positions can also be applied from airplanes as a dust or spray. If desir~d, application of the compositions of the invention to plants can be accomplished by incorporating the compositions in the soil or other media.
The above exarnples also illustrate that the crop may be protected by treating the crop seed Wit}l an efrcctive ~nount of safening ayent r~rior to plantillg. Gelle~ally, ~nall amounts of safening ayc?nt are re~lircd to treat such sec~s. Table XVI illustrates that a weight ratio of as 30 little as 0.6 parts of safener per 1000 parts of seed may be efective. The amount of safener utilized in treating the seed may be incrcased if desired. Generally, however, a weight ratio of safening agent to seed weight may range from 0.1 to 10.0 parts of safening agent per 1000 parts of seed.
The determination of the effective amount of safening agentrequired is well within the skill of the art.
Since only a very small amount of active safening agent is us~ally requixed for the seed treatment, the compound -61- ~Z6g71 ~ G-1152 preferably is formulated as a powder or an ernulsifiable concentrate which can be diluted with water by the seed treater for use in the seed treating appara-tus. Of course, under certain conditions, it may be desirable to dissolve 5 the safening agent in an organic solvent for use as a seed treatment or the pure compound alone may be u sed under properly controlled conditions.
There are thus also provided by this invention novel seed treating compositions containing one or more of 10 the described active safening agents intimately dispersed in an inert carrier or diluent for the intended use. Such carriers may be either solids, such as talc, clay, diato-maceous earth, sawdust, calcium carbonate, and the like or liquids such as water, kerosene, acetone, benzene, toluene, 15 xylene, and the 1 ike in which the active agent may be either dissolvrd or d ispersed. Emulsifyiny agents are 2dvisably used to achieve a suitable emul sion if two immiscible liquids are used as a carrier. Wetting agents may also be used to aid in dispersing the active safeniny agent in liquids used 20 as a carrier in which the agent is not completely soluble.
Emulsifying agents and wetting agents are sold under numerous tradenames and may be either pure compounds, mixtures of compounds of the sarne general groups, or they may be mixtures of compounds of different classes. Typical sat:isfa( tory 25 surface-active agents which may be usl:rl .Ire -3lkali me-tal hiqher al ky] 3~yl sul ron;t~ s sllch as ;(~ 1m ~]o(ll-cyl L,en~ene-sulEonate and the solium salts of ~lkylnapilthalellesulEonic acids, fatty alcohol sulfates such as the sodium salts of monoesters of sulfuric acid with n-aliphatic alcohols con-30 taining 8-18 carbon atoms, long chain quaternary ~mnonium compounds, sodium salts of petroleum-derived alkylsulfonic acids, polyethylene sorbitan monooleate, alkylaryl polyether alcohols, water-soluble, lignin sulfonate salts, alkali-casein compositions, long chain alcohols usually containing 35 10-18 carbon atoms, and condensation products of ethylene oxide with fatty acids, alkylphenols and mercaptans.

--62- ~æ~97iL AG--1~ 52 PREPARATION OF THE SAFENING AGENTS
The 2, 4-disubstituted-S-thiazolecarboxylic acids and derivatives of the foregoing formula may be prepared generally utilizing one of two procedures. The first method encompasses the preparation of 2-oxo-2 ,3-dihydro-4-substi-tuted-5--thiazolecarbGxylates by reacting portions of ~-aminoacrylates and ch]orocarbonylsulfenyl chloride. Crystal-lization of the resulting mixture from hexane yields the appropriate 2-oxo-2,3-dihydro-4-substituted-5-thiazolecar-boxylate which may be converted to the appropriate 2-chloro-4-substituted-5-thiazolecarboxylate by reaction with excess phosphorus oxychloride. Excess phosphorus oxychloride is removed under reduced pressure and the residue oured into ice water. Extraction with ether and washing with 5% sodium hydxoxide reslllts in the 2-chloro-4-substituted--5-thiazole-carboxylate. For purposes of clarification, this method is sulrlmarized by the following scheme:
O O
- ..
R - C = C -- C - OR' + C1 -- C - S - C1 O O
R - C = C - C - OR' + POCl ~ R - C = C - C - OR' I \ 3 1 \
H - N S N S
\C/ ~C/

O Cl ~-aminoacrylates may be prepared according to known procedures such as that specified in Lutz et al, Journal of Heterocyclic Chemistry, Volume 9, Page 513 (1972) or they may be prepared by mixing 0.5 moles of ethyl acetoacetate or methyl acetoacetate in 200 ml. of methanol and 100 ml. of saturated sodium acetate and passing through the appropriate nitrile (perfluorinated if R is to be perfluorinated) for several hours. The reaction mixture is poured into ice water and the organic layer extracted with ether. The ether solu-tion is dried and concentrated and the residue distilled.
..

-63~ 12~i9~ 5-1152 A mixture of about û.l mole of said residue and 50 ml. of 3096 ammonium hydroxide or sodium hydroxide is stirred for a long period. The reaction mixture is extracted with methylene chloride and the methylene chloride extracts dried 5 and concentrated. Fractional distillation of the residue results in the ,~-aminoacrylate.
In order to more fully illustrate the manner in which the 2,4-disubstituted-5-thiazolecarboxylates of the present invention are prepared, the following examples are 10 presented EXamP1e 10 Pre aratio_i E hyl 2-Ch.~ om t~=
Thiazol_ca oxylate. A mixture of 13.0 g (0.0992 Imole) of chlorocarbonylsl1lfenyl ch] ori~e, 17 g (0.0928 mole) of ethyl 3-~mino--4,4,4-trifluorocrotonate and 50 ml. of chlorobenzene was heat-d at 135C. for 2 hours, cooled and triturated with 200 ml. of pet:role~lm ether. The light yellow precipitate was recrystallized from hexane-ether to give 12.2 g (55~) of white prisms, m.p. 121-123C., which was identified as ethyl 2 0 2~3-dihydro-2-oxo-4-trifluorornethyl-5-thiazolecarboxylate~
A mixture of 10 g (0.0415 mole) of ethyl 2,3~ihydro-2-oxo-4-trifluorornethyl-5-thiazolecarboxylate, 30 ml. of POC13 and 1 ml. of dimethylformamide was held at reflux for 87 hours.
The reaction mixture was poured into 500 ml. of ice water and extracted three times wi-th 60 ml. ol~ e~ C~ ~`he ether solution was wa~ td w;th sal~lr.~ iuln chlor:ide solution, dricd (MgSO~) and concen1 rated urlder redllced pressure to give 10.2 g of light yellow solid, m.p. 57-60C., which was recrystallized from hexane to glve 9.95 g (92.4%) of ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate as light yellow solid, m.p. 58-59C.
Anal. Calc'd. for C7H5F3ClNO2S: C, 32.38; H, 1.94; N, 5.40.
, Found: C, 32.33; H, 1.98; N, 5.35.
Example ~,1 Preparation of Ethyl 2-Chloro-4-Pentafluoroethyl-5--T_iazolecarboxylate. To a stirred mixture of 65 g (0.4995 mole) of ethyl acetoacetate, 200 ml. of methanol and 100 ml.
of saturated sodium acetate at 50C. was introduced 100 g -64~ AG-1152 (0.769 mole) of pentafluoropropioni.rile in 3 hours. The reaction mixture was poured into 1200 ml. of water. An oil separated from the reaction mixture. The aqueous solution was extracted with ether. The ether solution was combined with the oil, dried (MgSO4) and concentrated under reduced pressure. The residue was distilled to give 40 g (37%) of ethyl 2-acetyl--3-amino-4,4,5,5,5-pentafluoro-2-pentenoate.
A mi~ture of 21.8 g (0.0790 mole) of ethyl 2-acetyl-3-amino-4,4,5,5,5-pentafluoro-2-pentenoate and 75 ml. of 58%
ammonium hydroxide was stirred for 66 hours. The reaction rnixture was ext:racted with ether. The ether solution was dried (MgSO4) and concentrated under reduced pressure. The residue was distillc~ to give 16.3 g (88~) of ethyl 3-amino-4~4~5~5~5--L~f nt:a f lnoro-2-p~nt(-noate, n25 - 1.4011. A well 15 s-lirr~ m;~ture of 54 g (0.23 mole) oE ethyl 3-amino-4~4~5~5~5-pentafluoro-2-penteJIoate and 31 g (0.237 mole) of chloLocarbonylsulfenyl chloride was held at 100C. for 1 hour. The reaction mixture was cooled and triturated with hexane. The solid precipitate was washed with water and recrystallized from hexane-ether to give 31 g (46~) of ethyl 2,3-dihydro-2-oxo-4-pentafluoroethyl-5-thiazole-carhoxylate, m.p. 95~97C. A mixture of 10 g (0.0344 mole) of ethyl 2,3-d:ihydro-2-oxo-4-pentafluoroethyl-5-thiazole-c~rboxylate, 4 g (0.0506 mole) o pyr;dine and l50 ml. of phosphorus oxych]oLi~e w~s held at reflllY. for 18 hc)ul-s.
lxcess yhosl)l]orus oxychlo~i(le was r(ln(Jved llnder reduced prc~ssure. The residue was treated with water alld extrac-ted wlth ether. The ether solution was dried (MgSO4) and concenlrated under reduced pressure. The residue was dis-30 tlll~ to give 7.5 g (71%) of ethyl 2-chloro-4-pentafluoro-ethyl-5-thiazolecar~oxylate, nD5 = 1.4460.
Anal. Calc'd. for C8H5ClF5NO2S: C, 31.03; H, 1.63; N, 4.52.
Found: C, 30.62; H, 1.18; N, 5.08.
Exarnple 12 Preparation of Methyl 2-Chloro-4-Heptafluoropropyl-S-Thiazolecarboxylate. The procedure of Example 11 was _ _ _ . _ _ _ _ _ _ -repeated utilizing rnethyl acetoacetate in lieu of ethyl acetoacetate and heptafluorobutyronitrile in lieu of --65~ 697~ AG-1152 pentafluoropropionitrile to prepare 0.3 g of methyl 2~chloro-4-heptafluoropropyl-5-thiazolecaxboxylate as a colorless liquid; nD = 1.4352.
Anal. Calc'd. for C8H3ClF7NO2S: C, 27.80; H, 0.87; N, 4.05.
Found: C, 27.42; H, 0.87; N, 4.03.
Example 13 , . _ _ _ .
Preparation of Ethyl 2-Chloro-4-Trichlorometh~l-5-Thiazolecarboxylate. To 130.14 g (1.00 mole) of ethyl aceto--acetate was added 1.5 g of sodium. The reaction t~nperature increased spontaneously to 50C. The reaction mixture was cooled with an ice bath. To the cooled reaction mixture was added, with vigorous stirring at 30-50C., 144.3 g (1.00 mole) of trichloroacetonitrile in 30 minutes. After complete ncldition of the tr:ichloroacet(-,nitrile, the ~e~lction mixture was cooled with a dry ice bath. No precipi-tate of the ethyl 2-ace-tyl-3-alnino-4,4,4-trichlorocrotonate formed. Part of the above pcoduct was stirred with 100 ml.
of concentrated 28-30% ~nmonium hydroxide for 2 hours. The reaction mixture was then extracted with ether. The ether solution was dried (CaSO4) and concentrated to give 180 g (82.5%) of crude ethyl 3-amino~4,4,4-trichlorocrotonate.
Part of this crude material (20 g) was distilled at 0.5 mm Hg to give 11.7 g of pure product, m.p. 91-95C. To a cold (10C.) solution of 21.8 y (0.0937 rnole) oE crude ethyl 3-25 amlno-4,4,4-trichlorocrolonlte in 15 Inl. oE clllorobcn7ene was added 13.5 g (0.]03 mole) o~ chl~rocarbollylsulf(lnyl chloride.
The reaction temperature rose spontaneously to 35C. after the ice water bath was rernoved. The reactlon mixture was stirred at 65C. for 1 hour, coolc~ and triturated with 30 petroleum ether to yive 10.3 g (38%) of ethyl 2,3-dihydro-2-oxo-4-trichlorolnethyl-5-thiazolecarboxylate, m.p. 109-110C.
A mixture of 14.5 g (0.05 mole) of ethyl 2,3-dihydro-2-oxo-4-trichloromethyl-5-thi~zolecarboxylate, 10.4 g (0.05 mole) of phosphorus pentachloride, and 100 ml. of phosphorus oxy-chloride was held at.reflux for 7 days. Excess phosphorus oxychloride was removed under reduced pressure. The residue ~as trcated with ice water and the aqueous mixture was extracted with ether. The ether solution was extracted wi~h - 6 6 - 112~71 A G--1152 10% sodium hydroxide, dried (CaSO4) and concentrated under reduced pressure to give 3.2 g of oil wnich was chromato-graphed on silica gel using 5% ethyl acetate-petroleum ether as eluant . The f irst 1.2 1. of eluant gave 2.27 g of solid 5 which was recrystallized from petroleum ether at low tem-perature to give 2.13 g (13.8%) of ethyl 2 -chloro-4--tri-chloromethyl-5-thiazolecarboxylate, m.p. 42.5-43.5C .
Anal. Calc'd. for C7H5C14NO2S: C, 27.18; H, 1.62; N, 4.53;
Cl, 45.86.
10Found: C, 27.27; H, 1.66; N, 4.53;
Cl, 45.89.
Various esters may be prepared by reacting the compound of Exarnple 10 with sodium hydroxide to forrn the Eree acid and then forming the acid chloride by reaction 15with l hionyl chloride. Reaction of 1:he acid chloride with an alco}]ol results in the desiLc~ ester.
EYam le 14 Preparation of 2-Chloro-4-Trifluoromethyl-5-T iazolecarboxylic Acid. A mixture of 116 g (0.4468 mole) of 20ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate, 18 g (0.45 mole) of sodium hydroxide, 200 ml. of water, 400 ml.
of t etr ahydr of uran wa s st irr ed at r oom t ernpera -t~r e f or 16 hours and made acidic with 50 ml. of concentrated hydro-chloric acid. The reaction rnixture was extracted twice with 200 ml. of ether. The ether-tetra]ly(ll-ofllrl~n solut:-iorl was dried (MgS04) and concellkral~ed l~nder rl dl~ced pr~ssure. The residual oil was trcated with bc~nzene and the benzene solu-tion was concentrated under reduced pressure to remove the last trace of water. The residual solid was recrystallized Erorn hexane-benzene to give 76 g (73.4%) of 2-chloro-4-trifluoromethyl-S-thiazoleca~rboxylic acid, m.p. 131-131.5C.
Anal. Calc'd. for C5HlClE'3N02S: C, 25.92; H, 0.47; Cl, 15.31;
N, 6.05.
Found: C, 26.07; H, 0.52; Cl, 15.64;
N, 6.10.
E ample 1 5 Preparation of _hloro-4-Trifluoro e_yl-5-rrhiazolecarboxylic Acid Chloride. A mixture of 36.0 g (0.1554 mole) of the acid of Example 14 and 171 g (1.437 --67 l~Z6971 AG-1152 mole) of thionyl chloride were held at reflux for 6 hours.
Excess thionyl chloride was r~oved under reduced pressure and the residue (38.1 g, 98%) was reacted as described in Examples ~6-28.
Examp e ]6 Preparation of Isopropyl-2-chl-oro-4-Trifluoro-met yl~5-Th~azolecarboxylate. The acid chloride of Example 15 (5.2 g), and 10 g of isopropanol were held at reflllx for 16 hours. EXCeSS alcohol was removed under reduced pressure.
The residue was dissolved in 50 ml. of ether. The ether solution was .~ashed with sodium bicarbonate, dried (MgSO4) and concentrated under reduced pressure. The crude product was distilled at 1 mm. on a Kugelrohr to give 4.9 g (86%) of the desired product as colorless liquid, nD5 = l.4655.
~nal. Calc'd. for C8H/CIF3NO2S: C, 35.10; H, 2.58; N, 5.12;
Cl, 12.96.
Found: C, 35.15; H, 2.62; N, 5.11;
Cl, 12.90.
Example 17 Preparation of_B nzyl_2-Chloro-4-Tl^~fluoromethy 5-Thiazolecarboxylate. The procedure of Example 16 was repeated utilizing benzyl alcohol in lieu of isopropanol to give 2.85 g of a white solid, m.p. 56-58C.
Anal. Calc'd. for C12H7CLF3NO2S: C, 44.80; H, 2.]9; N, 4.35;
Cl, ll.02.
~olJr~ C, 44.86; H, 2.19; N, 4.34;
C1, 11.09.
EY._ ples 1~
Utiliziny the appropriate alcohol and the proce-dure of Example 17, the following compounds have heen pre-parc~.
2,2,2-Trichloroethy~ _-Chlo_o-4-Trifluorolnethyl-5-Thiazolecarkoxy]ate, 'nD = 1.5094.
Anal~ Calc'd. for C7H7C14F3NO2S: C, 23.16; H, 0.56; N, 3.86;
. Cl, 38.95.
Found: C, 23.24; H, 0.62; N, 3.92;
- C1, 38.96.

.

~. .

-68-- 13 23~97:¦ AG-l ] 52 2-33utoxyethyl 2-Chloro-4-Trif luoromethyl-5-Thiazolecarboxylate, nD - 1.4683.
Anal.Calc'd. for CllH13ClF3NO2S: C, 39.82; H, 3.95; N, 4.22;
Cl, 10.68.
5 Found: C, 40.07; H, 3.87; N, 4.22;
Cl, 11.53.
2~hloroeth~1 2-Chloro-4-Triflllorome~yl-5-Thiazole-c_boxylate, nD = 1.4965.
~nal-Calc'd. for C7H4C12F3NO2S: C, 28.59; H, 1.37; N, 4.76;
Cl, 24.11.
Found: C, 28.67; H, 1.40; N, 4.76;
Cl, 24.06.
n -Butyl 2-Chloro-4 -Tr if luoromethyl-5-Thiazole-_ _ _ _ _ . _ _ _ __ _ . _ _ _ __ _ __ ._ __ carboxylate, nD = I.4685.
15 Anal. Calc'd. for C9HgClF3NO2S C, 37.57; H, 3.15; N, 4.87.
Fvund: C, 37.54; H, 3.17; N, 4.90.n--llexyl 2--Chl oro-4-Trif luoro]nethyl-5-Thiazole-, . , . _ .,, , , ., _ . _ _ . , . , _ . . _ . .. .
carboxylate, n25 = 1.4657.
__~ D
Anal. Calc'd. for CllH13ClF3NO2S: C, 41.84; H, 4.15; N, 4.44.
20Found: C, 41.86; H, 4.15; N, 4.43.
n-Octyl 2-Chloro-4-Tr; f luorolnethyl-5-'rhiazole------- ----- _ _ _ _ _ carboxy,late, nD = 1.4658.
Anal. Calc'd. for C13H17ClF3NO2S: C, 45.42; H, 4.98; N, 4.07.
Found: C, 45.58; H, 5.05; N, 4.04.
25Phenyl 2-Chl~?ro-4-Tr;fluo,rr?nlet}lyl-5-Th;azo,le-cc~-rboxy] ate, n1) - ] .5389.
Anal. Calc'd. Eor C~lH5ClE3NO2S: C, 42.94; H, 1.64; N, 4.55.
Found: C, 42.97; H, 1.67; N, 4.58.
p-Ch,~orophenyl 2-C_loro-4-Tri~luo-t-ornethyl-5-_ 30' h lzole_arbo_y_clte, nD5 = 1.5552.
Anal. Calc'd. ,E~or CllH4C12F3N02S: C, 38.60; H, 1.17; N, 4.09.
Found: C, 39.08; H, 1.00. N, 4.09.
,,A, llyl 2,~,,_1o~o-4-T, r,i"f,l ,t,Jororn(et_yl-S-' hiazole-carboxylate, b.p. 68C. at 0.1 mm; nD = 1.4816.
_ _ _ _ _ . . . .
35Anal. Calc'd. for C8H5ClF3NO2S: C, 35.37; H, 1.86; N, 5.16.
Found: C, 35.50; H, 1.93; N, 5.22.
Methyl 2 -Chloro -4 -T_f luoromethyl - T iazole-carboxylate. The residue was crystallized at low te~nperature __ _ -69- ~2697~ ~ G-1152 from hexane to give 3.25 g (95%) of methyl 2-chloro-4-tri-fluoromethyl-5-thiazolecarboxylate as light yellow prisms, m.p. 32-34C.
Anal. Calc'd. for C6H3F3NO3S: C, 31.72; Hr 1.77; N, 6.17.
Found: C, 31.88; H, 1.80; N, 6.20.
Propargyl 2-Chloro-4-Trifluoromethyl-_-Thiazole-carboxylate. A mixture of 4.63 g (0.02 mole) of 2-c~oro-___ _~ _ 4-trifluoromethyl-5-thiazolecarboxylic acid, 2.42 g (0.02 mole) of propargyl bromide, 2.59 g (0.02 mole) of diisopropyl-amine, and 50 ml. of methylene chloride was stirred for 16 hours. The methylene chloride solution was washed success-ively with diluted hydrochloric acid and saturated sodium bicar~onate, dried (MgS04) and concentrated under reduced pressure. The residue was Kugelrohr distilled to give propargyl 2-chloro-4-t:rifluororrlethyl-5-thiazo]ecarboxylate as a colorless ]i~luid.
Anal. Calc'd. for C8H3ClF3NO2S: C, 35.63; H, ~.12.
Found: C, 35.59; H, 1.29.
The 2,4-disubstituted-5-thiazolecaxboxylates of the invention may also be prepared in accordance with the following reaction scheme:
SO Cl R - C - CH2 - C - OR' 2 2 R - C - CH - C - OR' ,- - .. . .................. ..
O Cl o S O
ll2N ~ CNH2 R -- C --= C - C - OR' > I
N S
~C/

o 1) NaNO2 , HX ' "
~ R - C = C - C - OR' 2) CuX or KI
C
X

~Z697~

In accordance with the above reaction sch~ne, ketoesters in chloroform are added dropwise to one equivalent of sulfuryl chloride. The reaction mixture is held at reflux for a number of hours and the chloroform r~oved under reduced pressure. An equimolar portion of the resultant 2-chloro-3-ketoester is added to thiourea in ethanol and held at reflux for 16~20 hours. Ethanol is then removed under reduced pressure and the residue neutralized with sodium bicarbonate solution to give a 2-am ~lo-4-alkyl-5-thiazolecarboxylic acid ester. A solution of said ester in concentrated acid is diazotiz~ at -5 to 30C. with soclium nitrite. The resulting diazonium salt solution is poured into the corresponding cuprous halide or potassium iodide solution. After gas evolution has subsided, the reaction mixtllre is extracted with elher. ~rhe etller ~x~ract is dried and concentrated and the residue is purified by either Kugelrohr distillation at rc~uced pressure or by chrornatography.
Example 29 Preparation of_Ethyl 2- h oro-4-Ethyl-5 -T hiazole-carboxylate. Ethyl 2-chloro-3--oxo-pentanoate is prepared . . . _ from ethyl 3-oxo-pentanoate and sulfuryl chloride utilizing the procedure of Bankowski et al, Rocz. Chem , Volume 49, Page 1899 (1971). A mi~ture of 9.2 g (0.0515 mole) of ethyl 2-chloro-3-oxo-pentanoate, 3.92 g (0.0515 mole) of thiourea and 30 ml. of et-hanol was held at refll1x ior 17 l-lours.
Ethanol was r-mOV(~ ull~ler r~1ucl-~ L)rr ,s-]re al~ld ~i~e resi~ue was treate~ with 300 ml. of saturdted sodium bicarbonate solution. The solid precipitate was collected to give 11.2 g of white solid, m.p. 165-170C. which was recrystallized from ethanol to give 7.7 g (75%) of ethyl 2-amino-4-ethyl-5-thiazolecarkoxylate as colorless prisms, m.p. 177-179C. To a solution of 7.0 g (0.0349 mole) of ethyl 2-amino-4-ethyl-5-thiazolecarboxylate and 0.2 g of CaS04 in 60 ml. of concen-trated HCl was added dropwise a solution of NaN02 in 20 ml.
of water in such a way that the reaction temperature did not exceed 30C. The reaction mixture was stirrc~ for 30 minutes -and poured into a solution of 3.5 g (0.035 mole) of cuprous chloride in 30 ml. of 6N HCl. The resulting dark blue -71- ~2~971 AG-1152 solution was stirred for 30 minutes and e:~tracted with ether.
The ether solution was dried and concentrated under reduced pressure. The residue was Kugelrohr distilled at 2 mm. to give 4.35 g of yellow liouid which was c}~omatographed on silica gel to give 4.0 g (52~) of the desired product as colorless liquid, ~ 5 = 1.5189.
Anal- Calc'd- for C8H10ClN2S C, 43-73; H~ 4.59; N~ 6-38-Found: C, 43.88; ~, 4.62; N, 6.34.
Exam~le 3?
Preparation of Ethyl 2-Chloro-4-Is~ pyl-5-Thiazolecarboxylate. Ethyl 2-chloro-4 methyl-3-oxo-__,___ _ __ _ pentanoate is prepared in accordance with the literature procc~ure discussed in Example 30. A mixture of 15.0 g (0.0799 Inole) of ethyl 2-chloro-4-methyl--3-oxo-pelltalloate, J.5 6.1 g (0.0802 mole) of thiollrc~a and 60 ml. of ethanol was hel.d at reflllx for 21 hours. Ethanol was removed under reduced pressure and the residual oil was treated with 400 ml.
of saturated sodium bicarbonate solution. The precipitate was collected to give 14.9 g of white solid, m.p. 172-174C., which was recrystallized from ethanol-water to give 13.6 g (82%) of ethyl 2-amino-4-isopropyl--5-thiazolecarboxylate as white prisms, m.p. 174-178C. A solution of 2.14 g (0.010 mole) of ethyl 2-amino-4-isopropyl-5-thiazolecarboxylate and 0.1 g of CaSO4 in 40 ml. of concentra-ted hydrochloric acid was cooled with an :ice bath. I~hen the ~(~mrJ(~rr,L~Ire o the reaction sollltion drol.,p~d below lUC., t ]le hydrOC}l.l.Oride salt precipitated out of solution. The reaction mixture was allowed to warm to room temperature and the hydrochloride salt gradually dissolved again. To the above solution was add-d dropwise 1.0 g (0.0144 mole) of NaNO2 in 10 ml. of water in 15 minutes. After completion of addition of the NaNO2 solution, the reaction mixture was stirred for another 5 minutes. Cuprous ch~orlde (1.0 g, 0.010 mole) was added to the above solution. A vigorous evolution of gas occurred.
The dark blue mixture turned light blue after stirring for 5 minutes. The reaction mixture was extracted twice with -50 ml. of ether. The ether solution was washed successively with water, saturated sodium bicarbonate and saturated NaCl -72- ~i26~71 AG-1152 solution, dried (MsSO4) and concentrated under reduced pressure to give 1.8 g of oil which was crystallized from hexane to give 0.05 g of 2,2'-bis-(ethyl 4-isopropyl-5-thiazolecarboxylate) as white needles, m.p. 192-194~C.
The mother liquor was concentrated under r~duced pressure and the residue was chromatographed on a silica gel column with Et2O-petroleum ether as eluant. The first fraction (using 1 1. of 1% ether-petroleum ether as eluant) contained 1.2 g of oil which was distilled on a Kugelrohr at 2 n~. (pot temperature 100-120C.) to give 1.15 g (49~) of ethyl 2-chloro-4-isopropyl-5-thiazolecarboxylate as a colorless liquid, nD5= 1.5145.
Anal. Calc'd. for CgH12ClNO2S: C, 46.24; H, 5.18; N, 5.99.
Found: C, 96.40; H, 5.22; N, 6.06.
~xample 31 PreFd~at ion of Ethy1 2-C loro-4-t-3u yl-5-Thiazolec rhoxylate. Utilizing ethyl 2-chloro-4,4-dimethyl-3-oxo-pentanoate and the procedure of Example 31, ethyl 2-chloro-4-t-butyl-5-thiazolecarboxylate is prepared.
Anal. Calc'd. for CloH14ClNO2S: C, 48.48; H, 5.70; N, 5.56.
Found: C, 48.41; H, 5.73; N, 5.62.
Example 32 Preparation of Ethyl 2-lodo-4~Trifluoromet~y1-5-T iazolecarboxylate. To a cold (-5C.) solution of 4.0 g (0.0166 mole) of etilyl 2--am;no--4-!:ri~luololne~hyL-5-khia~ole-car~x~xylate, pl:epclred ~Iccor(~irlg to U.S. l'~ t No. 2,726,237, in 30 ml. of 85% phosphoric acid ~nd 30 ml. of 70% nitric acid was added a solution of 1.26 g (0.0166 mole) of sodium nltrite in 10 ml. of water in 10 minutes. The reaction mix-ture was stirred for 10 rninutes and poured into a solution of 10 q of potassium iodide in 100 ml. of water. The reaction mixture was stirred overnight and extracted with ether. The ether solution was driéd and concentrated and the residue was chromatographed on silica gel to give 1.5 g of the desired product, m.p. 75-76C.
Anal- Calc'd- for c7~5F3l~O3s: C~ 23-94; H~ 1-44; N~ 3-99;
- I, 36.15.
Found: C, 23.93; H, 1.44; N, 3.95;
I, 36.08.

-7 ~ G-ll52 ~Z69':7~
~xample 3 3 Preparation of E-hYl 2-3romo-4-Tr_f_uor m thyl-5-_ Thiazolecarboxylate. To a solution of 4.5 g (0.0187 mole) .
of ethyl 2-amino-4-trifluoromethyl-5-thiazolecarboxylate in 50 ml. of 85% phosphoric acid at -10C. was added 25 ml. of nitric acid. To this mixture was added dropwise at -10C.
to -5~C. a solution of 4.0 g (0.0579 mole) of sodium nitrite in 20 ml. of water in 30 minutes. This mixture was stirred for 10 minutes at -10C. to -5~C. and poured into a solution 10 of 2.70 g (0.0187 mole) of freshly prepared cuprous bromide in 20 ml. of hydrobromic acid. A viyorous evolution of gas occurred. The reaction mixture was stirred for 5 minutes and diluted with water. The solid cuspension was filtered and air-dried to give 4.8 g of solid which was chromato-15 grauh~ on silica ~el using (~ her/petroleum e-tht?r (1:4) as eluant. The first 1 liter of eluate yave 3.7 g of solid which was recrystallized from pe-troleum ether to give 2.9 g (51%) of the desired product as white needles, m.p. 75.5-76.5C.
20 Anal. Calc'd. for C7H5BrF3NO2S: C, 27.64; H, 1.66; N, 4.61;
Br, 26.28.
Your.d: C, 27.65; H, 1.65; N, 4.61;
Br, 26.27.
FJXal! P1 e_34 Preparation of ~ yl 2-~luol o-9--Trifluoro~ -t~ yl-5-~_hi.l70le~a:rboxyl_t-e. ~ 111 iXt:Ur(_ of ~6 g (O. 1 IllOle) oE thyl 2-chioro-4-trifluoromethyl-5--thiazolecarboxylate, 37 g (0.55 mole) of potassium fluoride, and 0.11 g of 1,4,7,10,13, 16-hexaoxacyclooctadc-cane (18-CROWN-6, Aldrich Chernical Company) was held at reflux for 23 hours. Since an analysis showed the reaction to be inccmplete, another 45 g (0.77 mole) of potassium fluoride was added and the reaction mix-ture held at reflux for, 64 hours. To said mixture, 0.15 g of 18~ROWN-6 and an additional 27 g (0.40 mole) of potassium was added and held at reflux for 22 hours. Due to poor cooling overnight some of the solvent had evaporated. The reaction mixture was cooled and 300 ml. of acetonitrile added.
The acetonitrile was filtered and concentrated. The residue was Kugelrohr distilled to give 13.7 g of a material which was .

-74- ~ ~ Z~ ~ ~ A~-1152 separated by spinning band column at 15 mm Hg to give 4.2 g of the desired product, nD = 1.4348.
Thiazolecarboxylates of the invention in which X
is lower alkoxy or phenoxy or substituted phenoxy may be S prepared by reacting the halogenated analogue with sodium alXoxide or phenol in the presence of potassium carbonate.
Example 35 Pr_parat on_of Ethyl 2-Phe oxy-4-Tr_fluoromethyl-5-Thiazolecarboxylate. A mixture of 5.2 g (0.02 mole) of ethyl 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate, 1.88 g (0.02 mole) of phenol, 2.76 g (0.02 mole) of K~CO3 and 50 ml. of acetone was held at reflux for 3 days. Acetone was removed under reduced pressure. The residue was treated with water, extracted with ether. The ether solution was J5 (~r;ed (MySO4) and concentrated under reduced pressure. The res:idual solid was heated with hcxane, cooled and filtered to give 4.8 g (76%) of the desired product, m.p. 52-54C.
~nal- Calc'd- for C13HlOF3NO2S C, 49-21; H~ 3-18; N~ 4-41-Found: C, 49.27; H, 3.19; N, 4.38.
Exam_le 36 Preparation of Ethyl 2--Ethoxy-4-Triethoxymethyl-5-Th;~zolec.1rbox~_ te. To a warm solution of sodium ethoxide prepared from 2.0 g (0.0869 mole) of Na and 50 ml. of ethanol was added 5.2 g (0.02 mole) of ethyl 2-chloro-4-trifluol-o-met:hyl-5-thiazo]ecarboxylate. The mixtllre W;.15 ';~ i rrt-d For 4 hours. Ethanol was rellloved url(1c~r r(duc(~ pressli:re. ~rhe residue was kreated with wa~er and extracted with e-ther.
The ether solution was washed with saturated sodium bicar-bonate, dried (MgSO4) and concentrated under reduced pressure. The residue was distilled to yive 2.2 g of the de~sired product as an oil, b.p. 115C. at 0.1 mm; nD = 1.4776.
Anal. Calc'd. for C15H25NO6S: C, 51.86; H, 7.25; N, 4.03.
~Found: C, 51.36; H, 7.03; N, 4.57.
xample 37 Preparation of Ethyl 2-Ethoxy-4-Trifluoromethyl-5-Thiazolecarboxylate. To a cold (0C.) solution of sodium _ _____ ____ ~ethoxide, prepared from 0.46 g (0.02 mole) of sodium and 40 ml. of dricd ethanol, was added 5.2 g (0.02 mole) of ethyl ( _75_ ~i2 AG-1152 2-chloro-4-trifluoromethyl-5-thiazolecarboxylate. A preci-pitate formed immediately. The reaction mix-ure was heated to 80C. and then poured into ice water. The precipitate was collected to give 4.2 g (78%) of the desired product as a white solid, m.p. 30.5-31.5C.
Anal. Calc'd. for CgHloF3NO3S: C, 40.15; H, 3.74; N, 5.20.
Found: C, 40.11; H, 3.75; N, 5.19.
Fxample 3~_ Prepar_tion of thyl 2-(2',4'-Dichloropheno~ 4_ Meth ~ te. A mixture of 6.24 g (0.03 mole) of ethyl 2-chloro-4-methyl-5-thiazolecarboxylate, 4.89 g (0.03 mole) of 2,4-dichlorophenol, 4.14 g (0.03 mole) of potassium carbonate and 40 ml. of acetone was held at reflux for 89 hours. Acetone was r~novc~ uncler reduced pressure. ~rhe residue was treated with 50 ml. of water and ex-tracted with ether. The ether solution was washed successively with saturated sodium bicarbonate, 30 ml. of 10% sodium hydroxide and 50 ml. of water. The ether solution was dried (MgSO4) and concentrated. The residue was recrystallized from hexane to give 5.8 g (58~) of ethyl 2-(2',4'-dichlorophenoxy)-4-methyl-5-thiazolecarboxylate as a white solid, m.p. 71-73C.
Anal. Calc'd. for C13HllC12N03S: C, 47.00; H, 3.34; N, 4.22;
CL, 21.34.
Found: C, 47.04; H, 3.34; N, 4.21;
Cl, 21.36.
Amides are prepared by reacting the appronriate acid chloride with t:he appropriate amine.
F.xample 39 Prep.lrat_on_of N ! N-D_ethyl-2-Chloro-4~Trifluoro-methyl-5-Thiazolecarboxamide. To a well-stirred solution of .._ _ __ ._ . _ __._ _~_ . . _ ._ 4.0 g (0.0160 mole) o the acid chloride of Example 16 in 20 ml. of ether was added dropwise 2.34 g (0.032 mole) of diethylamine in 5 ml. of ether. The insoluble salt was filtered. The ether solution was washed with water, dried and concentrat~d under rrYIuced pressure. The residue was 'crystallized from hexane at low temperature to give 4.1 g of the desired product, m.p. 40-41C.

-76- ~ ~ ~9~ AG-1152 A~lal. Calc'd. for CgH~oClF3N2OS: C, 37.70; H, 3.51; N, 9.77;
Cl, 12.38.
Found: C, 37.66; H, 3.53; N, 9.78;
Cl, 12.33.
Salts may be prepared by reaction of the free acid with the appropriate base.
Fxample 40 Pre~a ation of .Sodium _Salt of 2-Chl ro-4-~rlfluoro~nethyl-5-Thiazolecar~oxylic Acid, Monohydrate. A mixture of 116 g 10 (0.4468 mole) of ethyl 2-chloro-4-trifluoromethyl-5-thlazole-carboxylate, 18 g (0.45 mole) of sodium hydroxide, 200 ml. of water and 400 ml. of tetrahydrofuran was stirred at room temperature for 16 hours. The aqueous solution was concen-t.rated and dried under vacuum to give the sodium Sâ]t of 2-1~ ch1cro-4-lriEluort.,inethyl-5-th;azolecarboxylate, monohydrate as a wh:i~e solid, m.p. 2Ll-215~C.
Anal. Calc'd. for C5H2ClF3NO3S: C, 22.10; H, 0.74; N, 5.16.
Found: C, 22.14; H, 0.71; N, 5.21.
Example_41_ Preparation of Triethanolamine Salt of 2-Chloro--4-Tri-f uoro_ethyl-5-Thiazolecarbo~ylic-A-cid. To a cold (5C.) solu-tion of 6.93 g (0.03 mole) of 2-chloro 4-trifluoromethyl-5-thiazolecarboxylic acid in 20 ml. of ether was added 4.47 g (0.03 mole) of triethanolamine. The rehction mixture was st:;rred at room temperature ~or 18 ~ours ~ d Eiltecl:~ l-o g:ive

8.78 g (77~) of the d~siLed pro~ ct:, 'n.L). L()1~ 2C.
Anal- Calc'd- ~(~r CllH16~ll;'3N25S: C, 34.69i H, 4.23; N, 7.36.
Found: C, 34.89; H, 4.07; N, 7.39.
Example 4 2 ____ __ Pre~acat-.ion of_Isopropxl m ne _ lt of_ -Chloro-4-Trifluoro~
nethyl-5-Thiazolecarboxylic Acid. To a cold (6C.) solu-tion of 4.55 g (0.0196 mole) of the free acid in 20 ml. of ether was addcd dropwise a sdlution of 1.16 g (0.0196 mole) of isopropyla!nine in 10 ml. of ether. The reaction mixture was stirred at room temperature for 1 hour and the white precipi-tate was filtered to give 5.50 g (96.5~) of the desired roduct, m.p. 132-134C.
Anal. Calc'd. for C8HloClF3N2O2S: C, 33.05; H, 3.47; N, 9.64.
Found: C, 33.47; H, 3.55; N, 9.72.

I --77- ~2697~ AG-1152 ~.xample 43 Pre-~aration of Diechylamine Salt of 2-Chloro-4-~rifluoro-... . . .. ~
methyl-5-Thiazoleearboxylie_ Acid To a cold (6C.) solu-tion of 6.93 g (0.03 mole) of the free acid in 20 ml. of ether was added 2.19 g (0.03 mole) of diethylamine in 100 ml.
of ether. The preci2itate, which formed immediately, was filtered to give 7.95 g (86.4~) of the desired product, m.p. 131-132C.
Anal. Calc'd. for CgH12ClF3N202S C, 35.47; H, 3.97; N, 9.20.
Found: C, 35.60; H, 3.97, N, 9.21.
In accordance with the novel aspects of the precent i.nvention, the thiazolecarboxylates have been found to be effeetive in reducing herbicidal injury to selected crop plants due to application of acetamide herbicides. A
preferred em~odj.lnent are those th.iazolecarboxylates substi-I-u~ed .in the ~--positi.on with a trifluorornethyl moiety. Sueh compounds have been found to be quite superior in their ability to reduce herbicidal injury. .~s illustrated in Table IX, thiazolecarboxylates substituted by a trifluoro-methyl in the 4-position are clearly superior to those substituted in the 4-position by rnethyl in rc~ucing herbi-eidal injury to sorghum. Another preferred g:rollp of thia-zolecarbo~ylates are those substituted in the 2-position with a halogen, espeeially ehloro. Most preferred are those ..
thiazole alkyl esters of the thi.i~o1.ecarkll)xyl.ie acid having a chloro i.n thc~ 2-pos.il:ion ~Irld a tr;l1~ rr~ yl. i.n l,he 4 -E~siti.on.
While the compounds of the i.nvention generally tendto safen riee and sorghum erops to the herbieidal effects of aeetamide herbi.eides, espeeially acetanilide herbieides, those skilled i.n the art will appreeiate that the compounds of the invention may be used most effeetively in safening soryhum against injury,due to alaehlor and 2-ehloro-N-(2-methoxy-l-methyle-thyl)-6'-ethyl-o-aceto-toluidider especially alaehlor, and riee, especially direet-seeded riee, against the herbieidal effeets of butaehlor.
Although this invention has been described with respeet to speeifie modi.fications, the details thereof are not to be eonstrued as limitations, for it will be apparent , - -7~ Z~97~ AG-1152 that various equivalents, changes and modiications may be resorted to without departing from the spirit and scope thereof and it is understood that such equi~7alent embodiments are intended to be included herein.

' -:

, ~

Claims (21)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A method of reducing injury to sorghaum or rice crop plants due to the application thereto of acetamide her-bicides which comprises applying to the plant focus a safening effective amount of a compound having the formula wherein n is zero or one; x is selected from the group con-sisting of chloro, bromo, iodo, fluoro, lower alkoxy, phenoxy and phenoxy substituted by one or two groups independently selected from the group consisting of lower alkyl and halogen;
R is alkyl having up to nine carbon atoms; when n is one, R' is selected from the group consisting of hydrogen, agriculturally acceptable cations, alkyl, lower alkenyl, lower alkynyl, alkoxy-alkyl, haloalkyl, benzyl, phenyl and phenyl substituted by one or (two members selected from the group consisting of halogen, lower alkyl, triflouromethyl and nitro; when n is zero, R' is selected from the group consisting of chloro, amino and mono-or dialkylamino.

2. A method according to Claim 1 wherein said herbicide is an acetanilide.

3. A method according to claim 1 wherein n is one.

4. A method according to claim 3 wherein X is chloro.

5. A method according to claim 3 wherein R' is hydrogen, alkyl, benzyl, phenyl or phenyl substituted by one member selected from the group consisting of halogen, lower alkyl, trifluoromethyl and nitro.

6. A method according to claim 3 wherein X is halogen and R' is alkyl.

7. A method according to claim 6 wherein X is chloro.

8. A method according to claim 3 wherein X is halogen and R' is benzyl.

9. A method for reducing herbicidal injury to sorghum or rice crop plants which comprises applying to the plant locus an effective amount of a mixture comprising a herbi-cidally effective amount of an acetamide herbicide and a safening effective amount of a compound having the formula wherein n is zero or one; X is selected from the group consisting of chloro, bromo, iodo, fluoro, lower alkoxy, phenoxy and phenoxy substituted by one or two groups indepen-dently selected from the group consisting of lower alkyl and halogen; R is alkyl having up to nine carbon atoms; when n is one, R' is selected from the group consisting of hydrogen, agriculturally acceptable cations, alkyl, lower alkenyl, lower alkynyl, alkoxyalkyl, haloalkyl, benzyl, phenyl and phenyl substituted by one or two members selected from the group consisting of halogen, lower alkyl, trifluoromethyl and nitro;
when n is zero, R' is selected from the group consisting of chloro, amino and mono- or dialkylamino.

10. A method for reducing herbicidal injury to sorghum or rice crop plants by application thereto of an acetamide herbicide which comprises coating the seed of a sorghum or rice plant with a safening effective amount of a compound having the formula wherein n is zero or one; x is selected from the group consist-ing of chloro, bromo, iodo, fluoro, lower alkoxy, phenoxy and phenoxy substituted by one or two groups independently selected from the group consisting of lower alkyl and halogen; R is alkyl having up to nine carbon atoms; when n is one, R' is selected from the group consisting of hydrogen, agriculturally acceptable cations, alkyl, lower alkenyl, lower alkynyl, alkoxy-alkyl, haloalkyl, benzyl, phenyl and phenyl substituted by one or two members selected from the group consisting of halogen, lower alkyl, trifluoromethyl and nitro; when n is zero R' is selected from the group consisting of chloro, amino and mono-or dialklamino.

11. A method according to claim 10 wherein said herbicide is an acetanilide.

12. A method according to claim 10 wherein n is one.

13. A method according to claim 12 wherein x is chloro.

14. A method according to claim 12 wherein R' is hydrogen, alkyl, benzyl, phenyl or phenyl substituted by one member selected from the group consisting of halogen, lower alkyl, trifluormethyl and nitro.

15. A method according to claim 12 wherein R' is alkyl.

16. A method according to claim 12 wherein x is halogen and R' is alkyl.

17. A method according to claim 15 wherein x is chloro.

18. A method according to claim 12 wherein x is halogen and R' is benzyl.

19. A mixture which comprises a herbicidally effective amount of an acetamide herbicide and a safening effective arnount of a cornpound having the formula wherein n is zero or one; X is selected from the group con-sisting of chloro, bromo, iodo, fluoro, lower alkoxy, phenoxy and phenoxy substituted by one or two groups independently selected from the group consisting of lower alkyl and halogen;
R is alkyl having up to nine carbon atoms; when n is one, R' is selected from the group consisting of hydrogen, agricul-turally acceptable cations, alkyl, lower alkenyl, lower alkynyl, alkoxyalkyl, haloalkyl, benzyl, phenyl and phenyl substituted by one or two member selected from the group consisting of halogen, lower alkyl, trifluoromethyl and nitro; when n is zero, R' is selected from the group consisting of chloro, amino and mono- or dialkylamino.

20. Seed, the plants grown from which are resistant to injury by an acetamide herbicide, comprising crop seed coated with a safening effective amount of a compound having the formula wherein n is zero or one; x is selected from the group consisting of chloro, bromo, iodo, fluoro, lower alkoxy, phenoxy and phenoxy substituted by one or two groups indepen-dently selected from the group consisting of lower alkyl and halogen; R is alkyl having up to nine carbon atoms; when n is one, R' is selected from the group consisting of hydrogen, agriculturally acceptable cations, alkyl, lower alkenyl, lower alkynyl, alkoxyalkyl, haloalkyl, benzyl, phenyl and phenyl substituted by one or two members selected from the group consisting of halogen, lower alkyl, trifluoromethyl and nitro;
when n is zero, R' is selected from the group consisting of chloro, amino and mono- or dialkylamino.

21. A method for selectively preventing the growth of weeds in the presence of sorghum plants which comprises applying to the sorghum plant locus a herbicidally effective amount of 2-chloro-N-(2-methoxy-1-methylethyl)-6'-ethyl-o-acetotoluidide having the formula said sorghum plants having been germinated from seeds treated with a safening effective amount of a compound of the formula wherein R is alkyl having up to 9 carbon atoms and R' is selected from the group consisting of hydrogen, agriculturally acceptable cations, alkyl having from one to ten carbon atoms, inclusive, and benzyl.