CA2042111A1 - Herbicides which contain cyclohexenone derivatives as herbicidal active ingredients and naphthalene derivatives as antidotes - Google Patents

Abstract

O.Z. 0050/41599 Herbicides which contain cyclohexenone derivatives as herbicidal active ingredients and naphthalene derivatives as antidotes Summary Herbicidal agents containing a naphthalene derivative I
I

(R = alkyl, alkylthio, haloalkyl, alkoxy, halogen, OH, NO2 and/or benzyl;
m = 0, 1, 2 or 3;
R3 = -CN, -C(NH2)NOH, -C(Z)TR5, , oder ;
R4 = halogen, -NR7R9, -N=CH-R7, -NR7-SO2R9, COOR5, OH, or ;
Z = O; S; T = O, -NR5;
R5 = H, substituted or unsubstituted alkyl, phenyl or benzyl;
R6 = substituted or unsubstituted phenyl;
R7 = H, substituted or unsubstituted alkyl or phenyl;
R8 = H, substituted or unsubstituted alkyl;
R9 = substituted or unsubstituted alkyl, phenyl or a substituted or unsubstituted heteroaromatic structure;
R10 = substituted or unsubstituted alkyl or phenyl, or together are a sub-stituted alkylene or alkenylene chain, or a substituted or unsubsti-tuted, fused benzene ring;
R11, R12 = alkyl or, together with the common carbon atom, are cycloalkyl;
B = H, substituted or unsubstituted alkyl, alkoxycarbonyl, phenyl or -NR7R8-) as antidote and one or more herbicidal active ingredient from the group of cyclohexenone derivatives.

Description

~21~ ~
O.Z. 0050/41~99 Herbiçide~ which contain c~clohexenone derivat.ive~
as herbicidal active inqredients and naPh~halene derivative~ as.antidote~
Th~ pre~ent invention relate~ to herbicide3 which contain cyclohexenone deriva~ives a~ herbicidal active ingredient~ and naphthalen~ derivatives as antidote~, and methods for selectively con~rolling unde~irable plant growth with these herbicides.
Th~ herbicidal active ingredient~ rom the group consisting of the cyclohexenone derivative3 are compounds of the formula II
~ Xn (~I) where ~1 iS cl-~6-a~
A is a C4~al~ylene or C4-alkenylene chain/ where the~e chain~ may carry from one to three Cl~C3-alkyl groups and/or halogen atoms;
: ~ is hydrogen, nitro, cyano, halogen, Cl-C4-al~yl, Cl-C4-alko2y, Cl C4-alkylthio~ Cl-C4-haloalkyl, Cl-C4-haloalkoxy, : 20 carboxyl, Cl-C4-alko~ycarbonyl, benzyloxycarbonyl and/or ~ phenyl, where the aromatic radicals may carry from one to : three o~ the following sub~tituents: nitro, cyano, halo-gen, Cl~C4-alkyl, Cl-C4-alkoxy, Cl-C4-alXylthio, Cl-C4-haloalkyl,C1-C4-haloalkoxy,carboxyl,C1-C4-alkoxycarbonyl and/or b~n~yloxycarbonyl;
n is from 1 to 3, or is from 1 to 5 when X is hydrogen or halogen;
R2 ~ Cl-C4-alkoxy-Cl-C6-alkyl or Cl-C4-alkylthio-Cl-C6-alkyl, C3-C7-cyclo~lkyl or C~-C7-cycloalkenyl, where these group~
may carry from one to three o~ th~ following ~ubstitu-ents: C1-C4-alkyl, C1-C4-alkoxy, Cl-C4-alkylthio/ Cl-C4-haloalkyl, hydro~yl and/or halogen, :~ a 5 membered 3aturated heterocyclic structure which contain~ one or tw~ oxygan and/or 3ulfur atom~ a~ hetero 2 ~

- 2 - O.Z. 0~50/41599 atoms and which may car~y from one to three of the followinggroup~s Cl-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio and/or Cl-C4-haloalkyl, a 6~membered or 7-membered haterocyclic structure con-taining one or two oxygen and/or sulfur atom~ and one or two double bonds, where this ring may carry from one to three of the following substituent~: hydroxyl, halogen, Cl-C4-alkyl, Cl-C4-alkoxy, C1-C4-alkylthio and/or Cl-C4-haloalkyl, a 5-membered heteroaromatic structure containing one or two nitrogen atoms and one oxygen atom or one ~ulfur atom, where this ring may carry from one to three of the following substituent~: halogen, cya~o, C1-C4-alkyl, Cl-C4-alkoxy, Cl-C~,-alkylthio, (::l-C4-haloalkyl, C2-C6-alkenyl, C2-C6-alkenyloxy, C2 C6-haloalkenyl and/or Cl-C4-alkoxy-Cl-C4,-alkyl, phenyl or pyridyl, where the~e group~ may carry from one to three of the following ~ub~tituent~: halogen, nitro, cyano, Cl~C4-alkyl, C1-C4-alkoxy, Cl-C4-alkylthio, Cl-C4-haloalkyl,C3-C6-alkenyloxy,C3-C8-alkynyloxy,Cl-C4-alkoxy-Cl-C4-alkyl, C1 C4-alkylthio-C1-C4 al~yl and/or -NRl3Rl4, whera R13 1~ hydrogen, C1-C4-alkyl, C3-CB alkenyl or C3-C6-alkynyl and Rl4 i~ hydrogen, Cl-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C~-acyl or ben~oyl, where the aromatic ring may carry from ona to thxee o~ the following ~ub~titu~nts: nitro, cyano, halogen, Cl-C4~alky}~ Cl-C4-alko~y, Cl-C4-alkylthio and/or Cl~C4-haloalkyl, and their agriçulturally useful ~alts and ester~ of Cl-C1O-ca.rboxylic acid3 and inorganic acid~.
The cyclohexonones IX are e~idently acidic, ie.
they can form slmple reaction pxoduct~, such as sal.t~ of alkali metal or alkaline earth metal compounds or enol : 35 e~ter3.
The compounds of the formula II can occur in a plura.lity of tau~omeric form~, and the claim rela~e~ to ~ ~ .

:

2 ~ ~ 2 ~

- 3 O.Z. 0050/41599 all of the~e.
The cyclohexenones of the formula II can be prepared in a conventional manner from known derivative~
of th~ formula III (EP-A-80 301~ EP-A-125 0~4, EP-A-142 741, US-A-4 249 937, EP-A-137 174 and EP~A-177 913) and the corresponding hydro~ylamines of the formula IV
(Houben-Weyl, 10/1, page 1181 et ~eq.) (EP-A-169 521).

0~ NOA~ ~ ~f n III ~V ~I

The reaction i~ advantageou~ly carried out i~ the ~ heterogeneous phase in a solvent at an adequate tempera-: 10 ture balow about 8noc, in the pre~ence of a base, and the hydroxylamine IV i8 u3ed in the form of it~ ammlonium sal~.
~xample~ o suitable base~ are carboIlates, bicarbonate~, acetate~ 9 alcoholate~ or oxid2~ o alkali metal~ or of alkaline earth metal~, in parti~ular ~odium hydroxide, potassiu~ hydroxide~ magnesium o~ide and caIcium oxide. Organic basss, such a~ pyridine or tertiary amin*s, can al~o be uxed. The ba~e i~ added, for example, in an amount of from ~.5 to 2 mol equiva-lent~, based on the ammonium compound.
Examples o~ ~uitable ~olvent~ are dimethyl ~ulfoxide, alcohol~t ~uch a~ methanol, e~hanol and isopropanol, aromatic hydrocarbons, ~uch a~ henzene and toluene, chlorohydrocarbon~, such a~ chloroform and dichloxoethane, allphatic hydrocarbon~, ~uch as hexane and cyclohexane, ester~, ~uch as ethyl acetate, and ether~, such a~ diethyl ether, dioxane and ~etrahydro-furan. The reaction i praferably carrisd out i.n ~ethan-ol, using sodi~n blcarbonato as ~he ba~e.
The r~ac~ion is comple~e a~ter a few hour~. The desirsd compound can be isolated, for examp~e, by , :i :

.
.. . . .
~ . .

: ' - 4 - O.Z. 0050/41599 evaporating down the mixture, partitioning the re idue betwesn methylene chloride and water and distilling off the solvent under reduced pressure.
~owever, the free hydroxylamine base, for example in the form of an aqueous solution, can also be used directly for this reaction; a single-pha~e or two-pha~e reaction mixture is obtained, depending on the solvent used for the compound III.
Suitable solvents for thi~ variant are, for example, alcohols, such as methanol, ethanol, isopropanol and cyclohexanol, aliphatic and aromatic hydrocarbons and chlorohydrocarbon , ~uch as hexane, cyclohexane, meth-ylene chloride, toluene and dichloroethane r e~ter~, such as ethyl acetate, nitriles, such a~ acetonitrile, and cyclic ether~, such a3 dioxane and tetrahydrofuran.
Alkali metal salt~ of the compound~ II can be obtained by treating 3-hydroxy compounds with sodium hydroxide~ pota99ium hydroxide or a sodium or potassium - alcoholate in aqueous solution or in an organic ~olvent, ~uch as methanol, ethanol, a~etone or toluene.
Other metal alts, such a~ mangana3e, copper, 2inc, iron. calcium, magnesium and barium salt~, can bo prepared from the ~odium ~alt~ in a con~entional manner, as can ammonium and phosphonium salt~ using ammonia or ammonium, pho~phonium, sulfonium or sulfoxonium hydroxides.
The compounds of type III can be prepared, for example, from the corresponding cyclohexane-1,3-dione of the ormula V
OH
R2~ V
y whare Y i~ hydrogen or methoxycarbonyl, by known method~
(Tetrahedron Latt. (1975), 2491).
It i~ also po3~ible to prepsre ~he compound~ of the formula III via the enol e~t~r intenmaditlte~ VI, .
:` ' ~ - ' ' ' ' .:"' ' ' - , : - -~21~

- 5 - O. Z . 0050/41599 which are obtained in the reaction of compounds of the formula V with acyl chloride~ VII in the pre~ence oP a base and subsequently undergo a rearrangement reaction with certain imidazole and pyridine derivati~res (Japane~e Preliminary Publication Application79/063 052).
OH O O ~R ~ Oh ., R 2~ ~ R I J~C l --`~ R 2~ 0 - Dl R 2{~(/
Y O Y O O
V Vlr Vl ~

- ~rhe compounds o:f the formula V are obtained via a series of known proces~ steps, starting from hlown intermediate~ .
The hydroxylamine~ IV in which A ie a substituted or un~ubstituted but-2-enylene bridge are s~nthesized in accordance with the reaction ~cheme below, s~ar~ing from aniline derivatiYes VIIX, by diazo ization and ~ub~equent coupling of the diazoniu~ salt to a corre~pondingly sub~tituted butadiene IX. The re~ulting mixture of Xa and Xb i9 coupled to a cyclic hydroximide XI, and the protected hydroxyl~mine derivative XII obtained i~
cleaved with 2-aminoethanol to give the free hydroxyl-amin~ IV.
~n~ ¦ ) Diazotlzation /Hal~ Xn 2-- - D ~C~12--CR~=CRb~ /RC-H~31 \~ 2) Cil2=CR~CR~:CHRC ~=~
VI I I IX Xa Xn Rd ~H 2--C~Rb--C~RC
)1~I Xh J~ Xn xa ~ Xb ~ o~N~H ~ O~N~CHRC--CRb=CRa-C~I2~<

X I I ~ H 2N~ OH ~ I v : ~ :
' . :

.' 2~2~

- 6 - O.Z. OOSO/41599 R~, Rb and Rc independently of one another are hydrogen, C1-C3-alkyl and/or halogen. Hal is halogen, preerably chlorine.
E~ampl~ of suitable cycli~ hydroximides are the S following substance~s ~'`IOH ¢~N--OH ~N~OH
O O O
O O O
~NOH ~N--aH ¢¢N--3H
O O O
o ~<H{:)H
~a .
The halids Xa required for the ~ynthesi~ of the novel hydroxylamine~ of the formula IV can be prepared, as a mixture with Xb, by method~ known from the litera-ture, for example by reacting a diazonium salt of an :~ 10 aromatic or heteroaromatic aniline with a diene. The range of application~ of the reaction i~ di~cu~ed in Organic Rea~tionc 11 (1960), 189 and 24 (1976), 22!j.
Coupling of the isomeric halides Xa and Xb to a cyclic hydroximide o~ the onmula XI results exclu~ively in the cyclic imidoethers of the formula XII, which give the hydroxyl~nine~ IV after the protective group on the nitrogen atom has been eliminated.
The reaction of the mixture o~ Xa and Xb with a hydroximide XI i8 carried out in the presence of an acid acceptor and of a solvent. For re~ons of co t, a preferrod hydroximide XI i8 hydroxyph~halimide.
Suitable acid acceptor~ are alkali metal ~: :
. ~
: . .

.

_ 7 o.Z. 0050/4159g carbonate~, such a~ pota~i~m carbonat~ or sodium car-bonate, alkali metal bicarbonates, such as potassium bicarbonate or sodium bicarbonate, tertiary amines, ~uch as trimsthylamine or triethylamine, and basic hetero cycle~, such as pyridine. For rea~on~ of cost, pota~ium carbonate and sodium carbonate are preferred.
Suitable solvents are aproti.c dipolar organic solvents, for example dimethylformam:ide, dLmethyl sul-foxide and/or sulfolane.
Alkylation under phase transfer condition~ is also pos~ible. The organic solvents used here are water-immiscible compounds, ~uch as hydrocarbons or chloro-hydrocarbons. Suitable phase transfer catalysts are qua~ernary ammonium and phosphonium salts.
The cyclic imidoeth~r3 XII are cleaved by a proce~s similar to that described in EP-A-244 7861 using alkanolamines. The hydroxylamines IV can ba i~olated as free ba~e~ after thi~ proce~ or a salts after precipi-tation with acids. Readily cry~talli2ing salt~ are obtained by reacting the base3 wi~h o~alic acid.
With regard to the biological c~i~ity, preferred cyclohexenones of the formula II are those in which the sub~tituent~ hav~ the following meaninys:
Rl i3 branched or straight~chai~ Cl-C6-alkyl, such a~
methyl, et~yl, propyl~ methylethyl, butyl, l~methyl-propyl, 2-methylpropyl, l,1-dimethylethyl, pentyl, l-methylbutyl, 2-methylbutyl, 3-mathylbutyl, l,l-di-met~ylpropyl, 1,2-di~ethylpropyl, 2,~-dimathylpropyl, l-ethylpropyl, hexyl, l-methylpentyl, 2 methylpentyl, 3-mathylpentyl, 4-methylpentyl, 1~1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2 t 2 dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, l-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2 trimethyl-pxopyl, l-eth~l-l-methylpropyl or 1-ethyl-2-methylpropyl, in particular ethyl or propyl;
A is C4-alkylane or C4 alkenylen0, ~uch a~ butylene, but~
2-enylene or but-3-enylene, whi.ch may be monosubs~ituted ~ 8 ~ O.~. 0050/41599 to trisubstituted by, in particular, methyl or ethyl and~or fluorine or chlorine; in the case of the unsatu-ratPd chains, both the cis and the trans form can occur;
but-2-enylene is particularly preerred;
X is halogent such a3 fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine;
Cl-C4-alkyl, such a~ methyl, ethyl, propyl, l-methylathyl, butyl, l-methylpropyl, 2-methylpropyl or l,1-dimethyl-~thyl, in particular methyl or l,1-dLmethylethyl, 0 Cl C4 alkoxy, such as methoxy, ethoxy, propoxy, l~methyl~
ethoxy, butoxy, l-methylpropoxy, ~-methylpropo~y or 1,1~
dLmethylethoxy, in particular methoxy, ethoxy, 1-methyl-ethoxy or l,1-dimeth~l~thoxy~
Cl-C4-alkylthio, such a~ methylthio~ e~hylthio, propyl-thio, 1-mathylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio or l,1-dlmethylethylthio, in par-ticular methylthio or ethylthio, partly or completely halogenated Cl-C4-alkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, chlorodi-; 20 fluoromethyl, dichlorofluoromethyl, trichloromethyl, 1 ; fluoroethyl, 2-fluoroe~hyl, 2,2-difluoroethyl, 2,2,2-tri~luoroeth~l,2-chloro-2,2-difluoroethyl,2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroeth~l or penta~luoroethyl, in particular difluoromethyl r tri1uoromethyl, 2,2,2-trifluoroethyl or pentafluoroethyl, partly or completely halogenated C1-C4-alkoxy, such as difluorom~thoxy,trifluorome~hoxy,chlorodifluorsmethoxy, dichlorofluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1,1,~,2-tetrafluoroethoxy, 2,2~2-trifluoroetho~y, 2-chloro~1,1,2-tri~luoroetho~y or penta1uoroethoxy, in par~icular tri~luoromethoxy, C1 C,4-alko~yearbonyl, ~uch as methoxyearbonyl, etho~y carbonyl, propoxycarbonyl, l-methylethoxycarbonyl, butoxyearbonyl or 1,l-dimethyletho~yearbonyl, in par-tieular ~ethoxycarbonyl, ethoxycarbonyl or 1,3. dimethyl-ethoxycarborl~l, e~peeially me~hoxycarbonyl, or ; hydrogen, ni~ro, cyano, carboxyl 2 ~
- 9 - O.Z. 0050/~1599 ben2yloxycar~0nyl or phenyl, where the aromatic radicals in turn may carry from one to thrPe of tha following radical~: nitro, cyano, carboxyl, benzyloxycarbonyl, halogen as ~tated in general and in particular for X, alkyl as stated fox Rl, in particular methyl, ethyl or 1-methylethyl, alko~y a~ staked above, in particular methoxy or ethoxy, alkylthio as ~tated above, in par~
ticular methylthio, haloalkyl a~ s ated above, in par-ticular trifluoromethyl, haloalkoxy a~ stated above, in particular difluoromethoxy or trifluorometho~y, andJor alkoxycarbonyl a~ stated above, in particular methoxy~
carbonyl or ethoxycarbonyl.
Un~ub~tituted or monosub~titutPd aromatic radi-cals o thi~ type are particularly preferred.
lS n i3 1, 2 or 3, in particular l or 2. Where there is a plurality of radicals X, the sub~ituen~s may be identical or different.
R2 is alkyl as ~tated under Rl, whîch may carry one of tha alkoxy or ~lkylthio group~ stated under X, preera~1y in the l-, 2- or 3 po~ition, in particular 2-ethylthiopropyl, 5 me~bered heterocycloalkyl, ~uch as tetrahydrofuranyl r tetrahydrothienyl, dioxolanyl, dithiolanyl or oxathiolan-yl, in particular tetrahydrofuranyl, tetrahydroth.ienyl or dioxolanyl, where these ring~ may carry ~ro~ one to three of khe Cl-C4-alkyl, Cl-C4-alko~y, Cl-C4 allylthio and/or Cl C4 haloalkyl groups 3tated under X, 5-mcmbered hetaryl, such as pyrrolyl, pyrazolyl, Lmidaz olyl, i~oxszol.yl, oxazolyl, i~othiazolyl, thiazolyl, furanyl or thienyl, in particular isoxazolyl or furanyl, a 6-membered or 7-membered heterocyclic ~tructure, quch a~ ~etrahydropyran-3-y~, dihydropyran-3 yl7 tetrahydro-pyran~4-yl, dihydropyran-4-yl, tetrahydrothiopyran 3-yl, dihydrokhiopyran-3-yl,tetrahydrothiopyran-4-yl,dihydro-th~opyran-4~yl or dioxepan-5-yl, in particular tetra-hydropyran-3-yl, tetrahydropyran-4-yl or tetrahydrothio-pyran-3~yl, 2~2~ ~

- 10 - O.Z. 0050~41599 phenyl or pyridyl, where the cyclic radical~ may carry from one to three of the alkyl, alkoxy, alkylthio and/or haloalkyl group~
~a~ed under X.
Tha 5-membered heteroaroma~ic radical~ R2 may carry the following radical~ a~ substituent~:
halogen as ~tated under X, in particular fluorine or chlorine~
alkoxyalkyl, such a~ metho~ymethyl, 2-methoxyethyl, 2 metho~ypxopyl, 3-methoxypropyl, 2-metho~y-1-methylethyl, ethoxymethyl, 2-ethoxye~hyl, 2-ethoxypropyl, 3-etho~y-propyl, 2-ethoxy-1-methylethyl or 1-etho~y-1-methyllethyl, in particular methoxyethyl or ethoxyethyl, ~lkenyl, such a~ ethenyl, 1-propenyl, 2-propenyl, 1-methylethe~yl, 1-butenyl, 2-butenyl t 3-butenyl, 1-mlethyl-l-pxopenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-mathyl-2-propenyl, l~pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, l-methyl-l-butenyl, 2-methyl-1-buteny:L, 3-methyl-l~butenyl,1-methyl-2-butenyl,~-methyl-2-butenyl 3-methyl 2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-n~ethyl-3-butenyl, 1,1-dimethyl-2~propenyl, 1-dimethyl-1-propenyl, 1,2-dimethyl-2-propen~l, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, l-haxenyl, 2-hexenyl, 3-hexenyl, 4-hexanyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl~l-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-: methyl-2-p2n~enyl r 4-meth~1-2 pentenyl, 1-methyl-3-pentenyl, 2-meth~1-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pante~yl, 1-methyl-4-pentenyl, 2~met~lyl-4-pentenyl, 3-meth~1-4-pantenyl, 4 methyl-4-pen~eny~0 1,1-dimethyl-2-butenyl,l,l-dimathyl-3-butenyl,1,2 dimethyl-l-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butanyl, 1,3-dimathyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl,2t3-d~nethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3l3-dimathyl-1-bute~yl, 1-ethyl-1-butenyl, 1-eth~l-2-butanyl, 1-ethyl-3-butQnyl, 2-ethyl-1-butenyl, ~ ~., ., .;,., ,. .

:' .

2~
~ O.Z. 0050/~1599 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 r 1,2-trim thyl-2 propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-l-propenyl or l-ethyl-2-methyl-2-propenyl, in particular l-methylethenyl or corresponding alkenylo~ and/or halo-alkenyl.
Th~ 6-membered and 7-membered heterocyclic structures may also carry hydroxyl group~ in addition to the abovementioned substituent~.
Suitable substituents for the phenyl or pyridyl radical , in addition to the abovementioned groups, are ~he following radical~
alkenyloxy, such as 2-propenyloxy, 2-butenyloxy, 3-buten~loxy, l-methyl-2-propenyloxy, 2-methyl-2-propenyl-oxy, 2-pente~ylo~y, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-2-but~nyloxy, 2-methyl-2-butenyloxy, 3-methyl-2 butenyloxy~1-methyl-3-hutenyloxy,2 methyl-3-butenyloxy/
3-m~thyl-3-butenyloxy, 1,1-dimekhyl-2-propenylo~y, 1,2-dimethyl 2~propenyloxy,1-ethyl-2 propenyloxy,2-hexenyl-oxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, l-methyl-2-pentenyloxy,2-methyl-2 pentenylo~y,3-methyl 2-penten-yloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy, 2-methyl-3-pentenyloxy,3-methyl-3-pentenyloxy,4-methyl-3-pentanyloxy,1-me~hyl-4-pentenyloxy,2-me~hyl-4-penten-yloxy, 3-m~thyl-4-pent~nyloxy, 4-methyl-4-pentenyloxy, 1,1-dimethyl~2-butenylo~y, 1,1 dimethyl-3-butenyloxy, 1,2 dimethyl-2 butenyloxy, 1,2-dLmethyl-3-butenyloxy 1,3-dimethyl-2-butenyloxy, 1,3-dimethyl-3-butenyloxy~
2,2-dimethyl-3-butenyloxy, 2,3 dimethyl-2-butenylo~y, 2,3-dimethyl-3-butenylo~y,l-ethyl-2-butenyloxy,l-el:hyl-3-butenyloxy,2-ethyl-2-butenylo~,2-ethyl-3-buten~loxy, 1,1,2-trimethyl~2-propenyloxy, 1-othyl-1-methyl-2-propen-yloxy or l-ethyl-2-me~hyl-2-propenyloxy, in particular 2-propenyloxy or 2-butenyloxy, alkynyloxy, such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, }-methyl-2-propynyloxy~ 2-pentynyloxy, 3-pentynylo~y, 4-pentyny7Oxy, l-methyl-3-butynyloxy, 2-methyl-3-butynylo~y,1-m2thyl-2-bu~ynyloxy,1,1-dimethyl-2~3~21~
- 12 - O.Z. 0050/41599 2-propynylo~y, 1 ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynylo~y, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy,l-methyl-3-pentynyloxy,l-methyl~4-pentynyl-oxy, 2-methyl-3-pentynyloxy, 2-methyl-4-pentynyloxy, 3-methyl-4-pentynyloxyt 4-~ethyl-2-pentynyloxy, 1,1-dimethyl-2-butynyloxy, 1,l-d ~ethyl-3~butynylo~, 1,2-dimethyl-3-butynyloxy, 2,2-dimethyl--3-butynyloxy, 1-ethyl-2~butynyloxy, 1-ethyl~3~butynyloxy, 2-ethyl-3-butynyloxy or l-ethyl-l-methyl-~-propynyloxyI in par-ticular 2-propynyloxy or 2-butynyloxy~
amino which may carry one or two of the following radicals: alkyl as ~tated for Xl in particular methyl or ethyl, o~ alkenyl as stated above, in particular 2-propenyl or 2-butenyl, al~ynyl, such as ethynyl, l-propynyl, 2~propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propyny.l, 1-pentynyl, ~-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 3-methyl-l-butynyl, l,l-dimethyl-2-propynyl, 1-ethyl-2~
propynyl, 1-he~ynyl, 2-he~ynyl, 3-hexynyl, 4-al}~ynyl, 5-hexynyl, 1-methyl-2-pentynyl, l-methyl-3-pentynyl, 1-meth~l-4~pentynyl, 2-methyl-3-pentynyl, 2-methyl-4 pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl r 4~
methyl-1-pentynyl, 4-methyl-2-pant~nyl, 1,1-dLmethyl-2 butyn~l, 1,1-dimethyl 3-butynyl, 1,2-dLmethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1 ethyl-2-but~nyl, 1-ethyl~3-buty~yl, 2-ethyl-3-butynyl or 1-ethyl-1-methyl-2-propynyl, in particular 2-propynyl or 2-butynyl and/or acyl, such as acetyl, propionyl, butyryl, 2-me~hyl-propionyl, pen~anoyl, 2-methylbutyryl, 3-methylbut~yryl, 2,2-dimethylpropionyl, hexanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 2,2 dimethylbutyryl, 2,3-dimethylbu~yryl, 3,3-dimethylbutyryl or 2-ethyl-butyryl~ in particular acetyl, propionyl or benzoyl.
Specific e~ample~ of cyclohexenone~ of the ormula II who~e toleration by crop~ carl be improved by - 13 - O.Z. 0050/41599 naphthalene derivakive~ of the formula I are sho~ in Tablas A and B below:

: , " ~, : .
,~ . : ~ : ',.. - '.' 2~'~2 ~

14 O.Z. 0050/41599 Table A

NO-A
~5 Rl o Rl A Xn CH2CH3 (CH2~4 H
(CH2)2CH3 (CH2)4 H
CH2CH3 (cH2)2cH=cH H
(CH2)2CH3 (CH2)2CH=CH H
CH2CH3 (CH2)4 4-CF3 (CH2)2CH3 (CH2)4 4-CF3 CH2CH3 (CH2)4 3-F
(CH2)2CH3 (CH2)4 3-F
CH2CH3 (CH2)4 4-F
(CH2)2CH3 (CH2)4 4-F
CH2CH3 (CH2)4 3-CH3 (CH2)2CH3 (CH2)4 3-CH3 CH2CH3 (CH2~4 4-OCH3 ~CH212CH3 (CH2)4 4-OCH3 CH2CH3 (CH2)4 3-N02 (CH2) 2CH3 (CH2)4 3-N02 CH2CH3 (CHz)4 3-CN
(CH2)2CH3 (CH214 3-CN
CH2CH3 (CH2)4 3-cO2cH3 (CH2)2CH3 (CH2)4 3-cO2cH3 CH2C~3 ~CH2¦4 3-CO2Ph (cH2l2cH3 (CH2)4 3-C02Ph CH2CH3 (CH2)4 4-OCHF2 (CH2)2CH3 (CH2)4 4-OCHF2 CH2CH3 (CH2)4 3-CH3,4-CI
(C~12)2CH3 (CH2)'~ 3-CH3,4-Cl . . :
: `, . : ' .'.. - ' ', ' -. . -, . ~ :
, .. , . . ~ . , .

~2~

O.Z. 0050/41599 Table B
X

R2 ~ / H2CH CH CH2 ~ (n = 1) R~ R2 __ __ X
CH2CH3 ~ H

(CH2)2CH3 ~ O H

CH2CH3 ~ 0 4-F

~CH2)2C~l3 ~ O 4-F

CH2C~13 ~ O 3-CH3 (CH2~2CH3 ~ O 3-CH3 CH2CH3 ~ O 3-CF3 (CH2)2CH3 ~ 0 3-CF3 CH2C~13 ~ O 4-C(CH3)3 (C~12)2CH3 ~ 1O 4-C(CH3)3 CH2CH3 ~ 0 3-Cl (CH2~2CH3 ~ O 3-Cl , - : .
' . '.: :
.
.
:

.

2~l~2~

16 O.Z. 0050/41599 Table B (contd.) Rl R2 _ X
CH2CH3 ~ S H

(CH2)2CH3 ~ S H

CHzCH3 ~ S 4-F

(CH2)2CH3 ~ S 4-F

CH2CH3 ~ 3-CH3 (CH2)2CH3 ~ 3-CH3 CHzCH3 ~ S 3-CF3 (CH2)2CH3 ~ S 3-CF3 CHzCH3 ~ 4-C(CH3)3 (CH2)2CH3 ~ S 4-C~CH3)3 CH2CH3 ~ S 3-CI

(CH2)2C~3 ~ S 3-CI

CH2C~l3 ~ H

(CHz~zcH3 l o~ H

`.~

: . .

~2 l:~

17 O.Z. 0050/41599 Tab I e B ( c ontd . j Rl R2 X
CH 2CH 3 l~ 4-F

tCH2) 2C~3 l~ ~-F

CH2CH3 1 O~ 3-CH3 (~H2)2CH3 ~ 3-CH3 CH2CH3 1 O~ 3-CF3 (CH2)2CH3 ~ 3-CF3 CH2CH3 ~ 4-C(CH3)3 (CH2)2CH3 ~ 4-C(CH3)3 CH 2CH 3 ~ 3-CI

(CH2) 2CH3 ~ 3-Cl CH 2C~I 3 1 ~ CH3 H

(CH2)2C~I3 1 ~ C~3 H

CH2CH3 1 ~ CH3 4-F

2 ~

1 ~ O . Z . 0050/4 1 599 Tab 1 e B ( c ontd . ~
Rl R2 _ _ X

(CH2)2CH3 1 O 1 CH3 4~F

C~3 (C~l2)2CH3 1 ~ CH3 3_CH3 (CH2)2CH3 1 ~ CH3 3-CF3 CH2CH3 1 ~ CH3 4-C(CH3)3 (CH2)2C~3 1 ~ CH3 4-C(CH3)3 CH 2CH3 1 ~ CH3 3-CI

(CH2)2CH3 1 ~ CH3 3-CI

CH2CH3 1 ~

(C~12)2CH3 1~ H

CH2CH3 1 ~ 4-F

:
`- ~ . , ' . ' ~'. ~ `

L 2 ~

19 O.Z. 0050/41599 Table B (contd. ) Rl , _R2 _ _ _ ,, _ _ X _ ~CH2) 2CH3 S~ 4-F

CH 2CH 3 l~ 3-CH 3 (CH2) 2CH3 S~ 3-CH3 CH 2Clt 3 l~ 3-CF 3 ( CH 2 ) 2CH 3 5~ 3-CF 3 CH2CH3 l~ 4-C(CH3) 3 (CH2)2CH3 S~ 4-C(CH3)3 CH2CH3 l~ 3-Cl ~ctl2) 2CH3 1~ 3-CI

C~ 2C~ 3 ~? H

~CH2) 2CH3 ~ H

CH 2CH 3 ~) 4-F

~CH2) 2CH3 {0 4-F

.

~2~

O.Z. 0050/41599 Table B (contd.) R1 . R2 _ _ X
CH2CH3 ~? 3-CH3 (CH212CH3 ~ 3-CH3 CH2CH3 ~? 3-CF3 (CH2)2CH3 ~ ? 3-CF3 CH2CH3 ~ 4-C(CH313 (CH2)2CH3 ~ ? 4-C(CH3)3 CH2CH3 ~ ? 3-CI

(CH2)2CH3 ~ ? 3-Cl Br Br .
CH2CH3 ~ ? H :~

: Br Br (CH2)2C~13 ~ ? H

Br Br CH2CH3 ~? 4-F

Br Br (CH2)2CH3 ~ ? 4-F

Br Br CH2CH3 ~? 3-CH3 - , ~2~
900~43 21 O.Z. 0050~l~1599 Tabl~ B (contd. ) Rl , R 2, ,_ _ X
Br Br (CH2) 2CH3 ~ 3-CH3 Br Br CH 2CH 3 ~? 3-CF 3 Br Br (CH2) 2CH3 ~? 3-CF3 Br Br CH2C113 ~ 4--C(CH3) 3 Br Br (CH2) 2CH3 ~ 4-C(CH3) 3 Br Br \~\ 3-C 1 Br Br (CH2) 2CH3 ~ 3-Cl CH 2CH 3 ~S--N

(CH2) 2CH3 ~I~N H

CH2C1~3 ~S--N 4-F

~CH2) 2CH3 ~N 4-F

CH 2CH 3 J S~--N 3 -CH 3 .
: , . ~-... `' ~ :

~2~

22 O.Z. 0050/41599 Table B (contd.) Rl -- R2 X

(CH2)2CH3 ~ ~S-I 3-CH3 CH2CH3 ~S~N 3-CF3 (CH2)2CH3 ~ -N 3-CF3 CH2CH3 ~ -N 4-C(CH3)3 (cH2~2cH3 ~S-N 4-C(CH3)3 CH2CH3 ~ ~N 3-CI

(CH2)2CH3 ~S-N 3--CI
o CH2CH3 ~ ~ CH3 3-CF3 (CH2)2CH3 ~0 ~ CH3 3-CF3 CH2CH3 ~ ~ CH3 4-C~CH3)3 (CH2)2CH3 ~0 ~ CH3 4-C(CH3)3 CH2CH3 ~o~ ~CH3 (C~l2)2cH3 ~O ~ C~13 H

CH2CH3 ~oJ H

2~2~

23 O.Z. 005~/41599 Table B (contd.~
R1 _ R2 _ _ X
( CH 2 3 2CH 3 ,rOJ

CH2CH3 ~ J 3-CF3 (CH2)2CH3 ~oJ 3-CF3 CH~CH3 ~ J 4-C(CH3)3 (CH2)2CH3 ~oJ 4-C(CH3~3 (CH2) 2CH3 0 H

(CH2)2CH3 O 3-CF3 ; CH2CH3 O 4-C(CH3)3 (CH2)2CH3 O 4-C(CH3)3 CH2CH3 ~ H
~CH2)2CH3 ~ H

CH2CH3 ~ 3-CF3 (CH2)2CH3 _ ~ 3--CF3 CH2CH3 ~ 4-C(CH3)3 (CH2)2CH3 ~ 4-C(CH333 2~121~:~

24 O.Z. 0050/41599 The herbicidal cyclohexe~one derivatives of the formula II are predom-inantly used for combating unwanted grasses in dicotyledonous crops and in grasses which do not belong to the Gramineae family. Depending on the structure of the substituents and the application rate, compounds from this class may also be used for selectively combating unwanted grasses in graminaceous crops such as wheat and rice.
Naphthalene derivatives have been described in the literature both as herbicides and as antidotes of the formula I
R ~COR I ', where the substituents have for example the following meanings:

R' is hydrogen, halogen, nitro, C1-C5-alkyl or phenyl and R is hydroxy, alkoxy, alkylthio, amino or substituted amino (HU-A 21 318, HU-A 21 319, HU-A 21 320, Hl)-A 21 321, HU-A 21 322, HU-A 21 323 and BE 884 634). These antidotes are recommended for reducing damage caused by herbicides of the following classes: ureas, thio-carbamates, triazines, and chloroacetanilide and uracil derivatives.

The object of the present invention was therefore to provide compounds able to reduce the damage to crop plants caused by herbicides of the cyclohexenone type II.

We have now found that naphthalene derivatives cf the formula I

~I Rm I, where the substituents and the index have the following meanings:

R is C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkyl, C1-C4-alkoxy, halogen, hydroxy, nitro or benzyl;

"., . , :

' : . .. .

: ., , ..

-- 2 ~
9002~3 3.Z. 0050/41599 m is 0, 1, 2 or 3, the radicals R being identical or different when m is 2 or 3;
R3 is -CN; -C(NH2)NOH; -c(z~-rR5;
O O N O
-C-Azol , -C-o-N=cRllRl2 , ~ N ~ R6 ;
R4 is halogen; -NR7R~; -N=CH-R7; -NR7-502R9; CooR5; OH
~lo R10 I I or -NR7-C-B and O ¦ O O
Z is oxygen or sulfur;
10 T is oxygen or -NR5;
R5 is hydrogen, C1-C6--alkyl which is unsubstituted or ~ono- to trisubstituted by haloyen, C1~C4-alkylamino, di-(C1-C4-alkyl)amino, Cl-C4-alkoxy or C1-C4-alkylthio;
phenyl or benzyl which may bear one to three of the ~ollowing gro~ps:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, cyano, nitro and/or halogen;
R6 is phenyl which may bear one or two of the Following groups: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, cyano and/or nitro;
25 R7 is hydrogen;
C1-C6-alkyl which is unsubstituted or mono- to trisubstituted by halogen, C1-Cb,-alkylamino, di-(C1-C4-alkyl)amino, C1-C4-alkoxy, C1-C4-alkylthio, phenyl and/or (C1-C4-alkyl~oxycarbonyl;
phenyl which is unsubstituted or mono- to trisubstituted by halogen, Cl-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, Cl-C~-haloalkyl, cyano and/or nitro;
R8 is hydrogen;
3S Cl-C6-alkyl which is unsubstituted or mono- to trisubstituted by halogen, Cl-C4-alkylamino, di-(Cl-C4-alkyl)amino, Cl-C4-alkoxy, Cl-C4-alkylthio and/or phenyl;

. : .. : : , ~ ~3 ~

~6 O.Z. 0050/41599 R9 is C1-C6-alkyl which is unsubstituted or mono- to trisubstituted by C1- C4-alkoxy, C1- C4-alkyl~hio, C1-C4 alkylamino, di-(C1-C4-alkyl)amino, phenyl and/or one to five halogen atoms;
phenyl or 5- or 6-membered hetaryl, and these rings may bear from one to three of the following yroups: C1-C4-alkyl, C1-C4-alkoxy, Cl-C4-alkylthio, C1-C4-haloalkyl, nitro, cyano and/or halogen;
R10 is C1-C6-alkyl or C2-C6-alkenyl, these groups being unsubstituted or mono- to trisubstituted by: halogen, C1-C4-alkoxy, Cl-C4-alkylthio and/or phenyl;
phenyl which is unsubstituted or mono- to trisubstituted by Cl-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, nitro, cyano and/or halogen;
or RlO...Rlo together form a C2-C4-alkylene or C2-C4-alkenylene chain, and these bridges may bear fro~ one to three of the following substituents: C1-C~-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen and/or phenyl, or form a fused ben~ene ring which may bear ~rom one to four halogen ~ atoms and/or from one to three of the following radicals: C1-C4-alkyl, : 25 C1-C4-alkoxy, Cl-C~,-alkylthio, C1-C4-haloalkyl, cyano, nitro and/or phenyl;

R1l,R12 are each C1 C4-alkyl or, together with the carbon atom to which they are bonded, form C3-C6-cycloalkyl;
B is hydrogen, C1-C6-alkyl which is unsubstituted or mono- to trisubstituted by halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino, di--(C1-C4-alkyl)amino, phenyl and/or C1-C4-alkoxycarbonyl;
C1-C4-alkoxycarbonyl;
-NR~RS- or phenyl which may bear from one to five halogen atoms and/vr from one to three of the following substituents: C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-haloalkyl, cyano and/or nitro;

. .

~2~

27 O.Z. 0050/41599 provide excellent protection for crop plants from the Gramineae family and improve the tolerance of herbicides of the cyclohexenone type II specific-ally in crops such as milletr rice, Indian corn, cereals (wheat, rye, barley, oatS), cotton, sugarbeets, sugarcane, soybeans and sorghum. The 5 damage to crop plants is reduced or completely suppressed. Unwanted grassy species are combated, it being irrelevant for the action whether -these herbicidal agents consiSting of herbicidal active ingredient and safener are formulated and applied together or separately, and irrelevant, when the active ingredient and safener are applied separately, in which order 10 they are applied.

The compounds I are manufactured in accordance with methods generally known in the literature.

15 Derivatives I in which R3 and R4 occupy adjacent ring positions are obtained for instance by reacting a corresponding nitronaphthyl derivative XIII under conditions analogous to those described by Y. Tomioka ~Chem.
Pharm. Bull. 33 (4), 1360-1366 (1985)~ to give the cyanonaphthylamine Ia (R3 = CN, R4 - NH2). This reaction seqUence is shown below for the 20 synthesis of 2-aminonaphthalene-1-carbonitrile derivatives:
,~ " ~'`~NO2 base m ~ + NC ~ C02CH2CH3 XIII
CN CN
m ~ N ~ CO2CH2CH3~ N ~ co2cH2cH3 CN
hydrolysis R ~ NH2 la The corresponding compounds I can be synthesized by methods described in the literature from the derivatives Ia ~derivatives of the cyano group:
Methoden der organ. Chem. (Houben-Weyl) V01. E5, pp. 263 et seq., 25 pp. 710 et seq., pp. 790 et seq., pp. 941 et seq., pp. 1242 et seq., pp. 1313; Vol. X/4 (1968), pp. 209 et s0q.; derivatives o~ the amino group: Methoden der organ. Chem. (Houben-Weyl) Vol. XI (2), pp. 3 et Seq., Vol. V (2) p. 846), 3~ Numerous methods have been described in the literature of synthesizing naphthalene derivatives I in Which R3 and R4 do not occupy adjacent ring positions. The literature citations are listed together With the corres-ponding compounds in Tables 8 and 9 a~ter the synthesis examples.

, . . ~ .

; .
.

~2~
9002~3 BASF AktiengesellschaFt 28 O.Z. 0050/41599 With regard to biological activity, those naphthalene derivatives are preferred in which the substituents have the following meanings:
R is alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, l-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, especially methyl and ethyl;
haloalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and 1,2,2-trifluoroethyl, especially trifluoromethyl and 2,2,2-trifluoroethyl;
alkoxy such as methoxy, ethoxy, propoxy, isopropoxy and tert-butoxy, especially methoxy and ethoxy;
alkylthio such as methylthio, ethylthio, isopropylthio and tert-butyl-thio, especially methylthio;
halogen such as fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine; hydroxyl; nitro or benzyl;
m is 0, 1, 2 or 3, R baing identical or different when m is 2 or 3;
R3 is cyano; a carboxaminoxime, a carboxylic acid, a thiocarboxylic acid, a carboxamide, a thiocarboxamide, oxadiazole, an oxime ester group, where R11 and Rl2 are methyl, ethyl, propyl, butyl, cyclopentyl or cyclohexyl, or a radical -C(0)-azole, where azole is a l-imidazolyl, 1-pyrazolyl and especially a 1-triazolyl radical.
Where R3 denotes an acid or an acid amide function, this radical may 30 additionally be substituted by one of the abovementioned alkyl groups, a phenyl radical or a benzyl radical.
The following are particularly preferred:
35 - cyano, ~ carboxamide and thiocarboxamide radicals which are unsubstituted or substituted by methyl, ethyl, phenyl and/or benzyl, and . :

~2~

29 0.~. 0050/41599 - 3-oxadiazolyl radicals substituted in the 5-position by a phenyl ring, and this phenyl substituent may in turm bear up to three substituents.
Suitable substituents are the halogen atoms, alkyl, alkoxy, alkylthio, haloalkyl and/or cyano or nitro groups already mentioned for R.

R4 may denote halogen, as under R, fluorine, chlorine and bromine being preferred.
R4 may also be a carboxylic acid group, a hydroxyl group, an amino group or a derivative of a hydroxyl or an amino group. The following are particularly preferred:
- dialkylamino, such as dimethylamino and diethylamino 15 - diacylamino, such as diacetylamino, maleimino, dichloromaleimino, methylmaleimino, phthalimino, tetrabromophthalimino and 3,4,5,6-tetrahydrophthalimino, - acylamino, such as acetylamino, glutarylamino, benzoylamino and ethyloxaloylamino - sulfonylamino, such as phenylsulfonylamino and N-(phenylsul-fonyl)-N-(1-carboxylyl)-methylamino - imino, such as benzalimino.
Suitable derivatives of hydroxy groups are salts such as alkali metal salts or esters with inorganic or organic acids such as alkylsulfonic acids, phosphoric acids and carboxylic acids.
Particularly preferred compounds I are those in which the radicals R3 and R4 occupy adjacent ring positions.
Examples illustrating the synthesis of the cyclohexenone deriYatives of 35 the formula II
Manufacturing instructions for Example 3.2 a) At 0C, 69.1 9 (1 mol) of sodium nitrite in 100 ml of water was added to a solution o~ 93.1 g ~I mol) of aniline in 340 ml of water and 225 ml of concentrated sulfuric acid.

2 ~

30 O.Z. 0050/41599 b) At -15C, 67.6 9 (1.25 mol) of butadiene was gassed into 840 ml of acetone and 50 ml o~ water. 15.5 9 of copper(II) chloride and 22.5 9 of calcium oxide were added and the diazoniu~ salt prepared under a) was introduced over a period of 2 hours. This reaction mixture was allowed to heat up to 25C. After it had been stirred for 6 hours, it was extracted with methyl-t-butyl ether, the organic extract was evaporated down and distilled in a thin~film evaporator (0.2 mm Hg;
80C). There was obtained a mixture of 1-chloro--4-phenylbut-2-ene and 3-chloro-4-phenylbut-1-ene (78:22) in a total yield of 55%.
c) 78.3 g (0.48 mol) of N-hydroxyphthalimide and 44.2 g (0.32 mol) of potassium carbonate were added one after the other to 480 ml of anhydrous N-methylpyrrolidone. At an internal temperature of 40C, 88.8 g (0.54 mol) of the chloride mixture obtained in accordance with example b) was dripped in. The mixture was heated to 60C and stirred for a further 6 hours. After the mixture had cooled it was poured into 2 liters of ice water and filtered. Washing and drying gave 9ah of theory of (E)-N-(4-phenyl-2-butenyloxy)-phthalimide.
Mp.: 70-71C (isopropanol) d) At 60C and while stirring, 11.6 9 (0.19 mol) of ethanolamine was added to 55.5 g (0.19 mol) of the phthalimid ether e) in 190 ml of ethyl acetate. After 5 hours the precipitated N-(hydroxyethyl)-phthalimide was filtered off and 18.8 g of oxalic acid in 30 ml of ethyl acetate was added to the filtrate. there was obtained 95% of theory of (E)-4-phenyl-2-butenyloxy amine as the oxalate salt.
Mp.: 127-129C.
e) 4.3 g (0.016 mol) of 2-propionyl-5-(3-tetrahydrothiopyranyl)-cyclo-hexane-1,3-dione, 4.5 g (0.018 mol) o~ 4-Phenyl-but-2-enyloxyammonium oxalate and 3.0 g of sodium bicarbonate were stirred for 16 hours in 100 ml of methanol at 25C. The solvent was distilled off under reduced pressure and the residue was chromatographed on silica gel using a mixture of toluene and ethyl acetate in a volume ratio of 8:2.
After removal of the solvent, there was obtained 2.2 g (34.3% of theory) of 3-hydroxy-2-~1-(4-phenyl-but-2 enyloximino)-propyl]-5-(3-tetrahydrothiopyranyl~-cyclohex-2-en-1-one as a resin.

40 Unless stated otherwise in the tables below, the alkenyl radicals are in the E configuration. The IH-NMR details relate to characteristic signals.

:
.

goo243 31 O.Z. 0050/41599 Manufacturing instructions for example 5.26 a) 71.5 9 (0.23 mol) of N-(4-(4-fluorophenyl)-3-butenyloxy)phthalimide (prepared as in DE-OS 38 38 310) is dissolved in 300 ml of tetrahydro-furan. 2 9 of palladium on activated carbon is added, followed by hydrogenation at slightly superatmospheric pressure until 1.2 times the theoretical amount of hydrogen has been consumed.
The mixture was filtered through kieselguhr, evaporated down and recrystallized from isopropanol.
Yield: 62.8 g (87%); mp.: 67-68C
250-MHz 1H-NMR (DMSO-d6) 3 (ppm) = 1.8-1.9 (m,4H); 2.65 (t, 2H); 4.15 (t,2H) 7.0-7.35 (m, 4H); 7.86 (s,4H).
b) 61.8 ~ (0.197 mol) of the chlorophthalimide prepared above is added in portions to 92 ml of ethanolamine. The mixture is heated for 3 hours at 60C, cooled, poured into 400 ml of ice water, and extracted three times with 100 ml of dichloromethane. The combined or~anic phases are washed with saturated sodium chloride solution, dried and evaporated down under reduced pressure.
4-(4-Fluorophenyl)-butyloxyamine is isolated as an oil.
250-MHz IH-NMR (CDC13) (ppm) = 1.5-1.75 (m,4H); 2.61 (t,2H); 3.68 (t,2H);
5.4 (broad s, 2H), 6.9-7.2 (m,4H) 3 g (11 mol) of 2-butyryl-3-hydroxy-5-tetrahydrothiopyran-3-yl-cyclohex-2-enone is dissolved in 100 ml of anhydrous methanol, and 2.2 9 (12 mmol) of 4-(4-fluorophenyl)-butoxyamine is added. The mixture was stirred for 16 hours at room temperature and evaporated to dryness under reduced 35 pressure. The residue is taken up in diethyl ether and chromatographed on silica gel. There is obtained 3.6 g (~0% of theory) of the title compound 2-(1-[4-(4-fluorophenyl)-butyloximino]-buty1-5-tetrahydrothiopyran-3-yl-3-hydroxy-cyclohex-2-enone ~compound 5.04).

2 ~

o-~t ~ _ E ~3 O ~ _~ In O
~i ` ~ O U~
I I I I I ~ :1: I X ~ 3:
o E E E ~E I-- E E E I E Ei E
O --l O O O O -- O O U~ O
E ~ D O ~ o O ~ 9 c ~ o ~
._ I I t ~ I x ~U --- .
X ~ * _ _, _ _ _ _ _ _ _ __ _ _ _ _ z ~ m ~ m m o ~ ~
.. ~t ~ ~ ~ ~t -~ ~t ~t t ~ ~ ~ ~ -t O -~z ,~
0~0 C O ~ O O ~ ~ ~ ~ O --~ ~
Y~ -~r e ~. ~ o O O O _~ O X -+) ~ L ~ L ~ O :~, 3 ~ O O O O S O S

x t t ~ t ~ -t ~ ;~
c r c c c c c c ç:: c c c ~ ~ ~ c a~ c c c c :: C

a~ a~ 3 ~ ' cn a) 3 3 ~ a~ 3 3 ~ ~
.~

._ _ ~" L L L,~ Q C~. n tL tL ~ Q ë

.a . O O O O IOn D o CO C~- O, . ~ ~ ~ U, O ~ ~ ~ . I . . ; . . . ~ . . *

. .
. .......... ~. .
~ . . . ..
i .
. . ., .

--' ?J~2~

c~

In o - -1~i E
O ~ E E
~r ._ O ,o y D
cn ,~ In In :~:
_ _ a~
:~ ~I U~ I ~) S E 01~ ~
CL ~ ~tl ~ In ~) r~ _ r-~ _ ~1 C
l l l l T ~ D n ~ ~

0~0 r _ r r I I t~
y 3 ~ ;1 ;t 3 _~ ~0 ,_ Z ~:
,7 r-~ X
r ~~ L G~
::~
ILI I

r~
r~ ~ r~
_~ ~ L
t~l LLI ~ ILI ~ r-a) ._ ~ ~ ~ u~
5~ . O O O O
O

~, - . ' : ' .
. .

~2~

CJ~ _ ~
I I I I ~: I T I I
E E E ~ E E E E E E E E
o , ~ O o o ~ o o o o o o O ~ _ o _ _ ~ ~:L __ s E

I ~
S 3 ~ ~ 3 S
~,-- -- s ~ s ~, ~' ~ E c~ ~ ~ s ~
O ~1 I I ~ '-- L l:L S '' 1:~. L I I S
n ~ ~ L ~ ~) L L ~ r~ ~-- ~ n L
O 1 0r~ C
' :: ~ ~ L Q) i ~-- S I L

~r ~ Q~
c~: 3 ~ ~ ~ ~ ~ n ~ ~ ~ ~ ~ n ~ ~ ~

L L L L LL L L L ~ ~t '-- '-- ~ -- L L
S C S S r-.C S ~ S ~ ~
O O O O O O O O O O O O O
~J S L ,~ a ~ L ~ L L

_~ L ~ L L L ~) ~ V

~1 ,--~ ~ o o o o o o o o c~
o ~ v~ i *

:

2~2 ~

~ ~ _ __ _ _ ~ _ _ ~ _ _ _ _ _ _ o ._ E EE E E E E E E E E E E E E E
o o o_ o o o o o o o ~ o. o o o o s O rU ~
O ~ o s E ~' `:t . . . . . . . . . .

c q~ -- c ~ -- ~ c c ~

~ ~ c ~ ~ a s ~ +~ C
.Q I ,~ n ~ I --~ .a D I 1~
-- .- S~ ~ ~ S ~ S
~, ::-7 ~ C _ _~ ~, C
C ~> E I C (:: ~ E I C C ~ E I C Ca~ E
~ s o ~ o ~ I) ~ O ~ ~) ~ ' O
Q ~ o ~ ~ ~ ~ L ~ Q, c~ ~ o I ~ S ~ L
O ~ ~ O O ~ ~ ~ O O ~, ~ ~ O O
O ~ ~ ~ O ~ 1 ~ ~I O O ~ 1-- r~ ~ O O ~ 4_ , ~ _ C ~ ~ . C~ C ~--LO~SI ~ ~ L~
~ ~ ~ 3 ~ ~ ~ ~ ~ 3 ~ ~ ~ ~ D ~ Q ;t ~ ~ ~ 3 l l l l l l l l l l l l l l l l l l LLL LLLLL LLL L L LLLLL
~ ~ ~ Q
LLL LLLLL LLL OL L LLLLL
s ~~ s ~ ' LLL LLLLL LL~ L L LLLLL
,~ ~ V ~ ' O ~ Q~ ~_ ~ sr~ OOOOO C~S ~ S OOOOO
_ ~ ~ LL L L L ~ ~ ~ ~ ~ LLLLL

n . ~ m ~o r~ o ; . ~ . , ,:

. ~ , . ~ . .

2~2~

C~l E E
_ _ o U~
~ _ , _ ~ _ _ _ _ _ _ _ _ a~ ~ I ~ I O I :~: T :lC I I I T
~ U~
~ c~ E ` E ` E E E E E E E E ~1 o _ ~
o ._ o ~In ~ u~ D O U~
o ~o . ~. ~ . . .. . . . . _ ~ 0 ~ D <L) ~ ~
,_ ~ _. o _~ ~ ~ ~ o .
* .,~ .~, . . . . . . . .
~ _~. ~ _^ ~ _ _ ~ _ _ _ _.. _ _ ~ /a ~ I-- I -- I I I I I I I :C T
O ~ o O~ _ _ _ _ _ _ _ _ _ _ _, _ _ _, ~ .
s ~ . . . . . . . . .... .

T , ~ , , T
.1~ ~ ~1 ~ Q
~ ' Q D ~ 1~

D Cr) ~ ~ '- C Q, C~ ~ ~ a) 1:: E
~)Q) ~ ~ ~ I I /11 1 1 1 I L
c s-- c s ~ ~) S ~'1 t~ t''7 ~1 0 O ~ O ~ O ~ ~ o ~ V ~ ~,--~ ~ L ~ ~ L ~1 3 o s O ~ ~ L 1 V ~ ~ LL C C t~ C ~
C ~ '- c S `-- I
~ I I I II I I I I I ~t 3 ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ n o .~:
I I ~ I I I I I I c c l ~
O O O O O O O ~ ~ ~ ~ ~ ~ r_ .~ _ L L C L L O
,C S S S S S
O r~ O _~ O ~-- O r-~ O _ ' O _~ O _~ O O O O O E
L:-~ L :~ L~-~ L :- ~ L :1~> L :~ L :~ L L L L L O C
~C ~C roC ~C WC ;O Cra C 1~ ~0 ~ la ~ cl l:L.
L~a L 10 L~ L11~ L1~1 L IU L n~ L L L L L I O Vl ~1 ~L +~ L +-L ~L ~ L ~ S_ /J L1-~ ~IJ 1 r~
C ~ r-~
_~ C,~ ~ S ~ LO ~ ~ L ~ L L

D . ~~1 ~1 O

, . . . . . .
. , ' , ' - - ..

:''~ -., ~ ' ' ' ' ~ ,' ' :

~ ~ -'1 2 ~

T
_ In 0~ ,_ L~ E
~ ~ E -- -- E E -- E
o _ _ ~ _ _ _ In ._ ~ .
o ~ ~o ~ ~ ~ .
O ~O ~ O
~ In Ln U~ ~ I ~
_~ ~ . . . . U~ o * U~
O ~: ~ u 7 ~o n Z ~
-- I I I :1: ^ _ T
_ ~1 ~1 ~I ~I
~ ~ ~
O ~ O ~ ~ ~ ~ ~ E
_ _ ~
Q. ~ ~ ~ ~ n In .-- o In E ;~ ;t ;~ ~ ;i ;t ~ ~ ~ I ~ ~ I :~
1~ C C _ C
C
I I ~ 1 ~ ~ n ~ s ~ ~ s ~
3 1 ~Q. 3 ~5:-- n,-- ~ D ~- D
_ _:-, _ ~ ~ _ s .1:: C E ~: ~ E s ~ . ~ o o Sr~ S S ~ a~
t t:r~ t O t C~ O O
L ~ r-r~ L :~ ~ r~ ~
O Ot~ r~ ~ O C ~ --::1 ~ I V ._ C _ ~ ._ C
:~

`: 3 ~ Q ~ t ;t n ~

O O O O O O O ~ t_ L L L L t L L t Q~

S C S ~ ~ X X
t ~ ' t_ ~ L
~ I) O O
O O O OO O O IJ
O:~ O:>~ O :-7 0::~7 0 ~ O>~ ~ ~ r~
.r~I .r~ I r~ r~ I S .
OC Ot_ O ~ O t_ O~ O ~ O C ~ ~
~t~L ~ L ~ L ~ L ~L ~:t L E ~r _ K ~it L ~i t~fi CL ~it~ ~) t~ CL ~) t L ~ ~t C
~i .~-r~t~ O O o L L ~
L r . ~ ' a) r~
~ o ~ ~r,'5~ ~
~ Z

,, : ,. ,,, - . ., ~

:' . ' , , - . . '. . . , :, ~ ~ . , '. -. ' . . ' ' " : ' ~ ' : ' , - : :

2 ~

X ~ c I
E E ~ E E e E
o o o o o o o u~ E . . . . . . ~
o ~-- ~ E E E EE -- E E E F
o Co ~ ooooo~oooo 1~1 _ l l I l I l l l I
O ~:
.~ _ _ _ _ _ _ _ __ _~ _ _ _ _ _ _ _ _,_ _ _ _ _ __ _~ _, __ _ _ _ _ Eco COCO 01:) 0 /X~ r~

c ~~ c ~ ~ ~. .
~ ~~ ~ ~ ~ I I
+, ~~ I ~ .,,, (~1 1 .a 8 ~ ::1~ 3 8 9 n 8 n a:~ ~ C ~: ~ c~ I I ~ O ~ ~ ~_ s s J ~ O O O
s.c c~ s s1- 1 1 1 1 1 ~ ~ L ~ L
c~ n. ~ ~ ~ ~ ~ ~ ~ ~ s ~- o o o X X X X X X 8 3n n ~ '~ o~ c s s O O O O O O .~ 7 L ~ ~ O
S~~ S S S r ~ ~ S O
c C C C ~ ,-- G Q Cl sIE ~ ~ S 3~ s s f _ ~
:
C ~ ~ C
L L ~ ~ ;~ L ~1 ;t ~ ~ ~ c ~ ~
Q.Q. i_ ~ c c c~ iC ~ i- 1~ Q. ~ ~1 C
o o ~ ~ ~ ~ o o ,n ~ ~ o o o o r~
S Si--L L L .-- r L L L ._ S .C r L
L L O L L i~_ L L LO L L LO
V ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
.CC~ S S ~~ S S .C: S S S r r- c L:~, L:--, LL L L L :.~ L :~ L L L L ~, L :~ L ~, L ::~, L U~

L ~ L ~ L ~ ~ LL i_ t ' L L L iJ L +~

:

2 ~

I ~
,~
~i ~

E-- u~ o ~ _ T ~C T
` ---- --` E ~ E E E
o E I I I ~`I E ~I ~`I ~`I
Ln ~ ~
O CO
_ . ~ ~ ~ . . . .
_ ~ y * U~ ~ ~ ~ ~ .-- o o o O ~ W U~
o ~ _ I I I I I I I ~:
o ~ o _ ~ ~ ~ ~ -1 _ ~ _ _ ~_ _ _ _ _ ~:: E

~,~
3 a~ o~
n ~ ~ ~:~ ~ ~ ~ ~ ~
c ~ ~ - ~ - - n ~ D
O
L L C ~ C ~' C
o wa~ s ~c s a) a) kl _ S ' ~ S S S
S ~C~ O O r~ I:L CL C~
._ E E L L S E E
o ~ _ ~ o o O
I _~ L L ,-- S W L L
~ ~ S m C3 1~3 _ 7 _ _ ~ ~ ~ ~ ~ ~
I ~ I
3 ~ I ~ ;l ~ ;l ~- s: C ~ ~ ~
I ~ ~u ~U ~ ~ I I I
L L L
~ CL O O. ~ O. r ~:
1~ O O _ ~ ~ t ~- C ~: S ~ S ~
CL ~ ~ ~ I~ ~ n. ~ n.
L L L OL L L
~1 -a ~~ S ~ S S S ~ S ~:
_~ ~ .~ r~ ~ r ~ . ~a ~ ~
L ~, L :~, L :~ L~^, L ~ L L V) O Q CL
-- ''~ L OL S OL OL L L L +~ ~ ;

n . l - 1` 1-- r~ r- 1` 1~1~ r-o ~ *

:

2~l~2~ ~

o' ~
~ r~ T I I
~ ~ ~ ~ ~ ~ _ _ _ ~ E 3~
o Q E E E E E E E E E
r _ _ _ _ O .. _ O O --~O
O * ~ L~ In n In . . .
~: In U~ ~ In z ~ ~ I I T I I
O ~a ^
o ~ v~ V ~ r~ o -- -- -- --u~ ~ I cr~
~, Q u~ In u~ I L~ ~ ~D I ~ ~D ~ u~
_ -:t ;t J L~ ~ ~J cO

~ ~ ~ ~ r ~
T T,,, T T T T,,, , .............. ....
J~ 1 .0 D ~ ~ .Q n ~
~ ~ ~ ~ r ~ ~ ~- r c ~ 1;:
.c s s s s ~ s s r r s O ~. ~
I ~ ~
~,5~ ,C , a~ C~Q
~, o a~x S s ~ o c~: ~ ~ --~ E :~ Z .~ ~ ,_ o o c ~ al ~ c .~ c o~ o r o Q I .C ~ C .s:
~ O C~ 7 Q
_~ a ~ ~ ~ U O O ~ --C C L L ~ I .~ ~ 3 c ~ L L c ~1 S c I ~ E
u S L ~LO ~ ~ L L ~ L ~ L

~ C~ O
,~ . O O O O o o o o o ,_ ~ ~
~- 2 ~ t ~ ~ ~ ~ ~ ~ ~ ~ ~ *

:

~ ~ ' ' .
,: .
' ' , ~ ' ' ~ ' ` , .

~21;l:~

_ T

L O ~ O
n D ~ ~ ro a ~t L L L L L LO 0~ In OL
n D .Q a .a O .Q ~
o _ _ _ __ _ _ _ _ _ o _~ n n n n n n ~ n n o E ~ o o o o o o o o ~ o o 1~1 O . ` _ _ _ _ _ _ ~
'O V I I I I I ~1: V
O O
~_ ~ ~ ~ ~ ~ V
O ^ *`._ _ _ _ _ _ _ ._ o . a, o~
z O O O O O O
O O O O O O
a ~ a a ;l X ~ ;~ ;I' J ;l ;I' ~ ~ ;t' .
~) ~ rr~ _ ~ I I 0 0 1~
t~l ~ L ~ t ~ L L
I I ~ ~ ~ I I I e c CL
1~1 o o o ~ o ~ O O
(~ L L ~~ -- L C L L L L ~
,~ O O O O O O O O O O O O
Z~ L L L L L L L L L L L

0 1 ~0 S ' S S S .C S C ~ S S S
J L L L L L L L L L L L L
Y ~ a) ~ ~ a) 1) ~ a. a~ a) ~ Q~
~`I
~:

S O S O .C O C O S O .C O
r.~ ~ L ~ L ~ L 1.) L +~ L ~ L
n a _. ,~ n LD 1~ o~ o o o o o o O O O . ~ ~
Ln Ln n In n n n Ln Ln Ln .n Ln *

2 ~

_ _ _ _ I ~
E E I :1: I E E
_ ~
_ V
T 19 ,5 U~ O
~ . ~ ~
O ~
O _ U~
o ~ ~
_ ~ C ~ ~ ~ ~ ~
O ._ ~ ~ ~ ` ~ ` _ ` _ ` `
(U ~ __ _ ~_ T _ I -- --_ _ T I I ~

O U~ ~ _ _ _ _ _ _ _ ~ _ _ S Z .

. r ~ ~> ~ O>
I I ~ I
l l ~ ~ ~a 8 .R .0 .CI
_ _ I ' r~ _ ~ ~ .
C ~ C ~~I) ~
~I S S ~ ) S '' ~ C`l O O ~ ~ O O 1' ~
L ~ D O n s . ~ s ~ ~ C ~ y C
3 ;~ ~ ;t ~ S
O ~ : ---- -- I:LC. --~ CL ~.
z~ a:
Y 3 -:t ~ ~ ;1~ ~;t ;i ~o c~
J ~ O O O O O X X
'~f :~ L L L L '~1) CP
X t:L ~ ~ Q ~ ~ S
S
O S ~ S S S
+l ~., ,,~
E~ E E E E~-- -U ~
.~ E E
S S .C S S
S ,~ ~ ~ ~ L
"~
1~ S .C C SS ~0 C ~ C
I ~ 1~ 1~ ~ ~ ` ~ ` ~ Vl J 11.1 1~ I~J 11.1 11.1 ~O I D I --~ V) S S .C S S S ~ O (1) _. ~ W ~ '~ ~ ~ ~ L ,.~.

_. O O O O O C:~' O
~_ Z D ~O ~O

, ' 2 ~

_ __ I I I 1: I
.~
_ _ _ _ _ 1~
U~ ~ ~ Ln O~
U~ _ _ _ _ _ ~ I T T
O r_ Y
O _ _ _ _ _ _ O E
C .
~ ~ ~J
O ._ ~
~ 'O I T T I T
O _ ~ _ _ _ _ O V~
E O O O O o Z ~ ~ ~
r~ ' r ~1 ~
C ~ C C
a~ cL) a *~
1~: C C
~ a) C) C~
.
q~ ~ a) a~
S C
cL n. ~
O O O O O
O O O O O
IL ~ ~ ~ ~
l l l l l 3 ~ ~t ~ ;1 ~
I ~ _ _ -- -- -- ;
0~0 ~
~ l l Ly C :~ ~, :>, ~ ~ I
_ ~ ~7 Q ~ C C
O O ~ ~ ~
._ .-- L L L
C C :~ ~ Q
O O O O O
L L L L L
.C S C S
L L L L _ Ul ~: ~ ~ ~ ~ ~ U) _~ L ~ L _ ~: ~ ~ ~ C~ ~ L~
r~
.a . Q O O O O
l_ zO r~ *

-.: :

.. :
~.
~:` :

2 ~

44 O.Z. 0050/~1599 Examples illustrating the synthesis of naphthalenes of the formula I
Example 8.008 5 2-Benzoylaminonaphthalene-l-carbonitrile ~H~

3.0 9 (17.8 mmol) of 2-aminonaphthalene-1-carbonitrile (Chem. Pharm. BUll.
33 (4), 1360-1366 (1985)) was stirred with 2.5 9 (18.1 mmol) of benzoyl chloride and 4 ml of triethylamine in 100 ml of toluene for 15 hours at 10 80C. Upon completion of the reaction the product was filtered off and dried. There was obtained 1.5 g (31% of theory) of the title compound of mp. 205C.
Example 9.010 1-(N-Phthalimido)naphthalene-2-carbonitrile ~0 IN
~ CN

3.0 g (17.9 mmol) of l-aminonaphthalene-2-carbonitrile (Chem. Pharm. Bull.
33 (4jj 1360-1366 (1985~) and 2.7 g (17.9 mmol) of phthalic anhydride were boiled for 15 hours in 40 ml of concentrated acetic acid. Upon completion 20 of the reaction the mixture stirred into 200 ml of wa$er, and the precipi-tate was isolated and dried. There was obt~ined 3.5 g (66% of theory) of the title compound of melting point 196C.
Example 9.069 5-(3-Chlorophenyl)-3-(1'-aminonaphth-2'-yl)-oxadiazole NH2 Nl NJ~C I

, ,:
~ ~ ' -:
'~ ', ' : '`' O.Z. 0050/~1599 a) 1~Aminonaphthal~ne-2-carboxamide oxime ¦ ~N-OH
~C~NH

33.6 9 (0.20 mol) of 1-aminonaphthalene-2-carbonitrile ~Chem. Pharm.
8ull. 33, 1360-1366 (1985)), 18.8 g (0.27 mol) of hydroxylammonium chloride and 22.7 g (0.27 mol) of sodium bicarbonate were refluxed for lS hours in 300 ml of ethanol/water (3:2). After cooling, suction filtration was effected and the filter ca.~e was washed with n-propan-ol. Yield: 30.0 g (75%) of the title compound of m.p. 178-180C
(active ingredient example g.031).
` ' b) 6.0 g (30 mmol) of the compound obtained under a), 6.9 ml (50 mmol) of methyl 3-chlorobenzoate and 3.2 9 (60 mmol) of sodium methylate were boi1ed for 15 hours in 70 ml of methanol. Upon completion of the reaction the mixture was stirred into 500 ml of water, the precipi-tated product was filtered off and dried. There was obtained 5.4 9 (56% of theory) of the title compound of melting point 160C (active ingredient example 9.069).
Example 8.001 , 2-Chloronaphthalene-1-carborlitrile CN
~ ~Cl 33.6 g t0.2 molj of 2-aminonaphthalene-1-carbonitrile ~cf. Example 1) in 250 ml (abs.) of acetonitrile were added, at 65C, to a suspension of 32.3 g (0.24 mol) of anhydrous copper(II~ chlorid and 30.9 g (0.3 mol) of tert-butylnitrile in 800 ml ~abs.) of acetonitrile. Upon cornpletion o-f gas 25 evolution the reaction mixture was allowed to cool, 2000 ml of 20%
strength hydrochloric acid was added, and the precipitate was isolated, washed and dried. There was obtained 31.7 g (70% of theory) o~ the title compound of melting point 82-83C.

.
:

-2 ~

a~
_ _ C~
~o ~ ~
o ~ _ _ o ~ o~
. ~ ~ . U.
~ ~ _ ~ , ~
. ~ ~ ~
In ~ ~ o- I
o , ,~I oo, tr~ I E E
O
L S ~
a~ cL s o o o ~ I:n o o o o E E O s~
c;~ a) cJ ~:
.c r o _ . C~
c.~ a~ oo o E o~ n o G: T

E O
l ~ ~) C.) Ç~ ~ ~ I O S O o ~ ~ ~e~l ~ ~ ~ t_~ t.~ ~.) t_) ) J~--~ _~ L I I T ~ I
J ~ ~IZZZ;ZZZZZZ I--~
O ~ O

(-~ Z 2 Z Z Z Z Z Z Z Z Z Z Z

0~
r~ O O O O O O O O O r~
n . o o o o ~ o o o o o o o o :: .

~2 ~o _ ~ cJ~ n In ~ ,_ ~
Q) ~ 00 L _ --' ~ O
O~ ~ ~ 0 m ._ ~ L O t~
O ~ LL ~ a n co ~
o . ~4 o E E
1~i ~ I s E ~J~ E
O . . ~ ~ a~
~ CU ~ ~ ~ O . o o '~ ~ E E ,~, oo ~ E

~D
_ ~ ;~ ~
o ~ n ~ m ~ m ~_ r7 C~ O ID O O ~ 0~ ~ ~ O I n ;l A

t'l N N ~ ~
I O O
E

m m O O O _ ~ ~ ~ S S
~ ~ _ ~a~ ~ ~ ~ N N O
\\ / 1 \\ ~/ 1 \\ // O O O O O ~
I 2 ~ I T t_) U) tJ') N
t~ I I a~ IIIIIIIIII
'`I '`J ~I O ~) ~) ~ ':t ;t ~ ~ ~ ;l' ;

'ti C Z Z Z ZZZZZZZZZZ

0~
a~ ~ ~ o _- ~ ~ ~ In D
n o o o o o o o o o o o o o 1- 2 ~ 00 a) Ot~ 00 a~ ~) ~

' . ' ' .
. . .

~2 _ ~ _ . _ ~
,a~
~ a oo cn ~
G) _ _ ~ ., _ L O~n ~
~ r~ O
cr ~ r~ ._ ~ ~ n a'~ L (~l _ ~
n ~ . oo .
~ ._ n . ,~
o tL ~ ~ ~ E
o OE t~
~I s v o ~
v~ E E
o ~ sE s ~ 0 00 ~., e mv ~
o ~ E ~ >
O ~ ~
01 r-> V ~U .8 T m .

,~
o ~ ~
~ o~ 1~ cJ~ n co ~t o E ~ ~ ~ c~ ~ a7 _, ..
I S
O O
'`I N t~l C~ ~
L I ~' ~ L ~--L I ~' L :1: r~ L L I r~

C~: ~ LA~ LD LD LD ~r~ r~ r~ oO OD cC) ~ ~ ~ m m cx r~
~: ~
~: Z 2' Z Z Z Z Z Z Z 2 Z Z Z Z O O O O O O
O V C.t ~.) V V V V V V V V V V ~ V ~ 4 V V V

,: 00 ~ I~ 00 C~ O .~ n ~D r~ ~ ~ o .~ n ~o '~o ooo ooooooooooooooooo : ' : ' :.
;
.:
:
, ~ : ' ~: :
.

2 ~ ~ ~

~- ~
r_ u~
a- _ ~> a- , - 0 L _ -- _ 0 In 0 ~ ,~ O
~n L. ~ ~ O a ~ u~
~ W .~
O ~ _. ~ 1_ ~ 0 0 u~ ~1 ~I 0 ~ I ~ ~) ~ `I
O W ~ O ~ W -1~i s o I ,~ o ~_, o W
O U~
~) o ~ ~ ~ ~ ~ a-1 . .*
E m u~ w E ~ n E ~D
~ o ~ ~ o v~ W r~ O O W ~n o o 0 c~ ~ E 0 0 ~ ~ 0 0 C~ 0 0 v) ~ s ~

c~
_ ~ ~ ~ ~I
~~ ~ ~ ~ O ~ 00 1`
E
_t e~
cy E

_.
.,.
r~ 1 N t~
:~ -- L I _~ T_. T L I`~ L I ,~
~t Z C.~ Z ~ Z ~ Z ~ Z Z t_~ Z ~ Z Z
c~c~ ~ ~ ~ ~ ~ ~ ~ ~ Ln Ln n Ln Ln 1~ r~ r~

e~J ~ ~ ~
.~ :1~ t: -r s: O~mv~OOOooooooooooooo O~ YIIYY1~YY~YIYYYYYIY

a:
W 1-- 0 0~ O . t~l ~ ;t Lt-) ~D 1`` 01~ C~ O ~ ~1 ~) ~t Ln LD
8 ~ ' t t ~ Ln Ln L Ln Lo o Lo o ~ o o o o o o o O 0~ 0!:) Ot) CO 0~ 00 0 CO 00 0 Ot) 0~ 00 0;~ 0 ~O 0 0 0 0 ~ 2~f ~

.
cr Q) ~ ~n L Cl~
~_ a~
~ ._ U~ I _ ~n ~1 g ~ ~ .
cl: E
~ O S
o ,E u) c~
~ ~ E
<~I o ~> o U~
$ s D
cn r~ ~n ~ ~ ~ a~
I_ C~. O
E ~ I o o Lt~
O C~. Ia .` U ~ 5:
X~

L T I ~ I i I
E l:n C,) 1~ 0 1~ 1~ 1--U~

~7 T
S_ I r~ L r _ T O T T
Z t~a~ 1~1~ Z Z Z ~ Q O
~ C o ~Crl ~ ;l ~~t;t ~J t~J 11~ T I T

Z I~I

I ~ Z O ~ J
~ T I\ li z z 1: ~~ ~ Z Q O
O O O O O O O O O O O O O l l l V CC I I ~ I Y Y I I S~ I Y Y Y= I = I =

I~ ) a~ o ~ <~I ~7 ~ ~ D 1` a~ ~ o .--OOOOOOOOOOOO O O O
1- z oo co c~ ) CO 00 .
' ~ ''., ~ " ~ , - .
:~. ~ ' ' ., ' ' ' :
'~ .

2 ~

u~ ~ ,n ~o CO CO
, o o o S~ L ~1 ~I t~l Ct ~ C~
._ W LLI ~
Uo o a o o o $

o~

~ ~ ~ ~ o ~ ._ O ~ ~~ a~
~ ~ oo ~ a) ~ o ~ o _ ~ ~ ~ _I
U~

~ ~i ~: E ,~

~ ~ I I T
o=~
Z
_ ~ ,~, _ ~' I -r I
~ C~

~ Zl l ~t l l l IJ l Zl=o ~1~= Zl=o 1= ~

oo a o ~ ~ ~ ~
' O O O O O O ~ O O O O O O

.

~211 . .
o r--o~
`I
L I_ ~ U~
cn ~ c~
U-) L
~ a) ~o .
n ~
o o.E
o~
o O~a In ;t o ol_ ~o oo oo <~

o r-o O ~
_ ~ co ~n Q. I I l_ o ~ ~ ~ oo ~
E ~ a:) ~ ~,~, ~ ~ _ ._ ~n ~Y

C~ L

Cl: ~ ~ .

_~ L t~ r ~ ~ ~
I O ;i~ O ~ O ~1 0 ~ ~ Z Z ~ Y X 2 O~
._ ~ ~ ~ ~ ~ r. o~ ~ o . o o o o o o o oo o o o o ~ a a~

:

a~ ._ L
~ V
n L
LL `I
g E E
~ ~ V
o v .Q .a ~ ~ ~' o o O O O ~ O O O O o æ
m U~
~Q u~
O ~ ~ ,~
In ~ o ~ a- I~ ~ ~
E _. ._ ~ _.~ ,. ~ ~ ~ ~ . .

.

E m v l l l l I
, L _~ L T ~ L I ~ L T ,_ ~: ~7 ~ ~ ~ ~ ~ u~u )~)~oUO 1~ 1-- r-- oo oo ca I

o ~ ~ v c~ y ~ ~ ~ y u v ~ ~

a-n . o o o o o o o o O O o O O O O o o o o ;

:
:

: .

o~

L ~D
~ ~ - ~1 ~ ~ ~nl ~9 ~n E
._ ~ ~
o ~ ~: _ U~
o oo I . a~
~1 L et O O O ~) O o ~n ~
~ . o ~ o- CO ~ o o -:t ~D ~)OO--OO~ O O
~1 V~ S V~

Q.
o ~ ~
~' ~ .
~ a~
._ ~D 00~ ~ CO ~ 0 O ~ _ E~_ _. ~ ~ ~ c~l ~ ~ ~ ~ . ~
':
In : ` ' e~ ~ O
L I _~ L T _~ I T
tn z ~ ~ z e ~ Z z z Z Z ~ y z ~ z c) Z

I I ~t O O e~ 'r N ~ ,~ S
I :~: T I C T '-- I I I I ~C

o ~ ~ ~ ~In ~ r-- ~o ~ O .-- ~ ~ ~ Il~ D ~ 00 .
~O O~OO OO OOOOOC:OOOOOO

: : : :
i 2 ~

, . C~7 a L ~
O~ ~ In 0 ~D
n~ a~
~) L r-a.
cn ;t I
O J O~
11') ~1 ct-O r~ r~ u 1~1 a- o E
o ~ , Q~
~ o o o o o o 0;:~ E o o cc ~ o~ o~
cs7 n s u~ . . ~ In V~

._ In ~O ~ 00 r_ ~D
o o ~ n ~ ~ ~ ~ I
I~ ~ O ~ ~D I
E ~ ~ ~ ~ ~ c~
In U~

~E I I ~ I I I I I I I

L 1~ T ,~
Z IL ~ ~ ~ Z ~ 2 t ~ Z t.~ Z ~ 2 ~ Z
~: ~ I tl tl t'l I U~ I 00 00 t~ I -- I tl I I t~ tJO

~a I T ~ T I T O
r~ ~ ~ ~ ~ N ~ ~ r~
C OOOOOOOOOOOOOOOOOOO
O ~ ~ _) C y y y V y t~ ) V ~ y y ~:C t~t~lt~Jt~lt~t~ It~Jt~lt~lt~t~lt~lt~lt~lt~lt~t~lt~
Cr~
. oooooooot,oooooooooo a~ t,. o~ t~

.
- .

- 2 ~

L
O~~
1~-) L
._ ~._ O . ~

O

O

~t ~ ~
,_ I ~ o ~ o r. ~I O O ~ 00 E ~
~D
~, ~
~' ~`
, E ~ I I I i I I I

T I ~ ~ I ~ L L
~ Z Z y ~ Z 1 ~ I
.
r.4 r~ ~: I

o ~ ~ z '1~ o l=o O
CO ~ O ~ ~ ~ ~ U~

~1 0 ~ Z cn o~ ~ , ,:
.

~2~

~u a-I
- o~ .
U~
oo o o a-r ~ ~ o~
o ~
. ~ ~g E o~
u~

E

C~ ~0 ~ ~

~n C I C~
U ~ ~ l ~ Zl--a~

~ ~ I~
,- 1-- 1` 1-- 1~
g . O O O O
o CJ~

': :
~ "' ' '~''~ ' :
~:

: ' . ' 2 :L ~ ~
~00243 58 O.Z. 0050/41599 Examples demonstrating biological action The influence of various representatives of the herbicidal a~ents, or combinations of herbicide and safening compound, according to the 5 invention on the growth of crop and unwanted plants compared with that of the herbicidal active ingredient alone is demonstrated by the following examples in the greenhouse:
The vessels employed were plastic flowerpots having a volume of 300 cm3 10 and filled with a sandy loam containing about 3.~/O humus. The seeds of the test plants were sown separately, according to species. The vessels were then covered with transparent plastic hoods until the seeds had unifor~ly germinated and the plants had taken root.
15 For the postemergence treatment, the plants were grown, depsndiny on growth form, to a height of 3 to 20 cm before being treated with the com-pounds, suspended or emulsified in water, by spraying them through finely distributing nozzles.
20 The cyclohexenone derivative II used in the experiments was compound 3.34.
The herbicidal active ingredients and safening compounds may be applied together or separately to the leaves and shoots of the crop plants and unwanted grasses. Preferably, the safener is applied together with the 25 herbicidal active ingredient. Separate application is also possibie, in which case the safener is applied first to the field, followed by the herbicidal active ingredient. The herbicidal active ingredient and the safener may be formulated, together or separately, as a spray liquor in the form of a suspension, emulsion or solution.
It is also possible to treat the seed of the crop plants with the safener before sowing, The herbicidal active ingredient is then applied on its own in the usual manner.
35 For the same cyclohexenone derivative II, different amounts of safener are required, depending on the crop in which it is to be used. rhe ratio of cyclohexenone derivative II to naphthalene derivative I may vary within a wide range, and is dependent on the structure of the cyclohexenone and naphthalene derivatives, and on the crop involved. Suitable ratios of ~0 herbicidal active ingredient to safener are from 1:40 to 1:0.1, and preferably from 1:4 to 1:0.25, parts by weight.
The novel herbicidal active ingredients may contain, in addition to the naphthalene derivative I as safener and the herbicide from the group of cyclohexenones II, further herbicidal or growth-regulating active ingredi-en-ts of different chemical structure, without losing the safening effect.

`' : ' , ' . ~

, :~ , " ' ' , ' - . :

59 OOZ. 0050/41599 The agents according to the invention, or, when applied separately, the herbicidal active ingredients and the safener, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (includ-ing high-percentage aqueous, oily or other suspensions), dispersions, 5 emulsions, oil dispersions, pas$es, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used.
10 For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils o~ vege-table or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as ben~ene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated 15 naphthalenes and their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chloro-benzene, isophorone, etc., and strongly polar solvents such as N,N-di-methylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by 25 means of wetting or dispersing agents, adherents or emulsifiers. Concen-trates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.
30 Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, phenolsulfonic acid and naphthalenesulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates, and alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulfonic acid, lauryl ether and fatty alcohol sul-fates, fatty 35 acid salts of alkali metals and alkaline earth metals, salts of sulFated hexadecanols, heptadec~nols and octadecanols, salts oF sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, l~0 polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxyl-ated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

, 2 ~

O.Z. 0050/41599 Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredient and/or safener with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be 5 prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, a-ttapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium lO sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, ~ood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by 15 weight of active ingredient and safener. The application rates of herbicidal active ingredient are from 0.05 to ~ kg/ha.
The herbicidal active ingredient Il is formulated as a 10 to 20wt% emul-sion concentrate (EC) and employed in the spray liquor ~ogether with a 20 solvent system used in the same amount in ~hich the safener is applied in the tables.
All safening compounds are formulated in a mixture consisting of 80% of solvent (cyclohexenone) and 20% of surfactant (Emulphor~ EL = ethoxylated 25 castor oil), together wi~h lOwt% of active ingredient.
The vessels were set up ir. the greenhouse - heat-loving species at 18 to 35C, and species from mors moderate climates at 10 to 25C.
30 The experiments were carried out for from 3 to 5 weeks. During this time, the plants were tended and their reactions to the various treatments assessed. Damage by the chemical agents was evaluated on a 0 to 100% scale (compared with untreated control plants), 0 denoting no damage and 100 denotiny complete destruction of the plants.
The plants employed were Setaria viridis (green foxtail), Zea mays (Indian corn) and Sorghum vulgare (shattercane).
The tables below demonstrate the safeniny action of compounds nos. 3.003 40 and ~.094 and the tolerance of cyclohexenone derivative no. 3.34 by crop p I ants .

- ~ : ,: :
.
- -.' . ,, ' :

. . ~ . .

~ ~3 61 O.Z. OOS0/~1599 Tab1e lO Improved tolerance of herbicide no. 3.34 by Indian corn as a result of adding safening compound no. 8.094;
postemergence application in the greenhouse 5 Appl. rate [kg/ha] Test plants and damage [%]
Herbicide Safener Crop plant Unwarted plant No. 3.34 No. 8.094 Zea mays Se-taria viridis 0.25 -85 100 0.25 0.75 10 98 Table 11 Improved tolerance of herbicide no. 3.34 by Indian corn as a result of adding safening compounds nos. 8.003 and 8.094;
postemergence application in the greenhouse Appl. rate [k~/ha] Test plants and damage [%]
Herbicide Safener Safener Crop plants Unwanted plant No. 3.34 No. Zea Sorghum Setaria mays vulg. viridis _ _ _ _ _ _ _ 0 . 25 - - 90 1 00 1 00 0.25 0.75 B.003 10 20 100 0 . 25 0 . 75 8.094 20 65 98 l~O

Claims (6)

1. A herbicide which contains one or more naph-thalene derivatives of the formula I
I

where R is C1-C4-alkyl, C1-C4-alkylthio, C1-C4-haloalkyl, C1-C4-alkoxy, halogen, hydroxyl, nitro or benzyl;
m is 0, 1, 2 or 3, and the radicals R may be different when m is, 2 or 3;
R3 is -CN, -C(NH2)NOH, -C(Z)TR5, , or ;
R4 is halogen, -NR7R8, -N=CH-R7, -NR7-SO2R9, COOR5, OH, or Z is oxygen or sulfur;
T is oxygen or -NR5;
R5 is hydrogen, C1-C8-alkyl which may carry from one to three of the following substituents: halogan, C1-C4-alkylamino, di-C1-C4-alkylamino, C1-C4 alkoxy or C1-C4-alkylthio;
phenyl or benzyl which may carry from one to three of the following groups C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkyl-thio, C1-C4-haloalkyl, cyano, nitro and/or halogen;
R6 is phenyl which may carry one or two of the following groups; halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylkhio, C1-C4-haloalkyl, cyano and/or nitro;
R7 is hydrogen, C1-C6-alkyl which may carry from one to three of the following subsituents: halogen, C1-C4-alkylamino, di-C1-C4-alkylamino, C1-C4-alkoxy, C1-C4-alkylthio, phenyl and/or (C1-C4-alkyl)-oxycarbonyl, or phenyl which may carry from one to threo of the following O.Z. 0050/41599 substituents: halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4- haloalkyl, cyano and/or nitro R8 is hydrogen, C1-C6-alkyl which may carry from one to three of the following substituents: halogen, C1-C4-alkylamino, di-C1-C4-alkylamino, C1-C4-alkoxy, C1-C4--alkylthio and/or phenyl;
R9 is C1-C8-alkyl which may carry from one to three of the following substituents: C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamimo, di-C1-C4-alkylamino, phenyl and/or from one to five halogen atoms, or phenyl or 5 membered or 6-membered hetaryl, where these rings may carry from one to three of the following groups: C1-C4-alkyl, C1-C4-alkoxy, C1-C4 alkylthio, C1-C4-haloalkyl, nitxo, cyano and/or halogen;
R10 is C1-C6-alkyl or C2-C6-alkenyl, where these groups may carry from one to three of the following substitulents:
halogen, C1-C4-alkoxy, C1-C4-alkylthio and/or phenyl, or phenyl which may carry from one to three of the following substituents: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, nitro, cyano and/or halogen;
or R10...R10 together form a C2-C4-alkylene or C2-C4-alkenylene chain, where these bridges may carry from one to three of the following sub-stituents: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen and/or phenyl, or a fused benzene ring, which may carry from one to four halogen atoms and/or from one to three of the following radicals: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, cyano, nitro and/or phenyl;
R11 and R12 are each C1-C4-alkyl, or, together with the carbon atom to which they are bonded, form C3-C6-cyclo-alkyl;
B is hydrogen, C1-C8-alkyl, which may carry from one to three of the following substituents: halogen, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylamino, di-C1-C4 alkylamino, phenyl O.Z. 0050/41599 and/or C1-C4-alkoxycaxbonyl, C1-C4-alkoxycarbonyl, -NR7R8- or phenyl which may carry from one to five halogen atoms and/or from one to three of the following substituents:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, cyano and/or nitro, as an antagonistic compound and one or more herbicidal active ingredients of the group consisting of the cyclo-hexenone derivatives of the formula II

(II) where R1 is C1-C6-alkyl;
A is a C4-alkylene or C4-alkenylene chain, where these chains may carry from one to three C1-C3-alkyl groups and/or halogen atoms;
X is hydrogen, nitro, cyano, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, C1-C4-haloalkoxy, carboxyl, C1-C4-alkoxycarbonyl, benzyloxycarbonyl and/or phenyl, where the aromatic radicals may carry from one to three of the following substituents nitro, cyano, halo-gen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl,C1-C4-haloalkoxy,carboxyl,C1-C4-alkoxycarbonyl and/or benzyloxycarbonyl;
n is from 1 to 3, or is from 1 to 5 when X is hydrogen or halogen;
R2 is C1-C4-alkoxy-C1-C6-alkyl or C1-C4-alkylthio-C1-C6-alkyl C3-C7-cycloalkyl or C5-C7-cycloalkenyl, where these groups may carry from one to three of the following sub-stituents: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl, hydroxyl and/or halogen, a 5-membered saturated heterocyclic structure which contains one or two oxygen and/or sulfur atoms as hetero atoms and which may carry from one to three of the O.Z. 0050/41599 ollowing groups: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and/or C1-C4-haloalkyl, a 6-membered or 7-membered heterocyclic structure con-taining one or two oxygen and/or sulfur atoms and up to two double bonds where this ring may carry from one to three of the following substituents: hydroxyl, halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio and/or C1-C4-haloalkyl, a 5-membered heteroaromatic structure containing one or two nitrogen atoms and one oxygen atom or one sulfur atom, where this ring may carry from one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4 haloalkyl, C2-C8-alkenyl, C2-C6-alkenyloxy, C2-C6-haloalkenyl and/or C1-C4-alkoxy-C1-C4-alkyl, or phenyl or pyridyl, where these groups may carry from one to three of the following substituents: halogan, nitro, cyano, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-haloalkyl,C3-C6-alkenyloxy,C3-C6-alkynyloxy,C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl and/or -NR13R14, where R13 is hydrogen, C1-C4- alkyl, C3-C6-alkenyl or C3-C6-alkynyl and R14 is hydrogen, C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-acyl or benzoyl, where the aromatic ring may carry from one to three of the following substituents: nitro, cyano, halogen, C1-C4 alkyl, C1-C4-alkoxy, C1-C4-alkylthio and/or C1-C4-haloalkyl.

2. A herbicide as claimed in claim 1, wherein the weight ratio o the herbicide of the formula II to the naphthalene derivative I for combined or separate appli-cation is from 1 : 40 to 1 : 0.01.

3. A method for selectively controlling undesirable plant growth, wherain a naphthalene derivative of the formula I as claimed in claim 1 and a cyclohexenone derivative of the formula II are applied simultaneously or in succesion in any order, before, during or after O.Z. 0050/41599 sowing of the crops or before or during emergence of he crops.

4. A method for preventing damage to crops by herbicidal cyclohexenone derivatives of the formula II as claimed in claim 1, wherein the seed of the crops is treated with an antagonistic amount of a naphthalene derivative of the formula I as claimed in claim 1.

5. A method for selectively controlling undesirable plant growth, wherein the leaves of the crops and of the undesirable plants are treated simultaneously or in succession, by the postemergence method, with a naph-thalane derivative of the formula I as claimed in claim 1 and with a cyclohexenone derivative of the formula II.

6. A method as claimed in claim 3 or 4 or 5, wherein the crops are barley, wheat, corn, sorghum and rice.