CA1339688C - N-substituted 3,4,5,6-tetrahydrophtalimides and their intermediates - Google Patents
N-substituted 3,4,5,6-tetrahydrophtalimides and their intermediatesInfo
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- CA1339688C CA1339688C CA000616913A CA616913A CA1339688C CA 1339688 C CA1339688 C CA 1339688C CA 000616913 A CA000616913 A CA 000616913A CA 616913 A CA616913 A CA 616913A CA 1339688 C CA1339688 C CA 1339688C
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Abstract
Disclosed are compounds of the general formula:
(see fig. I) where A is -NO2 or -NH2 B is -CH2-, -CH2-CHR1-, -CH2-CHR1-CH2-, -CH=, -CH=CR1- or -CH=CR1-CH=, R1 being -H, -Cl, -Br or -CH3, D is (see fig. II) or (see fig. III), depending on the terminal group B, X is -H, -Cl or -Br Y is -H, C1-C7-alkyl, -Cl, -Br, -CN, -CONH2 or -CO2R2, where R2 is H, C1-C6-alkyl, C5- or C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, C1-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, .alpha.-phenylethyl, .alpha.-pehenylpropyl, C2-C4-alkyl which is monosubstituted, disubstituted or trisubstituted by F or Cl, or CH3-substituted or Cl-substituted allyl, and Z
is -COOR2, -CONR3R4, (see fig. IV) or -COR2, where R3 and R4 are each H or C1-C4-alkyl or together form a 5-membered or 6-membered cycloaliphatic ring whose carbon chain may be interrupted by an oxygen atom. These compounds are useful as intermediates for the preparation of compounds of the same formula where A is (see fig. V), which are useful as herbicides.
(see fig. I) where A is -NO2 or -NH2 B is -CH2-, -CH2-CHR1-, -CH2-CHR1-CH2-, -CH=, -CH=CR1- or -CH=CR1-CH=, R1 being -H, -Cl, -Br or -CH3, D is (see fig. II) or (see fig. III), depending on the terminal group B, X is -H, -Cl or -Br Y is -H, C1-C7-alkyl, -Cl, -Br, -CN, -CONH2 or -CO2R2, where R2 is H, C1-C6-alkyl, C5- or C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, C1-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, .alpha.-phenylethyl, .alpha.-pehenylpropyl, C2-C4-alkyl which is monosubstituted, disubstituted or trisubstituted by F or Cl, or CH3-substituted or Cl-substituted allyl, and Z
is -COOR2, -CONR3R4, (see fig. IV) or -COR2, where R3 and R4 are each H or C1-C4-alkyl or together form a 5-membered or 6-membered cycloaliphatic ring whose carbon chain may be interrupted by an oxygen atom. These compounds are useful as intermediates for the preparation of compounds of the same formula where A is (see fig. V), which are useful as herbicides.
Description
133~88 The present application is a division of application serial n~ 528,764 filed on February 2, 1987.
The invention as broadly disclosed hereinafter relates to N-substituted 3,4,5,6-tetrahydrophthalimides and their intermediates of the general formula (I):
A ~ x (I) ~-D
o where ~
The invention as broadly disclosed hereinafter relates to N-substituted 3,4,5,6-tetrahydrophthalimides and their intermediates of the general formula (I):
A ~ x (I) ~-D
o where ~
2' 2 ~N - , such compounds being here-o inafter identified as compounds Ia, Ib and Ic respectively;
B is -Cl12-, -CH2-CHR -, -CH2-CIIR -Cl{2-, -CII=, -C}l=CR1- or -Cl~=CR -Cl~=, R being -H, -Cl, -Br or -CH3;
D is -C~ or =C_ , depending on the terminal group B;
X is -H, -Cl or -Br;
Y is.-H, C1-C7-alkyl, -Cl, -Br, -CN, -CONl~2 or -CO2R2, where R is H, Cl-C6-alkyl, C5- or C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, . Cl-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, a-phenylethyl, a-pehenylpropyl, C2-C4-alkyl which is monosubstituted, disubstituted or trisubstituted by F or Cl, or Cl~3-substituted or Cl-substituted allyl; and CN
Z is -cooR2, -CoNR3R4 -CH ~ or -CORZ, where R3 ~C02R2 and R4 are each ll or C1-C4-alkyl or together form a 5-~membered or 6-membered cycloaliphatic ring whose carbon chain may be interrupte d by an oxygen atom.
2 133~8 The invention as claimed in the present application is however restricted to:
(1) the compouds of the formula (Ib), with the exception of 5-amino-2-chlorocinnamic acid and with the proviso that Z is not -COOR2 with R2 denoting hydrogen, Cl-C6-alkyl, c5-C6-cycloalkyl, Cl-C4-alkoxy-C2-C4-alkyl or Cl-C4-alkyl-mercapto-C2-C4-alkyl when:
B is -CH=CRl-, Rl is -CH3, D is -CH and, at the same time, Y is hydrogen; or B is -CH-CRl-CH=, Rl is -H or -CH3, D is =C and, at the same time, Y is hydrogen or Cl-C4-alkyl, (2) the compounds of the formula (Ia) with the exception of 2-chloro-5-nitrocinnamic acid and of methyl and ethyl 3'-nitro-6'-chloro-benzylidene acetoacetate and with the proviso that:
(i) Y is not hydrogen, Cl-C7-alkyl, -CN, -COOH or -C02-C2-H5 when B is -CH=, D is =C~ , X is hydrogen and Z is -CO2R2 where R2 is hydrogen or Cl-C6-alkyl;~0 (ii) Z is not -COCH3 or -COC2H5 when B is -CH=, D is =C _, X is hydrogen and Y is -C02R2 where R2 is hydrogen, Cl-C5-alkyl, C5- or C6-cycloalkyl or propargyl;
(iii) Z is not -COOR2 where R2 is hydrogen, Cl-C6-alkyl, c5-C6-cycloalkyl, Cl-C4-alkoxy-C2-C4-alkyl or Cl-C4-alkyl-mercapto-C2-C4-alkyl, when B is -CH=CRl-, Rl is -CH3, D is -CH and, at the same time, Y is hydrogen, or when B is -CH=CRl-CH=, Rl is -H or -CH3, D is =C_ and, at the same time, Y is hydrogen or Cl-C4-alkyl; and~0 (iv) X is not hydrogne when B is -CH2-, D is -CH , Y is chlorine and Z is -COOR2 or -CoNR3R~ where R2, R3 and R4 are defined as above.
Preferably, X is -Cl or -Br.
~339688 The invention as disclosed hereinafter also relates to the preparation of the compounds of the general formula (I), the use of the N-substituted 3,4,5,6-tetrahy-drophthalimides (Ic) as herbicides, and herbicides which contain the compounds of the formula (Ic).
Japanese laid-open patent Application 59/]55 358 published on 04.09.1984 in the name of SUMITOMO KAGAKU KOGYO
K.K. discloses N-substituted 3,4,5,6-tetrahydrophthalimides of type I' o Cl CR'-CQ1'-C00Q2' (I~) where R' and Rl are each hydrogen or methyl and R is alkyl, in particular ethyl.
Similar compounds, e.g. (I"):
C~l (") o CN
are disclosed in European Laid-Open patent Application 68,822 published on 05.01.83 in the name of ~OIIM AND HAAS
CO .
These compour~ds have been recommer-ded as herbicides but are unsatisfactory in this respect.
13.~9~88 The object of the invention disclosed and claimed in application n~ 528,764 to provide more effective herbicides. It has been found that this object is achieved by the novel N-substituted 3,4,5,6-tetrahydrophthalimides of formula (Ic) defined at the outset. It has also been found that the compounds (Ic) are very useful herbicides.
Processes for the preparation of the compounds of formula (Ic) have also been found.
The present invention as claimed hereinafter is directed to the new intermediatesof formula (Ia) and (Ib) that can be used for preparing the compounds of formula (Ic), and to processes for their preparation.
As disclosed in application n~ 528,764, the 3,4,5,6-tetrahydrophthalimide group is characteristic of the general herbicidal action of (Ic).
With regard to the more powerful action and the selective action of the herbicides, on the other hand, the moiety - B - D
\ z has an advantageous effect.
The compounds of type I are obtainable by the following specific methods:
a) Preparation of the nitrobenzene derivatives (Ia):
A 2-halo-5-nitrobenzaldehyde (IIa) ~2~X
CHt) 13.39~,8 or a 2-halo-5-nitrophenylacetaldehyde 11-' Z ~% I I I a CHO
or a Z-halo-5-nitrocinnamaldehyde 11 ~2~
CHO
is reacted in a conventional manner with a cyanoacetamide, cyanoacetate, a monoester or diester of malonic acid or a C3-Cs-aldehyde. When a monoester of malonic acid is used, the decarboxylation product Il-lll is obtained.
COOH
02N~ COOR2 ' CO2 ~ ~2~X
CHO
II-) ( Il-lll) ~-(C1-C3)-Alkylcinnam;c acids of type II~ and their de,rivatives are readily obtainable by reaction with C3-Cs-aldehydes under basic cond;tions, followed by oxidation 02N~ lk 02N~X ~ 02N~X
CHO CH2-CHO ~<_ <Alk \~Alk CHO COO~
Working up is carried out in a conventional manner. If at all necessary, la can be purified by re-crystallization, alcohol/water mixtures generally being su;table.
The nitrobenzaldehydes lla and nitrocinnamalde-hydes IIa" are known or are obtainable by known methods, so that further information in this respect is superfluous.
b~ Preparation of the aniline derivatives Ib The aniline derivatives possessing a saturated 1339~8 side chain ~-D are formed by catalytic hydrogenation of the nitrobenzene derivatives la. Selective catalytic hydrogenation, for example with platinum oxide as a cata-lyst (Rylander, Catalytic Hydrogenation over Platinum Metals, page 176, Academic Press, New York 1967), and the use of metals, such as iron, for reduction in a conven-tional manner leave the double bonds in the side chain unaffected.
c) Preparation of the N-substituted 3,4,5,6-tetrahydro-phthalimides Ic To prepare these compounds, 3,4,5,6-tetrahydro-phthalic anhydride is reacted with an aniline of type Ib by a conventional method. The react;on is carr;ed out, for example, in a boiling carboxylic acid, eg. acetic acid, propionic acid or butyric acid. Another possible method is to carry out the reaction in an inert solvent with con-tinuous removal of the water of reaction, in the presence of a catalytic amount of an acid, preferably p-toluene-sulfonic acid. Examples of suitable inert solvents are benzene derivatives, such as toluene, benzene, chloro-benzene or xylene.
The halogen X of the aromatic can also be intro-duced into Ic at the end of the reaction sequence by re-action with a halogenating agent, eg. sulfuryl chloride, in an organic acid at from 80 to 130~C.
Chlorine-containing and bromine-containing groups P-D can be prepared by starting from unsaturated groups ~-D and converting them to the dihalo compounds, which are converted to the monohalide, if appropriate by dehydro-halogenation.
Preferred compounds Ic are those in which the group B is -CH2- or -CH=. Preferred radicals X are chlorine and bromine. Preferred radicals Y are -CH3, -C2Hs, -Cl and -Pr. Z is preferably -COOR2, with the proviso that R2 is methyl, ethyl, isopropyl, n-butyl, isobutyl, isoamyl, 2-methoxyethyl or 1-methoxyProp-2-yl.
Examples of suitable compounds Ic are:
7 13~9~,3 N-t3-(acrylic acid methyl ester)-4-chlorophenyl]-3,4,5,h-tetrahydrophthalimide N-[3-(acrylic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-methylacrylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid methyl ester)-4-chloroohenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid isopropyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid-n-butyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid isobutyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid isoamyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid benzyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(a-cyanoacrylic acid cyclohexyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(a-cyanoacrylic acid Z,Z,Z-trifluoroethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid Z-methoxyethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid allyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(a-cyanoacrylic acid 3-methylallyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid 2-chloroethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid propargyl ester)-4-chlorophe-nyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid 1-methoxyprop-Z-yl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-bromoacrylic acid methyl ester)-4-chloroPhenyl~-13~ ~88 3,4,5,6-tetrahydrophthalimide N-C3-(a-methylacrylic ac;d ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(a-methylacrylic acid isobutyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(acryl;c acid ;sopropyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acryl;c acid n-butyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(acrylic acid isobutyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid isoamyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic ac;d benzyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(acryl;c acid cyclohexyl ester)-4-chloroohenyl]-3,4,5,6-tetrahydrophthal;m;de N-C3-(acrylic acid 2,2,2-trifluoroethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(acrylic acid Z-methoxyethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(acrylic acid allyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid 3-methylallyl ester~-4-chlorophenyl]-ZS 3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid Z-chloroethyl ester)-4-chloropllenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid propargyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid 1-methoxyprop-Z-yl ester)-4-chloro-phenyl)-3,4,5,6-tetrahydrophthalimide N-C3-(a-methylacrylic ac;d 2-methoxyethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(a-methylacrylic acid dimethylamide)-4-chlorophenyl]-3,4,5,6-tetrahvdrophthal;mide N-C3-(a-methylacryl;c acid N-morpholide)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide 13~ 88 g N-C3-(a-cyanopropionic 3C id ethyl ester)-4-chloroPhenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(~-cyanopropionic acid methyl ester)-4-chloroPhenylJ
3,4,5,6-tetrahydrophthalimide S N-C3~ cyanopropionamide)-4-chlorophenyl]-3,4,5,6-tetra-hydrophthalimide N-C3-(propionic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(propionic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-methylpropionic acid methyl ester)-4-chtoro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-methylpropionic acid ethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(methylmalonic acid diethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(methylmalonic acid dimethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(1,3-butadiene-1,1-dicarboxylic acid dimethyl ester)-Z0 4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(1-cyano-1,3-butadiene-l-carboxytic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(1-cyano-1,3-butadiene-1-carboxylic acid methyl ester)-4-chtorophenyl]-3,4,5,6-tetrahydrophthalimide Z5 N-C3-(l-cyano-1,3-butadiene-1-carboxamide)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(1-cyano-3-methyl-1,3-butadiene-1-carboxylic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal-imide N-C3-(1-cyano-3-methyt-1~3-butadiene-1-carboxylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal-imide N-[3-(~-bromoacrylic acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(ct-bromoacrylic acid ethyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(~-chloroacrylic acid ethyl ester)-4-bromophenyl]-lo 13~9~88 3,4,5,6-tetrahydrophthalimide N-[3-(a-methylacryLic acid ethyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(a-cyanoacrylic acid methyl ester)-4-bromoPhenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-carboxamidoacrylic acid methyl ester)-4-bromo-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acryl;c acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid ethyl ester)-4-bromopheny~]-3,4,5,6-tetrahydrophthalimide N-t3-(1-cyano-1,3-butadiene-1-carboxylic acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(1-cyano-3-methyl-1,3-butadiene-1-carboxylic acid 1S ethyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthal-imide N-t3-(a-cyanopentanoic acid methyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(~-cyanopentanoic acid ethyl ester)-4-chlorophenyl]-Z0 3,4,5,6-tetrahydrophthalimide N-t3-(n-propane-1,1-malonic acid diethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(1-cyano-3-methylpentanoic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide ~5 N-[3-(1-cyano-3-methylpentanoic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(3-methylisobutane-1,1-malonic acid diethy~ ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide The N-substituted 3,4,5,6-tetrahydrophthalimides of the formula Ic and the herbicidal agents which contain these compounds can be used, for example, in the form of directly sprayable so~utions, powders, suspensions, in-cluding aqueous, oily or other suspensions containing a high percentage of the compound, dispersions, emulsions, oil dispersions, pastes, dusting agents, broadcasting agents or granules, by spraying, misting, dusting, broad-casting or watering The forms for use depend on the 11 ~3~3~g~8 intended uses, they should in any case ensure a very fine distribution of the active ingredients according to the invention.
Suitable suostances for the preparation of direct-ly sprayable solutions, emulsions, pastes or oil disper-sions are mineral oil fractions having a medium to high boiling point, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. toluene, xylene, paraffin, tetrahydronaphthalene, alkylnaphtha-lenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, iso-phorone and highly polar solvents, such as N,N-dimethyl-formamide, dimethyl sulfoxide, N-methylpyrrolidone or water.
Aqueous forms for use can be prepared from emul-sion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water. rO pre-pare emulsions, pastes or oil dispersions, the substrates as such, or dissolved in an oil or solvent, can be homo-genized in water using wetting agents, binders, dispersants or emulsifiers. However, it is also possible to prepare concentrates which consist of the active ingredient, wetting agents, binders, dispersants or emulsifiers and, Z5 if required, solvents or oil, and which are suitable for dilution with water.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. ligninsulfonic, phenolsulfonic, naphthalenesulfonic or dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl-, laurylether- and fatty alcohol sulfates, and salts of sulfated hexadeca-nols, heptadecanols and octadecanols and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphtha-tene and of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, 12 1 3 3 9 b 8 8 oxyethylated isooctyl-, octyl- and nonylphenol, alkyl-phenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, oxyethylated S castor oil, polyoxyethylene atkyl ethers and ~olyoxypro-pylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, ligninsulfite waste liquors and methylcellulose Powders, broadcasting agents and dusting agents can be prepared by mixing or milling the active ingre-dients together with a solid carrier Granules, for example coated granules, impregnated granules and homogeneous granules, can be nrepared by binding the active ingredients to solid carriers. The latter are mineral earths, such as si~icas, silica gets, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, do~omite, diatomaceous earth, calcium sul-fate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal meal, bark meal, wood meal and nutshell meal, cellulose po~der and other solid carriers.
The formulations contain in general from 0.1 to 95, preferably from 0.5 to 9û, % by weight of active ingredient.
Z5 Application may be effected by the pre-emergence or post-emergence method. If the active ingredients are less well tolerated by certain crops, it is possible to use an application technique in which the herbicides are sprayed with the aid of a sprayer in such a way that, as far as possible, the active ingredients do not come into contact with the leaves of the sensitive crops but reach the leaves of undesirable plants growing underneath, or the exposed soil surface (post-directed, lay-by method) The application rates of the active ingredient are from 0.01 to 5.0, preferably from O.OS to 0.5, kg/ha, depending on the season, the target p~ants and the stage of growth.
13~f 6~8 Taking into account the action spectrum which can be utilized for weed control, the toleration by crops or the desired effect on the growth of the latter, and in view of the wide variety of methods of application, the novel compounds can be used in a large number of croPs, depending on the pattern of substitution.
Examples of suitable crops are-~otanical name Common name A(lium cepa onions 10 Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats ~eta vulgaris spp. altissima sugarbeets 15 ~eta vulgaris spp. rapa fodder beets 8eta vulgaris spp. esculenta table beets, red beets ~rassica napus var. napus rapeseed ~rassica napus var. napobrassica swedes ~rassica napus var. rapa turnips 20 ~rassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons 25 Citrus maxima grapefruits Citrus reticulata mandarins Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants 30 Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon 8ermuda grass in turf and lawns Daucus carota carrots 35 Elaeis guineensis oil palms Fragaria vesca strawberries Glycine max soybeans ' 14 1339~88 Potanical name Common name Gossypium hirsutum (Gossypium arboreum Gossypium herbaceum Gossypium vitifolium) cotton Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) ZO Mentha piperita peppermint Musa spp banana plants Nicotiana tabacum tobacco (N rustica) Olea europaea olive trees Z5 Oryza sativa rice Panicum miliaceum millet Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum pearl millet Petroselinum crispum parsley spp tuberosum Picea abies Norway spruce Abies alba fir trees Pinus sPP. pine trees Pisum sativum English peas ~33~688 Botanical name Common name Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Ricinus communis castor-oil plants 10 Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum 15 Sorghum dochna sorgo Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Z0 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes 25 ~ea mays Indian corn, sweet corn, maize In order to broaden the action spectrum and to achieve syriergistic effects, the tetrahydrophthalimides of the formula Ic can be mixed with a large number of typica( compounds of other groups of herb;cidal or growth-regulating active ingredients, and applied together.
Examples of suitable components for the mixture are dia-zines, 4~-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, other ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-tives, cyclohexane-1,3-dione derivatives and others ' ' 1339688 It may also be useful if the novel compounds of the formula Lc, alone or in combinat;on with other herbi-cides, are applied as a mixture with other crop protection agents, for example with agents for controlling Pests or 5 phytopathogenic fungi or bacteria Miscibility with mineral salt solutions which are used to eliminate nutri-ent and trace element deficiencies is also of interest Nonphytotoxic oils and oil concentrates may also be added EXAMPLES
Preparation of nitrobenzene derivatives Ia ~2 ~ (Ia) 2-Chloro-5-nitrocinnamic acid (Y=H, Z=COOH) 8 5 9 of piperidine were added to 185 5 9 (1 mole) of 2-chloro-5-nitrobenzaldehyde and 125 9 (1 2 moles) of malonic acid in 400 ml of pyridine, and the mixture was stirred at 110~C until the evolution of C02 was complete (about 3 hours) The reaction mixture was then poured on to a mixture of 1 l of ice and 350 ml of concentrated HCl, a yellow solid being precipitated. The product was fil-tered off under suction, washed with water and dr;ed to give 220 g (97~ of theory) of the above compound of melt-ing point 193-196~C
Methyl Z-chloro-5-nitrocinnamate (Y=H, Z=COOCH3) A solution of 34.1 g (150 millimoles) of the pro-duct from Example 1 in 30û ml of methanol was saturated with HCl gas, after which further HCl gas was passed in during the reaction time of 5 hours The solid obtained on cooling was stirred thoroughly with NaHC03/water and taken up in methylene chloride The CHzCl2 solution was washed with water and dried over MgS04, and the abovemen-tioned product was obtained by evaporating down the solu-tion and triturating the residue with diethyl ether.
1339~i88 Y;eld: 24 g (63~); mp 159-162~C
Ethyl Z-chloro-5-nitrocinnamate (Y=H 2=C00C2H5) 33 g (250 millimoles) of monoethy( malonate and Z7 g (150 millimoles) of 2-chloro-5-nitrobenzaldehyde in 100 ml of pyridine were reacted similarly to Examole 1 and the mixture was worked up in a conventional manner Yield: 31% mp 138-140~C
Ethyl 3-nitrocinnamate (X=H Y=H ~=COOCzHs) The reaction and working up were carried out as described in Example 3 and the product of melting point 67-70~C was obtained in 7Z~ yield Methyl 3-nitrocinnamate (X=H Y-H Z=C00CH3) The procedure followed was similar to that des-cribed in Example 4 and the product of melting point 101-103~C was obtained in 74% yield 2-Chloro-5-nitro-a-methylcinnamaldehyde (Y=CH3 Z-CHO) 4 9 of NaOH dissolved ;n 20 ml of water were added to a suspension of 185 5 9 (1 mole) of 2-chloro-5-nitrobenzaldehyde in 500 ml of methanol after which 70 g (1.2 moles) of propionaldehyde were added dropwise while 2S cooling to 10-15~C. The mixture was stirred for 2 days at room temperature and then neutralized with glacial acetic acid and the precipitated solid was isolated by filtration under suction washed with water and dried at S0~C under reduced pressure to give the product of melting point 99-lOZ~C in 78% yield.
Z-Chloro-5-nitro-~-methylcinnamic acid (Y=CH3 Z=COOH) 371 9 (2 moles) of 2-chloro-5-nitrobenzaldehyde were mixed with 192 9 (2 moles) of sodium propionate and 780 g (6 moles) of propionic anhydride The stirred mix-ture was then heated for 6 hours at 140-160~C solid mate-r;al going into solutiorl. The solution was then left to 1~3968~
cool to 90~C, 200 ml of ice water were added and the pre-cipitated solid was isolated by filtration under suction, washed with water and recrystallized from acetone to give 318 9 (66~ of theory) of product of melting point ZZ8-Z30~C
Methyl 2-chloro-5-nitro-a-methylcinnamate (Y=CH3, Z=COOCH3) Reacting the acid obtained in Example 7 with thionyl chloride in toluene in a conventional manner gave the acid chloride, which was refluxed in excess methanol and gave the ester of melting point 98-99~C in 72~ yield Ethyl 2-chloro-5-nitro-o!-cyanoc;nnamate (Y=CN, Z=COOc2Hs) 29 7 9 (300 millimoles) of ethyl cyanoacetate were added to a solution of 55 7 9 (300 millimoles) of 2-chloro-5-nitrobenzaldehyde in 200 ml of tetrahydrofuran, after which 1 ml of piperidine was addod as a catalyst at 0~C The mixture was stirred for 16 hours at room temperature, neutralized with acetic acid and then worked Z0 up in a conventional manner to give a product of melting point 83-85~C in 71~ yietd Dimethyl 3-nitrobenzylidenemalonate (X=H, Y and Z=COOCH3) 75 5 9 (500 millimoles) of 3-nitrobenzaldehyde and 73 9 (550 millimoles) of dimethyl malonate were stirred for 4 hours at 60~C, similarly to Example 9.
After the addition of 5 ml of glacial acetic acid, the m;xture was worked up in a conventional manner The pro-duct of melting point 78-80~C was obtained in 96~ yield 1-(2-Chloro-5-nitrophenyl)-4-cyano-4-methoxycarbonyl-trans-buta-1,3-diene (r=H~ Z=-CH=C(CN)COOCH3) 15 9 (70 millimoles) of 2-chloro-5-nitrocinnamal-dehyde (mp~ 115-117~C) and 10 9 (0 1 mole) of methyl cyanoacetate in 200 ml of toluene were heated under a water separator in the presence of 1 9 of ammonium ace-tate and 1 ml of acetic acid until water no longer lg 13~968~
distilled over. The product crystallized out on cooling.
After the usua( working up procedure, 58% of the product of melting point 193-194~C remained.
Preparation of aniline derivatives Ib H~N- ~ X (Ib) ~ ,Y
~--0~
Preparation of aniline derivatives Ib having unsaturated side chains A solution of 1 equivalent of a nitro compound la in 50 ml of alcohol and 50 ml of glacial acetic acid was prepared by warming and was added to a susPension of 3 3 equivalents of iron powder in a mixture of 100 ml of the alcohol corresponding to the ester group in Z and Z5 ml of glacial acetic acid at 50~C, and the mixture was heated at the boil for 3 hours. It was worked up by fil-tering it, pouring the filtrate into 500 ml of water and extracting with ethyl acetate or methylene chloride. The organic phase was dried and the solvent distilled off under reduced pressure, and the product, without further purification, was condensed with tetrahydrophthalic anhy-dride as described in Example 22. Further properties are summarized in Table 1.
Compounds H2 ~
Ex 2 Y X mp.~C Yield 12 COOCH3 H Cl 70- 12 91 13 cooC2Hs H Cl 68- 70 8-1~ COOtH3 CH3 Cl 82- 8~ 86 COOCH3 CN Cl 8B- 90 89 16 Cooc2Hs CN Cl 89- 85 8R
,CN
17 -CH=C~ ~ Cl127-129 90 EXAMPLES 19 T0 21 1~3~8~
Preparation of an;line derivatives Ib having a saturated side chain 0.2 mole of a nitro compound la was hydrogenated in the presence of 5 g of 10~ strength Pd/C at from 20 to 40~C under atmospheric pressure in 500 ml of tetrahydro-furan or ethyl acetate, and the mixture was workod up in a conventional manner. The results are shown in Table Z.
TA~LE 2 Compounds Hz~J~X
Ex. ~ y X mP-~CYield no l9 COOCzHs H H Ol53 COOC2H5 CN Cl Olâ5 21 COOCH3 COOCH3 H Ol ~ l O0 20 Preparation of N-substituted 3,4,5,6-tetrahydrophthali-mides Ic ~X ( I c ) O --;!
General method A mixture of 0.1 mole of 3,4,5,6-tetrahydrophtha-(ic anhydride and 0.1 mole of an aniline of the generalformula Ib in 150 ml of acetic acid is heated at the boil until thin layer chromatography shows that the components have been converted, which is the case after from 2 to 3 hours. The product is generally precipitated on cooling and is then isolated by filtration under suction. If this is not the case, the reaction mixture is evaporated down under reduced pressure, the residue is dissolved in 1333~
ethyl acetate and the solution is extracted with water.
After the solution has been dried and the ethyl acetate stripped off, the product remains in the form of an oil, which crystallizes out on trituration with petroleum ether. rhe physical properties of the active ingredients are summarized in Tables 3, 4 and 5.
In the unsaturated compounds (Table 3), cis-trans isomers occur in various ratios. ~oth isomers and mix-tures of them are claimed.
N-C3-(a-Cyanopropionic acid ethyl ester)-4-chloro~henyl]-3,4,S,6-tetrahydrophthalimide C~N~C1 O --Cozc2H5 14 9 (55 millimoles) of the saturated aniline derivative corresponding to Example 18 and 9 g (60 milli-20 moles) of 3,4,5,6-tetrahydrophthalic anhydride were re-ftuxed with Z00 ml of xylene under a water separator until water no longer passed over. Working up in a conventiona( manner and chromatography with 7:3 toluene/tetrahydro-furan over silica gel gave the product in the form of an 25 Oil in 61~ y;eld.
EXAMPLE 23N-[3-(Propionic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide C~N~1 O C02Et 16 9 (49 millimoles) of N-t3-(propionic acid ethyl ester)-phenyl]-3,4,5,6-tetrahydrophthalimide were dis-solved in 150 ml of glacial acetic acid. 7.3 9 (54 milli-moles) of sulfuryl chloride, dissolved in 20 ml of glacial ~ 3 3 ~ b ~ 8 acetic acid, were added dropwise at 80~C, after which the mixture was stirred for 2 hours at 110~C. After the usual working up procedure, the crude product was purified by chromatography over silica gel (1:1 cycLohexane/ethyl acetate). The product was obtained in the form of an oil in 54X yield.
Preparation of N-substituted 3,4,5,6-tetrahydrophthal-imides ~c having halogen-containing side chain ~
Y = halogen N-c3-(a~B-~ibromopropionic acid methyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide as an intermediate o O¢~C1 0 ~r A solution of 4.6 g (30 millimoles) of bromine in 10 ml of methylene chloride was added dropwise to a solu-tion of 10 9 (30 millimoles) of the active ingredient 1 from Table 3 in 50 ml of methylene chloride at a bath 25 temperature of 50~C. After the mixture had been stirred for 2 hours, the reaction was complete. The product was generally used without further isolation for dehydro-bromination according to Example 25. A sample isolated by evaporating off methylene chloride had a melting Point of 90-94~C.
N-C3-(~-~romoacrylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide o C02CH~
23 1339b88 The dibromide obtained as described above was then dehydrobrominated directly in 150 ml of methylene chloride at room temperature with 10.1 9 (lO0 millimoles) of triethylamine, by stirring at Z5~C for one hour. The reaction mixture was boiled for 15 minutes and then oolJred onto water. The methylene chloride phase was seDarated off, washed with water, dried and evaporated down. rri-turation with diethyl ether gave lO g ~85~) of a solid of melting point of 92-94~C.
N-t3-(a-~romoacrylic acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide a) Z-~romo-5-nitrobenzaldehyde A nitrating acid prepared at -10~C by adding 55 ml of concentrated H2S04 to 20 ml of 98 percent HN03 was added dropwise, in the course of 60 minutes, to a solution of 63.4 9 (0.34 mole) of 2-bromobenzaldehyde in 110 ml of concentrated HzS04 at -5~C. Stirring was con-tinued for a further 45 minutes, after which the reaction mixture was poured onto 550 9 of ice, and the precipi-tated solid was filtered off under suction, washed with water, then with 10 percent strength Na2C03 solution and again with water. Drying under reduced pressure at 50~C
gave 7Z 9 (9ZX of theory) of product as a yellow solid of Z5 melting point 86-88~C.
b) Z-Elromo-5-nitrocinnamic acid This reaction was carried out similarly to Example 1, with Z-bromo-5-nitrobenzaldehyde and malonic acid in pyridine and with piperidine. The product of melting point 185~C was obtained in 57% yield.
c) Methyl 2-bromo-5-nitrocinnamate This product was prepared similarly to Example 8, by converting the cinnamic acid obtained under b) into the acid chloride (mp. 106-108~C, 98% yield) and then reacting the latter with methanol/pyridine. Yield 70X of theory, mp. 150-15Z~C.
133~'Q88 d) Methyl 2,a-dibromo-5-nitrocinnamate 19.2 9 (0.12 mole) of bromine were added dropwise at 40~C in the course of 2 1/Z hours to a solution of 28.6 9 (0.1 mole) of the ester obtained under c), in 20û ml of methylene chloride; thereafter, the mixture was heated at the boil for a further 3 hours. After the mix-ture had been cooled to Z0~C, Z0.2 9 (0.2 mole~ of tri-ethylamine were added dropwise. After 3 hours, 150 mL of water were added to the reaction mixture and the mixture was then transferred to a separating funnol. rhe methy-lene chloride phase was extracted with twice 100 ml of water, after which the organic phase was dried over MgS04 and evaPorated down under reduced pressure. rrituration with diisopropyl ether gave 30 g of a crude oroduct, whicl was chromatographed over silica gel using to~uene as the mobile phase. The toluene solution was evaporated down to give 20 9 (56%) of the product of melting point 95-96~C.
e) Methyl 2,a-dibromo-5-aminocinnamate Zû 9 (0.056 mole) of the nitro compound prepared 20 under d) were added a little at a time to a suspension of 15.7 g (0.28 mole) of iron in 200 ml of methanol and 10û ml of glacial acetic acid at 60~C. The mixture was refluxed for 5 hours, after which it was cooled, poured into 1.5 l of water and extracted twice with Z00 ml of Z5 ethyl acetate. The organic phase was washed with water, dried and evaporated down under reduced pressure to give 18 g (~- 96X of theory) of product in the form of an oil.
f) N-t3-(a-Bromoacrylic acid methyl ester)-4-bromophenyl~-3,4,5,6-tetrahydrophthalimide ~J~
N~flr ~ ~<~ C02CI~3 ~ cis t Il ~<
O ~r Wirkstof f Nr . 67 Active ingredient No. 67 8.1 9 (0.053 mole) of tetrahydrophthalic anhydride 1~'.3~8 were added to a solution of 18 9 (0 053 mole) of the pro-duct obtained under e) in 50 ml of glacial acetic acid The mixture was stirred for 3 hours at 110~C and then evaporated down under reduced pressure, the residue was dissolved in ethyl acetate and the solution was extracted with 10~ strength Na~C03 solution and with water. The ethyl acetate phase was dried with MgS04 and then evapora-ted down under reduced pressure. Trituration with diiso-propyl ether gave 23 g (92% of theory) of the product of melting point 83-85~C
NMR analysis showed that the compound con,isted of 8SX of the cis form and 15% of tho trans form.
N-C3-(a-Chloroacrylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide 0 COzCH3 Active ingredient No 49 a) Methyl 3-[2'-chlorophenyl]-2,3-dichloropropionate 21 3 g (0 3 mole) of chlorine gas were passed slowly into a solution of 39.3 9 (0 2 mole) of methyl 2'-chlorophenylcinnamate in 200 ml of 1,1,1-trichloroethane at 60~C in the course of 3 hours, after which the mixture was stirred for a further hour at 70~C The reaction mix-ture was then washed twice with 150 ml of water and the organic phase was dried over MgS04 The solvent was stripped off under reduced pressure to give 52 9 (97~) of the product in the form of an oil.
b) Methyl 2,~-dichlorocinnamate 40.4 9 (0 4 mo(e) of triethylamine were added dropwise at 25~C to a solution of 52 g (0~194 mole) of the ester obtained under a) in 400 ml of methylene chlor-ide, and the mixture was then stirred for l hour at 40~C
133~8 Thereafter, 200 ml of water were added and the organic phase was separated off, washed with water and dried with MgS04 to give 42 9 (93X of theory) of the nroduct in the form of an oil.
c) Methyl 2,a-dichloro-S-nitrocinnamate A nitrating acid was prepared by adding 47 ml of concentrated HzS04 dropwise to 16 ml of 98 percent strength HN03 at -1û~C, and this nitrating acid was added dropwise to a solution of 42 9 (0.182 mote) of the a-chlorocinnamate described under b), in 150 ml of con-centrated HzS04, at -5~C. Stirring was continued for - 30 minutes at 0~C, after which the reaction mixture was stirred in 600 ml of ice water and the precipitated pro-duct was isolated by filtration under suction. It was washed several times with water, and the still moist pro-duct was then recrystallized from methanol. 28 9 (54X of theory) of crystats of melting point 108-110~C were obtained.
d) Methyl 2,~-dichloro-5-aminocinnamate 100 9 (0.36 mole) of the nitro product described under c) were reduced with 61.6 9 (1.1 motes) of iron powder in 500 ml of methanol and 500 ml of glacial acetic acid, as described in ~xample Z5e. After the working up procedure described there, 70 9 (80% of theory) of the desired product were obtained in the form of yellow crystals of melting point 104-105~C.
e) Tetrahydrophthalimide derivative 7.6 9 (0.05 mole) of tetrahydrophthalic anhydride were added to 1Z.3 9 (0.05 mole) of the aniline derivative prepared under d), in 50 ml of glacial acetic acid, and the mixture was stirred for 3 hours at 10~C. The acetic acid was stripped off under reduced pressure, the residue was taken up in ethyl acetate and the solution was washed with 10% NaHC03 solution and then with water. The organic phase was dried over MgS04 and the solvent was stripped off to give 13 9 (68X of theory) of white crystals of metting point 138-1~0~C. NMR analysis showed that the compound was 1339b88 a pure trans isomer.
The active ingredients summarized in Tables 3 to 5 were obtained by the methods stated above.
o ~N~y Serial . x r R2 Mp.
I Cl H CH3 139-1~0 2 Cl H C2~5 l~a- 149 3 C1 H C3H7-i 106-107 Cl H C4Hg-n 7~- 76 Cl H C4Hg-i 52- 53 6 Cl H csH11-i 1 a~- 1 a6 7 Cl H Cycloh~xyl 131-133 a cl H 2-Methoxy-ethyl 76- ?3 9 Cl H l-Methoxy-prop-2-yl30- 31 Cl H Allyl 11~-111 11 Cl H 3-Methylallyl 102-l a3 12 Cl CH3 H 212-2~3 13 Cl CH3 CH3 132-133 1~ C1 CH3 C2H5 6Z- 63 Cl CH3 C3H7-n 79- 90 16 Cl CH3 C3H7-i 7~ 75 17 Cl CH3 C4H9~n ~- 16 la Cl CH3 C4Hg-i 86- 69 19 Cl CH3 CsHll-n ~7- 49 28 133~
Serial No. X r R2 Hp. (~c~
C1 CH3 CsH1~-i 54- 65 21 Cl CH3 9enzyl 15-22 Cl CH3 2-Phenylethyl oil Z3 Cl CH3 1-Phenyl-prop-2-yl 108-109 2~ Cl CH3 ?ropar~yl 151-152 Cl CH3 3-Methyl~uten-2-yl 49- 51 26 Cl CH3 3-Methyl~ucan-3-yL Ojl Cl CH~ 2-Metnoxyethyl 41-44 28 Cl CH3 2-Ethoxyetnyl 39~ 40 29 ~1 CH3 2-~n-~3utaxy~-ethyl oil Cl CH3 l-Methoxy-prop-2-yl 45~ 47 31 C1 CH3 2-Methoxy-prap-1-yl 89- sa 3Z C1 CH3 1-Ethoxy-prop-2-yl oil 33 Cl CH3 1-Methoxy-but-2yl 55- 56 3~ C1 CH3 2-Ethyl-thio-ethyl 99- ~0 C1 CH3 2-~I~opropylthio)-~thylô7- 68 36 C1 C2H5 CH3 1 a3- 1 O-37 C1 CzH5 CzH5 ~9_ 50 33 Cl C2H5 2-MQthoxyethyl ~6- ~3 39 C1 C2H5 1-MQthoxyprop-2yl 32- 33 ~0 C1 CzH5 n~C3H7 ~7-~1 Cl C2~5 n-C4~9 Oj~
~z C1 i-C3H7 CH3 75- 76 ~3 C1 n-C3H7 CH3 oil C1 n-C3H7 2-MethoxyQthyl ~il ~5 C1 n-C4Hg CH3 oil ~6 Cl n-C4Hg 2-Methoxyethyl ~il ~7 C1 n-csH1l CH3 oil C1 n-C5H11 2-Methoxyethyl ~il 29 1 3 3 ~ b Seria~
Nb. X Y ~2 Mp ( ~9 Cl Cl CH3 13~ o Cl Cl CzHs 37- a 9 51 Cl Cl n-C3H7 83-85 52 Cl Cl i-C3H7 140-141 53 Cl Cl n-C4Hg 90-91 5~ Cl C1 n-CsHll 112-114 Cl C1 i-CSHll 68-70 56 Cl Cl 2-~ethoxyethyl 1Z~-170 57 Cl Cl 2-EthqxyetnyL 58-60 5~ Cl Cl 2-ln-autoxy~-etnyL ~il 59 Cl 8r CH3 94- 95 6~ Cl 9r C2H5 91- 92 6l Cl 3r n-C3~7 79- 80 62 Cl 9r i-C3H~ 119-121 63 C1 9r n-C4Hg 73- 74 6~ Cl 9r 2-Methoxyetnyl 136-137 9r H CH3 66 9r H n-C~g 6t 9r 3r CH3 a~- ~5 6a Cl CN. H 1~a-15l 69 Cl CN CH3 15~-155 Cl CN C2H5 1~0-1~2 71 Cl CN l-C~H~ 132-133 72 Cl CN i-C4Hg 13~ 135 73 Cl CN OQnzyl 1 az- 163 7~ Cl CN 2-M~thoxyQthyl 11~-116 Cl CN Z-~opropoxyethyl 63- 65 76 Cl CN 1-~ethoxyproF2-y( 56- 57 7t Cl C~ 2-~ethoxyprop-1-yl 12C-123 78 C1 C~2CH3 CHg l9a-1~0 79 H H CH3 1~ 2 133~88 Ser; al No. X r R2 MF. ~~c Cl H C2H5 oil 81 C1 CN C2H5 oil 3 Z Cl C02CH3 CH3 oil 2 0 ~¢N~y Serial X r ~2 ~ ( ~ C ) 8 ~ Cl CH~ CN 112-113 9~ Cl H ~C0zCH~ 176-178 CN
C~ H ~C02C2H5 184--186 CN
1~3~6~3 The following active ingredients of the formula (I) can be obtained in a similar manner:
o ~X
~ C02R2 No. X Y R2 la1 Cl CH3 Allyl 10 2 Cl CH3 2 -~ethyl- thioethyl 10~ Cl CH3 Cyclohexyl l 0~ Cl CH3 Cyclopentyl 105 Cl CH3 2-Chloroethyl 106 Cl CH3 2, Z, 2-Trifluor oethyl lO7 Cl C2H5 i-C3H7 108 Cl C2H5 i-C~Hg lO9 Cl C2H5 n-CsH11 110 Cl C2Hs i-CsHtt lll Cl C2H5 2-Ethoxyethyl 1l2 Gl C2H5 Z-~n-3utoxy)-ethyl 113 Cl C2H5 Cyclohexyl 1l~ Cl C2Hs Cyclopentyl 115 Cl C2H5 2-Ch1oroethyl, 11 ~ Cl Cl 2 - Chloroethyl 11~ Cl Cl i-C4Hg ll9 Cl Cl sec.-C4Hg l l9 Cl 8r l-C~Hg 120 Cl ~r n-CsH
32 ~33~;88 Nb. X Y R
121 Cl 3r n-C6H13 122 Cl ~. 2-Chlor~thyl 123 Cl 3r ;-CsHll 12~ Cl 9r Cyclohexyl 125 Cl Br Cyciopentyl 12a 3r er CzHs 127 e- Br n-C3H7 1Z~ P. e. t--1ethoxyethy 129 Br Br Z-Ethoxyethyl 130 Br Cl CH3 131 Br Cl C2H5 132 Br Cl n-C3H7 133 ~r Cl 2-Methoxyethyl 134 3r Cl 2-Ethoxyethyl 135 Cl C2H5 Allyl 136 Cl C2H5 3-Methylallyl 137 Cl Cl Allyl 13a Cl Cl 3-~ethylallyl 139 Br Cl Allyl l~0 Cl 3r 3-Methylallyl l~l Br 3r Allyl 1~2 ~3r 8r 3-Methylallyl 1~3 Er ar 2-Chlor~thyl 1~ ~ 8r Cl Allyl 1~5 9r Cl 3-~ethylallyl 1~6 Br Cl 2-Chlo~thYl Examples of use The act;on of the N-substituted 3,4,5,6-tetra-hydrophthalimides of the formula Ic on the growth of test plants was demonstrated by the greenhouse trials below.
Plastic flowerpots having a capacity of 300 cm3 were used as the culture vessels, and loamy sand contain-ing about 3% of humus was used as the substrate. The seeds of the test plants were sowed to a shallow depth, separately according to species.
For the purpose of Post-emergence treatment, plants which had been e;ther directly sown or grown in the same vessels were selected, or the plants were first grown separately as seedlings and transplanted into the test vessels a few days before the treatment.
The test plants, at a height of from 3 to 15 cm, depending on the form of growth, were then treated with the active ingredients suspended or emulsified in water as a distributing agent. The said suspension or emulsion was sprayed through nozzles which produced a fine spray.
The application rate for the postemergence treatment varied and was from 0.06 to 3.0 kg of active ingredient per ha.
The test vessels were placed in a greenhouse, warmer regions (from 20 to 35~C) being preferred for heat-loving species and 10-20~C for those of temperate climates.
The trial period extended over 2 to 4 weeks. During this time, the plants were tended and their reaction to the individual treatments were evaluated.
The plants used in the greenhouse trials con-sisted of the following species:
34 133~8 ~otanical name Common name Abutilon theophrasti velvetleaf Amaranthus spp. foxtail grasses Avena sativa oats Heta vulgaris beets Centaurea cyanus cornflower Chenopodium album lambs'-quarter Chrysantemum cor. crown daisy Galium aparine catchweed Glycine max soybeans Hordeum vulgare barley Mercurialis annua annual mercury Solanum nigrum black nightshade Triticum aestivum wheat Veronica spp speedwell Viola tricolor wild pansy When 3 0 kg of active ingredient per ha were used in the postemergence method, ;t was possible to control monocotyledon and d;coty(edon plants from the Examples very well with the active ingredients No 69, 7~ and 81 When 0 25 kg of active ingredient per ha was applied by the postemergence method, active ingredient No 2 had a herbicidal action against a number of unde-sirable dicotyledon plants, the soybeans suffering only slight damage When the active ingredients No 59 and 82 were applied by the postemergence method, economically important weeds were successfully controlled with as little as 0 06 kg of active ingredient per ha The crop plant soybean was only insignificantly impaired, if at all.
Active ingredient No. 13 was suitable, for exam-ple, for controlling the dicotyledon weeds in cereal when applied by the postemergence method at a rate of û 06 kg of active ingredient per ha.
1339~
Active ingredients No. 1, 4, 6, 8, 11, 60, 69 and 80 are useful for controlling broad-leaved plants by the postemergence method. When the treatment was carried out using 0.1ZS kg/ha of active ingredient No. 69, sugar-beet as the crop was not significantly impaired in any case.
Galium aparine, as a weed from the Examples, in gramineous crops can be controlled reliably by the post-emergence method using low application rates (0.06 kg/ha) of the active ingredients No 6 and 60; neither wheat nor barley suffer significant damage as a result.
B is -Cl12-, -CH2-CHR -, -CH2-CIIR -Cl{2-, -CII=, -C}l=CR1- or -Cl~=CR -Cl~=, R being -H, -Cl, -Br or -CH3;
D is -C~ or =C_ , depending on the terminal group B;
X is -H, -Cl or -Br;
Y is.-H, C1-C7-alkyl, -Cl, -Br, -CN, -CONl~2 or -CO2R2, where R is H, Cl-C6-alkyl, C5- or C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, . Cl-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, a-phenylethyl, a-pehenylpropyl, C2-C4-alkyl which is monosubstituted, disubstituted or trisubstituted by F or Cl, or Cl~3-substituted or Cl-substituted allyl; and CN
Z is -cooR2, -CoNR3R4 -CH ~ or -CORZ, where R3 ~C02R2 and R4 are each ll or C1-C4-alkyl or together form a 5-~membered or 6-membered cycloaliphatic ring whose carbon chain may be interrupte d by an oxygen atom.
2 133~8 The invention as claimed in the present application is however restricted to:
(1) the compouds of the formula (Ib), with the exception of 5-amino-2-chlorocinnamic acid and with the proviso that Z is not -COOR2 with R2 denoting hydrogen, Cl-C6-alkyl, c5-C6-cycloalkyl, Cl-C4-alkoxy-C2-C4-alkyl or Cl-C4-alkyl-mercapto-C2-C4-alkyl when:
B is -CH=CRl-, Rl is -CH3, D is -CH and, at the same time, Y is hydrogen; or B is -CH-CRl-CH=, Rl is -H or -CH3, D is =C and, at the same time, Y is hydrogen or Cl-C4-alkyl, (2) the compounds of the formula (Ia) with the exception of 2-chloro-5-nitrocinnamic acid and of methyl and ethyl 3'-nitro-6'-chloro-benzylidene acetoacetate and with the proviso that:
(i) Y is not hydrogen, Cl-C7-alkyl, -CN, -COOH or -C02-C2-H5 when B is -CH=, D is =C~ , X is hydrogen and Z is -CO2R2 where R2 is hydrogen or Cl-C6-alkyl;~0 (ii) Z is not -COCH3 or -COC2H5 when B is -CH=, D is =C _, X is hydrogen and Y is -C02R2 where R2 is hydrogen, Cl-C5-alkyl, C5- or C6-cycloalkyl or propargyl;
(iii) Z is not -COOR2 where R2 is hydrogen, Cl-C6-alkyl, c5-C6-cycloalkyl, Cl-C4-alkoxy-C2-C4-alkyl or Cl-C4-alkyl-mercapto-C2-C4-alkyl, when B is -CH=CRl-, Rl is -CH3, D is -CH and, at the same time, Y is hydrogen, or when B is -CH=CRl-CH=, Rl is -H or -CH3, D is =C_ and, at the same time, Y is hydrogen or Cl-C4-alkyl; and~0 (iv) X is not hydrogne when B is -CH2-, D is -CH , Y is chlorine and Z is -COOR2 or -CoNR3R~ where R2, R3 and R4 are defined as above.
Preferably, X is -Cl or -Br.
~339688 The invention as disclosed hereinafter also relates to the preparation of the compounds of the general formula (I), the use of the N-substituted 3,4,5,6-tetrahy-drophthalimides (Ic) as herbicides, and herbicides which contain the compounds of the formula (Ic).
Japanese laid-open patent Application 59/]55 358 published on 04.09.1984 in the name of SUMITOMO KAGAKU KOGYO
K.K. discloses N-substituted 3,4,5,6-tetrahydrophthalimides of type I' o Cl CR'-CQ1'-C00Q2' (I~) where R' and Rl are each hydrogen or methyl and R is alkyl, in particular ethyl.
Similar compounds, e.g. (I"):
C~l (") o CN
are disclosed in European Laid-Open patent Application 68,822 published on 05.01.83 in the name of ~OIIM AND HAAS
CO .
These compour~ds have been recommer-ded as herbicides but are unsatisfactory in this respect.
13.~9~88 The object of the invention disclosed and claimed in application n~ 528,764 to provide more effective herbicides. It has been found that this object is achieved by the novel N-substituted 3,4,5,6-tetrahydrophthalimides of formula (Ic) defined at the outset. It has also been found that the compounds (Ic) are very useful herbicides.
Processes for the preparation of the compounds of formula (Ic) have also been found.
The present invention as claimed hereinafter is directed to the new intermediatesof formula (Ia) and (Ib) that can be used for preparing the compounds of formula (Ic), and to processes for their preparation.
As disclosed in application n~ 528,764, the 3,4,5,6-tetrahydrophthalimide group is characteristic of the general herbicidal action of (Ic).
With regard to the more powerful action and the selective action of the herbicides, on the other hand, the moiety - B - D
\ z has an advantageous effect.
The compounds of type I are obtainable by the following specific methods:
a) Preparation of the nitrobenzene derivatives (Ia):
A 2-halo-5-nitrobenzaldehyde (IIa) ~2~X
CHt) 13.39~,8 or a 2-halo-5-nitrophenylacetaldehyde 11-' Z ~% I I I a CHO
or a Z-halo-5-nitrocinnamaldehyde 11 ~2~
CHO
is reacted in a conventional manner with a cyanoacetamide, cyanoacetate, a monoester or diester of malonic acid or a C3-Cs-aldehyde. When a monoester of malonic acid is used, the decarboxylation product Il-lll is obtained.
COOH
02N~ COOR2 ' CO2 ~ ~2~X
CHO
II-) ( Il-lll) ~-(C1-C3)-Alkylcinnam;c acids of type II~ and their de,rivatives are readily obtainable by reaction with C3-Cs-aldehydes under basic cond;tions, followed by oxidation 02N~ lk 02N~X ~ 02N~X
CHO CH2-CHO ~<_ <Alk \~Alk CHO COO~
Working up is carried out in a conventional manner. If at all necessary, la can be purified by re-crystallization, alcohol/water mixtures generally being su;table.
The nitrobenzaldehydes lla and nitrocinnamalde-hydes IIa" are known or are obtainable by known methods, so that further information in this respect is superfluous.
b~ Preparation of the aniline derivatives Ib The aniline derivatives possessing a saturated 1339~8 side chain ~-D are formed by catalytic hydrogenation of the nitrobenzene derivatives la. Selective catalytic hydrogenation, for example with platinum oxide as a cata-lyst (Rylander, Catalytic Hydrogenation over Platinum Metals, page 176, Academic Press, New York 1967), and the use of metals, such as iron, for reduction in a conven-tional manner leave the double bonds in the side chain unaffected.
c) Preparation of the N-substituted 3,4,5,6-tetrahydro-phthalimides Ic To prepare these compounds, 3,4,5,6-tetrahydro-phthalic anhydride is reacted with an aniline of type Ib by a conventional method. The react;on is carr;ed out, for example, in a boiling carboxylic acid, eg. acetic acid, propionic acid or butyric acid. Another possible method is to carry out the reaction in an inert solvent with con-tinuous removal of the water of reaction, in the presence of a catalytic amount of an acid, preferably p-toluene-sulfonic acid. Examples of suitable inert solvents are benzene derivatives, such as toluene, benzene, chloro-benzene or xylene.
The halogen X of the aromatic can also be intro-duced into Ic at the end of the reaction sequence by re-action with a halogenating agent, eg. sulfuryl chloride, in an organic acid at from 80 to 130~C.
Chlorine-containing and bromine-containing groups P-D can be prepared by starting from unsaturated groups ~-D and converting them to the dihalo compounds, which are converted to the monohalide, if appropriate by dehydro-halogenation.
Preferred compounds Ic are those in which the group B is -CH2- or -CH=. Preferred radicals X are chlorine and bromine. Preferred radicals Y are -CH3, -C2Hs, -Cl and -Pr. Z is preferably -COOR2, with the proviso that R2 is methyl, ethyl, isopropyl, n-butyl, isobutyl, isoamyl, 2-methoxyethyl or 1-methoxyProp-2-yl.
Examples of suitable compounds Ic are:
7 13~9~,3 N-t3-(acrylic acid methyl ester)-4-chlorophenyl]-3,4,5,h-tetrahydrophthalimide N-[3-(acrylic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-methylacrylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid methyl ester)-4-chloroohenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid isopropyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid-n-butyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid isobutyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid isoamyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid benzyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(a-cyanoacrylic acid cyclohexyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(a-cyanoacrylic acid Z,Z,Z-trifluoroethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid Z-methoxyethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid allyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(a-cyanoacrylic acid 3-methylallyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-cyanoacrylic acid 2-chloroethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid propargyl ester)-4-chlorophe-nyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-cyanoacrylic acid 1-methoxyprop-Z-yl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-bromoacrylic acid methyl ester)-4-chloroPhenyl~-13~ ~88 3,4,5,6-tetrahydrophthalimide N-C3-(a-methylacrylic ac;d ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(a-methylacrylic acid isobutyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(acryl;c acid ;sopropyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acryl;c acid n-butyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(acrylic acid isobutyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid isoamyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic ac;d benzyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(acryl;c acid cyclohexyl ester)-4-chloroohenyl]-3,4,5,6-tetrahydrophthal;m;de N-C3-(acrylic acid 2,2,2-trifluoroethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(acrylic acid Z-methoxyethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(acrylic acid allyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid 3-methylallyl ester~-4-chlorophenyl]-ZS 3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid Z-chloroethyl ester)-4-chloropllenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid propargyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid 1-methoxyprop-Z-yl ester)-4-chloro-phenyl)-3,4,5,6-tetrahydrophthalimide N-C3-(a-methylacrylic ac;d 2-methoxyethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthal;mide N-C3-(a-methylacrylic acid dimethylamide)-4-chlorophenyl]-3,4,5,6-tetrahvdrophthal;mide N-C3-(a-methylacryl;c acid N-morpholide)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide 13~ 88 g N-C3-(a-cyanopropionic 3C id ethyl ester)-4-chloroPhenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(~-cyanopropionic acid methyl ester)-4-chloroPhenylJ
3,4,5,6-tetrahydrophthalimide S N-C3~ cyanopropionamide)-4-chlorophenyl]-3,4,5,6-tetra-hydrophthalimide N-C3-(propionic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(propionic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-methylpropionic acid methyl ester)-4-chtoro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(~-methylpropionic acid ethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(methylmalonic acid diethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(methylmalonic acid dimethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(1,3-butadiene-1,1-dicarboxylic acid dimethyl ester)-Z0 4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(1-cyano-1,3-butadiene-l-carboxytic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(1-cyano-1,3-butadiene-1-carboxylic acid methyl ester)-4-chtorophenyl]-3,4,5,6-tetrahydrophthalimide Z5 N-C3-(l-cyano-1,3-butadiene-1-carboxamide)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(1-cyano-3-methyl-1,3-butadiene-1-carboxylic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal-imide N-C3-(1-cyano-3-methyt-1~3-butadiene-1-carboxylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthal-imide N-[3-(~-bromoacrylic acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(ct-bromoacrylic acid ethyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(~-chloroacrylic acid ethyl ester)-4-bromophenyl]-lo 13~9~88 3,4,5,6-tetrahydrophthalimide N-[3-(a-methylacryLic acid ethyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(a-cyanoacrylic acid methyl ester)-4-bromoPhenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(a-carboxamidoacrylic acid methyl ester)-4-bromo-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acryl;c acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(acrylic acid ethyl ester)-4-bromopheny~]-3,4,5,6-tetrahydrophthalimide N-t3-(1-cyano-1,3-butadiene-1-carboxylic acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide N-[3-(1-cyano-3-methyl-1,3-butadiene-1-carboxylic acid 1S ethyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthal-imide N-t3-(a-cyanopentanoic acid methyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(~-cyanopentanoic acid ethyl ester)-4-chlorophenyl]-Z0 3,4,5,6-tetrahydrophthalimide N-t3-(n-propane-1,1-malonic acid diethyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide N-C3-(1-cyano-3-methylpentanoic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide ~5 N-[3-(1-cyano-3-methylpentanoic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide N-t3-(3-methylisobutane-1,1-malonic acid diethy~ ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide The N-substituted 3,4,5,6-tetrahydrophthalimides of the formula Ic and the herbicidal agents which contain these compounds can be used, for example, in the form of directly sprayable so~utions, powders, suspensions, in-cluding aqueous, oily or other suspensions containing a high percentage of the compound, dispersions, emulsions, oil dispersions, pastes, dusting agents, broadcasting agents or granules, by spraying, misting, dusting, broad-casting or watering The forms for use depend on the 11 ~3~3~g~8 intended uses, they should in any case ensure a very fine distribution of the active ingredients according to the invention.
Suitable suostances for the preparation of direct-ly sprayable solutions, emulsions, pastes or oil disper-sions are mineral oil fractions having a medium to high boiling point, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg. toluene, xylene, paraffin, tetrahydronaphthalene, alkylnaphtha-lenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, iso-phorone and highly polar solvents, such as N,N-dimethyl-formamide, dimethyl sulfoxide, N-methylpyrrolidone or water.
Aqueous forms for use can be prepared from emul-sion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water. rO pre-pare emulsions, pastes or oil dispersions, the substrates as such, or dissolved in an oil or solvent, can be homo-genized in water using wetting agents, binders, dispersants or emulsifiers. However, it is also possible to prepare concentrates which consist of the active ingredient, wetting agents, binders, dispersants or emulsifiers and, Z5 if required, solvents or oil, and which are suitable for dilution with water.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, eg. ligninsulfonic, phenolsulfonic, naphthalenesulfonic or dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl-, laurylether- and fatty alcohol sulfates, and salts of sulfated hexadeca-nols, heptadecanols and octadecanols and of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its derivatives with formaldehyde, condensates of naphtha-tene and of naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, 12 1 3 3 9 b 8 8 oxyethylated isooctyl-, octyl- and nonylphenol, alkyl-phenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, oxyethylated S castor oil, polyoxyethylene atkyl ethers and ~olyoxypro-pylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, ligninsulfite waste liquors and methylcellulose Powders, broadcasting agents and dusting agents can be prepared by mixing or milling the active ingre-dients together with a solid carrier Granules, for example coated granules, impregnated granules and homogeneous granules, can be nrepared by binding the active ingredients to solid carriers. The latter are mineral earths, such as si~icas, silica gets, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, do~omite, diatomaceous earth, calcium sul-fate, magnesium sulfate, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal meal, bark meal, wood meal and nutshell meal, cellulose po~der and other solid carriers.
The formulations contain in general from 0.1 to 95, preferably from 0.5 to 9û, % by weight of active ingredient.
Z5 Application may be effected by the pre-emergence or post-emergence method. If the active ingredients are less well tolerated by certain crops, it is possible to use an application technique in which the herbicides are sprayed with the aid of a sprayer in such a way that, as far as possible, the active ingredients do not come into contact with the leaves of the sensitive crops but reach the leaves of undesirable plants growing underneath, or the exposed soil surface (post-directed, lay-by method) The application rates of the active ingredient are from 0.01 to 5.0, preferably from O.OS to 0.5, kg/ha, depending on the season, the target p~ants and the stage of growth.
13~f 6~8 Taking into account the action spectrum which can be utilized for weed control, the toleration by crops or the desired effect on the growth of the latter, and in view of the wide variety of methods of application, the novel compounds can be used in a large number of croPs, depending on the pattern of substitution.
Examples of suitable crops are-~otanical name Common name A(lium cepa onions 10 Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) Asparagus officinalis asparagus Avena sativa oats ~eta vulgaris spp. altissima sugarbeets 15 ~eta vulgaris spp. rapa fodder beets 8eta vulgaris spp. esculenta table beets, red beets ~rassica napus var. napus rapeseed ~rassica napus var. napobrassica swedes ~rassica napus var. rapa turnips 20 ~rassica rapa var. silvestris Camellia sinensis tea plants Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons 25 Citrus maxima grapefruits Citrus reticulata mandarins Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants 30 Cucumis melo melons Cucumis sativus cucumbers Cynodon dactylon 8ermuda grass in turf and lawns Daucus carota carrots 35 Elaeis guineensis oil palms Fragaria vesca strawberries Glycine max soybeans ' 14 1339~88 Potanical name Common name Gossypium hirsutum (Gossypium arboreum Gossypium herbaceum Gossypium vitifolium) cotton Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce Lens culinaris lentils Linum usitatissimum flax Lycopersicon lycopersicum tomatoes Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) ZO Mentha piperita peppermint Musa spp banana plants Nicotiana tabacum tobacco (N rustica) Olea europaea olive trees Z5 Oryza sativa rice Panicum miliaceum millet Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans Pennisetum glaucum pearl millet Petroselinum crispum parsley spp tuberosum Picea abies Norway spruce Abies alba fir trees Pinus sPP. pine trees Pisum sativum English peas ~33~688 Botanical name Common name Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees Pyrus communis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Ricinus communis castor-oil plants 10 Saccharum officinarum sugar cane Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum 15 Sorghum dochna sorgo Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Z0 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes 25 ~ea mays Indian corn, sweet corn, maize In order to broaden the action spectrum and to achieve syriergistic effects, the tetrahydrophthalimides of the formula Ic can be mixed with a large number of typica( compounds of other groups of herb;cidal or growth-regulating active ingredients, and applied together.
Examples of suitable components for the mixture are dia-zines, 4~-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, other ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-tives, cyclohexane-1,3-dione derivatives and others ' ' 1339688 It may also be useful if the novel compounds of the formula Lc, alone or in combinat;on with other herbi-cides, are applied as a mixture with other crop protection agents, for example with agents for controlling Pests or 5 phytopathogenic fungi or bacteria Miscibility with mineral salt solutions which are used to eliminate nutri-ent and trace element deficiencies is also of interest Nonphytotoxic oils and oil concentrates may also be added EXAMPLES
Preparation of nitrobenzene derivatives Ia ~2 ~ (Ia) 2-Chloro-5-nitrocinnamic acid (Y=H, Z=COOH) 8 5 9 of piperidine were added to 185 5 9 (1 mole) of 2-chloro-5-nitrobenzaldehyde and 125 9 (1 2 moles) of malonic acid in 400 ml of pyridine, and the mixture was stirred at 110~C until the evolution of C02 was complete (about 3 hours) The reaction mixture was then poured on to a mixture of 1 l of ice and 350 ml of concentrated HCl, a yellow solid being precipitated. The product was fil-tered off under suction, washed with water and dr;ed to give 220 g (97~ of theory) of the above compound of melt-ing point 193-196~C
Methyl Z-chloro-5-nitrocinnamate (Y=H, Z=COOCH3) A solution of 34.1 g (150 millimoles) of the pro-duct from Example 1 in 30û ml of methanol was saturated with HCl gas, after which further HCl gas was passed in during the reaction time of 5 hours The solid obtained on cooling was stirred thoroughly with NaHC03/water and taken up in methylene chloride The CHzCl2 solution was washed with water and dried over MgS04, and the abovemen-tioned product was obtained by evaporating down the solu-tion and triturating the residue with diethyl ether.
1339~i88 Y;eld: 24 g (63~); mp 159-162~C
Ethyl Z-chloro-5-nitrocinnamate (Y=H 2=C00C2H5) 33 g (250 millimoles) of monoethy( malonate and Z7 g (150 millimoles) of 2-chloro-5-nitrobenzaldehyde in 100 ml of pyridine were reacted similarly to Examole 1 and the mixture was worked up in a conventional manner Yield: 31% mp 138-140~C
Ethyl 3-nitrocinnamate (X=H Y=H ~=COOCzHs) The reaction and working up were carried out as described in Example 3 and the product of melting point 67-70~C was obtained in 7Z~ yield Methyl 3-nitrocinnamate (X=H Y-H Z=C00CH3) The procedure followed was similar to that des-cribed in Example 4 and the product of melting point 101-103~C was obtained in 74% yield 2-Chloro-5-nitro-a-methylcinnamaldehyde (Y=CH3 Z-CHO) 4 9 of NaOH dissolved ;n 20 ml of water were added to a suspension of 185 5 9 (1 mole) of 2-chloro-5-nitrobenzaldehyde in 500 ml of methanol after which 70 g (1.2 moles) of propionaldehyde were added dropwise while 2S cooling to 10-15~C. The mixture was stirred for 2 days at room temperature and then neutralized with glacial acetic acid and the precipitated solid was isolated by filtration under suction washed with water and dried at S0~C under reduced pressure to give the product of melting point 99-lOZ~C in 78% yield.
Z-Chloro-5-nitro-~-methylcinnamic acid (Y=CH3 Z=COOH) 371 9 (2 moles) of 2-chloro-5-nitrobenzaldehyde were mixed with 192 9 (2 moles) of sodium propionate and 780 g (6 moles) of propionic anhydride The stirred mix-ture was then heated for 6 hours at 140-160~C solid mate-r;al going into solutiorl. The solution was then left to 1~3968~
cool to 90~C, 200 ml of ice water were added and the pre-cipitated solid was isolated by filtration under suction, washed with water and recrystallized from acetone to give 318 9 (66~ of theory) of product of melting point ZZ8-Z30~C
Methyl 2-chloro-5-nitro-a-methylcinnamate (Y=CH3, Z=COOCH3) Reacting the acid obtained in Example 7 with thionyl chloride in toluene in a conventional manner gave the acid chloride, which was refluxed in excess methanol and gave the ester of melting point 98-99~C in 72~ yield Ethyl 2-chloro-5-nitro-o!-cyanoc;nnamate (Y=CN, Z=COOc2Hs) 29 7 9 (300 millimoles) of ethyl cyanoacetate were added to a solution of 55 7 9 (300 millimoles) of 2-chloro-5-nitrobenzaldehyde in 200 ml of tetrahydrofuran, after which 1 ml of piperidine was addod as a catalyst at 0~C The mixture was stirred for 16 hours at room temperature, neutralized with acetic acid and then worked Z0 up in a conventional manner to give a product of melting point 83-85~C in 71~ yietd Dimethyl 3-nitrobenzylidenemalonate (X=H, Y and Z=COOCH3) 75 5 9 (500 millimoles) of 3-nitrobenzaldehyde and 73 9 (550 millimoles) of dimethyl malonate were stirred for 4 hours at 60~C, similarly to Example 9.
After the addition of 5 ml of glacial acetic acid, the m;xture was worked up in a conventional manner The pro-duct of melting point 78-80~C was obtained in 96~ yield 1-(2-Chloro-5-nitrophenyl)-4-cyano-4-methoxycarbonyl-trans-buta-1,3-diene (r=H~ Z=-CH=C(CN)COOCH3) 15 9 (70 millimoles) of 2-chloro-5-nitrocinnamal-dehyde (mp~ 115-117~C) and 10 9 (0 1 mole) of methyl cyanoacetate in 200 ml of toluene were heated under a water separator in the presence of 1 9 of ammonium ace-tate and 1 ml of acetic acid until water no longer lg 13~968~
distilled over. The product crystallized out on cooling.
After the usua( working up procedure, 58% of the product of melting point 193-194~C remained.
Preparation of aniline derivatives Ib H~N- ~ X (Ib) ~ ,Y
~--0~
Preparation of aniline derivatives Ib having unsaturated side chains A solution of 1 equivalent of a nitro compound la in 50 ml of alcohol and 50 ml of glacial acetic acid was prepared by warming and was added to a susPension of 3 3 equivalents of iron powder in a mixture of 100 ml of the alcohol corresponding to the ester group in Z and Z5 ml of glacial acetic acid at 50~C, and the mixture was heated at the boil for 3 hours. It was worked up by fil-tering it, pouring the filtrate into 500 ml of water and extracting with ethyl acetate or methylene chloride. The organic phase was dried and the solvent distilled off under reduced pressure, and the product, without further purification, was condensed with tetrahydrophthalic anhy-dride as described in Example 22. Further properties are summarized in Table 1.
Compounds H2 ~
Ex 2 Y X mp.~C Yield 12 COOCH3 H Cl 70- 12 91 13 cooC2Hs H Cl 68- 70 8-1~ COOtH3 CH3 Cl 82- 8~ 86 COOCH3 CN Cl 8B- 90 89 16 Cooc2Hs CN Cl 89- 85 8R
,CN
17 -CH=C~ ~ Cl127-129 90 EXAMPLES 19 T0 21 1~3~8~
Preparation of an;line derivatives Ib having a saturated side chain 0.2 mole of a nitro compound la was hydrogenated in the presence of 5 g of 10~ strength Pd/C at from 20 to 40~C under atmospheric pressure in 500 ml of tetrahydro-furan or ethyl acetate, and the mixture was workod up in a conventional manner. The results are shown in Table Z.
TA~LE 2 Compounds Hz~J~X
Ex. ~ y X mP-~CYield no l9 COOCzHs H H Ol53 COOC2H5 CN Cl Olâ5 21 COOCH3 COOCH3 H Ol ~ l O0 20 Preparation of N-substituted 3,4,5,6-tetrahydrophthali-mides Ic ~X ( I c ) O --;!
General method A mixture of 0.1 mole of 3,4,5,6-tetrahydrophtha-(ic anhydride and 0.1 mole of an aniline of the generalformula Ib in 150 ml of acetic acid is heated at the boil until thin layer chromatography shows that the components have been converted, which is the case after from 2 to 3 hours. The product is generally precipitated on cooling and is then isolated by filtration under suction. If this is not the case, the reaction mixture is evaporated down under reduced pressure, the residue is dissolved in 1333~
ethyl acetate and the solution is extracted with water.
After the solution has been dried and the ethyl acetate stripped off, the product remains in the form of an oil, which crystallizes out on trituration with petroleum ether. rhe physical properties of the active ingredients are summarized in Tables 3, 4 and 5.
In the unsaturated compounds (Table 3), cis-trans isomers occur in various ratios. ~oth isomers and mix-tures of them are claimed.
N-C3-(a-Cyanopropionic acid ethyl ester)-4-chloro~henyl]-3,4,S,6-tetrahydrophthalimide C~N~C1 O --Cozc2H5 14 9 (55 millimoles) of the saturated aniline derivative corresponding to Example 18 and 9 g (60 milli-20 moles) of 3,4,5,6-tetrahydrophthalic anhydride were re-ftuxed with Z00 ml of xylene under a water separator until water no longer passed over. Working up in a conventiona( manner and chromatography with 7:3 toluene/tetrahydro-furan over silica gel gave the product in the form of an 25 Oil in 61~ y;eld.
EXAMPLE 23N-[3-(Propionic acid ethyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide C~N~1 O C02Et 16 9 (49 millimoles) of N-t3-(propionic acid ethyl ester)-phenyl]-3,4,5,6-tetrahydrophthalimide were dis-solved in 150 ml of glacial acetic acid. 7.3 9 (54 milli-moles) of sulfuryl chloride, dissolved in 20 ml of glacial ~ 3 3 ~ b ~ 8 acetic acid, were added dropwise at 80~C, after which the mixture was stirred for 2 hours at 110~C. After the usual working up procedure, the crude product was purified by chromatography over silica gel (1:1 cycLohexane/ethyl acetate). The product was obtained in the form of an oil in 54X yield.
Preparation of N-substituted 3,4,5,6-tetrahydrophthal-imides ~c having halogen-containing side chain ~
Y = halogen N-c3-(a~B-~ibromopropionic acid methyl ester)-4-chloro-phenyl]-3,4,5,6-tetrahydrophthalimide as an intermediate o O¢~C1 0 ~r A solution of 4.6 g (30 millimoles) of bromine in 10 ml of methylene chloride was added dropwise to a solu-tion of 10 9 (30 millimoles) of the active ingredient 1 from Table 3 in 50 ml of methylene chloride at a bath 25 temperature of 50~C. After the mixture had been stirred for 2 hours, the reaction was complete. The product was generally used without further isolation for dehydro-bromination according to Example 25. A sample isolated by evaporating off methylene chloride had a melting Point of 90-94~C.
N-C3-(~-~romoacrylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide o C02CH~
23 1339b88 The dibromide obtained as described above was then dehydrobrominated directly in 150 ml of methylene chloride at room temperature with 10.1 9 (lO0 millimoles) of triethylamine, by stirring at Z5~C for one hour. The reaction mixture was boiled for 15 minutes and then oolJred onto water. The methylene chloride phase was seDarated off, washed with water, dried and evaporated down. rri-turation with diethyl ether gave lO g ~85~) of a solid of melting point of 92-94~C.
N-t3-(a-~romoacrylic acid methyl ester)-4-bromophenyl]-3,4,5,6-tetrahydrophthalimide a) Z-~romo-5-nitrobenzaldehyde A nitrating acid prepared at -10~C by adding 55 ml of concentrated H2S04 to 20 ml of 98 percent HN03 was added dropwise, in the course of 60 minutes, to a solution of 63.4 9 (0.34 mole) of 2-bromobenzaldehyde in 110 ml of concentrated HzS04 at -5~C. Stirring was con-tinued for a further 45 minutes, after which the reaction mixture was poured onto 550 9 of ice, and the precipi-tated solid was filtered off under suction, washed with water, then with 10 percent strength Na2C03 solution and again with water. Drying under reduced pressure at 50~C
gave 7Z 9 (9ZX of theory) of product as a yellow solid of Z5 melting point 86-88~C.
b) Z-Elromo-5-nitrocinnamic acid This reaction was carried out similarly to Example 1, with Z-bromo-5-nitrobenzaldehyde and malonic acid in pyridine and with piperidine. The product of melting point 185~C was obtained in 57% yield.
c) Methyl 2-bromo-5-nitrocinnamate This product was prepared similarly to Example 8, by converting the cinnamic acid obtained under b) into the acid chloride (mp. 106-108~C, 98% yield) and then reacting the latter with methanol/pyridine. Yield 70X of theory, mp. 150-15Z~C.
133~'Q88 d) Methyl 2,a-dibromo-5-nitrocinnamate 19.2 9 (0.12 mole) of bromine were added dropwise at 40~C in the course of 2 1/Z hours to a solution of 28.6 9 (0.1 mole) of the ester obtained under c), in 20û ml of methylene chloride; thereafter, the mixture was heated at the boil for a further 3 hours. After the mix-ture had been cooled to Z0~C, Z0.2 9 (0.2 mole~ of tri-ethylamine were added dropwise. After 3 hours, 150 mL of water were added to the reaction mixture and the mixture was then transferred to a separating funnol. rhe methy-lene chloride phase was extracted with twice 100 ml of water, after which the organic phase was dried over MgS04 and evaPorated down under reduced pressure. rrituration with diisopropyl ether gave 30 g of a crude oroduct, whicl was chromatographed over silica gel using to~uene as the mobile phase. The toluene solution was evaporated down to give 20 9 (56%) of the product of melting point 95-96~C.
e) Methyl 2,a-dibromo-5-aminocinnamate Zû 9 (0.056 mole) of the nitro compound prepared 20 under d) were added a little at a time to a suspension of 15.7 g (0.28 mole) of iron in 200 ml of methanol and 10û ml of glacial acetic acid at 60~C. The mixture was refluxed for 5 hours, after which it was cooled, poured into 1.5 l of water and extracted twice with Z00 ml of Z5 ethyl acetate. The organic phase was washed with water, dried and evaporated down under reduced pressure to give 18 g (~- 96X of theory) of product in the form of an oil.
f) N-t3-(a-Bromoacrylic acid methyl ester)-4-bromophenyl~-3,4,5,6-tetrahydrophthalimide ~J~
N~flr ~ ~<~ C02CI~3 ~ cis t Il ~<
O ~r Wirkstof f Nr . 67 Active ingredient No. 67 8.1 9 (0.053 mole) of tetrahydrophthalic anhydride 1~'.3~8 were added to a solution of 18 9 (0 053 mole) of the pro-duct obtained under e) in 50 ml of glacial acetic acid The mixture was stirred for 3 hours at 110~C and then evaporated down under reduced pressure, the residue was dissolved in ethyl acetate and the solution was extracted with 10~ strength Na~C03 solution and with water. The ethyl acetate phase was dried with MgS04 and then evapora-ted down under reduced pressure. Trituration with diiso-propyl ether gave 23 g (92% of theory) of the product of melting point 83-85~C
NMR analysis showed that the compound con,isted of 8SX of the cis form and 15% of tho trans form.
N-C3-(a-Chloroacrylic acid methyl ester)-4-chlorophenyl]-3,4,5,6-tetrahydrophthalimide 0 COzCH3 Active ingredient No 49 a) Methyl 3-[2'-chlorophenyl]-2,3-dichloropropionate 21 3 g (0 3 mole) of chlorine gas were passed slowly into a solution of 39.3 9 (0 2 mole) of methyl 2'-chlorophenylcinnamate in 200 ml of 1,1,1-trichloroethane at 60~C in the course of 3 hours, after which the mixture was stirred for a further hour at 70~C The reaction mix-ture was then washed twice with 150 ml of water and the organic phase was dried over MgS04 The solvent was stripped off under reduced pressure to give 52 9 (97~) of the product in the form of an oil.
b) Methyl 2,~-dichlorocinnamate 40.4 9 (0 4 mo(e) of triethylamine were added dropwise at 25~C to a solution of 52 g (0~194 mole) of the ester obtained under a) in 400 ml of methylene chlor-ide, and the mixture was then stirred for l hour at 40~C
133~8 Thereafter, 200 ml of water were added and the organic phase was separated off, washed with water and dried with MgS04 to give 42 9 (93X of theory) of the nroduct in the form of an oil.
c) Methyl 2,a-dichloro-S-nitrocinnamate A nitrating acid was prepared by adding 47 ml of concentrated HzS04 dropwise to 16 ml of 98 percent strength HN03 at -1û~C, and this nitrating acid was added dropwise to a solution of 42 9 (0.182 mote) of the a-chlorocinnamate described under b), in 150 ml of con-centrated HzS04, at -5~C. Stirring was continued for - 30 minutes at 0~C, after which the reaction mixture was stirred in 600 ml of ice water and the precipitated pro-duct was isolated by filtration under suction. It was washed several times with water, and the still moist pro-duct was then recrystallized from methanol. 28 9 (54X of theory) of crystats of melting point 108-110~C were obtained.
d) Methyl 2,~-dichloro-5-aminocinnamate 100 9 (0.36 mole) of the nitro product described under c) were reduced with 61.6 9 (1.1 motes) of iron powder in 500 ml of methanol and 500 ml of glacial acetic acid, as described in ~xample Z5e. After the working up procedure described there, 70 9 (80% of theory) of the desired product were obtained in the form of yellow crystals of melting point 104-105~C.
e) Tetrahydrophthalimide derivative 7.6 9 (0.05 mole) of tetrahydrophthalic anhydride were added to 1Z.3 9 (0.05 mole) of the aniline derivative prepared under d), in 50 ml of glacial acetic acid, and the mixture was stirred for 3 hours at 10~C. The acetic acid was stripped off under reduced pressure, the residue was taken up in ethyl acetate and the solution was washed with 10% NaHC03 solution and then with water. The organic phase was dried over MgS04 and the solvent was stripped off to give 13 9 (68X of theory) of white crystals of metting point 138-1~0~C. NMR analysis showed that the compound was 1339b88 a pure trans isomer.
The active ingredients summarized in Tables 3 to 5 were obtained by the methods stated above.
o ~N~y Serial . x r R2 Mp.
I Cl H CH3 139-1~0 2 Cl H C2~5 l~a- 149 3 C1 H C3H7-i 106-107 Cl H C4Hg-n 7~- 76 Cl H C4Hg-i 52- 53 6 Cl H csH11-i 1 a~- 1 a6 7 Cl H Cycloh~xyl 131-133 a cl H 2-Methoxy-ethyl 76- ?3 9 Cl H l-Methoxy-prop-2-yl30- 31 Cl H Allyl 11~-111 11 Cl H 3-Methylallyl 102-l a3 12 Cl CH3 H 212-2~3 13 Cl CH3 CH3 132-133 1~ C1 CH3 C2H5 6Z- 63 Cl CH3 C3H7-n 79- 90 16 Cl CH3 C3H7-i 7~ 75 17 Cl CH3 C4H9~n ~- 16 la Cl CH3 C4Hg-i 86- 69 19 Cl CH3 CsHll-n ~7- 49 28 133~
Serial No. X r R2 Hp. (~c~
C1 CH3 CsH1~-i 54- 65 21 Cl CH3 9enzyl 15-22 Cl CH3 2-Phenylethyl oil Z3 Cl CH3 1-Phenyl-prop-2-yl 108-109 2~ Cl CH3 ?ropar~yl 151-152 Cl CH3 3-Methyl~uten-2-yl 49- 51 26 Cl CH3 3-Methyl~ucan-3-yL Ojl Cl CH~ 2-Metnoxyethyl 41-44 28 Cl CH3 2-Ethoxyetnyl 39~ 40 29 ~1 CH3 2-~n-~3utaxy~-ethyl oil Cl CH3 l-Methoxy-prop-2-yl 45~ 47 31 C1 CH3 2-Methoxy-prap-1-yl 89- sa 3Z C1 CH3 1-Ethoxy-prop-2-yl oil 33 Cl CH3 1-Methoxy-but-2yl 55- 56 3~ C1 CH3 2-Ethyl-thio-ethyl 99- ~0 C1 CH3 2-~I~opropylthio)-~thylô7- 68 36 C1 C2H5 CH3 1 a3- 1 O-37 C1 CzH5 CzH5 ~9_ 50 33 Cl C2H5 2-MQthoxyethyl ~6- ~3 39 C1 C2H5 1-MQthoxyprop-2yl 32- 33 ~0 C1 CzH5 n~C3H7 ~7-~1 Cl C2~5 n-C4~9 Oj~
~z C1 i-C3H7 CH3 75- 76 ~3 C1 n-C3H7 CH3 oil C1 n-C3H7 2-MethoxyQthyl ~il ~5 C1 n-C4Hg CH3 oil ~6 Cl n-C4Hg 2-Methoxyethyl ~il ~7 C1 n-csH1l CH3 oil C1 n-C5H11 2-Methoxyethyl ~il 29 1 3 3 ~ b Seria~
Nb. X Y ~2 Mp ( ~9 Cl Cl CH3 13~ o Cl Cl CzHs 37- a 9 51 Cl Cl n-C3H7 83-85 52 Cl Cl i-C3H7 140-141 53 Cl Cl n-C4Hg 90-91 5~ Cl C1 n-CsHll 112-114 Cl C1 i-CSHll 68-70 56 Cl Cl 2-~ethoxyethyl 1Z~-170 57 Cl Cl 2-EthqxyetnyL 58-60 5~ Cl Cl 2-ln-autoxy~-etnyL ~il 59 Cl 8r CH3 94- 95 6~ Cl 9r C2H5 91- 92 6l Cl 3r n-C3~7 79- 80 62 Cl 9r i-C3H~ 119-121 63 C1 9r n-C4Hg 73- 74 6~ Cl 9r 2-Methoxyetnyl 136-137 9r H CH3 66 9r H n-C~g 6t 9r 3r CH3 a~- ~5 6a Cl CN. H 1~a-15l 69 Cl CN CH3 15~-155 Cl CN C2H5 1~0-1~2 71 Cl CN l-C~H~ 132-133 72 Cl CN i-C4Hg 13~ 135 73 Cl CN OQnzyl 1 az- 163 7~ Cl CN 2-M~thoxyQthyl 11~-116 Cl CN Z-~opropoxyethyl 63- 65 76 Cl CN 1-~ethoxyproF2-y( 56- 57 7t Cl C~ 2-~ethoxyprop-1-yl 12C-123 78 C1 C~2CH3 CHg l9a-1~0 79 H H CH3 1~ 2 133~88 Ser; al No. X r R2 MF. ~~c Cl H C2H5 oil 81 C1 CN C2H5 oil 3 Z Cl C02CH3 CH3 oil 2 0 ~¢N~y Serial X r ~2 ~ ( ~ C ) 8 ~ Cl CH~ CN 112-113 9~ Cl H ~C0zCH~ 176-178 CN
C~ H ~C02C2H5 184--186 CN
1~3~6~3 The following active ingredients of the formula (I) can be obtained in a similar manner:
o ~X
~ C02R2 No. X Y R2 la1 Cl CH3 Allyl 10 2 Cl CH3 2 -~ethyl- thioethyl 10~ Cl CH3 Cyclohexyl l 0~ Cl CH3 Cyclopentyl 105 Cl CH3 2-Chloroethyl 106 Cl CH3 2, Z, 2-Trifluor oethyl lO7 Cl C2H5 i-C3H7 108 Cl C2H5 i-C~Hg lO9 Cl C2H5 n-CsH11 110 Cl C2Hs i-CsHtt lll Cl C2H5 2-Ethoxyethyl 1l2 Gl C2H5 Z-~n-3utoxy)-ethyl 113 Cl C2H5 Cyclohexyl 1l~ Cl C2Hs Cyclopentyl 115 Cl C2H5 2-Ch1oroethyl, 11 ~ Cl Cl 2 - Chloroethyl 11~ Cl Cl i-C4Hg ll9 Cl Cl sec.-C4Hg l l9 Cl 8r l-C~Hg 120 Cl ~r n-CsH
32 ~33~;88 Nb. X Y R
121 Cl 3r n-C6H13 122 Cl ~. 2-Chlor~thyl 123 Cl 3r ;-CsHll 12~ Cl 9r Cyclohexyl 125 Cl Br Cyciopentyl 12a 3r er CzHs 127 e- Br n-C3H7 1Z~ P. e. t--1ethoxyethy 129 Br Br Z-Ethoxyethyl 130 Br Cl CH3 131 Br Cl C2H5 132 Br Cl n-C3H7 133 ~r Cl 2-Methoxyethyl 134 3r Cl 2-Ethoxyethyl 135 Cl C2H5 Allyl 136 Cl C2H5 3-Methylallyl 137 Cl Cl Allyl 13a Cl Cl 3-~ethylallyl 139 Br Cl Allyl l~0 Cl 3r 3-Methylallyl l~l Br 3r Allyl 1~2 ~3r 8r 3-Methylallyl 1~3 Er ar 2-Chlor~thyl 1~ ~ 8r Cl Allyl 1~5 9r Cl 3-~ethylallyl 1~6 Br Cl 2-Chlo~thYl Examples of use The act;on of the N-substituted 3,4,5,6-tetra-hydrophthalimides of the formula Ic on the growth of test plants was demonstrated by the greenhouse trials below.
Plastic flowerpots having a capacity of 300 cm3 were used as the culture vessels, and loamy sand contain-ing about 3% of humus was used as the substrate. The seeds of the test plants were sowed to a shallow depth, separately according to species.
For the purpose of Post-emergence treatment, plants which had been e;ther directly sown or grown in the same vessels were selected, or the plants were first grown separately as seedlings and transplanted into the test vessels a few days before the treatment.
The test plants, at a height of from 3 to 15 cm, depending on the form of growth, were then treated with the active ingredients suspended or emulsified in water as a distributing agent. The said suspension or emulsion was sprayed through nozzles which produced a fine spray.
The application rate for the postemergence treatment varied and was from 0.06 to 3.0 kg of active ingredient per ha.
The test vessels were placed in a greenhouse, warmer regions (from 20 to 35~C) being preferred for heat-loving species and 10-20~C for those of temperate climates.
The trial period extended over 2 to 4 weeks. During this time, the plants were tended and their reaction to the individual treatments were evaluated.
The plants used in the greenhouse trials con-sisted of the following species:
34 133~8 ~otanical name Common name Abutilon theophrasti velvetleaf Amaranthus spp. foxtail grasses Avena sativa oats Heta vulgaris beets Centaurea cyanus cornflower Chenopodium album lambs'-quarter Chrysantemum cor. crown daisy Galium aparine catchweed Glycine max soybeans Hordeum vulgare barley Mercurialis annua annual mercury Solanum nigrum black nightshade Triticum aestivum wheat Veronica spp speedwell Viola tricolor wild pansy When 3 0 kg of active ingredient per ha were used in the postemergence method, ;t was possible to control monocotyledon and d;coty(edon plants from the Examples very well with the active ingredients No 69, 7~ and 81 When 0 25 kg of active ingredient per ha was applied by the postemergence method, active ingredient No 2 had a herbicidal action against a number of unde-sirable dicotyledon plants, the soybeans suffering only slight damage When the active ingredients No 59 and 82 were applied by the postemergence method, economically important weeds were successfully controlled with as little as 0 06 kg of active ingredient per ha The crop plant soybean was only insignificantly impaired, if at all.
Active ingredient No. 13 was suitable, for exam-ple, for controlling the dicotyledon weeds in cereal when applied by the postemergence method at a rate of û 06 kg of active ingredient per ha.
1339~
Active ingredients No. 1, 4, 6, 8, 11, 60, 69 and 80 are useful for controlling broad-leaved plants by the postemergence method. When the treatment was carried out using 0.1ZS kg/ha of active ingredient No. 69, sugar-beet as the crop was not significantly impaired in any case.
Galium aparine, as a weed from the Examples, in gramineous crops can be controlled reliably by the post-emergence method using low application rates (0.06 kg/ha) of the active ingredients No 6 and 60; neither wheat nor barley suffer significant damage as a result.
Claims (8)
1. A nitrobenzene derivative of the general formula (Ia):
(Ia) where:
B is -CH2-, -CH2-CHR1 CH2-CHR1-CH2-, , -CH=CR1- or , R1 denoting -H, -Cl, -Br or -CH3, D is or , depending on the terminal group for B, X is -H, -Cl or -Br, Y is -H, C1-C7-alkyl, -Cl, -Br, -CN, CONH2 or -CO2R2, R2 denoting H, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, C1-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, .alpha.-phenylethyl, .alpha.-phenylpropyl, C2-C4-alkyl which is mono- to tri-substituted by F or Cl, or allyl which is substituted by -CH3 or -Cl;
Z is -COOR2, -CONR3R4, or -COR2, where R2 is defined as above and R3 and R4 are each H or C1-C4-alkyl or together form a 5- or 6-membered cycloaliphatic ring whose carbon chain may be interrupted by an oxygen atom, with the exception of 2-chloro-5-nitrocinnamic acid and of methyl and ethyl 3'-nitro-6'-chloro-benzylidene acetoacetate and with the proviso that:
(i) Y is not hydrogen, C1-C7-alkyl, -CN, -COOH or -CO2-C2 H5 when B is , D is , X is hydrogen and Z is -CO2R2 where R2 is hydrogen or C1-C6-alkyl;
(ii) Z is not -COCH3 or -COC2H5 when B is , D is X is hydrogen and Y is -CO2R2 where R2 is hydrogen, C1-C5-alkyl, C5- or C6-cycloalkyl or propargyl;
(iii) Z is not -COOR2 where R2 is hydrogen, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl or C1-C4-alkyl-mercapto-C2-C4-alkyl, when B is -CH=CR1-, R1 is -CH3, D is and, at the same time, Y is hydrogen, or when B is , R1 is -H or -CH3, D is and, at the same time, Y is hydrogen or C1-C4-alkyl;
and (iv) X is not hydrogen when B is -CH2-, D is , Y is chlorine and Z is -COOR2 or -CONR3R4 where R2, R3 and R4 are defined as above.
(Ia) where:
B is -CH2-, -CH2-CHR1 CH2-CHR1-CH2-, , -CH=CR1- or , R1 denoting -H, -Cl, -Br or -CH3, D is or , depending on the terminal group for B, X is -H, -Cl or -Br, Y is -H, C1-C7-alkyl, -Cl, -Br, -CN, CONH2 or -CO2R2, R2 denoting H, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, C1-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, .alpha.-phenylethyl, .alpha.-phenylpropyl, C2-C4-alkyl which is mono- to tri-substituted by F or Cl, or allyl which is substituted by -CH3 or -Cl;
Z is -COOR2, -CONR3R4, or -COR2, where R2 is defined as above and R3 and R4 are each H or C1-C4-alkyl or together form a 5- or 6-membered cycloaliphatic ring whose carbon chain may be interrupted by an oxygen atom, with the exception of 2-chloro-5-nitrocinnamic acid and of methyl and ethyl 3'-nitro-6'-chloro-benzylidene acetoacetate and with the proviso that:
(i) Y is not hydrogen, C1-C7-alkyl, -CN, -COOH or -CO2-C2 H5 when B is , D is , X is hydrogen and Z is -CO2R2 where R2 is hydrogen or C1-C6-alkyl;
(ii) Z is not -COCH3 or -COC2H5 when B is , D is X is hydrogen and Y is -CO2R2 where R2 is hydrogen, C1-C5-alkyl, C5- or C6-cycloalkyl or propargyl;
(iii) Z is not -COOR2 where R2 is hydrogen, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl or C1-C4-alkyl-mercapto-C2-C4-alkyl, when B is -CH=CR1-, R1 is -CH3, D is and, at the same time, Y is hydrogen, or when B is , R1 is -H or -CH3, D is and, at the same time, Y is hydrogen or C1-C4-alkyl;
and (iv) X is not hydrogen when B is -CH2-, D is , Y is chlorine and Z is -COOR2 or -CONR3R4 where R2, R3 and R4 are defined as above.
2. The nitrobenzene derivative of the general formula (Ia) as set forth in claim 1, wherein X is -Cl or -Br.
3. A process for the manufacture of a nitro-benzene benzene derivative of the formula (Ia) as set forth in claim 1 or 2, wherein a corresponding nitrobenzaldehyde of formula (IIa), nitrophenylacetaldehyde of formula (IIa') or nitrocinnaldehyde of formula (IIa"):
(IIa), (IIa'), (IIa'), where X is defined as in claim 1, is condensed under dehydrogenating conditions with a compound (IIb):
(IIb) where Y and Z are defined as in claim 1, and the compound of the formula (Ia) that is so obtained with an unsaturated side chain is recovered or hydrogenated or halogenated or dehydrohalogenated after addition of halogen, or the corresponding halogen-free starting compound (X=H) is subjected to the same reaction condition and halogen is then introduced into the molecule.
(IIa), (IIa'), (IIa'), where X is defined as in claim 1, is condensed under dehydrogenating conditions with a compound (IIb):
(IIb) where Y and Z are defined as in claim 1, and the compound of the formula (Ia) that is so obtained with an unsaturated side chain is recovered or hydrogenated or halogenated or dehydrohalogenated after addition of halogen, or the corresponding halogen-free starting compound (X=H) is subjected to the same reaction condition and halogen is then introduced into the molecule.
4. An aniline derivative of the general formula (Ib):
(Ib) where:
B is -CH2-, -CH2-CHR1-, -CH2-CHR1-CH2-,-CH=,-CH=CR1-or -CH=CR1-CH=, R1 denoting -H, -Cl, -Br or -CH3, D is or , depending on the terminal group for B, X is -H, -Cl or -Br Y is -H, C1-C7-alkyl, -Cl, -Br, -CN, CONH2 or -CO2R2, R2 denoting H, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, C1-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, .alpha.-phenylethyl, .alpha.-phenylpropyl, C2-C4-alkyl which is mono- to tri-substituted by F or C1, or allyl which is substituted by -CH3 or -C1;
Z is -COOR2, -CONR3R4, or -COR2, where R3 and R4 are each H or C1-C4-alkyl, or together form a 5- or 6-membered cycloaliphatic ring whose carbon chain may be interrupted by an oxygen atom, with the exception of 5-amino-2-chlorocinnamic acid and with the proviso that:
Z is not -COOR2 with R2 denoting hydrogen, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl or C1-C4-alkyl-mercapto-C2-C4-alkyl when:
B is -CH=CR1-, R1 is -CH3, D is and, at the same time, Y is hydrogen; or B is -CH=CR1-CH=, R1 is -H or -CH3, D is and, at the same time, Y is hydrogen or C1-C4-alkyl.
(Ib) where:
B is -CH2-, -CH2-CHR1-, -CH2-CHR1-CH2-,-CH=,-CH=CR1-or -CH=CR1-CH=, R1 denoting -H, -Cl, -Br or -CH3, D is or , depending on the terminal group for B, X is -H, -Cl or -Br Y is -H, C1-C7-alkyl, -Cl, -Br, -CN, CONH2 or -CO2R2, R2 denoting H, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl, C1-C4-alkylmercapto-C2-C4-alkyl, propargyl, benzyl, .alpha.-phenylethyl, .alpha.-phenylpropyl, C2-C4-alkyl which is mono- to tri-substituted by F or C1, or allyl which is substituted by -CH3 or -C1;
Z is -COOR2, -CONR3R4, or -COR2, where R3 and R4 are each H or C1-C4-alkyl, or together form a 5- or 6-membered cycloaliphatic ring whose carbon chain may be interrupted by an oxygen atom, with the exception of 5-amino-2-chlorocinnamic acid and with the proviso that:
Z is not -COOR2 with R2 denoting hydrogen, C1-C6-alkyl, C5-C6-cycloalkyl, C1-C4-alkoxy-C2-C4-alkyl or C1-C4-alkyl-mercapto-C2-C4-alkyl when:
B is -CH=CR1-, R1 is -CH3, D is and, at the same time, Y is hydrogen; or B is -CH=CR1-CH=, R1 is -H or -CH3, D is and, at the same time, Y is hydrogen or C1-C4-alkyl.
5. The aniline derivative of the general formula (Ib) as defined in claim 4, wherein X is -Cl or -Br.
6. A process for the manufacture of an aniline derivative of the formula (Ib) as set forth in claim 4 or 5, wherein a nitro derivative (Ia) as set forth in claim 1 is reduced to obtain the corresponding aniline derivative.
7. A process as set forth in claim 6, wherein use is made of iron powder as reducing agent.
8. A process as set forth in claim 6, wherein use is made of hydrogen in the presence of a hydrogenation agent as reducing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000616913A CA1339688C (en) | 1986-02-07 | 1994-09-01 | N-substituted 3,4,5,6-tetrahydrophtalimides and their intermediates |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3603789.3 | 1986-02-07 | ||
| DE19863603789 DE3603789A1 (en) | 1986-02-07 | 1986-02-07 | N-SUBSTITUTED 3,4,5,6-TETRAHYDROPHTHALIMIDES |
| CA000528764A CA1337657C (en) | 1986-02-07 | 1987-02-02 | N-substituted 3,4,5,6-tetrahydrophthalimides and their intermediates |
| CA000616913A CA1339688C (en) | 1986-02-07 | 1994-09-01 | N-substituted 3,4,5,6-tetrahydrophtalimides and their intermediates |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000528764A Division CA1337657C (en) | 1986-02-07 | 1987-02-02 | N-substituted 3,4,5,6-tetrahydrophthalimides and their intermediates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339688C true CA1339688C (en) | 1998-02-24 |
Family
ID=25671225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000616913A Expired - Fee Related CA1339688C (en) | 1986-02-07 | 1994-09-01 | N-substituted 3,4,5,6-tetrahydrophtalimides and their intermediates |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1339688C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8980937B2 (en) | 2007-04-23 | 2015-03-17 | Bayer Cropscience Ag | Insecticidal aryl pyrrolidines |
| US9266830B2 (en) | 2007-04-23 | 2016-02-23 | Bayer Intellectual Property Gmbh | Pesticidal arylpyrrolidines |
-
1994
- 1994-09-01 CA CA000616913A patent/CA1339688C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8980937B2 (en) | 2007-04-23 | 2015-03-17 | Bayer Cropscience Ag | Insecticidal aryl pyrrolidines |
| US9266830B2 (en) | 2007-04-23 | 2016-02-23 | Bayer Intellectual Property Gmbh | Pesticidal arylpyrrolidines |
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