CA1084937A - Process for the manufacture of iso-imides or mixtures of iso-imides and imides - Google Patents
Process for the manufacture of iso-imides or mixtures of iso-imides and imidesInfo
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- CA1084937A CA1084937A CA271,440A CA271440A CA1084937A CA 1084937 A CA1084937 A CA 1084937A CA 271440 A CA271440 A CA 271440A CA 1084937 A CA1084937 A CA 1084937A
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
- C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/90—Benzo [c] furans; Hydrogenated benzo [c] furans with an oxygen atom in position 1 and a nitrogen atom in position 3, or vice versa
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyrrole Compounds (AREA)
- Indole Compounds (AREA)
- Furan Compounds (AREA)
Abstract
Abstract of the Disclosure A process for the manufacture of iso-imides of the formula (I) and mixtures of iso-imides of formula (I) and imides of formula (Ia) wherein A is -CH=CH- or , n is 1 or 2 and Q repre-sents phenyl, 1- or 2-naphthyl, phenylene or naphthylene or certain such substituted groups, is described by reacting corresponding amide-acids with ketene at temperatures of about -10°C to +80°C. According to the process of the inven-tion, the iso-imides or mixtures of iso-imides and imides can be manufactured in a simple, economical manner and in good to very good yields. The acetic anhydride formed during the reaction with ketene can easily be recovered.
ABSTRACT OF THE DISCLOSURE: Bisdithiocarbamate esters of di-lower alkyl formals and related compounds are disclosed. The final products are useful a rubber cure accelerators, biocides, antioxidants, corrosion inhibitors, and sulfur bearing oil additives.
ABSTRACT OF THE DISCLOSURE: Bisdithiocarbamate esters of di-lower alkyl formals and related compounds are disclosed. The final products are useful a rubber cure accelerators, biocides, antioxidants, corrosion inhibitors, and sulfur bearing oil additives.
Description
~08~937 The present invention relates to a process for the manufacture of iso-imides or mixtures of iso-imides and imides.
Various processes for the manufacture of N-substituted isomaleimides and isophthalimides and of N,N'-bis-isomaleimides and N,N'-bis-isophthalimides are known from the literature.
Thus, N-substituted maleamic or phthalamic acids and also N,N-bis-maleamic acids or N,N'-bis-phthalamic acids can be converted into the corresponding iso-imides in the presence of various dehydrating agents, such as acetic anhydride, trifluoroacetic anhydride, acetyl chloride, thionyl chloride or dichloroacetyl chloride, preferably with the additional use of a tertiary amine, such as triethylamine, or in the presence of carbodi-imides, for example, dicyclohexylcarbodiimide ~compare U.S.
Patent Specifications 2, 995 5 577, 2,998,429, 3,035,065 and 7,472,817 and also J. Org. ~hem., 28, 2, 018-2,024 (1963), 34,
Various processes for the manufacture of N-substituted isomaleimides and isophthalimides and of N,N'-bis-isomaleimides and N,N'-bis-isophthalimides are known from the literature.
Thus, N-substituted maleamic or phthalamic acids and also N,N-bis-maleamic acids or N,N'-bis-phthalamic acids can be converted into the corresponding iso-imides in the presence of various dehydrating agents, such as acetic anhydride, trifluoroacetic anhydride, acetyl chloride, thionyl chloride or dichloroacetyl chloride, preferably with the additional use of a tertiary amine, such as triethylamine, or in the presence of carbodi-imides, for example, dicyclohexylcarbodiimide ~compare U.S.
Patent Specifications 2, 995 5 577, 2,998,429, 3,035,065 and 7,472,817 and also J. Org. ~hem., 28, 2, 018-2,024 (1963), 34,
2,275-2,279 (1969) and 36, 821-823 (1971)]. According to U.S. Patent Specification 2,980,701, ammonium salts of N-substituted maleamic acids can also be converted into the corresponding iso-imides in the presence of esters of acid halides, such as ethyl chloroformate.
These known processes are relatively involved and in some cases also require expensive dehydrating agents. Above all, however, with these processes considerable amounts of one or more by-products are obtained, the working up of which, if it is possible at all, is very laborious and costly. Finally, the elimination, in a manner which meets the current regulations for environmental protection, of by-products which cannot be ~.
~L~8~937 utilised again, for example the elimination of the salts obtained when the reaction is carried out in the presence of acetyl chloride, acetic anhydride or trifluoroacetic anhydride and a tertiary amine, is frequently problematical and extremely expensive.
It has now been found that it is possible, whilst avoiding the abovementioned disadvantages, to manufacture iso-imides of the formula . _l _ A / C \O (I) \C/
_ _ _ Q
n or mixtures of iso-imides of the formula I and imides of the formula Ia l A/\ N -1 Q (In) lCI/
. O n in which A represents -CH=CH- or ~ , n represents the number 1 or 2 and, when n = 1, Q represents an unsubstituted or substi-tuted aryl group, and when n = 2, Q represents an unsubstituted or substituted arylene group or a group of the formulae
These known processes are relatively involved and in some cases also require expensive dehydrating agents. Above all, however, with these processes considerable amounts of one or more by-products are obtained, the working up of which, if it is possible at all, is very laborious and costly. Finally, the elimination, in a manner which meets the current regulations for environmental protection, of by-products which cannot be ~.
~L~8~937 utilised again, for example the elimination of the salts obtained when the reaction is carried out in the presence of acetyl chloride, acetic anhydride or trifluoroacetic anhydride and a tertiary amine, is frequently problematical and extremely expensive.
It has now been found that it is possible, whilst avoiding the abovementioned disadvantages, to manufacture iso-imides of the formula . _l _ A / C \O (I) \C/
_ _ _ Q
n or mixtures of iso-imides of the formula I and imides of the formula Ia l A/\ N -1 Q (In) lCI/
. O n in which A represents -CH=CH- or ~ , n represents the number 1 or 2 and, when n = 1, Q represents an unsubstituted or substi-tuted aryl group, and when n = 2, Q represents an unsubstituted or substituted arylene group or a group of the formulae
- 3 -1~84937 in which X denotes the bridge member -O-, -S-, -S-S-, -S02-, -CH2-, -CO- or CH~
--C--and the substituents on the aryl or arylene groups Q are free from acid hydrogen atoms, in a simple, economical manner and in good to very good yields by reacting an amide-acid of the for-mula II
~ OOH
A .
CO~ v _ Q (II) n in which that stated under formula I applies in respect of A, Qand n, with ketene at a temperature of about -10C to +80C.
A pre~erably represents -CH=CH-.
The aryl or arylene groups represented by Q are, in parti-cular, phenyl, l- or 2-naphthyl, phenylene or naphthylene groups, especially the 1,3- or 1,4-phenylene group and 1,2-, 1,8- or Z,3-naphthylene group. Groups of this type can be unsubstituted or substituted. Possible substituents on the aryl or arylene groups Q which are free from acid hydrogen atoms are, for example, those which follow: halogen atoms, for example F, Cl, Br and I; alkyl groups, especially those with 1-8 carbon atoms;
halogenoalkyl groups with 1-3 carbon atoms, such as the tri-fluoromethyl groups; alkylthio and N,N-dialkylamino groups, each with, preferably, 1-4 carbon atoms in the alkyl parts;
~084937 alkoxy groups, above all those with 1-4 carbon atoms; phenoxy groups; alkoxycarbonyl and alkanoyl groups with, preferably, 2-5 carbon atoms, such as the methoxycarbonyl, ethoxycarbonyl and n-butoxycarbonyl group and the acetyl and propionyl group;
phenylsulphonyl and alkylsulphonyl groups, the latter prefer-ably containing 1-4 carbon atoms; and cyano and nitro groups.
Aryl and arylene groups Q can contain 1 to 3, and pre~erably 1 or 2, substituents of this type. When n = 1, Q preferably represents the 1- or 2-naphthyl group or a phenyl group which is substituted by one or two halogen atoms, especially chlorine atoms, one or two alkyl groups, each with 1-4, and especially 1 or 2, carbon atoms in the alkyl parts, or a trifluoromethyl, nitro or cyano group. When n = 1, Q particularly preferen-tially denotes an unsubstituted phenyl group.
If n denotes the number 2, Q preferably represents the 1,3-phenylene group or 4,4'-diphenyl ether group, but above all the 4,4'-diphenylmethane group.
If the group Q has highly electronegative substituents, such as halogen atoms or nitro, cyano, alkyl or phenylsulphonyl groups, it is possible, depending on the position of these sub-stituents on the radical Q, for relatively small or relatively large amounts of the corresponding imides of the formula Ia also to be formed, in addition to the iso-imides of the ~ormula I, by the process according to the invention. The group Q
therefore preferably has at most 2 of the highly electronegative substituents mentioned.
~ he reaction according to the invention is advantageously - -` 108~937 carried out in the presence of an organic solvent which is inert under the reaction conditions. Examples of suitable solvents are optionally chlorinated aromatic hydrocarbons, such as ben-zene, toluene, xylenes and chlorobenzene, chlorinated aliphatic hydrocarbons, such as chloroform, methylene chloride and 1,2-dichloroethane, aliphatic and cycloaliphatic ketones, such as acetone, methyl ethyl ketone and cyclohexanone, and also ali-phatic and cyclic ethers, such as diethyl ether and dioxane.
Particularly preferentially, the reaction is carried out in acetic anhydride, on the one hand because particularly high yields are achieved by this means and on the other hand because the acetic anhydride formed during the reaction with the ketene can, after distillation, be re-used for further reactions.
The amide-acids of the formula II are known or can be manufactured according to methods which are in themselves known, for example by reacting maleic anhydride or phthalic anhydride with monoamines or diamines of the formula H2N-Q or H2N-Q-NH2 respectively.
The amide-acids of the formula II and ketene are prefer-ably employed in a stoichiometric amount, that is to say when n = 1, the amide-acid of the formula II and ketene are prefer-ably employed in a molar ratio of 1:2, whilst when n = 2, the molar ratio of the amide-acid of the formula II to ketene is advantageously 1:4. However, it is also possible to use a small excess of one or other of the reactants, for example to use an up to about 10% strength molar excess of the amide-acid o~ the formula II or ketene.
iO84937 The acetic anhydride formed during the reaction can, as already mentioned, be recovered in a very simple manner by means of distillation and optionally re-used for further reac-tions.
The preferred reaction temperatures are between about 0 and f60C. After the reaction has ended, the iso-imides of the formula I, or the mixtures of iso-imides of the formula I and imides of the formula Ia, can be isolated, and optionally purified, in a manner which is in itself known, for example by filtration, distillation and/or evaporation and subsequent washing with sodium bicarbonate solution and water or recry-stallisation from suitable solvents, such as toluene, cyclo-hexane, acetone and methyl ethyl ~etone.
Iso-imides which can be manufactured by the process according to the invention are in themselves known. N-substituted isomaleimides and N,N'-disubstituted bis-isomale-imides or bis-isophthalimides can be reacted with diamines, for example by the methods described in U.S. Patent Specifications 2,980,701, 2,995,577, 2,998,429, 3,035,065 and 3,144,435 and Journal of Polymer Science: Polymer Chemistry Edition, 13, 1,691-1,698 (1975), to give linear polymers. N-substituted isophthalimidesareused, for example, as intermediate products for the manufacture of pharmaceuticals [compare, for example, J. Med. Chem., 10, 982 (1967)]. Iso-imides of the formula I, wherein A represents the group -CH=CH-, can also be used as fungicides or defoliating agents.
Finally, the iso-imides of the formula I manufactured iC~84937 according to the invention can also be isomerised in a manner which is in itself known to the corresponding imides of the formula Ia, for example by treating them with catalytic amounts of an alkali metal salt or ammonium salt of lower fatty acids, such as sodium acetate (see, for example, U.S. Patent Specifi-cation 2,980,694). The imides of the formula Ia, in turn, are used, inter alia, as insecticides and/or for the manufacture of polymers.
Example l OOH ~
+ 2 C~2=C=0 ~ 0 + (CH3C0)20 19.2 g (0.1 mol) of N-phenylmaleamic acid are suspended in 100 ml of acetic anhydride. Using a heating bath, the suspension is warmed to 45C, whilst stirring, the heating bath is then removed and about 0.2 mol of ketene are passed into the suspension. The temperature then rises to 50-52C and a clear yellow solution forms. This solution is concentrated in a rotary evaporator. The residual yellow oil is poured onto ice water. The precipitate hereupon formed is filtered off, washed with saturated sodium bicarbonate solution and water and dried in vacuo over phosphorus pentoxide. This gives 16.0 g (92% of theory) of N-phenyl-isomaleimide; melting point 58-61C.
I~ spectrum (CHC13): Ama~ inter alia 5.55/5.95 ~.
Analysis for ClO~ N~2 (molecular weight 173.17):
1()84937 calculated: C 69.36% H 4.08% N 8.0~/o found: C 69.37% H 4.24% N 8.04%
The acetic anhydride recovered when the solution is concentrated can be re-used after distillation.
Example 2 OOH HOOC
O~H ~ C~2 ~ NHOC 3 ~ 4 Cl~2=C-+ 2 (~H3C0~20 N~CH2~N' ' .
~ 0 g (0.2 mol) of N,N'-4,4'-diphenylmethane-bis-male-amic acid are suspended in 600 ml of acetic anhydride, the suspension is heated to 45C, whilst stirring, and 0.8 mol of ketene are passed in without heating. The temperature then rises to 49-50C. An almost clear yellow-orange solution forms and this is filtered whilst it is still warm The fil-trate is concentrated in a rotary evaporator to about 1/~ of its original volume. The reaction product is then allowed to crystallise out in a refrigerator, the mixture is filtered and the residue is washed with saturated sodium bicarbonate solution and water. The resulting yellow c~ystals are dried in vacuo. This gives 56.7 g (7~/0 of theory) of N,N'-4,4'-diphenylmethane-bis-isomaleimide; melting point 154-155C.
_ g ~084937 IR spectrum (CHC13): AmaX inter alia 5.55/5.95 ~.
Analysis for C21H14N204 (molecular weight 358.~5):
calculated: C 70.39% H 3.94% N 7.82%
found: C 70.34% H 3.95% N 7.650/o The acetic anhydride recovered can be re-used after distillation.
Example 3 N ~ CH3 Analogously to the process described in Example 1, 10.3 g (0.05 mol) of N-p-tolylmaleamic acid in 75 ml of acetic ~nhydride and 0.1 mol of ketene give 8.6 g (92% of theory) of N-p-tolyl-isomaleimide with a melting point of 71-73C.
IR spectrum (CHC13): AmaX inter alia 5.59/5.99 ~.
Analysis for CllHgN02 (molecular weight 187.20):
calculated: C70,58% H 4.85% N 7.48%
found: C70.67% H 4.77% N 7.53%
Example 4 0 ~b C~
Analogously to the process described in Example 1, 26.0 g (0.1 mol) of N-3,5-dichlorophenylmaleamide in 200 ml of acetic anhydride and 0.2 mol of ketene give 23.1 g (95% of . -- 10 --- ~84937 theory) of N-3,5-dichlorophenyl-isomaleimide; melting point 82-85C.
IR spectrum (Nujol): ~max inter alia 5.55/5.80 ~.
Analysis for CloH5C12N02 (molecular weight 242.06):
calculated: C 49.62% H 2.08% N 5.79% Cl 29.2~,~
found: C 49.26% H 2.21% N 5.670/o Cl 28.750,6 Example 5 ~0 + ~\N~No2 Analogously to the procedure described in Example 1, about 0.08 mol of ~etene are introduced into a suspension of 10.0 g (0.042 mol) of N-p-nitrophenylmaleamic acid in 75 ml of acetic anhydride. This gives 8.6 g (94% of theory) of the reaction product which, according to the IR spectrum and NMR
spectrum, consists of a mixture of N-p-nitrophenyl-maleimide and N-p-nitrophenyl-isomaleimide; melting point 97-150C.
IR spectrum (CHC13): ~max inter alia 5.48/5.54/5.90 ~ (iso-imide);
5.78 ~ (imide).
Analysis for CloH6N204 (molecular weight 218.17):
calculated: C 55.05% H 2.77% N 12.84%
found: C 54.75~0 H 2.78% ~ 12.8~/o Example 6 N ~ Cl Analogously to the procedure described in Example 1, 0.6 mol of ketene is passed into a suspension of 67.5 g (0.
mol) of N-p-chlorophenylmaleamic acid in 600 ml of acetic anhydride. This gives 59.4 g (95% of theory) of the reaction product which, according to the IR spectrum, consists in the main of N-p-chlorophenyl-isomaleimide and in small pro-portions of N-p-chlorophenyl-maleimide; melting point 85-95C.
IR spectrum (CHC13): ~max inter alia 5.55/5.95 ~ (iso-imide);
5.70 ~ (imide).
Analysis for CloH6ClN02 (molecular weight 207.62):
calculated: C57.85% H 2.91% N 6.75% Cl 17.08%
found: C57.63% H 3.02% N 6.~2% Cl 17.03%
Example 7 ~ Jo r~ o~
N ~ 0 ~ ~
40 g (o.i mol) of N,N'-(4,4'-diphenyl ether)-bis-maleamic acid are suspended in 400 ml of acetic anhydride.
The suspension is warmed to 45C, whilst stirring. Sub-sequently, the heating is removed and 0.4 mol of ketene is passed in. The temperature then rises to 52C. An orange-yellow suspension is obtained and this is filtered whilst still warm (conversion 88%; 5 g of residue consisting of unconverted bis-maleamic acid3. The filtrate is concen-trated to dryness in a rotary evaporator at a bath te~r.-ra.;ure o~ 60C.
~084937 The residue is suspended in 100 ml of diethyl ether, the suspension is filtered and the product is rinsed with 20 ml of diethyl ether and dried in vacuo over potassium hydroxide.
This gives 25.5 g (80% of theory, based on an 88% conversion) of orange-yellow N,N'-(4,4'-diphenyl ether)-bis-isomaleimide;
melting point 155-159C.
IR spectrum (CHC13): A~aX inter alia 5.55/5.95 !1-Analysis for C20Hl2N2o5 (molecular weight 360.33):
calculated: C 66.670~ H 3.36% N 7.78%
found: C 66.14% H 3.51% N- 7.690/o Example 8 n ,COOH HOOC
i ~ ~ 4 CH2=c=o ~ ~ ~0 ~¦ ~ 2 (CH3CO) 2 ~CONH ~ N~OC' ~ ~
Analogously to the procedure described in Example 7, 30.4 g (0.1 mol) of N,N'-1,3-phenylene-bis-maleamic acid in 400 ml of acetic anhydride and 0.4 mol of ketene give 22.0 g (82% of theory) of N,N'-1,3-phenylene-bis-isomaleimide;
melting point 172-177C.
IR spectrum (CHC13): i~maX inter alia 5.55/5.95 ~.
Analysis for C14H8N204 (molecular weight 268.23):
calculated: C 62.690~o H 3.01% N 10.44%
found: C 62.29% H 3.02% N 10.60%
.
iO8~937 Example 9 0 ~ + ~ ~ 52 ~ - ~
40.5 g (0.091 mol) of N,N'-4,4'-diphenylsulphone-bis-maleamic acid are suspended in 400 ml of acetic anhydride.
Using a heating bath, the resulting suspension is warmed to 45C, whilst stirring, the heating bath is then removed and 0.4 mol of ketene is passed into the suspension. The temperature then rises to 48C. Unconverted amide-acid (0.500 g, that is to say 99% conversion) is removed by filter-ing off and the filtrate is evaporated in a rotary evaporator.
The yellow solid residue is suspended in saturated sodium bicarbonate solution, the suspension is filtered and the pro-duct is rinsed with water. After drying in vacuo at 20-25C, this gives 34.8 g (95% of theory) of a product which, according to the IR spectrum, consists in the main of N,N'-
--C--and the substituents on the aryl or arylene groups Q are free from acid hydrogen atoms, in a simple, economical manner and in good to very good yields by reacting an amide-acid of the for-mula II
~ OOH
A .
CO~ v _ Q (II) n in which that stated under formula I applies in respect of A, Qand n, with ketene at a temperature of about -10C to +80C.
A pre~erably represents -CH=CH-.
The aryl or arylene groups represented by Q are, in parti-cular, phenyl, l- or 2-naphthyl, phenylene or naphthylene groups, especially the 1,3- or 1,4-phenylene group and 1,2-, 1,8- or Z,3-naphthylene group. Groups of this type can be unsubstituted or substituted. Possible substituents on the aryl or arylene groups Q which are free from acid hydrogen atoms are, for example, those which follow: halogen atoms, for example F, Cl, Br and I; alkyl groups, especially those with 1-8 carbon atoms;
halogenoalkyl groups with 1-3 carbon atoms, such as the tri-fluoromethyl groups; alkylthio and N,N-dialkylamino groups, each with, preferably, 1-4 carbon atoms in the alkyl parts;
~084937 alkoxy groups, above all those with 1-4 carbon atoms; phenoxy groups; alkoxycarbonyl and alkanoyl groups with, preferably, 2-5 carbon atoms, such as the methoxycarbonyl, ethoxycarbonyl and n-butoxycarbonyl group and the acetyl and propionyl group;
phenylsulphonyl and alkylsulphonyl groups, the latter prefer-ably containing 1-4 carbon atoms; and cyano and nitro groups.
Aryl and arylene groups Q can contain 1 to 3, and pre~erably 1 or 2, substituents of this type. When n = 1, Q preferably represents the 1- or 2-naphthyl group or a phenyl group which is substituted by one or two halogen atoms, especially chlorine atoms, one or two alkyl groups, each with 1-4, and especially 1 or 2, carbon atoms in the alkyl parts, or a trifluoromethyl, nitro or cyano group. When n = 1, Q particularly preferen-tially denotes an unsubstituted phenyl group.
If n denotes the number 2, Q preferably represents the 1,3-phenylene group or 4,4'-diphenyl ether group, but above all the 4,4'-diphenylmethane group.
If the group Q has highly electronegative substituents, such as halogen atoms or nitro, cyano, alkyl or phenylsulphonyl groups, it is possible, depending on the position of these sub-stituents on the radical Q, for relatively small or relatively large amounts of the corresponding imides of the formula Ia also to be formed, in addition to the iso-imides of the ~ormula I, by the process according to the invention. The group Q
therefore preferably has at most 2 of the highly electronegative substituents mentioned.
~ he reaction according to the invention is advantageously - -` 108~937 carried out in the presence of an organic solvent which is inert under the reaction conditions. Examples of suitable solvents are optionally chlorinated aromatic hydrocarbons, such as ben-zene, toluene, xylenes and chlorobenzene, chlorinated aliphatic hydrocarbons, such as chloroform, methylene chloride and 1,2-dichloroethane, aliphatic and cycloaliphatic ketones, such as acetone, methyl ethyl ketone and cyclohexanone, and also ali-phatic and cyclic ethers, such as diethyl ether and dioxane.
Particularly preferentially, the reaction is carried out in acetic anhydride, on the one hand because particularly high yields are achieved by this means and on the other hand because the acetic anhydride formed during the reaction with the ketene can, after distillation, be re-used for further reactions.
The amide-acids of the formula II are known or can be manufactured according to methods which are in themselves known, for example by reacting maleic anhydride or phthalic anhydride with monoamines or diamines of the formula H2N-Q or H2N-Q-NH2 respectively.
The amide-acids of the formula II and ketene are prefer-ably employed in a stoichiometric amount, that is to say when n = 1, the amide-acid of the formula II and ketene are prefer-ably employed in a molar ratio of 1:2, whilst when n = 2, the molar ratio of the amide-acid of the formula II to ketene is advantageously 1:4. However, it is also possible to use a small excess of one or other of the reactants, for example to use an up to about 10% strength molar excess of the amide-acid o~ the formula II or ketene.
iO84937 The acetic anhydride formed during the reaction can, as already mentioned, be recovered in a very simple manner by means of distillation and optionally re-used for further reac-tions.
The preferred reaction temperatures are between about 0 and f60C. After the reaction has ended, the iso-imides of the formula I, or the mixtures of iso-imides of the formula I and imides of the formula Ia, can be isolated, and optionally purified, in a manner which is in itself known, for example by filtration, distillation and/or evaporation and subsequent washing with sodium bicarbonate solution and water or recry-stallisation from suitable solvents, such as toluene, cyclo-hexane, acetone and methyl ethyl ~etone.
Iso-imides which can be manufactured by the process according to the invention are in themselves known. N-substituted isomaleimides and N,N'-disubstituted bis-isomale-imides or bis-isophthalimides can be reacted with diamines, for example by the methods described in U.S. Patent Specifications 2,980,701, 2,995,577, 2,998,429, 3,035,065 and 3,144,435 and Journal of Polymer Science: Polymer Chemistry Edition, 13, 1,691-1,698 (1975), to give linear polymers. N-substituted isophthalimidesareused, for example, as intermediate products for the manufacture of pharmaceuticals [compare, for example, J. Med. Chem., 10, 982 (1967)]. Iso-imides of the formula I, wherein A represents the group -CH=CH-, can also be used as fungicides or defoliating agents.
Finally, the iso-imides of the formula I manufactured iC~84937 according to the invention can also be isomerised in a manner which is in itself known to the corresponding imides of the formula Ia, for example by treating them with catalytic amounts of an alkali metal salt or ammonium salt of lower fatty acids, such as sodium acetate (see, for example, U.S. Patent Specifi-cation 2,980,694). The imides of the formula Ia, in turn, are used, inter alia, as insecticides and/or for the manufacture of polymers.
Example l OOH ~
+ 2 C~2=C=0 ~ 0 + (CH3C0)20 19.2 g (0.1 mol) of N-phenylmaleamic acid are suspended in 100 ml of acetic anhydride. Using a heating bath, the suspension is warmed to 45C, whilst stirring, the heating bath is then removed and about 0.2 mol of ketene are passed into the suspension. The temperature then rises to 50-52C and a clear yellow solution forms. This solution is concentrated in a rotary evaporator. The residual yellow oil is poured onto ice water. The precipitate hereupon formed is filtered off, washed with saturated sodium bicarbonate solution and water and dried in vacuo over phosphorus pentoxide. This gives 16.0 g (92% of theory) of N-phenyl-isomaleimide; melting point 58-61C.
I~ spectrum (CHC13): Ama~ inter alia 5.55/5.95 ~.
Analysis for ClO~ N~2 (molecular weight 173.17):
1()84937 calculated: C 69.36% H 4.08% N 8.0~/o found: C 69.37% H 4.24% N 8.04%
The acetic anhydride recovered when the solution is concentrated can be re-used after distillation.
Example 2 OOH HOOC
O~H ~ C~2 ~ NHOC 3 ~ 4 Cl~2=C-+ 2 (~H3C0~20 N~CH2~N' ' .
~ 0 g (0.2 mol) of N,N'-4,4'-diphenylmethane-bis-male-amic acid are suspended in 600 ml of acetic anhydride, the suspension is heated to 45C, whilst stirring, and 0.8 mol of ketene are passed in without heating. The temperature then rises to 49-50C. An almost clear yellow-orange solution forms and this is filtered whilst it is still warm The fil-trate is concentrated in a rotary evaporator to about 1/~ of its original volume. The reaction product is then allowed to crystallise out in a refrigerator, the mixture is filtered and the residue is washed with saturated sodium bicarbonate solution and water. The resulting yellow c~ystals are dried in vacuo. This gives 56.7 g (7~/0 of theory) of N,N'-4,4'-diphenylmethane-bis-isomaleimide; melting point 154-155C.
_ g ~084937 IR spectrum (CHC13): AmaX inter alia 5.55/5.95 ~.
Analysis for C21H14N204 (molecular weight 358.~5):
calculated: C 70.39% H 3.94% N 7.82%
found: C 70.34% H 3.95% N 7.650/o The acetic anhydride recovered can be re-used after distillation.
Example 3 N ~ CH3 Analogously to the process described in Example 1, 10.3 g (0.05 mol) of N-p-tolylmaleamic acid in 75 ml of acetic ~nhydride and 0.1 mol of ketene give 8.6 g (92% of theory) of N-p-tolyl-isomaleimide with a melting point of 71-73C.
IR spectrum (CHC13): AmaX inter alia 5.59/5.99 ~.
Analysis for CllHgN02 (molecular weight 187.20):
calculated: C70,58% H 4.85% N 7.48%
found: C70.67% H 4.77% N 7.53%
Example 4 0 ~b C~
Analogously to the process described in Example 1, 26.0 g (0.1 mol) of N-3,5-dichlorophenylmaleamide in 200 ml of acetic anhydride and 0.2 mol of ketene give 23.1 g (95% of . -- 10 --- ~84937 theory) of N-3,5-dichlorophenyl-isomaleimide; melting point 82-85C.
IR spectrum (Nujol): ~max inter alia 5.55/5.80 ~.
Analysis for CloH5C12N02 (molecular weight 242.06):
calculated: C 49.62% H 2.08% N 5.79% Cl 29.2~,~
found: C 49.26% H 2.21% N 5.670/o Cl 28.750,6 Example 5 ~0 + ~\N~No2 Analogously to the procedure described in Example 1, about 0.08 mol of ~etene are introduced into a suspension of 10.0 g (0.042 mol) of N-p-nitrophenylmaleamic acid in 75 ml of acetic anhydride. This gives 8.6 g (94% of theory) of the reaction product which, according to the IR spectrum and NMR
spectrum, consists of a mixture of N-p-nitrophenyl-maleimide and N-p-nitrophenyl-isomaleimide; melting point 97-150C.
IR spectrum (CHC13): ~max inter alia 5.48/5.54/5.90 ~ (iso-imide);
5.78 ~ (imide).
Analysis for CloH6N204 (molecular weight 218.17):
calculated: C 55.05% H 2.77% N 12.84%
found: C 54.75~0 H 2.78% ~ 12.8~/o Example 6 N ~ Cl Analogously to the procedure described in Example 1, 0.6 mol of ketene is passed into a suspension of 67.5 g (0.
mol) of N-p-chlorophenylmaleamic acid in 600 ml of acetic anhydride. This gives 59.4 g (95% of theory) of the reaction product which, according to the IR spectrum, consists in the main of N-p-chlorophenyl-isomaleimide and in small pro-portions of N-p-chlorophenyl-maleimide; melting point 85-95C.
IR spectrum (CHC13): ~max inter alia 5.55/5.95 ~ (iso-imide);
5.70 ~ (imide).
Analysis for CloH6ClN02 (molecular weight 207.62):
calculated: C57.85% H 2.91% N 6.75% Cl 17.08%
found: C57.63% H 3.02% N 6.~2% Cl 17.03%
Example 7 ~ Jo r~ o~
N ~ 0 ~ ~
40 g (o.i mol) of N,N'-(4,4'-diphenyl ether)-bis-maleamic acid are suspended in 400 ml of acetic anhydride.
The suspension is warmed to 45C, whilst stirring. Sub-sequently, the heating is removed and 0.4 mol of ketene is passed in. The temperature then rises to 52C. An orange-yellow suspension is obtained and this is filtered whilst still warm (conversion 88%; 5 g of residue consisting of unconverted bis-maleamic acid3. The filtrate is concen-trated to dryness in a rotary evaporator at a bath te~r.-ra.;ure o~ 60C.
~084937 The residue is suspended in 100 ml of diethyl ether, the suspension is filtered and the product is rinsed with 20 ml of diethyl ether and dried in vacuo over potassium hydroxide.
This gives 25.5 g (80% of theory, based on an 88% conversion) of orange-yellow N,N'-(4,4'-diphenyl ether)-bis-isomaleimide;
melting point 155-159C.
IR spectrum (CHC13): A~aX inter alia 5.55/5.95 !1-Analysis for C20Hl2N2o5 (molecular weight 360.33):
calculated: C 66.670~ H 3.36% N 7.78%
found: C 66.14% H 3.51% N- 7.690/o Example 8 n ,COOH HOOC
i ~ ~ 4 CH2=c=o ~ ~ ~0 ~¦ ~ 2 (CH3CO) 2 ~CONH ~ N~OC' ~ ~
Analogously to the procedure described in Example 7, 30.4 g (0.1 mol) of N,N'-1,3-phenylene-bis-maleamic acid in 400 ml of acetic anhydride and 0.4 mol of ketene give 22.0 g (82% of theory) of N,N'-1,3-phenylene-bis-isomaleimide;
melting point 172-177C.
IR spectrum (CHC13): i~maX inter alia 5.55/5.95 ~.
Analysis for C14H8N204 (molecular weight 268.23):
calculated: C 62.690~o H 3.01% N 10.44%
found: C 62.29% H 3.02% N 10.60%
.
iO8~937 Example 9 0 ~ + ~ ~ 52 ~ - ~
40.5 g (0.091 mol) of N,N'-4,4'-diphenylsulphone-bis-maleamic acid are suspended in 400 ml of acetic anhydride.
Using a heating bath, the resulting suspension is warmed to 45C, whilst stirring, the heating bath is then removed and 0.4 mol of ketene is passed into the suspension. The temperature then rises to 48C. Unconverted amide-acid (0.500 g, that is to say 99% conversion) is removed by filter-ing off and the filtrate is evaporated in a rotary evaporator.
The yellow solid residue is suspended in saturated sodium bicarbonate solution, the suspension is filtered and the pro-duct is rinsed with water. After drying in vacuo at 20-25C, this gives 34.8 g (95% of theory) of a product which, according to the IR spectrum, consists in the main of N,N'-
4,4'-diphenylsulphone-bis-maleimide and in smaller proportions of N,N'-4,4'-diphenylsulphone-bis-isomaleimide; melting point 195-205~.
IR spectrum (CHC13): AmaX inter alia 5.55/5.90 ~ (iso-imide);
IR spectrum (CHC13): AmaX inter alia 5.55/5.90 ~ (iso-imide);
5.80 ~ (imide).
Analysis ~or C20H12N206~ (molecular weight 408.38):
calculated: C 58 82% H 2.96% N 6.86% S 7 . 85%
- ~4 -~' ' found: C 58. 62% H 3.18% N 6 . 66~o S 7 . 76%
Example 10 40 g (0.1 mol) of N,N'-4,4'-diphenylmethane-bis-male-amic acid are suspended in 150 ml of acetone. 0.4 mol of ketene is passed in at 35C. The resulting yellow suspen-sion is filtered (15.2 g of residue consisting of unconverted bis-maleamic acid, conversion = 62C~)~ the filtrate is poured onto ice water and the precipitate is filtered off, washed with saturated sodium bicarbonate solution and finally dried in vacuo at 20-25C. This gives 20.8 g (92% of theory, based on a 62% conversion) of N,N'-4,4'-diphenylmethane-bis-iso-maleimide.
IR spectrum (CHC13): ~max inter alia 5.55/5.95 Example 11 2 CH2-C=O--~ ~ + (CH3CO)2O
`CON~ ~ CH3 . ~ ~ H3 25.6 g (0.1 mol) of N-p-tolyl-phthalamic acid are sus-pended in 250 ml of acetic anhydride at 20-25C. 0.2 mol of ketene is then passed in and the temperature rises to 33C.
A clear, pale yellowish solution forms and is concentrated in vacuo in a rotary evaporator (bath temperature 60C) and the residue is suspended in saturated sodium bicarbonate solution, the suspen~ion is filtered and the product is washed with water.
After drying in vacuo at 40C, this gives 21.0 g (88% of theory) of ~-p-tolyl-isophthalimide; melting point 116-11~C.
1~84937 IR spectrum (CHC13): AmaX inter alia 5.55/5.85 ~.
Analysis for C15HllN02 (molecular weight 237.26):
calculated: C 75.94% H 4.67% N 5.91%
found: C 75.64% H 4.65% N 6.01%
Example 12 COOH
+ 2 CH2-C=0 ---~ + (C~3CO)20 100.1 g (0.457 mol) of N-(2,6-dimethylphenyl)-maleamic acid are suspended in 750 ml o~ acetic anhydride. Using a heating bath, the suspension is warmed to 30C, the heating bath is then removed and about 0.9 mol of ketene is passed into the suspension, whilst stirring. The temperature then rises to 40C and a yellow homogeneous solution forms. The acetic anhydride is removed in a rotary evaporator, the residue is taken up in benzene and the solution is washed with saturated sodium bicarbonate solution and water, dried and evaporated in a rotary evaporator. This gi~es 90.4 g (98% of theory) of deep yellow crystalline N-(2,6-dimethylphenyl)-isomaleimide ~rith a melting point of 60-62C.
TR spectrum (CHC13): AmaX inter alia 5.50/5.55/5.90 ~.
Analysis f~r C12HllN02 (molecular weight 201.23):
calculated: C 71.63% H 5.51% N 6.96% 0 15.90%
found: C 71.45% H 5.59% N 7.2~,~ 0 15.9
Analysis ~or C20H12N206~ (molecular weight 408.38):
calculated: C 58 82% H 2.96% N 6.86% S 7 . 85%
- ~4 -~' ' found: C 58. 62% H 3.18% N 6 . 66~o S 7 . 76%
Example 10 40 g (0.1 mol) of N,N'-4,4'-diphenylmethane-bis-male-amic acid are suspended in 150 ml of acetone. 0.4 mol of ketene is passed in at 35C. The resulting yellow suspen-sion is filtered (15.2 g of residue consisting of unconverted bis-maleamic acid, conversion = 62C~)~ the filtrate is poured onto ice water and the precipitate is filtered off, washed with saturated sodium bicarbonate solution and finally dried in vacuo at 20-25C. This gives 20.8 g (92% of theory, based on a 62% conversion) of N,N'-4,4'-diphenylmethane-bis-iso-maleimide.
IR spectrum (CHC13): ~max inter alia 5.55/5.95 Example 11 2 CH2-C=O--~ ~ + (CH3CO)2O
`CON~ ~ CH3 . ~ ~ H3 25.6 g (0.1 mol) of N-p-tolyl-phthalamic acid are sus-pended in 250 ml of acetic anhydride at 20-25C. 0.2 mol of ketene is then passed in and the temperature rises to 33C.
A clear, pale yellowish solution forms and is concentrated in vacuo in a rotary evaporator (bath temperature 60C) and the residue is suspended in saturated sodium bicarbonate solution, the suspen~ion is filtered and the product is washed with water.
After drying in vacuo at 40C, this gives 21.0 g (88% of theory) of ~-p-tolyl-isophthalimide; melting point 116-11~C.
1~84937 IR spectrum (CHC13): AmaX inter alia 5.55/5.85 ~.
Analysis for C15HllN02 (molecular weight 237.26):
calculated: C 75.94% H 4.67% N 5.91%
found: C 75.64% H 4.65% N 6.01%
Example 12 COOH
+ 2 CH2-C=0 ---~ + (C~3CO)20 100.1 g (0.457 mol) of N-(2,6-dimethylphenyl)-maleamic acid are suspended in 750 ml o~ acetic anhydride. Using a heating bath, the suspension is warmed to 30C, the heating bath is then removed and about 0.9 mol of ketene is passed into the suspension, whilst stirring. The temperature then rises to 40C and a yellow homogeneous solution forms. The acetic anhydride is removed in a rotary evaporator, the residue is taken up in benzene and the solution is washed with saturated sodium bicarbonate solution and water, dried and evaporated in a rotary evaporator. This gi~es 90.4 g (98% of theory) of deep yellow crystalline N-(2,6-dimethylphenyl)-isomaleimide ~rith a melting point of 60-62C.
TR spectrum (CHC13): AmaX inter alia 5.50/5.55/5.90 ~.
Analysis f~r C12HllN02 (molecular weight 201.23):
calculated: C 71.63% H 5.51% N 6.96% 0 15.90%
found: C 71.45% H 5.59% N 7.2~,~ 0 15.9
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the manufacture of an iso-imide of the formula I
(I) or a mixture of an iso-imide of the formula I and an imide of the formula Ia (Ia) in which A represents -CH=CH- or , n represents the number 1 or 2 And, when n = 1, Q represents a phenyl, 1-naphthyl or 2-naphthyl group, and, when n = 2, Q represents a pheny-lene or naphthylene group, or said phenyl, 1- or 2- naphthyl, phenylene or naphthylene groups substituted by 1 or 2 moieties which are free from acid hydrogen atoms and which are selected from the group consisting of halogen, alkyl with 1 to 8 carbon atoms, halogenoalkyl with 1 to 3 carbon atoms, alkylthio with 1 to 4 carbon atoms, N,N-dialkylamino with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenoxy, alkoxycarbonyl with 2 to 5 carbon atoms, alkanoyl with 2 to 5 carbon atoms, phenylsulphonyl, alkylsulphonyl with 1 to 4 carbon atoms, cyano and nitro, or when n = 2, Q also represents a group of the formula or in which X denotes the bridge member -O-, -S-, -S-S-, -SO2-, -CH2-,-CO- or , by reacting an amide-acid of the formula II
(II) in which that stated under formula I applies in respect of A, and n, with ketene at a temperature of about -10°C to +80°C.
(I) or a mixture of an iso-imide of the formula I and an imide of the formula Ia (Ia) in which A represents -CH=CH- or , n represents the number 1 or 2 And, when n = 1, Q represents a phenyl, 1-naphthyl or 2-naphthyl group, and, when n = 2, Q represents a pheny-lene or naphthylene group, or said phenyl, 1- or 2- naphthyl, phenylene or naphthylene groups substituted by 1 or 2 moieties which are free from acid hydrogen atoms and which are selected from the group consisting of halogen, alkyl with 1 to 8 carbon atoms, halogenoalkyl with 1 to 3 carbon atoms, alkylthio with 1 to 4 carbon atoms, N,N-dialkylamino with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, phenoxy, alkoxycarbonyl with 2 to 5 carbon atoms, alkanoyl with 2 to 5 carbon atoms, phenylsulphonyl, alkylsulphonyl with 1 to 4 carbon atoms, cyano and nitro, or when n = 2, Q also represents a group of the formula or in which X denotes the bridge member -O-, -S-, -S-S-, -SO2-, -CH2-,-CO- or , by reacting an amide-acid of the formula II
(II) in which that stated under formula I applies in respect of A, and n, with ketene at a temperature of about -10°C to +80°C.
2. A process according to Claim 1, wherein an amide-acid of the formula II in which A represents -CH=CH- is used.
3. A process according to Claim 1, wherein an amide-acid of the formula II is used in which n represents the number 1 and Q represents the 1- or 2-naphthyl group, or a phenyl group which is substituted by 1 or 2 halogen atoms, one or 2 alkyl groups, each with 1-4 carbon atoms in the alkyl parts, or a trifluoromethyl, nitro or cyano group.
4. A process according to Claim 3, wherein an amide-acid of the formula II is used in which n represents the number 1 and Q represents a phenyl group which is substituted by one or two alkyl groups each with 1 or 2 carbon atoms in the alkyl parts.
5. A process according to Claim 1, wherein an amide-acid of the formula II is used in which A represents -CH=CH-, n represents the number 1 and Q represents an unsubstituted phenyl group.
6. A process according to Claim 1, wherein an amide-acid of the formula II is used in which A represents -CH=CH-, n represents the number 2 and Q represents the 1,3-phenylene group, the 4,4'-diphenyl ether group or the 4,4'-diphenyl-methane group.
7. A process according to Claim 1, wherein the reaction is carried out in the presence of an organic solvent which is inert under the reaction conditions, selected from the group consisting of aromatic hydrocarbons, chlorinated aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, aliphatic and cycloaliphatic ketones, aliphatic and cyclic ethers and acetic anhydride.
8. A process according to Claim 1, wherein the reaction is carried out in the presence of acetic anhydride.
9. A process according to Claim 1, wherein the reaction is carried out at a temperature between about 0 and 60°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1648/76 | 1976-02-11 | ||
| CH164876A CH598213A5 (en) | 1976-02-11 | 1976-02-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1084937A true CA1084937A (en) | 1980-09-02 |
Family
ID=4215366
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA271,440A Expired CA1084937A (en) | 1976-02-11 | 1977-02-09 | Process for the manufacture of iso-imides or mixtures of iso-imides and imides |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS6055514B2 (en) |
| BE (1) | BE851277A (en) |
| CA (1) | CA1084937A (en) |
| CH (1) | CH598213A5 (en) |
| DE (1) | DE2705186A1 (en) |
| FR (1) | FR2340942A1 (en) |
| GB (1) | GB1523705A (en) |
| NL (1) | NL7701315A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4794190A (en) * | 1987-01-28 | 1988-12-27 | Amoco Corporation | Aromatic maleimide-isomaleimide compound |
| US5892061A (en) * | 1996-12-06 | 1999-04-06 | Mitsui Chemicals, Inc. | Process for preparing isoimides |
| KR20130016041A (en) * | 2011-08-04 | 2013-02-14 | 재단법인 의약바이오컨버젼스연구단 | Novel aniline derivatives and use thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3035065A (en) * | 1959-11-05 | 1962-05-15 | Union Carbide Corp | Isomaleimides and a process for the preparation thereof |
-
1976
- 1976-02-11 CH CH164876A patent/CH598213A5/xx not_active IP Right Cessation
-
1977
- 1977-02-07 GB GB494777A patent/GB1523705A/en not_active Expired
- 1977-02-07 FR FR7703306A patent/FR2340942A1/en active Granted
- 1977-02-08 DE DE19772705186 patent/DE2705186A1/en active Granted
- 1977-02-08 NL NL7701315A patent/NL7701315A/en not_active Application Discontinuation
- 1977-02-09 CA CA271,440A patent/CA1084937A/en not_active Expired
- 1977-02-10 JP JP1404677A patent/JPS6055514B2/en not_active Expired
- 1977-02-10 BE BE174803A patent/BE851277A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2340942B1 (en) | 1980-02-08 |
| DE2705186C2 (en) | 1988-10-27 |
| FR2340942A1 (en) | 1977-09-09 |
| GB1523705A (en) | 1978-09-06 |
| CH598213A5 (en) | 1978-05-12 |
| JPS5297959A (en) | 1977-08-17 |
| JPS6055514B2 (en) | 1985-12-05 |
| DE2705186A1 (en) | 1977-08-18 |
| BE851277A (en) | 1977-08-10 |
| NL7701315A (en) | 1977-08-15 |
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