DE2705186A1 - PROCESS FOR THE PREPARATION OF ISOIMIDES OR MIXTURES OF ISOIMIDES AND IMIDES - Google Patents

Description

CIBA-GEIGY AG. CH-4002 Basel / Schv; eiz

Process for the production of Isolmi. den or mixtures of

Isoimides and iinides

The present invention relates to a method of manufacture from T. so imide η or mixtures of isoimides and imides.

Various processes for the preparation of N-substituted maleic and phthalic acid isoimides or Ν, Ν'-bis-maleic and N ₁ N ¹ -bis-phthalic acid isoimides are known from the literature. For example, N-substituted maleic or phthalamic acids and NN-bis-maleic or N, N'-bis-phthalamic acids can be used in counterv / type of various dehydrating agents, such as acetic anhydride, trifluoroacetic anhydride, acetyl chloride, thionyl chloride or dichloroacetyl chloride, preferably using a tertiary amine , such as triethylamine, or in the presence of carbodiimides, for example dicyclohexylcarbodiimide, converted into the corresponding isoimides [cf. U.S. Patents 2,995,577, 2,998,429, 3,035,065 and 3,472,817 and J.Org.Chem., £ 8, 2018-2024 (1963), 3_4, 2275-2279 (1969) and 3J>, 821 -823 (1971)], according to US Pat. No. 2,980,701, ammonium salts of N-substituted maleamic acids can also be converted to the corresponding isoimides in the presence of esters of acid halides, such as ethyl chloroformate.

0 9

u 2 2

CIBA-GtIGY

270S186

These known methods are relatively cumbersome and require partly also expensive dehydrating agents. But especially considerable amounts of one or more by-products occur in these processes, their reprocessing, if It is possible at all, very tedious and costly. Schl.iessl5.cl; It is often the case that by-products that cannot be recycled are disposed of in a manner that is sufficient for today's environmental protection regulations problematic and extremely: expensive, e.g. the elimination of the implementation in the presence of Ace ty Ich Ιοί: Id, acetic anhydride or trifluoroacetic anhydride and a tertiary amine obtained Salts.

It has now been found that, avoiding the above-mentioned Disadvantages in a simple, economical manner and with good to very good yields of isoimides of the formula

I!

V ⁰

Il

N

(D

or mixtures of isoimides of the formula I and imides of the formula Ia

(Ia)

produce kaiin, in which A -CH = CH- or

η Q »

the number 1 or 2, if.η = 1, an unsubstituted or substituted one Aryl group and,

when η = 2, an unsubstituted or substituted arylene group or a group of the formulas 7 0 9! "■ '.'? / 1 0 2

ci :: A-GriGV

86

or

represent, where

the UrLickeng] ied -0 -, - S-,

-CO- or

CH,

-ΟΙ

means and the substituents on aryl or arylene groups Q are free of acidic hydrogen atoms, in that mnn is an A-iid acid of the formula II

COOH

CONH -

(II),

where for A, Q and η what is ^{stated under formula I applies, reacts with ketene at a temperature of about -10 c} C to -f80 ° C. A preferably represents -CH-CH-.

Aryl or arylene groups represented by Q are are in particular phenyl, 1- or 2-naphthyl, phenylene or naphthylene groups, especially the 1,3- or 1,4-phenylene and the 1,2-, 1,8- or 2,3-naphthylene group. Such groups can be unsubstituted or substituted. As substituents on aryl or arylene groups Q which are free from acidic hydrogen Atoms are, for example, the following: halogen atoms, for example F, Cl, Br and J; Alkyl groups, especially those with 1-8 carbon atoms; Haloalkyl groups with 1-3 carbon atoms, like the trifluoromethyl group; Alkylthio and N, N-dialkylamino groups with preferably 1-4 carbon atoms in each of the alkyl parts; Alkoxy groups, especially those with 1-4 Carbon atoms; Phenoxy groups, alkoxycarbonyl and alkanoyl groups with preferably 2-5 carbon atoms, such as the methoxy, Ethoxy and n-butoxycarbonyl groups, the acetyl and propionyl groups; Phenylsulfonyl and alkylsulfony groups, where the

709 ^Ί / "'■ 022

.-, or.ov _ _Λ > 27Π5186

the latter preferred. I-A Ku '<: le; istoffaLome have, -cyano- and Nitro groups. Aryl and arylene groups Q can be 1 to 3, preferably have 1 or 2 such substituents. Preferred Q at η = 1 represents the 1- or 2-naphthy group or a Phenyl group represented by one or two halogen atoms, especially Chlorine atoms, one or two alkyl groups with 1-4, especially 1 or 2 carbon atoms in the alkyl parts, substituted by a trifluoromethyl, nitro or cyano group; is. Quite particularly preferably, when η = 1, Q is an unsubstituted one Phenyl group.

If η is the number 2, Q preferably represents the 1,3-phenylene or 4,4'-diphenyl ether group, but especially the 4,4'-diphenylmethane group represent.

If the group Q has strongly electronegative substituents, such as halogen atoms, nitro, cyano, alkyl or phenylsulfonyl groups on, so can according to the process according to the invention Position of these substituents on the radical Q next to the isoimides of Formula I also smaller or larger proportions of the corresponding Imides of the formula Ia are formed. The group Q therefore preferably has at most 2 of the strongly electronegative ones mentioned Substituents on.

The reaction according to the invention is advantageously carried out in the presence of an organic substance which is inert under the reaction conditions Solvent carried out. Suitable solvents are, for example, optionally chlorinated aromatic hydrocarbons, such as Benzene, 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 aliphatic and cyclic ethers such as diethyl ether and dioxane. The reaction is very particularly preferably carried out in acetic anhydride , on the one hand, particularly high yields are achieved and on the other hand because this is formed during the implementation with the ketene

7 0 9/0 2

■ Acetic anhydride again for further reactions after the distillation can be used.

The amic acids of the formula II are known or can be prepared by methods known per se, for example by reacting maleic or phthalic anhydride with mono-diamine diamines of the form HNQ or H _? NQ-NIL ·.

The amic acids of Formula II and the ketene are preferred used in stoichiometric amounts, i.e. sets at η = 1 the amic acid of the formula II and the ketene are preferably introduced in a molar ratio of 1: 2, while when η = 2 the molar ratio from amic acid of the formula II to ketene is advantageously 1: 4. But there can also be a slight excess of one or the other Reaction component can be used, for example a bis about 107o molar excess of amic acid of the formula II or ketene.

The acetic anhydride formed during the reaction can, as already mentioned, be recovered in a very simple manner by means of distillation and possibly used again for further implementations.

The preferred reaction temperatures are between about 0 ° and +60 ⁰ C. After completion of the reaction, the isoimides of the formula I or the mixtures of isoimides of the formula I and imides of the formula Ia in a known manner is isolated and optionally purified v / ground , for example by filtration, distillation and / or evaporation, subsequent washing with sodium hydrogen carbonate solution and water or recrystallization from suitable solvents such as toluene, cyclohexane, acetone and methyl ethyl ketone.

The isoimides which can be prepared by the process according to the invention are known per se. N-substituted maleic isoimides and N, N ¹ -disubstituted bis-maleic or bis-phthalic acid iso-

7 0 9 & 33 / 'iO22

imides can be identified, for example, according to the US Pat. No. 2,980,701, 2,995,577, 2,998,429, 3,035,065 and 3,144,436 and Journal of Polymer Science: Polymer Chemistry Edition,} 3, 1691-1698 (1975) described methods with Diauiinen implement linear polymers. N-substituted phthalic acid isoimides are used, for example, as intermediates for the production of pharmaceuticals [cf. e.g. J.Med.Chem., ΙΌ, 982 (1967)]. Isoimides of the formula I, in which A represents the group -CH = CH-, can also be used as fungicides or defoliants be used.

Finally, the isoimides of the formula I prepared according to the invention can also be added in a manner known per se to the corresponding imides of the formula Ia are isomerized, e.g. by treating them with catalytic amounts of an alkali metal or Ammonium salt of lower fatty acids such as sodium acetate (see e.g. U.S. Patent 2,980,694). The imides of the formula Ia for their part, they are used, among other things, as insecticides and / or for the production of polymers

example 1

COOH 1

r-. +2 CH ₀ = C = O > Η J) + (CH-CO) ₀ O ONH- <£)) V ^

S-

19.2 g (0.1 mol) of N-phenylmaleamic acid are suspended in 100 ml of acetic anhydride. ^{The suspension is heated to 45 °} C. with a heating bath while stirring, then the heating bath is removed and about 0.2 mol of ketene are introduced. The temperature rises to 50-52 ° C. and a clear yellow solution is formed. This solution is concentrated on a rotary evaporator. The remaining yellow oil is poured onto ice water. The precipitate formed is filtered off,

709833/1022

CLUA-GcIGY

with saturated \ ^T £ i; ri 'j; :: i:. y <: rogen carl onate solution and' ater and dried in vacuo over phosphorus pentoxide. 16.0 g (927th of theory) of N-phenybnalein isoimide are obtained; Mp. 5S-61 ⁰ C.

IR spectrum (ClICl.): Λ i.a. 5.55 / 5.95 .u.

ό ΠΙ 3 X · /

Analysis for C ₁₀ H ₇ NO ₂ (molecular weight 173.17): calculated: C 69.36% H 4.08% N 8.09% found: C 69.37% H 4.24% N 8.04%.

The acetic anhydride recovered when the solution is concentrated can can be used again after distillation.

Example 2

CH ₉ = CO

2 (CH ₃ CO) ₂ O

80 grams (0.2 moles) of N, N'-4,4'-diphenylmethane-bis-dialeinamic acid are suspended in 600 ml of acetic anhydride, the suspension is heated to 45 ° C. with stirring and 0.8 without heating Mol ketene initiated. The temperature rises to 49-5O ° C. The result is an almost clear, yellow-orange solution, which is filtered while still warm. The filtrate is on a rotary evaporator concentrated to about 1/3 of the original volume. The reaction product is then left in a refrigerator

709G33 / 1022

CI [JA-GCIGY

Crystallize, filter and wash the residue with saturated sodium hydrogen carbonate solution and water. The yellow crystals obtained are dried in vacuo. 56.7 g (79% of theory) of N, N'-4,4 ^1- diphenylmethane-bis-maleinisoimide are obtained; M.p. 154-155 ° C.

IR spectrum (CHCl ₃ ): / ^ _max ^u - ^a - 5

Analysis for ^c ₂ i ^H i /. ^N 2 ^O 4 O ^v l ° weight 358.35):

calculated C 70.39% H 3.94% N 7.82% found C 70.34% H 3.95% N 7.65%

The recovered acetic anhydride can be used after the distillation can be used again.

Example 3

Analogously to the process described in Example 1, one obtains from 10.3 g (0.05 mol) of N-p-tolylmaleic acid in 75 ml of acetic anhydride and 0.1 mol of ketene, 8.6 g (92% of theory) of N-p-tolyl-maleinisoimide of m.p. 71-73 ° C.

IR spectrum (CHCl ..): K et al. 5.59 / 5.99 11.

O Tu el X *

Analysis for C ₁₁ H ₉ NO ₂ (molecular weight 187.20): calculated C 70.58%, H 4.85%, N 7.48%, found C 70.67%, H 4.77%, N 7.53%.

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CIBA GEIGY _ α.

Example 4

Analogously to the process described in Example 1, one obtains from 26.0 g (0.1 mol) of N-3, S-dichlorophenyl maleic acid amide in 200 ml of acetic anhydride and 0.2 mol of feces 23.1 g (95% of theory) N-3,5-dichlorophenyl dialein isoimide; S; np. 82-85 ° C.

IR spectrum (Nujol): k _a et al 5.55 / 5.80 µ.

ITl 3 λ /

Analysis for C ₁₀ H ₅ Cl ₂ NO ₂ (molecular weight 242.06):

Calculated C 49.62% H 2.08% N 5.79% Cl 29.29% found C 49.2 6% H 2.21% N 5.67% Cl 28.75%.

Example 5

Earth analogously to the procedure described in Example 1 in a suspension of 10.0 g (0.042 mol) of N-p-nitrophenyl maleic acid initiated about 0.08 mol of ketene in 75 ml of acetic anhydride. 8.6 g (94% of theory) of the reaction product are obtained according to the IR and NMR spectrum from a mixture of N-p-nitrophenyl maleimide and N-p-nitrophenyl maleic isoimide consists of j M.p. 97-15O ° C.

IR spectrum (CHCIo): k _nv ua 5, 48 / 5.54 / 5, 90 yu (I so im id) j

5.78 Jd (ImId).

Analysis for C ₁₀ H ₅ N ₂ O ₄ (molecular weight 218.17):

709833/1022

Calculated C 55.05% H 2.77% N 12.84% found C 54.75% H 2.78% N 12.89%.

Example 6

Cl

Analogously to the procedure described in Example 1, 0.6 mol of ketene are introduced into a suspension of 67.5 g (0.3 mol) of Np-chlorophenylmaleamic acid in 600 ml of acetic anhydride. 59.4 g (95% of theory) of reaction product are obtained which, according to the IR spectrum, consists mainly of Np-chlorophenylmaleimide and small amounts of Np-chlorophenylmaleimide; Mp. 85-95 ⁰ C.

IR spectrum (CHCl-): λ ua 5.55 / 5.95 μ (isoimide), ·

5, 70 yes (imid).

Analysis for C ₁₀ H ₆ ClNO ₂ (molecular weight 207.62):

Calculated C 57.85% H 2.91% N 6.75% Cl 17.08% found C 57.63% H 3.02% N 6.92% Cl 17.03%.

Example 7

40 g (0.1 mol) of N, N ^l -4.4 ^l -diphenylether-bis-maleinaniidic acid are suspended in 400 ml of acetic anhydride. The suspension

709833/1022

CIEiA-GfIGY

is heated under Rlihren at 45 ⁰ C. The heating is then removed and 0.4 mol of ketene is introduced. The temperature rises to 52 ^C C. One obtains a orange-yellow suspension, which is still v / filtered arm (conversion 88%; 5 g residue from unreacted bis-maleamic acid). The filtrate is concentrated to dryness on a rotary evaporator at a bath temperature of 60 ^{° C.}

The residue is suspended in 100 ml of diethyl ether, filtered off, Washed with 20 ml of diethyl ether and dried in vacuo over potassium hydroxide. 25.5 g (80% of theory, based on 88% conversion) orange-yellow N, N'-4,4'-diphenyl ether bis-maleinisoimide; M.p. 155-159 ° C.

IR spectrum (CHCl,.): Λ i.a. 5.55 / 5.95 u.

Analysis for C. 0 ^H 12 ^N 2 ° 5 (Molecular weight 360.3 3, 36% N 7, 3): calculated C. 66 67% H 3, 51% N 7, 78% found 66 14% H 69%. Example 8

COOH

HOOC-

/ COOH HOOC-v,

C J

Nx) NH- | ^ r-NHOCT

+ 4

+ 2 (CH ₃ CO) ₂ O

Analogously to the procedure described in Example 7, from 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, 22.0 g of N, N ¹ -1 »3-phenylenebis-maleinisoimide (82% of theory), m.p. 172-177 ° C.

IR spectrum (CHCl-): λ _ i.a. 5.55 / 5.95

709833/1022

CIDA-GF-IGY, ", ^ δ

Analysis for C ₁₄ Il ₈ N ₂ O ₄ (molecular weight 26Ö, 23):

Calculated C 62.69% H 3.01% N 10.44% found C 62.29% H 3.02% N 10.60%.

Example 9

40.5 g (0.091 mol) of N, N'-4,4'-diphenylsulfonic bis-maleamic acid are suspended in 400 ml of acetic anhydride. The resulting suspension is heated under stirring with a heating bath at 45 ⁰ C, then the heating bath is removed, and there are introduced 0.4 mole of ketene. The temperature rises to 48 ° C. Unreacted amide acid (0.500 g, ie 997 _O conversion) is removed by filtration and the filtrate is spun off. The yellow, solid residue is suspended in saturated sodium hydrogen carbonate solution, filtered and washed with water. After drying in vacuo at 20-25 ° C., 34.8 g (95% of theory) of a product are obtained which, according to the IR spectrum, is mainly composed of N, N'-4,4 ^l -diphenylsulfone-bis- maleinimid and too smaller! Parts of N, N ¹ -4,4'-diphenylsulfon-bis-maleinisoimide consist of m.p. 195-2O5 ° C.

IR spectrum (CHCl-): / f including 5.55 / 5.9Ou (isoimide) j

5.80 / 1 (imide).

Analysis for C ₂₀ H ₁₂ N ₂ O ₆ S (molecular weight 408.38):

Calculated C 58.82% H 2.96% N 6.86% S 7.85% found C 58.62% H 3.18% N 6.66% S 7.76%.

709833/1022

° "^{; Λί: ααΥ} -yS ^ 27-5186

Bp i game 1.0

40 g (0.1 mol) of N, N'-4,4'-diphenylmethn-bis ~ iY) aleinamic acid are suspended in 150 ml of acetone. At 35 ^° C., 0.4 mol of ketene are introduced. The resulting yellow suspension -is (15.2 g residue of unreacted Bismal einamidsäure, turnover - ■ = 627) filtered, the filtrate is poured onto Eisvasser and the precipitate filtered off, washed with saturated sodium bicarbonate solution and finally ¹ ini vacuum at 2O-25 ^C C dried. 20.8 g (92% of theory, based on 62% conversion) of N, N'-4,4'-diphenylm & than-bis-ma] einisoimid are obtained.

IK spectrum (CHCl-): λ ua 5.55 / 5.95, u.

») 'ΓΠ3Χ · ■

Example11

25.6 g (0.1 mol) of Np-tolyl-phthalamic acid are suspended in 250 ml of acetic anhydride at 20-25 ° C. Subsequently, 0.2 mol of ketene be started, whereby the temperature rises to 33 ⁰ C. A clear, slightly yellowish solution, which is concentrated on a rotary evaporator under reduced pressure (bath temperature 60 ⁰ C), the residue is suspended in saturated sodium bicarbonate solution, filtered and washed with water. After drying in vacuo at 40 ^° C., 21.0 g (88% of theory) of Np-tolyl-phthalic acid isoimide are obtained; M.p. 116-118 ° C.

709833/1022

CIiJA-GLIGY

IR spectrum (CIiC :. ). λ ua 5.55 / 5.85 u.

■ J Ι 1 (-1λ. /

Analysis for C ₁₅ H _n NO (molecular weight 237.26):

calculated C 75.947 »H 4.67% Ir 5.91% ' found C 75.64% H 4.65% N 6, Ol%.

Example 12

COOH

CH

100.1 g (0.457 mol) of N- (2,6-dimethylphenyl) maleamic acid are suspended in 750 ml of acetic anhydride. ^{The suspension is heated to 30 °} C. with a heating bath, then the heating bath is removed and about 0.9 mol of ketene are introduced with stirring. The temperature rises to 40 ^° C., and a yellow, homogeneous solution is formed. The acetic anhydride is spun off, the residue is taken up in benzene, washed with saturated sodium hydrogen carbonate solution and water, dried and spun off. 90.4 g (98% of theory) of deep yellow crystalline N- (2,6-dimethylphenyl) maleic isoimide with a melting point of 60 ° -62 ° C. are obtained.

IR spectrum (CHCl-.): \ I.a. 5.50 / 5.55 / 5.9 Ou.

• j ΙΏΗΧ · J

Analysis for ^c i2 ^H H ^NO 2 ( ^{mole weight} 201.23): calculated C 71.63% H 5.51% N 6.96% 0 15.90% found C 71.45% H 5.59% N 7.20% 0 15.98%.

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ORIGINAL INSPECTED

Claims (9)

CIHA-GtIGY P a te η ta η sp . ruche Process for the preparation of isoimides of the formula I. Il V ⁰ (D or mixtures of isoimides of the formula I and imides of the Formula Ia wherein
A. Il O (Ia) -CH = CH- or the number 1 or 2, if η ^β 1, an unsubstituted or substituted one Aryl group and, when η = 2, an unsubstituted or substituted one Arylene group or a group of the formulas or represent, where the bridge link -0 -, - S-, -S-S-, - -CO- or CH ₃ —C-I 709833/1022 ORIGINAL INSPECTED CKA-CMGV means and the substitutions on aryl or arylene groups Q are free of acidic hydrogen atoms by using an amic acid of the formula II OOH (II), CONH - wherein for A, Q and η which converts under formula I Specified applies, at a temperature of about -10 ° C to-80 -l ^ü C with ketene. 2. The method according to claim 1, characterized in that an amic acid of the formula II is used, wherein Q when η = 1 is a phenyl, 1- or 2-naphthyl and when η = 2 is a phenylene or naphthylene group, each of which by 1 to 3, especially 1 or 2, halogen atoms, alkyl groups with 1-8 carbon atoms, trifluoromethyl groups, alkoxy, alkylthio, alkylsulfonyl or N, N ¹ -dialkylamino groups with 1-4 carbon atoms each in the alkyl parts, phenoxy groups, alkoxycarbonyl or alkanoyl groups each with 2-5 carbon atoms, phenylsulfonyl groups, cyano or nitro groups can be substituted. 3. The method according to claim 1, characterized in that an amic acid of the formula II is used in which A Represents -CH-CH-. 4. The method according to claim 1, characterized in that an amic acid of the formula II is used, wherein η is the Number 1 and Q represent the 1- or 2-naphthyl group or a phenyl group, which by 1 or 2 halogen atoms, a or 2 alkyl groups each with 1-4, especially 1 or 2, carbon atoms in the alkyl parts, a trifluoromethyl, nitro or cyano group is substituted. 709833/1022 CIKA-Gc (GY y, 5. Method according to claim 1, characterized in that that an amino acid of the formula II is used, in which A -CH = CH-, η is the number 1 and Q is an unsubstituted one Represent phenyl group. 6. The method according to claim 1, characterized in that that an amide acid of the formula II is used, in which A -CH-CH-, η the number 2 and Q the 1,3-phenylene-, 4,4'-diphenyl ii the r- and especially the 4,4 * -diphenylmethan- represent group. 7. The method according to claim 1, characterized in that the reaction is carried out in the presence of an organic solvent which is inert under the reaction conditions. 8. The method according to claim 1, characterized in that the reaction is carried out in the presence of acetic anhydride. 9. The method according to claim 1, characterized in that that you can carry out the reaction at a temperature between about 0 and 60 ° C. 709-33 / 1022