DE2334632A1 - N,N-disubstd. carboxylic acid amides prepn - by catalytic reaction of carboxylic acid anhydrides and allyl-substd. tert. amines - Google Patents

Abstract

Cpds. of formula (I)(CH(R2)=C(R3)-CH(R4))2-n-N(R1n)-CO-R5 (where R1 and R5 are each 1-10C alk(en)yl, Ph, -CH2Ph or -CHPh2; R2 and R4 are each H, or one is 1-5C alk(en)yl; R3 is H or Me; and n = 0 or 1) are prepd. by reacting carboxylic acid anhydrides, of formula (II): (CH(R2)=C(R3)-CH(R4)3-n-R1n, and tert. amines of formula (III) O=C(R5)-O-C(R5)=0; and cpds. (I; R2 and R4 = H; R5 = -(CH2)m-COOCH2-C(R3)=CH2; and m = 2 or 3) are prepd by reacting (II; R2 and R4 = H) with (III; both R5 gps. form -(CH2)m-). The catalyst used is a cpd.or complex of Pd and a tert. phosphine, pref. a salt or complex of bivalent Pd and triphenylphosphine. Reaction pref. proceeds in the absence of O2. (I) are used as solvents, plasticisers, in plant protection and as inters. for conversion to double bonds.

Description

FARBV / ERKE HOECHST AKTIENGESELLSCHAFT 2334632

formerly Master Lucius & Brüning

File number ': HOE 73 / F 196

Date: July 6, 1973 Dr.MA/Pt

Procedure. for the production of Ν, Ν-disubstituted carboxamides

The invention relates to a process for the implementation of tertiary amines which contain two or three allyl groups, with carboxylic anhydrides to form Ν, Ν-disubstituted carboxamides.

Ν, Ν-dialkyl-substituted carboxamides are known as Solvent, as a plasticizer and important in crop protection and suitable as intermediates for reactions at the double bond.

Technical processes for the production of Ν, Ν-disubstituted Carboxamides with one or two allyl groups on the nitrogen are mostly based on the reaction of the correspondingly substituted secondary amine with carboxylic anhydride, chlorides or -star.

The secondary amines required for this are usually obtained by reacting alkyl halides with ammonia or primary amines Amines produced. The disadvantage here, however, is that some of the secondary amines are further converted to tertiary amines.

The proportion of tertiary amines is particularly high when ally! Halides are used which are in the 2-position with are substituted by an alkyl radical. For example, at

4098 84/1431

the reaction of 2-Methylallylchlorld with a 10-fold molar Excess of ammonia, the proportion of tertiary amine is almost 30%, based on the amount of di (2-methylallyl) amine. A Process that converts these tertiary allylamines, which otherwise occur as a by-product, into N, N-disubstituted ones Concerning carboxamides is therefore of particular interest.

The present invention now relates to a process for the preparation of Ν, Ν-disubstituted carboxamides of the general formula Ia or Ib

III l «5

Ia: (CH = C-CH) _O N-C-R; η - 0 or

f
(CH R ³
I.
= C - R ⁴
CH) ₂ _ _n N -R ⁵ H R ³ H R ¹ L.
ι
- C
Il M.
O

HJ III l ⁿ ₆

Ib: (CH = C - CH) ₀ NCR; η = 0 or

2-n "

which can contain up to 22 carbon atoms, where

1 5
R and R are each alkyl or alkenyl with up to 10 carbon atoms

Phenyl, -CH ₂ (phenyl) or - CH (phenyl) ₂

2 4
R and R each either H or one of the two radicals H and the other is alkyl or alkenyl with up to 5 carbon atoms

R ³ = H or methyl and

HR ³ H

6 III

R = - (CH _n ) -COOCH - C = CH; m = 2 or δ m

is, which is characterized in that one for the production of

40-98 84/1431

Ia open-chain carboxylic acid anhydrides of the general formula Ha or, for the preparation of Ib, cyclic carboxylic acid anhydrides of the general formula Hb

Ha: R ⁵ R ⁵ Hb

with tertiary amines of the general formula IHa or HIb

R ² R ³ R ⁴ Ri

III l ⁿ

IHa: (CH = C-CH) ₀ N; η - 0 or

H . R ³ HR *

I'll l ⁿ

IIIb: (CH = C - CH) ₀ "N; η = 0 or

ο — η

converts to catalysts which consist of a compound or a complex of palladium and tertiary phosphine.

From an open-chain carboxylic acid anhydride of the formula Ha and Thus, tertiary amine of the formula IHa forms an N, N-disubstituted one Carboxamide of the formula Ia. Against it arises from a cyclic carboxylic anhydride of the formula Hb and a tertiary amine of the formula IHb a Ν, Ν-disubstituted carboxamide of the formula Ib, which still contains an ester group.

As tertiary allylamines in the process according to the invention

... 4 4098 84 / U31

for example: triallylamine, tri (2-methylallyl) b amine, tri (2,3-dimethylallyl) amine, tri (3-methylallyl) amine (= Tricrotylamine), tri (3-butylallyl) amine and tri (2,7-octadlenyl) =. amine. Furthermore, tertiary amines can be implemented which contain two, optionally substituted allyl groups and an alkyl or Contain aryl group, such as: diallylethylamine, diallylbutylamine, Di- (2.7 octadienyl) butylamine, di (2-methylallyl) methylamine, Benzyldiallylamine or Ν, Ν-diallylaniline. The tertiary allylamines can also contain longer-chain allyl, alkyl or alkenyl groups, which in turn are also substituted with heteroatoms could be.

Also allyldialkylamines, e.g. allyldibutylamine and allylmorpholine, can be carried out on the catalyst system according to the invention with carboxylic acid anhydrides convert to allyl esters and dialkyl-substituted carboxamides.

It is often of particular advantage that mixtures of secondary and tertiary allylamines, such as those used during production, are also obtained secondary amines can be used in the process according to the invention without separation by distillation. This is how it reacts in action a mixture of secondary and tertiary AlIylarain das secondary amine in a known manner with the carboxylic acid anhydride to form carboxylic acid amide and carboxylic acid, which sets the tertiary amine according to the invention with the carboxylic anhydride to the same Carboxamide and to the carboxylic acid allyl ester.

In the process according to the invention, anhydrides of the simple saturated or unsaturated aliphatic carboxylic acids can be used such as acetic anhydride or the anhydrides of propionic acid, caproic acid, 2-ethylhexanoic acid, acrylic acid and crotonic acid, but also anhydrides of aromatic carboxylic acids, e.g. benzoic acid anhydride, phenylacetic acid or diphenylacetic acid anhydride. Mixed anhydrides can also be used in the same way

A09884 / U31

use two carboxylic acids. Cyclic carboxylic anhydrides e.g. succinic anhydride or glutaric anhydride react with tertiary allylamines to form compounds that combine both the allyl ester and the carboxamide fraction in contain a molecule.

In addition to the implementation of the tertiary allylamines with carboxylic acid anhydrides to give Ν, Ν-disubstituted carboxamides, the catalyst used can also carry out an allyl rearrangement of compounds with allyl groups which are substituted in the 1- or 3-position.

If, according to the invention, a tertiary amine is used which is contained in 1-position contains alkyl-substituted allyl groups, with a Carboxylic anhydride to, so can often be found in the reaction product in addition to compounds with allyl groups in the 1-position alky! are substituted, also detect those products whose Allyl groups are substituted in the 3-alky! Position. The same applies to the use of tertiary amines which have alkyl-substituted allyl groups in the 3-position. For example, contains the reaction solution after the reaction of dicrotylmethylamine with acetic anhydride in addition to crotyl acetate and N-crotyl-N-methylacetamide also 1-methylallyl acetate and N-1-methyl-allyl-N-methylacetamide.

The catalyst used for the process according to the invention consists of a combination of a palladium compound with a tertiary phosphine. Both catalyst components for alone, i.e. a phosphorus-free palladium compound or a tertiary phosphine, catalyze the conversion of a tertiary allylamines with a carboxylic acid anhydride practically not.

The catalyst used in the process of the invention

... 409884 / U31

formed when a palladium compound and a tertiary phosphine are combined. For the formation of the active catalyst, it does not matter whether the palladium compound and the tertiary phosphine are added separately to the reaction mixture, or whether the phosphine is already completely or partially contained in the palladium compound before the addition. In both cases, a reactive catalyst system forms under the reaction conditions.

Palladium compounds can be used to represent the catalyst system of very different chemical compositions can be used, e.g. salts of inorganic and / or organic acids, such as palladium chloride and palladium acetate, or double salts of palladium chloride with alkali halides, but also, for example, complex palladium compounds, such as benzonitrile palladium chloride, palladium acetylacetonate, Bis (pyridine) palladium chloride and palladium compounds with polymeric organic or inorganic counterions, such as e.g. Ion exchangers or zeolites. An example of a phosphine-containing palladium compound is bis (triphenylphosphine) palladium chloride insert.

Tertiary phosphines of the general formula PR3 are used as the second component of the catalyst system. At R can they are aromatic and / or aliphatic radicals, such as in tributylphosphine or triphenylphosphine Case is. Triphenylphosphine is preferred as the second catalyst component.

The tertiary phosphines also have a stabilizing effect on such palladium compounds, especially in the case of higher Temperatures and in the presence of certain organic compounds, e.g. acetic acid, easily to metallic palladium can be reduced.

. . A0988A / U31

It is characteristic of the method according to the invention, that even very small amounts of the catalytically active system cause the conversion of tertiary allylamine and carboxylic acid anhydride cause. The palladium concentration can vary within wide limits, e.g. between 0.1 mol% and 5 mol%, but also smaller and larger concentrations quite suitable.

The molar ratio of palladium compound to tertiary phosphine can also vary within wide limits. As a minimal The atomic ratio of phosphorus: palladium should be around 2-3: 1. For example, the atomic ratio 2: 1 is self catalytically active bis (triphenylphosphine) palladium chloride. However, the ratio can also go up to very high values, e.g. 100 - 1000: 1 can be selected.

In the process according to the invention, the reactants can brought to reaction with the catalyst in very different mixing ratios with or without a solvent will. As a rule, however, it is expedient to react both reactants with one another in equimolar amounts. So is it is possible, for example, to carry out the implementation according to the invention according to the template of the one reactant with dropwise addition or introduction perform the other.

For example, aliphatic or aromatic hydrocarbons or polar ones containing oxygen or nitrogen can be used as solvents Solvents such as methyl ethyl ketone, dioxane or dimethylformamide are suitable. Of course, such substances separate as Solvents that undesirably react with either the catalyst, the carboxylic anhydride or the amine.

The reaction is preferably carried out under normal pressure, but it can also, depending on the boiling point of the reaction

409884/1431

- 8 components can be worked with overpressure or underpressure.

The reaction temperature is usually between 50 ~ 150 ° C chosen. But even at a lower temperature, the reaction rate according to the invention is reduced with a reduced reaction rate Implementation possible. The use of a higher temperature with a view to an increased space-time yield only takes place a limit in the thermal stability of the substances involved in the reaction.

In principle, the reaction of the invention Carry out the process not only in the liquid phase but also in the gas phase. Be for implementation in the gas phase the catalyst components then expediently placed on a support.

Since it is possible that the catalyst effecting the reaction of a tertiary allylamine with a carboxylic acid anhydride loses its activity over time, if the reaction is carried out in the presence of atmospheric oxygen, it is advisable to with the exclusion of oxygen, for example in a closed reaction vessel or under protective gas, to work like nitrogen or argon.

409884/1431

example 1

33.5 g triallylamine and 26.8 g acetic anhydride in one The reaction flask was heated to 130-135 ° C. for 75 minutes together with 0.4 g of palladium acetate and 2.9 g of triphenylphosphine. Thereafter In addition to small amounts of triallylamine and acetic anhydride, only allyl acetate can be found in the reaction product by gas chromatography and detect N, N-diallylacetamide. After working up by distillation, 23 g of Ν, Ν-diallylacetamide are obtained, which corresponds to a yield of 83%.

Example 2

The procedure is as in Example 1, except that 28 g of triallylamine and 26 g of propionic anhydride are used together with 100 mg of palladium acetate and 500 mg triphenylphosphine. After heating the solution to 130-135 ° C. for 5 hours, the reaction mixture persists according to gas chromatography Analysis of 80% from allyl acetate and N, N-diallylpropionic acid amide in a molar ratio of 1: 1. The rest are unreacted starting products.

Example 3

A solution of 32 g of diallylethylamine, 26.8 g of acetic anhydride, 0.4 g of palladium acetate and 1.4 g of triphenylphosphine is heated to 120-130 ° C. for 3 hours. According to gas chromatographic analysis, the reaction mixture then contains almost only allyl acetate and allyl ethyl acetamide. Work-up by distillation gives 32 g of allyl ethyl acetamide, which corresponds to a yield of 98 %.

Example 4

When heated for 4 hours, 35.2 g of diallylbutylamine and 23.1 g of acetic anhydride react together with 0.4 g of palladium acetate and 1.4 g Triphenylphosphine at 130 ° C selective to butylallylacetamide and allyl acetate. 29.6 g of butylallylacetamide are isolated by distillation,

A09884 / U31

233Λ632 - ίο -

this corresponds to a yield of 84%.

Example 5

42.5 g benzyl diallylamine, 25.5 g acetic anhydride, 0.4 g palladium acetate and 1.4 g of triphenylphosphine are heated to 115-130 ° C. for 4 hours. According to gas chromatographic analysis, the reaction mixture contains apart from the unreacted starting materials, 32.9% allyl acetate and 59% benzylallylacetamide.

Example 6

A solution of 42.6 g Ν, Ν-diallylaniline, 26.8 g acetic anhydride, 0.4 g of palladium acetate and 1.4 g of triphenylphosphine are heated to 130 ° C. for 3 hours. Allyl acetate and N-allylacetanilide are formed in a molar ratio of 1: 1. The distillation gives 37 g of N-allylacetanilide, accordingly the yield is 86%.

Example 7

17.9 g of tri (2-methylallyl) amine, 9.2 g of acetic anhydride, 0.4 g of palladium acetate and 1.4 g of triphenylphosphine are reacted. After slowly heating up to the reaction temperature, 135-138 ° C., for half an hour, a sample of 1.75 g is taken and rapidly cooled. Gas chromatographic analysis shows that the acetic anhydride content in the reaction mixture had fallen from 32% at the beginning of the reaction to 12.8%. This corresponds to a conversion of 60 %.

After a further reaction time of 2 1/2 hours at 135 ° C., the experiment is ended. The reaction solution now contains loud Gas chromatographic analysis only 1.2% acetic anhydride and apart from the unreacted, excess tri (2-methylallyl) amine only methylallylacetate and dimethallylacetamide in a molar ratio of 1: 1. After working up by distillation, 13.9 g fall Dimethallylacetamide, so the yield is 85%.

... 11 409884 / U31

Example 8

To 32.9 g of an amine mixture with 58.4 wt .-% diallylamine and 41.6 wt .-% triallylamine, in which 4 g triphenylphosphine and 0.4 g of palladium chloride are dissolved, 28.5 g of acetic anhydride are added dropwise with cooling. After 4 hours of heating at 130 ° C enths the reaction solution 19% acetic acid, 60% dially / acetamide.

The distillation of the reaction mixture yields 35.8 g of diallylacetamide, i.e. 8.3 g more than could have been formed solely on the basis of the known reaction of diallylamine with acetic anhydride.

Example 9

0.1 mol of di (2.7 octadienyl) butylamine and 0.1 mol of acetic anhydride are mixed with 0.3 g of palladium acetate and 1.5 g of triphenylphosphine and heated to 130 ° C. _{under N 2.} N-butyl-N-octadienylacetamides and octadienyl acetate can be detected as newly formed products by gas chromatography after a reaction time of just 30 minutes.

Example 3 0

13.7 g of triallylamine and 22.6 g of benzoic anhydride are reacted with the addition of 0.4 g of benzonitrile palladium chloride and 1.4 g of triphenylphosphine. After heating to 130 ° C. for 3 hours, the reaction _{solution contains a total of 70% N 1} N-DIaIIyI-benzoic acid amide and allyl benzoate in a molar ratio of 1: 1.

Example 11

In the autoclave, 25 g of succinic anhydride, 25 g of dimethylformamide, 33.5 g of triallylamine, 0.2 g of palladium acetate and 0.7 g of triphenylphosphine were heated to 130 ° C. for 6 hours. In the case of the distillative

-2

Working up falls to a fraction (40 g) which boils in vacuo (^ 10 mm Hg) above 100 ^° C. and, according to the ester number and NMR spectrum, contains about 60% allyl succinate-N ^ -diallylamide.

... 12 409884/1431

Claims (4)

PATENT CLAIMS: ! Process for the preparation of Ν, Ν-disubstituted carboxamides of the general formula Ia or Ib Ia: (CH-C-CH) _{O n} N-C-R; η - 0 or 1 2 R. 3 R. 4th R. R. C.
H -R ⁵ I.
(CH I.
- C - ^CH ) ₂ -n N - O H R ³ H R ¹ 1 I. I. l ⁿ C.
Il -R ⁶ I.
(CH I.
= C - ^CH > 2-n I.
N - O Ib: (CH = C - CH) _n "NCR: η = 0 or 1 which can contain up to 22 carbon atoms, where R and R are each alkyl or alkenyl with up to 10 carbon atoms Phenyl, -CH «(phenyl) or -CH (phenyl)« 2 4
R and R each either H or one of the two radicals H and the other is alkyl or alkenyl with up to 5 carbon atoms 3
R - H or methyl and HR ³ H 6 III R - - (CH ₀ ) -COOCH - C ^a CH; m = 2 or 3 is, characterized in that open-chain carboxylic acid anhydrides of the general formula Ha or for the preparation of Ib cyclic carboxylic acid anhydrides of the general formula Hb ... 13 409884 / U31 HOE 73/196 13 - ^IIa '' Ϋ f ^IIb: < ^CH 2> mm - 2 or C ^^ with tertiary amines of the general formula IIIa or IIIb R ² R ³ R ⁴ r \ IHa: (CH-C-CH) "" N; η = Oor 1 «3-η HR ³ H Rl
I It \ ⁿ
IHb: (CH-C-CH) " _M N; η - O or 1 converts to catalysts which consist of a compound or a complex of palladium and tertiary phosphine. 2) Method according to claim 1, characterized in that there is a salt or a compound or complex of palladium Complex of 2-valent palladium used. 3) Process according to claim 1, characterized in that triphenylphosphine is used as the tertiary phosphine. 4) Process according to claim 1, characterized in that the reaction is carried out with the exclusion of oxygen. 409884/1431