DE2354602A1 - PROCESS FOR MANUFACTURING N-SUBSTITUTED METHACRYLIC OR ACRYLIC ACID AMIDES - Google Patents

Description

¹¹ Process for the production of N-substituted methacrylic or acrylic acid amides "

Priority: October 31, 1972, Japan, No. 108 471/1972 November 1, 1972, Japan, No. 108 810/1972

The invention relates to a process for the production of N-substituted ones Methacrylic or acrylic acid amides.

N-substituted methacrylic or acrylic acid amides are suitable, for example for modifying or finishing fibers, plastics, paints, coatings or paper. So far, however no satisfactory and economical process for the preparation of these compounds has yet been found.

Examples of methods of N-substituted methacrylic or Are acrylic acid amides; ·

(1) A method in which an acid halide such as an acrylic acid or methacrylic acid halide, or a lactone such as

• ß-propiolactone, which has a relatively high activity,

4098 19/1210

Γ Ί

is reacted with an amine;

(2) a process in which an amine is directly treated with methacrylic or:

Acrylic acid or a corresponding ester is reacted;

(3) a process in which the double bond of a metha.crv.l- or acrylic acid or its /

/ Derivatives a hydrogen halide, an amine, an alcohol or acetic acid is added on, the product obtained is amidated with an amine and the double bond by splitting off the hydrogen halide, the amine, the alcohol or the acetic acid is restored.

However, all of these conventional methods have disadvantages and leave something to be desired in terms of their economic efficiency.

For example, the method (1) has the disadvantage that the acid halide or lactone used as the starting compound is expensive and is not easily available in stores. In addition, it is difficult to carry out the amidation selectively. In the end occurs when using an acid halide as the starting compound, salt formation as an additional complication, while must be dehydrated after the reaction when using a lactone.

In the method (2), it is extremely difficult to carry out amidation in high yields and to carry out polymerization reactions and to prevent the addition of amine across the double bond.

In process (3) the addition reaction goes to the double ~ bond does not occur easily and the re-establishment of the double bond gives poor yields. _l

409819/1210

The object of the invention is to provide a simple and economical To provide a process for the preparation of N-substituted methacrylic or acrylic acid amides, in which the disadvantages conventional procedures can be avoided.

The invention thus relates to a process ₍ for the preparation of N-substituted methacrylic or acrylic acid amides of the general formula I.

CH ₀ = C -

in which R is a hydrogen atom or the methyl group and one

2 3
the radicals R and R ^ are a hydrogen atom and the other is an alkylaminoalkyl group, or R and R ^ together form a cyclic amine, which is characterized in that a Diels-Alder obtained from cyclopentadiene and methacrylic or acrylic acid or a corresponding derivative Adduct with an amine of the general formula II

HU

2 3

in which R and R · ^ have the above meaning, to one 5-carboxamide-2-norbornene of the general formula ΙΪΙ

(Ill)

1 2 " ³ p
in which R, R and R have the above meaning

and the compound of the general formula III subsequently to L

4098 19/1210

"V 235A602

Cyclopentadiene and an N-substituted methacrylic or acrylic acid amide pyrolyzed.

In the above general formulas they contain directly an

2 the nitrogen atom of the -CONC group bonded alkyl radicals R

■ x

or R ^ generally 1 to 5 carbon atoms and preferably 1 to 3 carbon atoms. The alkyl radicals in the alkylamino radical generally contain 1 to 3 carbon atoms. Examples

2 5

for cyclic amines, which are formed by the radicals R and R ^, are aziridine, azetidine, pyrrolidine, piperidine, pyrrole, pyrroline, pyrrolidone, indole, carbazole, piperazine, phenothiazine, Imidazole, pyrazole, morpholine, phenoxazine, pyrazoline, pyrazolidine

and pyrazolidone, 2-pipecoline, 3-pipecoline, 4-pipecoline, 3,5-lupetidine and N-methylpiperazine or /. Derivatives of these compounds.

The compounds of the general formula III are obtained in a manner known per se by the Diels-Alder reaction of cyclopentadiene and methacrylic acid or acrylic acid or a corresponding derivative, for example an ester, and subsequent amidation of the adduct made with an amine.

their derivatives,

Examples of methacrylic acid and acrylic acid or of these Diels-Alder reactions that can be used are acrylic acid, methacrylic acid, ethyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, Propyl acrylate, propyl methacrylate, butyl acrylate and butyl methacrylate.

This Diels-Alder reaction proceeds easily in high yields. The. starting compounds used for this are cheap in the trade j

40981 9/1210

available.

Since the double bond in the norbornene skeleton of the Diels-Alder

olefinic

Adduct represents an internal / double bond and therefore in the Ver equal to the double bond of the acrylic group is inert, the reaction conditions, such as catalyst, reaction temperature and

Reaction time, compared to the amidation of acrylic acid or

Methacrylic acid or its derivatives)

^ Can be chosen relatively freely. Because of this, can

carry out the amidation in high yields.

Carrying out the amidation in the process according to the invention is not critical. Various common procedures can be used. The following two amidation processes are preferred because they are easy to perform and using inexpensive starting compounds in high yields get lost.

(1) For Diels-Alder adducts made from methacrylic acid or acrylic acid and cyclopentadiene is this adduct with an amine of the general Formula II implemented in the presence of a suitable dehydrating agent. Examples of such dehydrating agents. are phosphorus pentoxide, phosphoric acid, aluminum oxide, zeolite and sodium hydroxide.

(2) When using methacrylic acid or acrylic acid ester, the adduct obtained is with an amine of the general formula II in the presence of a suitable acidic or basic one Catalyst implemented, with the amidation under alcohol

• The spin-off is in progress. Examples of such acidic or ba- _j

409 8 19/1210

sic catalysts are sulfuric acid, p-toluenesulfonic acid, Alkali metals, alkali metal alcoholates, alkali metal amides or alkali metal hydrides.

Primary or secondary specific examples of / amines of the general formula II which can be used in the amidation process according to the invention are N ¹ , N ^f -dirnethylaminomethylamine, N ¹ , N'-diethylarainomethylamine, N ¹ , N'-dimethylaminoethylamine, N ¹ , N '-Diethylaminoethylamine, N'-Monoäthylaminoäthylamin, N ¹ -Monomethylaminoäthylamin, N ¹ , N'-Dimethylaminopropylamine, N ¹ , N'-Diethylaminopropylamine, N'-Monoäthylaminopropylamin, Ν', Ν'-Dimethylaminoisopropylamin, N ¹ , N'-Diethylaminopropylamine, N 1, N'-Diethylaminopropylamine / lamin, N'-monomethylaminomethylamine, N'-monoethylaminomethylamine, N ¹ -moncmethy ^ ö. / rinoisopropylamine and N'-mona ^ thylaminoisopropylamine. Examples of cyclic amines are aziridine, azetidine, pyrrolidine, piperidine, pyrrole, pyrroline, pyrrolidone, indole, carbazole, piperazine, phenothiazine, imidazole, pyrazole, morpholine, phenoxazine, pyrazoline, pyrazolidine, pyrazolidone, 2-pipecoline, 3-pipecoline, 4 -Pipecolin, 3,5-lupetidine and N-methylpiperazine.

In the pyrolysis of the compounds of general formula III, the N-substituted methacrylic and acrylic acid amides are the general formula I and cyclopentadiene formed as a by-product in almost quantitative yield. The cyclopentadiene can be used again after recovery in the aforementioned Diels-Alder reaction. According to the method according to the invention highly pure N-substituted methacrylic or acrylic acid amides can be used Manufacture cheaply in high yields (generally greater than 80 percent).

4098 19/1210

The pyrolysis may be in either the vapor phase or in liquid phase, generally at temperatures from 200 to 600 ° C, preferably 300 to 500 ⁰ C is performed.

When performing pyrolysis in the vapor phase, for example a method used in which a compound of general formula III in vapor form, optionally in dilution with an inert gas, such as nitrogen, is passed through a heated tube, optionally with Raschig rings Glass, corrosion-resistant steel or porcelain is filled to facilitate heat exchange.

When carrying out the pyrolysis in the liquid phase, both ■ for example the compound of general formula III by direct Heat to the boiling point or by introducing this compound into a vessel that is an inert liquid with high Heat stability, such as terphenyl or paraffin, and pyrolyzed when heated to the desired temperature. The product is then distilled off according to its rate of formation. The polymerization of the pyrolyzed products can be carried out by Addition of a polymerization inhibitor such as hydroquinone or catechol in an inert solvent can be prevented.

The pure compound of the general formula I is obtained by separating off the cyclopentadiene formed as a by-product, with the different boiling points are used.

The examples illustrate the invention.

409819/1210

t.

example 1

(A) 172 g of methyl acrylate are placed in a reaction vessel and 132 g of cyclopentadiene are added dropwise with stirring, the reaction temperature being kept ^{at a maximum of 40 ° C. by cooling with ice.} After the addition, the reaction

, and then distilled ; tion mixture stirred for 5 hours. 282 g of 2-norbornene-5-

carboxylic acid methyl ester.

(B) A 200 ml reaction vessel equipped with a thermometer and a stirrer is charged with 76 g of methyl 2-norbornene-5r-carboxylate, 48 g of N ¹ , N'-dimethylarainoethylamine and 1.2 g of sodium hydride. This mixture is brought 6 hours at 7O ⁰ C for reaction. When the reaction has ended, the reaction mixture is distilled. 81 g of 5-N- (N ·, N * -dimethylaminoethyl) -carboxamid-2-norbornene are obtained.

(C) 20.8 g of 5-N- (N ¹ , N ¹ -dimethylaminoethyl) -carboxamid-2-norbornene are evaporated by heating under a pressure of 5 Torr and passed through a decomposition tube made of heat-resistant glass with Raschig rings filled and heated to 450 ° C. The pyrolyzed product is first cooled in an ice-cooled condenser, 11.3 g of N- (N ¹ , N ¹ -dimethylaminoethyl) acrylamide being obtained. The remaining product is then cooled to -70 ° C. in a second condenser, 5.9 g of cyclopentadiene being obtained.

Example 2 (A) 144 g of acrylic acid are placed in a reaction vessel and

^ 132 g of cyclopentadiene are added dropwise while stirring, J

409819/1210

. π

wherein the temperature is maintained by cooling with ice to not more than 4O ⁰ C. After the addition, the reaction mixture is stirred for 4 hours and then distilled. 262 g of 2-norbornene-5-carboxylic acid are obtained.

(B) A reaction vessel is charged with 69 g of (A) obtained 2-norbornene- • 5-carboxylic acid, 26 g of phosphorus trichloride and 100 ml of benzene. ^{The mixture is heated to 70 °} C. for 5 hours while stirring. The subsequent distillation gives 56 g of 2-norbornene-5-carboxylic acid chloride.

(C) 31 »2 g of 2-norbornene-5-carboxylic acid chloride obtained according to (B) are dissolved in 100 ml of benzene. The solution is added with stirring and cooling to 5 ⁰ C and 31 g of 3- (N ^1, N-dimethylamino) propylamine. The reaction mixture is then stirred at room temperature for 2 hours and then extracted with a mixture of an aqueous alkali solution and benzene. The benzene phase is distilled. 25 g of 5-N- (3-N ^!, N'-dimethylaminopropyl) -carboxamid-2-norbornene are obtained.

(D) 22 g of 5-N- (3-N ', N ¹ -dimethylaminopropyl) -carboxamid-2-norbornene are pyrolyzed according to Example 1. First condensate then be 11 g N- (3-N ¹ _t ^f N-dimethylaminopropyl) acrylamide, and receive as a second condensate 5.8 g of cyclopentadiene.

Example 3

(A) A 200 ml reaction vessel is filled with 76 g of methyl 2-norbornene-5-carboxylate obtained according to Example 1 (A), 61. g of diethylaminoethylarain and 1.2 g of sodium hydride are charged. _j

4 09819/1210

The reaction mixture is reacted for 6 hours at 70 ^° C. with stirring. After the reaction, the reaction product is distilled. 95.1 g of 5-N- (N ¹ , N'-diethylaminoethyl) -carboxamid-2-norbornene are obtained.

(B) 23.6 g of 5-N- (N ', N'-diethylaminoethyl) -carboxamide-2-norbornene obtained according to (A) are pyrolyzed according to Example 1. 13.5 g of N- (N ¹ , N ¹ -diethylaminoethyl) acrylamide are obtained as the first condensate and 5.9 g of cyclopentadiene as the second condensate.

Example 4

(A) 172 g of methyl acrylate are placed in a reaction vessel

and 132 g of cyclopentadiene are added dropwise with stirring, the reaction temperature being kept ^{at a maximum of 40 ° C. by cooling with ice.} After the addition, the reaction mixture is stirred for 5 hours and then distilled. 282 g of methyl 2-norbornene-5-carboxylate are obtained.

(B) A 200 ml electromagnetically stirred autoclave is charged with 76 g of methyl 2-norbornene-5-carboxylate obtained in accordance with (A), 23.8 g of aziridine and 1.2 g of sodium hydride. The reaction mixture is ^{reacted at 70 °} C. for 6 hours. After the reaction, the reaction mixture is distilled. 76.7 g of 5-carboxyaziridide-2-norbornene are obtained.

(C) 16.3 g of 5-carboxyaziridide -2-norbornene are evaporated by heating at 5 torr and passed through a decomposition tube made of heat-resistant Glass that is filled with Raschig rings

ι - _t

_and is heated to 450 ⁰ C. The pyrolyzed product becomes- J

409819/1210

only condensed in an ice-cooled condenser, with 8.6 g of acrylylaziridide having a boiling point of 96 ° C./4 torr. . Thereafter, the remaining product is cooled in a second capacitor to -7O ⁰ C to yield 5.7 g of cyclopentadiene.

Example 5

(A) A 200 ml flask equipped with a reflux condenser and a stirrer is charged with 76 g of methyl Z-norbornene-S-carboxylate obtained in Example 4 (A), 39.1 g of pyrrolidine and 1.2 g of sodium hydride . The reaction mixture is ^{reacted at 70 °} C. for 6 hours. After the reaction, the reaction mixture is distilled. 69.1 g of 2-norbornene-5-carboxypyrrolidide are obtained.

(B) 19.1 g of 5-carboxypyrrolidide-2-norbornene obtained according to (A) are pyrolyzed according to Example 4. The first condensate obtained is 10.6 g of acrylylpyrrolidide with a boiling point of 98 ° C./4 torr and 5.5 g of cyclopentadiene as the second condensate.

Example 6

(A) 144 g of acrylic acid are placed in a reaction vessel and, while stirring, 132 g of cyclopentadiene are added dropwise, with the temperature is kept at a maximum of 40 ° C by ice cooling. After the addition, the mixture is stirred for 4 hours and so-

262 g

then distilled. / 2-norbornene-5-carboxylic acid is obtained.

(B) Ein.Reaktionsgefäß is obtained with 69 g according to (A)

_L 2-Noi ^ bornen-5-carboxylic acid, 26 g phosphorus trichloride and 100 ml _j

4098 19/1210

Charged with benzene. The Reaktiqnsgemisch is heated with stirring for 5 hours at 70 ⁰ C. The product is then distilled.

56 g of 2-norbornene-5-carboxylic acid chloride are obtained.

(C) 31.2 g of 2-norbornene-5-carboxylic acid chloride obtained in accordance with (B) are dissolved in 100 ml of benzene. The solution is cooled to 5 ° C. and 34 g of piperidine are added dropwise with stirring. After the addition, the mixture is stirred at room temperature for 2 hours. The precipitate is filtered off and the filtrate occurred distilled. 28.6 g of 5-carboxypiperidide-2-norbornene are obtained. In the pyrolysis according to Example 4, 11.5 g are obtained Acrylyl piperidide with a boiling point of 110 ° C / 7 Torr as the first condensate and 5.8 g of cyclopentadiene as the second condensate.

Example 7

(A) 76.1 g of 2-norbornene-5-car- obtained according to Example 4 (A)

Nat r iuinTiy d rid bonsäuremethylester, 53.4 g of morpholine and 1.2 g / are according to Example 5 (A) implemented. The reaction product is distilled. 79.6 g of 5-carboxymorpholide-2-norbornene are obtained.

(B) 20.7 g of 5-carboxymorpholide-2-norbornene obtained according to (A) are pyrolyzed according to Example 4. Be the first to receive condensate 11.6g of acrylylmorpholide with a boiling point of 104 ° C / 3 Torr and as the second condensate 5.7 g of cyclopentadiene.

409819/1210

Claims (1)

Claims 1. Process for the preparation of N-substituted methacrylic or Acrylic acid amides of the general formula I f ^ R ^ (I) CH ₀ = G - CON ,) ■ 2 ^ 5 ₀ 2 1
in which R is a hydrogen atom or the methyl group and one 2 "'" 5
the radicals R and R a hydrogen atom and the other one 2 ^ alkylaminoalkyl group or R and R ^ together form cyclic amine, marked thereby net that one made of · cyclopentadiene and methacrylic or Diels-Alder adduct obtained from acrylic acid or a corresponding derivative with an amine of the general formula II 2 3
in which R and R have the above meaning to a 5-carboxamide-'2-norbornene of the general formula III (Ill) 12 ^
in which R, R and R ^ are as defined above, and the compound of the general formula III is then pyrolyzed to cyclopentadiene and an N-substituted methacrylic or acrylic acid amide. 409 8Ϊ9 / 12 10. 2. The method according to claim 1, characterized in that amines of the general formula II are used in which the alkyl radicals of the alkylaminoalkyl group which are directly attached to the nitrogen atom the - CON <group, have 1 to 5 carbon atoms. 3. The method according to claim 1, characterized in that the amine Ν ', Ν'-dimethylaminomethylamine, N ¹ , N'-diethylaminomethylamine, N ¹ , N ¹ -dimethylaminoethylamine, N', N'-diethylaminoethylamine, N ^f -monoethylaminoethylamine , N'-monomethylaminoethylarain, N'jN'-dimethylaminopropylamine, N ', N'-diethylarainopropylamine, N'-monoethylaminopropylamine, N ¹ , N'-dimethylaminoisopropylamine, N ^f , N ¹ -diethylaminoisopropylamine, N'-monomethylaminomethylamine, N'-monomethylaminomethylamine Monoäthylaminomethylamin, N'-Monomethy 1-aminoi sopropylamin or N ^f -Mono, Ä thylaminoi sopropylarain used. 4. The method according to claim 1, characterized in that the amine is aziridine, azetidine, pyrrolidine, piperidine, pyrrole, Pyrroline, pyrrolidone, indole, carbazole, piperazine, phenothiazine, Imidazole, pyrazole, morpholine, phenoxazine, pyrazoline, pyrazolidine, pyrazolidone, 2-pipecolin, 3-pipecolin, 4-pipecolin, 3,5-lupetidine or N-methylpiperazine are used. 5. The method according to claim 1, characterized in that one a Diels-Alder adduct formed from cyclopentadiene and methacrylic or acrylic acid is used. - '40981 9/1210 • 6. "Process according to claim 1, characterized in that the Diels-Alder adduct with an amine of the general formula
II is reacted in the presence of a dehydrating agent. 7. The method according to claim 6, characterized in that the dehydrating agent used is phosphorus pentoxide, phosphoric acid,
Alumina, zeolite or sodium hydroxide are used. 8. The method according to claim 1, characterized in that one of Cyclopentadien.und a methacrylic or acrylic acid ester formed Diels-Alder adduct is used. 9. The method according to claim 8, characterized in that one the Diels-Aider adduct with an amine of the general formula II in the presence of an acidic or basic catalyst. 10. The method according to claim 9, characterized in that the catalyst used is sulfuric acid, p-toluenesulfonic acid, an alkali metal, an alkali metal alcoholate, an alkali metal amide or
an alkali metal hydride is used. 11. The method according to claim 1, characterized in that
one carries out the pyrolysis at temperatures of 200 to 600 ⁰ C. 12. The method according to claim 1, characterized in that the pyrolysis is carried out at temperatures of 300 to 500 ° C. 409819/1210 13. The method according to claim 1, characterized in that the pyrolysis is carried out in the vapor phase. 14. The method according to claim 1, characterized in that the pyrolysis is carried out in the liquid phase. 4098 19/1210