DE1618735B2 - PROCESS FOR THE MANUFACTURING OF ACRYLIC AND METHACRYLIC ACID ESTERS OF UNIVERSAL POLYAMINO ALCOHOLS - Google Patents

Description

CH, N

HIGH

CH ₂ N

R ¹

R ¹

20th

R ³

HOC _n H _2n NC _n H _2n N

R ¹

R ²

C _n H _2n N

HOC _n H _2n N

R ¹

R ¹

C "H," N

R ²

45

in which

—N

R ¹

R ²

a secondary aliphatic, a tertiary aliphatic or a heterocyclic amino group having a total number of carbon atoms of 2 to 12, R ³ is an alkyl radical having at most 6 carbon atoms, and η is the number 2 or 3, is reacted.

55

60 molecule contains an easily polymerizable double bond and several secondary or tertiary amino groups.

It is known that the copolymerization is less Quantities of acrylates or methacrylates which only contain one amino group in the ester residue, with other vinyl monomers these give the polymeric materials obtained good mechanical properties Properties that give high adhesion to various materials, improve the dyeability and the Increase resistance to temperature fluctuations. On the basis of such monomers Strongly basic anion exchangers can be produced (see US-PS 21 38 763).

The aim of the invention is to create a process for the production of acrylic and methacrylic acid esters, which contain several secondary or tertiary amino groups in the ester residue.

The stated aim is achieved by either acrylic acid or methacrylic acid or their Acid chlorides or their alkyl esters with an alcohol with a maximum of 4 carbon atoms in per se known Way with a monohydric polyamino alcohol

of the formulas _t

CH ₂ N,

HIGH .

CH ₂ N

35 R ²

R ¹

or

40

R ³ R ¹

I /

HOC _n H _2n NC _n H _2n N

R ²

or R ¹

C _n H _2n N

HOC _n H

R ¹

C "H," N

in which —N

R ¹

R ²

The invention relates to a method of manufacture 65
of acrylic and methacrylic acid esters monovalent
Polyamino alcohols. a secondary aliphatic, a tertiary aliphatic

The process products are monomers, in whose or a heterocyclic amino group with a

Total number of carbon atoms from 2 to 12, R ^{1 is} an alkyl radical with a maximum of 6 carbon atoms and η denotes the number 2 or 3.

The acrylic and methacrylic acid required for the claimed process, their acid chlorides and their alkyl esters with a maximum of 4 carbon atoms are produced on an industrial scale and are easily accessible Products. The monohydric polyamino alcohols are made from easily accessible large-scale obtained products. The 1,3-bis-aminoisopropanols are produced by the reaction of the corresponding Amines made with the epichlorohydrin according to the scheme:

C1CH, CH

H, + 2H-N

R ¹

R ²

R ¹

alkaline agent

-HCl

\
> N-CH ₂ -CH-CH ₂ N

R ²

OH

R ¹

R ²

Instead of epichlorohydrin, the a.y-dichlorohydrin of glycerol is also used.

R ¹

Cl-CH ₂ -CH-CH ₂ Cl + 2H -N

OH R ₂

35

R ¹ R ¹

alkaline agent / 40> N-CH ₂ -CH-CH ₂ -N-2HCl

R ²

OH

R ²

45

The N - alkyl - N - (aminoalkyl) aminoalkanols are obtained by alkylating the corresponding alkylaminoalkanols prepared with haloalkylamines in the presence of an alkaline agent according to the scheme:

R ¹

NC _n H _2n X + HNC _n H _2n OH R ² R ³

alkaline agent

R ¹

-HX

R ³

NC _n H _2n NC _n H _2n OH

55

60

R ²

65

X represents a chlorine, bromine or iodine atom. The N, N-bis (aminoalkyl) aminoalkanols are prepared by alkylating the aminoalkanols with haloalkylamines according to the scheme:

R ¹ H

NC _n H _2n X H-NC _n H _2n OH

R ² H

15th

20 R ¹

N
/

alkaline agent R ²
- 2HX R ¹

R ²

NC _n H

N-CH

N-C "H," 0H

where X is a chlorine, bromine or iodine atom.

The esterification of acrylic or methacrylic acid is carried out in such a way that an amino alcohol, acrylic or methacrylic acid, a solvent for azeotropic distillation of the water formed, is first placed in a reaction vessel equipped with a stirrer, thermometer and reflux condenser with a water separator Esterification catalyst and a polymerization inhibitor are introduced. The mixture is then heated with stirring until no more water separates in the separator. The reaction mixture is then cooled to room temperature and treated with an alkaline agent to neutralize the unsaturated acid which has not reacted. After the solvent has been distilled off, the residue is distilled in vacuo. The reaction can be carried out under normal, positive or negative pressure in an air, nitrogen or other gas medium which is inert towards the components of the mixture. The temperature of the reaction mixture depends on the solvent and the aminoalcohol from which come to be used, and is usually held in a range of 80 to 200 ⁰ C. The esterification catalysts used are sulfuric acid, iron and aluminum sulfate, sodium bisulfate and metallic sodium. The catalysts used are preferably ferric sulfates and aluminum sulfates in the hydrate form in an amount of 0.1 to 10 percent by weight, based on the sum of the reagents.

As solvents, benzene, toluene, xylenes and other solvents come into question, which with Water form azeotropic mixtures. Polymerization inhibitors are p-oxydiphenylamine, diphenyl-p-phenylenediamine, Phenothiazine and other aromatic amines, phenols and naphthols are used.

The yields of monomeric polyamino esters prepared by this procedure are 60 up to 70% of theory.

By reacting (acylating) the corresponding monohydric polyamino alcohols with the chlorides

of acrylic or methacrylic acid, the monomeric polyamino esters are obtained in yields which exceed 90% of theory. The reaction is carried out as follows. To the solution of the acid chloride in anhydrous solvent (benzene, toluene, ether, acetonitrile, dimethylformamide, and others) are added in the presence of a polymerization inhibitor, with stirring at a temperature from 0 to 120 ⁰ C (preferably from 20 to 80 ° C) gradually, a solution the stoichiometric amount of the monohydric polyamino alcohol in the same solvent. To complete the reaction, the mixture is stirred for some time at an elevated temperature. The free base of the monomeric polyamino ester is isolated from the monohydrochloride formed during the reaction by treating the reaction products with an aqueous or alcoholic solution of an alkali or alkaline earth metal hydroxide or carbonate.

The solution of the free base of the polyamino ester in an organic solvent is of the aqueous Solution of the metal salt (in the event that the reaction products with an aqueous solution of an alkaline Agent) separately or from the precipitate of the metal chloride (in the case of that the neutralization was carried out with alcoholic solution) filtered off, after which they the Is subjected to distillation.

In a number of cases it is advisable to carry out the acylation in the presence of such substances through which the hydrogen chloride formed in the reaction is bound, e.g. B. pyridine, Triethylamine and other tertiary amines. The acylation can also be carried out without a polymerization inhibitor be performed. In this case, the inhibitor is only used during the isolation of the ester Rectification added.

The best way to prepare the monomeric polyamino ester of acrylic and methacrylic acid is the transesterification of the alkyl esters of the acids mentioned with an alcohol with a maximum of 4 carbon atoms by appropriate polyamino alcohols.

The process is carried out as follows.

A mixture of a polyaminomonoalkanol, an acrylic or methacrylic acid alkyl ester, which is preferably used in excess, and a polymerization inhibitor is heated to the reaction temperature in a reactor connected to a rectification column and a transesterification catalyst is added to the mixture. If the starting reagents contain some water, some alkyl ester is distilled off from the mixture before the catalyst is added. The water present in the reaction mixture is removed in the form of an azeotropic mixture with the starting ester. The required amount of the catalyst can be added either once completely or to make any in smaller portions throughout the transesterification process _f. The low molecular weight alkanol that forms in the reaction is removed in the form of an azeotropic mixture with the starting alkyl ester. The reaction is carried out at a temperature which is sufficient for the azeotropic mixture to be distilled off rapidly. In general, the temperature of the azeotropic mixture is kept in a range of 60 to 160 ⁰ C, preferably from 80 to 130 ⁰ C.

The reaction is carried out under normal, positive or negative pressure in a nitrogen, air or a carried out another gas medium which is inert to the components of the mixture. To distilling off the low molecular weight alkanol in an amount close to theory the reaction products isolated by vacuum distillation or by another method.

The transesterification catalysts used are alkali metals, their alcoholates and other alcoholates Metals, e.g. B. of titanium and aluminum. They are particularly effective and easy to use Sodium methylate in the form of a 25-30% solution in anhydrous methanol and titanium tetra-n-butylate. The stated catalysts are expediently used in an amount of 0.1 to 10 mol percent (preferably 1 to 5 mol percent), based on the amino alcohol used.

The polymerization inhibitor used is phenols, aromatic amines, aminophenols, e.g. B. hydroquinone, 2,6 - di (tert - butyl) - 4 - methyl - phenol (Jonol), pyrocatechol, tert. - Alkylpyrocatechins, j1, ß ^l - Dioxy-α, Μ ¹ -dinaphthyl (di-ß-naphthol), phenyl - /; - naphthylamine, Ν, Ν ¹ -diphenyl-p-phenylenediamine, thiodiphenylamine (phenothiazine).

The yields of monomers prepared by the transesterification under the conditions described above Polyamino esters are 80 to 90% of theory, based on the polyamino alcohol used.

The acrylic and methacrylic acid esters of the monohydric polyamino alcohols are colorless liquids, which are soluble in organic solvents.

The esters, whose molecules contain dimethylamino groups, are easily soluble in water. the The water solubility of other esters decreases sharply with the chain growth of the substituents on the nitrogen atoms in the amino groups. When mixed with methyl iodide, the amino esters form with tertiary ones Amino groups the corresponding quaternary salts. When passing through anhydrous hydrogen chloride the amino ester solutions in organic solvents form their hydrochlorides.

The hydrochlorides and alkyl iodides of the esters produced are colorless crystals that light up in water are soluble. The picrates are yellow crystals that can be crystallized from alcohols.

The monomeric polyamino esters can be polymerized rapidly in the presence of azobisisobutyric acid dinitrile and at elevated temperature (40 to 100 ^° C.) with the formation of colorless Idar polymers of various strengths - from soft to solid vitreous resin. The polymerization of the monomeric esters on storage is prevented by adding small amounts (0.05 to 0.5 percent by weight) of polymerization inhibitors which are used in the process of making them.

It has been found that polymers based on the process products with several Amino groups are produced in the molecule and are usable as ion exchangers, as a result of their high amino nitrogen content have a greater exchange capacity compared to such resins, obtained on the basis of unsaturated acid ester with an amino group in the molecule will.

The following table shows the full exchange capacities for the weakly basic anion exchangers given for chlorine ions.

Freely the manufacture of the anion exchanger used monomer

1. Dimethylaminoethyl methacrylate (known from US-PS 21 38 763)

2. 1,3-bis (dimethylamino) isopropyl methacrylate

3. Diethylaminoethyl methacrylate (known from US-PS 21 38 763)

4. 1,3-bis (diethylamino) isopropyl methacrylate

5. 1,3-bis (diethylamino) isopropyl acrylate

6. 1,3-bis (diallylamino) isopropyl methacrylate

7. 3- [N, N-bis- (2-dimethylaminoethyl) -amino] -n-propyl methacrylate

8. 1,3-Di (N-piperidyl) isopropyl methacrylate

Full exchange capacity the anion exchanger for chlorine ions

(in Val / g exchanger)

4.74

6.43

4.15

5.36 5.69

5.14

7.58 5.18

determined. Almost the theoretical amount of methanol is formed over 2.5 to 3 hours. That The reaction mixture is cooled to room temperature, filtered from the precipitate and poured on a short rectification column distilled under reduced pressure. After distilling off the unreacted Methyl methacrylate becomes pure 13-bis (dimethylamino) isopropyl methacrylate at a temperature of 117 to 117.5 ° C. 20 Torr distilled.

Yield 95.7 g (89.4% of theory); nl ° 1.4475; d ⁷ i 0.9230; MR _D 62.00; calculated 62.06. Found: N 12.98%; 12.87%, C ₁₁ H ₂₂ N ₂ O ₂ . Calculated: N 13.07%. The reaction with methyl iodide is used to detect the ester obtained.

Dimethoiodide - colorless crystals (from ethanol). Mp. 218 to 219 C (with decomposition). Found: N 5.63%; 5.73%. C,., H ₂₈ I ₂ N ₂ O ₂ . Calculated: N 5.62%.

Example 2
1,3-bis (dimethylamino) isopropyl acrylate

CH ₂ N (CHj) ₂

CH ₉ = CHCOOCH

It is clear from the data given that the exchange capacity depends on the number of amino groups in the molecule (more precisely on the content of amino nitrogen) depends. A similar increase The exchange capacity of anion exchangers can be found in a number of other amino-alkyl acrylates and methacrylates with two or more amino groups compared to those from monomers with only observe an amino group.

Example 1 1,3-bis (dimethylamino) isopropyl methacrylate

CH ₃

CH, = C

CH ₂ N (CH ₃

COOCH

CH ₂ N (CH ₃ J ₂

In one to a rectification column with a capacity of about ten theoretical plates connected flasks are 72g of 1,3-bis (dimethylamino) isopropanol, 150 g of technical methyl methacrylate and 1.5 g of p-oxydiphenylamine were introduced. The mixture is heated to 90 ° C. in an oil bath and 0.5 ml of a 25% solution of Add sodium methylate in anhydrous methanol. In the further the catalyst is in portions of Add 0.1-0.2 ml every 5 to 10 minutes until the total is 3 to 4 ml. The temperature of the bath is kept in a range from 120 to 140 ° C. throughout the reaction.

The methanol which forms in the reaction is distilled off in the form of an azeotropic mixture with the methyl methacrylate at 64 to 66.degree. The methanol content of the mixture is refractometrically CH ₂ N (CH ₃ ) ₂

In a four-necked flask fitted with a mechanical stirrer, thermometer, dropping funnel and a re-nut condenser fitted with a calcium chloride tube, 18.2 g of acryloyl chloride, 0.5 g introduced p-oxydiphenylamine and 100 ml of anhydrous benzene.

A solution of 29.2 g of 3-bis (dimethylamino) isopropanol in 20 ml of anhydrous pyridine is then added to the solution while stirring at a temperature of 20 to 25 ° C. over a period of 30 minutes. The mixture is then heated to 80 ° C., stirred for a further 1 hour, cooled to room temperature and, without stopping stirring, a solution of 11.5 g of potassium hydroxide in 40 ml of methanol is added. The precipitate which has separated out is filtered off and the filtrate is distilled in vacuo. 30.1 g (75.3% of theory) of 1,3-bis (dimethylamine) isopropyl acrylate are obtained: boiling point 99 to 100 ° C./18 torr; n'S 1.4478; d \ ° 0.9290; MR ₀ 57.69; calculated 57.45. Found: N 13.70%; 13.87%. C ₁₀ H ₂₀ N ₂ O ₂ . Calculated: N 13.98%.

Dimethoiodide. F. 200 to 201 ° C (from ethanol). Found: N 5.57%. C ₁₂ H ₂₆ I ₂ N ₂ O ₂ . Calculated: N 5.78%.

Example 3
1,3-bis (diethylamino) isopropyl methacrylate

CH ₃ O CH ₂ N (C ₂ H ₅ ),

CH ₂ = CC-OCH

CH ₂ N (C ₂ H ₅ J ₂

a) In a transesterification reactor, as described in Example 1, 101 g of l, 3-bis (diethyl

amino) isopropanol, 1.5 g of p-oxydiphenylamine and 150 g of methyl methacrylate were introduced. The mixture is ^{heated to 90 0} C and with 1 ml of 25% igc solution

609 650/41

added by sodium methylate in anhydrous methanol. The addition of the catalyst is continued at 0.2 ml each every 10 minutes. 3.2 ml of catalyst solution are added over a period of 2 hours and 24.4 g of azeotropic mixture, which contains 17.8 g of methanol, is distilled off. After filtering the reaction products and vacuum distillation, 115.2 g (85.4% of theory) 1,3-bis (diethylaminoHsopropylmethacrylat; bp. 118 to 120 ° C / 6 Torr; nf 1.4528; df 0, 9104; MR _n 80.26; calculated | _O 80.53. Found: N 10.30%; 10.48%. C ₁₅ H ₃₀ N ₂ O _2. Calculated: N 10.37%.

b) 60.5 g of 1,3-bis (diethylamino) isopropanol, 50 ml of m-xylene, 2 g of diphenyl-phenylenediamine, 3 g of iron (III) sulfate (Fe ₂ (SO ₄ ) ₃ -9H ₂ O) and 28.4 g of methacrylic acid were introduced. The temperature of the mixture rises to 50 ⁰ C. The mixture is heated at 150 to 170 ° C with stirring for 3 hours. During this time, 5.3 ml of aqueous phase containing some methacrylic acid collect in the separator. The reaction mixture is cooled to room temperature, washed with aqueous potassium carbonate solution and distilled under vacuum in a short column. After the removal of m-xylene, the unreacted 1,3-bis- (diethylamino) -isopropanol is first distilled off in an amount of 11.5 g (boiling point 84 to 87 ° C / Torr; ηϊ 1.4770); then a small transition fraction (2.5 g, b.p. 87 to 10 8 ° C. -3 Torr, nf 1.4498) and then pure 1,3-bis (diethy'.amino) -isopropyl methacrylate are distilled off. Bp 108-112 ° C / 3 torr; nl ° 1.4528. Yield 57.1 g (70.4%, based on the diamino alcohol used). The yield of diamino ester is 92.3%, based on the diamino alcohol which has reacted.

Example 4
1,3-bis (diethylamino) isopropyl acrylate

CH ₂ N (C ₂ H ₅

CH ₂ = CH-C-OCH

CH ₂ N (C ₂ H ₅ J ₂

a) In a reactor as described in Example 2, 70 ml of anhydrous benzene, 10 g of acryloyl chloride and introduced 1 g of p-oxydiphenylamine. While stirring, 20.2 g of 1,3-bis (diethylamino) isopropanol are dissolved over a period of 30 to 40 minutes in 30 ml of benzene are added, the temperature of the reaction mixture being kept below 50.degree.

15 minutes after adding the diamino alcohol, 11 g of triethylamine are added and stirring is continued for a further 30 minutes. The mixture is then cooled to room temperature and 6 g of potassium hydroxide, dissolved in 30 ml of water, are added, two phases being formed. The organic layer is washed twice with water, the solvent is distilled off, and the residue is subjected to vacuum distillation. 23.8 g (93.1% of theory) of 1,3-bis (diethylamino) isopropyl acrylate are obtained; Bp 87 to 88 ° C / l torr; nf 1.4510; df 0.9124; MR _D 75.71; calculated 75.92. Found: N 10.88%; 10.90%. Ci ₄ H ₂₈ N ₂ O ₂ . Calculated: N 10.93%.

Dimethoiodide: F. 185 to 186 ° C (from ethanol). Found: N 5.09%; 5.23%. C ₁₆ H ₃₄ N ₂ O ₂ I ₂ . Calculated: N 5.19%.

b) 101 g of 1,3-bis (diethylamino) isopropanol, 50 gm - Xylene, 3 g of hydrated aluminum sulfate (A1 ₂ (SO ₄ ) ₃ · 18 H ₂ O), 4 g of diphenyl - ρ - phenylenediamine and 36 g of acrylic acid were introduced. The temperature of the mixture rises to 55 ° C. Dry nitrogen is passed through the mixture and the mixture is heated in an oil bath by removing the water which forms during the reaction and which also contains an admixture of acrylic acid.

15.6 ml of the aqueous phase are distilled off at a temperature of 140 to 155 ° C. over a period of 5 hours. The mixture is cooled to room temperature and, without ceasing the nitrogen bubbling, treated with 40% aqueous sodium hydroxide solution, then the organic layer is washed with sodium chloride solution, dried over anhydrous magnesium sulfate and distilled in a short column. 10.2 g of unreacted diamino alcohol, a small amount of a transition fraction and 77.45 g (60.5% of theory) of 1,3-bis (diethylamino) isopropyl acrylate are obtained; Bp 86 to 89 ° C / 1 torr; ng 1.4513. The yield of diamino ester is 75.7%, based on the diamino alcohol which has reacted.

Example 5
1,3-bis (diallylamino) isopropyl methacrylate

CH ₃ O CH ₂ N (CH ₂ -CH = CH ₂ ) ₂

CH ₂ = C CO-CH

45 CH ₂ N (CH ₂ -CH = CH ₂ ) ₂

From 25.0 g of 1,3-bis- (diallylamino) -isopropanol and 30 g of methyl methacrylate, in the presence of 1 g of di- / i-naphthol and sodium methylate under the conditions as described in Example 1, 30.1 is obtained g (94.7% of theory). 1,3-bis (diallylamino) isopropyl methacrylate; Bp 136-138 ° C / 2 torr; nl ° 1.4778; df 0.9278; MR _D 97.06. Calculated 97.14. Found: N 8.76%; 9.02%. C ₁₉ H ₃₀ N ₂ O ₂ . Calculated: N 8.79%.

Example 6
1,3-bis (diallylamino) isopropyl acrylate

ο CH ₂ N (CH ₂ -CH = CH ₂ ) ₂

CH ₂ = CHC-O-CH

^ CH ₂ N (CH ₂ -CH = CH ₂ ) ₂

To the solution of 10 g of acryloyl chloride in 10 ml of anhydrous benzene, which is placed in a reactor

is as described in Example 2, is added over 40 minutes, 25 g 1,3-bis - (diallylamino) - isopropanol, dissolved in 30 ml of benzene, added by maintaining the temperature of the reaction mixture is maintained at about 50 ⁰ C. Then the mixture is heated to 75 to 8O ⁰ C for 1 hour, then cooled to room temperature and treated with 100 g of 10% aqueous potassium hydroxide solution. The organic layer is washed with water, 0.5 g of dinaphthol is added, the benzene is distilled off and the residue is distilled under vacuum. 27.1 g (89.1% of theory) 1,3-bis (diallylamino) isopropyl acrylate are obtained; Bp 135-137 ° C / 2.5 torr; ni ° 1.4788; df 0.9390; MR ₀ 91.90; calculated 92.52. Found: N 9.25%; 9.28%. Ci ₈ H ₂₈ N ₂ O ₂ . Calculated: N 9.21%.

Example 7 1,3-Di (N-piperidyl) isopropyl methacrylate

, Ο

CH, = C C — O — CH

The reaction is carried out under the conditions as described in Example 1. From 67.8 g of 3-di (N-piperidyl) isopropanol and 90 g of methyl methacrylate, 75.5 g (85.6% of theory) of 1,3-di (N-piperidyl) isopropyl methacrylate are obtained. The reaction time is 3 to 3.5 hours. Boiling point of the product 132 to 133 ° C / 1 torr; n $ 1.4844; df 0.9808; MR _D 85.86; calculated 85.37. Found: N 9.27%; 9.41%. C ₁₇ H ₃₀ N ₂ O ₂ . Calculated: N 9.51%.

Example 8 1,3-Di (N-piperidyl) isopropyl acrylate

CH ₇ = CHCOOCH

a) From 10 g of acryloyl chloride and 22.6 g of 1,3-di- (N-piperidyl) -isopropanol, under the conditions as described in Example 6, 25.4 g (90% of theory) 1.3 -Di- (N-piperidyl) -isopropyl acrylate obtained. Bp 114 ° C / 0.4 torr; n'S 1.4859; df 0.9974; MR ₀ 80.71; calculated 80.75. Found: N 9.67%; 9.86%. C ₁₆ H ₂₈ N ₂ O ₂ . Calculated: N 9.99%. b) From 113 g of 1,3-di- (N-piperidyl) -isopropanol and 39.5 g of acrylic acid, 88.65 g (63.3% of theory) are obtained under the conditions as described in Example 4b. 1,3-di (N-piperidyl) isopropyl acrylate; Bp 115 to 116 ° C / 0.5 torr; nf 1.4860.

Example 9

1,3-Di (tert-butylamino) isopropyl methacrylate CH ₂ = C (CH ₃ ) - COOCH [CH ₂ NH - C (CH ₃ ) ₃ ] ₂

From 72.1 g of 1,3-di- (tert-butylamino) -isopropanol and 100 g of methyl methacrylate, 71.2 g (74, 5% of theory) 1,3-di (tert-butylamino) isopropyl methacrylate; Bp 104-108 ° C / l torr; n'i 1.4470. Found: N 10.08%; 10.15%. C ₁₅ H ₃₀ N ₂ O ₂ . Calculated: N 10.37%. Neutralization equivalent 135.5; calculated 135.

Dipicrate: yellow crystals; F. 205 to 206 ° C (from Methanol).

Example 10!, S-Di-Ctert.-hexylamino / isopropyl methacrylate

CH ₂ = C

Example 11
1-diethylamino-S-diallylarnino-isopropyl acrylate

CH ₂ N (C ₂ H ₅ J ₂

CH ₂ = CHC-O-CH
O

CH ₂ N (CH ₂ -CH = CH ₂ ) ₂

From 9 g of acryloyl chloride and 18.1 g of 1-diethylamino-3-diallylamino-isopropanol, under the conditions as described in Example 6, 20.5 g (91.5% of theory) of 1-di-ethylamino- 3-diallylamino-isopropyl acrylate; Bp 91.5 ° C / 0.4 torr; n ² g 1.4662; rf? 0.9249; MR _D 84.00; calculated 84.22. Found: N9.55%. C ₁₆ H ₂₈ N ₂ O ₂ . Calculated: N9.99%.

Example 12
1-diethylamino-3- (N-piperidyl) isopropyl acrylate

CH ₂ N (C ₂ H ₅ J ₂

CH ₂ = CHC-O-CH

CH ₇ N

CH ₂ -CH ₂

OH2 C Γ12

CH,

CH ₇ N

CH ₇ N

From 25.8 g of 3-di- (tert-hexylamino) isopropanol and 30 g of methyl methacrylate, 18.6 are obtained in the presence of 2 g of diphenyl-ρ-phenylenediamine and sodium methylate under the conditions as described in Example 1 g (57.7% of theory) 1,3-di (tert-hexylamino) isopropyl methacrylate; Bp 101-103 ° C / 0.5 torr; ng 1.4570; rf? 0.9042; MR ₀ 98.40; calculated 98.33. Found: N 8.50%; 8.72%. C ₁₉ H ₃₈ N ₂ O ₂ . Calculated: N 8.57%. Neutralization equivalent 162, calculated 163.

Dipicrate: yellow crystals; F. 202 to 203 ⁰ C (from methanol).

From 21.4 g of 1-diethylamino-3 - (N-piperidyl) -isopropanol and 9.9 g of acryloyl chloride, under the conditions as described in Example 6, 25.3 g (84.4% of theory) are obtained 1-Diethylamino -3 - (N - piperidyl) - isopropyl acrylate. Bp 93 to 94 ° C / 0.4 Torr; ηϊ; 1.4693; rf? 0.9553; MR ₀ 78.29; calculated 78.34. Found: N 10.03%. C ₁₅ H ₂₈ N ₂ O ₂ . Calculated: N 10.42%.

C (CH ₃ J ₂ CH ₂ CH ₂ CH ₃
H

^ C (CH ₃ J ₂ CH ₂ CH ₂ CH ₃

Example 13
1-diethylamino-3- (N-piperidyl) isopropyl methacrylate

CH ₃

CH ₂ N (C ₂ H ₅ ),

CH ₇ = C-COOCH

CH ₇ N

CH ₇

CH ₇ -CH ₇

From 7.8 g methacryloyl chloride and 15.77 g 1-diethylamino-3- (N-piperidyl) isopropanol under the conditions as described in Example 6, 18.2 g (88.5% of theory) of 1-diethylamino are obtained - 3 - (N - piperidyl) - isopropyl methacrylate. Kp.

98 to 100 ° C / 0.5 torr, nf 1.4684; df 0.9431; MR ₀ 83.28; calculated 83.155. Found: N 10.15%; 10.30%. C ₁₆ H ₃₀ N ₂ O ₂ . Calculated: 9.94%.

Example 14

1-diethylamino-3- (N-morpholyl) isopropyl methacrylate

CH ₃
CH ₇ = C-COOCH

CH ₂ N (C ₂ H ₅ ),

CH ₇ N

, CH ₂ CH ₇

CH ₂ -CH ₂

In a transesterification reactor, as described in Example 1, 24.4 g of l-diethylamino-3- (N-morpholyl) -isopropanol, 34 g of methyl methacrylate, 1 g of diphenyl - ρ - phenylenediamine and 0.5 ml of 25% sodium methylate solution in anhydrous methanol brought in. The mixture is heated on the oil bath and the azeotropic mixture is methanol and methyl methacrylate distilled off at 64 to 65 ° C. Another 0.3 ml is added to the reaction mixture Add catalyst solution, 0.1 ml each time, every 15 to 20 minutes. The reaction has ended after 1 hour. That The mixture is filtered off and distilled under vacuum.

24.4 g (75.7% of theory) of 1-diethylamino - 3 - (N - morpholyl) - isopropyl methacrylate are obtained. Bp 115-116 ° C / 0.7 torr; n ^! g 1.4690. Found: N 9.50%; 9.74%. C ₁₅ H ₂₈ N ₂ O ₃ . Calculated: N 9.84%.

Example 15

1- [N-methyl-N- (2-dirnethylaminoethyl) amino] ethyl methacrylate

CH,

CH ₃

From 17.4 g of 2- [N-methyl-N- (2-diethylaminoethyl) amino] ethanol and 25.8 g of methyl acrylate, under the conditions as described in Example 16, 18.4 g (80 , 7% of theory) corresponding diamino ester. Bp 109-110 ° C / 6 torr; nf 1.4540; df 0.9257; MR _D 66.80; calculated 66.68. Found: N 12.16%; 12.32. C ₁₂ H ₂₄ N ₂ O ₂ . Calculated: 12.27%.

'5

CH ₂ = C-COOCH ₂ CH ₂ NCH ₂ CH ₂ N (CH _{3) 2}

Obtained from 72 g of 2- [N-methyl-N- (2-dimethylaminoethyl) amino] ethanol and 150 g of methyl methacrylate one under the conditions as described in Example 1, 96.6 g (90.2% of theory) corresponding Diamino ester.

Bp 96.5 ° C / 4 torr; n? 1.4557; df 0.9405; MR ₀ 61.90; calculated 62.06. Found: N 12.88%; 12.99%. C ₁₁ H ₂₂ N ₂ O ₂ . Calculated: N 13.07%.

Example 16

2- [N-methyl-N- (2-dimethylaminoethyl) amino] ethyl acrylate

CH ₂ = CHCOOCH ₂ CH ₂ N (CH ₃ ) CH ₂ Ch ₂ N (CHj) ₂

In a transesterification reactor, as described in Example 1, 72 g of 2- [N-methyl-N- (2-dimethylaminoethyl) - amino] - ethanol, 129 g of methyl acrylate, 1 g of p-oxydiphenylamine and 5 g of titanium tetra-butoxide brought in. The mixture is heated and the methanol which forms in the reaction is in the form an azeotropic mixture with methyl acrylate at 62.5 to 64 ° C distilled off. During 3 hours 14.6g of methanol (91% of the calculated amount) was distilled off. The excess methyl acrylate will distilled off using a water pump and the residue in a short rectification column distilled under vacuum. 85.7 g (85.7% of theory) of 2- [N-methyl-N- (2-dimethylaminoethyl) are obtained - amino] - ethyl acrylate.

Bp 89 to 92 ° C / 6 torr; η? 1.4552; df 0.9495; MR _D 57.25; calculated 57.45. Found: N 13.73%; 13.82%. C ₁₀ H ₂₀ N ₂ O ₂ . Calculated: N 13.95%.

Dimethiodide: M.p. 176 to 179 ° C (with decomposition). Found: J 52.40%; N 5.32%; N 5.32%. C ₁₂ H ₂₆ I ₂ N ₂ O ₂ . Calculated: J 52.42%; N 5.78%.

Example 17

2- [N-methyl-N- (2-diethylaminoethyl) amino] ethyl acrylate

CH ₃
CH ₂ = CHCOOCh ₂ CH ₂ NCH ₂ CH ₂ N (C ₂ H ₅ J ₂

Example 18

2- [N-allyl-N- (2-diethylaminoethyl) amino] ethyl acrylate

CH ₇ = CHCOOCh ₇ CH ₇ N

CH ₇ CH = CH,

CH ₂ CH ₂ N (C ₂ H ₅ I ₂

20.0 g of 2- [N-AlIyI-N- (2-diethylaminoethyl) -amino] -ethanol, 34.4 g of methacrylate and Ig diphenyl-p-phenylenediamine are introduced into a transesterification reactor. The mixture is heated to the boiling point, a few grams of methyl acrylate are distilled off to remove traces of water which may be present in the mixture, and 1 g of titanium tetraisopropoxide is added. After a few minutes, the temperature of the vapors drops to the boiling point of the azeotropic mixture of methanol / methyl acrylate. 7.1 g of azeotropic mixture, which contains 2.92 g of methanol, are distilled off over the course of 65 minutes. This means that the transesterification took place to 94.3%. The reaction products are distilled under vacuum; 19.3 g (75.8% of theory) of the corresponding diamino ester are obtained. . Kp 107 to 109 ⁰ C / 2 Torr; «IP 1.4640; df 0.9338. MR ₀ 75.14; calculated 75.45. Found: N 12.66%; 12.88%. C ₁₄ H ₂₆ N ₂ O ₂ . Calculated: 11.02%.

Example 19
2- [N, N-bis (2-diethylaminoethyl) amino] -

ethyl acrylate

CH ₂ = CHCOOCh ₂ CH ₂ N

40 CH ₂ CH ₂ N (C ₂ Hj) ₂

CH ₂ CH ₂ N (C ₂ H ₅

55

60 25.9 g of 2- [N, N-bis- (2-diethylaminoethyl) amino] ethanol, dissolved in 25 ml of acetonitrile, are added to the solution of acryloyl chloride in 50 ml of anhydrous acetonitrile with stirring over the course of 20 minutes. while maintaining the temperature of the mixture to at most 50 ⁰ C. The mixture is heated for 1 hour, cooled to room temperature, 4.5 g of dry, crushed sodium hydroxide are added and the mixture is stirred until it dissolves. The precipitated sodium chloride is filtered off, 0.1 phenothiazine is added to the filtrate and the solvent is distilled off in vacuo. Vacuum distillation of the residue gives 23.6 g (75.4% of theory) of the corresponding triamino ester, boiling point 145 to 149 ° C. / 0.8 to 0.9 torr; n ^! S 1.4650. Found: N 13.67%; 13.71%. C ₁₇ H ₃₅ N ₃ O ₂ . Calculated: N 13.41%.

Example 20

3- [N, N-bis (2-dimethylaminoethyl) amino] propyl methacrylate

CH ₃
CH ₇ = CCOOCH ₇ CHoCH ₇ N '

CH ₂ CH ₂ N (CHj) ₂

CH ₂ CH ₂ N (CH _{3 2} J

609 650/41

21.7 g of 3- (N, N-bis (2-dimethylaminoethyl) amino] propanol, 30 g of methyl methacrylate, 0.3 g of phenothiazine and 1 g of titanium tetra-η-butoxide are placed in a transesterification flask The azeotropic methanol-methyl methacrylate mixture is distilled off at 64 to 65 ° C. 2.88 g (90%) of methanol are distilled off over 45 minutes, 22.9 g (80.3% of theory) of 3 being obtained by vacuum distillation - [N, N-bis (2-dimethylaminoethyl) amino] propyl methacrylate in the form of a colorless liquid; bp 90 to 93 ° C / 1 Torr; n ' _D ° 1.4576. Found: N 14.46% 14.37%. C ₁₅ H ₃₁ N ₂ O _2. Calculated: N 14.72%.

At s ρ i el 21 ' ⁵

3- [N, N-bis (2-diethylaminoethyl) amino] propyl methacrylate

CH ₃ CH ₂ CH ₂ N (C ₂ H ₅ I ₂

CH ₂ = C-COOCH ₂ CH ₂ Ch ₂ N

CH ₂ CH ₂ N (C ₂ H ₅ I ₂

From 13.7 g of 3 - [N, N - bis - (2 - diethylaminoethyl) amino] propanol and 20 g of methyl methacrylate, the procedure described in Example 20 in the presence of 1 g of titanium tetra-n-butoxide and 0 gives , 2 g phenothiazine 12.6 g (74.2% of theory) ₃ q corresponding triamino ester. Bp. 130 to 134 ° C / 0.5 Torr; «? 1.4680; df 0.9190; MR ₁ , 103.3; calculated 102.95. Found: N 12.41%; 12.48%. C ₁₉ H ₃₉ N ₃ O ₂ . Calculated: N 12.30%.

Example 22

3- [N, N-bis (2-diethylaminoethyl) amino] propyl acrylate

CH, = CHCOOCH, CH, CH, N

CH ₂ CH ₂ N (C ₂ H ₅

CH ₂ CH ₂ N (C ₂ H ₅ I ₂

To the solution of 5 g of acryloyl chloride in 30 ml of anhydrous dimethylformamide, introduced into the acylation reactor described in Example 2, 13.65 g of 3- [N, N-bis- (2-diethylaminoethyl) -amino] -propanol are added with stirring for 20 minutes , dissolved in the same volume of dimethylformamide, introduced. The temperature of the mixture rises from room temperature to 50 ^° C. The mixture is ^{heated to 100 °} C., stirred for a further 30 minutes, cooled and 3 g of sodium hydroxide, dissolved in 4 ml of water, are added. The precipitated sodium chloride is filtered off and the filtrate is distilled in vacuo. 12.55 g (76.8% of theory) of 3- [N, N-bis (2-diethylaminoethyl) amino] propyl acrylate are obtained; Bp. 139 to 142 ° C / 0.6 Torr; « ^? ₀ ° 1.4670; d ? 0.9292; MK _D 97.81; calculated 98.33. Found: N 12.82%; 12.85%. Q ₈ H ₃₇ N ₃ O ₂ . Calculated: N 12.83%.

Claims (1)

Claim: Process for the production of acrylic and methacrylic acid esters of monohydric polyamino alcohols, characterized in that either acrylic acid or methacrylic acid or their acid chlorides or their alkyl esters with an alcohol with a maximum of 4 carbon atoms in a manner known per se with a monohydric polyamino alcohol of the formulas