CS223883B2 - Method of making the n-substituted amide alpha,beta-nonsaturated carboxyl acids - Google Patents

Abstract

alpha, beta-Unsatd. N-substd. amides of formula R-CH=CH-CO-NH-Y-Z (I), where R is H or CH3; Y is an (un)branchd 30C (2-18C) residue, esp. of formula -Y1/m-Y2/n-Y3/t, in which the Y gps. are alkylene or the residue of a 5- or 6-member organic ring, and m+n+t is 2 or 3; and Z is H or the residue of an amine of formula -NR1R2, in which R1 and R2 are 1-4C alkyl, are prepd. by (a) amidation of a beta-hydroxy-carboxylic acid amide (II) with an amine of formula H2N-Y-Z, followed by (b) catalytic dehydration of the N-substd. beta-hydroxy-carboxylic acid amide (III) in the gas phase. The process is simple and gives high yields. Formation of polyester, with elimination of amine, is avoided.

Description

N-substituted alkyl acrylamides have long been known. They can be obtained by reacting acrylonitrile with 1-olefins (JACS 73, 1951, 4076), and by reacting primary or secondary amines with the maleic anhydride and triphenylphosphine addition compound (JP-PS 6 920 083). According to GB-PS 746 747, N-substituted acrylamides can be obtained by dehydrohalogenation of β-chloropropionamides and according to DE-OS 2 344 070 by pyrolysis of β-methoxypropionamides. Further, they can be produced by the Schotten-Baumann reaction by treating the corresponding diamines with acryloyl chloride (US-PS 2 951 907), by catalytic addition of functionalized amines to acetylene under carbon monoxide (US-PS 2 773 063), by reductive amination of diacetone acrylamide []. Polym. Sci. 10, (1972), 595], and by pyrolysis of norbornene derivatives (DE-OS 2 353 602). Further, these compounds can also be obtained by the process of DE-OS 2 502 247, DE-OS 2 656 682 and US-PS 3 878 247, wherein amines are added to the acrylic or methacrylic esters with simultaneous aminolysis. The resulting N-substituted β-aminopropionamides are pyrolytically cleaved to the corresponding N, β-unsaturated N-substituted carboxylic acid amides. The earlier unpublished German patent applications 28 19 735 and P 28 36 520 describe methods for producing N-substituted α, β-unsaturated carboxylic acid amides by reacting β-hydroxy or β-alkoxy acids with amines to eliminate ammonia, from the resulting N-substituted hydroxy- or alkoxy-acid amides by dehydration or by cleavage of the alcohol, the corresponding N-substituted amides of the corresponding N, β-unsaturated carboxylic acids are obtained. The dehydration or cleavage of the alcohol is carried out by heating in the liquid phase in the presence of catalysts.

It has now been found that N-substituted amides of N, N-unsaturated acids can also be obtained technically and in high yield by N-substituted amides of β-hydroxy- or β-alkoxycarboxylic acids dehydrated or dealcoholized in the gas phase to the desired N-substituted amides of N, N-unsaturated carboxylic acids.

The present invention provides a process for the preparation of the β-unsaturated carboxylic acid amides of formula (I)

HR ^C ^ ^C ^ C-NH

II о

(Y) - (XJ (I) wherein

R ¹ or R ² is hydrogen or methyl,

Y represents a divalent linear or branched organic radical having 2 to 30, preferably 2 to 18 carbon atoms, preferably a group of the formula wherein each of Y ₁ , Y ₂ and Y ₃ represents an alkyl group or a radical of a cyclic system of 5 or 6 carbon atoms values of numbers m, nat is number 2 or 3 a

X represents hydrogen or an amine residue of the formula --N (R ^z ') (R ⁵ ) wherein each of R ^Z1 and R ⁵ is C 1 -C 4 alkyl, by reamidation of 4-substituted carboxylic acid amides with primary amines of formula II

H ₂ N - (Y) - (X) (П) where

X and Y are as defined above while eliminating ammonia and converting the resulting N-substituted carboxylic acid amides into N-substituted carboxylic acid amides and α-unsaturated carboxylic acids, wherein ω-substituted carboxylic acid amides are used as starting materials. of formula III fZ)

O (lil) where

R ¹ and R ² are hydrogen or methyl,

Z is hydroxy or an alcohol moiety of the formula R ⁸ O-, wherein R ⁸ is C 1 -C 4 alkyl, the resulting N-substituted (Z-hydroxy- or) 3-alkoxycarboxylic acid amides being N-substituted amides; - the unsaturated carboxylic acids are converted by gently evaporating, their vapors are passed through solid catalysts for dehydration or the removal of alcohols at a temperature of 200 to 400 ° C, using metal oxides as solid catalysts for dehydration of amides / 3-hydroxycarboxylic acids, preferably alumina and silica or impregnated support catalysts, preferably acidic alumina or pumice stone impregnated with phosphoric acid or a salt, preferably aluminum phosphate or boron phosphate, and inorganic acid oxides are used as solid catalysts for the cleavage of alcohols from amides / 3-alkoxycarboxylic acids of an alkaline or basic nature, preferably alumina, silica or barium oxide, which are optionally still impregnated.

The conversion of the N-substituted amides of the (3-hydroxy- or Z-alkoxycarboxylic acids) to the N-substituted amides of the [alpha], [3-unsaturated carboxylic acids] by dehydration or by cleavage of the alcohol is thus not carried out in the liquid phase; The hydroxy- or .beta.-alkoxycarboxylic acids are evaporated, preferably under gentle conditions, to remove the water or alcohol, and their vapors pass through a solid catalyst. The catalyst is conveniently located in a heatable reaction tube. The gentle evaporation is preferably carried out under vacuum in a vacuum evaporator. Compared to liquid phase pyrolysis, in which the product in the boiler is subjected to thermal stress for a longer period of time, the residence time in the hot reaction tube in this process is very short. This minimizes the risk of side reactions such as polymerization or auto-condensation of the N-substituted amide / 3-hydroxycarboxylic acid amide to the polyester while cleaving the amine, which cannot be avoided in the liquid phase process at high temperatures.

The reamldation is conveniently carried out at a temperature in the range of from 100 to 200 ° C, optionally with the addition of a catalytic amount of acids. Acetic acid in an amount of from 0.5 to 1.0 mole% is particularly suitable as a catalyst using ω-3-alkoxycarboxylic acid amides. The acid amide and the amine can be reacted in a solvent-free reaction by simply heating, with the reaction equilibrium shifting in the direction of the desired [N-substituted amide (Z-hydroxy- or β-alkoxycarboxylic acid) amide products by stripping off the resulting ammonia.

The reamidation can also be carried out at normal pressure without the addition of a catalyst, with the eye lying in place to maintain the reaction time.

6ο 6 hours, amines with boiling points above 110 ° C are used.

Preferably, amines are used which additionally form a homogeneous phase with the acid amide melt or are partially soluble in the acid amide melt or dissolve part of the acid amide themselves.

Lower ^and fine mod ^{p and} expanded ustnos ^t mffie in ^E ST к initial slow down the reaction. However, as the degree of conversion increases, the reaction rate increases because the resulting N-substituted (hydroxy- or) -alkoxycarboxylic acid amide serves as a solubilizer and a homogeneous phase is formed. Order. remove the initial induction period is above ODN ^{h e s: p} and t ^{to Ca} u ^{t BC} IDA ^5-10 θθ ^N -sulfonyl ^b stituovaného amide of β-hydroxy or (--alkoxykarboxylové acid which is formed during the reaction itself.

The amine can always be used in excess of the hydroxy or alkoxy acid amide.

The dehydration or cleavage of the alcohol is preferably carried out at a temperature of from 20 to 400 ° C, for amides of amine-containing hydroxyl or boxylic acids, temperatures up to 250 ° C are sufficient.

Jalka dehydratateň katotyzátoJty ^h is a particular example oxides ^says. metals such as alumina. Further suitable also mixed oxides of j and ^k o is napřtaad blend ^alkyl sl ^IR her ^to at toimtolio and ^ hčrnku krémimtéta NETIO also impregnated carriers, such as acidic alumina, or pumice impregnated with phosphoric acid or also salts, such as fos ^f ore ^No. nan Rotten or borate phosphate.

As solid catalysts for elimination alkotato with ^H for ^{the DI} particularly anorgamc ^a l ^ky pulcherrima ^{ky ky} with ^artificial or ^b Ažić ^to e ^{p ovahy,} as well as alumina and kíemičRý therefrom kysltomk ^b Arnat which are optionally also impregnated with ^P of manufacture and ^{d kl alkyl} sellnou axis ^{f f} ore ^No. Nou or bases napnktad ^{hydroxyacetophenone id} em sulfate.

Amide such as β-hydroxycarboxylic acids according to the invention preferably utilizes amide β-hydroxypropionic acid or amide / 3hydroxym ^{á é} numerical kyselmy.

Pr ^IKL and ^d y vhochiých otactaho amine ^of the formula II

H ₂ N - Y) - X) ⁽¹ ') may be mentioned 2-dimethylamino ^{hyl yl} lammoet ^amш, 2- ^di ethylammoettylamn tedimethylammopropyl · amine, benzylamine, cyclohexylamine, dodecylamine and stearylamine.

Preferred amines are those of the general formula II.

where

R ⁶ and R ^{7 Pla d} represent alkytekupin ^ preferably lower alkyl groups having 1 to 4 carbon atoms, especially methyl or arylsku ^pi ny or ^R6 and ^{R7 d} o ^h roma ^dy Ivon aliphatic ring, especially cyclohexyl or cyclopentyl radical, n is 0 to 10 a

X represents a residue of an amine of formula - N (R 4) (R) ^kd e ^R4 and ^R5 pose a ^p alk ^yl group ^{Y 1} AIZ 4 carbon atoms or cycloalkyl having ³ to 8 carbon atoms .When.

The divalent organic radical Y may be a straight or branched alkylene radical which is optionally substituted. When Y represents a group of the general formula

-'Υί) «- (γ ₂ ) _η - (γ ₃ ) _ι can each of the residues

Y _b Y 2 and Y- represent a straight or branched optionally substituted alkylene group or a radical of a cyclic organic system having 5 or 6 carbon atoms.

The cycloalkyl radical may also be substituted, for example by alkyl groups.

When X represents the radical of an amine of formula -N (R ⁴⁾ (R) residues of ^R4 and ^R5 is a scaled ^to the same ^{e b} of not гй ^^ represent straight or branched alkyl, for example methyl, ethyl, propyl, isopropyl, or n-butyl or also cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

The radical Z in formula (III) may, when it is a radical of the formula ^{r @ 8} O--, ^k de ^{r @ 8} represents a straight or branched alkyl radical, for example methyl, ethyl, propyl, isopropyl or n-butyl.

Examples of preferred amines are. uv ^E ST amine type ^{y N ', Nt} 2/2 ^{- yl} eframeth ^p ro ^py ene-l, 3-diamine (dimethylamrnoneopentylamin-u) (Formula H', n = 1 ^{R 6} = R ⁷ = CH ^-) especially the following amines:

3 ^ <^ im <^ t ^ ^ ylamino-í - (^ ii ^^^ tl ^ 5 ^ 1] ^] ^ op ^; la ^ in

CH-CH 2

N — CH3 — C — CH2 — NH2,

ZI

CH ₃ CH (11 ')

1- (aminomethylene) -1- (dimethylaminomethylene) cyclohexene

Г

F

3-diethylamino-2,2-dimethylpropylamine

С ₂ Н ₅ CH

N — СН ₂ —С — СН _{2 —} NH ₂ ,

С ₂ Н ₅ CH

3-Dibutylamino-2,2-dimethylpropylamine

С ₄ Н ₉ СН \ I

N — СН ₂ —С — СН _{2 —} NH ₂ , / I

С ₄ НуСНз

4-dimethylamino-3,3-dimethylbutylamine

СНзСН \ / n-ch ₂ -c — ch ₂ -ch ₂ -nh ₂ , \

СНзСНз

5-dimethylamino-4,4-dimethylpentylamine

СНзСН \ I

N — СН ₂ - С — СН ₂ —СН ₂ —СН ₂ - nh ₂ ,

СНз 'СНз

5-diethylamino-4,4-dimethylpentylamine

С ₂ Н ₅ СН ₃

N — сн ₂ —с — сн ₂ —сн ₂ —сн ₂ —nh ₂₁ / I

С ₂ Н ₅ СНз

3-dimethylamino-2-ethyl-2-methylpropylamine

СН ₃ СН ₃ \ I

N — СН ₂ —С — СН _{2 —} NH ₂ ,

СНз С ₂ Н ₅

3-dimethyliamino-2-methyl-2-phenylpropylamine

СН ₃ СН ₃ \ I

N — СН ₂ —С — СН _{2 —} NH ₂₎ / I

СНз С ₆ Н ₅ and 3-dimethylamino-2-ethyl-2-bu, tylpropylamine

СНз С ₂ Н ₅

N — СН ₂ —С — CH ₂ -NH ₂ а

Z I

СН ₃ С ₄ Н ₉

In these amines, the carbon atom in the β position relative to the tertiary amino group carries no hydrogen atom, but is substituted by an alkyl group. According to the invention, these amines of the formula II which do not carry a hydrogen atom on the carbon atom in the β-position relative to the tertiary nitrogen are preferred because the reaction products produced using these amines cannot undergo ε-elimination of the amine. Such cleavage of the amine, which could result in the formation of a further terminal double bond in addition to the α, δ-double bond in monomeric N-substituted amides and α, δ-unsaturated carboxylic acids, is highly undesirable from the viewpoint of using monomeric acid amides for water-soluble polymers since this double bond could cause undesired cross-linking.

In addition, the hydrophilicity or hydrophobicity of the monomers and polymers produced therefrom can be modified by a suitable choice of the D-substituents.

The present invention further provides a process for the preparation of novel N-substituted amides and .beta.-unsaturated carboxylic acids of the general formula:

(Г) where

R ¹ and R ² are hydrogen or methyl,

R ⁶ and R ⁷ represent alkyl, preferably lower C 1 -C 4 alkyl, in particular methyl or aryl, or R ⁶ and R ⁷ taken together form part of an aliphatic ring, in particular a cyclopentyl or cyclohexyl ring, n is an integer of 0 to 10 and

X represents the residue of an amine of formula -N ^{(R4) (R5)} wherein ^R4 and ^R5 represents an alkyl group having 1 to carbon atoms or to cyktealkylskupinu -C8 ^y uhhto.

The N-substituted amides and / or unsaturated carboxylic acids prepared by the process of the invention can be readily polymerized either alone or together with other polymerizable monomers by methods known per se, except for copolymers, copolymers and other mixed polymers. These polymers are excellent flocculating agents, drainage and waste water treatment and is ^{suitably continued} for ZTE e ^ sov ^ i ^{p p} and ^p evnosti handbook and dry. wet and as retention aids. In these polymers, the elimination of the amine would cause a decrease in specific activity and, ultimately, a complete loss of efficacy.

Monomeric products produced by VYN ^AL Cutting of ^l ^ Rzovat neu and / kvar Neto ^t era ^also regarded.

The invention is illustrated by the following examples.

Example 1

N- (N ^ N ^^^ tetramethylammopropyl) 1 acrylamide (= TEMAPA)

471 g (3-hyddOxypropionamidu and 722 g of N, N, _2.> 2 - etгamethylpropylen-l, 3-diamieu heated for 7 hours at 140 to 160 ° C until ammonia evolution ceases. ^P o iiásledujkí distillation using an evaporator to thin film evaporation to give 1058 g of e-hydroxy-N- (N ',.', ² ', ^2' -te.tramethylaminopropyl) ^p ropionamidu, b.p. ²⁰⁶ ° ^C / ^1.33 to ^P.

NMR: (CDCl 3). δ = 0.9 (s, 6),

2.25 (s, 2h.)

2.3 (6 ^s), 2. 45 (t, 2), 3.2 (d, 21, 3.9 (t, 2).

917 g of hydroxyproduct are evaporated in a thin-layer evaporator (evaporator temperature 230 ° C, vacuum 1 kPa) and the vapors are passed through a reaction tube filled with 700 g of aluminum oxide heated to 200 ° C. f ^ j ^ new procedure ^of i ^kA 727 ^g of N- (N ', ^N', 2 ^', 2'-tetra ^m ethyl a ^m inopropyljakrylamtáu. boiling point ¹³⁷ ° C / 1 mbar.

NMR: (CDCl ₃ ) δ = 0.9 (s, 6), ² &^gt; ³ (m, 8),

3.25 (d @ 2)

5.4 to 6.2 (m, 3), (see Figure ¹ ).

Example 2

N- (N ^{', N'-2,} 2-te ^{t ramethyl-3-aminopropyl)} -3-methoxypropionamide

A mixture of 412.5 g (40 moles) of 3-methoxypropionamide, 547 g (42 moles) of NN, 2,2-tetramol-4-ylpropyl-1,4-dimethylamine and 4 ml of ice The acetic acid was heated at 145-170 ° C for 8 hours until the ammonia evolution had ceased. The following distillation under high VA ^to UA zfeká 8 ² 0 ^g (32 mol - 95% of theory) of a colorless liquid, bp 105-108 ° C (26.7 Pa).

NMR (in CC1 _4): delta = 0.9 (s, 6), ^{2,0 and 2,5} 1 °)

^3, 05 (d ^ 2

3.33L

^3, 55 (t 22 ^7, 401).

N- (N ^{', N'} - ^{2, 2} ~ te l ^! R ^ i ^ 1 ^ 1 ^ '^ ^L - ³ -iai ^ ii ^ i ^] ^) ro ^p' yl) acrylamide

To ^B & ^ňky from ^P and ^R s ^when U zahHvané to ¹⁷⁰ to 180 ° C was continuously brought in total 820 ^g of frames ^(3, 8 mol) of N- (N ^{', N', 2, 2, h} y ^l tetramethyl - 1 3-aminopropyl) -3-methoxypropioeamidu and vapor under vacuum 1.4 psi fed into the reaction tube (1000 mm length, 30 mm diameter) packed with spherical particles of alumina impregnated with 1% ^{hydroxypropyl 0 d} Roxi in solution. The reaction tube is heated to 300 ° C with an external heating mantle. At head temperature of ^{150-2 20} ° C in ^P r ^u b u ^{EH 2} ^ n Liot collected about 4 ^{75 g} amber ^eh oo ^{l eje,} which has been purified by vacuum distillation. There were obtained 383 ^{g of} a RAM ^(2, 1 motorcycle = ^52% of theory based on 3-methoxypropioeamid) of product boiling at 98-102 ° C (26.7 Pa).

NMR (in CC1 _4): O =

0.9 (s, 6), 12.2 (s, ² L)

2.3 (s, 7),

^3, 15 (^ 2 ^

5.3 to ^{6.5 3} L ^8.0 (m ¹⁾ , (see Figure 1).

Example 3

N- (N \ N ^{', 2} 2-1etr Amethi · ^L -3-aminopropyl) -2-methyl-3-methoxypropioe.amid

One proceeds as described in Preparation ^kl and ^{DE 2} to 46 ^{8.6 g (4.0} mol) of 2-methyl131 -metlioxypropmnamidu zfelrá with 857 ^{g (3, 7, 9} moto = 3% 'of theory) of a colorless ^é liquid of boiling point 102 to 106 ° C (26.7 Pa).

NMR (in CC1 _4): O =

0.9 (s, 6),

^1, 05 (^ 3L

2.0 to 2.7 (m, 9),

3.05 2 ^

3.2 to 3.6 (m, 5),

7.3 1).

N- (N ^{', N', 2, 2-tetramethyl-l} 1 ³ -amieo ^p r opy ^ ME1 thakrylamid (= TEMAPA)

Following the procedure described in Example 2, 510 g of the product are obtained from 857 g (3.7 moles) of the precursor, and 420 g (2.1 moles = 53 why, theory based on 2-methyl-) are obtained under high vacuum distillation. 3-methoxypropionamide] b.p. 92-94 ° C.

NMR (in CC1 _4): δ = 0.9 (s, 6),

1.9 (d, 3)

2.2 (s, 2),

2.3 (s, 7),

3.1 (d.2),

5.1 to 5.7 (m, 2)),

8.0 (m, 1), (see Figure 2).

Example 4

N- (N ‘, N‘, 2 ‘, 2‘-tetramethylaminopropyl) crotonamide

412 g of i-hydroxybutyric acid amide and 546 g of N, N, 2,2-, tetra ^; of methyl propylene-1,3-diamine was heated to 148-160 ° C for 16 hours. 829 g of the reaction product were successively evaporated in a thin-layer evaporator (250 ° C, 1 kPa) and the vapors were fed into a reaction tube containing 700 g of alumina heated to 220 220 ° C. A total of 543 g of N- (N &apos;, N &apos;, 2 &apos;, 2 &apos; -tetramethylaminopropyl) crotonamide, b.p.

NMR (CDCl 3): δ = 0.9 (s, 6),

1.9 (dd, 3)

2.15 to 2.6 (m, 8)

3.35 (m, 2),

5.6 to 7.0 (m, 2'j, (see Fig. 3)).

Example 5

3-Methoxybutyric acid N- (N ‘, N‘, 2,2-tetramethyl-3-aminopropyl) amide

The procedure is as described in Example 2 and is obtained from 468.6 g (4.0 mol) of 3-methoxybutyric acid amide 800 g (3.5 mol = 87% of theory), a pale yellow liquid, boiling 112-114 ° C. .

NMR (CDCl 3): δ = 0.9 (s, 6),

1.15 (d.3)

2.0 to 2.5 (m, 10)

3.1 (d, 2), 3.35 (s, 3);

3.7 (q, 1)

7.7 (m, 1).

I .....

N- (N ‘, N‘, 2,2-tetramethyl-3dminopropyl) protonamide

By the method described in Example 2, not from 800 g (3.5 mol) of the precursor 587 g of product, which after distillation under high vacuum yielded 516 g (2.6 mol = 65% of theory), based on 3-methoxybutyric acid amide, light Yellow viscous oil, b.p. 104-108 ° C.

NMR (in CCl4): δ = 0.9 (s, 6),

1.8 (dd, 3)

2.1 (s, 2),

2.3 (s, 6),

5.6 to 7.0 (m, 2),

7.6 (m, 1).

.........AND

Examples 6 to 22

Analogously to Examples 1 to 5, the following compounds are obtained by reacting the corresponding amines with the corresponding amides of (Z-hydroxy- or) -S-methoxycarboxylic acids in a ratio of molar equivalents:

6 .:

N- (3-diethylamino-2,2-dimethylpropyl) acrylamide

Boiling point 110 ° C / 10 Pa, NMR see Figure 4

7.:

N- (3-diethylamino-2,2-dimethylpropyl) methacrylamide

Boiling point 117 ° C / 10 Pa, NMR see Figure 5

8.:

N- (3-diethylamino-2,2-dimethylpropyl) crotonamide

Boiling point 113 ° C / 3.5 Pa, NMR see Fig. 6

9 .:

N- (3-dibutylamino-2,2-dimethylpropyl) acrylamide

Boiling point 155 ° C / 9 Pa, NMR see Fig. 7

10 .:

N- (3-dibutylamino-2,2-dimethylpropyl) methacrylamide

Boiling point 125 ° C / 3.2 Pa, NMR see Figure 8

11 .:

N- (3-butylamino-2,2-dimethylpropyl) crotonamide

Boiling point 129 ° C / 3 Pa, NMR see Fig. 9

12 .:

N- (4-dimethylamino-3,3-dimethylbutyl) acrylamide

Boiling point 107 ° C / 8 Pa, NMR see Figure 10

13.:

N- (4-dimethylamino-3,3-dimethylbutyl) methacrylamide

Boiling point 113 ° C / 14 Pa, NMR see Figure 11

14 .:

N- (4-dimethylamino-3,3-dimethylbutyl) crotonamide

Boiling point 120 ° C / 3 Pa, NMR see Fig. 12

15 .:

N- (5-dimethylamino-4,4-dimethylpentyl) acrylamide

Boiling point 127 ° C / 3 Pa, NMR see Fig. 13

16 .:

N- (5-Dimethyl-amino-4,4-diine-1-pentyl) -methacrylamide

Boiling point 127 ° C / 4 Pa, NMR see Fig. 14

17 .:

N- (5-dimethylam crotonamide)

Boiling point 134 ° C / 3 Pa, NMR see Fig. 15

18 .:

N- ^{(5-diethyl hy} lammOc ^4, 4-dimethyl ^{r t} h ^hl pe.n ^yl) acrylamide

The boiling point of 0 · ¹³ ° C / 6 ^mbar, see NM ^R a R ^{b. 16}

19 .:

N- (5-diethylamino) -44-dimethyldterityl) methacryptam

Boiling point 132 ° C / 3.5 Pa, NMR see Fig. 17

20 .:

N- (3-dimethylaminocyclohexyl) -acrylamide,

Boiling point 98 ° C / 3 Pa, NMR see Fig. 18

21 .:

N- (3-dimethylaminocyclohexyl-C-methylpropyl) methacrylamide

Boiling point 98 ° C / 6 Pa, NMR see Fig. 19

22 .:

N- (3-dimerhylamino-2-methyl-2-methylpropyl) acrylamide

Boiling point 128 ° C / 6 Pa, NMR see Fig. 20

23.:

1- (acrylamidomeehylene) C1-4-methylamino-cyclohexene

Boiling point 122 ° C / 4 Pa, NMR (CClJ see Fig. 21)

24.:

1- (methacrylamidomethylene) -1-dimethylaminomethylene-cyclohexene

Boiling point 122 ° C / 5 Pa, NMR (CCl-) see Fig. 22.

After the ^above-P from Sanyo Úsobí ^p · produced amino compound may be converted by reaction with a suitable acid (e.g., sulfuric acid) to the corresponding amine salts, or they can be using the appropriate alkyl halide or alkyl sulfate quaternized. These procedures are illustrated in the following examples.

Example 2 3

T.rimethyl 3- (Ia ^to ryIam: up to _2; 2cdImrthylpropy) amoniummethosulfát

The mites ^to 2.8 with ^{9.5 g} of N ^ N ^ N ^^^ - tet ramethy] aminopropy1) ιak.rylamidu in 317 g of water under stirring and cooling with ice, 185.4 g of dimethyl sulfate over 2.5 ^d him in. After triḥ ^d ^ ine reaction with zfeká. 60% quaternary product solution.

EXAMPLE 24 (3-Acrylamide O, 2,2-Dimethylpropyl Hrimethylammonium Chloride)

A solution of 376 g of Nc (3-dimethylamino-2,2-di-methylpropyl) -acrylamide = TEMAPA from Example 1 in 320 g of water is pressurized with 103 g of methyl chloride over 3.5 hours with vigorous stirring at 80 ° C. The working pressure is 40 kPa. An aqueous solution of the quaternary product is obtained.

Claims (2)

A process for the preparation of N-substituted amides of N, β-unsaturated carboxylic acids of the general formula I c = c (Y) -W II o wherein: R ^{1, C o, PR} and ^P ad ^e R ^{2 BC} constitutes e ^d in ^{b thanks} not a methyl group, Y represents a divalent linear or branched organic radical having 2 to 30, preferably 2 to ¹⁸ carbon UMI Rednose ^t ^ ^p n ^of a group of formula _ (Υ ¹⁾ .._ (Υ ^2)! 1_ (Υ ³⁾ .where each symbol Yb Y2 and Y3 represents alkylenskuplnu radical or ring system having 5 or 6 carbon atoms and sum ^h o ^d m not ^numbers, the NAT is not insl 2 and 3 of ^b X represents hydrogen or a residue of an amine of formula -N (R ⁴⁾ (R ⁵⁾ e ^{k d} k ý ^moves from the MboI ^{Y of R 4} and R ⁵ e ^d constitute ^straight alkyl group having 1 to 4 carbon atoms or cycloalkyl of 3 to 8 carbon atoms , reamidam ^ ^ -substituted amide ^{of the} acid arboxylových primary amines of formula II H ^and Nc, (ϊ) -c (χι (II), where X and Y are as defined above preferably at a temperature of 100 to 200 ° C and optionally with a catalytic amount of acid; with the above ^h ou ^{d 0.5 and 1.0%} · motérmho ^alkyl selrny acetic ^Currently for elimination of ammonia and converting the resulting N-subs.tituovaných carboxylic amide on the N-substituted amides, N-unsaturated carboxylic acids, wherein 3. The method according to claim 1, wherein the 3-substituted carboxylic acid amides of formula III are used as starting materials II (Z) -CCC 2 R Y ^Z (III) wherein R ¹ and R ² are hydrogen or methyl, Z is hydroxy or an alcohol moiety of the formula R ⁸ O- wherein R ⁸ is C 1 -C 4 alkyl, the resulting N-substituted β-hydroxy- or β-alkoxycarboxylic acid amides to N-substituted α, β-3- amides unsaturated carboxylic acids convert so that they evaporate sparingly, their vapors are passed through solid catalysts for dehydration or dehydration of alcohols at a temperature of from 200 to 400 ° C, using metal oxides, preferably metal oxides, as solid catalysts for dehydration of amides / N-hydroxycarboxylic acids alumina or mixtures of oxides, preferably mixtures of alumina and silica or impregnated supported catalysts, preferably acidic alumina or pumice soaked with phosphoric acid or salt, preferably aluminum phosphate or boron phosphate, and as solid catalysts for the cleavage of alcohols from amides / S-alkoxycarboxy Inorganic oxides of an acidic or basic nature, preferably alumina, silica or barium oxide, which are optionally impregnated, are used. 2. A process according to claim 1, wherein the primary amines of formula II are those of the formula II * (X) wherein: R ⁶ and R ⁷ are alkyl, preferably C 1 -C 4 alkyl, especially methyl, or aryl, or R ⁶ and R ⁷ together form an aliphatic ring, especially a cyclohexyl or cyclopentyl ring, n is an integer of 0 to 10 and X is an amine residue of the formula -N (R ⁴ ) (R ⁵ ) wherein R ⁴ and R ⁵ are C 1 -C 4 alkyl or C 3 -C 8 cycloalkyl groups.