Method of producing derivatives of n-substituted ethyl(meth)acrylamide

专利摘要:
The invention relates to amides of carboxylic acids, in particular to the preparation of derivatives of N-substituted ethyl (meth) acrylamide formulas CH 2 = C (R) -CONH-CH (OR 2 ) -CH (OR 1 ) 2 , where RH, CH 3 R 1 - C 1 -C 4 -alkyl R 2 -H, C 1 -C 4 -alkyl which can be used as monomers for the preparation of the corresponding copolymers. The goal is to develop a method for obtaining new compounds with useful properties. The preparation is carried out by reacting (meth) acrylamide with dialkoxy-2,2-ethanal foryles (R 1 O) 2 CH-CHO, where R is indicated above, R 2 -H, followed by isolation of the target product, where R 2 -H or by esterifying it with a C 1 -C 4 alkanol in the presence of catalytic amounts of H 2 SO 4 followed by isolation of the compound Formula 1, where R 1 and R 2 are the same or different C 1 -C 4 alkyls. 3 tab.
公开号:SU1544184A3
申请号:SU874202148
申请日:1987-03-12
公开日:1990-02-15
发明作者:Шастретт Франсин；Стамбули Абдельхамид
申请人:Сосьете Франсэз Хехст (Фирма)；
IPC主号:

专利说明:

one
(21) 4202148 / 23-04
(22) 03/12/87
(31) 8603587
(32) 03/13/86
(33) FR
(46) 02.15.90. Bup. № 6
(71) Societe Frances Höchst (FR)
(72) Francine Schastrett (FR)
and Abdelhamid Istanbul (AI)
(53) 547.298.1.07 (088.8)
(56) European application N 0002767, cl. C 08 F 20/58, 1979.
(54) METHOD FOR PRODUCING N-SUBSTITUTED DERIVATIVES. ETHYL (MET) ACRYLAMIDE
(57) The invention relates to amides of carboxylic acids, in particular to the preparation of derivatives of N-substituted ethyl (meth) acryl amide and formulas (R) -CONH-CH (OR2) -CH (OR,) 1, where R is H R4 is C1-C4-alkyl; R is H, -alkyl, which can be used as monomers for the preparation of monomers for the preparation of the corresponding copolymers. The goal is to develop a method for obtaining new compounds with useful properties. The preparation is carried out by the reaction of (meth) - acrylamide with dialkoxy-2,2-ethanal formyl () ZCH-CHO, where R is indicated above; H. followed by isolation of the desired product, where R4 is H, or esterification of its Sc with C-alkanol in the presence of catalytic amounts of NdZO. followed by release of compound g of Formula I, where R1 and R are the same or different C 4 -Guly-GL. 3 tab.
The invention relates to a process for the preparation of new derivatives of N-substituted ethyl (meth) acrylamide of the general formula
ORi CHr C-CONH-CH-CH:
R
OR,
Wj
where R is hydrogen or methyl}
R is C4-C-alkyl;
R is hydrogen or C4-C4-alkyl, which can be used as monomers for the preparation of the corresponding copolymers.
The aim of the invention is to develop an affordable method of obtaining
derivatives of N-substituted ethyl (meth) - acrylamide of formula I, which can be used to obtain copolymers that do not even contain traces of formaldehyde.
Nuclear magnetic resonance spectra were recorded in deuterated chloroform. Chemical shifts are expressed in parts per million relative to tetramethylsilane, which is used as internal ethanol. The 4H NMR spectra were measured on a Varian radio spectrometer of the Varian company at 60 MHz, and NMR C spectra were measured on a Varian XL100 instrument at a frequency of 25.2 MHz with a Fourier transform. Mass spectra were taken on a Varian MatCH5 instrument at 70 eV.
SP
4 4
00
Ј

cm
Example 1. For 2 hours at 70 ° C in an inert atmosphere, 23.8 mmol of diethoxy-2,2-ethanal, 24 mmol of acrylamide, 0.1 mmol of paramethoxyphenol are heated.
This gives 23.3 mmol of N- - (diethoxy-2,2-hydroxy-1-ethyl) propen-2-amide, the NMR spectrum of this Compound has the following parameters 15.26 (2q, 2CH,), 63.53 (t, CH2), 63.96 (t, CHI), 73.6 (d, N-CHO). 102 (d, 0-CHO), 127.3 (m, CH2), 166 (s, N-CO), 130.8 (m, CH).
This product is dissolved in 1.38 g (30 mmol) of ethanol containing 0.49 g of concentrated sulfuric acid Lots per 1 l, then the solution is heated in an inert atmosphere at 70 ° C for 4 hours. The cooled reaction mixture is then diluted with water and the product obtained is extracted with dichloromethane. The combined organic phases are then washed in water, dried, filtered and evaporated in vacuo. After that, 5.1 g (21.2 mmol) of L- (triethoxy-1,2-ethyl) propen-2-amide are obtained under f melting point 33 + 2 C, the yield is 89% of the theoretical value, calculated with respect to K, taking the amount of ethoxy-2,2-ethanol.
Physical analysis: NMR H: 1.2 (t, 9H), 3.6 (t, 6H), 4.5 (d, 1H), 5.4 (dd, 1H), 5.8 (dd, H), 6 , 2 (t, 2H) „
NMR ° C: 15.08 (q, CH,), 15.18 (q, CH,), 15.25 (q, CH3), 63.36 (t, CH2) 64.0t (2t, CHa), 79.04 (d, 0-CH-N), 101.71 (d, 0-CHO), 127.2 (t, CH), 130.7 (m, CH2), 165.9 (s, NC-0).
Mass: (M231) (0%), 186 (2%), 161 (2%), 141 (5%), 139 (5%). 128 (6%), 103 (100%), 75 (53%), 59 (25%), 55 (20%)
Example 2. The following products are heated in an inert atmosphere at 70 ° C for 2 h: 67 mmol of acrylamide, 69 mmol of dimethoxy-2,2-ethanal, 0.14 mmol of paramethoxyphenol.
67 mmol of N- (dimethoxy-2,2-hydroxy-1-ethyl) propen-2-amide are obtained in the form of a colorless liquid. The NMR spectrum H at a frequency of 200 MHz in deuterated dimethyl sulfoxide is as follows: 8.41 (d, 1H, t - 9.1 Hz, NH), 6.31 (dd, 1H, f - 9.8 Hz and tf 17 Hz,) ,
1Н, С- У, о 1Ц And f - I / ii-i ,, v ../
6.14 (dd, 1H, t 2.6 Hz and Ј-17 Hz, CH, CH trans), 5.93 (d, 1H, - 5 Hz, OH), 5.62 (dd, 1H, 6 Hz
0
five
0
five
and Ј 9.8 Hz, cis), 5.25 (t, 1H, CH-N) 4.20 (d, 1H, 5.3 Hz, CH- (OMe) 4). 3.32 (s, 3N, OSI,), 3.29 (s, 3N, OSI) In an inert atmosphere at 70 ° C for 4 h, 67 mmol N- - (dimethoxy-2.2-hydroxy-1-ethyl ) - propen-2-amide, which is obtained as described above, 84 mmol of methanol containing 5 mmol of concentrated sulfuric acid per liter.
The reaction mixture is then diluted with water, and the product is extracted with dichloromethane. The mixture of organic phases is washed with water, dried, filtered and concentrated in vacuo. You get 40 mmol of M- (trimethoxy-1,2,2-ethyl) - propen-2-amide, which has a melting point of 70 + 3 C.
Physical analysis.
 (at a frequency of 200 11 Hz in a solution of deuterated dimethyl sulfoxide): 3.20 (s, 1H, OCH3), 3.29 (s, 3N. OCH}), 3.31 (s, 3N, OCH3),
Ome
4.30 (d, 1H, t 5.2 Hz, -SNSG
Ome
0 5.03 (dd, 1H. B 5.2 Hz, fr 9.5 Hz N-CH-0), 5.67 (dd, 1H, 2.5 Hz, about 9.8 Hz,), 6.16 (dd , 1H, C 2.5 Hz, 17 Hz,), 6.36 (dd, 1H, s-9.8 Hz, Ј 17 Hz,), 8.43 (d, 1H, 9.5 Hz, NH).
NMR ° C: 5.41 (OSIj), 54.5 (OSI),
five

0
0
five
55 (OSI a), 80 (N-CH), 103.1 (CH (),
126.6 (SND) 131.3 (CH), 165.3 (CO).
Example 3 According to Example 1, the reaction of acrylamide and dibutoxy-2 2-ethanal is carried out to obtain L crystallized M- (dibutoxy-2,2-β-hydroxy-1-ethyl) proton-2-amide, which has a melting point of 51 + 26 . Then, the resulting product is reacted with butanol in the presence of sulfuric acid, as in Example 1, to obtain crystallized M- (tribotox-1,2,2-ethyl) propen-2-amide with a melting point of 38 + 3 ° C.
Example 4. As in Example 1, the reaction was carried out: methacrylamide and dimethoxy-2,2-ethanal, the crystallized N- (dimethoxy-2,2-hydroxy-1-ethyl) methyl-2-propen-2-amide was obtained which has a melting point of 78 ° C.
five
The wire reacting the obtained compound in methanol in the presence of sulfuric acid, as in Example 1, gives crystallized M- (trimethoxy-1,2,2-ethyl) methyl 2-propen-2- -amide, which has a melting point of 38 ± 1 ° С.
Example 5. The reaction wire, as in Example 1, methacrylamide and dimethoxy-2 2-ethanal, gives crystallized No.- (dibutoxy-2,2-hydr-oxy-1-ethyl) methyl-2-propene -2-amide, which has a melting point
The resulting compound is reacted with butanol in the presence of sulfuric acid, as in Example 1, to obtain y- (tributoxy-1,2,2-ethyl) -methyl-2-propen-2-amide as a colorless liquid. The spectrum at 200 MHz in deuterated chloroform is as follows:
6.60 (d, 1H, 1 9.4 Hz, NH), 5.75 (s, 1H, trans), 5.39 (s, 1H, cis), 5.27 Cdd, IH. h 2.3 Hz and t 9.4 Hz, N-CH), 4.49 (d, 1H, 2.3 Hz, CH- (OVi) a), 3.7-3.4 Cm, 6, OCHg) 5 1.98 (s, 3N, C-CH,), 1.60-1.25 (m, 12H, CH2), 0.96-0; 85 (t, 9H, OC).
Examples 6-14. An emulsion is obtained by mixing at ambient temperature 459 g of a mixture of monomers containing, by weight. %: x is butyl acrylate, y is ethyl acrylate, z is methyl methacrylate, q is acrylic acid, p is the monomer (c) of formula (I) (example 2); 18 g of an emulsion mixture containing, in wt.%: Ethoxylated nonylphenol with 30 mol of ethylene oxide 37.5j ethoxylated oleoacetyl alcohol with 25 mol of ethylene oxide 37.5. sodium laurylether sulfate 25; 1 sodium hydrogen carbonate, 1.2 g sodium peroxodisulfate, 270.8 g water.
This emulsion having a pH of 4.65. then in 4 hours with stirring, injected in 250 g of water, kept at 80 + 2 ° C.
After the introduction is complete, cool the reaction mixture to ambient temperature, filter it to possibly remove some mechanical impurities, then adjust its pH to 5.7+ +0.2 if necessary.
In this way, 1000 g of a dispersion having characteristics, as specified, are obtained.
listed in table. 1, in which the following abbreviations are used: ES — dry extract, sustained in weight percent and determined by drying 1 g of the dispersion for 3 hours
 at 105 ° C
V is the Brookfield viscosity, determined at ambient temperature with a Brookfield viscometer RVT, equipped with an axis ax, 1-5, rotating - s with a speed of 100 rpm,
D is the particle size (average order of Z);
TG is the degree of swelling, determined at ambient temperature by immersion in trichlorethylene of a round flat sample with a diameter of 50 mm, cut from a dry film of the tested dispersion. The degree of swelling is simultaneously measured on a thermally unprocessed film (TGg) and on a film treated for 10 minutes at 150 ° C (TGt). It is calculated by the ratio
tg - di di TG
.100.
where dj is the initial diameter of the sample;
d.Ј - its final diameter
Tq - vitreous temperature
transition determined by differential thermal analysis on a film of the tested dispersion;
1 - the number of polydispersity in the slice;
Тг is the coefficient of free formaldehyde determined by high-resolution chromatography on a sample of dispersion.
Examples 15-18. An emulsion is obtained by mixing at ambient temperature 471.2 g of a mixture of monomers containing, by weight. %: x - butyl acrylate; u - ethyl acrylate; z is methyl methacrylate; q - acrylic acid, p - monomer (a) of the general formula (I), s-methacryloxy-2-propyl, MAHPI 21.6 g of an emulsion mixture containing, by weight. %: sodium lauryl ethyl sulfate 20.83, ethoxylated nonylphenol with 30 mol of ethylene oxide 47.92, ethoxylated oleoacetyl alcohol with 25 mol of ethylene oxide 31.25. 0.68 g sodium acetate, 1.22 g sodium peroxodisulfate, 275.03 g water.
This pre-emulsion, i'm blowing. pH 5.75. then in 4 hours while stirring, they are introduced into 250 g of water and Os, 27 g of sodium peroxodisulfate, maintained at 80 + 2 ° C.
After the introduction is complete, cool the reaction mixture to ambient temperature, filter it for possible removal of some mechanical impurities, then adjust its pH to 5.7 + 0.2, if necessary.
In this way, 1020 g of disperse having the characteristics indicated in Table 2 are obtained. 1 for dispersions devoid of methacryloxy-2-propane and in Table. 2 for other dispersions
Example 19. An emulsion is obtained by mixing at ambient temperature 450 g of a mixture of monomers containing, by weight. %:
Butyl Acrylate 21.05 Lauryl Acrylate, Air21.05
Methylmetac-
relate52.40
Acrylic
acid 0.50
N- (Dimethoxy-2, 2-hydro-
Si-1-ethyl) -met- acrylamide
(DMNEMA) 5.0
18 g of an emulsion mixture, identical to the mixture used in Examples 1-9, 1 g of sodium hydrogen carbonate, 1.2 g of sodium peroxodisulfate, 279.8 of water.
Then this emulsion is introduced in 4 hours with stirring into 250 g of water, which is held out at 80 + 2 ° C.
After the introduction is complete, cool the reaction mixture to ambient temperature, then filter it to possibly remove some mechanical impurities.
In this way, 1000 g of an aqueous dispersion having the characteristics indicated in Table 2 are obtained. 2
Example 20. An emulsion is obtained by mixing at ambient temperature 450 g of a mixture of monomers containing, by weight, %:
Ethyl acrylate 56.3 (253.35 g) Butyl acrylate 7.9 (35.55 g) Methyl methacrylate 34.3 (154.35 g) Acrylic acid 0, 5 (2.25 g) Acrylamide 1.0 (4.5 g)
21.6 g of an emulsion mixture, identical to the mixture used in Examples 150, 68 g of sodium acetate, 1.22 g of sodium peroxodisulfate, 266.23 g of water.
This pre-emulsion, having a pH of 4.20, is then introduced over 4 hours with stirring into 250 g of water and 0.27 g of ammonium peroxodisulfate, maintained at 80+. 2 sec.
At the end of the introduction, the pH of the reaction medium is adjusted to 8 by adding sodium hydroxide 5N, then added with stirring, maintaining the temperature of 40 + 2 ° C, 6.60 g (63 mmol) of dimethoxyethanal in a solution of 7.2 g of water, then leaving the reaction mixture for 1 h with stirring at 40 ° C, then it is cooled to ambient temperature and filtered.
In this way, 1010 g of dispersion are obtained, the copolymer of which contains, by weight. %: ethyl acrylate 55.49, methyl metharylate 33.8, butyl acrylate 7.79. DKNEA 2.43, acrylic acid 0.49. The characteristics of this dispersion are given in table. 2
Characteristics of the obtained monomers are presented in table. 3
Comparative examples.
The compounds were prepared according to the method described for Examples 6-14, and the characteristics of the dispersions obtained are given in Table. 2 in the lines Ct and C.
The copolymer of dispersion C contains only butyl acrylate 42.1%, ethyl acrylate 57.40% and acrylic acid 0.5% and is a film completely soluble in trichloroethylene, even after heat treatment.
The C2 dispersion copolymer contains 40.95% based on butyl acrylate, 55.80% ethyl acrylate, 0.5% acrylic acid and N-methyl acrylamide (NMA), 2.75% and the corresponding dispersion contains 550 ppm of free formaldehyde.
Thus, the proposed aqueous dispersions do not even emit any traces of formaldehyde.

权利要求:
Claims (1)
[1]
Invention Formula
The method of obtaining derivatives of N-substituted ethyl (meth) acrylamide of the general formula
CH C-CONH CH-CH
R
OR,
x x
OR, OR,
e R
R
- H, CH
B
T
R2-l and
C, -C al kil; N. C1-C4-alkyl, read
topics what
(meth) acrylamide is reacted with dialkoxy-2,2-ethanal of formula
one
The sample is soluble in trichloroethyl, which indicates the absence of retnculation.
Rto
h,
R (CrCH-CHO
where R, have the indicated meanings, followed by isolation of the target product, where Ra is hydrogen, or by the esterification of its C, -C4 alkanol in the presence of catalytic amounts of sulfuric acid, followed by isolation of the compound of the above formula, where R and Kr are the same or different -C + alkyl
Table 1
Lauril acrylate. N-methylolacrylamide.
13
DMNEA DMNEMA
H me
H N
H
Me
H
Me h
Me
H N
Me Me nBn nBn
1544184
14 Table 3
Liquid Solid colorless
Same it
 it Liquid
77
51 37 70 38 38

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同族专利:

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公开号 | 公开日

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AT49955T|1990-02-15|

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FR2595694A1|1987-09-18|

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CA1291166C|1991-10-22|

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EP0237435B1|1990-01-31|

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JPS62230758A|1987-10-09|

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FR2595694B1|1988-11-10|

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EP0237435A1|1987-09-16|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

---

FR8603587A|FR2595694B1|1986-03-13|1986-03-13|NOVEL SUBSTITUTED N-ETHYLACRYLAMIDE DERIVATIVES AND PROCESS FOR THEIR PREPARATION|

---