Process for the preparation of N-substituted acrylamides

Details Process for the preparation of N-substituted acrylamides Process for the preparation of N-substituted acrylamides

2000-02-02

2002-04-09

Kumar, Shailendra (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Fatty compounds having an acid moiety which contains the...

C554S035000, C564S143000, C564S204000

Reexamination Certificate

active

06369249

ABSTRACT:

FIELD OF INVENTION
This invention relates to a process for the preparation of N-substituted acrylamides. More particularly it relates to an improved process for the preparation of N-substituted acrylamides of the general formula CH
2
═CH—CONHR, wherein, R is alkyl group having carbon 1 to 22 or acyl group having carbon 1 to 18 by Friedel-Craft's alkylation and acylation of acrylamide respectively, in the presence of a Lewis acid catalyst.
BACKGROUND OF THE INVENTION
Copolymers of N-alkylacrylamides with various other monomers are finding diverse applications as follows:
1) Poly (&bgr; napthyl 6 acrylamidocaproate-co-acrylic acid) as plant growth regulator (C.J. Boundreaux, W. C. Bunyard and C. L. Mccormick, J. Controlled Rel. 40,223 (1996).
2) Poly (N-dodecylacrylamide-co-N-methyl 4vinyl pyridinium Na) as salt resistant viscosity builder (D. Christine, B. Alain and L. Pierre, Macromol. Symp. 102,233 (1995), D. Christine, B. Alain, B. Fransis and V. M. Laure, Polymer 36,2095 (1995).
3) Poly (N-stearoyl acrylamide-co-2(3-acrylamidopropyl) dimethyl aminoethyl isoproply phosphate) as phosphatidylcholine analogous material (W. Yenfeng, C. Tianming, K. Masaya and N. Taiao, J. Polym. Sci. Chem. Edn. 34,449 (1996).
4) Poly (N-tert-octylacrylamide-co-N-alkylacrylamide) as thickner in cosmetics (J. Mondet and B. Lion Eur. Pat. Appl. EP 494,022.
5) Poly (N-octylacrylamide-co-3 acrylamido-3 methyl butanoate Na) for oil recovery (A. Kitagawa and T. Koichi, Jpn. Kokai Tokkyo Koho JP 07,188,347) and so on.
Crosslinked hydrogels based on N-alkylacrylamides also find various applications such as thermosensetive polymeric drug carriers (C. L. Mecormick and J. C. Brent, Polym. Mater. Sci. Eng. 55,366 (1986), M. Akashi, A. Kishida, S. Sakuma and H. Kikuchi, PCT Int. Appln. WO 9730730. H. Yu and D. W. Grainger, Polym. Prepr. 34,820 (1993), materials for hard contact lenses (S. Q. Zhou, L. Xiugao and Y. Wang PCT Intl. Appln. WO 9735,896), concentration of aqueous protein solutions (J. Manrong. Z. Guiying, W. Changfa, L. Peiyi and H. Wei, Gaofenzi Xubao 3, 321 (1995), Stationary phases for HPLC ((N. Shoji, I. Hirotaka and H. Chuichi, Polymer J. (Tokkyo 25, 609 (1993)) etc.
In order to meet these growing demands of N-alkylacrylamides. various methods for their synthesis have been developed. These methods can broadly be classified into three types viz.
1) Reaction of acryloyl chloride with alkyl amine,
2) Pyrolysis or thermal decomposition of carboxylic acid amides, and
3) Reaction of olefins with nitriles.
The above mentioned processes are described in brief hereinbelow:
Methods of Type 1
Reaction of Acryloyl Chloride with Alkylamine
In this method N-alkylacrylamides are synthesized by reacting acryloyl chloride with alkyl amines in the presence of acid quencher i.e. triethyl amine at 0° C. (C. G. Overberger, C. Frazier and J. Mandehman, J. Am. Chem. Soc. 75,3326 (1953), J. Lal and G. S. Trick, J. Polym. Sci. A2, 4559 (1964), E. F. Jr. Jordan, G. R. Riser and B. Artymyshyn, J. Appl. Polym. Sci. 13,1777 (1969), K. J. Shea, G. J. Stoddard, D. M. Shavelle, F. Wakui and R. M. Chaote, Macromolecules 23,4497 (1990).
Methods of Type 2
Thermal Decomposition of Carboxylic Acid Amides.
A number of patents which are based on this technique have been filed. A Japanese patent No. Jpn. Kokai Tokkyo JP 07,145122, discloses the synthesis of N,N diethylacrylamide as follows. Methyl acrylate was reacted with diethylamine to give Michael addition product methyl &bgr; N,N diethylaminopropionate. This was treated with sodium methoxide for 46 hrs and then with phosphoric acid for 1 hr. at 50° C. to give N,N diethyl &bgr; diethylaminopropionic acid amide which was then thermally decomposed at 180° C. and 100 torr pressure for 4 hrs. to give N,N diethylacrylamide (K. Motomasu, I. Seiichi and I. Massasane, Jpn. Kokai Tokkyo Koho JP 07,145 122). Similar process for the synthesis of N,N dialkyl acryl and methacrylamides has been reported wherein, thermal decomposition of carboxylic acid amide was carried out in the presence of H
2
SO
4
at 195° C. (T. Maruyama,
0
. Kido, I. Okidaka and R. Hiraoka, Jpn. Kokai Tokkyo Koho JP 04,208 258).
N-alkylacrylamides have also been synthesized by amidation of bicyclic carboxylic acids followed by the thermal decomposition of the carboxamide. Thus N,N dimethylacrylamide was synthesized by reacting dimethylamine with bicyclo [2.2.1]hept-2-ene-2-carboxylic acid in autoclave to give N,N dimethyl bicyclo [2.2.1]hept-2ene-2-carboxylic acid in autoclave to give N,N dimethyl bicyclo [2.2.1]hept-2-ene-2-carboxamide, followed by its thermal decomposition at 200° C. in vacuo (A. Ohshima and K. Tsubashima Jpn. Tokkyo Koho 7909 170, A. Oshima, K. Tsubashima and N. Takahashi Ger. Offen. 2,217,623). The use of pyrolysis for preparation of N-alkylacrylamides has also been reported. In this, N(1,1 dimethyl 1-3 oxybutyl)-3 methoxy propionamide was hydrogenated in the presence of dimethylamine p-toluenesulfonic acid and Pt. catalyst to give N(1,1 dimethyl -3 dimethyl aminobutyl) 3 methoxy propionamide. This was heated with NaOH at 80 to 90° C. for 3 hrs to give N(1,1dimethyl-3 dimethylaminobutyl) acrylamide (D. I. Hoke, U.S. Pat. No. 3,943,114).
Methods of Type 3
Reaction of Olefins with Nitriles
N-alkylacrylamides have also been synthesized by reacting acryloni{acute over (t)}rile with various olefins. A Japanese patent No. Japan Kokai 7391011 discloses the synthesis of N-tert-octylacrylamide by reacting acrylonitrile with 2,4,4 trimethyl 1-pentene at 40° C. for 3 hrs using 65% H
2
SO
4
as solvent (T. Takada, Y. Kawakatsu, T. Mihamisawa and K. Hara, Japan Kokai-7391011). Similarly, acrylonitrile has been reacted with dimethylamine at 200° C. in the presence of Lewis acid ZnCl
2
to give N,N dimethylacrylamide (Asahi Chemical Ind. Co. Ltd. Fr. 2,046 122). N-alkylacrylamide has also been synthesized by oxidative carbonylation. In this, PdCl
2
, CuCl
2
, CuCl and propylamine in 1:10:10:120 ratio were treated with methane, carbon monoxide and oxygen to give N-propylacrylamide (G. Biale U.S. Pat. No. 3,523,971).
Amongst the above sighted processes for preparation of alkylacrylamides, methods of the type 1) cannot be used to synthesize N-acylacrylamides, monomers, that are gaining increasing importance. Besides, it is also not attractive for large scale productions since it uses acryloyl chloride which is an expensive and hazardous reagent.
Other processes sighted for the preparation of alkylacrylamides i.e. methods of type 2) and 3) suffer from the drawbacks of harsh reaction condition such as high temperatures, high vacuum and tedious work up procedures. Also in most of the cases N-alkylacrylamide with small alkyl chain length were synthesized.
OBJECTS OF THE INVENTION
It is therefore an object of the present invention to provide process for the preparation of N-substituted acrylamides.
Another object of the present invention is to provide a process with mild reaction conditions such as reaction at room temperature and atmospheric (normal) pressure which will obviate tedious work up procedures used in the conventional processes.
It is also an object of the present invention that such a process be applicable for the preparation of N-substituted acrylamides with long alkyl chain length.
SUMMARY OF THE INVENTION
Friedel-Craft's alkylation is an effective and convenient method which is widely used to synthesize linear alkyl benzenes (LABs). Despite this, its use in the synthesis of N-alkylacrylamides has not been reported yet. It has now been found that N-alkylacrylamides and N-acylacrylamides can be produced in high yields by alkylation and acylation of acrylamide respectively, in the presence of a Lewis acid catalyst in suitable solvent at room temperature and atmospheric pressure.
DETAILED DESCRIPTION OF THE INVENTION
Accordingly the present invention provides an improved process for the preparation of N-substituted acrylamides of the general formula CH
2
═CH—CONHR wherein, R is alkyl group having carbon 1 to 22 or R is acyl group having carbon 1 to 18 which c

Affiliated with

Also associated with

Rating

Process for the preparation of N-substituted acrylamides does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for the preparation of N-substituted acrylamides, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the preparation of N-substituted acrylamides will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2881604