US3846493A

US3846493A - Nitro substituted acrylic acid amides

Info

Publication number: US3846493A
Application number: US00110626A
Authority: US
Inventors: W Gilligan; H Adolph
Original assignee: US Department of Navy
Current assignee: US Department of Navy
Priority date: 1971-01-28
Filing date: 1971-01-28
Publication date: 1974-11-05
Anticipated expiration: 1991-11-05

Abstract

Compounds of the formula

WHEREIN N IS 1 OR 2, X is F, NO2, H or CH3, R1 is H or CH3 and R2 is H or lower alkyl of 1-4 carbon atoms which can be polymerized to produce high-energy binders used in explosive compositions are prepared by reacting an amine of the formula

AND TRIFLUOROACETIC ANHYDRIDE IN THE PRESENCE OF PTOLUENESULFONIC ACID WHEN N IS 2.
WHEN N IS 1 AND WITH

Description

United States Patent 1191 Gilligan et al.

[ Nov. 5, 1974 NITRO SUBSTITUTED ACRYLIC ACID AMIDES [75] Inventors: William H. Gilligan, Oxon Hill;

Horst G. Adolph, Beltsville, both of Md.

[73] Assignee: The United States of America as represented by the Secretary of the Navy, Washington, DC.

221 Filed: Jan. 28, 1971 211 Appl. No.: 110,626

Primary Examiner-Leland A. Sebastian Attorney, Agent, or Firm-R. S. Sciascia; J. A. Cooke; M. G. Berger [57] ABSTRACT Compounds of the formula wherein n is l or 2, X is F. N02. H or CH;,. R. is H or CH;, and R is H or lower alkyl of I4 carbon atoms which can be polymerized to produce high-energy binders used in explosive compositions are prepared by reacting an amine of the formula with R1 RzCH=-'CCI 15 7 when n is l and with R1 RQ-o11=c' c-on and trifluoroacetic anhydride in the presence of p-tolnenesul fonic acid when n is 2.

9 Claims, No Drawings BACKGROUND OF THE INVENTION This invention relates generally to explosive compounds and more particularly to carboxylic acid amides which can be polymerized for binders useful in explosive compositions and to a method of preparation thereof.

For an explosive binder to be considered good it must not only be stable and compatible with the other components of the explosive composition but must also be sufficiently energetic to release energy when the composition is detonated. The latter is desirable so that the explosive composition when detonated will release as much energy as possible per unit weight. Thus a continuing search has long existed for highly energetic explosive binders and for monomers which are the precursors for these binders.

SUMMARY OF THE INVENTION Accordingly one object of this invention is to provide new organic compounds.

Another object of this invention is to provide organic compounds which can be polymerized into highly energetic binders for explosive compositions.

A still further object of this invention is to provide a method for the preparation of organic compounds which can be polymerized into highly energetic binders for explosive compositions.

These and other objects of this invention are accomplished by providing compounds of the formula when n is l and with and trifluoroacetic anhydride in the presence of p-toluenesulfonic acid when n is 2.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The carboxylic acid amides of this invention are prepared in two alternative ways depending-on the value the desired structure.

of n in formula (I). When n is l the amides are prepared by contacting in solution an acid chloride of the formula with an amino of the formula N02 NH2-CHz-( J.-X

and trifluoroacetic anhydride with an amine of the forpreferably in the presence of a catalyst such as p-tol- EXAMPLE 1 N (2-fluoro-2,2-dinitroethyl) acrylamide To a solution of 11.6g of 2-fluoro-2,2-dinitroethylamine the preparation of which is disclosed in Application Ser. No. 849,277 filed Aug. 5, 1969, now abandoned, entitled Chemical and Method of Preparation Thereof by Horst G. Adolph and Richard R. Minesinger, in 50 ml of methylene chloride and 7.3 ml of pyridine, containing a little hydroquinone, was added 7.3 ml of acryloyl chloride, dropwise, at ice-bath tempera.- ture. After standing overnight at 10C the solution was washed with dilute sulfuric acid, dried with anhydrous magnesium sulfate, and filtered. After evaporation of the solvent, the residual oil was crystallized from methylene chloride to give 2.43g of the desired product, mp 73-74.5C whose IR and NMR were consistent with EXAMPLE 2 N,N-Bis(2-fluoro-2,2-dinitroethyl) acrylamide To a slurry of 1.0g (3.46 mole) of bis(2-fluoro-2,2- dinitroethyl) amine, the preparation of which is disclosed in application Ser. No. 849,277 filed Aug. 5', l969-entitled Chemical and Method of Preparation Thereof by Horst G. Adolph and Richard R. Minesinger, in 3 ml of trifluoroacetic anhydride was added 1.5 ml of acrylic acid and 0.1g of p-toluene sulfonic acid monohydrate with stirring. After 15 minutes the bis-amine had completely dissolved and the solution was allowed to stand at ambient temperature for days. The solution was then taken up in 50 ml of methylcnc chloride and washed consecutively with 2-50 ml portions of water, 1-50 ml portion of saturated aqueous sodium bicarbonate and l-50 ml portion of water. After drying with anhydrous magnesium sulfate and filtering, the solvent was removed on a rotavap to give an oil which spontaneously crystallized. Upon recrystallization from methylene chloride, 0.82g (69 percent yield) of the desired compound was obtained, m.p. l l ll 13C.

The other compounds of formula I can be prepared in the same manner except that one would substitute the appropriate starting materials.

Numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described herein.

What is claimed as new and desired to be secured by Letters Patent of the United States is:

l. A compound of the formula wherein n is an interger from I to 2 inclusive, X is selected from the group consisting of F, N0 H and CH R is selected from the group consisting of H and CH and R is selected from the group consisting of H and lower alkyl of 1-4 carbon atoms.

2. A compound according to claim 1 wherein X is F.

3. A compound of claim 2 wherein R and R are both H.

4. A compound according to claim 3 which is N-(2- fluoro-2,2-dinitroethyl)acrylamide.

5. A compound according to claim 3 which is N,N- bis(2-fluoro-2,2-dinitroethyl) acrylamide.

6. A method of preparing the compounds of claim 1 wherein n is 1 comprising contacting in solution an amine of the formula with an acid chloride of the formula in the presence of an esterification catalyst at a temperature between 0C and room temperature.

7. A method of preparing the compounds of claim 1 wherein n is 2 comprising contacting in solution an acid of the formula and trifluoroacetic anhydride with an amine of formula in the presence of an amidation catalyst at about room temperature.

8. A method of preparing the compounds of claim 1 wherein n is 1 comprising contacting in solution an amine of the formula with an acid chloride of the formula of the formula and trifluoroacetic anhydride with an amine of formula at about room temperature.

Claims

1. A COMPOUND OF THE FORMULA

2. A compound according to claim 1 wherein X is F.

3. A compound of claim 2 wherein R1 and R2 are both H.

4. A compound according to claim 3 which is N-(2-fluoro-2,2-dinitroethyl)acrylamide.

5. A compound according to claim 3 which is N,N-bis(2-fluoro-2, 2-dinitroethyl) acrylamide.

6. A method of preparing the compounds of claim 1 wherein n is 1 comprising contacting in solution an amine of the formula

7. A method of preparing the compounds of claim 1 wherein n is 2 comprising contacting in solution an acid of the formula

8. A method of preparing the compounds of claim 1 wherein n is 1 comprising contacting in solution an amine of the formula

9. A method of preparing the compounds of claim 1 wherein n is 2 comprising contacting in solution an acid of the formula