USH428H - 1,2,4,5-tetrakis (Diazidomethyl) benzene energetic polyazide - Google Patents
1,2,4,5-tetrakis (Diazidomethyl) benzene energetic polyazide Download PDFInfo
- Publication number
- USH428H USH428H US07/024,097 US2409787A USH428H US H428 H USH428 H US H428H US 2409787 A US2409787 A US 2409787A US H428 H USH428 H US H428H
- Authority
- US
- United States
- Prior art keywords
- benzene
- tetrakis
- diazidomethyl
- polyazide
- energetic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
- C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
- C07C247/08—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being unsaturated
- C07C247/10—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being unsaturated and containing rings
Definitions
- This invention relates to 1, 2, 4, 5-tetrakis (diazidomethyl) benzene which is a powerful explosive.
- the maximum nitrogen content of the product of the art is that disclosed in the Statutory Invention Registration H138 (issued Oct. 7, 1986) which was 62%.
- the starting compound, 1, 2, 4, 5-tetrakis (dibromomethyl) benzene was prepared by the photochemical bromination of the corresponding tetrakis (bromomethyl) benzene by the procedure of Kerfanto and Soyer, Compt. Rend. Series C, 264, 1072 (1967). Tetrakis (bromomethyl) benzene is commercial available from the Aldrich Chemical Company, Milwaukee, Wis.
- the mixture was poured into water, 6 drops of 15% hydrochloric acid were added, and the mixture was allowed to stand for 3 hours for complete separation of the suspended solid. It was filtered and washed with water. The filter paper with product was removed from the filter, dried to constant weight, and the dry product was then easily removed.
- the crude yield varied from 83% to 95% in multiple check runs.
- the melting point (ex methanol) was 106°-8° C., and it decomposed with gas evolution at that temperature.
- the product was easily detonated by a hammer blow on a hard surface, or by scraping with a spatula. It also exploded upon addition to 80% sulfuric acid at 90° C. However, slow heating in a melting point apparatus showed melting at 106°-8° C. with gas evolution, and continued heating to 180° C. gave further gas evolution and color formation, but without detonation. Detonation did occur upon rapid heating on a spatula over a low flame. No visual change was noted upon heating for 5 hours at 95°.
- the product of the present invention is less stable and more sensitive.
- the material with only primary azide groups was less easily detonated by impact with a hammer, and not easily detonated by scraping with a spatula. It could be decomposed by 80% sulfuric acid at 90 C. without explosion.
- the product of the art i.e. hexakis-azidomethyl benzene had a high melting point (162°-5°), and like the product of this invention decomposed with gas evolution at the melting point. Both products exploded upon rapid heating.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
1,2,4,5-tetrakis (diazidomethyl) benzene and a method of making the same byeacting 1,2,4,5-tetrakis (dibromomethyl) benzene with sodium azide in dimethylformamide for three hours at 70° to 80° C.
Description
This invention relates to 1, 2, 4, 5-tetrakis (diazidomethyl) benzene which is a powerful explosive.
Compounds containing the azidomethyl groups on the benzene ring are known. However, a literature search has not revealed the presence of a benzene ring having multiple diazidomethyl groups.
It is an object of this invention to provide a solid energetic polyazide which is high in azide nitrogen content (72.7%), a solid melting above 80° C., and inexpensively prepared. The maximum nitrogen content of the product of the art is that disclosed in the Statutory Invention Registration H138 (issued Oct. 7, 1986) which was 62%.
The starting compound, 1, 2, 4, 5-tetrakis (dibromomethyl) benzene was prepared by the photochemical bromination of the corresponding tetrakis (bromomethyl) benzene by the procedure of Kerfanto and Soyer, Compt. Rend. Series C, 264, 1072 (1967). Tetrakis (bromomethyl) benzene is commercial available from the Aldrich Chemical Company, Milwaukee, Wis.
1, 2, 4, 5-tetrakis (dibromomethyl) benzene (1.0 g-1.3 mmole), ground sodium azide (1.0 g-15.3 mmole), and N,N-dimethylformamide (15 ml) were mixed and stirred magnetically in a test tube for 3 hours in a 70°-80° C. water bath.
The mixture was poured into water, 6 drops of 15% hydrochloric acid were added, and the mixture was allowed to stand for 3 hours for complete separation of the suspended solid. It was filtered and washed with water. The filter paper with product was removed from the filter, dried to constant weight, and the dry product was then easily removed.
The crude yield varied from 83% to 95% in multiple check runs. The melting point (ex methanol) was 106°-8° C., and it decomposed with gas evolution at that temperature.
The product 1, 2, 4, 5-tetrakis (diazidomethyl) benzene, was tested and found to give the following data for its structure, viz. IR(KBr): 2100 (asym. azide) (S), 1370 (m), 1330 (m), 1240 (sym. azide) (S), 1180 (S), 945 (S), 830 (S), 740 (S), 550 (W), 400 (W) cm-1. The structure of I was also established by NMR as follows: 1 H NMR (acetone d6): δ8.03 (S,2, ArH), δ6.87 (S, 4, ArCH); 13 C NMR (acetone d6): δ135.4 (ArC), 127.25 (ArCH), 75.3 (--CH).
The product was easily detonated by a hammer blow on a hard surface, or by scraping with a spatula. It also exploded upon addition to 80% sulfuric acid at 90° C. However, slow heating in a melting point apparatus showed melting at 106°-8° C. with gas evolution, and continued heating to 180° C. gave further gas evolution and color formation, but without detonation. Detonation did occur upon rapid heating on a spatula over a low flame. No visual change was noted upon heating for 5 hours at 95°.
In comparison with materials which contain only primary azide groups, the product of the present invention is less stable and more sensitive. The material with only primary azide groups was less easily detonated by impact with a hammer, and not easily detonated by scraping with a spatula. It could be decomposed by 80% sulfuric acid at 90 C. without explosion. The product of the art, i.e. hexakis-azidomethyl benzene had a high melting point (162°-5°), and like the product of this invention decomposed with gas evolution at the melting point. Both products exploded upon rapid heating.
Claims (4)
1. 1, 2, 4, 5-tetrakis (diazidomethyl) benzene.
2. A method of preparing 1, 2, 4, 5-tetrakis (diazidomethyl) benzene comprising mixing, in ratio, about 1.0 g of 1, 2, 4, 5-tetrakis (dibromomethyl) benzene with about 1.0 g of sodium azide in about 15 ml. of dimethylformamide for about three hours at 70° to 80° C.
3. The method of claim 2 additionally comprising, in sequence, pouring the resultant mixture into several volumes of water, adding 15 percent hydrochloric acid to said water, and allowing the aqueous mixture to stand for about three hours for the separation of solids.
4. The method of claim 3 additionally comprising, in sequence, filtering solid$ out of said aqueous mixture, washing said solids, and drying to constant weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/024,097 USH428H (en) | 1987-03-02 | 1987-03-02 | 1,2,4,5-tetrakis (Diazidomethyl) benzene energetic polyazide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/024,097 USH428H (en) | 1987-03-02 | 1987-03-02 | 1,2,4,5-tetrakis (Diazidomethyl) benzene energetic polyazide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH428H true USH428H (en) | 1988-02-02 |
Family
ID=21818856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/024,097 Abandoned USH428H (en) | 1987-03-02 | 1987-03-02 | 1,2,4,5-tetrakis (Diazidomethyl) benzene energetic polyazide |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USH428H (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150274646A1 (en) * | 2012-11-07 | 2015-10-01 | Council Of Scientific & Industrial Research | 2, 2'-bis (4-hydroxyphenyl) alkyl azides and process for the preparation thereof |
-
1987
- 1987-03-02 US US07/024,097 patent/USH428H/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150274646A1 (en) * | 2012-11-07 | 2015-10-01 | Council Of Scientific & Industrial Research | 2, 2'-bis (4-hydroxyphenyl) alkyl azides and process for the preparation thereof |
| US9562004B2 (en) * | 2012-11-07 | 2017-02-07 | Council Of Scientific & Industrial Research | 2, 2′-bis (4-hydroxyphenyl) alkyl azides and process for the preparation thereof |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| AS | Assignment |
Owner name: UNITED STATES OF AMERICA, THE, AS REPRESENTED BY T Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:GILBERT, EVERETT E.;REEL/FRAME:004883/0624 Effective date: 19870220 |