US3450778A - Dodecanitroquaterphenyl - Google Patents

Description

United States Patent Int. Cl. C07c 79/10 US. Cl. 260-645 1 Claim The invention described herein may be manufactured and used by or for the Government of the United States of America for governmental purposes without the payment of any royalties thereon or therefor.

This invention pertains to a novel high energy compound .and more particularly to a novel explosive and a method for its preparation.

Due to the advent of higher and higher speeds in missiles and aircrafts and the resulting increase in aerodynamic heating, there is a continuing need for new thermally stable explosives which may be used, for example, as boosters, detonators and the like.

Accordingly, it is an object of this invention to provide a new high energy compound.

It is another object of this invention to provide a compound that may be utilized as a thermally stable explosive.

These and other objects will become more readily apparent from reading the following detailed description of the invention.

The objects of this invention are accomplished by producing the compound, 2,2',2",2"',4,4',4",4'",6,6',6",6"',- dodecanitroquaterphenyl (Dodeca).

Dodeca is generally prepared by coupling two molecules of a 3-halo-2,2,4,4',6,6-hexanitrobiphenyl by the Ullmann reaction. More particularly, the haloexanitrobiphenyl is reacted with finely divided copper at an elevated temperature, preferably above about 120 C. with good results being obtained at about 190 C., in a high boiling organic solvent that is inert to the reaction; e.g., nitrobenzene, xylene, etc., said solvent functioning as a diluent to control the reaction. The halohexanitrobiphenyl utilized is generally either a 3-chloro-, bromo-, or i0do-2,2',4,4', 6, 6'-hexanitrobiphenyl and it is to be understood that these compounds may be used either singularly or in combination with each other in the reaction; e.g., chlorohexanitrobiphenyl may be coupled with bromohexanitrobiphenyl. The amount of finely divided copper utilized may vary from stoichiometric quantities to amounts from about 25 to 50% over stoichiometric quantities with the manner of mixing the copper and halohexanitrobiphenyl being of no particular importance since equally good results are obtained by either adding the copper to the halohexanitrobiphenyl or by adding the halohexanitrobiphenyl to the copper.

The Dodeca produced by the above reaction is recovered from the solvent and recrystallized from a mixed solvent such as acetone-toluene, acetone-acetic acid, acetone-acetonitrile, and the like. The Dodeca may be recrystallized more than once and it is to be understood that either the same or different mixed solvents may be utilized in each recrystallization.

The following example is illustrative of the invention but it is not to be construed as limiting the invention in any manner.

EXAMPLE A solution of 118 g. (0.257 mole of 3-chloro-2,2',4,4', 6,6-hexanitrobiphenyl in 400 ml. of dry nitrobenzene was made in a 1000 ml. 3-neck bottom flask fitted with a mechanical stirrer, powder funnel and thermometer. The temperature was raised to 180 C. on an oil bath and 12 g. of copper bronze (Venus Natural Copper Pine 3,450,778 Patented June 17, 1969 ice 44-F, United States Bronze Powder Works, Flemington, NJ.) was added in one portion with vigorous stirring. The temperature was raised to 190 C. over a period of seven minutes. At this temperature, the copper began to lose its metallic luster. Starting approximately five minutes after the first copper addition, an additional 28 g. of copper was added in four portions over a 15-minute period. The reaction was slightly exothermic and the temperature rose to 190 C. during the addition. After the addition was complete, the temperature was held at about 190 C. for 15 minutes after which the heating bath was removed. The mixture was allowed to cool to about C. and filtered with suction through a fiber glass filter. The solid inorganic residue was washed with acetone until the filtrate was nearly colorless. The solvent was then removed from the filtrate by steam distillation, after which the aqueous layer was removed by decantation. The dark solid product was then digested for 30 minutes in 1000 ml. of refluxing methanol. The mixture was then filtered and the product was thoroughly washed with additional methanol. After drying in a warm oven, the light brown solid weighed 94 g. Thin-layer chromatographic analysis on Silica Gel G, using benzene as the developer, indicated that the product was mainly 2,2',2",2"',4,4',4",4"',6,6',6,6 dodecanitroquaterphenyl (Dodeca) but contained a trace of 2,2',4,4', 6,6'-hexanitrobenzene and a larger quantity of an apparently more polar material which remained at the origin.

The crude Dodeca was dissolved in 2000 ml. of hot acetone, treated with 50 g. of carbon black (Darco G-60), filtered and the carbon pad was washed with acetone. The filtrate, which was still dark, was concentrated by distillation on a steam bath with moderate stirring until precipitation just started. A volume of 500 ml. of toluene was then added through an addition funnel, as the distillation continued, at about the same rate as the distillate was removed. When distillation on the steam bath ceased, the bath was removed and the mixture was allowed to stand for two hours. It was then filtered, the product was thoroughly washed with toluene and dried in a warm oven. The yield was 76 g. (70%) of a cream colored finely crystalline product. It showed no tendency to melt at 450 C. but began to darken in the range 300-350 C. thin-layer chromatographic analysis indicated that it was pure Dodeca.

Recrystallization of Dodeca In efforts to obtain maximum purity and higher bulk density, samples of the above product, or similar products were recrystallized a second time from four solvent combinations as described below.

Recrystallization from acetone-toluene A 21.5 g. sample of the above once recrystallized product was dissolved in 300 ml. of acetone, treated with 15 g. of Darco 6-60, and filtered with suction through a fiber glass filter. The amber colored solution was distilled on a steam bath with moderate stirring until 100 ml. of solvent had been removed. Then, as slow distillation continued, ml. of toluene was added through an addition funnel at approximately the same rate as that at which the distillate was removed. When 75 ml. of toluene had been added, the solution was seeded whereupon crystallization started immediately. When distillation could no longer be effected on the steam bath, the mixture was allowed to cool then filtered and thoroughly washed with toluene. The cream colored fine crystalline Dodeca was dried at 150 C. for 16.5 hours. The recovery was 21.2 g., 98.5%.

Recrystallization from acetone-acetic acid A 25 g. sample of the above once recrystallized product was dissolved in acetone, treated with Darco G6() and distilled as described above. A volume of 150 m1. of glacial acetic acid was added as described above instead of toluene. The first crop of product was removed by filtration and washed with 50 ml. of acetone-acetic acid 1:1. On concentration of the mother liquor to a volume of about 100 ml. on the hot plate, a second crop of about 1.5 g. was obtained. The two crops were combined and stirred in 150 ml. of a 50% (vol.) solution of methanol in water. The slurry was filtered and the product was Washed with 100 ml. of methanol on the funnel and dried at 150 C. for 16.5 hours. The Dodeca resembled that from acetone-toluene and the recovery was 23.3 g., 93%.

Recrystallization from acetone-acetonitrile A solution of 25 g. of the above once recrystallized product was made and treated as described above. To this was added 200 ml. of acetonitrile and the solution 'Was distilled with moderate stirring. When about 100 ml. of distillate had been removed, an additional 200 ml. of acetonitrile was added at about the same rate as that at which the distillate was removed. When the volume had reached about 125 ml. and marked crystallization had occurred, the mixture was cooled to room temperature, filtered and the product was washed first with 100 ml. of cold acetonitrile then with 100 ml. of ether. After the glistening cream colored crystalline Dodeca was dried at 150 C. for 16.5 hours, the recovery was 23.5 g. or 94%.

treated with g. of Darco G-60, filtered through a fiber glass filter and the carbon pad was washed with 35 ml.

of acetone. The amber colored solution was distilled as described above until 30 ml. of distillate had been removed. Then as the distillation continued, ml. of benzene Was added at about the same rate as that at which the distillate was removed. When a total of ml. of distillate had been removed, the solution Was seeded and crystallization started immediately. When the temperature of the distillate reached 79 C., the distillation was discontinued, the mixture was cooled to room temperature and filtered. The product was washed thoroughly with benzene and dried at 150 C. for 16.5 hours. The Dodeca was similar to that from acetone-toluene and the recovery was 6.2 g., 89%.

The compound of this invention, 2,2,2",2",4,4',4", 4"',6,6',6",6-dodecanitroquaterphenyl (Dodeca) is sensitive to impact at all temperatures and thermally stable. Accordingly, it may be used in a mild detonating fuse in missiles and aircraft applications and as a thermally stable booster explosive.

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

What is claimed is:

1. The compound 2,2,2",2"',4,4,4",4'",6,6',6,6"'- dodecanitroquaterphenyl.

References Cited Wirth et al.: Makromol. Chem., vol. 77, 1964, pp. 90 to 113 (only pp. and 111 relied on).

LELAND A. SEBASTIAN, Primary Examiner.

US. Cl. X.R. 149105

Claims (1)

1. THE COMPOUND 2,2'',2",2"'',4,4'',4",4"'',6,6'',6"6"''DODECANTIROQUATERPHENYL.