United States Patent Office Patented Feb
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3,562,333 United States Patent Office Patented Feb. 9, 1971 1 2 3,562,333 lower alkyl radicals represented by R2, R3 and R4 are FLUORO-ALKYL-SUBSTITUTED POLYNITRO the following: -—CF3, —CH2CF3, —CH2CHF2, AROMATIC AMINES AND NITRAMINES Josef .l. Schmidt-Collerus, Denver, (1010., and Don N. Gray, Towson, Md., assignors to the United States of —CH2CH2CH2CHF3, '—‘CH3, _C2H5, —~C3H8, 01' Oth?r America as represented by the Secretary of the Air 5 monovalent lower alkyl and ?uorine-containing lower Force N0 Drawing. Filed Jan. 28, 1964, Ser. No. 340,837 alkyl radicals either straight chained or branched in Int. Cl. C07c 87/60 structure. U.S. Cl. 260—-577 6 Claims The compounds of this invention represent a new class 10 of explosives; namely, N-?uoro-alkyl and ?uoro-alkyl This invention relates to fluoro-alkyl-substituted poly substituted picramides and nitramines. Typical com nitro aromatic amines and nitramines. More speci?cally, pounds of the invention are conveniently prepared by this invention concerns itself with ?uoro-substituted alkyl nitrating an appropriate substituted trinitroaniline. This group derivatives of picramide (I) and tetryl (II) as represented by the following structural formulas: starting compound is in turn prepared by effecting a re 15 action between an equimolar mixture of a ?uoro-substi IIQH2 OzNN CH3 tuted trinitrobenzene, such as picryl ?uoride; or a chloro substituted trinitrobenzotri?uoride, with ammonia or an appropriate substituted amine. The synthesis schemes dis closed by the following examples produce speci?c com 20 pounds but is also representative of the method for syn thesizing the whole generic group by the judicious choice Ill 0 2 (I) N 0 2 (II) of appropriately substituted starting materials. in which ?uorine is substituted in the N-alkyl group or on The following examples illustrate the new compounds the benzene nucleus of the aromatic ring. The preferred of this invention and the basic synthesis scheme by which compounds of this invention are the tri?uoromethyl sub 25 they are prepared. These examples, however, are by way stituted derivatives of picramide and tetryl. of illustration only and are not to be considered as limit Picramide, tetryl, ethyl tetryl and butyl tetryl are well ing the scope of the invention in any way. known for their use in military munitions as primary ex EXAMPLE 1 plosives, boosters, and detonators. These explosives ex hibit a much higher explosive potential than TNT or 30 To a solution of 52.5 g. (0.17 mole) of 3-chloro-2,4,6 picric acid; but are distinctly more sensitive to shock and trinitrobenzotri?uoride in 250 ml. of benzene in a 1-liter heat. Consequently, their military utility is minimized be separatory funnel was added a solution of 50 ml. of 40% cause of the severe conditions encountered by the military monomethylamine in 150 ml. of distilled water. This mix during ?eld operations. With this invention, however, it ture was shaken and kept cool by holding the funnel under has been found that the undesirable sensitivity charac 35 the water tap. After ten minutes shaking, the solution teristics of the above referred to explosives can be abro was dark red. At this point a solution of 20 g. of sodium gated by providing a new class of ?uoro-alkyl-substituted carbonate in 200 ml. of water was added and again the derivatives of picramide and tetryl. These new compounds, mixture shaken. The benzene layer was removed, and although exhibiting a high explosive potential are dis— evaporated on a steam bath, leaving a bright-yellow solid tinctly more resistant to shock and heat. As a result, they 40 residue. Recrystallization from 95% ethanol gave an are much more useful when employed by the military as 82% yield of 3 - tri?uoromethyl-2,4,6~trinitro-N-methyl primary explosives, detonators, boosters and in other ex aniline; M.P. 137-138° C. plosive applications. Additionally, the compounds of this EXAMPLE 2 invention are useful as dyestuffs in the coloration of 45 Five grams of 3-chloro-2,4,6-trinitrobenzotri?uoride cellulosic textile materials and as intermediates in the was dissolved in 30 ml. of dry methyl alcohol and the production of other novel and useful compounds. solution cooled in an ice bath. Gaseous ammonia was then Accordingly, the primary object of this invention is to bubbled through the solution until a permanent red color provide a new class of explosives Which are characterized was present. The solution was then ?ltered through a hard by a high explosive potential coupled with a high degree 50 ?lter and the alcohol solution was concentrated to one of thermal and shock resistivity. third its volume under reduced pressure to give a dark Another object of this invention is to provide a new red precipitate. This was ?ltered and the ?lter cake washed class of ?uoro-substituted alkyl group derivatives of with a benzene-n-hexane (50:50) solution. This gave 3 picramide and tetryl. tri?uoromethyl picramide which decomposed at 195° C. A further object of this invention is the preparation of and changed from the red to the yellow isomorphic form. novel dyestuffs and dyed textile materials. 55 The new compounds of this invention have the fol EXAMPLE 3 lowing structural formula: The nitration of 3 - trifluoromethyl-2,4,6-trinitro-N methylaniline from Example 1 was accomplished :by dis solving 12.5 g. (0.04 mole) of the amine in 100 ml. of 60 concentrated sulfuric acid, cooling externally with an ice bath, then slowly adding 15 ml. of concentrated nitric acid with stirring. After the reaction solution had been allowed to stand for several hours at room temperature it was- poured over about 500 g. of shaved ice and the precipitated white solid was collected on a ?lter and air wherein R1 may be hydrogen or a nitro radical and R2, dried. Recrystallized from 95% ethanol yielded 12 g. R3 and R4 may each represent hydrogen, a monovalent (84.5% yield) of 3-tri?uoromethyl-2,4,6-trinitrophenyl lower alkyl radical having from 1 to 5 carbon atoms, or methylnitramine as a white solid. a ?uoro-substituted monovalent lower alkyl radical hav ing from 1 to 5 carbon atoms provided that at least one 70 EXAMPLE 4 of the substituents R2, R3 and R4 is a ?uoro-alkyl group. To a solution of 49.4 g. (0.2 mole) picryl fluoride in Illustrative of the lower alkyl and ?uoro-substituted 400 ml. of 95% ethanol was added 33.5 g. (0.25 mole) of 3,562,333 4 tri?uoroethylamine hydrochloride. This suspension was mine, the reaction product from Example 5, is between heated to dissolve the solids, then cooled externally with 340° C. and 360° C. and, hence, is more stable to heat an ice bath. At this point, 50 g. (0.5 mole) of solid sodium than those prior known explosives set forth in Table I. carbonate was added slowly with moderate stirring. Evi The explosion temperature of ethyl tetry-l is between 260° dence of the reaction was noted by a slight temperature 5 C. and 280° C. The explosion temperature of Table I is rise, evolution of CO2 and the presence of the character defined as that temperature in degrees centigrade required istic amine odor. The deep~orange solution was then heated to cause an explosion in 5 seconds. on the steam bath for about one hour, poured onto ice TABLE II and acidi?ed with 3 N hydrochloric acid to congo red. Impact sensitivity The light-yellow solid was collected on a ?lter, washed 10 with cold water and air-dried. Recrystallized from 95% Explosive: Impact height, cm. ethanol yielded 38.8 g. (62.5% yield) of N-beta,beta,beta Tetryl _____________________________ __ 2742 tri?uoroethyl - 2,4,6 - trinitroaniline as a yellow solid; M.P.=67—70° C. Further recrystallization from 95% RDX _____________________________ _ _ 25 PETN ____________________________ _ ._ 12-1 3 ethanol yielded 28.7 g. of pale-yellow crystals; M.P.= 15 Nitro glycerin ______________________ __ 4-6 73.5—74.0° C. " Picric acid _________________________ _ _ 73-93 Analysis.—-Calculated for CBH5N4OSF3 (percent): C, TNT _____________________________ _ _ l 5 8-—l7 1 30.98; H, 1.62; N, 18.06; F, 18.4. The actual values found Ethyl tetryl 1 _______________________ __ 81 were (percent): C, 31.24; H, 1.74; N, 18.21; F, 18.3. 20 TP ethyl tetryl 2 ____________________ __ f1 5 6 EXAMPLE 5 1 2,4,G-trinitrophenyletllylnitramine. The nitration of N-beta,beta,beta-tri?uoroethyl-2,4,6 2 2,4,S-trinitrophenyl-beta,beta,beta-tri?uoroethylnitramine. trinitroaniline of Example 4 was accomplished by dis From an examination of the information presented in solving 12.5 g. (0.035 mole) of the amine in 250 ml. of Table II, it can be seen that 2,4,6-trinitrophenyl-beta,beta, beta-tri?uoroethylnitramine, the reaction product from concentrated sulfuric acid, cooling externally with an ice N) Or bath, then slowly adding 14 ml. of concentrated (90%) Example 5, is less impact sensitive, with the exception of nitric acid with stirring, keeping the temperature below TNT, than the prior known explosives referred to in 10° C. during the addition. After the reaction solution Table II. The impact height of Table II is de?ned as that had been allowed to stand for several ‘hours at room tem height in centimeters for 50% ?re using an ERL machine with a type 12 tool (25 kilograms weight). perature, it was poured over about 1 kg. of shaved ice.