US3562332A - Fluoro-alkyl-substituted polynitroamines - Google Patents
Fluoro-alkyl-substituted polynitroamines Download PDFInfo
- Publication number
- US3562332A US3562332A US340836A US3562332DA US3562332A US 3562332 A US3562332 A US 3562332A US 340836 A US340836 A US 340836A US 3562332D A US3562332D A US 3562332DA US 3562332 A US3562332 A US 3562332A
- Authority
- US
- United States
- Prior art keywords
- substituted
- fluoro
- alkyl
- compounds
- polynitroamines
- 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.)
- Expired - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- BLNWTAHYTCHDJH-UHFFFAOYSA-O hydroxy(oxo)azanium Chemical group O[NH+]=O BLNWTAHYTCHDJH-UHFFFAOYSA-O 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 12
- 239000002360 explosive Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- CBCIHIVRDWLAME-UHFFFAOYSA-N hexanitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O CBCIHIVRDWLAME-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010930 yellow gold Substances 0.000 description 2
- 229910001097 yellow gold Inorganic materials 0.000 description 2
- QDKLRENLCOOJCN-UHFFFAOYSA-N 2-chloro-1,3,5-trinitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(=C(C(=C1Cl)[N+]([O-])=O)C(F)(F)F)[N+]([O-])=O QDKLRENLCOOJCN-UHFFFAOYSA-N 0.000 description 1
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000006342 heptafluoro i-propyl group Chemical group FC(F)(F)C(F)(*)C(F)(F)F 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/04—Compositions containing a nitrated organic compound the nitrated compound being an aromatic
Definitions
- R X Y R1 l wherein R and R each represents a fluoro-alkyl radical having from 1 to 5 carbon atoms, X represents a nitro radical, and Y is selected from the group consisting of hydrogen and a nitro radical.
- Illustrative of the fluoroalkyl radicals represented by R and R are the following: -CF CH CF CH CHF CH CH F, CF CF CF(CF3)2. CH CH CF CH CH CH CH CF or other fluorine-containing alkyl groups in which the alkyl group may be either straight chained or branched in structure.
- hexanitrodiphenylamine more commonly referredto as hexil, hexyl or hexite
- This compound exhibits a greater explosive potential than either TNT or picric acid; but unfortunately is distinctly more sensitive to shock and heat.
- the utility of this compound has been appreciably lessened, especially when emploeyd under the severe conditions encountered during military field operations.
- the primary object of this invention is to provide a new class of explosive compounds which exhibit a high explosive potential together with a high degree of thermal and shock resistivity.
- Another object of this invention is to provide a new class of fluoro-alkyl-substituted polynitrodiphenylamine compounds.
- a further object of this invention is the preparation of novel dyestuffs and dyed textile materials.
- EXAMPLE 1 Exactly 30.0 gms. of 3-chloro-2,4,6-trinitrobenzotrifluoride was dissolved in a solution consisting of 5.6 gins. of m-aminobenzotrifluoride in 20 ml. of absolute ethanol. The red platelets that precipitated were filtered, washed with sodium bicarbonate (1%), then n-hexane and subsequently air-dried. The resultant reaction product, 2,4,6- trinitro-3,3-di(trifluoromethyl) diphenylamine, had a melting point of 161162 C.
- EXAMPLE 2 The reaction product from the process of Example 1, above, was nitrated at ambient temperature by dissolving the product in 20 ml. of sulfuric acid and adding drop-wise with stirring 10 ml. of fuming nitric acid. The reaction mixture was then poured onto crushed ice to yield a reaction product of 2,2',4,4-6,6'-heXanit1'o-3,3'-di-(trifluoromethyl)diphenylamine as an orange precipitate having a melting point of 234-236 C.
- a five percent solution of the compound produced by the process of this example dyes cotton cloth a yellow-gold. When the compound is dissolved in an ammonium solution, an intense coloration occurs followed by precipitation of the ammonium salt which has no definite melting point, but rather decomposes.
- the ammonium salt is soluble in both water and alcohol giving a red solution.
- the new class of compounds disclosed by this invention have been found to be especially useful when employed in military applications as primary explosives since they exhibit a high explosive potential coupled with a minimum susceptibility to shock and heat. Additionally, these compounds are useful as dyestuffs as illustrated by referring to Example 2.
- Example 2 a representative compound; namely, 2,2, 4,4,6,6-hexanitro-3,3'-di(trifluoromethyl)- diphenylamine, dyes cotton cloth a yellow-gold. It will be seen, therefore, that the instant invention provides a new class of compounds that are useful in explosive applications, the coloration of textile materials, and as intermediates in the production of new compounds.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
1. THE COMPOUNDS HAVING THE FORMULA:
1-((2,4,6-TRI(X-),3-R-PHENYL)-NH-),2,4,6-TRI(Y-),R1-BENZENE
WHERE R AND R1 EACH REPRESENTS A FLUORO-ALKYL RADICAL HAVING FROM 1 TO 5 CARBON ATOMS, X REPRESENTS A NITRO RADICAL AND Y IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND A NITRO RADICAL.
1-((2,4,6-TRI(X-),3-R-PHENYL)-NH-),2,4,6-TRI(Y-),R1-BENZENE
WHERE R AND R1 EACH REPRESENTS A FLUORO-ALKYL RADICAL HAVING FROM 1 TO 5 CARBON ATOMS, X REPRESENTS A NITRO RADICAL AND Y IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND A NITRO RADICAL.
Description
United States Patent 3,562,332 FLUORO-ALKYL-SUBSTITUTED POLYNITROAMINES Josef J. Schmidt-Collerus, Denver, Colo., Don N. Gray, Towson, Md., and Claibourne D. Smith, Eugene, 0reg., assignors to the United States of America as represented by the Secretary of the Air Force No Drawing. Filed Jan. 28, 1964, Ser. No. 340,836 Int. Cl. C07c 87/60 US. Cl. 260-576 3 Claims The invention relates to fluoro-substituted polynitroamines. More specifically, this invention relates to fluoroalkyl-substituted polynitrodiphenylamines having the general formula:
R X Y R1 l wherein R and R each represents a fluoro-alkyl radical having from 1 to 5 carbon atoms, X represents a nitro radical, and Y is selected from the group consisting of hydrogen and a nitro radical. Illustrative of the fluoroalkyl radicals represented by R and R are the following: -CF CH CF CH CHF CH CH F, CF CF CF(CF3)2. CH CH CF CH CH CH CF or other fluorine-containing alkyl groups in which the alkyl group may be either straight chained or branched in structure.
Various diphenylamines are well known for their utility in explosive applications. For example, hexanitrodiphenylamine, more commonly referredto as hexil, hexyl or hexite, is well known as both a primary explosive and a booster. This compound exhibits a greater explosive potential than either TNT or picric acid; but unfortunately is distinctly more sensitive to shock and heat. As a result, the utility of this compound has been appreciably lessened, especially when emploeyd under the severe conditions encountered during military field operations.
With the present invention, however, it has been discovered that the above noted prior art defects can be abrogated by providing a new class of fluoro-alkyl-substituted polynitrodiphenylamines. These compounds, although exhibiting a high explosive potential, are considerably more resistant to heat and shock and, therefore, do not suffer from the undesirable sensitivity of prior known diphenylamine explosives. As a result, the compounds of this invention have been found to be especially useful as primary explosives, detonators, boosters, and, in other explosive applications, utilized by the military. Additionally, the compounds of this invention are useful in the production of dyestuffs and the coloration of textile materials because of their unique afiinity for cellulosic materials.
Accordingly, the primary object of this invention is to provide a new class of explosive compounds which exhibit a high explosive potential together with a high degree of thermal and shock resistivity.
Another object of this invention is to provide a new class of fluoro-alkyl-substituted polynitrodiphenylamine compounds.
A further object of this invention is the preparation of novel dyestuffs and dyed textile materials.
3,562,332 Patented Feb. 9, 1971 "ice It has been found that the above stated objects can be accomplished by reacting chloro-substituted polynitrobenzotrifiuorides with an appropriate substituted amine. The resultant product from the aforementioned reaction can be nitrated to produce additional compounds which come within the scope of this invention as an additional embodiment thereof.
The novel features which are believed to be characteristic of this invention are set forth in the appended claims. However, the invention both as to its organization and method of operation may best be understood by referring to the following detailed examples which are presented as illustrative embodiments of the invention. These examples, however, are not to be construed as limiting the invention in any way.
EXAMPLE 1 Exactly 30.0 gms. of 3-chloro-2,4,6-trinitrobenzotrifluoride was dissolved in a solution consisting of 5.6 gins. of m-aminobenzotrifluoride in 20 ml. of absolute ethanol. The red platelets that precipitated were filtered, washed with sodium bicarbonate (1%), then n-hexane and subsequently air-dried. The resultant reaction product, 2,4,6- trinitro-3,3-di(trifluoromethyl) diphenylamine, had a melting point of 161162 C.
EXAMPLE 2 The reaction product from the process of Example 1, above, was nitrated at ambient temperature by dissolving the product in 20 ml. of sulfuric acid and adding drop-wise with stirring 10 ml. of fuming nitric acid. The reaction mixture was then poured onto crushed ice to yield a reaction product of 2,2',4,4-6,6'-heXanit1'o-3,3'-di-(trifluoromethyl)diphenylamine as an orange precipitate having a melting point of 234-236 C. A five percent solution of the compound produced by the process of this example dyes cotton cloth a yellow-gold. When the compound is dissolved in an ammonium solution, an intense coloration occurs followed by precipitation of the ammonium salt which has no definite melting point, but rather decomposes. The ammonium salt is soluble in both water and alcohol giving a red solution.
The new class of compounds disclosed by this invention have been found to be especially useful when employed in military applications as primary explosives since they exhibit a high explosive potential coupled with a minimum susceptibility to shock and heat. Additionally, these compounds are useful as dyestuffs as illustrated by referring to Example 2. In Example 2, a representative compound; namely, 2,2, 4,4,6,6-hexanitro-3,3'-di(trifluoromethyl)- diphenylamine, dyes cotton cloth a yellow-gold. It will be seen, therefore, that the instant invention provides a new class of compounds that are useful in explosive applications, the coloration of textile materials, and as intermediates in the production of new compounds.
It will be understood by those skilled in the art to which the present invention pertains, that while the compounds disclosed herein illustrate preferred embodiments of the invention, various modifications and alterations may be made without departing from the spirit and scope thereof, and that all such modifications as fall within the scope of the appended claims are intended to be included herein.
3 What is claimed is: 2. 2,4,6-trinitro-3,3'-di(trifiuoromethyl)diphenylamine. 1. The compounds having the formula: 3. 2,2,4,4,6,6' hexanitro-3,3-di(trifluorornethyl) diphenylamine. 1 H i References Cited X- 1lr -Y 5 -UNITED STATES PATENTS 3,418,372 12/1968 Taylor 149-105X X Y Where R and R each represents a fiuoro-alkyl radical hav- LELAND SEBASTIAN Pnmary Exammer ing from 1 to 5 carbon atoms, X represents a nitro radical 10 U S Cl X R and Y is selected from the group consisting of hydrogen and :1 nitro radical. 149105; 260-646
Claims (1)
1. THE COMPOUNDS HAVING THE FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34083664A | 1964-01-28 | 1964-01-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3562332A true US3562332A (en) | 1971-02-09 |
Family
ID=23335135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US340836A Expired - Lifetime US3562332A (en) | 1964-01-28 | 1964-01-28 | Fluoro-alkyl-substituted polynitroamines |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3562332A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117167A (en) * | 1974-03-07 | 1978-09-26 | Imperial Chemical Industries Limited | Dinitroaniline derivatives |
| US4128665A (en) * | 1974-11-06 | 1978-12-05 | Imperial Chemical Industries Limited | Substituted dinitrotrifluoromethyldiphenylamine and pesticidal compositions containing same |
| US4145969A (en) * | 1975-10-02 | 1979-03-27 | Dynamit Nobel Ag | Priming system for high-temperature stable propellants |
-
1964
- 1964-01-28 US US340836A patent/US3562332A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4117167A (en) * | 1974-03-07 | 1978-09-26 | Imperial Chemical Industries Limited | Dinitroaniline derivatives |
| US4128665A (en) * | 1974-11-06 | 1978-12-05 | Imperial Chemical Industries Limited | Substituted dinitrotrifluoromethyldiphenylamine and pesticidal compositions containing same |
| US4145969A (en) * | 1975-10-02 | 1979-03-27 | Dynamit Nobel Ag | Priming system for high-temperature stable propellants |
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