[go: up one dir, main page]

US3000970A - Metal-aci-salts of nitro compounds - Google Patents

Metal-aci-salts of nitro compounds Download PDF

Info

Publication number
US3000970A
US3000970A US677193A US67719357A US3000970A US 3000970 A US3000970 A US 3000970A US 677193 A US677193 A US 677193A US 67719357 A US67719357 A US 67719357A US 3000970 A US3000970 A US 3000970A
Authority
US
United States
Prior art keywords
aci
metal
salts
sodium
tetranitrobutane
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
Application number
US677193A
Inventor
Milton B Frankel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aerojet Rocketdyne Inc
Original Assignee
Aerojet General Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Aerojet General Corp filed Critical Aerojet General Corp
Priority to US677193A priority Critical patent/US3000970A/en
Application granted granted Critical
Publication of US3000970A publication Critical patent/US3000970A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B41/00Compositions containing a nitrated metallo-organic compound
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/01Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to acyclic carbon atoms
    • C07C205/02Compounds containing nitro groups bound to a carbon skeleton having nitro groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/07Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
    • C07C205/08Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to acyclic carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F3/00Compounds containing elements of Groups 2 or 12 of the Periodic Table
    • C07F3/02Magnesium compounds

Definitions

  • This invention relates to' new compositions of. matter and methods of synthesizing them.
  • it relates to metal-aci-salts of nitroalkyls having the general formula:
  • M is a metal radical of an alkali or alkaline earth metal element, and R is a nitroalkyl radical.
  • the polynitro compounds of this invention because of their favorable oxygen balance, find valuable use as burning rate accelerators for rocket propellants.
  • they are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge.
  • An example of such a missile is disclosed in US. Patent No. 2,470,162, issued May 17, 1949.
  • One way of using the high explosives in a device such as that disclosed in US. Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed.
  • a charge thus prepared is sutficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.
  • X is a halogen radical
  • M and R are as. defined above, and R is an alkyl radical.
  • the final solution was allowed to warm to room temperature with stirring, after which it was ex.- tracted with ether to remove any unreacted starting materials.
  • the aqueous layer resulting from the ether extraction was to 5" C.
  • This layer contained sodium-acito the desired metal salt by the action of an alkali or alkaline earth metal iodide in alcoholic solution.
  • esters such as 2-chloro-2,2-dinitro-ethyl propio-' nate; 2-iodo-2,2-dinitroethyl valerate; and 2-fluoro-2,2- dinitroethyl butyrate react with lithium-aci-Ll-dinitrw propane; magnesium-aci-l,1,3,3-tetranitrobutane; and calcium-aci-l,1,3,3-tetranitropentane to yield lithium-aci-l, 1,3,3-tetranitropentane; magnesium-aci-l,1,3,3,5,5-hexanitrohexane; and calcium-aci-1,l,3,3,5 ,S-hexanitroheptane, respectively. It is apparent that any member of my series of new compounds can be produced by reacting appropriate starting materials as taught herein.
  • Reaction temperature is not critical in the practice of the present invention, the only eifect of temperature variation being a corresponding increase or decrease in the rate of reaction.
  • compositions of matter the alkali and alkaline earth metal-aci-salts of nitro compounds, having the formula:
  • compositions of matter the alkali and alkaline earth metal-aci-salts of nitro compounds, having the formula:
  • A is a radical selected from the group consisting of hydrogen and lower alkyl radicals and M is a metal radical selected from the group consisting of alkali and alkaline earth metals.
  • compositions of matter having the wherein A is a radical selected from the group consisting of hydrogen and lower alkyl radicals and M is a metal radical selected from the group consisting of alkali and alkaline earth metals.
  • X is a halogen radical
  • M is a metal radical
  • R is a lower nitroalkyl radical, and R is a lower alkyl radical.
  • R is a lower nitroalkyl radical and R is a lower alkyl radical.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

. n d StatCs This invention relates to' new compositions of. matter and methods of synthesizing them. In particular, it relates to metal-aci-salts of nitroalkyls having the general formula:
NO: I
M- --CH2R wherein M is a metal radical of an alkali or alkaline earth metal element, and R is a nitroalkyl radical.
The polynitro compounds of this invention, because of their favorable oxygen balance, find valuable use as burning rate accelerators for rocket propellants. In addition, they are useful as high explosives and can be used in any conventional explosive missile, projectile, rocket, or the like, as the main explosive charge. An example of such a missile is disclosed in US. Patent No. 2,470,162, issued May 17, 1949. One way of using the high explosives in a device such as that disclosed in US. Patent No. 2,470,162 is to pack the crystalline explosive in powder form into the warhead of the missile. Alternatively, the crystals can be first pelletized and then packed. A charge thus prepared is sutficiently insensitive to withstand the shock entailed in the ejection of a shell from a gun barrel or from a rocket launching tube under the pressure developed from ignition of a propellant charge, and can be caused to explode on operation of an impactor time-fuse mechanism firing a detonating explosive such as lead azide or mercury fulminate.
The nitro compounds of this invention are conveniently prepared in accordance with the general reaction scheme set forth below:
wherein X is a halogen radical, M and R are as. defined above, and R is an alkyl radical.
The following examples are presented to more clearly illustrate my invention. It should be understood that these examples are intended to merely illustrate the invention, and should not be interpreted to limit the scope of this invention in any manner.
EXAMPLE I Formation of sdium-aci-1,1 ,3-trinitrobutane from sodium-aci-nitro-ethane A S-necked reactor was fitted with a mechanical stirrer, thermometer and dropping funnel and charged with a suspension of 490 gm. mole) of sodium nitroethane and 1500 ml. of methanol. A solution of 640 gm. (2.5 mole) of 2-bromo-2,2-dinitroethyl acetate in 1500 ml. of methanol was added while maintaining the temperature between -15" C. The white suspension of the salt became orange as the reaction proceeded and gradually Went into solution. The solution was evaporated to atent dryness leaving an orange salt; this salt being sodium-aci- 1, 1,3 -trinitrobutane.
EXAMPLE II A 3-necked flask, fitted with a mechanical stirrer, thermometer, and dropping tunnel was charged with 1 mole of 1,1-dinitroethane. The reactor was cooled inan ice bath and a solution containing 1 mole of sodium hydroxide in water was added. To this solution, a solution of 2-bromo-2,2-dinitroethyl acetate in methanol was added dropwise with stirring until half a mole of the 2-bromo- 2,2-dinitroethyl acetate had been added. The solution to which the methanol solution was added was maintained at 10 C. until the dropwise addition of the latter was completed. The final solution was allowed to warm to room temperature with stirring, after which it was ex.- tracted with ether to remove any unreacted starting materials. The aqueous layer resulting from the ether extraction was to 5" C. This layer contained sodium-acito the desired metal salt by the action of an alkali or alkaline earth metal iodide in alcoholic solution. The
following examples are provided to more clearly illustrate this alternative synthesis.
EXAMPLE Ill Preparation of 1-br0mo-l,1,3,3-tetranitr0'batane An aqueoussolution of sodium-aci-l,l,3,3-tetranitrobutane was cooled to about 5 C. and treated with 0.5 mole of bromine. The solution was extracted with ether and then dried and concentrated. 1-br0mo-1,1,3,3-tetranitrobutane was obtained in good yield.
EXAMPLE IV Preparation of potassium-aci-l ,1 ,3,3-tetranitrobutane l-bromo-1,1,3,3-tetranitrobutane was methanol and cooled to 0 C. The. solution was treated with potassium iodide in 50% methanol. A purple reaction mixture formed which was filtered off leaving a yellow salt, which was washed with ether and recrystal lized from ethanol. The product was subsequently identified as potassium-aci-l,1,3,3-tetranitrobutane, having a melting point of 137-138" C. Analysis was as follows: Calculated: percent C, 17.39; percent H, 1.83; percent N,
20.29. Found: percent C, 17.71; percent H, 1.83; percent N, 20.69. a
While the examples have been limited to the use of romine compositions as starting materials, the other halogens can also be employed in this reaction. Similarly, any of the alkali and alkaline earth metal nitroalkyl compounds can be reacted to effect a direct synthesis'of themetal salts of this invention.
Thus, esters such as 2-chloro-2,2-dinitro-ethyl propio-' nate; 2-iodo-2,2-dinitroethyl valerate; and 2-fluoro-2,2- dinitroethyl butyrate react with lithium-aci-Ll-dinitrw propane; magnesium-aci-l,1,3,3-tetranitrobutane; and calcium-aci-l,1,3,3-tetranitropentane to yield lithium-aci-l, 1,3,3-tetranitropentane; magnesium-aci-l,1,3,3,5,5-hexanitrohexane; and calcium-aci-1,l,3,3,5 ,S-hexanitroheptane, respectively. It is apparent that any member of my series of new compounds can be produced by reacting appropriate starting materials as taught herein.
Reaction temperature is not critical in the practice of the present invention, the only eifect of temperature variation being a corresponding increase or decrease in the rate of reaction.
dissolved .in v
This application is a continuation-in-part of my copending U.S. patent application Ser. No. 451,704, filed August 23, 1954, now abandoned, which was a continuation-impart of my U.S. patent application Ser. No. 248,876, filed September 28, 1951, now abandoned.
I claim:
1. As compositions of matter, the alkali and alkaline earth metal-aci-salts of nitro compounds, having the formula:
N03 M-(|3-OH2R wherein R is a lower nitroalkyl radical and M is a metal radical selected from the group consisting of alkali and alkaline earth metals.
2. As compositions of matter, the alkali and alkaline earth metal-aci-salts of nitro compounds, having the formula:
wherein A is a radical selected from the group consisting of hydrogen and lower alkyl radicals and M is a metal radical selected from the group consisting of alkali and alkaline earth metals.
3. As compositions of matter, the alkali and alkaline earth metal-aci-salts of nitro compounds, having the wherein A is a radical selected from the group consisting of hydrogen and lower alkyl radicals and M is a metal radical selected from the group consisting of alkali and alkaline earth metals.
4. As a composition of matter, sodium-aci-1,1,3-trinitrobutane having the structural formula:
ll or N02 Na-C-CHrO-CHa NO: H
5. As a composition of matter, sodium-aci-1,1,3,3-tetranitrobutane having the structural formula:
N02 N02 Na-C-OHr-C-CEE 6. As a composition of matter, potassium-aci-1,l,3,3- tetranitrobutane having the structural formula:
IFTO: N O: P(I'JCH7COHa N02 N02 7. As a composition of matter, lithium-aci-1,l,1,3-tetranitropentane.
8. As a composition of matter, magnesium-aci-1,1,3,3, 5,5-hexanitrohexane.
9. As a composition of matter, calcium-aci-1,l,3,3,5, S-hexanitroheptane.
10. The method of preparing alkali and alkaline earth metal-aci-salts of nitro compounds having the formula:
4. which comprises reacting an ester having the formula:
N02 X-C l-GHr-O( 7-R' with a metal-aci-salt having the formula:
wherein X is a halogen radical, M is a metal radical.
selected from the group consisting of the alkali and alkaline earth metals, R is a lower nitroalkyl radical, and R is a lower alkyl radical.
11. The method of preparing sodium-aci-salts of nitro compounds, having the formula:
NBCCHz-R N02 7 which comprises reacting an ester having the formula:
N02 Br( 3-OHz-O-( 3 R' with a sodium-aci-salt having the formula:
Na-R
wherein R is a lower nitroalkyl radical and R is a lower alkyl radical.
12. The method of preparing sodium-aci-1,1,3-trinitrobutane which comprises reacting 2-bromo-2,2-dinitroethyl acetate with sodium-aci-nitroethane.
13. The method of claim 12 wherein the reaction is conducted in the presence of an inert organic solvent.
14. The method of preparing sodium-aci-l,1,3,3-tetranitrobutane which comprises reacting 2-brorno-2,2-dinitroethyl acetate with sodium-aci-1,1-dinitroethane.
15. The method of claim 14 wherein the reaction is conducted in the presence of an inert organic solvent.
16. The method of preparing lithium-aci-1,l,3,3 tetranitropentane which comprises reacting 2-chloro-2,2-dinitroethyl propionate with lithium-aci-l,l-dinitropropane.
17. The method of preparing ma'gnesium-aci-1,l,3,3,5, S-hexanitrohexane which comprises reacting 2-iodo-2,2- dinitroethyl valerate with magnesium-aci-l,1,3,3-tetranitrobutane.
18. The method of preparing calcium-aci-1,1,3,3,5,5- hexanitroheptane which comprises reacting 2-fluoro-2,2- dinitroethylbutyrate with calcium-aci-1,1,3,3-tetranitropentane.
19. The method of preparing potassium-aei-1,1,3,3- tetranitrobutane which comprises reacting an ester having the formula:
with sodium-aci-l,l-dinitroethane to obtain sodium-aci- 1,1,3,3-tetranitrobutane; reacting I the sodium-aci,l,l,3,3- tetranitrobutane with bromine to obtain 1-bromo-1,1,3,3- tetranitrobutane; and reacting the 1-bromo-1,l,3,3-tetranitrobutane with potassium iodide; wherein X is a halogen radical and R is a lower alkyl radical.
20. The method of claim 19 wherein the reaction between the 1-bromo1,1,3,3-tetranitrobutane and the potassium iodide is conducted in alcoholic solution.
No references cited;

Claims (1)

1. AS COMPOSITIONS OF MATTER, THE ALKALI AND ALKALINE EARTH METAL-ACI-SALTS OF NITRO COMPOUNDS, HAVING THE FORMULA:
US677193A 1957-08-07 1957-08-07 Metal-aci-salts of nitro compounds Expired - Lifetime US3000970A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US677193A US3000970A (en) 1957-08-07 1957-08-07 Metal-aci-salts of nitro compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US677193A US3000970A (en) 1957-08-07 1957-08-07 Metal-aci-salts of nitro compounds

Publications (1)

Publication Number Publication Date
US3000970A true US3000970A (en) 1961-09-19

Family

ID=24717698

Family Applications (1)

Application Number Title Priority Date Filing Date
US677193A Expired - Lifetime US3000970A (en) 1957-08-07 1957-08-07 Metal-aci-salts of nitro compounds

Country Status (1)

Country Link
US (1) US3000970A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356714A (en) * 1965-09-15 1967-12-05 Mortimer J Kamlet 4-fluoro-4, 4-dinitrobutyric acids and esters thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356714A (en) * 1965-09-15 1967-12-05 Mortimer J Kamlet 4-fluoro-4, 4-dinitrobutyric acids and esters thereof

Similar Documents

Publication Publication Date Title
US3111524A (en) Preparation of 3, 5-dinitro-1, 2, 4-triazole
US3000970A (en) Metal-aci-salts of nitro compounds
US3020317A (en) Polynitro alcohols and salts thereof
US3000942A (en) N,n'-(nitrazaalkyl) oxamides
US2901512A (en) Tetranitrodiethylamine salts
US3399235A (en) Polynitro trifluoromethyl amines
US3000939A (en) N-nitro,n,n'-bis(trinitroalkyl)-urea
US2985683A (en) Tetranitrodiethylamine derivatives
US2934558A (en) Nitrazaalkylnitrates
US2940997A (en) Gem-dinitro amino acids
US3000895A (en) Polynitropiperidines
US2880232A (en) Polynitro amino dialkanoate
US3000928A (en) Polynitro nitrate compounds and method of preparation
US3000957A (en) Polynitro alcohols
US3000955A (en) Dinitramines
US2967198A (en) Polynitroamides
US3000968A (en) Method of preparing nitro compounds
US2978494A (en) Polynitro esters
US3159678A (en) Nitramines
US3038939A (en) Diethylamines
US1560427A (en) Explosive and process of making same
US2934565A (en) Polynitroamine salts
US3000931A (en) Process for the preparation of nitrocarbamates
US2978489A (en) Nitro-dicarbamates
US3041382A (en) Method of preparing 2, 2, 4, 4-tetranitro-1, 5-pentanediol