USH78H - 5-aza-3,3,7,7-tetranitrononane-1,9-diols and method of preparation - Google Patents
5-aza-3,3,7,7-tetranitrononane-1,9-diols and method of preparation Download PDFInfo
- Publication number
- USH78H USH78H US06/492,276 US49227683A USH78H US H78 H USH78 H US H78H US 49227683 A US49227683 A US 49227683A US H78 H USH78 H US H78H
- Authority
- US
- United States
- Prior art keywords
- compound
- cooch
- diol
- diols
- sub
- 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
Links
- 238000002360 preparation method Methods 0.000 title description 8
- 238000000034 method Methods 0.000 title description 4
- LDXXJKWFWNXACG-UHFFFAOYSA-N 4-[(4-hydroxy-2,2-dinitrobutyl)amino]-3,3-dinitrobutan-1-ol Chemical class OCCC([N+]([O-])=O)([N+]([O-])=O)CNCC([N+]([O-])=O)([N+]([O-])=O)CCO LDXXJKWFWNXACG-UHFFFAOYSA-N 0.000 title description 3
- 125000004965 chloroalkyl group Chemical group 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 6
- 125000004407 fluoroaryl group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- -1 chloroaryls Chemical group 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 150000002009 diols Chemical class 0.000 abstract description 17
- 150000005690 diesters Chemical class 0.000 abstract description 5
- 125000002009 alkene group Chemical group 0.000 abstract description 3
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- MYUKBCFSIRJMOK-UHFFFAOYSA-N 2,2-dinitrobutane-1,4-diol Chemical compound OCCC(CO)([N+]([O-])=O)[N+]([O-])=O MYUKBCFSIRJMOK-UHFFFAOYSA-N 0.000 description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 8
- IVLKBZHWMZOSPZ-UHFFFAOYSA-N 3,3,3-trinitropropan-1-ol Chemical compound OCCC([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O IVLKBZHWMZOSPZ-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- IEICTPVPNGVHHJ-UHFFFAOYSA-N 3,3,3-trinitropropyl acetate Chemical compound CC(=O)OCCC([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O IEICTPVPNGVHHJ-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000004471 Glycine Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZOJXZAUSRHQSFR-UHFFFAOYSA-N 3,3-dinitropropyl acetate;potassium Chemical compound [K].CC(=O)OCCC([N+]([O-])=O)[N+]([O-])=O ZOJXZAUSRHQSFR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- SXSIWXCBQCNXCG-UHFFFAOYSA-N [4-[(4-acetyloxy-2,2-dinitrobutyl)-nitroamino]-3,3-dinitrobutyl] acetate Chemical compound CC(=O)OCCC([N+]([O-])=O)([N+]([O-])=O)CN([N+]([O-])=O)CC([N+]([O-])=O)([N+]([O-])=O)CCOC(C)=O SXSIWXCBQCNXCG-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YNJUKATZJNTQQX-UHFFFAOYSA-N 2-[bis(2,2-dinitropropyl)amino]acetic acid Chemical compound [O-][N+](=O)C([N+]([O-])=O)(C)CN(CC(O)=O)CC(C)([N+]([O-])=O)[N+]([O-])=O YNJUKATZJNTQQX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WKJCKXFCZQYEJJ-UHFFFAOYSA-N [4-[(4-acetyloxy-2,2-dinitrobutyl)amino]-3,3-dinitrobutyl] acetate Chemical compound CC(=O)OCCC([N+]([O-])=O)([N+]([O-])=O)CNCC([N+]([O-])=O)([N+]([O-])=O)CCOC(C)=O WKJCKXFCZQYEJJ-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006344 deformylation reaction Methods 0.000 description 2
- WINNISSSXBRWMA-UHFFFAOYSA-N dinitromethane Chemical class [O-][N+](=O)C[N+]([O-])=O WINNISSSXBRWMA-UHFFFAOYSA-N 0.000 description 2
- MKYNHKOAYQRSBD-UHFFFAOYSA-N dioxouranium;nitric acid Chemical compound O=[U]=O.O[N+]([O-])=O.O[N+]([O-])=O MKYNHKOAYQRSBD-UHFFFAOYSA-N 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- XDBPKWWDUBMCPW-UHFFFAOYSA-N n,n-bis(4-hydroxy-2,2-dinitrobutyl)nitramide Chemical compound OCCC([N+]([O-])=O)([N+]([O-])=O)CN([N+]([O-])=O)CC([N+]([O-])=O)([N+]([O-])=O)CCO XDBPKWWDUBMCPW-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JGAGBYRIJUMEDB-UHFFFAOYSA-N 2,2,2-trinitroethanol Chemical compound OCC([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O JGAGBYRIJUMEDB-UHFFFAOYSA-N 0.000 description 1
- IPLRZPREFHIGIB-UHFFFAOYSA-N 2,2-dinitropropan-1-ol Chemical compound OCC(C)([N+]([O-])=O)[N+]([O-])=O IPLRZPREFHIGIB-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- BQQSWNSBIOEUEG-UHFFFAOYSA-N 2-[bis(2,2-dinitropropyl)amino]propanoic acid Chemical compound [O-][N+](=O)C(C)([N+]([O-])=O)CN(C(C)C(O)=O)CC(C)([N+]([O-])=O)[N+]([O-])=O BQQSWNSBIOEUEG-UHFFFAOYSA-N 0.000 description 1
- IUKSYUOJRHDWRR-UHFFFAOYSA-N 2-diazonio-4,6-dinitrophenolate Chemical compound [O-]C1=C([N+]#N)C=C([N+]([O-])=O)C=C1[N+]([O-])=O IUKSYUOJRHDWRR-UHFFFAOYSA-N 0.000 description 1
- PCNWBUOSTLGPMI-UHFFFAOYSA-N 2-nitro-1-propanol Chemical compound OCC(C)[N+]([O-])=O PCNWBUOSTLGPMI-UHFFFAOYSA-N 0.000 description 1
- XXJLFAZNQQGWQH-UHFFFAOYSA-N 3,3-dinitropropan-1-ol;potassium Chemical compound [K].OCCC([N+]([O-])=O)[N+]([O-])=O XXJLFAZNQQGWQH-UHFFFAOYSA-N 0.000 description 1
- ALYGFHXDFBTXMD-UHFFFAOYSA-N 4,4,4-trinitrobutanoic acid Chemical compound OC(=O)CCC([N+]([O-])=O)([N+]([O-])=O)[N+]([O-])=O ALYGFHXDFBTXMD-UHFFFAOYSA-N 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- RCDMSRYMRAIHER-UHFFFAOYSA-N [4-[(4-acetyloxy-2,2-dinitrobutyl)-cyanoamino]-3,3-dinitrobutyl] acetate Chemical compound CC(=O)OCCC([N+]([O-])=O)([N+]([O-])=O)CN(C#N)CC([N+]([O-])=O)([N+]([O-])=O)CCOC(C)=O RCDMSRYMRAIHER-UHFFFAOYSA-N 0.000 description 1
- JNWHZYQMQQJOIK-UHFFFAOYSA-N [4-[(4-acetyloxy-2,2-dinitrobutyl)-nitrosoamino]-3,3-dinitrobutyl] acetate Chemical compound CC(=O)OCCC([N+]([O-])=O)([N+]([O-])=O)CN(N=O)CC([N+]([O-])=O)([N+]([O-])=O)CCOC(C)=O JNWHZYQMQQJOIK-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- XVBBKASCLOBEFK-UHFFFAOYSA-N bis(4-hydroxy-2,2-dinitrobutyl)cyanamide Chemical compound OCCC([N+]([O-])=O)([N+]([O-])=O)CN(C#N)CC([N+]([O-])=O)([N+]([O-])=O)CCO XVBBKASCLOBEFK-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ATDGTVJJHBUTRL-UHFFFAOYSA-N cyanogen bromide Chemical compound BrC#N ATDGTVJJHBUTRL-UHFFFAOYSA-N 0.000 description 1
- 230000006198 deformylation Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- SPWVRYZQLGQKGK-UHFFFAOYSA-N dichloromethane;hexane Chemical compound ClCCl.CCCCCC SPWVRYZQLGQKGK-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- MDKXBBPLEGPIRI-UHFFFAOYSA-N ethoxyethane;methanol Chemical compound OC.CCOCC MDKXBBPLEGPIRI-UHFFFAOYSA-N 0.000 description 1
- 150000002332 glycine derivatives Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
-
- 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
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
- C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
- C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
- C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/10—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
- C07C229/12—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of acyclic carbon skeletons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
- C07C243/02—N-nitro compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C261/00—Derivatives of cyanic acid
- C07C261/04—Cyanamides
Definitions
- This invention relates to alcohols and more particularly to energetic polynitro substituted diols.
- polynitrodiols such as A-Diol and DINOL were used as components of energetic polymers. These diols are known to fragment easily with loss of formaldehyde and formation of labile dinitromethane derivatives. Thus when free hydroxy groups are present in the polymer they provide sites for initiation of thermal decomposition and chemical reactions (incompatibility with other ingredients, degradation during aging). In particular, it would be desirable to provide diols which will be more stable toward weak bases or nucleophiles such as water (atmospheric moisture) or oxygen and nitrogen containing components of energetic binder systems.
- an object of this invention is to provide new energetic diols.
- Another object of this invention is to provide new energetic diols which can be used as components in energetic propellant and explosive binders.
- a further object of this invention is to provide new polynitro diols which resist deformylation by mild bases.
- Yet another object of this invention is to provide new polynitro diols which are compatible with oxygen and nitrogen containing components of propellant and explosive composites.
- the compounds of the present invention are energetic diols of the formula ##STR4## and their corresponding diesters of the formula ##STR5## wherein R is --H, --NO, --NO 2 , --CN, --COOCH 3 , --COOCH 2 C(NO 2 ) 2 CH 3 , or --COOCH 2 C(NO 2 ) 3 and R' is an alkyl, fluoroalkyl, chloroalkyl, aryl, fluoroaryl, chloroalkyl, aralkyl, fluoroaralkyl, chloroaralkyl, or alkene group.
- the critical feature of the diols of the present invention is that the gem-dinitro groups are located in the ⁇ position to the hydroxy groups
- these prior art diols are known to fragment easily in the presence of oxygen or nitrogen containing components of energetic binder systems. As a result, loss of formaldehyde and formation of labile dinitromethane derivatives occurs. Polymers made with these ⁇ -dinitro diols are therefor less stable. In the present diols, the additional methylene group between the gem-dinitro and the hydroxy group prevents the deformylation reaction. Therefore, binder polymers made with these new diols will be much more stable than those of the prior art. The addition of still more methylene groups is not desirable as they will lower the energy content of the present diols without significantly improving their stability.
- 5-aza-3,3-7,7-tetranitrononane-1,9-diol can be prepared by reacting one mole of ammonia with two moles of 2,2-dinitrobutane-1,4-diol under the conditions given in example 7.
- a method of preparing 2,2-dinitrobutane-1,4-diol is disclosed in U.S. Pat. Ser. No. 492,277, filed on May 6, 1983, entitled “2,2-Dinitrobutane-1,4-diol and Monoesters," by Horst G. Adolph and Michael Wegmann, which was filed concurrently with the present case, herein incorporated by reference.
- 3,3,3-trinitropropanol is reacted with potassium iodide to produce the salt potassium 3,3-dinitropropanol.
- 5-aza-3,3,7,7-tetranitrononane-1,9-diol-1,9-diesters of the formula ##STR8## can be formed by reacting one mole of ammonia with two moles of a monoester of the formula ##STR9##
- the monoester may be prepared according to the procedure disclosed in U.S. Patent Application Ser. No. 492,277, filed on May 6, 1983, entitled “2,2-DINITROBUTANE-1,4-DIOL AND MONOESTERS,” supra, which was filed concurrently with the present application, and herein incorporated by reference.
- 3,3,3-trinitropropanol is esterified by conventional means to produce a compound of the formula ##STR10##
- the alcohol may be reacted with the appropriate acid chloride ##STR11##
- Example 2 illustrates this step for R' equal to --CH 3 ##STR12##
- Example 4 illustrates this step for R equal to --CH 3 ##STR16##
- the ester groups can be hydrolyzed off by conventional means (for instance see Example 6). Because the ##STR17## serves only as a blocking group and is later hydrolyzed off, selection of R is not critical.
- R may be an alkyl, fluoroakyl, chloroalkyl, aryl, fluoroaryl, chloroalkyl, aralkyl, fluoroaralkyl, chloroaralkyl, or alkene group.
- R should contain no groups that will interfer with the esterification of the 3,3,3-trinitropropanol or with the reaction between the 2,2-dinitrobutane-1,4-diol monoester and ammonia. (Amino and hydroxy containing groups are therefore not included in R.)
- R is preferably low in molecular weight.
- R when R is an alkyl, fluoroalkyl, or chloroalkyl group, R preferable contains from 1 to 12, and more preferably from 1 to 4 carbon atoms.
- R is an aryl, fluoroaryl, or chloroaryl groups, R preferably contains from 6 to 18, and more preferably 6 carbon atoms.
- R When R is an aralkyl, fluoroalkyl, or chloroaralkyl group, R preferably contains from 7 to 18, and more preferably from 7 to 10 carbon atoms. Of all the groups available, R equals to --CH 3 is most preferred for industrial purposes because of cost.
- R equal to --CH ⁇ CH 2 , ##STR18## --CF 3 , --CCl 3 , etc.
- the 3,3,7,7-tetranitro-5-azanonane-1,9-diol and its 1,9-diester derivatives are secondary amines with an active N-hydrogen which can be replaced with a more energetic group.
- Example 5 illustrate the nitration of the diacetate to form 3,3,5,7,7-pentanitro-5-azanonane-1,9-diol-1,9-diacetate using 90% nitric acid and acetic anhydride, ##STR19##
- Example 6 shows the acid hydrolysis of this diacetate to form 3,3,5,7,7-pentanitro-5-azanonane-1,9-diol, ##STR20##
- Acetic acid and sodium nitrite, NaNO 2 have been used under standard conditions to nitrosate 3,3,7,7-tetranitro-5-azanone-1,9-diol-1,9-diacetate to form 3,3,7,7-tetranitro-5-nitroso-5-azanonane-1,9-diol-1,9-diacetate ##STR21##
- acetic acid and sodium nitrite may be used under standard conditions to nitrosate 3,3,7,7-tetranitro-5-azanone-1,9-diol to form 3,3,7,7-tetranitro-5-nitroso-5-azanone-1,9-diol. ##STR22##
- the 1,9 diester By reacting 2 moles of a 4-monoester of 2,2-dinitrobutane-1,4-diol with glycine ##STR24## the 1,9 diester can be produced.
- the carboxylic acid group on the N,N-disubstituted glycine product could then be esterified with the appropriate alcohol by standard methods. For instance if methanol is used the product ester would be [HOCH 2 CH 2 C(NO 2 ) 2 CH 2 ] 2 NCH 2 COOCH 3 . If 2,2-nitropropanol is used the product ester would be [HOCH 2 CH 2 C(NO 2 ) 2 CH 2 ] 2 NCH 2 COOCH 2 C(NO 2 ) 2 CH 3 .
- the product ester will be [HOCH 2 CH 2 C(NO 2 ) 2 CH 2 ] 2 NCH 2 COOCH 2 C(NO 3 ) 3 .
- the 1,9-ester groups could be hydrolyzed off by conventional means to yield the diol ##STR25##
- Bis-(2,2-dinitropropyl)-glycine (IV) A solution of 7.5 g. (0.1 mole) of glycine, 4.0 g. (0.1 mole) of sodium hydroxide and 50 ml. of water was mixed with 15.0 g. (0.1 mole) of 2,2-dinitropropanol. The temperature rose to 42° and the yellow solution formed was allowed to stand overnight. Upon addition of dilute sulfuric acid a viscous, colorless oil separated and solidified on standing. The product 15.6 g. (92.0%) was collected and recrystallized from methanol-water to give white crystals, m.p. 123°-124°.
- Methyl Bis-(2,2-dinitropropyl)-glycine A mixture of 20 g. (0.059 mole) of bis-(2,2-dinitropropyl)-glycine, 100 ml. of methanol and 10.0 ml. of concentrated sulfuric acid was refluxed for 90 minutes. The solution was diluted with 250 ml. of methylene chloride and washed with water, 5% sodium carbonate solution and water. The solvent was evaporated to yield 14.0 g. (67.3%) of white solid. Recrystallization from methanol-ether gave crystals, m.p. 94°-95°.
- 4,4,4-Trinitrobutyric acid (210 g, 0.94 mol) was added to 534 ml (908 g) of trifluoromethanesulfonic acid stirred in a 2000 ml, 3-neck, round-bottom flask.
- the solution was heated to 60° C. (oil bath) and sodium azide (100 g, 1.54 mol) was added in approximately 2 g portions over a six-hour period. (A stream of nitrogen was kept flowing over the reaction mixture during the addition to dilute and expel excess HN 3 .) Stirring was stopped and the thick mixture was heated overnight at 50° C. before it was poured onto ice to give an aqueous solution (2500 ml) which was extracted with 3 ⁇ 300 ml of methylene chloride.
- Acetyl chloride (125 ml) was added to a dried (MgSO 4 ) solution of 150 g of crude 3,3,3-trinitropropanol as prepared above and cooled in an icebath. The solution was slowly warmed to reflux temperature and held overnight. The reaction solution was concentrated to 800 ml by distillation before it was cooled and poured onto ice water. The mixture was stirred for 30 minutes before the CH 2 Cl 2 layer was separated, dried over MgSO 4 , and the solvent removed to give 183 g (100 percent) of crude 3,3,3-trinitropropyl acetate as a light green solid.
- Potassium iodide (338 g, 2.03 mol) was added to 183 g (0.77 mol) of crude 3,3,3-trinitropropyl acetate in 2100 ml of methanol. The mixture was stirred at 40° C. for 24 hours before it was cooled to 20° C. and the yellow salt removed by filtration. The product was stirred with 600 ml of methanol at 20° C. to give 88.5 g (50 percent) of yellow salt.
- Acetic anhydride (315 ml) was stirred in an ice bath to maintain a temperature of 20°-23° C. during the slow addition of 95 ml of 90 percent nitric acid. The solution was then cooled to 5° C. while 3,3,7,7-tetranitro-5-azanonane-1,9-diol-1,9-diacetate was added in portions with good stirring. The solution was stirred at ambient temperature overnight before it was poured into ice water. The mixture was stirred for one hour and the solid (66.5 g, 97 percent, mp 87°-89° C.) was removed by filtration.
- aqueous ammonium hydroxide (0.60 g, 0.0105 mol) was diluted to 5 ml with distilled water before it was slowly added over a 1.5 hour period to a solution of 1.80 g 0.01 mol) of 2,2-dinitrobutane-1,4-diol and 1.20 g (0.022 mol) of ammonium chloride in 25 ml of distilled water stirred at ambient temperature.
- the aqueous solution was decanted from a sticky semisolid percipitate which was washed with water and then dissolved in ether. A very small amount of ether insoluble solid was removed before the ether was evaporated to give 0.28 g of solid, mp 67°-72° C.
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Abstract
Energetic diols of the formula ##STR1## wherein R is --H, --NO, --NO2, --CN, or --CH2 COOH, and diesters of the formula ##STR2## wherein R is --H, --NO, --NO2, --CN, --CH2 COOCH3, --CH2 COOCH2 C(NO2)2 CH3, or --CH2 COOCH2 C(NO2)3 and R' is an alkyl, fluoroalkyl, chloroalkyl, aryl, fluoroaryl, chloroalkyl, aralkyl, fluoroaralkyl, chloroaralkyl, or alkene group.
Description
This invention relates to alcohols and more particularly to energetic polynitro substituted diols.
Previously, polynitrodiols such as A-Diol and DINOL were used as components of energetic polymers. These diols are known to fragment easily with loss of formaldehyde and formation of labile dinitromethane derivatives. Thus when free hydroxy groups are present in the polymer they provide sites for initiation of thermal decomposition and chemical reactions (incompatibility with other ingredients, degradation during aging). In particular, it would be desirable to provide diols which will be more stable toward weak bases or nucleophiles such as water (atmospheric moisture) or oxygen and nitrogen containing components of energetic binder systems.
Accordingly, an object of this invention is to provide new energetic diols.
Another object of this invention is to provide new energetic diols which can be used as components in energetic propellant and explosive binders.
A further object of this invention is to provide new polynitro diols which resist deformylation by mild bases.
Yet another object of this invention is to provide new polynitro diols which are compatible with oxygen and nitrogen containing components of propellant and explosive composites.
These and other objects of this invention are accomplished by providing diols of the formula ##STR3## wherein R is --H, --NO, --NO2, --CN, --CH2 COOCH3, --CH2 COOCH2 C(NO2)2 CH3, or --CH2 COOCH2 C(NO2)3.
The compounds of the present invention are energetic diols of the formula ##STR4## and their corresponding diesters of the formula ##STR5## wherein R is --H, --NO, --NO2, --CN, --COOCH3, --COOCH2 C(NO2)2 CH3, or --COOCH2 C(NO2)3 and R' is an alkyl, fluoroalkyl, chloroalkyl, aryl, fluoroaryl, chloroalkyl, aralkyl, fluoroaralkyl, chloroaralkyl, or alkene group.
The critical feature of the diols of the present invention is that the gem-dinitro groups are located in the γ position to the hydroxy groups
--C(NO.sub.2).sub.2 CH.sub.2 CH.sub.2 OH.
In similar prior art diols the gem-dinitro groups are located in the β position adjacent to the hydroxy groups
--C(NO.sub.2).sub.2 CH.sub.2 OH.
As stated in the background of the invention, these prior art diols are known to fragment easily in the presence of oxygen or nitrogen containing components of energetic binder systems. As a result, loss of formaldehyde and formation of labile dinitromethane derivatives occurs. Polymers made with these β-dinitro diols are therefor less stable. In the present diols, the additional methylene group between the gem-dinitro and the hydroxy group prevents the deformylation reaction. Therefore, binder polymers made with these new diols will be much more stable than those of the prior art. The addition of still more methylene groups is not desirable as they will lower the energy content of the present diols without significantly improving their stability.
5-aza-3,3-7,7-tetranitrononane-1,9-diol can be prepared by reacting one mole of ammonia with two moles of 2,2-dinitrobutane-1,4-diol under the conditions given in example 7. ##STR6## A method of preparing 2,2-dinitrobutane-1,4-diol is disclosed in U.S. Pat. Ser. No. 492,277, filed on May 6, 1983, entitled "2,2-Dinitrobutane-1,4-diol and Monoesters," by Horst G. Adolph and Michael Sitzmann, which was filed concurrently with the present case, herein incorporated by reference. In the process, 3,3,3-trinitropropanol is reacted with potassium iodide to produce the salt potassium 3,3-dinitropropanol.
C(NO.sub.2).sub.3 CH.sub.2 CH.sub.2 OH+KI→K.sup.+ .sup.- C(NO.sub.2).sub.2 CH.sub.2 CH.sub.2 OH.
The salt is then reacted with formaldehyde and the solution is acidified to yield the 2,2-dinitrobutane-1,4-diol ##STR7##
5-aza-3,3,7,7-tetranitrononane-1,9-diol-1,9-diesters of the formula ##STR8## can be formed by reacting one mole of ammonia with two moles of a monoester of the formula ##STR9##
The monoester may be prepared according to the procedure disclosed in U.S. Patent Application Ser. No. 492,277, filed on May 6, 1983, entitled "2,2-DINITROBUTANE-1,4-DIOL AND MONOESTERS," supra, which was filed concurrently with the present application, and herein incorporated by reference. First, 3,3,3-trinitropropanol is esterified by conventional means to produce a compound of the formula ##STR10## For example, the alcohol may be reacted with the appropriate acid chloride ##STR11## Example 2 illustrates this step for R' equal to --CH3 ##STR12##
Next, the ester is reacted with potassium iodide to produce a potassium salt ##STR13## Example 3 illustrates this step for R' equal to --CH3 ##STR14##
Reaction of the potassium salt of the ester, formaldehyde, and ammonia yields the desired diester ##STR15## Example 4 illustrates this step for R equal to --CH3 ##STR16## The ester groups can be hydrolyzed off by conventional means (for instance see Example 6). Because the ##STR17## serves only as a blocking group and is later hydrolyzed off, selection of R is not critical. For example, R may be an alkyl, fluoroakyl, chloroalkyl, aryl, fluoroaryl, chloroalkyl, aralkyl, fluoroaralkyl, chloroaralkyl, or alkene group. The only restrictions are that R should contain no groups that will interfer with the esterification of the 3,3,3-trinitropropanol or with the reaction between the 2,2-dinitrobutane-1,4-diol monoester and ammonia. (Amino and hydroxy containing groups are therefore not included in R.) As a practical matter, R is preferably low in molecular weight. For example, when R is an alkyl, fluoroalkyl, or chloroalkyl group, R preferable contains from 1 to 12, and more preferably from 1 to 4 carbon atoms. When R is an aryl, fluoroaryl, or chloroaryl groups, R preferably contains from 6 to 18, and more preferably 6 carbon atoms. When R is an aralkyl, fluoroalkyl, or chloroaralkyl group, R preferably contains from 7 to 18, and more preferably from 7 to 10 carbon atoms. Of all the groups available, R equals to --CH3 is most preferred for industrial purposes because of cost.
Other common examples are R equal to --CH═CH2, ##STR18## --CF3, --CCl3, etc.
The 3,3,7,7-tetranitro-5-azanonane-1,9-diol and its 1,9-diester derivatives are secondary amines with an active N-hydrogen which can be replaced with a more energetic group. For instance, Example 5 illustrate the nitration of the diacetate to form 3,3,5,7,7-pentanitro-5-azanonane-1,9-diol-1,9-diacetate using 90% nitric acid and acetic anhydride, ##STR19## Example 6 shows the acid hydrolysis of this diacetate to form 3,3,5,7,7-pentanitro-5-azanonane-1,9-diol, ##STR20##
Acetic acid and sodium nitrite, NaNO2, have been used under standard conditions to nitrosate 3,3,7,7-tetranitro-5-azanone-1,9-diol-1,9-diacetate to form 3,3,7,7-tetranitro-5-nitroso-5-azanonane-1,9-diol-1,9-diacetate ##STR21## Similarly, acetic acid and sodium nitrite may be used under standard conditions to nitrosate 3,3,7,7-tetranitro-5-azanone-1,9-diol to form 3,3,7,7-tetranitro-5-nitroso-5-azanone-1,9-diol. ##STR22##
3,3,7,7-tetranitro-5-cyano-5-azanonane-1,9-diol
[HOCH.sub.2 CH.sub.2 C(NO.sub.2).sub.2 CH.sub.2 ].sub.2 NCN
and its diester derivatives (e.g., 3,3,7,7-tetranitro-5-cyano-5-azanonane-1,9-diol 1,9-diacetate where R'=CH3) ##STR23## can be prepared by reaction of the corresponding secondary amines with cyanogen bromide.
By reacting 2 moles of a 4-monoester of 2,2-dinitrobutane-1,4-diol with glycine ##STR24## the 1,9 diester can be produced. The carboxylic acid group on the N,N-disubstituted glycine product could then be esterified with the appropriate alcohol by standard methods. For instance if methanol is used the product ester would be [HOCH2 CH2 C(NO2)2 CH2 ]2 NCH2 COOCH3. If 2,2-nitropropanol is used the product ester would be [HOCH2 CH2 C(NO2)2 CH2 ]2 NCH2 COOCH2 C(NO2)2 CH3. Finally, if 2,2,2-trinitroethanol is used, the product ester will be [HOCH2 CH2 C(NO2)2 CH2 ]2 NCH2 COOCH2 C(NO3)3. Alternately, the 1,9-ester groups could be hydrolyzed off by conventional means to yield the diol ##STR25##
The feasibility of these glycine syntheses is illustrated by similar syntheses in "The Mannich Reaction of 2,2-Dinitro-1-alkanols with Ammonia, Glycine and Hydrazine," by Milton B. Frankel and Karl Klager, Journal of the American Chemical Society, Vol. 79, pp. 2953-6 (1957), herein incorporated by reference. In particular the following 2 Examples are quoted from that article p. 2954, col. 2:
Bis-(2,2-dinitropropyl)-glycine (IV). A solution of 7.5 g. (0.1 mole) of glycine, 4.0 g. (0.1 mole) of sodium hydroxide and 50 ml. of water was mixed with 15.0 g. (0.1 mole) of 2,2-dinitropropanol. The temperature rose to 42° and the yellow solution formed was allowed to stand overnight. Upon addition of dilute sulfuric acid a viscous, colorless oil separated and solidified on standing. The product 15.6 g. (92.0%) was collected and recrystallized from methanol-water to give white crystals, m.p. 123°-124°.
Methyl Bis-(2,2-dinitropropyl)-glycine. A mixture of 20 g. (0.059 mole) of bis-(2,2-dinitropropyl)-glycine, 100 ml. of methanol and 10.0 ml. of concentrated sulfuric acid was refluxed for 90 minutes. The solution was diluted with 250 ml. of methylene chloride and washed with water, 5% sodium carbonate solution and water. The solvent was evaporated to yield 14.0 g. (67.3%) of white solid. Recrystallization from methanol-ether gave crystals, m.p. 94°-95°.
The general nature of this invention having been set forth, the following examples are set forth as specific illustrations thereof. It will be understood that the invention is not limited to these specific examples but is susceptible to various modifications that will be recognized by one of ordinary skill in the art.
4,4,4-Trinitrobutyric acid (210 g, 0.94 mol) was added to 534 ml (908 g) of trifluoromethanesulfonic acid stirred in a 2000 ml, 3-neck, round-bottom flask. The solution was heated to 60° C. (oil bath) and sodium azide (100 g, 1.54 mol) was added in approximately 2 g portions over a six-hour period. (A stream of nitrogen was kept flowing over the reaction mixture during the addition to dilute and expel excess HN3.) Stirring was stopped and the thick mixture was heated overnight at 50° C. before it was poured onto ice to give an aqueous solution (2500 ml) which was extracted with 3×300 ml of methylene chloride. Two grams of unreacted trinitrobutyric acid were recovered from the CH2 Cl2 extracts. The aqueous solution was cooled at 10°-14° C. while a solution of 140 g of sodium hydroxide in 200 ml of water was added dropwise with good stirring. The solution was then heated to 35° C. before a solution of 121 g (1.75 mol) of sodium nitrite in 400 ml of water was added over a 30 minute period. (Some cooling was necessary to maintain the temperature at approximately 40° C. during the addition.) The solution was heated at 60° C. for one and a half hours before it was cooled to 25° C. and extracted with 2×500 ml methylene chloride. It was then saturated with sodium chloride and extracted with 3×500 ml CH2 Cl2. The combined extracts contained 161 g (87.7 percent) of crude 3,3,3-trinitropropanol.
Acetyl chloride (125 ml) was added to a dried (MgSO4) solution of 150 g of crude 3,3,3-trinitropropanol as prepared above and cooled in an icebath. The solution was slowly warmed to reflux temperature and held overnight. The reaction solution was concentrated to 800 ml by distillation before it was cooled and poured onto ice water. The mixture was stirred for 30 minutes before the CH2 Cl2 layer was separated, dried over MgSO4, and the solvent removed to give 183 g (100 percent) of crude 3,3,3-trinitropropyl acetate as a light green solid. A similar reaction employing 31.9 g of crude 3,3,3-trinitropropanol, 50 ml of methylene chloride and 25 ml of acetyl chloride gave, after addition of hexane to the CH2 Cl2 solution and chilling, filtering off the solid, concentrating and chilling again, 34.5 g (88.9 percent) of 3,3,3-trinitropropyl acetate. A second recrystallization from CH2 Cl2 /hexane gave material of mp 47°-49° C.; .sup. 1 H NMR (CDCl3); δ2.06 (s, 3H), 3.45 (t, 2H), 4.55 (t, 2H).
Analysis:
Calculated for C5 H7 N3 O8 : C, 25.32; H, 2.98; N, 17.72. Found: C, 25.31; H, 3.01; N, 17.27.
Potassium iodide (338 g, 2.03 mol) was added to 183 g (0.77 mol) of crude 3,3,3-trinitropropyl acetate in 2100 ml of methanol. The mixture was stirred at 40° C. for 24 hours before it was cooled to 20° C. and the yellow salt removed by filtration. The product was stirred with 600 ml of methanol at 20° C. to give 88.5 g (50 percent) of yellow salt.
A similar reaction using 32.1 g of purified 3,3,3-trinitropropyl acetate gave 20.4 g (66 percent) of potassium 3,3-dinitropropyl acetate. 1 H NMR (D2 O with TMS capillary): δ2.54 (s, 3H), 3.94 (t, 2H), 4.93 (t, 2H).
A solution of potassium 3,3-dinitropropyl acetate (87 g, 0.38 mol) in 1050 ml of distilled water and 84 ml of 36 percent formalin was stirred in an ice bath while 45 ml of concentrated hydrochloric acid was added (pH approximately 3). The mixture was heated at 40° C. for 30 minutes, then cooled to 20° C. and 42.6 g of ammonium chloride was added. The mixture was stirred vigorously in an ice bath while concentrated ammonium hydroxide solution was added over several hours until the aqueous phase remained yellow and the pH was 5.5 to 6. At this point an appreciable amount of semisolid had separated from solution and adhered to the walls of the flask. The mixture was stirred overnight before the semisolid was extracted into methylene chloride. Addition of hexane and cooling to 5° C. gave 58.1 g of white crystals, mp 75°-76° C. The mother liquor was cooled in dry ice-acetone to give a semisolid which was stirred with water and then crystallized from methylene chloride-hexane to give an additional 3.0 g of product, mp 66°-70° C. Total yield (61.1 g) is 76 percent of theoretical. The analytical sample had mp 75.5°-76° C. 1 H NMR (CDCl3): δ2.06 (s, 3H), 2.91 (t, 2H), 3.85 (d, 2H), 4.27 (t, 2H).
Analysis:
Calculated for C8 H14 N6 O12 : C, 33.89; H, 4.50; N, 16.47. Found: C, 33.93; H, 4.62; N, 16.19.
Acetic anhydride (315 ml) was stirred in an ice bath to maintain a temperature of 20°-23° C. during the slow addition of 95 ml of 90 percent nitric acid. The solution was then cooled to 5° C. while 3,3,7,7-tetranitro-5-azanonane-1,9-diol-1,9-diacetate was added in portions with good stirring. The solution was stirred at ambient temperature overnight before it was poured into ice water. The mixture was stirred for one hour and the solid (66.5 g, 97 percent, mp 87°-89° C.) was removed by filtration. A recrystallized sample (CH2 Cl2 /hexane) had mp 88°-89° C.; 1 H NMR (CDCl3): δ2.09 (s, 3H), 3.00 (t, 2H), 4.35 (t, 2H), 5.20 (s, 2H).
Crude 3,3,5,7,7-pentanitro-5-azanonane-1,9-diol-1,9-diacetate (66.5 g) was stirred in 615 ml of warm (50° C.) MeOH in a 2000 ml round-bottom flask. Distilled water (265 ml) was added followed by 19 ml of concentrated hydrochloric acid. The mixture was heated at 67°-69° C. (mild reflux) overnight before nearly all the solvent was removed under reduced pressure on a rotary evaporator (water bath at 35° C.). The white solid (mp 118°-120° C.) was removed by filtration and washed with cold water. Crystallization from methanol-water gave 50.0 g, mp 121.5°-123° C. The second crop (2.9 g, mp 118°-120° C.) raised the yield to 52.9 g (97 percent). 1 H NMR (acetone-d6 +1 dr. D2 O): δ3.00 (t, 2H), 2.90 (t, 2H), 5.57 (s, 2H).
Analysis:
Calculated for C8 H14 N6 O12 : C, 24.88; H, 3.65; N, 21.76. Found: C, 24.97; H, 3.70; N, 21.66.
Thirty percent aqueous ammonium hydroxide (0.60 g, 0.0105 mol) was diluted to 5 ml with distilled water before it was slowly added over a 1.5 hour period to a solution of 1.80 g 0.01 mol) of 2,2-dinitrobutane-1,4-diol and 1.20 g (0.022 mol) of ammonium chloride in 25 ml of distilled water stirred at ambient temperature. The aqueous solution was decanted from a sticky semisolid percipitate which was washed with water and then dissolved in ether. A very small amount of ether insoluble solid was removed before the ether was evaporated to give 0.28 g of solid, mp 67°-72° C. Crystallization from methylene chloride raised the melting point to 76°-78° C. 1 H NMR (CD2 Cl2): δ3.95 (d, 4H), 3.88 (t, 4H), 2.86 (t, 4H), 2.36 (m, 1H), 1.91 (s, 2H); IR (KBr) 3600-3100 (OH), 3380 (NH), 1590, 1570 (NO2) cm-1.
Analysis:
Calculated for C8 H15 N15 O10 : C, 28.16; H, 4.43; N, 20.52. Found: C, 28.28; H, 4.40; N, 20.34.
Obviously numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described herein.
Claims (22)
1. A compound of the formula ##STR26## wherein R is selected from the group consisting of --H, --NO, --NO2, --CN, and --CH2 COOH.
2. The compound of claim 1 wherein R is H.
3. The compound of claim 1 wherein R is --NO.
4. The compound of claim 1 wherein R is --NO2.
5. The compound of claim 1 wherein R is --CN.
6. The compound of claim 1 wherein R is --CH2 COOH.
7. A compound of the formula ##STR27## wherein R is selected from the group consisting of --H, --NO, --NO2, --CN, --CH2 COOCH3, --CH2 COOCH2 C(NO2)2 CH3, and --CH2 COOCH2 C(NO2)3 and R' is selected from the group consisting of alkyls, fluoroalkyls, chloroalkyls, aryls, fluoroaryls, chloroaryls, aralkyls, fluoroaralkyls, chloroaralkyls, and alkenes.
8. The compound of claim 7 wherein R is --H.
9. The compound of claim 7 wherein R is --NO.
10. The compound of claim 7 wherein R is --NO2.
11. The compound of claim 7 wherein R is --CN.
12. The compound of claim 7 wherein R is --CH2 COOCH3.
13. The compound of claim 7 wherein R is --CH2 COOCH2 C(NO2)2 CH3.
14. The compound of claim 7 wherein R is --CH2 COOCH2 C(NO2)3.
15. The compound of claim 7 wherein R is --CH2 COOH.
16. The compound of claim 7 wherein R' is selected from the group consisting of alkyls, fluoroalkyls, and chloroalkyls having from 1 to 12 carbon atoms.
17. The compound of claim 16 wherein R' contains from 1 to 4 carbon atoms.
18. The compound of claim 7 wherein R' is selected from the group consisting of aryls, fluoroaryls, and chloroaryls having from 6 to 18 carbon atoms.
19. The compound of claim 18 wherein R' has 6 carbon atoms.
20. The compound of claim 7 wherein R' is selected from the group consisting of aralkyls, fluoroaralkyls, and chloroaralkyls of from 7 to 18 carbon atoms.
21. The compound of claim 20 wherein R' contains from 7 to 10 carbon atoms.
22. The compound of claim 7 wherein R' is vinyl.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/492,276 USH78H (en) | 1983-05-06 | 1983-05-06 | 5-aza-3,3,7,7-tetranitrononane-1,9-diols and method of preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/492,276 USH78H (en) | 1983-05-06 | 1983-05-06 | 5-aza-3,3,7,7-tetranitrononane-1,9-diols and method of preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
USH78H true USH78H (en) | 1986-07-01 |
Family
ID=23955649
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/492,276 Abandoned USH78H (en) | 1983-05-06 | 1983-05-06 | 5-aza-3,3,7,7-tetranitrononane-1,9-diols and method of preparation |
Country Status (1)
Country | Link |
---|---|
US (1) | USH78H (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6425966B1 (en) | 1999-09-15 | 2002-07-30 | Alliant Techsystems Inc. | Energetic plasticizer, and explosive and propellant composition containing same |
US6989186B2 (en) * | 2002-06-27 | 2006-01-24 | Haygood David L | Upholstery fabric tack strips |
-
1983
- 1983-05-06 US US06/492,276 patent/USH78H/en not_active Abandoned
Non-Patent Citations (3)
Title |
---|
Fridman, et al. "Formation of gamma . . . " Zhur. Org. Khim. 10(10) p. 206, 1975. |
Mukhametshin, et al. "Behavior of Nitrated Nitroso . . ." Zhur. Org. Khim. 6(5) 928-929, 1970. |
Mukhametshin, et al. "Cyclization of Nitro . . . " 4(5) 920, 1968. |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6425966B1 (en) | 1999-09-15 | 2002-07-30 | Alliant Techsystems Inc. | Energetic plasticizer, and explosive and propellant composition containing same |
US6989186B2 (en) * | 2002-06-27 | 2006-01-24 | Haygood David L | Upholstery fabric tack strips |
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