JP2008208111A - アゾジカルボン酸ビス(2−アルコキシエチル)エステル化合物、その製造中間体 - Google Patents
アゾジカルボン酸ビス(2−アルコキシエチル)エステル化合物、その製造中間体 Download PDFInfo
- Publication number
- JP2008208111A JP2008208111A JP2007252331A JP2007252331A JP2008208111A JP 2008208111 A JP2008208111 A JP 2008208111A JP 2007252331 A JP2007252331 A JP 2007252331A JP 2007252331 A JP2007252331 A JP 2007252331A JP 2008208111 A JP2008208111 A JP 2008208111A
- Authority
- JP
- Japan
- Prior art keywords
- mmol
- bis
- alkoxyethyl
- water
- ester
- 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.)
- Granted
Links
- -1 azodicarboxylate ester compound Chemical class 0.000 title claims abstract description 132
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 22
- SPFPGSYLNIIQMG-UHFFFAOYSA-N (carboxyamino)carbamic acid Chemical compound OC(=O)NNC(O)=O SPFPGSYLNIIQMG-UHFFFAOYSA-N 0.000 claims description 19
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 30
- 238000006751 Mitsunobu reaction Methods 0.000 abstract description 29
- 230000018044 dehydration Effects 0.000 abstract description 7
- 238000006297 dehydration reaction Methods 0.000 abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 6
- 239000011574 phosphorus Substances 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 118
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 107
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 72
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 61
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 60
- 239000000243 solution Substances 0.000 description 50
- 238000005481 NMR spectroscopy Methods 0.000 description 48
- 238000006243 chemical reaction Methods 0.000 description 41
- 239000012043 crude product Substances 0.000 description 36
- 238000004440 column chromatography Methods 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 239000000741 silica gel Substances 0.000 description 33
- 229910002027 silica gel Inorganic materials 0.000 description 33
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 29
- 239000012044 organic layer Substances 0.000 description 29
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 29
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 26
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002904 solvent Substances 0.000 description 19
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 238000005259 measurement Methods 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octane-2-ol Natural products CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 16
- 239000000126 substance Substances 0.000 description 15
- SJWFXCIHNDVPSH-QMMMGPOBSA-N (2S)-octan-2-ol Chemical compound CCCCCC[C@H](C)O SJWFXCIHNDVPSH-QMMMGPOBSA-N 0.000 description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 12
- WAPNOHKVXSQRPX-ZETCQYMHSA-N (S)-1-phenylethanol Chemical compound C[C@H](O)C1=CC=CC=C1 WAPNOHKVXSQRPX-ZETCQYMHSA-N 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- GTCCGKPBSJZVRZ-RFZPGFLSSA-N (2r,4r)-pentane-2,4-diol Chemical compound C[C@@H](O)C[C@@H](C)O GTCCGKPBSJZVRZ-RFZPGFLSSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- HVSDVQCMFAIRJJ-LLVKDONJSA-N [(1r)-1-phenylethyl] 4-nitrobenzoate Chemical compound O([C@H](C)C=1C=CC=CC=1)C(=O)C1=CC=C([N+]([O-])=O)C=C1 HVSDVQCMFAIRJJ-LLVKDONJSA-N 0.000 description 10
- BGMDLHOQWYCYBI-GFCCVEGCSA-N [(2r)-octan-2-yl] 4-nitrobenzoate Chemical compound CCCCCC[C@@H](C)OC(=O)C1=CC=C([N+]([O-])=O)C=C1 BGMDLHOQWYCYBI-GFCCVEGCSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000000921 elemental analysis Methods 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 9
- 239000005711 Benzoic acid Substances 0.000 description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000010233 benzoic acid Nutrition 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 6
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000003849 aromatic solvent Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000012230 colorless oil Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 239000011344 liquid material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 4
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 4
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- VFXOTLKPJVOIAI-ZJUUUORDSA-N [(2s,4r)-4-hydroxypentan-2-yl] benzoate Chemical compound C[C@@H](O)C[C@H](C)OC(=O)C1=CC=CC=C1 VFXOTLKPJVOIAI-ZJUUUORDSA-N 0.000 description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000004210 ether based solvent Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- GSJFXBNYJCXDGI-UHFFFAOYSA-N methyl 2-hydroxyacetate Chemical compound COC(=O)CO GSJFXBNYJCXDGI-UHFFFAOYSA-N 0.000 description 4
- 235000010270 methyl p-hydroxybenzoate Nutrition 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KEFIPSVKRJAYLH-ZJUUUORDSA-N (2r,4s)-4-(4-methoxyphenoxy)pentan-2-ol Chemical compound COC1=CC=C(O[C@@H](C)C[C@@H](C)O)C=C1 KEFIPSVKRJAYLH-ZJUUUORDSA-N 0.000 description 3
- QACLFMNGNFHTBM-ZJUUUORDSA-N (2r,4s)-4-phenoxypentan-2-ol Chemical compound C[C@@H](O)C[C@H](C)OC1=CC=CC=C1 QACLFMNGNFHTBM-ZJUUUORDSA-N 0.000 description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- UEXDANOGZHELCU-PVUWLOKVSA-N [(1s,2s,5r)-1-hydroxy-5-methyl-2-propan-2-ylcyclohexyl] 4-nitrobenzoate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@]1(O)OC(=O)C1=CC=C([N+]([O-])=O)C=C1 UEXDANOGZHELCU-PVUWLOKVSA-N 0.000 description 3
- WARXKCSTKHDFFE-CYBMUJFWSA-N [(2r)-octan-2-yl] benzoate Chemical compound CCCCCC[C@@H](C)OC(=O)C1=CC=CC=C1 WARXKCSTKHDFFE-CYBMUJFWSA-N 0.000 description 3
- JHMVLXLFWKUQNS-BDAKNGLRSA-N [(2s,4r)-4-hydroxypentan-2-yl] 4-nitrobenzoate Chemical compound C[C@@H](O)C[C@H](C)OC(=O)C1=CC=C([N+]([O-])=O)C=C1 JHMVLXLFWKUQNS-BDAKNGLRSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 3
- QOKVTSLMIYIQQF-UHFFFAOYSA-N methyl 2-(1-methyltetrazol-5-yl)sulfanylacetate Chemical compound COC(=O)CSC1=NN=NN1C QOKVTSLMIYIQQF-UHFFFAOYSA-N 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 2
- YKYUEQRWYGVUKB-UHFFFAOYSA-N 1-(2-hydroxyethyl)-2h-tetrazole-5-thione Chemical compound OCCN1N=NN=C1S YKYUEQRWYGVUKB-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- XOHZHMUQBFJTNH-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione Chemical compound CN1N=NN=C1S XOHZHMUQBFJTNH-UHFFFAOYSA-N 0.000 description 2
- BZUNJUAMQZRJIP-UHFFFAOYSA-N 15-hydroxypentadecanoic acid Chemical compound OCCCCCCCCCCCCCCC(O)=O BZUNJUAMQZRJIP-UHFFFAOYSA-N 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 2
- BJSVKBGQDHUBHZ-UHFFFAOYSA-N 2,4,6-trifluoroaniline Chemical compound NC1=C(F)C=C(F)C=C1F BJSVKBGQDHUBHZ-UHFFFAOYSA-N 0.000 description 2
- MBYLNRRTUYQZAW-UHFFFAOYSA-N 2-(2-phenylethyl)isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1CCC1=CC=CC=C1 MBYLNRRTUYQZAW-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- PGHKJMVOHWKSLJ-UHFFFAOYSA-N 2-methoxyethyl n-(2-methoxyethoxycarbonylimino)carbamate Chemical compound COCCOC(=O)N=NC(=O)OCCOC PGHKJMVOHWKSLJ-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- QKCFJEOMSWDTFX-UHFFFAOYSA-N 5,6-dihydro-[1,3]thiazolo[2,3-e]tetrazole Chemical compound N1=NN=C2SCCN21 QKCFJEOMSWDTFX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FKUPPRZPSYCDRS-UHFFFAOYSA-N Cyclopentadecanolide Chemical compound O=C1CCCCCCCCCCCCCCO1 FKUPPRZPSYCDRS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- GUPWNYUKYICHQX-UHFFFAOYSA-N carbonobromidic acid Chemical compound OC(Br)=O GUPWNYUKYICHQX-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical compound OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BEGGYZIIAZQKDA-UHFFFAOYSA-N n,4-dimethyl-n-octan-2-ylbenzenesulfonamide Chemical compound CCCCCCC(C)N(C)S(=O)(=O)C1=CC=C(C)C=C1 BEGGYZIIAZQKDA-UHFFFAOYSA-N 0.000 description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FAVDDVFCEHOGER-KCXAZCMYSA-N CC(C)[C@H](CC[C@@H](C)C1)[C@H]1OC(c(cc1)ccc1[N+]([O-])=O)=O Chemical compound CC(C)[C@H](CC[C@@H](C)C1)[C@H]1OC(c(cc1)ccc1[N+]([O-])=O)=O FAVDDVFCEHOGER-KCXAZCMYSA-N 0.000 description 1
- YNKOACTWIOMRLA-KEKZHRQWSA-N CCCCCC[C@@H](C)OC(c(cc1)ccc1[N+]([O-])=O)O Chemical compound CCCCCC[C@@H](C)OC(c(cc1)ccc1[N+]([O-])=O)O YNKOACTWIOMRLA-KEKZHRQWSA-N 0.000 description 1
- DILYKJLMSQIHJW-UHFFFAOYSA-N COCCOC(NNC(OCCOC)=O)=O Chemical compound COCCOC(NNC(OCCOC)=O)=O DILYKJLMSQIHJW-UHFFFAOYSA-N 0.000 description 1
- 0 C[*+]c(cc1)ccc1[N+]([O-])=O Chemical compound C[*+]c(cc1)ccc1[N+]([O-])=O 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005604 azodicarboxylate group Chemical group 0.000 description 1
- QFWACQSXKWRSLR-UHFFFAOYSA-N carboniodidic acid Chemical compound OC(I)=O QFWACQSXKWRSLR-UHFFFAOYSA-N 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- GWLOGZRVYXAHRE-UHFFFAOYSA-N n,4-dimethylbenzenesulfonamide Chemical compound CNS(=O)(=O)C1=CC=C(C)C=C1 GWLOGZRVYXAHRE-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 1
- SAFWHKYSCUAGHQ-UHFFFAOYSA-N sodium;hypoiodite Chemical compound [Na+].I[O-] SAFWHKYSCUAGHQ-UHFFFAOYSA-N 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/20—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group the two nitrogen atoms of the functional groups being doubly-bound to each other, e.g. azoformamide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/02—Compounds containing any of the groups, e.g. carbazates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
(1) 常温で液体であることから、蒸留による精製が必須となる。しかし、一般的にアゾ化合物は熱に対して不安定であり、加熱するのは危険である。実際、アゾジカルボン酸ジメチルエステルおよびアゾジカルボン酸ジエチルエステルを合成する際には注意が必要であることが示されている(非特許文献2参照)。
(2) 例えば、リン化合物と併用して脱水縮合を行う光延反応または酸化反応などを行うと、副生成物として1,2−ヒドラジンジカルボン酸ジエステルが生成するが、水に不溶であり有機溶媒にも適度に溶解するため、生成物と除去・分離するのに多くの工程を必要とする。
Synthesis,1,1(1981)= シンセシス、第1版、p1、1981年 Org.Synth.Coll.Vol.IV,411(1963)=オーガニック・シンセシス・コレクティブ・ボリューム、第4版、p411、1963年
項1. 一般式(1);
工程(b):一般式(3);
を含有するアゾジカルボン酸ビス(2−アルコキシエチル)エステル化合物の製造方法。
で表されるハロ炭酸(2−アルコキシエチル)エステル化合物とを反応させ、一般式(3);
この工程は、ヒドラジンと上記一般式(2)で表されるハロ炭酸(2−アルコキシエチル)エステル化合物を反応させることにより、上記一般式(3)で表される1,2−ヒドラジンジカルボン酸ビス(2−アルコキシエチル)エステル化合物を得る工程である。
上記一般式(2)で表されるハロ炭酸(2−アルコキシエチル)エステル化合物の使用量は、ヒドラジン1モルに対して2.0〜5.0モルが好ましく、2.0〜3.0モルがより好ましい。
この工程は、上記一般式(3)で表される1,2−ヒドラジンジカルボン酸ビス(2−アルコキシエチル)エステル化合物の酸化により、上記一般式(1)で表される、1,2−ヒドラジンジカルボン酸ビス(2−アルコキシエチル)エチルエステル化合物を得る工程である。
Mp: 71.3-76.5oC
IR (KBr): 3258, 1748, 1694, 1518, 1454, 1256, 1244, 1207, 1103, 1105, 1066, 1043, 860 cm―1.
1H NMR (400MHz, CDCl3): δ 7.02 (brs, 2H), 4.27-4.25 (m, 4H), 3.58-3.56 (m, 4H), 3.49 (s, 6H).
13C NMR (400MHz, CDCl3): δ 156.59, 70.40, 64.68, 58.69.
元素分析
計算値:C8H16N2O6: C, 40.68; H, 6.83; N, 11.96.
測定値:C, 40.88; H, 7.49; N, 12.07.
1H NMR (400MHz, CDCl3): δ 7.02 (brs, 2H), 4.27-4.25 (m, 4H), 3.58-3.56 (m, 4H), 3.49 (s, 6H).
1H NMR (400MHz, CDCl3): δ 7.02 (brs, 2H), 4.27-4.25 (m, 4H), 3.58-3.56 (m, 4H), 3.49 (s, 6H).
1H NMR (400MHz, CDCl3): δ7.02 (brs, 2H), 4.27-4.25 (m, 4H), 3.58-3.56 (m, 4H), 3.49 (s, 6H).
1H NMR (400MHz, CDCl3): δ 7.02 (brs, 2H), 4.27-4.25 (m, 4H), 3.58-3.56 (m, 4H), 3.49 (s, 6H).
Mp: 39.9-40.4oC
IR (KBr): 2940, 2899, 1782, 1450, 1371, 1281, 1240, 1200m 1136, 1094, 1036, 1016, 962, 866, 810, 527 cm―1.
1H NMR (400MHz, CDCl3): δ 4.51-4.49 (m, 4H), 3.66-3.63 (m, 4H), 3.32 (s, 6H).
13C NMR (400MHz, CDCl3): δ 156.59, 70.40, 64.68, 58.69.
元素分析
計算値:C8H14N2O6: C, 41.03; H, 6.03; N, 11.96.
測定値:C, 41.09; H, 6.65; N, 11.98.
1H NMR (400MHz, CDCl3): δ 4.51-4.49 (m, 4H), 3.66-3.63 (m, 4H), 3.32 (s, 6H).
1H NMR (400MHz, CDCl3): δ 4.51-4.49 (m, 4H), 3.66-3.63 (m, 4H), 3.32 (s, 6H).
Mp: 48.4-50.7oC
比旋光度:[α]D 20 = +9.86 (c 1.23, MeOH).
IR (KBr): 3416, 2972, 1722, 1607, 1530, 1350, 1285, 1103, 874, 719 cm―1.
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.9 Hz, 2H), 8.18 (d, J = 8.9 Hz, 2H), 5.34 (m, 1H), 3.95 (m, 1H), 2.01 (m, 1H), 1.72 (m, 1H), 1.55 (brd, 1H), 1.41 (d, J = 6.2 Hz, 3H), 1.24 (d, J = 6.2 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 164.15, 150.30, 135.89, 130.50, 123.34, 71.10, 65.18, 44.93, 23.81, 20.04.
元素分析
計算値:C12H15NO5: C, 56.91; H, 5.97; N, 5.53.
測定値:C, 56.82; H, 6.27; N, 5.60.
比旋光度:[α]D 20 = +33.1 (c 1.12, MeOH).
IR (KCl, neat): 3416, 2972, 2932, 1715, 1450, 1315, 1279, 1111, 1099, 1070, 1026, 712 cm―1.
1H NMR (600MHz, CDCl3): δ 7.97 (d, J = 7.6 Hz, 2H), 7.45 (d, J = 7.6 Hz, 1H), 7.34 (d, J = 7.6 Hz, 2H), 5.28 (m, 1H), 3.96 (m, 1H), 2.00 (m, 1H), 1.70 (m, 1H), 1.65 (brs, 1H), 1.38 (d, J = 6.2 Hz, 3H), 1.23 (d, J = 6.2 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 166.11, 132.79, 130.43, 129.39, 128.23, 69.95, 65.29, 45.17, 23.61, 20.25.
元素分析
計算値:C12H16O3: C, 69.21; H, 7.74.
測定値:C, 68.84; H, 7.63.
50mlフラスコに安息香酸(300.6mg、2.46mmol)、トリフェニルホスフィン(776.2mg、2.95mmol)、(2R、4R)−2,4−ペンタンジオール(309.1mg、2.95mmol)、THF(12mL)を加えた後に、20℃でTHF(6ml)に溶解した40%ジイソプロピルアゾジカルボン酸エステル−トルエン溶液(1.55ml、2.95mmol)を滴下し、6時間反応を行った。水(0.5ml)を加え濃縮した後に、水(10ml)を加えジエチルエーテル(10ml×2回)で抽出し、有機層を水(10ml)、飽和食塩水(10mL)で洗浄し無水硫酸マグネシウムで脱湿した。次いで濃縮して得られた粗品をカラムクロマトグラフィー(シリカゲル、40%酢酸エチル−ヘキサン溶液)で精製することで、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルを含む(4S,2R)−4−ベンゾイロキシペンタン−2−オールを525.3mgの無色油状物質として得た。1H−NMRの測定より、(4S,2R)−4−ベンゾイロキシペンタン−2−オールが380mg(収率74%/安息香酸)、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルが146mg含まれていた。
比旋光度:[α]D 20 = +6.92 (c 1.09, MeOH).
IR (KCl, neat): 3430, 2840, 1510, 1240, 1040, 830 cm―1.
1H NMR (600MHz, CDCl3): δ 6.87 (d, J = 9.3 Hz, 2H), 6.80 (d, J = 6.3 Hz, 2H), 4.44 (m, 1H), 4.06 (m, 1H), 3.75 (s, 3H), 2.70 (brs, 1H), 1.89 (m, 1H), 1.66 (ddd, J = 14.4, 4.2, 2.9 Hz, 1H), 1.24 (d, J = 5.9, Hz, 3H), 1.20 (d, J = 6.4 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 154.13, 150.94, 117.81, 114.52, 74.90, 66.67, 55.47, 45.32, 23.55, 19.77.
マススペクトル分析:MS (M+), m/z (%) 210 (12), 186 (9), 162 (20), 150 (10), 124 (100), 109 (30), 108 (10).
高分解能マススペクトル分析
計算値:C12H18O3, 210.1256
測定値:210.1242.
50mlフラスコに4−メトキシフェノール(300mg、2.41mmol)、トリフェニルホスフィン(762mg、2.89mmol)、(2R、4R)−2,4−ペンタンジオール(303mg、2.89mmol)、THF(12ml)を加えた後に、20℃でTHF(6ml)に溶解した40%ジイソプロピルアゾジカルボン酸エステル−トルエン溶液(1.53mL、2.89mmol)を滴下し、17時間反応を行った。水(0.5ml)を加え濃縮した後に、水(10ml)を加えジエチルエーテル(10ml×2回)で抽出し、有機層を水(10ml)、飽和食塩水(10ml)で洗浄し無水硫酸マグネシウムで脱湿した。次いで濃縮して得られた粗品をカラムクロマトグラフィー(シリカゲル、30%酢酸エチル−ヘキサン溶液)で精製することで、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルを含む(4S,2R)−4−(4−メトキシフェノキシ)ペンタン−2−オールを543mgの無色油状物質として得た。1H−NMRの測定より、(4S,2R)−4−ベンゾイロキシペンタン−2−オールが420mg(収率83%/4−メトキシフェノール)、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルが123mg含まれていた。
比旋光度:[α]D 20 = +24.6 (c 0.65, MeOH).
IR (KCl, neat): 3437, 2972, 1714, 1605, 1508, 1435, 1283, 1254, 1171, 1113, 849, 772 cm―1.
1H NMR (600MHz, CDCl3): δ 7.96 (dm, J = 8.9 Hz, 2H), 6.91 (dm, J = 8.9 Hz, 2H), 4.68 (m, 1H), 4.01 (m, 1H), 3.86 (s, 3H), 1.96 (ddd, J = 14.4, 8.8, 7.6 Hz, 1H), 1.69 (ddd, J = 14.4, 6.4, 3.4 Hz, 1H), 1.58 (brs, 1H), 1.33 (d, J = 5.9, Hz, 3H), 1.22 (d, J = 6.4 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 166.79, 161.25, 131.58, 122.45, 115.14, 72.82, 66.08, 51.80, 45.17, 23.82, 19.61.
高分解能マススペクトル分析
計算値:C13H18O4, 238.1205.
測定値:238.1181.
50mlフラスコに4−ヒドロキシ安息香酸メチル(300mg、1.97mmol)、トリフェニルホスフィン(621mg、2.36mmol)、(2R、4R)−2,4−ペンタンジオール(247mg、2.36mmol)、THF(12ml)を加えた後に、20℃でTHF(6ml)に溶解した40%ジイソプロピルアゾジカルボン酸エステル−トルエン溶液(1.25ml、2.36mmol)を滴下し、17時間反応を行った。水(0.5ml)を加え濃縮した後に、水(10ml)を加えジエチルエーテル(10ml×2回)で抽出し、有機層を水(10ml)、飽和食塩水(10ml)で洗浄し無水硫酸マグネシウムで脱湿した。次いで濃縮して得られた粗品をカラムクロマトグラフィー(シリカゲル、40%酢酸エチル−ヘキサン溶液)で精製することで、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルを含む4−((1S,3R)−3−ヒドロキシ−1−メチルブトキシ)安息香酸エステルを643mgの無色油状物質として得た。1H−NMRの測定より、4−((1S,3R)−3−ヒドロキシ−1−メチルブトキシ)安息香酸エステルが426mg(収率91%/4−ヒドロキシ安息香酸メチル)、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルが217mg含まれていた。
比旋光度:[α]D 20 = +14.97 (c 1.00, MeOH).
IR (KCl, neat): 3400, 2940, 1600, 1500, 1380, 1250, 1120, 760, 700 cm―1.
1H NMR (600MHz, CDCl3): δ 7.28-7.21 (m, 2H), 6.95-6.90 (m, 3H), 4.58 (m, 1H), 4.04 (m, 1H), 2.15 (brs, 1H), 1.93 (ddd, J = 14.2, 8.8, 5.9 Hz, 1H), 1.68 (ddd, J = 14.2, 4.3, 3.0 Hz, 1H), 1.29 (d, J = 6.0, Hz, 3H), 1.23 (d, J = 6.3 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 157.08, 129.40, 120.97, 116.00, 73.25, 66.46, 45.30, 23.55, 19.72.
元素分析
計算値:C11H6O2: C, 73.30; H, 8.95.
測定値:C, 72.93; H, 8.67.
比旋光度:[α]D 20 = -40.6 (c 1.06, MeOH)
IR (KCl, neat): 2930, 2859,1742, 1450, 1314, 1275, 1109, 1069, 1026, 712 cm―1.
1H NMR (600MHz, CDCl3): δ 7.97 (d, J = 7.6 Hz, 2H), 7.47 (t, J = 7.6 Hz, 1H), 7.36 (t, J = 7.6 Hz, 2H), 5.08 (m, 1H), 1.66 (m, 1H), 1.53 (m, 1H), 1.35-1.18 (m, 11H), 0.80 (t, J = 6.9 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 163.96, 150.18, 136.06, 130.36, 120.19, 72.83, 35.71, 31.49, 28.91, 25.17, 22.35, 19.68, 13.79.
50mlフラスコに(S)−2−オクタノール(300mg、2.30mmol)、トリフェニルホスフィン(728mg、2.76mmol)、安息香酸(338mg、2.76mmol)、THF(12ml)を加えた後に、20℃でTHF(6ml)に溶解した40%ジイソプロピルアゾジカルボン酸エステル−トルエン溶液(1.45ml、2.76mmol)を滴下し、2時間反応を行った。水(0.5mL)を加え濃縮した後に、水(10ml)を加えジエチルエーテル(10ml×2回)で抽出し、有機層を水(10ml)、飽和食塩水(10ml)で洗浄し無水硫酸マグネシウムで脱湿した。次いで濃縮して得られた粗品をカラムクロマトグラフィー(シリカゲル、10%酢酸エチル−ヘキサン溶液)で精製することで、(R)−2−ベンゾイロキシオクタンを無色液体物質として得た(503mg、収率93%/(S)−2−オクタノール)。
1H NMR (600MHz, CDCl3): δ 7.97 (d, J = 7.6 Hz, 2H), 7.47 (t, J = 7.6 Hz, 1H), 7.36 (t, J = 7.6 Hz, 2H), 5.08 (m, 1H), 1.66 (m, 1H), 1.53 (m, 1H), 1.35-1.18 (m, 11H), 0.80 (t, J = 6.9 Hz, 3H).
Mp: 124.4-125.7oC
IR (KBr): 2396, 1709, 1429, 1396, 1360, 1101, 1069, 870, 756, 710, 530 cm―1.
1H NMR (600MHz, CDCl3): δ 7.81 (m, 2H), 7.69 (m, 2H), 7.28-7.18 (m, 5H), 3.91 (t, J = 7.6 Hz, 2H), 2.97 (t, J = 7.6 Hz, 2H).
13C NMR (100MHz, CDCl3): δ 168.11, 137.96, 133.85, 132.02, 128.80, 128.50, 126.59, 123.17, 39.24, 34.60.
元素分析
計算値:C16H13NO2: C, 76.48; H, 5.21; N, 5.57.
測定値:C, 75.27; H, 5.59; N, 5.84.
1H NMR (600MHz, CDCl3): δ 7.66 (d, J = 8.2 Hz, 2H), 7.266 (d, J = 8.2 Hz, 2H), 3.96 (m, 1H), 2.64 (s, 3H), 2.39 (s, 3H), 1.37-1.16 (m, 10H), 0.95-0.83 (m, 6H).
13C NMR (100MHz, CDCl3): δ 142.80, 137.29, 129.50, 127.01, 52.75, 34.26, 31.67, 28.95, 27.21, 26.33, 22.53, 21.44, 17.29, 14.05.
IR (KCl, neat): 2955, 2928, 2857, 1597, 1460, 1383, 1339, 1153, 1090, 939, 816, 731, 712, 694, 654, 646, 567, 552 cm―1.
元素分析
計算値:C16H27NO2S: C, 64.60; H, 9.15; N, 4.71; S, 10.78.
測定値:C, 64.41; H, 9.00; N, 4.83; S, 11.08.
IR (KCl, neat): 2959, 1755, 1506, 1441, 1358, 1227, 1200, 1148, 1032, 999, 812, 721, 677, 579 cm―1.
1H NMR (600MHz, CDCl3): δ 4.14 (s, 2H), 3.96 (s, 3H), 3.76 (s, 3H).
13C NMR (100MHz, CDCl3): δ 167.82, 152.80, 53.08, 34.77, 33.48.
元素分析
計算値:C5H8N4O2S: C, 31.91; H, 4.28; N, 29.77; S, 17.04.
測定値:C, 32.02; H, 4.63; N, 30.08; S, 16.44.
50mlフラスコにグリコール酸メチルエステル(300mg、3.33mmol)、トリフェニルホスフィン(1050mg、4.00mmol)、1−メチル−5−メルカプト−1H−テトラゾール(465mg、4.00mmol)、THF(12ml)を加えた後に、20℃でTHF(6ml)に溶解した40%ジイソプロピルアゾジカルボン酸エステル−トルエン溶液(2.10ml、4.00mmol)を滴下し、3時間反応を行った。水(0.5mL)を加え濃縮した後に、水(10ml)を加え酢酸エチル(10ml×2回)で抽出し、有機層を水(10mL)、飽和食塩水(10ml)で洗浄し無水硫酸マグネシウムで脱湿した。次いで濃縮して得られた粗品をカラムクロマトグラフィー(シリカゲル、70%酢酸エチル−ヘキサン溶液)で精製することで、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルを含む(1−メチル−1H−テトラゾール−5−イルスルファニル)酢酸メチルエステルを610mgの無色油状物質として得た。1H−NMRの測定より、(1−メチル−1H−テトラゾール−5−イルスルファニル)酢酸メチルエステルが406mg(収率65%/グリコール酸メチルエステル)、ジイソプロピル1,2−ヒドラジンジカルボン酸エステルが204mg含まれていた。
比旋光度:[α]D 20 = +21.6 (c 1.02, MeOH).
Mp: 94.1-94.7oC
IR (KBr): 2965, 2920, 2853, 1713, 1599, 1530, 1348, 1279, 1123, 1103, 1013, 920, 874, 839, 719 cm―1.
1H NMR (600MHz, CDCl3): δ 8.27 (dm, J = 9.0 Hz, 2H), 8.18 (dm, J = 9.0 Hz, 2H), 5.47 (d, J = 2.0 Hz, 1H), 2.07 (ddd, J = 14.4, 5.9, 4.7 Hz, 1H), 1.84 (m, 1H), 1.66 (m, 2H), 1.11 (m, 1H), 0.90 (d, J = 5.9 Hz, 3H), 0.87 (d, J = 7.1 Hz, 3H), 0.85 (d, J = 7.1 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 163.99, 150.43, 136.37, 130.60, 123.55, 73.17, 46.92, 39.10, 34.71, 29.43, 26.82, 25.37, 22.10, 20.92, 20.75.
元素分析
計算値:C17H23NO4: C, 66.86; H, 7.59; N, 4.59.
測定値:C, 66.99; H, 8.11 N, 4.59.
50mlフラスコにL−メントール(300mg、1.92mmol)、トリフェニルホスフィン(605mg、2.30mmol)、4−ニトロ安息香酸(387mg、2.30mmol)、THF(12ml)を加えた後に、20℃でTHF(6ml)に溶解した40%ジイソプロピルアゾジカルボン酸エステル−トルエン溶液(1.21ml、2.30mmol)を滴下し、15時間反応を行った。水(0.5mL)を加え濃縮した後に、水(10ml)を加えジエチルエーテル(10ml×2回)で抽出し、有機層を水(10ml)、飽和食塩水(10ml)で洗浄し無水硫酸マグネシウムで脱湿した。次いで濃縮して得られた粗品をカラムクロマトグラフィー(シリカゲル、5%酢酸エチル−ヘキサン溶液)で精製することで、(1S,2S,5R)−1−(4−ニトロベンゾイロキシ)−2−イソプロピル−5−メチルシクロヘキサノールを白色固体物質として得た(423mg、収率72%/L−メントール)。
1H NMR (600MHz, CDCl3): δ 8.27 (dm, J = 9.0 Hz, 2H), 8.18 (dm, J = 9.0 Hz, 2H), 5.47 (d, J = 2.0 Hz, 1H), 2.07 (ddd, J = 14.4, 5.9, 4.7 Hz, 1H), 1.84 (m, 1H), 1.66 (m, 2H), 1.11 (m, 1H), 0.90 (d, J = 5.9 Hz, 3H), 0.87 (d, J = 7.1 Hz, 3H), 0.85 (d, J = 7.1 Hz, 3H).
Mp: 107.7-109.8oC
IR (KBr): 3034, 2963, 1472, 1452, 1435, 1418, 1312, 1213, 1157, 1121, 1063, 955, 862, 712, 660, 546, 484 cm―1.
1H NMR (600MHz, CDCl3): δ 4.57 (t, J = 7.6 Hz, 2H), 4.19 (t, J = 7.6 Hz, 2H).
13C NMR (100MHz, CDCl3): δ 161.94, 44.96, 37.55.
計算値:C3H4N4S: C, 28.12; H, 3.15; N, 43.72;S, 25.02.
測定値:C, 28.69; H, 3.32; N, 43.36; S, 24.30.
Mp: 33.9-35.8oC
IR (KBr): 2930, 2857, 1736, 1460, 1350, 1258, 1236, 1221, 1167, 1142, 1107, 1070, 719 cm―1.
1H NMR (600MHz, CDCl3): δ 4.11 (t, J = 5.5 Hz, 2H), 2.30 (t, J = 6.9 Hz, 2H), 1.66-1.58 (m, 4H), 1.39 (m, 2H), 1.32-1.29 (m, 18H).
13C NMR (100MHz, CDCl3): δ 173.91, 63.84, 34.31, 28.29, 27.65, 27.02, 27.00, 26.78, 26.55, 26.20, 25.89, 25.78, 25.69, 24.99, 24.84.
計算値:C15H28O2: C, 74.95; H, 11.74.
測定値:C, 75.33; H, 12.16.
比旋光度:[α]D 20 = -43.9 (c 1.21, MeOH).
IR (KBr): 3109, 2982, 2934, 1722, 1607, 1528, 1350, 1273, 1115, 1103, 1061, 1015, 874, 841, 719, 698cm―1.
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.6 Hz, 2H), 8.18 (d, J = 8.6 Hz, 2H), 5.17 (m, 1H), 1.38-1.26 (m, 11H), 0.85 (t, J = 6.5 Hz, 3H).
13C NMR (100MHz, CDCl3): δ 163.96, 150.18, 136.06, 130.36, 120.19, 72.83, 35.71, 31.49, 28.91, 25.17, 22.35, 19.68, 13.79.
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.6 Hz, 2H), 8.18 (d, J = 8.6 Hz, 2H), 5.17 (m, 1H), 1.38-1.26 (m, 11H), 0.85 (t, J = 6.5 Hz, 3H).
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.6 Hz, 2H), 8.18 (d, J = 8.6 Hz, 2H), 5.17 (m, 1H), 1.38-1.26 (m, 11H), 0.85 (t, J = 6.5 Hz, 3H).
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.6 Hz, 2H), 8.18 (d, J = 8.6 Hz, 2H), 5.17 (m, 1H), 1.38-1.26 (m, 11H), 0.85 (t, J = 6.5 Hz, 3H).
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.6 Hz, 2H), 8.18 (d, J = 8.6 Hz, 2H), 5.17 (m, 1H), 1.38-1.26 (m, 11H), 0.85 (t, J = 6.5 Hz, 3H).
比旋光度:[α]D 20 = -46.6 (c 1.09, MeOH).
IR (KCl, neat): 3111, 2955, 2930, 2859, 1719, 1607, 1528, 1466, 1348, 1280, 1113, 1103, 1015, 874, 841, 719 cm―1.
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.9 Hz, 2H), 8.21 (d, J = 8.9 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.32 (d, J = 7.6 Hz, 1H), 6.14 (q, J = 6.9 Hz, 1H), 1.69 (d, J = 6.9 Hz, 2H).
13C NMR (100MHz, CDCl3): δ 163.79, 150.36, 140.88, 135.74, 130.62, 128.57, 128.15, 126.02, 123.39, 74.07, 22.10.
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.9 Hz, 2H), 8.21 (d, J = 8.9 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.32 (d, J = 7.6 Hz, 1H), 6.14 (q, J = 6.9 Hz, 1H), 1.69 (d, J = 6.9 Hz, 2H).
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.9 Hz, 2H), 8.21 (d, J = 8.9 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.32 (d, J = 7.6 Hz, 1H), 6.14 (q, J = 6.9 Hz, 1H), 1.69 (d, J = 6.9 Hz, 2H).
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.9 Hz, 2H), 8.21 (d, J = 8.9 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.32 (d, J = 7.6 Hz, 1H), 6.14 (q, J = 6.9 Hz, 1H), 1.69 (d, J = 6.9 Hz, 2H).
1H NMR (600MHz, CDCl3): δ 8.26 (d, J = 8.9 Hz, 2H), 8.21 (d, J = 8.9 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.37 (t, J = 7.6 Hz, 2H), 7.32 (d, J = 7.6 Hz, 1H), 6.14 (q, J = 6.9 Hz, 1H), 1.69 (d, J = 6.9 Hz, 2H)
Claims (6)
- アルキル基がメチル基であることを特徴とする請求項1に記載の化合物。
- 工程(a):ヒドラジンと一般式(2);
工程(b):一般式(3);
を含有するアゾジカルボン酸ビス(2−アルコキシエチル)エステル化合物の製造方法。 - アルキル基がメチル基であることを特徴とする請求項4に記載の化合物。
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JP2013237626A (ja) * | 2012-05-14 | 2013-11-28 | Toyobo Co Ltd | アゾジカルボン酸ビス(2−アルコキシエチル)エステル化合物の製造方法 |
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CN102898328B (zh) * | 2012-10-26 | 2014-12-24 | 山东师范大学 | 偶氮二甲酸二乙酯及其中间体的合成方法 |
CN103193683B (zh) * | 2013-04-26 | 2014-07-09 | 山东师范大学 | 酯化法制备氢化偶氮二甲酸二烷基酯 |
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US2533189A (en) * | 1946-01-16 | 1950-12-05 | Wingfoot Corp | Hydrazo esters |
US2554141A (en) * | 1946-01-16 | 1951-05-22 | Wingfoot Corp | Azo esters |
US2903361A (en) * | 1956-01-12 | 1959-09-08 | Wallace & Tiernan Inc | Procedures and compositions for the treatment of flour |
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US3192196A (en) * | 1962-11-27 | 1965-06-29 | Wallace & Tiernan Inc | Oxidation of aliphatic hydrazo compounds to the corresponding aliphatic azo compounds |
US3347845A (en) * | 1963-08-01 | 1967-10-17 | Wallace & Tiernan Inc | Shock stable azodiformate esters |
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US6153633A (en) * | 1998-08-11 | 2000-11-28 | Rohm And Haas Company | Stable 3-isothiazolone compositions |
US6806357B1 (en) * | 2001-08-20 | 2004-10-19 | University Of Pittsburgh | Fluorous nucleophilic substitution of alcohols and reagents for use therein |
JP4094654B1 (ja) * | 2007-01-31 | 2008-06-04 | 東洋化成工業株式会社 | アゾジカルボン酸ビス(2−アルコキシエチル)エステル化合物、その製造中間体 |
CL2009001233A1 (es) * | 2008-05-21 | 2009-08-07 | Gruenenthal Gmbh | Procedimiento para la obtencion del acetato de 3 alfa-hidrocicloromadinona por reduccion del acetato de cloromadinona con un hidruro,con posterior inversion de la configuracion de la posicion 3; y uno de los compuestos intermediarios considerados. |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2013237625A (ja) * | 2012-05-14 | 2013-11-28 | Toyobo Co Ltd | アゾジカルボン酸ジエステル化合物の製造方法 |
JP2013237626A (ja) * | 2012-05-14 | 2013-11-28 | Toyobo Co Ltd | アゾジカルボン酸ビス(2−アルコキシエチル)エステル化合物の製造方法 |
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EP2112136A4 (en) | 2010-10-20 |
ES2385624T3 (es) | 2012-07-27 |
CN101595087A (zh) | 2009-12-02 |
US20100048881A1 (en) | 2010-02-25 |
EP2112136B1 (en) | 2012-05-23 |
JP4094654B1 (ja) | 2008-06-04 |
US7820802B2 (en) | 2010-10-26 |
US7947816B2 (en) | 2011-05-24 |
KR101025202B1 (ko) | 2011-03-31 |
CN101595087B (zh) | 2012-11-21 |
US20110028701A1 (en) | 2011-02-03 |
KR20090088420A (ko) | 2009-08-19 |
EP2112136A1 (en) | 2009-10-28 |
WO2008093702A1 (ja) | 2008-08-07 |
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