WO2001012580A1 - Process for the preparation of 5-[(4-chlorophenyl)-methyl]-2,2-dimethylcyclopentanone - Google Patents
Process for the preparation of 5-[(4-chlorophenyl)-methyl]-2,2-dimethylcyclopentanone Download PDFInfo
- Publication number
- WO2001012580A1 WO2001012580A1 PCT/JP2000/005401 JP0005401W WO0112580A1 WO 2001012580 A1 WO2001012580 A1 WO 2001012580A1 JP 0005401 W JP0005401 W JP 0005401W WO 0112580 A1 WO0112580 A1 WO 0112580A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methyl
- chlorophenyl
- oxocyclopentanecarboxylate
- dimethyl
- ethyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 16
- DLPBZANLIRTMKU-UHFFFAOYSA-N 5-[(4-chlorophenyl)methyl]-2,2-dimethylcyclopentan-1-one Chemical compound O=C1C(C)(C)CCC1CC1=CC=C(Cl)C=C1 DLPBZANLIRTMKU-UHFFFAOYSA-N 0.000 title abstract description 7
- -1 methyl halide Chemical class 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 239000005868 Metconazole Substances 0.000 claims abstract description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000417 fungicide Substances 0.000 claims abstract description 10
- XWPZUHJBOLQNMN-UHFFFAOYSA-N metconazole Chemical compound C1=NC=NN1CC1(O)C(C)(C)CCC1CC1=CC=C(Cl)C=C1 XWPZUHJBOLQNMN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012312 sodium hydride Substances 0.000 claims abstract description 10
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 10
- 230000000855 fungicidal effect Effects 0.000 claims abstract description 9
- 230000007062 hydrolysis Effects 0.000 claims abstract description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 96
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 claims description 18
- 150000004703 alkoxides Chemical class 0.000 claims description 11
- 229960002944 cyclofenil Drugs 0.000 claims description 11
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- JQZAEUFPPSRDOP-UHFFFAOYSA-N 1-chloro-4-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1 JQZAEUFPPSRDOP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- FTGZMZBYOHMEPS-UHFFFAOYSA-N 2,2-dimethylcyclopentan-1-one Chemical compound CC1(C)CCCC1=O FTGZMZBYOHMEPS-UHFFFAOYSA-N 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 2
- IIHIJFJSXPDTNO-UHFFFAOYSA-N methyl cyclopentanecarboxylate Chemical compound COC(=O)C1CCCC1 IIHIJFJSXPDTNO-UHFFFAOYSA-N 0.000 claims description 2
- JHZPNBKZPAWCJD-UHFFFAOYSA-N ethyl 2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCCC1=O JHZPNBKZPAWCJD-UHFFFAOYSA-N 0.000 claims 3
- DMHZDOTYAVHSEH-UHFFFAOYSA-N 1-(chloromethyl)-4-methylbenzene Chemical compound CC1=CC=C(CCl)C=C1 DMHZDOTYAVHSEH-UHFFFAOYSA-N 0.000 claims 1
- SNPWJRNYYANSRB-UHFFFAOYSA-N 1-[(4-chlorophenyl)methyl]-3-methyl-2-oxocyclopentane-1-carboxylic acid Chemical compound O=C1C(C)CCC1(C(O)=O)CC1=CC=C(Cl)C=C1 SNPWJRNYYANSRB-UHFFFAOYSA-N 0.000 claims 1
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- JBDSSBMEKXHSJF-UHFFFAOYSA-N cyclopentanecarboxylic acid Chemical compound OC(=O)C1CCCC1 JBDSSBMEKXHSJF-UHFFFAOYSA-N 0.000 claims 1
- ORLZPOSPUFSCMW-UHFFFAOYSA-N ethyl 3,3-dimethyl-2-oxocyclopentane-1-carboxylate Chemical compound CCOC(=O)C1CCC(C)(C)C1=O ORLZPOSPUFSCMW-UHFFFAOYSA-N 0.000 claims 1
- YBEUXWGGKSZODV-UHFFFAOYSA-N ethyl 5-oxocyclopentene-1-carboxylate Chemical compound CCOC(=O)C1=CCCC1=O YBEUXWGGKSZODV-UHFFFAOYSA-N 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- OGIKPUCMXHEUMK-UHFFFAOYSA-N tert-butyl 2-oxocyclopentane-1-carboxylate Chemical compound CC(C)(C)OC(=O)C1CCCC1=O OGIKPUCMXHEUMK-UHFFFAOYSA-N 0.000 claims 1
- DCLNQHDBQDTZAT-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-3-methyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(C)C1=O DCLNQHDBQDTZAT-UHFFFAOYSA-N 0.000 abstract description 3
- QGUHMUXBDNKLNM-UHFFFAOYSA-N methyl 1-[(4-chlorophenyl)methyl]-3,3-dimethyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OC)CCC(C)(C)C1=O QGUHMUXBDNKLNM-UHFFFAOYSA-N 0.000 abstract description 2
- VHDUPMOJGBENBV-UHFFFAOYSA-N ethyl 1-[(4-chlorophenyl)methyl]-3,3-dimethyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OCC)CCC(C)(C)C1=O VHDUPMOJGBENBV-UHFFFAOYSA-N 0.000 abstract 1
- HHMMBIXXONUWEH-UHFFFAOYSA-N ethyl 1-[(4-chlorophenyl)methyl]-3-methyl-2-oxocyclopentane-1-carboxylate Chemical compound C=1C=C(Cl)C=CC=1CC1(C(=O)OCC)CCC(C)C1=O HHMMBIXXONUWEH-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 239000002904 solvent Substances 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 14
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 229940102396 methyl bromide Drugs 0.000 description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- PZBBESSUKAHBHD-UHFFFAOYSA-N methyl 2-oxocyclopentane-1-carboxylate Chemical compound COC(=O)C1CCCC1=O PZBBESSUKAHBHD-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- HLQZCRVEEQKNMS-UHFFFAOYSA-N 1-(chloromethyl)-4-phenylbenzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=CC=C1 HLQZCRVEEQKNMS-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007069 methylation reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- QZURFQCUAZFMSV-UHFFFAOYSA-N C(=O)(OC)C1C(CCC1)=O.[Na] Chemical compound C(=O)(OC)C1C(CCC1)=O.[Na] QZURFQCUAZFMSV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- TZHZMYGNHVTEFA-UHFFFAOYSA-N methyl 1-methyl-2-oxocyclopentane-1-carboxylate Chemical compound COC(=O)C1(C)CCCC1=O TZHZMYGNHVTEFA-UHFFFAOYSA-N 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GQFNCVHPAIWUFJ-UHFFFAOYSA-N 3-[(4-chlorophenyl)methyl]-2,2-dimethylcyclopentan-1-one Chemical compound ClC1=CC=C(C=C1)CC1C(C(CC1)=O)(C)C GQFNCVHPAIWUFJ-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- DPBQIRNFTKVJPK-UHFFFAOYSA-N 3-methyl-2-oxocyclopentane-1-carboxylic acid Chemical compound CC1CCC(C(O)=O)C1=O DPBQIRNFTKVJPK-UHFFFAOYSA-N 0.000 description 1
- ZCODXJQJFVYHSG-UHFFFAOYSA-N CC1(CCC(=C1)CC2=CC=C(C=C2)Cl)C Chemical class CC1(CCC(=C1)CC2=CC=C(C=C2)Cl)C ZCODXJQJFVYHSG-UHFFFAOYSA-N 0.000 description 1
- HEYNUKXGQVTHAD-UHFFFAOYSA-N CC1CCC(=O)C1CC2=CC=C(C=C2)Cl Chemical compound CC1CCC(=O)C1CC2=CC=C(C=C2)Cl HEYNUKXGQVTHAD-UHFFFAOYSA-N 0.000 description 1
- PIDXJHBKNROJFM-UHFFFAOYSA-N COC(=O)CCCCC(=O)OC.CCOC(=O)CCCCC(=O)OCC Chemical compound COC(=O)CCCCC(=O)OC.CCOC(=O)CCCCC(=O)OCC PIDXJHBKNROJFM-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JBQLQIMCKFDOHK-UHFFFAOYSA-N Stephanol Natural products CC(O)C1(O)CCC2(O)C3(O)CC=C4CC(O)CCC4(C)C3C(O)C(O)C12C JBQLQIMCKFDOHK-UHFFFAOYSA-N 0.000 description 1
- XJWGVBQKHKZLIC-UHFFFAOYSA-N [Na].CC1C(C(CC1)C(=O)OC)=O Chemical compound [Na].CC1C(C(CC1)C(=O)OC)=O XJWGVBQKHKZLIC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 210000000540 fraction c Anatomy 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
- C07C45/676—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton by elimination of carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Definitions
- the present invention relates to a method for producing 5-[(4-chlorophenyl) methyl] -2,2-dimethylcyclopentanone, which is an important intermediate of an agricultural and horticultural fungicide metconazole.
- JP-A-1-93357 and JP-A-1-31664 describe 5-[(4-chlorophenyl) methyl] -12,2-dimethylcyclopentanone. And converting the carbonyl group of the compound into an epoxy group, followed by azolylation to obtain 5 — [(4-chlorophenyl) methyl] —2,2-dimethyl-1— (1H— It is described that 1,2,4-triazole-1-ylmethyl) cyclopentanol (methconazole) can be derived. As a process for producing this 5-[[(4-chlorophenyl) methyl]]-2,2-dimethylcyclopentene, Japanese Patent Application Laid-Open No. Hei 11-93574 describes the method of the following reaction formula 1. I have.
- reaction formula 3 the production method of the compound (4) in the reaction formula 2 does not have the power yield described in JP-A-1-93574 as in the following reaction formula 3. Reaction formula 3
- the present invention has been made in view of the above-mentioned circumstances, and has as its object a simple operation of a high-quality 5- [(4-cloguchifu) which is an important intermediate of the agricultural and horticultural fungicide metconazole.
- V provides a method for producing high-yield [methyl]]-2,2-dimethylcyclopentanone.
- a first gist of the present invention is that 1-[(4-chlorophenyl) methyl] -3-methyl-2-methyl 2-oxocyclopentanecarboxylate or 1-[(4-chlorophenyl) methyl 1-[(4-chlorophenyl) methyl] —3,3-dimethyl-methyl 3-ethyl-1-oxocyclopentanecarboxylate treated with sodium hydride and methyl halide To obtain methyl 2-oxocyclopentanecarboxylate or 1-[(4-chlorophenyl) methyl] -3,3-dimethyl-2-ethyl 2-oxocyclopentanecarboxylate and hydrolyze it 5- (4-chlorophenyl) methyl] —2,2-dimethylcyclopentanone.
- the second gist of the present invention is to (1) react dimethyl adipate or getyl adipate with a metal alkoxide, (2) react with a methyl halide after removing generated alcohol, and (3) After completion of the reaction, it is reacted again with the metal alkoxide, (4) after removing the formed alcohol, and then reacting with (4-phenylphenyl) methyl chloride.
- the third gist of the present invention is to (1) react dimethyl adipate or getyl adipate with a metal alkoxide, (2) react with a methyl halide after removing generated alcohol, and (3) react After completion, it is reacted with the metal alkoxide again, and (4) after removing the formed alcohol, it is reacted with (4-chlorophenyl) methyl chloride.
- 1 [(4-chlorophenyl) methyl] —3
- the present invention relates to a method for producing methyl methyl-2-oxocyclopentanecarboxylate or 1-[(4-chlorophenyl) methyl] -13-methyl-12-oxocyclopentanecarboxylate.
- a fourth gist of the present invention is to provide 5- (4-chlorophenyl) methyl] -2,2-dimethylcyclopentanone as an intermediate for producing metconazole or an agricultural / horticultural fungicide. Lies in the method used as an intermediate for the production.
- a fifth gist of the present invention is to provide 1-[(4-chlorophenyl) methyl] -13-methyl-2-methyl oxocyclopentanecarboxylate or 11-[(4-chlorophenyl) methyl] 13— Ethyl methyl-2-oxocyclopentanecarboxylate is converted to 5- (4-chlorophenyl) methyl] —2,2-dimethylcyclopentanone, an intermediate for the production of metconazole.
- the present invention relates to a method used as an intermediate for producing a body or agricultural / horticultural fungicide.
- a sixth gist of the present invention is that 1-[(4-cyclophenyl) methyl] -3,3-dimethyl-2-oxocyclopentanecarboxylate or 1-[(4-cyclophenyl) methyl Methyl] —3,3-Dimethyl-2-oxocyclopentaneUsed as an intermediate for the production of ethyl carboxylate, an intermediate for the production of metconazole, or an intermediate for the production of agricultural and horticultural fungicides The way to be.
- Methyl oxocyclopentanecarboxylate is 1-[(4-chlorophenyl) methyl] —3-methyl-1-2-cyclooxopentanecarboxylate and 1-[(4-chlorophenyl) methyl ] -3,3-Dimethyl-2-ethyl oxocyclopentanecarboxylate is chemically substantially equivalent to that of the present invention.
- the production of methyl [1- (4-chlorophenyl) methyl] —3—methyl-2-oxooxopentanecarboxylate in a high yield can be carried out by the above-mentioned first to fourth steps. This can be achieved by performing the process continuously without the purification process and by performing the following operations (prepared amounts, reaction conditions, etc.).
- the reaction of the first step is carried out in a solvent since the product 2-sodium oxocyclopentanecarboxylic acid methyl ester sodium salt is a solid.
- a solvent to be used an aprotic solvent having a boiling point of 75 ° C. or more is preferable because methanol must be removed by distillation.
- aromatic compounds such as benzene, toluene, xylene, and benzene
- ether compounds such as dimethoxetane and dioxane. More preferred solvents include toluene, xylene, and benzene.
- Dimethyl adipate and metal methoxide are charged into this solvent, and the resulting mixture is heated under normal pressure or reduced pressure, and methanol is distilled off together with the solvent.
- the reaction temperature is usually 70 to 150 ° C, preferably 80 to 130 ° C. If necessary, add additional solvent.
- the metal methoxide include sodium methoxide and potassium methoxide, and preferably sodium methoxide.
- the metal methoxide may be in the form of a powder or a solution in methanol.
- the amount of metal methoxide to be used is usually 0.9 to 1.0 mol per mol of dimethyl adipate charged. If the amount is less than 0.9 mol, the conversion of dimethyl adipate decreases. If the amount is more than 1.0 mol, it is difficult to remove methanol in the reaction system, and the yield is reduced.
- the product 2-oxocyclopentanecarboxylic acid methyl ester, sodium salt, precipitates 5 '.
- aprotic polar solvent examples include DMS0, N-methylpyrrolidone, dimethylimidaridinone, dimethylacetamide, and dimethylformamide.
- the 2-oxocyclopentanecarboxylic acid methyl ester sodium salt obtained in the first step is reacted with methyl halide.
- the reaction temperature is usually 50 to 120, more preferably 70 to 100 ° C.
- Methyl halides include methyl chloride, methyl bromide, and methyl iodide.
- the amount of methyl halide used is usually 0.9 to 1.1 mol per 1 mol of dimethyl adipate charged in the first step. If the amount is less than 0.9 mol, the reaction is not completed. If it is more than 1.1 mol, there is no noticeable adverse effect on the reaction, but if it is used more than this, there is no advantageous effect. After the reaction is completed, excess methyl halide is removed by distillation, if any. Proceeding to the next step with excess methyl halide remaining will consume the metal methoxide added in the next step and adversely affect the reaction.
- the reaction product of the second step is charged with metal methoxide, and the resulting mixture is heated under normal pressure or reduced pressure in the same manner as in the first step, and methanol is distilled off together with the solvent.
- the reaction temperature is usually from 70 to 150 ° C, preferably from 80 to 130 ° C. If necessary, add additional solvent.
- the metal main Tokishido it forces? Preferable to use the same as the first step.
- the amount of the metal methoxide to be used is generally 0.9 to 1.0 mol per 1 mol of dimethyl adipate charged in the first step. If it is less than 0.9 mol, the conversion of dimethyl adipate decreases. If the amount is more than 1.0 mol, it becomes difficult to remove methanol from the reaction system, and the yield is reduced.
- the sodium methyl ester of 3-methyl-12-oxocyclopentanecarboxylic acid obtained in the third step is reacted with (4-chlorophenyl) methyl chloride.
- the reaction temperature is usually 60 to 150. C, preferably 80 to 130 ° C.
- the amount of the methyl chloride used is usually 0.9 to 1.0 mol per 1 mol of dimethyl adipate charged in the first step. If the amount is less than 0.9 mol, the product of the third step, 3-methyl-2-oxocyclopentane-potassium sulfonic acid methyl ester sodium salt, remains without being consumed, resulting in a decrease in yield.
- the solvent used as long as it aprotic solvents do not react with the hydrogenation Natoriumu Ya halogenated alkyl le not particularly limited power?, It can be exemplified the following compounds.
- Aromatic compounds such as benzene, toluene, xylene, and benzene, ether compounds such as THF, dimethoxetane, and dioxane; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide
- Non-protonic polar compounds may be used alone, or a plurality of them may be used in combination.
- a mixed solvent of an aromatic compound and an ether compound or an aprotic polar compound is preferred.
- the amount of sodium hydride used in the fifth step is usually 1 to 0.3 to 1.3 mol, preferably 1 to 1 mol of methyl [(4-chlorophenyl) methyl] -3-methyl-2-oxocyclopentanecarboxylate. Is 1.1 to 1.2 mol. If the amount is less than 1.0 mol, the reaction will not be completed, and the yield will decrease. If the amount is more than 1.3 mol, the post-treatment after the completion of the reaction becomes complicated.
- methyl halide examples include methyl chloride, methyl bromide, and methyl iodide, and methyl bromide and methyl iodide are preferred.
- a catalytic amount of sodium iodide or potassium iodide may be added.
- the amount of methyl halide used is usually from 1.0 to 1.3 moles per mole of 1-[((4-chlorophenyl) methyl) -methyl-3-oxomethyl-2-oxocyclopentanecarboxylate] , Preferably from 1.0 to 1.2 moles. If the amount is less than 1.0 mol, the reaction is not completed and the yield is reduced. If the amount is more than 1.3 mol, the unit consumption of methyl halide is deteriorated.
- the reaction in the fifth step is a strongly exothermic reaction, which produces hydrogen. So, first add sodium hydride to the solvent, and maintain the reaction temperature to obtain 1-[(4-chlorophenyl) methyl] 13. The method of adding methyl 2-methyl-1-oxocyclopentanecarboxylate and methyl halide is preferred.
- reaction temperature at this time is usually from 50 ° C to the reflux point, preferably from 80 ° C to the reflux point.
- reaction When the reaction is performed under basic conditions, the reaction is performed in a system using a lower alcohol or an aromatic hydrocarbon in addition to water.
- the base include alkali metal bases, preferably sodium hydroxide and hydroxylamine.
- the reaction temperature at this time is usually 50 ° C to reflux point, preferably 80 ° C to reduction point.
- a 2-liter 4-neck flask was charged with 1 liter of toluene as a solvent, 174.2 g of dimethyl adipate, 189.1 lg of 28% sodium methylate, and 15 g of DMF. Then, the mixture was heated under normal pressure while stirring under nitrogen, and methanol / toluene was distilled off. On the way,
- a 1-liter four-necked flask was charged with 44.1 g of 60% sodium hydride, and paraffin was removed by decanting with toluene. To this, 100 ml of toluene, 2 Om 1 of dimethoxetane and 1 g of sodium iodide were added. The reactor was fitted with a dry ice condenser, immersed in a bath at 80 ° C, and obtained from Example 1 with [1- (4-chlorophenyl) methyl] —3-methyl-1-oxocyclopentane. 277.7 g of methyl carboxylate and 100 g of methyl bromide were slowly added dropwise.
- Example 1 When the same operation as in Example 1 was performed except that the same molar number of powdered sodium methylate was used instead of 28% sodium methylate, the same result as in Example 1 was obtained.
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Abstract
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Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CZ20030664A CZ303562B6 (en) | 2000-08-11 | 2000-08-11 | Process for preparing 5-[(4-chlorophenyl)methyl]-2,2-diemethyl cyclopentanone |
IL15420700A IL154207A0 (en) | 2000-08-11 | 2000-08-11 | Process for the preparation of 5-[(4-chlorophenyl)-methyl]-2,2-dimethylcyclopentanone |
DE60031454T DE60031454T2 (en) | 2000-08-11 | 2000-08-11 | PROCESS FOR PREPARING 5- (4-CHLOROPHENYL) -METHYL-2,2-DIMETHYLCYCLOPENTANONE |
CNB008198101A CN1196665C (en) | 2000-08-11 | 2000-08-11 | Process for the preparation of 5-[4-chlorophenyl)-methyl]-2, 2-dimethylcyclopentanone |
HU0300723A HUP0300723A3 (en) | 1999-08-13 | 2000-08-11 | Process for the preparation of 5-[(4-chlorophenyl)-methyl]-2,2-dimethylcylopentanone |
KR1020037001725A KR100697737B1 (en) | 2000-08-11 | 2000-08-11 | Process for the preparation of 5-[4-chlorophenyl)-methyl]-2, 2-dimethylcyclopentanone |
US10/332,471 US7166750B1 (en) | 2000-08-11 | 2000-08-11 | Process for the preparation of 5-[(4-chlorophenyl)methyl]-2,2-dimethylcyclopentanone |
AU2000264750A AU2000264750A1 (en) | 1999-08-13 | 2000-08-11 | Process for the preparation of 5-[(4-chlorophenyl)-methyl]-2,2-dimethylcyclopentanone |
JP2001516881A JP4979170B2 (en) | 1999-08-13 | 2000-08-11 | Process for producing 5-[(4-chlorophenyl) methyl] -2,2-dimethylcyclopentanone |
BRPI0017310-0A BR0017310B1 (en) | 1999-08-13 | 2000-08-11 | process for producing 5 - [(4-chlorophenyl) methyl] -2,2-dimethylcyclopentanone. |
PL362899A PL203074B1 (en) | 1999-08-13 | 2000-08-11 | Process for the preparation of 5−[(4−chlorophenyl)−methyl]−2,2−dimethylcyclopentanone |
EP00951956A EP1308432B1 (en) | 2000-08-11 | 2000-08-11 | Process for the preparation of 5- (4-chlorophenyl)-methyl|-2,2-dimethylcyclopentanone |
UA2003021098A UA73364C2 (en) | 1999-08-13 | 2000-11-08 | A method for the preparation of 5-[(4-chlorophenyl)methyl]-2,2-dimethylcyclopentanone and a method for the preparation of intermediary compounds (variants) |
IL154207A IL154207A (en) | 1999-08-13 | 2003-01-30 | Process for the preparation of 5 - [(4 - chlorophenyl) - methyl] - 2, 2 - dimethylcyclopentanone |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26429299 | 1999-08-13 | ||
JP11/264292 | 1999-08-13 |
Publications (1)
Publication Number | Publication Date |
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WO2001012580A1 true WO2001012580A1 (en) | 2001-02-22 |
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ID=17401150
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2000/005401 WO2001012580A1 (en) | 1999-08-13 | 2000-08-11 | Process for the preparation of 5-[(4-chlorophenyl)-methyl]-2,2-dimethylcyclopentanone |
Country Status (12)
Country | Link |
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JP (1) | JP4979170B2 (en) |
AR (1) | AR025233A1 (en) |
AU (1) | AU2000264750A1 (en) |
BR (1) | BR0017310B1 (en) |
HU (1) | HUP0300723A3 (en) |
IL (1) | IL154207A (en) |
IN (1) | IN2005DE05932A (en) |
PH (1) | PH12000002167B1 (en) |
PL (1) | PL203074B1 (en) |
TW (1) | TW591012B (en) |
UA (1) | UA73364C2 (en) |
WO (1) | WO2001012580A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012169468A1 (en) | 2011-06-07 | 2012-12-13 | 株式会社クレハ | Method for producing cyclopentanone compound, and intermediate compound |
WO2015075981A1 (en) * | 2013-11-22 | 2015-05-28 | 株式会社クレハ | Method for producing carbonyl compound |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0267778A2 (en) * | 1986-11-10 | 1988-05-18 | Kureha Kagaku Kogyo Kabushiki Kaisha | Azole derivatives useful in controlling plant diseases and regulating plant growth |
EP0413448A1 (en) * | 1989-08-15 | 1991-02-20 | Kureha Kagaku Kogyo Kabushiki Kaisha | An Azole-substituted cycloalkanol derivative, a process to produce the same and a use of the derivative as an agricultural and horticultural fungicide |
EP0537909A1 (en) * | 1991-09-18 | 1993-04-21 | Kureha Chemical Industry Co., Ltd. | 3-(Unsubstituted or substituted benzyl)-1-alkyl-2-oxocyclopentane carboxylic acid alkyl ester derivatives, and their preparation and use |
EP0731083A1 (en) * | 1995-03-10 | 1996-09-11 | Kureha Kagaku Kogyo Kabushiki Kaisha | Process for the producing of alkylcyclopentanone derivatives |
-
2000
- 2000-08-09 TW TW089116041A patent/TW591012B/en not_active IP Right Cessation
- 2000-08-11 JP JP2001516881A patent/JP4979170B2/en not_active Expired - Lifetime
- 2000-08-11 AR ARP000104172A patent/AR025233A1/en not_active Application Discontinuation
- 2000-08-11 WO PCT/JP2000/005401 patent/WO2001012580A1/en active IP Right Grant
- 2000-08-11 BR BRPI0017310-0A patent/BR0017310B1/en not_active IP Right Cessation
- 2000-08-11 AU AU2000264750A patent/AU2000264750A1/en not_active Abandoned
- 2000-08-11 HU HU0300723A patent/HUP0300723A3/en unknown
- 2000-08-11 PH PH12000002167A patent/PH12000002167B1/en unknown
- 2000-08-11 PL PL362899A patent/PL203074B1/en unknown
- 2000-11-08 UA UA2003021098A patent/UA73364C2/en unknown
-
2003
- 2003-01-30 IL IL154207A patent/IL154207A/en not_active IP Right Cessation
-
2005
- 2005-12-20 IN IN5932DE2005 patent/IN2005DE05932A/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0267778A2 (en) * | 1986-11-10 | 1988-05-18 | Kureha Kagaku Kogyo Kabushiki Kaisha | Azole derivatives useful in controlling plant diseases and regulating plant growth |
EP0413448A1 (en) * | 1989-08-15 | 1991-02-20 | Kureha Kagaku Kogyo Kabushiki Kaisha | An Azole-substituted cycloalkanol derivative, a process to produce the same and a use of the derivative as an agricultural and horticultural fungicide |
EP0537909A1 (en) * | 1991-09-18 | 1993-04-21 | Kureha Chemical Industry Co., Ltd. | 3-(Unsubstituted or substituted benzyl)-1-alkyl-2-oxocyclopentane carboxylic acid alkyl ester derivatives, and their preparation and use |
EP0731083A1 (en) * | 1995-03-10 | 1996-09-11 | Kureha Kagaku Kogyo Kabushiki Kaisha | Process for the producing of alkylcyclopentanone derivatives |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012169468A1 (en) | 2011-06-07 | 2012-12-13 | 株式会社クレハ | Method for producing cyclopentanone compound, and intermediate compound |
JPWO2012169468A1 (en) * | 2011-06-07 | 2015-02-23 | 株式会社クレハ | Method for producing cyclopentanone compound and intermediate compound |
US8975434B2 (en) | 2011-06-07 | 2015-03-10 | Kureha Corporation | Method for producing cyclopentanone compound, and intermediate compound |
WO2015075981A1 (en) * | 2013-11-22 | 2015-05-28 | 株式会社クレハ | Method for producing carbonyl compound |
Also Published As
Publication number | Publication date |
---|---|
AR025233A1 (en) | 2002-11-13 |
HUP0300723A3 (en) | 2006-06-28 |
HUP0300723A2 (en) | 2003-09-29 |
IL154207A (en) | 2008-12-29 |
JPWO0112580A1 (en) | 2003-03-11 |
PL362899A1 (en) | 2004-11-02 |
IN2005DE05932A (en) | 2008-05-09 |
BR0017310B1 (en) | 2011-10-04 |
PH12000002167B1 (en) | 2008-10-28 |
AU2000264750A1 (en) | 2001-03-13 |
UA73364C2 (en) | 2005-07-15 |
BR0017310A (en) | 2003-07-08 |
PL203074B1 (en) | 2009-08-31 |
TW591012B (en) | 2004-06-11 |
JP4979170B2 (en) | 2012-07-18 |
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