JPS63222123A - Production of homoallyl alcohol - Google Patents
Production of homoallyl alcoholInfo
- Publication number
- JPS63222123A JPS63222123A JP62056238A JP5623887A JPS63222123A JP S63222123 A JPS63222123 A JP S63222123A JP 62056238 A JP62056238 A JP 62056238A JP 5623887 A JP5623887 A JP 5623887A JP S63222123 A JPS63222123 A JP S63222123A
- Authority
- JP
- Japan
- Prior art keywords
- group
- lead
- formula
- protected
- linear
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- ZSPTYLOMNJNZNG-UHFFFAOYSA-N 3-Buten-1-ol Chemical compound OCCC=C ZSPTYLOMNJNZNG-UHFFFAOYSA-N 0.000 title description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 150000002611 lead compounds Chemical class 0.000 claims abstract description 5
- 239000002798 polar solvent Substances 0.000 claims abstract description 5
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 4
- 229930195735 unsaturated hydrocarbon Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- -1 allyl halide Chemical class 0.000 abstract description 27
- 239000002994 raw material Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 150000001299 aldehydes Chemical class 0.000 abstract description 4
- 150000002576 ketones Chemical class 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract 1
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000001721 carbon Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000001425 triazolyl group Chemical group 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000006432 1-methyl cyclopropyl group Chemical group [H]C([H])([H])C1(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- XOYUVEPYBYHIFZ-UHFFFAOYSA-L diperchloryloxylead Chemical compound [Pb+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O XOYUVEPYBYHIFZ-UHFFFAOYSA-L 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000002350 geranyl group Chemical group [H]C([*])([H])/C([H])=C(C([H])([H])[H])/C([H])([H])C([H])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005980 hexynyl group Chemical group 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
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([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
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004998 naphthylethyl group Chemical group C1(=CC=CC2=CC=CC=C12)CC* 0.000 description 1
- 125000004923 naphthylmethyl group Chemical group C1(=CC=CC2=CC=CC=C12)C* 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000005981 pentynyl group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229960003857 proglumide Drugs 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はホモアリルアルコールの製造法に関するもので
あり、さらに詳しくはアルデヒド又はケトン類とアリル
ハライドとを反応させるＣとにより、ホモアリルアルコ
ールを製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing homoallyl alcohol, more specifically, producing homoallyl alcohol by reacting an aldehyde or ketone with an allyl halide. It is about the method.
従来、一般式
％式％（）
〔式中 Ｒ１及びｒｔ” Ｆｉ水素、ＣＩ−Ｃ，。の直
鎖あるいは分岐のアルキル基、Ｃ３〜ＣｔＳの脂環式基
、Ｃ２〜Ｃ，の側ｆｉＹ少なくとも１つ有する脂環式基
。Conventionally, the general formula % formula % () [wherein R1 and rt'' Fi hydrogen, CI-C, straight chain or branched alkyl group, C3-CtS alicyclic group, C2-C, side fiY at least One alicyclic group.
Ｃ２〜Ｃ，、の直鎖あるいは分岐の不飽和炭比水素基、
アリール基、複素環基、アラルキル基又は了り−ルオキ
シ基であり、これらが置換基を有する場合がある。置換
基としては水酸基、保護された水酸基、アシルオキシ基
、ハロゲン、Ｃ１〜Ｃ５の直鎖あるいは分岐のアルキル
基、Ｃ！〜Ｃ６の直鎖あるいは分岐の不飽和炭］こ水素
基、アラルキル基、アｉ／Ｍ、Ｃ，〜Ｃ！の直鎖あるい
は分岐のアルキル基で置換されｔアミン基、保護された
アミン基、ニトロ基、保纏され之チオール基、カルボキ
シル基、保護されたカルボキシル基、スルホン酸基。C2-C, linear or branched unsaturated hydrocarbon group,
An aryl group, a heterocyclic group, an aralkyl group, or an aryloxy group, which may have a substituent. Examples of substituents include hydroxyl group, protected hydroxyl group, acyloxy group, halogen, C1 to C5 linear or branched alkyl group, C! ~C6 linear or branched unsaturated carbon] hydrogen group, aralkyl group, i/M, C, ~C! An amine group, a protected amine group, a nitro group, a protected thiol group, a carboxyl group, a protected carboxyl group, a sulfonic acid group substituted with a straight-chain or branched alkyl group.
保護されｔスルホン酸基、シアノ基であり、当該置換基
の数は少なくとも１つであり２以上の場合は同一であっ
ても異なってもよい。尚、Ｒ１とＲ２が同一である場合
を含む。〕
で表わされるケトン又はアルデヒドと一般式％式％（）
〔式中、Ｘは塩素、臭素、又はヨウ素である。〕で表わ
されるアリルハライドと反応させ、一般式〔式中、Ｒ１
、Ｈｚ は前記と同じである。〕で表わされるホモアリ
ルアルコールの製造法としては金属塩と還元性物質の存
在下で行う方法が知られており１例えば金属塩として５
ｎＣ１，、還元性物質としてＡＩ Ｙ用いる方法或いは
金属塩としてＢ１Ｃ１、、還元性物質としてＡＩ、Ｚｎ
又はＦｅを用いろ方法がある。しかし、これらの方法で
は触媒の使用量が多く、経済的に好ましくない上に、後
処理において公害問題ヶひき起す危険性ヲニらんでいる
。ヌ収高的にも充分とはいえる状態にはなっていない。It is a protected t-sulfonic acid group or a cyano group, and the number of substituents is at least one, and when there are two or more, they may be the same or different. Note that this includes the case where R1 and R2 are the same. ] A ketone or aldehyde represented by the general formula % formula % ( ) [wherein, X is chlorine, bromine, or iodine]. ] is reacted with allyl halide represented by the general formula [wherein R1
, Hz are the same as above. ] is known as a method for producing homoallylic alcohol represented by 1 in the presence of a metal salt and a reducing substance.
nC1, a method using AI Y as a reducing substance or B1C1 as a metal salt, AI, Zn as a reducing substance
Alternatively, there is a method using Fe. However, these methods require a large amount of catalyst, which is economically undesirable, and there is a risk of causing pollution problems during post-treatment. However, the situation is still not satisfactory in terms of yield.
さらに１本発明者等は鉛及びテトラプチルアンモニ９ム
プロマイド系の触媒システムを開発したが、このシステ
ムにおいても触媒量及び収率の点で満足と言、える状態
には至ってぃなかつｔｏ
発明の目的
本発明の目的に上記の従来から行われて来を方法の欠点
がなく、容易に効率良くホモアリルアルコールＹｌｌ造
する方法を提供することにある。Furthermore, although the present inventors have developed a catalyst system based on lead and tetrabutyl ammonium 9-promide, even this system has not reached a state where it can be said that the amount of catalyst and yield are satisfactory. The object of the present invention is to provide a method for easily and efficiently producing homoallyl alcohol Yll without the above-mentioned drawbacks of conventional methods.
発明の内容
本発明は一般式
％式％（）
で表わされるアルデヒド又はケトンと、一般式ＣＨ，＝
ＣＨＣＨ，Ｘ （■）で表わされるアリル
ハライドとを極性溶媒又は水と極性溶媒との混合溶媒中
、鉛１ヒ合物及び鉛よりイオン１）Ｓ傾向の大きい金属
の存在下で反応させろことｔＩ＃徴とする。一般式
で表わされるホモアリルアルコールの製造法である。Contents of the invention The present invention relates to an aldehyde or ketone represented by the general formula %() and a chemical compound of the general formula CH,=
React with the allyl halide represented by CHCH, # sign. This is a method for producing homoallyl alcohol represented by the general formula.
このホモアリルアルコールは医薬、ａｓｓの原料として
有用な物質である。本発明においてｌ（１及びＲ２は水
素、Ｃ１〜Ｃ９の直鎖あるいは分岐のアルキル基、Ｃ１
〜Ｃ２６の脂環式基、Ｃ，−Ｃｔｏの側鎖を少なくとも
１つ有する脂環式基％ Ｃ，〜Ｃ？０の直鎖あるいは分
岐の不飽和炭１と水素基、アリール基、複素環基、アラ
ルキル基又はアリールオキシ基であり、これらが置換基
を有する場合がある。This homoallyl alcohol is a substance useful as a raw material for medicine and ass. In the present invention, 1 (1 and R2 are hydrogen, C1 to C9 straight chain or branched alkyl group, C1
~C26 alicyclic group, C, alicyclic group having at least one -Cto side chain % C, ~C? 0 linear or branched unsaturated carbon 1 and a hydrogen group, an aryl group, a heterocyclic group, an aralkyl group, or an aryloxy group, which may have a substituent.
置換基としては水酸基、保護されｔ水酸基、アシルオキ
シ基、ハロゲンｓ Ｃ１〜Ｃ５の直鎖あるいは分岐のア
ルキル基、Ｃ１〜Ｃ６の直鎖あるいは分岐の不飽和炭１
と水素基、アラルキル基、アミノ基。Substituents include hydroxyl group, protected hydroxyl group, acyloxy group, halogen s, C1-C5 straight chain or branched alkyl group, C1-C6 straight chain or branched unsaturated carbon 1
and hydrogen groups, aralkyl groups, and amino groups.
Ｃ１〜Ｃ３の直鎖あるいは分岐のアルキル基でｔ換され
ｔアミン基、保護されたアミノ基、ニトロ基、保護され
たチオール基、カルボキシル基、保護すれたカルボキシ
ル基、スルホン醸基、保護すれ几スルホン酸基、シアノ
基であり、当該置換基の数は少なくとも１つであり２以
上の場合は同一であっても異なってもよい。尚、Ｒ１と
Ｒ２が同一である場合を含む。又Ｘは塩素、臭素、又は
ヨウ素である。０１〜Ｃ，の直鎖あるいは分岐のアルキ
ル基の具体例としては、メチル、工≠ル、プロピル。Amine group substituted with a C1-C3 straight or branched alkyl group, protected amino group, nitro group, protected thiol group, carboxyl group, protected carboxyl group, sulfone group, protected group These are sulfonic acid groups and cyano groups, and the number of substituents is at least one, and when there are two or more, they may be the same or different. Note that this includes the case where R1 and R2 are the same. Moreover, X is chlorine, bromine, or iodine. Specific examples of straight chain or branched alkyl groups of 01 to C are methyl, ethyl, and propyl.
イソプロピル、ブチル、イソブチル、ｔ−ブチル。Isopropyl, butyl, isobutyl, t-butyl.
アミル、イソアミル、ヘキシル、オクチル、デシル、ド
デシル基等を挙げることができる。Ｃ８〜Ｃ１゜の脂環
式基の具体例としては、シクロプロピル。Examples include amyl, isoamyl, hexyl, octyl, decyl, and dodecyl groups. A specific example of the C8-C1° alicyclic group is cyclopropyl.
シクロブチル、シクロペンチル、シクロヘキシル。Cyclobutyl, cyclopentyl, cyclohexyl.
シクロオクチル、シクロデシル、シクロフチニル。cyclooctyl, cyclodecyl, cyclofuthynyl.
シクロペンテニル、シクロヘキセニル、シクロオクテニ
ル、シクロオクタジェニル基等を挙げることができる。Examples include cyclopentenyl, cyclohexenyl, cyclooctenyl, and cyclooctagenyl groups.
Ｃ１〜Ｃやの側＠を少なくとも１つ有する脂環式基とし
ては１−メチルシクロプロピル。The alicyclic group having at least one @ side of C1 to C is 1-methylcyclopropyl.
２−メチルシクロプロピル、２，２−ジメチルシクロプ
ロピル、３−メチルシクロブチル、１−メチルシクロペ
ンチル、２−メチルシクロペンチル。2-methylcyclopropyl, 2,2-dimethylcyclopropyl, 3-methylcyclobutyl, 1-methylcyclopentyl, 2-methylcyclopentyl.
６−メチルシクロペンチル、３−エチルシクロペンチル
、３−ｔ−ブチルシクロペンチル、４−イソプロピルシ
クロヘキシル、４−１−ブチルシクロへキシル基等を例
示することができる。又Ｃ２〜Ｃ２゜の直鎖あるいは分
岐の不飽和炭］と水素基の具体例としてはビニル、エチ
ニル、１−プロペニル、２−フロベニル、プロピニル、
６−メチル−２−ブテニル、３−ブテニル、フチニル、
ペンテニル。Examples include 6-methylcyclopentyl, 3-ethylcyclopentyl, 3-t-butylcyclopentyl, 4-isopropylcyclohexyl, and 4-1-butylcyclohexyl. Specific examples of C2-C2° straight chain or branched unsaturated carbon and hydrogen groups include vinyl, ethynyl, 1-propenyl, 2-flobenyl, propynyl,
6-methyl-2-butenyl, 3-butenyl, futhynyl,
Pentenyl.
ペンチニル、ヘキセニル、ヘキシニル、ヘフテニル、ヘ
プチニル、オクテニル、オクチニル、９″′デセニル、
プレニル、ゲラニル基等を挙げること ・ができ
る。アリール基はフェニル基又は多核芳香原炭１と水素
基であり、多核芳香原炭１と水素基の具体例としてはα
−ナフチル、β−ナフチル、アンソラニル、ピレニル基
等を挙げることができる。pentynyl, hexenyl, hexynyl, heftenyl, heptynyl, octenyl, octynyl, 9″′decenyl,
Examples include prenyl and geranyl groups. The aryl group is a phenyl group or a polynuclear aromatic raw carbon 1 and a hydrogen group, and a specific example of the polynuclear aromatic raw carbon 1 and a hydrogen group is α
-naphthyl, β-naphthyl, anthoranyl, pyrenyl groups, and the like.
複素環基としては酸素、窒素、硫黄原子等乞食む環状基
ｌ挙げることができ、その例としてはテトラヒト°ロフ
リル、フリル、テトラヒドロピラニル。Examples of the heterocyclic group include cyclic groups such as oxygen, nitrogen, and sulfur atoms, examples of which include tetrahydrofuryl, furyl, and tetrahydropyranyl.
ピラニル、ピロリル、ピペリジニル、ピリジル、オキサ
ゾリニル、モルホリニル、テトラヒドロチェニル、チェ
ニル、チアジアゾリル、トリアゾリル、チアゾリル、ト
リアゾリル、テトラゾリル基等である。アラルキル基の
例としてはベンジル、フェネチル、フェニルブチル、ジ
フェニルメチル、トリフェニルメチル、ナフチルメチル
、ナフチルエチル基等を挙げることができろ。アリール
オキシ基の例としてはフェノキシ、α−ナフチルオキシ
、β−ナフチルオキシ、アントラニルオキシ。These include pyranyl, pyrrolyl, piperidinyl, pyridyl, oxazolinyl, morpholinyl, tetrahydrochenyl, chenyl, thiadiazolyl, triazolyl, thiazolyl, triazolyl, and tetrazolyl groups. Examples of aralkyl groups include benzyl, phenethyl, phenylbutyl, diphenylmethyl, triphenylmethyl, naphthylmethyl, and naphthylethyl groups. Examples of aryloxy groups are phenoxy, α-naphthyloxy, β-naphthyloxy, anthranyloxy.
ピＶニルオキシ基等を挙げることができる。Examples include pV-nyloxy group.
次に本発明に用いる溶媒は極性溶媒であり、この溶媒中
に水を含む場合及び水り含まない場合のいずれもがある
。好ましい溶媒はアルコール類。Next, the solvent used in the present invention is a polar solvent, which may or may not contain water. Preferred solvents are alcohols.
エーテル類、ニトリル類、アミド類等であり、具体的に
はジメチルホルムアミド、ジメチルスルホキシド、Ｎ−
メチル−２−ピロリドン、１．６−シメチルー２−イミ
ダゾリジノン、ジオキサン、及びこれらの内の１ｆｉと
水との混合物、テトラヒドロフランと水との混合物、メ
タノールと水との混合物等を挙げることができる、溶媒
の使用量は原料物質に対して特に制限はないが、少なく
とも原料物質が完全に溶解する竜であることが好ましい
。These include ethers, nitrites, amides, etc., specifically dimethylformamide, dimethylsulfoxide, N-
Examples include methyl-2-pyrrolidone, 1,6-dimethyl-2-imidazolidinone, dioxane, and mixtures of 1fi of these and water, mixtures of tetrahydrofuran and water, mixtures of methanol and water, etc. The amount of solvent to be used is not particularly limited depending on the raw material, but it is preferably at least a solvent that completely dissolves the raw material.
しかし特にそれ以下であっても１反応は進行するので問
題はないが、操作が行いにくくなるか或いは収率が低下
する等の難点が生ずる場合がある。However, even if the amount is less than that, there is no problem because one reaction will proceed, but there may be problems such as making the operation difficult or reducing the yield.
鉛＋１）Ｓ合物は鉛の原子価が０価、２価又は４価のい
ずれでも良く、又場合に二り水和物の形態であっても良
い。例えばフッ１じ鉛、塩ｉｔＳ鉛、臭１じ鉛、ヨウ１
じ鉛等のハロゲン１じ物、硝酸鉛、硫酸鉛、過塩素酸鉛
、ホウ酷鉛、炭酬鉛、リン酸鉛等の無機酸鉛、酢酸鉛、
シュウ酸鉛、ステアリン酸鉛、ギ酸鉛等の脂肪酸鉛、醐
１ヒ鉛、水Ｍ１と鉛及びこれらの鉛１じ合物とエチレン
ジアミンテトラ酢酸又はニトリロトリ酢酸等のキレート
剤からなる各稽鉛錯体等が使用し得るものとして挙げら
れるが、％に好ましいものはハロゲン地物、さらに詳し
くは奥１ヒ物、塩！し物である。この鉛１ヒ合物の使用
量は原料物質１当量に対してｏ、ｏｏ１〜０．５当量が
好ましく。In the lead+1)S compound, the valence of lead may be zero, divalent or tetravalent, and in some cases, it may be in the form of a dihydrate. For example, 1 part lead of fluoride, 1 part lead of salt, 1 part lead of odor, 1 part iodine
Halogens such as lead, lead nitrate, lead sulfate, lead perchlorate, lead borax, lead carbonate, inorganic acids such as lead phosphate, lead acetate,
Fatty acid leads such as lead oxalate, lead stearate, and lead formate, various lead complexes consisting of lead 1 arsenic, water M1 and lead, and combinations of these lead and chelating agents such as ethylenediaminetetraacetic acid or nitrilotriacetic acid, etc. are mentioned as things that can be used, but the most preferable ones are halogen substances, more specifically, salt! It is a gift. The amount of the lead monomerizate to be used is preferably 1 to 0.5 equivalents of o and oo per 1 equivalent of the raw material.
０．００１当量より少ない場合は効果が少なく、又０．
５当ｔより多い場合は効果忙変わりはないものの経済的
ではない。鉛よりイオン１じ傾向の大きい金属としては
アルミニウム、鉄、ニッケル、スズ。If it is less than 0.001 equivalent, the effect will be small, and if it is less than 0.001 equivalent, the effect will be small.
If the number of hits is more than 5 tons, the effect is still the same, but it is not economical. Metals that have a greater ion tendency than lead include aluminum, iron, nickel, and tin.
コバルトのいずれか、あるいはＣｎらの混合物が挙げら
れるが特に好ましいのはアルミニウムである。使用に際
してこれら金属の形状には特に制限はなく、粉状、板状
、箔状、塊状、針状等様々な形状で用いることができる
。又この使用量は原料物質１当ｔＫ対して０．３〜４白
量の範囲であることが好オしく、０．５当ｔ未満では反
応がすすまないか、或いは反応の進行が遅くなる定め好
ましくなく、４当？より多い場合は経済的でない上に制
反応が多くなり収率が低下する。本方法くおいては以上
の溶媒及び触媒の存在が必須であり、そのいずれが欠け
ても本発明の目的を達成することはできない。又１と合
物（Ｔ）に対し１ヒ金物（Ｉｆ）は当モル以上を使用す
るのが好ましい。本発明における反応温度は原料物質、
溶媒、触媒により好ましい範囲が変１ヒするが通常１０
〜４０℃の範囲で行われ。Examples include cobalt or a mixture of Cn and the like, but aluminum is particularly preferred. There is no particular restriction on the shape of these metals when used, and they can be used in various shapes such as powder, plate, foil, lump, and needle. The amount used is preferably in the range of 0.3 to 4 tK per tK of the raw material, and if it is less than 0.5 tK, the reaction will not proceed or the reaction will proceed slowly. Unfavorable, 4 wins? If the amount is larger than that, it is not economical and more reaction is required, resulting in a lower yield. In this method, the presence of the above-mentioned solvent and catalyst is essential, and the object of the present invention cannot be achieved without any of them. Further, it is preferable to use at least the equivalent molar amount of 1 and the compound (T) of 1 and the compound (T). The reaction temperature in the present invention is the raw material,
The preferred range varies depending on the solvent and catalyst, but is usually 10
Performed at a temperature of ~40°C.
反応時間は１〜１５時間で充分である。A reaction time of 1 to 15 hours is sufficient.
以上記した通り１本発明は鉛化合物、鉛よりイオン１と
傾向の大きい金属及び溶媒の相乗効果により温和な条件
下で収率良くホモアリルアルコールｌ得る方法を提供す
るものである。As described above, the present invention provides a method for obtaining homoallyl alcohol 1 in good yield under mild conditions by the synergistic effect of a lead compound, a metal with a higher tendency to ion 1 than lead, and a solvent.
実施例 以下に実施例り示し、本発明ｔより具体的に説明する。Example The present invention will be explained in more detail by way of examples below.
実施例１
丸底フラスコに臭１ト鉛１）ｍｇ（０，０３ミリモル）
と細かく切つｔアルミ箔３０ｍｇ（１，１ミリモル）を
とり、これにジメチルホルムアミド４！Ｒ１及ヒベンズ
アルデヒドＣＩ）１０６ｍｇ（１ミリモル）と臭ｌｌｌ
５アリル（ＩＩ） １３３ｍｇ（１，１ミリモル）ン加
えて室温下で２時間かきまぜて反ＣＹ行つｔ０反応終了
後。Example 1 Odor 1 lead 1) mg (0.03 mmol) in a round bottom flask
Take 30 mg (1.1 mmol) of finely cut aluminum foil and add 4! of dimethylformamide to it. R1 and hibenzaldehyde CI) 106 mg (1 mmol) and odor
After the completion of the t0 reaction, 133 mg (1.1 mmol) of 5-allyl (II) was added and stirred at room temperature for 2 hours to carry out anti-CY reaction.
反応液に水４虹を加え酢酸エチルで抽出しｔｏこの抽出
液を飽和重曹水及び飽和食塩水で洗浄し。Water was added to the reaction solution, extracted with ethyl acetate, and the extract was washed with saturated aqueous sodium bicarbonate and saturated brine.
無水硫酸マグネシウムで乾燥しｔ後、濃縮をし淡黄色結
晶Ｚ得ｔ、この結晶をシリカゲルカラムを用いて精製す
ることにより白色結晶を得た。このもののＮＭＲスペク
トルは（し合物（１■）の構造トよく一致しており、ベ
ンズアルデヒド基準の収率は９４％であった。After drying over anhydrous magnesium sulfate, the mixture was concentrated to obtain pale yellow crystals Z. This crystal was purified using a silica gel column to obtain white crystals. The NMR spectrum of this product was in good agreement with the structure of compound (1), and the yield was 94% based on benzaldehyde.
実施例２〜１７
実施例１と同様の方法で原料物質、溶媒１反応時間？変
えて実験を行つ九〇その条件及び結果を第１表にまとめ
九〇
蔗二二り二毘
第 １ 表
Ｂｒ ： 臭１ヒアリル
ｃｇ：ｍ比了すル
ＤＭＦ ： ジメチルホルムアミドＭｃＯＩ（：
メタノールExamples 2 to 17 Using the same method as in Example 1, using raw materials and solvent 1 reaction time. The conditions and results of the experiments are summarized in Table 1. Table 1: Odor 1 Hyaryl cg:m ratio DMF: Dimethylformamide McOI (:
methanol
Claims (2)
直鎖あるいは分岐のアルキル基、Ｃ＿１〜Ｃ＿１＿６の
脂環式基、Ｃ＿１〜Ｃ＿２＿０の側鎖を少なくとも１つ
有する脂環式基、Ｃ＿２〜Ｃ＿２＿０の直鎖あるいは分
岐の不飽和炭化水素基、アリール基、複素環基、アラル
キル基又はアリールオキシ基であり、これらが置換基を
有する場合がある。置換基としては水酸基、保護された
水酸基、アシルオキシ基、ハロゲン、Ｃ＿１〜Ｃ＿５の
直鎖あるいは分岐のアルキル基、Ｃ＿２〜Ｃ＿６の直鎖
あるいは分岐の不飽和炭化水素基、アラルキル基、アミ
ノ基、Ｃ＿１〜Ｃ＿５の直鎖あるいは分岐のアルキル基
で置換されたアミノ基、保護されたアミノ基、ニトロ基
、保護されたチオール基、カルボキシル基、保護された
カルボキシル基、スルホン酸基、保護されたスルホン酸
基、シアノ基であり、当該置換基の数は少なくとも１つ
であり、２以上の場合は同一であつても異なつてもよい
。尚、Ｒ＾１とＲ＾２が同一である場合を含む。〕で表
わされるケトン又はアルデヒドを極性溶媒又は水と極性
溶媒との混合溶媒中、鉛化合物及び鉛よりイオン化傾向
の大きい金属の存在下で一般式 ＣＨ＿２＝ＣＨＣＨ＿２Ｘ（II） 〔式中、Ｘは塩素、臭素、又はヨウ素である。〕で表わ
されるアリルハライドと反応させることを特徴とする一
般式 ▲数式、化学式、表等があります▼（III） 〔式中、Ｒ＾１、Ｒ＾２は前記と同じである。〕で表わ
されるホモアリルアルコールの製造法。(1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, R^1 and R^2 are hydrogen, C_1 to C_2_0 are linear or branched alkyl groups, and C_1 to C_1_6 are alicyclic groups. group, an alicyclic group having at least one side chain of C_1 to C_2_0, a linear or branched unsaturated hydrocarbon group of C_2 to C_2_0, an aryl group, a heterocyclic group, an aralkyl group, or an aryloxy group, and these may have a substituent. Substituents include hydroxyl group, protected hydroxyl group, acyloxy group, halogen, C_1 to C_5 linear or branched alkyl group, C_2 to C_6 linear or branched unsaturated hydrocarbon group, aralkyl group, amino group, C_1 Amino group substituted with ~C_5 linear or branched alkyl group, protected amino group, nitro group, protected thiol group, carboxyl group, protected carboxyl group, sulfonic acid group, protected sulfonic acid The number of substituents is at least one, and in the case of two or more, they may be the same or different. Note that this includes the case where R^1 and R^2 are the same. ] in a polar solvent or a mixed solvent of water and a polar solvent in the presence of a lead compound and a metal with a greater ionization tendency than lead to form the general formula CH_2=CHCH_2X(II) [wherein, X is chlorine] , bromine, or iodine. ] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (III) [In the formula, R^1 and R^2 are the same as above. ] A method for producing homoallylic alcohol.
、鉄、ニッケル、スズ、コバルト、マグネシウムのいず
れか、あるいはこれらの混合物である特許請求の範囲第
１項記載の製造法。(2) The manufacturing method according to claim 1, wherein the metal having a greater ionization tendency than lead is aluminum, iron, nickel, tin, cobalt, magnesium, or a mixture thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62056238A JPH0816071B2 (en) | 1987-03-11 | 1987-03-11 | Method for producing homoallyl alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62056238A JPH0816071B2 (en) | 1987-03-11 | 1987-03-11 | Method for producing homoallyl alcohol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63222123A true JPS63222123A (en) | 1988-09-16 |
| JPH0816071B2 JPH0816071B2 (en) | 1996-02-21 |
Family
ID=13021515
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62056238A Expired - Lifetime JPH0816071B2 (en) | 1987-03-11 | 1987-03-11 | Method for producing homoallyl alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0816071B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045391A1 (en) * | 1996-05-31 | 1997-12-04 | Kaneka Corporation | Process for preparing optically active alcoholic compounds |
| KR100349035B1 (en) * | 2000-07-01 | 2002-08-17 | 한국과학기술연구원 | Method for the allkylation of aldehyde and reduction of nitro group in one-pot using indium and acid |
| JP2008255093A (en) * | 2007-03-09 | 2008-10-23 | Japan Science & Technology Agency | Method for producing homoallyl alcohol or homoallyl hydrazide |
| JP2009215240A (en) * | 2008-03-11 | 2009-09-24 | Japan Science & Technology Agency | Method for producing homo allyl alcohol, and asymmetric catalyst |
-
1987
- 1987-03-11 JP JP62056238A patent/JPH0816071B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997045391A1 (en) * | 1996-05-31 | 1997-12-04 | Kaneka Corporation | Process for preparing optically active alcoholic compounds |
| KR100349035B1 (en) * | 2000-07-01 | 2002-08-17 | 한국과학기술연구원 | Method for the allkylation of aldehyde and reduction of nitro group in one-pot using indium and acid |
| JP2008255093A (en) * | 2007-03-09 | 2008-10-23 | Japan Science & Technology Agency | Method for producing homoallyl alcohol or homoallyl hydrazide |
| JP2009215240A (en) * | 2008-03-11 | 2009-09-24 | Japan Science & Technology Agency | Method for producing homo allyl alcohol, and asymmetric catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0816071B2 (en) | 1996-02-21 |
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