CA1121813A - Asymmetric synthesis of chrysanthemate - Google Patents
Asymmetric synthesis of chrysanthemateInfo
- Publication number
- CA1121813A CA1121813A CA000258220A CA258220A CA1121813A CA 1121813 A CA1121813 A CA 1121813A CA 000258220 A CA000258220 A CA 000258220A CA 258220 A CA258220 A CA 258220A CA 1121813 A CA1121813 A CA 1121813A
- Authority
- CA
- Canada
- Prior art keywords
- phenyl
- amino
- group
- propanol
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000011914 asymmetric synthesis Methods 0.000 title description 5
- -1 alkyl diazoacetate Chemical compound 0.000 claims abstract description 58
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 239000002262 Schiff base Substances 0.000 claims abstract description 17
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 17
- 150000004699 copper complex Chemical class 0.000 claims abstract description 15
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 10
- DZPCYXCBXGQBRN-UHFFFAOYSA-N 2,5-Dimethyl-2,4-hexadiene Chemical compound CC(C)=CC=C(C)C DZPCYXCBXGQBRN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 125000005605 benzo group Chemical group 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 4
- BXEFQPCKQSTMKA-UHFFFAOYSA-N OC(=O)C=[N+]=[N-] Chemical compound OC(=O)C=[N+]=[N-] BXEFQPCKQSTMKA-UHFFFAOYSA-N 0.000 claims description 14
- 150000001414 amino alcohols Chemical class 0.000 claims description 13
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 12
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000004471 Glycine Substances 0.000 claims description 7
- CNUDAOFHRABHSO-UHFFFAOYSA-N 2-[[1,1-bis(2,5-dibutoxyphenyl)-1-hydroxy-3-phenylpropan-2-yl]iminomethyl]phenol Chemical compound CCCCOC1=CC=C(OCCCC)C(C(O)(C(CC=2C=CC=CC=2)N=CC=2C(=CC=CC=2)O)C=2C(=CC=C(OCCCC)C=2)OCCCC)=C1 CNUDAOFHRABHSO-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000002950 monocyclic group Chemical group 0.000 claims description 4
- 125000003367 polycyclic group Polymers 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- VQNXJGJEWVUTGU-UHFFFAOYSA-N 2-[[1,1-bis(2-butoxy-5-tert-butylphenyl)-1-hydroxy-3-phenylpropan-2-yl]iminomethyl]phenol Chemical compound CCCCOC1=CC=C(C(C)(C)C)C=C1C(O)(C=1C(=CC=C(C=1)C(C)(C)C)OCCCC)C(N=CC=1C(=CC=CC=1)O)CC1=CC=CC=C1 VQNXJGJEWVUTGU-UHFFFAOYSA-N 0.000 claims description 2
- YRKKSAPJFMZMSB-UHFFFAOYSA-N 2-[[1,1-bis(2-butoxyphenyl)-1-hydroxy-3-methylbutan-2-yl]iminomethyl]phenol Chemical compound CCCCOC1=CC=CC=C1C(O)(C=1C(=CC=CC=1)OCCCC)C(C(C)C)N=CC1=CC=CC=C1O YRKKSAPJFMZMSB-UHFFFAOYSA-N 0.000 claims description 2
- BQTOWHRHEUPBKG-UHFFFAOYSA-N 2-[[1,1-bis(5-tert-butyl-2-octoxyphenyl)-1-hydroxypropan-2-yl]iminomethyl]-6-methoxyphenol Chemical compound COC1=C(C(C=NC(C(O)(C2=C(C=CC(=C2)C(C)(C)C)OCCCCCCCC)C2=C(C=CC(=C2)C(C)(C)C)OCCCCCCCC)C)=CC=C1)O BQTOWHRHEUPBKG-UHFFFAOYSA-N 0.000 claims description 2
- TYUONIIDQIALAQ-UHFFFAOYSA-N 2-[[1,1-bis(5-tert-butyl-2-octoxyphenyl)-1-hydroxypropan-2-yl]iminomethyl]phenol Chemical compound CCCCCCCCOC1=CC=C(C(C)(C)C)C=C1C(O)(C=1C(=CC=C(C=1)C(C)(C)C)OCCCCCCCC)C(C)N=CC1=CC=CC=C1O TYUONIIDQIALAQ-UHFFFAOYSA-N 0.000 claims description 2
- BDZMXIRGEBTOOW-UHFFFAOYSA-N 2-[[1,1-bis(5-tert-butyl-2-propan-2-yloxyphenyl)-1-hydroxy-3-phenylpropan-2-yl]iminomethyl]phenol Chemical compound C(C=1C(O)=CC=CC=1)=NC(C(O)(C1=C(C=CC(=C1)C(C)(C)C)OC(C)C)C1=C(C=CC(=C1)C(C)(C)C)OC(C)C)CC1=CC=CC=C1 BDZMXIRGEBTOOW-UHFFFAOYSA-N 0.000 claims description 2
- XTSJJTXCWCJMQQ-UHFFFAOYSA-N 2-[[1,1-bis(5-tert-butyl-2-propan-2-yloxyphenyl)-1-hydroxypropan-2-yl]iminomethyl]phenol Chemical compound CC(C)OC1=CC=C(C(C)(C)C)C=C1C(O)(C=1C(=CC=C(C=1)C(C)(C)C)OC(C)C)C(C)N=CC1=CC=CC=C1O XTSJJTXCWCJMQQ-UHFFFAOYSA-N 0.000 claims description 2
- KPNZZCZTBVDMEA-UHFFFAOYSA-N 2-[[1-hydroxy-3-phenyl-1,1-bis(2-propan-2-yloxyphenyl)propan-2-yl]iminomethyl]phenol Chemical compound CC(C)OC1=CC=CC=C1C(O)(C=1C(=CC=CC=1)OC(C)C)C(N=CC=1C(=CC=CC=1)O)CC1=CC=CC=C1 KPNZZCZTBVDMEA-UHFFFAOYSA-N 0.000 claims description 2
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims description 2
- NUGOTBXFVWXVTE-UHFFFAOYSA-N 2-hydroxy-3-nitrobenzaldehyde Chemical compound OC1=C(C=O)C=CC=C1[N+]([O-])=O NUGOTBXFVWXVTE-UHFFFAOYSA-N 0.000 claims description 2
- KBHBGCGYQBSXRO-UHFFFAOYSA-N 2-hydroxy-6-methyl-3-propan-2-ylbenzaldehyde Chemical compound CC(C)C1=CC=C(C)C(C=O)=C1O KBHBGCGYQBSXRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 2
- JHZOXYGFQMROFJ-UHFFFAOYSA-N 3,5-dibromo-2-hydroxybenzaldehyde Chemical compound OC1=C(Br)C=C(Br)C=C1C=O JHZOXYGFQMROFJ-UHFFFAOYSA-N 0.000 claims description 2
- OFQBYHLLIJGMNP-UHFFFAOYSA-N 3-ethoxy-2-hydroxybenzaldehyde Chemical compound CCOC1=CC=CC(C=O)=C1O OFQBYHLLIJGMNP-UHFFFAOYSA-N 0.000 claims description 2
- FUGKCSRLAQKUHG-UHFFFAOYSA-N 5-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Cl)C=C1C=O FUGKCSRLAQKUHG-UHFFFAOYSA-N 0.000 claims description 2
- UWEUXILWZYYMSH-UHFFFAOYSA-N C(/C=1C(O)=CC=CC1)=NC(C(O)(C1=C(C=CC(=C1)C(C)(C)C)OCCCCCCC)C1=C(C=CC(=C1)C(C)(C)C)OCCCCCCC)CC1=CC=CC=C1 Chemical compound C(/C=1C(O)=CC=CC1)=NC(C(O)(C1=C(C=CC(=C1)C(C)(C)C)OCCCCCCC)C1=C(C=CC(=C1)C(C)(C)C)OCCCCCCC)CC1=CC=CC=C1 UWEUXILWZYYMSH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- JJVNINGBHGBWJH-UHFFFAOYSA-N ortho-vanillin Chemical compound COC1=CC=CC(C=O)=C1O JJVNINGBHGBWJH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- RKNYIJQVTXBQOX-UHFFFAOYSA-N 1-[[1-hydroxy-3-phenyl-1,1-bis(2-propan-2-yloxyphenyl)propan-2-yl]iminomethyl]naphthalen-2-ol Chemical compound CC(C)OC1=CC=CC=C1C(O)(C=1C(=CC=CC=1)OC(C)C)C(N=CC=1C2=CC=CC=C2C=CC=1O)CC1=CC=CC=C1 RKNYIJQVTXBQOX-UHFFFAOYSA-N 0.000 claims 1
- OITQDWKMIPXGFL-UHFFFAOYSA-N 1-hydroxy-2-naphthaldehyde Chemical compound C1=CC=C2C(O)=C(C=O)C=CC2=C1 OITQDWKMIPXGFL-UHFFFAOYSA-N 0.000 claims 1
- BJESMBBTQNGLAB-UHFFFAOYSA-N 2-[[1,1-bis(2-butoxy-5-phenylphenyl)-1-hydroxy-3-phenylpropan-2-yl]iminomethyl]phenol Chemical compound CCCCOC1=CC=C(C=2C=CC=CC=2)C=C1C(O)(C=1C(=CC=C(C=1)C=1C=CC=CC=1)OCCCC)C(N=CC=1C(=CC=CC=1)O)CC1=CC=CC=C1 BJESMBBTQNGLAB-UHFFFAOYSA-N 0.000 claims 1
- QNQGKRMNIZWKFQ-UHFFFAOYSA-N 2-[[1,1-bis(2-butoxy-5-tert-butylphenyl)-1-hydroxy-4-methylpentan-2-yl]iminomethyl]phenol Chemical compound CCCCOC1=CC=C(C(C)(C)C)C=C1C(O)(C=1C(=CC=C(C=1)C(C)(C)C)OCCCC)C(CC(C)C)N=CC1=CC=CC=C1O QNQGKRMNIZWKFQ-UHFFFAOYSA-N 0.000 claims 1
- QTMJLKAUHQMSLE-UHFFFAOYSA-N 2-[[1,1-bis(2-butoxy-5-tert-butylphenyl)-1-hydroxypropan-2-yl]iminomethyl]phenol Chemical compound CCCCOC1=CC=C(C(C)(C)C)C=C1C(O)(C=1C(=CC=C(C=1)C(C)(C)C)OCCCC)C(C)N=CC1=CC=CC=C1O QTMJLKAUHQMSLE-UHFFFAOYSA-N 0.000 claims 1
- KINDEUTXGVWIEC-UHFFFAOYSA-N 2-[[1-hydroxy-1,1-bis(2-methoxyphenyl)-3-phenylpropan-2-yl]iminomethyl]phenol Chemical compound COC1=CC=CC=C1C(O)(C=1C(=CC=CC=1)OC)C(N=CC=1C(=CC=CC=1)O)CC1=CC=CC=C1 KINDEUTXGVWIEC-UHFFFAOYSA-N 0.000 claims 1
- XSTIWHDRMIKWFL-UHFFFAOYSA-N 2-ethoxy-6-[[1-hydroxy-3-phenyl-1,1-bis(2-propan-2-yloxyphenyl)propan-2-yl]iminomethyl]phenol Chemical compound C(C)OC1=C(C(C=NC(C(O)(C2=C(C=CC=C2)OC(C)C)C2=C(C=CC=C2)OC(C)C)CC2=CC=CC=C2)=CC=C1)O XSTIWHDRMIKWFL-UHFFFAOYSA-N 0.000 claims 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 238000006193 diazotization reaction Methods 0.000 claims 1
- XLOPRKKSAJMMEW-SFYZADRCSA-N Chrysanthemic acid Natural products CC(C)=C[C@@H]1[C@@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 230000003287 optical effect Effects 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001879 copper Chemical class 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- ARIRLMOIPLAKEK-UHFFFAOYSA-N 2-diazonio-1-(5-methyl-2-propan-2-ylcyclohexyl)oxyethenolate Chemical compound CC(C)C1CCC(C)CC1OC(=O)C=[N+]=[N-] ARIRLMOIPLAKEK-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229960005335 propanol Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NDLIRBZKZSDGSO-UHFFFAOYSA-N tosyl azide Chemical compound CC1=CC=C(S(=O)(=O)[N-][N+]#N)C=C1 NDLIRBZKZSDGSO-UHFFFAOYSA-N 0.000 description 2
- SJWFXCIHNDVPSH-QMMMGPOBSA-N (2S)-octan-2-ol Chemical compound CCCCCC[C@H](C)O SJWFXCIHNDVPSH-QMMMGPOBSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 125000000579 2,2-diphenylethyl 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])C([H])([H])* 0.000 description 1
- PLSMHHUFDLYURK-UHFFFAOYSA-N 2,3,4-trimethyl-3-pentanol Chemical compound CC(C)C(C)(O)C(C)C PLSMHHUFDLYURK-UHFFFAOYSA-N 0.000 description 1
- PVOPOJUNKWJIBJ-UHFFFAOYSA-N 2-(2-hydroxyethyliminomethyl)phenol Chemical compound OCCN=CC1=CC=CC=C1O PVOPOJUNKWJIBJ-UHFFFAOYSA-N 0.000 description 1
- AWXVZQXIMPKRGJ-UHFFFAOYSA-N 2-diazo-3-oxobutanoic acid Chemical compound [N+](=[N-])=C(C(=O)O)C(=O)C AWXVZQXIMPKRGJ-UHFFFAOYSA-N 0.000 description 1
- NQJHQUYXNPMZCK-UHFFFAOYSA-N 2-diazonio-1-(2,3,4-trimethylpentan-3-yloxy)ethenolate Chemical compound CC(C)C(C)(C(C)C)OC(=O)C=[N+]=[N-] NQJHQUYXNPMZCK-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 125000004135 2-norbornyl group Chemical group [H]C1([H])C([H])([H])C2([H])C([H])([H])C1([H])C([H])([H])C2([H])* 0.000 description 1
- ZNBGBHISQKMEPA-UHFFFAOYSA-N 2-oxoacetyl chloride Chemical compound ClC(=O)C=O ZNBGBHISQKMEPA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 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
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003670 adamantan-2-yl group Chemical group [H]C1([H])C(C2([H])[H])([H])C([H])([H])C3([H])C([*])([H])C1([H])C([H])([H])C2([H])C3([H])[H] 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 230000003197 catalytic effect Effects 0.000 description 1
- UOCJDOLVGGIYIQ-PBFPGSCMSA-N cefatrizine Chemical group S([C@@H]1[C@@H](C(N1C=1C(O)=O)=O)NC(=O)[C@H](N)C=2C=CC(O)=CC=2)CC=1CSC=1C=NNN=1 UOCJDOLVGGIYIQ-PBFPGSCMSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229940076286 cupric acetate Drugs 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical group C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- ROBXZHNBBCHEIQ-BYPYZUCNSA-N ethyl (2s)-2-aminopropanoate Chemical compound CCOC(=O)[C@H](C)N ROBXZHNBBCHEIQ-BYPYZUCNSA-N 0.000 description 1
- YVPJCJLMRRTDMQ-UHFFFAOYSA-N ethyl diazoacetate Chemical compound CCOC(=O)C=[N+]=[N-] YVPJCJLMRRTDMQ-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 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
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/12—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
- C07C245/14—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom having diazo groups bound to acyclic carbon atoms of a carbon skeleton
- C07C245/18—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom having diazo groups bound to acyclic carbon atoms of a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP94349/75 | 1975-08-01 | ||
| JP50094349A JPS5910336B2 (ja) | 1975-08-01 | 1975-08-01 | 第一菊酸エステルの不斉合成法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121813A true CA1121813A (en) | 1982-04-13 |
Family
ID=14107796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000258220A Expired CA1121813A (en) | 1975-08-01 | 1976-07-30 | Asymmetric synthesis of chrysanthemate |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5910336B2 (nl) |
| BE (1) | BE844631A (nl) |
| CA (1) | CA1121813A (nl) |
| CH (1) | CH621767A5 (nl) |
| DE (1) | DE2634663C3 (nl) |
| DK (1) | DK142765B (nl) |
| FR (1) | FR2319623A1 (nl) |
| GB (1) | GB1499094A (nl) |
| IL (1) | IL50100A (nl) |
| IT (1) | IT1070323B (nl) |
| NL (1) | NL7608508A (nl) |
| SU (1) | SU719491A3 (nl) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2919820A1 (de) * | 1979-05-16 | 1980-11-20 | Bayer Ag | Fluor-substituierte oxyalkenyl-cyclopropancarbonsaeureester, verfahren zu ihrer herstellung sowie ihre verwendung als insektizide und akarizide |
| EP0023075A1 (en) * | 1979-07-13 | 1981-01-28 | Imperial Chemical Industries Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| EP0022608B1 (en) * | 1979-07-13 | 1983-07-06 | Imperial Chemical Industries Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| EP0024796A1 (en) * | 1979-07-13 | 1981-03-11 | Imperial Chemical Industries Plc | Chiral amino-alcohol complexes and process for their preparation |
| EP0024795A1 (en) * | 1979-07-13 | 1981-03-11 | Imperial Chemical Industries Plc | Chiral compounds and process for their preparation |
| EP0024797A1 (en) * | 1979-07-13 | 1981-03-11 | Imperial Chemical Industries Plc | Chiral sugar complexes and process for their preparation |
| JPS59158260A (ja) * | 1983-02-28 | 1984-09-07 | Seikei Giken:Kk | 転写装置 |
| JPS59158261A (ja) * | 1983-07-19 | 1984-09-07 | Seikei Giken:Kk | 転写装置 |
| JPH01232619A (ja) * | 1988-03-11 | 1989-09-18 | Toska Co Ltd | キートップの印字方法 |
| JPH0671852A (ja) * | 1992-08-31 | 1994-03-15 | Shizuoka Giken Sanki Kk | 曲面真空プレス熱転写方法及びその装置 |
| JP4576642B2 (ja) * | 1998-01-29 | 2010-11-10 | 住友化学株式会社 | 光学活性な菊酸の製造方法 |
| ITMI20041211A1 (it) * | 2004-06-16 | 2004-09-16 | Endura Spa | Catalizzatori a base di complessi metallici per la sintesi di acido crisantemico otticamente attivo |
| CN103789789B (zh) * | 2014-02-11 | 2016-06-29 | 华东师范大学 | 电化学合成具有光学活性的苯乙烯环状碳酸酯的方法 |
| CN103789791B (zh) * | 2014-02-12 | 2016-08-17 | 华东师范大学 | 一种电化学合成具有光学活性的2-苯丙酸方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL44167A (en) * | 1973-02-14 | 1979-09-30 | Sumitomo Chemical Co | Chiral copper-complex catalyst |
-
1975
- 1975-08-01 JP JP50094349A patent/JPS5910336B2/ja not_active Expired
-
1976
- 1976-07-22 IL IL50100A patent/IL50100A/xx unknown
- 1976-07-28 BE BE6045627A patent/BE844631A/xx not_active IP Right Cessation
- 1976-07-30 CA CA000258220A patent/CA1121813A/en not_active Expired
- 1976-07-30 FR FR7623388A patent/FR2319623A1/fr active Granted
- 1976-07-30 NL NL7608508A patent/NL7608508A/nl not_active Application Discontinuation
- 1976-07-30 GB GB31985/76A patent/GB1499094A/en not_active Expired
- 1976-07-30 IT IT68927/76A patent/IT1070323B/it active
- 1976-07-30 SU SU762387252A patent/SU719491A3/ru active
- 1976-07-30 CH CH977576A patent/CH621767A5/de not_active IP Right Cessation
- 1976-07-30 DK DK345276AA patent/DK142765B/da not_active IP Right Cessation
- 1976-08-02 DE DE2634663A patent/DE2634663C3/de not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT1070323B (it) | 1985-03-29 |
| JPS5910336B2 (ja) | 1984-03-08 |
| NL7608508A (nl) | 1977-02-03 |
| DK142765C (nl) | 1981-08-17 |
| DE2634663A1 (de) | 1977-03-17 |
| CH621767A5 (en) | 1981-02-27 |
| SU719491A3 (ru) | 1980-02-29 |
| BE844631A (fr) | 1976-11-16 |
| IL50100A (en) | 1982-02-28 |
| DE2634663C3 (de) | 1980-01-17 |
| IL50100A0 (en) | 1976-09-30 |
| DE2634663B2 (de) | 1979-05-31 |
| FR2319623A1 (fr) | 1977-02-25 |
| DK142765B (da) | 1981-01-19 |
| DK345276A (nl) | 1977-02-02 |
| GB1499094A (en) | 1978-01-25 |
| FR2319623B1 (nl) | 1979-09-28 |
| JPS5217448A (en) | 1977-02-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1121813A (en) | Asymmetric synthesis of chrysanthemate | |
| AOYAMA et al. | New methods and reagents in organic synthesis. 17. Trimethylsilydiazomethane (TMSCHN2) as a stable and safe substitute for hazardous diazomethane. Its application to the Arndt-Eistert synthesis | |
| Uneyama et al. | Tandem alkylation-defluorination reaction: Synthesis of 2-(N-alkyl-N-aryl) amino-3, 3-difluoropropenoates from 2-(N-aryl) imino-3, 3, 3-trifluoropropanoates | |
| Rosen et al. | A convenient assay for the optical purity of monomethyl 3-hydroxypentanedioate | |
| US4029683A (en) | Copper complex | |
| US4197408A (en) | Asymmetric synthesis of alkyl chrysanthemate | |
| US20100168441A1 (en) | Process for production of substituted benzene | |
| US4923999A (en) | Optically active borane complex and a method for producing an optically active alcohol derivative by the use thereof | |
| HU185330B (en) | Process for preparing /+/-4-substituted-2-indazoles | |
| KR20040084915A (ko) | 신규의 보로네이트 에스테르 | |
| US4473709A (en) | Pyrethroid intermediates and process | |
| US4603218A (en) | Asymmetric synthesis of cyclopropanecarboxylate derivatives using chiral copper complex as catalyst | |
| CN116496316A (zh) | 一种氟烯基磷的合成方法 | |
| US3910958A (en) | Process for preparing arylacetic acids and esters thereof | |
| JPH029857A (ja) | ハロスルホンの製造方法 | |
| US5095136A (en) | Method for preparing isoprenoid cyclopropane 1,1-dicarboxylates and derivatives thereof and novel intermediates | |
| TERASHIMA et al. | Synthesis of optically active α-alkyl or α-aryl acids from L-α-amino acids by the use of organocopper reagents | |
| US4515731A (en) | Asymmetric catalysis | |
| USH49H (en) | Process for producing 3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates | |
| JPS599555B2 (ja) | Ｐ− チカンスチリルユウドウタイノ セイゾウホウホウ | |
| CA1084522A (en) | Alkyl 3-cyano-3-(phenoxyphenyl)-2-ketopropionates and their preparation | |
| US4383112A (en) | Chiral amino-alcohol complexes | |
| US4447637A (en) | Epimerization of trans chrysanthemates | |
| US4477679A (en) | Production of alkyl-5-substituted-3-furoate compounds | |
| JPS597135A (ja) | マロン酸エステルの製造法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |