CA1121813A - Asymmetric synthesis of chrysanthemate - Google Patents

Asymmetric synthesis of chrysanthemate

Info

Publication number: CA1121813A
Authority: CA; Canada
Prior art keywords: phenyl; amino; group; propanol; butyl
Prior art date: 1975-08-01
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

Application number

CA000258220A

Other languages

English (en)

French (fr)

Inventor

Fumio Fujita

Tadatoshi Aratani

Yukio Yoneyoshi

Tsuneyuki Nagase

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Sumitomo Chemical Co Ltd

Original Assignee

Sumitomo Chemical Co Ltd

Priority date (The priority date 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 date listed.)

1975-08-01

Filing date

1976-07-30

Publication date

1982-04-13

1976-07-30 Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd

1982-04-13 Application granted granted Critical

1982-04-13 Publication of CA1121813A publication Critical patent/CA1121813A/en

Status Expired legal-status Critical Current

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)

CA000258220A 1975-08-01 1976-07-30 Asymmetric synthesis of chrysanthemate Expired CA1121813A (en)

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 (ja)
BE (1)	BE844631A (ja)
CA (1)	CA1121813A (ja)
CH (1)	CH621767A5 (ja)
DE (1)	DE2634663C3 (ja)
DK (1)	DK142765B (ja)
FR (1)	FR2319623A1 (ja)
GB (1)	GB1499094A (ja)
IL (1)	IL50100A (ja)
IT (1)	IT1070323B (ja)
NL (1)	NL7608508A (ja)
SU (1)	SU719491A3 (ja)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
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
EP0024796A1 (en) *	1979-07-13	1981-03-11	Imperial Chemical Industries Plc	Chiral amino-alcohol complexes 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
DE3064018D1 (en) *	1979-07-13	1983-08-11	Ici Plc	Process for the preparation of cyclopropane carboxylic acid esters
EP0024795A1 (en) *	1979-07-13	1981-03-11	Imperial Chemical Industries Plc	Chiral compounds 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)

* Cited by examiner, † Cited by third party
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 FR FR7623388A patent/FR2319623A1/fr active Granted
- 1976-07-30 CA CA000258220A patent/CA1121813A/en not_active Expired
- 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
- 1976-07-30 IT IT68927/76A patent/IT1070323B/it active
- 1976-07-30 NL NL7608508A patent/NL7608508A/xx not_active Application Discontinuation
- 1976-07-30 SU SU762387252A patent/SU719491A3/ru active
- 1976-07-30 GB GB31985/76A patent/GB1499094A/en not_active Expired
- 1976-08-02 DE DE2634663A patent/DE2634663C3/de not_active Expired

Also Published As

Publication number	Publication date
DE2634663B2 (de)	1979-05-31
DK345276A (ja)	1977-02-02
IL50100A0 (en)	1976-09-30
IT1070323B (it)	1985-03-29
FR2319623B1 (ja)	1979-09-28
JPS5910336B2 (ja)	1984-03-08
DE2634663C3 (de)	1980-01-17
DE2634663A1 (de)	1977-03-17
SU719491A3 (ru)	1980-02-29
DK142765C (ja)	1981-08-17
FR2319623A1 (fr)	1977-02-25
JPS5217448A (en)	1977-02-09
CH621767A5 (en)	1981-02-27
GB1499094A (en)	1978-01-25
IL50100A (en)	1982-02-28
NL7608508A (nl)	1977-02-03
BE844631A (fr)	1976-11-16
DK142765B (da)	1981-01-19

Legal Events

Date	Code	Title	Description
1999-04-13	MKEX	Expiry

Publication	Publication Date	Title
CA1121813A (en)	1982-04-13	Asymmetric synthesis of chrysanthemate
AOYAMA et al.	1981	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.	1996	Tandem alkylation-defluorination reaction: Synthesis of 2-(N-alkyl-N-aryl) amino-3, 3-difluoropropenoates from 2-(N-aryl) imino-3, 3, 3-trifluoropropanoates
WO2021212734A1 (zh)	2021-10-28	氮杂环卡宾基混配型镍 (ii) 配合物在合成 2- 直链烷基苯并噻唑类化合物反应中的应用
Rosen et al.	1984	A convenient assay for the optical purity of monomethyl 3-hydroxypentanedioate
US4107439A (en)	1978-08-15	Process for preparing arylalkanoic acid derivatives
US4197408A (en)	1980-04-08	Asymmetric synthesis of alkyl chrysanthemate
US20100168441A1 (en)	2010-07-01	Process for production of substituted benzene
US4923999A (en)	1990-05-08	Optically active borane complex and a method for producing an optically active alcohol derivative by the use thereof
HU185330B (en)	1985-01-28	Process for preparing /+/-4-substituted-2-indazoles
KR20040084915A (ko)	2004-10-06	신규의 보로네이트 에스테르
US4473709A (en)	1984-09-25	Pyrethroid intermediates and process
US4603218A (en)	1986-07-29	Asymmetric synthesis of cyclopropanecarboxylate derivatives using chiral copper complex as catalyst
CN116496316A (zh)	2023-07-28	一种氟烯基磷的合成方法
US3910958A (en)	1975-10-07	Process for preparing arylacetic acids and esters thereof
JPH029857A (ja)	1990-01-12	ハロスルホンの製造方法
TERASHIMA et al.	1979	Synthesis of optically active α-alkyl or α-aryl acids from L-α-amino acids by the use of organocopper reagents
KR20080073658A (ko)	2008-08-11	4차 탄소 상에 트리플루오로메틸기를 함유하는 유기화합물의 제조
US4515731A (en)	1985-05-07	Asymmetric catalysis
USH49H (en)	1986-04-01	Process for producing 3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylates
JPS599555B2 (ja)	1984-03-03	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)	1980-08-26	Alkyl 3-cyano-3-(phenoxyphenyl)-2-ketopropionates and their preparation
US4383112A (en)	1983-05-10	Chiral amino-alcohol complexes
US4447637A (en)	1984-05-08	Epimerization of trans chrysanthemates
US4477679A (en)	1984-10-16	Production of alkyl-5-substituted-3-furoate compounds