CH627149A5 - Process for the preparation of lower alkyl esters of racemic cis- or trans-3-formyl-2,2-disubstituted-1-cyclopropanecarboxylic acids - Google Patents
Process for the preparation of lower alkyl esters of racemic cis- or trans-3-formyl-2,2-disubstituted-1-cyclopropanecarboxylic acids Download PDFInfo
- Publication number
- CH627149A5 CH627149A5 CH1630677A CH1630677A CH627149A5 CH 627149 A5 CH627149 A5 CH 627149A5 CH 1630677 A CH1630677 A CH 1630677A CH 1630677 A CH1630677 A CH 1630677A CH 627149 A5 CH627149 A5 CH 627149A5
- Authority
- CH
- Switzerland
- Prior art keywords
- ppm
- racemic
- compound
- methyl
- trans
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 22
- 238000002360 preparation method Methods 0.000 title claims description 19
- 230000008569 process Effects 0.000 title claims description 13
- 125000005907 alkyl ester group Chemical group 0.000 title claims description 10
- -1 trans-3-formyl-2,2-disubstituted-1-cyclopropanecarboxylic acids Chemical class 0.000 title description 37
- 150000001875 compounds Chemical class 0.000 claims description 68
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- RLWFMZKPPHHHCB-PWNYCUMCSA-N (1r,2r)-cyclopropane-1,2-dicarboxylic acid Chemical compound OC(=O)[C@@H]1C[C@H]1C(O)=O RLWFMZKPPHHHCB-PWNYCUMCSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 5
- 230000009471 action Effects 0.000 claims description 5
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 5
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- QAKGVPAQOZSDOZ-IUYQGCFVSA-N (1r,2r)-2-(hydroxymethyl)cyclopropane-1-carboxylic acid Chemical compound OC[C@@H]1C[C@H]1C(O)=O QAKGVPAQOZSDOZ-IUYQGCFVSA-N 0.000 claims description 3
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 39
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 37
- 239000002253 acid Substances 0.000 description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 13
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 12
- 229910052753 mercury Inorganic materials 0.000 description 12
- 150000008064 anhydrides Chemical class 0.000 description 11
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- 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 10
- 239000000284 extract Substances 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- 150000005690 diesters Chemical class 0.000 description 8
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 229940126062 Compound A Drugs 0.000 description 7
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 6
- 150000004702 methyl esters Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 229910014033 C-OH Inorganic materials 0.000 description 5
- 229910014570 C—OH Inorganic materials 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 4
- 239000012346 acetyl chloride Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- HCRFKZNNRFJHKW-UHFFFAOYSA-N (2,2-dimethylcyclopropyl)methanol Chemical compound CC1(C)CC1CO HCRFKZNNRFJHKW-UHFFFAOYSA-N 0.000 description 3
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 3
- AIZZFYPYPULRFL-DTWKUNHWSA-N 1-o-tert-butyl 3-o-ethyl (3s,4s)-4-aminopyrrolidine-1,3-dicarboxylate Chemical compound CCOC(=O)[C@H]1CN(C(=O)OC(C)(C)C)C[C@H]1N AIZZFYPYPULRFL-DTWKUNHWSA-N 0.000 description 3
- ZJVMHPVIAUKERS-UHFFFAOYSA-N 2-hexylbutanedioic acid Chemical compound CCCCCCC(C(O)=O)CC(O)=O ZJVMHPVIAUKERS-UHFFFAOYSA-N 0.000 description 3
- FNZSVEHJZREFPF-UHFFFAOYSA-N 2-pentylbutanedioic acid Chemical compound CCCCCC(C(O)=O)CC(O)=O FNZSVEHJZREFPF-UHFFFAOYSA-N 0.000 description 3
- QUQGLWQONNOVTJ-UHFFFAOYSA-N 3,3-diethylcyclopropane-1,2-dicarboxylic acid Chemical compound C(C)C1(C(C1C(=O)O)C(=O)O)CC QUQGLWQONNOVTJ-UHFFFAOYSA-N 0.000 description 3
- MSPJNHHBNOLHOC-UHFFFAOYSA-N 3,3-dimethylcyclopropane-1,2-dicarboxylic acid Chemical compound CC1(C)C(C(O)=O)C1C(O)=O MSPJNHHBNOLHOC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 3
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- LVRUQHVDOPYPPI-RNFRBKRXSA-N (1S,2S)-2-methoxycarbonylspiro[2.4]heptane-1-carboxylic acid Chemical compound COC(=O)[C@H]1[C@@H](C11CCCC1)C(=O)O LVRUQHVDOPYPPI-RNFRBKRXSA-N 0.000 description 2
- NAVMUAYQFUQERP-UHFFFAOYSA-N (2,2-diethylcyclopropyl)methanol Chemical compound CCC1(CC)CC1CO NAVMUAYQFUQERP-UHFFFAOYSA-N 0.000 description 2
- AVWGIXFPIHHWCV-UHFFFAOYSA-N 2,2-diethyl-3-methoxycarbonylcyclopropane-1-carboxylic acid Chemical compound COC(=O)C1C(C1C(=O)O)(CC)CC AVWGIXFPIHHWCV-UHFFFAOYSA-N 0.000 description 2
- GZVJRUASQZSDKH-UHFFFAOYSA-N 3-(hydroxymethyl)-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(CO)C1C(O)=O GZVJRUASQZSDKH-UHFFFAOYSA-N 0.000 description 2
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- QRAKRDZMIONMRZ-UHFFFAOYSA-M cyclohexyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C1CCCCC1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 QRAKRDZMIONMRZ-UHFFFAOYSA-M 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012259 ether extract Substances 0.000 description 2
- PXRHRRHQZZSESU-UHFFFAOYSA-N methyl 2,2-diethyl-3-formylcyclopropane-1-carboxylate Chemical compound CCC1(CC)C(C=O)C1C(=O)OC PXRHRRHQZZSESU-UHFFFAOYSA-N 0.000 description 2
- IGRAMTXKZJINPM-UHFFFAOYSA-M pentan-3-yl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(CC)CC)C1=CC=CC=C1 IGRAMTXKZJINPM-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000006257 total synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VQQJTCQHVJPKIY-RKDXNWHRSA-N (1S,2S)-2-ethoxycarbonylspiro[2.5]octane-1-carboxylic acid Chemical compound C(C)OC(=O)[C@H]1[C@@H](C11CCCCC1)C(=O)O VQQJTCQHVJPKIY-RKDXNWHRSA-N 0.000 description 1
- NKQGMMDAKXWNPX-HTQZYQBOSA-N (1S,2S)-2-methoxycarbonylspiro[2.5]octane-1-carboxylic acid Chemical compound COC(=O)[C@H]1[C@@H](C11CCCCC1)C(=O)O NKQGMMDAKXWNPX-HTQZYQBOSA-N 0.000 description 1
- VOVAKSXCTQYGIH-IUYQGCFVSA-N (1r,2r)-2-formylcyclopropane-1-carboxylic acid Chemical class OC(=O)[C@@H]1C[C@H]1C=O VOVAKSXCTQYGIH-IUYQGCFVSA-N 0.000 description 1
- OVTKAEXICUFZQY-UHFFFAOYSA-N (2,2-diethyl-3-methylcyclopropyl)methanol Chemical compound CC1C(C1CO)(CC)CC OVTKAEXICUFZQY-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VUROAZUCSQPSOK-UHFFFAOYSA-N 1,1-diethylcyclopropane Chemical compound CCC1(CC)CC1 VUROAZUCSQPSOK-UHFFFAOYSA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- WGRVNPSPBGJQRH-UHFFFAOYSA-N 2,2-diethylcyclopropane-1-carbaldehyde Chemical compound CCC1(CC)CC1C=O WGRVNPSPBGJQRH-UHFFFAOYSA-N 0.000 description 1
- PQTDYOQEPYGGHF-UHFFFAOYSA-N 2,2-dimethylcyclopropane-1-carbaldehyde Chemical compound CC1(C)CC1C=O PQTDYOQEPYGGHF-UHFFFAOYSA-N 0.000 description 1
- QAKGVPAQOZSDOZ-UHFFFAOYSA-N 2-(hydroxymethyl)cyclopropane-1-carboxylic acid Chemical compound OCC1CC1C(O)=O QAKGVPAQOZSDOZ-UHFFFAOYSA-N 0.000 description 1
- VOVAKSXCTQYGIH-UHFFFAOYSA-N 2-formylcyclopropane-1-carboxylic acid Chemical class OC(=O)C1CC1C=O VOVAKSXCTQYGIH-UHFFFAOYSA-N 0.000 description 1
- BSGFWDKMEPYNOA-UHFFFAOYSA-N 3-ethoxycarbonyl-2,2-diethylcyclopropane-1-carboxylic acid Chemical compound CCC1(C(C1C(=O)OCC)C(=O)O)CC BSGFWDKMEPYNOA-UHFFFAOYSA-N 0.000 description 1
- QNVOIUHBTIEXDR-UHFFFAOYSA-N 3-ethoxycarbonyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CCOC(=O)C1C(C(O)=O)C1(C)C QNVOIUHBTIEXDR-UHFFFAOYSA-N 0.000 description 1
- NTUIKGUMDLSOBX-UHFFFAOYSA-N 3-hexyloxolane-2,5-dione Chemical compound CCCCCCC1CC(=O)OC1=O NTUIKGUMDLSOBX-UHFFFAOYSA-N 0.000 description 1
- LNIQYJXNDLAPKL-UHFFFAOYSA-N 3-methoxycarbonyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound COC(=O)C1C(C(O)=O)C1(C)C LNIQYJXNDLAPKL-UHFFFAOYSA-N 0.000 description 1
- ACFUDHKIBASUAN-UHFFFAOYSA-N 6,6-diethyl-3-oxabicyclo[3.1.0]hexane-2,4-dione Chemical compound C(C)C1(C2C1C(=O)OC2=O)CC ACFUDHKIBASUAN-UHFFFAOYSA-N 0.000 description 1
- QKAHKEDLPBJLFD-UHFFFAOYSA-N 6,6-dimethyl-3-oxabicyclo[3.1.0]hexane-2,4-dione Chemical compound O=C1OC(=O)C2C1C2(C)C QKAHKEDLPBJLFD-UHFFFAOYSA-N 0.000 description 1
- QNVOIUHBTIEXDR-PHDIDXHHSA-N CCOC(=O)[C@H]1[C@H](C(O)=O)C1(C)C Chemical compound CCOC(=O)[C@H]1[C@H](C(O)=O)C1(C)C QNVOIUHBTIEXDR-PHDIDXHHSA-N 0.000 description 1
- 0 C[C@](C1(*)*)([C@]1(N)[N+]([O-])O1)*1=* Chemical compound C[C@](C1(*)*)([C@]1(N)[N+]([O-])O1)*1=* 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 241000764238 Isis Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical class [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- BFKVXNPJXXJUGQ-UHFFFAOYSA-N [CH2]CCCC Chemical compound [CH2]CCCC BFKVXNPJXXJUGQ-UHFFFAOYSA-N 0.000 description 1
- PQGAHNJECSVDEI-UHFFFAOYSA-N [CH2]CCCCC Chemical compound [CH2]CCCCC PQGAHNJECSVDEI-UHFFFAOYSA-N 0.000 description 1
- BQOWUDKEXDCGQS-UHFFFAOYSA-N [CH]1CCCC1 Chemical compound [CH]1CCCC1 BQOWUDKEXDCGQS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- HXCKCCRKGXHOBK-UHFFFAOYSA-N cycloheptane Chemical compound [CH]1CCCCCC1 HXCKCCRKGXHOBK-UHFFFAOYSA-N 0.000 description 1
- OTYCTZAZOKYGSA-UHFFFAOYSA-N cyclohexylmercury Chemical compound [Hg]C1CCCCC1 OTYCTZAZOKYGSA-UHFFFAOYSA-N 0.000 description 1
- HAHAYKHJHDURJR-UHFFFAOYSA-N cyclopentylmercury Chemical compound C1(CCCC1)[Hg] HAHAYKHJHDURJR-UHFFFAOYSA-N 0.000 description 1
- RLWFMZKPPHHHCB-UHFFFAOYSA-N cyclopropane-1,2-dicarboxylate;hydron Chemical compound OC(=O)C1CC1C(O)=O RLWFMZKPPHHHCB-UHFFFAOYSA-N 0.000 description 1
- JMYVMOUINOAAPA-UHFFFAOYSA-N cyclopropanecarbaldehyde Chemical class O=CC1CC1 JMYVMOUINOAAPA-UHFFFAOYSA-N 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 238000010438 heat treatment Methods 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
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KVSRWNPBUMDYOQ-UHFFFAOYSA-N methyl 3-formyl-2,2-dimethylcyclopropane-1-carboxylate Chemical compound COC(=O)C1C(C=O)C1(C)C KVSRWNPBUMDYOQ-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- PMOIAJVKYNVHQE-UHFFFAOYSA-N phosphanium;bromide Chemical compound [PH4+].[Br-] PMOIAJVKYNVHQE-UHFFFAOYSA-N 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical class [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- HSOZCYIMJQTYEX-UHFFFAOYSA-M triphenyl(propan-2-yl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(C)C)C1=CC=CC=C1 HSOZCYIMJQTYEX-UHFFFAOYSA-M 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH279881A CH627731A5 (en) | 1977-12-30 | 1981-04-29 | Lower alkyl esters of racemic cis- or trans-2,2-disubstituted-3-formylcyclopropane-1-carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7639533A FR2376120A1 (fr) | 1976-12-30 | 1976-12-30 | Procede de preparation d'esters d'alcoyle inferieur d'acides cis ou trans 3-formyl cyclopropane 1-carboxyliques 2,2-disubstitues racemiques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH627149A5 true CH627149A5 (en) | 1981-12-31 |
Family
ID=9181716
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1630677A CH627149A5 (en) | 1976-12-30 | 1977-12-30 | Process for the preparation of lower alkyl esters of racemic cis- or trans-3-formyl-2,2-disubstituted-1-cyclopropanecarboxylic acids |
Country Status (5)
| Country | Link |
|---|---|
| JP (2) | JPS5384947A (en, 2012) |
| BE (1) | BE862461A (en, 2012) |
| CH (1) | CH627149A5 (en, 2012) |
| FR (1) | FR2376120A1 (en, 2012) |
| GB (1) | GB1596030A (en, 2012) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241081A (en) | 1978-10-23 | 1980-12-23 | Shell Oil Company | Cyclopropanecarboxylate pesticides |
| US4258207A (en) | 1978-10-23 | 1981-03-24 | Shell Oil Company | Cyclopropanecarboxylate pesticides preparation |
| US4219562A (en) | 1979-03-08 | 1980-08-26 | Shell Oil Company | 3-(Hydrocarbylthiomethyl)-2,2-dimethylcyclopropanecarboxylate pesticides |
| FR2491921A1 (fr) * | 1980-10-10 | 1982-04-16 | Roussel Uclaf | Nouveaux esters terbutiliques derives de l'acide 2,2-dimethyl cyclopropane 1,3-dicarboxylique, leur preparation et les nouveaux intermediaires obtenus |
| FR2491920A1 (fr) * | 1980-10-10 | 1982-04-16 | Roussel Uclaf | Nouveaux esters methyliques derives de l'acide 2,2-dimethyl cyclopropane 1,3-dicarboxylique, leur preparation et les intermediaires nouveaux obtenus |
| US4487955A (en) * | 1980-10-10 | 1984-12-11 | Roussel Uclaf | Process for preparing cis or trans, optically active monoalkyl esters of cyclopropane-1,3-dicarboxylic acids |
| DE3147105A1 (de) * | 1980-12-01 | 1982-07-01 | Shell Internationale Research Maatschappij B.V., 2596 's-Gravenhage | Verfahren zur herstellung von cyclopropan-derivaten |
| CH694730A5 (de) * | 2000-02-09 | 2005-06-30 | Sumitomo Chemical Co | Verfahren zum Herstellen optisch aktiver Hemiester. |
| AU2003261948A1 (en) * | 2002-09-10 | 2004-04-30 | Sumitomo Chemical Company, Limited | Process for production of 2-(hydroxymethyl)cyclo- propanecarboxylic acids |
| HUP0501182A3 (en) * | 2003-04-24 | 2011-08-29 | Incyte Corp | Aza spiro alkane derivatives as inhibitors of metallproteases and pharmaceutical compositions containing them |
| DE602004030239D1 (de) * | 2003-06-17 | 2011-01-05 | Schering Corp | Verfahren und zwischenprodukte zur herstellung von (1r,2s,5s)-6,6-dimethyl-3-azabicycloä3,1,0 ühexan-2-carboxylaten oder salzen davon |
| CN114456065B (zh) * | 2021-12-23 | 2024-09-13 | 上海璨谊生物科技有限公司 | 一种卡龙酸二酯类化合物及卡龙酸衍生物的合成方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5142101B2 (en, 2012) * | 1972-05-16 | 1976-11-13 |
-
1976
- 1976-12-30 FR FR7639533A patent/FR2376120A1/fr active Granted
-
1977
- 1977-12-28 JP JP15752177A patent/JPS5384947A/ja active Granted
- 1977-12-29 BE BE183959A patent/BE862461A/xx not_active IP Right Cessation
- 1977-12-29 GB GB5417877A patent/GB1596030A/en not_active Expired
- 1977-12-30 CH CH1630677A patent/CH627149A5/fr not_active IP Right Cessation
-
1985
- 1985-11-20 JP JP25881885A patent/JPS61171453A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB1596030A (en) | 1981-08-19 |
| JPS61171453A (ja) | 1986-08-02 |
| FR2376120B1 (en, 2012) | 1980-10-03 |
| JPS5384947A (en) | 1978-07-26 |
| FR2376120A1 (fr) | 1978-07-28 |
| BE862461A (fr) | 1978-06-29 |
| JPS623141B2 (en, 2012) | 1987-01-23 |
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| PL | Patent ceased | ||
| PL | Patent ceased |