JPS6139934B2 - - Google Patents
Info
- Publication number
- JPS6139934B2 JPS6139934B2 JP52157520A JP15752077A JPS6139934B2 JP S6139934 B2 JPS6139934 B2 JP S6139934B2 JP 52157520 A JP52157520 A JP 52157520A JP 15752077 A JP15752077 A JP 15752077A JP S6139934 B2 JPS6139934 B2 JP S6139934B2
- Authority
- JP
- Japan
- Prior art keywords
- dimethoxyethane
- trans
- ethyl
- dicarboxylate
- racemic
- 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
- 238000000034 method Methods 0.000 claims description 31
- -1 2,2-disubstituted trans-cyclopropane-1,3-dicarboxylic acid Chemical class 0.000 claims description 30
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 30
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 24
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003791 organic solvent mixture Substances 0.000 claims description 6
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 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 1
- 150000001875 compounds Chemical class 0.000 description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 21
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 20
- 238000003756 stirring Methods 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- 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 8
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 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 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 5
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 150000001299 aldehydes Chemical class 0.000 description 4
- 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 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- MSPJNHHBNOLHOC-QWWZWVQMSA-N (1s,2s)-3,3-dimethylcyclopropane-1,2-dicarboxylic acid Chemical compound CC1(C)[C@@H](C(O)=O)[C@@H]1C(O)=O MSPJNHHBNOLHOC-QWWZWVQMSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000012259 ether extract Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- MPNQDJZRGAOBPW-UHFFFAOYSA-M triphenyl(propyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 MPNQDJZRGAOBPW-UHFFFAOYSA-M 0.000 description 3
- DDMOZUBZYFKJDS-UHFFFAOYSA-N triphenyl(propylidene)-$l^{5}-phosphane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=CCC)C1=CC=CC=C1 DDMOZUBZYFKJDS-UHFFFAOYSA-N 0.000 description 3
- 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 2
- IHDRXDWUDBSDAN-UHFFFAOYSA-N 2-diazopropane Chemical compound CC(C)=[N+]=[N-] IHDRXDWUDBSDAN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- WZYWSVSFFTZZPE-UHFFFAOYSA-M cyclopentyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C1CCCC1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WZYWSVSFFTZZPE-UHFFFAOYSA-M 0.000 description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- PQUNDWWERWQRQT-UHFFFAOYSA-N diphenyl(propan-2-yl)sulfanium Chemical compound C=1C=CC=CC=1[S+](C(C)C)C1=CC=CC=C1 PQUNDWWERWQRQT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005406 washing Methods 0.000 description 2
- 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 1
- HAJBDAKAEJHSED-RNFRBKRXSA-N (1S,2S)-spiro[2.5]octane-1,2-dicarboxylic acid Chemical compound [C@@H]1([C@@H](C12CCCCC2)C(=O)O)C(=O)O HAJBDAKAEJHSED-RNFRBKRXSA-N 0.000 description 1
- AVWGIXFPIHHWCV-RNFRBKRXSA-N (1S,3S)-2,2-diethyl-3-methoxycarbonylcyclopropane-1-carboxylic acid Chemical compound CCC1([C@H]([C@@H]1C(=O)OC)C(=O)O)CC AVWGIXFPIHHWCV-RNFRBKRXSA-N 0.000 description 1
- BSGFWDKMEPYNOA-HTQZYQBOSA-N (1S,3S)-3-ethoxycarbonyl-2,2-diethylcyclopropane-1-carboxylic acid Chemical compound C(C)OC(=O)[C@@H]1C([C@H]1C(=O)O)(CC)CC BSGFWDKMEPYNOA-HTQZYQBOSA-N 0.000 description 1
- 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 1
- WNXVEFMOQSAQJV-UHFFFAOYSA-N 1-methyl-4-propan-2-ylsulfinylbenzene Chemical compound CC(C)S(=O)C1=CC=C(C)C=C1 WNXVEFMOQSAQJV-UHFFFAOYSA-N 0.000 description 1
- KQBWBGCGYFAUCN-UHFFFAOYSA-N 2-(2-ethoxy-2-oxoethyl)heptanoic acid Chemical compound CCCCCC(C(O)=O)CC(=O)OCC KQBWBGCGYFAUCN-UHFFFAOYSA-N 0.000 description 1
- FRSAPRKXSWUGEJ-UHFFFAOYSA-N 2-(2-methoxy-2-oxoethyl)octanoic acid Chemical compound CCCCCCC(C(O)=O)CC(=O)OC FRSAPRKXSWUGEJ-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
- 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
- BRTOZTJYVGGLOX-UHFFFAOYSA-N CN(C)C1=C(C=CC(=C1)[S+]=O)C Chemical compound CN(C)C1=C(C=CC(=C1)[S+]=O)C BRTOZTJYVGGLOX-UHFFFAOYSA-N 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
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- MPRMNWDIYNBXRC-HTQZYQBOSA-N diethyl (1s,2s)-3,3-dimethylcyclopropane-1,2-dicarboxylate Chemical compound CCOC(=O)[C@H]1[C@H](C(=O)OCC)C1(C)C MPRMNWDIYNBXRC-HTQZYQBOSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- DFKFOZAZBDPTPB-UHFFFAOYSA-M diphenyl(propan-2-yl)sulfanium;iodide Chemical compound [I-].C=1C=CC=CC=1[S+](C(C)C)C1=CC=CC=C1 DFKFOZAZBDPTPB-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- FIMAYKDZLLQUDW-UHFFFAOYSA-N fluoro(dioxido)borane;trimethyloxidanium Chemical compound C[O+](C)C.C[O+](C)C.[O-]B([O-])F FIMAYKDZLLQUDW-UHFFFAOYSA-N 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- IETUTOPPRNJSGW-UHFFFAOYSA-N imino-(4-methylphenyl)-oxo-propan-2-yl-lambda6-sulfane Chemical compound C(C)(C)S(=O)(=N)C1=CC=C(C=C1)C IETUTOPPRNJSGW-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- NYEFUKPRSIREFK-UHFFFAOYSA-N lithium;dichloromethane Chemical compound [Li+].Cl[CH-]Cl NYEFUKPRSIREFK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- UNCDTOWUBXXLHM-UHFFFAOYSA-M pentan-2-yl(triphenyl)phosphanium iodide Chemical compound [I-].C1(=CC=CC=C1)[P+](C(C)CCC)(C1=CC=CC=C1)C1=CC=CC=C1 UNCDTOWUBXXLHM-UHFFFAOYSA-M 0.000 description 1
- MGHBEFDWKZMKBL-UHFFFAOYSA-M pentan-3-yl(triphenyl)phosphanium;bromide Chemical group [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C(CC)CC)C1=CC=CC=C1 MGHBEFDWKZMKBL-UHFFFAOYSA-M 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006257 total synthesis reaction Methods 0.000 description 1
- MSXNDXIAUQJHNS-UHFFFAOYSA-N triphenyl(propyl)phosphanium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCC)C1=CC=CC=C1 MSXNDXIAUQJHNS-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more PâC bonds
- C07F9/535—Organo-phosphoranes
- C07F9/5352—Phosphoranes containing the structure P=C-
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more PâC bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã
æ¬çºæã®äž»é¡ã¯ãã©ã»ãïŒã»ïŒâãžçœ®ætrans
âã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žã®äœçŽ
ã¢ã«ãã«ãšã¹ãã«ã®æ°èŠãªè£œé æ³ã«ããã
âã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žã®äœçŽ
ã¢ã«ãã«ãšã¹ãã«ã®æ°èŠãªè£œé æ³ã«ããã
ããã«è©³ããã¯ãæ¬çºæã®äž»é¡ã¯ã次ã®äžè¬åŒ
ïŒããã§ïŒ²ã¯ïŒãïŒåã®ççŽ ååãå«æããã¢ã«
ãã«åºãè¡šãããã¯ïŒãïŒåã®ççŽ ååãå«æ
ããã¢ã«ãã«åºãè¡šãããåã¯ïŒåã®ïŒžåºã¯ãã
ãã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠïŒãïŒ
åã®ççŽ ååãå«æããã·ã¯ãã¢ã«ãã«åºãè¡šã
ãïŒ ã®ã©ã»ãïŒã»ïŒâãžçœ®ætransâã·ã¯ããããã³
âïŒã»ïŒâãžã«ã«ãã³é žã®äœçŽã¢ã«ãã«ãšã¹ãã«
ã®è£œé æ³ã§ãã€ãŠãææ©æº¶åªåã¯ææ¶æ··åç©äžã§
匷塩åºã®ååšäžã«æ¬¡åŒ ïŒããã§ïŒ²ã¯åèšã®æå³ãæããïŒ ã®ããã«é žã¢ã«ãã«åã¯ãã¬ã€ã³é žã¢ã«ãã«ã次
åŒ ïŒããã§ïŒžã¯åèšã®æå³ãæããHalã¯å¡©çŽ ãè
çŽ åã¯ããçŽ ååãè¡šããïŒ ã®ããã²ã³åããªããšãã«ãã¹ãããŠã ãšåå¿ã
ããããšãç¹åŸŽãšãããã®ã§ããã
ïŒããã§ïŒ²ã¯ïŒãïŒåã®ççŽ ååãå«æããã¢ã«
ãã«åºãè¡šãããã¯ïŒãïŒåã®ççŽ ååãå«æ
ããã¢ã«ãã«åºãè¡šãããåã¯ïŒåã®ïŒžåºã¯ãã
ãã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠïŒãïŒ
åã®ççŽ ååãå«æããã·ã¯ãã¢ã«ãã«åºãè¡šã
ãïŒ ã®ã©ã»ãïŒã»ïŒâãžçœ®ætransâã·ã¯ããããã³
âïŒã»ïŒâãžã«ã«ãã³é žã®äœçŽã¢ã«ãã«ãšã¹ãã«
ã®è£œé æ³ã§ãã€ãŠãææ©æº¶åªåã¯ææ¶æ··åç©äžã§
匷塩åºã®ååšäžã«æ¬¡åŒ ïŒããã§ïŒ²ã¯åèšã®æå³ãæããïŒ ã®ããã«é žã¢ã«ãã«åã¯ãã¬ã€ã³é žã¢ã«ãã«ã次
åŒ ïŒããã§ïŒžã¯åèšã®æå³ãæããHalã¯å¡©çŽ ãè
çŽ åã¯ããçŽ ååãè¡šããïŒ ã®ããã²ã³åããªããšãã«ãã¹ãããŠã ãšåå¿ã
ããããšãç¹åŸŽãšãããã®ã§ããã
ãã®æ¹æ³ã¯ãäžèšã®ååŠåŒã«ããäŸç€ºãã
ãã
ãã
åèšã®åŒã«ãããŠãã¯äŸãã°ãã¡ãã«ããš
ãã«ãçŽéè¥ããã¯åæéãããã«ãçŽéè¥ãã
ã¯åæéããã«ãçŽéè¥ããã¯åæéãã³ãã«å
ã¯çŽéè¥ããã¯åæéããã·ã«åºãè¡šãããæã
ã¯ïŒåã®ïŒžåºã¯ãããã®çµåããŠããççŽ ååãš
äžç·ã«ãªã€ãŠã·ã¯ããããã«ãã·ã¯ãããã«ãã·
ã¯ããã³ãã«ãã·ã¯ãããã·ã«åã¯ã·ã¯ãããã
ã«åºãè¡šãããã¯ã¡ãã«ããšãã«ãçŽéè¥ãã
ã¯åæéãããã«ãçŽéè¥ããã¯åæéããã«ã
çŽéè¥ããã¯åæéãã³ãã«åã¯çŽéè¥ããã¯å
æéããã·ã«åºãè¡šããã
ãã«ãçŽéè¥ããã¯åæéãããã«ãçŽéè¥ãã
ã¯åæéããã«ãçŽéè¥ããã¯åæéãã³ãã«å
ã¯çŽéè¥ããã¯åæéããã·ã«åºãè¡šãããæã
ã¯ïŒåã®ïŒžåºã¯ãããã®çµåããŠããççŽ ååãš
äžç·ã«ãªã€ãŠã·ã¯ããããã«ãã·ã¯ãããã«ãã·
ã¯ããã³ãã«ãã·ã¯ãããã·ã«åã¯ã·ã¯ãããã
ã«åºãè¡šãããã¯ã¡ãã«ããšãã«ãçŽéè¥ãã
ã¯åæéãããã«ãçŽéè¥ããã¯åæéããã«ã
çŽéè¥ããã¯åæéãã³ãã«åã¯çŽéè¥ããã¯å
æéããã·ã«åºãè¡šããã
æ¬çºæã®æ¹æ³ã«ãã補é ã§ããäžè¬åŒã®åå
ç©ã®äžã§ããç¹ã«ãã©ã»ãtransâïŒã»ïŒâãžã¡
ãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ã
ã«ãã©ã»ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ããã
ãã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãã©ã»ã
transâïŒã»ïŒâãžãšãã«ã·ã¯ããããã³âïŒã»
ïŒâãžã«ã«ãã³é žã¡ãã«ãã©ã»ãtransâïŒã»ïŒ
âãžãšãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³
é žãšãã«ãã©ã»ãtransâã¹ãããïŒã»ïŒããã
ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ãã©ã»ã
transâã¹ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãž
ã«ã«ãã³é žãšãã«ãã©ã»ãtransâã¹ãããïŒã»
ïŒããªã¯ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«åã³
ã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿ã³âïŒã»
ïŒâãžã«ã«ãã³é žãšãã«ããããããã
ç©ã®äžã§ããç¹ã«ãã©ã»ãtransâïŒã»ïŒâãžã¡
ãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ã
ã«ãã©ã»ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ããã
ãã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãã©ã»ã
transâïŒã»ïŒâãžãšãã«ã·ã¯ããããã³âïŒã»
ïŒâãžã«ã«ãã³é žã¡ãã«ãã©ã»ãtransâïŒã»ïŒ
âãžãšãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³
é žãšãã«ãã©ã»ãtransâã¹ãããïŒã»ïŒããã
ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ãã©ã»ã
transâã¹ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãž
ã«ã«ãã³é žãšãã«ãã©ã»ãtransâã¹ãããïŒã»
ïŒããªã¯ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«åã³
ã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿ã³âïŒã»
ïŒâãžã«ã«ãã³é žãšãã«ããããããã
ããã«é
žãšã¹ãã«åã¯ãã¬ã€ã³é
žãšã¹ãã«ãšã
ãã²ã³åãã¹ãããŠã ãšã®çž®åãè¡ãªãéã«ååš
ããã匷塩åºã¯ã奜ãŸããã¯ãã¢ã«ã«ãªã¢ã«ã³ã©
ãŒããæ°ŽçŽ åã¢ã«ã«ãªãã¢ã«ã«ãªã¢ããåã³ã¢ã«
ãã«ãªããŠã èªå°äœãããªã矀ããéžã°ããã
ãã²ã³åãã¹ãããŠã ãšã®çž®åãè¡ãªãéã«ååš
ããã匷塩åºã¯ã奜ãŸããã¯ãã¢ã«ã«ãªã¢ã«ã³ã©
ãŒããæ°ŽçŽ åã¢ã«ã«ãªãã¢ã«ã«ãªã¢ããåã³ã¢ã«
ãã«ãªããŠã èªå°äœãããªã矀ããéžã°ããã
æ¬çºæã®è£œé æ³ãå®æœãã奜ãŸããæ¹æ³ã«ãã
ã°ããã®åŒ·å¡©åºã¯ããã«ãªããŠã ã§ããããã«é ž
ãšã¹ãã«åã¯ãã¬ã€ã³é žãšã¹ãã«ãšããã²ã³åã
ã¹ãããŠã ãšã®çž®åãè¡ãªãéã«ååšãããææ©
溶åªåã¯ææ©æº¶åªæ··åç©ã¯å¥œãŸããã¯ãžã¡ãã«ã¹
ã«ããã·ãããžã¡ããã·ãšã¿ã³ããžã¡ãã«ãã«ã
ã¢ããããããµã¡ãã«ãã¹ãã«ããªã¢ãããèèª
æçåæ°ŽçŽ ãè³éŠæåç°åŒçåæ°ŽçŽ ãã·ã¯ãã¢ã«
ã«ã³åã¯ãããã®æº¶åªã®æ··åç©ãããªã矀ããéž
ã°ããã
ã°ããã®åŒ·å¡©åºã¯ããã«ãªããŠã ã§ããããã«é ž
ãšã¹ãã«åã¯ãã¬ã€ã³é žãšã¹ãã«ãšããã²ã³åã
ã¹ãããŠã ãšã®çž®åãè¡ãªãéã«ååšãããææ©
溶åªåã¯ææ©æº¶åªæ··åç©ã¯å¥œãŸããã¯ãžã¡ãã«ã¹
ã«ããã·ãããžã¡ããã·ãšã¿ã³ããžã¡ãã«ãã«ã
ã¢ããããããµã¡ãã«ãã¹ãã«ããªã¢ãããèèª
æçåæ°ŽçŽ ãè³éŠæåç°åŒçåæ°ŽçŽ ãã·ã¯ãã¢ã«
ã«ã³åã¯ãããã®æº¶åªã®æ··åç©ãããªã矀ããéž
ã°ããã
æ¬çºæã®è£œé æ³ãå®æœããã®ã«å¥œãŸããæ¹æ³ã«
ããã°ãææ©æº¶åªæ··åç©ã¯ããžã¡ããã·ãšã¿ã³ãš
ãã³ã¿ã³ãšã®æ··åç©ã§ããã
ããã°ãææ©æº¶åªæ··åç©ã¯ããžã¡ããã·ãšã¿ã³ãš
ãã³ã¿ã³ãšã®æ··åç©ã§ããã
ç¹ã«æçãªçµæã¯ã匷塩åºãããã«ãªããŠã ã§
ããäžã€ææ©æº¶åªæ··åç©ããã³ã¿ã³ãšãžã¡ããã·
ãšã¿ã³ãšã®æ··åç©ã§ãããšãã«åŸãããã
ããäžã€ææ©æº¶åªæ··åç©ããã³ã¿ã³ãšãžã¡ããã·
ãšã¿ã³ãšã®æ··åç©ã§ãããšãã«åŸãããã
ãã®æ··åç©ãšããã«ãªããŠã ãçšããããå Žå
ã«ã¯ã䟿å©ãªå®æœæ æ§ã¯ããã¹ãããŠã å¡©ã®ãžã¡
ããã·ãšã¿ã³æžæ¿æ¶²åã¯æº¶æ¶²äžã«ããã«ãªããŠã
ã®ãã³ã¿ã³æº¶æ¶²ãçŽïŒâã§åŸã ã«å°å ¥ããããšã
ããªãããã®å Žåã«ã¯ã奜ãŸããã¯ãããã«é žãš
ã¹ãã«ïŒã¢ã«ã«å¯ŸããŠ1.2ã1.6ã¢ã«çšåºŠã®éå°ã®
ãã¹ãããŠã å¡©åã³ããã«é žãšã¹ãã«åã¯ãã¬ã€
ã³é žãšã¹ãã«ïŒã¢ã«ã«å¯ŸããŠ1.1ã1.5ã¢ã«çšåºŠã®
éå°ã®ããã«ãªããŠã ãçšããããã
ã«ã¯ã䟿å©ãªå®æœæ æ§ã¯ããã¹ãããŠã å¡©ã®ãžã¡
ããã·ãšã¿ã³æžæ¿æ¶²åã¯æº¶æ¶²äžã«ããã«ãªããŠã
ã®ãã³ã¿ã³æº¶æ¶²ãçŽïŒâã§åŸã ã«å°å ¥ããããšã
ããªãããã®å Žåã«ã¯ã奜ãŸããã¯ãããã«é žãš
ã¹ãã«ïŒã¢ã«ã«å¯ŸããŠ1.2ã1.6ã¢ã«çšåºŠã®éå°ã®
ãã¹ãããŠã å¡©åã³ããã«é žãšã¹ãã«åã¯ãã¬ã€
ã³é žãšã¹ãã«ïŒã¢ã«ã«å¯ŸããŠ1.1ã1.5ã¢ã«çšåºŠã®
éå°ã®ããã«ãªããŠã ãçšããããã
ããã«é
žã¢ã«ãã«ã¯ãæ¬çºæã®æ¹æ³ã®åå¿ã®å
š
ãŠã«ãããŠãçæãšã¹ãã«ã®åçåã³ç¹è³ªã®ç¹
ã§äœãå€æŽãªã察å¿ãããã¬ã€ã³é žã¢ã«ãã«ã«ã
ã€ãŠçœ®ãæããããšãã§ãããã€ãªãã補é ãã
ã匷塩åºã®ååšäžã§ã¯ãã¬ã€ã³é žãšã¹ãã«ã¯ãã
ã«é žãšã¹ãã«ã«å®éçã«ç°æ§åããããã®ãšæã
ããã
ãŠã«ãããŠãçæãšã¹ãã«ã®åçåã³ç¹è³ªã®ç¹
ã§äœãå€æŽãªã察å¿ãããã¬ã€ã³é žã¢ã«ãã«ã«ã
ã€ãŠçœ®ãæããããšãã§ãããã€ãªãã補é ãã
ã匷塩åºã®ååšäžã§ã¯ãã¬ã€ã³é žãšã¹ãã«ã¯ãã
ã«é žãšã¹ãã«ã«å®éçã«ç°æ§åããããã®ãšæã
ããã
æ¬çºæã®æ¹æ³ã¯ã容æã«å
¥æã§ããååç©ãã
åºçºãäžã€å·¥æ¥åã®å®¹æãªå®æœæ¹åŒã«ãã€ãŠãäž
è¬åŒã®å šåæãäžæ®µéã§éæããããã
åºçºãäžã€å·¥æ¥åã®å®¹æãªå®æœæ¹åŒã«ãã€ãŠãäž
è¬åŒã®å šåæãäžæ®µéã§éæããããã
ãã¡ãã«åºãè¡šããäžè¬åŒã®ãžãšã¹ãã«ã
å³ã¡ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ããããã³
âïŒã»ïŒâãžã«ã«ãã³é žäœçŽã¢ã«ãã«ã補é ãã
æ¹æ³ã¯æ¢ã«ååšããŠãããããããªãããããã
ã®æ¹æ³ã¯ãæ¬çºæã®æ¹æ³ãšã¯éåžžã«ç°ãªã€ãåå¿
åçãçšãããã®ã§ãã€ãŠãæ¬çºæãšæ¯èŒããŠå€§
ããªäžå©çãæäŸãããã®ã§ãã€ãã
å³ã¡ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ããããã³
âïŒã»ïŒâãžã«ã«ãã³é žäœçŽã¢ã«ãã«ã補é ãã
æ¹æ³ã¯æ¢ã«ååšããŠãããããããªãããããã
ã®æ¹æ³ã¯ãæ¬çºæã®æ¹æ³ãšã¯éåžžã«ç°ãªã€ãåå¿
åçãçšãããã®ã§ãã€ãŠãæ¬çºæãšæ¯èŒããŠå€§
ããªäžå©çãæäŸãããã®ã§ãã€ãã
P.C.GuhaãD.K.Sankaraäž¡æ°ã«ããèšèŒãã
ãæ¹æ³ãBer.70Bã1683âïŒïŒ1937ïŒãã¯ãäºã€
ã®åå¿æ®µéãå³ã¡â18âã§ãžã¡ãã«ãžã¢ãŸã¡ã¿ã³
ãšããã«é žãšã¹ãã«ãšãçž®åããã次ãã§çãã
çž®åçæç©ã250âã«å ç±ããããšãå å«ãã
ããããããå·¥æ¥åããã®ãå°é£ãªè©Šå€ïŒãžã¡ã
ã«ãžã¢ãŸã¡ã¿ã³ïŒãšæäœæ¡ä»¶ïŒ250âãŸã§å ç±ã
ãããšïŒãçšãããã®ã§ãããããã«ããã®æ¹æ³
ã®ç·åçã¯æ®éã§ããã
ãæ¹æ³ãBer.70Bã1683âïŒïŒ1937ïŒãã¯ãäºã€
ã®åå¿æ®µéãå³ã¡â18âã§ãžã¡ãã«ãžã¢ãŸã¡ã¿ã³
ãšããã«é žãšã¹ãã«ãšãçž®åããã次ãã§çãã
çž®åçæç©ã250âã«å ç±ããããšãå å«ãã
ããããããå·¥æ¥åããã®ãå°é£ãªè©Šå€ïŒãžã¡ã
ã«ãžã¢ãŸã¡ã¿ã³ïŒãšæäœæ¡ä»¶ïŒ250âãŸã§å ç±ã
ãããšïŒãçšãããã®ã§ãããããã«ããã®æ¹æ³
ã®ç·åçã¯æ®éã§ããã
ãŸããE.J.CoreyãM.Jautelatäž¡æ°ã«ããèšèŒ
ãããæ¹æ³ãã»Am.Chem.Soc.89ïŒ15ïŒã3912
â14ïŒã¯ãã€ãœãããã«ãžããšãã«ã¹ã«ãããŠã
ã€ãªããšããã«é žãšã¹ãã«ãâ70âã§åå¿ããã
ããšãããªãã
ãããæ¹æ³ãã»Am.Chem.Soc.89ïŒ15ïŒã3912
â14ïŒã¯ãã€ãœãããã«ãžããšãã«ã¹ã«ãããŠã
ã€ãªããšããã«é žãšã¹ãã«ãâ70âã§åå¿ããã
ããšãããªãã
ããããã€ãœãããã«ãžããšãã«ã¹ã«ãããŠã
ã€ãªããåŸãããã«ã¯ããžããšãã«ã¹ã«ãã€ããš
ãã«ãªãã»ãé žããªãšãã«ãªããœããŠã ãåå¿ã
ããçãããã«ãªãã»ãé žãžããšãã«ã¹ã«ãããŠ
ã ã«ãå¡©åã¡ãã¬ã³ãšãªããŠã ãžã€ãœãããã«ã¢
ãããšã®äœçšã«ãããã®å Žã§åœ¢æããããžã¯ãã«
ã¡ãã«ãªããŠã ãäœçšããã次ãã§ããåã¡ãã«
ãäœçšãããŠããåãžããšãã«ã€ãœãããã«ã¹ã«
ãããŠã ãåŸãããã«ãªããŠã ãžã€ãœãããã«ã¢
ãããäœçšãããããšãããªããããããã®åå¿
ã¯ã©ããâ50ãâ70âã§è¡ãªãããã
ã€ãªããåŸãããã«ã¯ããžããšãã«ã¹ã«ãã€ããš
ãã«ãªãã»ãé žããªãšãã«ãªããœããŠã ãåå¿ã
ããçãããã«ãªãã»ãé žãžããšãã«ã¹ã«ãããŠ
ã ã«ãå¡©åã¡ãã¬ã³ãšãªããŠã ãžã€ãœãããã«ã¢
ãããšã®äœçšã«ãããã®å Žã§åœ¢æããããžã¯ãã«
ã¡ãã«ãªããŠã ãäœçšããã次ãã§ããåã¡ãã«
ãäœçšãããŠããåãžããšãã«ã€ãœãããã«ã¹ã«
ãããŠã ãåŸãããã«ãªããŠã ãžã€ãœãããã«ã¢
ãããäœçšãããããšãããªããããããã®åå¿
ã¯ã©ããâ50ãâ70âã§è¡ãªãããã
ãŸãããã®çš®ã®æ¹æ³ã¯ãå®æœã«å¿
èŠãšãããäœ
ã枩床䞊ã³ã«æ¬çºæã®æ¹æ³ã®ããã€ãªããããã
ã€ãšè£œé ããã®ãå°é£ãªåºçºã€ãªããåŸãããšã®
å°é£æ§ã®äºã€ã®çç±ããå·¥æ¥åããã®ã«çµè²»ãã
ããäžã€å°é£ã䌎ãªãããšãããã€ãã
ã枩床䞊ã³ã«æ¬çºæã®æ¹æ³ã®ããã€ãªããããã
ã€ãšè£œé ããã®ãå°é£ãªåºçºã€ãªããåŸãããšã®
å°é£æ§ã®äºã€ã®çç±ããå·¥æ¥åããã®ã«çµè²»ãã
ããäžã€å°é£ã䌎ãªãããšãããã€ãã
C.R.JohnsonãE.R.Janigaäž¡æ°ã«ããèšèŒãã
ãæ¹æ³ãJ.Am.Chem.Soc.95ïŒ23ïŒã1973ãp76â
92ïŒã¯ãïœâããªã«ã€ãœãããã«ã¹ã«ããã·ãã
ãããªãŠã ã¢ãžããšåå¿ãããçããã€ãœããã
ã«ïœâããªã«ã¹ã«ããã·ã€ãã³ããã«ãªãã»ãé ž
ããªã¡ãã«ãªããœããŠã ãšåå¿ããããã«ãªãã»
ãé žãžã¡ãã«ã¢ããã€ãœãããã«ïœâããªã«ã¹ã«
ãããœããŠã ã«ãããªãŠã ã¢ãããšãžã¡ãã«ãã«
ã ã¢ãããäœçšããã次ãã§åŸããããžã¡ãã«ã¢
ããïœâããªã«ãªããœã¹ã«ãããŠã ãšããªããã
ãã«é žãžã¡ãã«ãšåå¿ãããããšãããªãããã®
æ¹æ³ã¯ãæ¬çºæã®æ¹æ³ãããæããã«éåžžã«è€é
ã§ãããçµè²»ããããã
ãæ¹æ³ãJ.Am.Chem.Soc.95ïŒ23ïŒã1973ãp76â
92ïŒã¯ãïœâããªã«ã€ãœãããã«ã¹ã«ããã·ãã
ãããªãŠã ã¢ãžããšåå¿ãããçããã€ãœããã
ã«ïœâããªã«ã¹ã«ããã·ã€ãã³ããã«ãªãã»ãé ž
ããªã¡ãã«ãªããœããŠã ãšåå¿ããããã«ãªãã»
ãé žãžã¡ãã«ã¢ããã€ãœãããã«ïœâããªã«ã¹ã«
ãããœããŠã ã«ãããªãŠã ã¢ãããšãžã¡ãã«ãã«
ã ã¢ãããäœçšããã次ãã§åŸããããžã¡ãã«ã¢
ããïœâããªã«ãªããœã¹ã«ãããŠã ãšããªããã
ãã«é žãžã¡ãã«ãšåå¿ãããããšãããªãããã®
æ¹æ³ã¯ãæ¬çºæã®æ¹æ³ãããæããã«éåžžã«è€é
ã§ãããçµè²»ããããã
ããã«ãæ¬çºæã®æ¹æ³ã¯ãã¡ãã«åºãšç°ãªã€ã
åçš®ã®åºã«ããïŒäœçœ®ã眮æãããäžè¬åŒã®ãž
ãšã¹ãã«ãåŸãã®ãå¯èœã«ãããã®ã§ãåèšã®æ¹
æ³ãããäžè¬çç¹è³ªãæããã
åçš®ã®åºã«ããïŒäœçœ®ã眮æãããäžè¬åŒã®ãž
ãšã¹ãã«ãåŸãã®ãå¯èœã«ãããã®ã§ãåèšã®æ¹
æ³ãããäžè¬çç¹è³ªãæããã
æ¬çºæã®æ¹æ³ã«ããåŸãããããçš®ã®ååç©
ïŒïŒãäŸãã°transâïŒã»ïŒâãžã¡ãã«ã·ã¯ãã
ããã³âïŒã»ïŒâãžã«ã«ãã³é žãžãšãã«ã¯ãæ¢ç¥
ã®ååç©ã§ãããæ¬çºæã®æ¹æ³ã«ãã補é ã§ãã
ãããã®æ¢ç¥ã®ååç©ïŒïŒäžŠã³ã«æ°èŠãªååç©
ïŒïŒã¯ã次ã®äžè¬åŒA ã®cisåã¯transæ§é ã®ã¢ã«ãããã®è£œé ã«ç¹ã«æ
çšã§ããããããã®ã¢ã«ãããèªäœã¯ããŠã€ãã
ããåå¿ã«ãã€ãŠãéåžžã«å€ãã®ã·ã¯ããããã³
ã«ã«ãã³é žã§ãã€ãŠãã®ãšã¹ãã«ã殺è«æ§ãä»äž
ãããŠãããã®ã®è£œé ã®ããã®éèŠãªæ®µéããªã
ãã®ã§ããã
ïŒïŒãäŸãã°transâïŒã»ïŒâãžã¡ãã«ã·ã¯ãã
ããã³âïŒã»ïŒâãžã«ã«ãã³é žãžãšãã«ã¯ãæ¢ç¥
ã®ååç©ã§ãããæ¬çºæã®æ¹æ³ã«ãã補é ã§ãã
ãããã®æ¢ç¥ã®ååç©ïŒïŒäžŠã³ã«æ°èŠãªååç©
ïŒïŒã¯ã次ã®äžè¬åŒA ã®cisåã¯transæ§é ã®ã¢ã«ãããã®è£œé ã«ç¹ã«æ
çšã§ããããããã®ã¢ã«ãããèªäœã¯ããŠã€ãã
ããåå¿ã«ãã€ãŠãéåžžã«å€ãã®ã·ã¯ããããã³
ã«ã«ãã³é žã§ãã€ãŠãã®ãšã¹ãã«ã殺è«æ§ãä»äž
ãããŠãããã®ã®è£œé ã®ããã®éèŠãªæ®µéããªã
ãã®ã§ããã
ååç©ïŒïŒããåºçºããäžè¬åŒAã®ã¢ã«ã
ããã®è£œé ã¯ãæ¬åºé¡äººã«ããåæ¥ã«åºé¡ããã
ãã©ã³ã¹åœç¹èš±åºé¡ç¬¬76â39533å·ãçºæã®å
称ïŒã©ã»ãïŒã»ïŒâãžçœ®æcisåã¯transâïŒâã
ã«ãã«ã·ã¯ããããã³âïŒâã«ã«ãã³é žã®äœçŽã¢
ã«ãã«ãšã¹ãã«ã®è£œé æ³ãã«èšèŒãããŠããã
ããã®è£œé ã¯ãæ¬åºé¡äººã«ããåæ¥ã«åºé¡ããã
ãã©ã³ã¹åœç¹èš±åºé¡ç¬¬76â39533å·ãçºæã®å
称ïŒã©ã»ãïŒã»ïŒâãžçœ®æcisåã¯transâïŒâã
ã«ãã«ã·ã¯ããããã³âïŒâã«ã«ãã³é žã®äœçŽã¢
ã«ãã«ãšã¹ãã«ã®è£œé æ³ãã«èšèŒãããŠããã
äžè¬åŒã®ååç©ããåºçºããã¢ã«ãããïŒ
AïŒã®è£œé ã¯ãååŠåŒã§äŸç€ºãããã
AïŒã®è£œé ã¯ãååŠåŒã§äŸç€ºãããã
æ¬çºæã®æ¹æ³ã«çšããããããã²ã³åããªããš
ãã«ãã¹ãããŠã ã¯ãäžè¬ã«ãæ¬¡åŒ ïŒããã§Halã¯ããçŽ ãèçŽ åã¯å¡©çŽ ååãè¡šã
ãïŒ ã®ããã²ã³èªå°äœã«ããªããšãã«ãã¹ãã€ã³ãäœ
çšãããããšã«ãã€ãŠè£œé ããããšãã§ããã
ãã«ãã¹ãããŠã ã¯ãäžè¬ã«ãæ¬¡åŒ ïŒããã§Halã¯ããçŽ ãèçŽ åã¯å¡©çŽ ååãè¡šã
ãïŒ ã®ããã²ã³èªå°äœã«ããªããšãã«ãã¹ãã€ã³ãäœ
çšãããããšã«ãã€ãŠè£œé ããããšãã§ããã
èåããªããšãã«ã€ãœãããã«ãã¹ãããŠã
ã¯ãM.Schlosseræ°ã«ããChen.Ber.97ã3219
ïŒ1964ïŒã«èšèŒãããŠããã
ã¯ãM.Schlosseræ°ã«ããChen.Ber.97ã3219
ïŒ1964ïŒã«èšèŒãããŠããã
èåããªããšãã«ã·ã¯ããã³ãã«ãã¹ãããŠã
ã¯ãF.Ramirezæ°ã«ããJ.Org.21ã488ïŒ1956ïŒ
ã«èšèŒãããŠããã
ã¯ãF.Ramirezæ°ã«ããJ.Org.21ã488ïŒ1956ïŒ
ã«èšèŒãããŠããã
èåããªããšãã«ã·ã¯ãããã·ã«ãã¹ãããŠã
ã¯ãH.J.Bestmannæ°ä»ã«ããBer.96ã1899
ïŒ1963ïŒã«èšèŒãããŠããã
ã¯ãH.J.Bestmannæ°ä»ã«ããBer.96ã1899
ïŒ1963ïŒã«èšèŒãããŠããã
æç®ã«èšèŒã®ããåããªããšãã«ïŒâãã³ãã«
ãã¹ãããŠã ãMichaelisæ°å€ãA.229ã325åã³
W.E.Bondinellæ°å€ãJ.Org.Chem.33ã4351
ïŒ1968ïŒãã¯ãããåããªããšãã«ïŒâãã³ãã«ã
ã¹ãããŠã ãšããåããªããšãã«ïŒâãã³ãã«ã
ã¹ãããŠã ãšã®æ··åç©ã§ãããšæãããã
ãã¹ãããŠã ãMichaelisæ°å€ãA.229ã325åã³
W.E.Bondinellæ°å€ãJ.Org.Chem.33ã4351
ïŒ1968ïŒãã¯ãããåããªããšãã«ïŒâãã³ãã«ã
ã¹ãããŠã ãšããåããªããšãã«ïŒâãã³ãã«ã
ã¹ãããŠã ãšã®æ··åç©ã§ãããšæãããã
ãã®ååç©ã¯ããªããšãã«ãããã«ãã¹ãããŠ
ã ã€ãªãã«ããåãšãã«ãäœçšãããŠè£œé ããã
ãšã奜ãŸããããã®è£œé äŸã¯å®éšã®éšã«ç€ºãã
ã ã€ãªãã«ããåãšãã«ãäœçšãããŠè£œé ããã
ãšã奜ãŸããããã®è£œé äŸã¯å®éšã®éšã«ç€ºãã
èåããªããšãã«ïŒâãã³ãã«ãã¹ãããŠã
ã¯ãæ¬çºæã®æ¹æ³ãå®æœããäžéäœãšããŠç¹ã«æ
çšãªæ°èŠãªå·¥æ¥çšååç©ãšããŠæ¬çºæã®äžéšãæ§
æããã
ã¯ãæ¬çºæã®æ¹æ³ãå®æœããäžéäœãšããŠç¹ã«æ
çšãªæ°èŠãªå·¥æ¥çšååç©ãšããŠæ¬çºæã®äžéšãæ§
æããã
ãã¡ãã«åºãšç°ãªãäžè¬åŒã®ååç©ã¯ãæ°
èŠã§ãã€ãŠããã¯ãæ¬çºæã®äžéšãæ§æããã
èŠã§ãã€ãŠããã¯ãæ¬çºæã®äžéšãæ§æããã
ãããã®ååç©ã®äžã§ããç¹ã«ãããšãã«åº
ãè¡šããäžã€ïŒ²ãã¡ãã«åºãè¡šããããåã¯ïŒžã
ãšãã«åºãè¡šããäžã€ïŒ²ããšãã«åºãè¡šãããã
åã¯ïŒåã®ïŒžåºããããã®çµåããŠããççŽ åå
ãšäžç·ã«ãªã€ãŠã·ã¯ããã³ãã«åºãè¡šããäžã€ïŒ²
ãã¡ãã«åºãè¡šããããåã¯ïŒåã®ïŒžåºãããã
ã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠã·ã¯ãã
ã³ãã«åºãè¡šããäžã€ïŒ²ããšãã«åºãè¡šãããã
åã¯ïŒåã®ïŒžåºããããã®çµåããŠããççŽ åå
ãšäžç·ã«ãªã€ãŠã·ã¯ãããã·ã«åºãè¡šããäžã€ïŒ²
ãã¡ãã«åºãè¡šããããåã¯ïŒåã®ïŒžåºãããã
ã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠã·ã¯ãã
ãã·ã«åºãè¡šããäžã€ïŒ²ããšãã«åºãè¡šããäžè¬
åŒã®ååç©ãå³ã¡ãã©ã»ãtransâïŒã»ïŒâãž
ãšãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žã¡
ãã«ãã©ã»ãtransâïŒã»ïŒâãžãšãã«ã·ã¯ãã
ããã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãã©ã»ã
transâã¹ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãž
ã«ã«ãã³é žã¡ãã«ãã©ã»ãtransâã¹ãããïŒã»
ïŒãããã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãã©
ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿ã³âïŒã»ïŒ
âãžã«ã«ãã³é žã¡ãã«åã³ã©ã»ãtransâã¹ãã
ãïŒã»ïŒããªã¯ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žãšã
ã«ããããããã
ãè¡šããäžã€ïŒ²ãã¡ãã«åºãè¡šããããåã¯ïŒžã
ãšãã«åºãè¡šããäžã€ïŒ²ããšãã«åºãè¡šãããã
åã¯ïŒåã®ïŒžåºããããã®çµåããŠããççŽ åå
ãšäžç·ã«ãªã€ãŠã·ã¯ããã³ãã«åºãè¡šããäžã€ïŒ²
ãã¡ãã«åºãè¡šããããåã¯ïŒåã®ïŒžåºãããã
ã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠã·ã¯ãã
ã³ãã«åºãè¡šããäžã€ïŒ²ããšãã«åºãè¡šãããã
åã¯ïŒåã®ïŒžåºããããã®çµåããŠããççŽ åå
ãšäžç·ã«ãªã€ãŠã·ã¯ãããã·ã«åºãè¡šããäžã€ïŒ²
ãã¡ãã«åºãè¡šããããåã¯ïŒåã®ïŒžåºãããã
ã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠã·ã¯ãã
ãã·ã«åºãè¡šããäžã€ïŒ²ããšãã«åºãè¡šããäžè¬
åŒã®ååç©ãå³ã¡ãã©ã»ãtransâïŒã»ïŒâãž
ãšãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žã¡
ãã«ãã©ã»ãtransâïŒã»ïŒâãžãšãã«ã·ã¯ãã
ããã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãã©ã»ã
transâã¹ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãž
ã«ã«ãã³é žã¡ãã«ãã©ã»ãtransâã¹ãããïŒã»
ïŒãããã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãã©
ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿ã³âïŒã»ïŒ
âãžã«ã«ãã³é žã¡ãã«åã³ã©ã»ãtransâã¹ãã
ãïŒã»ïŒããªã¯ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žãšã
ã«ããããããã
ãããã®äŸã¯ãæ¬çºæãäŸç€ºãããã®ã§ããã
ãå¶éãããã®ã§ã¯ãªãã
ãå¶éãããã®ã§ã¯ãªãã
ãããã®äŸã«ãããŠãæ瀺ïŒïŒžïŒã·ã¯ããã³
ãã«åã¯ã·ã¯ãããã·ã«ã¯ãïŒåã®çœ®æåºïŒžãã
ããã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠã·ã¯
ããã³ãã«åã¯ã·ã¯ãããã·ã«åºãè¡šããããšã
æå³ããã
ãã«åã¯ã·ã¯ãããã·ã«ã¯ãïŒåã®çœ®æåºïŒžãã
ããã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠã·ã¯
ããã³ãã«åã¯ã·ã¯ãããã·ã«åºãè¡šããããšã
æå³ããã
äŸ ïŒ
ã©ã»ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ãããã
ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ã
ïŒã¡ãã«ãïŒãšãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã«
0.576ïœã®èåããªããšãã«ã€ãœãããã«ãã¹ã
ããŠã ãå°å ¥ãã次ãã§0.090ïœã®ããã«ãªããŠ
ã ã0.7c.c.ã®ãã³ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâ
ã§ãã€ãããšå ããïŒâã§30åãããŸãã0.156
ïœã®ããã«é žãžãšãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ãã
ã·ãšã¿ã³ã«æº¶è§£ããŠãªã溶液ãå°å ¥ããïŒâã§15
åãããŸãã枩床ã20âãŸã§åã³äžæãããè±è²
ãããŸã§ãå³ã¡çŽïŒæéãããŸããæ°Žãå ããã
ããŸãããšãŒãã«ã§æœåºãããšãŒãã«æœåºç©ãæ°Ž
æŽãã次ãã§å¡©åãããªãŠã 飜å氎溶液ã§æŽæµ
ããè±æ°Žããæ¿çž®ããæžå§äžã«ç²Ÿçãã0.108ïœ
ã®ã©ã»ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ãããã
ã³ïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãåŸããBPïŒ82
âïŒ0.7mmHgã
ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ã
ïŒã¡ãã«ãïŒãšãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã«
0.576ïœã®èåããªããšãã«ã€ãœãããã«ãã¹ã
ããŠã ãå°å ¥ãã次ãã§0.090ïœã®ããã«ãªããŠ
ã ã0.7c.c.ã®ãã³ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâ
ã§ãã€ãããšå ããïŒâã§30åãããŸãã0.156
ïœã®ããã«é žãžãšãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ãã
ã·ãšã¿ã³ã«æº¶è§£ããŠãªã溶液ãå°å ¥ããïŒâã§15
åãããŸãã枩床ã20âãŸã§åã³äžæãããè±è²
ãããŸã§ãå³ã¡çŽïŒæéãããŸããæ°Žãå ããã
ããŸãããšãŒãã«ã§æœåºãããšãŒãã«æœåºç©ãæ°Ž
æŽãã次ãã§å¡©åãããªãŠã 飜å氎溶液ã§æŽæµ
ããè±æ°Žããæ¿çž®ããæžå§äžã«ç²Ÿçãã0.108ïœ
ã®ã©ã»ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ãããã
ã³ïŒã»ïŒâãžã«ã«ãã³é žãšãã«ãåŸããBPïŒ82
âïŒ0.7mmHgã
äŸ ïŒ
ã©ã»ãtransâïŒã»ïŒâãžã¡ãã«ã·ã¯ãããã
ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ã
ïŒã¡ãã«ãïŒãšãã«ïŒã®è£œé äŸïŒãšåãæ æ§ã§ãããããã ã0.156ïœã®ã
ãã«é žãžãšãã«ãšã¹ãã«ã0.156ïœã®ãã¬ã€ã³é ž
ãžãšãã«ãšã¹ãã«ã§çœ®æããŠå®æœããããšã«ã
ããäŸïŒãšåãåçã§åãç¹è³ªã®ã©ã»ãtransâ
ïŒã»ïŒâãžã¡ãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«
ã«ãã³é žãšãã«ãåŸãã
ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ã
ïŒã¡ãã«ãïŒãšãã«ïŒã®è£œé äŸïŒãšåãæ æ§ã§ãããããã ã0.156ïœã®ã
ãã«é žãžãšãã«ãšã¹ãã«ã0.156ïœã®ãã¬ã€ã³é ž
ãžãšãã«ãšã¹ãã«ã§çœ®æããŠå®æœããããšã«ã
ããäŸïŒãšåãåçã§åãç¹è³ªã®ã©ã»ãtransâ
ïŒã»ïŒâãžã¡ãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«
ã«ãã³é žãšãã«ãåŸãã
äŸ ïŒ
ã©ã»ãtransâïŒã»ïŒâãžãšãã«ã·ã¯ãããã
ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ã
ïŒãšãã«ãïŒã¡ãã«ïŒã®è£œé 1300c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ äžã«55ïœã®ã
ãåããªããšãã«ïŒâãã³ãã«ãã¹ãããŠã ãå°
å ¥ãã次ãã§55c.c.ã®2.1Nããã«ãªããŠã ãã³ã¿
ã³æº¶æ¶²ãïŒâã§ãã€ãããšå ãã25âã§30åãã
ãŸããïŒâã«å·åŽãã14.4ïœã®ããã«é žãžã¡ãã«
ãšã¹ãã«ïŒåã¯14.4ïœã®ãã¬ã€ã³é žãžã¡ãã«ãšã¹
ãã«ïŒãéåžžã«ãã€ãããšå°å ¥ããåå¿æ··åç©ã
è±è²ãããŸã§ïŒçŽïŒæéãèŠããïŒ25âã§ãããŸ
ããæ°Žãå ãããšãŒãã«ã§æœåºãããšãŒãã«æœåº
ç©ãå¡©åãããªãŠã 飜å溶液ã§æŽæµãã也ç¥ãã
æ¿çž®ä¹Ÿåºããæ®çç©ãæžå§äžã«ç²ŸçããïŒïœã®ã©
ã»ãtransâïŒã»ïŒâãžãšãã«ã·ã¯ããããã³â
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ãåŸããBPïŒ65
âïŒ0.1mmHgãMPïŒ25ã30âã
ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ã
ïŒãšãã«ãïŒã¡ãã«ïŒã®è£œé 1300c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ äžã«55ïœã®ã
ãåããªããšãã«ïŒâãã³ãã«ãã¹ãããŠã ãå°
å ¥ãã次ãã§55c.c.ã®2.1Nããã«ãªããŠã ãã³ã¿
ã³æº¶æ¶²ãïŒâã§ãã€ãããšå ãã25âã§30åãã
ãŸããïŒâã«å·åŽãã14.4ïœã®ããã«é žãžã¡ãã«
ãšã¹ãã«ïŒåã¯14.4ïœã®ãã¬ã€ã³é žãžã¡ãã«ãšã¹
ãã«ïŒãéåžžã«ãã€ãããšå°å ¥ããåå¿æ··åç©ã
è±è²ãããŸã§ïŒçŽïŒæéãèŠããïŒ25âã§ãããŸ
ããæ°Žãå ãããšãŒãã«ã§æœåºãããšãŒãã«æœåº
ç©ãå¡©åãããªãŠã 飜å溶液ã§æŽæµãã也ç¥ãã
æ¿çž®ä¹Ÿåºããæ®çç©ãæžå§äžã«ç²ŸçããïŒïœã®ã©
ã»ãtransâïŒã»ïŒâãžãšãã«ã·ã¯ããããã³â
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ãåŸããBPïŒ65
âïŒ0.1mmHgãMPïŒ25ã30âã
NMRã¹ãã¯ãã«ïŒåå¡©åççŽ ïŒ
ÎŽïŒ0.76â1.08ppmïŒããªãã¬ããã6HïŒ
ÎŽïŒ1.24â2.92ppmïŒãã«ããã¬ããã4HïŒ
ÎŽïŒ2.08ppmïŒã·ã³ã°ã¬ããã2HïŒ
ÎŽïŒ3.63ppmïŒã·ã³ã°ã¬ããã6HïŒ
äŸïŒã®åºçºæã§çšããããåããªããšãã«ïŒâ
ãã³ãã«ãã¹ãããŠã ã¯ãäžèšã®æ¹æ³ã§è£œé ãã
ããšãã§ããã
ãã³ãã«ãã¹ãããŠã ã¯ãäžèšã®æ¹æ³ã§è£œé ãã
ããšãã§ããã
(a) ããåïœâãããã«ããªããšãã«ãã¹ãããŠ
ã ã®è£œé 10-1ã¢ã«ã®ããªããšãã«ãã¹ãã€ã³ãš10-1ã¢
ã«ã®ããåïœâãããã«ãïŒæééæµïŒ120
âïŒããããçæããå¡©ããã³ãŒã³ã次ã§ãšãŒ
ãã«ã§æŽæµããããåïœâãããã«ããªããšã
ã«ãã¹ãããŠã ã81ïŒ ã®åçã§åŸããMPïŒ165
âã
ã ã®è£œé 10-1ã¢ã«ã®ããªããšãã«ãã¹ãã€ã³ãš10-1ã¢
ã«ã®ããåïœâãããã«ãïŒæééæµïŒ120
âïŒããããçæããå¡©ããã³ãŒã³ã次ã§ãšãŒ
ãã«ã§æŽæµããããåïœâãããã«ããªããšã
ã«ãã¹ãããŠã ã81ïŒ ã®åçã§åŸããMPïŒ165
âã
(b) ïœâããããªãã³ããªããšãã«ãã¹ãã©ã³ã®
補é 0.5Ã10-1ã¢ã«ã®ããåïœâãããã«ããªã
ãšãã«ãã¹ãããŠã ã50c.c.ã®ãžã¡ããã·ãšã¿ã³
ã«å ããŠãªãæžæ¿æ¶²ã«ïŒâã§0.6Ã10-1ã¢ã«ã®
ããã«ãªããŠã ãæ·»å ãã30åéãããŸããïœ
âããããªãã³ããªããšãã«ãã¹ãã©ã³ãåŸ
ãã
補é 0.5Ã10-1ã¢ã«ã®ããåïœâãããã«ããªã
ãšãã«ãã¹ãããŠã ã50c.c.ã®ãžã¡ããã·ãšã¿ã³
ã«å ããŠãªãæžæ¿æ¶²ã«ïŒâã§0.6Ã10-1ã¢ã«ã®
ããã«ãªããŠã ãæ·»å ãã30åéãããŸããïœ
âããããªãã³ããªããšãã«ãã¹ãã©ã³ãåŸ
ãã
(c) ããåããªããšãã«ïŒâãã³ãã«ãã¹ãããŠ
ã ã®è£œé ïŒÃ10-1ã¢ã«ã®ããåãšãã«ã30c.c.ã®ãžã¡ã
ãã·ãšã¿ã³ã«æº¶è§£ããŠãªã溶液ã«ïŒâã§0.5Ã
10-1ã¢ã«ã®ïœâããããªãã³ããªããšãã«ãã¹
ãã©ã³ãå ãã60âã§ïŒæéãããŸããåé¢ã
ãåŸãããåããªããšãã«ïŒâãã³ãã«ãã¹ã
ããŠã ã80ïŒ ã®åçã§åŸããMPïŒ190âã
ã ã®è£œé ïŒÃ10-1ã¢ã«ã®ããåãšãã«ã30c.c.ã®ãžã¡ã
ãã·ãšã¿ã³ã«æº¶è§£ããŠãªã溶液ã«ïŒâã§0.5Ã
10-1ã¢ã«ã®ïœâããããªãã³ããªããšãã«ãã¹
ãã©ã³ãå ãã60âã§ïŒæéãããŸããåé¢ã
ãåŸãããåããªããšãã«ïŒâãã³ãã«ãã¹ã
ããŠã ã80ïŒ ã®åçã§åŸããMPïŒ190âã
äŸ ïŒ
ã©ã»ãtransâïŒã»ïŒâãžãšãã«ã·ã¯ãããã
ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ã
ïŒãšãã«ãïŒã¡ãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ äžã§0.688ïœã®
ããåããªããšãã«ïŒâãã³ãã«ãã¹ãããŠã ã
å°å ¥ãã0.05ïœã®ããã«ãªããŠã ã0.7c.c.ã®ãã³
ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâã§ãã€ãããšå
ããïŒâã§30åãããŸãã0.128ïœã®ããã«é žãž
ã¡ãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ããã·ãšã¿ã³ã«æº¶è§£
ããŠãªã溶液ãå°å ¥ããïŒâã§15åãããŸããæž©
床ã20âã«äžæãããè±è²ãããŸã§ãå³ã¡çŽïŒæ
éãããŸããæ°Žãå ãããããŸããäŸïŒã«ããã
ããã«åŠçããæ®çç©ãã·ãªã«ã²ã«ã§ã¯ãããã°
ã©ãã€ãŒããïŒïŒ ã®é ¢é žãšãã«ãå«æãããã³ãŒ
ã³æ··åç©ã§æº¶é¢ãã0.150ïœã®ã©ã»ãtransâïŒã»
ïŒâãžãšãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ã
ã³é žã¡ãã«ãåŸããé¡äŒŒã®æ¹æ³ã§ããã«é žãšãã«
ãšããåïŒâãã³ãã«ããªããšãã«ãã¹ãããŠã
ããåºçºããŠã©ã»ãtransâïŒã»ïŒâãžãšãã«ã·
ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒå
åç©ãïŒãšãã«ãïŒãšãã«ïŒãåŸããBP
ïŒ83â85âïŒ0.5mmHgã
ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ã
ïŒãšãã«ãïŒã¡ãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ äžã§0.688ïœã®
ããåããªããšãã«ïŒâãã³ãã«ãã¹ãããŠã ã
å°å ¥ãã0.05ïœã®ããã«ãªããŠã ã0.7c.c.ã®ãã³
ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâã§ãã€ãããšå
ããïŒâã§30åãããŸãã0.128ïœã®ããã«é žãž
ã¡ãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ããã·ãšã¿ã³ã«æº¶è§£
ããŠãªã溶液ãå°å ¥ããïŒâã§15åãããŸããæž©
床ã20âã«äžæãããè±è²ãããŸã§ãå³ã¡çŽïŒæ
éãããŸããæ°Žãå ãããããŸããäŸïŒã«ããã
ããã«åŠçããæ®çç©ãã·ãªã«ã²ã«ã§ã¯ãããã°
ã©ãã€ãŒããïŒïŒ ã®é ¢é žãšãã«ãå«æãããã³ãŒ
ã³æ··åç©ã§æº¶é¢ãã0.150ïœã®ã©ã»ãtransâïŒã»
ïŒâãžãšãã«ã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ã
ã³é žã¡ãã«ãåŸããé¡äŒŒã®æ¹æ³ã§ããã«é žãšãã«
ãšããåïŒâãã³ãã«ããªããšãã«ãã¹ãããŠã
ããåºçºããŠã©ã»ãtransâïŒã»ïŒâãžãšãã«ã·
ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒå
åç©ãïŒãšãã«ãïŒãšãã«ïŒãåŸããBP
ïŒ83â85âïŒ0.5mmHgã
äŸ ïŒ
ã©ã»ãtransâã¹ãããïŒã»ïŒãããã¿ã³â
ïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ãïŒ
ïŒã·ã¯ããã³ãã«ãïŒãšãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã§
0.616ïœã®èåããªããšãã«ã·ã¯ããã³ãã«ã¹ã«
ãããŠã ãå°å ¥ãã0.090ïœã®ããã«ãªããŠã ã
0.7c.c.ã®ãã³ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâã§ã
ã€ãããšå ããïŒâã§30åãããŸãã0.156ïœã®
ããã«é žãžãšãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ããã·ãš
ã¿ã³ã«æº¶è§£ããŠãªã溶液ãå°å ¥ããïŒâã§15åã
ããŸãã枩床ã20âã«äžæãããè±è²ãããŸã§ã
å³ã¡çŽïŒæéãããŸããæ°Žãå ãããããŸãããš
ãŒãã«ã§æœåºãããšãŒãã«æœåºç©ãæ°ŽæŽãã次ã
ã§å¡©åãããªãŠã 氎溶液ã§æŽæµããè±æ°Žããæ¿çž®
ããæžå§äžã«ç²Ÿçãã0.125ïœã®ã©ã»ãtransâã¹
ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãžã«ã«ãã³é ž
ãšãã«ãåŸããBPïŒ105âïŒ0.7mmHgã
ïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ãïŒ
ïŒã·ã¯ããã³ãã«ãïŒãšãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã§
0.616ïœã®èåããªããšãã«ã·ã¯ããã³ãã«ã¹ã«
ãããŠã ãå°å ¥ãã0.090ïœã®ããã«ãªããŠã ã
0.7c.c.ã®ãã³ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâã§ã
ã€ãããšå ããïŒâã§30åãããŸãã0.156ïœã®
ããã«é žãžãšãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ããã·ãš
ã¿ã³ã«æº¶è§£ããŠãªã溶液ãå°å ¥ããïŒâã§15åã
ããŸãã枩床ã20âã«äžæãããè±è²ãããŸã§ã
å³ã¡çŽïŒæéãããŸããæ°Žãå ãããããŸãããš
ãŒãã«ã§æœåºãããšãŒãã«æœåºç©ãæ°ŽæŽãã次ã
ã§å¡©åãããªãŠã 氎溶液ã§æŽæµããè±æ°Žããæ¿çž®
ããæžå§äžã«ç²Ÿçãã0.125ïœã®ã©ã»ãtransâã¹
ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãžã«ã«ãã³é ž
ãšãã«ãåŸããBPïŒ105âïŒ0.7mmHgã
äŸ ïŒ
ã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿ã³â
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ãïŒ
ïŒã·ã¯ãããã·ã«ãïŒã¡ãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ äžã§0.638ïœã®
èåããªããšãã«ã·ã¯ãããã·ã«ãã¹ãããŠã ã
å°å ¥ãã0.090ïœã®ããã«ãªããŠã ã0.7c.c.ã®ãã³
ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâã§ãã€ãããšæ·»å
ããïŒâã§30åãããŸãã0.128ïœã®ããã«é žãž
ã¡ãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ããã·ãšã¿ã³ã«æº¶è§£
ããŠãªã溶液ãå°å ¥ããïŒâã§15åãããŸããæž©
床ã20âã«äžæãããè±è²ãããŸã§ãå³ã¡çŽïŒæ
éãããŸããæ°Žãå ãããããŸããäŸïŒã«ããã
ããã«åŠçããæ®çç©ãã·ãªã«ã²ã«ã§ã¯ãããã°
ã©ãã€ãŒããïŒïŒ ã®é ¢é žãšãã«ãå«æãããã³ãŒ
ã³æ··åç©ã§æº¶é¢ãã0.164ïœã®ã©ã»ãtransâã¹ã
ããïŒã»ïŒããªã¯ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡
ãã«ãåŸãã
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ãïŒ
ïŒã·ã¯ãããã·ã«ãïŒã¡ãã«ïŒã®è£œé 15c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ äžã§0.638ïœã®
èåããªããšãã«ã·ã¯ãããã·ã«ãã¹ãããŠã ã
å°å ¥ãã0.090ïœã®ããã«ãªããŠã ã0.7c.c.ã®ãã³
ã¿ã³ã«æº¶è§£ããŠãªã溶液ãïŒâã§ãã€ãããšæ·»å
ããïŒâã§30åãããŸãã0.128ïœã®ããã«é žãž
ã¡ãã«ãšã¹ãã«ãïŒc.c.ã®ãžã¡ããã·ãšã¿ã³ã«æº¶è§£
ããŠãªã溶液ãå°å ¥ããïŒâã§15åãããŸããæž©
床ã20âã«äžæãããè±è²ãããŸã§ãå³ã¡çŽïŒæ
éãããŸããæ°Žãå ãããããŸããäŸïŒã«ããã
ããã«åŠçããæ®çç©ãã·ãªã«ã²ã«ã§ã¯ãããã°
ã©ãã€ãŒããïŒïŒ ã®é ¢é žãšãã«ãå«æãããã³ãŒ
ã³æ··åç©ã§æº¶é¢ãã0.164ïœã®ã©ã»ãtransâã¹ã
ããïŒã»ïŒããªã¯ã¿ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡
ãã«ãåŸãã
äŸ ïŒ
ã©ã»ãtransâã¹ãããïŒã»ïŒãããã¿ã³â
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ãïŒ
ïŒã·ã¯ããã³ãã«ãïŒã¡ãã«ïŒã®è£œé 4300c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã«
160ïœã®èåããªããšãã«ã·ã¯ããã³ãã«ãã¹ã
ããŠã ãå°å ¥ãã160c.c.ã®2.1Nããã«ãªããŠã ã
ã³ã¿ã³æº¶æ¶²ãïŒâã§ãã€ãããšå ãã25âã§30å
ãããŸããïŒâã«å·åŽãã43.2ïœã®ããã«é žãžã¡
ãã«ãšã¹ãã«ãååã«ãã€ãããšå°å ¥ãã25âã§
åå¿æ··åç©ãè±è²ãããŸã§ïŒçŽïŒæéãèŠããïŒ
ãããŸããæ°Žãå ãããšãŒãã«ã§æœåºããäŸïŒã«
ãããããã«åŠçãã15.2ïœã®ã©ã»ãtransâã¹
ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãžã«ã«ãã³é ž
ã¡ãã«ãåŸããBPïŒ89âïŒ0.08mmHgã
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ãïŒ
ïŒã·ã¯ããã³ãã«ãïŒã¡ãã«ïŒã®è£œé 4300c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã«
160ïœã®èåããªããšãã«ã·ã¯ããã³ãã«ãã¹ã
ããŠã ãå°å ¥ãã160c.c.ã®2.1Nããã«ãªããŠã ã
ã³ã¿ã³æº¶æ¶²ãïŒâã§ãã€ãããšå ãã25âã§30å
ãããŸããïŒâã«å·åŽãã43.2ïœã®ããã«é žãžã¡
ãã«ãšã¹ãã«ãååã«ãã€ãããšå°å ¥ãã25âã§
åå¿æ··åç©ãè±è²ãããŸã§ïŒçŽïŒæéãèŠããïŒ
ãããŸããæ°Žãå ãããšãŒãã«ã§æœåºããäŸïŒã«
ãããããã«åŠçãã15.2ïœã®ã©ã»ãtransâã¹
ãããïŒã»ïŒãããã¿ã³âïŒã»ïŒâãžã«ã«ãã³é ž
ã¡ãã«ãåŸããBPïŒ89âïŒ0.08mmHgã
NMRãã¯ãã«ïŒãžã¡ãã«ã¹ã«ããã·ãïŒ
ÎŽïŒ1.40â1.80ppmïŒãã«ããã¬ããã8HïŒ
ÎŽïŒ2.22ppmïŒã·ã³ã°ã¬ããã2HïŒ
ÎŽïŒ3.64ppmïŒã·ã³ã°ã¬ããã6HïŒ
äŸ ïŒ
ã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿ã³â
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ãïŒ
ïŒã·ã¯ãããã·ã«ãïŒã¡ãã«ïŒã®è£œé 3200c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã«
115ïœã®èåããªããšãã«ã·ã¯ãããã·ã«ãã¹ã
ããŠã ãå°å ¥ãã112c.c.ã®2.1Nããã«ãªããŠã ã
ã³ã¿ã³æº¶æ¶²ãïŒâã§ãã€ãããšå°å ¥ãã25âã§30
åãããŸããïŒâã«å·åŽãã32.5ïœã®ããã«é žãž
ã¡ãã«ãšã¹ãã«ãéåžžã«ãã€ãããšå°å ¥ãã25â
ã§åå¿æ··åç©ãè±è²ãããŸã§ïŒçŽïŒæéãèŠã
ãïŒãããŸããæ°Žãå ãããšãŒãã«ã§æœåºãããš
ãŒãã«æœåºç©ãå¡©åãããªãŠã 飜å氎溶液ã§æŽæµ
ãã也ç¥ããæ¿çž®ããæ®çç©ãæžå§äžã«ç²Ÿçãã
20.4ïœã®ã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿
ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ãåŸããBPïŒ
133ã138âïŒ0.5mmHgã
ïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ïŒååç©ãïŒ
ïŒã·ã¯ãããã·ã«ãïŒã¡ãã«ïŒã®è£œé 3200c.c.ã®ãžã¡ããã·ãšã¿ã³ã«çªçŽ é°å²æ°äžã«
115ïœã®èåããªããšãã«ã·ã¯ãããã·ã«ãã¹ã
ããŠã ãå°å ¥ãã112c.c.ã®2.1Nããã«ãªããŠã ã
ã³ã¿ã³æº¶æ¶²ãïŒâã§ãã€ãããšå°å ¥ãã25âã§30
åãããŸããïŒâã«å·åŽãã32.5ïœã®ããã«é žãž
ã¡ãã«ãšã¹ãã«ãéåžžã«ãã€ãããšå°å ¥ãã25â
ã§åå¿æ··åç©ãè±è²ãããŸã§ïŒçŽïŒæéãèŠã
ãïŒãããŸããæ°Žãå ãããšãŒãã«ã§æœåºãããš
ãŒãã«æœåºç©ãå¡©åãããªãŠã 飜å氎溶液ã§æŽæµ
ãã也ç¥ããæ¿çž®ããæ®çç©ãæžå§äžã«ç²Ÿçãã
20.4ïœã®ã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿
ã³âïŒã»ïŒâãžã«ã«ãã³é žã¡ãã«ãåŸããBPïŒ
133ã138âïŒ0.5mmHgã
NMRã¹ãã¯ãã«ïŒãžã¡ãã«ã¹ã«ããã·ãïŒ
ÎŽïŒ1.20â1.80ppmïŒãã«ããã¬ããã10HïŒ
ÎŽïŒ2.12ppmïŒã·ã³ã°ã¬ããã2HïŒ
ÎŽïŒ3.68ppmïŒã·ã³ã°ã¬ããã6HïŒ
é¡äŒŒã®æ
æ§ã§ãèåã·ã¯ãããã·ã«ããªããšã
ã«ãã¹ãããŠã ãšããã«ãžãšãã«ãšã¹ãã«ããåº
çºããŠãã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿
ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ã
ïŒïŒžïŒã·ã¯ãããã·ã«ãïŒãšãã«ïŒãåŸãã
BPïŒ90ã103âïŒ0.08mmHgã
ã«ãã¹ãããŠã ãšããã«ãžãšãã«ãšã¹ãã«ããåº
çºããŠãã©ã»ãtransâã¹ãããïŒã»ïŒããªã¯ã¿
ã³âïŒã»ïŒâãžã«ã«ãã³é žãšãã«ïŒååç©ã
ïŒïŒžïŒã·ã¯ãããã·ã«ãïŒãšãã«ïŒãåŸãã
BPïŒ90ã103âïŒ0.08mmHgã
ãããããªæ§é ã®ïŒºãæãã
ã·ã¯ããããã³ã«ã«ãã³é
žãšã¹ãã«
äŸãã°ïŒºïŒ2â²âã¡ãã«â1â²âããããã«
åã¯ã·ã¯ããã³ããªãã³ã¡ãã«
Claims (1)
- ãç¹èš±è«æ±ã®ç¯å²ã ïŒ æ¬¡ã®äžè¬åŒ ïŒããã§ïŒ²ã¯ïŒãïŒåã®ççŽ ååãå«æããã¢ã«
ãã«åºãè¡šãããã¯ïŒãïŒåã®ççŽ ååãå«æ
ããã¢ã«ãã«åºãè¡šãããåã¯ïŒåã®ïŒžåºã¯ãã
ãã®çµåããŠããççŽ ååãšäžç·ã«ãªã€ãŠïŒãïŒ
åã®ççŽ ååãå«æããã·ã¯ãã¢ã«ãã«åºãè¡šã
ãïŒ ã®ã©ã»ãïŒã»ïŒâãžçœ®ætransâã·ã¯ããããã³
âïŒã»ïŒâãžã«ã«ãã³é žã®äœçŽã¢ã«ãã«ãšã¹ãã«
ã補é ããã«ããããææ©æº¶åªåã¯ææ©æº¶åªæ··å
ç©äžã§åŒ·å¡©åºã®ååšäžã«æ¬¡åŒ ïŒããã§ïŒ²ã¯åèšã®æå³ãæããïŒ ã®ããã«é žã¢ã«ãã«åã¯ãã¬ã€ã³é žã¢ã«ãã«ã次
åŒ ïŒããã§ïŒžã¯åèšã®æå³ãæããHalå¡©çŽ ãèçŽ
åã¯ããçŽ ååãè¡šããïŒ ã®ããã²ã³åããªããšãã«ãã¹ãããŠã ãšåå¿ã
ããããšãç¹åŸŽãšããã©ã»ãïŒã»ïŒâãžçœ®æ
transâã·ã¯ããããã³âïŒã»ïŒâãžã«ã«ãã³é ž
ã®äœçŽã¢ã«ãã«ãšã¹ãã«ã®è£œé æ³ã ïŒ åŒ·å¡©åºãã¢ã«ã«ãªã¢ã«ã³ã©ãŒããæ°ŽçŽ åã¢ã«
ã«ãªãã¢ã«ã«ãªã¢ããåã³ã¢ã«ãã«ãªããŠã èªå°
äœãããªã矀ããéžã°ããããšãç¹åŸŽãšããç¹èš±
è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã ïŒ å¡©åºãããã«ãªããŠã ã§ããããšãç¹åŸŽãšã
ãç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã ïŒ ææ©æº¶åªåã¯ææ©æº¶åªæ··åç©ããžã¡ãã«ã¹ã«
ããã·ãããžã¡ããã·ãšã¿ã³ããžã¡ãã«ãã«ã ã¢
ããããããµã¡ãã«ãã¹ãã«ããªã¢ãããèèªæ
çåæ°ŽçŽ ãè³éŠæåç°åŒçåæ°ŽçŽ ãã·ã¯ãã¢ã«ã«
ã³åã¯ãããã®æº¶åªã®æ··åç©ãããªã矀ããéžã°
ããããšãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé èšèŒ
ã®æ¹æ³ã ïŒ ææ©æº¶åªæ··åç©ããžã¡ããã·ãšã¿ã³ãšãã³ã¿
ã³ãšã®æ··åç©ã§ããããšãç¹åŸŽãšããç¹èš±è«æ±ã®
ç¯å²ç¬¬ïŒé èšèŒã®æ¹æ³ã ïŒ åŒ·å¡©åºãããã«ãªããŠã ã§ãããææ©æº¶åªæ··
åç©ããã³ã¿ã³ãšãžã¡ããã·ãšã¿ã³ãšã®æ··åç©ã§
ããããšãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒãïŒé
ã®ããããã«èšèŒã®æ¹æ³ã
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7639532A FR2376119A1 (fr) | 1976-12-30 | 1976-12-30 | Procede de preparation d'esters d'alcoyle inferieur d'acides trans cyclopropane-1,3-dicarboxyliques 2,2-disubstitues racemiques et nouveaux esters desdits acides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5384946A JPS5384946A (en) | 1978-07-26 |
| JPS6139934B2 true JPS6139934B2 (ja) | 1986-09-06 |
Family
ID=9181715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15752077A Granted JPS5384946A (en) | 1976-12-30 | 1977-12-28 | Preparation of lower alkylesters of racemicc2 * 22d11substituteddtrans cyclopropanee1 * 33d1carboxylic acid and new ester of said acid |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5384946A (ja) |
| BE (1) | BE862460A (ja) |
| CH (1) | CH626319A5 (ja) |
| DE (1) | DE2758624A1 (ja) |
| FR (1) | FR2376119A1 (ja) |
| GB (1) | GB1596029A (ja) |
| IT (1) | IT1093080B (ja) |
| NL (1) | NL7714499A (ja) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2923776A1 (de) * | 1979-06-12 | 1980-12-18 | Bayer Ag | Verfahren zur herstellung von 3,3-dimethyl-cyclopropan-1,2-dicarbonsaeureestern sowie zwischenprodukte zu deren herstellung |
| DE2923774A1 (de) * | 1979-06-12 | 1980-12-18 | Bayer Ag | Verfahren zur herstellung von 3,3-dimethyl-cyclopropan-1,2-dicarbonsaeureestern |
| 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 |
| 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 |
| DE3111849A1 (de) * | 1981-03-26 | 1982-10-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von caronaldehydsaeure und deren derivaten |
| FR2624511B1 (fr) * | 1987-12-11 | 1990-09-21 | Roussel Uclaf | Procede enantioselectif pour preparer des derives de l'aldehyde hemicaronique de structure trans ou cis |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4911854A (ja) * | 1972-05-16 | 1974-02-01 | ||
| JPS52148049A (en) * | 1976-06-01 | 1977-12-08 | American Cyanamid Co | Process for manufacture of cyclopropane carboxylic acid and ester thereof |
-
1976
- 1976-12-30 FR FR7639532A patent/FR2376119A1/fr active Granted
-
1977
- 1977-12-21 IT IT5232677A patent/IT1093080B/it active
- 1977-12-28 NL NL7714499A patent/NL7714499A/xx not_active Application Discontinuation
- 1977-12-28 JP JP15752077A patent/JPS5384946A/ja active Granted
- 1977-12-29 BE BE183958A patent/BE862460A/xx not_active IP Right Cessation
- 1977-12-29 DE DE19772758624 patent/DE2758624A1/de active Granted
- 1977-12-29 GB GB5417777A patent/GB1596029A/en not_active Expired
- 1977-12-30 CH CH1630577A patent/CH626319A5/fr not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4911854A (ja) * | 1972-05-16 | 1974-02-01 | ||
| JPS52148049A (en) * | 1976-06-01 | 1977-12-08 | American Cyanamid Co | Process for manufacture of cyclopropane carboxylic acid and ester thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1093080B (it) | 1985-07-19 |
| JPS5384946A (en) | 1978-07-26 |
| GB1596029A (en) | 1981-08-19 |
| CH626319A5 (en) | 1981-11-13 |
| FR2376119B1 (ja) | 1982-09-17 |
| BE862460A (fr) | 1978-06-29 |
| NL7714499A (nl) | 1978-07-04 |
| DE2758624A1 (de) | 1978-07-13 |
| FR2376119A1 (fr) | 1978-07-28 |
| DE2758624C2 (ja) | 1987-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB1586990A (en) | Process for the preparation of cyclobutanones | |
| JP5376939B2 (ja) | 觊åªã¹ã¯ãªã£ãŒãã³åå¿ | |
| JPS6139934B2 (ja) | ||
| CN105175346B (zh) | äžç§åæçèäŒä»æ±éäžéŽäœçæ¹æ³ | |
| WO2008015977A1 (en) | PROCESS FOR PRODUCTION OF (±)-3a,6,6,9aâ TETRAMETHYLDECAHYDRONAPHTHO[2,1-b]FURAN-2(1H)-ONE | |
| JPS623141B2 (ja) | ||
| JPS6148830B2 (ja) | ||
| JPS5810371B2 (ja) | ã«ã³ãžãšãŠã±ãã³ãªãšããœãã»ã€ã㊠| |
| JPH047346B2 (ja) | ||
| JP5408821B2 (ja) | ããã¿ãã·ã¢ãã³ååç©åã³ãã®è£œé æ¹æ³ | |
| Takaki et al. | Addition reactions of lithium ester enolates, α-lithionitriles, and sodium amides to dimethyl (vinyl) sulphonium salts | |
| JPS647065B2 (ja) | ||
| JP3563424B2 (ja) | ïŒïœâãã©ã³âïŒâãªã³ã®è£œé æ¹æ³ | |
| US4808340A (en) | Process for preparing methyl 4-oxo-5-tetradecynoate | |
| JP4234939B2 (ja) | ç°ç¶ã¢ã»ãã¬ã³ååç©åã³ãã®è£œé æ³ | |
| JPH0519545B2 (ja) | ||
| JP2581186B2 (ja) | ïŒâ眮æâïŒâã·ã¯ããã³ããã³ãšã¹ãã«èªå°äœã®è£œé æ³ | |
| JPS602296B2 (ja) | äžé£œåã«ã«ãã³é žããã³ãã®è£œæ³ | |
| JP2724634B2 (ja) | å åŠæŽ»æ§ãæããïŒâãã§ãã«ãããªãã³èªå°äœåã³ãã®è£œé äžéäœäžŠã³ã«ãããã®è£œé æ¹æ³ | |
| KR100614546B1 (ko) | ì 첎ì íì±ìŽ ëì í ížëŒíìŽëë¡íšë ê³ ëŠ¬íí©ë¬Œê³Œ ìŽìì ì¡°ë°©ë² | |
| KR101014890B1 (ko) | ì ê· ê³ ëŠ¬íí©ë¬Œê³Œ ìŽì ì ì¡°ë°©ë² | |
| SU1538899A3 (ru) | СпПÑПб пПлÑÑеМО 6-бÑПЌ-3-ЌеÑОл-1-ÑÑОЌеÑОлÑОлПкÑО-1,3,5-гекÑаÑÑОеМа | |
| JPS61218532A (ja) | 眮æãªã¯ã¿ãããã¢ã³ãã©ã»ã³ããã³ãã®è£œé æ¹æ³ | |
| DK161704B (da) | Cyclopropancarboxylsyrelactonderivater og fremgangsmaader til fremstilling deraf | |
| JP2018104317A (ja) | ãã©ã³ç°ãæããαâãªã¬ãã£ã³ã®è£œé æ¹æ³ |