GB1596029A - Cyclopropane dicarboxylic acid esters - Google Patents
Cyclopropane dicarboxylic acid esters Download PDFInfo
- Publication number
- GB1596029A GB1596029A GB5417777A GB5417777A GB1596029A GB 1596029 A GB1596029 A GB 1596029A GB 5417777 A GB5417777 A GB 5417777A GB 5417777 A GB5417777 A GB 5417777A GB 1596029 A GB1596029 A GB 1596029A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dicarboxylate
- racemic trans
- ethyl
- methyl
- compound
- 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
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- FDKLLWKMYAMLIF-UHFFFAOYSA-N cyclopropane-1,1-dicarboxylic acid Chemical class OC(=O)C1(C(O)=O)CC1 FDKLLWKMYAMLIF-UHFFFAOYSA-N 0.000 title description 3
- -1 trans-2,2-disubstituted-1,3-cyclopropanedicarboxylic acids Chemical class 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims description 48
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 26
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 239000011369 resultant mixture Substances 0.000 claims description 10
- 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 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000004042 decolorization Methods 0.000 claims description 8
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 claims description 8
- 229960004419 dimethyl fumarate Drugs 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 7
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 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 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 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 6
- 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 claims description 6
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 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 claims description 5
- PUOAHFUILIFQIA-HTQZYQBOSA-N CCOC(=O)[C@H]1[C@@H](C12CCCC2)C(=O)O Chemical compound CCOC(=O)[C@H]1[C@@H](C12CCCC2)C(=O)O PUOAHFUILIFQIA-HTQZYQBOSA-N 0.000 claims description 5
- 241000786363 Rhampholeon spectrum Species 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 claims description 5
- 239000000284 extract Substances 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 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 claims description 4
- AXAXMIPDTWLLTN-UHFFFAOYSA-N 1,1,2-triethylcyclopropane Chemical compound CCC1CC1(CC)CC AXAXMIPDTWLLTN-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- VRAHXXPBEUDBMF-UHFFFAOYSA-N 1,1-diethyl-2-methylcyclopropane Chemical compound CCC1(CC)CC1C VRAHXXPBEUDBMF-UHFFFAOYSA-N 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- YUDRVAHLXDBKSR-UHFFFAOYSA-N [CH]1CCCCC1 Chemical compound [CH]1CCCCC1 YUDRVAHLXDBKSR-UHFFFAOYSA-N 0.000 claims description 3
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 150000001924 cycloalkanes Chemical class 0.000 claims description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004678 hydrides Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 claims description 3
- BXIIJPAVISPOGI-UHFFFAOYSA-N 1,1,2-trimethylcyclopropane Chemical compound CC1CC1(C)C BXIIJPAVISPOGI-UHFFFAOYSA-N 0.000 claims description 2
- UDCRTPSZNQOKRO-UHFFFAOYSA-N 2-ethyl-1,1-dimethylcyclopropane Chemical compound CCC1CC1(C)C UDCRTPSZNQOKRO-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012259 ether extract Substances 0.000 claims description 2
- 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 claims 1
- 150000001299 aldehydes Chemical class 0.000 abstract description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000000749 insecticidal effect Effects 0.000 abstract description 3
- 125000005907 alkyl ester group Chemical group 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 abstract 1
- 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 7
- 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 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 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
- 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 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 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
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical group CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-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
- 238000013019 agitation Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material 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
- DWCSXQCXXITVKE-UHFFFAOYSA-N triethyloxidanium Chemical compound CC[O+](CC)CC DWCSXQCXXITVKE-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
- 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
- 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
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-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
- 238000007239 Wittig reaction Methods 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 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
- 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
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 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
- 150000002688 maleic acid derivatives Chemical class 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
- 150000003839 salts Chemical class 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- QDNCLIPKBNMUPP-UHFFFAOYSA-N trimethyloxidanium Chemical compound C[O+](C)C QDNCLIPKBNMUPP-UHFFFAOYSA-N 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
- 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 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 P—C 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 P—C 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)
Abstract
The lower alkyl esters of racemic trans-2,2-disubstituted-1,3-cyclopropanedicarboxylic acids are prepared by reaction of a triphenylphosphonium with an alkyl fumarate or maleate. The esters are intermediates which are useful especially for the preparation of aldehydes themselves leading to pyrethrinoid derivatives having insecticidal properties. <IMAGE>
Description
(54) CYCLOPROPANE DICARBOXYLIC ACID ESTERS
(71) We, ROUSSEL UCLAF, a
French Body Corporate of 35 Boulevard des Invalides, Paris 7eme, France, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- This invention relates inter alia to a process for preparing lower alkyl esters of racemic 2,2 - disubstituted trans cyclopropane - 1,3 - dicarboxylic acids said esters having the general formula I,
(wherein R represents an alkyl radical containing from 1 to 6 carbon atoms and either X represents an alkyl radical containing from 1 to 6 carbon atoms or the two radicals X, together with the carbon atom to which they are attached, represent a cycloalkyl radical containing from 3 to 7 carbon atoms).
A number of processes are already known for preparing compounds of general formula I wherein X represents a methyl radical, i.e. trans alkyl 2,2 - dimethyl cyclopropane - 1,3 - dicarboxylates. Thus
P. C. Guha and D. K. Sankara [Ber., 70 B, 1683-8 (1937)] describe a two stage process involving the condensation dimethyldiazomethane with a fumarate at -18"C followed by heating of the resultant condensation product to 2500C. However, the use of reagents such as dimethyldiazomethane and operating conditions such as heating to 250"C make this process difficult to industrialise. In addition, the overall yield of the process is mediocre.
E. J. Corey and M. Jautelat [J. Am.
Chem. Soc., 89 (15), 3912-14] describe a process which comprises reacting isopropyl diphenyl sulphide with triethyl oxonium at -70"C The isopropyl diphenyl suiphonium ylide is obtained by reacting diphenyl sulphide with triethyl oxonium fluoborate, subjecting the resultant diphenyl sulphonium fluoborate to the action of dichloromethyl lithium, formed in situ by reacting methylene chloride with lithium diisopropylamide, then to the action of methyl iodide to obtain diphenyl isopropyl sulphonium iodide which is finally treated with lithium diisopropylamide to yield the desired ylide, the above reactions being carried out at from -50 to 700 C. Due to the low operating temperatures required and the difficulty of obtaining the starting ylide, this process has also proved to be both expensive and difficult to industrialise.
A further process has been described by
C. R. Johnson and E. R. Janiga [J. Am.
Chem. Soc., (23) 95, 1973, p. 76-92] which comprises reacting p-tolyl isopropyl sulphoxide with sodium azide to form isopropyl p-tolyl sylphoximine which is then treated with trimethyloxonium fluoborate, subjecting the dimethyl - amino isopropyl - p - tolyl - sulphoxonium fluoborate obtained to the action of sodamide and dimethylformamide and then reacting the dimethyl - amino - p - tolyl oxosulphonium ethylide thus formed with dimethyl fumarate. As will be appreciated, this process is obviously complicated and expensive to industrialise.
We have now found a novel process for preparing not only trans alkyl 2,2 - dimethyl cyclopropane - 1,3 - dicarboxylates but also other 2,2 - dialkyl substituted trans alkyl cyclopropane - 1,3 - dicarboxylates, which involves only a single stage and uses readily available starting materials and operating conditions which are easily industrialised.
Thus, according to the present invention, there is provided a process for the preparation of compounds of general formula I as hereinbefore defined which comprises reacting a compound of formula
II,
(wherein R is as defined above) with a compound of formula III
(wherein Xis as defined above, z represents a phenyl radical and Hal represents a chlorine, bromine or iodine atom) in the presence of a strong base and of an organic solvent.
The process according to the invention may, for example, be used to prepare racemic trans methyl 2,2- dimethyl cyclopropane - 1,3 - dicarboxylate; racemic trans ethyl 2,2 - dimethyl cyclopropane - 1,3 - dicarboxylate, racemic trans methyl 2,2 - diethyl cyclopropane - 1,3 - dicarboxylate; racemic trans ethyl 2,2 - diethyl cyclopropane - 1,3 - dicarboxylate; racemic trans methyl spiro - [2,4] - heptane - 1,2 - dicarboxylate; racemic trans ethyl spiro - [2,4] - heptane - 1,2 dicarboxylate; racemic trans methyl spiro [2,5] - ostane - 1,2 - dicarboxylate; and racemic trans ethyl spiro - [2,51 - octane 1,2 - dicarboxylate.
The compound of formula II may be in either the cis or trans form, i.e. in the form of a maleate or fumarate with substantially no variation in yield. Whilst we do not wish to be limited by theoretical considerations, it is believed that it is the fumarate form which reacts with the compound of formula
III, the maleate form in the presence of the strong base being isomerised substantially quantitatively into the fumarate form.
The base preferably comprises an alkali metal alcoholate, hydride or amide or an alkyl lithium derivative, particularly preferred being butyl lithium. The organic solvent preferably comprises dimethylsulphoxide, dimethoxyethane, dimethylformamide, hexamethylphosphorotriamide, an aliphatic hydrocarbon, an aromatic monocyclic hydrocarbon, a cycloalkane or mixtures thereof.
Particularly preferred is a solvent comprising a mixture of dimethoxyethane and pentane.
According to an especially preferred
embodiment of the present invention the
base comprises butyl lithium and the solvent
comprises a mixture of dimethoxyethane and pentane. Conveniently, in this preferred
embodiment, the butyl lithium, in solution
in pentane is gradually introduced at about 0 C into a suspension or solution of the
compound of formula III in dimethoxyethane.
In the process according to the invention
it is preferred to use an excess of the
compound of formula III with respect to the compound of formula II, e.g. from 1.2 to 1.6 moles of the compound of formula III per mole of the compound of formula II. Also preferred is the use of an excess of the base with respect to the compound of formula II, e.g. from 1.1 to 1.5 moles of base per mole of the compound of formula II.
Certain of the compounds of general formula I are known. However, the compounds of general formula I wherein X is other than a methyl radical are novel compounds forming a further feature of the present invention.
Preferred novel compounds of general formula I are those wherein X represents an ethyl radical, especially those wherein R represents a methyl or ethyl radical. Also preferred are compounds of general formula I wherein the two radicals X, together with the carbon atom to which they are attached, represent a cyclopentyl or cyclohexyl radical; especially those wherein
R represnts a methyl or ethyl radical.
Specific compounds of general formula I which may be mentioned are:
racemic trans methyl 2,2 - diethyl
cyclopropane - 1,3 - dicarboxylate,
racemic trans ethyl 2,2 - diethyl
cyclopropane - 1,3 - dicarboxylate,
racemic trans methyl spiro - [2,4]
heptane - 1.2 - dicarboxylate,
racemic trans ethyl spiro - [2,4] - heptane - 1,2 - dicarboxylate,
racemic trans methyl spiro - [2,5] - octane - 1,2 - dicarboxylate
and racemic trans ethyl spiro - [2,51 - octane - 1,2 - dicarboxylate.
The compounds of general formula III, useful as starting material in the process according to the invention may be prepared, for example, by the action of triphenyl phosphine on a compound of formula:
(wherein X and Hal are as hereinbefore defined).
Triphenyl isopropyl phosphonium bromide is described by M. Schlosser [Chem. Ber. 97, 3219 (1964)1. Triphenyl cyclopentylphosphonium bromide is described by F. Ramirez [J. Org. 21. 488 (1956)1. Triphenyl cyclohexylphosphonium bromide is described by H. J. Bestmann et al [Ber. 96, 1899 (1963)].
The triphenyl 3 - pentylphosphonium iodide described in the literature [c.f.
Michaelis et al A, 229, 325 and W. E.
Bondinell et al, [J. Org. Chem. 33, 4351 (1968)] seems to be a mixture of triphenyl 3 - pentyl phosphonium iodide and triphenyl 2 - pentyl phosphonium iodide. It is thus preferable to prepare this compound by the action of ethyl iodide on triphenyl propyl phosphonium ylide. An example of this preparation in given hereinafter in the experimental portion.
The compounds of general formula I are useful intermediates in the preparation of a number of cyclopropane carboxylic acid esters having good insecticidal properties.
Thus, the compounds of general formula I may be converted into cis or trans aldehydes of formula IV,
(wherein X and R are as hereinbefore defined).
The aldehydes of general formula IV and their preparation from compounds of general formula I are described in our copending British Patent Application No.
54178/77 (Serial No. 1596030) of even date herewith. The conversion of compounds of general formula I into aldehydes of general formula IV is illustrated in the accompanying drawings. The aldehydes of general formula IV may, for example, be converted by a Wittig reaction into a cyclopropane carboxylic acid and then esterified to give a compound endowed with good insecticidal activity.
The following non-limiting Examples serve to illustrate the present invention. In the Examples X+X= cyclopentyl or cyclohexyl indicates that the two X radicals in formula I, together with the carbon atom to which they are attached represent a cyclopentyl or cyclohexyl radical respectively.
Example 1
Preparation of racemic trans ethyl 2,2
dimethyl - cyclopropane - 1,3
dicarboxylate (compound of formula I
with X=methyl and R=ethyl).
Into 15 cm3 of 1,2 - dimethoxyethane are introduced, under nitrogen, 0.576 g of triphenyl isopropyl phosphonium bromide, followed slowly at OOC by 0.090 g of butyl lithium in solution in 0.7 cm3 of pentane.
The mixture obtained is agitated for 30 minutes at 0 C and then 0.156 g of diethyl fumarate, in solution in 5 cm3 of 1,2 dimethoxyethane, are added thereto. The resultant mixture is agitated for 15 minutes at 0 C, the temperature is then allowed to rise again to 20"C and agitated until the mixture is subsequently decolourised (about 2 hours). Water is then added and the mixture thus formed is agitated and then extracted with ether. The ethereal extracts are washed with water, then with a saturated aqueous solution of sodium chloride, dried and concentrated to dryness. The residue is rectified under reduced pressure. 0.108 g of racemic trans. ethyl 2,2 dimethylcyclopropane - 1,3 - dicarboxylate are obtained. B.Pt. =82"C under 0.7 mm of mercury.
Example 2
Preparation of racemic trans ethyl 2,2
dimethyl - cyclopropane - 1,3
dicarboxylate (compound of formula I
with X=methyl and R=ethyl).
Operating in the same manner as in
Example 1 but replacing the 0.156 g of diethyl fumarate with 0.156 g of diethyl maleate racemic trans ethyl 2,2 dimethylcyclopropane - 1,3 - dicarboxylate is obtained with the same yield and of the same quality as in Example 1.
Example 3
Preparation of racemic trans methyl 2,2
diethyl - cyclopropane - 1,3
dicarboxylate (compound of formula I
with X=ethyl and R=methyl).
Into 1,300 cm3 of 1,2 - dimethoxyethane are introduced, under nitrogen, 55 g of triphenyl 3 - pentyl phosphonium iodide, followed slowly at OOC by 55 cm3 of 2.1 N butyl lithium solution in pentane. The solution obtained is agitated for 30 minutes at 25"C and then cooled to OOC. 14.4 g of dimethyl fumarate (or 14.4 g of dimethyl maleate are subsequently introduced therein very slowly and the resultant mixture is agitated at 250C until decolorisation (about 5 hours). Water is then added and the mixture thus formed is extracted with ether. The ethereal extracts are washed with a saturated aqueous solution of sodium chloride, dried and concentrated to dryness. The residue is rectified under reduced pressure. 6 g of racemic trans methyl 2,2
diethyl - cyclopropane - 1,3 - dicarboxylate are obtained. B.Pt.=65 C under 0.1 mm of mercury. M.Pt.=25 to 30"C.
N.M.R. Spectrum (carbon tetrachloride) 6=0.76--1.08 p.p.m. (triplet, 6H); S=1.24--2.92 p.p.m. (multiplet, 4H); ops=2.08 p.p.m. (singlet, 2H); b=3.63 p.p.m. (singlet, 6H).
The triphenyl 3-pentyl phosphonium iodide used at the start of Example 3 can be prepared in the following manner:
a) Preparation of n-propyl triphenyl phosphonium iodide:
10-' mole of triphenyl phosphine and 10-'
mole of n-propyl iodide are refluxed (120"C) for one hour. The salt thus formed is washed with benzene and then with ether.
n-propyl triphenyl phosphonium iodide is obtained with a yield of 81% (M.Pt.=165"C); b) Obtention of n-propylidene triphenyl phosphorane:
To 0.5x10-' mole of n-propyl triphenyl phosphonium iodide, in suspension in 50 cm3 of dimethoxyethane, are added, at OOC, 0.6x 10-' mole of butyl lithium. The mixture obtained is agitated for 30 minutes and npropylidene triphenyl phosphorane is obtained;
c) Obtention of triphenyl 3-pentyl phosphonium iodide:
To a solution of 3x10-' mole of ethyl iodide in 30 cm3 of dimethoxyethane are added, at 0 C, 0.5x10-' mole of npropylidene triphenyl phosphorane. The mixture obtained is agitated for 3 hours at 60"C and, after isolation triphenyl 3-pentyl phosphonium iodide is obtained with a yield of 80% (M.Pt.=190"C).
Example 4
Preparation of racemic trans methyl 2,2
diethyl - cyclopropane - 1,3
dicarboxylate (compound of formula I
with X=ethyl and R=methyl).
Into 15 cm3 of dimethoxyethane are introduced, under nitrogen, 0.688 g of triphenyl 3-pentyl phosphonium iodide.
Slowly at 0 C 0.05 g of butyl lithium, in solution in 0.7 cm3 of pentane, are added thereto. The mixture obtained is agitated for 30 minutes at 0 C and 0.128 g of dimethyl fumarate, in solution in 5 cm3 of dimethoxyethane, are introduced therein.
The resultant mixture is agitated for 15 minutes at OOC, the temperature is allowed to rise again to 20"C and the mixture is then agitated until decolourisation occurs (about 2 hours). Water is then added and the solution obtained is agitated then treated as in Example 1. The residue is chromatographed on silica gel eluting with a mixture of benzene containing 30d of ethyl acetate. 0.150 g of racemic trans methyl 2,2 - diethyl - cyclopropane - 1,3 dicarboxylate are obtained.
In a similar manner, starting with ethyl fumarate and 3 - pentyl triphenyl phosphonium iodide, racemic trans ethyl 2,2 - diethyl - cyclopropane - I.3 - dicarboxylate is obtained (compound of formula I with X=ethyl and R=ethyl).
B.Pt.=83-850C under 0.5 mm of mercury.
Example 5
Preparation of racemic trans ethyl spiro [2,4] - heptane - 1,2 - dicarboxylate
(compound of formula I with
X+X=cyclopentyl and R=ethyl).
Into 15 cm3 of dimethoxyethane are introduced, under nitrogen, 0.616 g of triphenyl cyclopentyl phosphonium bromide. Slowly at OOC 0.090 g of butyl lithium, in solution in 0.7 cm3 of pentane, are added thereto and the mixture obtained is agitated for 30 minutes at 0 C. 0.156 g of diethyl fumarate, in solution in 5 cm3 of dimethoxyethane, are introduced therein and the resultant mixture is agitated for 15 minutes at OOC. The temperature of the mixture is allowed to rise again to 200C and agitation is continued until decolourisation takes place (about 2 hours). Water is then added and the resultant mixture is agitated, then extracted with ether. The ethereal extracts are washed with water, then with an aqueous solution of sodium chloride, dried and concentrated to dryness. The residue is rectified under reduced pressure. 0.125 g of racemic trans ethyl spiro - [2,41 - heptane 1,2 - dicarboxylate are obtained.
B.Pt.=105 C under 0.7 mm of mercury.
Example 6 Preparation of racemic trans methyl spiro [2,51 - octane - 1,2 - dicarboxylate
(compound of formula I with
X+X=cyclohexyl and R=methyl).
Into 15 cm3 of dimethoxyethane are introduced, under nitrogen, 0.638 g of triphenyl cyclohexyl phosphonium bromide and slowly at OOC 0.090 g of butyl lithium, in solution in 0.7 cm3 of pentane, are added
The mixture obtained is agitated for 30 30 minutes at OOC and 0.128 g of dimethyl fumarate, in solution in 5 cm3 of dimethoxyethane, are introduced therein
The resultant mixture is agitated for 15 minutes at OOC, the temperature is allowed to rise again to 200C and agitation is continued until decolourisation takes place (about two hours). Water is added thereto and the mixture obtained is agitated, then treated as in Example 1. The residue is chromatographed on silica gel eluting with a mixture of benzene containing 3 O of ethyl acetate. 0.164 g of racemic trans methyl spiro - [2,5] - octane - 1,2 - dicarboxylate are obtained.
Example 7
Preparation of racemic trans methyl spiro [2,41 - heptane - 1,2 - dicarboxylate
(compound of formula I with
X+X=cyclopentyl and R=methyl).
Into 4300 cm3 of dimethoxyethane are introduced. under nitrogen, 160 g of triphenyl cyclopentyl phosphonium bromide, followed slowly at 0 C by 160 cm3 of 2.1 N butyl lithium in solution in pentane.
The mixture obtained is agitated for 30 minutes at 25"C, cooled-to 0 C and then very slowly, 43.2 g of dimethyl fumarate, are introduced. The resultant mixture is agitated at 25"C until decolourisation takes place (about 5 hours). Water is then added and the mixture obtained is extracted with ether. The ether extracts are treated as in
Example 2 to yield 15.2 g of racemic trans methyl spiro - [2,4] - heptane - 1,2 dicarboxylate. B.Pt.=89 C under 0.08 mm of mercury.
N.M.R. Spectrum (dimethylsulphoxide) 6=1.40--1.80 p.p.m. (multiplet, 8H):
a=2.22 p.p.m. (singlet, 2H); a=3.64 p.p.m. (singlet 6H).
Example 8
Preparation of racemic trans methyl spiro
[2,5] - octane - 1,2 - dicarboxylate
(compound of formula I with
X+X=cyclohexyl and R=methyl).
Into 3200 cm3 of dimethoxyethane are introduced, under nitrogen, 115 g of triphenyl cyclohexyl phosphonium bromide followed slowly at 0 C by 112 cm3 of 2.1 N butyl lithium in solution in pentane. The mixture obtained is agitated for 30 minutes at 25"C, cooled to 0 C and then, very slowly, 32.5 g of dimethyl fumarate are introduced therein. The resultant mixture is agitated at 250C until decolourisation takes place (about 5 hours). Water is then added and the mixture obtained is extracted with ether. The ethereal extracts are washed with a saturated aqueous solution of sodium
chloride, dried and concentrated to dryness.
The residue is rectified under reduced pressure. 20.4 g of racemic trans methyl spiro - [2,5] - octane - 1,2 - dicarboxylate are obtained. B.Pt.=133 to 138"C under 0.5 mm of mercury.
N.M.R. Spectrum (dimethylsulphoxide) S=1.2e1.80 p.p.m. (multiplet, 10H); a=2.12 p.p.m. (singlet, 2H); .a=3.68 p.p.m. (singlet, 6H).
In a similar manner, starting with cyclohexyl triphenyl phosphonium bromide and diethyl fumarate, trans ethyl spiro [2,5] - octane - 1,2 - dicarboxylate is obtained (compound of formula I with
X+X=cyclohexyl and R=ethyl) B.Pt.=90-- 130"C under 0.08 mm of mercury.
WHAT WE CLAIM IS:
1. A process for the preparation of racemic compounds of general formula I,
(wherein R represents an alkyl radical containing from 1 to 6 carbon atoms and either X represents an alkyl radical containing from I to 6 carbon atoms or the two radicals X, together with the carbon atom to which they are attached, represent a cycloalkyl radical containing from 3 to 7 carbon atoms) which comprises reacting a compound of formula II,
(wherein R is as defined above) with a compound of formula III
(wherein X is as defined above 0 represents a phenyl radical and Hal represents a chlorine, bromide or iodine atom) in the presence of a strong base and of an organic solvent.
2. A process as claimed in claim 1 wherein the base comprises an alkali metal alcoholate, hydride or amide or an alkyl lithium derivative.
3. A process as claimed in claim 2 wherein the base comprises butyl lithium.
4. A process as claimed in any of the preceding claims wherein the organic solvent comprises dimethylsulphoxide, dimethoxyethane, dimethylformamide, hexamethylphosphorotriamide, an aliphatic hydrocarbon, an aromatic monocyclic hydrocarbon, a cycloalkane or mixtures thereof.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (24)
1. A process for the preparation of racemic compounds of general formula I,
(wherein R represents an alkyl radical containing from 1 to 6 carbon atoms and either X represents an alkyl radical containing from I to 6 carbon atoms or the two radicals X, together with the carbon atom to which they are attached, represent a cycloalkyl radical containing from 3 to 7 carbon atoms) which comprises reacting a compound of formula II,
(wherein R is as defined above) with a compound of formula III
(wherein X is as defined above 0 represents a phenyl radical and Hal represents a chlorine, bromide or iodine atom) in the presence of a strong base and of an organic solvent.
2. A process as claimed in claim 1 wherein the base comprises an alkali metal alcoholate, hydride or amide or an alkyl lithium derivative.
3. A process as claimed in claim 2 wherein the base comprises butyl lithium.
4. A process as claimed in any of the preceding claims wherein the organic solvent comprises dimethylsulphoxide, dimethoxyethane, dimethylformamide, hexamethylphosphorotriamide, an aliphatic hydrocarbon, an aromatic monocyclic hydrocarbon, a cycloalkane or mixtures thereof.
5. A process as claimed in claim 4 wherein
the organic solvent comprises a mixture of dimethoxyethane and pentane.
6. A process as claimed in any of the preceding claims wherein the compound of formula III is used in excess with respect to the compound of formula II.
7. A process as claimed in claim 6 wherein from 1.2 to 1.6 moles of the compound of formula III are used per mole of the compound of formula II.
8. A process as claimed in any of the preceding claims wherein the base is used in excess with respect to the compound of formula II.
9. A process as claimed in claim 8 wherein from 1.1 to 1.5 moles of base are used per mole of the compound of formula II.
10. A process as claimed in any of the preceding claims for the preparation of racemic trans methyl 2,2 - dimethyl cyclopropane - 1,3 - dicarboxylate; racemic trans ethyl 2,2 dimethyl - cyclopropane - 1,3 ,3 dicarboxylate; racemic trans methyl 2,2 diethyl - cyclopropane - 1,3 dicarboxylate: racemic trans ethyl 2,2 - diethylcyclopropane - 1,3 - dicarboxylate; racemic trans methyl spiro - [2,4] - heptane - 1,2 - dicarboxylate; racemic trans ethyl spiro - [2,4] - heptane - 1,2 dicarboxylate; racemic trans methyl spiro [2,5] - octane - 1,2 - dicarboxylate; or racemic trans ethyl spiro - [2,5] - octane 1,2 - dicarboxylate.
11. A process for the preparation of compounds of general formula I as claimed in claim 1 substantially as herein described.
12. A process for the preparation of compounds of general formula I as defined
in claim substantially as herein described in
any of Examples 1 to 8.
13. Compounds of general formula I as
defined in claim 1 whenever prepared by a process as claimed in any of claims 1 to 12.
14. Compounds of general formula I as defined in claim 1 wherein X is other than a
methyl radical.
15. Compounds of general formula I as defined in claim 1 wherein X represents an
ethyl radical.
16. Compounds as claimed in claim 15 wherein R represents a methyl or ethyl radical.
17. Compounds of general formula I as defined in claim 1 wherein the two radicals
X, together with the carbon atom to which they are attached, represent a cyclopentyl or cyclohexyl radical.
18. Compounds as claimed in claim 17 wherein R represents a methyl or ethyl radical.
19. Racemic trans methyl 2,2 - diethyl cyclopropane - 1,3 - dicarboxylate.
20. Racemic trans ethyl 2,2 - diethyl cyclopropane - 1,3 - dicarboxylate.
21. Racemic trans methyl spiro - [2,4] heptane - 1,2 - dicarboxylate.
22. Racemic trans ethyl spiro - [2,4] heptane - 1,2 - dicarboxylate.
23. Racemic trans methyl spiro - [2,5] octane - 1,2 - dicarboxylate.
24. Racemic trans ethyl spiro - [2,5] octane - 1,2 - dicarboxylate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7639532A FR2376119A1 (en) | 1976-12-30 | 1976-12-30 | PROCESS FOR PREPARING LOWER ALCOYL ESTERS OF TRANS CYCLOPROPANE-1,3-DICARBOXYLIC, 2,2-DISUBSTITUTED RACEMIC ACIDS AND NEW ESTERS OF SAID ACIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1596029A true GB1596029A (en) | 1981-08-19 |
Family
ID=9181715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB5417777A Expired GB1596029A (en) | 1976-12-30 | 1977-12-29 | Cyclopropane dicarboxylic acid esters |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS5384946A (en) |
| BE (1) | BE862460A (en) |
| CH (1) | CH626319A5 (en) |
| DE (1) | DE2758624A1 (en) |
| FR (1) | FR2376119A1 (en) |
| GB (1) | GB1596029A (en) |
| IT (1) | IT1093080B (en) |
| NL (1) | NL7714499A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2923776A1 (en) * | 1979-06-12 | 1980-12-18 | Bayer Ag | METHOD FOR THE PRODUCTION OF 3,3-DIMETHYL-CYCLOPROPAN-1,2-DICARBONIC ACID ESTERS AND INTERMEDIATE PRODUCTS FOR THE PRODUCTION THEREOF |
| DE2923774A1 (en) * | 1979-06-12 | 1980-12-18 | Bayer Ag | METHOD FOR PRODUCING 3,3-DIMETHYL-CYCLOPROPAN-1,2-DICARBONIC ACID ESTERS |
| FR2491920A1 (en) * | 1980-10-10 | 1982-04-16 | Roussel Uclaf | NOVEL METHYL ESTERS DERIVED FROM 2,2-DIMETHYL CYCLOPROPANE 1,3-DICARBOXYLIC ACID, THEIR PREPARATION AND NOVEL INTERMEDIATES OBTAINED |
| FR2491921A1 (en) * | 1980-10-10 | 1982-04-16 | Roussel Uclaf | NOVEL TERBUTILIC ESTERS DERIVED FROM 2,2-DIMETHYL CYCLOPROPANE 1,3-DICARBOXYLIC ACID, THEIR PREPARATION AND THE NEW INTERMEDIATES OBTAINED |
| DE3111849A1 (en) * | 1981-03-26 | 1982-10-14 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING CARONALDEHYDIC ACID AND THEIR DERIVATIVES |
| FR2624511B1 (en) * | 1987-12-11 | 1990-09-21 | Roussel Uclaf | ENANTIOSELECTIVE PROCESS FOR PREPARING HEMICARONIC ALDEHYDE DERIVATIVES WITH TRANS OR CIS STRUCTURE |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5142101B2 (en) * | 1972-05-16 | 1976-11-13 | ||
| US4083863A (en) * | 1976-06-01 | 1978-04-11 | American Cyanamid Corporation | Process for the preparation of cyclopropane carboxylic acids and esters |
-
1976
- 1976-12-30 FR FR7639532A patent/FR2376119A1/en active Granted
-
1977
- 1977-12-21 IT IT5232677A patent/IT1093080B/en active
- 1977-12-28 NL NL7714499A patent/NL7714499A/en not_active Application Discontinuation
- 1977-12-28 JP JP15752077A patent/JPS5384946A/en active Granted
- 1977-12-29 BE BE183958A patent/BE862460A/en not_active IP Right Cessation
- 1977-12-29 DE DE19772758624 patent/DE2758624A1/en active Granted
- 1977-12-29 GB GB5417777A patent/GB1596029A/en not_active Expired
- 1977-12-30 CH CH1630577A patent/CH626319A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| IT1093080B (en) | 1985-07-19 |
| JPS5384946A (en) | 1978-07-26 |
| CH626319A5 (en) | 1981-11-13 |
| FR2376119B1 (en) | 1982-09-17 |
| BE862460A (en) | 1978-06-29 |
| NL7714499A (en) | 1978-07-04 |
| DE2758624A1 (en) | 1978-07-13 |
| JPS6139934B2 (en) | 1986-09-06 |
| FR2376119A1 (en) | 1978-07-28 |
| DE2758624C2 (en) | 1987-08-20 |
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