JP5546947B2 - 含硫カルボン酸エステル類の製造方法 - Google Patents
含硫カルボン酸エステル類の製造方法 Download PDFInfo
- Publication number
- JP5546947B2 JP5546947B2 JP2010111483A JP2010111483A JP5546947B2 JP 5546947 B2 JP5546947 B2 JP 5546947B2 JP 2010111483 A JP2010111483 A JP 2010111483A JP 2010111483 A JP2010111483 A JP 2010111483A JP 5546947 B2 JP5546947 B2 JP 5546947B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- carbon atoms
- formula
- alkyl group
- 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.)
- Active
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 14
- 239000011593 sulfur Substances 0.000 title claims description 14
- 229910052717 sulfur Inorganic materials 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001733 carboxylic acid esters Chemical class 0.000 title description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 150000003566 thiocarboxylic acids Chemical class 0.000 claims description 7
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 3
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 3
- 229940106681 chloroacetic acid Drugs 0.000 claims description 3
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 3
- ZDYVRSLAEXCVBX-UHFFFAOYSA-N pyridinium p-toluenesulfonate Chemical compound C1=CC=[NH+]C=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 ZDYVRSLAEXCVBX-UHFFFAOYSA-N 0.000 claims description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims 2
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 claims 1
- -1 alkali metal alkoxide Chemical class 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000003205 fragrance Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000020176 deacylation Effects 0.000 description 5
- 238000005947 deacylation reaction Methods 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 150000004703 alkoxides Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OAPHLAAOJMTMLY-GQCTYLIASA-N Ethyl 2-methylbut-2-enoate Chemical compound CCOC(=O)C(\C)=C\C OAPHLAAOJMTMLY-GQCTYLIASA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- 239000001696 ethyl (E)-2-methylbut-2-enoate Substances 0.000 description 3
- IAZBJQPJANCKDO-UHFFFAOYSA-N ethyl 3-acetylsulfanyl-2-methylbutanoate Chemical compound CCOC(=O)C(C)C(C)SC(C)=O IAZBJQPJANCKDO-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZFDIRQKJPRINOQ-HWKANZROSA-N Ethyl crotonate Chemical compound CCOC(=O)\C=C\C ZFDIRQKJPRINOQ-HWKANZROSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- YWBKQHMUWNMQOP-UHFFFAOYSA-N ethyl 2-methyl-3-sulfanylbutanoate Chemical compound CCOC(=O)C(C)C(C)S YWBKQHMUWNMQOP-UHFFFAOYSA-N 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 2
- 239000001069 triethyl citrate Substances 0.000 description 2
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 2
- 235000013769 triethyl citrate Nutrition 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- FPBCNQQYLDBWMH-UHFFFAOYSA-N Ethyl 3-mercaptobutyrate Chemical compound CCOC(=O)CC(C)S FPBCNQQYLDBWMH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- JGVDBODXXHHCJH-UHFFFAOYSA-N butyl acetate;ethyl acetate Chemical compound CCOC(C)=O.CCCCOC(C)=O JGVDBODXXHHCJH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 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 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- LYHVMRGYESPMHE-UHFFFAOYSA-N ethyl 2-methyl-3-sulfanylpropanoate Chemical compound CCOC(=O)C(C)CS LYHVMRGYESPMHE-UHFFFAOYSA-N 0.000 description 1
- OUGJKAQEYOUGKG-UHFFFAOYSA-N ethyl 2-methylidenebutanoate Chemical compound CCOC(=O)C(=C)CC OUGJKAQEYOUGKG-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- SIHZGXAHFFTEBL-UHFFFAOYSA-N ethyl 3-acetylsulfanyl-2-methylpropanoate Chemical compound CCOC(=O)C(C)CSC(C)=O SIHZGXAHFFTEBL-UHFFFAOYSA-N 0.000 description 1
- HTFAPDVTXLGQAD-UHFFFAOYSA-N ethyl 3-sulfanylhexanoate Chemical compound CCCC(S)CC(=O)OCC HTFAPDVTXLGQAD-UHFFFAOYSA-N 0.000 description 1
- LCTWEFWNYQHBQO-UHFFFAOYSA-N ethyl 4-ethanethioyloxybutanoate Chemical compound CCOC(=O)CCCOC(C)=S LCTWEFWNYQHBQO-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 1
- ALBMLVQIWZKGIN-UHFFFAOYSA-N o-ethyl 3-methyl-4-oxopentanethioate Chemical compound CCOC(=S)CC(C)C(C)=O ALBMLVQIWZKGIN-UHFFFAOYSA-N 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/20—Synthetic spices, flavouring agents or condiments
- A23L27/202—Aliphatic compounds
- A23L27/2022—Aliphatic compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/32—Esters of monothiocarboxylic acids having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by carboxyl groups
Description
[1]酸触媒存在下、下記一般式(1)
で表されるα,β−不飽和カルボン酸エステルと、下記一般式(2)
で表されるチオカルボン酸とを反応させることを特徴とする下記式(3)
で表される含硫カルボン酸エステル類の製造方法。
[2]酸触媒が、パラトルエンスルホン酸(及びその水和物)、パラトルエンスルホン酸ピリジン塩、ナフタレンスルホン酸(及びその水和物)、メタンスルホン酸、カンファースルホン酸(及びその水和物)、硫酸、酢酸、トリフルオロ酢酸、クロロ酢酸及び塩酸の中から選ばれる少なくとも1種を使用することを特徴とする前記[1]に記載の製造方法。
[3]前記[1]又は[2]に記載の方法で製造される一般式(3)
で表される含硫カルボン酸エステル類を、炭素数1〜10のアルコール中で、炭素数1〜10のアルカリ金属アルコキシド又は炭酸アルカリ金属塩を用いて脱アシル化することを特徴とする下記一般式(4)
で表される3−メルカプトカルボン酸エステル類の製造方法。
[4]前記[1]乃至[3]に記載の方法で製造された、一般式(3)及び一般式(4)で表されるカルボン酸エステル類の少なくとも1種類以上を含むことを特徴とする香料組成物。
[5]前記[4]に記載の香料組成物を含有することを特徴とする飲食品、化粧品、洗剤、柔軟剤、芳香剤、消臭剤、入浴剤又は医薬品。
本発明の方法において、一般式(1)、(3)及び(4)の化合物において、R1、R2及びR3で表される基について説明する。R1は炭素数1〜10のアルキル基又は置換基を有していてもよいフェニル基(該置換基は炭素数1〜4のアルキル基、炭素数1〜4のアルコキシ基である。)を表し、R2及びR3はそれぞれ独立して、水素原子又は炭素数1〜10のアルキル基を表すか、又はR2とR3とでアルキレン基を形成してもよい。
キャピラリーカラム:TC−1(15m x 0.53mm)
カラム温度:50 → 250℃(10℃/分 昇温),
インジェクション温度:250℃ ,
ディテクター温度:250℃
チグリン酸エチル51.27g(0.40mol)、チオ酢酸76.12g(1.00mol)及びパラトルエンスルホン酸7.60g(0.04mol)の混合物を、窒素気流下、75℃で24時間撹拌した。冷却後、反応液にジエチルエーテル及び飽和炭酸水素ナトリウム水溶液を加えて、有機層を分液後、飽和食塩水で2回洗浄した。有機層から溶媒を留去後、減圧蒸留(68℃〜71℃/2torr)を行い76.36gの目的物が得られた(GC純度:98.3%、収率:91.8%、ジアステレオマー比:80.9/19.1)。
種々のα,β−不飽和カルボン酸エステルについて実施例1と同様の操作を行った結果を下記表1に示し、得られた含硫カルボン酸エステル類を下記式(3’)で示す。表中の純度はGC純度を表す。
(式中、Acはアセチル基を表し、R1、R2及びR3は、それぞれ下記表1に記載の基又は水素原子を表す。)
窒素気流下、3−アセチルチオ−2−メチル酪酸エチル40.00g(0.192mol)及びエタノール800mlの混合物を、−15℃に冷却し、20%ナトリウムエトキシドのエタノール溶液72.01g(0.212mol、1.1当量)を1時間で滴下後、3時間攪拌した。酢酸15.00gを反応液に加え中和後、減圧下でエタノールを留去した。残渣に食塩水を加え、ジエチルエーテルで抽出し、得られた有機層を飽和炭酸水素ナトリウム水溶液、飽和食塩水(2回)の順で洗浄した。有機層から溶媒を留去後、減圧蒸留(35℃〜36℃/2torr)を行い17.63gの目的物を得た(GC純度:99.3%、収率:56.1%、ジアステレオマー比:80.6/19.4)。
種々の3−アセチルチオカルボン酸エステルについて実施例9と同様の操作を行った結果を下記表2に示し、得られた3−メルカプトカルボン酸エステル類を下記式(4)で示す。表中の純度はGC純度を表す。
チグリン酸エチル3.20g(0.025mol)及びチオ酢酸4.76g(0.0625mol)の混合物を、窒素気流下で85℃、24時間反応させた。その結果、チグリン酸エチルの転化率は35.3%、目的物の選択率は91.6%であった。
実施例9で合成した3−メルカプト−2−メチル酪酸エチルを、クエン酸トリエチル(TEC)にて0.01%に希釈して香料組成物を調製した。
下記表3に示すように、実施例17の香料組成物を3重量%含有するフローラル香料100gを調製した。
Claims (1)
- パラトルエンスルホン酸(及びその水和物)、パラトルエンスルホン酸ピリジン塩、ナフタレンスルホン酸(及びその水和物)、メタンスルホン酸、カンファースルホン酸(及びその水和物)、硫酸、酢酸、トリフルオロ酢酸、クロロ酢酸及び塩酸の中から選ばれる少なくとも1種の酸触媒存在下、下記一般式(1)
で表されるα,β−不飽和カルボン酸エステルと、下記一般式(2)
で表されるチオカルボン酸とを反応させることを特徴とする下記式(3)
で表される含硫カルボン酸エステル類の製造方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010111483A JP5546947B2 (ja) | 2010-05-13 | 2010-05-13 | 含硫カルボン酸エステル類の製造方法 |
EP11162998A EP2452933A1 (en) | 2010-05-13 | 2011-04-19 | Method for producing sulfur-containing carboxylic acid esters |
US13/093,133 US8536364B2 (en) | 2010-05-13 | 2011-04-25 | Method for producing sulfur-containing carboxylic acid esters |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010111483A JP5546947B2 (ja) | 2010-05-13 | 2010-05-13 | 含硫カルボン酸エステル類の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2011236185A JP2011236185A (ja) | 2011-11-24 |
JP5546947B2 true JP5546947B2 (ja) | 2014-07-09 |
Family
ID=44584882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2010111483A Active JP5546947B2 (ja) | 2010-05-13 | 2010-05-13 | 含硫カルボン酸エステル類の製造方法 |
Country Status (3)
Country | Link |
---|---|
US (1) | US8536364B2 (ja) |
EP (1) | EP2452933A1 (ja) |
JP (1) | JP5546947B2 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102176838A (zh) * | 2008-10-10 | 2011-09-07 | 高砂香料工业株式会社 | 含硫醇的香料和调味料 |
WO2016156473A1 (en) | 2015-04-01 | 2016-10-06 | Basell Poliolefine Italia S.R.L. | Catalyst components for the polymerization of olefins |
JP6697429B2 (ja) * | 2017-11-06 | 2020-05-20 | 長谷川香料株式会社 | 新規アルカンチオ酸誘導体および該化合物を含有する香料組成物 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2540498B1 (fr) * | 1983-02-07 | 1986-02-14 | Roussel Uclaf | Nouveaux medicaments derives d'amides d'acide mercaptoacetique et de l'acide 3-mercaptopropionique et les compositions pharmaceutiques les renfermant |
US5565473A (en) * | 1990-10-12 | 1996-10-15 | Merck Frosst Canada, Inc. | Unsaturated hydroxyalkylquinoline acids as leukotriene antagonists |
US6037472A (en) * | 1993-11-04 | 2000-03-14 | Syntex (U.S.A.) Inc. | Matrix metalloprotease inhibitors |
JPH09278746A (ja) * | 1996-04-04 | 1997-10-28 | Kanegafuchi Chem Ind Co Ltd | 光学活性2−アラルキル−3−アシルチオプロピオン酸エステルの製造方法 |
JP3967790B2 (ja) * | 1997-03-07 | 2007-08-29 | 新日本石油株式会社 | メルカプトポリブテニル誘導体の製造方法 |
SG91339A1 (en) * | 2000-03-08 | 2002-09-17 | Givaudan Sa | Organoleptic compositions |
US6899911B2 (en) * | 2000-04-05 | 2005-05-31 | International Flavors & Fragrances, Inc. | Ethyl 4-(thioacetoxy)butyrate as a flavoring agent and methods for preparing and using same |
US20020150662A1 (en) * | 2000-04-19 | 2002-10-17 | Dewis Mark Lawrence | Ethyl 3-mercaptobutyrate as a flavoring or fragrance agent and methods for preparing and using same |
EP1325908A1 (en) * | 2001-12-14 | 2003-07-09 | Dsm N.V. | Process for the preparation of an enantiomerically enriched thio compound |
US6844460B2 (en) * | 2003-01-03 | 2005-01-18 | Dow Corning Corporation | Method of making mercaptoalkylalkyldialkoxysilanes |
JP2005015686A (ja) * | 2003-06-27 | 2005-01-20 | Kiyomitsu Kawasaki | フルーツ様香料組成物 |
CN102176838A (zh) * | 2008-10-10 | 2011-09-07 | 高砂香料工业株式会社 | 含硫醇的香料和调味料 |
-
2010
- 2010-05-13 JP JP2010111483A patent/JP5546947B2/ja active Active
-
2011
- 2011-04-19 EP EP11162998A patent/EP2452933A1/en not_active Withdrawn
- 2011-04-25 US US13/093,133 patent/US8536364B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
US20110282089A1 (en) | 2011-11-17 |
EP2452933A1 (en) | 2012-05-16 |
JP2011236185A (ja) | 2011-11-24 |
US8536364B2 (en) | 2013-09-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2004535412A (ja) | じゃ香性を有する芳香剤としてのシクロアルカンカルボン酸誘導体 | |
JP5546947B2 (ja) | 含硫カルボン酸エステル類の製造方法 | |
CN107417505A (zh) | α‑卤代四甲基环己酮及其与(2,3,4,4‑四甲基环戊基)甲基羧酸酯的制备方法 | |
US7585535B2 (en) | Flavour and fragrance compositions | |
KR101873838B1 (ko) | 신규 지환식 알코올 | |
CN107001192A (zh) | 方法 | |
US5049544A (en) | Perfumery composition comprising 2-cyclohexylpropionic acid or its derivative | |
US7642385B2 (en) | Alcohol compounds | |
JP2010534630A (ja) | エチルゲラノニトリルの製造方法 | |
JP3913594B2 (ja) | メルカプトアルコールカルボン酸エステル類、その香料組成物及び該エステル類の製造方法 | |
JP2009523716A (ja) | ファルネソールを含有していないか又はファルネソールの含有量が少ないビサボロールの製造方法 | |
TWI403497B (zh) | 6,8,10-十一碳三烯-3或4-醇及香料組成物 | |
CN113979980A (zh) | 一种高纯度丁位内酯的制备方法 | |
JP4786267B2 (ja) | ラクトンの製造方法及び製造されたラクトンの芳香物質としての用途 | |
ES2942280T3 (es) | Procesos para preparar ácido 2-isoprenil-5-metil-4-hexenoico, 2-isoprenil-5-metil-4-hexen-1-ol y un éster carboxilato del mismo | |
JP2020536918A (ja) | 香料としての脂肪族アルコールの合成 | |
JP5486177B2 (ja) | 新規ラクトン化合物とその製造方法及びその香料組成物 | |
JP4159700B2 (ja) | シクロヘキシルメタノール | |
JP2007297286A (ja) | 3,7−ジメチル−5−オクテン酸とその誘導体、およびそれらを含有する香料組成物。 | |
JPH05140071A (ja) | シクロペンチル−シアノメチル−シクロペンテン類、それらの製造方法及び芳香物質としての利用 | |
JPS5835180B2 (ja) | α、β不飽和ニトリルの製造法 | |
MX2009001381A (es) | Proceso para producir 2,2,3-trimetilciclopent-3-enecarbaldehido (aldehido camfolitico). | |
JP4789889B2 (ja) | (r)−2−アルキルシクロペンタノンの製造方法 | |
JP4217805B2 (ja) | 光学活性γ−ラクトンの製造方法 | |
JP2010083894A (ja) | ワインラクトン及びその中間体の製造法並びにその応用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20130312 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140129 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140304 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140418 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140513 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140514 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5546947 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |