WO2011108696A1 - α-アシロキシカルボニル化合物の製法及び新規なα-アシロキシカルボニル化合物 - Google Patents
α-アシロキシカルボニル化合物の製法及び新規なα-アシロキシカルボニル化合物 Download PDFInfo
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- WO2011108696A1 WO2011108696A1 PCT/JP2011/055043 JP2011055043W WO2011108696A1 WO 2011108696 A1 WO2011108696 A1 WO 2011108696A1 JP 2011055043 W JP2011055043 W JP 2011055043W WO 2011108696 A1 WO2011108696 A1 WO 2011108696A1
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- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- producing
- acyloxycarbonyl
- examples
- carboxylic acid
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 20
- 150000002576 ketones Chemical class 0.000 claims abstract description 18
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 8
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 7
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 7
- 150000002825 nitriles Chemical class 0.000 claims description 7
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 6
- 229940107816 ammonium iodide Drugs 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 5
- 150000002432 hydroperoxides Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000003759 ester based solvent Substances 0.000 claims description 4
- 239000004210 ether based solvent Substances 0.000 claims description 4
- LSMAIBOZUPTNBR-UHFFFAOYSA-N phosphanium;iodide Chemical compound [PH4+].[I-] LSMAIBOZUPTNBR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 41
- 239000000047 product Substances 0.000 description 74
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 62
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 37
- 239000005711 Benzoic acid Substances 0.000 description 31
- 235000010233 benzoic acid Nutrition 0.000 description 31
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 24
- -1 For example Chemical group 0.000 description 23
- 239000000758 substrate Substances 0.000 description 21
- 125000001424 substituent group Chemical group 0.000 description 17
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 125000003118 aryl group Chemical group 0.000 description 13
- 235000019439 ethyl acetate Nutrition 0.000 description 13
- 150000002085 enols Chemical class 0.000 description 12
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 238000005691 oxidative coupling reaction Methods 0.000 description 11
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 9
- 125000000304 alkynyl group Chemical group 0.000 description 9
- 125000000392 cycloalkenyl group Chemical group 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 229930194542 Keto Natural products 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 125000000000 cycloalkoxy group Chemical group 0.000 description 7
- 125000000468 ketone group Chemical group 0.000 description 7
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 150000002497 iodine compounds Chemical class 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 4
- 125000005336 allyloxy group Chemical group 0.000 description 4
- 150000001924 cycloalkanes Chemical class 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 150000003335 secondary amines Chemical class 0.000 description 4
- AEFPPQGZJFTXDR-UHFFFAOYSA-M tetraphenylphosphanium;iodide Chemical compound [I-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 AEFPPQGZJFTXDR-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical group [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000006575 electron-withdrawing group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 2
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
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- 230000000379 polymerizing effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- POXSDSRWVJZWCN-UHFFFAOYSA-N triphenylphosphanium;iodide Chemical compound I.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 POXSDSRWVJZWCN-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- NHOXPYKWAHZEHD-UHFFFAOYSA-N (1-oxo-1-phenylpropan-2-yl) benzoate Chemical compound C=1C=CC=CC=1C(=O)C(C)OC(=O)C1=CC=CC=C1 NHOXPYKWAHZEHD-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- MJUDFROXUXFMAA-UHFFFAOYSA-M 1,2-diphenylpropyl(trimethyl)azanium;iodide Chemical compound [I-].C=1C=CC=CC=1C(C)C([N+](C)(C)C)C1=CC=CC=C1 MJUDFROXUXFMAA-UHFFFAOYSA-M 0.000 description 1
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 1
- XYUWGADPPOLCNU-UHFFFAOYSA-N 3-phenylpent-2-enal Chemical compound O=CC=C(CC)C1=CC=CC=C1 XYUWGADPPOLCNU-UHFFFAOYSA-N 0.000 description 1
- GHEFQKHLHFXSBR-UHFFFAOYSA-N 4-chloro-1-phenylbutan-1-one Chemical compound ClCCCC(=O)C1=CC=CC=C1 GHEFQKHLHFXSBR-UHFFFAOYSA-N 0.000 description 1
- AGNFWIZBEATIAK-UHFFFAOYSA-N 4-phenylbutylamine Chemical compound NCCCCC1=CC=CC=C1 AGNFWIZBEATIAK-UHFFFAOYSA-N 0.000 description 1
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OBSYBRPAKCASQB-UHFFFAOYSA-N Episalvinorin A Natural products COC(=O)C1CC(OC(C)=O)C(=O)C(C2(C3)C)C1(C)CCC2C(=O)OC3C=1C=COC=1 OBSYBRPAKCASQB-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 208000028017 Psychotic disease Diseases 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical class [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- YKFKEYKJGVSEIX-UHFFFAOYSA-N cyclohexanone, 4-(1,1-dimethylethyl)- Chemical compound CC(C)(C)C1CCC(=O)CC1 YKFKEYKJGVSEIX-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 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
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 1
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- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
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- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- ZLHWTGZMAWUUMD-UHFFFAOYSA-M ethyl(tripropyl)azanium;iodide Chemical compound [I-].CCC[N+](CC)(CCC)CCC ZLHWTGZMAWUUMD-UHFFFAOYSA-M 0.000 description 1
- ZPEBBUBSCOELHI-UHFFFAOYSA-M ethyltrimethylammonium iodide Chemical compound [I-].CC[N+](C)(C)C ZPEBBUBSCOELHI-UHFFFAOYSA-M 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical compound C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- 238000007116 intermolecular coupling reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001786 isothiazolyl group Chemical group 0.000 description 1
- 125000000842 isoxazolyl group Chemical group 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- IQXUYSXCJCVVPA-UHFFFAOYSA-N salvinorin A Natural products CC(=O)OC1CC(OC(=O)C)C2(C)CCC34CC(CC3(C)C2C1=O)(OC4=O)c5occc5 IQXUYSXCJCVVPA-UHFFFAOYSA-N 0.000 description 1
- OBSYBRPAKCASQB-AGQYDFLVSA-N salvinorin A Chemical compound C=1([C@H]2OC(=O)[C@@H]3CC[C@]4(C)[C@@H]([C@]3(C2)C)C(=O)[C@@H](OC(C)=O)C[C@H]4C(=O)OC)C=COC=1 OBSYBRPAKCASQB-AGQYDFLVSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- KCSOHLKZTZMKQA-UHFFFAOYSA-M tetraheptylazanium;iodide Chemical compound [I-].CCCCCCC[N+](CCCCCCC)(CCCCCCC)CCCCCCC KCSOHLKZTZMKQA-UHFFFAOYSA-M 0.000 description 1
- VRKHAMWCGMJAMI-UHFFFAOYSA-M tetrahexylazanium;iodide Chemical compound [I-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC VRKHAMWCGMJAMI-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- NWOKSKQOENPYPP-UHFFFAOYSA-M tetraoctadecylazanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+](CCCCCCCCCCCCCCCCCC)(CCCCCCCCCCCCCCCCCC)CCCCCCCCCCCCCCCCCC NWOKSKQOENPYPP-UHFFFAOYSA-M 0.000 description 1
- KGPZZJZTFHCXNK-UHFFFAOYSA-M tetraoctylazanium;iodide Chemical compound [I-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC KGPZZJZTFHCXNK-UHFFFAOYSA-M 0.000 description 1
- FBLZDUAOBOMSNZ-UHFFFAOYSA-M tetrapentylazanium;iodide Chemical compound [I-].CCCCC[N+](CCCCC)(CCCCC)CCCCC FBLZDUAOBOMSNZ-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 125000005247 tetrazinyl group Chemical group N1=NN=NC(=C1)* 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- RLZMYANQLOCZOB-UHFFFAOYSA-M tributyl(methyl)phosphanium;iodide Chemical compound [I-].CCCC[P+](C)(CCCC)CCCC RLZMYANQLOCZOB-UHFFFAOYSA-M 0.000 description 1
- WMSWXWGJYOIACA-UHFFFAOYSA-M triethyl(phenyl)azanium;iodide Chemical compound [I-].CC[N+](CC)(CC)C1=CC=CC=C1 WMSWXWGJYOIACA-UHFFFAOYSA-M 0.000 description 1
- YOCNHAYWAZXNAZ-UHFFFAOYSA-M trimethyl(1-phenylethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)C(C)C1=CC=CC=C1 YOCNHAYWAZXNAZ-UHFFFAOYSA-M 0.000 description 1
- KKLAORVGAKUOPZ-UHFFFAOYSA-M trimethyl(phenyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)C1=CC=CC=C1 KKLAORVGAKUOPZ-UHFFFAOYSA-M 0.000 description 1
- XKGLSKVNOSHTAD-UHFFFAOYSA-N valerophenone Chemical compound CCCCC(=O)C1=CC=CC=C1 XKGLSKVNOSHTAD-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
- C07D213/46—Oxygen atoms
- C07D213/50—Ketonic radicals
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/14—Acetic acid esters of monohydroxylic compounds
- C07C69/145—Acetic acid esters of monohydroxylic compounds of unsaturated alcohols
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0255—Phosphorus containing compounds
- B01J31/0267—Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen
- B01J31/0268—Phosphonium compounds, i.e. phosphine with an additional hydrogen or carbon atom bonded to phosphorous so as to result in a formal positive charge on phosphorous
-
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
- C07C69/78—Benzoic acid esters
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
Definitions
- the present invention relates to a method for producing an ⁇ -acyloxycarbonyl compound and a novel ⁇ -acyloxycarbonyl compound.
- ⁇ -Oxycarbonyl compounds are useful skeletons for many natural products and pharmaceuticals.
- stoichiometric amounts of toxic heavy metal oxidants Pb, Mn, Tl
- a synthesis method using a hypervalent iodine compound instead of a heavy metal oxidant has also been reported.
- there is an intermolecular coupling reaction between Ochiai's ketone and acetic acid Non-patent Document 1.
- the present invention has been made to solve these problems, and is a method for producing an ⁇ -acyloxycarbonyl compound, which uses a Lewis acid or a carboxylic acid as a reaction substrate in a large excess.
- the main object is to provide a method that does not need to be applied and has a wide range of application of the reaction substrate.
- the present inventors have used a carbonyl compound selected from the group consisting of a carboxylic acid and a ketone, aldehyde and ester having a hydrogen atom at the ⁇ -position, using an iodide salt and hydroperoxide.
- a carbonyl compound selected from the group consisting of a carboxylic acid and a ketone, aldehyde and ester having a hydrogen atom at the ⁇ -position
- the method for producing an ⁇ -acyloxycarbonyl compound of the present invention uses a hydroperoxide as an oxidizing agent and an iodide salt as a catalyst precursor from a carboxylic acid and a ketone, aldehyde or ester having a hydrogen atom at the ⁇ -position.
- An acyloxy group derived from the carboxylic acid is introduced into the ⁇ -position of the carbonyl compound by performing an intermolecular reaction with a carbonyl compound selected from the group consisting of:
- an ⁇ -acyloxycarbonyl compound of the present invention it is not necessary to use a Lewis acid or a carboxylic acid as a reaction substrate in a large excess, and an ⁇ -acyloxycarbonyl compound can be obtained.
- ketones, aldehydes, and esters can be used as the carbonyl compound into which an acyloxy group derived from carboxylic acid is introduced, and the range of applications of reaction substrates is wide. In such a method for producing an ⁇ -acyloxycarbonyl compound, it is considered that the reaction proceeds according to the following formula.
- propiophenone is exemplified as the carbonyl compound
- benzoic acid is exemplified as the carboxylic acid.
- an iodide salt Z + I ⁇ , where Z + is a counter cation
- a hydroperoxide ROOH: R is hydrogen or alkyl
- ROH hydroperoxide
- the produced hypervalent iodine compound functions as a catalyst, and an intermolecular reaction between the carbonyl compound and the carboxylic acid proceeds to produce an ⁇ -acyloxycarbonyl compound.
- the hypervalent iodine compound returns to the iodide salt (catalyst precursor) again.
- the method for producing an ⁇ -acyloxycarbonyl compound of the present invention comprises a group consisting of a carboxylic acid and a ketone, aldehyde and ester having a hydrogen atom at the ⁇ -position, using hydroperoxide as an oxidizing agent and an iodide salt as a catalyst precursor.
- hydroperoxide as an oxidizing agent
- an iodide salt as a catalyst precursor.
- examples of the hydroperoxide include hydrogen peroxide water and organic hydroperoxide, with organic hydroperoxide being preferred.
- examples of the organic hydroperoxide include t-butyl hydroperoxide and cumene hydroperoxide, with t-butyl hydroperoxide being preferred. Since hydrogen peroxide water is inexpensive, even if the yield of ⁇ -acyloxycarbonyl compound is lower than that of organic hydroperoxide, it may be advantageous from an economic viewpoint.
- the hydroperoxide is preferably used in an amount of 1 to 5 equivalents, more preferably 1.1 to 2.5 equivalents, based on the carboxylic acid and carbonyl compound having a small number of moles.
- the usage form of hydroperoxide is preferably a form diluted with a solvent.
- an organic solvent for example, a hydrocarbon solvent such as decane
- water may be used as the solvent.
- examples of the iodide salt include ammonium iodide, phosphonium iodide, and alkali metal iodide.
- ammonium iodide tetraalkylammonium iodide (the four alkyls in tetraalkyl may be the same, two or three may be the same or all may be different), Tetraarylammonium iodide (the four aryls of tetraaryl may all be the same, two or three may be the same or all different), tetraarylalkylammonium iodide (The four arylalkyls in tetraarylalkyl may all be the same, or two or three may be the same, or all may be different).
- ammonium iodides include tetramethylammonium iodide, tetraethylammonium iodide, tetrapropylammonium iodide, tetrabutylammonium iodide, tetrapentylammonium iodide, tetrahexylammonium iodide, tetraheptylammonium iodide, tetra- n-octylammonium iodide, tetraoctadecylammonium iodide, ethyltrimethylammonium iodide, ethyltripropylammonium iodide, trimethylphenylammonium iodide
- the phosphonium iodide is the same as the ammonium iodide.
- Examples of the phosphonium iodide include tetraphenylphosphonium iodide, methyltriphenylphosphonium iodide, and tributylmethylphosphonium iodide. Among these, tetraphenylphosphonium iodide and methyltriphenylphosphonium iodide are preferable.
- the alkali metal iodide include potassium iodide and sodium iodide.
- a cyclic ether such as a crown ether capable of incorporating an alkali metal ion in order to increase the solubility.
- potassium iodide in combination with 18-crown-6.
- the iodide salt is preferably used in an amount of 1 to 50 mol%, more preferably 5 to 20 mol%, based on the carboxylic acid and carbonyl compound having a small number of moles. If the amount used is too small, the reaction rate is slow, and it takes a long time to complete the reaction, which is not preferable. On the other hand, if the amount used is too large, the yield is not greatly improved, which is not preferable from an economic standpoint. .
- ether solvents ether solvents
- ester solvents nitrile solvents
- ester solvents it is preferable to use at least one selected from the group consisting of ether solvents, ester solvents and nitrile solvents as a reaction solvent.
- a carboxylic acid or carbonyl compound used as a reaction substrate may be used as a reaction solvent, but it is not preferable when an expensive reaction substrate is used. For this reason, normally known reaction solvents are used. In that case, it is preferable to use one or more selected from the group consisting of ether solvents, ester solvents and nitrile solvents, and ester solvents.
- ether solvents include diethyl ether, tetrahydrofuran, 1,4-dioxane and the like.
- ester solvent include methyl acetate and ethyl acetate.
- nitrile solvent include acetonitrile, propionitrile, and butyronitrile.
- the reaction temperature may be appropriately set according to the reaction substrate, but is preferably 25 ° C. or higher, more preferably 50 ° C. or higher. If it is less than 25 degreeC, since reaction rate becomes slow and it takes a long time for completion
- the upper limit of the reaction temperature may be set as appropriate so that the reaction substrate is not decomposed and the side reaction does not become dominant, but may be, for example, 100 ° C. or less.
- the reaction time may be appropriately set according to the reaction substrate.
- the carbonyl compound has methylene (—CH 2 —) bonded to the carbonyl carbon, that is, has —C ( ⁇ O) —CH 2 — in the partial structure. It is preferable.
- the ⁇ -position hydrogen atom is the hydrogen atom of this methylene.
- the applicable range of the carbonyl compound and carboxylic acid which are reaction substrates is quite wide.
- the carbonyl compound any one of ketone, aldehyde, and ester can be used. This includes 1,3-diketones, 1,3-dialdehydes, 1,3-diesters, 1,3-ketoaldehydes and 1,3-ketoesters. Examples of such carbonyl compounds include those represented by R a —C ( ⁇ O) —CH 2 —R b or R a —C ( ⁇ O) —CH 2 —C ( ⁇ O) —R c .
- R a examples include a hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocycle, alkoxy, cycloalkoxy, allyloxy and the like, and those other than a hydrogen atom have a substituent. May be.
- R b examples include alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocycle, alkoxy, cycloalkoxy, allyloxy and the like, and these may have a substituent.
- R c examples include a hydrogen atom, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocycle, alkoxy, cycloalkoxy, allyloxy and the like, and these may have a substituent.
- R a and R b may be bonded to each other to form a hydrocarbon chain, and at least one hydrogen atom of the hydrocarbon chain may be substituted with a substituent.
- R a and R c may be bonded to each other to form a hydrocarbon chain, and at least one hydrogen atom of the hydrocarbon chain may be substituted with a substituent.
- One carbon atom of the hydrocarbon chain may be substituted with a heteroatom (O, S, NH, NR: where R is alkyl).
- a heteroatom O, S, NH, NR: where R is alkyl.
- Examples of such carbonyl compounds include tetrahydropyranone, indanone, tetralone, and derivatives thereof.
- alkyl examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, and the like.
- cycloalkyl examples include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, and the like.
- alkenyl examples include, but are not limited to, ethenyl, propenyl, butenyl and the like.
- the cycloalkenyl is not particularly limited, and examples thereof include cyclopentenyl, cyclohexenyl and the like.
- alkynyl Although it does not specifically limit as alkynyl, For example, ethynyl, propynyl, butynyl etc. are mentioned.
- alkyl, cycloalkyl, alkenyl, cycloalkenyl and alkynyl have a substituent
- examples of the substituent include a halogen atom, nitro, nitrile, aryl, heterocycle, alkoxycarbonyl, alkoxy, silyloxy and the like. Specific examples of aryl and heterocycle will be described later.
- the aryl is not particularly limited, and examples thereof include phenyl, naphthyl and those in which at least one hydrogen atom thereof is substituted with a substituent.
- the heterocycle is not particularly limited, and examples thereof include pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, tetrazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl and the like, and benzene, naphthalene. Or a condensed ring compound with cycloalkane, etc.
- substituents examples include a halogen atom, nitro, nitrile, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, cycloalkoxy, aryl and the like.
- alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl and alkynyl are as described above.
- alkoxy and cycloalkoxy are described later.
- alkoxy examples include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, benzyloxy, t-butyldimethylsilyloxy, methoxymethyloxy and the like. It is done.
- the cycloalkoxy is not particularly limited, and examples thereof include cyclopropoxy, cyclopentoxy, cyclohexoxy and the like.
- Allyloxy is not particularly limited, and examples thereof include phenoxy, naphthoxy, and those in which at least one hydrogen atom thereof is substituted.
- substituents in this case include a halogen atom, nitro, nitrile, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, cycloalkoxy, and the specific examples thereof are as described above.
- reaction substrate examples are represented by, for example, R a —C ( ⁇ O) —CH 2 —R b or R a —C ( ⁇ O) —CH 2 —C ( ⁇ O) —R c described above.
- R a , R b , and R c are selected from the substituents shown below.
- R a represents a hydrogen atom, methyl, t-butoxy, phenyl, methylphenyl, ethylphenyl, phenyl halide, methoxyphenyl, biphenyl, methylimidazolyl, phenylimidazolyl, methoxy, pyridyl, benzyl, or thienyl
- R b Is a hydrogen atom, benzyl, phenyl, or a C 1 -C 16 alkyl group (where the phenyl group or alkyl group is halogen (especially chloro or bromo), phenyl, ethoxycarbonyl, benzyloxy, t-butyldimethylsilyloxy, or methoxy
- R c may be a hydrogen atom, methyl, t-butoxy, phenyl, methylphenyl, ethylphenyl, which may be substituted with methyloxy and may have
- R a , —R b, and —C ( ⁇ O) CH 2 — may be bonded to each other to form a cycloalkane, for example, cyclohexane or cyclopentane.
- it may be a condensed ring compound of the cycloalkane and an aromatic ring, for example, phenyl.
- the cycloalkane and the aromatic ring may have a substituent, for example, an alkyl group (particularly a t-butyl group) or a halogen (particularly bromo).
- R a , —R b, and —C ( ⁇ O) CH 2 — may be bonded to each other to form a cyclic ether such as tetrahydropyran.
- an additive may be used for promoting the ⁇ -acyloxylation reaction or suppressing the formation of by-products.
- an amine is preferable, and a primary or secondary amine is more preferable.
- Specific examples include pyrrolidine, piperidine, 2,2,6,6-tetraalkylpiperidine, morpholine, 4-phenylbutylamine and the like.
- Such an additive is particularly effective when the reaction substrate is an aldehyde.
- Synthetic intermediates and monomers can also be used as reaction substrates.
- the applicable range of the other reaction substrate, carboxylic acid is also quite wide.
- the carboxylic acids those represented by R d CO 2 H are preferred.
- R d include alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl, heterocycle and the like, and those other than a hydrogen atom may have a substituent. Specific examples thereof are as described above.
- carboxylic acids include saturated aliphatic carboxylic acids such as acetic acid, propanoic acid, butanoic acid and pentanoic acid, unsaturated aliphatic carboxylic acids such as acrylic acid and methacrylic acid, and aromatic carboxylic acids such as benzoic acid, etc. Is mentioned.
- unsaturated aliphatic carboxylic acid has a molecular structure without oxidizing the unsaturated bond or proceeding the polymerization reaction even though the production method of the ⁇ -acyloxycarbonyl compound of the present invention is an oxidation reaction. Interoxidative coupling reaction proceeded selectively and efficiently.
- the amounts of carbonyl compound and carboxylic acid used may be appropriately set in consideration of reactivity.
- the mixing ratio of carboxylic acid and carbonyl compound is preferably 0.5: 2 to 2: 0.5, more preferably 1: 2 to 2: 1. From an economic point of view, it is preferable to use one equivalent of carboxylic acid relative to the carbonyl compound, but when the price of the carboxylic acid is higher than that of the carbonyl compound or when the excess of the carbonyl compound is more reactive
- the amount of carboxylic acid used may be less than 1 equivalent with respect to the carbonyl compound. On the contrary, when the price of the carbonyl compound is higher than that of the carboxylic acid or when the excess of the carboxylic acid is more reactive, the amount of the carboxylic acid used is more than 1 equivalent with respect to the carbonyl compound. Also good.
- the ⁇ -acyloxycarbonyl compound of the present invention is represented by the following formula (1).
- Ar is a phenyl group, a phenyl group having one or more alkyl groups, or a phenyl group having one or more halogen atoms
- R is an alkyl group
- X is an alkyl group or a halogen atom
- m is 0.
- N is an integer from 1 to 4
- k and k ′ are each an integer from 0 to 4 and k + k ′ is an integer from 1 to 4
- A is O, S, NH, NR Or it is CHR (R is an alkyl group).
- alkyl group examples include a branch having 1 to 8 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the ⁇ -acyloxycarbonyl compound of the formula (1) has an acrylic acid skeleton or a methacrylic acid skeleton, it is useful as a monomer for synthesizing a polymer.
- a polymer obtained by polymerizing such a monomer is expected to have high heat resistance or a high refractive index, or to suppress curing shrinkage.
- Examples of the ⁇ -acyloxycarbonyl compound of the formula (1) include those represented by the following formula.
- Example 2 In Example 1, 1.0 mmol of benzoic acid, 0.1 mmol of Bu 4 NI (10 mol% with respect to benzoic acid), 2.0 mmol of TBHP (2 equivalents with respect to benzoic acid) were used, and the mixture was heated for 50 hours. The product was obtained in the same manner as in Example 1 except for the above. The yield was 80%.
- Example 3 In Example 1, 2.0 mmol of benzoic acid, 0.1 mmol of Bu 4 NI (10 mol% relative to propiophenone) and 2.0 mmol of TBHP (2 equivalents relative to propiophenone) were used for 68 hours. A product was obtained in the same manner as in Example 1 except for heating. The yield was 80%.
- Example 4 In Example 1, 1 mmol of benzoic acid, 0.1 mmol of Bu 4 NI (10 mol% with respect to benzoic acid), 1.1 mmol of TBHP (1.1 equivalent with respect to benzoic acid) were used, and the mixture was heated for 29 hours. The product was obtained in the same manner as in Example 1 except for the above. The yield was 76%.
- Example 5 In Example 4, produced in the same manner as in Example 4 except that 1.1 mmol (1.1 equivalent to benzoic acid) of TBHP (70% aqueous solution) was used instead of TBHP (5.5 M decane solution). I got a thing. The yield was 72%.
- Example 6 In Example 1, 1.0 mmol of benzoic acid, 0.1 mmol of (C 18 H 37 ) 4 NI (10 mol% with respect to benzoic acid) instead of Bu 4 NI, and 2.0 mmol of TBHP (based on benzoic acid) 2 equivalents) was used and the product was obtained as in Example 1, except heated for 47 hours. The yield was 92%.
- (C 18 H 37 ) 4 NI was prepared from (C 18 H 37 ) 4 NBr by a conventional method.
- Example 7 In Example 1, 1.0 mmol of benzoic acid, 0.1 mmol of Ph 4 PI (10 mol% with respect to benzoic acid), and 2.0 mmol of TBHP (2 equivalents with respect to benzoic acid) were used instead of Bu 4 NI. Then, a product was obtained in the same manner as in Example 1 except that heating was performed for 52 hours. The yield was 76%.
- Example 8 In Example 1, 1.0 mmol of benzoic acid, 0.1 mmol of Ph 3 MePI (10 mol% with respect to benzoic acid), and 2.0 mmol of TBHP (2 equivalents with respect to benzoic acid) were used instead of Bu 4 NI. A product was obtained in the same manner as in Example 1 except that. The yield was 76%.
- Example 9 In Example 1, 0.05 mmol (10 mol% with respect to benzoic acid) and 18-crown-6 (10 mol% with respect to benzoic acid) were used in place of Bu 4 NI. The product was obtained as in Example 1. The yield was 84%. When 18-crown-6 was not used, the activity was low because potassium iodide was not dissolved in the solvent.
- Example 1 The results of Examples 1 to 9 are shown in Table 1.
- the oxidant equivalent and yield were calculated based on the smaller number of moles of ketone and carboxylic acid.
- Table 1 when ammonium iodide is used as the catalyst precursor, the reaction proceeds quantitatively when the mixing ratio of ketone and carboxylic acid is 2: 1 (Example 1). The reaction proceeded efficiently even when the ratio was 1: 1 (Example 2) or 1: 2 (Example 3).
- Example 10 the reaction temperature was not 75 ° C but 50 ° C. In Example 10, since the reaction temperature was lowered from 75 ° C. to 50 ° C. compared with Example 3, the yield was reduced accordingly. In Example 10, the solvent was ethyl acetate, but the target was obtained in an equivalent or slightly lower yield even when the solvent was changed to THF (Example 11), acetonitrile (Example 12), or diethyl ether (Example 13). A product was obtained. From this, it can be seen that the solvents of Examples 11 to 13 are suitable for this reaction as in the case of ethyl acetate.
- Example 14 to 42 Various intermolecular oxidative coupling reactions between carbonyl compounds and carboxylic acids were investigated.
- the carbonyl compound R 1 C ( ⁇ O) CH 2 R 2 and the carboxylic acid R 3 COOH such that the products shown in Table 3 and Table 4 are obtained
- the carboxylic acids shown in Table 3 and Table 4 are used.
- the reaction was carried out according to Example 1 with the number of moles and the reaction conditions. The results are shown in Tables 3 and 4. The oxidant equivalent and yield were calculated based on the smaller number of moles of ketone and carboxylic acid.
- the reaction proceeded efficiently even when the substituent (R) on the benzene ring of propiophenone was either an electron donating group or an electron withdrawing group.
- the reaction proceeded almost quantitatively even at 50 ° C.
- the reaction proceeded efficiently even when the substituent (R) on the benzene ring of benzoic acid was changed to either an electron donating group or an electron withdrawing group.
- the reaction proceeded efficiently even with a substrate in which an imidazol-2-yl group that was easily deprotected was introduced as an adjacent group of the carbonyl carbon.
- the product was obtained in high yield not only with aromatic carboxylic acids but also with saturated aliphatic carboxylic acids and unsaturated aliphatic carboxylic acids.
- acrylic acid (Examples 32 and 33) and methacrylic acid (Examples 34 and 35) are unsaturated aliphatic carboxylic acids that are easily polymerized, but both are selected not by a polymerization reaction but by an intermolecular oxidative coupling reaction. Progressed efficiently.
- Example 43 to 50 Various intermolecular oxidative coupling reactions between carbonyl compounds and carboxylic acids were investigated.
- Example 1 was carried out under the reaction conditions shown in Table 5 using a carbonyl compound R 1 C ( ⁇ O) CH 2 R 2 and a carboxylic acid R 3 CO 2 H that would yield the product shown in Table 5.
- the reaction was carried out according to.
- the results are shown in Table 5. The oxidant equivalent and yield were calculated based on the smaller number of moles of ketone and carboxylic acid.
- the reaction proceeded efficiently even when a ketone having a heterocycle was used as the carbonyl compound and benzoic acid was used as the carboxylic acid.
- the reaction proceeded efficiently even when 1,3-diketone or 1,3-ketoester was used as the carbonyl compound and benzoic acid was used as the carboxylic acid.
- propiophenone is used as the carbonyl compound and acrylic acid or methacrylic acid is used as the carboxylic acid as in Examples 47 to 50
- the unsaturated bond of acrylic acid or methacrylic acid is the same as in Examples 32 to 35.
- the intermolecular oxidative coupling reaction proceeded selectively and efficiently without being oxidized or the polymerization reaction of acrylic acid or methacrylic acid proceeding.
- Example 51 to 61 The intermolecular oxidative coupling reaction between the aldehyde and the carboxylic acid was carried out according to Example 1 with the reaction temperature and the reaction conditions shown in Table 6 at a reaction temperature of 50 ° C. The results are shown in Table 6.
- “EtOAc (0.2 M)” in the reaction formula of Table 6 represents the number of moles of aldehyde per volume of ethyl acetate.
- the main by-products were self-aldol condensation product and oxidative dehydrogenation product (3-phenyl-2-pentenal).
- Example 58 Even when 2,2,6,6, -tetramethylpiperidine (Example 58) or morpholine (Example 59) is added as an additive in an amount equivalent to the aldehyde, the effect of suppressing the formation of by-products is obtained. It was seen. In Example 58, it seems that the yield of the target product is falling, but since there are few by-products, it is expected that the yield of the target product will be improved if the reaction time is increased. In Examples 52 to 59, a secondary amine was used as an additive, while in Example 60, a primary amine was used as an additive. In this case, the same tendency as the secondary amine was observed, but the effect was higher with the secondary amine.
- the spectral data of the target products obtained in Examples 51 to 60 are as follows.
- Example 62 to 72 Intermolecular oxidative coupling reaction between aldehyde and carboxylic acid was performed using piperidine as an additive. That is, in Example 1 using the aldehyde R 1 CH 2 CH 2 CHO and the carboxylic acid R 2 CO 2 H that give the product shown in Table 7 in the presence of piperidine under the reaction conditions shown in Table 7. The reaction was carried out according to the above. The results are shown in Table 7.
- the reaction proceeded efficiently even when various aldehydes were used as the carbonyl compound.
- acrylic acid or methacrylic acid was used as the carboxylic acid as in Examples 62 and 63
- the unsaturated bond of acrylic acid or methacrylic acid was oxidized as in Examples 32 to 35 and 47 to 50.
- the intermolecular oxidative coupling reaction proceeded selectively and efficiently without the polymerization reaction of acrylic acid or methacrylic acid proceeding.
- Spectra data of the products obtained in Examples 62 to 72 are as follows.
- Example 73 to 77 The substrate concentration when intermolecular oxidative coupling reaction between propiophenone and benzoic acid was carried out using TBHP (decane solution) as an oxidizing agent and ethyl acetate as a solvent was examined.
- the experimental procedure was performed according to Example 1.
- Table 8 shows the results.
- the substrate concentration represents the number of moles of propiophenone per volume of ethyl acetate. As is apparent from Table 8, the reaction proceeded efficiently regardless of the substrate concentration (Examples 73 to 76). Even when ethyl acetate was not used, the reaction proceeded efficiently (Example 77).
- Example 83 to 87 Various intermolecular oxidative coupling reactions between 4-ter-butylcyclohexanone and methacrylic acid were investigated. That is, the reaction was carried out according to Example 1 under the reaction conditions shown in Table 10. The results are shown in Table 10. In this reaction, monoacyloxy and diacyloxy forms as well as unidentified by-products were obtained. Both monoacyloxy and diacyloxy were single diastereomers (all substituents were equatorial).
- Example 88 to 90 The type of oxidant used in the intermolecular oxidative coupling reaction was investigated. The results are shown in Table 11. Examples 88 and 89 are examples in which the reaction between propiophenone and methacrylic acid was performed using hydrogen peroxide water and cumene hydroperoxide as oxidizing agents, respectively. In Table 11, “%” of the oxidizing agent is mass%. For reference, the same reaction is shown in Table 11 together with the results of Example 49 using TBHP as an oxidizing agent. With either oxidizing agent, the target ⁇ -acyloxycarbonyl compound was obtained, regardless of the yield.
- Example 90 is an example in which cumene hydroperoxide was used as an oxidizing agent for the reaction between propiophenone and benzoic acid.
- the same reaction is shown in Table 11 together with the results of Example 74 using TBHP as an oxidizing agent.
- the target ⁇ -acyloxycarbonyl compound was obtained with any oxidizing agent.
- the present invention is mainly applicable to the chemical and chemical industry.
- polymers obtained by polymerizing ⁇ -acryloxyketone and ⁇ -methacryloxyketone obtained in Examples 25 to 28 are antifouling paint compositions (see, for example, JP-A-2009-144071) and positive resist materials ( For example, it can be used as JP 2009-169406).
- Salvinorin A has attracted attention as a lead compound for the treatment of diseases of the central nervous system such as psychosis and Alzheimer's disease. It is possible to obtain the final product in shorter steps.
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Abstract
Description
プロピオフェノン(134mg,1.0mmol)と、安息香酸(61.1mg,0.5mmol)と、Bu4NI(18.5mg,0.05mmol,安息香酸に対して10mol%)を酢酸エチル(5mL)に溶かし、TBHP(5.5M デカン溶液(Aldrich製);0.18mL,1.0mmol,安息香酸に対して2当量)を室温で入れた。反応混合液を75℃のオイルバスに入れて24時間加熱しなら撹拌した。反応終了後、反応液を室温に冷やして、Na2S2O3水溶液とNaHCO3水溶液で洗った。水層を酢酸エチルで抽出して、有機層を食塩水と水で洗った。得られた有機層を無水Na2SO4で乾燥させた。溶媒をエバポレーターで除いた後、シリカゲルカラムクロマトグラフィー(展開溶媒はHexane:EtOAc=20:1(v/v))によって目的とする生成物である2-ベンゾイロキシ-1-フェニル-1-プロパノンを単離した(126mg,0.495mmol,収率99%)。
実施例1において、安息香酸を1.0mmol、Bu4NIを0.1mmol(安息香酸に対して10mol%)、TBHPを2.0mmol(安息香酸に対して2当量)使用し、50時間加熱した以外は、実施例1と同様にして生成物を得た。収率は80%であった。
実施例1において、安息香酸を2.0mmol、Bu4NIを0.1mmol(プロピオフェノンに対して10mol%)、TBHPを2.0mmol(プロピオフェノンに対して2当量)使用し、68時間加熱した以外は、実施例1と同様にして生成物を得た。収率は80%であった。
実施例1において、安息香酸を1mmol、Bu4NIを0.1mmol(安息香酸に対して10mol%)、TBHPを1.1mmol(安息香酸に対して1.1当量)使用し、29時間加熱した以外は、実施例1と同様にして生成物を得た。収率は76%であった。
実施例4において、TBHP(5.5M デカン溶液)の代わりにTBHP(70%水溶液)を1.1mmol(安息香酸に対して1.1当量)使用した以外は、実施例4と同様にして生成物を得た。収率は72%であった。
実施例1において、安息香酸を1.0mmol、Bu4NIの代わりに(C18H37)4NIを0.1mmol(安息香酸に対して10mol%)、TBHPを2.0mmol(安息香酸に対して2当量)使用し、47時間加熱した以外は、実施例1と同様にして生成物を得た。収率は92%であった。なお、(C18H37)4NIは、(C18H37)4NBrから常法により調製した。
実施例1において、安息香酸を1.0mmol、Bu4NIの代わりにPh4PIを0.1mmol(安息香酸に対して10mol%)、TBHPを2.0mmol(安息香酸に対して2当量)使用し、52時間加熱した以外は、実施例1と同様にして生成物を得た。収率は76%であった。
実施例1において、安息香酸を1.0mmol、Bu4NIの代わりにPh3MePIを0.1mmol(安息香酸に対して10mol%)、TBHPを2.0mmol(安息香酸に対して2当量)使用した以外は、実施例1と同様にして生成物を得た。収率は76%であった。
実施例1において、Bu4NIの代わりにKIを0.05mmol(安息香酸に対して10mol%)、18-クラウン-6を0.05mmol(安息香酸に対して10mol%)使用した以外は、実施例1と同様にして生成物を得た。収率は84%であった。なお、18-クラウン-6を用いなかった場合には、ヨウ化カリウムが溶媒に溶解しないため、活性が低かった。
カルボニル化合物とカルボン酸との分子間酸化的カップリング反応を種々検討した。ここでは、表3及び表4に示す生成物が得られるようなカルボニル化合物R1C(=O)CH2R2とカルボン酸R3COOHとを用いて、表3及び表4に示すカルボン酸のモル数、反応条件で実施例1に準じて反応を行った。その結果を表3及び表4に示す。酸化剤の当量や収率は、ケトン及びカルボン酸のうちモル数の少ない方を基準として計算した。
カルボニル化合物とカルボン酸との分子間酸化的カップリング反応を種々検討した。ここでは、表5に示す生成物が得られるようなカルボニル化合物R1C(=O)CH2R2とカルボン酸R3CO2Hとを用いて、表5に示す反応条件で実施例1に準じて反応を行った。その結果を表5に示す。酸化剤の当量や収率は、ケトン及びカルボン酸のうちモル数の少ない方を基準として計算した。
アルデヒドとカルボン酸との分子間酸化的カップリング反応を、表6に示す反応式及び反応条件で、反応温度を50℃にし、実施例1に準じて行った。その結果を表6に示す。なお、表6の反応式の「EtOAc(0.2M)」は、酢酸エチルの体積あたりのアルデヒドのモル数を表す。また、主たる副生物はセルフアルドール縮合生成物と酸化的脱水素化生成物(3-フェニル-2-ペンテナール)であった。
アルデヒドとカルボン酸との分子間酸化的カップリング反応を、添加物としてピペリジンを用いて行った。すなわち、表7に示す生成物が得られるようなアルデヒドR1CH2CH2CHOとカルボン酸R2CO2Hとを用いて、ピペリジン存在下、表7に示す反応条件で、実施例1に準じて反応を行った。その結果を表7に示す。
プロピオフェノンと安息香酸との分子間酸化的カップリング反応を、酸化剤としてTBHP(デカン溶液)、溶媒として酢酸エチルを用いて行ったときの基質濃度について検討した。実験手順は実施例1に準じて行った。表8にその結果を示す。なお、基質濃度は、酢酸エチルの体積あたりのプロピオフェノンのモル数を表す。表8から明らかなように、基質濃度にかかわらず、反応は効率よく進行した(実施例73~76)。また、酢酸エチルを用いなかった場合でも、反応は効率よく進行した(実施例77)。
カルボニル化合物とカルボン酸との分子間酸化的カップリング反応を種々検討した。すなわち、表9に示す生成物が得られるようなケトンR1C(=O)CH2R2とカルボン酸(メタクリル酸又は安息香酸)とを用いて、表9に示す反応条件で、実施例1に準じて反応を行った。その結果を表9に示す。
4-ter-ブチルシクロヘキサノンとメタクリル酸との分子間酸化的カップリング反応を種々検討した。すなわち、表10に示す反応条件で、実施例1に準じて反応を行った。その結果を表10に示す。この反応では、モノアシロキシ体とジアシロキシ体のほか、未同定の副生物が得られた。モノアシロキシ体とジアシロキシ体は、両方とも単一なジアステレオマー(全ての置換基がエクアトリアル)であった。
分子間酸化的カップリング反応に用いる酸化剤の種類について検討した。その結果を表11に示す。実施例88,89は、プロピオフェノンとメタクリル酸との反応を、それぞれ過酸化水素水、クメンヒドロペルオキシドを酸化剤として用いた例である。表11で酸化剤の「%」は質量%である。参考までに、同様の反応をTBHPを酸化剤として用いた実施例49の結果も併せて表11に示した。いずれの酸化剤でも、収率の高低は別として、目的物であるα-アシロキシカルボニル化合物が得られた。また、実施例90は、プロピオフェノンと安息香酸との反応をクメンヒドロペルオキシドを酸化剤として用いた例である。参考までに、同様の反応をTBHPを酸化剤として用いた実施例74の結果も併せて表11に示した。この場合も、いずれの酸化剤でも目的物であるα-アシロキシカルボニル化合物が得られた。
Claims (11)
- 酸化剤であるヒドロペルオキシドと触媒前駆体であるヨージド塩とを用いて、カルボン酸とα位に水素原子を持つケトン、アルデヒド及びエステルからなる群より選ばれたカルボニル化合物との分子間反応を行うことにより、前記カルボニル化合物のα位に前記カルボン酸由来のアシロキシ基を導入する、
α-アシロキシカルボニル化合物の製法。 - 前記ヒドロペルオキシドは、有機ヒドロペルオキシドである、
請求項1に記載のα-アシロキシカルボニル化合物の製法。 - 前記ヒドロペルオキシドは、前記カルボン酸及び前記カルボニル化合物のうちモル数の少ないものに対して1~5当量使用する、
請求項1又は2に記載のα-アシロキシカルボニル化合物の製法。 - 前記ヨージド塩は、アンモニウムヨージド、ホスホニウムヨージド及びアルカリ金属ヨージドからなる群より選ばれた1種以上である、
請求項1~3のいずれか1項に記載のα-アシロキシカルボニル化合物の製法。 - 前記ヨージド塩は、前記カルボン酸及び前記カルボニル化合物のうちモル数の少ないものに対して1~50mol%使用する、
請求項1~4のいずれか1項に記載のα-アシロキシカルボニル化合物の製法。 - 反応溶媒として、エーテル系溶媒、エステル系溶媒及びニトリル系溶媒からなる群より選ばれる1種以上を用いる、
請求項1~5のいずれか1項に記載のα-アシロキシカルボニル化合物の製法。 - 25℃以上で反応を行う、
請求項1~6のいずれか1項に記載のα-アシロキシカルボニル化合物の製法。 - 前記カルボニル化合物は、部分構造に-C(=O)-CH2-を有する、
請求項1~7のいずれか1項に記載のα-アシロキシカルボニル化合物の製法。 - アミンの存在下で反応を行う、
請求項1~8のいずれか1項に記載のα-アシロキシカルボニル化合物の製法。 - 前記カルボン酸は、不飽和脂肪族カルボン酸である、
請求項1~9のいずれか1項に記載のα-アシロキシカルボニル化合物の製法。
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