JP3750248B2 - Method for producing an acrylate ester having a substituent at the 3-position - Google Patents
Method for producing an acrylate ester having a substituent at the 3-position Download PDFInfo
- Publication number
- JP3750248B2 JP3750248B2 JP01852897A JP1852897A JP3750248B2 JP 3750248 B2 JP3750248 B2 JP 3750248B2 JP 01852897 A JP01852897 A JP 01852897A JP 1852897 A JP1852897 A JP 1852897A JP 3750248 B2 JP3750248 B2 JP 3750248B2
- Authority
- JP
- Japan
- Prior art keywords
- substituent
- carbon atoms
- acrylate ester
- producing
- diazoacetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- -1 acrylate ester Chemical class 0.000 title claims description 49
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 125000001424 substituent group Chemical group 0.000 claims description 21
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000012327 Ruthenium complex Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- BXEFQPCKQSTMKA-UHFFFAOYSA-N OC(=O)C=[N+]=[N-] Chemical compound OC(=O)C=[N+]=[N-] BXEFQPCKQSTMKA-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 description 27
- 150000001299 aldehydes Chemical class 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 9
- 125000003342 alkenyl group Chemical group 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 239000012230 colorless oil Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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
- 150000001350 alkyl halides Chemical class 0.000 description 3
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexane-carboxaldehyde Natural products O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 3
- YVPJCJLMRRTDMQ-UHFFFAOYSA-N ethyl diazoacetate Chemical compound CCOC(=O)C=[N+]=[N-] YVPJCJLMRRTDMQ-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KBEBGUQPQBELIU-CMDGGOBGSA-N Ethyl cinnamate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1 KBEBGUQPQBELIU-CMDGGOBGSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 150000003934 aromatic aldehydes Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- KBEBGUQPQBELIU-UHFFFAOYSA-N cinnamic acid ethyl ester Natural products CCOC(=O)C=CC1=CC=CC=C1 KBEBGUQPQBELIU-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- BSAIUMLZVGUGKX-UHFFFAOYSA-N non-2-enal Chemical compound CCCCCCC=CC=O BSAIUMLZVGUGKX-UHFFFAOYSA-N 0.000 description 2
- GYHFUZHODSMOHU-UHFFFAOYSA-N nonanal Chemical compound CCCCCCCCC=O GYHFUZHODSMOHU-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- KMPQYAYAQWNLME-UHFFFAOYSA-N undecanal Chemical compound CCCCCCCCCCC=O KMPQYAYAQWNLME-UHFFFAOYSA-N 0.000 description 2
- MBDOYVRWFFCFHM-SNAWJCMRSA-N (2E)-hexenal Chemical compound CCC\C=C\C=O MBDOYVRWFFCFHM-SNAWJCMRSA-N 0.000 description 1
- DTCCTIQRPGSLPT-ONEGZZNKSA-N (E)-2-pentenal Chemical compound CC\C=C\C=O DTCCTIQRPGSLPT-ONEGZZNKSA-N 0.000 description 1
- SSNZFFBDIMUILS-ZHACJKMWSA-N (E)-dodec-2-enal Chemical compound CCCCCCCCC\C=C\C=O SSNZFFBDIMUILS-ZHACJKMWSA-N 0.000 description 1
- NDFKTBCGKNOHPJ-AATRIKPKSA-N (E)-hept-2-enal Chemical compound CCCC\C=C\C=O NDFKTBCGKNOHPJ-AATRIKPKSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- LHIPHZAUEPUWRF-UHFFFAOYSA-N 1-butoxy-2-diazonioethenolate Chemical compound CCCCOC(=O)C=[N+]=[N-] LHIPHZAUEPUWRF-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- MXUFWWKMAOJPQK-UHFFFAOYSA-N 2-diazonio-1-ethenoxyethenolate Chemical compound C=COC(=O)C=[N+]=[N-] MXUFWWKMAOJPQK-UHFFFAOYSA-N 0.000 description 1
- MIVRMHJOEYRXQB-UHFFFAOYSA-N 2-diazonio-1-methoxyethenolate Chemical compound COC(=O)C=[N+]=[N-] MIVRMHJOEYRXQB-UHFFFAOYSA-N 0.000 description 1
- UWBALSPTLHOGFE-UHFFFAOYSA-N 2-diazonio-1-phenoxyethenolate Chemical compound [N-]=[N+]=CC(=O)OC1=CC=CC=C1 UWBALSPTLHOGFE-UHFFFAOYSA-N 0.000 description 1
- SMVXVFLNCNOHHE-UHFFFAOYSA-N 2-diazonio-1-prop-2-enoxyethenolate Chemical compound C=CCOC(=O)C=[N+]=[N-] SMVXVFLNCNOHHE-UHFFFAOYSA-N 0.000 description 1
- KPTZIQYZCKOZFH-UHFFFAOYSA-N 2-diazonio-1-propoxyethenolate Chemical compound CCCOC(=O)C=[N+]=[N-] KPTZIQYZCKOZFH-UHFFFAOYSA-N 0.000 description 1
- QVTPWONEVZJCCS-UHFFFAOYSA-N 2-formylbenzonitrile Chemical compound O=CC1=CC=CC=C1C#N QVTPWONEVZJCCS-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical group O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- BJESURQWZKAHTR-UHFFFAOYSA-N [N+](=[N-])=CC(=O)OC=CCCC Chemical compound [N+](=[N-])=CC(=O)OC=CCCC BJESURQWZKAHTR-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- DTCCTIQRPGSLPT-UHFFFAOYSA-N beta-Aethyl-acrolein Natural products CCC=CC=O DTCCTIQRPGSLPT-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- VZSXFJPZOCRDPW-UHFFFAOYSA-N carbanide;trioxorhenium Chemical compound [CH3-].O=[Re](=O)=O VZSXFJPZOCRDPW-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- ZXUZSPAMPJMYSF-UHFFFAOYSA-N ethyl 2-(benzylidenehydrazinylidene)acetate Chemical compound CCOC(=O)C=NN=CC1=CC=CC=C1 ZXUZSPAMPJMYSF-UHFFFAOYSA-N 0.000 description 1
- DHNGCHLFKUPGPX-UHFFFAOYSA-N ethyl 3-(4-methoxyphenyl)prop-2-enoate Chemical compound CCOC(=O)C=CC1=CC=C(OC)C=C1 DHNGCHLFKUPGPX-UHFFFAOYSA-N 0.000 description 1
- SLGCKLRNFQEFEO-UHFFFAOYSA-N ethyl 3-cyclohexylprop-2-enoate Chemical compound CCOC(=O)C=CC1CCCCC1 SLGCKLRNFQEFEO-UHFFFAOYSA-N 0.000 description 1
- KODUAASIAODNCH-UHFFFAOYSA-N ethyl 5-phenylpent-2-enoate Chemical compound CCOC(=O)C=CCCC1=CC=CC=C1 KODUAASIAODNCH-UHFFFAOYSA-N 0.000 description 1
- NLKBBWBCWHTRAJ-UHFFFAOYSA-N ethyl 5-phenylpenta-2,4-dienoate Chemical compound CCOC(=O)C=CC=CC1=CC=CC=C1 NLKBBWBCWHTRAJ-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- NDFKTBCGKNOHPJ-UHFFFAOYSA-N hex-2-enal Natural products CCCCC=CC=O NDFKTBCGKNOHPJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000006772 olefination reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- DMEUUKUNSVFYAA-UHFFFAOYSA-N trinaphthalen-1-ylphosphane Chemical compound C1=CC=C2C(P(C=3C4=CC=CC=C4C=CC=3)C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 DMEUUKUNSVFYAA-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- IQKSLJOIKWOGIZ-UHFFFAOYSA-N tris(4-chlorophenyl)phosphane Chemical compound C1=CC(Cl)=CC=C1P(C=1C=CC(Cl)=CC=1)C1=CC=C(Cl)C=C1 IQKSLJOIKWOGIZ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、医農薬等のファインケミカルズの合成中間体や、ポリアクリル酸エステル樹脂の共重合用モノマーとして有用な３位に置換基を有するアクリル酸エステルの製造法に関する。
【０００２】
【従来の技術】
３位に置換基を有するアクリル酸エステルはアルデヒドのリンイリドによるオレフィン化反応（Ｗｉｔｔｉｇ反応）によって製造されるのが一般的である（Ｃｈｅｍｉｃａｌ Ｒｅｖｉｅｗｓ，１９８９，８９，８６３）。しかし、この方法ではリンイリドを発生させるために強塩基性の条件が必要とされることから、安全で入手が容易な製造原料を用いて、該アクリル酸エステルを温和な条件下で製造する方法が望まれていた。
【０００３】
その代表的なものとして、アルデヒドとジアゾ酢酸エステルを触媒存在下で反応させる方法が知られている。
この触媒として、例えば（１）モリブデン（VI）錯体〔ＭｏＯ2 （Ｓ2 ＣＮＥｔ2 ）〕を用いる方法（Ｊ．Ｏｒｇａｎｏｍｅｔａｌ．Ｃｈｅｍ．，１９８９，３７３，７７）は、アルデヒドとして芳香族アルデヒドを用いた場合にのみ反応が進行して、脂肪族アルデヒドやα，β−不飽和アルデヒドでは対応するアクリル酸エステルを製造することができないという問題を有していて、一般的な製造法となりえない。
【０００４】
また、（２）触媒としてヨウ化銅（Ｉ）を用いる方法（Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔｅｒｓ，１９８９，３７３，７７）は、反応に脱酸素剤として自然発火性のトリアルキルアンチモンを当量以上用いる必要があり、危険性を伴うという問題を有している。更に、（３）触媒としてメチルレニウムトリオキシドを用いる方法（Ｏｒｇａｎｏｍｅｔａｌｌｉｃｓ，１９９４，１３，４５３１）は、生成するアクリル酸エステルの立体選択性が低く、また副生物の生成を抑えるために多量（１０モル％）の触媒を必要とし、加えて触媒を調製する際に有毒なテトラメチルスズを用いる必要がある（Ｉｎｏｒｇ．Ｃｈｅｍ．，１９９２，３１，４４３１）など、実用性に難がある．
【０００５】
【発明が解決しようとする課題】
本発明は、安全で入手が容易な製造原料を用いて、３位に置換基を有するアクリル酸エステルを温和な条件下で製造することを課題とする。特に、本発明は、アルデヒドとジアゾ酢酸エステルを触媒存在下で反応させて３位に置換基を有するアクリル酸エステルを製造する方法において、安全で入手が容易な製造原料を用いて、低触媒濃度で、各種アルデヒドから、３位に置換基を有するアクリル酸エステルを高収率及び高立体選択性で製造することを課題とする。
【０００６】
【課題を解決するための手段】
本発明の課題は、アルデヒドとジアゾ酢酸エステルをホスフィン及びルテニウム錯体の存在下で反応させることを特徴とする３位に置換基を有するアクリル酸エステルの製造法によって達成される。
【０００７】
【発明の実施の形態】
以下に本発明を詳しく説明する。
本発明で使用されるアルデヒドは、式（II）で示される。
【０００８】
【化２】
【０００９】
式（II）において、Ｒ4 としては、炭素数１〜２０、特に１〜１１のアルキル基や、炭素数２〜２０、特に２〜１１のアルケニル基や、炭素数６〜２０、特に６〜１２のアリール基が好適に挙げられる。更に、Ｒ4 は、例えば、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１４のアリール基、炭素数６〜１４のアリールオキシ基、炭素数２〜１０のアルコキシカルボニル基、炭素数２〜１０のジアルキルアミノ基、シアノ基、ニトロ基、ハロゲン等を置換基として有していても差し支えない。
【００１０】
Ｒ4 が前記のアルキル基であるアルデヒドとしては、例えば、アセトアルデヒド、プロピオンアルデヒド、ブタナール（異性体を含む）、ペンタナール（異性体を含む）、ヘキサナール（異性体を含む）、ヘプタナール（異性体を含む）、オクタナール（異性体を含む）、ノナナール（異性体を含む）、デカナール（異性体を含む）、ウンデカナール（異性体を含む）、ドデカナール（異性体を含む）、シクロヘキサンカルボキシアルデヒド、ヒドロシンナムルデヒドなどが具体的に挙げられる。
【００１１】
Ｒ4 が前記のアルケニル基であるアルデヒドとしては、例えば、アクロレイン、ブテナール（異性体を含む）、ペンテナール（異性体を含む）、ヘキセナール、ヘプテナール（異性体を含む）、オクテナール（異性体を含む）、ノネナール（異性体を含む）、ドデセナール（異性体を含む）、トランスシンナムアルデヒドなどが具体的に挙げられる。
【００１２】
また、Ｒ4 が前記のアリール基であるアルデヒドとしては、例えば、ベンズアルデヒド、トルアルデヒド（ｏ、ｍ、ｐの各異性体を含む）、アニスアルデヒド（ｏ、ｍ、ｐの各異性体を含む）、シアノベンズアルデヒド（ｏ、ｍ、ｐの各異性体を含む）、ニトロベンズアルデヒド（ｏ、ｍ、ｐの各異性体を含む）、クロロベンズアルデヒド（ｏ、ｍ、ｐの各異性体を含む）、ナフトアルデヒド（α、βの各異性体を含む）などが具体的に挙げられる。
【００１３】
本発明で使用されるジアゾ酢酸エステルは、式(III) で示される。
【化３】
【００１４】
式(III) において、Ｒ5 としては、炭素数１〜１０、特に１〜４のアルキル基や、炭素数２〜１０、特に２〜５のアルケニル基や、炭素数６〜１０のアリール基が好適に挙げられる。更に、Ｒ5 は、例えば、炭素数１〜１０のアルキル基、炭素数１〜１０のアルコキシ基、炭素数６〜１４のアリール基、炭素数６〜１４のアリールオキシ基等を置換基として有していても差し支えない。
【００１５】
Ｒ5 が前記のアルキル基であるジアゾ酢酸エステルとしては、例えば、ジアゾ酢酸メチル、ジアゾ酢酸エチル、ジアゾ酢酸プロピル（異性体を含む）、ジアゾ酢酸ブチル（異性体を含む）などが具体的に挙げられる。
Ｒ5 が前記のアルケニル基であるジアゾ酢酸エステルとしては、例えば、ジアゾ酢酸ビニル、ジアゾ酢酸２−プロペニル、ジアゾ酢酸ブテニル（異性体を含む）、ジアゾ酢酸ペンテニル（異性体を含む）などが具体的に挙げられる。
また、Ｒ5 が前記のアリール基であるジアゾ酢酸エステルとしては、例えば、ジアゾ酢酸フェニル、ジアゾ酢酸トリル（異性体を含む）、ジアゾ酢酸ナフチル（異性体を含む）などが具体的に挙げられる。
【００１６】
本発明では、前記のアルデヒドとジアゾ酢酸エステルを、ホスフィン及びルテニウム錯体の存在下で反応させて、式（IV）で示される３位に置換基を有するアクリル酸エステルが製造される。
【化４】
【００１７】
本発明で使用されるホスフィンは、式（Ｖ）で示される。
【化５】
【００１８】
式（Ｖ）において、Ｒ6 、Ｒ7 、Ｒ8 としては、炭素数１〜１０、特に１〜６のアルキル基や、炭素数６〜１４、特に６〜１０のアリール基が好適に挙げられる。更に、Ｒ6 、Ｒ7 、Ｒ8 は、例えば、炭素数１〜１０のアルキル基、炭素数６〜１０のアリール基、ハロゲン等を置換基として有していても差し支えない。また、Ｒ6 、Ｒ7 、Ｒ8 は互いに同一であっても異なっていてもよい。
【００１９】
前記のホスフィンとしては、例えば、
トリメチルホスフィン、トリエチルホスフィン、トリプロピルホスフィン（異性体を含む）、トリブチルホスフィン（異性体を含む）、トリシクロペンチルホスフィン、トリシクロヘキシルホスフィン等のトリアルキルホスフィンや、
トリフェニルホスフィン、トリ（１−ナフチル）ホスフィン、トリトリルホスフィン（異性体を含む）、トリ（ｐ−クロロフェニル）ホスフィンのトリアリールホスフィンや、
ジフェニルメチルホスフィン、ジメチルフェニルホスフィンなどが具体的に挙げられる。
ホスフィンの中ではトリアリールホスフィンが好ましく、特にトリフェニルホスフィンが最も好ましい。
【００２０】
本発明で使用されるルテニウム錯体は、式（Ｉ）で示される。
【化６】
【００２１】
式（Ｉ）において、Ｘ1 、Ｘ2 はルテニウム原子に配位できる１価の陰イオン性のリガンドを表し、これらは互いに同一であっても異なっていてもよい。Ｘ1 、Ｘ2 で表されるルテニウム原子に配位できる１価の陰イオン性のリガンドとしては、−Ｆ、−Ｃｌ、−Ｂｒ、−Ｉ、−ＣｌＯ4 、−ＣＦ3 ＳＯ3 、−ＣＨ3 ＣＯ2 、−ＰＦ6 、−ＢＰｈ4 、−ＮＯ3 、−ＣＮ、−ＮＣＳ、−Ｃ5 Ｈ5 （シクロペンタジエニル）及び−Ｈが好適に挙げられる。
また、Ｒ1 、Ｒ2 、Ｒ3 は、前記のＲ6 、Ｒ7 、Ｒ8 と同様のアルキル基又はアリール基を表し、Ｒ6 、Ｒ7 、Ｒ8 と同様の置換基を有していてもよく、これらは互いに同一であっても異なっていても差し支えない。
【００２２】
なお、本発明で、ルテニウム錯体の非存在下で反応を行うと、目的の３位に置換基を有するアクリル酸エステルは生成せずに、式（VI）で示されるアジン化合物が生成する。
【化７】
【００２３】
前記のルテニウム錯体としては、例えば、ＲｕＣｌ2 （ＰＰｈ3 ）3 、ＲｕＦ2 （ＰＰｈ3 ）3 、ＲｕＢｒ2 （ＰＰｈ3 ）3 、ＲｕＩ2 （ＰＰｈ3 ）3 、ＲｕＣｌＨ（ＰＰｈ3 ）3 、ＲｕＨ（ＣＨ3 ＣＯ2 ）（ＰＰｈ3 ）3 、Ｒｕ（Ｃ5 Ｈ5 ）（ＰＦ6 ）（ＰＭｅ3 ）3 などが具体的に挙げられる。これらルテニウム錯体の中では、ＲｕＣｌ2 （ＰＰｈ3 ）3 が特に好ましい。
【００２４】
本発明では、例えば、前記のホスフィン、ルテニウム錯体及びアルデヒドを反応器に入れて、アルゴン等の不活性ガス雰囲気下で、ジアゾ酢酸エステルを滴下しながら、４０〜１３５℃、好ましくは４０〜７０℃の反応温度で反応が行われる。このとき、反応圧力は常圧、減圧、加圧のいずれでもよいが通常は常圧である。また、ホスフィンは、例えば、アルデヒドに対して０．０００１〜０．２倍モル、好ましくは０．０２〜０．０５倍モル使用され、ルテニウム錯体は、例えば、アルデヒドに対して０．０００１〜０．２倍モル、好ましくは０．０２〜０．０５倍モル使用される。ジアゾ酢酸エステルは、例えば、アルデヒドに対して１．０〜５．０倍モル、好ましくは１．０〜１．５倍モル使用される。
【００２５】
更に、本発明の反応には必要に応じて溶媒を使用しても差し支えない。溶媒は、例えば、アルデヒドに対して１〜１００重量倍、好ましくは１０〜５０重量倍使用される。
溶媒としては、沸点４０℃以上のものが好ましく、例えば、沸点４０℃以上のハロゲン化アルキル、エーテル、芳香族炭化水素が好適に使用される。具体的には、クロロホルム、ジクロロエタン等のハロゲン化アルキルや、テトラヒドロフラン、ジイソプロピルエーテル等のエーテルや、ベンゼン、トルエン、キシレン等の芳香族炭化水素が溶媒として使用される。これら溶媒の中では、クロロホルム、１，２−ジクロロエタン等のハロゲン化アルキルが特に好ましい。
【００２６】
反応終了後、生成した３位に置換基を有するアクリル酸エステルは、例えば、反応液から溶媒を留去した後、カラムクロマトグラフィー、再結晶などの方法により分離精製される。
【００２７】
【実施例】
次に、実施例及び比較例を挙げて本発明を具体的に説明する。
なお、単離された生成物は 1Ｈ−ＮＭＲ、13Ｃ−ＮＭＲ及び質量分析により既知化合物と同一であることを確認し、その異性体比をガスクロマトグラフィーにより決定した。また、収率（％）はアルデヒドに対して求めた。
【００２８】
ガスクロマトグラフィーの条件を次に示す。
カラム ：Ｇ−１００（４０ｍ）
カラム温度：１３５℃（１０分）、１０℃／分で２４０℃まで昇温、２４０℃（１５分）
インジェクション温度：２５０℃
ディテクター（ＦＩＤ）温度：２５０℃
【００２９】
実施例１
内容積２５ｍｌのシュレンク管に、ジクロロトリストリフェニルホスフィンルテニウム〔ＲｕＣｌ2 （ＰＰｈ3 ）3 〕（０．０２２５ｍｍｏｌ）とトリフェニルホスフィン（１．１ｍｍｏｌ）を入れ、アルゴンガス雰囲気に置換した後、１，２−ジクロロエタン（３ｍｌ）を加えて、溶液を５０℃に加熱した。次いで、ベンズアルデヒド（１．０ｍｍｏｌ）を加えた後、ジアゾ酢酸エチル／１，２−ジクロロエタン溶液（１．６ｍｌ、ジアゾ酢酸エチル：１．５ｍｍｏｌ）を滴下して、５０℃で４時間反応を行った。
反応終了後、反応液を室温まで冷却し、溶媒を減圧下で留去した。得られた残渣をカラムクロマトグラフィーで精製して、目的の３−フェニル−２−プロペン酸エチル（無色油状物）を収率９０％で得た。生成物の異性体比はＥ体／Ｚ体＝９７／３であった。
【００３０】
実施例２
ベンズアルデヒドをヒドロシンナムアルデヒド（１．０ｍｍｏｌ）に代え、反応時間を５時間に変えたほかは、実施例１と同様の操作を行った。その結果、目的の５−フェニル−２−ペンテン酸エチル（無色油状物）が収率９０％で得られ、その異性体比はＥ体／Ｚ体＝９５／５であった。
【００３１】
実施例３
ベンズアルデヒドをシクロヘキサンカルボキシアルデヒド（１．０ｍｍｏｌ）に代え、反応時間を１７時間に変えたほかは、実施例１と同様の操作を行った。その結果、目的の３−シクロヘキシル−２−プロペン酸エチル（無色油状物）が収率８２％で得られ、その異性体比はＥ体／Ｚ体＞９９／１であった。
【００３２】
実施例４
ベンズアルデヒドをｐ−アニスアルデヒド（１．０ｍｍｏｌ）に代え、反応時間を１２時間に変えたほかは、実施例１と同様の操作を行った。その結果、目的の３−（４’−メトキシフェニル）−２−プロペン酸エチル（無色油状物）が収率９２％で得られ、その異性体比はＥ体／Ｚ体＝９７／３であった。
【００３３】
実施例５
ベンズアルデヒドをトランスシンナムアルデヒド（１．０ｍｍｏｌ）に代え、反応時間を８時間に変えたほかは、実施例１と同様の操作を行った。その結果、目的の５−フェニル−２，４−ペンタジエン酸エチル（無色油状物）が収率９２％で得られ、その異性体比はＥ体／Ｚ体＝９０／１０であった。
【００３４】
比較例１
ジクロロトリストリフェニルホスフィンルテニウムを加えなかったほかは、実施例１と同様の操作を行った。その結果、アジン化合物（３，４−ジアザ−５−フェニル−２，４−ペンタジエン酸エチル）を収率７０％で得たのみで、目的の３−フェニル−２−プロペン酸エチルは全く得られなかった。
【００３５】
【発明の効果】
本発明により、温和な条件下、安全で入手が容易な製造原料を用いて、３位に置換基を有するアクリル酸エステルを製造することができる。
特に、アルデヒドとジアゾ酢酸エステルをホスフィン及びルテニウム錯体の存在下で反応させる本発明の方法は、（１）製造原料の取扱いが安全かつ容易であり、（２）脂肪族アルデヒド、α，β−不飽和アルデヒド、芳香族アルデヒド等の各種アルデヒドから、３位に置換基を有するアクリル酸エステルを何ら問題なく高収率で製造することができ、（３）生成した３位に置換基を有するアクリル酸エステルの立体選択性も高く（主生成物はＥ体）、（４）低触媒濃度で反応を行うことができるなどの利点がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing an acrylic ester having a substituent at the 3-position, which is useful as a synthetic intermediate for fine chemicals such as medical and agricultural chemicals, and a monomer for copolymerization of a polyacrylic ester resin.
[0002]
[Prior art]
An acrylic ester having a substituent at the 3-position is generally produced by an olefination reaction (Wittig reaction) of aldehyde with phosphorus ylide (Chemical Reviews, 1989, 89, 863). However, since this method requires strongly basic conditions for generating phosphorus ylide, there is a method for producing the acrylate ester under mild conditions using a safe and easily available production raw material. It was desired.
[0003]
A typical example is a method in which an aldehyde and a diazoacetate are reacted in the presence of a catalyst.
As this catalyst, for example, a method using (1) molybdenum (VI) complex [MoO 2 (S 2 CNEt 2 )] (J. Organometal. Chem., 1989, 373, 77) used an aromatic aldehyde as an aldehyde. In some cases, the reaction proceeds, and aliphatic aldehydes and α, β-unsaturated aldehydes have a problem that the corresponding acrylate cannot be produced, and cannot be a general production method.
[0004]
Also, (2) the method using copper (I) iodide as a catalyst (Tetrahedron Letters, 1989, 373, 77) requires the use of a pyrophoric trialkylantimony as an oxygen scavenger in the reaction in an equivalent amount or more. It has the problem of being accompanied by sex. Furthermore, (3) the method using methylrhenium trioxide as a catalyst (Organometallics, 1994, 13, 4531) has a low stereoselectivity of the produced acrylate ester and a large amount (10 mol) to suppress the formation of by-products. %) Catalyst, and in addition, it is necessary to use toxic tetramethyltin when preparing the catalyst (Inorg. Chem., 1992, 31, 4431).
[0005]
[Problems to be solved by the invention]
An object of the present invention is to produce an acrylic ester having a substituent at the 3-position under mild conditions using a safe and easily available production raw material. In particular, the present invention relates to a method for producing an acrylate ester having a substituent at the 3-position by reacting an aldehyde with a diazoacetate ester in the presence of a catalyst, using a safe and easily available production raw material, and a low catalyst concentration. Thus, it is an object to produce an acrylate ester having a substituent at the 3-position from various aldehydes with high yield and high stereoselectivity.
[0006]
[Means for Solving the Problems]
The object of the present invention is achieved by a method for producing an acrylate ester having a substituent at the 3-position, which comprises reacting an aldehyde with a diazoacetate ester in the presence of a phosphine and a ruthenium complex.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
The aldehyde used in the present invention is represented by the formula (II).
[0008]
[Chemical 2]
[0009]
In the formula (II), R 4 is an alkyl group having 1 to 20 carbon atoms, particularly 1 to 11 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, particularly 2 to 11 carbon atoms, or 6 to 20 carbon atoms, particularly 6 to 6 carbon atoms. Twelve aryl groups are preferred. Further, R 4 is, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or 2 to 10 carbon atoms. Or an alkoxycarbonyl group, a dialkylamino group having 2 to 10 carbon atoms, a cyano group, a nitro group, a halogen, or the like as a substituent.
[0010]
Examples of the aldehyde in which R 4 is the alkyl group include acetaldehyde, propionaldehyde, butanal (including isomers), pentanal (including isomers), hexanal (including isomers), and heptanal (including isomers). ), Octanal (including isomers), nonanal (including isomers), decanal (including isomers), undecanal (including isomers), dodecanal (including isomers), cyclohexanecarboxaldehyde, hydrocinnam Specific examples include rudehide.
[0011]
Examples of the aldehyde in which R 4 is the alkenyl group include acrolein, butenal (including isomers), pentenal (including isomers), hexenal, heptenal (including isomers), and octenal (including isomers). , Nonenal (including isomers), dodecenal (including isomers), transcinnamaldehyde, and the like.
[0012]
Examples of the aldehyde in which R 4 is the aryl group include benzaldehyde, tolualdehyde (including o, m, and p isomers) and anisaldehyde (including o, m, and p isomers). , Cyanobenzaldehyde (including o, m, and p isomers), nitrobenzaldehyde (including o, m, and p isomers), chlorobenzaldehyde (including o, m, and p isomers), naphtho Specific examples include aldehydes (including α and β isomers).
[0013]
The diazoacetic acid ester used in the present invention is represented by the formula (III).
[Chemical 3]
[0014]
In the formula (III), R 5 is an alkyl group having 1 to 10 carbon atoms, particularly 1 to 4 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, particularly 2 to 5 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Preferably mentioned. Furthermore, R 5 has, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, or the like as a substituent. You can do it.
[0015]
Specific examples of the diazoacetate wherein R 5 is the alkyl group include, for example, methyl diazoacetate, ethyl diazoacetate, propyl diazoacetate (including isomers), butyl diazoacetate (including isomers), and the like. It is done.
Specific examples of the diazoacetate wherein R 5 is the alkenyl group include vinyl diazoacetate, 2-propenyl diazoacetate, butenyl diazoacetate (including isomers), and pentenyl diazoacetate (including isomers). It is mentioned in.
Specific examples of the diazoacetate in which R 5 is the aryl group include phenyl diazoacetate, tolyl diazoacetate (including isomers), naphthyl diazoacetate (including isomers), and the like.
[0016]
In the present invention, the aldehyde and diazoacetate are reacted in the presence of a phosphine and a ruthenium complex to produce an acrylate ester having a substituent at the 3-position represented by the formula (IV).
[Formula 4]
[0017]
The phosphine used in the present invention is represented by the formula (V).
[Chemical formula 5]
[0018]
In formula (V), preferred examples of R 6 , R 7 and R 8 include alkyl groups having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and aryl groups having 6 to 14 carbon atoms, particularly 6 to 10 carbon atoms. . Further, R 6 , R 7 and R 8 may have, for example, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a halogen, or the like as a substituent. R 6 , R 7 and R 8 may be the same as or different from each other.
[0019]
Examples of the phosphine include:
Trialkylphosphine such as trimethylphosphine, triethylphosphine, tripropylphosphine (including isomers), tributylphosphine (including isomers), tricyclopentylphosphine, tricyclohexylphosphine,
Triphenylphosphine, tri (1-naphthyl) phosphine, tolylylphosphine (including isomers), triarylphosphine of tri (p-chlorophenyl) phosphine,
Specific examples include diphenylmethylphosphine and dimethylphenylphosphine.
Of the phosphines, triarylphosphine is preferable, and triphenylphosphine is most preferable.
[0020]
The ruthenium complex used in the present invention is represented by the formula (I).
[Chemical 6]
[0021]
In the formula (I), X 1 and X 2 each represent a monovalent anionic ligand capable of coordinating with a ruthenium atom, and these may be the same as or different from each other. Monovalent anionic ligands that can be coordinated to the ruthenium atom represented by X 1 and X 2 include —F, —Cl, —Br, —I, —ClO 4 , —CF 3 SO 3 , —CH. 3 CO 2 , —PF 6 , —BPh 4 , —NO 3 , —CN, —NCS, —C 5 H 5 (cyclopentadienyl) and —H are preferred.
Further, R 1, R 2, R 3 represents the same alkyl group or aryl group and wherein the R 6, R 7, R 8, have the same substituent as R 6, R 7, R 8 They may be the same or different from each other.
[0022]
In the present invention, when the reaction is carried out in the absence of the ruthenium complex, an azine compound represented by the formula (VI) is generated without generating the target acrylic ester having a substituent at the 3-position.
[Chemical 7]
[0023]
Examples of the ruthenium complex include RuCl 2 (PPh 3 ) 3 , RuF 2 (PPh 3 ) 3 , RuBr 2 (PPh 3 ) 3 , RuI 2 (PPh 3 ) 3 , RuClH (PPh 3 ) 3 , RuH ( Specific examples include CH 3 CO 2 ) (PPh 3 ) 3 , Ru (C 5 H 5 ) (PF 6 ) (PMe 3 ) 3 and the like. Among these ruthenium complexes, RuCl 2 (PPh 3 ) 3 is particularly preferable.
[0024]
In the present invention, for example, the phosphine, ruthenium complex and aldehyde are put into a reactor, and diazoacetic acid ester is added dropwise in an inert gas atmosphere such as argon, preferably 40 to 135 ° C, preferably 40 to 70 ° C. The reaction is carried out at the reaction temperature of At this time, the reaction pressure may be normal pressure, reduced pressure, or increased pressure, but is usually normal pressure. The phosphine is used, for example, in an amount of 0.0001 to 0.2 times mol, preferably 0.02 to 0.05 times mol for the aldehyde, and the ruthenium complex is, for example, 0.0001 to 0 mol to the aldehyde. .2 moles, preferably 0.02 to 0.05 moles are used. The diazoacetic acid ester is used, for example, in an amount of 1.0 to 5.0 times mol, preferably 1.0 to 1.5 times mol for the aldehyde.
[0025]
Furthermore, a solvent may be used in the reaction of the present invention as necessary. The solvent is used, for example, 1 to 100 times by weight, preferably 10 to 50 times by weight with respect to the aldehyde.
As the solvent, those having a boiling point of 40 ° C. or higher are preferable, and for example, alkyl halides, ethers and aromatic hydrocarbons having a boiling point of 40 ° C. or higher are preferably used. Specifically, alkyl halides such as chloroform and dichloroethane, ethers such as tetrahydrofuran and diisopropyl ether, and aromatic hydrocarbons such as benzene, toluene and xylene are used as the solvent. Among these solvents, alkyl halides such as chloroform and 1,2-dichloroethane are particularly preferable.
[0026]
After the completion of the reaction, the produced acrylic acid ester having a substituent at the 3-position is separated and purified by, for example, column chromatography, recrystallization and the like after distilling off the solvent from the reaction solution.
[0027]
【Example】
Next, the present invention will be specifically described with reference to examples and comparative examples.
The isolated product was confirmed to be the same as the known compound by 1 H-NMR, 13 C-NMR and mass spectrometry, and the isomer ratio was determined by gas chromatography. Moreover, the yield (%) was calculated | required with respect to the aldehyde.
[0028]
The conditions for gas chromatography are as follows.
Column: G-100 (40m)
Column temperature: 135 ° C. (10 minutes), raised to 240 ° C. at 10 ° C./min, 240 ° C. (15 minutes)
Injection temperature: 250 ° C
Detector (FID) temperature: 250 ° C
[0029]
Example 1
Dichlorotristriphenylphosphine ruthenium [RuCl 2 (PPh 3 ) 3 ] (0.0225 mmol) and triphenylphosphine (1.1 mmol) were placed in a Schlenk tube with an internal volume of 25 ml, and the atmosphere was replaced with an argon gas atmosphere. 2-Dichloroethane (3 ml) was added and the solution was heated to 50 ° C. Next, after adding benzaldehyde (1.0 mmol), ethyl diazoacetate / 1,2-dichloroethane solution (1.6 ml, ethyl diazoacetate: 1.5 mmol) was added dropwise, and the reaction was performed at 50 ° C. for 4 hours. .
After completion of the reaction, the reaction solution was cooled to room temperature, and the solvent was distilled off under reduced pressure. The resulting residue was purified by column chromatography to obtain the desired ethyl 3-phenyl-2-propenoate (colorless oil) in 90% yield. The isomer ratio of the product was E-form / Z-form = 97/3.
[0030]
Example 2
The same procedure as in Example 1 was performed, except that benzaldehyde was replaced with hydrocinnamaldehyde (1.0 mmol) and the reaction time was changed to 5 hours. As a result, the target ethyl 5-phenyl-2-pentenoate (colorless oil) was obtained with a yield of 90%, and the isomer ratio was E-form / Z-form = 95/5.
[0031]
Example 3
The same operation as in Example 1 was performed, except that benzaldehyde was replaced with cyclohexanecarboxaldehyde (1.0 mmol) and the reaction time was changed to 17 hours. As a result, the target ethyl 3-cyclohexyl-2-propenoate (colorless oil) was obtained in a yield of 82%, and the isomer ratio was E-form / Z-form> 99/1.
[0032]
Example 4
The same operation as in Example 1 was performed except that benzaldehyde was replaced with p-anisaldehyde (1.0 mmol) and the reaction time was changed to 12 hours. As a result, the target ethyl 3- (4′-methoxyphenyl) -2-propenoate (colorless oil) was obtained in a yield of 92%, and the isomer ratio was E-form / Z-form = 97/3. It was.
[0033]
Example 5
The same operation as in Example 1 was performed, except that benzaldehyde was replaced with transcinnamaldehyde (1.0 mmol) and the reaction time was changed to 8 hours. As a result, the desired ethyl 5-phenyl-2,4-pentadienoate (colorless oil) was obtained in a yield of 92%, and the isomer ratio was E-form / Z-form = 90/10.
[0034]
Comparative Example 1
The same operation as in Example 1 was performed except that dichlorotristriphenylphosphine ruthenium was not added. As a result, only the azine compound (ethyl 3,4-diaza-5-phenyl-2,4-pentadienoate) was obtained in a yield of 70%, and the desired ethyl 3-phenyl-2-propenoate was obtained at all. There wasn't.
[0035]
【The invention's effect】
According to the present invention, an acrylate ester having a substituent at the 3-position can be produced under mild conditions using a safe and easily available production raw material.
In particular, the method of the present invention in which an aldehyde and a diazoacetic acid ester are reacted in the presence of a phosphine and a ruthenium complex is (1) safe and easy to handle the raw material for production, and (2) an aliphatic aldehyde, α, β-insoluble. From various aldehydes such as saturated aldehydes and aromatic aldehydes, an acrylic acid ester having a substituent at the 3-position can be produced without any problem in a high yield, and (3) the resulting acrylic acid having a substituent at the 3-position The stereoselectivity of the ester is high (the main product is E-form), and (4) the reaction can be performed at a low catalyst concentration.
Claims (5)
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| JP01852897A JP3750248B2 (en) | 1997-01-31 | 1997-01-31 | Method for producing an acrylate ester having a substituent at the 3-position |
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| JP01852897A JP3750248B2 (en) | 1997-01-31 | 1997-01-31 | Method for producing an acrylate ester having a substituent at the 3-position |
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