JPH01193241A - Production of cinnamic acid ester derivative - Google Patents
Production of cinnamic acid ester derivativeInfo
- Publication number
- JPH01193241A JPH01193241A JP63018305A JP1830588A JPH01193241A JP H01193241 A JPH01193241 A JP H01193241A JP 63018305 A JP63018305 A JP 63018305A JP 1830588 A JP1830588 A JP 1830588A JP H01193241 A JPH01193241 A JP H01193241A
- Authority
- JP
- Japan
- Prior art keywords
- acid ester
- compound
- methyl
- unsaturated carboxylic
- carboxylic acid
- 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.)
- Granted
Links
- -1 cinnamic acid ester Chemical class 0.000 title claims abstract description 13
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 title claims abstract description 10
- 229930016911 cinnamic acid Natural products 0.000 title claims abstract description 10
- 235000013985 cinnamic acid Nutrition 0.000 title claims abstract description 10
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 12
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 10
- XMIIGOLPHOKFCH-UHFFFAOYSA-N beta-phenylpropanoic acid Natural products OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 12
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000003905 agrochemical Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 5
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 abstract description 5
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 abstract description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052753 mercury Inorganic materials 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 230000001678 irradiating effect Effects 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 241000127225 Enceliopsis nudicaulis Species 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000010948 rhodium Substances 0.000 description 17
- RPUSRLKKXPQSGP-UHFFFAOYSA-N methyl 3-phenylpropanoate Chemical compound COC(=O)CCC1=CC=CC=C1 RPUSRLKKXPQSGP-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- CCRCUPLGCSFEDV-UHFFFAOYSA-N cinnamic acid methyl ester Natural products COC(=O)C=CC1=CC=CC=C1 CCRCUPLGCSFEDV-UHFFFAOYSA-N 0.000 description 7
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003283 rhodium Chemical class 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LVFFZQQWIZURIO-UHFFFAOYSA-N 2-phenylbutanedioic acid Chemical compound OC(=O)CC(C(O)=O)C1=CC=CC=C1 LVFFZQQWIZURIO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000191368 Chlorobi Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JTVHIRUDQBMPCB-UHFFFAOYSA-M O=C=[Rh](Cl)=C=O Chemical class O=C=[Rh](Cl)=C=O JTVHIRUDQBMPCB-UHFFFAOYSA-M 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- ZXMSTCRBSAVFDO-UHFFFAOYSA-N dimethoxy(methyl)phosphane Chemical compound COP(C)OC ZXMSTCRBSAVFDO-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 150000002690 malonic acid derivatives Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- QILOUBBQVGUFNG-CMDGGOBGSA-N methyl (e)-2-methyl-3-phenylprop-2-enoate Chemical compound COC(=O)C(\C)=C\C1=CC=CC=C1 QILOUBBQVGUFNG-CMDGGOBGSA-N 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005538 phosphinite group Chemical group 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は桂皮酸エステル及び／又はヒドロ桂皮酸エステ
ルの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a cinnamic acid ester and/or a hydrocinnamic acid ester.
桂皮酸エステルは香料や感光性樹脂原料として使用され
るほか、医・農薬１食品などの原料として使用される有
用な化合物である。またヒドロ桂皮酸エステルも医・農
薬等の製造の重要な中間体であ°る。Cinnamic acid esters are useful compounds that are used as raw materials for fragrances and photosensitive resins, as well as for medicines, agricultural chemicals, and foods. Hydrocinnamic acid esters are also important intermediates in the production of medicines, agricultural chemicals, and the like.
桂皮酸エステルの製造法として、ベンズアルデヒドとマ
ロン酸誘導体との反応（Ｋｎｏａｖｅｎａｇｅｌ縮合）
、ベンズアルデヒドと酢酸エステルとの反応（Ｃｌａｉ
ｓｅｎ反応）、ベンズアルデヒドと無水酢酸との反応（
Ｐｅｒｋｉｎ反応）がある、しかしながら、これらの方
法はいずれも比較的高価なベンズアルデヒドを使用し、
また危険または特殊な塩基触媒の存在下に高温・長時間
の加熱を要する場合もあり、工業的実施の観点からは満
足出来るものではない。As a method for producing cinnamic acid ester, reaction between benzaldehyde and malonic acid derivative (Knoavenagel condensation)
, reaction of benzaldehyde and acetate (Clay
sen reaction), the reaction between benzaldehyde and acetic anhydride (
However, both of these methods use relatively expensive benzaldehyde and
Further, it may require heating at high temperature and for a long time in the presence of a dangerous or special base catalyst, which is unsatisfactory from the viewpoint of industrial implementation.
別の方法としては、スチレン誘導体とアルコール類とを
パラジウム触媒の存在下に酸化的にカルボニル化する方
法も知られている。しかし、この方法は爆発の危険性を
伴う上、炭酸ガスやフェニルコハク酸等の副生もあり、
工業的に満足できる水準には到達していない。Another known method is to oxidatively carbonylate a styrene derivative and an alcohol in the presence of a palladium catalyst. However, this method not only carries the risk of explosion, but also produces by-products such as carbon dioxide gas and phenylsuccinic acid.
It has not yet reached an industrially satisfactory level.
更に別の方法として、芳香族化合物とα、β−不飽和カ
ルボン酸エステルとをロジウム触媒の存在下に反応させ
る方法が知られているが（日本化学会誌、１９８５年、
４７９ページ）、２２０℃もの高温に於てさえ十分高い
生産性が得られず、工業的に有利な方法とは考えられな
い。Another known method is to react an aromatic compound with an α,β-unsaturated carboxylic acid ester in the presence of a rhodium catalyst (Journal of the Chemical Society of Japan, 1985).
(page 479), it is not possible to obtain sufficiently high productivity even at a high temperature of 220° C., and this method is not considered to be industrially advantageous.
ヒドロ桂皮酸誘導体の製造に関しては、一般的には桂皮
酸誘導体の水素添加によって製造されるため、上記した
桂皮酸誘導体の製造上の問題点を内包するものである。Regarding the production of hydrocinnamic acid derivatives, since they are generally produced by hydrogenation of cinnamic acid derivatives, they involve the above-mentioned problems in the production of cinnamic acid derivatives.
他に、スチレンをヒドロエステル化する方法も知られて
いるが、ヒドロアトロバ酸エステルが生成物の大部分を
占め、ヒドロ桂皮酸エステルの選択率は著しく低いのが
通例であって、工業的製造法としての意義は考えられな
い。Another known method is to hydroesterify styrene, but hydroatrobate esters account for most of the product, and the selectivity for hydrocinnamic esters is usually extremely low, making it difficult to use industrial production methods. I can't think of any significance as such.
桂皮酸又はヒドロ桂皮酸誘導体の製造法に係る上記の現
状に鑑み、原料的に有利な芳香族化合物とα、β−不飽
和カルボン酸エステルからの桂皮酸又はヒドロ桂皮酸誘
導体の製造法につき、それを低温で効率的に進行させる
べく、鋭意研究を行った。すなわち、本発明の目的は安
価な芳香族化合物とα、β−不飽和カルボン酸エステル
とから、湿和な条件下に桂皮酸エステル及び／又はヒド
ロ桂皮酸エステルを効率的に製造する方法を提供するこ
とにある。In view of the above-mentioned current state of the method for producing cinnamic acid or hydrocinnamic acid derivatives, we have proposed a method for producing cinnamic acid or hydrocinnamic acid derivatives from aromatic compounds and α,β-unsaturated carboxylic acid esters, which are advantageous in terms of raw materials. We conducted extensive research to develop this process efficiently at low temperatures. That is, an object of the present invention is to provide a method for efficiently producing a cinnamic acid ester and/or a hydrocinnamic acid ester from an inexpensive aromatic compound and an α,β-unsaturated carboxylic acid ester under humid conditions. It's about doing.
」；記の目的は、ロジウム化合物の存在下および光の照
射下に、少くとも１つの水素原子が芳香環に結合した芳
香族化合物と、β−炭素上に少くとも１つの水素原子が
結合したα、β−不飽和カルボン酸エステルとを反応さ
せることによって達成することができる。”; The purpose of this is to form an aromatic compound in which at least one hydrogen atom is bonded to an aromatic ring and at least one hydrogen atom bonded to a β-carbon in the presence of a rhodium compound and under irradiation with light. This can be achieved by reacting with α,β-unsaturated carboxylic acid ester.
本発明の製造方法に供しうる芳香族化合物は、その芳香
環に少くとも１つの水素原子が結合しているものであれ
ばいかなるものでも用いることができる。これらを具体
的に例示すれば、ベンゼン、トルエン、イソプロピルベ
ンゼン、ｔ−ブチルベンゼン、イソブチルベンゼン、キ
シレン、ナフタレン、メチルナフタレン、クロルベンゼ
ン、アニソール、ジフェニルエーテル、安息香酸メチル
等が挙げられる。Any aromatic compound that can be used in the production method of the present invention can be used as long as it has at least one hydrogen atom bonded to its aromatic ring. Specific examples of these include benzene, toluene, isopropylbenzene, t-butylbenzene, isobutylbenzene, xylene, naphthalene, methylnaphthalene, chlorobenzene, anisole, diphenyl ether, and methyl benzoate.
α、β−不飽和カルボン酸エステルとしては、β−炭素
上に少くとも１つの水素原子が結合しているものであれ
ばいかなるものでも本反応に供することが出来る。具体
的には、アクリル酸メチル、アクリル酸エチル、メタク
リル酸メチル、アトロバ酸メチル、クロトン酸メチル等
が例示される。Any α,β-unsaturated carboxylic acid ester can be used in this reaction as long as it has at least one hydrogen atom bonded to the β-carbon. Specific examples include methyl acrylate, ethyl acrylate, methyl methacrylate, methyl atrobate, and methyl crotonate.
本発明の反応はロジウム化合物の存在下に於て効率的に
進行する。ロジウム化合物としては反応系に少くとも一
部は可溶の化合物を用いるのが反応速度的には好ましい
、これらの化合物としては有機配位子を含む錯体が特に
好ましく用いられる。The reaction of the present invention proceeds efficiently in the presence of a rhodium compound. As the rhodium compound, it is preferable to use a compound that is at least partially soluble in the reaction system from the viewpoint of reaction rate, and complexes containing organic ligands are particularly preferably used as these compounds.
これらを例示すると、ロジウムカルボニル、クロロジカ
ルボニルロジウムダイマー、アセトアセタトジ力ルポニ
ルロジウム、クロロ（ＩＩ５−へキサジエン）ロジウム
ダイマー、クロロビス（エチレン）ロジウムダイマー、
一般式ＲｈＸＬ３（Ｘはハロゲン原子、しはホスフィン
、ホスフィナイト、ホスフォナイト、またはホスファイ
トを示す）、ＲｈＸ （Ｃｏ）Ｌ。Examples of these include rhodium carbonyl, chlorodicarbonyl rhodium dimer, acetoacetate dihydroponyl rhodium, chloro(II5-hexadiene) rhodium dimer, chlorobis(ethylene) rhodium dimer,
General formula RhXL3 (X is a halogen atom, and represents phosphine, phosphinite, phosphonite, or phosphite), RhX (Co)L.
（Ｘ及びＬは前記と同じ）、ＨＲｈ （ｃｏ）＋−３（
Ｌは前記と同じ）、又はＨＲｈ （ＧＯ）２Ｌ２（Ｌは
前記と同じ）で表わされる錯体が挙げられるが、これら
に制限されるものではない。またこれらのロジウム化合
物を単独でなく２種以上を共存させて実施してもよく、
更に。(X and L are the same as above), HRh (co)+-3(
Examples include complexes represented by (L is the same as above) or HRh (GO)2L2 (L is the same as above), but are not limited thereto. In addition, these rhodium compounds may be used not only alone but in combination of two or more,
Furthermore.
ロジウム化合物と共に前記りを添加して実施することも
本発明の有利な態様に含まれる。Ｌとしては具体的には
トリフェニルホスフィン、トリメチルホスフィン、トリ
ブチルホスフィン、メチルジメチルホスフィナイト、ジ
メチルメチルホスフォナイト、トリメチルホスファイト
等が挙げられる。An advantageous embodiment of the invention also includes the addition of the above together with a rhodium compound. Specific examples of L include triphenylphosphine, trimethylphosphine, tributylphosphine, methyldimethylphosphine, dimethylmethylphosphonite, trimethylphosphite, and the like.
本発明の反応は光の照射下において初めて効率的に進行
するが、その波長領域はいわゆる紫外、可視領域であれ
ばよく、水銀灯やキセノンランプの使用又は太陽光等に
よる光照射が好ましく用いられる。またフィルターやモ
ノクロメータ等を使用して波長領域を制御したり、単色
光を照射することも可能である。太陽光の場合は、自然
光をそのまま用いても本発明の反応を生起させることは
不可能であるが、レンズ等により集光してその照射強度
を増加させて照射するのが有利である。The reaction of the present invention proceeds efficiently only under light irradiation, and the wavelength range may be in the so-called ultraviolet or visible range, and light irradiation using a mercury lamp or a xenon lamp, or sunlight or the like is preferably used. It is also possible to control the wavelength range using a filter, monochromator, etc., or to irradiate monochromatic light. In the case of sunlight, it is impossible to cause the reaction of the present invention even if natural light is used as it is, but it is advantageous to concentrate the light with a lens or the like and increase the irradiation intensity.
本発明の反応は特に溶媒を使用することなく、反応に供
すべき芳香族化合物自身をα、β−不飽和カルボン酸エ
ステルに対して大過剰に用いることにより容易に実施さ
れる。しかし溶媒を用いることは本反応の生起にとって
障害となるものではなく、必要に応じ溶媒中で実施され
る。これらの溶媒の選択は反応させるべき芳香族化合物
とα、β−不飽和カルボン酸エステルの反応性を考慮し
て。The reaction of the present invention is easily carried out without using any particular solvent by using the aromatic compound itself to be subjected to the reaction in large excess relative to the α,β-unsaturated carboxylic acid ester. However, the use of a solvent is not an obstacle to the occurrence of this reaction, and the reaction may be carried out in a solvent if necessary. These solvents are selected in consideration of the reactivity of the aromatic compound to be reacted with the α,β-unsaturated carboxylic acid ester.
一般に用いられる溶媒、たとえば炭化水素系又はエーテ
ル系の溶媒の中から選ばれるのが好ましい。Preferably, the solvent is selected from commonly used solvents, such as hydrocarbon-based or ether-based solvents.
本発明の反応は、０℃以下でも進行するが、好ましい速
度を達するために２５０℃までの温度で加熱することも
できる。原料化合物の構造にもよるが、一般的に好まし
い温度領域はθ℃−２００℃である。The reactions of the present invention proceed below 0°C, but can also be heated at temperatures up to 250°C to achieve preferred rates. Although it depends on the structure of the raw material compound, the generally preferred temperature range is θ°C-200°C.
本反応においては、芳香環にα、β−不飽和カルボン酸
エステルがそのβ−炭素を介して結合した桂皮酸エステ
ル誘導体が得られるが、芳香環に水素原子が複数個結合
している場合、反応条件によって、α、β−不飽和カル
ボン酸エステルが１個又は複数個結合したものが主成分
として生成される。In this reaction, a cinnamic acid ester derivative is obtained in which an α,β-unsaturated carboxylic acid ester is bonded to the aromatic ring via its β-carbon, but when multiple hydrogen atoms are bonded to the aromatic ring, Depending on the reaction conditions, one or more α,β-unsaturated carboxylic acid esters are formed as a main component.
複数個結合したものは、光照射時間を長くすることによ
り生成させることができる。A combination of a plurality of molecules can be produced by increasing the light irradiation time.
反応後の生成物の分離は未反応原料等を蒸留等で分離後
、精留、再結晶、クロマトグラフィー等に付すことで、
容易に実施される。The products after the reaction can be separated by separating unreacted raw materials by distillation, etc., and then subjecting them to rectification, recrystallization, chromatography, etc.
easily implemented.
本発明によれば、安価かつ入手容易な芳香化合物とα、
β−不飽和カルボン酸エステルとから容易に桂皮酸エス
テル誘導体及び／又はヒドロ桂皮酸誘導体が得られ、そ
の産業的意義は多大である。According to the present invention, an inexpensive and easily available aromatic compound and α,
Cinnamic acid ester derivatives and/or hydrocinnamic acid derivatives can be easily obtained from β-unsaturated carboxylic acid esters, and have great industrial significance.
次に本発明を実施例により更に詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例Ｉ
ＲｈＣＱ（Ｃｏ）［Ｐ（Ｃ）１３）））！を０．７■に
濃度で含むベンゼン２９ｄ、アクリル酸メチル１−の混
合溶液を、 １００Ｖの内部照射型高圧水銀灯を用いて
照射し、室温で１９．５時間反応させた。ガスクロマト
グラフィーにより分析した結果、桂皮酸メチルがＲｈ錯
体基準で２４１２％、ヒドロ桂皮酸メチルが同じ＜ １
００８％の収率で生成していることが確認された。Example I RhCQ(Co)[P(C)13)))! A mixed solution of benzene 29d and methyl acrylate 1- containing 0.7 μm in concentration was irradiated with a 100 V internal irradiation type high-pressure mercury lamp and allowed to react at room temperature for 19.5 hours. As a result of analysis by gas chromatography, methyl cinnamate was 2412% based on Rh complex, and methyl hydrocinnamate was the same <1.
It was confirmed that the product was produced with a yield of 0.008%.
実施例２
光源を外部照射型５００ｖ高圧水銀灯に代えて、実施例
１と同様の反応を行った０反応時間６時間の時点での桂
皮酸メチル及びヒドロ桂皮酸メチルの収率は、それぞれ
１４６０％／Ｒｈ及び４４５％／Ｒｈであった。Example 2 The same reaction as in Example 1 was carried out except that the light source was replaced with an external irradiation type 500V high-pressure mercury lamp.The yields of methyl cinnamate and methyl hydrocinnamate at 0 reaction time of 6 hours were each 1460%. /Rh and 445%/Rh.
実施例３
照射光の透過率が１０％以上の波長領域が２９５〜４２
Ｏｎ１１となるフィルターを光源に装着して実施例２と
同様の反応を行った。桂皮酸メチルとヒドロ桂皮酸メチ
ルの収率はそれぞれ１３６１％／Ｒｈ、 ４４２％／Ｒ
ｈであった。Example 3 The wavelength range in which the transmittance of irradiated light is 10% or more is 295 to 42
The same reaction as in Example 2 was carried out by attaching an On11 filter to the light source. The yields of methyl cinnamate and methyl hydrocinnamate were 1361%/Rh and 442%/R, respectively.
It was h.
実施例４
照射光の透過率が１０％以上の波長領域が３２５ｎ■以
上となるフィルターを光源に装着して実施例２と同様の
反応を行った。桂皮酸メチルとヒドロ桂皮酸メチルの収
率はそれぞれ１５８６％／Ｒｈ、５２５％／Ｒｈであっ
た。Example 4 The same reaction as in Example 2 was carried out using a light source equipped with a filter in which the wavelength region in which the transmittance of irradiated light was 10% or more was 325 nm or more. The yields of methyl cinnamate and methyl hydrocinnamate were 1586%/Rh and 525%/Rh, respectively.
実施例５
照射光の透過率が１０％以上の波長領域が３６５ｎｍ以
上となるフィルターを光源に装着して実施例２と同様の
反応を行った。桂皮酸メチルとヒドロ桂皮酸メチルの収
率はそれぞれ６３３％／Ｒｈ、２１７％／Ｒｈであった
・
実施例６
ベンゼンの代りにトルエンを用いて実施例１と同様の反
応を行った。反応時間８時間の時点でガスクロマトグラ
フィーにより分析した結果、ベンゼン核にメチル基を有
する桂皮酸メチルとヒドロ桂皮酸メチルがそれぞれ９７
３％／％ｈ（ｏ：＋ｍ：ｐ＝０：６４：３６）。Example 5 The same reaction as in Example 2 was carried out using a light source equipped with a filter in which the wavelength range of irradiated light having a transmittance of 10% or more was 365 nm or more. The yields of methyl cinnamate and methyl hydrocinnamate were 633%/Rh and 217%/Rh, respectively. Example 6 The same reaction as in Example 1 was carried out using toluene instead of benzene. As a result of analysis by gas chromatography at the time of 8 hours of reaction time, methyl cinnamate and methyl hydrocinnamate each having a methyl group in the benzene nucleus were found to be 97%
3%/%h (o:+m:p=0:64:36).
５２５％／Ｒｈ（ｏ：ｍ：Ｐ＝０：６８：３２）の収率
で生成しているこが確認された。It was confirmed that the product was produced at a yield of 525%/Rh (o:m:P=0:68:32).
実施例７
ＲｈＣＱ（ＣＯ）（Ｐ（ＣＩ＋１）３）ｉに代えてＲｈ
Ｃ４（Ｃｏ）（Ｐ（ｎ−Ｃ，ｌ＋、）３１を用いて、実
施例１と同様の反応を行った結果、桂皮酸メチル及びヒ
ドロ桂皮酸メチルがそれぞれ４３４％／Ｒｈ、 ２２％
／Ｒｈの収率で生成した。Example 7 Rh in place of RhCQ(CO)(P(CI+1)3)i
As a result of carrying out the same reaction as in Example 1 using C4(Co)(P(n-C,l+,)31, methyl cinnamate and methyl hydrocinnamate were 434%/Rh and 22%, respectively.
/Rh yield.
実施例８
アクリル酸メチルの代りにメタクリル酸メチルを用いて
実施例１と同様の反応を１２時間行った。Example 8 The same reaction as in Example 1 was carried out for 12 hours using methyl methacrylate instead of methyl acrylate.
ガスクロマトグラフィーで分析した結果、α−メチル桂
皮酸メチルが１０９１％／Ｒｈ、α−メチルーβ−フェ
ニルプロピオン酸メチルが２５２％／Ｒｈの収率で生成
していることが判明した。Analysis by gas chromatography revealed that methyl α-methyl cinnamate was produced at a yield of 1091%/Rh, and methyl α-methyl-β-phenylpropionate was produced at a yield of 252%/Rh.
復代理人 弁理士 池 浦 敏 明Sub-Agent Patent Attorney Toshiaki Ikeura
Claims (2)
も１つの水素原子が芳香環に結合した芳香族化合物と、
β−炭素上に少くとも１つの水素原子が結合したα，β
−不飽和カルボン酸エステルを反応させることを特徴と
する桂皮酸エステル誘導体の製造方法。(1) an aromatic compound in which at least one hydrogen atom is bonded to an aromatic ring in the presence of a rhodium compound and under irradiation with light;
α, β with at least one hydrogen atom bonded to β-carbon
- A method for producing a cinnamic acid ester derivative, which comprises reacting an unsaturated carboxylic acid ester.
も１つの水素原子が芳香環に結合した芳香族化合物と、
β−炭素上に少くとも１つの水素原子が結合したα，β
−不飽和カルボン酸エステルとを反応させることを特徴
とするヒドロ桂皮酸エステル誘導体の製造方法。(2) an aromatic compound in which at least one hydrogen atom is bonded to an aromatic ring in the presence of a rhodium compound and under irradiation with light;
α, β with at least one hydrogen atom bonded to β-carbon
- A method for producing a hydrocinnamic acid ester derivative, which comprises reacting it with an unsaturated carboxylic acid ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63018305A JPH01193241A (en) | 1988-01-27 | 1988-01-27 | Production of cinnamic acid ester derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63018305A JPH01193241A (en) | 1988-01-27 | 1988-01-27 | Production of cinnamic acid ester derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01193241A true JPH01193241A (en) | 1989-08-03 |
| JPH0581580B2 JPH0581580B2 (en) | 1993-11-15 |
Family
ID=11967900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63018305A Granted JPH01193241A (en) | 1988-01-27 | 1988-01-27 | Production of cinnamic acid ester derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01193241A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7282618B2 (en) | 2000-12-13 | 2007-10-16 | Yeda Research And Development Co., Ltd. | Method for the production of aryl alkenes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878074A (en) * | 1973-07-26 | 1975-04-15 | Universal Oil Prod Co | Vinylation of aromatic compounds |
-
1988
- 1988-01-27 JP JP63018305A patent/JPH01193241A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3878074A (en) * | 1973-07-26 | 1975-04-15 | Universal Oil Prod Co | Vinylation of aromatic compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7282618B2 (en) | 2000-12-13 | 2007-10-16 | Yeda Research And Development Co., Ltd. | Method for the production of aryl alkenes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0581580B2 (en) | 1993-11-15 |
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