JPH03190869A - Production of coumarin - Google Patents
Production of coumarinInfo
- Publication number
- JPH03190869A JPH03190869A JP33315389A JP33315389A JPH03190869A JP H03190869 A JPH03190869 A JP H03190869A JP 33315389 A JP33315389 A JP 33315389A JP 33315389 A JP33315389 A JP 33315389A JP H03190869 A JPH03190869 A JP H03190869A
- Authority
- JP
- Japan
- Prior art keywords
- cyclohexanoyl
- formula
- methyl
- propionate
- catalyst
- 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
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229960000956 coumarin Drugs 0.000 title abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 150000004775 coumarins Chemical class 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XASDIFBXOWQKFW-UHFFFAOYSA-N [Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] XASDIFBXOWQKFW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 12
- GXGAKHNRMVGRPK-UHFFFAOYSA-N dimagnesium;dioxido-bis[[oxido(oxo)silyl]oxy]silane Chemical compound [Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O GXGAKHNRMVGRPK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000391 magnesium silicate Substances 0.000 abstract description 6
- 229940099273 magnesium trisilicate Drugs 0.000 abstract description 6
- 229910000386 magnesium trisilicate Inorganic materials 0.000 abstract description 6
- 235000019793 magnesium trisilicate Nutrition 0.000 abstract description 6
- 229910052763 palladium Inorganic materials 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000975 dye Substances 0.000 abstract description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 abstract 2
- 239000002304 perfume Substances 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 17
- SFPBROCOLFHXCW-UHFFFAOYSA-N methyl 4-cyclohexyl-4-oxobutanoate Chemical compound COC(=O)CCC(=O)C1CCCCC1 SFPBROCOLFHXCW-UHFFFAOYSA-N 0.000 description 11
- AIWROPDBVWQZOH-UHFFFAOYSA-N 4-cyclohexyl-4-oxobutanoic acid Chemical class OC(=O)CCC(=O)C1CCCCC1 AIWROPDBVWQZOH-UHFFFAOYSA-N 0.000 description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- VMUXSMXIQBNMGZ-UHFFFAOYSA-N 3,4-dihydrocoumarin Chemical compound C1=CC=C2OC(=O)CCC2=C1 VMUXSMXIQBNMGZ-UHFFFAOYSA-N 0.000 description 3
- DMSHWWDRAYHEBS-UHFFFAOYSA-N dihydrocoumarin Natural products C1CC(=O)OC2=C1C=C(OC)C(OC)=C2 DMSHWWDRAYHEBS-UHFFFAOYSA-N 0.000 description 3
- -1 hydrogen propyl 3(2-cyclohexanoyl)propionate Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RPUSRLKKXPQSGP-UHFFFAOYSA-N methyl 3-phenylpropanoate Chemical compound COC(=O)CCC1=CC=CC=C1 RPUSRLKKXPQSGP-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NQMUGNMMFTYOHK-UHFFFAOYSA-N 1-methoxynaphthalene Chemical compound C1=CC=C2C(OC)=CC=CC2=C1 NQMUGNMMFTYOHK-UHFFFAOYSA-N 0.000 description 1
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WGWRJAFRLQVTOW-UHFFFAOYSA-N butyl 4-cyclohexyl-4-oxobutanoate Chemical compound CCCCOC(=O)CCC(=O)C1CCCCC1 WGWRJAFRLQVTOW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Landscapes
- Pyrane Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は３−（２−シクロヘキサノイル）プロピオン酸
エステル類からクマリン類を製造する方法の改良に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an improvement in a method for producing coumarins from 3-(2-cyclohexanoyl)propionic acid esters.
クマリン類は特に香料工業において重要な化合物である
。また農薬、医薬および染料の中間体としても重要な化
合物である。Coumarins are particularly important compounds in the fragrance industry. It is also an important compound as an intermediate for agricultural chemicals, medicines, and dyes.
（従来技術）
クマリン類の製造法としては、３−（２−シクロヘキサ
ノイル）プロピオン酸エステル類にパラジウム等の貴金
属触媒の存在下に加熱して環化脱水素反応を行い製造す
る方法（米国特許第３．４４２．９１０号）、パラジウ
ム等の貴金属触媒と共に助触媒として硫酸バリウム、酸
化クロム等を共存させて環化脱水素させて製造する方法
（特開昭６０−１８１０８２号公報）等が知られている
。(Prior art) Coumarins can be produced by heating 3-(2-cyclohexanoyl)propionic acid esters in the presence of a noble metal catalyst such as palladium to carry out a cyclodehydrogenation reaction (U.S. Patent No. 3.442.910), a method of manufacturing by cyclodehydrogenation in the coexistence of barium sulfate, chromium oxide, etc. as co-catalysts with a noble metal catalyst such as palladium (Japanese Patent Laid-Open No. 181082/1982), etc. Are known.
（発明が解決しようとする課題）
しかしながら、従来の方法では必ずしもクマリン類の収
率が高くない。(Problems to be Solved by the Invention) However, conventional methods do not necessarily provide high yields of coumarins.
本発明者らは、収率及び経済性の良いクマリン及びその
誘導体の製造方法について鋭意研究を重ねた結果、新規
な助触媒を見出し、本発明を完成するに至った。The present inventors have conducted extensive research on methods for producing coumarin and its derivatives with good yield and economic efficiency, and as a result, have discovered a new cocatalyst and have completed the present invention.
（課題を解決するための手段）
すなわち本発明は一般式（Ｉ）、
（式中、Ｒ１−Ｒ１はそれぞれ水素原子、メチル基また
はエチル基を表し、Ｒ２−Ｒ４のうち少なくとも２つの
基は水素原子である。Ｒ５は炭素数１〜４のアルキル基
を示す。）で示される３（２−シクロヘキサノイル）プ
ロピオン酸ニ−（２−シクロヘキサノイル−３，４−ジ
エチル）プロピオン酸プロピル、３− （２−シクロヘ
キサノイル−３，４−ジメチル）プロピオン酸フロビル
、３− （２−シクロヘキサノイル−３，５−ジエチル
〉プロピオン酸メチル、３（２−シクロヘキサノイル−
３−エチル−６メチル）プロピオン酸メチル等が挙げら
れる。(Means for Solving the Problems) That is, the present invention has the general formula (I), (wherein R1-R1 each represents a hydrogen atom, a methyl group, or an ethyl group, and at least two groups among R2-R4 are hydrogen propyl 3(2-cyclohexanoyl)propionate di-(2-cyclohexanoyl-3,4-diethyl)propionate, represented by R5 represents an alkyl group having 1 to 4 carbon atoms; Furovir 3-(2-cyclohexanoyl-3,4-dimethyl)propionate, 3-(2-cyclohexanoyl-3,5-diethyl)methyl propionate, 3(2-cyclohexanoyl-
Examples include methyl 3-ethyl-6methyl propionate.
本発明に用いられる触媒は、周期律表のＩＩＡ族、ＩＡ
族またはＩＶＡ族の化合物、例えば炭素、アルミナ、シ
リカゲノペ硫酸バリウム等からなる群より選ばれた少な
くとも一種の担体にパラジウムを担持した固体金属触媒
である。The catalyst used in the present invention is group IIA of the periodic table, IA
It is a solid metal catalyst in which palladium is supported on at least one type of carrier selected from the group consisting of compounds of Group IVA or Group IVA, such as carbon, alumina, and barium sulfate.
これらの触媒は公知の方法、例えば含浸担持法（［触媒
実験マニュアル」触媒学会編集、槙書店発行）によって
担体に金属を含浸させ、これを高温で水素還元する方法
で得られるが、市販のものをそのまま使用しても良い。These catalysts can be obtained by a known method, for example, by impregnating a support with a metal using the impregnation support method ([Catalyst Experiment Manual] edited by the Catalyst Society, published by Maki Shoten), and then reducing the metal with hydrogen at high temperature. may be used as is.
触媒の使用量は少ないと反応活性が著しく低く、また逆
に多いと反応活性が高すぎて副生物が多く生成する上に
費用もかさむので、３−（ステル類をパラジウム触媒の
存在下に環化脱水素反応によって一般式（ＩＩ）、
（式中Ｒ１〜Ｒ４は前記した基と同一である。）で示さ
れるクマリン類を製造する方法において、助触媒として
三珪酸マグネシウムおよび／またはジルコニアの共存下
に行うことを特徴とするクマリン類の製造法である。If the amount of catalyst used is small, the reaction activity will be extremely low, and conversely, if it is used in a large amount, the reaction activity will be too high, producing many by-products and increasing costs. In a method for producing coumarins represented by the general formula (II) (wherein R1 to R4 are the same as the groups described above) by a hydrodehydrogenation reaction, the coexistence of magnesium trisilicate and/or zirconia as a cocatalyst. This is a method for producing coumarins characterized by carrying out the following steps.
本発明に用いられる３−（２−シクロヘキサノイル）プ
ロピオン酸エステル類としては、例えば、３−（２−シ
クロヘキサノイル）プロピオン酸メチル、３−（２−シ
クロヘキサノイル）プロピオン酸ブチル、１（２−シク
ロヘキサノイル−３−メチル）プロピオン酸メチル、３
（２−シクロヘキサノイル−５−メチル）プロピオン酸
メチノペ ３−（２−シクロヘキサノイル−４−エチル
）プロピオン酸プロピル、３４
２−シクロヘキサノイル）プロピオン酸エステル類に対
して通常約０．１〜５重量％、好ましくは約０．５〜２
．５重量％用いられる。Examples of the 3-(2-cyclohexanoyl)propionate esters used in the present invention include methyl 3-(2-cyclohexanoyl)propionate, butyl 3-(2-cyclohexanoyl)propionate, Methyl (2-cyclohexanoyl-3-methyl)propionate, 3
Methinope (2-cyclohexanoyl-5-methyl)propionate Propyl 3-(2-cyclohexanoyl-4-ethyl)propionate, 34 Usually about 0.1 per 2-cyclohexanoyl)propionate esters ~5% by weight, preferably about 0.5-2
．． 5% by weight is used.
本反応にはパラジウム触媒と共に、助触媒として三珪酸
マグネシウムおよび／またはジジレコニアが添加される
。助触媒は３−（２−シクロヘキサノイル）プロピオン
酸エステ月・類に対して約０，０１〜３重量％、好まし
くは０．０５〜０゜５重量％用いられる。In this reaction, along with a palladium catalyst, magnesium trisilicate and/or dizireconia are added as cocatalysts. The cocatalyst is used in an amount of about 0.01 to 3% by weight, preferably 0.05 to 0.5% by weight, based on the amount of 3-(2-cyclohexanoyl)propionic acid ester.
３−（２−シクロヘキサノイル）プロピオン酸エステル
類の環化脱水素反応は約１００〜３５０℃、好ましくは
約２３０〜２８０℃で行われる。温度が低いと反応活性
が低く、また高いと原料の分解等が起こるので好ましく
ない。The cyclodehydrogenation reaction of 3-(2-cyclohexanoyl)propionic acid esters is carried out at about 100-350°C, preferably at about 230-280°C. If the temperature is low, the reaction activity is low, and if the temperature is high, the raw materials may decompose, which is not preferable.
反応は溶媒を用いて行うこともできる。溶媒トシテハ、
フェニルエーテル、ベンジルエーテル、メチル−α−ナ
フチルエーテル、エチルチフタリン、ジメチルビフエニ
ノペ ドデカン、テトラテ゛カン、テトラリン、アセト
フ、−ノン、フェニルプＩｌピル’ｙ−トン、安息香酸
メチル、グノトタミン酸ジメチル等が挙げられる。The reaction can also be carried out using a solvent. Solvent toshiteha,
Examples include phenyl ether, benzyl ether, methyl-α-naphthyl ether, ethylthiphthaline, dimethylbipheninopedodecane, tetrathecane, tetralin, acetophyl-non, phenylpylene, methyl benzoate, dimethyl gnototamate, etc. .
反応は所定の温度で数時間から数十時間加熱して行われ
る。The reaction is carried out by heating at a predetermined temperature for several hours to several tens of hours.
反応結果、クマリン類が約２０〜３５％、３４−ジヒド
ロクマリン類が約３５〜４５％の収率で得られる。その
ほかにオルトエチルフエノル、ジヒドロケイ皮酸メチル
等が副生ずる。As a result of the reaction, coumarins are obtained in a yield of about 20 to 35%, and 34-dihydrocoumarins are obtained in a yield of about 35 to 45%. Other by-products include orthoethylphenol and methyl dihydrocinnamate.
３．４−ジヒドロクマリン類はさらに脱水素してクマリ
ン類に転化させるか、またはそのまま香料原料等として
用いられる。3.4-dihydrocoumarins are further dehydrogenated and converted into coumarins, or used as they are as raw materials for fragrances, etc.
（発明の効果）
本発明の助触媒として三珪酸マグネシウムおよび／また
はジルコニアを共存させることにより、クマリンの収率
を高くすることができる。(Effects of the Invention) By coexisting magnesium disilicate and/or zirconia as a promoter of the present invention, the yield of coumarin can be increased.
（実施例）
以下、本発明を実施例を挙げて具体的に説明するが、本
発明はこれら実施例に限定されない。(Examples) Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.
実施例１
３−（２−シクロヘキサノイル）プロピオン酸メチル２
００ｇと活性炭にパラジウムを５重７−
マリン及び３．４−ジヒドロクマリンの収率は３− ＜
２−’クロヘキサノイル）プロピオン酸メチルに対しそ
れぞれ２８．０％及び４０．６％であった。Example 1 Methyl 3-(2-cyclohexanoyl)propionate 2
The yield of 7-marin and 3,4-dihydrocoumarin is 3-<
They were 28.0% and 40.6%, respectively, relative to methyl 2-'clohexanoyl)propionate.
比較例１
０．３ｇのジルコニアを用いなかった以外は実施例２と
同様に行った。Comparative Example 1 The same procedure as Example 2 was carried out except that 0.3 g of zirconia was not used.
結果は３−（２−シクロヘキサノイル）プロピオン酸メ
チルの転化率は９９．７％であり、クマリン及び３，４
−ジヒドロクマリンの収率は３−（２−シクロヘキサノ
イル）プロピオン酸メチルに対しそれぞれ１９．２％及
び４７．２％であった。The results showed that the conversion rate of methyl 3-(2-cyclohexanoyl)propionate was 99.7%, and the conversion rate of methyl 3-(2-cyclohexanoyl)propionate was 99.7%.
The yields of -dihydrocoumarin were 19.2% and 47.2%, respectively, based on methyl 3-(2-cyclohexanoyl)propionate.
比較例２
助触媒として０．３ｇの硫酸バリウムを用いた以外は実
施例２と同様に行った。Comparative Example 2 The same procedure as in Example 2 was carried out except that 0.3 g of barium sulfate was used as a promoter.
結果は３−（２−シクロヘキサノイル）プロピオン酸メ
チルの転化率は９９．６％であり、クマリン及び３，４
−ジヒドロクマリンの収率は３− （２−シクロヘキサ
ノイル）プロピオン酸量％担持した触媒３ｇ、助触媒と
して０．２ ｇの三珪酸マグネシウムを四つロフラスコ
に混合し、窒素雪囲気下、撹拌数３０Ｏｒｐｍ、温度２
４０℃で１０時間加熱した。その後温度を２６０℃まで
昇温し５時間加熱した。さらに温度を２７０℃まで昇温
させ１５時間加熱した。The results showed that the conversion rate of methyl 3-(2-cyclohexanoyl)propionate was 99.6%, and the conversion rate of methyl 3-(2-cyclohexanoyl)propionate was 99.6%.
-The yield of dihydrocoumarin is 3- (2-cyclohexanoyl) propionic acid (3 g) of propionic acid supported catalyst and 0.2 g of magnesium trisilicate as a co-catalyst are mixed in a four-hole flask and stirred under a nitrogen atmosphere. Several 30 Orpm, temperature 2
Heated at 40°C for 10 hours. Thereafter, the temperature was raised to 260° C. and heated for 5 hours. The temperature was further increased to 270°C and heated for 15 hours.
反応終了後、反応混合液は触媒等をろ過した後、ガスク
ロマトグラフィーで分析した結果、３−（２−シクロヘ
キサノイル）プロピオン酸メチルの転化率は９９．８％
であり、クマリン及び３，４−ジヒドロクマリンの収率
は３−（２シクロヘキサノイル）プロピオン酸メチルに
対しそれぞれ２８．７％及び３６．６％であった。After the reaction was completed, the reaction mixture was filtered to remove the catalyst, etc., and analyzed by gas chromatography. As a result, the conversion rate of methyl 3-(2-cyclohexanoyl)propionate was 99.8%.
The yields of coumarin and 3,4-dihydrocoumarin were 28.7% and 36.6%, respectively, based on methyl 3-(2cyclohexanoyl)propionate.
実施例２
３−（２−シクロヘキサノイル）プロピオン酸メチル３
００ｇを用い、助触媒として０．２ｇの三珪酸マグネシ
ウムの代わりに０．３ｇのジルコニアを用いた以外は実
施例１と同様に行った。Example 2 Methyl 3-(2-cyclohexanoyl)propionate 3
Example 1 was carried out in the same manner as in Example 1, except that 0.00 g of magnesium trisilicate was used and 0.3 g of zirconia was used as a promoter instead of 0.2 g of magnesium trisilicate.
結果は３−（２−シクロヘキサノイル）プロピオン酸メ
チルの転化率は９９．７％であり、りメチルに対しそれ
ぞれ２７．０％及び３６，３％であった。The results showed that the conversion rate of methyl 3-(2-cyclohexanoyl)propionate was 99.7%, and was 27.0% and 36.3%, respectively, relative to dimethyl.
Claims (1)
またはエチル基を表し、Ｒ＿１〜Ｒ＿４のうち少なくと
も２つの基は水素原子である。Ｒ＿５は炭素数１〜４の
アルキル基を示す。）で示される３−（２−シクロヘキ
サノイル）プロピオン酸エステル類をパラジウム触媒の
存在下に環化脱水素反応によって一般式（II）、 ▲数式、化学式、表等があります▼（II） （式中Ｒ＿１〜Ｒ＿４は前記した基と同一である。）で
示されるクマリン類を製造する方法において、助触媒と
して三珪酸マグネシウムおよび／またはジルコニアの共
存下に行うことを特徴とするクマリン類の製造法。[Claims] 1. General formula (I), ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R_1 to R_4 each represent a hydrogen atom, a methyl group, or an ethyl group, and R_1 to R_4 At least two of the groups are hydrogen atoms. R_5 represents an alkyl group having 1 to 4 carbon atoms. In a method for producing coumarins represented by the general formula (II), ▲numerical formula, chemical formula, table, etc.▼(II) (in the formula, R_1 to R_4 are the same as the groups described above) by hydrogenation reaction. A method for producing coumarins, which is carried out in the coexistence of magnesium disilicate and/or zirconia as a cocatalyst.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1333153A JP3010660B2 (en) | 1989-12-21 | 1989-12-21 | Coumarin production method |
| ES90313952T ES2063294T3 (en) | 1989-12-21 | 1990-12-19 | CATALYTIC PRODUCTION OF CUMARINE COMPOUNDS. |
| KR1019900021013A KR0170382B1 (en) | 1989-12-21 | 1990-12-19 | Process for producing coumarin derivatives |
| EP90313952A EP0434410B1 (en) | 1989-12-21 | 1990-12-19 | Catalytic production of coumarin compounds |
| DE69013868T DE69013868T2 (en) | 1989-12-21 | 1990-12-19 | Catalytic preparation of coumarin compounds. |
| US07/631,316 US5231194A (en) | 1989-12-21 | 1990-12-21 | Process for producing coumarin derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1333153A JP3010660B2 (en) | 1989-12-21 | 1989-12-21 | Coumarin production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03190869A true JPH03190869A (en) | 1991-08-20 |
| JP3010660B2 JP3010660B2 (en) | 2000-02-21 |
Family
ID=18262885
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1333153A Expired - Lifetime JP3010660B2 (en) | 1989-12-21 | 1989-12-21 | Coumarin production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3010660B2 (en) |
-
1989
- 1989-12-21 JP JP1333153A patent/JP3010660B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP3010660B2 (en) | 2000-02-21 |
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