JPS63216857A - Production of alpha,beta-unsaturated nitrile - Google Patents
Production of alpha,beta-unsaturated nitrileInfo
- Publication number
- JPS63216857A JPS63216857A JP62051766A JP5176687A JPS63216857A JP S63216857 A JPS63216857 A JP S63216857A JP 62051766 A JP62051766 A JP 62051766A JP 5176687 A JP5176687 A JP 5176687A JP S63216857 A JPS63216857 A JP S63216857A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- reaction
- alpha
- nitrile
- triphenylphosphine
- 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
- 150000002825 nitriles Chemical class 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- -1 nitrile compound Chemical class 0.000 claims abstract description 16
- BFPFOLJFUVTHEP-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 BFPFOLJFUVTHEP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000007935 neutral effect Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 4
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012442 inert solvent Substances 0.000 abstract description 2
- 229940088623 biologically active substance Drugs 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- SUSQOBVLVYHIEX-UHFFFAOYSA-N phenylacetonitrile Chemical compound N#CCC1=CC=CC=C1 SUSQOBVLVYHIEX-UHFFFAOYSA-N 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000000126 substance Substances 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
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 1
- UVEWQKMPXAHFST-SDNWHVSQSA-N chembl1256376 Chemical compound C=1C=CC=CC=1/C=N/C1=CC=CC=C1 UVEWQKMPXAHFST-SDNWHVSQSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- USHSLSUBTWXMQR-SOFGYWHQSA-N ethyl (e)-2-cyanohex-2-enoate Chemical compound CCC\C=C(/C#N)C(=O)OCC USHSLSUBTWXMQR-SOFGYWHQSA-N 0.000 description 1
- JTCIMTCOXPDDFV-BQYQJAHWSA-N ethyl (e)-3-(2-cyanophenyl)prop-2-enoate Chemical compound CCOC(=O)\C=C\C1=CC=CC=C1C#N JTCIMTCOXPDDFV-BQYQJAHWSA-N 0.000 description 1
- PZAJJZJKRVXKCS-UHFFFAOYSA-N ethyl 2-cyano-2-cyclohexylideneacetate Chemical compound CCOC(=O)C(C#N)=C1CCCCC1 PZAJJZJKRVXKCS-UHFFFAOYSA-N 0.000 description 1
- USHSLSUBTWXMQR-UHFFFAOYSA-N ethyl 2-cyanohex-2-enoate Chemical compound CCCC=C(C#N)C(=O)OCC USHSLSUBTWXMQR-UHFFFAOYSA-N 0.000 description 1
- SJRXWMQZUAOMRJ-UHFFFAOYSA-N ethyl 2-hexenoate Chemical compound CCCC=CC(=O)OCC SJRXWMQZUAOMRJ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000017105 transposition Effects 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、生理活性物質またはその中間体として有用な
α、β−不飽和不飽和用トリル法に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a trill method for α,β-unsaturation useful as physiologically active substances or intermediates thereof.
〈従来の技術〉
従来、α、β−不飽和不飽和用トリル法としては塩基性
触媒によるアルドール型縮合反応が知られている。（日
本化学会編、新実験化学講座第１４巻、有機化合物の合
成と反応■、 第１４７５頁、丸善株式会社発行（１９
７８）参照）〈発明が解決しようとする問題点〉
しかしながら、塩基性触媒を用いる場合、゛カルボニル
化合物同士の縮合反応等の副反応が起こり易く、ａ、β
−不飽和二トリルの製造法として必ずしも充分なものと
は言えなかった。<Prior Art> Aldol-type condensation reaction using a basic catalyst has been known as the tolyl method for α,β-unsaturation. (Edited by the Chemical Society of Japan, New Experimental Chemistry Course Vol. 14, Synthesis and Reactions of Organic Compounds, p. 1475, Published by Maruzen Co., Ltd. (19
(See 78)) <Problems to be Solved by the Invention> However, when using a basic catalyst, side reactions such as condensation reactions between carbonyl compounds are likely to occur;
- It could not be said that the method for producing unsaturated nitrile was necessarily sufficient.
く問題点を解決するための手段〉
本発明者らは中性条件下でのアルドール型縮合反応につ
いて鋭意検討した結果、式
％式％））
で示されるジヒドリドテトラキス（トリフェニルホスフ
ィン）ルテニウムを用いることにより中性条件下で前記
一般式ＣＩ）で示されるα、β−不飽和不飽和用トリル
できることを見い出し本発明に至った。As a result of intensive studies on aldol-type condensation reactions under neutral conditions, the present inventors found that dihydridotetrakis(triphenylphosphine)ruthenium represented by the formula %) The present inventors have discovered that the α,β-unsaturated tolyl represented by the general formula CI) can be prepared under neutral conditions by using the above-mentioned triyl.
即ち、本発明は、カルボニル化合物とα−位に２個の水
素原子を有するニトリル化合物とをジヒドリドテトラキ
ス（トリフェニルホスフィン）ルテニウムの存在下で、
ホスフィン化合物の存在下または非存在下に反応させる
α、β−不飽和ニトリルの製造法である。That is, the present invention combines a carbonyl compound and a nitrile compound having two hydrogen atoms at the α-position in the presence of dihydridotetrakis(triphenylphosphine)ruthenium,
This is a method for producing α,β-unsaturated nitriles, which is reacted in the presence or absence of a phosphine compound.
本発明方法において、反応温度は通常、室温〜１００℃
であり、反応溶媒としてはテトラヒドロフラン等の不活
性溶媒が用いられる。該反応に用いられる試剤の量は、
ニトリル化合物１モルに対してカルボニル化合物は通常
１．００〜１．１０モル、ジヒドリドテトラキス（トリ
フェニルホスフィン）ルテニウムは０．０３モルであり
、さらにホスフィン化合物を０．０３モル程度添加する
こともできる。添加するホスフィン化合物としては、例
えばトリブチルホスフィン、１．２−ビス（ジフェニル
ホスフィノ）エタン等が挙げられる。ジヒドリドテトラ
キス（トリフェニルホスフィン）ルテニウムは、例えば
、日本化学会編、新実験化学講座第１２巻、有機金属化
学、第１６１〜１６２頁、丸善株式会社発行（１９７６
）に記載の方法により得ることができる。In the method of the present invention, the reaction temperature is usually room temperature to 100°C.
As the reaction solvent, an inert solvent such as tetrahydrofuran is used. The amount of reagents used in the reaction is
The carbonyl compound is usually 1.00 to 1.10 mol per mol of the nitrile compound, the dihydridotetrakis(triphenylphosphine)ruthenium is 0.03 mol, and about 0.03 mol of a phosphine compound may also be added. can. Examples of the phosphine compound to be added include tributylphosphine and 1,2-bis(diphenylphosphino)ethane. Dihydridotetrakis(triphenylphosphine)ruthenium is, for example, published by the Chemical Society of Japan, New Experimental Chemistry Course Volume 12, Organometallic Chemistry, pp. 161-162, published by Maruzen Co., Ltd. (1976).
) can be obtained by the method described in .
本発明方法において、ホスフィン化合物を添加すること
は必須ではないが、添加することにより反応を促進する
ことができる。In the method of the present invention, although it is not essential to add a phosphine compound, the reaction can be accelerated by adding it.
α：β−不飽和不飽和用トリルシアノ酢酸エチルまたは
フェニルアセトニトリルを用い、カルボニル化合物とし
てアルデヒド化合物を用いた場合、生成するα、β−不
飽和二トリルはシアノ基と水素原子とがトランス位にあ
る幾何異性体のみである。即ち、本発明方法はｌ）中性
条件下で進行する反応であり、ｉｉ ）一方の幾何異性
体のみを生成する立体特異的な反応を利用した製造法で
ある。α: β-unsaturated Tolyl for unsaturation When ethyl cyanoacetate or phenylacetonitrile is used and an aldehyde compound is used as the carbonyl compound, the α,β-unsaturated nitrile produced has a cyano group and a hydrogen atom in the trans position. Only geometric isomers. That is, the method of the present invention is l) a reaction that proceeds under neutral conditions, and ii) a production method that utilizes a stereospecific reaction that produces only one geometric isomer.
〈実施例〉 次に、実施例を挙げて詳しく説明する。<Example> Next, a detailed explanation will be given with reference to examples.
実施例１
乾燥テトラヒドロフラン０．５１ｎｔにシアノ酢酸エチ
ル２．０ ｍｍｏｌ 、ブタナール２．２ ｍｍｏｌお
よびジヒドリルテトラキス（トリフェニルホスフィン）
ルテニウムＱ、 ９６ｍｍｏｌ を加え、アルゴン雰囲
気下、２０℃にて２４時間攪拌した。次いで溶媒を留去
し、残渣をシリカゲルカラムクロマトグラフィ（溶出溶
媒、ヘキサン：エーテル−５；ｌ）にて処理し、無色油
状の■−２−シアノー２−ヘキセン酸エチルを得た。Example 1 2.0 mmol of ethyl cyanoacetate, 2.2 mmol of butanal and dihydryltetrakis (triphenylphosphine) in 0.51 nt of dry tetrahydrofuran.
Ruthenium Q (96 mmol) was added, and the mixture was stirred at 20° C. for 24 hours under an argon atmosphere. The solvent was then distilled off, and the residue was treated with silica gel column chromatography (elution solvent: hexane:ether-5; l) to obtain ethyl 2-cyano-2-hexenoate as a colorless oil.
収率 ８３％
Ｉ Ｒ（ｎｅａｔ） ２２４ Ｇ ａｍ−” （ＯＮ
）、１７４０ ｔｍ−” （Ｃｏ）’Ｈ−ＮＭＲ（ＣＤ
ＣＡ）
δ値 ０．７０〜１．８０（ｍ、ｌ０Ｈ）、４−８０（
ｑ。Yield 83% IR(neat) 224 G am-” (ON
), 1740 tm-” (Co)’H-NMR (CD
CA) δ value 0.70-1.80 (m, 10H), 4-80 (
q.
Ｊ−７，ＯＨ２，２Ｈ）、７．５７ （ｔ、 Ｊ−８，
ＱＨｚ。J-7, OH2, 2H), 7.57 (t, J-8,
QHz.
ＩＨ）
実施例２
２、２ ｍｍｏｌ 、ジヒドリドテトラキス（トリフェ
ニルホスフィン）ルテニウムＱ、Ｑ （ｌ ｍｍｏｌ
およびトリブチルホスフィン０．０６ｍｍｏｌ を加
え、アルゴン雰囲気下、４０℃にて２４時間攪拌した。IH) Example 2 2,2 mmol, dihydridotetrakis(triphenylphosphine)ruthenium Q,Q (l mmol
and 0.06 mmol of tributylphosphine were added, and the mixture was stirred at 40°C for 24 hours under an argon atmosphere.
次いで溶媒を留去し、残渣をシリカゲルカラムクロマト
グラフィにて処理し、無色油状のシクロヘキシリデンシ
アノ酢酸エチルを得た。Then, the solvent was distilled off, and the residue was treated with silica gel column chromatography to obtain ethyl cyclohexylidenecyanoacetate as a colorless oil.
収率７４％
” Ｒ（”ｔ） ２２２５ ｔｘ−” （ＯＮ ）’
、’Ｈ−ＮＭ Ｒ（ＣＤＧ＋３）
δ値 １．３ ｇ （ｔ、 Ｊ−７，□Ｈｚ、 ３Ｈ）
、１．６０〜２．１０（ｍ、６Ｈ）、２．６７ （ｔ、
Ｊ −６，Ｑ Ｈｚ。Yield 74% "R("t) 2225 tx-"(ON)'
, 'H-NMR (CDG+3) δ value 1.3 g (t, J-7, □Hz, 3H)
, 1.60-2.10 (m, 6H), 2.67 (t,
J-6, Q Hz.
２Ｈ）、２．９７（ｔ、Ｊ、、６．□Ｈｚ、２Ｈ）、４
．２５（ｔ、Ｊ−７，ＯＨ２，２Ｂ）上記の実施例と同
様に、ニトリル化合物とカルボニル化合物よりα、β−
不飽和二トリルが製造される例を下記第１表に示す、第
１表において実施例３〜７は実施例１と同様ホスフィン
化合物の非存在下に行ったものであり、実施例８および
９は実施例２と同様にトリブチルホスフィンの存在下に
行ったものである。2H), 2.97(t, J,, 6.□Hz, 2H), 4
．． 25 (t, J-7, OH2, 2B) Similar to the above example, α, β-
Examples in which unsaturated nitrites are produced are shown in Table 1 below. In Table 1, Examples 3 to 7 were conducted in the absence of a phosphine compound as in Example 1, and Examples 8 and 9 were was carried out in the same manner as in Example 2 in the presence of tributylphosphine.
次にホスフィン化令鴫を添加すること（こヨリ反応が促
進されることを実施例にて示す。Next, it will be shown in Examples that the addition of phosphine-formed phosphatide (Koyori reaction is accelerated).
実施例１Ｏ〜１２
乾燥テトラヒドロフラン０．５ ｒｎｔにベンジルシア
ニド２． Ｏｍｍｏｌ、ブタナール２．２ ｍｍｏｌ、
ジヒドリドテトラキス（トリフェニルホスフィン）ルテ
ニウム０．０６ ｍｍｏｌ および下記第２表に示す
リン化合物Ｑ、 Ｑ ５ ｍｍｏｌ を加え、アルゴン
雲囲気下封管中で６時間６０℃に加熱した。（Ｚ）−２
−フェニル−２−ヘキセンニトリルへの転化率およびそ
の収率をガスクロマトグラフィにより判定した。結果を
第２表７′
／′
７−′
／′
第 ２ 表
ｏ−ＣＨ２ＣＮ ＋ｎ−０３ＥＩ７ＣＨＯ本発明方法
の特徴の１つとして、シアノ基のα−位にのみ選択的に
アルドール型縮合反応を行なうことが挙げられ、その−
例として、一般にアルドール型縮合反応を起こし易いと
されるアセチルアセトンの共存下での反応例を参考例１
に示す。Examples 10-12 0.5 rnt of dry tetrahydrofuran and 2.0 m of benzyl cyanide. Ommol, butanal 2.2 mmol,
0.06 mmol of dihydridotetrakis(triphenylphosphine)ruthenium and 5 mmol of phosphorus compounds Q and Q shown in Table 2 below were added, and the mixture was heated at 60° C. for 6 hours in a sealed tube under an argon atmosphere. (Z)-2
The conversion rate to -phenyl-2-hexenenitrile and its yield were determined by gas chromatography. The results are shown in Table 2 7'/'7-'/' Table 2 o-CH2CN +n-03EI7CHOOne of the characteristics of the method of the present invention is that the aldol-type condensation reaction is selectively carried out only at the α-position of the cyano group. That is, the -
As an example, reference example 1 is a reaction example in the coexistence of acetylacetone, which is generally considered to easily cause an aldol-type condensation reaction.
Shown below.
参考例Ｉ
ｉ燥テトラヒドロフラン０．５１！Ｌｔにシアノ酢酸エ
チル２．１ ｍｍｏｌ 、アセチルアセトン２．Ｏｍｍ
ｏｌ 、’ ブタナーＪＬ／ ２．２ ’ｍｍｏｌ １
）リブチルホスフィンＱ、 Ｑ ５ ｍｍｏｌ および
ジヒドリドテトラキス（トリフェニルホスフィン）ルテ
ニウムＱ、９５ ｍｍｏｌを加え、アルゴン雰囲気下、
室温にて２４時間攪拌した。反応液をガスクロマトグラ
フィにてチェックしたところ（ト）−２−シアノ−２−
ヘキセン酸エチルが生成しており、アセチルアセトンは
全く反応していないことが判明した。溶媒を留去した後
、残渣をカラムクロマトグラフィに処し、（Ｅ）−２−
シアノ−２−ヘキセン酸エチルを収率８３％で得た。Reference Example I i Dry tetrahydrofuran 0.51! To Lt, 2.1 mmol of ethyl cyanoacetate and 2.1 mmol of acetylacetone were added. Omm
ol,'Butaner JL/2.2'mmol 1
) Add 5 mmol of butylphosphine Q and 95 mmol of dihydridotetrakis(triphenylphosphine)ruthenium Q, and under an argon atmosphere,
The mixture was stirred at room temperature for 24 hours. When the reaction solution was checked by gas chromatography, (t)-2-cyano-2-
It was found that ethyl hexenoate was produced and acetylacetone did not react at all. After distilling off the solvent, the residue was subjected to column chromatography to obtain (E)-2-
Ethyl cyano-2-hexenoate was obtained in a yield of 83%.
尚、本発明方法において原料化合物として用いられるカ
ルボニル化合物のがゎりに該力Ｊ’ ホ：−ル化合物の
誘導体、例えばイミン化合物を用いることも可能である
。以下にイミン化合物を用いた例を示す。Incidentally, in place of the carbonyl compound used as a raw material compound in the method of the present invention, it is also possible to use a derivative of the hole compound, such as an imine compound. An example using an imine compound is shown below.
参考例２
乾燥テトラヒドロフラン０．５ｄｌこシアノ酢酸エチル
２． Ｏｍｍｏｌ 、 Ｎ−ベンジリデンアニリン２
．２ ｍｍｏｌ およびジヒドリドテトラキス（トリ
フェニルホスフィン）ルテニウム０．０６ｍｍｏｌ
を加え、アルゴン雰囲気下、室温にて２４時間攪拌した
。次いで溶媒を留去し、残渣をカラムクロマトグラフィ
にて処理し、（Ｅ）−２−シアノ−桂皮酸エチルを収率
６８％で得た。Reference Example 2 0.5 dl of dry tetrahydrofuran and ethyl cyanoacetate2. Ommol, N-benzylideneaniline 2
．． 2 mmol and dihydridotetrakis(triphenylphosphine)ruthenium 0.06 mmol
was added and stirred at room temperature for 24 hours under an argon atmosphere. Then, the solvent was distilled off, and the residue was treated with column chromatography to obtain ethyl (E)-2-cyano-cinnamate in a yield of 68%.
〈発明の効果〉
本発明方法によれば中性条件下で、ニトリル化合物のα
−位に選択的に、カルボニル化合物を縮合させてα、β
−不飽和不飽和用トリルすることができる。<Effects of the Invention> According to the method of the present invention, α of a nitrile compound can be reduced under neutral conditions.
By selectively condensing a carbonyl compound at the − position, α, β
- Can be trilled for unsaturation.
Claims (1)
トリル化合物とを、ジヒドリドテトラキス（トリフェニ
ルホスフィン）ルテニウムの存在下で、ホスフィン化合
物の存在下または非存在下に反応させることを特徴とす
るα，β−不飽和ニトリルの製造法It is characterized by reacting a carbonyl compound and a nitrile compound having two hydrogen atoms at the α-position in the presence of dihydridotetrakis(triphenylphosphine)ruthenium in the presence or absence of a phosphine compound. Production method of α,β-unsaturated nitrile
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62051766A JPH0830052B2 (en) | 1987-03-05 | 1987-03-05 | Method for producing α, β-unsaturated nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62051766A JPH0830052B2 (en) | 1987-03-05 | 1987-03-05 | Method for producing α, β-unsaturated nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63216857A true JPS63216857A (en) | 1988-09-09 |
| JPH0830052B2 JPH0830052B2 (en) | 1996-03-27 |
Family
ID=12896070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62051766A Expired - Fee Related JPH0830052B2 (en) | 1987-03-05 | 1987-03-05 | Method for producing α, β-unsaturated nitrile |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0830052B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1637581A1 (en) * | 2004-09-16 | 2006-03-22 | Firmenich S.A. | Nitrile derivatives as perfuming ingredients |
-
1987
- 1987-03-05 JP JP62051766A patent/JPH0830052B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1637581A1 (en) * | 2004-09-16 | 2006-03-22 | Firmenich S.A. | Nitrile derivatives as perfuming ingredients |
| US7528103B2 (en) | 2004-09-16 | 2009-05-05 | Firmenich Sa | Nitrile derivatives as perfuming ingredients |
| US7648954B2 (en) | 2004-09-16 | 2010-01-19 | Firmenich Sa | Nitrile derivatives as perfuming ingredients |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0830052B2 (en) | 1996-03-27 |
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