WO2004089879A1 - Process for production of nitrile compounds - Google Patents
Process for production of nitrile compounds Download PDFInfo
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- WO2004089879A1 WO2004089879A1 PCT/JP2004/003659 JP2004003659W WO2004089879A1 WO 2004089879 A1 WO2004089879 A1 WO 2004089879A1 JP 2004003659 W JP2004003659 W JP 2004003659W WO 2004089879 A1 WO2004089879 A1 WO 2004089879A1
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- nitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Definitions
- the present invention provides a compound represented by the general formula (II):
- n represents an integer of 1 to 3, and a double line represented by a broken line and a solid line represents a single bond or a double bond.
- the nitrile compound (II) can be produced by the method described in [1] Hydrogenation of geranylnitrile in the presence of cobalt-modified Raney nickel (Maslozy, Promast). r. Prom—st.), p. 26 (1983)), [2] A method of reacting geranyl nitrile in the presence of methanol, magnesium, and hydrochloric acid (Journal of Organics, Inc.) Chemistry (cf. J. Or. Chem.), Vol. 40, p. 127 (1975)).
- an object of the present invention is to provide a method for producing nitrile compound (II) with good yield, economically and safely, and industrially advantageously. Disclosure of the invention
- n represents an integer of 1 to 3, and a double line represented by a broken line and a solid line represents a single bond or a double bond.
- nitrile compound (I) A nitrile compound having an unsaturated bond at the a, i3 position [hereinafter abbreviated as nitrile compound (I)] is represented by an amin compound and a palladium catalyst. This is achieved by providing a method for producing nitrile compound (II), characterized by selectively hydrogenating unsaturated bonds.
- Examples of the amine compound used in the present invention include trimethylamine, triethylamine, tri-n-butylamine, tri-n-octylamine, getylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, n-butylamine, sec —Ptylamine, tert-butylamine, n-octylamine, triethanolamine, diethanolamine, ethanolamine, N, N, N ′, N ′ —tetramethylethylenediamine, 3-methoxypropylamine, 3 —Ethoxypropylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3- (dibutylamino) propylamine, morpholine, 1,4-diazapicyclo [2.2.2] octane, 1,5-diazapicilo [ 4.
- Nonen 5, 5, 8 [5. 4. 0] aliphatic amines such as ndene-7 (hereinafter abbreviated as DBU); aromatic amines such as pyridine, N, N-dimethylaminopyridine and quinoline; You. These amine compounds can be used alone or in combination of two or more. They may be used in combination.
- the amount of the amine compound used varies depending on the type of the amine compound used, but is preferably in the range of 0.01 to 100% by mass based on the nitrile compound (I) to be used. From the viewpoint of economy, the content is more preferably in the range of 0.05 to 30% by mass.
- the palladium catalyst used in the present invention is preferably one in which palladium is supported on a carrier such as activated carbon, silica, alumina, or diatomaceous earth, and a commercially available palladium catalyst can be used as it is.
- the amount of the palladium catalyst used depends on the type and amount of the amine compound used, but is usually preferably in the range of 0.01 to 5% by mass based on the nitrile compound (I) used.
- the hydrogen pressure in the reaction of the present invention is more preferably in the range of 0.05 to 0.5% by mass from the viewpoint of efficiency and economy, although it varies depending on the type and amount of the amine compound used. Usually, it is preferably in the range of 101 kPa (normal pressure) to 9 MPa, and more preferably in the range of 0.5 to 2 MPa.
- the reaction temperature varies depending on the type and amount of the amine compound used, but is usually preferably in the range of 20 to 200 ° C, more preferably in the range of 70 to 150 ° C. preferable.
- the reaction can be performed in the presence or absence of a solvent.
- a solvent include, for example, alcohols such as methanol and ethanol.
- the amount used depends on the type and amount of the amine compound used, but is usually in the range of 1 to 200% by mass based on the nitrile compound (I) used. It is more preferably in the range of 1 to 10% by mass from the viewpoint of production efficiency and economy.
- the reaction method of the present invention is not particularly limited. For example, a method in which a nitrile compound (I), an amine compound, a palladium catalyst and, if necessary, a solvent are charged and the reaction is performed at a predetermined pressure and a predetermined temperature while supplying hydrogen. Etc. are applicable.
- the nitrile compound (II) thus obtained can be isolated and purified from the reaction mixture by a method generally used in the isolation and purification of organic compounds. For example, after cooling the reaction mixture to room temperature, the palladium catalyst is filtered off to obtain The filtrate can be isolated by distillation under reduced pressure or the like. The purity of the obtained nitrile compound (II) can be further increased by distillation, column chromatography, etc., if necessary.
- nitrile compound (I) used as a raw material in the reaction of the present invention for example, geranyl nitrile (in the general formula (I), n is 1 and a double line represented by a broken line and a solid line is a double bond. Some compounds) are manufactured industrially and commercially available products can be easily obtained.
- the nitrile compound (II) can be produced economically, safely, and industrially advantageously in a high yield.
- the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
- a nitrile compound obtained by the present invention for example, a compound in which, in the general formula (II), ⁇ is 1 and a double line represented by a broken line and a solid line is a double bond (ie, citronellyl nitrile) is (Fragrance Chemistry III, p. 188, by Osamu Okuda, published by Hirokawa Shoten, and US Pat. No. 5,965,518).
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Abstract
A process for the production of nitrile compounds represented by the general formula (I): (I) [wherein n is an integer of 1 to 3; and the double line constituted of a broken line and a solid line represents a single bond or a double bond], characterized by subjecting a nitrile compound represented by the general formula (I) which has an unsaturated bond between the α- and β-positions to selective hydrogenation of the unsaturated bond between the α- and β-positions in the presence of an amine and a palladium catalyst: (II) [wherein each symbol is as defined above]. According to the invention, nitrile compounds (II) can be industrially advantageously produced economically and safely in high yield.
Description
明 二トリル化合物の製造方法 技術分野 Akira Nitrile compound production method
本発明は、 一般式 （ I I)
The present invention provides a compound represented by the general formula (II):
(式中、 nは 1〜3の整数を表し、 破線と実線とで表される二重線は単結合また は二重結合を表す。 ） (In the formula, n represents an integer of 1 to 3, and a double line represented by a broken line and a solid line represents a single bond or a double bond.)
で示される二トリル化合物 [以下、 これを二卜リル化合物 （I I ) と略記する] の製造方法に関する。 背景技術 And a method for producing a nitrile compound [hereinafter abbreviated as nitrile compound (II)]. Background art
二トリル化合物 （I I) の製造方法としては、 [1] ゲラニルニトリルを、 コ バルトで変性されたラネ一ニッケルの存在下に水素添加する方法 （マスロージー ァ、 プロム—スト （Ma s l o— Z h i r. P r om— s t . ) , p. 26 (1 983年） 参照） 、 [2] ゲラニルニトリルを、 メタノール、 マグネシウムおよ び塩酸の存在下に反応させる方法 （ジャーナル · ォブ ·オーガニック ' ケミスト リ一 （J . O r . C h em. ) , 40巻、 p. 1 27 (1 97 5年） 参照） な どが知られている。 The nitrile compound (II) can be produced by the method described in [1] Hydrogenation of geranylnitrile in the presence of cobalt-modified Raney nickel (Maslozy, Promast). r. Prom—st.), p. 26 (1983)), [2] A method of reacting geranyl nitrile in the presence of methanol, magnesium, and hydrochloric acid (Journal of Organics, Inc.) Chemistry (cf. J. Or. Chem.), Vol. 40, p. 127 (1975)).
上記の方法 [1] は、 ゲラニルニトリルを原料とした反応において、 α, β位 の不飽和結合の水素添加と同時に、 ε， ζ位の不飽和結合や二トリル基への水素 添加も生じるため、 得られるシトロネリルニトリルの収率は 5 1 %と低いという 問題点を有している。 また、 上記の方法 [2] は、 α， /3位の不飽和結合の選択 的な水素添加が可能であるが、 高価な金属マグネシウムを大量に用いる必要があ るなどの問題点を有する。 したがって、 これらの方法はいずれも二トリル化合物 ( I I ) の工業的に有利な製造方法とは言い難い。
しかして、 本発明の目的は、 二トリル化合物 （ I I ) を収率よく、 経済的かつ 安全に、 工業的に有利に製造し得る方法を提供することにある。 発明の開示 In the above method [1], in the reaction using geranyl nitrile as a raw material, hydrogenation of the unsaturated bonds at the α and β positions and hydrogenation of the unsaturated bonds at the ε and ζ positions and the nitrile group occur simultaneously. However, there is a problem that the yield of citronellyl nitrile obtained is as low as 51%. In addition, the above method [2] enables selective hydrogenation of the unsaturated bond at the α, / 3 position, but has a problem in that a large amount of expensive metallic magnesium must be used. Therefore, none of these methods is an industrially advantageous method for producing nitrile compound (II). Accordingly, an object of the present invention is to provide a method for producing nitrile compound (II) with good yield, economically and safely, and industrially advantageously. Disclosure of the invention
本発明によれば、 上記の目的は、 一般式 （ I )
According to the present invention, the above object has the following general formula (I)
(式中、 nは 1〜3の整数を表し、 破線と実線とで表される二重線は単結合また は二重結合を表す。 ） (In the formula, n represents an integer of 1 to 3, and a double line represented by a broken line and a solid line represents a single bond or a double bond.)
で示される a， i3位に不飽和結合を有する二トリル化合物 [以下、 これを二トリ ル化合物 （ I ) と略記する] を、 ァミン化合物およびパラジウム触媒の存在下に， その a， i3位の不飽和結合を選択的に水素添加することを特徴とする二トリル化 合物 （ I I ) の製造方法を提供することにより達成される。 発明を実施するための最良の形態 A nitrile compound having an unsaturated bond at the a, i3 position [hereinafter abbreviated as nitrile compound (I)] is represented by an amin compound and a palladium catalyst. This is achieved by providing a method for producing nitrile compound (II), characterized by selectively hydrogenating unsaturated bonds. BEST MODE FOR CARRYING OUT THE INVENTION
本発明において使用するァミン化合物としては、 例えばトリメチルァミン、 ト リエチルァミン、 トリ n—プチルァミン、 トリ n—ォクチルァミン、 ジェチルァ ミン、 ジイソプロピルァミン、 ジ n—プチルァミン、 ジ s e c—ブチルァミン、 n—プチルァミン、 s e c—プチルァミン、 t e r t—プチルァミン、 n—ォク チルァミン、 トリエ夕ノールァミン、 ジエタノールァミン、 エタノールァミン、 N， N, N' , N' —テトラメチルエチレンジァミン、 3—メトキシプロピルァ ミン、 3—エトキシプロピルァミン、 3 - (メチルァミノ） プロピルァミン、 3 - (ジメチルァミノ） プロピルァミン、 3一 (ジブチルァミノ） プロピルァミン、 モルホリン、 1， 4 -ジァザピシクロ [2. 2. 2] オクタン、 1 , 5—ジァザ ピシクロ [4. 3. 0 ] ノネンー 5、 1， 8一ジァザビシク口 [5. 4. 0 ] ゥ ンデセン— 7 (以下、 これを DBUと略記する） などの脂肪族ァミン； ピリジン、 N, N—ジメチルァミノピリジン、 キノリンなどの芳香族ァミンなどが挙げられ る。 これらのァミン化合物は、 1種類のみを単独で使用しても、 2種類以上を混
合して使用してもよい。 Examples of the amine compound used in the present invention include trimethylamine, triethylamine, tri-n-butylamine, tri-n-octylamine, getylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine, n-butylamine, sec —Ptylamine, tert-butylamine, n-octylamine, triethanolamine, diethanolamine, ethanolamine, N, N, N ′, N ′ —tetramethylethylenediamine, 3-methoxypropylamine, 3 —Ethoxypropylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, 3- (dibutylamino) propylamine, morpholine, 1,4-diazapicyclo [2.2.2] octane, 1,5-diazapicilo [ 4. 3. 0] Nonen 5, 5, 8 [5. 4. 0] aliphatic amines such as ndene-7 (hereinafter abbreviated as DBU); aromatic amines such as pyridine, N, N-dimethylaminopyridine and quinoline; You. These amine compounds can be used alone or in combination of two or more. They may be used in combination.
ァミン化合物の使用量は、 使用するァミン化合物の種類によっても異なるが、 使用する二トリル化合物 （ I ) に対して 0 . 0 1 ~ 1 0 0質量％の範囲であるの が好ましく、 生産効率や経済性の観点から 0 . 0 5〜 3 0質量％の範囲であるの がより好ましい。 The amount of the amine compound used varies depending on the type of the amine compound used, but is preferably in the range of 0.01 to 100% by mass based on the nitrile compound (I) to be used. From the viewpoint of economy, the content is more preferably in the range of 0.05 to 30% by mass.
本発明において使用するパラジウム触媒は、 活性炭、 シリカ、 アルミナ、 ケィ ソゥ土などの担体にパラジウムが担持されたものが好ましく、 このようなパラジ ゥム触媒は市販品をそのまま使用することができる。 パラジウム触媒の使用量は、 使用するァミン化合物の種類や量によっても異なるが、 通常、 使用する二トリル 化合物 （ I ) に対して 0 . 0 1〜 5質量％の範囲であるのが好ましく、 生産効率 や経済的性の観点から 0 . 0 5〜 0 . 5 0質量％の範囲であるのがより好ましい 本発明の反応の水素圧力は、 使用するァミン化合物の種類や量によっても異な るが、 通常、 1 0 1 k P a (常圧） 〜 9 M P aの範囲であるのが好ましく、 0 . 5〜 2 M P aの範囲であるのがより好ましい。 The palladium catalyst used in the present invention is preferably one in which palladium is supported on a carrier such as activated carbon, silica, alumina, or diatomaceous earth, and a commercially available palladium catalyst can be used as it is. The amount of the palladium catalyst used depends on the type and amount of the amine compound used, but is usually preferably in the range of 0.01 to 5% by mass based on the nitrile compound (I) used. The hydrogen pressure in the reaction of the present invention is more preferably in the range of 0.05 to 0.5% by mass from the viewpoint of efficiency and economy, although it varies depending on the type and amount of the amine compound used. Usually, it is preferably in the range of 101 kPa (normal pressure) to 9 MPa, and more preferably in the range of 0.5 to 2 MPa.
反応温度は、 使用するァミン化合物の種類や量によっても異なるが、 通常、 2 0〜 2 0 0 °Cの範囲であるのが好ましく、 7 0〜 1 5 0 °Cの範囲であるのがより 好ましい。 The reaction temperature varies depending on the type and amount of the amine compound used, but is usually preferably in the range of 20 to 200 ° C, more preferably in the range of 70 to 150 ° C. preferable.
反応は、 溶媒の存在下または不存在下に行うことができる。 溶媒を使用する場 合の具体例としては、 例えばメタノール、 エタノールなどのアルコールなどが挙 げられる。 溶媒を存在させる場合、 その使用量は、 使用するァミン化合物の種類 や量によっても異なるが、 通常、 使用する二トリル化合物 （ I ) に対して 1〜 2 0 0質量％の範囲であるのが好ましく、 生産効率や経済性の観点から 1〜 1 0質 量％の範囲であるのがより好ましい。 The reaction can be performed in the presence or absence of a solvent. Specific examples of the case where a solvent is used include, for example, alcohols such as methanol and ethanol. When a solvent is used, the amount used depends on the type and amount of the amine compound used, but is usually in the range of 1 to 200% by mass based on the nitrile compound (I) used. It is more preferably in the range of 1 to 10% by mass from the viewpoint of production efficiency and economy.
本発明の反応方法に特に制限はなく、 例えば、 二トリル化合物 （ I ) 、 ァミン 化合物、 パラジウム触媒および必要に応じて溶媒を仕込み、 水素を供給しながら、 所定圧力および所定温度にて反応させる方法などが適用可能である。 The reaction method of the present invention is not particularly limited. For example, a method in which a nitrile compound (I), an amine compound, a palladium catalyst and, if necessary, a solvent are charged and the reaction is performed at a predetermined pressure and a predetermined temperature while supplying hydrogen. Etc. are applicable.
こうして得られた二トリル化合物 ( I I ) の反応混合物からの単離 ·精製は、 有機化合物の単離 ·精製において一般的に用いられる方法により行うことができ る。 例えば、 反応混合物を室温に冷却した後、 パラジウム触媒をろ別し、 得られ
たろ液を減圧蒸留する方法などによって単離することができる。 また、 得られた 二トリル化合物 （ I I ) は、 必要に応じて、 蒸留、 カラムクロマトグラフィーな どにより、 さらにその純度を高めることができる。 The nitrile compound (II) thus obtained can be isolated and purified from the reaction mixture by a method generally used in the isolation and purification of organic compounds. For example, after cooling the reaction mixture to room temperature, the palladium catalyst is filtered off to obtain The filtrate can be isolated by distillation under reduced pressure or the like. The purity of the obtained nitrile compound (II) can be further increased by distillation, column chromatography, etc., if necessary.
なお 本発明の反応で原料として使用する二トリル化合物 （ I ) 、 例えばゲラ ニルニトリル （一般式 （ I ) において、 nが 1であり、 破線と実線とで表される 二重線が二重結合である化合物） は工業的に製造されており市販品を容易に入手 することができる。 The nitrile compound (I) used as a raw material in the reaction of the present invention, for example, geranyl nitrile (in the general formula (I), n is 1 and a double line represented by a broken line and a solid line is a double bond. Some compounds) are manufactured industrially and commercially available products can be easily obtained.
本発明によれば、 二トリル化合物 （I I ) を収率よく、 経済的かつ安全に、 ェ 業的に有利に製造することができる。 以下、 実施例により本発明を具体的に説明するが、 本発明はこれら実施例によ り何ら制限されるものではない。 According to the present invention, the nitrile compound (II) can be produced economically, safely, and industrially advantageously in a high yield. Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples.
実施例 1 Example 1
内容積 500 m lのオートクレープに、 ゲラニルニトリル 27 5 g、 トリエチ ルァミン 68. 8 gおよびパラジウム—活性炭 （商品名 「E 1 0 1 OZW」 、 デグッサ社製、 パラジウム担持量： 5質量％、 含水率： 5 5質量％) 0. 77 g を仕込み、 次いで、 オートクレープ内を水素で置換し、 内圧を 0. 6MP aとし た後、 50でに加熱した。 オートクレープ内に適宜水素を供給して内圧 0. 6M P aを保持したまま 1 8時間反応させた。 反応終了後、 室温まで冷却してパラジ ゥム一活性炭をろ別し、 得られたろ液をガスクロマトグラフィーを用いて分析し た。 その結果、 ゲラニルニトリルの転化率は 99 %であり、 シトロネリル二トリ ルの選択率は 85. 0 %であった。 In a 500 ml autoclave, 275 g of geranyl nitrile, 68.8 g of triethylamine and palladium-activated carbon (trade name “E101 OZW”, manufactured by Degussa, palladium loading: 5% by mass, water content 0.75 g) was charged, then the inside of the autoclave was replaced with hydrogen, the internal pressure was adjusted to 0.6 MPa, and the mixture was heated to 50. Hydrogen was appropriately supplied into the autoclave, and the reaction was carried out for 18 hours while maintaining the internal pressure at 0.6 MPa. After the completion of the reaction, the reaction mixture was cooled to room temperature, palladium-activated carbon was filtered off, and the obtained filtrate was analyzed by gas chromatography. As a result, the conversion of geranyl nitrile was 99%, and the selectivity of citronellyl nitrile was 85.0%.
得られたろ液を減圧蒸留することにより、 シトロネリル二トリル 124. 6 g を得た （純度 97 %、 収率： 45 %、 沸点： 84°C/400 P a) 。 実施例 2 The obtained filtrate was distilled under reduced pressure to obtain 124.6 g of citronellyl nitrile (purity: 97%, yield: 45%, boiling point: 84 ° C / 400 Pa). Example 2
内容積 300 m lのオートクレーブに、 ゲラニルニトリル 1 80 g、 DBU 0. 9 gおよびパラジウム—活性炭 (商品名 ΓΕ 1 0 1 O/WJ 、 デグッサ社製） 0. 48 gを仕込み、 次いで、 オートクレーブ内を水素で置換し、 内圧を 1. 4
MP aとした後、 80°Cに加熱した。 ォ一トクレーブ内に適宜水素を供給して内 圧 1. 4 MP aを保持したまま 38時間反応させた。 反応終了後、 室温まで冷却 してパラジウム一活性炭をろ別し、 得られたろ液をガスクロマトグラフィーを用 いて分析した。 その結果 ゲラニルニトリルの転化率は 9 9 %であり、 シトロネ リル二トリルの選択率は 95. 0%であった。 In a 300 ml internal volume autoclave, 180 g of geranylnitrile, 0.9 g of DBU and 0.48 g of palladium-activated carbon (trade name ΓΕ101 O / WJ, manufactured by Degussa) were charged, and then the autoclave was filled. Replace with hydrogen and increase internal pressure to 1.4 After setting to MPa, the mixture was heated to 80 ° C. Hydrogen was appropriately supplied into the autoclave, and the reaction was carried out for 38 hours while maintaining the internal pressure at 1.4 MPa. After the completion of the reaction, the reaction mixture was cooled to room temperature, palladium-activated carbon was filtered off, and the obtained filtrate was analyzed by gas chromatography. As a result, the conversion of geranyl nitrile was 99%, and the selectivity of citronellyl nitrile was 95.0%.
得られたろ液を減圧蒸留することにより、 シトロネリル二トリル 148. 8 g を得た （純度 99 %、 収率： 82 %、 沸点： 84°C/400 P a) 比較例 1 The obtained filtrate was distilled under reduced pressure to obtain 148.8 g of citronellyl nitrile (purity: 99%, yield: 82%, boiling point: 84 ° C / 400 Pa). Comparative Example 1
内容積 300 m lのオートクレープに、 ゲラニルニトリル 90 gおよびパラジ ゥム /活性炭 （商品名 「E 1 0 1 0/W」 、 デグッサ社製） 0. 24 gを仕込 み、 次いで、 ォ一トクレーブ内を水素で置換し、 内圧を 0. 6MP aとした後、 50°Cに加熱した。 ォ一トクレーブ内に適宜水素を供給して内圧 0. 6MP aを 保持したまま 4. 5時間反応させた。 反応終了後、 室温まで冷却してパラジウム 一活性炭をろ別し、 得られたろ液をガスクロマトグラフィーを用いて分析した。 その結果、 ゲラニルニトリルの転化率は 99 %であり、 シトロネリル二トリルの 選択率は 55. 7 %であった。 なお、 α, /3位の不飽和結合と共に ε， ζ位の不 飽和結合も水素添加された化合物 （3， 7—ジメチルオクタン二トリル） が選択 率 39. 9 %で生成していた。 産業上の利用可能性 In a 300 ml autoclave, 90 g of geranyl nitrile and 0.24 g of palladium / activated carbon (trade name "E11010 / W", manufactured by Degussa) are charged, and then in an autoclave. Was replaced with hydrogen, the internal pressure was adjusted to 0.6 MPa, and the mixture was heated to 50 ° C. Hydrogen was appropriately supplied into the autoclave, and the reaction was carried out for 4.5 hours while maintaining the internal pressure at 0.6 MPa. After the completion of the reaction, the mixture was cooled to room temperature, palladium-activated carbon was filtered off, and the obtained filtrate was analyzed by gas chromatography. As a result, the conversion of geranyl nitrile was 99%, and the selectivity of citronellyl nitrile was 55.7%. The hydrogenated compound (3,7-dimethyloctane nitrile) was formed at the selectivity of 39.9%, as was the unsaturated bond at the ε and ζ positions along with the unsaturated bond at the α and / 3 positions. Industrial applicability
本発明により得られる二トリル化合物、 例えば、 一般式 （ I I ) において、 η が 1であり、 破線と実線とで表される二重線が二重結合である化合物 （すなわち、 シトロネリル二トリル） は、 香料として有用であり （香料化学総覧 I I I、 18 8頁、 奥田 治著、 廣川書店発行、 および米国特許明細書 5, 96 5, 5 18号 参照） 、 一般式 （I I ) において、 ηが 3であり、 破線と実線とで表される二重 線が二重結合である化合物 （すなわち、 3, 7, 1 1， 1 5—テトラメチルー 6, 1 0, 14—へキサデカトリエノ二トリル） は、 肝障害治療剤の合成中間体とし て有用である （特開昭 56— 1 67635号公報参照） 。
A nitrile compound obtained by the present invention, for example, a compound in which, in the general formula (II), η is 1 and a double line represented by a broken line and a solid line is a double bond (ie, citronellyl nitrile) is (Fragrance Chemistry III, p. 188, by Osamu Okuda, published by Hirokawa Shoten, and US Pat. No. 5,965,518). In the general formula (II), η is 3 And the compound in which the double line represented by the dashed and solid lines is a double bond (ie, 3,7,11,15-tetramethyl-6,10,14-hexadecatrienonitrile), It is useful as a synthetic intermediate for a therapeutic agent for disorders (see JP-A-56-167635).
Claims
1 . 一般式 （ I ) 1. General formula (I)
(式中、 nは 1〜3の整数を表し、 破線と実線とで表される二重線は単結合また は二重結合を表す。 ） (In the formula, n represents an integer of 1 to 3, and a double line represented by a broken line and a solid line represents a single bond or a double bond.)
で示される α， /3位に不飽和結合を有する二トリル化合物を、 ァミン化合物およ びパラジウム触媒の存在下に、 その α， |3位の不飽和結合を選択的に水素添加す ることを特徴とする一般式 （ I I ) Selectively hydrogenating a nitrile compound having an unsaturated bond at the α, / 3 position shown in the above in the presence of an amine compound and a palladium catalyst. General formula (II) characterized by
(式中、 ηおよび破線と実線とで表される二重線は上記定義のとおりである。 ） で示される二卜リル化合物の製造方法。
(Wherein, η and the double line represented by the dashed line and the solid line are as defined above).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006106141A1 (en) * | 2005-04-08 | 2006-10-12 | Basf Aktiengesellschaft | Method for producing saturated nitriles |
| CN105473549A (en) * | 2013-08-20 | 2016-04-06 | 帝斯曼知识产权资产管理有限公司 | Process for the manufacture of hydrogenated nitriles |
| CN113683532A (en) * | 2021-10-27 | 2021-11-23 | 山东新和成药业有限公司 | Preparation method of citronellonitrile and catalyst adopted by same |
Citations (1)
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| JPS6097054A (en) * | 1983-10-13 | 1985-05-30 | バイエル・アクチエンゲゼルシヤフト | Selective catalytic hydrogenation |
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2004
- 2004-03-18 WO PCT/JP2004/003659 patent/WO2004089879A1/en not_active Application Discontinuation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6097054A (en) * | 1983-10-13 | 1985-05-30 | バイエル・アクチエンゲゼルシヤフト | Selective catalytic hydrogenation |
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| ALI H.M. ET AL: "Selective reduction of conjugated double bonds with molecular hydrogen and palladium(II) complexed to ferrocenylamine sulfide catalysts.", TETRAHEDRON LETTERS, vol. 32, no. 40, 1991, pages 5489 - 5492, XP000226490 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006106141A1 (en) * | 2005-04-08 | 2006-10-12 | Basf Aktiengesellschaft | Method for producing saturated nitriles |
| JP2008540330A (en) * | 2005-04-08 | 2008-11-20 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing saturated nitrile |
| US7795466B2 (en) | 2005-04-08 | 2010-09-14 | Basf Aktiengesellschaft | Method for producing saturated nitriles |
| CN101151240B (en) * | 2005-04-08 | 2011-05-11 | 巴斯福股份公司 | Method for producing saturated nitriles |
| CN105473549A (en) * | 2013-08-20 | 2016-04-06 | 帝斯曼知识产权资产管理有限公司 | Process for the manufacture of hydrogenated nitriles |
| CN105473549B (en) * | 2013-08-20 | 2018-09-18 | 帝斯曼知识产权资产管理有限公司 | The method for manufacturing hydrogenated nitrile |
| CN113683532A (en) * | 2021-10-27 | 2021-11-23 | 山东新和成药业有限公司 | Preparation method of citronellonitrile and catalyst adopted by same |
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