JPS6319488B2 - - Google Patents
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- Publication number
- JPS6319488B2 JPS6319488B2 JP59139412A JP13941284A JPS6319488B2 JP S6319488 B2 JPS6319488 B2 JP S6319488B2 JP 59139412 A JP59139412 A JP 59139412A JP 13941284 A JP13941284 A JP 13941284A JP S6319488 B2 JPS6319488 B2 JP S6319488B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- highly reactive
- zinc powder
- reaction
- yield
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はハロゲン含有不飽和側鎖を有する芳香
族化合物を、高反応性金属粉で還元脱ハロゲン化
することによつて、相当する二重結合または三重
結合の不飽和側鎖を有する芳香族化合物の製法に
関するものである。
ハロゲンを含む不飽和側鎖を有する芳香族化合
物の脱ハロゲン化による二重または三重結合の不
飽和側鎖を有する芳香族化合物の合成において、
ハロゲン原子が側鎖に多数入つた場合に、全てを
脱ハロゲン化することは特に難かしい。
本発明者はこの点について鋭意研究した結果、
本発明をなすに至つた。
本発明の方法に従うと、
一般式
The present invention produces an aromatic compound having a corresponding double bond or triple bond unsaturated side chain by reductively dehalogenating an aromatic compound having a halogen-containing unsaturated side chain with a highly reactive metal powder. It is related to the manufacturing method. In the synthesis of aromatic compounds with double or triple bond unsaturated side chains by dehalogenation of aromatic compounds with unsaturated side chains containing halogens,
When a large number of halogen atoms are present in the side chain, it is particularly difficult to dehalogenate all of them. As a result of intensive research on this point, the inventor found that
The present invention has been accomplished. According to the method of the invention, the general formula
【式】（式中のR1はフエニル
基またはベンジル基を、R2およびR3は水素原子
またはアルキル基を、X1，X2およびX3はハロゲ
ン原子である）で示される、ハロゲン化ビニル基
を有する芳香族アリール化合物をアルコール中で
高反応性亜鉛末を用いて脱ハロゲン化を行ない、
一般式[Formula] (in the formula, R 1 is a phenyl group or benzyl group, R 2 and R 3 are hydrogen atoms or alkyl groups, and X 1 , X 2 and X 3 are halogen atoms), halogenated An aromatic aryl compound having a vinyl group is dehalogenated using highly reactive zinc powder in alcohol, and the general formula
【式】および[expression] and
【式】
（式中のR1，R2およびR3は前記と同じ意味を
持つ）で示される不飽和側鎖を持つ芳香族化合物
の製法である。
本発明の方法によれば反応条件を選ぶことによ
つて二重または三重結合を有する化合物のいずれ
か、または両者の混合物を選択して製造すること
ができる極めて有用な方法である。
本発明の方法を詳細に説明すると、反応に用い
られるアルコール類は脂肪族の炭素数１〜５まで
の直鎖状または枝分れした構造のアルコールを用
いることができる。また使用するアルコール類に
よつて、得られるビニル化合物とアセチレン化合
物の割合が異なることから、目的にあわせて数種
のアルコールの混合物も用いることができる。ア
ルコール類の添加量は原料および高反応性亜鉛末
の量に左右されるが、通常反応液の撹拌を均一に
行なうことができる量以上が用いられる。たとえ
ば原料に対して10〜20倍容までが用いられる。し
かし溶媒の量を多くすると高反応性亜鉛末の触媒
活性が急速に低下するため、溶媒のアルコールの
使用量は極力少ないほうが望ましい。
高反応性亜鉛末の使用量は、３当量から30当量
まで用いることができる。しかし余り加えすぎる
と全体を均一に撹拌できずに収率が低下する。
高反応性亜鉛末は調製してすぐ用いるのが好ま
しく、長期間保存すると触媒活性が低下したり、
酸化されるため目的の収率が得られない。
反応温度は溶媒のアルコールの沸点に左右さ
れ、反応温度が高い場合は反応は短時間で完了す
る。通常溶媒の沸点で反応を行なう場合、反応時
間は１〜８時間が適当で、触媒活性の高い場合ほ
ど反応は短時間でよい。
本発明によつて合成される不飽和側鎖を持つ芳
香族化合物は、有機合成中間体、高分子原料、有
機半導体および有機光化学蓄熱剤などの原料に用
いられる有用な化合物である。
次に実施例によつて本発明をさらに詳細に説明
する。
実施例 １
１，１，２−トリクロロ−３−フエニル−１−
プロペン2.21ｇ（0.01モル）を25mlのエチルアル
コ−ルに溶解し、これに無水塩化亜鉛4.10ｇ
（0.03モル）より製した高反応性亜鉛末を添加し、
溶媒の沸点で撹拌しながら８時間反応させた。反
応液はSE−30を充填した１ｍのカラムを用いて
ガスクロマトグラフ法によつて分折し、油分中に
アリルベンゼン3.86％（収率7.2％）およびベン
ジルアセチレン21.20％（収率40.3％）を得た。
アリルベンゼンおよびベンジルアセチレンに相当
するピークは標品のピークの流出時間とよく一致
した。反応液よりアルコールを回収して得た残油
分を分留して沸点52.5℃／20mmHg（d20 40.8888、
n20 D1.5131）留分(1)0.09ｇと沸点61.5〜63.0℃／16
mmHg（d20 40.9148、n20 D1.5196）の留分(2)0.47ｇを得
た。留分(1)は赤外線吸収スペクトルに末端二重結
合の吸収を波数1643cm-1に示すとともに、NMR
スペクトルに4.99，5.02および5.85ppmに３個のプ
ロトンの吸収を示しアリルベンゼンと確認され
た。留分(2)はNMRスペクトルに三重結合の末端
プロトンの吸収を3.05ppmに示すことからベンジル
アセチレンと確認された。
実施例 ２
１，１，２−トリクロロ−３−フエニル−１−
プロペン2.21ｇ（0.01モル）を25mlのエチルアル
コ−ルに溶解し、これに無水塩化亜鉛4.10ｇ
（0.03モル）より製した高反応性亜鉛末を添加し、
溶媒の沸点で撹拌しながら８時間反応させた。反
応液は実施例１と同様にしてガスクロマトグラフ
法により分折し、油分中にアリルベンゼン3.79％
（収率7.1％）およびベンジルアセチレン15.08％
（収率28.7％）を得た。
実施例 ３
１，１，２−トリクロロ−３−フエニル−１−
プロペン2.21ｇ（0.01モル）を25mlのエチルアル
コ−ルに溶解し、これに無水塩化亜鉛4.10ｇ
（0.03モル）より製した高反応性亜鉛末を添加し、
溶媒の沸点で撹拌しながら４時間反応させた。反
応液は実施例１と同様にしてガスクロマトグラフ
法により分折し、油分中にアリルベンゼン2.75％
（収率5.1％）およびベンジルアセチレン15.22％
（収率28.9％）を得た。
実施例 ４
１，１，２−トリクロロ−３−フエニル−１−
プロペン2.21ｇ（0.01モル）を25mlのエチルアル
コ−ルに溶解し、これに無水塩化亜鉛4.10ｇ
（0.03モル）より製した高反応性亜鉛末を添加し、
溶媒の沸点で撹拌しながら24時間反応させた。反
応液は実施例１と同様にしてガスクロマトグラフ
法により分折し、油分中にアリルベンゼン4.23％
（収率7.9％）およびベンジルアセチレン13.79％
（収率26.2％）を得た。
実施例 ５
１，１，２−トリクロロ−３−フエニル−１−
プロペン2.21ｇ（0.01モル）を25mlのエチルアル
コ−ルに溶解し、これに無水塩化亜鉛4.10ｇ
（0.03モル）より製した高反応性亜鉛末を添加し、
加熱還流下に撹拌しながら８時間反応させた。反
応液は実施例１と同様にガスクロマトグラフ法に
より分折し、油分中にアリルベンゼン0.22％（収
率0.4％）およびベンジルアセチレン4.95％（収
率9.4％）を得た。This is a method for producing an aromatic compound having an unsaturated side chain represented by the formula: (R 1 , R 2 and R 3 have the same meanings as above). The method of the present invention is an extremely useful method in which it is possible to selectively produce either a compound having double or triple bonds, or a mixture of the two, by selecting reaction conditions. To explain the method of the present invention in detail, the alcohol used in the reaction may be an aliphatic alcohol having 1 to 5 carbon atoms and having a linear or branched structure. Furthermore, since the ratio of the obtained vinyl compound to acetylene compound differs depending on the alcohol used, a mixture of several types of alcohols can also be used depending on the purpose. The amount of alcohol added depends on the amount of raw materials and highly reactive zinc powder, but is usually used in an amount that is at least sufficient to uniformly stir the reaction solution. For example, 10 to 20 times the volume of the raw material is used. However, if the amount of solvent is increased, the catalytic activity of the highly reactive zinc dust will rapidly decrease, so it is desirable that the amount of alcohol used as a solvent be as small as possible. The amount of highly reactive zinc powder used can range from 3 equivalents to 30 equivalents. However, if too much is added, the entire mixture cannot be stirred uniformly, resulting in a decrease in yield. It is preferable to use highly reactive zinc powder immediately after preparation; storing it for a long period of time may reduce the catalytic activity.
Due to oxidation, the desired yield cannot be obtained. The reaction temperature depends on the boiling point of the solvent alcohol, and if the reaction temperature is high, the reaction will be completed in a short time. Usually, when the reaction is carried out at the boiling point of the solvent, the reaction time is suitably 1 to 8 hours, and the higher the catalyst activity, the shorter the reaction time. Aromatic compounds with unsaturated side chains synthesized according to the present invention are useful compounds used as raw materials for organic synthesis intermediates, polymer raw materials, organic semiconductors, organic photochemical heat storage agents, and the like. Next, the present invention will be explained in more detail with reference to Examples. Example 1 1,1,2-trichloro-3-phenyl-1-
Dissolve 2.21 g (0.01 mol) of propene in 25 ml of ethyl alcohol and add 4.10 g of anhydrous zinc chloride.
(0.03 mol) of highly reactive zinc powder made from
The reaction was allowed to proceed for 8 hours while stirring at the boiling point of the solvent. The reaction solution was separated by gas chromatography using a 1 m column packed with SE-30, and 3.86% allylbenzene (7.2% yield) and 21.20% benzyl acetylene (40.3% yield) were found in the oil. Obtained.
The peaks corresponding to allylbenzene and benzyl acetylene were in good agreement with the runoff times of the standard peaks. The residual oil obtained by recovering alcohol from the reaction solution was fractionated to obtain a boiling point of 52.5℃/20mmHg (d 20 4 0.8888,
n 20 D 1.5131) Fraction (1) 0.09g and boiling point 61.5-63.0℃/16
0.47 g of fraction (2) with mmHg (d 20 4 0.9148, n 20 D 1.5196) was obtained. Fraction (1) shows absorption of the terminal double bond at a wave number of 1643 cm -1 in the infrared absorption spectrum, and NMR
The spectrum showed absorption of three protons at 4.99, 5.02, and 5.85 ppm, and it was confirmed to be allylbenzene. Fraction (2) was confirmed to be benzyl acetylene because its NMR spectrum showed an absorption of the terminal proton of the triple bond at 3.05 ppm. Example 2 1,1,2-trichloro-3-phenyl-1-
Dissolve 2.21 g (0.01 mol) of propene in 25 ml of ethyl alcohol and add 4.10 g of anhydrous zinc chloride.
(0.03 mol) of highly reactive zinc powder made from
The reaction was allowed to proceed for 8 hours while stirring at the boiling point of the solvent. The reaction solution was separated by gas chromatography in the same manner as in Example 1, and 3.79% allylbenzene was found in the oil.
(yield 7.1%) and benzylacetylene 15.08%
(yield 28.7%). Example 3 1,1,2-trichloro-3-phenyl-1-
Dissolve 2.21 g (0.01 mol) of propene in 25 ml of ethyl alcohol and add 4.10 g of anhydrous zinc chloride.
(0.03 mol) of highly reactive zinc powder made from
The reaction was allowed to proceed for 4 hours while stirring at the boiling point of the solvent. The reaction solution was separated by gas chromatography in the same manner as in Example 1, and 2.75% allylbenzene was found in the oil.
(yield 5.1%) and benzyl acetylene 15.22%
(yield 28.9%). Example 4 1,1,2-trichloro-3-phenyl-1-
Dissolve 2.21 g (0.01 mol) of propene in 25 ml of ethyl alcohol and add 4.10 g of anhydrous zinc chloride.
(0.03 mol) of highly reactive zinc powder made from
The reaction was allowed to proceed for 24 hours while stirring at the boiling point of the solvent. The reaction solution was separated by gas chromatography in the same manner as in Example 1, and 4.23% allylbenzene was found in the oil.
(yield 7.9%) and benzylacetylene 13.79%
(yield 26.2%). Example 5 1,1,2-trichloro-3-phenyl-1-
Dissolve 2.21 g (0.01 mol) of propene in 25 ml of ethyl alcohol and add 4.10 g of anhydrous zinc chloride.
(0.03 mol) of highly reactive zinc powder made from
The reaction was allowed to proceed for 8 hours while stirring and heating under reflux. The reaction solution was analyzed by gas chromatography in the same manner as in Example 1 to obtain 0.22% allylbenzene (0.4% yield) and 4.95% benzyl acetylene (9.4% yield) in the oil.
Claims (1)
子またはアルキル基を、X1，X2およびX3はハロ
ゲン原子である）で示される、ハロゲン化ビニル
基を有する芳香族アリール化合物をアルコール中
で高反応性亜鉛末（ジオキサン中で塩化亜鉛と金
属ナトリウムの反応により得られた亜鉛微粉末、
以下高反応性亜鉛末という。）を用いて脱ハロゲ
ン化を行ない、 一般式【式】および 【式】 （式中のR1，R2およびR3は前記と同じ意味を
持つ）で示される不飽和側鎖を持つ芳香族化合物
の製法。[Claims] 1 General formula [Formula] (In the formula, R 1 is a phenyl group or a benzyl group, R 2 and R 3 are a hydrogen atom or an alkyl group, and X 1 , X 2 and X 3 are a halogen atom. Highly reactive zinc powder (fine zinc powder obtained by the reaction of zinc chloride and metallic sodium in dioxane)
Hereinafter referred to as highly reactive zinc powder. ) to dehalogenate aromatic compounds with unsaturated side chains represented by the general formulas [formula] and [formula] (in which R 1 , R 2 and R 3 have the same meanings as above). Method of manufacturing compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13941284A JPS6118736A (en) | 1984-07-05 | 1984-07-05 | Production of aromatic compound bearing unsaturated side chain |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13941284A JPS6118736A (en) | 1984-07-05 | 1984-07-05 | Production of aromatic compound bearing unsaturated side chain |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6118736A JPS6118736A (en) | 1986-01-27 |
| JPS6319488B2 true JPS6319488B2 (en) | 1988-04-22 |
Family
ID=15244632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13941284A Granted JPS6118736A (en) | 1984-07-05 | 1984-07-05 | Production of aromatic compound bearing unsaturated side chain |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6118736A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182991U (en) * | 1987-05-20 | 1988-11-25 |
-
1984
- 1984-07-05 JP JP13941284A patent/JPS6118736A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63182991U (en) * | 1987-05-20 | 1988-11-25 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6118736A (en) | 1986-01-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |