JPS5912643B2 - Production method of phenethyl bromides - Google Patents
Production method of phenethyl bromidesInfo
- Publication number
- JPS5912643B2 JPS5912643B2 JP50039808A JP3980875A JPS5912643B2 JP S5912643 B2 JPS5912643 B2 JP S5912643B2 JP 50039808 A JP50039808 A JP 50039808A JP 3980875 A JP3980875 A JP 3980875A JP S5912643 B2 JPS5912643 B2 JP S5912643B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- hydrogen bromide
- phenethyl bromides
- production method
- formula
- 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
Links
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、医薬品その他の合成品の中間体として有用な
、フェネチルブロマイド類の製法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing phenethyl bromides, which are useful as intermediates for pharmaceuticals and other synthetic products.
詳記すれば、有機溶媒中スチレン類にアゾ重合開始剤の
存在下臭化水素を付加させることを特徴とする、フェネ
チルブロマイド類の製造方法に関する。５ スチレン類
に臭化水素を付加させる場合、通常α−ブロム体が生成
する為、従来β−ブロム体を得ようとするときは、ラウ
ロイルパーオキサイドのような過酸化物の存在下、スチ
レン類に臭化水素を付加させる方法が行われていた。More specifically, the present invention relates to a method for producing phenethyl bromides, which is characterized by adding hydrogen bromide to styrene in an organic solvent in the presence of an azo polymerization initiator. 5 When hydrogen bromide is added to styrene, α-bromine is usually produced, so conventionally when trying to obtain β-bromine, styrene was added in the presence of a peroxide such as lauroyl peroxide. The method used was to add hydrogen bromide to
しかしなが１０らこの方法は、生成物の収率、品質共に
不満足であると共に、取り扱いの難しい過酸化物を使用
するのが欠点であり、更により良い製造方法が望まれて
いた。本発明は、スチレン類に臭化水素を付加するに１
５際し、有機溶媒中アゾ重合開始剤を使用することによ
り、高収率で高品質のフェネチルブロマイド類が得られ
ることを見出し、達成されたものである。However, this method is disadvantageous in that both the yield and quality of the product are unsatisfactory, and it uses peroxide which is difficult to handle.Therefore, a better production method has been desired. The present invention provides a method for adding hydrogen bromide to styrenes.
5, it was discovered and achieved that phenethyl bromides of high quality can be obtained in high yield by using an azo polymerization initiator in an organic solvent.
２｜即、本発、＆を、一般式Ｒ０ＣＨ＝ＣＨ０（式中Ｒ
は、水素、低級アルキル基、ニトロ基、水酸基、スルホ
ン酸基、ハロゲン原子を示す。2 | Immediately, the present invention, &, the general formula R0CH=CH0 (in the formula R
represents hydrogen, lower alkyl group, nitro group, hydroxyl group, sulfonic acid group, and halogen atom.
）なる化合物と臭化水素との反応を、有機溶媒中、２５
アゾ重合開始剤の存在のもとに行なわせることを特徴と
する、式 □ＣＨ２ＣＨ２Ｂｒ
（式中Ｒは前記と同じ。) and hydrogen bromide in an organic solvent at 25%
A compound of the formula □CH2CH2Br (wherein R is the same as above), characterized in that it is carried out in the presence of an azo polymerization initiator.
）なる化合物の製造法で３０ある。本発明に使用される
原料スチレン類としては、例えば、スチレン、Ｐ−メチ
ルスチレン、０−クロルスチレン、Ｐ−ブロムスチレン
、Ｐ−ニトロスチレン、Ｐ−スチレンスルホン酸、Ｐ−
ヒドロ３５キシスチレン等が挙げられる。) There are 30 methods for producing the compound. The raw material styrenes used in the present invention include, for example, styrene, P-methylstyrene, 0-chlorostyrene, P-bromustyrene, P-nitrostyrene, P-styrenesulfonic acid, P-
Examples include hydro-35 xystyrene.
本発明に使用されるアゾ重合開始剤としては、２ 「Ｃ
〜７０℃の反応温度において至適重合活性を有するもの
が好ましく、例えば、アゾビスイソブチロニトリル、２
・２′−アゾビス（２・４−ジメチルワレロニトリル）
、２・２′−アゾビス（２・４−ジメチル−４−メトキ
シワレロニトリル）、アゾビス（α−メチルブチロニト
リル）等が挙げられる。As the azo polymerization initiator used in the present invention, 2 "C
Those having optimal polymerization activity at a reaction temperature of ~70°C are preferred, such as azobisisobutyronitrile, 2
・2'-azobis(2,4-dimethylvaleronitrile)
, 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), azobis(α-methylbutyronitrile), and the like.
スチレン類と臭化水素との反応は、有機溶媒中、アゾ重
合開始剤を存在させ加熱することによつて行われる。The reaction between styrenes and hydrogen bromide is carried out by heating in the presence of an azo polymerization initiator in an organic solvent.
使用される有機溶媒としては、例えばｎ−ヘキサン、ｎ
−ヘプタン、ベンゼン、トルエン、四塩化炭素、テトラ
クロロエチレン等のような、極性の少い溶媒を使用する
のが好ましい。反応温度は、２０℃〜７０℃で行うのが
好ましく、反応温度がこれ以下であつたり、これ以上で
あつたりすると、副生物の生成がみられるようになり、
本願発明の効果が十分発揮されない。臭化水素の使用量
は、スチレン類に対し、当量乃至若干過剰量使用するの
が好ましく、大過剰に使用してもさしたる利点はなく、
経済的でない。反応終了後生成物を単離するには、例え
ば反応終了液を水洗後溶媒を留去し、減圧蒸留する。以
上述べた如く本願発明方法は安定で爆発性がないので取
扱いが安全な、アゾ重合開始剤を使用する為、工業的に
有利な製法を提供すると共に、更に優れた利点は、収率
、品質共に飛躍的に向上したことであり、斯業に貢献す
る処極めて大きい。以下に実施例を述べ、本願発明を更
に説明する。実施例中数量を表わす部は重量部である。
実施例 １
メチルスチレン２３．６部と２・２′−アゾビス（２・
４−ジメチル−４−メトキシワレロニトリル）１．２部
とを四塩化炭素１５０部に溶解し、４５〜５０℃で臭化
水素１８部を２時間で導入した。Examples of organic solvents used include n-hexane and n-hexane.
- It is preferred to use less polar solvents such as heptane, benzene, toluene, carbon tetrachloride, tetrachloroethylene, etc. The reaction temperature is preferably 20°C to 70°C; if the reaction temperature is lower or higher than this, by-products will be produced.
The effects of the present invention are not fully exhibited. The amount of hydrogen bromide to be used is preferably equivalent to or slightly in excess of the amount of styrene; even if it is used in large excess, there is no significant advantage.
Not economical. To isolate the product after completion of the reaction, for example, the reaction completion solution is washed with water, the solvent is distilled off, and the product is distilled under reduced pressure. As mentioned above, the method of the present invention uses an azo polymerization initiator, which is stable and non-explosive and therefore safe to handle, thereby providing an industrially advantageous manufacturing method. Both have improved dramatically, and the contribution to this industry is extremely significant. Examples will be described below to further explain the present invention. In the examples, parts expressed are parts by weight.
Example 1 23.6 parts of methylstyrene and 2.2'-azobis(2.
1.2 parts of 4-dimethyl-4-methoxyvaleronitrile) were dissolved in 150 parts of carbon tetrachloride, and 18 parts of hydrogen bromide was introduced over 2 hours at 45 to 50°C.
４５〜５０℃で３時間反応後、水洗し、溶媒を留去して
から減圧蒸留により、Ｂｐ３ｍｌｔＨｇ８９−９２℃の
留分３１部を得た。After reacting at 45-50°C for 3 hours, the reaction mixture was washed with water, the solvent was distilled off, and then distilled under reduced pressure to obtain 31 parts of a fraction with Bp3mltHg89-92°C.
ガスクロマトグラフイ一により測定した含量は９９．１
％であつた。比較例
実施例１に於ける２・２′−アゾビス（２・４−ジメチ
ル−４−メトキシワレロニトリル）１．２部の代りにラ
ウロイルパーオキシド１．６部を用いて反応を行い、同
様に処理したところ、Ｂｐ３ｍｍＨｇ８７−９２℃の留
分１６部（収率４０．２％）を得た。The content measured by gas chromatography is 99.1
It was %. Comparative Example A reaction was carried out using 1.6 parts of lauroyl peroxide instead of 1.2 parts of 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) in Example 1, and the same result was obtained. As a result, 16 parts of a fraction (yield: 40.2%) with a Bp of 3 mmHg and a temperature of 87-92°C were obtained.
ガスクロマトグラフイ一により測定した含量は９８．８
％であつた。実施例 ２
クロルスチレン２８部と２・２′−アゾビス（２・４−
ジメチルワレロニトリル）１．３部とを、テトラクロル
エチレン２００部に溶解し、５０〜５５℃で臭化水素２
２部を２時間で導入した。The content measured by gas chromatography is 98.8
It was %. Example 2 28 parts of chlorstyrene and 2,2'-azobis(2,4-
1.3 parts of dimethylvaleronitrile) was dissolved in 200 parts of tetrachlorethylene, and 2 parts of hydrogen bromide was dissolved at 50 to 55°C.
Two parts were introduced in two hours.
更に同一温度で１時間反応後、実施例１と同様にして、
ガスクロマトグラフイ一による含量９８．４％なるクロ
ルフエネチルプロマイド３６部を得た。沸点は９１〜９
６℃（３１７ｍＨｇ）実施例 ３
Ｐ−ニトロスチレン３０部とアゾビスイソブチロニトリ
ル１．０部とｎ−ヘキサン２００部とを混合し、４０〜
５『Ｃ３時間で臭化水素２０部を導入した。After further reacting at the same temperature for 1 hour, in the same manner as in Example 1,
36 parts of chlorphenethylbromide with a content of 98.4% as determined by gas chromatography was obtained. Boiling point is 91-9
6°C (317 mHg) Example 3 30 parts of P-nitrostyrene, 1.0 part of azobisisobutyronitrile and 200 parts of n-hexane were mixed,
5.20 parts of hydrogen bromide were introduced over 3 hours.
Claims (1)
低級アルキル基、ニトロ基、ハロゲン原子を示す。 ）なる化合物と臭化水素との反応を、有機溶媒中、アゾ
重合開始剤の存在のもとに行なわせることを特徴とする
、式▲数式、化学式、表等があります▼（式中Ｒは前記
に同じ。 ）なる化合物の製造方法。[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is hydrogen,
Indicates a lower alkyl group, nitro group, or halogen atom. ) and hydrogen bromide in an organic solvent in the presence of an azo polymerization initiator. Same as above.) A method for producing a compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50039808A JPS5912643B2 (en) | 1975-04-03 | 1975-04-03 | Production method of phenethyl bromides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50039808A JPS5912643B2 (en) | 1975-04-03 | 1975-04-03 | Production method of phenethyl bromides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS51115429A JPS51115429A (en) | 1976-10-12 |
| JPS5912643B2 true JPS5912643B2 (en) | 1984-03-24 |
Family
ID=12563252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50039808A Expired JPS5912643B2 (en) | 1975-04-03 | 1975-04-03 | Production method of phenethyl bromides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5912643B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62282950A (en) * | 1986-06-02 | 1987-12-08 | Hitachi Ltd | Thermal recording head |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK1129066T3 (en) | 1998-11-11 | 2005-03-29 | Novartis Ag | Preparation of 2-amino-2- [2- (C2-20 alkylphenyl) ethyl] propane-1,3-diols |
-
1975
- 1975-04-03 JP JP50039808A patent/JPS5912643B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62282950A (en) * | 1986-06-02 | 1987-12-08 | Hitachi Ltd | Thermal recording head |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51115429A (en) | 1976-10-12 |
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