JPS5948816B2 - Method for producing 1-chloro-1,3-diphenylpropane - Google Patents

Method for producing 1-chloro-1,3-diphenylpropane

Info

Publication number
JPS5948816B2
JPS5948816B2 JP51049907A JP4990776A JPS5948816B2 JP S5948816 B2 JPS5948816 B2 JP S5948816B2 JP 51049907 A JP51049907 A JP 51049907A JP 4990776 A JP4990776 A JP 4990776A JP S5948816 B2 JPS5948816 B2 JP S5948816B2
Authority
JP
Japan
Prior art keywords
reaction
chloro
diphenylpropane
styrene
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.)
Expired
Application number
JP51049907A
Other languages
Japanese (ja)
Other versions
JPS52133958A (en
Inventor
有亮 泉
昌人 岡田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokuyama Corp
Original Assignee
Tokuyama Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokuyama Corp filed Critical Tokuyama Corp
Priority to JP51049907A priority Critical patent/JPS5948816B2/en
Publication of JPS52133958A publication Critical patent/JPS52133958A/en
Publication of JPS5948816B2 publication Critical patent/JPS5948816B2/en
Expired legal-status Critical Current

Links

Classifications

    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements 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)

Description

【発明の詳細な説明】 本発明は塩化ベンジルとスチレンとの反応に関し、その
1:1の付加物である1−クロルー1、3−ジフェニル
プロパンを収率よく製造することを目的とするものであ
る。
DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the reaction of benzyl chloride and styrene, and its purpose is to produce 1-chloro-1,3-diphenylpropane, which is a 1:1 adduct thereof, in a high yield. be.

塩化物のオレフィン類との付加反応は、古くからフリー
デルークラフツ反応の一連の研究において良く研究がな
されている。
The addition reaction of chloride with olefins has long been well studied in the series of Friedel-Crafts reactions.

例えばα−クロルエチルベンゼンは、イソブチレンとZ
nCl2触媒により95%の収率でl:1の付加物であ
る2ーメチルー2−クロルー4−フェニルペンタンを与
える。又、スチレンとの反応では50%の収率で1−ク
ロルー1、3−ジフェニルブタンを与える(G、A、O
lah)”゛FriedelCraftsandRe一
1atedReactions””、Vol、2、P、
768、In−tersciencePublishe
rs、Inc、、NewYork、)。しかしながら、
塩化ベンジルの如き一級の塩化物はオレフィン類に対し
て付加反応を起こさず、該オレフィン類が塩化ベンジル
の芳香環へアルキル化される。9 しかるに、本発明に
よればトリフェニルホスフィンと金属鉄とよりなる触媒
を用いることにより、フリーデルークラフト触媒では進
行しない塩化ベンジルとスチレンとの付加反応を可能に
し、その1:1の付加物である1−クロルーl、3−ジ
フ5 エニルプロパンを収率よく製造しうるものである
For example, α-chloroethylbenzene is a mixture of isobutylene and Z
nCl2 catalyst gives the l:1 adduct 2-methyl-2-chloro-4-phenylpentane in 95% yield. In addition, reaction with styrene gives 1-chloro-1,3-diphenylbutane with a yield of 50% (G, A, O
lah)"Friedel Crafts and Re-1ated Reactions"", Vol. 2, P.
768, In-tersciencePublish
rs, Inc., New York). however,
Primary chlorides such as benzyl chloride do not undergo addition reactions with olefins, and the olefins are alkylated to the aromatic ring of benzyl chloride. 9 However, according to the present invention, by using a catalyst consisting of triphenylphosphine and metallic iron, it is possible to carry out an addition reaction between benzyl chloride and styrene, which does not proceed with a Friedel-Crafts catalyst, and the 1:1 adduct can A certain 1-chlorol,3-diph5enylpropane can be produced with good yield.

本発明における触媒成分のうらトリフェニルホスフィン
は反応の過程において塩化ベンジルと反応してホスフオ
ニウム塩〔Ph3P−CH2Ph〕+Cl−(Phはフ
ェニル基)となつて触媒作用を発0揮する。なお、他の
触媒成分である金属鉄としては粒状で粒子径の小さいほ
ど好ましく、一般には20メッシュ以下特に200メッ
シュ以下の鉄粉が好適に用いられる。上記触媒成分のト
リフェニルホスフィンと金属鉄との混合割合は一般に金
属5鉄1ミリグラム原子に対してトリフェニルホスフィ
ン0.1〜100ミリモルの範囲で使用されるが、反応
後に該触媒成分をトリフェニルホスフィンの四級塩と塩
化第二鉄との錯塩として回収するためには両触媒成分を
等モルの割合で使用することが0望ましい。本発明の反
応系において上記触媒の濃度はスチレン1モルに対して
トリフェニルホスフィン0.001〜0.05モルの割
合で充分であり、これ以上の高濃度でもよいが経済的で
なく、一般には”5 スチレン1モルに対してトリフェ
ニルホスフィン0.005〜0.3モルの割合が実用的
な濃度で好ましい。
Triphenylphosphine, which is a catalyst component in the present invention, reacts with benzyl chloride during the reaction process to form a phosphonium salt [Ph3P-CH2Ph]+Cl- (Ph is a phenyl group) and exhibits a catalytic action. It is to be noted that the metal iron, which is another catalyst component, is preferably granular and has a smaller particle size, and generally iron powder of 20 mesh or less, particularly 200 mesh or less is preferably used. The mixing ratio of the above catalyst component triphenylphosphine and metal iron is generally used in the range of 0.1 to 100 mmol of triphenylphosphine per 1 milligram atom of metal penta-iron. In order to recover a complex salt of a quaternary salt of phosphine and ferric chloride, it is desirable to use both catalyst components in an equimolar ratio. In the reaction system of the present invention, the concentration of the above-mentioned catalyst is sufficient at a ratio of 0.001 to 0.05 moles of triphenylphosphine per mole of styrene, and although higher concentrations may be used, it is not economical and generally 5 Preferred concentration is 0.005 to 0.3 mol of triphenylphosphine per 1 mol of styrene.

また、本発明において反応に供する塩化ベンジルとスチ
レンとの割合は約1:l〜約10:1、好ましくは約2
:l〜約4:1の範囲から任意に選択することができる
Further, in the present invention, the ratio of benzyl chloride and styrene used in the reaction is about 1:1 to about 10:1, preferably about 2
:1 to about 4:1.

そのほか本発明の反応における条件は特に制限されず通
常の装置、手段で一般に常圧から加圧下、約95℃〜1
30℃で実施される。さらに、本発明の反応は触媒成分
のトリフエニルホスフインを溶解し易い溶媒、例えばイ
ソプロピルアルコール、n−ブタ/−ル等のアルコール
類、そのほかジメチルホルムアミドを反応系に用いるこ
とによつて、塩化ベンジルとスチレンとの1:1の付加
生成物である1−クロル−1,3−ジフエニルプロパン
の収率を向上せしめることができる。
In addition, the conditions for the reaction of the present invention are not particularly limited, and are generally carried out using ordinary equipment and means, under normal pressure to increased pressure, and from about 95°C to 100°C.
Performed at 30°C. Furthermore, the reaction of the present invention can be carried out using a solvent that easily dissolves the catalyst component triphenylphosphine, such as alcohols such as isopropyl alcohol and n-butyl alcohol, as well as dimethylformamide. The yield of 1-chloro-1,3-diphenylpropane, which is a 1:1 addition product of 1:1 and styrene, can be improved.

本願で得られる1−クロル−1,3−ジフエニルプロパ
ンは種々の原料又は中間原料として使用され、例えば向
神経剤、精神療法剤等に使用されるl−(1,3−ジア
リールプロピル)ピペラジンの原料として好適に使用さ
れる。
1-Chlor-1,3-diphenylpropane obtained in the present application is used as various raw materials or intermediate raw materials, such as l-(1,3-diarylpropyl)piperazine used in neurotropic agents, psychotherapeutic agents, etc. It is suitably used as a raw material.

実施例 1 塩化ベンジル40m1(0.348モル)、スチレン1
1.4m1(0.1モル)及び触媒としてトリフエニル
ホスフイン524m9(2ミリモノ(ハ)と金属鉄11
2〜(2ミリグラム原子)とを丸底フラスコに仕込んだ
Example 1 Benzyl chloride 40ml (0.348mol), styrene 1
1.4 m1 (0.1 mol) and 524 m9 of triphenylphosphine (2 mmol and 11 mol of metal iron) as a catalyst.
(2 milligram atoms) were charged into a round bottom flask.

反応系内を窒素ガスで置換した後、マグネチツクスター
ラ一で攪拌しながら、110℃の温度で4時間反応を行
つた。金属鉄は反応液に溶出し、反応液は黄色の均一溶
液となつた。冷却後に触媒残渣等を除去するため水洗を
2回行つた。水洗後に反応液は無色の溶液となつた。次
いで反応液を減圧蒸留することによつて沸点134〜1
35℃/2mmH9の留分9.1f1を留出した。これ
はガスクロマトグラフイ一、赤外線(IR)及び核磁気
共鳴(NMR)スペクトルより1−クロル−1,3−ジ
フエニルプロパンであることを確認した。スチレンから
の収率は39.5モル%である。実施例 2 実施例1における反応系にn−ブチルアルコール5m1
を溶媒として加えた以外は実施例1と全く同一の条件で
反応を実施した。
After purging the reaction system with nitrogen gas, the reaction was carried out at a temperature of 110° C. for 4 hours while stirring with a magnetic stirrer. Metallic iron was eluted into the reaction solution, and the reaction solution became a yellow homogeneous solution. After cooling, water washing was performed twice to remove catalyst residues and the like. After washing with water, the reaction solution became a colorless solution. Next, the reaction solution was distilled under reduced pressure to reduce the boiling point to 134-1.
Fraction 9.1f1 was distilled at 35°C/2mmH9. This was confirmed to be 1-chloro-1,3-diphenylpropane by gas chromatography, infrared (IR), and nuclear magnetic resonance (NMR) spectra. The yield from styrene is 39.5 mol%. Example 2 5ml of n-butyl alcohol was added to the reaction system in Example 1.
The reaction was carried out under exactly the same conditions as in Example 1, except that the following was added as a solvent.

反応後の水洗によつてn−ブチルアルコールは反応液か
ら除去された。1−クロル−1,3−ジフエニルプロパ
ンが10.89(スチレンからの収率46.9モル%)
得られた。
After the reaction, n-butyl alcohol was removed from the reaction solution by washing with water. 1-chloro-1,3-diphenylpropane is 10.89 (yield from styrene 46.9 mol%)
Obtained.

比較例 1 実施例1において触媒成分のうら、トリフエニルホスフ
インを除いた以外は、実施例1と全く同一の仕込条件で
110℃の温度下で反応を行つた。
Comparative Example 1 A reaction was carried out at a temperature of 110° C. under exactly the same charging conditions as in Example 1, except that triphenylphosphine was removed from the catalyst component.

反応開始後、約1時間経つと激しい発熱を伴つたスチレ
ンの重合反応が観測された。反応液は黄色の粘 な液と
なる。反応液をメタノール500m1の中に投入すると
、粘 な黄色オイルが得られた。これをデカンテーシヨ
ンによりメタノールから分離し真空下でメタノール、塩
化ベンジルを除くと14.99の黄色固体が得られた。
これはIRスベクトルからポリスチレンと固定された。
比較例 2 実施例2の仕込条件からトリフエニルホスフインを除い
て、すなわと、n−ブチルアルコール溶媒下で触媒とし
て金属鉄のみを使用して塩化ベンジルとスチレンの反応
を実施例1と全く同一の反応操作で行つた。
About 1 hour after the start of the reaction, a styrene polymerization reaction accompanied by intense heat generation was observed. The reaction solution becomes a yellow viscous liquid. When the reaction solution was poured into 500 ml of methanol, a viscous yellow oil was obtained. This was separated from methanol by decantation, and methanol and benzyl chloride were removed under vacuum, yielding 14.99 yellow solids.
This was fixed with polystyrene from the IR vector.
Comparative Example 2 The reaction between benzyl chloride and styrene was carried out exactly as in Example 1, except that triphenylphosphine was removed from the charging conditions of Example 2, and only metallic iron was used as a catalyst in an n-butyl alcohol solvent. The same reaction procedure was used.

減圧蒸留によつて、沸点125一138℃/2mmH9
の留分が5.89得られる。このもののIRスペクトル
には11000m−1に吸収が見られエーテル化合物で
あることを示唆しており、1−クロル−1,3−ジフエ
ニルプロパンは得ることができなかつた。比較例 3 金属鉄を塩化第二鉄329η(2ミリモル)にかえた以
外は実施例1と全く同一の条件で反応を行つた。
Boiling point 125-138℃/2mmH9 by vacuum distillation
A fraction of 5.89 is obtained. The IR spectrum of this product showed absorption at 11000 m-1, suggesting that it was an ether compound, and 1-chloro-1,3-diphenylpropane could not be obtained. Comparative Example 3 A reaction was carried out under exactly the same conditions as in Example 1, except that the metallic iron was changed to 329η (2 mmol) of ferric chloride.

Claims (1)

【特許請求の範囲】 1 塩化ベンジルとスチレンとをトリフェニルホスフィ
ンと金属鉄とよりなる触媒の存在下に反応させることを
特徴とする1−クロル−1,3−ジフェニルプロパンの
製造方法。 2 反応温度が95〜130℃である特許請求の範囲第
1項記載の1−クロル−1,3−ジフェニルプロパンの
製造方法。 3 トリフェニルホスフィンを溶解する溶媒を添加して
反応を行う特許請求の範囲第1項記載の1−クロル−1
,3−ジフェニルプロパンの製造方法。
[Scope of Claims] 1. A method for producing 1-chloro-1,3-diphenylpropane, which comprises reacting benzyl chloride and styrene in the presence of a catalyst consisting of triphenylphosphine and metallic iron. 2. The method for producing 1-chloro-1,3-diphenylpropane according to claim 1, wherein the reaction temperature is 95 to 130°C. 3. 1-chloro-1 according to claim 1, in which the reaction is carried out by adding a solvent that dissolves triphenylphosphine.
, 3-diphenylpropane manufacturing method.
JP51049907A 1976-05-04 1976-05-04 Method for producing 1-chloro-1,3-diphenylpropane Expired JPS5948816B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP51049907A JPS5948816B2 (en) 1976-05-04 1976-05-04 Method for producing 1-chloro-1,3-diphenylpropane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP51049907A JPS5948816B2 (en) 1976-05-04 1976-05-04 Method for producing 1-chloro-1,3-diphenylpropane

Publications (2)

Publication Number Publication Date
JPS52133958A JPS52133958A (en) 1977-11-09
JPS5948816B2 true JPS5948816B2 (en) 1984-11-29

Family

ID=12844071

Family Applications (1)

Application Number Title Priority Date Filing Date
JP51049907A Expired JPS5948816B2 (en) 1976-05-04 1976-05-04 Method for producing 1-chloro-1,3-diphenylpropane

Country Status (1)

Country Link
JP (1) JPS5948816B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62189122U (en) * 1986-05-22 1987-12-02

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62189122U (en) * 1986-05-22 1987-12-02

Also Published As

Publication number Publication date
JPS52133958A (en) 1977-11-09

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