JP2002265482A - Method for producing organic phosphorous compound - Google Patents
Method for producing organic phosphorous compoundInfo
- Publication number
- JP2002265482A JP2002265482A JP2001062167A JP2001062167A JP2002265482A JP 2002265482 A JP2002265482 A JP 2002265482A JP 2001062167 A JP2001062167 A JP 2001062167A JP 2001062167 A JP2001062167 A JP 2001062167A JP 2002265482 A JP2002265482 A JP 2002265482A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- allyl
- organic phosphorus
- general formula
- phosphorus compound
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は有機高分子化合物の
難燃剤などの用途に用いられる有機リン化合物の製造方
法に関するものである。一般式（３）で表わされる有機
リン化合物は，二重結合を有するため，種々の難燃性樹
脂の原料として有用である。詳しくは本発明は、触媒及
び特定の溶媒を用いて一般式（１）の有機リン化合物と
一般式（２）のハロゲン化アリル化合物を原料とした効
率の良い有機リン化合物の製造方法に関する。The present invention relates to is a method of manufacturing an organic phosphorus compound used in applications such as flame retardants in the organic polymer compound. Since the organic phosphorus compound represented by the general formula (3) has a double bond, it is useful as a raw material for various flame-retardant resins. More specifically, the present invention relates to a method for efficiently producing an organic phosphorus compound using a catalyst and a specific solvent as starting materials for the organic phosphorus compound of the general formula (1) and the allyl halide compound of the general formula (2).
【０００２】[0002]
【従来の技術】従来この種の合成法としては， １）有機リン化合物とハロゲン化アリル化合物を原料と
して直接合成する方法、 ２）有機リン化合物のアルカリ塩とハロゲン化アリル化
合物を原料とする合成方法、 ３）有機リン化合物と大過剰のハロゲン化アリル化合物
を原料とする合成方法、等が知られていた。2. Description of the Related Art Conventionally, as a synthesis method of this kind, 1) a method of directly synthesizing an organic phosphorus compound and an allyl halide compound as raw materials, 2) a synthesis using an alkali salt of an organic phosphorus compound and an allyl halide compound as raw materials And 3) a synthesis method using an organic phosphorus compound and a large excess of an allyl halide compound as raw materials.
【０００３】しかし，これらの合成方法を本発明に関す
る化合物の合成に用いようとした場合には，１）の直接
反応ではリン化合物の融点が高い為に反応温度が高くな
り副生物がかなりの割合で起こる上，反応を完結させる
為に過剰のハロゲン化アリルを必要とする。However, if you try to use these synthetic methods for the synthesis of compounds related to the present invention, 1) a significant proportion of the reaction temperature is high becomes byproducts because a high melting point of the phosphorus compound in the direct reaction of And requires an excess of allyl halide to complete the reaction.
【０００４】２）の方法を適用した場合には無水系では
水溶液中で塩を作った後，脱水に時間を要する。一般的
に二重結合を有した有機化合物はマイケル付加反応を起
こし、その二重結合がなくなる傾向がある。また，水溶
性媒体中で合成するときはハロゲン化アリル化合物が不
安定である為に，ハロゲン化アリル化合物が加水分解さ
れてアリルアルコールになる副反応がかなりの割合で起
こり，原料と副生物との分離回収等の操作が複雑になる
上に製造コストもかかる。[0004] When the method 2) is applied, in the case of an anhydrous system, it takes time for dehydration after forming a salt in an aqueous solution. Generally, an organic compound having a double bond causes a Michael addition reaction, and the double bond tends to disappear. Also, when synthesized in an aqueous medium, the allyl halide compound is unstable, so that a considerable proportion of side reactions occur when the allyl halide compound is hydrolyzed to allyl alcohol. The operation such as separation and recovery of the material becomes complicated, and the manufacturing cost is also high.
【０００５】３）の方法は，大過剰にハロゲン化アリル
化合物を使用する為に反応温度が上がらずに長時間の反
応を要し，副生物ができる。In the method 3), a large excess of the allyl halide compound is used, so that the reaction temperature does not rise and a long reaction time is required, and a by-product is formed.
【０００６】[0006]
【発明が解決しようとする課題】従って本発明は，反応
性を持つビニル基を付与した有機リン化合物を効率良く
製造する方法を提案するものである。一般式（１）の有
機リン化合物は，一般的に二重結合を有した有機化合物
とマイケル付加反応を起こし，その二重結合が無くなる
傾向がある。SUMMARY OF THE INVENTION Accordingly, the present invention proposes a method for efficiently producing an organic phosphorus compound having a vinyl group having reactivity. The organic phosphorus compound of the general formula (1) generally causes a Michael addition reaction with an organic compound having a double bond, and the double bond tends to disappear.
【０００７】本発明の課題は上記のような従来技術の欠
点を考慮し、反応条件をコントロールすることによりビ
ニル基を損なうことなく，副反応がほとんど無く，高収
率で高品質の一般式（３）で示される有機リン化合物を
合成することである。The object of the present invention is to control the reaction conditions in consideration of the above-mentioned drawbacks of the prior art, without impairing the vinyl group, with few side reactions, and with high yield and high quality of the general formula ( The synthesis of the organic phosphorus compound represented by 3) is to be performed.
【０００８】[0008]
【課題を解決するための手段】そこで本発明者らは，こ
れらの欠点や不利な問題点を解決すべく研究を重ねた結
果，ハロゲン化銅化合物がアルキル化反応に対して従来
知られている触媒よりも非常に優れていることを見いだ
した。つまり，従来知られている触媒よりも，反応中で
起こる副反応がほとんど無い上に，反応時間が短くてす
む極めて高い活性及び高選択性を有する。The inventors of the present invention have conducted studies to solve these drawbacks and disadvantages, and as a result, copper halide compounds have been known for alkylation reactions. It was found to be much better than the catalyst. In other words, there are almost no side reactions occurring during the reaction and extremely high activity and high selectivity requiring a short reaction time as compared with conventionally known catalysts.
【０００９】更に、水不溶性で反応において不活性であ
り、沸点が７０〜１６０℃である溶媒を用いることによ
り、融点の高い有機リン化合物を溶解させ、反応条件の
範囲を広げて、更に効率良く目的とする有機リン化合物
を製造出来ることを見いだし本願発明に到達した。Furthermore, by using a solvent which is insoluble in water and inert in the reaction and has a boiling point of 70 to 160 ° C., an organic phosphorus compound having a high melting point is dissolved, and the range of reaction conditions is widened to further improve the efficiency. They have found that the desired organophosphorus compound can be produced, and have reached the present invention.
【００１０】すなわち本発明は、一般式（１）で示され
る有機リン化合物That is, the present invention provides an organic phosphorus compound represented by the general formula (1)
【００１１】[0011]
【化４】 ＜式（１）でＲ１，Ｒ２及びＲ３は、それぞれ同一又は
相異なり，水素原子，ハロゲン原子，低級アルキル基，
シクロアルキル基，アリール基，またはアラルキル基を
表わす。＞と一般式（２）で示されるハロゲン化アリル
化合物Embedded image <In the formula (1), R1, R2 and R3 are the same or different and are each a hydrogen atom, a halogen atom, a lower alkyl group,
Represents a cycloalkyl group, an aryl group, or an aralkyl group. > And an allyl halide compound represented by the general formula (2)
【００１２】[0012]
【化５】 ＜式（２）中でＸはハロゲン原子を示す。＞を反応させ
て，一般式（３）Embedded image <X represents a halogen atom in the formula (2). > With the general formula (3)
【００１３】[0013]
【化６】 （式（３）でＲ１，Ｒ２及びＲ３は、それぞれ式（１）
のＲ１，Ｒ２及びＲ３と同様である。）で示されるアリ
ル基を有する有機リン化合物を製造する方法において，
触媒としてハロゲン化銅化合物を用いることとする。Embedded image (In the formula (3), R1, R2 and R3 are each represented by the formula (1)
Are the same as R1, R2 and R3. In the method for producing an organophosphorus compound having an allyl group represented by
A copper halide compound is used as a catalyst.
【００１４】[0014]
【発明の実施の形態】本発明をその実施態様例について
説明する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described with reference to embodiments.
【００１５】一般式（１）の有機リン化合物の原料とし
て具体的には，９，１０−ジヒドロ−９−オキサ−１０
−ホスファフェナントレン−１０−オキサイド，８−メ
チル−９，１０−ジヒドロ−９−オキサ−１０−ホスフ
ァフェナントレン−１０−オキサイド，６,８−ジクロ
ロ−９,１０−ジヒドロ−９−オキサ−１０−ホスファ
フェナントレン−１０−オキサイド，２,６,８−トリ−
ｔ−ブチル−９,１０−ジヒドロ−９−オキサ−１０−
ホスファフェナントレン−１０−オキサイド，６,８−
ジシクロヘキシル−９,１０−ジヒドロ−９−オキサ−
１０−ホスファフェナントレン−１０−オキサイド等が
挙げられるが，これらのみに限定されるものではない。As a raw material of the organic phosphorus compound of the general formula (1), specifically, 9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide, 8-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6,8-dichloro-9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide, 2,6,8-tri-
t-butyl-9,10-dihydro-9-oxa-10-
Phosphaphenanthrene-10-oxide, 6,8-
Dicyclohexyl-9,10-dihydro-9-oxa-
Examples include, but are not limited to, 10-phosphaphenanthrene-10-oxide.
【００１６】一般式（１）において、ハロゲン原子とは
臭素原子である。In the general formula (1), the halogen atom is a bromine atom.
【００１７】さらに低級アルキル基とは炭素数が１〜４
の直鎖アルキル基又は分枝を有するアルキル基である。[0017] The further the lower alkyl group with a carbon number of 1 to 4
Is a linear alkyl group or a branched alkyl group.
【００１８】また、シクロアルキル基とはシクロヘキシ
ル基及び３−メチル−シクロペンチル基である。The cycloalkyl group is a cyclohexyl group and a 3-methyl-cyclopentyl group.
【００１９】アリール基とはフェニル基、トリル基及び
ナフチル基である。Aryl groups are phenyl, tolyl and naphthyl.
【００２０】さらにまたアラルキル基とはベンジル基及
びフェネチル基である。Further, the aralkyl groups are a benzyl group and a phenethyl group.
【００２１】一般式（２）のハロゲ化アリル化合物の原
料として具体的には，フッ化アリル，塩化アリル，臭化
アリル，ヨウ化アリルが挙げられるが、工業的に安価な
臭化アリル又は塩化アリルが好ましい。ハロゲン化アリ
ル化合物の使用量としては、一般式（１）の有機リン化
合物に対して理論量は最低限必要であり，反応効率，反
応速度を考慮すれば更に過剰モル使用したほうがよい。
しかし，ハロゲン化アリル化合物をあまりに大過剰量用
いても，その過剰量に見合う効果が出ないので経済的に
好ましくない。通常一般式（２）のハリゲン化アリル化
合物は一般式（１）の有機リン化合物の原料としての理
論量に対して１．０〜４．０倍，より好ましくは１．１
〜２．２倍程度を使用する。Specific examples of the raw material of the allyl halide compound of the general formula (2) include allyl fluoride, allyl chloride, allyl bromide and allyl iodide. Allyl is preferred. As for the amount of the halogenated allyl compound to be used, a theoretical amount is required at least with respect to the organic phosphorus compound of the general formula (1), and it is better to use an excess molar amount in consideration of the reaction efficiency and the reaction rate.
However, it is not economically preferable to use an excessively large amount of the allyl halide compound, since the effect corresponding to the excessive amount is not obtained. Usually, the halogenated allyl compound of the general formula (2) is 1.0 to 4.0 times, more preferably 1.1 times the theoretical amount as a raw material of the organic phosphorus compound of the general formula (1).
Use about 2.2 times.
【００２２】その際の仕込み方法としては反応の最初に
仕込んでもよいし，反応途中に順次加えてもよい。At that time, as a charging method, it may be charged at the beginning of the reaction or may be added sequentially during the reaction.
【００２３】触媒として用いるハロゲン化銅化合物とし
て具体的には，塩化銅,臭化銅,ヨウ化銅等が挙げられる
が，これらに限られるものではなく，特にヨウ化銅又は
塩化銅が性能的にみて好ましい。また上記の二種以上を
混合しても使うことができる。Specific examples of the copper halide compound used as the catalyst include copper chloride, copper bromide, copper iodide and the like, but are not limited thereto. In particular, copper iodide or copper chloride has high performance. This is preferable. A mixture of two or more of the above may be used.
【００２４】触媒の使用量としては，一般式（１）の有
機リン化合物に対して０．１重量％〜３．０重量％，好
ましくは０．２重量％〜２．０重量％である。この場合
も少なすぎる場合には反応が遅くなるし，多い場合には
その量に見合う効果が得られないばかりか、副反応の為
にかえって収率が低下してしまう場合すらある。The amount of the catalyst used is from 0.1% by weight to 3.0% by weight, preferably from 0.2% by weight to 2.0% by weight, based on the organic phosphorus compound of the general formula (1). In this case as well, when the amount is too small, the reaction is slowed down. When the amount is too large, not only the effect corresponding to the amount is not obtained, but also the yield may even decrease due to side reactions.
【００２５】溶媒としては、水に不溶性であり、反応に
不活性なものから選ばれる。又その溶媒の沸点は、一般
式（２）のハロゲン化アリル化合物の回収がしやすく、
反応温度のコントロールをしやすくする為に７０〜１６
０℃の範囲から選ばれる。The solvent is selected from those which are insoluble in water and inert to the reaction. The boiling point of the solvent is such that the allyl halide compound of the general formula (2) can be easily recovered,
70-16 to facilitate control of reaction temperature
It is selected from the range of 0 ° C.
【００２６】具体的にはトルエン,キシレン,エチルベン
ゼン、シクロヘキサン、クロロベンゼン、メチルイソブ
チルケトン、酢酸エチル等が挙げられるが，これらに限
られるものではない。その使用量は，反応操作や後処理
に好適な程度の量であるが，原料の３．０倍重量以下，
好ましくは０．５〜１．５倍重量である。Specific examples include, but are not limited to, toluene, xylene, ethylbenzene, cyclohexane, chlorobenzene, methyl isobutyl ketone, and ethyl acetate. The amount used is an amount suitable for the reaction operation and post-treatment, but not more than 3.0 times the weight of the raw material.
Preferably it is 0.5 to 1.5 times the weight.
【００２７】反応の形態としては一般式（１）の有機リ
ン化合物と一般式（２）のハロゲン化アリル化合物を溶
媒中で触媒の存在下に加熱するという方法をとる。反応
温度は３０℃〜１６０℃，好ましくは７０℃〜１１０℃
の範囲から選ばれ，常圧下で行なわれることが望まし
い。更に反応を効率的に行なうためには，生成するハロ
ゲン化水素を反応系外に速やかに除去させたほうがよ
い。反応時間は各種反応条件により異なるが，反応開始
後，約１０〜３５時間で完結する。As a form of the reaction, a method is employed in which the organic phosphorus compound of the general formula (1) and the allyl halide compound of the general formula (2) are heated in a solvent in the presence of a catalyst. The reaction temperature is 30 ° C to 160 ° C, preferably 70 ° C to 110 ° C.
It is preferable to be carried out under normal pressure. In order to carry out the reaction more efficiently, it is better to promptly remove the generated hydrogen halide out of the reaction system. The reaction time varies depending on various reaction conditions, but is completed in about 10 to 35 hours after the start of the reaction.
【００２８】本反応で生成した有機リン化合物の単離法
としては反応時の着色が少ない為に，未反応のハロゲン
化アリル化合物を溜出後，公知の手段で触媒を分離後，
アルカリ水洗，脱水，濃縮するだけで製品として得るこ
とができる。この製品を適当な手段で精製すれば，更に
高品質の製品が得られる。As a method for isolating the organophosphorus compound formed in the reaction, since there is little coloring during the reaction, after distilling off the unreacted allyl halide compound, the catalyst is separated by a known means.
It can be obtained as a product simply by washing with alkali water, dehydration and concentration. If Purify the product by suitable means, is obtained with higher quality products.
【００２９】[0029]
【実施例】以下，実施例により本発明を更に詳細に説明
するが，本発明はこれらに限定されるものではない。EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.
【００３０】実施例 １ 温度計，還流冷却器，窒素吹き込み口及び攪拌機を具備
した１０００ｍｌ四ッ口フラスコに９，１０−ジヒドロ
−９−オキサ−１０−ホスファフェナントレン−１０−
オキサイド（以下ＨＣＡという；三光（株）商品名）３
７８ｇ（１．７５モル），臭化アリル４８４ｇ（４．０
モル），臭化銅３．８ｇを仕込み窒素気流中で昇温し
た。７０℃で還流が始まり，臭化水素ガスが発生した。
反応開始から２．０時間後に系内は均一になった。２８
時間後に，反応温度は７２℃となり，反応を終了した。
その後，同温度にて窒素ガスを反応系内に吹き込み，臭
化水素を追い出し，トルエン５００ｇを加えて、水洗、
触媒を除去したのち，濃縮・脱水，熱濾過をし，結晶を
析出させた。濾過，乾燥して白色結晶３７７．３ｇが得
られた。純度８８．９％，収率８４．２％（対ＨＣＡ） 実施例 ２ 温度計，還流冷却器，窒素吹き込み口及び攪拌機を具備
した１０００ｍｌ四ッ口フラスコにＨＣＡ３７８ｇ
（１．７５モル），塩化アリル２０１ｇ（２．６３モ
ル），ヨウ化銅３．８ｇ，トルエン２５２ｇを仕込み窒
素気流中で昇温した。７３℃で還流が始まり，塩化水素
ガスが発生した。反応開始から１．０時間後に系内は均
一になった。１０時間後に，更に塩化アリル９４ｇ
（１．２３モル）を１時間かけて滴下した。２４時間
後、反応温度は８０℃となり，反応を終了した。その
後，同温度にて窒素ガスを反応系内に吹き込み，塩化水
素を追い出し，トルエン２５０ｇを加えて、水洗、触媒
を除去したのち，濃縮・脱水，熱濾過をし，結晶を析出
させた。濾過，乾燥して白色結晶３９８ｇが得られた。
純度９９．０％，収率８８．８％（対ＨＣＡ） 実施例 ３ 塩化アリルの代わりに臭化アリル２９５ｇ（３．８６モ
ル）を使用した以外は，実施例２と同様の装置を用い
て，同様の操作を行い，白色結晶４０３．６ｇが得られ
た。純度９９．２％，収率９０．１％（対ＨＣＡ） 実施例 ４ 触媒のヨウ化銅の代わりに臭化銅と溶媒のトルエンの代
わりにキシレンを使用した以外は，実施例２と同様の装
置を用いて，同様の操作を行い，白色結晶３８１gが得
られた。純度８９．８%，収率８５．１%（対ＨＣＡ） 実施例 ５ 触媒のヨウ化銅の代わりに塩化銅と溶媒のトルエンの代
わりにキシレンを使用した以外は，実施例２と同様の装
置を用いて，同様の操作を行い，白色結晶３７６gが得
られた。純度８９．４%，収率８３．９%（対ＨＣＡ） 比較例 １ 実施例２に記載の仕込み量で、溶媒と触媒を使用しない
で、一般式（１）の有機リン化合物を溶融状態で塩化ア
リルを滴下しながら反応させたのち、水洗、濃縮・脱
水，熱濾過をし，結晶を析出させて有機リン化合物を得
た。結果は表１に示した。Example 1 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10- was placed in a 1000 ml four-necked flask equipped with a thermometer, a reflux condenser, a nitrogen inlet and a stirrer.
Oxide (hereinafter referred to as HCA; trade name of Sanko Co., Ltd.) 3
78 g (1.75 mol), allyl bromide 484 g (4.0
Mol) and 3.8 g of copper bromide were charged and heated in a nitrogen stream. Reflux started at 70 ° C., and hydrogen bromide gas was generated.
System in the 2.0 hours after the start of the reaction became homogeneous. 28
After an hour, the reaction temperature reached 72 ° C. and the reaction was terminated.
Thereafter, nitrogen gas was blown into the reaction system at the same temperature to expel hydrogen bromide, 500 g of toluene was added, and water was washed.
After removing the catalyst, concentration and dewatering, heat filtered, to precipitate crystals. After filtration and drying, 377.3 g of white crystals were obtained. Example 8 Purity: 88.9%, Yield: 84.2% (based on HCA) Example 2 378 g of HCA in a 1000 ml four-necked flask equipped with a thermometer, a reflux condenser, a nitrogen inlet, and a stirrer.
(1.75 mol) of allyl chloride 201g (2.63 mol), copper iodide 3.8 g, was heated in a nitrogen stream of toluene were charged 252 g. Reflux started at 73 ° C., and hydrogen chloride gas was generated. 1.0 hour after the start of the reaction, the inside of the system became homogeneous. After 10 hours, another 94 g of allyl chloride
(1.23 mol) was added dropwise over 1 hour. After 24 hours, the reaction temperature reached 80 ° C., and the reaction was completed. Thereafter, nitrogen gas was blown into the reaction system at the same temperature to expel hydrogen chloride, and 250 g of toluene was added. After washing with water and removing the catalyst, concentration, dehydration, and hot filtration were performed to precipitate crystals. Filtered and dried to white crystals 398g was obtained.
Purity 99.0%, Yield 88.8% (based on HCA) Example 3 The same apparatus as in Example 2 was used except that 295 g (3.86 mol) of allyl bromide was used instead of allyl chloride. The same operation was performed to obtain 403.6 g of white crystals. Purity 99.2%, Yield 90.1% (vs. HCA) Example 4 Same as Example 2 except that copper bromide was used in place of copper iodide as a catalyst and xylene was used in place of toluene as a solvent. The same operation was carried out using an apparatus to obtain 381 g of white crystals. Purity: 89.8%, Yield: 85.1% (vs. HCA) Example 5 The same apparatus as in Example 2 except that copper chloride was used instead of copper iodide as a catalyst and xylene instead of toluene as a solvent. And 376 g of white crystals were obtained. Purity: 89.4%, Yield: 83.9% (based on HCA) Comparative Example 1 The amount of the organic phosphorus compound represented by the general formula (1) was changed to the amount described in Example 2 without using a solvent and a catalyst. The reaction was carried out while dropping allyl chloride, followed by washing with water, concentration / dehydration, and hot filtration to precipitate crystals to obtain an organic phosphorus compound. The results are shown in Table 1.
【００３１】比較例 ２ 塩化アリルの代わりに臭化アリルを用いて比較例１に記
載した方法により有機リン化合物を得た。結果は表１に
示した。[0031] to obtain an organic phosphorus compound according to the method described in Comparative Example 1 using allyl bromide in place of Comparative Example 2 Allyl chloride. The results are shown in Table 1.
【００３２】比較例 ３ 溶媒を使用しないで，触媒として塩化亜鉛と，臭化アリ
ルを用いて実施例２に記載した方法により有機リン化合
物を得た。結果は表１に示した。Comparative Example 3 An organic phosphorus compound was obtained in the same manner as in Example 2 except that no solvent was used and zinc chloride and allyl bromide were used as catalysts. The results are shown in Table 1.
【００３３】比較例 ４ 触媒を使用しないで，塩化アリルと溶媒としてキシレン
を用いて実施例２に記載した方法により有機リン化合物
を得た。結果は表１に示した。Comparative Example 4 An organophosphorus compound was obtained by the method described in Example 2 without using a catalyst and using allyl chloride and xylene as a solvent. The results are shown in Table 1.
【００３４】[0034]
【表１】 実施例 ６ 一般式（１）の有機リン化合物を８−メチル−９，１０
−ジヒドロ−９−オキサ−１０−ホスファフェナントレ
ン−１０−オキサイドに変える以外は実施例２に記載し
た方法により有機リン化合物を得た。結果を表２に示し
た。[Table 1] The organic phosphorus compound of Example 6 Formula (1) 8-methyl-9,10
An organophosphorus compound was obtained by the method described in Example 2 except that -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was used. The results are shown in Table 2.
【００３５】実施例 ７ 実施例６において、触媒を用いなかった以外は、実施例
２に記載した方法により有機リン化合物を得た。結果を
表２に示した。Example 7 An organic phosphorus compound was obtained in the same manner as in Example 6, except that no catalyst was used. The results are shown in Table 2.
【００３６】比較例 ５ 実施例６において、触媒と溶媒を用いなかった以外は、
実施例２に記載した方法により有機リン化合物を得た。
結果を表２に示した。Comparative Example 5 In Example 6, except that no catalyst and solvent were used.
To obtain an organic phosphorus compound by the method described in Example 2.
The results are shown in Table 2.
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【発明の効果】本発明によれば，アリル基を有した有機
リン化合物を，経済的な方法により高収率で，高品質の
製品として製造することが出来る。According to the present invention, an organophosphorus compound having an allyl group can be produced as a high-quality product at a high yield by an economical method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石橋 孝 大阪府茨木市五日市１丁目10番24号 三光 株式会社工場製品事業本部研究所内 Ｆターム(参考） 4H039 CA22 CA90 CD10 CD20 4H050 AA02 BA05 BA37 BB11 BB46 BB49 WA12 WA26 ──────────────────────────────────────────────────の Continued on front page (72) Inventor Takashi Ishibashi 1-10-24, Itokaichi, Ibaraki-shi, Osaka Sanko Co., Ltd. F-term (in reference) 4F039 CA22 CA90 CD10 CD20 4H050 AA02 BA05 BA37 BB11 BB46 BB49 WA12 WA26
Claims (7)
相異なり，水素原子，ハロゲン原子，低級アルキル基，
シクロアルキル基，アリール基，またはアラルキル基を
表わす。＞と一般式（２）で示されるハロゲン化アリル
化合物 【化２】 ＜式（２）中でＸはハロゲン原子を示す。＞を反応させ
て，一般式（３） 【化３】 （式（３）でＲ１，Ｒ２及びＲ３は、それぞれ式（１）
のＲ１，Ｒ２及びＲ３と同様である。）で示されるアリ
ル基を有する有機リン化合物を製造する方法において，
触媒としてハロゲン化銅化合物を用いることを特徴とす
る有機リン化合物の製造方法。An organophosphorus compound represented by the general formula (1): <In the formula (1), R1, R2 and R3 are the same or different and are each a hydrogen atom, a halogen atom, a lower alkyl group,
Represents a cycloalkyl group, an aryl group, or an aralkyl group. > An allyl halide compound represented by the general formula (2) ## STR2 ## <X represents a halogen atom in the formula (2). > To give a compound of the general formula (3) (In the formula (3), R1, R2 and R3 are each represented by the formula (1)
Are the same as R1, R2 and R3. In the method for producing an organophosphorus compound having an allyl group represented by
A method for producing an organic phosphorus compound, comprising using a copper halide compound as a catalyst.
溶媒として水に不溶性であって沸点が７０〜１６０℃で
ある溶媒を用いる請求項１に記載の有機リン化合物の製
造方法。2. In producing the organic phosphorus compound,
The method for producing an organic phosphorus compound according to claim 1, wherein a solvent which is insoluble in water and has a boiling point of 70 to 160 ° C is used as the solvent.
る請求項１または２に記載の有機リン化合物の製造方
法。3. The method according to claim 1, wherein the copper halide compound is copper iodide.
請求項１〜３のいずれかに記載の有機リン化合物の製造
方法。4. The method for producing an organic phosphorus compound according to claim 1, wherein said copper halide compound is copper chloride.
ル又は塩化アリルである請求項１〜４のいずれかに記載
の有機リン化合物の製造方法。5. The method according to claim 1, wherein the allyl halide compound is allyl bromide or allyl chloride.
る請求項２〜５のいずれかに記載の有機リン化合物の製
造方法。6. The method according to claim 2, wherein the solvent is toluene or xylene.
合物が、９，１０−ジヒドロ−９−オキサ−１０−ホス
ファフェナントレン−１０−オキサイドである請求項１
〜６のいずれかに記載の有機リン化合物の製造方法。7. The organic phosphorus compound represented by the general formula (1) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.
Method for producing an organic phosphorus compound according to any 6 of.
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|---|---|---|---|
| JP2001062167A JP2002265482A (en) | 2001-03-06 | 2001-03-06 | Method for producing organic phosphorous compound |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160643A (en) * | 2004-12-06 | 2006-06-22 | Nagase Chemtex Corp | METHOD FOR MANUFACTURING beta,gamma-UNSATURATED PHOSPHINIC ESTER |
| JP2010126460A (en) * | 2008-11-26 | 2010-06-10 | Nicca Chemical Co Ltd | Method for producing organophosphorus compound |
| JP2012527469A (en) * | 2009-05-19 | 2012-11-08 | アルベマール・コーポレーシヨン | DOPO derivative flame retardant |
| CN110938236A (en) * | 2019-12-13 | 2020-03-31 | 中国民用航空飞行学院 | DOPO functionalized molybdenum disulfide flame retardant and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5225727A (en) * | 1975-08-19 | 1977-02-25 | Ube Ind Ltd | Process for preparation of o-alkoxy-p-allylphenols |
| JP2000336261A (en) * | 1999-03-24 | 2000-12-05 | Asahi Chem Ind Co Ltd | Curable resin composition |
-
2001
- 2001-03-06 JP JP2001062167A patent/JP2002265482A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5225727A (en) * | 1975-08-19 | 1977-02-25 | Ube Ind Ltd | Process for preparation of o-alkoxy-p-allylphenols |
| JP2000336261A (en) * | 1999-03-24 | 2000-12-05 | Asahi Chem Ind Co Ltd | Curable resin composition |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006160643A (en) * | 2004-12-06 | 2006-06-22 | Nagase Chemtex Corp | METHOD FOR MANUFACTURING beta,gamma-UNSATURATED PHOSPHINIC ESTER |
| JP4517235B2 (en) * | 2004-12-06 | 2010-08-04 | ナガセケムテックス株式会社 | Process for producing β, γ-unsaturated phosphinic acid ester |
| JP2010126460A (en) * | 2008-11-26 | 2010-06-10 | Nicca Chemical Co Ltd | Method for producing organophosphorus compound |
| JP2012527469A (en) * | 2009-05-19 | 2012-11-08 | アルベマール・コーポレーシヨン | DOPO derivative flame retardant |
| CN110938236A (en) * | 2019-12-13 | 2020-03-31 | 中国民用航空飞行学院 | DOPO functionalized molybdenum disulfide flame retardant and preparation method thereof |
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