JPH1045779A - Chlorination of phenylphosphonic acid - Google Patents
Chlorination of phenylphosphonic acidInfo
- Publication number
- JPH1045779A JPH1045779A JP8200057A JP20005796A JPH1045779A JP H1045779 A JPH1045779 A JP H1045779A JP 8200057 A JP8200057 A JP 8200057A JP 20005796 A JP20005796 A JP 20005796A JP H1045779 A JPH1045779 A JP H1045779A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- phenylphosphonic
- chlorinating
- chloroimide
- phenylphosphonic acid
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリエステルやポ
リウレタン等の各種繊維の難燃剤及び又はその中間体と
して有用なクロロフェニルホスホン酸類を得るフェニル
ホスホン酸の塩素化方法に関する。TECHNICAL FIELD The present invention relates to a method for chlorinating phenylphosphonic acid to obtain chlorophenylphosphonic acids useful as flame retardants for various fibers such as polyester and polyurethane and / or intermediates thereof.
【０００２】[0002]
【従来の技術】カナディアン・ジャーナル・ケミスト
リ，６５巻，１７２９頁（１９８７年）〔Ｃａｎ．Ｊ．
Ｃｈｅｍ．，６５，１７２９（１９８７）〕に於て、無
水臭化ニッケルの存在下、クロロヨードベンゼン又はク
ロロブロモベンゼンとトリエチルフォスファイトを１８
０℃で反応させた後、濃塩酸で還流することにより、ハ
ロゲン化フェニルホスホン酸を得ている。2. Description of the Related Art Canadian Journal Chemistry, 65, 1729 (1987) [Can. J.
Chem. , 65, 1729 (1987)] in the presence of anhydrous nickel bromide in the presence of chloroiodobenzene or chlorobromobenzene and triethyl phosphite.
After reacting at 0 ° C., the mixture is refluxed with concentrated hydrochloric acid to obtain halogenated phenylphosphonic acid.
【０００３】[0003]
【化１】 Embedded image
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記製造法で
は、原料となるクロロヨードベンゼンやクロロブロモベ
ンゼンが高価であり、又、臭化ニッケルも使用後の処理
の点で好ましくなく、かつ高温を要する。さらに目的物
を得るためには、過剰量の濃塩酸による加水分解が必要
で２工程を要する。However, in the above-mentioned production method, chloroiodobenzene or chlorobromobenzene as a raw material is expensive, and nickel bromide is not preferable in terms of treatment after use, and high temperatures are required. It costs. Further, to obtain the desired product, hydrolysis with an excessive amount of concentrated hydrochloric acid is required, and two steps are required.
【０００５】本発明者は、この従来技術の問題を解決す
るために研究を行い本発明を完成した。本発明の目的
は、安価な原料から温和な条件下で１工程で目的とする
ハロゲン化フェニルホスホン酸類を得るフェニルホスホ
ン酸の塩素化方法を提供することにある。The present inventor has conducted research to solve the problem of the prior art and completed the present invention. An object of the present invention is to provide a method for chlorinating phenylphosphonic acid to obtain the desired halogenated phenylphosphonic acids in one step from inexpensive raw materials under mild conditions.
【０００６】[0006]
【課題を解決するための手段】即ち、本発明は、強酸を
溶媒として、フェニルホスホン酸を直接塩素化イソシア
ヌル酸で塩素化しクロロフェニルホスホン酸類を得るこ
とを特徴とするフェニルホスホン酸の塩素化方法に関す
る。That is, the present invention relates to a method for chlorinating phenylphosphonic acid, which comprises chlorinating phenylphosphonic acid directly with chlorinated isocyanuric acid using a strong acid as a solvent to obtain chlorophenylphosphonic acids. .
【０００７】[0007]
【発明の実施の形態】以下、更に本発明を詳細に説明す
る。原料のフェニルホスホン酸は、日産化学工業（株）
で製造している製品を使用することができる。Ｎ−クロ
ロイミド型クロル化剤としては、Ｎ−クロロサクシイミ
ド、Ｎ−クロログルタルイミド、１，３−ジクロロ−
５，５−ジメチルヒダントイン、トリクロロイソシアヌ
ル酸、ジクロロイソシアヌル酸ナトリウム塩及びジクロ
ロイソシアヌル酸カリウム塩を挙げることができる。こ
れらの中で特に好ましいものは、安価で入手容易なトリ
クロロイソシアヌル酸である。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The raw material phenylphosphonic acid is manufactured by Nissan Chemical Industries, Ltd.
Can be used. Examples of N-chloroimide type chlorinating agents include N-chlorosuccinimide, N-chloroglutarimide, 1,3-dichloro-
Examples include 5,5-dimethylhydantoin, trichloroisocyanuric acid, sodium dichloroisocyanurate and potassium dichloroisocyanurate. Of these, particularly preferred is trichloroisocyanuric acid, which is inexpensive and easily available.
【０００８】その使用量は、フェニルホスホン酸に塩素
原子１個入れる場合は、フェニルホスホン酸に対し有効
塩素元素当たり１〜１５倍が好ましく、塩素原子２個入
れる場合は、有効塩素元素当たり２〜２０倍が好まし
い。溶媒として用いる強酸としては、硫酸、発煙硫酸及
び三酸化硫黄等の無機強酸或いはトリフルオロ酢酸、メ
タンスルホン酸、エタンスルホン酸等の有機の強酸が挙
げられる。これらの酸は組み合わせて使うことも可能で
ある。反応収率及びコストの面で無機強酸が好ましい。
溶媒の使用量は、反応基質に対し１〜５０重量倍が可能
で有るが、より好ましくは、２〜１０重量倍が適切であ
る。When one chlorine atom is added to phenylphosphonic acid, it is preferably used in an amount of 1 to 15 times per available chlorine element with respect to phenylphosphonic acid. Twenty times is preferred. Examples of the strong acid used as the solvent include inorganic strong acids such as sulfuric acid, fuming sulfuric acid and sulfur trioxide and organic strong acids such as trifluoroacetic acid, methanesulfonic acid and ethanesulfonic acid. These acids can be used in combination. In terms of reaction yield and cost, strong inorganic acids are preferred.
The amount of the solvent used can be 1 to 50 times by weight of the reaction substrate, but more preferably 2 to 10 times by weight.
【０００９】反応温度は、２０〜１８０℃間が、特に
は、３０〜１５０℃が好ましく、更には、塩素原子１個
入れる場合は、５０〜１００℃が好ましく、塩素原子２
個入れる場合は８０〜１５０℃が好ましい。反応時間
は、液体クロマトグラフィーによる反応液の分析により
決定することができる。The reaction temperature is preferably from 20 to 180 ° C., particularly preferably from 30 to 150 ° C., more preferably from 50 to 100 ° C. when one chlorine atom is added.
In the case of individual pieces, 80 to 150 ° C. is preferable. The reaction time can be determined by analyzing the reaction solution by liquid chromatography.
【００１０】反応は、常圧でも加圧でも可能であり、ま
た回分式でも連続式でも行う事ができる。反応後、反応
液を水で希釈した後有機溶媒等で抽出することにより生
成物を分離することができる。得られた生成物は、再結
晶法等で精製することができる。以下実施例によって本
発明をさらに具体的に説明するが、本発明はこれらによ
って限定されるものではない。The reaction can be carried out under normal pressure or under pressure, and can be carried out batchwise or continuously. After the reaction, the product can be separated by diluting the reaction solution with water and extracting it with an organic solvent or the like. The obtained product can be purified by a recrystallization method or the like. Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto.
【００１１】[0011]
〔実施例１〕フェニルホスホン酸０．７９ｇ（５ミリモ
ル）、トリクロロイソシアヌル酸（有効塩素量９０％）
０．５６ｇ（２．２ミリモル）及び９７％硫酸５ｇを５
０ｍｌ反応フラスコに仕込み、６０℃で４時間撹拌し
た。[Example 1] 0.79 g (5 mmol) of phenylphosphonic acid, trichloroisocyanuric acid (effective chlorine amount 90%)
0.56 g (2.2 mmol) and 5 g of 97% sulfuric acid
A 0 ml reaction flask was charged and stirred at 60 ° C. for 4 hours.
【００１２】冷却後氷に反応液を滴下した。濾過により
析出した結晶を除いた後、濾液に酢酸エチルを添加し抽
出した。この酢酸エチル溶液を濃縮、乾燥すると結晶
１．２ｇが得られた。この結晶を液体クロマトグラフィ
ーで分析すると８１．８％の純度であった。この結晶を
酢酸エチルとヘプタンの混合液で再結晶を繰り返し、純
度９３．１％の結晶０．６ｇを得た。この結晶の分析結
果は、以下の通りであった。After cooling, the reaction solution was dropped on ice. After removing the crystals precipitated by filtration, ethyl acetate was added to the filtrate and extracted. The ethyl acetate solution was concentrated and dried to obtain 1.2 g of crystals. The crystals were analyzed by liquid chromatography to be 81.8% pure. The crystals were repeatedly recrystallized with a mixed solution of ethyl acetate and heptane to obtain 0.6 g of crystals having a purity of 93.1%. The analysis results of the crystals were as follows.
【００１３】ＭＡＳＳ（ｍ／ｅ（％））：１９２（Ｍ
+ ，２８），１７３（３），１６３（９），１３９
（９），１２８（１００），１１１（１０），９４
（８），７５（３０），６５（２６），５０（２０）1 Ｈ−ＮＭＲ（ｄ6 −ＤＭＳＯ，δｐｐｍ）：７．７６
〜７．７０（２Ｈ，ｍ），７．６６〜７．６３（１Ｈ，
ｍ），７．６０〜７．５４（１Ｈ，ｍ） 以上から、主生成物は、３−クロロフェニルホスホン酸
（３−ＣＰＰと略記する。）であることを確認した。MASS (m / e (%)): 192 (M
+ , 28), 173 (3), 163 (9), 139
(9), 128 (100), 111 (10), 94
(8), 75 (30) , 65 (26), 50 (20) 1 H-NMR (d 6 -DMSO, δppm): 7.76
７7.70 (2H, m), 7.66 to 7.63 (1H,
m), 7.60 to 7.54 (1H, m) From the above, it was confirmed that the main product was 3-chlorophenylphosphonic acid (abbreviated as 3-CPP).
【００１４】〔実施例２〕実施例１に於て、トリクロロ
イソシアヌル酸０．８６ｇ（３．４ミリモル）、反応温
度１４０℃とした他は同様に反応させた後、後処理を行
った。酢酸エチルで抽出、濃縮後乾燥して得られた結晶
は、１．３ｇで液体クロマトグラフィーでの純度は９
０．１％であった。Example 2 A reaction was carried out in the same manner as in Example 1 except that 0.86 g (3.4 mmol) of trichloroisocyanuric acid was used and the reaction temperature was 140 ° C., followed by post-treatment. The crystals obtained by extraction with ethyl acetate, concentration and drying were 1.3 g and had a purity by liquid chromatography of 9 g.
0.1%.
【００１５】この結晶を酢酸エチルとヘプタンの混合液
で再結晶を繰り返し、純度９６．６％の結晶０．７ｇを
得た。この結晶の分析結果は以下の通りであった。 ＭＡＳＳ（ｍ／ｅ（％））：２２７（Ｍ+ ，２０），１
９３（７０），１７５（３０），１６４（１００），１
４７（２２），１３０（４８），１１１（４８），９３
（５２），７６（９０）1 Ｈ−ＮＭＲ（ｄ6 −ＤＭＳＯ，δｐｐｍ）：７．８８
〜７．８１（１Ｈ，ｍ），７．６７〜７．５８（２Ｈ，
ｍ） 以上から、主生成物は、３，５−ジクロロフェニルホス
ホン酸（３，５−ＤＣＰＰと略記する。）であることを
確認した。The crystals were repeatedly recrystallized with a mixture of ethyl acetate and heptane to obtain 0.7 g of crystals having a purity of 96.6%. The analysis results of the crystals were as follows. MASS (m / e (%)): 227 (M + , 20), 1
93 (70), 175 (30), 164 (100), 1
47 (22), 130 (48), 111 (48), 93
(52), 76 (90) 1 H-NMR (d 6 -DMSO, δppm): 7.88
-7.81 (1H, m), 7.67-7.58 (2H,
m) From the above, it was confirmed that the main product was 3,5-dichlorophenylphosphonic acid (abbreviated as 3,5-DCPP).
【００１６】〔実施例３〕実施例１に於て、トリクロロ
イソシアヌル酸を０．４７ｇ（１．９ミリモル）、反応
温度４５℃、反応時間９時間とした他は、同様に反応さ
せた。この反応液を液体クロマトグラフィーで分析した
結果、３−ＣＰＰが７１面積％で、３，５−ＤＣＰＰが
１３面積％であった。Example 3 A reaction was carried out in the same manner as in Example 1, except that 0.47 g (1.9 mmol) of trichloroisocyanuric acid was used, the reaction temperature was 45 ° C., and the reaction time was 9 hours. As a result of analyzing the reaction solution by liquid chromatography, 3-CPP was 71 area% and 3,5-DCPP was 13 area%.
【００１７】〔実施例４〕実施例１に於て、トリクロロ
イソシアヌル酸を０．７４ｇ（２．９ミリモル）、溶媒
を１０％発煙硫酸、反応温度を９５℃、さらに反応時間
を１時間に変えた他は同様に反応させた。この反応液を
液体クロマトグラフィーで分析した結果、３−ＣＰＰが
３２面積％で、３，５−ＤＣＰＰが６８面積％であっ
た。Example 4 In Example 1, 0.74 g (2.9 mmol) of trichloroisocyanuric acid, 10% fuming sulfuric acid as a solvent, a reaction temperature of 95 ° C., and a reaction time were changed to 1 hour. Others were similarly reacted. As a result of analyzing this reaction solution by liquid chromatography, 3-CPP was 32 area% and 3,5-DCPP was 68 area%.
【００１８】〔実施例５〕実施例１に於て、トリクロロ
イソシアヌル酸０．４３ｇ（１．７ミリモル）、反応温
度７０℃、さらに反応時間７時間とした他は同様に反応
させた。この反応液を液体クロマトグラフィーで分析し
た結果、未反応フェニルホスホン酸が１２．７面積％、
３−ＣＰＰが７６．８面積％及び３，５−ＤＣＰＰが
４．２面積％であった。Example 5 A reaction was carried out in the same manner as in Example 1 except that 0.43 g (1.7 mmol) of trichloroisocyanuric acid was used, the reaction temperature was 70 ° C., and the reaction time was 7 hours. As a result of analyzing this reaction solution by liquid chromatography, unreacted phenylphosphonic acid was 12.7 area%,
3-CPP was 76.8 area% and 3,5-DCPP was 4.2 area%.
Claims (3)
をＮ−クロロイミド型クロル化剤で塩素化しクロロフェ
ニルホスホン酸類を得ることを特徴とするフェニルホス
ホン酸の塩素化方法。1. A method for chlorinating phenylphosphonic acid, comprising chlorinating phenylphosphonic acid with an N-chloroimide type chlorinating agent using a strong acid as a solvent to obtain chlorophenylphosphonic acids.
ロロイソシアヌル酸、ジクロロイソシアヌル酸のナトリ
ウム塩或いはカリウム塩である請求項１記載のフェニル
ホスホン酸の塩素化方法。2. The method for chlorinating phenylphosphonic acid according to claim 1, wherein the N-chloroimide type chlorinating agent is a sodium or potassium salt of trichloroisocyanuric acid or dichloroisocyanuric acid.
中から選ばれた少なくとも一種の化合物である請求項１
又は２記載のフェニルホスホン酸の塩素化方法。3. The strong acid is at least one compound selected from sulfuric acid, fuming sulfuric acid and sulfur trioxide.
Or the chlorination method of phenylphosphonic acid according to 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20005796A JP3817782B2 (en) | 1996-07-30 | 1996-07-30 | Chlorination of phenylphosphonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20005796A JP3817782B2 (en) | 1996-07-30 | 1996-07-30 | Chlorination of phenylphosphonic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1045779A true JPH1045779A (en) | 1998-02-17 |
| JP3817782B2 JP3817782B2 (en) | 2006-09-06 |
Family
ID=16418126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20005796A Expired - Fee Related JP3817782B2 (en) | 1996-07-30 | 1996-07-30 | Chlorination of phenylphosphonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3817782B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111224165B (en) * | 2020-01-11 | 2023-02-10 | 山东理工大学 | Preparation method of flame-retardant lithium salt with high organic compatibility and composite flame-retardant electrolyte thereof |
-
1996
- 1996-07-30 JP JP20005796A patent/JP3817782B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3817782B2 (en) | 2006-09-06 |
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