JPH06247990A - New phosphoric diester polyvalent metal salt and its production - Google Patents
New phosphoric diester polyvalent metal salt and its productionInfo
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- JPH06247990A JPH06247990A JP24126493A JP24126493A JPH06247990A JP H06247990 A JPH06247990 A JP H06247990A JP 24126493 A JP24126493 A JP 24126493A JP 24126493 A JP24126493 A JP 24126493A JP H06247990 A JPH06247990 A JP H06247990A
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- polyvalent metal
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、油ゲル化能に優れた新
規リン酸ジエステル多価金属塩及びその製造法、並びに
該製造法に有用な新規リン酸ジエステル及びその塩、製
造法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phosphoric acid diester polyvalent metal salt having excellent oil gelling ability, a process for producing the same, and a novel phosphoric acid diester, a salt thereof and a process for producing the same.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
金属石鹸、デキストリン脂肪酸エステル、ジアルキルリ
ン酸エステル金属塩、有機変性ベントナイトは、その油
ゲル化能を活かして、化粧品のゲル基剤、Ｗ／Ｏ乳化安
定剤、顔料分散剤等に使用されている。2. Description of the Related Art Conventionally, the problems to be solved by the invention
Metal soaps, dextrin fatty acid esters, metal salts of dialkyl phosphates, and organically modified bentonites are used as gel bases for cosmetics, W / O emulsion stabilizers, pigment dispersants, etc. by utilizing their oil gelling ability. .
【０００３】しかしながら、これらのうち、金属石鹸、
デキストリン脂肪酸エステル、ジアルキルリン酸エステ
ル金属塩は、これらを加温して油に溶解した後、相転移
温度（Ｔｃ）以下に冷却すると、脆く固いゲルとなるた
め、指などで応力を与えると元の状態に復元しなくな
り、再び元の状態にもどすにはＴｃ以上に加熱しなけれ
ばならないという問題があった。そこで、十分なチキソ
トロピー性を得るため、アルキル鎖が分岐し鎖長が短
く、Ｔｃが室温以下のものが使用されているが、これら
もゲルの粘性が強く、曳糸性があるため使用性及び使用
感に難があった。また、有機変性ベントナイトは、油に
チキソトロピックなレオロジー特性を付与することがで
きるが、インターカレーションされている物質の油剤に
よる溶け出し、すなわち、安全性や、ソフトなゲルがで
きないといった問題があった。一方、シリコーン油のゲ
ル化に関しては、シリコーン系ゲル化剤が用いられてい
るが、これらはいずれも高価であるといった問題を有し
ていた。However, among these, metal soaps,
Dextrin fatty acid ester and dialkyl phosphoric acid ester metal salts become brittle and hard gel when they are dissolved in oil by heating them and then cooled to below the phase transition temperature (Tc). There was a problem that it was necessary to heat above Tc in order to return to the original state again without returning to the state of. Therefore, in order to obtain sufficient thixotropy, an alkyl chain is branched and the chain length is short and Tc at room temperature or less is used, but these are also viscous gels and have spinnability, so that the usability and It was difficult to use. In addition, organically modified bentonite can impart thixotropic rheological properties to oil, but there is a problem that the intercalated substance is dissolved by an oil agent, that is, safety and soft gel cannot be formed. It was On the other hand, for gelling silicone oil, silicone gelling agents have been used, but all of them have a problem that they are expensive.
【０００４】従って、油剤にチキソトロピックなレオロ
ジー特性を付与し、安全性が高く、透明で、使用感がよ
く、しかも曳糸性のないゲルを得ることができる、油ゲ
ル化剤として有用な化合物が望まれていた。Therefore, a compound useful as an oil gelling agent which imparts thixotropic rheological properties to an oily agent, is highly safe, is transparent, has a good feeling in use, and is free from spinnability. Was desired.
【０００５】[0005]
【課題を解決するための手段】かかる実情において、本
発明者らは鋭意研究を行った結果、後記一般式（１）で
表わされるリン酸ジエステル多価金属塩が、油剤にチキ
ソトロピックなレオロジー特性を付与し、安全性が高
く、透明で、使用感が良く、しかも曳糸性のないゲルを
安価で与え、更に油脂類、炭化水素類、シリコーン油等
の広範囲の油剤に適用し得ることを見出し、本発明を完
成した。Under such circumstances, as a result of intensive studies by the present inventors, the phosphoric acid diester polyvalent metal salt represented by the following general formula (1) has thixotropic rheological properties as an oil agent. It is possible to give a gel that is highly safe, transparent, has a good feeling of use, and has no spinnability at a low cost, and can be applied to a wide range of oils such as oils and fats, hydrocarbons and silicone oils. Heading, completed the present invention.
【０００６】すなわち、本発明は、一般式（１）で表わ
されるリン酸ジエステル多価金属塩及びその製造法を提
供するものである。That is, the present invention provides a phosphodiester polyvalent metal salt represented by the general formula (1) and a method for producing the same.
【０００７】[0007]
【化６】 [Chemical 6]
【０００８】（式中、Ｒ1 は炭素数１〜２０の直鎖又は
分岐鎖のアルキル基を示し、Ｒ2 及びＲ4 は同一又は異
なって、炭素数２〜３の直鎖又は分岐鎖のアルキレン基
を示し、Ｒ3 は炭素数３〜２０の直鎖又は炭素数５〜２
０の分岐鎖のアルキレン基を示し、Ａは−ＣＯＯ−又は
−Ｏ−を示し、ｘ及びｙは同一又は異なって、０〜１０
の整数を示し、Ｌは炭素数１〜４０の直鎖若しくは分岐
鎖のアルキル基又はR1-(OR2)x-A-R3-(OR4)y-（式中、Ｒ
1 、Ｒ2 、Ｒ3 、Ｒ4 、Ａ、ｘ及びｙは前記と同じ意味
を有する）を示し、Ｍは２価以上の多価金属イオンを示
し、ｍは多価金属イオンの原子価と同じ数を示す）(In the formula, R 1 represents a straight-chain or branched-chain alkyl group having 1 to 20 carbon atoms, R 2 and R 4 are the same or different, and are straight-chain or branched-chain groups having 2 to 3 carbon atoms. Represents an alkylene group, R 3 is a straight chain having 3 to 20 carbon atoms or 5 to 2 carbon atoms
0 represents a branched alkylene group, A represents —COO— or —O—, x and y are the same or different, and 0 to 10
Where L is a linear or branched alkyl group having 1 to 40 carbon atoms or R 1- (OR 2 ) x -AR 3- (OR 4 ) y- (wherein R is
1 , R 2 , R 3 , R 4 , A, x and y have the same meanings as described above), M represents a divalent or higher polyvalent metal ion, and m represents the valence of the polyvalent metal ion. Show the same number)
【０００９】このリン酸ジエステル多価金属塩（１）の
製造法において用いられる後記一般式（２）で表わされ
るリン酸ジエステルのうち、式中、Ｒ3 が炭素数７〜２
０の直鎖又は分岐鎖のアルキレン基のものは、新規化合
物である。従って、また本発明は、一般式（２′）で表
わされるリン酸ジエステル及びその塩、並びにその製造
法を提供するものである。Among the phosphoric acid diesters represented by the following general formula (2) used in the method for producing the phosphoric acid diester polyvalent metal salt (1), in the formula, R 3 has 7 to 2 carbon atoms.
Those with 0 straight or branched chain alkylene groups are novel compounds. Therefore, the present invention also provides a phosphodiester represented by the general formula (2 ') and a salt thereof, and a method for producing the same.
【００１０】[0010]
【化７】 [Chemical 7]
【００１１】（式中、Ｒ1 、Ｒ2 、Ｒ4 、Ａ、ｘ及びｙ
は前記と同じ意味を示し、Ｒ3′は炭素数７〜２０の直
鎖又は分岐鎖のアルキレン基を示し、Ｌ′は炭素数１〜
４０の直鎖若しくは分岐鎖のアルキル基又はR1-(OR2)x-
A-R3′-(OR4)y-（式中、Ｒ1 、Ｒ2 、Ｒ3′、Ｒ4 、
Ａ、ｘ及びｙは前記と同じ意味を有する）を示し、Ｘは
水素原子、アルカリ金属、アンモニウム、アルキルアミ
ン又はアルカノールアミンを示す）(Wherein R 1 , R 2 , R 4 , A, x and y
Represents the same meaning as described above, R 3 ′ represents a linear or branched alkylene group having 7 to 20 carbon atoms, and L ′ represents 1 to 1 carbon atom.
40 linear or branched alkyl groups or R 1- (OR 2 ) x-
AR 3 ′-(OR 4 ) y − (wherein R 1 , R 2 , R 3 ′, R 4 ,
A, x and y have the same meaning as described above), and X represents a hydrogen atom, an alkali metal, ammonium, an alkylamine or an alkanolamine).
【００１２】本発明のリン酸ジエステル多価金属塩は、
前記一般式（１）で表わされるものであり、式中、Ｒ1
で示される炭素数１〜２０の直鎖又は分岐鎖のアルキル
基としては、例えばメチル、エチル、ｎ−プロピル、イ
ソプロピル、ｎ−ブチル、イソブチル、ｔ−ブチル、ペ
ンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシ
ル、ウンデシル、ドデシル、トリデシル、テトラデシ
ル、ペンタデシル、ヘキサデシル、ヘプタデシル、オク
タデシル、ノナデシル、エイコサデシル、ネオペンチ
ル、２−エチルヘキシル、３，３−ジメチルブチル、
１，１，３，３−テトラメチルブチル、３，７−ジメチ
ルオクチル、３，７−ジメチルオクタン−３−イル、２
−ヘキシルデシル、２−ヘプチルウンデシル、２−オク
チルドデシル、３，７，１１−トリメチルドデシル、
３，７，１１，１５−テトラメチルヘキサデシル、３，
５，５−トリメチルヘキシル、２，３，４−トリメチル
ペンタン−３−イル、２，３，４，６，６−ペンタメチ
ルヘプタン−３−イル、イソステアリル等の基が挙げら
れる。The phosphoric acid diester polyvalent metal salt of the present invention is
It is represented by the general formula (1), wherein R 1
Examples of the linear or branched alkyl group having 1 to 20 carbon atoms represented by are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl. , Decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosadecyl, neopentyl, 2-ethylhexyl, 3,3-dimethylbutyl,
1,1,3,3-tetramethylbutyl, 3,7-dimethyloctyl, 3,7-dimethyloctane-3-yl, 2
-Hexyldecyl, 2-heptylundecyl, 2-octyldodecyl, 3,7,11-trimethyldodecyl,
3,7,11,15-tetramethylhexadecyl, 3,
Examples include groups such as 5,5-trimethylhexyl, 2,3,4-trimethylpentan-3-yl, 2,3,4,6,6-pentamethylheptan-3-yl, and isostearyl.
【００１３】Ｒ2 及びＲ4 で示される炭素数２〜３の直
鎖又は分岐鎖のアルキレン基としては、例えばエチレン
基、メチルエチレン基等が挙げられる。また、Ｒ3 で示
される炭素数３〜２０の直鎖又は炭素数５〜２０の分岐
鎖のアルキレン基としては、例えばトリメチレン、テト
ラメチレン、ペンタメチレン、ヘキサメチレン、ヘプタ
メチレン、オクタメチレン、ノナメチレン、デカメチレ
ン、ウンデカメチレン、ドデカメチレン、トリデカメチ
レン、テトラデカメチレン、ペンタデカメチレン、ヘキ
サデカメチレン、ヘプタデカメチレン、オクタデカメチ
レン、ノナデカメチレン、エイコサデカメチレン、３−
メチルペンタン−１，５−ジイル、２−エチルヘキサン
−１，６−ジイル、３，７−ジメチルオクタン−１，８
−ジイル、３，７−ジメチルオクタン−３，８−ジイル
等の基が挙げられる。Examples of the linear or branched alkylene group having 2 to 3 carbon atoms represented by R 2 and R 4 include ethylene group and methylethylene group. In addition, examples of the straight chain having 3 to 20 carbon atoms or the branched chain having 5 to 20 carbon atoms represented by R 3 include, for example, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, Decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene, octadecamethylene, nonadecamethylene, eicosadecamethylene, 3-
Methyl pentane-1,5-diyl, 2-ethylhexane-1,6-diyl, 3,7-dimethyloctane-1,8
Examples thereof include groups such as -diyl and 3,7-dimethyloctane-3,8-diyl.
【００１４】更に、Ｌのうち、炭素数１〜４０の直鎖又
は分岐鎖のアルキル基としては、前記炭素数１〜２０の
アルキル基のほか、２−ドデシルヘキサデシル基、２−
テトラデシルオクタデシル基、２−ヘキサデシルエイコ
シル基等が挙げられる。Further, as the straight-chain or branched-chain alkyl group having 1 to 40 carbon atoms in L, in addition to the alkyl group having 1 to 20 carbon atoms, 2-dodecylhexadecyl group, 2-
Examples thereof include tetradecyl octadecyl group and 2-hexadecyl eicosyl group.
【００１５】また、Ｍで示される２価以上の多価金属イ
オンとしては、例えばＣａ2+、Ａｌ 3+、Ｆｅ3+、Ｆ
ｅ2+、Ｂａ2+、Ｔｉ4+、Ｚｎ2+、Ｚｒ4+等が挙げられ、
特にＣａ 2+、Ａｌ3+が好ましい。The polyvalent metal represented by M is a polyvalent metal having a valence of 2 or more.
When turned on, for example, Ca2+, Al 3+, Fe3+, F
e2+, Ba2+, Ti4+, Zn2+, Zr4+Etc.,
Especially Ca 2+, Al3+Is preferred.
【００１６】これらのリン酸ジエステル多価金属塩
（１）は、例えば一般式（２）These phosphoric acid diester polyvalent metal salts (1) are represented by the general formula (2), for example.
【００１７】[0017]
【化８】 [Chemical 8]
【００１８】（式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ａ、
Ｌ、ｘ及びｙは前記と同じ意味を示し、Ｘは水素原子、
アルカリ金属、アンモニウム、アルキルアミン又はアル
カノールアミンを示す）で表わされるリン酸ジエステル
又はその塩に、一般式（３）：(Wherein R 1 , R 2 , R 3 , R 4 , A,
L, x and y have the same meanings as described above, X is a hydrogen atom,
Alkali metal, ammonium, alkylamine or alkanolamine) is represented by the general formula (3):
【化９】MpYq （３） （式中、Ｍは前記と同じ意味を示し、Ｙは有機又は無機
アニオンを示し、ｐはＹ、ｑはＭの原子価に対応する整
数で、最少比のものを示す）で表わされる多価金属塩を
反応させることにより製造される。## STR00009 ## M p Y q (3) (In the formula, M has the same meaning as described above, Y represents an organic or inorganic anion, p is Y, and q is an integer corresponding to the valence of M. It is produced by reacting a polyvalent metal salt represented by the ratio).
【００１９】ここで用いられるリン酸ジエステル又はそ
の塩（２）は、例えば一般式（４）： R1-(OR2)x-A-R3-(OR4)y-OH （４） （式中、Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ａ、ｘ及びｙは前記
と同じ意味を示す）で表わされるアルコール、又は一般
式（４）で表わされるアルコールと一般式（５）：The phosphoric acid diester or salt (2) thereof used herein is, for example, represented by the general formula (4): R 1- (OR 2 ) x -AR 3- (OR 4 ) y -OH (4) (wherein , R 1 , R 2 , R 3 , R 4 , A, x and y have the same meanings as described above), or the alcohol represented by the general formula (4) and the general formula (5):
【化１０】L″-OH （５） （式中、Ｌ″は炭素数１〜４０の直鎖又は分岐鎖のアル
キル基を示す）で表わされるアルコールの混合物に、リ
ン酸化剤を反応させ、次いで所望により１価の塩基で中
和することにより製造される。Embedded image A mixture of alcohols represented by L ″ -OH (5) (wherein L ″ represents a linear or branched alkyl group having 1 to 40 carbon atoms) is reacted with a phosphorylating agent, Then, if desired, it is produced by neutralizing with a monovalent base.
【００２０】一般式（４）で表わされるアルコールは、
例えば一般式（６）で表わされるアルコール又は一般式
（７）で表わされるカルボン酸The alcohol represented by the general formula (4) is
For example, an alcohol represented by the general formula (6) or a carboxylic acid represented by the general formula (7)
【００２１】[0021]
【化１１】 [Chemical 11]
【００２２】（式中、Ｒ1 、Ｒ2 及びｘは前記と同じ意
味を示す）に、塩化チオニル、臭化チオニル、三塩化リ
ン、五塩化リン、三臭化リン、五臭化リン、塩化水素、
臭化水素等のハロゲン化剤を反応させて対応するハロゲ
ン化物とし、これにトルエン、キシレン等の不活性溶媒
中、水酸化ナトリウム等の塩基の存在下に、過剰のジオ
ール（８）：(Wherein R 1 , R 2 and x have the same meaning as described above), thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide, chloride hydrogen,
A corresponding halogenating agent is reacted with a halogenating agent such as hydrogen bromide to obtain a corresponding halide, and the excess diol (8) is added to the corresponding halide in the presence of a base such as sodium hydroxide in an inert solvent such as toluene or xylene.
【化１２】HO-R3-(OR4)y-OH （８） （式中、Ｒ3 、Ｒ4 及びｙは前記と同じ意味を示す）を
反応させることにより、得ることができる。It can be obtained by reacting HO—R 3 — (OR 4 ) y —OH (8) (wherein R 3 , R 4 and y have the same meanings as described above).
【００２３】これらのアルコールと反応させるリン酸化
剤としては、例えば五酸化リン；オキシ塩化リン等のオ
キシハロゲン化リン；ポリリン酸などが挙げられる。Examples of the phosphorylating agent to be reacted with these alcohols include phosphorus pentoxide; phosphorus oxyhalides such as phosphorus oxychloride; and polyphosphoric acid.
【００２４】リン酸化剤として五酸化リンを用いる場合
には、アルコール（４）又はアルコール（４）とアルコ
ール（５）の混合物に、１〜０．１モル倍、好ましくは
０．５〜０．２モル倍の五酸化リンを５０〜９０℃で３
〜１５時間反応させればよい。When phosphorus pentoxide is used as the phosphorylating agent, it is added to the alcohol (4) or the mixture of the alcohol (4) and the alcohol (5) in an amount of 1 to 0.1 mole times, preferably 0.5 to 0. 2 mole times phosphorus pentoxide at 50-90 ℃ 3
The reaction may be performed for up to 15 hours.
【００２５】また、リン酸化剤としてオキシハロゲン化
リンを用いる場合には、アルコール（４）又はアルコー
ル（４）とアルコール（５）の混合物に、１〜０．１モ
ル倍、好ましくは０．６〜０．４モル倍のオキシハロゲ
ン化リンを、−６０℃〜３０℃、好ましくは−４０℃〜
１０℃で１〜３６時間反応させればよい。この際、必要
に応じて、テトラヒドロフラン、エーテル等の溶媒やト
リエチルアミン、ピリジン等の３級アミン類を添加する
ことができる。反応終了後、オキシハロゲン化リンに対
し、１〜２倍当量の水を加え、オキシハロゲン化リンを
完全に加水分解することにより、リン酸ジエステル
（２）を製造することができる。When phosphorus oxyhalide is used as the phosphorylating agent, it is added to the alcohol (4) or the mixture of the alcohol (4) and the alcohol (5) in an amount of 1 to 0.1 mole times, preferably 0.6. ~ 0.4 mol times phosphorus oxyhalide, -60 ℃ ~ 30 ℃, preferably -40 ℃ ~
The reaction may be performed at 10 ° C for 1 to 36 hours. At this time, if necessary, a solvent such as tetrahydrofuran or ether or a tertiary amine such as triethylamine or pyridine can be added. After completion of the reaction, the phosphoric acid diester (2) can be produced by adding 1 to 2 equivalents of water to the phosphorus oxyhalide to completely hydrolyze the phosphorus oxyhalide.
【００２６】なお、この反応においては目的とするリン
酸ジエステルの他にピロ体リン酸モノエステル等も副生
するため、より高純度のリン酸ジエステルが必要な場合
には、例えば特公平１−２９１９５号記載の方法に従っ
て、反応混合物に水を加えて酸性状態で加水分解を行
い、次いで塩基を加えて加水分解を行ってリン酸モノエ
ステルをオルトリン酸及び有機ヒドロキシ化合物に変換
し、これらを除去すればよい。In addition, in this reaction, a pyromeric phosphoric acid monoester and the like are by-produced in addition to the desired phosphoric acid diester. Therefore, when a higher-purity phosphoric acid diester is required, for example, Japanese Patent Publication No. No. 29195, water is added to the reaction mixture for hydrolysis in an acidic state, and then a base is added for hydrolysis to convert the phosphoric acid monoester to orthophosphoric acid and an organic hydroxy compound and remove them. do it.
【００２７】また、アルコール（４）とアルコール
（５）の混合物を用いる場合には、まずアルコール
（４）を用いてリン酸モノエステル化を行い、次いでア
ルコール（５）を反応させてリン酸ジエステルとしても
よい。When a mixture of alcohol (4) and alcohol (5) is used, phosphoric acid monoesterification is first carried out using alcohol (4), and then alcohol (5) is reacted to form phosphoric acid diester. May be
【００２８】得られたリン酸ジエステルは、所望により
１価の塩基で中和することにより、リン酸ジエステル塩
とすることができる。１価の塩基としては、例えばアル
カリ金属の水酸化物又は炭酸塩、アンモニア、アルキル
アミン、アルカノールアミン等が挙げられ、具体的には
水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、
炭酸水素ナトリウム、アンモニア、トリエチルアミン、
トリエタノールアミン等が挙げられる。The obtained phosphoric acid diester can be converted to a phosphoric acid diester salt by optionally neutralizing with a monovalent base. Examples of the monovalent base include hydroxides or carbonates of alkali metals, ammonia, alkylamines, alkanolamines and the like, and specifically, sodium hydroxide, potassium hydroxide, sodium carbonate,
Sodium hydrogen carbonate, ammonia, triethylamine,
Examples include triethanolamine.
【００２９】このようにして得られるリン酸ジエステル
又はその塩（２）と反応させる多価金属塩（３）として
は、例えば酢酸カルシウム、酢酸アルミニウム、酢酸バ
リウム、塩化カルシウム、炭酸カルシウム、硫酸アルミ
ニウム、塩化アルミニウム、塩化第２鉄、酢酸マグネシ
ウム、硝酸アルミニウム、過塩素酸第２鉄等が挙げら
れ、特に酢酸カルシウム、酢酸アルミニウム、塩化カル
シウム、塩化アルミニウムが好ましい。Examples of the polyvalent metal salt (3) to be reacted with the thus obtained phosphoric acid diester or its salt (2) include, for example, calcium acetate, aluminum acetate, barium acetate, calcium chloride, calcium carbonate, aluminum sulfate, Aluminum chloride, ferric chloride, magnesium acetate, aluminum nitrate, ferric perchlorate and the like can be mentioned, with calcium acetate, aluminum acetate, calcium chloride and aluminum chloride being particularly preferred.
【００３０】反応は、例えばリン酸ジエステル又はその
塩（２）に対し１／１０〜１０当量、好ましくは１〜２
当量の多価金属塩（３）を、１〜１００重量倍、好まし
くは２〜２０重量倍の極性溶媒中、２０〜８０℃で１〜
６時間攪拌混合させることにより行われる。極性溶媒と
しては特に制限されないが、リン酸ジエステル又はその
塩（２）を溶解し得るものが好ましく、例えば水、テト
ラヒドロフラン、メチルアルコール、エチルアルコー
ル、アセトン等が挙げられ、１種又は２種以上を組合わ
せて使用することができる。なお、反応終了後、目的物
が結晶として析出している場合には、その結晶を濾別す
ればよく、また目的物が溶媒に溶解している場合には、
ヘキサン、エーテル、酢酸エチル等の溶媒を添加して抽
出するかあるいはアセトン等の溶媒を添加して沈殿させ
ればよい。The reaction is, for example, 1/10 to 10 equivalents, preferably 1 to 2 with respect to the phosphoric acid diester or its salt (2).
1 to 100 times by weight, preferably 2 to 20 times by weight, of a polar solvent in an equivalent amount of the polyvalent metal salt (3) at 20 to 80 ° C.
It is carried out by stirring and mixing for 6 hours. The polar solvent is not particularly limited, but those capable of dissolving the phosphoric acid diester or its salt (2) are preferable, and examples thereof include water, tetrahydrofuran, methyl alcohol, ethyl alcohol, acetone, and the like, and one or more kinds thereof can be used. It can be used in combination. After the completion of the reaction, if the desired product is precipitated as crystals, the crystals may be filtered out, and if the desired product is dissolved in a solvent,
Extraction may be performed by adding a solvent such as hexane, ether or ethyl acetate, or precipitation may be performed by adding a solvent such as acetone.
【００３１】このようにして得られる本発明化合物
（１）の好ましい具体例としては、次の化合物（１−
１）〜（１−３３）が挙げられる。Specific preferred examples of the compound (1) of the present invention thus obtained include the following compound (1-
1) to (1-33).
【００３２】[0032]
【化１３】 [Chemical 13]
【００３３】[0033]
【化１４】 [Chemical 14]
【００３４】[0034]
【化１５】 [Chemical 15]
【００３５】[0035]
【化１６】 [Chemical 16]
【００３６】[0036]
【化１７】 [Chemical 17]
【００３７】本発明のリン酸ジエステル多価金属塩
（１）は広範囲の油剤をゲル化することができ、かかる
油剤としては、オリーブ油、ツバキ油等の油脂類；流動
パラフィン、ワセリン、スクワラン等の炭化水素類；ラ
ウリン酸、ステアリン酸等の脂肪酸類；ステアリルアル
コール、イソステアリルアルコール等の高級アルコール
類；ミリスチン酸イソプロピル、パルミチン酸イソプロ
ピル等のエステル類；ポリシロキサン構造を有するシリ
コーン油等が挙げられる。また、本発明のリン酸ジエス
テル多価金属塩のうち、特に一般式（１）中、Ｒ 1 又は
Ｌ′で示されるアルキル基の末端の少なくとも１個が
（ＣＨ3）3Ｃ−であるものは、シリコーン油類のゲル化
能に優れている。Phosphoric acid diester polyvalent metal salt of the present invention
(1) can gel a wide range of oil agents,
Oils and fats such as olive oil and camellia oil;
Hydrocarbons such as paraffin, petrolatum and squalane; LA
Fatty acids such as uric acid and stearic acid; stearyl al
Higher alcohols such as coal and isostearyl alcohol
Kind; Isopropyl myristate, Isopro palmitate
Esters such as pills; Sili with polysiloxane structure
Corn oil etc. are mentioned. In addition, the phosphate of the present invention
Among the polyvalent metal salts of ter, especially in the general formula (1), R 1Or
At least one of the terminals of the alkyl group represented by L'is
(CH3)3C- is a gelling agent for silicone oils
It is excellent in Noh.
【００３８】[0038]
【発明の効果】本発明のリン酸ジエステル多価金属塩
（１）は、油剤にチキソトロピックなレオロジー特性を
付与し、安全性が高く、透明で、使用感が良く、しかも
曳糸性のないゲルを安価で与え、更にシリコーン油を含
んだ広範囲の油剤に適用し得るものである。また、本発
明のリン酸ジエステル及びその塩（２）を用いれば、リ
ン酸ジエステル多価金属塩（１）を効率よく製造するこ
とができる。The phosphoric acid diester polyvalent metal salt (1) of the present invention imparts thixotropic rheological properties to an oil agent, has high safety, is transparent, has a good feeling in use, and has no spinnability. The gel is inexpensive and can be applied to a wide range of oils including silicone oil. Further, by using the phosphoric acid diester and the salt thereof (2) of the present invention, the phosphoric acid diester polyvalent metal salt (1) can be efficiently produced.
【００３９】[0039]
【実施例】次に、実施例を挙げて本発明を更に説明する
が、本発明はこれら実施例に限定されるものではない。EXAMPLES Next, the present invention will be further described with reference to examples, but the present invention is not limited to these examples.
【００４０】実施例１ （１）１，６−ヘキサンジオール３５０ｇ（３．００mo
l ）、水酸化ナトリウム５０ｇ（１．２５mol ）及びキ
シレン１ｌを、ディーンスタークトラップを取り付けた
３ｌ四つ口フラスコに入れ、窒素導入下、１００℃まで
昇温した。次に、２−エチルヘキシルブロマイド１２０
ｇ（０．６２mol ）を滴下した後、水が溜出しなくなる
まで還流した。反応終了後、トルエン１ｌで希釈し、希
塩酸、水、飽和重曹水、水、飽和食塩水で洗浄した後、
無水硫酸マグネシウムで乾燥した。濾過後、溶媒を留去
した後、減圧蒸留により精製し、１２５ｇのモノエーテ
ル体を無色オイルとして得た。ＧＬＣ分析により純度は
９７％であった。２００ＭＨｚ 1Ｈ−ＮＭＲにてδ＝
１．５に水酸基、δ＝１．２−１．５，３．３，３．３
５，３．６５にメチン及びメチレン基、δ＝０．８５−
０．９５にメチル基のプロトンシグナルを認め、モノエ
ーテル体の生成を確認した。Example 1 (1) 350 g (3.00 mol) of 1,6-hexanediol
l), 50 g (1.25 mol) of sodium hydroxide and 1 l of xylene were placed in a 3 l four-necked flask equipped with a Dean Stark trap, and the temperature was raised to 100 ° C. under introduction of nitrogen. Next, 2-ethylhexyl bromide 120
g (0.62 mol) was added dropwise, and the mixture was refluxed until water stopped distilling. After completion of the reaction, the reaction mixture was diluted with 1 l of toluene, washed with diluted hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, water and saturated saline,
It was dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by vacuum distillation to obtain 125 g of a monoether body as a colorless oil. The purity was 97% by GLC analysis. Δ = at 200 MHz 1 H-NMR
Hydroxyl group at 1.5, δ = 1.2-1.5, 3.3, 3.3
5,3.65 methine and methylene groups, δ = 0.85-
A methyl group proton signal was observed at 0.95, confirming the formation of a monoether body.
【００４１】（２）（１）で得られたモノエーテル体１
１５ｇ（０．５０mol ）を３００ml四つ口フラスコに入
れ、攪拌しながら、五酸化リン２４．０ｇ（０．１６７
mol ）を反応温度を７０℃以下に保ちながら加えた。次
に反応温度を７５〜８５℃に保ち、そのまま４時間攪拌
を続けた後、水１０mlを加え、更に４時間攪拌した。こ
れを１ｌオートクレーブに移し、水酸化ナトリウム１
５．３ｇを１５％水溶液として加え、攪拌しながら１４
５℃まで昇温し、そのまま７時間攪拌した。ジャケット
付きの１ｌ三つ口フラスコに移し、１０％硫酸水溶液３
５０mlを加え、６０℃まで昇温し、そのまま１時間攪拌
した。その後、室温で静置し、分層してきた有機層を水
洗した。溶媒を留去し得られた残渣を減圧蒸留により精
製し、５０ｇの黄色オイルとしてリン酸ジエステル（２
ａ）を得た。31Ｐ−ＮＭＲより純度は９９％、２００Ｍ
Ｈｚ 1Ｈ−ＮＭＲ（溶媒ＣＤＣｌ3、ＴＭＳ標準）よ
り、δ＝１．２−１．５，３．３，３．３５，４．０５
にメチン及びメチレン基、δ＝０．８５−０．９５にメ
チル基のプロトンシグナルを認め、リン酸ジエステルの
生成を確認した。(2) Monoether body 1 obtained in (1)
15 g (0.50 mol) was placed in a 300 ml four-necked flask, and while stirring, 24.0 g (0.167) of phosphorus pentoxide was added.
mol) was added while keeping the reaction temperature below 70 ° C. Next, the reaction temperature was maintained at 75 to 85 ° C., and the stirring was continued for 4 hours as it was, then 10 ml of water was added, and the mixture was further stirred for 4 hours. Transfer this to a 1 liter autoclave and add sodium hydroxide 1
5.3 g was added as a 15% aqueous solution, and stirred to 14
The temperature was raised to 5 ° C., and the mixture was stirred as it was for 7 hours. Transfer to a jacketed 1 liter 3-necked flask and add 10% sulfuric acid solution 3
50 ml was added, the temperature was raised to 60 ° C., and stirring was continued for 1 hour. Then, the mixture was allowed to stand at room temperature and the separated organic layer was washed with water. The solvent was distilled off and the obtained residue was purified by distillation under reduced pressure to obtain 50 g of a phosphoric diester (2
a) was obtained. Purity 99%, 200M from 31 P-NMR
From Hz 1 H-NMR (solvent CDCl 3 , TMS standard), δ = 1.2-1.5, 3.3, 3.35, 4.05.
The formation of phosphodiester was confirmed by observing the proton signals of the methine and methylene groups at 1, and the methyl group at δ = 0.85-0.95.
【００４２】[0042]
【化１８】 [Chemical 18]
【００４３】（３）（２）で得られたリン酸ジエステル
（２ａ）５０ｇにエタノール１００ml、酢酸カルシウム
１６ｇ及び水１００mlを加え、６０℃で２時間攪拌し、
室温まで冷却した後、ヘキサン２００mlを加えて分層さ
せた。有機層を水洗した後、溶媒を留去し、アセトンで
再沈させた。４３ｇの白色固体としてリン酸ジエステル
カルシウム塩（１−１）を得た。31Ｐ−ＮＭＲより純度
は９９％、２００ＭＨｚ 1Ｈ−ＮＭＲより、δ＝１．２
−１．５，３．３，３．３５，３．８５にメチン及びメ
チレン基、δ＝０．８５−０．９５にメチル基のプロト
ンシグナルを認め、リン酸ジエステルカルシウム塩の生
成を確認した。(3) To 50 g of the phosphoric acid diester (2a) obtained in (2), 100 ml of ethanol, 16 g of calcium acetate and 100 ml of water were added, and the mixture was stirred at 60 ° C. for 2 hours,
After cooling to room temperature, 200 ml of hexane was added to separate the layers. After the organic layer was washed with water, the solvent was distilled off and reprecipitated with acetone. 43 g of a phosphoric acid diester calcium salt (1-1) was obtained as a white solid. Purity is 99% from 31 P-NMR, and δ = 1.2 from 200 MHz 1 H-NMR.
Proton signals of methine and methylene groups at −1.5, 3.3, 3.35, and 3.85 and methyl groups at δ = 0.85−0.95 were observed, and formation of phosphodiester calcium salt was confirmed. .
【００４４】実施例２ リン酸ジエステル（２ａ）７５ｇにエタノール１００m
l、酢酸アルミニウム３０ｇ及び水１００mlを加え、６
０℃で２時間攪拌し、室温まで冷却した後、析出してき
た固体を濾過により集め、７０ｇの白色固体としてリン
酸ジエステルアルミニウム塩（１−２）を得た。31Ｐ−
ＮＭＲより純度は９９％、２００ＭＨｚ 1Ｈ−ＮＭＲよ
り、δ＝１．２−１．６，３．３，３．３５，３．８に
メチン及びメチレン基、δ＝０．８５−０．９にメチル
基のプロトンシグナルを認め、リン酸ジエステルアルミ
ニウム塩の生成を確認した。Example 2 75 g of phosphoric acid diester (2a) was added with 100 m of ethanol.
l, 30 g of aluminum acetate and 100 ml of water were added, and 6
After stirring at 0 ° C. for 2 hours and cooling to room temperature, the precipitated solid was collected by filtration to obtain 70 g of a phosphoric acid diester aluminum salt (1-2) as a white solid. 31 P-
Purity is 99% from NMR, and methine and methylene groups are found at δ = 1.2-1.6, 3.3, 3.35, 3.8 from δ = 0.85-0.9 from 200 MHz 1 H-NMR. A proton signal of a methyl group was observed at the position, and formation of phosphoric acid diester aluminum salt was confirmed.
【００４５】実施例３ （１）１，９−ノナンジオール５００ｇ（３．０４mol
）、水酸化ナトリウム５０ｇ（１．２５mol ）及びキ
シレン１ｌを、ディーンスタークトラップを取り付けた
３ｌ四つ口フラスコに入れ、窒素導入下、１００℃まで
昇温した。次に、２−エチルヘキシルブロマイド１２０
ｇ（０．６２mol ）を滴下した後、水が溜出しなくなる
まで還流した。反応終了後、トルエン１ｌで希釈し、析
出してきた結晶を濾過により除き、母液を希塩酸、水、
飽和重曹水、水、飽和食塩水で洗浄した後、無水硫酸マ
グネシウムで乾燥した。濾過後、溶媒を留去し、減圧蒸
留により精製して、１３５ｇのモノエーテル体を無色オ
イルとして得た。ＧＬＣ分析により純度は９９％であっ
た。２００ＭＨｚ 1Ｈ−ＮＭＲにてδ＝１．５に水酸
基、δ＝１．２−１．６，３．３，３．３５，３．６５
にメチン及びメチレン基、δ＝０．８５−０．９５にメ
チル基のプロトンシグナルを認め、モノエーテル体の生
成を確認した。Example 3 (1) 500 g (3.04 mol) of 1,9-nonanediol
), 50 g (1.25 mol) of sodium hydroxide and 1 l of xylene were placed in a 3 l four-necked flask equipped with a Dean Stark trap, and the temperature was raised to 100 ° C. under introduction of nitrogen. Next, 2-ethylhexyl bromide 120
g (0.62 mol) was added dropwise, and the mixture was refluxed until water stopped distilling. After completion of the reaction, the reaction mixture was diluted with 1 l of toluene, the precipitated crystals were removed by filtration, and the mother liquor was diluted with dilute hydrochloric acid, water,
The extract was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by vacuum distillation to obtain 135 g of a monoether body as a colorless oil. The purity was 99% by GLC analysis. Hydroxyl group at δ = 1.5 in 200 MHz 1 H-NMR, δ = 1.2-1.6, 3.3, 3.35, 3.65.
Proton signals of methine and methylene groups were observed at 1, and a methyl group at δ = 0.85-0.95, and the formation of a monoether was confirmed.
【００４６】（２）（１）で得られたモノエーテル体１
３６ｇ（０．５０mol ）を３００ml四つ口フラスコに入
れ、攪拌しながら、五酸化リン２４．０ｇ（０．１６７
mol ）を、反応温度を７０℃以下に保ちながら加えた。
次に反応温度を７５〜８５℃に保ち、そのまま４時間攪
拌を続けた後、水１０mlを加え、更に４時間攪拌した。
これを１ｌオートクレーブに移し、水酸化ナトリウム１
５．３ｇを１５％水溶液として加え、攪拌しながら１４
５℃まで昇温し、そのまま７時間攪拌した。ジャケット
付きの１ｌ三つ口フラスコに移し、１０％硫酸水溶液３
５０mlを加え、６０℃まで昇温し、そのまま１時間攪拌
した。その後、室温で静置し、分層してきた有機層を水
洗した。溶媒を留去し得られた残渣を減圧蒸留により精
製し、６０ｇの黄色オイルとしてリン酸ジエステル（２
ｂ）を得た。31Ｐ−ＮＭＲより純度は９９％、２００Ｍ
Ｈｚ 1Ｈ−ＮＭＲ（溶媒ＣＤＣｌ3、ＴＭＳ標準）よ
り、δ＝１．２−１．５，３．３，３．３５，４．０５
にメチン及びメチレン基、δ＝０．８５−０．９５にメ
チル基のプロトンシグナルを認め、リン酸ジエステルの
生成を確認した。(2) Monoether body 1 obtained in (1)
36 g (0.50 mol) was placed in a 300 ml four-necked flask, and while stirring, 24.0 g (0.167) of phosphorus pentoxide.
mol) was added keeping the reaction temperature below 70 ° C.
Next, the reaction temperature was maintained at 75 to 85 ° C., and the stirring was continued for 4 hours as it was, then 10 ml of water was added, and the mixture was further stirred for 4 hours.
Transfer this to a 1 liter autoclave and add sodium hydroxide 1
5.3 g was added as a 15% aqueous solution, and stirred to 14
The temperature was raised to 5 ° C., and the mixture was stirred as it was for 7 hours. Transfer to a jacketed 1 liter 3-necked flask and add 10% sulfuric acid solution 3
50 ml was added, the temperature was raised to 60 ° C., and stirring was continued for 1 hour. Then, the mixture was allowed to stand at room temperature and the separated organic layer was washed with water. The solvent was distilled off and the obtained residue was purified by distillation under reduced pressure to give 60 g of a phosphoric acid diester (2
b) was obtained. Purity 99%, 200M from 31 P-NMR
From Hz 1 H-NMR (solvent CDCl 3 , TMS standard), δ = 1.2-1.5, 3.3, 3.35, 4.05.
The formation of phosphodiester was confirmed by observing the proton signals of the methine and methylene groups at 1, and the methyl group at δ = 0.85-0.95.
【００４７】[0047]
【化１９】 [Chemical 19]
【００４８】（３）（２）で得られたリン酸ジエステル
（２ｂ）をエタノールに溶解し、１０％水酸化ナトリウ
ム水溶液で当量中和した。溶媒を留去し、乾燥させる
と、黄白色固体としてリン酸ジエステルナトリウム塩
（２ｃ）を得た。31Ｐ−ＮＭＲより純度は９９％、２０
０ＭＨｚ 1Ｈ−ＮＭＲより、δ＝１．２−１．５，３．
３，３．３５，３．９５にメチン及びメチレン基、δ＝
０．８５−０．９５にメチル基のプロトンシグナルを認
め、リン酸ジエステルナトリウム塩の生成を確認した。(3) The phosphoric acid diester (2b) obtained in (2) was dissolved in ethanol and neutralized in an equivalent amount with a 10% aqueous sodium hydroxide solution. The solvent was evaporated, and the residue was dried to give phosphodiester sodium salt (2c) as a pale yellow solid. Purity is 99% from 31 P-NMR, 20
From 0 MHz 1 H-NMR, δ = 1.2-1.5, 3.
Methine and methylene groups at 3, 3.35 and 3.95, δ =
A methyl group proton signal was observed at 0.85-0.95, and the formation of phosphodiester sodium salt was confirmed.
【００４９】[0049]
【化２０】 [Chemical 20]
【００５０】実施例４ （１）１，９−ノナンジオール５００ｇ（３．０４mol
）、水酸化ナトリウム５０ｇ（１．２５mol ）及びキ
シレン１ｌを、ディーンスタークトラップを取り付けた
３ｌ四つ口フラスコに入れ、窒素導入下、１００℃まで
昇温した。次に、２−エチルヘキシルブロマイド１２０
ｇ（０．６２mol ）を滴下した後、水が溜出しなくなる
まで還流した。反応終了後、トルエン１ｌで希釈し、析
出してきた結晶を濾過により除き、母液を希塩酸、水、
飽和重曹水、水、飽和食塩水で洗浄した後、無水硫酸マ
グネシウムで乾燥した。濾過後、溶媒を留去し、減圧蒸
留により精製して、１３５ｇのモノエーテル体を無色オ
イルとして得た。ＧＬＣ分析により純度は９９％であっ
た。２００ＭＨｚ 1Ｈ−ＮＭＲにてδ＝１．５に水酸
基、δ＝１．２−１．６，３．３，３．３５，３．６５
にメチン及びメチレン基、δ＝０．８５−０．９５にメ
チル基のプロトンシグナルを認め、モノエーテル体の生
成を確認した。Example 4 (1) 500 g (3.04 mol) of 1,9-nonanediol
), 50 g (1.25 mol) of sodium hydroxide and 1 l of xylene were placed in a 3 l four-necked flask equipped with a Dean Stark trap, and the temperature was raised to 100 ° C. under introduction of nitrogen. Next, 2-ethylhexyl bromide 120
g (0.62 mol) was added dropwise, and the mixture was refluxed until water stopped distilling. After completion of the reaction, the reaction mixture was diluted with 1 l of toluene, the precipitated crystals were removed by filtration, and the mother liquor was diluted with dilute hydrochloric acid, water,
The extract was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by vacuum distillation to obtain 135 g of a monoether body as a colorless oil. The purity was 99% by GLC analysis. Hydroxyl group at δ = 1.5 in 200 MHz 1 H-NMR, δ = 1.2-1.6, 3.3, 3.35, 3.65.
Proton signals of methine and methylene groups were observed at 1, and a methyl group at δ = 0.85-0.95, and the formation of a monoether was confirmed.
【００５１】（２）（１）で得られたモノエーテル体１
５０ｇ（０．５１５mol ）を３００ml四つ口フラスコに
入れ、攪拌しながら、五酸化リン２５．０ｇ（０．１７
２mol）を、反応温度を７０℃以下に保ちながら加え
た。次に反応温度を７５〜８５℃に保ち、そのまま４時
間攪拌を続けた後、水１７．５mlを加え、更に４時間攪
拌した。これを１ｌオートクレーブに移し、水酸化ナト
リウム１０．５ｇを１５％水溶液として加え、攪拌しな
がら、１４５℃まで昇温し、そのまま７時間攪拌した。
ジャケット付きの１ｌ三つ口フラスコに移し、１０％硫
酸水溶液３５０mlを加え、６０℃まで昇温し、そのまま
１時間攪拌した。その後、室温で静置し、分層してきた
有機層を水洗した。これにエタノール１００ml、酢酸カ
ルシウム２０ｇ及び水１００mlを加え、６０℃で２時間
攪拌し、室温まで冷却した後、ヘキサン２００mlを加え
て分層させた。有機層を水洗した後、溶媒を留去し、ア
セトンで再沈させた。析出してきた固体を濾過により集
め、乾燥させ、６２ｇの白色固体としてリン酸ジエステ
ルカルシウム塩（１−３）を得た。31Ｐ−ＮＭＲより純
度は９９％、２００ＭＨｚ 1Ｈ−ＮＭＲより、δ＝１．
２−１．６，３．３，３．３５，３．８５にメチン及び
メチレン基、δ＝０．８５−０．９５にメチル基のプロ
トンシグナルを認め、リン酸ジエステルカルシウム塩の
生成を確認した。(2) Monoether body 1 obtained in (1)
50 g (0.515 mol) was placed in a 300 ml four-necked flask, and 25.0 g (0.17
2 mol) was added while keeping the reaction temperature below 70 ° C. Next, the reaction temperature was maintained at 75 to 85 ° C., and the stirring was continued for 4 hours as it was, then 17.5 ml of water was added, and the mixture was further stirred for 4 hours. This was transferred to a 1 liter autoclave, 10.5 g of sodium hydroxide was added as a 15% aqueous solution, the temperature was raised to 145 ° C. with stirring, and the mixture was stirred for 7 hours as it was.
The mixture was transferred to a jacketed 1-liter three-necked flask, 350 ml of a 10% sulfuric acid aqueous solution was added, the temperature was raised to 60 ° C., and the mixture was stirred for 1 hour as it was. Then, the mixture was allowed to stand at room temperature and the separated organic layer was washed with water. To this, 100 ml of ethanol, 20 g of calcium acetate and 100 ml of water were added, and the mixture was stirred at 60 ° C. for 2 hours, cooled to room temperature, and 200 ml of hexane was added to separate layers. After the organic layer was washed with water, the solvent was distilled off and reprecipitated with acetone. The precipitated solid was collected by filtration and dried to obtain 62 g of a phosphoric acid diester calcium salt (1-3) as a white solid. 31 P-NMR than purity 99%, from 200MHz 1 H-NMR, δ = 1.
Proton signals of methine and methylene groups at 2-1.6, 3.3, 3.35, and 3.85 and methyl groups at δ = 0.85-0.95 were observed, confirming the formation of phosphodiester calcium salt. did.
【００５２】実施例５ （１）１，６−ヘキサンジオール３５０ｇ（３．００mo
l ）、水酸化ナトリウム５０ｇ（１．２５mol ）及びキ
シレン１ｌを、ディーンスタークトラップを取り付けた
３ｌ四つ口フラスコに入れ、窒素導入下、１００℃まで
昇温した。次に、３，７−ジメチルオクチルクロライド
１１１ｇ（０．６３１mol ）を滴下した後、水が溜出し
なくなるまで還流した。反応終了後、トルエン１ｌで希
釈し、希塩酸、水、飽和重曹水、水、飽和食塩水で洗浄
後、無水硫酸マグネシウムで乾燥した。濾過後、溶媒を
留去した後、減圧蒸留により精製し、１２５ｇのモノエ
ーテル体を無色オイルとして得た。ＧＬＣ分析により純
度は９８％であった。また、２００ＭＨｚ 1Ｈ−ＮＭＲ
にてδ＝１．５に水酸基、δ＝１．２−１．５，３．
３，３．３５，３．６５にメチン及びメチレン基、δ＝
０．８５−０．９にメチル基のプロトンシグナルを認
め、モノエーテル体の生成を確認した。Example 5 (1) 1,6-hexanediol 350 g (3.00 mol)
l), 50 g (1.25 mol) of sodium hydroxide and 1 l of xylene were placed in a 3 l four-necked flask equipped with a Dean Stark trap, and the temperature was raised to 100 ° C. under introduction of nitrogen. Next, 111 g (0.631 mol) of 3,7-dimethyloctyl chloride was added dropwise, and the mixture was refluxed until water stopped distilling. After completion of the reaction, the reaction mixture was diluted with 1 l of toluene, washed with diluted hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, water and saturated saline, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by vacuum distillation to obtain 125 g of a monoether body as a colorless oil. The purity was 98% by GLC analysis. In addition, 200 MHz 1 H-NMR
At δ = 1.5, δ = 1.2-1.5, 3.
Methine and methylene groups at 3, 3.35 and 3.65, δ =
A methyl group proton signal was observed at 0.85-0.9 to confirm the formation of a monoether body.
【００５３】（２）モノエーテル体１１０．４ｇ（０．
４２８mol ）を３００ml四つ口フラスコに入れ、攪拌し
ながら、五酸化リン２１．１ｇ（０．１４９mol ）を、
反応温度を７０℃以下に保ちながら加えた。次に反応温
度を７５〜８５に保ち、そのまま４時間攪拌を続けた
後、水１３mlを加え、更に４時間攪拌した。これを１ｌ
オートクレーブに移し、水酸化ナトリウム１１．９ｇを
１０％水溶液として加え、攪拌しながら１４５℃まで昇
温し、そのまま８時間攪拌した。ジャケット付きの１ｌ
三つ口付に移し、１０％硫酸水溶液３５０mlを加え、６
０℃まで昇温し、そのまま１時間攪拌した。その後、室
温で静置し、分層してきた有機層を水洗した。これにエ
タノール２００ml、酢酸カルシウム５０ｇ及び水２００
mlを加え、６０℃で２時間攪拌し、室温まで冷却した
後、ヘキサン３００mlを加えて分層させた。有機層を水
洗した後、溶媒を留去し、アセトンで再沈させた。析出
してきた固体を濾過により集め、乾燥させ、５３ｇの白
色固体としてリン酸ジエステルカルシウム塩（１−４）
を得た。31Ｐ−ＮＭＲより純度は９８％、２００ＭＨｚ
1Ｈ−ＮＭＲより、δ＝１．２−１．６，３．３，３．
３５，３．８５にメチン及びメチレン基、δ＝０．８５
−０．９にメチル基のプロトンシグナルを認め、リン酸
ジエステルカルシウム塩の生成を確認した。(2) Monoether body 110.4 g (0.
428 mol) in a 300 ml four-necked flask and, with stirring, 21.1 g (0.149 mol) of phosphorus pentoxide,
It was added while maintaining the reaction temperature at 70 ° C or lower. Next, the reaction temperature was maintained at 75 to 85, and the stirring was continued for 4 hours, 13 ml of water was added, and the mixture was further stirred for 4 hours. 1 l of this
The mixture was transferred to an autoclave, 11.9 g of sodium hydroxide was added as a 10% aqueous solution, the temperature was raised to 145 ° C. with stirring, and the mixture was stirred as it was for 8 hours. 1l with jacket
Transfer to 3 necks and add 350 ml of 10% sulfuric acid aqueous solution.
The temperature was raised to 0 ° C., and stirring was continued for 1 hour. Then, the mixture was allowed to stand at room temperature and the separated organic layer was washed with water. 200 ml of ethanol, 50 g of calcium acetate and 200 water
ml was added, the mixture was stirred at 60 ° C. for 2 hours, cooled to room temperature, and 300 ml of hexane was added to separate layers. After the organic layer was washed with water, the solvent was distilled off and reprecipitated with acetone. The precipitated solid was collected by filtration and dried to give 53 g of a phosphoric acid diester calcium salt (1-4) as a white solid.
Got Purity is 98% from 31 P-NMR, 200 MHz
From 1 H-NMR, δ = 1.2-1.6, 3.3, 3.
35, 3.85 with methine and methylene group, δ = 0.85
A proton signal of a methyl group was observed at −0.9, which confirmed the formation of phosphodiester calcium salt.
【００５４】実施例６ （１）２−（２−エチルヘキシロキシ）エタノール５０
０ｇ（２．８１mol ）及び塩化チオニル５００ｇを２ｌ
四つ口フラスコに入れ、２時間加熱還流した。その後、
減圧蒸留により、５１０ｇの２−（２−エチルヘキシロ
キシ）エチルクロライドを無色オイルとして得た。Example 6 (1) 2- (2-Ethylhexyloxy) ethanol 50
2 g of 0 g (2.81 mol) and 500 g of thionyl chloride
The mixture was placed in a four-necked flask and heated under reflux for 2 hours. afterwards,
Distillation under reduced pressure gave 510 g of 2- (2-ethylhexyloxy) ethyl chloride as a colorless oil.
【００５５】（２）１，９−ノナンジオール５００ｇ
（３．０４mol ）、水酸化ナトリウム５０ｇ（１．２５
mol ）及びキシレン１ｌを、ディーンスタークトラップ
を取り付けた３ｌ四つ口フラスコに入れ、窒素導入下、
１００℃まで昇温した。次に、２−（２−エチルヘキシ
ロキシ）エチルクロライド１２０ｇ（０．６２mol ）を
滴下した後、水が溜出しなくなるまで還流した。反応終
了後、トルエン１ｌで希釈し、析出してきた結晶を濾過
により除き、母液を希塩酸、水、飽和重曹水、水、飽和
食塩水で洗浄後、無水硫酸マグネシウムで乾燥した。濾
過後、溶媒を留去した後、減圧蒸留により精製し、１４
０ｇのモノエーテル体を無色オイルとして得た。ＧＬＣ
分析により純度は９８％であった。２００ＭＨｚ 1Ｈ−
ＮＭＲにてδ＝１．２−１．５，３．３５，３．４５，
３．５５，３．６５にメチン及びメチレン基、δ＝０．
８５−０．９にメチル基のプロトンシグナルを認め、モ
ノエーテル体の生成を確認した。(2) 500 g of 1,9-nonanediol
(3.04 mol), sodium hydroxide 50 g (1.25
mol) and 1 liter of xylene were placed in a 3 liter four-necked flask equipped with a Dean Stark trap, and nitrogen was introduced.
The temperature was raised to 100 ° C. Next, 120 g (0.62 mol) of 2- (2-ethylhexyloxy) ethyl chloride was added dropwise, and the mixture was refluxed until water did not distill. After completion of the reaction, the reaction mixture was diluted with 1 l of toluene, the precipitated crystals were removed by filtration, the mother liquor was washed with diluted hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by vacuum distillation.
0 g of monoether body was obtained as a colorless oil. GLC
The purity was 98% by analysis. 200MHz 1 H-
Δ = 1.2-1.5, 3.35, 3.45 by NMR,
Methine and methylene groups at 3.55 and 3.65, δ = 0.
A methyl group proton signal was observed at 85-0.9 to confirm the formation of a monoether body.
【００５６】（３）モノエーテル体１４０ｇ（０．５０
７mol ）を３００ml四つ口フラスコに入れ、攪拌しなが
ら、五酸化リン２５．０ｇ（０．１７２mol ）を、反応
温度を７０℃以下に保ちながら加えた。次に反応温度を
７５〜８５℃に保ち、そのまま４時間攪拌を続けた後、
水１７．５mlを加え、更に４時間攪拌した。これを１ｌ
オートクレーブに移し、水酸化ナトリウム１０．５ｇを
１５％水溶液として加え、攪拌しながら、１４５℃まで
昇温し、そのまま７時間攪拌した。ジャケット付きの１
ｌ三つ口フラスコに移し、１０％硫酸水溶液３５０mlを
加え、６０℃まで昇温し、そのまま１時間攪拌した。そ
の後、室温まで冷却し、エーテルを加えて分層させた。
分層してきた有機層を更に水洗した後、溶媒を留去し
た。これにエタノール１００ml、酢酸カルシウム２０
ｇ、水１００mlを加え、６０℃で２時間攪拌し、室温ま
で冷却した後、エーテル３００mlを加えて分層させた。
有機層を水洗した後、溶媒を留去し、アセトンで再沈さ
せた。析出してきた固体を濾過により集め、乾燥させ、
６０ｇの白色固体としてリン酸ジエステルカルシウム塩
（１−５）を得た。31Ｐ−ＮＭＲより純度は９９％、２
００ＭＨｚ 1Ｈ−ＮＭＲより、δ＝１．２−１．６，
３．３５，３．４５，３．５５，３．８５にメチン及び
メチレン基、δ＝０．８５−０．９にメチル基のプロト
ンシグナルを認め、リン酸ジエステルカルシウム塩の生
成を確認した。(3) 140 g of monoether (0.50
7 mol) was placed in a 300 ml four-necked flask, and 25.0 g (0.172 mol) of phosphorus pentoxide was added with stirring while maintaining the reaction temperature at 70 ° C or lower. Next, after maintaining the reaction temperature at 75 to 85 ° C. and continuing stirring for 4 hours,
Water (17.5 ml) was added, and the mixture was further stirred for 4 hours. 1 l of this
The mixture was transferred to an autoclave, 10.5 g of sodium hydroxide was added as a 15% aqueous solution, the temperature was raised to 145 ° C. with stirring, and the mixture was stirred as it was for 7 hours. 1 with jacket
The mixture was transferred to a 1-necked 3-necked flask, 350 ml of a 10% sulfuric acid aqueous solution was added, the temperature was raised to 60 ° C., and the mixture was stirred for 1 hour. After that, it was cooled to room temperature, and ether was added to separate the layers.
The separated organic layer was washed with water and the solvent was distilled off. Add 100 ml of ethanol and 20 calcium acetate.
g and 100 ml of water were added, the mixture was stirred at 60 ° C. for 2 hours, cooled to room temperature, and 300 ml of ether was added to separate layers.
After the organic layer was washed with water, the solvent was distilled off and reprecipitated with acetone. The precipitated solid is collected by filtration, dried,
60 g of phosphoric acid diester calcium salt (1-5) was obtained as a white solid. Purity is 99% from 31 P-NMR, 2
From 00 MHz 1 H-NMR, δ = 1.2-1.6,
Proton signals of methine and methylene groups were observed at 3.35, 3.45, 3.55 and 3.85, and methyl groups were observed at δ = 0.85-0.9, confirming the formation of phosphodiester calcium salt.
【００５７】実施例７ （１）２，３，４−トリメチルペンタン−３−カルボン
酸５００ｇ（３．０９mol ）、塩化チオニル５００ｇを
２時間加熱還流した。その後、減圧蒸留により、５１８
ｇの２，３，４−トリメチルペンタン−３−カルボニル
クロライドを無色オイルとして得た。Example 7 (1) 500 g (3.09 mol) of 2,3,4-trimethylpentane-3-carboxylic acid and 500 g of thionyl chloride were heated under reflux for 2 hours. Then, by vacuum distillation, 518
g of 2,3,4-trimethylpentane-3-carbonyl chloride was obtained as a colorless oil.
【００５８】（２）１，６−ヘキサンジオール１００ｇ
（０．８５mol ）を５００mlナスフラスコに入れ、トリ
エチルアミン７０ｇ、ベンゼン５０mlに溶解した。２，
３，４−トリメチルペンタン−３−カルボニルクロライ
ド５０ｇ（０．２９mol ）をベンゼン５０mlに溶解して
滴下し、２晩攪拌した。水１００mlを加えた後、エーテ
ル抽出した。有機層を希塩酸、水、飽和重曹水、水、飽
和食塩水で洗浄後、無水硫酸マグネシウムで乾燥した。
濾過後、溶媒を留去した後、減圧蒸留により精製し、５
１．５ｇのモノエステル体を無色オイルとして得た。Ｇ
ＬＣ分析により純度は９７％であった。２００ＭＨｚ 1
Ｈ−ＮＭＲにてδ＝２．０に水酸基、δ＝１．２−１．
５，３．７，４．０にメチン及びメチレン基、δ＝０．
８５−０．９５にメチル基のプロトンシグナルを認め、
モノエステル体の生成を確認した。(2) 100 g of 1,6-hexanediol
(0.85 mol) was placed in a 500 ml eggplant-shaped flask and dissolved in 70 g of triethylamine and 50 ml of benzene. Two
50 g (0.29 mol) of 3,4-trimethylpentane-3-carbonyl chloride was dissolved in 50 ml of benzene and added dropwise, and the mixture was stirred for 2 nights. After adding 100 ml of water, the mixture was extracted with ether. The organic layer was washed with diluted hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous magnesium sulfate.
After filtration, the solvent was distilled off, and the residue was purified by vacuum distillation.
1.5 g of monoester was obtained as a colorless oil. G
The purity was 97% by LC analysis. 200MHz 1
By H-NMR, hydroxyl group at δ = 2.0, δ = 1.2-1.
5, 3.7, 4.0 at methine and methylene groups, δ = 0.
A proton signal of a methyl group was observed at 85-0.95,
The production of monoester was confirmed.
【００５９】（３）モノエステル体４０ｇ（０．１５５
mol ）を２００ml四つ口フラスコに入れ、攪拌しなが
ら、五酸化リン７．８０ｇ（０．５１５mol ）を、反応
温度７０℃以下に保ちながら加えた。次に反応温度を７
５〜８５℃に保ち、そのまま４時間攪拌を続けた後、水
５．０mlを加え、更に８時間攪拌した。これを５００ml
オートクレーブに移し、水酸化ナトリウム４．１ｇを１
０％水溶液として加え、攪拌しながら１４５℃まで昇温
し、そのまま７時間攪拌した。ジャケット付きの１ｌ三
つ口フラスコに移し、１０％硫酸水溶液１０５mlを加
え、６０℃まで昇温し、そのまま２時間攪拌した。その
後、室温まで冷却し、エーテルを加えて分層させた。分
層してきた有機層を水洗した後、溶媒を留去した。これ
にエタノール１００ml、酢酸カルシウム１０ｇ及び水１
００mlを加え、６０℃で２時間攪拌し、室温まで冷却し
た後、エーテル１００mlを加えて分層させた。有機層を
水洗した後、溶媒を留去し、アセトンで再沈させた。析
出してきた固体を濾過により集め、乾燥させ、１２ｇの
白色固体としてリン酸ジエステルカルシウム塩（１−
６）を得た。31Ｐ−ＮＭＲより純度は９９％、２００Ｍ
Ｈｚ 1Ｈ−ＮＭＲより、δ＝１．２−１．５，３．８
５，４．０にメチン及びメチレン基、δ＝０．８５−
０．９にメチル基のプロトンシグナルを認め、リン酸ジ
エステルカルシウム塩の生成を確認した。(3) 40 g of monoester (0.155
mol) was placed in a 200 ml four-necked flask, and 7.80 g (0.515 mol) of phosphorus pentoxide was added with stirring while maintaining the reaction temperature at 70 ° C or lower. Then set the reaction temperature to 7
After maintaining the temperature at 5-85 ° C and continuing stirring for 4 hours, 5.0 ml of water was added, and the mixture was further stirred for 8 hours. 500 ml of this
Transfer to an autoclave and add 4.1 g of sodium hydroxide to 1
The mixture was added as a 0% aqueous solution, heated to 145 ° C. with stirring, and stirred as it was for 7 hours. The mixture was transferred to a jacketed 1 liter three-necked flask, 105 ml of 10% sulfuric acid aqueous solution was added, the temperature was raised to 60 ° C., and the mixture was stirred for 2 hours as it was. After that, it was cooled to room temperature, and ether was added to separate the layers. The separated organic layer was washed with water and the solvent was distilled off. Add 100 ml of ethanol, 10 g of calcium acetate and 1 part of water.
After adding 00 ml and stirring at 60 ° C. for 2 hours and cooling to room temperature, 100 ml of ether was added to separate layers. After the organic layer was washed with water, the solvent was distilled off and reprecipitated with acetone. The precipitated solid was collected by filtration and dried, and 12 g of a phosphoric acid diester calcium salt (1-
6) was obtained. Purity 99%, 200M from 31 P-NMR
From Hz 1 H-NMR, δ = 1.2-1.5, 3.8
Methine and methylene group at 5,4.0, δ = 0.85-
A methyl group proton signal was observed at 0.9, confirming the formation of the phosphodiester calcium salt.
【００６０】実施例８ （１）１，９−ノナンジオール５００ｇ（３．０４mol
）、水酸化ナトリウム５０ｇ（１．２５mol ）及びキ
シレン１ｌを、ディーンスタークトラップを取り付けた
３ｌ四つ口フラスコに入れ、窒素導入下、１００℃まで
昇温した。次に、２−エチルヘキシルブロマイド１２０
ｇ（０．６２mol ）を滴下した後、水が溜出しなくなる
まで還流した。反応終了後、トルエン１ｌで希釈し、析
出してきた結晶を濾過により除き、母液を希塩酸、水、
飽和重曹水、水、飽和食塩水で洗浄後、無水硫酸マグネ
シウムで乾燥した。濾過後、溶媒を留去した後、減圧蒸
留により精製し、１３５ｇのモノエーテル体を無色オイ
ルとして得た。ＧＬＣ分析により純度は９９％であっ
た。また、２００ＭＨｚ 1Ｈ−ＮＭＲにてδ＝１．５に
水酸基、δ＝１．２−１．６，３．３，３．３５，３．
６５にメチン及びメチレン基、δ＝０．８５−０．９５
にメチル基のプロトンシグナルを認め、モノエーテル体
の生成を確認した。Example 8 (1) 500 g (3.04 mol) of 1,9-nonanediol
), 50 g (1.25 mol) of sodium hydroxide and 1 l of xylene were placed in a 3 l four-necked flask equipped with a Dean Stark trap, and the temperature was raised to 100 ° C. under introduction of nitrogen. Next, 2-ethylhexyl bromide 120
g (0.62 mol) was added dropwise, and the mixture was refluxed until water stopped distilling. After completion of the reaction, the reaction mixture was diluted with 1 l of toluene, the precipitated crystals were removed by filtration, and the mother liquor was diluted with dilute hydrochloric acid, water,
The extract was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off and the residue was purified by vacuum distillation to obtain 135 g of a monoether body as a colorless oil. The purity was 99% by GLC analysis. In 200 MHz 1 H-NMR, δ = 1.5 is a hydroxyl group, and δ = 1.2-1.6, 3.3, 3.35, 3.
Methine and methylene group at 65, δ = 0.85-0.95
A proton signal of a methyl group was observed at the position, and formation of a monoether body was confirmed.
【００６１】（２）モノエーテル体１５０ｇ（０．５１
５mol ）を３００ml四つ口フラスコに入れ、攪拌しなが
ら、五酸化リン２５．０ｇ（０．１７２mol ）を、反応
温度を７０℃以下に保ちながら加えた。次に反応温度を
７５〜８５℃に保ち、そのまま４時間攪拌を続けた後、
水１７．５mlを加え、更に４時間攪拌した。これを１ｌ
オートクレーブに移し、水酸化ナトリウム１０．５ｇを
１５％水溶液として加え、攪拌しながら１４５℃まで昇
温し、そのまま７時間攪拌した。ジャケット付きの１ｌ
三つ口フラスコに移し、１０％硫酸水溶液３５０mlを加
え、６０℃まで昇温し、そのまま１時間攪拌した。その
後、室温で静置し、分層してきた有機層を更に水洗し
た。これにエタノール１００ml、酢酸アルミニウム３０
ｇ及び水１００mlを加え、６０℃で２時間攪拌し、室温
まで冷却した後、析出してきた固体を濾過により集め、
乾燥させ、７０ｇの白色固体としてリン酸ジエステルア
ルミニウム塩（１−９）を得た。31Ｐ−ＮＭＲより純度
は９９％、２００ＭＨｚ 1Ｈ−ＮＭＲより、δ＝１．２
−１．６，３．３，３．３５，３．８にメチン及びメチ
レン基、δ＝０．８５−０．９にメチル基のプロトンシ
グナルを認め、リン酸ジエステルアルミニウム塩の生成
を確認した。(2) Monoether 150 g (0.51)
5 mol) was put in a 300 ml four-necked flask, and 25.0 g (0.172 mol) of phosphorus pentoxide was added with stirring while keeping the reaction temperature at 70 ° C or lower. Next, after maintaining the reaction temperature at 75 to 85 ° C. and continuing stirring for 4 hours,
Water (17.5 ml) was added, and the mixture was further stirred for 4 hours. 1 l of this
The mixture was transferred to an autoclave, 10.5 g of sodium hydroxide was added as a 15% aqueous solution, the temperature was raised to 145 ° C. with stirring, and the mixture was stirred as it was for 7 hours. 1l with jacket
The mixture was transferred to a three-necked flask, 350 ml of a 10% aqueous sulfuric acid solution was added, the temperature was raised to 60 ° C., and the mixture was stirred for 1 hour as it was. Then, the mixture was allowed to stand at room temperature, and the separated organic layer was further washed with water. 100 ml of ethanol and 30 parts of aluminum acetate
g and 100 ml of water were added, the mixture was stirred at 60 ° C. for 2 hours, cooled to room temperature, and the precipitated solid was collected by filtration.
Dried to obtain 70 g of phosphoric acid diester aluminum salt (1-9) as a white solid. Purity is 99% from 31 P-NMR, and δ = 1.2 from 200 MHz 1 H-NMR.
Proton signals of methine and methylene groups at -1.6, 3.3, 3.35 and 3.8, and methyl group at δ = 0.85-0.9 were observed, and formation of phosphodiester aluminum salt was confirmed. .
【００６２】実施例９ （１）１，９−ノナンジオール５００ｇ（３．０４mol
）、水酸化ナトリウム５０ｇ（１．２５mol ）及びキ
シレン１ｌを、ディーンスタークトラップを取り付けた
３ｌ四つ口フラスコに入れ、窒素導入下、１００℃まで
昇温した。次に、２−エチルヘキシルブロマイド１２０
ｇ（０．６２mol ）を滴下した後、水が溜出しなくなる
まで還流した。反応終了後、トルエン１ｌで希釈し、析
出してきた結晶を濾過により除き、母液を希塩酸、水、
飽和重曹水、水、飽和食塩水で洗浄後、無水硫酸マグネ
シウムで乾燥した。濾過後、溶媒を留去した後、減圧蒸
留により精製し、１３５ｇのモノエーテル体を無色オイ
ルとして得た。ＧＬＣ分析により純度は９９％であっ
た。また、２００ＭＨｚ 1Ｈ−ＮＭＲにてδ＝１．５に
水酸基、δ＝１．２−１．６，３．３，３．３５，３．
６５にメチン及びメチレン基、δ＝０．８５−０．９５
にメチル基のプロトンシグナルを認め、モノエーテル体
の生成を確認した。Example 9 (1) 1,9-Nonanediol 500 g (3.04 mol)
), 50 g (1.25 mol) of sodium hydroxide and 1 l of xylene were placed in a 3 l four-necked flask equipped with a Dean Stark trap, and the temperature was raised to 100 ° C. under introduction of nitrogen. Next, 2-ethylhexyl bromide 120
g (0.62 mol) was added dropwise, and the mixture was refluxed until water stopped distilling. After completion of the reaction, the reaction mixture was diluted with 1 l of toluene, the precipitated crystals were removed by filtration, and the mother liquor was diluted with dilute hydrochloric acid, water,
The extract was washed with saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off and the residue was purified by vacuum distillation to obtain 135 g of a monoether body as a colorless oil. The purity was 99% by GLC analysis. In 200 MHz 1 H-NMR, δ = 1.5 is a hydroxyl group, and δ = 1.2-1.6, 3.3, 3.35, 3.
Methine and methylene group at 65, δ = 0.85-0.95
A proton signal of a methyl group was observed at the position, and formation of a monoether body was confirmed.
【００６３】（２）オキシ塩化リン５０ｇ（０．３２７
mol ）をテトラヒドロフラン（ＴＨＦ）に溶解し、５０
０ml四つ口フラスコに入れ、窒素導入下、−６０℃に冷
却し、攪拌しながらモノエーテル体１００ｇ（０．３４
３mol ）及びトリエチルアミン３３ｇをＴＨＦに溶かし
て滴下した。この時反応温度は−３０℃以下に保った。
そのまま４時間攪拌を続けた後０℃まで昇温し、ヘキサ
デカノール８３ｇ（０．３４３mol ）及びトリエチルア
ミン３３ｇをＴＨＦに溶かして滴下した。この時反応温
度５℃以下に保った。そのまま０℃で２４時間攪拌した
後、水６．２ｇを加え、更に６時間攪拌した。その後析
出してきた固体を濾過により除き、溶媒を留去して得ら
れた残渣をエタノールに溶かし、酢酸カルシウム６０
ｇ、水及びエタノールを加えて６０℃で４時間攪拌した
後、室温まで冷却し、エーテルで分層させた。有機層を
水洗し、溶媒を留去して得られた残渣をアセトンで再沈
させた。析出してきた固体を濾過により集め、乾燥さ
せ、１５０ｇの白色固体としてリン酸ジエステルカルシ
ウム塩（１−１２）を得た。31Ｐ−ＮＭＲより純度は９
９％、２００ＭＨｚ 1Ｈ−ＮＭＲより、δ＝１．２−
１．６，３．３，３．３５，３．８５にメチン及びメチ
レン基、δ＝０．８５−０．９にメチル基のプロトンシ
グナルを認め、リン酸ジエステルカルシウム塩の生成を
確認した。(2) 50 g of phosphorus oxychloride (0.327
mol) in tetrahydrofuran (THF),
It was put in a 0 ml four-necked flask, cooled to −60 ° C. under nitrogen introduction, and stirred to give 100 g of monoether (0.34
3 mol) and 33 g of triethylamine were dissolved in THF and added dropwise. At this time, the reaction temperature was kept at -30 ° C or lower.
After continuing stirring for 4 hours, the temperature was raised to 0 ° C., 83 g (0.343 mol) of hexadecanol and 33 g of triethylamine were dissolved in THF and added dropwise. At this time, the reaction temperature was kept below 5 ° C. After stirring as it was at 0 ° C. for 24 hours, 6.2 g of water was added, and the mixture was further stirred for 6 hours. After that, the precipitated solid was removed by filtration, the solvent was distilled off, and the resulting residue was dissolved in ethanol.
g, water and ethanol were added and the mixture was stirred at 60 ° C. for 4 hours, cooled to room temperature, and separated into layers with ether. The organic layer was washed with water, the solvent was distilled off, and the resulting residue was reprecipitated with acetone. The precipitated solid was collected by filtration and dried to obtain 150 g of a phosphoric acid diester calcium salt (1-12) as a white solid. The purity is 9 from 31 P-NMR.
9%, from 200 MHz 1 H-NMR, δ = 1.2-
Proton signals of methine and methylene groups at 1.6, 3.3, 3.35, and 3.85, and methyl group at δ = 0.85-0.9 were observed, and formation of phosphodiester calcium salt was confirmed.
【００６４】実施例１０ （１）ｔｅｒｔ−ブタノール２００ｇ（２．７ｍｏ
ｌ）、１，９−ノナンジオール１００ｇ（０．６２５ｍ
ｏｌ）及び硫酸２ｇを５００mlナスフラスコに入れ、５
時間加熱還流後、水酸化ナトリウム水溶液で中和した。
未反応ｔｅｒｔ−ブタノールを留去後、ヘキサンを加え
攪拌した。ヘキサン不溶のジオールを濾過により除き、
ヘキサン層を水洗後、無水硫酸ナトリウムで乾燥した。
濾過後、溶媒を留去し、得られた残渣をシリカゲルカラ
ムクロマトグラフィー（展開ヘキサン／クロロホルム）
で精製し、３５ｇの９−ｔｅｒｔ−ブトキシ−１−ノナ
ノールを無色オイルとして得た。ＧＬＣ分析より純度は
９９％以上であった。２００ＭＨｚ 1Ｈ−ＮＭＲ（溶
媒ＣＤＣｌ3 、ＴＭＳ標準）より、δ＝１．２にｔｅｒ
ｔ−ブチル由来のメチル、δ＝１．３，１．５〜１．
６，３．３５，３．６５にメチレンのそれぞれプロトン
シグナルを認め、モノエーテル体の生成を確認した。Example 10 (1) 200 g (2.7 mo) of tert-butanol
l), 100 g of 1,9-nonanediol (0.625 m
ol) and 2 g of sulfuric acid are put in a 500 ml eggplant flask, and 5
After heating under reflux for an hour, the mixture was neutralized with an aqueous sodium hydroxide solution.
After unreacted tert-butanol was distilled off, hexane was added and the mixture was stirred. Hexane-insoluble diol was removed by filtration,
The hexane layer was washed with water and dried over anhydrous sodium sulfate.
After filtration, the solvent was distilled off, and the resulting residue was subjected to silica gel column chromatography (developing hexane / chloroform).
Purification was carried out at 35 g to obtain 35 g of 9-tert-butoxy-1-nonanol as a colorless oil. The purity was 99% or more by GLC analysis. From 200 MHz 1 H-NMR (solvent CDCl 3 , TMS standard), ter = δ = 1.2
Methyl derived from t-butyl, δ = 1.3, 1.5-1.
Proton signals of methylene were observed at 6, 3.35 and 3.65, respectively, and formation of a monoether body was confirmed.
【００６５】（２）オキシ塩化リン５．０ｇ（０．０３
３ｍｏｌ）をＴＨＦに溶かし、窒素導入下−５０℃以下
に冷却し、これに（１）で得られたモノエーテル体１５
ｇ（０．０６９ｍｏｌ）とトリエチルアミン７．０ｇ
（０．０６９ｍｏｌ）をＴＨＦに溶解したものを滴下し
た。滴下終了後、０℃まで昇温し、そのまま一晩攪拌し
た。１．２６ｇの水を滴下し、しばらく攪拌後、析出し
てきたトリエチルアミン塩酸塩を濾過により除き、溶媒
を留去して黄色オイルとしてジアルキルリン酸エステル
トリエチルアミン塩を定量的に得、これを31Ｐ−ＮＭＲ
により確認した。(2) 5.0 g (0.03) of phosphorus oxychloride
3 mol) was dissolved in THF and cooled to −50 ° C. or lower under nitrogen introduction, and the monoether body 15 obtained in (1) was added thereto.
g (0.069 mol) and triethylamine 7.0 g
What melt | dissolved (0.069 mol) in THF was dripped. After the dropping was completed, the temperature was raised to 0 ° C. and the mixture was stirred overnight. Of water are added dropwise 1.26 g, after a while stirring, the triethylamine hydrochloride which has precipitated was removed by filtration, the solvent was distilled off to quantitatively obtain the dialkyl phosphate ester triethylamine salt as a yellow oil which 31 P- NMR
Confirmed by.
【００６６】（３）（２）で得られたジアルキルリン酸
エステルトリエチルアミン塩４ｇを１．５Ｎ塩酸に分散
させ、４０〜５０℃で３時間攪拌した。ヘキサンで抽出
し、水洗後、溶媒を留去して、無色オイルとしてジアル
キルリン酸エステルを得た。こうして得られたジアルキ
ルリン酸エステルをエタノールに溶解し、４ｇの酢酸ア
ルミニウム／エタノール／水を加え、５０℃で３０分攪
拌した。倍量の水を加え、室温まで冷却後、析出してき
た固体を濾過により集め、水、エタノール、アセトンで
洗浄後、乾燥し、２．５ｇの白色固体としてジアルキル
リン酸エステルアルミニウム塩（１−２１）を得た。31
Ｐ−ＮＭＲより純度は９９％以上、２００ＭＨｚ 1Ｈ
−ＮＭＲ（溶媒ＣＤＣｌ3 、ＴＭＳ標準）より、δ＝
１．２にメチル、δ＝１．３，１．５，１．６８，３．
３，３．９８にメチレンのそれぞれプロトンシグナルを
認め、ジアルキルリン酸エステルアルミニウム塩の生成
を確認した。(3) 4 g of the dialkyl phosphate ester triethylamine salt obtained in (2) was dispersed in 1.5N hydrochloric acid, and the mixture was stirred at 40 to 50 ° C. for 3 hours. After extracting with hexane and washing with water, the solvent was distilled off to obtain a dialkyl phosphate ester as a colorless oil. The dialkyl phosphate thus obtained was dissolved in ethanol, 4 g of aluminum acetate / ethanol / water was added, and the mixture was stirred at 50 ° C. for 30 minutes. Double the amount of water was added, and after cooling to room temperature, the precipitated solid was collected by filtration, washed with water, ethanol, and acetone, and dried to give 2.5 g of a white solid dialkyl phosphate aluminum salt (1-21 ) Got. 31
Purity of 99% or more by P-NMR, 200 MHz 1 H
-From NMR (solvent CDCl 3 , TMS standard), δ =
1.2 to methyl, δ = 1.3, 1.5, 1.68, 3.
Proton signals of methylene were observed at 3, 3.98, respectively, and formation of aluminum dialkyl phosphate ester was confirmed.
【００６７】実施例１１ （１）実施例１０の（１）の１，９−ノナンジオールの
代わりに、分岐率３４％のジオールの混合物（１，９−
ノナンジオール：２−メチル−１，８−オクタンジオー
ル＝６６：３４の混合ジオール）を用いて実施例１０の
場合と同様にして合成した。31Ｐ−ＮＭＲより純度は９
９％以上、２００ＭＨｚ 1Ｈ−ＮＭＲ（溶媒ＣＤＣｌ
3 、ＴＭＳ標準）より、δ＝０．８８，１．２にメチ
ル、δ＝１．３〜１．５，１．７，３．３，３．９８に
メチレン及びメチンのそれぞれプロトンシグナルを認
め、ジアルキルリン酸エステルアルミニウム塩（１−２
３）の生成を確認した。Example 11 (1) Instead of the 1,9-nonanediol of (1) of Example 10, a mixture of diols having a branching rate of 34% (1,9-
Nonanediol: 2-methyl-1,8-octanediol = 66: 34 mixed diol) was used and synthesized in the same manner as in Example 10. The purity is 9 from 31 P-NMR.
9% or more, 200 MHz 1 H-NMR (solvent CDCl
3 , TMS standard), methyl signals at δ = 0.88 and 1.2, and methylene and methine proton signals at δ = 1.3 to 1.5, 1.7, 3.3 and 3.98, respectively. , Dialkyl phosphate aluminum salt (1-2
Generation of 3) was confirmed.
【００６８】実施例１２ （１）３，３−ジメチル−１−ブタノール１０ｇ（０．
１０ｍｏｌ）、ピリジン８ｇ（０．１０ｍｏｌ）をベン
ゼンに溶かし、塩化チオニル１２ｇのベンゼン溶液を氷
冷下、滴下し、８０℃で５時間還流させた。水１００ml
を氷冷下加え、ヘキサンで抽出した。希塩酸、水、飽和
重曹水、水、飽和食塩水で洗浄後、無水硫酸マグネシウ
ムで乾燥した。濾過後、溶媒を留去し、淡黄色オイルと
して得られた５ｇの１−クロロ−３，３−ジメチルブタ
ンをトルエンに溶解した。１，９−ノナンジオール２５
ｇ（０．１５６ｍｏｌ）をトルエンに溶かし、水酸化ナ
トリウム３．２ｇ（０．０８ｍｏｌ）を加え、ディーン
スタークトラップを用いて１時間共沸脱水させた。次に
１−クロロ−３，３−ジメチルブタンのトルエン溶液を
滴下し、そのまま５時間加熱還流を続け、室温まで放置
した。倍量のヘキサンを加え、不溶分を濾過により除
き、ヘキサン／トルエン層を水洗、濃縮して、モノエー
テル：ジエーテル＝６０：４０の混合物を黄色オイルと
して得た。シリカゲルカラムクロマトグラフィー（展開
クロロホルム）により精製し、５ｇのモノエーテル体を
淡黄色オイルとして得た。ＧＬＣより純度は９５％であ
った。２００ＭＨｚ 1Ｈ−ＮＭＲ（溶媒ＣＤＣｌ3 、
ＴＭＳ標準）よりδ＝０．９にｔｅｒｔ−ブチル由来の
メチル、δ＝１．３２，１．５５〜１．７，３．４５，
３．６５にメチレンのそれぞれプロトンシグナルを認
め、モノエーテル体の生成を確認した。Example 12 (1) 10 g of 3,3-dimethyl-1-butanol (0.
10 mol) and 8 g (0.10 mol) of pyridine were dissolved in benzene, and a benzene solution of 12 g of thionyl chloride was added dropwise under ice cooling, and the mixture was refluxed at 80 ° C. for 5 hours. 100 ml of water
Was added under ice cooling and extracted with hexane. The extract was washed with diluted hydrochloric acid, water, saturated aqueous sodium hydrogen carbonate, water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and 5 g of 1-chloro-3,3-dimethylbutane obtained as a pale yellow oil was dissolved in toluene. 1,9-nonanediol 25
g (0.156 mol) was dissolved in toluene, 3.2 g (0.08 mol) of sodium hydroxide was added, and azeotropic dehydration was carried out for 1 hour using a Dean Stark trap. Then, a toluene solution of 1-chloro-3,3-dimethylbutane was added dropwise, heating and refluxing were continued for 5 hours, and the mixture was allowed to stand at room temperature. Double amount of hexane was added, insoluble matter was removed by filtration, the hexane / toluene layer was washed with water and concentrated to obtain a mixture of monoether: diether = 60: 40 as a yellow oil. Purification by silica gel column chromatography (developed chloroform) gave 5 g of a monoether as a pale yellow oil. The purity was 95% by GLC. 200 MHz 1 H-NMR (solvent CDCl 3 ,
TMS standard), methyl derived from tert-butyl at δ = 0.9, δ = 1.32, 1.55 to 1.7, 3.45,
Proton signals of methylene were observed at 3.65, and the formation of monoether was confirmed.
【００６９】（２）オキシ塩化リン０．９１ｇ（０．０
０５９ｍｏｌ）をＴＨＦに溶かし、窒素導入下０℃以下
に冷却し、これに（２）で得られたモノエーテル体３．
７ｇ（０．０１５ｍｏｌ）とトリエチルアミン１．２ｇ
（０．０１２ｍｏｌ）をＴＨＦに溶解したものを滴下し
た。滴下終了後、そのまま１８時間攪拌した。２００mg
の水をＴＨＦに溶かして滴下し、しばらく攪拌後、２Ｎ
塩酸に分散させ、５０℃で２時間攪拌した。ヘキサンで
抽出し、水洗後、溶媒を留去して得られた残渣をエタノ
ールに溶解し、５．０ｇの酢酸アルミニウム／エタノー
ル／水を加え、５０℃で１．５時間攪拌した。倍量の水
を加え、室温まで冷却後、析出してきた固体を濾過によ
り集め、水、エタノール、アセトンで洗浄後、乾燥し、
１．５ｇの淡黄色固体としてジアルキルリン酸エステル
アルミニウム塩（１−２８）を得た。31Ｐ−ＮＭＲより
純度は９９％以上、２００ＭＨｚ 1Ｈ−ＮＭＲ（溶媒
ＣＤＣｌ3 、ＴＭＳ標準）よりδ＝０．９にメチル、δ
＝１．３２，１．５５〜１．７，３．４５，４．０にメ
チレンのそれぞれプロトンシグナルを認め、ジアルキル
リン酸エステルアルミニウム塩の生成を確認した。(2) Phosphorus oxychloride 0.91 g (0.0
(059 mol) was dissolved in THF and cooled to 0 ° C. or lower under introduction of nitrogen, and the monoether body obtained in (2) 3.
7 g (0.015 mol) and triethylamine 1.2 g
What melt | dissolved (0.012 mol) in THF was dripped. After completion of dropping, the mixture was stirred for 18 hours as it was. 200 mg
Of water is dissolved in THF and added dropwise, and after stirring for a while, 2N
It was dispersed in hydrochloric acid and stirred at 50 ° C. for 2 hours. After extraction with hexane and washing with water, the solvent was distilled off and the obtained residue was dissolved in ethanol, 5.0 g of aluminum acetate / ethanol / water was added, and the mixture was stirred at 50 ° C. for 1.5 hours. Double the amount of water was added, and after cooling to room temperature, the precipitated solid was collected by filtration, washed with water, ethanol, and acetone, and then dried.
Dialkyl phosphoric acid ester aluminum salt (1-28) was obtained as a pale yellow solid (1.5 g). Purity is 99% or more from 31 P-NMR, 200 MHz 1 H-NMR (solvent CDCl 3 , TMS standard) gives δ = 0.9 methyl, δ
= 1.32, 1.55 to 1.7, 3.45, and 4.0, methylene proton signals were observed, and production of a dialkyl phosphate aluminum salt was confirmed.
【００７０】試験例１ 各種リン酸ジエステル多価金属塩の油ゲル化能を評価し
た。すなわち、各化合物１ｇをサンプル管にとり、これ
に油剤１９ｇを加えたのち、超音波ミキサーで約３分間
混合し、均一に分散又は溶解させた。これを一昼夜静置
した後、状態を肉眼観察し、下記の基準で評価した。結
果を表１に示す。 ◎：透明の粘稠なゲル、 ○：粘度の低いゲル、 △：ゲルを形成するが油のしみ出しがみられる、 ×：不溶Test Example 1 The oil gelling ability of various phosphoric acid diester polyvalent metal salts was evaluated. That is, 1 g of each compound was placed in a sample tube, 19 g of the oil agent was added thereto, and then the mixture was mixed with an ultrasonic mixer for about 3 minutes to be uniformly dispersed or dissolved. This was left to stand for a whole day and night, and then the state was visually observed and evaluated according to the following criteria. The results are shown in Table 1. ⊚: Transparent viscous gel, ◯: Gel with low viscosity, Δ: Gel is formed but oil oozes out, ×: Insoluble
【００７１】[0071]
【表１】 [Table 1]
【００７２】試験例２ 試験例１と同様に各種リン酸ジエステル多価金属塩の油
ゲル化能を評価した。試験方法としては、評価する油剤
に対して、各化合物が２重量％になるように添加し、１
〜３日間室温で放置した。その後、４０〜８０℃の温度
で１〜４時間加熱攪拌し、均一に分散又は溶解させて更
に一昼夜静置した後、状態を肉眼で観察し、下記の基準
で評価した。結果を表２に示す。 ◎：油剤をゲル化、 ○：油剤をゲル化するが未溶解物が残る、 △：油剤とゲルが分離、 ×：ゲル化せずTest Example 2 In the same manner as in Test Example 1, the oil gelling ability of various phosphoric acid diester polyvalent metal salts was evaluated. As a test method, 1% of each compound was added to the oil agent to be evaluated, and 1
Leave at room temperature for ~ 3 days. Then, the mixture was heated and stirred at a temperature of 40 to 80 ° C. for 1 to 4 hours, uniformly dispersed or dissolved, and allowed to stand still for a whole day and night. Then, the state was visually observed and evaluated according to the following criteria. The results are shown in Table 2. ⊚: Gelation of oil agent, ◯: Gelation of oil agent but undissolved matter remained, △: Separation of oil agent and gel, ×: No gelation
【００７３】[0073]
【表２】 [Table 2]
Claims (7)
テル多価金属塩。 【化１】 （式中、Ｒ1 は炭素数１〜２０の直鎖又は分岐鎖のアル
キル基を示し、Ｒ2 及びＲ4 は同一又は異なって、炭素
数２〜３の直鎖又は分岐鎖のアルキレン基を示し、Ｒ3
は炭素数３〜２０の直鎖又は炭素数５〜２０の分岐鎖の
アルキレン基を示し、Ａは−ＣＯＯ−又は−Ｏ−を示
し、ｘ及びｙは同一又は異なって、０〜１０の整数を示
し、Ｌは炭素数１〜４０の直鎖若しくは分岐鎖のアルキ
ル基又はR1-(OR2)x-A-R3-(OR4)y-（式中、Ｒ1 、Ｒ2 、
Ｒ3 、Ｒ4 、Ａ、ｘ及びｙは前記と同じ意味を有する）
を示し、Ｍは２価以上の多価金属イオンを示し、ｍは多
価金属イオンの原子価と同じ数を示す）1. A phosphoric acid diester polyvalent metal salt represented by the general formula (1). [Chemical 1] (In the formula, R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, R 2 and R 4 are the same or different, and represent a linear or branched alkylene group having 2 to 3 carbon atoms. Shows, R 3
Represents a straight-chain or branched-chain alkylene group having 3 to 20 carbon atoms, A represents -COO- or -O-, x and y are the same or different, and are integers from 0 to 10. L is a linear or branched alkyl group having 1 to 40 carbon atoms or R 1- (OR 2 ) x -AR 3- (OR 4 ) y- (in the formula, R 1 , R 2 ,
R 3 , R 4 , A, x and y have the same meanings as above)
, M represents a polyvalent metal ion having two or more valences, and m represents the same number as the valence of the polyvalent metal ion).
アルキル基の末端の少なくとも１個が（ＣＨ3）3Ｃ−で
あることを特徴とする請求項１記載のリン酸ジエステル
多価金属塩。2. The phosphoric acid diester according to claim 1, wherein in the general formula (1), at least one terminal of the alkyl group represented by R 1 or L is (CH 3 ) 3 C-. Polyvalent metal salt.
である請求項１又は２記載のリン酸ジエステル多価金属
塩。3. In the general formula (1), M is Ca 2+ or Al 3+.
The phosphoric acid diester polyvalent metal salt according to claim 1 or 2.
キル基を示し、Ｒ2 及びＲ4 は同一又は異なって、炭素
数２〜３の直鎖又は分岐鎖のアルキレン基を示し、Ｒ3
は炭素数３〜２０の直鎖又は炭素数５〜２０の分岐鎖の
アルキレン基を示し、Ａは−ＣＯＯ−又は−Ｏ−を示
し、ｘ及びｙは同一又は異なって、０〜１０の整数を示
し、Ｌは炭素数１〜４０の直鎖若しくは分岐鎖のアルキ
ル基又はR1-(OR2)x-A-R3-(OR4)y-（式中、Ｒ1 、Ｒ2 、
Ｒ3 、Ｒ4 、Ａ、ｘ及びｙは前記と同じ意味を有する）
を示し、Ｘは水素原子、アルカリ金属、アンモニウム、
アルキルアミン又はアルカノールアミンを示す）で表わ
されるリン酸ジエステル又はその塩に、一般式（３）： MpYq （３） （式中、Ｍは２価以上の多価金属イオンを示し、Ｙは有
機又は無機アニオンを示し、ｐはＹ、ｑはＭの原子価に
対応する整数で、最少比のものを示す）で表わされる多
価金属塩を反応させることを特徴とする請求項１又は２
記載のリン酸ジエステル多価金属塩の製造法。4. General formula (2): (In the formula, R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, R 2 and R 4 are the same or different, and represent a linear or branched alkylene group having 2 to 3 carbon atoms. Shows, R 3
Represents a straight-chain or branched-chain alkylene group having 3 to 20 carbon atoms, A represents -COO- or -O-, x and y are the same or different, and are integers from 0 to 10. L is a linear or branched alkyl group having 1 to 40 carbon atoms or R 1- (OR 2 ) x -AR 3- (OR 4 ) y- (in the formula, R 1 , R 2 ,
R 3 , R 4 , A, x and y have the same meanings as above)
X is a hydrogen atom, an alkali metal, ammonium,
Alkylamine or alkanolamine) is added to the phosphoric acid diester or salt thereof, and the compound represented by the general formula (3): M p Y q (3) (wherein, M represents a divalent or higher polyvalent metal ion, Y Represents an organic or inorganic anion, p is an integer corresponding to the valence of Y, and q is an integer corresponding to the valence of M, and represents a minimum ratio). Two
A process for producing the described phosphoric acid diester polyvalent metal salt.
キル基を示し、Ｒ2 及びＲ4 は同一又は異なって、炭素
数２〜３の直鎖又は分岐鎖のアルキレン基を示し、
Ｒ3′は炭素数７〜２０の直鎖又は分岐鎖のアルキレン
基を示し、Ａは−ＣＯＯ−又は−Ｏ−を示し、ｘ及びｙ
は同一又は異なって、０〜１０の整数を示し、Ｌ′は炭
素数１〜４０の直鎖若しくは分岐鎖のアルキル基又はR1
-(OR2)x-A-R3′-(OR4)y-（式中、Ｒ1 、Ｒ2 、Ｒ3′、
Ｒ4 、Ａ、ｘ及びｙは前記と同じ意味を有する）を示
し、Ｘは水素原子、アルカリ金属、アンモニウム、アル
キルアミン又はアルカノールアミンを示す）で表わされ
るリン酸ジエステル及びその塩。5. The general formula (2 ′): (In the formula, R 1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, R 2 and R 4 are the same or different, and represent a linear or branched alkylene group having 2 to 3 carbon atoms. Shows,
R 3 'represents a linear or branched alkylene group having 7 to 20 carbon atoms, A is shows a -COO- or -O-, x and y
Are the same or different and each represents an integer of 0 to 10, and L'is a linear or branched alkyl group having 1 to 40 carbon atoms or R 1
-(OR 2 ) x -AR 3 ′-(OR 4 ) y — (wherein R 1 , R 2 , R 3 ′,
R 4 , A, x and y have the same meanings as defined above, and X represents a hydrogen atom, an alkali metal, ammonium, an alkylamine or an alkanolamine) and a salt thereof.
れるアルキル基の末端の少なくとも１個が（ＣＨ3）3Ｃ
−であることを特徴とする請求項５記載のリン酸ジエス
テル及びその塩。6. In the general formula (2 ′), at least one terminal of the alkyl group represented by R 1 or L ′ is (CH 3 ) 3 C.
-The phosphoric acid diester and its salt of Claim 5 characterized by these.
キル基を示し、Ｒ2 及びＲ4 は同一又は異なって、炭素
数２〜３の直鎖又は分岐鎖のアルキレン基を示し、
Ｒ3′は炭素数７〜２０の直鎖又は分岐鎖のアルキレン
基を示し、Ａは−ＣＯＯ−又は−Ｏ−を示し、ｘ及びｙ
は同一又は異なって、０〜１０の整数を示す）で表わさ
れるアルコール、又は一般式（４）で表わされるアルコ
ールと一般式（５）： 【化５】L″-OH （５） （式中、Ｌ″は炭素数１〜４０の直鎖又は分岐鎖のアル
キル基を示す）で表わされるアルコールの混合物に、リ
ン酸化剤を反応させ、次いで所望により１価の塩基で中
和することを特徴とする請求項５又は６記載のリン酸ジ
エステル及びその塩の製造法。7. General formula (4): embedded image R 1- (OR 2 ) x -AR 3 ′-(OR 4 ) y —OH (4) (wherein R 1 has 1 to 20 carbon atoms). And a linear or branched alkyl group of R 2 and R 4 are the same or different and represent a linear or branched alkylene group having 2 to 3 carbon atoms,
R 3 'represents a linear or branched alkylene group having 7 to 20 carbon atoms, A is shows a -COO- or -O-, x and y
Are the same or different and each represents an integer of 0 to 10), or an alcohol represented by the general formula (4) and the general formula (5): L ″ -OH (5) (wherein , L ″ represents a linear or branched alkyl group having 1 to 40 carbon atoms), a phosphorylating agent is reacted with a mixture of alcohols, and the mixture is optionally neutralized with a monovalent base. The method for producing the phosphodiester and its salt according to claim 5 or 6.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24126493A JP3197703B2 (en) | 1992-12-28 | 1993-09-28 | Novel phosphoric acid diester polyvalent metal salt and method for producing the same |
| TW082111037A TW251302B (en) | 1992-12-28 | 1993-12-27 | |
| PCT/JP1993/001924 WO1994014822A1 (en) | 1992-12-28 | 1993-12-28 | Polyvalent metal salts of phosphoric diester and organo(poly)siloxanes modified with polyvalent metal salt of phosphoric diester |
| US08/454,181 US5872272A (en) | 1992-12-28 | 1993-12-28 | Polyvalent metal salts of phosphoric diester and organo(poly)siloxanes modified with polyvalent metal salt of phosphoric diester |
| SG1996001411A SG50437A1 (en) | 1992-12-28 | 1993-12-28 | Polyvalvent metal salts of phosphoric diester and organo (poly) siloxanes modified with polyvalent metal salt of phosphoric diester |
| DE69308891T DE69308891T2 (en) | 1992-12-28 | 1993-12-28 | MULTI-VALUE METAL SALTS FROM PHOSPHORIC ACID DIESTERS AND ORGANO (POLY) SILOXANES MODIFIED WITH METAL SALTS FROM PHOSPHORIC ACID DIESTERS |
| EP94903096A EP0675891B1 (en) | 1992-12-28 | 1993-12-28 | Polyvalent metal salts of phosphoric diester and organo(poly)siloxanes modified with polyvalent metal salt of phosphoric diester |
| HK97101676A HK1000154A1 (en) | 1992-12-28 | 1997-08-22 | Polyvalent metal salts of phosphoric diester and organo(poly)siloxanes modified with polyvalent metal salt of phosphoric diester |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-348616 | 1992-12-28 | ||
| JP34861692 | 1992-12-28 | ||
| JP24126493A JP3197703B2 (en) | 1992-12-28 | 1993-09-28 | Novel phosphoric acid diester polyvalent metal salt and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06247990A true JPH06247990A (en) | 1994-09-06 |
| JP3197703B2 JP3197703B2 (en) | 2001-08-13 |
Family
ID=26535167
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24126493A Expired - Fee Related JP3197703B2 (en) | 1992-12-28 | 1993-09-28 | Novel phosphoric acid diester polyvalent metal salt and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3197703B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013536842A (en) * | 2010-08-31 | 2013-09-26 | ザ ルブリゾル コーポレイション | Preparation of phosphorus-containing antiwear compounds for use in lubricating compositions |
| US8895556B2 (en) | 2007-12-26 | 2014-11-25 | Critical Outcome Technologies Inc. | Compounds and method for treatment of cancer |
| US8987272B2 (en) | 2010-04-01 | 2015-03-24 | Critical Outcome Technologies Inc. | Compounds and method for treatment of HIV |
| US9284275B2 (en) | 2007-01-11 | 2016-03-15 | Critical Outcome Technologies Inc. | Inhibitor compounds and cancer treatment methods |
-
1993
- 1993-09-28 JP JP24126493A patent/JP3197703B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9284275B2 (en) | 2007-01-11 | 2016-03-15 | Critical Outcome Technologies Inc. | Inhibitor compounds and cancer treatment methods |
| US8895556B2 (en) | 2007-12-26 | 2014-11-25 | Critical Outcome Technologies Inc. | Compounds and method for treatment of cancer |
| US8987272B2 (en) | 2010-04-01 | 2015-03-24 | Critical Outcome Technologies Inc. | Compounds and method for treatment of HIV |
| US9422282B2 (en) | 2010-04-01 | 2016-08-23 | Critical Outcome Technologies Inc. | Compounds and method for treatment of HIV |
| US9624220B2 (en) | 2010-04-01 | 2017-04-18 | Critical Outcome Technologies Inc. | Compounds and method for treatment of HIV |
| JP2013536842A (en) * | 2010-08-31 | 2013-09-26 | ザ ルブリゾル コーポレイション | Preparation of phosphorus-containing antiwear compounds for use in lubricating compositions |
| US9382275B2 (en) | 2010-08-31 | 2016-07-05 | The Lubrizol Corporation | Preparation of phosphorus—containing antiwear composition for use in lubricant compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3197703B2 (en) | 2001-08-13 |
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