JP2904882B2 - Method for producing phosphorus-containing metal complex - Google Patents
Method for producing phosphorus-containing metal complexInfo
- Publication number
- JP2904882B2 JP2904882B2 JP17873990A JP17873990A JP2904882B2 JP 2904882 B2 JP2904882 B2 JP 2904882B2 JP 17873990 A JP17873990 A JP 17873990A JP 17873990 A JP17873990 A JP 17873990A JP 2904882 B2 JP2904882 B2 JP 2904882B2
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- JP
- Japan
- Prior art keywords
- general formula
- water
- complex
- reaction
- phosphorus
- Prior art date
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Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、光安定剤や熱安定剤等の用途に有用な含リ
ン金属錯体の製造方法に関する。The present invention relates to a method for producing a phosphorus-containing metal complex useful for applications such as light stabilizers and heat stabilizers.
（ロ）従来の技術 従来、この種の化合物の合成方法としては水に不溶
なベンゼン、トルエン、キシレンのような芳香族炭化水
素に有機リン化合物を溶かし、金属塩の水溶液と接触さ
せて目的物を得る方法、前記溶剤中、有機リン酸と単
体の金属を高温下で反応させて目的物を得る方法が代表
的な方法であった。しかしながら、上記の方法について
は各々欠点があった。例えば、の方法については一種
の抽出反応であるため反応が不十分であり、反応後の純
度が極めて悪かった。またの方法については高温で長
時間反応させるため、原料物質である有機リン化合物及
び目的物質である含リン金属錯体の変色、劣化、分解が
避けられず、そのため収率が低く、生成物が褐色に着色
し、高純度の目的物が得られなかった。(B) Conventional technology Conventionally, as a method for synthesizing this type of compound, an organic phosphorus compound is dissolved in an aromatic hydrocarbon such as benzene, toluene, and xylene which is insoluble in water, and the target compound is brought into contact with an aqueous solution of a metal salt. And a method of reacting an organic phosphoric acid with a simple metal in the above-mentioned solvent at a high temperature to obtain a desired product. However, each of the above methods has drawbacks. For example, the method (1) was a kind of extraction reaction, so the reaction was insufficient, and the purity after the reaction was extremely poor. In the other method, since the reaction is carried out at a high temperature for a long time, discoloration, deterioration, and decomposition of the organic phosphorus compound as the raw material and the phosphorus-containing metal complex as the target substance are inevitable, so that the yield is low and the product is brown. And a high-purity target product could not be obtained.
（ハ）発明が解決しようとする課題 本発明は上記の事情に鑑みてなされたものであり、そ
の目的とするところは該含リン金属錯体を、容易に、か
つ高収率、高純度で合成できる製造方法を提供すること
にある。(C) Problems to be Solved by the Invention The present invention has been made in view of the above circumstances, and an object of the present invention is to easily synthesize the phosphorus-containing metal complex with high yield and high purity. An object of the present invention is to provide a manufacturing method which can be performed.
（ニ）課題を解決するための手段 本発明者らは、高収率で、高純度の該含リン金属錯体
を合成するために鋭意研究を進めた結果、水または／お
よび水に可溶な有機溶剤中で反応させることにより、容
易に高収率で高純度の含リン金属錯体の製造が可能であ
ることを見出すに至った。(D) Means for Solving the Problems The present inventors have conducted intensive studies to synthesize the phosphorus-containing metal complex with high yield and high purity, and as a result, water and / or water-soluble By reacting in an organic solvent, they have found that it is possible to easily produce a high-purity phosphorus-containing metal complex in high yield.
本発明によれば、一般式（Ｉ）： （式中、Ｌは水素原子、アルカリ金属またはアンモニウ
ム、Ｚは硫黄原子、ＲはC1-3のアルキル基）で示される
有機リン化合物と、一般式（II）： MeX2 （II） （式中、Meは２価の金属、Ｘは２価の金属と塩を形成し
うる無機または有機の酸残基）で示される化合物または
その水和物とを、Ｌが水素原子のときはC1-3のアルコー
ル中で、Ｌがアルカリ金属またはアンモニウムのときは
水または水とC1-3のアルコールとの混合溶剤中で反応さ
せ、反応生成物を反応に使用したのと同一の溶剤で洗浄
して、高純度の一般式（III）： （式中、ＲおよびＺは一般式（Ｉ）での定義と同一意
味、Meは一般式（II）での定義と同一意味、ｎは錯体の
リガンドのMeに対する比）で示される含リン金属錯体を
得ることを特徴とする含リン金属錯体の製造方法が提供
される。According to the present invention, general formula (I): (Wherein L is a hydrogen atom, an alkali metal or ammonium, Z is a sulfur atom, R is a C 1-3 alkyl group) and an organic phosphorus compound represented by the general formula (II): MeX 2 (II) In the formula, Me is a divalent metal, X is an inorganic or organic acid residue capable of forming a salt with the divalent metal, or a hydrate thereof; and when L is a hydrogen atom, C 1 -3 When L is an alkali metal or ammonium, react in water or a mixed solvent of water and C 1-3 alcohol, and wash the reaction product with the same solvent as used in the reaction. And the high-purity general formula (III): Wherein R and Z have the same meanings as defined in the general formula (I), Me has the same meaning as defined in the general formula (II), and n is a ratio of the ligand of the complex to Me. There is provided a method for producing a phosphorus-containing metal complex, which comprises obtaining a complex.
上記一般式（III）および一般式（Ｉ）において、Ｒ
は有機残基を意味する。有機残基としては、直鎖または
分枝状のアルキル基、シクロアルキル基、アラルキル
基、アリール基が挙げられる。アルキル基およびアリー
ル基は置換されていてもよく、またＲ同志が連ながった
環状構造を有してもよい。In the general formulas (III) and (I), R
Means an organic residue. Examples of the organic residue include a linear or branched alkyl group, cycloalkyl group, aralkyl group, and aryl group. The alkyl group and the aryl group may be substituted, and may have a cyclic structure in which Rs are linked.
一般式（III）および一般式（II）において、Meは２
価の金属を示すが、具体的にはコバルト、ニッケル、
銅、亜鉛などが挙げられる。一般式（II）におけるＸ
は、２価の金属と塩を形成しうる無機または有機の酸残
基を意味するが、具体的にはハロゲン、SO4、NO3、CO3
のような有機酸残基、HCOO、CH2COO、CH3CH2COOなどの
有機酸残基が好ましい例である。In the general formulas (III) and (II), Me is 2
Valence metal, but specifically, cobalt, nickel,
Copper, zinc and the like can be mentioned. X in general formula (II)
Means an inorganic or organic acid residue capable of forming a salt with a divalent metal, specifically, halogen, SO 4 , NO 3 , CO 3
And organic acid residues such as HCOO, CH 2 COO and CH 3 CH 2 COO are preferred examples.
本発明の方法においては、水または／および水に可溶
な有機溶剤が用いられる。水に可溶な有機溶剤として
は、メタノール、エタノール、イソプロピルアルコール
のようなアルコール類が挙げられる。これらの有機溶剤
は単独または水との任意の割合での混合物として用いる
ことができる。複数の有機溶剤を組合せることもでき
る。これらの溶剤は少なくとも原料の一般式（Ｉ）また
は（II）の化合物を溶解するに足る量用いられる。In the method of the present invention, water or / and an organic solvent soluble in water are used. Examples of water-soluble organic solvents include alcohols such as methanol, ethanol, and isopropyl alcohol. These organic solvents can be used alone or as a mixture with water at an arbitrary ratio. A plurality of organic solvents can be combined. These solvents are used in an amount sufficient to dissolve at least the compound of the general formula (I) or (II) as a raw material.
一般式（Ｉ）および一般式（II）の化合物は、当モル
量かまたは一般式（II）の化合物を若干過剰量用いられ
る。The compounds of the general formulas (I) and (II) are used in an equimolar amount or a slight excess of the compound of the general formula (II).
反応は常温ないし使用した溶剤の沸点の間好ましくは
30〜50℃で行うことができる。反応時間は一般に30分〜
数時間である。The reaction is preferably carried out at room temperature to the boiling point of the solvent used.
It can be performed at 30-50 ° C. Reaction time is generally 30 minutes to
A few hours.
反応が終了すると目的とする一般式（III）の含リン
金属錯体は、一般に固体として反応系より析出する。こ
れを濾取し、反応に使用したと同一の溶剤で１〜数回洗
浄するのが望ましい。それによって再結晶を行ったと同
じかそれ以上の純度の目的物を得ることができる。When the reaction is completed, the target phosphorus-containing metal complex of the general formula (III) is generally precipitated from the reaction system as a solid. This is preferably filtered and washed one to several times with the same solvent used in the reaction. As a result, a target product having the same or higher purity as that obtained by recrystallization can be obtained.
なお、本発明に使用される一般式（Ｉ）および一般式
（II）の化合物は、工業的に入手可能な化合物である
か、公知の方法によって容易に作り得るものである。The compounds of the general formulas (I) and (II) used in the present invention are industrially available compounds or can be easily prepared by known methods.
次に本発明によって得られる好ましい化合物の代表例
を第１表に示す。なお、表中のＲ、Ｚ、ｎおよびＭは、
一般式（Ｉ）のＲ、Ｚおよびｎ、ならびに一般式（II）
のMeに対応する。また、No.1およびNo.16は参考例であ
る。Next, Table 1 shows typical examples of preferred compounds obtained by the present invention. Note that R, Z, n and M in the table represent
R, Z and n of the general formula (I) and the general formula (II)
Corresponds to Me. No. 1 and No. 16 are reference examples.
本発明の目的とする含リン金属錯体は、光安定剤、熱
安定剤、酸化防止剤、紫外線吸収剤、潤滑油添加剤など
として有用な化合物である。 The phosphorus-containing metal complex intended for the present invention is a compound useful as a light stabilizer, a heat stabilizer, an antioxidant, an ultraviolet absorber, a lubricant additive, and the like.
（ホ）実施例 以下、実施例により本発明の含リン金属錯体の製造方
法について更に詳細に説明するが、本発明はこれらの実
施例により限定されるものではない。(E) Examples Hereinafter, the method for producing the phosphorus-containing metal complex of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例１ ジエチルジチオリン酸ナトリウム塩20.8g（0.1モル）
の50％水溶液にNiCl2・6H2O13.1g（0.055モル）の50％
水溶液を加え、30〜40℃にて３時間撹拌した。反応後、
析出した固体を濾取し、水で３回洗浄し、乾燥すると2
1.1g（収率98.5％、純度100％）の紫色結晶であるジエ
チルジチオリン酸ニッケル錯体が得られた。Example 1 Diethyldithiophosphate sodium salt 20.8 g (0.1 mol)
50% aqueous solution NiCl 2 · 6H 2 O13.1g of (0.055 mol) of 50%
An aqueous solution was added, and the mixture was stirred at 30 to 40 ° C for 3 hours. After the reaction,
The precipitated solid is collected by filtration, washed three times with water, and dried to give 2
1.1 g (yield 98.5%, purity 100%) of purple diethyl nickel nickel dithiophosphate complex was obtained.
実施例２ ジエチルジチオリン酸18.6（0.1モル）をエタノール1
50mlに溶かし、NiCl2・6H2O13.1g（0.055モル）をエタ
ノール50mlに溶かした溶液を加え、30〜40℃、４時間撹
拌した。反応後、析出した固体を濾取し、エタノールで
３回洗浄し、乾燥すると21.2g（収率99.0％、純度100
％）の紫色結晶であるジエチルジチオリン酸ニッケル錯
体が得られた。Example 2 18.6 (0.1 mol) of diethyldithiophosphoric acid was added to ethanol 1
Dissolved in 50 ml, was added a solution of NiCl 2 · 6H 2 O13.1g a (0.055 mol) in ethanol 50 ml, 30 to 40 ° C., and stirred for 4 hours. After the reaction, the precipitated solid was collected by filtration, washed three times with ethanol, and dried to obtain 21.2 g (yield 99.0%, purity 100%).
%), Which is a purple crystal of a nickel diethyldithiophosphate complex.
実施例３ ジイソプロピルジチオリン酸ナトリウム塩23.6g（0.1
モル）の50％水溶液にCuSO4・5H2O13.7g（0.055モル）
の50％水溶液を加え、30〜40℃にて３時間撹拌した。反
応後、析出した固体を濾取し、水で３回洗浄し、乾燥す
ると24.2g（収率98.8％、純度100％）の白色結晶である
ジイソプロピルジチオリン酸銅錯体が得られた。Example 3 Diisopropyl dithiophosphate sodium salt 23.6 g (0.1
CuSO 50% aqueous solution of mol) 4 · 5H 2 O13.7g (0.055 mol)
Was added and stirred at 30-40 ° C. for 3 hours. After the reaction, the precipitated solid was collected by filtration, washed three times with water, and dried to obtain 24.2 g (yield 98.8%, purity 100%) of a copper diisopropyldithiophosphate complex as white crystals.
実施例４ ジイソプロピルジチオリン酸21.3g（0.1モル）をエタ
ノール−水150ml（1:2V/V）に溶かし、Zn（CH2COO）２
・2H2O12.1g（0.055モル）をエタノール−水50ml（1:2V
/V））に溶かした溶液を加え、30〜40℃、４時間撹拌し
た。反応後、析出した固体を濾取し、エタノール−水
（1:2V/V）で３回洗浄し、乾燥すると24.2g（収率98.3
％、純度100％）の白色結晶であるジイソプロピルジチ
オリン酸亜鉛錯体が得られた。Example 4 21.3 g (0.1 mol) of diisopropyldithiophosphoric acid was dissolved in 150 ml of ethanol-water (1: 2 V / V), and Zn (CH 2 COO) 2
・ 12.1 g (0.055 mol) of 2H 2 O was added to 50 ml of ethanol-water (1: 2 V
/ V)), and the mixture was stirred at 30 to 40 ° C for 4 hours. After the reaction, the precipitated solid was collected by filtration, washed three times with ethanol-water (1: 2 V / V), and dried to obtain 24.2 g (yield 98.3 g).
%, A purity of 100%) as a white crystal of zinc diisopropyldithiophosphate complex.
実施例５ ジフェニルジチオリン酸ナトリウム塩30.4g（0.1モ
ル）をエタノール−水150ml（2:1V/V）に溶かし、CoCl2
・6H2O13.1g（0.055モル）をエタノール−水150ml（2:1
V/V）に溶かした溶液を加え、40〜50℃、３時間撹拌し
た。反応後、析出した固体を濾取し、エタノール−水
（2:1V/V）で３回洗浄し、乾燥すると30.3g（収率97.6
％、純度100％）の緑色結晶であるジフェニルジチオリ
ン酸コバルト錯体が得られた。Example 5 30.4 g (0.1 mol) of diphenyldithiophosphate sodium salt was dissolved in 150 ml of ethanol-water (2: 1 V / V), and CoCl 2
・ 13.1 g (0.055 mol) of 6H 2 O was added to 150 ml of ethanol-water (2: 1
(V / V), and the mixture was stirred at 40 to 50 ° C for 3 hours. After the reaction, the precipitated solid was collected by filtration, washed three times with ethanol-water (2: 1 V / V), and dried to obtain 30.3 g (yield 97.6 g).
%, Purity 100%) as a green crystalline cobalt diphenyldithiophosphate complex.
比較例１ ジエチルジチオリン酸18.6g（0.1モル）をトルエン15
0mlに溶かし、NiCl2・6H2O13.1g（0.055モル）の30％水
溶液を加え、30〜40℃、３時間撹拌した。反応後、水洗
し、トルエンを除去すると17.9g（収率83.5％）の紫色
固体であるジエチルジチオリン酸ニッケル錯体が得られ
た。これは純度90.1％で、さらに純度を100％に上げる
には２回の再結晶が必要であった。Comparative Example 1 18.6 g (0.1 mol) of diethyldithiophosphoric acid was added to toluene 15
The solution was dissolved in 0 ml, and a 30% aqueous solution of 13.1 g (0.055 mol) of NiCl 2 .6H 2 O was added, followed by stirring at 30 to 40 ° C. for 3 hours. After the reaction, the mixture was washed with water and toluene was removed to obtain 17.9 g (yield: 83.5%) of a purple solid nickel diethyldithiophosphate complex. This was 90.1% pure and required two recrystallizations to further increase the purity to 100%.
比較例２ ジイソプロピルジチオリン酸21.3g（0.1モル）をトル
エン150mlに溶かし、CuSO4・5H2O13.7g（0.055モル）30
％水溶液を加え、30〜40℃、３時間撹拌した。反応後、
水洗し、トルエンを除去すると20.0g（収率81.6％）の
白色固体であるジイソプロピルジチオリン酸銅錯体が得
られた。これは純度92.3％で、さらに純度を100％に上
げるには２回の再結晶が必要であった。Comparative Example 2 Diisopropyl dithiophosphates 21.3g (0.1 mol) dissolved in toluene 150ml, CuSO 4 · 5H 2 O13.7g (0.055 mol) 30
% Aqueous solution and stirred at 30-40 ° C for 3 hours. After the reaction,
After washing with water and removing toluene, 20.0 g (yield 81.6%) of a copper diisopropyldithiophosphate complex as a white solid was obtained. This was 92.3% pure and required two recrystallizations to further increase the purity to 100%.
（ヘ）発明の効果 本発明によれば、水または／および水に可溶な有機溶
剤を用いることによって、光安定剤や熱安定剤として有
用な含リン金属錯体が従来より容易に、かつ、高収率、
高純度に合成することができる。(F) Effects of the Invention According to the present invention, by using water or / and an organic solvent soluble in water, a phosphorus-containing metal complex useful as a light stabilizer or a heat stabilizer can be produced more easily and conventionally. High yield,
It can be synthesized with high purity.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 油化学，第27巻，第５号（1978）ｐ. 277−281 Ｚ．Ｎａｔｕｒｆｏｒｓｃｈ．Ｂ，Ｃ ｈｅｍ．Ｓｃｉ．，Ｖｏｌ．45，Ｎｏ. ２（1990）ｐ．245−257 Ｉｎｏｒｇａｎｉｃａ Ｃｈｅｍｉｃ ａ Ａｃｔａ，Ｖｏｌ．24，Ｎｏ．３ （1977）ｐ．255−260 Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃ ｔ，Ｖｏｌ．73，41302 (58)調査した分野(Int.Cl.6，ＤＢ名) C07F 9/17 C07F 15/04 C07F 15/06 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References Oil Chemistry, Vol. 27, No. 5, (1978) p. 277-281 Natureforsch. B, Chem. Sci. , Vol. 45, No. 2 (1990) p. 245-257 Inorganica Chemical Acta, Vol. 24, No. 3 (1977) p. 255-260 Chemical Abstract, Vol. 73, 41302 (58) Field surveyed (Int.Cl. 6 , DB name) C07F 9/17 C07F 15/04 C07F 15/06
Claims (1)
ム、Ｚは硫黄原子、ＲはC1-3のアルキル基）で示される
有機リン化合物と、一般式（II）： MeX2 （II） （式中、Meは２価の金属、Ｘは２価の金属と塩を形成し
うる無機または有機の酸残基）で示される化合物または
その水和物とを、Ｌが水素原子のときはC1-3のアルコー
ル中で、Ｌがアルカリ金属またはアンモニウムのときは
水または水とC1-3のアルコールとの混合溶剤中で反応さ
せ、反応生成物を反応に使用したのと同一の溶剤で洗浄
して、高純度の一般式（III）： （式中、ＲおよびＺは一般式（Ｉ）での定義と同一意
味、Meは一般式（II）での定義と同一意味、ｎは錯体の
リガンドのMeに対する比）で示される含リン金属錯体を
得ることを特徴とする含リン金属錯体の製造方法。1. A compound of the general formula (I): (Wherein L is a hydrogen atom, an alkali metal or ammonium, Z is a sulfur atom, R is a C 1-3 alkyl group) and an organic phosphorus compound represented by the general formula (II): MeX 2 (II) In the formula, Me is a divalent metal, X is an inorganic or organic acid residue capable of forming a salt with the divalent metal, or a hydrate thereof; and when L is a hydrogen atom, C 1 -3 When L is an alkali metal or ammonium, react in water or a mixed solvent of water and C 1-3 alcohol, and wash the reaction product with the same solvent as used in the reaction. And the high-purity general formula (III): Wherein R and Z have the same meanings as defined in the general formula (I), Me has the same meaning as defined in the general formula (II), and n is a ratio of the ligand of the complex to Me. A method for producing a phosphorus-containing metal complex, which comprises obtaining a complex.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17873990A JP2904882B2 (en) | 1990-07-05 | 1990-07-05 | Method for producing phosphorus-containing metal complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17873990A JP2904882B2 (en) | 1990-07-05 | 1990-07-05 | Method for producing phosphorus-containing metal complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0482894A JPH0482894A (en) | 1992-03-16 |
| JP2904882B2 true JP2904882B2 (en) | 1999-06-14 |
Family
ID=16053740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17873990A Expired - Fee Related JP2904882B2 (en) | 1990-07-05 | 1990-07-05 | Method for producing phosphorus-containing metal complex |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2904882B2 (en) |
-
1990
- 1990-07-05 JP JP17873990A patent/JP2904882B2/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| Ｃｈｅｍｉｃａｌ Ａｂｓｔｒａｃｔ，Ｖｏｌ．７３，４１３０２ |
| Ｉｎｏｒｇａｎｉｃａ Ｃｈｅｍｉｃａ Ａｃｔａ，Ｖｏｌ．２４，Ｎｏ．３（１９７７）ｐ．２５５−２６０ |
| Ｚ．Ｎａｔｕｒｆｏｒｓｃｈ．Ｂ，Ｃｈｅｍ．Ｓｃｉ．，Ｖｏｌ．４５，Ｎｏ．２（１９９０）ｐ．２４５−２５７ |
| 油化学，第２７巻，第５号（１９７８）ｐ．２７７−２８１ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0482894A (en) | 1992-03-16 |
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