JP2008266303A - Organic molybdenum compound, friction modifier comprising the same and lubricating composition containing the modifier - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound which is free of phosphorus, useful as a friction modifier, etc., modifying friction to the optimum, and to provide a friction modifier comprising the compound and a lubricating composition containing the modifier. <P>SOLUTION: The invention relates to an organomolybdenum compound represented by general formula (1), [wherein, -A is -OR or -NR'<SB>2</SB>, R is an alkyl group, and R' is an alkyl group (with the proviso that two R' groups may form a five-membered or a six-membered ring together with N)], and a friction modifier comprising them, and a lubricating composition comprising the modifier. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel organomolybdenum compound, a friction modifier comprising the same, and a lubricating composition containing the same.

  In order to adjust the friction characteristics of the lubricant to an appropriate level, there is a friction modifier (friction modifier), and friction compositions that reduce friction in lubricating compositions such as gear oil and engine oil aiming at fuel saving. In the lubricating composition used for the wet clutch portion of the automatic transmission, a friction modifier having a friction improving effect is used in order to maintain a somewhat high friction level. Many types of friction modifiers have been proposed.

また、特許文献１〜５においても１分子中に２個のＭｏ元素含有化合物が開示されている。
そして、前記一般式（２）で示されるように分子中にリンを含有する化合物は、エンジン油に使用される場合、排ガス清浄機の触媒毒となるという問題を含んでおり、リンを含まない化合物が求められている。 The most typical friction modifier is an organomolybdenum compound. As shown in Non-Patent Document 1, these organomolybdenum compounds are represented by the following formulas (2) and (3). As shown, the compound contains two Mo elements in one molecule.

Patent Documents 1 to 5 also disclose two Mo element-containing compounds in one molecule.
And, as shown by the general formula (2), the compound containing phosphorus in the molecule contains a problem that it becomes a catalyst poison of an exhaust gas purifier when used in engine oil, and does not contain phosphorus. There is a need for compounds.

July 25, 1986, published by Koshobo Co., Ltd., edited by Toshio Sakurai, “New Version Petroleum Product Additives” Japanese Patent No. 3495764 Japanese Patent Publication No. 45-24562 JP-A 52-19629 JP-A-52-106824 JP-A 48-56202

A first object of the present invention is to provide a novel compound useful as a friction modifier that optimally adjusts friction, and a friction modifier comprising the compound that does not contain phosphorus.
The second object of the present invention is to provide a lubricating composition using the same.

〔式中、−Ａは、−ＯＲまたは−ＮＲ′_２であり、Ｒはアルキル基、Ｒ′はアルキル基（ただし、２つのＲ′がＮと共に５員環、または６員環を形成していてもよい）よりなる群から選択されたものである。〕
で示される有機モリブデン化合物に関する。
本発明の第２は、塩化モリブデンＭｏＣｌ_５１当量に対し４〜６当量の下記一般式で表されるキサントゲン酸カリウムとの反応により生成された有機モリブデン化合物に関する。

〔式中、−Ａは、−ＯＲまたは−ＮＲ′_２であり、Ｒはアルキル基、Ｒ′はアルキル基（ただし、２つのＲ′がＮと共に５員環、または６員環を形成していてもよい）よりなる群から選択されたものである。〕
本発明の第３は、請求項１または２記載の有機モリブデン化合物よりなる摩擦調整剤に関する。
本発明の第４は、請求項１または２記載の有機モリブデン化合物を含有する潤滑組成物に関する。 The first of the present invention is the following general formula (1)

Wherein, -A _is' a _2, R is an alkyl group, R '-OR or -NR an alkyl group (provided that the two R' is to form a 5- or 6-membered ring together with the N It may be selected from the group consisting of: ]
It relates to the organomolybdenum compound shown by.
The second of the present invention relates to an organomolybdenum compound produced by a reaction with 4 to 6 equivalents of potassium xanthate represented by the following general formula per 1 equivalent of molybdenum chloride MoCl ₅ .

Wherein, -A _is' a _2, R is an alkyl group, R '-OR or -NR an alkyl group (provided that the two R' is to form a 5- or 6-membered ring together with the N It may be selected from the group consisting of: ]
3rd of this invention is related with the friction modifier which consists of an organomolybdenum compound of Claim 1 or 2.
4th of this invention is related with the lubricating composition containing the organomolybdenum compound of Claim 1 or 2.

前記式中、Ｒは例えばＣ数１〜３０のアルキル基、Ｒ′は、例えばＣ数１〜３０のアルキル基であるか、２つのＲ′がＮと一緒になって、５員環、または６員環を形成していてもよい。 The compound of the present invention can be produced, for example, by the following reaction.

In the above formula, R is, for example, an alkyl group having 1 to 30 carbon atoms, R ′ is, for example, an alkyl group having 1 to 30 carbon atoms, or two R ′ together with N is a 5-membered ring, or A 6-membered ring may be formed.

（前記式中Ｒは、Ｃ_ｎＨ_２ｎ＋１で示される直鎖状または分岐鎖状の炭化水素である。） Or it can manufacture also with the following method.

(In the above formula, R is a linear or branched hydrocarbon represented by C _n H _{2n + 1.} )

  The alkyl group having 1 to 30 carbon atoms in R and R ′ may be linear or branched. For example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n- Examples include decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the like.

として表すことができる。式中、Ｚ^１〜Ｚ^４は、Ｃ、Ｏ、ＮおよびＳよりなる群からそれぞれ独立して選ばれた元素であり、これらのうちＣやＮの場合には隣りのＣやＮと２重結合を形成してもよい。Ｒ^１〜Ｒ^４およびＲ^１′〜Ｒ^４′は、水素および炭素数１〜３０のアルキル基よりなる群からそれぞれ独立して選ばれた基であるがＺ^１〜Ｚ^４が環形成で結合手が飽和している場合はこれらの基は存在しない。

Can be expressed as In the formula, Z ^{1 to} Z ⁴ are elements independently selected from the group consisting of C, O, N and S, and among these, in the case of C and N, the adjacent C and N are doubled. A bond may be formed. R ^{1 to} R ⁴ and R ^{1 ′ to} R ^{4 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group having 1 to 30 carbon atoms, but Z ^{1 to} Z ⁴ are bonded to form a ring. These groups are absent when the hand is saturated.

として表すことができる。式中、Ｚ^５〜Ｚ^９は、Ｃ、Ｏ、ＮおよびＳよりなる群からそれぞれ独立して選ばれた元素であり、これらのうちＣやＮの場合には隣りのＣやＮと２重結合を形成してもよい。Ｒ^５〜Ｒ^９およびＲ^５′〜Ｒ^９′は、水素および炭素数１〜３０のアルキル基よりなる群からそれぞれ独立して選ばれた基であるがＺ^５〜Ｚ^９が環形成で結合手が飽和している場合はこれらの基は存在しない。

Can be expressed as In the formula, Z ^{5 to} Z ⁹ are elements independently selected from the group consisting of C, O, N, and S. Among these, in the case of C or N, the adjacent C or N is doubled. A bond may be formed. R ^{5 to} R ⁹ and R ^{5 ′ to} R ^{9 ′} are groups independently selected from the group consisting of hydrogen and an alkyl group having 1 to 30 carbon atoms, but Z ^{5 to} Z ⁹ are bonded to form a ring. These groups are absent when the hand is saturated.

Specific examples of the 5-membered ring or 6-membered ring include the following cases.

The 5-membered ring such as the tetrazole type and the 6-membered ring such as the morpholine type may have substituents represented by R ^{1 to} R ⁹ and R ^{1 ′ to} R ^{9 ′} . The alkyl group having 1 to 30 carbon atoms, which is the locating group, may be linear or branched. For example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n- Examples include decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-pentadecyl, n-octadecyl, n-nonadecyl, n-eicosyl and the like.

Examples of compounds when -A is -OR are molybdenum methoxyxanthate (IV)
Molybdenum ethoxyxanthate (IV)
Molybdenum n-propoxyxanthate (IV)
Iso-Propoxyxanthate Molybdenum (IV)
Molybdenum n-butoxyxanthate (IV)
sec-Butoxyxanthate Molybdenum (IV)
Molybdenum t-butoxyxanthate (IV)
Molybdenum n-pentyloxyxanthate (IV)
Molybdenum 2-methylbutoxyxanthate (IV)
Molybdenum n-hexyloxyxanthate (IV)
Molybdenum 2-ethylhexyloxyxanthate (IV)
Molybdenum n-octyloxyxanthate (IV)
Molybdenum n-nonyloxyxanthate (IV)
Molybdenum (IV) n-decanyloxyxanthate
Molybdenum (IV) n-undecanyloxyxanthate
Molybdenum (IV) n-tridecanyloxyxanthate
Molybdenum (IV) n-tetradecanyloxyxanthate
n-Pentadecanyloxyxanthate molybdenum (IV)
n-Hexadecanyloxyxanthate molybdenum (IV)
Molybdenum (IV) n-heptadecanyloxyxanthate
Molybdenum (IV) n-octadecanyloxyxanthate
Molybdenum n-nonadecanyloxyxanthate (IV)
Molybdenum n-eicosanyloxyxanthate (IV)

Wherein -A is _'a case _2, R' -CNR Examples of cases is an alkyl group,
(Dimethylamino) molybdenum xanthate (IV)
(Diethylamino) molybdenum xanthate (IV)
(Di-n-propylamino) molybdenum xanthate (IV)
(Di-iso-propylamino) molybdenum xanthate (IV)
(Di-n-butylamino) molybdenum xanthate (IV)
(Di-sec-butylamino) molybdenum xanthate (IV)
(Di-t-butylamino) molybdenum xanthate (IV)
(Di-n-pentylamino) molybdenum xanthate (IV)
(Di-2-methylbutylamino) molybdenum xanthate (IV)
(Di-n-hexylamino) molybdenum xanthate (IV)
(Di-2-ethylhexylamino) molybdenum xanthate (IV)
(Di-n-octylamino) molybdenum xanthate (IV)
(Di-n-nonanylamino) molybdenum xanthate (IV)
(Di-n-decanylamino) molybdate (IV) xanthate
(Di-n-undecanylamino) molybdenum xanthate (IV)
(Di-n-tridecanylamino) molybdenum xanthate (IV)
(Di-n-tetradecanylamino) molybdenum xanthate (IV)
(Di-n-pentadecanylamino) molybdenum xanthate (IV)
(Di-n-hexadecanylamino) molybdenum xanthate (IV)
(Di-n-heptadecanylamino) molybdenum xanthate (IV)
(Di-n-octadecanylamino) molybdenum xanthate (IV)
(Di-n-nonadecanylamino) molybdate (IV) xanthate
(Di-n-eicosanylamino) molybdenum xanthate (IV)

Examples of the compound in the case where —CNR ′ ₂ as —A is a 5-membered ring include
Molybdenum tetrazolylxanthate (IV)
Molybdenum triazolyl xanthate (IV)
Pyrazolylxanthogenate molybdenum (IV)
Pyrazolidinyl molybdenum xanthate (IV)
Molybdenum imidazolylxanthate (IV)
Oxazolidinyl molybdenum xanthate (IV)
Molybdenum thiazolidinylxanthate (IV)
Molybdenum pyrrolidinylxanthate (IV)
Molybdenum pyrrolinylxanthate (IV)
Molybdenum pyrrolylxanthate (IV)

Examples of the compound in the case where —CNR ′ ₂ as —A is a 6-membered ring include
Piperazinyl molybdenum xanthate (IV)
Pyrazinyl xanthate molybdenum (IV)
Thiomorpholinyl molybdenum xanthate (IV)
Molybdenum thiazinylxanthate (IV)
Morpholinylxanthate molybdenum (IV)
Molybdenum oxazinylxanthate (IV)
Piperidinyl molybdenum xanthate (IV)

(1) A new Mo-based friction modifier containing no phosphorus was obtained.
(2) The compound of the present invention exhibits a low coefficient of friction and can be used as an additive for various energy-saving lubricating oils.
(3) Since the compound of the present invention does not contain phosphorus, it is particularly suitable for the use of fuel-saving engine oil.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Ａｒ置換した２００ｍｌナスフラスコに精製水２０ｍｌと塩化メチレン２０ｍｌの混合溶液を作り、ペンチルキサントゲン酸カリウム７．４１ｇ（３６．６ｍｍｏｌ）を溶解させ、そこにＭｏＣｌ_５２ｇ（７．３２ｍｍｏｌ）をゆっくり加え、３０分間撹拌した。有機層を抽出し、精製水２０ｍｌ用いて数回洗浄し、有機層を取り出し、硫酸マグネシウムにより乾燥させた。塩化メチレン／ｎ−ヘキサンの２：１の混合溶液を用いたカラムクロマトグラフィーにより紫色の液体を単離した。
化合物データ
収率 ６５％ Example 1 Synthesis of Mo [S ₂ CO (C ₅ H ₁₁ )] ₄

Ar make a mixed solution of substituted 200ml round-bottomed flask in purified water 20ml of methylene chloride 20ml, dissolved pliers Ruki Santo potassium Gen acid 7.41 g (36.6 mmol), there was added slowly MoCl ₅ 2g (7.32mmol), Stir for 30 minutes. The organic layer was extracted and washed several times with 20 ml of purified water, and the organic layer was taken out and dried over magnesium sulfate. The purple liquid was isolated by column chromatography using a 2: 1 mixed solution of methylene chloride / n-hexane.
Compound data Yield 65%

Ａｒ置換した２００ｍｌナスフラスコに精製水２０ｍｌと塩化メチレン２０ｍｌの混合溶液を作り、イソプロピルキサントゲン酸カリウム６．３８ｇ（３６．６ｍｍｏｌ）を溶解させ、そこにＭｏＣｌ_５２ｇ（７．３２ｍｍｏｌ）をゆっくり加え、３０分間撹拌した。反応終了後、有機層を抽出し、精製水２０ｍｌ用いて数回洗浄し、有機層を取り出し、硫酸マグネシウムにより乾燥させた。塩化メチレンのカラムクロマトグラフィーにより赤紫色の液体を単離した。
化合物データ
収率 ７５％ Example 2 Synthesis of Mo [S ₂ COCH (CH ₃ ) ₂ ] ₄

A mixed solution of 20 ml of purified water and 20 ml of methylene chloride was prepared in an Ar-substituted 200 ml eggplant flask, and 6.38 g (36.6 mmol) of potassium isopropylxanthate was dissolved therein, and 2 g (7.32 mmol) of MoCl ₅ was slowly added thereto. Stir for 30 minutes. After completion of the reaction, the organic layer was extracted and washed several times with 20 ml of purified water, and the organic layer was taken out and dried over magnesium sulfate. A purple-red liquid was isolated by column chromatography with methylene chloride.
Compound data Yield 75%

Ａｒ置換した２００ｍｌナスフラスコに精製水２０ｍｌと塩化メチレン２０ｍｌを加えて混合溶液を作り、エチルキサントゲン酸カリウム５．８７ｇ（３６．６ｍｍｏｌ）を溶解させ、そこにＭｏＣｌ_５２ｇ（７．３２ｍｍｏｌ）をゆっくり加え、３０分間撹拌した。有機層を抽出し、精製水２０ｍｌ用いて数回洗浄し、有機層を取り出し、硫酸マグネシウムにより乾燥させた。塩化メチレン／ｎ−ヘキサンの２：１の混合溶液を用いたカラムクロマトグラフィーにより紫色の液体を単離した。
化合物データ
収率 ６８％ Example 3 Synthesis of Mo [S ₂ COC ₂ H ₅ ] ₄

Ar substituted 200ml round-bottomed flask was added with purified water 20ml of methylene chloride 20ml make a mixed solution, dissolve the potassium ethyl xanthate 5.87 g (36.6 mmol), there slowly MoCl ₅ 2g (7.32mmol) Added and stirred for 30 minutes. The organic layer was extracted and washed several times with 20 ml of purified water, and the organic layer was taken out and dried over magnesium sulfate. The purple liquid was isolated by column chromatography using a 2: 1 mixed solution of methylene chloride / n-hexane.
Compound data Yield 68%

Ａｒ置換した１００ｍｌナスフラスコにエチルジチオカルバミル酸ナトリウム０．８３ｇ（３．７ｍｍｏｌ）と精製水１５ｍｌを加えてよく撹拌し、ついでそこに塩化メチレン１５ｍｌを注ぎ、ＭｏＣｌ_５０．２ｇ（０．７３２ｍｍｏｌ）をゆっくり加え、３０分間撹拌した。得られた有機層を精製水２０ｍｌ用いて数回洗浄し、有機層を取り出し、硫酸マグネシウムにより乾燥させた。塩化メチレンのカラムクロマトグラフィーにより黒紫色の液体を単離した。
化合物データ
収率 ８０％
ＭＳ（ＥＩ^＋，７０ｅＶ）Ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）
６９０（Ｍ^＋，１０．３３）、５４２［Ｍｏ〔Ｓ_２ＣＮ（Ｃ_２Ｈ_５）_２〕_３，９．５０］ Example 4 Synthesis of Mo [S ₂ CN (C ₂ H ₅ ) ₂ ] ₄

To an Ar-substituted 100 ml eggplant flask, 0.83 g (3.7 mmol) of sodium ethyldithiocarbamate and 15 ml of purified water were added and stirred well. Then, 15 ml of methylene chloride was poured therein, and 0.2 g (0.732 mmol) of MoCl _{5 was} added. ) Was added slowly and stirred for 30 minutes. The obtained organic layer was washed several times with 20 ml of purified water, and the organic layer was taken out and dried over magnesium sulfate. A black-purple liquid was isolated by column chromatography with methylene chloride.
Compound data Yield 80%
MS (EI ⁺ , 70 eV) M / z (relative intensity)
690 (M ⁺ , 10.33), 542 [Mo [S ₂ CN (C ₂ H ₅ ) ₂ ] ₃ , 9.50]

Ａｒ置換した２００ｍｌナスフラスコに水酸化ナトリウム０．８３ｇ（４５ｍｍｏｌ）を３０ｍｌの水に溶かした溶液にジヘキシルアミン５ｍｌ（４５ｍｍｏｌ）を加え、１０分間撹拌し、そこに二硫化炭素１３ｍｌ（４５ｍｍｏｌ）を加え、さらに１５分撹拌して、配位子となるジオクチルチオカルバミン酸ナトリウムを合成した。その母液に塩化メチレン３０ｍｌを注ぎ、さらにＭｏＣｌ_５０．９３ｇ（３．４ｍｍｏｌ）をゆっくり加え、３０分間撹拌した。得られた有機層を精製水３０ｍｌで数回洗浄し、有機層を取り出し、硫酸マグネシウムを用いて乾燥させた。溶媒を減圧除去し、塩化メチレン／ｎ−ヘキサン１：１溶液を用いてカラムクロマトグラフィーで茶褐色の生成物を単離した。
化合物データ
収率 ５５％
ＭＳ（ＥＩ^＋，７０ｅＶ）Ｍ／ｚ（ｒｅｌａｔｉｖｅ ｉｎｔｅｎｓｉｔｙ）
１１３８（Ｍ^＋，５．２１）、８７８［Ｍｏ〔Ｓ_２ＣＮ（Ｃ_６Ｈ_１３）_２〕_３，５．２６］ Example 5 Synthesis of Mo [S ₂ CN (C ₆ H ₁₃ ) ₂ ] ₄

To an Ar-substituted 200 ml eggplant flask, 0.83 g (45 mmol) of sodium hydroxide dissolved in 30 ml of water was added 5 ml (45 mmol) of dihexylamine, stirred for 10 minutes, and 13 ml (45 mmol) of carbon disulfide was added thereto. The mixture was further stirred for 15 minutes to synthesize sodium dioctylthiocarbamate as a ligand. 30 ml of methylene chloride was poured into the mother liquor, and 0.93 g (3.4 mmol) of MoCl ₅ was slowly added, followed by stirring for 30 minutes. The obtained organic layer was washed several times with 30 ml of purified water, and the organic layer was taken out and dried using magnesium sulfate. The solvent was removed under reduced pressure, and the brown product was isolated by column chromatography using a 1: 1 solution of methylene chloride / n-hexane.
Compound data Yield 55%
MS (EI ⁺ , 70 eV) M / z (relative intensity)
1138 (M ⁺ , 5.21), 878 [Mo [S ₂ CN (C ₆ H ₁₃ ) ₂ ] ₃ , 5.26]

Ａｒ置換した１００ｍｌナスフラスコにピロリジンチオカルバミル酸アンモニウム６ｇ（３６．６ｍｍｏｌ）と精製水１５ｍｌを加えてよく撹拌し、ついでそこに塩化メチレン１５ｍｌを注ぎ、ＭｏＣｌ_５０．２ｇ（７．３ｍｍｏｌ）をゆっくり加え、３０分間撹拌した。得られた有機層を精製水２０ｍｌ用いて数回洗浄し、有機層を取り出し、硫酸マグネシウムにより乾燥させた。塩化メチレンのカラムクロマトグラフィーにより赤褐色の固体を単離した。
化合物データ
収率 ８５％ Example 6 Synthesis of Mo [S ₂ CNC ₄ H ₈ ] ₄

Add 6 g (36.6 mmol) of ammonium pyrrolidinethiocarbamate and 15 ml of purified water to an Ar-substituted 100 ml eggplant flask and stir well. Then, pour 15 ml of methylene chloride there, and add 0.2 g (7.3 mmol) of MoCl _5. Slowly added and stirred for 30 minutes. The obtained organic layer was washed several times with 20 ml of purified water, and the organic layer was taken out and dried over magnesium sulfate. A reddish brown solid was isolated by methylene chloride column chromatography.
Compound data Yield 85%

ＳＲＶ摩擦係数は、３０分間でコンピュータが１０００回測定するので、そのなかの最小値がＳＲＶ摩擦係数最小値であり、１０００回の測定値の平均がＳＲＶ摩擦係数平均値である。
本発明の摩擦調整剤を含まない比較例１と比較して、実施例７〜１２は、低い摩擦係数を示すことが分かった。 Examples 7-12 and Comparative Example 1
Each compound obtained in Examples 1 to 6 was added to ester oil (diisononyl adipic acid) (kinematic viscosity at 100 ° C .: 3.04 mm ² / s) so that the Mo content was 500 ppm, and a dispersant ( Examples 7-12 were prepared by adding 5% by mass of an alkenyl succinic acid polyalkylene polyimide product name Infinium C9266). As Comparative Example 1, a sample to which no Mo compound was added was also prepared.
These sample oils were measured and evaluated for 30 minutes by the SRV tester (cylinder-on-disk type reciprocating tester shown in FIG. 1) under the conditions shown in Table 3 below, and the results are shown in Table 4. The specimen is 52100 steel.
Test conditions

Since the SRV friction coefficient is measured 1000 times by the computer in 30 minutes, the minimum value among them is the SRV friction coefficient minimum value, and the average of 1000 measurement values is the SRV friction coefficient average value.
It turned out that Examples 7-12 show a low friction coefficient compared with the comparative example 1 which does not contain the friction modifier of this invention.

（実験方法）
５００ｍｌのナス型フラスコにジ（２−エチルヘキシル）アミン（９．６５ｇ、４０ｍｍｏｌ）と水酸化ナトリウム水溶液（１．７０ｇ、４３ｍｍｏｌ）１７０ｍｌを加え、５分間撹拌した。その後、二硫化炭素（２．７０ｍｌ、４５ｍｍｏｌ）を加え、さらに３０分間撹拌し、配位子となるジ（２−エチルヘキシル）ジチオカルバミン酸ナトリウムを合成した。白濁色に変化した溶液を吸引ろ過し、得られたろ液にモリブデン酸ナトリウム水溶液（７．００ｇ、２９ｍｍｏｌ）１００ｍｌを加えた。その後、この溶液を３〜５℃に冷却し、希硝酸（濃硝酸５．４１ｇに水を加え、全量を８６ｍｌにしたもの）を滴下漏斗を用いて約３０分間かけて滴下し、さらに１時間撹拌した。得られた紫色の反応混合物をデカンテーションにより洗浄した後、トルエン３０ｍｌに溶解させ、さらに７０％ｔ−ブチルヒドロペルオキシド０．６ｍｌを加え、３０分間撹拌し、反応式（２）の反応を完結させた。橙色に変化した溶液にペンタン１２０ｍｌを加え、約５℃で一日放置した後に溶媒を減圧留去し、紫色油状の２ａを得た。
形状 紫色油状物質
収率 ２２％
（２）錯体２ａ′の合成
モリブデンテトラ（２−エチルヘキシル）ジチオカルバマト錯体（錯体２ａ′）

アルゴン雰囲気下で還流管を付けた２００ｍｌの二口フラスコに錯体２ａ（０．１８ｇ、０．２４ｍｍｏｌ）とトリフェニルホスフィン（ＰＰｈ_３）（０．１２ｇ、０．４５ｍｍｏｌ）と１，２−ジクロロエタン（３ｍｌ、蒸留溶媒）を加え、２０分間加熱還流を行った後に、１，２−ジクロロエタンを減圧留去した。得られた紫色の反応混合物にアセトン（３ｍｌ、蒸留溶媒）とＳ_８（２．４ｍｇ、０．００９ｍｍｏｌ）を加え、３時間加熱還流を行った後に、アセトンを減圧留去した。
形状 赤紫色油状物質
収率 １６％ Example 13 Synthesis of Mo [S ₂ CN (iso-C ₈ H ₁₇ ) ₂ ] ₄ [molybdenum tetra (2-ethylhexyl) dithiocarbamato complex] Complex 2a: Target complex via molybdenum di (2-ethylhexyl) dithiocarbamate complex 2a 'is synthesized.
(1) Synthesis of complex 2a Molybdenum di (2-ethylhexyl) dithiocarbamato complex (complex 2a)

(experimental method)
Di (2-ethylhexyl) amine (9.65 g, 40 mmol) and 170 ml of aqueous sodium hydroxide solution (1.70 g, 43 mmol) were added to a 500 ml eggplant-shaped flask and stirred for 5 minutes. Thereafter, carbon disulfide (2.70 ml, 45 mmol) was added, and the mixture was further stirred for 30 minutes to synthesize di (2-ethylhexyl) dithiocarbamate sodium as a ligand. The solution changed to a cloudy color was subjected to suction filtration, and 100 ml of an aqueous sodium molybdate solution (7.00 g, 29 mmol) was added to the obtained filtrate. Thereafter, this solution was cooled to 3 to 5 ° C., and diluted nitric acid (water was added to concentrated nitric acid 5.41 g to make the total volume 86 ml) was dropped over about 30 minutes using a dropping funnel, and further for 1 hour. Stir. The resulting purple reaction mixture is washed by decantation, then dissolved in 30 ml of toluene, and further 0.6 ml of 70% t-butyl hydroperoxide is added and stirred for 30 minutes to complete the reaction of reaction formula (2). It was. Pentane (120 ml) was added to the orange-colored solution and allowed to stand at about 5 ° C. for one day, and then the solvent was distilled off under reduced pressure to obtain purple oil 2a.
Shape Purple oily substance Yield 22%
(2) Synthesis of complex 2a ′ Molybdenum tetra (2-ethylhexyl) dithiocarbamato complex (complex 2a ′)

In a 200 ml two-necked flask equipped with a reflux tube under an argon atmosphere, complex 2a (0.18 g, 0.24 mmol), triphenylphosphine (PPh ₃ ) (0.12 g, 0.45 mmol) and 1,2-dichloroethane ( 3 ml, distilled solvent) was added and the mixture was heated to reflux for 20 minutes, and then 1,2-dichloroethane was distilled off under reduced pressure. Acetone (3 ml, distillation solvent) and S ₈ (2.4 mg, 0.009 mmol) were added to the resulting purple reaction mixture, and the mixture was heated to reflux for 3 hours, and then acetone was distilled off under reduced pressure.
Shape Red purple oily substance Yield 16%

Example 14
For the compound synthesized in Example 13, the SRV friction coefficient minimum value and the SRV friction coefficient average value were determined in the same manner as in Examples 7-12. The results are shown in Table 5 below.

It is an operation schematic diagram of a cylinder on disk type reciprocating test machine.

Claims (4)

The following general formula (1)

Wherein, -A _is' a _2, R is an alkyl group, R '-OR or -NR an alkyl group (provided that the two R' is to form a 5- or 6-membered ring together with the N It may be selected from the group consisting of: ]
An organomolybdenum compound represented by An organomolybdenum compound produced by a reaction with 4 to 6 equivalents of potassium xanthate represented by the following general formula per 1 equivalent of molybdenum chloride MoCl ₅ .

Wherein, -A _is' a _2, R is an alkyl group, R '-OR or -NR an alkyl group (provided that the two R' is to form a 5- or 6-membered ring together with the N It may be selected from the group consisting of: ]   A friction modifier comprising the organomolybdenum compound according to claim 1 or 2.   A lubricating composition containing the organomolybdenum compound according to claim 1.

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