JP6215083B2 - Alkyl bismuth alkoxide compound and method for producing the same - Google Patents

Description

  The present invention relates to a bismuth compound useful as a synthetic catalyst and a material for CVD (Chemical Vapor Deposition) such as medical pesticides, organic materials and intermediates thereof, and a method for producing the same.

  A bismuth compound as a CVD material is desired to be a compound having sufficient vaporization characteristics and excellent thermal stability. Sufficient vaporization characteristics are specifically lower boiling points than triphenylbismuth, and excellent thermal stability means that they do not explode due to heating or impact. It is desired that the bismuth compound as a synthesis catalyst is also excellent in thermal stability.

As a bismuth compound for CVD materials, dialkylaryl bismuth prepared by a reaction in which methylmagnesium bromide is allowed to act on bismuth halide is known (Formula 9). By introducing two methyl groups on the bismuth atom, vaporization characteristics required as a CVD material are obtained (Patent Document 1).

Since the bismuth-carbon (sp ³ carbon) bond is unstable to heat, care must be taken when forming a film by CVD. Here, if an oxygen functional group is introduced instead of an alkyl group, the binding energy with bismuth increases, and thermal stability can be ensured. As a conventional method for synthesizing an alkyl bismuth alkoxide compound, a method in which sodium ethoxide is allowed to act on an alkyl halogenated bismuth represented by Formula 10 is known (Non-Patent Document 1).
MeBiBr ₂ + 2NaOEt → MeBi (OEt) ₂ + 2NaBr (10)

In order to avoid this, alkali metal salts such as sodium salts have an unfavorable effect on the electrical characteristics of the product. To avoid this, a method using no alkali metal is also known (Patent Document 2). The purpose of this is to produce dielectrics such as Bi ₂ Ta ₂ O ₉ and Bi ₄ Ti ₃ O ₁₂ and Sr—Bi—Ca—Cu—O high temperature superconductors, in which alcohol and metal strontium react in advance. Strontium alkoxide is prepared and reacted with bismuth chloride.
2BiCl ₃ + 3Sr (OCH (CH ₃ ) ₂ ) ₂ → 2Bi (OCH (CH ₃ ) ₂ ) ₃ + 3SrCl ₂ (11)

As a reaction for directly phenoxylating an alkyl group on a bismuth atom, that is, for partially phenoxylating a trialkylbismuth, as shown in Formula 12, triethylbismuth and phenol or 2,3,4,5,6-penta A reaction to obtain poly (diethylphenoxybismuth) or poly (diethyl (2,3,4,5,6-pentafluorophenoxy) bismuth) by reaction with fluorophenol has also been reported (Non-patent Document 2).
Et ₃ Bi + PhOH (or C ₆ F ₅ OH) → [Et ₂ Bi (OPh)] _∞ (or [Et ₂ Bi (OC ₆ F ₅ )] _∞ ) (12)

As a reaction for performing alkoxylation on a bismuth atom with an aliphatic alcohol, there is a method in which an alcohol is allowed to act on trisdimethylaminobismuth Bi (NMe ₂ ) ₃ (Non-patent Document 3) (Non-Patent Document 3). Reference 4).
Bi (NMe ₂ ) ₃ + 3 (CH ₃ ) ₂ CHOH → Bi (OCH (CH ₃ ) ₂ ) ₃ (13)

JP-A-2005-97235 Japanese Patent No. 3484582

Z. Anorg. Allg. Chem. 423 (1), 40-46 (1976) J. Chem. Soc., Chem. Commun. 1021-1022 (1992) J. Inorg. Nucl. Chem. 37, 2011-2013 (1975) Inorg. Chem. vol. 29, 358-360 (1990)

  However, a bismuth compound useful as a CVD material or the like having sufficient vaporization characteristics and excellent thermal stability has not been known so far. Accordingly, an object of the present invention is to provide a novel bismuth compound useful as a CVD material or the like having sufficient vaporization characteristics and excellent thermal stability. A further object of the present invention is to provide a method by which the novel bismuth compound can be produced in a relatively simple and efficient manner.

  In order to achieve the above object, the present inventors planned to obtain an alkyl bismuth alkoxide compound represented by the following general formula (1) or general formula (2), and studied a production method. The alkyl bismuth alkoxide compound represented by the following general formula (1) or general formula (2) is a novel compound, and of course, there is no report on a production method, and it can be easily obtained from a trialkyl bismuth in one step. Was considered difficult.

As a method for obtaining a compound other than the alkyl bismuth alkoxide compound, (1) a method of reacting a bismuth halide and an alcohol or a metal alkoxide, (2) a method of reacting a phenol with triethylbismuth, (3) Bi (NMe ₂ ) A method of reacting ₃ with alcohols is known.

  However, the method of (1) requires a plurality of reaction steps because it is necessary to prepare bismuth alkyl halide in advance in order to obtain the desired product (Non-patent Document 1), and the electrical characteristics as impurities are remarkably increased. There was a problem that a large amount of alkali metal salt that could be reduced and difficult to remove completely was produced as a by-product. The method of reacting bismuth chloride with strontium alkoxide (Patent Document 2) requires the removal of a large amount of by-product strontium salt, and the price of strontium is expensive and difficult to obtain. There was a problem.

The method (2) is limited to alkyl bismuth phenoxides such as [Et ₂ Bi (OPh)] _{∞ of} Non-Patent Document 2. In this document, the substrate is limited to phenols, and an example in which an aliphatic alcohol is applied to a similar reaction is not shown, and there is still a problem. Since the phenoxylation requires a high temperature of 100 ° C. or higher and a long time of 40 hours, when this reaction condition is applied to an alcohol having a boiling point lower than 100 ° C., the alcohol volatilizes and it is difficult to contribute to the reaction. It is. In addition, a product in which two alkyl groups on the bismuth atom are replaced with two phenoxy groups has not been obtained.

Method (3) is a method through the Bi (NMe _{2) 3,} must be reacted difficult dimethylamino lithium prepared as bismuth chloride to obtain a Bi (NMe _{2) 3,} further Bi (NMe ₂ ) ₃ yield is 20 to 52%, which is not efficient (Non-patent Document 3). In order to obtain an alkyl bismuth alkoxide compound represented by the general formula (1) or (2), a bismuth compound in which a dimethylamino group and an alkyl group coexist on a bismuth atom must be prepared in advance. However, the alkylbismuth alkoxide compound could not be obtained simply and in one step, which was difficult.

  This invention is made | formed in order to solve the said subject in such a condition.

  The present inventors can solve the problems of the production method in the above prior art, and can produce the alkylbismuth alkoxide compound represented by the general formula (1) or the general formula (2) relatively simply and efficiently. The method was studied earnestly. As a result, the trialkylbismuth compound represented by the general formula (7) is reacted with the fluorinated alcohol represented by the general formula (8), thereby being represented by the general formula (1) or the general formula (2). The present inventors have found a method capable of efficiently producing an alkylbismuth alkoxide compound, and have completed the present invention.

式中、Ｒ₁、Ｒ₂及びＲ₃は、各々独立に、直鎖、分枝若しくは環状の、炭素数１〜１０のアルキル基を表す。Ｂｉはビスマス原子を表す。

In the formula, R ₁ , R ₂ and R ₃ each independently represent a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Bi represents a bismuth atom.

式中、Ｒ₄およびＲ₅は、各々独立に、
フッ素原子、塩素原子およびヒドロキシル基からなる群から選ばれる置換基で置換された、若しくは未置換の直鎖、分枝若しくは環状の、炭素数１〜１０のアルキル基、
フッ素原子、塩素原子およびヒドロキシル基からなる群から選ばれる置換基で置換された、若しくは未置換のアリール基、
または水素原子を表す。
ｎは１〜１０の整数を表す。
ｘおよびｙは、各々独立に、０または１を表す。ｋは１、２または３を表す。但し、ｘ、ｙおよびｋの合計は３である。Ｆはフッ素原子、Ｏは酸素原子を表す。

Wherein R ₄ and R ₅ are each independently
A linear or branched or cyclic alkyl group having 1 to 10 carbon atoms, substituted or unsubstituted with a substituent selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group,
A substituted or unsubstituted aryl group substituted with a substituent selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group,
Or represents a hydrogen atom.
n represents an integer of 1 to 10.
x and y each independently represents 0 or 1. k represents 1, 2 or 3. However, the sum of x, y and k is 3. F represents a fluorine atom, and O represents an oxygen atom.

（式中Ｒ₁およびＲ₂は、各々独立に、直鎖、分枝または環状の、炭素数１〜１０のアルキル基を表し、
Ｒ₄およびＲ₅は、各々独立に、フッ素原子、塩素原子およびヒドロキシル基からなる群から選ばれる置換基で置換された、若しくは未置換の直鎖、分枝若しくは環状の、炭素数１０以下のアルキル基、フッ素原子、塩素原子およびヒドロキシル基からなる群から選ばれる置換基で置換された、若しくは未置換のアリール基、または水素原子を表わし、
ｎは１〜１０の整数を表し、
ｘおよびｙは、各々独立に、０または１を表し、ｋは１、２または３を表し、但し、ｘ、ｙおよびｋの合計は３であり、Ｆはフッ素原子、Ｏは酸素原子、Ｂｉはビスマス原子を表す。）

（式中Ｒ₁は、直鎖、分枝または環状の、炭素数１〜１０のアルキル基を表し、Ｆはフッ素原子、Ｏは酸素原子、Ｂｉはビスマス原子を表す。）

(Wherein R ₁ and R ₂ each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R ₄ and R ₅ are each independently substituted with a substituent selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group, or unsubstituted, linear, branched or cyclic, and having 10 or less carbon atoms Represents a substituted or unsubstituted aryl group substituted with a substituent selected from the group consisting of an alkyl group, a fluorine atom, a chlorine atom and a hydroxyl group, or a hydrogen atom;
n represents an integer of 1 to 10,
x and y each independently represents 0 or 1, k represents 1, 2 or 3, provided that the sum of x, y and k is 3, F is a fluorine atom, O is an oxygen atom, Bi Represents a bismuth atom. )

(In the formula, R ₁ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, F represents a fluorine atom, O represents an oxygen atom, and Bi represents a bismuth atom.)

（式中Ｒ₁およびＲ₂は、各々独立に、直鎖、分枝または環状の、炭素数１〜１０のアルキル基を表し、
Ｒ₄およびＲ₅は、各々独立に、フッ素原子、塩素原子およびヒドロキシル基からなる群から選ばれる置換基で置換された、若しくは未置換の直鎖、分枝若しくは環状の、炭素数１〜１０のアルキル基、フッ素原子、塩素原子およびヒドロキシル基からなる群から選ばれる置換基で置換された、若しくは未置換のアリール基、または水素原子を表わし、
ｎは１〜１０の整数を表し、
ｘおよびｙは、各々独立に、０または１を表し、ｋは１、２または３を表し、但し、ｘ、ｙおよびｋの合計は３であり、Ｆはフッ素原子、Ｏは酸素原子、Ｂｉはビスマス原子を表す。）
［２］
一般式（２）で表されるアルキルビスマスアルコキシド化合物。

（式中Ｒ₁、Ｆ、Ｏ、Ｂｉは[１]の定義と同じである。）
［３］
Ｒ₁およびＲ₂で表されるアルキル基が、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基およびｔｅｒｔ−ブチル基からなる群から選ばれるアルキル基である［１］に記載のアルキルビスマスアルコキシド化合物。
［４］
ｎが１〜３であり、ｘが１、ｙが０、ｋが２である［１］または［３］に記載のアルキルビスマスアルコキシド化合物。
［５］
Ｒ₄がフッ素原子、塩素原子およびヒドロキシル基からなる群から選ばれる置換基でされた、若しくは未置換の直鎖、分枝若しくは環状の炭素数１〜６のアルキル基、フェニル基、または水素原子である［１］、［３］または[４]のいずれかに記載のアルキルビスマスアルコキシド化合物。
［６］
前記一般式（１）で表されるアルキルビスマスアルコキシド化合物が、式（３）で表されるジメチルビスマス２，２，２−トリフルオロ−１−トリフルオロメチルエトキシドである［１］および［３］〜［５］のいずれかに記載のアルキルビスマスアルコキシド化合物。

［７］
前記一般式（１）で表されるアルキルビスマスアルコキシド化合物が、式（４）で表されるジメチルビスマス２，２，２−トリフルオロ−１−トリフルオロメチル−１−フェニルエトキシドである［１］および［３］〜［５］のいずれかに記載のアルキルビスマスアルコキシド化合物。

（式中Ｐｈはフェニル基を表す。）
［８］
前記一般式（１）で表されるアルキルビスマスアルコキシド化合物が、式（５）で表されるジメチルビスマス２，２，２−トリフルオロエトキシドである［１］および［３］のいずれかに記載のアルキルビスマスアルコキシド化合物。

[９]
Ｒ₁で表されるアルキル基が、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基およびｔｅｒｔ−ブチル基からなる群から選ばれるアルキル基である[２]に記載のアルキルビスマスアルコキシド化合物。
[１０]
前記一般式（２）で表されるアルキルビスマスアルコキシド化合物が、式（６）で表される１−メチル−３，３，４，４−テトラキストリフルオロメチル−１−ビスマ−２，５−ジオキソランである[２]、または[９]のいずれかに記載のアルキルビスマスアルコキシド化合物。

[１１]
一般式（７）で表されるトリアルキルビスマス化合物に、一般式（８）で表されるフッ素化アルコールを反応させる、一般式（１）または一般式（２）で表されるアルキルビスマスアルコキシド化合物の製造方法。

（式中、Ｒ₁、Ｒ₂およびＢｉは［１］の定義と同じであり、Ｒ₃は直鎖、分枝若しくは環状の炭素数１〜１０のアルキル基を表す。）

（式中、Ｒ₄、Ｒ₅、ｋ、ｎ、ｘ、ｙ、ＦおよびＯは［１］の定義と同じである。）

（式中Ｒ₁、Ｒ₂、Ｒ₄、Ｒ₅、ｋ、ｎ、ｘ、ｙ、Ｆ、ＯおよびＢｉは［１］の定義と同じである。）

（式中Ｒ₁、Ｆ、Ｏ、Ｂｉは［１］の定義と同じである。）
［１２］
前記一般式（８）で表されるフッ素化アルコールが、１，１，１，３，３，３−ヘキサフルオロ−２−プロパノール、１，１，１，４，４，４−ヘキサフルオロ−２，３−ビス（トリフルオロメチル）−２，３−ブタンジオール、１，１，１，３，３，３−ヘキサフルオロ−２−フェニル−２−プロパノール、または２，２，２−トリフルオロエタノールである［１１］に記載のアルキルビスマスアルコキシド化合物の製造方法。
［１３］
前記一般式（７）で表されるトリアルキルビスマス化合物が、トリメチルビスマスである［１１］または［１２］に記載のアルキルビスマスアルコキシド化合物の製造方法。
［１４］
前記反応は０〜１００℃の範囲の温度で実施する、［１１］〜［１３］のいずれかに記載のアルキルビスマスアルコキシド化合物の製造方法。 The present invention is as follows.
[1]
The alkyl bismuth alkoxide compound represented by General formula (1).

(Wherein R ₁ and R ₂ each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R ₄ and R ₅ are each independently a substituted, unsubstituted, or straight chain, branched or cyclic carbon group having 1 to 10 carbon atoms selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group A substituted or unsubstituted aryl group substituted with a substituent selected from the group consisting of an alkyl group, a fluorine atom, a chlorine atom and a hydroxyl group, or a hydrogen atom,
n represents an integer of 1 to 10,
x and y each independently represents 0 or 1, k represents 1, 2 or 3, provided that the sum of x, y and k is 3, F is a fluorine atom, O is an oxygen atom, Bi Represents a bismuth atom. )
[2]
The alkyl bismuth alkoxide compound represented by General formula (2).

(Wherein R ₁ , F, O and Bi are the same as defined in [1].)
[3]
The alkyl group represented by R ₁ and R ₂ is selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. The alkyl bismuth alkoxide compound according to [1], which is an alkyl group.
[4]
The alkyl bismuth alkoxide compound according to [1] or [3], wherein n is 1 to 3, x is 1, y is 0, and k is 2.
[5]
R ₄ is a substituent selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a hydrogen atom The alkylbismuth alkoxide compound according to any one of [1], [3] and [4].
[6]
The alkyl bismuth alkoxide compound represented by the general formula (1) is dimethyl bismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide represented by the formula (3) [1] and [3 ] The alkylbismuth alkoxide compound according to any one of [5] to [5].

[7]
The alkylbismuth alkoxide compound represented by the general formula (1) is dimethylbismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenylethoxide represented by the formula (4) [1. ] And the alkylbismuth alkoxide compound according to any one of [3] to [5].

(In the formula, Ph represents a phenyl group.)
[8]
The alkylbismuth alkoxide compound represented by the general formula (1) is dimethyl bismuth 2,2,2-trifluoroethoxide represented by the formula (5), according to any one of [1] and [3] Alkyl bismuth alkoxide compounds.

[9]
The alkyl group represented by R ₁ is an alkyl group selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. The alkylbismuth alkoxide compound according to [2].
[10]
The alkylbismuth alkoxide compound represented by the general formula (2) is a 1-methyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane represented by the formula (6). The alkylbismuth alkoxide compound according to any one of [2] or [9].

[11]
An alkyl bismuth alkoxide compound represented by the general formula (1) or the general formula (2), wherein the trialkylbismuth compound represented by the general formula (7) is reacted with the fluorinated alcohol represented by the general formula (8). Manufacturing method.

(Wherein R ₁ , R ₂ and Bi are the same as defined in [1], and R ₃ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

(Wherein R ₄ , R ₅ , k, n, x, y, F and O are the same as defined in [1].)

(Wherein R ₁ , R ₂ , R ₄ , R ₅ , k, n, x, y, F, O and Bi are the same as defined in [1].)

(Wherein R ₁ , F, O, and Bi are the same as defined in [1].)
[12]
The fluorinated alcohol represented by the general formula (8) is 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,1,4,4,4-hexafluoro-2. , 3-bis (trifluoromethyl) -2,3-butanediol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, or 2,2,2-trifluoroethanol [11] The method for producing an alkylbismuth alkoxide compound according to [11].
[13]
The method for producing an alkylbismuth alkoxide compound according to [11] or [12], wherein the trialkylbismuth compound represented by the general formula (7) is trimethylbismuth.
[14]
The said reaction is implemented at the temperature of the range of 0-100 degreeC, The manufacturing method of the alkylbismuth alkoxide compound in any one of [11]-[13].

  According to the present invention, it is possible to provide an alkylbismuth alkoxide compound represented by the above general formula (1) or general formula (2) which has not been reported so far and has been difficult to synthesize. Furthermore, according to the production method of the present invention, the alkylbismuth alkoxide compound can be easily and in one step without requiring a long-time reaction at a high temperature and without producing a large amount of by-product salts such as alkali metal salts. can get. The obtained alkyl bismuth alkoxide compound has sufficient thermal stability superior to trimethyl bismuth, as is apparent from the DSC measurement results shown in the Examples. Moreover, the alkylbismuth alkoxide compound obtained has sufficient vaporization characteristics superior to triphenylbismuth, as is apparent from the TG measurement results shown in the Examples. The present invention has high utility value industrially.

  The present invention is described in detail below.

<Compound of general formula (1)>
In general formula (1): R ₁ and R ₂ each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Specific examples of R ₁ and R ₂ include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group. N-pentyl group, cyclopentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, tert-pentyl group, 1-ethylpropyl group, hexyl group, cyclohexyl group and the like. The alkyl group represented by R ₁ and R ₂ is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group from the viewpoint that the corresponding alkyl lithium is relatively easily available. An alkyl group selected from the group consisting of a group, a sec-butyl group and a tert-butyl group.

R ₄ and R ₅ are each independently a substituted, unsubstituted, or straight chain, branched or cyclic carbon number of 1 to 10 carbon atoms selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group It represents an alkyl group, represents an aryl group substituted or unsubstituted with a substituent selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group, or represents a hydrogen atom.

Specific examples of R ₄ and R ₅ include hydrogen atom, trifluoromethyl group, phenyl group, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, cyclopentyl group, neopentyl group, 1-methylbutyl group, 2-methylbutyl group, isopentyl group, tert-pentyl group, 1-ethylpropyl group, hexyl group, Examples include cyclohexyl group, benzyl group, 1,1,2,2,2-pentafluoroethyl group, 1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl group and the like.

  n represents an integer of 1 to 10, preferably an integer of 1 to 3. k represents 1, 2 or 3, and is preferably 2. When k is 2, x is 1 and y is 0. More preferably, n is 1 to 3, x is 1, y is 0, and k is 2. The compound with k = 2 has a larger number of fluorine atoms in the vicinity of the oxygen atom than the compound with k = 1, so that the electron withdrawing property causes an electron shortage on the oxygen atom and promotes the reaction. It is preferable from the viewpoint of.

  Specific examples of the alkylbismuth alkoxide represented by the general formula (1) are shown below.

R ₁ and / or R ₂ = methyl group:
Dimethyl bismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenyl ethoxide,
Dimethyl bismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Dimethyl bismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Dimethyl bismuth 2,2,2-trifluoro-1,1-bistrifluoromethyl-ethoxide,
Dimethyl bismuth 2,2,2-trifluoroethoxide,

R ₁ and / or R ₂ = ethyl group:
Diethyl bismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenyl ethoxide,
Diethyl bismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Diethyl bismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Diethyl bismuth 2,2,2-trifluoro-1,1-bistrifluoromethyl ethoxide,
Diethyl bismuth 2,2,2-trifluoroethoxide,

R ₁ and / or R ₂ = n-propyl group di-n-propyl bismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenyl ethoxide,
Di-n-propylbismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Di-n-propyl bismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Di-n-propyl bismuth (2,2,2-trifluoro-1,1-bistrifluoromethyl ethoxide),
Di-n-propyl bismuth 2,2,2-trifluoroethoxide,

R ₁ and / or R ₂ = isopropyl group diisopropyl bismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenyl ethoxide,
Diisopropyl bismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Diisopropyl bismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Diisopropyl bismuth 2,2,2-trifluoro-1,1-bistrifluoromethyl ethoxide,
Diisopropyl bismuth 2,2,2-trifluoroethoxide,

R ₁ and / or R ₂ = n-butyl group di-n-butyl bismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenyl ethoxide,
Di-n-butylbismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Di-n-butylbismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Di-n-butylbismuth 2,2,2-trifluoro-1,1-bistrifluoromethyl ethoxide,
Di-n-butylbismuth 2,2,2-trifluoroethoxide,

R ₁ and / or R ₂ = sec-butyl group disec-butylbismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenylethoxide,
Di-sec-butylbismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Di-sec-butylbismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Di-sec-butylbismuth 2,2,2-trifluoro-1,1-bistrifluoromethyl ethoxide,
Di-sec-butylbismuth 2,2,2-trifluoroethoxide,

R ₁ and / or R ₂ = tert-butyl group ditert-butylbismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenylethoxide,
Di-tert-butylbismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Di-tert-butylbismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Di-tert-butylbismuth 2,2,2-trifluoro-1,1-bistrifluoromethyl ethoxide,
Ditert-butylbismuth 2,2,2-trifluoroethoxide,

R ₁ and / or R ₂ = isobutyl group diisobutyl bismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenyl ethoxide,
Diisobutyl bismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide,
Diisobutyl bismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide,
Diisobutyl bismuth 2,2,2-trifluoro-1,1-bistrifluoromethyl ethoxide,
Diisobutyl bismuth 2,2,2-trifluoroethoxide,

<Compound of general formula (2)>
In general formula (2): R ₁ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Specific examples of R ₁ include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n- Examples include a pentyl group, a cyclopentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a tert-pentyl group, a 1-ethylpropyl group, a hexyl group, and a cyclohexyl group. The alkyl group represented by R ₁ is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec from the viewpoint that the corresponding alkyl lithium is relatively easily available. -An alkyl group selected from the group consisting of a butyl group and a tert-butyl group.

  Specific examples of the alkylbismuth alkoxide represented by the general formula (2) are shown below.

1-methyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane,
1-ethyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane,
1-n-propyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane,
1-isopropyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane,
1-n-butyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane,
1-isobutyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane,
1-sec-butyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane,
1-tert-butyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane.

<Compound of general formula (7)>
R ₁ , R ₂ and Bi are the same as defined above. R ₃ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Specific examples of R ₃ include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclobutyl group, n- Examples include a pentyl group, a cyclopentyl group, a neopentyl group, a 1-methylbutyl group, a 2-methylbutyl group, an isopentyl group, a tert-pentyl group, a 1-ethylpropyl group, a hexyl group, and a cyclohexyl group.

  Specific examples of the trialkyl bismuth compound represented by the general formula (7) include trimethyl bismuth, triethyl bismuth, tri n-propyl bismuth, triisopropyl bismuth, tricyclopropyl bismuth, tri n-butyl bismuth, triisobutyl bismuth. , Tri-sec-butyl bismuth, tri-tert-butyl bismuth, tricyclobutyl bismuth, tri-n-pentyl bismuth, tricyclopentyl bismuth, trineopentyl bismuth, tri-1-methylbutyl bismuth, tri-2-methylbutyl bismuth, triisopentyl Bismuth, tri tert-pentyl bismuth, tri 1-ethylpropyl bismuth, trihexyl bismuth, tricyclohexyl bismuth, etc. are mentioned. These compounds are available as commercially available products or obtained by reacting commercially available raw materials. Trimethyl bismuth and triethyl bismuth are preferred. The reason for this is that it can be prepared from a commercially available organolithium reagent or organomagnesium reagent and bismuth bromide or bismuth chloride and can be purified by distillation, that is, a high-purity one is readily available. For example, trimethylbismuth can be synthesized from commercially available methyllithium and bismuth bromide.

  As shown in Reference Example 2, this reaction does not proceed from triphenylbismuth. The reason is that when an electron-withdrawing substituent such as a phenyl group is bonded to a bismuth atom, the unshared electron pair on the bismuth atom is delocalized with the phenyl group, so that the bismuth-carbon bond is This is thought to be due to the fact that the bismuth-oxygen bond of the same bond is difficult to proceed.

<Compound of general formula (8)>
R ₄ and R ₅ are the same as defined above. Specific examples of the fluorinated alcohol compound represented by the general formula (8) include 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2 -Trifluoromethyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethyl-2-propanol, 1-ethyl-1-trifluoromethyl-1-propanol, 1- Methyl-1-trifluoromethyl-1-propanol, 1,1-bistrifluoromethyl-1-propanol, 1-isopropyl-1-trifluoromethyl-2-methyl-1-propanol, 1-methyl-1-trifluoro Methyl-2-methyl-1-propanol, 1-ethyl-1-trifluoromethyl-2-methyl-1-propanol, 1,1-bistrifluoromethyl-2-methyl-1-propanol, 2,2,3, 3,3-pentafluoropropanol, 1- (1,1,2,2,2-pentafluoroethyl) -2,2,3,3,3-pentafluoro-1-propanol, 1- Til-2,2,3,3,3-pentafluoro-1-propanol, 1-ethyl-2,2,3,3,3-pentafluoro-1-propanol, 1-trifluoromethyl-2,2, 3,3,3-pentafluoro-1-propanol, 1,1-dimethyl-2,2,3,3,3-pentafluoro-1-propanol, 1-methyl-1-ethyl-2,2,3, 3,3-pentafluoro-1-propanol, 1- (1,1,2,2,2-pentafluoroethyl) -1-methyl-2,2,3,3,3-pentafluoro-1-propanol, 1- (1,1,2,2,2-pentafluoroethyl) -1-ethyl-2,2,3,3,3-pentafluoro-1-propanol, 1,1-bis (1,1,2 , 2,2-pentafluoroethyl) -2,2,3,3,3-pentafluoro-1-propanol, 2-trifluoromethyl-1,1,1,3,3,3-hexafluoro-2- Propanol, 1,1-bis (1,1,2,2,2-pentafluoroethyl) -1-propanol, 1-methyl-1- (1,1,2,2,2-pentafluoroethyl) -2 -Methyl-1-propanol, 1-ethyl-1- (1,1,2,2,2-pentafur Oloethyl) -2-methyl-1-propanol, 1,1-bis (1,1,2,2,2-pentafluoroethyl) -2-methyl-1-propanol, 1,1,1,4,4, 4-hexafluoro-2,3-bis (trifluoromethyl) -2,3-butanediol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol, 1,1, Examples include 1,3,3,3-hexafluoro-2-cyclohexyl-2-propanol.

  The fluorinated alcohol compound represented by the general formula (8) is preferably 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,1,4,4,4-hexafluoro. -2,3-bis (trifluoromethyl) -2,3-butanediol, 1,1,1,3,3,3-hexafluoro-2-trifluoromethyl-2-propanol, 1,1,1, 3,3,3-hexafluoro-2-phenyl-2-propanol. The preferred reason is that there are many fluorine atoms near the hydroxy group, and the hydrogen atom of the hydroxy group is easily dissociated as a hydrogen ion due to the electron withdrawing property of the fluorine atom, and the lone pair of trialkylbismuth is dissociated into the hydrogen ion. This is because the reaction easily proceeds by acting easily. Many of the fluorinated alcohol compounds represented by the general formula (8) are commercially available.

  The mixing ratio of the fluorinated alcohol compound to be mixed with the alkyl bismuth compound may be, for example, in the range of 0.01 to 30 mol of the fluorinated alcohol compound with respect to 1 mol of the alkyl bismuth compound. This range is preferably 0.5-5 mol. By being this preferable range, the ratio of the residual raw material with respect to the target object becomes low, and can acquire the target object easily.

  As shown in Reference Example 1, when methanol was used as the alcohol compound in this reaction, the target product was not obtained. The reason for this is considered to be due to the difference in ease of dissociation between hydrogen on oxygen atoms in the methanol molecule and hydrogen on oxygen atoms in the fluorinated alcohol molecule. That is, in the reactions shown in Examples 1 to 3, it is considered that the oxygen-hydrogen bond of the alcohol molecule is replaced with the oxygen-bismuth bond before and after the reaction, and the oxygen-hydrogen bond of the alcohol molecule is dissociated during the reaction. . A numerical value indicating the ease of dissociation between an oxygen atom of an alcohol molecule and a hydrogen atom bonded thereto (which indicates that the larger the value is, the more difficult it is to dissociate) is known as the acid dissociation constant (pKa). Since the methanol of Reference Example 1 is 15.5 and the 1,1,1,3,3,3-hexafluoro-2-propanol of Example 1 is 9.3, the oxygen-hydrogen bond is difficult to dissociate. It is presumed that the reaction did not proceed with methanol.

  In the reaction of the present invention, a solvent can be used. The solvent that can be used is not particularly limited as long as it is an aprotic solvent. For example, hydrocarbons such as pentane, hexane, heptane, halogenated hydrocarbons such as dichloromethane, dibromomethane, chloroform, bromoform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-trichloroethane, benzene, toluene Aromatic hydrocarbons such as xylene and ethers such as diethyl ether and tetrahydrofuran can be used. These solvents may be used alone or in combination of two or more. Among these, preferred solvents are hexane, heptane, and dichloromethane from the viewpoint of easy availability and easy distillation.

  The solvent used in the reaction of the present invention is preferably a solvent that has been dehydrated (with molecular sieve 4A for 1 day) and deoxygenated (the operation of depressurizing at about 2 kPa for 3 seconds and then returning to normal pressure with nitrogen 5 times). As shown in Reference Example 3, this reaction may not proceed unless dehydration and deoxygenation are performed. The reason is considered that the alkyl bismuth compound is immediately oxidized in the presence of oxygen, and the alkyl bismuth compound is immediately hydrolyzed in the presence of water.

  Examples of the method for producing an alkyl bismuth alkoxide compound in the present invention include (a) a method in which an alkyl bismuth compound acts on an alcohol compound, and (b) a method in which the alcohol compound acts on an alkyl bismuth compound. It is done. At this time, alkyl bismuth compounds and alcohol compounds dissolved in a solvent can also be used. The order of charging is not particularly limited, and the drugs to be used may be charged in any order.

  In the production of the alkyl bismuth alkoxide compound in the present invention, the temperature for mixing the alkyl bismuth compound and the alcohol compound may be −80 to 50 ° C., more preferably 0 to 30 ° C.

  As reaction temperature in the case of manufacture of the alkylbismuth alkoxide compound in this invention, it may be -10-130 degreeC, More preferably, it is 0-100 degreeC, More preferably, it is 20-50 degreeC.

  As reaction time in the case of manufacture of the alkylbismuth alkoxide compound in this invention, what is necessary is just 1 to 120 hours, More preferably, it is 4 to 24 hours.

  The alkyl bismuth alkoxide compound obtained by the production method of the present invention can be purified as desired. For example, it can be highly purified using recrystallization or preparative HPLC. In particular, the alkyl bismuth alkoxide compound used as a CVD material is preferably purified to a higher purity by distillation or sublimation.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to these Examples.

The following reaction was performed under a dry nitrogen gas atmosphere. Hexane, toluene, dichloromethane, and dimethyl sulfoxide-d6 were used after dehydration (molecular sieve 4A for 1 day) and deoxygenation (the operation of returning to normal pressure with nitrogen after reducing pressure at about 2 kPa for 3 seconds). As the alcohol compound, a commercially available product was dehydrated (one day with molecular sieve 3A). Trimethylbismuth was synthesized from bismuth tribromide and methyllithium in a diethyl ether-tetrahydrofuran mixed solvent and distilled. The chemical structure of the compound thus obtained was confirmed by ¹ H-NMR, ¹³ C-NMR, ¹⁹ F-NMR (NMR is JNM-ECA500 manufactured by JEOL Ltd.). The NMR sample tube used was made of glass outer diameter 5 mm, inner diameter 4 mm, ¹ H-NMR and ¹³ C-NMR standards were tetramethylsilane ((CH ₃ ) ₄ Si) 0 ppm each, and ¹⁹ F-NMR standards were Trichlorofluoromethane (CFCl ₃ ) was adjusted to 0 ppm.

  Mass spectrometry of the obtained compound was performed in a negative mode (detection of monovalent anions) by ESI ionization using a Dartonics micro TOF manufactured by Bruker.

  The thermal stability of the obtained compound was measured by differential scanning calorimetry in the range of 30 to 500 ° C. under a nitrogen atmosphere under a temperature rising rate of 10 ° C./min using DSC-6200 manufactured by Seiko Instruments Inc. Confirmed by doing. The measurement container is made of stainless steel and has an outer diameter of 5.5 mm and an inner diameter of 3.5 mm. An empty container was used as a reference. The decomposition heat generation starting temperature of DSC of trimethylbismuth was 231 ° C., and the temperature at the peak of heat generation was 315 ° C.

  The vaporization characteristics of the obtained compound were measured by thermogravimetry in the range of 30-500 ° C under the condition of a temperature increase rate of 10 ° C / min under a nitrogen atmosphere using TG / DTA-6200 manufactured by Seiko Instruments Inc. Confirmed by doing. The measurement container is made of aluminum and has an outer diameter of 5 mm and an inner diameter of 4.8 mm, and an empty container was used as a reference. The vaporization start point was the temperature at which 10% of the sample vaporizes. The vaporization start temperature of TG of triphenylbismuth is 230 ° C. (Patent Document 1).

Example 1
Synthesis of dimethyl bismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide (Formula 14)

  1,1,1,3,3,3-hexafluoro-2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.) 153 mg (0.90 mmol) and hexane 8 ml for 76.0 mg (0.30 mmol) of trimethylbismuth at room temperature Was added. After stirring at room temperature for 18 hours and further at 50 ° C. for 1 hour, the solvent and unreacted raw material were distilled off under reduced pressure to obtain 78.4 mg (yield 64%) of the title compound (white solid).

The analysis results of the compound obtained in Example 1 are shown below.
Dimethylbismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide
¹ H-NMR (500 MHz, (CD ₃ ) ₂ SO): 1.16 (s, 6H), 4.83 (br s, 1H)
¹³ C-NMR (126 MHz, (CD ₃ ) ₂ SO): 35.6, 72.5-73.8 (m), 124.2 (q, J _CF = 292 Hz)
¹⁹ F-NMR (471 MHz, (CD ₃ ) ₂ SO): -74.3 (s, 6F)
DSC decomposition heat generation start temperature: 258 ℃, exothermic peak temperature: 315 ℃
Vaporization start temperature at TG: 190 ° C

Example 2
Synthesis of dimethyl bismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenyl ethoxide (Formula 15)

  1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 156 mg (0.64 mmol) to 54.0 mg (0.21 mmol) of trimethylbismuth at room temperature And 8 ml of hexane was added. After stirring at 50 ° C. for 5 hours, the resulting white solid was cooled to room temperature, filtered, washed with hexane, and then dried under reduced pressure to obtain 12.3 mg (yield 12%) of the title compound.

The analysis results of the compound obtained in Example 2 are shown below.
Dimethylbismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenylethoxide
¹ H-NMR (500 MHz, (CD ₃ ) ₂ SO): 1.32 (s, 6H), 7.43-7.53 (m, 3H), 7.67-7.77 (m, 2H)
¹³ C-NMR (126 MHz, (CD ₃ ) ₂ SO): 37.2, 82.6 (hept, J _CF = 28 Hz), 122.4 (q, J _CF = 292 Hz), 126.7, 127.9, 129.8, 130.8
¹⁹ F-NMR (471 MHz, (CD ₃ ) ₂ SO): -70.4 (s, 6F)
DSC decomposition heat generation start temperature: 254 ° C, exothermic peak temperature: 316 ° C
Vaporization start temperature in TG: 200 ° C

Example 3
Synthesis of dimethyl bismuth 2,2,2-trifluoroethoxide (Formula 16)

  Under a nitrogen atmosphere at room temperature, 0.22, g (2.2 mmol) of 2,2,2-trifluoroethanol (manufactured by Wako Pure Chemical Industries) and 10 ml of hexane were added to 0.20 g (0.79 mmol) of trimethylbismuth. Thereafter, the mixture was stirred at 50 ° C. for 5 hours, cooled to room temperature, and about half of the solvent was distilled off under reduced pressure to precipitate a solid (white). The produced white solid was separated by filtration and washed with hexane, and then the solid was dried under reduced pressure to obtain 24.2 mg (yield 9.1%) of the title compound.

The analysis results of the compound obtained in Example 3 are shown below.
Dimethylbismuth 2,2,2-trifluoroethoxide
¹ H-NMR (500 MHz, (CD ₃ ) ₂ SO): 1.11 (s, 6H), 4.10 (q, 2H, J _HF = 10 Hz)
¹³ C-NMR (126 MHz, (CD ₃ ) ₂ SO): 32.5, 63.5-66.0 (m), 127.0 (q, J _CF = 282 Hz)
¹⁹ F-NMR (471 MHz, (CD ₃ ) ₂ SO): -74.9 (br s, 3F)
DSC decomposition heat generation start temperature: 246 ° C, exothermic peak temperature: 323 ° C
Vaporization start temperature in TG: 185 ℃

室温にて窒素雰囲気下、トリメチルビスマス50.7mg（0.20mmol）に対し1,1,1,4,4,4-ヘキサフルオロ-2,3-ビス(トリフルオロメチル)-2,3-ブタンジオール(東京化成工業製)66.8mg（0.20mmol）およびヘキサン10ｍｌを加えた。その後室温にて18時間撹拌後、溶媒および未反応の原料を減圧下留去することにより表題化合物の2：1（モル比）混合物（白色固体）60.6mg（それぞれ収率36％、収率18％）を得た。また、HSQC-NMRおよびHMBC-NMRにより、この混合物の¹H-NMR, ¹³C-NMRのピークがそれぞれどちらの成分に由来するかを決定した。 Example 4
1-methyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane and dimethylbismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2 Of 2-hydroxypropoxide (Formula 17)

1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2,3-butanediol (50.7mg (0.20mmol)) of trimethylbismuth at room temperature 66.8 mg (0.20 mmol) manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 ml of hexane were added. Thereafter, the mixture was stirred at room temperature for 18 hours, and then the solvent and unreacted raw materials were distilled off under reduced pressure to obtain 60.6 mg (white solid) of a 2: 1 (molar ratio) mixture of the title compounds (yield 36%, yield 18 respectively). %). Further, it was determined by HSQC-NMR and HMBC-NMR which component each derived from the ¹ H-NMR and ¹³ C-NMR peaks of this mixture.

The analysis results of the compound obtained in Example 4 are shown below.
1-Methyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane
¹ H-NMR (500 MHz, (CD ₃ ) ₂ SO): 2.22 (s, 3H)
¹³ C-NMR (126 MHz, (CD ₃ ) ₂ SO): 10.6, 82.1-82.8 (m), 122.8 (q, J _CF = 298Hz)
¹⁹ F-NMR (471 MHz, (CD ₃ ) ₂ SO): -68.7 (s, 12F)
TOF / MS m / z (exact mass of monovalent anion (ESI negative mode) from which methyl cation is eliminated from the compound) = 540.957 (C ₆ BiF ₁₂ O ₂ ) Theoretical value 540.951

Dimethylbismuth 1,1,2-tristrifluoromethyl-3,3,3-trifluoro-2-hydroxypropoxide
¹ H-NMR (500 MHz, (CD ₃ ) ₂ SO): 1.09 (s, 6H), 8.91 (br s, 1H)
¹³ C-NMR (126 MHz, (CD ₃ ) ₂ SO): 75.6, 86.8-87.3 (m),
87.3-87.8 (m), 124.8 (q, J _CF = 294Hz), 126.1 (q, J _CF = 295Hz)
¹⁹ F-NMR (471 MHz, (CD ₃ ) ₂ SO): -69.1 (s, 6F), -69.1 (s, 6F)
TOF / MS m / z (exact mass of monovalent anion (ESI negative mode) from which proton is eliminated from the compound) = 571.004 (C ₈ H ₆ BiF ₁₂ O ₂ ) Theoretical value 571.998

Reference example 1
When using methanol Under a nitrogen atmosphere at room temperature, 5 ml of 32 mg (1.0 mmol) of hexane was added to a mixture of 254 mg (1.0 mmol) of trimethylbismuth and 68 mg of diethyl ether. After stirring at room temperature for 18 hours, ¹ H-NMR of the reaction solution was measured. Nothing other than trimethylbismuth, methanol, diethyl ether and hexane was observed.

Reference example 2
When using triphenylbismuth 210 mg (0.9 mmol) of 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol to 126 mg (0.3 mmol) of triphenylbismuth under nitrogen atmosphere at room temperature ), 5 ml of hexane was added. Thereafter, after stirring at 40 ° C. for 7 hours, ¹ H-NMR and ¹⁹ F-NMR of the reaction solution were measured, but triphenylbismuth, 1,1,1,3,3,3-hexafluoro-2-phenyl- Nothing other than 2-propanol and hexane was observed. In addition, the solvent was changed to dichloromethane and toluene, and the mixture was heated and refluxed to the boiling point under atmospheric pressure, respectively. Similarly, in ¹ H-NMR and ¹⁹ F-NMR, triphenylbismuth, 1,1,1,3, Nothing other than 3,3-hexafluoro-2-phenyl-2-propanol and solvent was observed.

Reference example 3
When using a solvent that does not dehydrate and deoxygenate, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propylene with respect to 54.0 mg (0.2 mmol) of trimethylbismuth in a nitrogen atmosphere at room temperature 156 mg (0.6 mmol) of propanol (manufactured by Tokyo Chemical Industry) and 8 ml of hexane not subjected to dehydration and deoxygenation were added. After stirring at 50 ° C for 5 hours, the reaction solution was concentrated and ¹⁹ F-NMR was measured, but the peak of dimethylbismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenylethoxide was observed. Was not.

  The alkyl bismuth alkoxide compound obtained by the present invention is useful as a synthetic catalyst such as medical pesticides, organic materials and intermediates thereof, and a material for CVD.

Claims (14)

The alkyl bismuth alkoxide compound represented by General formula (1).

(Wherein R ₁ and R ₂ each independently represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms,
R ₄ and R ₅ are each independently a substituted, unsubstituted, or straight chain, branched or cyclic carbon group having 1 to 10 carbon atoms selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group A substituted or unsubstituted aryl group substituted with a substituent selected from the group consisting of an alkyl group, a fluorine atom, a chlorine atom and a hydroxyl group, or a hydrogen atom,
n represents an integer of 1 to 10,
x and y each independently represents 0 or 1, k represents 1, 2 or 3, provided that the sum of x, y and k is 3, F is a fluorine atom, O is an oxygen atom, Bi Represents a bismuth atom. ) The alkyl bismuth alkoxide compound represented by General formula (2).

(Wherein R ₁ , F, O and Bi are the same as defined in claim 1). The alkyl group represented by R ₁ and R ₂ is selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. The alkyl bismuth alkoxide compound according to claim 1, which is an alkyl group.   The alkylbismuth alkoxide compound according to claim 1 or 3, wherein n is 1 to 3, x is 1, y is 0, and k is 2. R ₄ is a substituent selected from the group consisting of a fluorine atom, a chlorine atom and a hydroxyl group, or an unsubstituted linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, a phenyl group, or a hydrogen atom The alkylbismuth alkoxide compound according to any one of claims 1, 3, and 4. The alkylbismuth alkoxide compound represented by the general formula (1) is dimethylbismuth 2,2,2-trifluoro-1-trifluoromethyl ethoxide represented by the formula (3), or claim 1 Item 6. The alkylbismuth alkoxide compound according to any one of Items 3 to 5.

The alkylbismuth alkoxide compound represented by the general formula (1) is dimethylbismuth 2,2,2-trifluoro-1-trifluoromethyl-1-phenylethoxide represented by the formula (4). The alkyl bismuth alkoxide compound according to claim 1 or any one of claims 3 to 5.

(In the formula, Ph represents a phenyl group.) The alkyl bismuth alkoxide compound represented by the general formula (1) is dimethyl bismuth 2,2,2-trifluoroethoxide represented by the formula (5). Bismuth alkoxide compound.

The alkyl group represented by R ₁ is an alkyl group selected from the group consisting of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl group. The alkyl bismuth alkoxide compound according to claim 2. The alkylbismuth alkoxide compound represented by the general formula (2) is a 1-methyl-3,3,4,4-tetrakistrifluoromethyl-1-bisma-2,5-dioxolane represented by the formula (6). The alkyl bismuth alkoxide compound according to claim 2, which is:

An alkyl bismuth alkoxide compound represented by the general formula (1) or the general formula (2), wherein the trialkylbismuth compound represented by the general formula (7) is reacted with the fluorinated alcohol represented by the general formula (8). Manufacturing method.

(Wherein R ₁ , R ₂ and Bi are the same as defined in claim 1, and R ₃ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.)

(Wherein R ₄ , R ₅ , k, n, x, y, F and O are the same as defined in claim 1).

(Wherein R ₁ , R ₂ , R ₄ , R ₅ , k, n, x, y, F, O and Bi are the same as defined in claim 1).

(Wherein R ₁ , F, O and Bi are the same as defined in claim 1).   The fluorinated alcohol represented by the general formula (8) is 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,1,4,4,4-hexafluoro-2. , 3-bis (trifluoromethyl) -2,3-butanediol, 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol or 2,2,2-trifluoroethanol A method for producing an alkyl bismuth alkoxide compound according to claim 11.   The method for producing an alkyl bismuth alkoxide compound according to claim 11 or 12, wherein the trialkyl bismuth compound represented by the general formula (7) is trimethyl bismuth.   The said reaction is implemented at the temperature of the range of 0-100 degreeC, The manufacturing method of the alkylbismuth alkoxide compound in any one of Claims 11-13.