JP2002030006A - Method for producing cyclododecene - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To partially add hydrogen to cyclododecene from cyclododecatriene with higher reaction activity than conventional catalysts without the need for additives which were indispensable for conventional homogeneous ruthenium (II) complex catalysts. It is to find a method that can be produced by the reaction. An object of the present invention is to provide a method for producing cyclododecene by a partial hydrogenation reaction by bringing cyclododecatriene into contact with hydrogen, wherein a novel ruthenium (II) complex represented by the general formula (1) is used as a catalyst. This can be achieved by a method for producing cyclododecene, which is a feature. Embedded image

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing cyclododecene, which can be used as an intermediate material for useful chemicals such as dodecanedioic acid and laurolactam.

[0002]

BACKGROUND OF THE INVENTION It is already known that cyclododecene (hereinafter referred to as CDEN) can be produced by partial hydrogenation of cyclododecatriene (hereinafter referred to as CDT). This partial hydrogenation catalyst contains Pd /
Al ₂ O ₃ (for example, Chem. Abstract, 1974, 81, 1721)
6) and the like, but as a homogeneous system, a cobalt complex system (for example, B
Chem. Soc. Jpn. 1967, 40, 2718), nickel complex system (eg, USP-3,490,050, 1970) and ruthenium complex system are known, but due to their high CDEN selectivity,
The most widely studied is a ruthenium complex system (see, for example, (a) JP-A-5-331075, 333076).
(b) USP-5,321,176. 1994. (c) USP-5,180,870.1993.
(d) USP-5,177,278.1993. (e) USP-5,128,296.1992.
(f) TetrahedronLett., 1977, 1083. (g) USP-3,925,49
4. 1975. (h) USP-3,804,914. 1974. (i) J. Org. Che
m. 1973, 38, 80. (j) J. Org. Chem. 1973, 38, 3343.
). By the way, it has been pointed out that a heterogeneous Pd / Al ₂ O ₃ catalyst has a high reaction rate, but a low yield of CDEN to be produced (80 to 90%). On the other hand, in the homogeneous catalyst, a high CDEN selectivity (〜98%) is obtained, but in addition to the low reaction rate, an excessive amount of phosphine relative to the catalyst is required for stabilizing the reactive species. The use of additives such as bases and the like is problematic. In order to produce CDEN by partial hydrogenation of CDT, a high production rate and a high CDEN yield are required from the viewpoint of productivity and operability, and a homogeneous complex catalyst for achieving this is required. The development of was desired.

[0003]

The inventors of the present invention have conducted intensive studies on the above problems, and as a result, when a novel ruthenium complex is used as a catalyst, an additive which is indispensable for a conventional homogeneous catalyst is not required. Furthermore, they have found that CDEN can be produced from CDT by a partial hydrogenation reaction with a higher reaction activity than conventional homogeneous catalysts in a short time, and the present invention has been accomplished.

[0004]

The object of the present invention is to provide:
A method for producing cyclododecene by contacting cyclododecatriene with hydrogen to produce partial hydrogenation can be achieved by using a novel ruthenium complex represented by the general formula (1) as a catalyst.

Embedded image (Wherein R ¹ , R ² , and R ³ are an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms)
To 12 aryl groups, which may be the same or different. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵ is a hydrogen atom and having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 18 carbon atoms, 7 carbon atoms
Represents an aralkyl group having from 20 to 20 and an alkoxy group having from 1 to 10 carbon atoms. R ⁴ and R ⁵ may combine to form a ring.
R ⁶ , R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group or a dialkylamino group, and Or different groups, and two adjacent groups may be bonded to each other to form a ring. )

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The novel ruthenium complex used in the present invention is
It is a compound represented by the general formula (1).

Embedded image (Wherein R ¹ , R ² , and R ³ are an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms)
To 12 aryl groups, which may be the same or different. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵ is a hydrogen atom and having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 18 carbon atoms, 7 carbon atoms
Represents an aralkyl group having from 20 to 20 and an alkoxy group having from 1 to 10 carbon atoms. R ⁴ and R ⁵ may combine to form a ring.
R ⁶ , R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group or a dialkylamino group, and Or different groups, and two adjacent groups may be bonded to each other to form a ring. )

An example of a method for synthesizing a novel ruthenium complex represented by the general formula (1) is as follows. After forming the sodium salt of the Schiff base ligand represented by the general formula (2) with sodium hydride in a tetrahydrofuran (THF) solvent, this solution is added to a commercially available ruthenium trichloride hydrate in one step, RuHCl obtained in high yield
(CO) (PPh ₃ ) ₃ complex (J. Am. Chem. Soc., 1961, 83, 126
2) or RuHCl (CO) (PCy ₃ ) ₂ complex (J. Mol. Cat. A, 19
97, 126, 115.) and a transmetallation reaction. The obtained complex is stable even in air in a solid state.

In the synthesis of the Schiff base ligand represented by the general formula (2), the corresponding amine and salicylaldehyde are reacted in an alcohol solvent under heating or at room temperature, and the Schiff base ligand is precipitated by cooling. It can be obtained very easily by filtering off the compound.

Embedded image

Here, R ¹ , R ² and R ³ in the general formulas (1) and (2) represent an alkyl group having 1 to 10 carbon atoms,
Cycloalkyl group having 5 to 8 carbon atoms, or 6-1 carbon atom
Represents two aryl groups, which may be the same or different.

The alkyl group having 1 to 10 carbon atoms for R ¹ , R ² and R ³ includes, for example, methyl group, ethyl group, propyl group and its isomers, butyl group and its isomers, pentyl group and its isomers Hexyl group and its isomers, heptyl group and its isomers, octyl group and its isomers, nonyl group and its isomers, decyl group and its isomers, and the like.

Examples of the cycloalkyl group having 5 to 8 carbon atoms for R ¹ , R ² and R ³ include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.

The aryl group having 6 to 12 carbon atoms for R ¹ , R ² and R ³ includes, for example, phenyl group, tolyl group and its isomer, xylyl group and its isomer, naphthyl group and its isomer, dimethyl Examples include a naphthyl group and its isomer.

R ⁴ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms,
8 represents an aryl group and an aralkyl group having 7 to 20 carbon atoms.

R ⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, and 7 to 20 carbon atoms.
Represents an aralkyl group or an alkoxy group having 1 to 10 carbon atoms. Further, R ⁴ and R ⁵ may combine to form a ring.

Examples of the alkyl group having 1 to 20 carbon atoms for R ⁴ and R ⁵ include a methyl group, an ethyl group, a propyl group and its isomers, a butyl group and its isomers, a pentyl group and its isomers, and hexyl. And its isomers, heptyl group and its isomers, octyl group and its isomers, nonyl group and its isomers, decyl group and its isomers, and the like.

The cycloalkyl group having 3 to 12 carbon atoms for R ⁴ includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, Examples thereof include a cyclodecyl group, an adamantyl group, a cycloundecyl group, and a cyclododecyl group.

The aryl group having 6 to 18 carbon atoms of R ⁴ and R ⁵ includes, for example, phenyl group, tolyl group and its isomer, xylyl group and its isomer, naphthyl group and its isomer, dimethylnaphthyl group and Its isomers and the like can be mentioned.

Examples of the aralkyl group having 7 to 20 carbon atoms for R ⁴ and R ⁵ include benzyl, phenethyl, phenylpropyl, phenylbutyl, naphthylmethyl, naphthylethyl, naphthylpropyl and naphthylmethyl. And a diphenylmethyl group.

The alkoxy group having 1 to 10 carbon atoms for R ⁵ includes, for example, methoxy group, ethoxy group, propoxy group and its isomer, butoxy group and its isomer, pentanoxy group and its isomer, hexanoxy group and its Examples include isomers, heptanoxy groups and isomers thereof, octanoxy groups and isomers thereof, nonanoxy groups and isomers thereof, and decanoxy groups and isomers thereof.

Further, R ⁶ , R ⁷ , R in the formula (1)
⁸ and R ⁹ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group or a dialkylamino group. And two adjacent groups may be bonded to each other to form a ring.

Examples of the halogen atom of R ⁶ , R ⁷ , R ⁸ and R ⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group of R ⁶ , R ⁷ , R ⁸ and R ^{9 is} an alkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, such as methyl, ethyl, propyl and isomers thereof. Isomer, butyl group and its isomer, pentyl group and its isomer, hexyl group and its isomer, heptyl group and its isomer, octyl group and its isomer, nonyl group and its isomer, decyl group and its isomer , Undecyl group and its isomer, dodecyl group and its isomer, and the like.

The cycloalkyl group represented by R ⁶ , R ⁷ , R ⁸ and R ⁹ has 3 to 12 carbon atoms and includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclohexyl, Examples include a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cycloundecyl group, a cyclododecyl group, and the like.

The alkenyl group for R ⁶ , R ⁷ , R ⁸ and R ^{9 is} an alkenyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, such as vinyl, propenyl and isomers thereof. , Butenyl group and its isomers, pentenyl group and its isomers, hexenyl group and its isomers, heptenyl group and its isomers, octenyl group and its isomers, nonenyl group and its isomers, decenyl group and its isomers, Examples include an undecenyl group and its isomer, a dodecenyl group and its isomer, and the like.

The aryl group of R ⁶ , R ⁷ , R ⁸ and R ^{9 is} an aryl group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, such as phenyl group, tolyl group and isomers thereof. , A xylyl group and its isomer, a naphthyl group and its isomer, a dimethylnaphthyl group and its isomer, and the like.

The aralkyl group represented by R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably an aralkyl group having 7 to 14 carbon atoms, for example, benzyl group, phenethyl group, phenylpropyl group,
Examples include a phenylbutyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group, a naphthylbutyl group, and a diphenylmethyl group.

As the alkoxy group for R ⁶ , R ⁷ , R ⁸ and R ^9, an alkoxy group having 1 to 10 carbon atoms is preferable, and a methoxy group, an ethoxy group, a propoxy group and its isomer, a butoxy group and its isomer Pentaoxy group and its isomer, hexanoxy group and its isomer, heptanoxy group and its isomer, octanoxy group and its isomer, nonanoxy group and its isomer, decanoxy group and its isomer, and the like.

As the aryloxy group for R ⁶ , R ⁷ , R ⁸ and R ^9, an aryloxy group having 6 to 14 carbon atoms is preferable, and a phenoxy group, a toloxy group and its isomer, a xylyloxy group and its isomer, Examples include a naphthoxy group and its isomer, a dimethylnaphthoxy group and its isomer, and the like.

The dialkylamino group of R ⁶ , R ⁷ , R ⁸ and R ⁹ is preferably a dialkylamino group having 2 to 10 carbon atoms, such as a dimethylamino group, a diethylamino group, a dipropylamino group and isomers thereof. No.

The above R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹
Is a hydrogen atom bonded to the carbon atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, a nitro group, a cyano group Alternatively, it may be further substituted with a dialkylamino group or the like.

In addition, other than the above, R ⁴ , R ⁵ , R ⁶ ,
In the substituents represented by R ⁷ , R ⁸ and R ⁹ , the hydrogen atom bonded to the carbon atom is a trifluoromethyl group, a trichloromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a nonafluorobutyl C1 of group etc.
To 6 haloalkyl groups, methylthio groups, ethylthio groups,
C1-C6 alkyl or arylthio groups such as propylthio group, butylthio group, pentylthio group, hexylthio group and phenylthio group; C2 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group
10 to 10 alkoxycarbonyl groups; trimethylsiloxy, triethylsiloxy, triisopropylsiloxy, tributylsiloxy, methyldiisopropylsiloxy, t-butyldimethylsiloxy, methyldi-t-butylsiloxy, tribenzylsiloxy, tri- 3 to 24 carbon atoms such as p-xylylsiloxy group, t-butyldiphenylsiloxy group, triphenylmethyldimethylsiloxy group, etc.
May be substituted with a hydroxyl group or the like.

Specific examples of the novel ruthenium complex represented by the general formula (1) are shown below.

Embedded image

The CDT used in the present invention is, for example, TiT
Butadiene can be obtained by trimerization in the presence of -Al catalyst. Specifically, it is 1,5,9-cyclododecatriene, and there are cis-form and trans-form, both of which can be used, and the use ratio is not limited at all. When used, there is no problem even if a commercially available product is used as it is, but preferably, a product distilled once is used.

The method for producing CDEN by partial hydrogenation of CDT is not particularly limited, but is usually carried out under a hydrogen atmosphere under homogeneous reaction conditions in which a ruthenium complex and CDT are dissolved in a reaction solvent. Will be At this time, it is not necessary to add additives such as a basic compound and tertiary phosphine, but they may be added.

The amount of the ruthenium complex to be used is not particularly limited, but is preferably 0.04 to the reaction substrate CDT.
It is from 0.01 to 50 mol%, particularly preferably from 0.01 to 1.0 mol%. The concentration of the catalyst in the solvent is not particularly limited, but is preferably 0.01 to 20 mmol / l, more preferably 1 to 10 mmol / l.

There is no particular limitation on the hydrogen pressure.
Preferably 1 to 50 kgf / cm ² , more preferably 5 to 15 k
gf / cm ² . If the hydrogen pressure is too low, the reaction rate will be slow.
AN)) tends to increase.

Examples of the reaction solvent include aromatic hydrocarbons, aliphatic ethers, cyclic ethers, and carboxylate esters, and are preferably carboxylate esters. Specific examples of the reaction solvent include aromatic hydrocarbons such as benzene, toluene, and xylene. Specific examples of the aliphatic ethers or cyclic ethers include diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dioxane, tetrahydrofuran and the like. Specific examples of the carboxylic acid ester include methyl formate, ethyl formate, propyl formate,
Butyl formate, phenyl formate, methyl acetate, ethyl acetate,
Examples include propyl acetate, butyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and butyl benzoate. The alkyl group in these esters includes isomers such as normal, iso and tertiary.

[0038] The substrate concentration of CDT is not particularly limited, but is preferably 1 to 80 wt%, more preferably 5 to 80 wt%.
50 wt%.

Although the reaction temperature is not particularly limited, it is preferably 80 to 160 ° C, more preferably 100 to 150 ° C. If the reaction temperature is too low, the reaction rate will decrease significantly.
If the reaction temperature is too high, decomposition of the catalyst may occur, which is not preferable.

The reaction time depends on the reaction temperature, the hydrogen pressure and the amount of the catalyst used, but usually 10 hours or less is sufficient.

The obtained CDEN is used as an intermediate material for chemicals such as dodecanedioic acid and laurolactam.

[0042]

The present invention will be specifically described below with reference to examples and comparative examples. The analysis was carried out by gas chromatography, and the area of each compound peak obtained on gas chromatography was calculated in terms of area percentage with the same relative sensitivity.

Example 1 Synthesis of cyclododecene (CDEN) by partial hydrogenation reaction of 1,5,9-cyclododecatriene (CDT) (1d system of novel rhenium complex catalyst) Ruthenium complex in a Schlenk flask (25 ml) in a nitrogen box 1d (29 mg; 0.031 mmol) was weighed, the Schlenk flask was taken out, and ethyl acetate (5 ml) was added under an argon stream. The catalyst solution was transferred to an autoclave (50 ml; one obtained by purging with argon under high vacuum three times) under a stream of argon with a syringe, and then CDT (3.1 mmol) was added. After connecting the autoclave to the hydrogen line and introducing hydrogen up to 20 kgf / cm 2, the autoclave was disconnected from the hydrogen line and
It was put into an oil bath at 40 ° C. to start the reaction. After reacting for 5 hours, the autoclave was quickly cooled to room temperature in a water bath, the reaction solution was taken out, and the reaction product was analyzed by gas chromatography. As a result, the conversion of CDT was 99% or more, the yield of CDEN as the target substance was 99.1%, and the cyclododecadienes (CDDE)
The yield of N) was 0.6%, and the yield of cyclododecane (CDAN) was 0.3%. Table 1 summarizes the reaction conditions and the results obtained.

Examples 2 to 17 Example 1 was repeated except that the novel ruthenium complexes 1a to 1q were used.
The same operation as described above was performed, and the reaction product was analyzed. Table 1 summarizes the individual reaction conditions and reaction results.

Example 18 Synthesis of cyclododecene (CDEN) by partial hydrogenation reaction of 1,5,9-cyclododecatriene (CDT) (catalyst system of novel complex 1d) Example 1 was repeated except that the reaction time was 2 hours. The reaction was performed in the same manner. After the reaction, the reaction solution was taken out, and the reaction product was analyzed by gas chromatography. As a result, the conversion of CDT was 99% or more, the yield of the target product CDEN was 91.1%, and other cyclododecadienes ( CDDEN)
Was 8.9%, and the yield of cyclododecane (CDAN) was a trace amount. Reaction conditions and reaction results are summarized in Table 1.

Comparative Example 1 Synthesis of cyclododecene (CDEN) by partial hydrogenation of 1,5,9-cyclododecatriene (CDT) (known method) RuCl ₂ (CO) ₂ (PPh ₃ ) _{2 was} added to an autoclave (50 ml). (23m
g, 0.031 mmol), Na ₂ CO ₃ (1.7 mg, 0.016 m
mol) and triphenylphosphine (81 mg, 0.31 mmol) were weighed and replaced with argon three times, and then ethanol (5 ml) was added under an argon stream. Next, CDT (560 ml, 3.1 mm
ol), the autoclave was connected to a hydrogen line, and after purging with hydrogen sufficiently, the autoclave was removed from the hydrogen line at a hydrogen pressure of 20 kgf / cm 2, and the autoclave was charged into an oil bath at 140 ° C. to start the reaction. After reaction for 5 hours,
The autoclave was quickly cooled to room temperature in a water bath, the reaction solution was taken out, and the reaction product was analyzed by gas chromatography. As a result, the conversion of CDT was 99
%, The yield of the desired product CDEN is 98.1%,
Other yields of cyclododecadienes (CDDEN) 1.9
%, The yield of cyclododecane (CDAN) was a trace amount. Reaction conditions and reaction results are summarized in Table 1.

Comparative Example 2 Synthesis of Cyclododecene (CDEN) by Partial Hydrogenation of 1,5,9-Cyclododecatriene (CDT) (Known Method) The same reaction as in Comparative Example 1 except that the reaction time was 2 hours. went. After the reaction, the reaction solution was taken out, and the reaction product was analyzed by gas chromatography.
Is 95%, and the yield of the target product CDEN is 3%.
9.0%, the yield of other cyclododecadienes (CDDEN) was 56.0%, and the yield of cyclododecan (CDAN) was a trace amount. Reaction conditions and reaction results are summarized in Table 1.

Comparative Example 3 Synthesis of Cyclododecene (CDEN) by Partial Hydrogenation of 1,5,9-Cyclododecatriene (CDT) (Known Method) The reaction was carried out in the same manner as in Comparative Example 2 except that the reaction solvent was ethyl acetate. went. After the reaction, the reaction solution was taken out, and the reaction product was analyzed by gas chromatography.
The conversion rate of T is 99 or more, the yield of the target product CDEN is 18.5%, and other cyclododecadienes (CD
The yield of DEN) is 81.5%, cyclododecane (CDA)
The yield of N) was a trace amount. Reaction conditions and reaction results are summarized in Table 1.

[0049]

[Table 1]

[0050]

According to the novel ruthenium complex of the present invention, CDEN can be obtained from CDT in a short time and in a high yield without the need to add phosphine or a base.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07F 15/00 C07F 15/00 A F-term (Reference) 4G069 AA06 AA08 BA27A BA27B BC70A BC70B BE13A BE13B BE26A BE26B BE33A BE34B BE37A BE37B BE38A BE38B BE42A BE42B CB02 DA02 FA01 4H006 AA02 AB84 AC11 BA23 BA47 BB17 4H039 CA40 CB10 4H050 AB40 WB11 WB13 WB14 WB16 WB21

Claims (2)

[Claims] 1. A method for producing cyclododecene by contacting cyclododecatriene with hydrogen and subjecting it to partial hydrogenation, wherein the novel ruthenium complex represented by the general formula (1) is used as a catalyst. Embedded image (Wherein R ¹ , R ² , and R ³ are an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 carbon atoms)
To 12 aryl groups, which may be the same or different. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁵ is a hydrogen atom and having 1 to 20 carbon atoms
Alkyl group, aryl group having 6 to 18 carbon atoms, 7 carbon atoms
Represents an aralkyl group having from 20 to 20 and an alkoxy group having from 1 to 10 carbon atoms. R ⁴ and R ⁵ may combine to form a ring.
R ⁶ , R ⁷ , R ⁸ and R ⁹ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a nitro group, a cyano group or a dialkylamino group, and Or different groups, and two adjacent groups may be bonded to each other to form a ring. ) 2. The process for producing cyclododecene according to claim 1, wherein a carboxylic acid ester is used as a reaction solvent.