JP2011201839A - Method for producing sulfolane compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily producing a sulfolane compound used as the extraction solvent of benzene, toluene, xylene, etc., a solvent for producing a liquid crystal or semi-conductor, a reaction solvent of an aromatic compound and a production intermediate of a pest-controlling agent, etc., in a good efficiency.SOLUTION: This method for producing the sulfolane compound expressed by formula (2) [wherein, Rto Rare each independently H or 1-6C alkyl] is provided by hydrogenating a sulfolene compound expressed by formula (1) [wherein, the Rto Rare each the same as in the formula (1)] in the presence of a metal catalyst and another metal having a higher ionization tendency than that of the metal kind in the metal catalyst.

Description

  The present invention relates to a method for producing a sulfolane compound.

  Sulfolane compounds are used in extraction solvents such as benzene, toluene and xylene, solvents for liquid crystal and semiconductor production, reaction solvents for aromatic compounds, and production intermediates for pest control agents.

  As a manufacturing method of a sulfolane compound, the method of hydrogenating a sulfolene compound and obtaining a sulfolane compound is mentioned. However, in the hydrogenation reaction of the sulfolene compound, if sulfur dioxide, which is a raw material for producing the sulfolene compound, remains, it poisons the metal catalyst, so that the reaction takes time or a large amount of hydrogenation catalyst is added. There was a problem such as need. Therefore, as a method for producing a sulfolane compound, after reacting a diene compound and sulfur dioxide to obtain a sulfolene compound, sulfur dioxide remaining in the reaction system is removed by introducing an inert gas before the hydrogenation reaction. Has been proposed (Patent Document 1).

JP-A-6-321936

  However, even when the method described in Patent Document 1 is adopted, the sulfolene compound is decomposed during the hydrogenation reaction to produce sulfur dioxide, so that the effect is not sufficient, and a method for producing the sulfolane compound more efficiently. The proposal of was desired.

  An object of the present invention is to provide a method for suppressing the activity of a hydrogenation catalyst in a reaction to obtain a sulfolane compound by hydrogenating a sulfolene compound, and to complete the reaction in a short time.

  The present invention relates to formula (1):

（式中、Ｒ^１〜Ｒ^６は、それぞれ独立して、水素原子または炭素数１〜６のアルキル基を示す。）で表されるスルフォレン化合物を、金属触媒および該金属触媒の金属種よりイオン化傾向の大きい金属の存在下で水素化させる式（２）：

(Wherein R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A sulfolene compound represented by Hydrogenation in the presence of a highly prone metal (2):

（式中、Ｒ^１〜Ｒ^６は、式（１）におけるＲ^１〜Ｒ^６と同じ基を示す。）で表されるスルフォラン化合物の製造方法に関する。

^(Wherein, R 1 to R ⁶ has the formula (1) represents the same group as ^R 1 to R ⁶ in.) Relates to a method for manufacturing a sulfolane compound represented by.

  Hereinafter, the present invention will be described in detail.

  The sulfolene compound used in the present invention is represented by the formula (1).

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^{1 to} R ⁶ in the formula (1) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. And n-hexyl group.

  Specific examples of the sulfolene compound represented by the formula (1) include, for example, 3-sulfolene, 3-methyl-3-sulfolene, 3-ethyl-3-sulfolene, 3-propyl-3-sulfolene, 3-butyl- 3-sulfolene, 3-isobutyl-3-sulfolene, 3-tert-butyl-3-sulfolene, 3-hexyl-3-sulfolene, 3,4-dimethyl-3-sulfolene, 3,4-diethyl-3-sulfolene, 3,4-dibutyl-3-sulfolene, 3-hexyl-4-methyl-3-sulfolene, 2,5-dimethyl-3-sulfolene, 2,3,5-trimethyl-3-sulfolene, 2,5-dimethyl- 3-hexyl-3-sulfolene, 2,3,4,5-tetramethyl-3-sulfolene, 2,5-diethyl-3-sulfone 2,5-diethyl-2-methyl-3-sulfolene, 2,5-diethyl-2,5-dimethyl-3-sulfolene, 2,5-diethyl-3,4-dimethyl-3-sulfolene, 2, 5-diethyl-3-sulfolene, 2,5-dipropyl-3-sulfolene, 2,5-dipropyl-3-methyl-3-sulfolene, 2,5-dipropyl-3,4-dimethyl-3-sulfolene and the like It is done.

  The metal catalyst used in the present invention is not limited as long as it is generally used for the catalytic hydrogenation reaction.

  Examples of the metal species of the metal catalyst include nickel, palladium, rhodium, ruthenium and platinum. Among these, nickel is preferable from the viewpoint of price.

  Specific examples of the metal catalyst include Raney nickel, nickel carbon, palladium carbon, palladium chloride, palladium acetate, ruthenium carbon, rhodium carbon, and platinum carbon.

  Examples of the form of the metal catalyst include fine powders, activated carbon, aluminum oxide, silica gel, diatomaceous earth, zeolite and other supports, phosphine, amine complexes and the like. Can be mentioned.

  These metal catalysts may be used individually by 1 type, or may be used in combination of 2 or more type.

  The amount of the metal catalyst used is not particularly limited, but is preferably 0.1 to 6.0 parts by weight, preferably 0.2 to 3.0 parts by weight with respect to 100 parts by weight of the sulpholene compound. It is more preferable that When the amount of the metal catalyst used is less than 0.1 parts by weight, the reaction may not be completed sufficiently, and the yield of the sulfolane compound may be reduced. When the amount exceeds 6.0 parts by weight, the amount used is commensurate with the amount used. Not effective and not economical.

  Examples of the metal having a higher ionization tendency than the metal species of the metal catalyst include zinc, magnesium, aluminum, and iron. Among these, aluminum and iron are preferable from the viewpoint of ease of handling and safety.

  A metal having a greater ionization tendency than the metal species of these metal catalysts may be used alone or in combination of two or more.

  The amount of the metal having a higher ionization tendency than the metal species of the metal catalyst is not particularly limited, but may be 0.01 to 10.0 parts by weight with respect to 100 parts by weight of the metal catalyst. Preferably, it is 0.05 to 7.0 parts by weight. When the amount of the metal having a high ionization tendency is less than 0.01 parts by weight, the reaction may not be completed sufficiently, and the yield of the sulfolane compound may be reduced. When the amount exceeds 10.0 parts by weight, There is a risk of reducing the catalytic activity.

  In addition, the method of using the metal with a larger ionization tendency than the metal seed | species of a metal catalyst is not specifically limited. For example, it may be added to the reaction system separately from the metal catalyst, or may be added simultaneously with the metal catalyst.

  In the present invention, the reason why the hydrogenation reaction of the sulfolene compound proceeds smoothly due to the presence of the metal catalyst and a metal having a higher ionization tendency than the metal species of the metal catalyst is not clear, but for example, thermal decomposition of the sulfolene compound Sulfur dioxide, etc. generated by acidification of the reaction solvent makes the metal component of the metal catalyst easier to elute and the catalytic activity decreases. However, the metal having a higher ionization tendency than the metal species of the metal catalyst is preferentially dissolved. Therefore, it is considered that the decrease in catalyst activity is suppressed.

  In the present invention, examples of the reaction solvent used in the hydrogenation reaction include alcohols such as methanol, ethanol, isopropanol, propanol, butanol and pentanol, sulfolane, 2-methylsulfolane, 3-methylsulfolane, and 3- Examples include sulfone compounds such as ethyl sulfolane, organic amide compounds such as N-methyl-2-pyrrolidone and N, N-dimethylformamide, and water. Among these, water is preferably used from the viewpoint of price and ease of handling.

  Although the usage-amount of the said reaction solvent is not necessarily limited, It is preferable that it is 10-8000 weight part with respect to 100 weight part of sulfone compounds, and it is more preferable that it is 20-4000 weight part. If the amount of the reaction solvent used is less than 10 parts by weight, the reaction may not proceed smoothly due to the precipitation of raw materials, etc., and the yield may be reduced. It is not economical because there is no effect corresponding to the amount.

  In the present invention, examples of the hydrogenation reaction method include a method in which hydrogen gas is introduced into a reaction vessel and reacted in a hydrogen atmosphere.

  The pressure in the reaction vessel is, for example, 0.1 to 6 MPa in a hydrogen atmosphere. In the present specification, the pressure in the reaction vessel is represented by a gauge pressure based on the atmospheric pressure (the atmospheric pressure is 0).

  The reaction temperature is preferably 0 to 150 ° C, and more preferably 15 to 100 ° C. If the reaction temperature is less than 0 ° C, the reaction may be insufficient and the yield may decrease. If the reaction temperature exceeds 150 ° C, the sulfolene compound will decompose and by-products may be produced, resulting in a decrease in yield. There is a risk.

  The reaction time varies depending on the reaction temperature, but is usually 50 to 300 minutes.

  The sulfolane compound thus obtained can be obtained by purging the hydrogen gas remaining in the reaction vessel, filtering the reaction solution, and removing the solvent by distillation under reduced pressure.

  The sulfolane compound obtained by the present invention is represented by the above formula (3), and specific examples thereof include sulfolane, 3-methyl sulfolane, 3-ethyl sulfolane, 3-propyl sulfolane, 3-butyl sulfolane, 3- Isobutyl sulfolane, 3-tert-butyl sulfolane, 3-hexyl sulfolane, 3,4-dimethyl sulfolane, 3,4-diethyl sulfolane, 3,4-dibutyl sulfolane, 3-hexyl-4-methyl sulfo Forane, 2,5-dimethylsulfolane, 2,3,5-trimethylsulfolane, 2,5-dimethyl-3-hexylsulfolane, 2,3,4,5-tetramethylsulfolane, 2,5-diethyl Sulfolane, 2,5-diethyl-2-methylsulfolane, 2,5-diethyl-2,5-diethyl Rufolane, 2,5-diethyl-3,4-dimethylsulfolane, 2,5-diethylsulfolane, 2,5-dipropylsulfolane, 2,5-dipropyl-3-methylsulfolane and 2,5-dipropyl -3,4-dimethyl sulfolane and the like.

  According to the present invention, a sulfolane compound can be produced easily and efficiently.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

Example 1
A 500 mL stainless steel autoclave equipped with a stirrer, a pressure gauge, a thermometer and a heater was charged with 200 g of a 32 wt% 3-sulfolene aqueous solution (0.54 mol of 3-sulfolene), 0.455 g of Raney nickel catalyst as a metal catalyst, and As a metal having a higher ionization tendency than the metal catalyst, 0.025 g of aluminum (5.5 parts by weight with respect to 100 parts by weight of the metal catalyst) was added. Next, hydrogen was introduced into the autoclave, pressurized to 1.0 MPa, and stirred at 1000 rpm with a stirrer to initiate a hydrogenation reaction. The reaction temperature was maintained in the range of 30 to 40 ° C., and the pressure was maintained by replenishing hydrogen until the end of the reaction. Sampling was performed every 120 to 30 minutes after the start of the reaction, and the time point at which disappearance of 3-sulfolene was confirmed by gas chromatography was defined as the reaction end point. As a result, the reaction time from the start of the reaction to the end of the reaction was 150 minutes, and after the completion of the reaction, the reaction rate of 3-sulfolane by an absolute calibration curve method of gas chromatography was 99.8%.

  Thereafter, the metal catalyst in the reaction solution was removed by filtration, distilled under reduced pressure at 300 mmHg and 160 ° C., water was distilled off, and further distilled under reduced pressure at 5 mmHg and 135 ° C. to give 61.7 g (0. 51 mol) was obtained.

Example 2
In Example 1, a hydrogenation reaction was performed in the same manner as in Example 1 except that 0.000455 g of iron (0.1 part by weight with respect to 100 parts by weight of the metal catalyst) was added instead of 0.025 g of aluminum. went. As a result, the reaction time was 150 minutes, and after completion of the reaction, the reaction rate of 3-sulfolane according to the absolute calibration curve method of gas chromatography was 99.9%.

  Moreover, it distilled under reduced pressure similarly to Example 1, and obtained 61.1 g (0.51 mol) of 3-sulfolane.

Comparative Example 1
In Example 1, a hydrogenation reaction was performed in the same manner as in Example 1 except that 0.025 g of aluminum was not added. As a result, the reaction time was 240 minutes, and after completion of the reaction, the reaction rate of 3-sulfolane according to the absolute calibration curve method of gas chromatography was 99.8%.

  Moreover, it distilled under reduced pressure similarly to Example 1, and obtained 60.6 g (0.50 mol) of 3-sulfolane.

Claims (3)

Formula (1):

(Wherein R ^{1 to} R ⁶ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) A sulfolene compound represented by a metal catalyst and a metal species of the metal catalyst are ionized. Hydrogenation in the presence of a highly prone metal (2):

^(Wherein, R 1 to R ⁶ has the formula (1) represents the same group as ^R 1 to R ⁶ in.) The method of producing sulfolane compounds represented by.   The method for producing a sulfolane compound according to claim 1, wherein the metal species of the metal catalyst is nickel, palladium, rhodium, platinum or ruthenium.   The method for producing a sulfolane compound according to claim 2, wherein the metal having a large ionization tendency is aluminum or iron.