JP4420150B2 - Method for synthesizing 3- (2-oxo-1-pyrrolidinyl) propylsilanes - Google Patents

Description

（式中、Ｘはハロゲン原子を表し、Ｒ¹、Ｒ²は炭素数１〜１０の置換又は非置換の一価炭化水素基を表し、ｎは０〜２の正数を表す。）
【０００８】
以下、本発明につき更に詳しく説明する。
本発明の上記式（２）の３−（２−オキソ−１−ピロリジニル）プロピルシラン類を得る方法は、まず、２−ピロリドンとアルカリ金属化合物とを反応させて２−ピロリドンのアルカリ金属塩を製造する。
【０００９】
本発明で用いられるアルカリ金属化合物としては、リチウムメトキシド、リチウムエトキシド、リチウムプロポキシド、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムプロポキシド、ポタシウムメトキシド、ポタシウムエトキシド、ポタシウムプロポキシドなどのアルカリ金属アルコキシド類、水素化リチウム、水素化ナトリウム、水素化カリウム等のアルカリ金属水素化物類が挙げられる。ここで、アルカリ金属アルコキシド類は、結晶状態で用いても、対応するアルコールの溶液として用いてもよい。好ましくはナトリウムメトキシド、ナトリウムエトキシドが挙げられる。
【００１０】
２−ピロリドンとアルカリ金属化合物であるアルカリ金属アルコキシド類との反応は、アルカリ金属アルコキシド類を結晶状態で用いる場合には、溶媒存在下両者を混合した後に、副生するアルコール類を溶媒と共に留去して合成する。アルカリ金属アルコキシド類を対応するアルコール溶液として用いる場合には、無溶媒で反応を行った後、溶媒を加えてアルコール類を溶媒と共に留去してもよく、また初めから溶媒を用いて反応を行った後、溶媒と共にアルコールの留去を行ってもよい。溶媒としては、副生するアルコール類よりも沸点の高い化合物が好ましく、トルエン、キシレン、エチルベンゼン、メシチレン等の炭化水素溶媒が挙げられる。アルコールと溶媒の留去は、２−ピロリドンのアルカリ金属塩と３−ハロプロピルシラン類との反応を非プロトン性極性溶媒中行う場合には、溶媒をできる限り留去することが好ましい。２−ピロリドンのアルカリ金属塩と３−ハロプロピルシラン類との反応を相関移動触媒を用いて行う場合には、留出液の沸点が溶媒の沸点に達して留出液にアルコール類が無くなるまで行えばよく、残留する溶媒は次の２−ピロリドンのアルカリ金属塩と３−ハロプロピルシラン類との反応の溶媒としてそのまま用いることができる。
【００１１】
アルカリ金属化合物の使用量は、２−ピロリドン１モルに対して０．５〜２モル、特に０．９〜１．０モルが好ましい。少なすぎると２−ピロリドンが残留して収率が低下し、多すぎると未反応のアルカリ金属化合物が３−ハロプロピルシランと反応し、副生成物が生じて収率が低下する場合がある。
【００１２】
本発明は、次いで、上記２−ピロリドンのアルカリ金属塩と下記式（１）の３−ハロプロピルシランとを反応させることにより、下記式（２）の３−（２−オキソ−１−ピロリジニル）プロピルシラン類を得るものである。
【００１３】
【化４】

（式中、Ｘはハロゲン原子を表し、Ｒ¹、Ｒ²は炭素数１〜１０の置換又は非置換の一価炭化水素基を表し、ｎは０〜２の正数を表す。）
【００１４】
ここで、Ｘのハロゲン原子としては、Ｃｌ，Ｂｒ，Ｉ等が挙げられる。また、Ｒ¹、Ｒ²としては、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、シクロヘキシル等のアルキル基、ビニル、アリル、プロペニル、ブテニル、ヘキセニル等のアルケニル基、フェニル、トリル、キシリル等のアリール基、ベンジル、フェニルエチル、フェニルプロピル等のアラルキル基などや、これらの基の水素原子の一部又は全部をアルコキシ基、シアノ基などで置換した基が挙げられる。この場合、Ｒ²としてはアルキル基が好ましい。
【００１５】
具体的には、３−ハロプロピルシラン類としては、３−クロロプロピルトリメトキシシラン、３−クロロプロピルメチルジメトキシシラン、３−クロロプロピルジメチルメトキシシラン、３−クロロプロピルエチルジメトキシシラン、３−クロロプロピルトリエトキシシラン、３−クロロプロピルメチルジエトキシシラン、３−クロロプロピルジメチルエトキシシラン、３−ブロモプロピルトリメトキシシラン、３−ブロモプロピルメチルジメトキシシラン、３−ブロモプロピルジメチルメトキシシラン、３−ブロモプロピルトリエトキシシラン、３−ブロモプロピルメチルジエトキシシラン、３−ブロモプロピルジメチルエトキシシラン、３−ヨードプロピルトリメトキシシラン、３−ヨードプロピルメチルジメトキシシラン、３−ヨードプロピルジメチルメトキシシラン、３−ヨードプロピルトリエトキシシラン、３−ヨードプロピルメチルジエトキシシラン、３−ヨードプロピルジメチルエトキシシラン等が挙げられる。
【００１６】
２−ピロリドンのアルカリ金属塩と３−ハロプロピルシラン類の反応は、非プロトン性極性溶媒存在下行うか、又は相関移動触媒存在下非極性溶媒を用いて反応させることができる。
【００１７】
非プロトン性極性溶媒としては、ジメチルホルムアミド、ジメチルアセトアミド、１，３−ジメチル−２−イミダゾリジノン、ジメチルスルホキシド等が挙げられる。好ましくは、ジメチルホルムアミドが挙げられる。
【００１８】
相関移動触媒としては、テトラ−ｎ−ブチルアンモニウムクロライド、テトラ−ｎ−ブチルアンモニウムブロマイド、テトラ−ｎ−ブチルアンモニウムアイオダイド等が挙げられる。好ましくは、テトラ−ｎ−ブチルアンモニウムブロマイドが挙げられる。相関移動触媒を用いて反応を行う場合の非極性溶媒としては、トルエン、キシレン、エチルベンゼン、メシチレン等が挙げられるが、２−ピロリドンとアルカリ金属化合物との反応で用いた溶媒を用いることが好ましい。
【００１９】
相関移動触媒の使用量は、２−ピロリドン１モルに対して０．００１〜０．１モル、好ましくは０．００５〜０．０５モルであることが好ましい。相関移動触媒は、全量を１度に加えてもよいが、反応中数回に分けて加えることが好ましい。
【００２０】
３−ハロプロピルシラン類の使用量は、２−ピロリドン１モルに対して０．５〜２モル、好ましくは０．９〜１．１モルであることがよい。少なすぎると収率が低下し、多く用いても収率の向上はなく、不経済である。
【００２１】
反応温度は、通常２０〜１５０℃、好ましくは８０〜１２０℃であり、反応時間は、通常３０分〜１０時間、好ましくは２〜６時間である。反応は不活性ガス雰囲気下で行うことが好ましく、不活性ガスとしては、窒素、アルゴンなどが挙げられる。
【００２２】
【発明の効果】
本発明によれば、ピロリジン様の不快臭のしない３−（２−オキソ−１−ピロリジニル）プロピルシラン類を製造することができる。
【００２３】
【実施例】
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。
【００２４】
［実施例１］
５００ｍｌの４つ口ガラスフラスコに還流冷却器付きの蒸留装置、温度計、滴下漏斗、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、ナトリウムメトキシドの２８％メタノール溶液７７．２ｇ（０．４ｍｏｌ）を仕込んだ。
【００２５】
次いで、内温２７〜２８℃で２−ピロリドン３４．０ｇ（０．４ｍｏｌ）のトルエン４０ｍｌ溶液を３０分で滴下した。滴下終了後、トルエン８０ｍｌを加え、フラスコを油浴により加熱し、メタノールとトルエンを１３３．６ｇ留去した。トルエン１００ｍｌを加えた後、油浴の温度を１３０℃として更にメタノールとトルエンを留出が無くなるまで留去した。この時の留出液量は９９．０ｇであった。フラスコを冷却した後、ＤＭＦ１６０ｍｌを加えた。油浴により内温を９５〜１０５℃に保ちながら、３−クロロプロピルトリメトキシシラン７９．５ｇ（０．４ｍｏｌ）を１．５時間で滴下した。滴下終了後更に３時間熟成した。生成した塩を濾過により除いた後、減圧下に濃縮を行った。得られた濃縮液を減圧下蒸留し、沸点１３６〜１３９℃／４００Ｐａの留分を分取することにより、３−（２−オキソ−１−ピロリジニル）プロピルトリメトキシシラン６７．３ｇを得た。収率は６８．０％であった。この蒸留液の臭いをかいだところ、ピロリジン様の不快臭はしなかった。
【００２６】
［実施例２］
５００ｍｌの４つ口ガラスフラスコに還流冷却器付きの蒸留装置、温度計、滴下漏斗、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、ナトリウムメトキシドの２８％メタノール溶液７７．２ｇ（０．４ｍｏｌ）を仕込んだ。
【００２７】
次いで、内温２５〜２６℃で２−ピロリドン３４．０ｇ（０．４ｍｏｌ）のトルエン４０ｍｌ溶液を３０分で滴下した。滴下終了後、トルエン８０ｍｌを加え、フラスコを油浴により加熱し、メタノールとトルエンを１３０．８ｇ留去した。トルエン１００ｍｌを加えた後、油浴の温度を１３０℃として更にメタノールとトルエンを留出が無くなるまで留去した。この時の留出液量は１０２．３ｇであった。フラスコを冷却した後、ＤＭＦ１６０ｍｌを加えた。油浴により内温を９５〜１０５℃に保ちながら、３−クロロプロピルメチルジメトキシシラン７９．５ｇ（０．４ｍｏｌ）を１．５時間で滴下した。滴下終了後、更に３時間熟成した。生成した塩を濾過により除いた後、減圧下に濃縮を行った。得られた濃縮液を減圧下蒸留し、沸点１２３〜１２６℃／２００Ｐａの留分を分取することにより、３−（２−オキソ−１−ピロリジニル）プロピルメチルジメトキシシラン６５．０ｇを得た。収率は７０．２％であった。この蒸留液の臭いをかいだところ、ピロリジン様の不快臭はしなかった。
【００２８】
［比較例１］
２００ｍｌの４つ口ガラスフラスコに還流冷却器、温度計、滴下漏斗、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、１−アリル−２−オキソピロリジン５０．１ｇ（０．４ｍｏｌ）と、白金１，３−ジビニル−１，１，３，３−テトラメチルジシロキサン錯体（白金金属を３％含有）１．３ｇ（０．０００２ｍｏｌ）を仕込んだ。
【００２９】
水浴により内温を２３．５〜２８℃に保ちながらメチルジメトキシシラン４２．５ｇ（０．４ｍｏｌ）を４時間で滴下した。滴下終了後、更に室温で１３時間熟成した。得られた反応液を減圧下蒸留し、沸点１２５〜１２７℃／２００Ｐａの留分を分取することにより、３−（２−オキソ−１−ピロリジニル）プロピルメチルジメトキシシラン８１．０ｇを得た。収率は８７．５％であった。この蒸留液の臭いをかいだところ、実施例２の蒸留液に比較してピロリジン様の不快な臭気が強く感じられた。
【００３０】
［実施例３］
５００ｍｌの４つ口ガラスフラスコに還流冷却器付きの蒸留装置、温度計、滴下漏斗、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、ナトリウムメトキシドの２８％メタノール溶液７７．２ｇ（０．４ｍｏｌ）を仕込んだ。
【００３１】
次いで、内温２４〜２５℃で２−ピロリドン３４．０ｇ（０．４ｍｏｌ）のトルエン４０ｍｌ溶液を３０分で滴下した。滴下終了後、トルエン８０ｍｌを加え、フラスコを油浴により加熱し、メタノールとトルエンを１３０．９ｇ留去した。トルエン１００ｍｌを加えた後、油浴の温度を１３０℃として更にメタノールとトルエンを留出が無くなるまで留去した。この時の留出液量は１０１．２ｇであった。フラスコを冷却した後、ＤＭＦ１６０ｍｌを加えた。油浴により内温を９５〜１０５℃に保ちながら、３−クロロプロピルトリエトキシシラン９６．３ｇ（０．４ｍｏｌ）を１．５時間で滴下した。滴下終了後、更に４．５時間熟成した。生成した塩を濾過により除いた後、減圧下に濃縮を行った。得られた濃縮液を減圧下蒸留し、沸点１３８〜１４０℃／１．３ｋＰａの留分を分取することにより、３−（２−オキソ−１−ピロリジニル）プロピルトリエトキシシラン８２．３ｇを得た。収率は７１．１％であった。この蒸留液の臭いをかいだところ、ピロリジン様の不快臭はしなかった。
【００３２】
［実施例４］
２００ｍｌの４つ口ガラスフラスコに還流冷却器付きの蒸留装置、温度計、滴下漏斗、及び撹拌機を取り付け、内部を窒素置換した。このフラスコに、ナトリウムメトキシド１０．８ｇ（０．２ｍｏｌ）、２−ピロリドン１７．０ｇ（０．２ｍｏｌ）、トルエン８０ｍｌを仕込んだ。
【００３３】
フラスコを油浴により加熱し、メタノールとトルエンを１９．４ｇ留去した。トルエン１９．４ｇ、テトラ−ｎ−ブチルアンモニウムブロマイド０．６４ｇ（０．００２ｍｏｌ）を加えた後、油浴により内温を９０〜１００℃に保ちながら３−クロロプロピルトリメトキシシラン３９．７ｇ（０．２ｍｏｌ）を３０分で滴下した。滴下終了後、１時間熟成した後にテトラ−ｎ−ブチルアンモニウムブロマイド０．６４ｇ（０．００２ｍｏｌ）を加え、１時間還流下に熟成し、更にテトラ−ｎ−ブチルアンモニウムブロマイド０．６４ｇ（０．００２ｍｏｌ）を加え、４時間還流下に熟成した。生成した塩を濾過により除いた後、減圧下に濃縮を行った。得られた濃縮液を減圧下蒸留し、沸点１４０〜１４８℃／４００Ｐａの留分を分取することにより、３−（２−オキソ−１−ピロリジニル）プロピルトリメトキシシラン３１．９ｇを得た。収率は６４．５％であった。この蒸留液の臭いをかいだところ、ピロリジン様の不快臭はしなかった。[0001]
BACKGROUND OF THE INVENTION
The present invention includes a surface treatment agent and a silane coupling agent for imparting antifogging properties to the surfaces of various substrates, a raw material for synthesizing a fiber treatment agent that imparts flexibility and hydrophilicity to fibers and has an effect of preventing yellowing, The present invention relates to a synthesis method in which unpleasant odors of 3- (2-oxo-1-pyrrolidinyl) propylsilanes useful as a synthetic raw material for cosmetic additives are reduced.
[0002]
[Prior art and problems to be solved by the invention]
3- (2-Oxo-1-pyrrolidinyl) propylsilanes provide surface treatment agents and silane coupling agents for imparting antifogging properties to the surfaces of various substrates, impart flexibility and hydrophilicity to fibers, and yellow It is a compound useful as a synthetic raw material for fiber treatment agents having an effect of preventing change or as a synthetic raw material for cosmetic additives.
[0003]
Conventionally, as a method for producing 3- (2-oxo-1-pyrrolidinyl) propylsilanes, a method in which 1-allyl-2-oxopyrrolidine is hydrosilylated with hydrosilanes in the presence of a platinum catalyst is known ( JP-A-3-47191).
[0004]
However, when synthesized by a hydrosilylation reaction, a compound having an unpleasant odor like pyrrolidine is by-produced and cannot be removed by distillation. This is considered to be due to the generation of a trace impurity having a pyrrolidine ring by a side reaction accompanied by a reduction reaction of the carbonyl group by hydrosilane during the hydrosilylation reaction. This unpleasant odor is not preferable when it is used as a raw material for fiber treatment agents, and particularly as a raw material for cosmetic additives.
[0005]
The present invention has been made in view of the above circumstances, and provides a method for synthesizing 3- (2-oxo-1-pyrrolidinyl) propylsilanes with reduced unpleasant odor.
[0006]
Means for Solving the Problem and Embodiment of the Invention
As a result of intensive studies to achieve the above object, the present inventors have made 2-pyrrolidone and an alkali metal compound react to form an alkali metal salt of 2-pyrrolidone, and then represented by the following formula (1). It has been found that by reacting 3-halopropylsilane, 3- (2-oxo-1-pyrrolidinyl) propylsilanes represented by the following formula (2) with reduced unpleasant odor can be obtained. It came to an eggplant.
[0007]
[Chemical 3]

(In the formula, X represents a halogen atom, R ¹ and R ² represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents a positive number of 0 to 2).
[0008]
Hereinafter, the present invention will be described in more detail.
In the method for obtaining 3- (2-oxo-1-pyrrolidinyl) propylsilanes of the above formula (2) of the present invention, first, 2-pyrrolidone and an alkali metal compound are reacted to obtain an alkali metal salt of 2-pyrrolidone. To manufacture.
[0009]
Examples of the alkali metal compound used in the present invention include alkali metals such as lithium methoxide, lithium ethoxide, lithium propoxide, sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium ethoxide, and potassium propoxide. Alkali metal hydrides such as alkoxides, lithium hydride, sodium hydride, potassium hydride and the like can be mentioned. Here, the alkali metal alkoxides may be used in a crystalline state or as a solution of a corresponding alcohol. Sodium methoxide and sodium ethoxide are preferable.
[0010]
The reaction between 2-pyrrolidone and an alkali metal alkoxide, which is an alkali metal compound, is carried out in the case where the alkali metal alkoxide is used in a crystalline state. To synthesize. When alkali metal alkoxides are used as the corresponding alcohol solutions, the reaction may be carried out without solvent, and then the solvent may be added to distill off the alcohols together with the solvent, or the reaction may be carried out using the solvent from the beginning. Then, the alcohol may be distilled off together with the solvent. As the solvent, a compound having a boiling point higher than that of the by-produced alcohol is preferable, and examples thereof include hydrocarbon solvents such as toluene, xylene, ethylbenzene, and mesitylene. The alcohol and solvent are preferably distilled off as much as possible when the reaction between the alkali metal salt of 2-pyrrolidone and the 3-halopropylsilane is performed in an aprotic polar solvent. When the reaction between the alkali metal salt of 2-pyrrolidone and 3-halopropylsilanes is carried out using a phase transfer catalyst, the boiling point of the distillate reaches the boiling point of the solvent and no alcohols are present in the distillate. The remaining solvent can be used as it is as a solvent for the subsequent reaction between the alkali metal salt of 2-pyrrolidone and 3-halopropylsilanes.
[0011]
The amount of the alkali metal compound used is preferably 0.5 to 2 mol, particularly 0.9 to 1.0 mol, per 1 mol of 2-pyrrolidone. If the amount is too small, 2-pyrrolidone remains and the yield decreases. If the amount is too large, an unreacted alkali metal compound reacts with 3-halopropylsilane to produce a by-product, which may decrease the yield.
[0012]
The present invention then reacts the alkali metal salt of 2-pyrrolidone with 3-halopropylsilane of the following formula (1) to give 3- (2-oxo-1-pyrrolidinyl) of the following formula (2). Propylsilanes are obtained.
[0013]
[Formula 4]

(In the formula, X represents a halogen atom, R ¹ and R ² represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents a positive number of 0 to 2).
[0014]
Here, examples of the halogen atom for X include Cl, Br, and I. R ¹ and R ² are alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, vinyl, allyl, propenyl, butenyl, hexenyl, etc. Alkenyl groups, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl, phenylethyl and phenylpropyl, etc., and groups in which some or all of the hydrogen atoms of these groups are substituted with alkoxy groups, cyano groups, etc. Is mentioned. In this case, R ² is preferably an alkyl group.
[0015]
Specifically, as 3-halopropylsilanes, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyldimethylmethoxysilane, 3-chloropropylethyldimethoxysilane, 3-chloropropyl Triethoxysilane, 3-chloropropylmethyldiethoxysilane, 3-chloropropyldimethylethoxysilane, 3-bromopropyltrimethoxysilane, 3-bromopropylmethyldimethoxysilane, 3-bromopropyldimethylmethoxysilane, 3-bromopropyltri Ethoxysilane, 3-bromopropylmethyldiethoxysilane, 3-bromopropyldimethylethoxysilane, 3-iodopropyltrimethoxysilane, 3-iodopropylmethyldimethoxysilane, 3-iodo B pills dimethyl silane, 3-iodo-propyl triethoxysilane, 3-iodo-propyl methyl diethoxy silane, 3-iodo-propyl dimethyl ethoxy silane, and the like.
[0016]
The reaction between the alkali metal salt of 2-pyrrolidone and 3-halopropylsilanes can be carried out in the presence of an aprotic polar solvent or can be carried out using a nonpolar solvent in the presence of a phase transfer catalyst.
[0017]
Examples of the aprotic polar solvent include dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide and the like. Preferably, dimethylformamide is used.
[0018]
Examples of the phase transfer catalyst include tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, and tetra-n-butylammonium iodide. Preferably, tetra-n-butylammonium bromide is used. Examples of the nonpolar solvent in the case of performing the reaction using the phase transfer catalyst include toluene, xylene, ethylbenzene, mesitylene and the like, but it is preferable to use the solvent used in the reaction of 2-pyrrolidone and the alkali metal compound.
[0019]
The amount of the phase transfer catalyst used is 0.001 to 0.1 mol, preferably 0.005 to 0.05 mol, per 1 mol of 2-pyrrolidone. The total amount of the phase transfer catalyst may be added at once, but it is preferable to add it in several times during the reaction.
[0020]
The usage-amount of 3-halopropyl silanes is 0.5-2 mol with respect to 1 mol of 2-pyrrolidone, Preferably it is 0.9-1.1 mol. If the amount is too small, the yield will decrease, and even if it is used in large amounts, the yield will not improve and it will be uneconomical.
[0021]
The reaction temperature is usually 20 to 150 ° C., preferably 80 to 120 ° C., and the reaction time is usually 30 minutes to 10 hours, preferably 2 to 6 hours. The reaction is preferably performed in an inert gas atmosphere, and examples of the inert gas include nitrogen and argon.
[0022]
【The invention's effect】
According to the present invention, 3- (2-oxo-1-pyrrolidinyl) propylsilanes having no pyrrolidine-like unpleasant odor can be produced.
[0023]
【Example】
EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[0024]
[Example 1]
A distillation apparatus equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer were attached to a 500 ml four-necked glass flask, and the inside was purged with nitrogen. This flask was charged with 77.2 g (0.4 mol) of a 28% methanol solution of sodium methoxide.
[0025]
Next, a solution of 34.0 g (0.4 mol) of 2-pyrrolidone in 40 ml of toluene was added dropwise at an internal temperature of 27 to 28 ° C. in 30 minutes. After completion of dropping, 80 ml of toluene was added, the flask was heated with an oil bath, and 133.6 g of methanol and toluene were distilled off. After adding 100 ml of toluene, the temperature of the oil bath was set to 130 ° C., and methanol and toluene were further distilled off until no distillation occurred. The amount of distillate at this time was 99.0 g. After the flask was cooled, 160 ml of DMF was added. While maintaining the internal temperature at 95 to 105 ° C. with an oil bath, 79.5 g (0.4 mol) of 3-chloropropyltrimethoxysilane was added dropwise over 1.5 hours. After completion of dropping, the mixture was further aged for 3 hours. The formed salt was removed by filtration, and then concentrated under reduced pressure. The obtained concentrated liquid was distilled under reduced pressure, and a fraction having a boiling point of 136 to 139 ° C./400 Pa was fractionated to obtain 67.3 g of 3- (2-oxo-1-pyrrolidinyl) propyltrimethoxysilane. The yield was 68.0%. When the smell of this distillate was checked, there was no pyrrolidine-like unpleasant odor.
[0026]
[Example 2]
A distillation apparatus equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer were attached to a 500 ml four-necked glass flask, and the inside was purged with nitrogen. This flask was charged with 77.2 g (0.4 mol) of a 28% methanol solution of sodium methoxide.
[0027]
Then, a toluene 40 ml solution of 34.0 g (0.4 mol) of 2-pyrrolidone was added dropwise in 30 minutes at an internal temperature of 25 to 26 ° C. After completion of dropping, 80 ml of toluene was added, the flask was heated with an oil bath, and 130.8 g of methanol and toluene were distilled off. After adding 100 ml of toluene, the temperature of the oil bath was set to 130 ° C., and methanol and toluene were further distilled off until no distillation occurred. The amount of distillate at this time was 102.3 g. After the flask was cooled, 160 ml of DMF was added. While maintaining the internal temperature at 95 to 105 ° C. with an oil bath, 79.5 g (0.4 mol) of 3-chloropropylmethyldimethoxysilane was added dropwise over 1.5 hours. After completion of the dropwise addition, the mixture was further aged for 3 hours. The formed salt was removed by filtration, and then concentrated under reduced pressure. The obtained concentrated liquid was distilled under reduced pressure, and a fraction having a boiling point of 123 to 126 ° C./200 Pa was fractionated to obtain 65.0 g of 3- (2-oxo-1-pyrrolidinyl) propylmethyldimethoxysilane. The yield was 70.2%. When the smell of this distillate was checked, there was no pyrrolidine-like unpleasant odor.
[0028]
[Comparative Example 1]
A 200 ml four-necked glass flask was equipped with a reflux condenser, a thermometer, a dropping funnel and a stirrer, and the inside was purged with nitrogen. To this flask, 50.1 g (0.4 mol) of 1-allyl-2-oxopyrrolidine and platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (containing 3% platinum metal) 1.3 g (0.0002 mol) was charged.
[0029]
42.5 g (0.4 mol) of methyldimethoxysilane was added dropwise over 4 hours while maintaining the internal temperature at 23.5 to 28 ° C. with a water bath. After completion of dropping, the mixture was further aged at room temperature for 13 hours. The obtained reaction liquid was distilled under reduced pressure, and a fraction having a boiling point of 125 to 127 ° C./200 Pa was fractionated to obtain 81.0 g of 3- (2-oxo-1-pyrrolidinyl) propylmethyldimethoxysilane. The yield was 87.5%. When the odor of this distillate was checked, a pyrrolidine-like unpleasant odor was strongly felt as compared with the distillate of Example 2.
[0030]
[Example 3]
A distillation apparatus equipped with a reflux condenser, a thermometer, a dropping funnel, and a stirrer were attached to a 500 ml four-necked glass flask, and the inside was purged with nitrogen. This flask was charged with 77.2 g (0.4 mol) of a 28% methanol solution of sodium methoxide.
[0031]
Subsequently, a toluene 40 ml solution of 34.0 g (0.4 mol) of 2-pyrrolidone was added dropwise at an internal temperature of 24 to 25 ° C. in 30 minutes. After completion of dropping, 80 ml of toluene was added, the flask was heated in an oil bath, and 130.9 g of methanol and toluene were distilled off. After adding 100 ml of toluene, the temperature of the oil bath was set to 130 ° C., and methanol and toluene were further distilled off until no distillation occurred. The amount of distillate at this time was 101.2 g. After the flask was cooled, 160 ml of DMF was added. 96.3 g (0.4 mol) of 3-chloropropyltriethoxysilane was added dropwise over 1.5 hours while maintaining the internal temperature at 95 to 105 ° C. with an oil bath. After completion of dropping, the mixture was further aged for 4.5 hours. The formed salt was removed by filtration, and then concentrated under reduced pressure. The obtained concentrated liquid was distilled under reduced pressure, and a fraction having a boiling point of 138 to 140 ° C./1.3 kPa was separated to obtain 82.3 g of 3- (2-oxo-1-pyrrolidinyl) propyltriethoxysilane. It was. The yield was 71.1%. When the smell of this distillate was checked, there was no pyrrolidine-like unpleasant odor.
[0032]
[Example 4]
A 200 ml four-necked glass flask was equipped with a distillation apparatus with a reflux condenser, a thermometer, a dropping funnel, and a stirrer, and the inside was purged with nitrogen. To this flask, 10.8 g (0.2 mol) of sodium methoxide, 17.0 g (0.2 mol) of 2-pyrrolidone and 80 ml of toluene were charged.
[0033]
The flask was heated with an oil bath, and 19.4 g of methanol and toluene were distilled off. After adding 19.4 g of toluene and 0.64 g (0.002 mol) of tetra-n-butylammonium bromide, 39.7 g (0 of 3-chloropropyltrimethoxysilane was maintained while maintaining the internal temperature at 90 to 100 ° C. with an oil bath. .2 mol) was added dropwise in 30 minutes. After completion of the dropwise addition, the mixture was aged for 1 hour and then added with 0.64 g (0.002 mol) of tetra-n-butylammonium bromide and aged for 1 hour under reflux. Further, 0.64 g (0.002 mol) of tetra-n-butylammonium bromide was added. ) And aged for 4 hours under reflux. The formed salt was removed by filtration, and then concentrated under reduced pressure. The concentrated solution thus obtained was distilled under reduced pressure, and a fraction having a boiling point of 140 to 148 ° C./400 Pa was fractionated to obtain 31.9 g of 3- (2-oxo-1-pyrrolidinyl) propyltrimethoxysilane. The yield was 64.5%. When the smell of this distillate was checked, there was no pyrrolidine-like unpleasant odor.

Claims (3)

After reacting 2-pyrrolidone with an alkali metal compound to give an alkali metal salt of 2-pyrrolidone, the following formula (1)

(In the formula, X represents a halogen atom, R ¹ and R ² represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents a positive number of 0 to 2).
The following formula (3) , wherein the reaction is carried out in an aprotic polar solvent selected from dimethylformamide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, and dimethylsulfoxide represented by the following formula ( 2)

(Wherein R ¹ and R ² represent a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents a positive number of 0 to 2)
A method for synthesizing 3- (2-oxo-1-pyrrolidinyl) propylsilanes represented by the formula: After reacting 2-pyrrolidone with an alkali metal compound to give an alkali metal salt of 2-pyrrolidone, the following formula (1)

(Wherein X represents a halogen atom, R ¹ , R ² Represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents a positive number of 0 to 2. )
The following formula (2), wherein the reaction is carried out in the presence of a phase transfer catalyst:

(Wherein R ¹ , R ² Represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n represents a positive number of 0 to 2. )
A method for synthesizing 3- (2-oxo-1-pyrrolidinyl) propylsilanes represented by the formula: The amount of 3-halopropylsilane used is 0.5 to 2 moles per mole of 2-pyrrolidone, and the reaction between the alkali metal salt of 2-pyrrolidone and 3-halopropylsilane is performed at a temperature of 20 to 150 ° C. The synthesis method according to claim 1 or 2, which is carried out in an inert gas atmosphere.