JP5008404B2 - Method for producing methylene disulfonate compound - Google Patents
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Description
本発明は、メチレンジスルホネート化合物の製造方法に関する。 The present invention relates to a method for producing a methylene disulfonate compound.
メチレンジスルホネート化合物は、白血病動物治療薬等の医薬品として有用な化合物である。 A methylene disulfonate compound is a compound useful as a pharmaceutical product such as a leukemia animal therapeutic agent.
メチレンジスルホネート化合物の製造方法としては、種々の方法が知られている。例えば、スルホニルクロリドと炭酸銀とを反応させて得られるスルホン酸銀をジヨードメタンと反応させる方法（特許文献１参照）、 Various methods are known for producing methylene disulfonate compounds. For example, a method of reacting silver sulfonate obtained by reacting sulfonyl chloride and silver carbonate with diiodomethane (see Patent Document 1),
アルカンジスルホン酸等とメチレンジアセテート等とを反応させる方法（特許文献２参照） Method of reacting alkanedisulfonic acid or the like with methylene diacetate or the like (see Patent Document 2)
等が知られている。 Etc. are known.
これらの方法と同様にして、種々のメチレンジスルホネート化合物を製造することができるが、これらの方法には不具合な点がある。例えば、特許文献１に記載の製造方法によると、使用する炭酸銀やジヨードメタンが高価であり、反応速度が遅いという問題がある。また、特許文献２に記載の製造方法によると、使用するメチレンジアセテート等は入手が必ずしも容易ではなく、また高価であるという問題がある。 Various methylene disulfonate compounds can be produced in the same manner as these methods, but these methods have drawbacks. For example, according to the production method described in Patent Document 1, there is a problem that silver carbonate and diiodomethane to be used are expensive and the reaction rate is slow. Further, according to the production method described in Patent Document 2, there is a problem that methylene diacetate to be used is not always easy to obtain and is expensive.
本発明は、メチレンジスルホネート化合物を工業的に安価で容易に製造する方法を提供することを目的とする。 An object of this invention is to provide the method of manufacturing a methylene disulfonate compound industrially cheaply and easily.
本発明は、一般式（１）： The present invention relates to a general formula (1):
（式中、Ｒ１は、水素原子、ハロゲン原子、水素原子がハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基、置換基を有してもよい芳香環基、または一般式（２）： (Wherein R 1 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, an aromatic ring group that may have a substituent, or a general formula; (2):
（式中、Ｒ２およびＲ３は、それぞれ独立して、水素原子、または水素原子がハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基を示す。）で表される基を示す。）で表されるスルホン酸無水物とホルムアルデヒド化合物とを反応させることを特徴とする、一般式（３）： (Wherein R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). Show. The sulfonic acid anhydride represented by the formula (3) is reacted with a formaldehyde compound, the general formula (3):
（式中、Ｒ１は、前記一般式（１）におけるＲ１と同じ基を示す。）で表されるメチレンジスルホネート化合物の製造方法に関する。 (In the formula, R 1,. Showing the same group as R 1 in the general formula (1)) The method for producing a methylene disulfonate compound represented by.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明に用いられるスルホン酸無水物は、下記一般式（１）で表される化合物である。 The sulfonic anhydride used in the present invention is a compound represented by the following general formula (1).
一般式（１）において、Ｒ１は、水素原子、ハロゲン原子、水素原子がハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基、置換基を有してもよい芳香環基、または一般式（２）： In General Formula (1), R 1 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms in which the hydrogen atom may be substituted with a halogen atom, an aromatic ring group that may have a substituent, Or general formula (2):
（式中、Ｒ２およびＲ３は、それぞれ独立して、水素原子、または水素原子がハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基を示す。）で表される基を示す。 (Wherein R 2 and R 3 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms in which the hydrogen atom may be substituted with a halogen atom). Show.
Ｒ１で示されるハロゲン原子としては、例えば、フッ素原子、塩素原子および臭素原子等が挙げられる。 Examples of the halogen atom represented by R 1 include a fluorine atom, a chlorine atom, and a bromine atom.
Ｒ１で示される、水素原子がハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基、ｉｓｏ−プロピル基、ｎ−ブチル基、ｉｓｏ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、クロロメチル基、ブロモメチル基、フルオロメチル基およびトリフルオロメチル基等が挙げられる。 Examples of the alkyl group having 1 to 4 carbon atoms in which the hydrogen atom optionally substituted with a halogen atom represented by R 1 include, for example, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl. Group, iso-butyl group, sec-butyl group, tert-butyl group, chloromethyl group, bromomethyl group, fluoromethyl group, trifluoromethyl group and the like.
Ｒ１で示される、置換基を有してもよい芳香環基としては、例えば、フェニル基、ナフチル基、ピリジル基、トリル基、ドデシルフェニル基およびクロロフェニル基等が挙げられる。 Examples of the aromatic ring group which may have a substituent represented by R 1 include a phenyl group, a naphthyl group, a pyridyl group, a tolyl group, a dodecylphenyl group and a chlorophenyl group.
Ｒ１が一般式（２）で表される基において、Ｒ２およびＲ３で示される水素原子がハロゲン原子で置換されていてもよい炭素数１〜３のアルキル基としては、例えば、メチル基、エチル基、ｎ−プロピル基およびｉｓｏ−プロピル基等が挙げられる。一般式（２）で表される基の具体例としては、Ｎ−メチルアミノ基、Ｎ，Ｎ−ジメチルアミノ基等が挙げられる。 In the group in which R 1 is represented by the general formula (2), as the alkyl group having 1 to 3 carbon atoms in which the hydrogen atom represented by R 2 and R 3 may be substituted with a halogen atom, for example, a methyl group , Ethyl group, n-propyl group, iso-propyl group and the like. Specific examples of the group represented by the general formula (2) include an N-methylamino group and an N, N-dimethylamino group.
これらの中で、Ｒ１の好ましい例としては、メチル基、トリル基およびＮ，Ｎ−ジメチルアミノ基が好ましい。 Among these, preferred examples of R 1 are a methyl group, a tolyl group, and an N, N-dimethylamino group.
一般式（１）で表されるスルホン酸無水物の具体例としては、例えば、メタンスルホン酸無水物、トリフルオロメタンスルホン酸無水物、ベンゼンスルホン酸無水物、パラトルエンスルホン酸無水物およびＮ，Ｎ−ジメチルスルファミン酸無水物等を挙げることができる。 Specific examples of the sulfonic acid anhydride represented by the general formula (1) include, for example, methanesulfonic acid anhydride, trifluoromethanesulfonic acid anhydride, benzenesulfonic acid anhydride, paratoluenesulfonic acid anhydride, and N, N. -Dimethylsulfamic acid anhydride etc. can be mentioned.
本発明において、前記スルホン酸無水物は、市販のものを使用してもよいし、適宜製造したものを使用してもよい。スルホン酸無水物を製造する方法としては、例えば、メタンスルホン酸、トリフルオロメタンスルホン酸、ベンゼンスルホン酸およびパラトルエンスルホン酸等のスルホン酸化合物と、五酸化リン、五塩化リン、オキシ塩化リン、塩化チオニル、塩化アセチルおよび無水酢酸等の脱水剤とを反応させる方法等を挙げることができる。 In the present invention, as the sulfonic acid anhydride, commercially available products may be used, or those appropriately produced may be used. Examples of the method for producing sulfonic acid anhydride include sulfonic acid compounds such as methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and paratoluenesulfonic acid, and phosphorus pentoxide, phosphorus pentachloride, phosphorus oxychloride, and chloride. Examples include a method of reacting with a dehydrating agent such as thionyl, acetyl chloride, and acetic anhydride.
本発明に用いられるホルムアルデヒド化合物としては、例えば、パラホルムアルデヒド、パラホルムアルデヒドを加熱処理して得られる無水ホルムアルデヒド、パラホルムアルデヒドを酸処理して得られるトリオキサン、および、メチラール等のホルムアルデヒドのアセタール化物等が挙げられる。これらの中でも、パラホルムアルデヒド、無水ホルムアルデヒドおよびトリオキサンが好適に用いられる。これらホルムアルデヒド化合物は、それぞれ単独で、あるいは２種以上を組み合わせて用いてもよい。 Examples of formaldehyde compounds used in the present invention include paraformaldehyde, anhydrous formaldehyde obtained by heat treatment of paraformaldehyde, trioxane obtained by acid treatment of paraformaldehyde, and acetalization products of formaldehyde such as methylal. It is done. Among these, paraformaldehyde, anhydrous formaldehyde and trioxane are preferably used. These formaldehyde compounds may be used alone or in combination of two or more.
ホルムアルデヒド化合物の使用割合は、スルホン酸無水物１モルに対して、０．５〜１０モルの割合であることが好ましく、０．８〜３モルの割合であることがより好ましい。ホルムアルデヒド化合物の使用割合が０．５モル未満である場合、反応が完結しないおそれがあり、１０モルを超える場合、使用量に見合う効果がなく経済的でない。 The use ratio of the formaldehyde compound is preferably 0.5 to 10 mol, more preferably 0.8 to 3 mol, relative to 1 mol of the sulfonic anhydride. When the use ratio of the formaldehyde compound is less than 0.5 mol, the reaction may not be completed.
本発明において、必要に応じて反応に不活性な溶媒を用いてもよい。反応に不活性な溶媒としては、例えば、トルエン、キシレン、モノクロロベンゼン、ジクロロベンゼン、トリクロロベンゼン、ヘキサン、ヘプタン、デカン等の炭化水素系溶媒；ジエチルエーテル、エチレングリコールジメチルエーテル、ジイソプロピルエーテル、ジフェニルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒；アセトン、メチルエチルケトン等のケトン系溶媒；ジメチルホルムアミド、ヘキサメチル燐酸トリアミド等のアミド系溶媒；酢酸エチル等の酢酸エステル系溶媒；アセトニトリル等のニトリル系溶媒；ジメチルスルホキシド、スルホラン等のスルホキシド・スルホン系溶媒等が挙げられる。 In the present invention, if necessary, a solvent inert to the reaction may be used. Examples of the solvent inert to the reaction include hydrocarbon solvents such as toluene, xylene, monochlorobenzene, dichlorobenzene, trichlorobenzene, hexane, heptane, decane; diethyl ether, ethylene glycol dimethyl ether, diisopropyl ether, diphenyl ether, tetrahydrofuran, Ether solvents such as dioxane; ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as dimethylformamide and hexamethylphosphoric triamide; acetate solvents such as ethyl acetate; nitrile solvents such as acetonitrile; dimethyl sulfoxide, sulfolane and the like Examples thereof include sulfoxide and sulfone solvents.
溶媒の使用量は、スルホン酸無水物１００重量部に対して、通常、５００重量部以下である。 The amount of the solvent used is usually 500 parts by weight or less with respect to 100 parts by weight of the sulfonic anhydride.
本発明の反応温度は、通常、０〜２００℃であり、好ましくは５０〜１５０℃である。また、反応時間は反応温度により異なるが、通常、０．１〜１０時間である。 The reaction temperature of this invention is 0-200 degreeC normally, Preferably it is 50-150 degreeC. Moreover, although reaction time changes with reaction temperature, it is 0.1 to 10 hours normally.
かくして得られるメチレンジスルホネート化合物は、下記一般式（３）で表される化合物である。 The methylene disulfonate compound thus obtained is a compound represented by the following general formula (3).
一般式（３）において、Ｒ１は、前記一般式（１）におけるＲ１と同じ基を示す。 In the general formula (3), R 1 represents the same group as R 1 in the general formula (1).
一般式（３）で表されるメチレンジスルホネート化合物の具体例としては、例えばメチレンジメタンスルホネート、メチレンジトリフルオロメタンスルホネート、メチレンジベンゼンスルホネートおよびメチレンジパラトルエンスルホネート等を挙げることができる。 Specific examples of the methylene disulfonate compound represented by the general formula (3) include methylene dimethane sulfonate, methylene ditrifluoromethane sulfonate, methylene dibenzene sulfonate, and methylene diparatoluene sulfonate.
本発明で得られるメチレンジスルホネート化合物は、例えば、反応液から溶媒等を用いて抽出後、水洗等を経て晶析させる方法、反応液を濾過し、濾液を濃縮する方法、および、反応液から昇華精製させる方法等により単離することができる。 The methylene disulfonate compound obtained in the present invention is extracted from, for example, a reaction solution using a solvent or the like, then crystallized through washing with water, the method of filtering the reaction solution and concentrating the filtrate, and the reaction solution. It can be isolated by a method such as sublimation purification.
本発明によれば、メチレンジスルホネート化合物を安価で容易に製造することができる。 According to the present invention, a methylene disulfonate compound can be easily produced at low cost.
以下、実施例を挙げ、本発明を具体的に説明するが、本発明はこの実施例によってなんら限定されるものではない。 Examples Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples.
実施例１
撹拌機、冷却管および温度計を備え付けた２００ｍｌ容の四つ口フラスコにメタンスルホン酸無水物８．７ｇ（０．０５モル）を仕込み、撹拌下、室温で９２％パラホルムアルデヒド１．６ｇ（０．０５モル）を添加した。添加終了後、１２０℃まで昇温して１時間撹拌した。その後、室温まで冷却し、水と塩化メチレンを添加して分液し、得られた有機層を水洗後、濃縮することにより、前記一般式（３）におけるＲ１がメチル基であるメチレンジメタンスルホネートの淡褐色結晶３．６ｇを得た。得られたメチレンジメタンスルホネートの収率は、メタンスルホン酸に対して３５．３モル％であった。
Example 1
A 200 ml four-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 8.7 g (0.05 mol) of methanesulfonic anhydride and 1.6 g (0%) of 92% paraformaldehyde at room temperature under stirring. .05 mol) was added. After completion of the addition, the temperature was raised to 120 ° C. and stirred for 1 hour. After cooling to room temperature, water and methylene chloride were added and the mixture is separated, washed with water and the resulting organic layer and concentrated, methylenedioxy methane R 1 in the general formula (3) is a methyl group 3.6 g of light brown crystals of sulfonate were obtained. The yield of the obtained methylene dimethanesulfonate was 35.3 mol% with respect to methanesulfonic acid.
なお、この淡褐色結晶がメチレンジメタンスルホネートであることを下記の分析結果により確認した。
１Ｈ−ＮＭＲ（４００ＭＨｚ、ＣＤ３ＣＮ）δ（ｐｐｍ）：３．２２（ｓ，６Ｈ），５．８３（ｓ，２Ｈ）
In addition, it confirmed from the following analysis result that this light brown crystal | crystallization was a methylene dimethanesulfonate.
1 H-NMR (400 MHz, CD 3 CN) δ (ppm): 3.22 (s, 6H), 5.83 (s, 2H)
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| ES2633805T3 (en) | 2009-08-07 | 2017-09-25 | Wako Pure Chemical Industries, Ltd. | New disulfonic acid ester as an additive for an electrolyte for a secondary lithium battery |
| WO2012017998A1 (en) * | 2010-08-05 | 2012-02-09 | 和光純薬工業株式会社 | Nonaqueous electrolyte solution, method for producing same, and nonaqueous electrolyte battery using the electrolyte solution |
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