JP5250199B2 - Method for producing trichloromethanesulfonyl chloride - Google Patents
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- JP5250199B2 JP5250199B2 JP2006316031A JP2006316031A JP5250199B2 JP 5250199 B2 JP5250199 B2 JP 5250199B2 JP 2006316031 A JP2006316031 A JP 2006316031A JP 2006316031 A JP2006316031 A JP 2006316031A JP 5250199 B2 JP5250199 B2 JP 5250199B2
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- chlorine
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- trichloromethanesulfonyl
- trichloromethanesulfonyl chloride
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- ZCPSWAFANXCCOT-UHFFFAOYSA-N trichloromethanesulfonyl chloride Chemical compound ClC(Cl)(Cl)S(Cl)(=O)=O ZCPSWAFANXCCOT-UHFFFAOYSA-N 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000012359 Methanesulfonyl chloride Substances 0.000 claims description 10
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 238000007664 blowing Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、トリクロロメタンスルホニルクロライドの製造方法に関する。 The present invention relates to a method for producing trichloromethanesulfonyl chloride.
トリクロロメタンスルホニルクロライドは、アクリルニトリルなどの重合開始剤として知られている。また、帯電防止剤として有用な（ＣＦ３ＳＯ２）２ＮＬiの製造原料としても使用されている。
塩化トリクロロメチルスルホニルの製造法としては、ＣＣｌ３Ｓ（Ｏ）ＯＨに塩素を反応させて製造する方法（非特許文献１）、ＣＣｌ３ＳＣｌをＨ２Ｏ２などの酸化剤により酸化して製造する方法（非特許文献２）などが知られている。
しかしながら、メタンスルホニルクロライドを塩素ガスと反応させることにより製造する方法については行われていなかった。
Trichloromethanesulfonyl chloride is known as a polymerization initiator such as acrylonitrile. It is also used as a raw material for producing (CF 3 SO 2 ) 2 NLi useful as an antistatic agent.
Trichloromethylsulfonyl chloride is produced by reacting CCl 3 S (O) OH with chlorine (Non-patent Document 1), and producing CCl 3 SCl by oxidizing it with an oxidizing agent such as H 2 O 2. A method (Non-Patent Document 2) is known.
However, a method for producing methanesulfonyl chloride by reacting it with chlorine gas has not been performed.
本発明の課題は、上記方法よりも、入手が容易で安価な原料を使用し、安全に製造することのできる、工業的に有利な方法を提供することにある。 An object of the present invention is to provide an industrially advantageous method that can be produced safely by using raw materials that are easier to obtain and cheaper than the above methods.
本発明者らは、メタンスルホニルクロライドを塩素と反応させることにより効率よくトリクロロメタンスルホニルクロライドを製造できることを見出し、本発明を完成するに至った。 The present inventors have found that trichloromethanesulfonyl chloride can be efficiently produced by reacting methanesulfonyl chloride with chlorine, and have completed the present invention.
すなわち本発明は、メタンスルホニルクロライドを塩素ガスと反応させることによりトリクロロメタンスルホニルクロライドを製造する方法である。
また、本発明は溶媒中で紫外線照射下において塩素ガスを吹き込みながら行うことを特徴とする上記方法である。
That is, the present invention is a method for producing trichloromethanesulfonyl chloride by reacting methanesulfonyl chloride with chlorine gas.
Further, the present invention is the above-mentioned method, which is carried out while blowing chlorine gas in a solvent under ultraviolet irradiation.
本発明の製法により、入手が容易で安価な原料を使用することができ、安全に製造することができ、かつ収率よくトリクロロメタンスルホニルクロライドを製造することができる。 By the production method of the present invention, it is possible to use an easily available and inexpensive raw material, which can be produced safely, and trichloromethanesulfonyl chloride can be produced in a high yield.
本発明のトリクロロメタンスルホニルクロライドの製造法につき、以下に説明する。
本発明の製造法は、通常、溶媒中、紫外線照射下に塩素を吹き込みながら以下の反応行う。
ＣＨ３ＳＯ２Ｃｌ → ＣＣｌ３ＳＯ２Ｃｌ
The method for producing trichloromethanesulfonyl chloride of the present invention will be described below.
In the production method of the present invention, the following reaction is usually carried out in a solvent while blowing chlorine under ultraviolet irradiation.
CH 3 SO 2 Cl → CCl 3 SO 2 Cl
原料であるメタンスルホニルクロライドは不安定な液体であるが、安価に入手可能な原料である。
塩素化には、通常使用される塩素化剤も可能であるが、塩素含有ガスであることが好ましい。塩素含有ガスとしては、塩素ガス単独、あるいは窒素または空気などで希釈・混合されたガスなどが使用でき、装置などの条件に応じて選択できる。塩素の使用量は、通常、メタンスルホニルクロライドに対して３倍モルから大過剰、好ましくは５〜１０倍モルを使用する。
塩素の吹き込み時間は、塩素ガスの濃度、温度などによって異なるので一概には決定することができないが、通常、１〜１００時間程度である。
The raw material methanesulfonyl chloride is an unstable liquid, but it is a raw material that can be obtained at low cost.
For chlorination, a commonly used chlorinating agent can be used, but a chlorine-containing gas is preferred. As the chlorine-containing gas, chlorine gas alone or a gas diluted or mixed with nitrogen or air can be used, and can be selected according to the conditions of the apparatus. The amount of chlorine used is usually from 3 times mol to large excess, preferably 5 to 10 times mol, of methanesulfonyl chloride.
The chlorine blowing time varies depending on the concentration and temperature of the chlorine gas and cannot be determined unconditionally, but is usually about 1 to 100 hours.
また、反応温度は特に限定されるものではなく、反応速度を高める観点及び反応の制御を容易にする観点から、４０℃〜１５０℃、好ましくは６０〜１００℃である。
また、本発明における塩素化反応は、通常、光照射下で行われるが、紫外線照射下で行うことが好ましい。
Further, the reaction temperature is not particularly limited, and is 40 ° C. to 150 ° C., preferably 60 to 100 ° C. from the viewpoint of increasing the reaction rate and facilitating control of the reaction.
The chlorination reaction in the present invention is usually performed under light irradiation, but is preferably performed under ultraviolet irradiation.
紫外線 の照射に使用する光源としては、例えば、水銀ランプ、メタルハライドランプ、無電極ランプ等の公知のものが挙げられる。通常、紫外線 の照射波長は、２００〜４５０ｎｍ程度であることが好ましい。
紫外線の照射線量は、十分に塩素化を進行させるとともに、過剰に照射することによって生成物が切断されるのを防ぐことを考慮して決める。
Examples of the light source used for ultraviolet irradiation include known ones such as a mercury lamp, a metal halide lamp, and an electrodeless lamp. Usually, the irradiation wavelength of ultraviolet rays is preferably about 200 to 450 nm.
The irradiation dose of ultraviolet rays is determined in consideration of sufficient chlorination and preventing the product from being cut by excessive irradiation.
溶媒は、トリクロロメタンスルホニルクロライドの製造に対して影響を与えないものであれば特に制限はないが、クロロホルムを除いた四塩化炭素などの塩素系、ジクロロベンゼン等のハロゲン置換芳香族系が好ましい。無溶媒でもよい。したがって、溶媒は、生産性、操作性等の理由から、メタンスルホニルクロライドに対して通常０〜１０倍量程度を使用する。 The solvent is not particularly limited as long as it does not affect the production of trichloromethanesulfonyl chloride, but is preferably a chlorine type such as carbon tetrachloride excluding chloroform, or a halogen-substituted aromatic type such as dichlorobenzene. It may be solventless. Accordingly, the solvent is usually used in an amount of about 0 to 10 times the amount of methanesulfonyl chloride for reasons such as productivity and operability.
反応終了後の処理方法としては、窒素などで過剰の塩素を追い出し、反応溶液を減圧濃縮又は冷却して結晶化後、ろ過、洗浄し、必要に応じて再結晶、クロマトグラフィー精製等の手段により単離することができる。 As a treatment method after completion of the reaction, excess chlorine is expelled with nitrogen, etc., the reaction solution is concentrated under reduced pressure or cooled, crystallized, filtered, washed, if necessary, by means of recrystallization, chromatographic purification, etc. It can be isolated.
以下、実施例により本発明をより具体的に説明するが、本発明の技術的範囲はこれらの例示に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.
実施例１
四塩化炭素３００ｍｌに、メタンスルホニルクロライド２０．０ｇ（０．１７ｍｏｌ）を加えた。ＵＶランプ（４００Ｗ）を照射し、内温を７６度にした。そこへ塩素を５０ｍｌ／ｍｉｎで２０時間吹き込んだ後、窒素で過剰の塩素を追い出した。この溶液を減圧濃縮してトリクロロメタンスルホニルクロライドの粗結晶を３６．５ｇ（純度：９７．２％）を得た。収率９３．３％。融点１３５℃。
Example 1
20.0 g (0.17 mol) of methanesulfonyl chloride was added to 300 ml of carbon tetrachloride. A UV lamp (400 W) was irradiated to adjust the internal temperature to 76 degrees. Chlorine was blown into it at 50 ml / min for 20 hours, and then excess chlorine was expelled with nitrogen. This solution was concentrated under reduced pressure to obtain 36.5 g (purity: 97.2%) of crude crystals of trichloromethanesulfonyl chloride. Yield 93.3%. Melting point 135 ° C.
実施例２
メタンスルホニルクロライド３００ｍｌ（４４３．１ｇ）に、ＵＶランプ（４００Ｗ）を照射し、内温を７８度にした。そこへ塩素を５０ｍｌ／ｍｉｎで３６時間吹き込んだ。この時点でメタンスルホニルクロライド：トリクロロメタンスルホニルクロライドの比率が１：１程度になる（ＧＣ分析）。窒素で過剰の塩素を追い出した後、この溶液を１０℃まで冷却すると結晶が析出してスラリーになる。このスラリーを５℃に冷却して濾過し、少量のＮ−ヘキサンで洗浄して粗トリクロロメタンスルホニルクロライド２０７．０ｇ（純度９８．３％）を得た。融点１３８℃。尚、濾液中には１００．９ｇのトリクロロメタンスルホニルクロライドが溶解していた（ＧＣ分析）。
尚、上記実施例において定量に用いたＧＣの分析条件は以下の通りである。
ＧＣ分析条件／カラム：パックドカラム３．２φ×２ｍ 、充填剤：Ｓｉｌｉｃｏｎ ＤＣ−５５０（２０％）、キャリア：Ｈｅ、温度 １６０℃。
Example 2
300 ml (443.1 g) of methanesulfonyl chloride was irradiated with a UV lamp (400 W) to adjust the internal temperature to 78 degrees. Chlorine was blown into it at 50 ml / min for 36 hours. At this point, the ratio of methanesulfonyl chloride: trichloromethanesulfonyl chloride is about 1: 1 (GC analysis). After excess chlorine is purged with nitrogen, the solution is cooled to 10 ° C. to precipitate crystals and form a slurry. The slurry was cooled to 5 ° C., filtered, and washed with a small amount of N-hexane to obtain 207.0 g (purity 98.3%) of crude trichloromethanesulfonyl chloride. Melting point 138 ° C. In the filtrate, 100.9 g of trichloromethanesulfonyl chloride was dissolved (GC analysis).
The GC analysis conditions used for quantification in the above examples are as follows.
GC analysis conditions / column: packed column 3.2φ × 2 m, filler: Silicon DC-550 (20%), carrier: He, temperature 160 ° C.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006316031A JP5250199B2 (en) | 2006-11-22 | 2006-11-22 | Method for producing trichloromethanesulfonyl chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006316031A JP5250199B2 (en) | 2006-11-22 | 2006-11-22 | Method for producing trichloromethanesulfonyl chloride |
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| JP5250199B2 true JP5250199B2 (en) | 2013-07-31 |
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| FR3008093B1 (en) * | 2013-07-04 | 2015-12-11 | Rhodia Operations | PROCESS FOR FLUORINATION OF HALIDE COMPOUNDS OF SULFONYL |
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| JP2784082B2 (en) * | 1990-05-24 | 1998-08-06 | ダイセル化学工業株式会社 | Chlorination reaction method and chlorination reactor |
| JP2823414B2 (en) * | 1992-02-26 | 1998-11-11 | セントラル硝子株式会社 | Method for chlorinating side chains of 2-chloro-methylpyridines |
| US5252759A (en) * | 1993-01-29 | 1993-10-12 | Arco Chemical Technology, L.P. | Process for producing optically active epoxy alcohol derivatives |
| JP2001058966A (en) * | 1999-08-20 | 2001-03-06 | Mitsubishi Chemicals Corp | Production of trichloromethane derivative |
| JP4474700B2 (en) * | 1999-09-02 | 2010-06-09 | 日本軽金属株式会社 | Method for producing chloromethylstyrene |
| FR2817258B1 (en) * | 2000-11-27 | 2003-01-10 | Atofina | PROCESS FOR THE PHOTOCHEMICAL SULFOCHLORINATION OF GASEOUS ALKANES |
| JP2003342252A (en) * | 2002-05-28 | 2003-12-03 | Toyo Kasei Kogyo Co Ltd | Method for producing alkanesulfonyl chloride |
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