JPH0328423B2 - - Google Patents
Info
- Publication number
- JPH0328423B2 JPH0328423B2 JP57065387A JP6538782A JPH0328423B2 JP H0328423 B2 JPH0328423 B2 JP H0328423B2 JP 57065387 A JP57065387 A JP 57065387A JP 6538782 A JP6538782 A JP 6538782A JP H0328423 B2 JPH0328423 B2 JP H0328423B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- formula
- represented
- fatty acid
- sch
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- -1 Acyloxymethyl sulfide Chemical compound 0.000 claims description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 14
- 229930195729 fatty acid Natural products 0.000 claims description 14
- 239000000194 fatty acid Substances 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 9
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XAARLLNXZJTFPQ-UHFFFAOYSA-N 1-methyl-4-(methylsulfanylmethylsulfonyl)benzene Chemical compound CSCS(=O)(=O)C1=CC=C(C)C=C1 XAARLLNXZJTFPQ-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000000066 S-methyl group Chemical group [H]C([H])([H])S* 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KFZUDNZQQCWGKF-UHFFFAOYSA-M sodium;4-methylbenzenesulfinate Chemical compound [Na+].CC1=CC=C(S([O-])=O)C=C1 KFZUDNZQQCWGKF-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はメチルチオメチルアリールスルホンの
製造法に関する。さらに詳しくは本発明は、
(1) 一般式〔〕
（R1CO）2O 〔〕
〔式中R1は低級アルキル基を示す〕で表わ
される脂肪酸無水物とジメチルスルホキシドと
を反応させて
一般式〔〕
CH3SCH2OCOR1 〔〕
〔式中R1は低級アルキル基を示す〕で表わ
されるアシロキシメチルスルフイドを得、つい
で該化合物と
一般式〔〕
R2SO2M 〔〕
〔式中R2はアリール基を、Ｍはアルカリ金
属またはアルカリ土類金属を示す〕で表わされ
るスルフイン酸塩とを、脂肪酸の共存下に反応
させることを特徴とする
一般式〔〕
CH3SCH2SO2R2 〔〕
〔式中R2はアリール基を示す〕で表わされ
るメチルチオメチルアリールスルホンの製造
法、および
(2) 一般式〔〕
CH3SCH2OCOR1 〔〕
〔式中R1は低級アルキル基を示す〕で表わ
されるアシロキシメチルスルフイドと
一般式〔〕
R2SO2M 〔〕
〔式中R2はアリール基を、Ｍはアルカリ金
属またはアルカリ土類金属を示す〕で表わされ
るスルフイン酸塩とを、脂胞酸の共存下に反応
させることを特徴とする
一般式〔〕
CH3SCH2SO2R2 〔〕
〔式中R2はアリール基を示す〕で表わされ
るメチルチオメチルアリールスルホンの製造法
に関する。
上記一般式〔〕で表わされるメチルチオメチ
ルアリールスルホン（以下本化合物と称す）は有
機合成の反応試薬として有用であり、たとえば、
農薬および医薬等の中間体として用いられるカル
ボチオ酸Ｓ−メチルはカルボン酸エステルと本化
合物とを反応させることによつて合成出来る。
従来、本化合物の製造法としては、アリールス
ルホニルアセトンとトルエンチオスルホン酸Ｓ−
メチルとを塩基性条件下で反応させる方法〔ジヤ
ーナル・オブ・ザ・ケミカル・ソサエテイ（J.
Chem.Soc.）1932年1819頁〕、ハロメチルスルホ
ンのメタンチオラートアニオンによる置換反応
〔ジヤーナル・オブ・ザ・ケミカル・ソサエテイ
（J.Chem.Soc.）Ｃ，1968年2180頁〕、および相当
するα位にメチルチオ基を有するスルホンをマン
ガン酸カリウムまたはアルカリ性過酸化水素水で
酸化する方法〔ブルテン・オブ・ザ・ケミカル・
ソサエテイ・オブ・ジヤパン（Bull.Chem.Soc.
Jap.）53巻1414頁（1980年）〕などが知られてい
る。しかし、これらの方法を本化合物の製造に利
用する場合、出発原料の入手が困難であつたり、
出発原料の合成に多くの工程を必要とする等の理
由から工業的に有利な製造法ではなかつた。
本発明者は本化合物の優れた新規製造法につい
て鋭意研究した結果、脂肪酸無水物とジメチルス
ルホキシドとを反応させてアシロキシメチルスル
フイドを得、ついでこの化合物とスルフイン酸塩
とを、脂胞酸またはその塩の共存下に反応させて
メチルチオメチルアリールスルホンを容易にかつ
収率良く得る製造法を見出して、本発明を完成し
た。
本発明において、一般式〔〕（R1CO）2O〔〕
で表わされる脂肪酸無水物のR1としては低級ア
ルキル基たとえばメチル基、エチル基、プロピル
基、イソプロピル基などがあげられるが、メチル
基が好ましい。脂肪酸無水物とジメチルスルホキ
シドとの反応において、モル比は限定されるもの
ではないが、当量またはいずれかを過剰に使用し
てもよい。溶媒は特に必要としないが、所望なら
ベンゼン、トルエン、キシレン、クロルベンゼ
ン、クロロホルム、ジオキサン、テトラヒドロフ
ラン等、非プロトン性溶媒を用いても良い。
反応温度と時間は特に限定されるものではな
く、使用する原料および溶媒の種類によつても異
り、室温では反応が遅く、加温することによつて
反応を促進出来る。反応温度の範囲としては25〜
150℃が好ましい。一般式〔〕の脂肪酸無水物
とジメチルスルホキシドとの反応生成物である一
般式〔〕CH3SCH2OCOR1〔〕〔式中R1は低級
アルキル基を示す〕で表わされるアシロキシメチ
ルスルフイドは、蒸留などの操作によつて単離し
たのち次の反応を行なつても良いし、あるいは単
離することなしに一段で次の反応まで行なつても
良い。
本発明における一般式〔〕のアシロキシメチ
ルスルフイドと反応させる一般式〔〕R2SO2M
〔〕で表わされるスルフイン酸塩のR1としては
アリール基たとえばフエニル基、ｏ−トリル基、
ｍ−トリル基、ｐ−トリル基、ｏ−エチルフエニ
ル基、ｎ−エチルフエニル基、ｐ−エチルフエニ
ル基、キシリル基（置換基の位置はいずれでも良
い）、ｏ−クロロフエニル基、ｍ−クロロフエニ
ル基、ｐ−クロロフエニル基、α−ナフチル基、
β−ナフチル基などがあげられ、Ｍとしてはアル
カリ金属またはアルカリ土類金属、たとえばカリ
ウム、ナトリウム、カルシウムなどがあげられ
る。アシロキシメチルスルフイドとスルフイン酸
塩との反応に共存させる脂肪酸としては、たとえ
ば酢酸、プロピオン酸、酪酸などがあげられる
が、反応の収率が良いことおよび安価に入手出来
ること等の理由から酢酸が好ましい。アシロキシ
メチルスルフイドとスルフイン酸塩とを脂肪酸の
共存下に反応させる際のモル比は特に限定される
ものではなく、アシロキシメチルスルフイドに対
してスルフイン酸塩と脂肪酸をそれぞれ１当量も
しくは過剰に用いると良い。反応温度と時間は限
定されるものではないが、反応温度は25〜150℃、
特に80〜150℃が好ましい。この反応において脂
肪酸のアルカリ金属塩またはアルカリ土類金属塩
を添加することによつて収率の向上がはかれる。
本発明に係る化合物、一般式〔〕
CH3SCH2SO2R2〔〕〔式中R2はアリール基を示
す〕で表わされるメチルチオメチルアリールスル
ホンを反応生成物より単離するには、通常の分離
精製操作、すなわち、抽出、洗浄、乾燥、カラム
クロマトグラフイー、再結晶等の操作法を用うれ
ば良い。
以下、本発明に係る製造法を実施例によつてさ
らに詳細に説明するが、本発明はこれらに限定さ
れるものではない。
実施例 １
ジメチルスルホキシド6.808ｇ（87.14mmol）
と無水酢酸11.942ｇ（117.0mmol）の混合物を、
80℃にて24時間加熱撹拌した。その後室温にもど
し、酢酸80mlを加え、続いてｐ−トルエンスルフ
イン酸ナトリウム23.00ｇ（129.2mmol）を加え、
100℃にて26時間加熱撹拌した。反応終了後、ジ
クロロメタン50mlと水100mlを加えた。ジクロロ
メタン（50ml×４）で抽出し、有機層を水で洗浄
（200ml×３）し、無水硫酸ナトリウムにて乾燥し
た。ロ過後、減圧濃縮し、残査を95％エタノール
にて再結晶した。無色の針状結晶を4.051ｇ
（18.73mmol）得た。母液は再び減圧濃縮し、カ
ラムクロマトグラフイー（シリカゲル、１：ヘキ
サン、２：ベンゼン）にて分離してメチルチオメ
チルｐ−トリルスルホンを6.713ｇ（31.04mmol）
得た。
合計収率は57％であつた。
The present invention relates to a method for producing methylthiomethylarylsulfone. More specifically, the present invention is directed to (1) reacting a fatty acid anhydride represented by the general formula [] (R 1 CO) 2 O [] [wherein R 1 represents a lower alkyl group] with dimethyl sulfoxide; An acyloxymethyl sulfide represented by the formula [] CH 3 SCH 2 OCOR 1 [] [in the formula, R 1 represents a lower alkyl group] is obtained, and then the compound and the general formula [] R 2 SO 2 M [] General formula [] CH 3 SCH characterized by reacting a sulfinate represented by [wherein R 2 is an aryl group and M is an alkali metal or alkaline earth metal] in the coexistence of a fatty acid. 2 SO 2 R 2 [] [In the formula, R 2 represents an aryl group] A method for producing methylthiomethylarylsulfone, and (2) General formula [] CH 3 SCH 2 OCOR 1 [] [In the formula, R 1 represents a lower alkyl group] and acyloxymethyl sulfide represented by the general formula [] R 2 SO 2 M [] [In the formula, R 2 represents an aryl group and M represents an alkali metal or alkaline earth metal] It is characterized by reacting a sulfinate represented by the following in the presence of a fatty acid : The present invention relates to a method for producing methylthiomethylarylsulfone. Methylthiomethylarylsulfone (hereinafter referred to as the present compound) represented by the above general formula [] is useful as a reaction reagent for organic synthesis, for example,
S-methyl carbothioate, which is used as an intermediate for agricultural chemicals and medicines, can be synthesized by reacting a carboxylic acid ester with this compound. Conventionally, as a method for producing this compound, arylsulfonylacetone and toluenethiosulfonic acid S-
Method of reacting with methyl under basic conditions [Journal of the Chemical Society (J.
Chem.Soc.) 1932, p. 1819], substitution reaction of halomethylsulfone with methanethiolate anion [J.Chem.Soc. C, 1968, p. 2180], and equivalents. A method of oxidizing a sulfone having a methylthio group at the α-position with potassium manganate or alkaline hydrogen peroxide [Bulletin of the Chemicals]
Society of Japan (Bull.Chem.Soc.
Jap.) vol. 53, p. 1414 (1980)]. However, when these methods are used to produce the present compound, it may be difficult to obtain starting materials, or
This is not an industrially advantageous production method because many steps are required to synthesize the starting materials. As a result of intensive research into an excellent new method for producing this compound, the present inventor reacted fatty acid anhydride with dimethyl sulfoxide to obtain acyloxymethyl sulfide, and then combined this compound with a sulfinate to The present invention was completed by discovering a method for producing methylthiomethylarylsulfone easily and in good yield by reacting it in the presence of an acid or its salt. In the present invention, the general formula [](R 1 CO) 2 O[]
Examples of R 1 in the fatty acid anhydride represented by the formula include lower alkyl groups such as methyl, ethyl, propyl, and isopropyl groups, with methyl being preferred. In the reaction between fatty acid anhydride and dimethyl sulfoxide, the molar ratio is not limited, but an equivalent amount or an excess of either of them may be used. Although a solvent is not particularly required, an aprotic solvent such as benzene, toluene, xylene, chlorobenzene, chloroform, dioxane, tetrahydrofuran, etc. may be used if desired. The reaction temperature and time are not particularly limited and vary depending on the type of raw materials and solvent used; the reaction is slow at room temperature and can be accelerated by heating. The reaction temperature range is 25~
150°C is preferred. Acyloxymethyl sulfate represented by the general formula [] CH 3 SCH 2 OCOR 1 [] [in which R 1 represents a lower alkyl group] is a reaction product of a fatty acid anhydride of the general formula [] and dimethyl sulfoxide. The compound may be isolated by an operation such as distillation before the next reaction, or the next reaction may be carried out in one step without isolation. In the present invention, the general formula [] R 2 SO 2 M to be reacted with the acyloxymethyl sulfide of the general formula []
R 1 of the sulfinate represented by [] is an aryl group such as a phenyl group, an o-tolyl group,
m-tolyl group, p-tolyl group, o-ethylphenyl group, n-ethylphenyl group, p-ethylphenyl group, xylyl group (the position of the substituent may be any), o-chlorophenyl group, m-chlorophenyl group, p- Chlorophenyl group, α-naphthyl group,
Examples include β-naphthyl group, and M includes alkali metals or alkaline earth metals, such as potassium, sodium, calcium, and the like. Examples of fatty acids used in the reaction between acyloxymethyl sulfide and sulfinate include acetic acid, propionic acid, butyric acid, etc. Acetic acid is preferred. The molar ratio when reacting acyloxymethyl sulfide and sulfinate in the presence of a fatty acid is not particularly limited, and the sulfinate and fatty acid are each equivalent to 1 equivalent to acyloxymethyl sulfide. Or use it in excess. The reaction temperature and time are not limited, but the reaction temperature is 25-150℃,
Particularly preferred is 80 to 150°C. In this reaction, the yield can be improved by adding an alkali metal salt or an alkaline earth metal salt of a fatty acid. Compound according to the present invention, general formula []
To isolate the methylthiomethylarylsulfone represented by CH 3 SCH 2 SO 2 R 2 [ ] [in the formula, R 2 represents an aryl group] from the reaction product, usual separation and purification operations, such as extraction and washing, are carried out. , drying, column chromatography, recrystallization, etc. may be used. Hereinafter, the manufacturing method according to the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 Dimethyl sulfoxide 6.808g (87.14mmol)
A mixture of and acetic anhydride 11.942g (117.0mmol),
The mixture was heated and stirred at 80°C for 24 hours. After that, the temperature was returned to room temperature, 80 ml of acetic acid was added, followed by 23.00 g (129.2 mmol) of sodium p-toluenesulfinate.
The mixture was heated and stirred at 100°C for 26 hours. After the reaction was completed, 50 ml of dichloromethane and 100 ml of water were added. Extraction was performed with dichloromethane (50 ml x 4), and the organic layer was washed with water (200 ml x 3) and dried over anhydrous sodium sulfate. After filtration, it was concentrated under reduced pressure, and the residue was recrystallized from 95% ethanol. 4.051g colorless needle crystals
(18.73 mmol) was obtained. The mother liquor was again concentrated under reduced pressure and separated using column chromatography (silica gel, 1:hexane, 2:benzene) to obtain 6.713g (31.04mmol) of methylthiomethyl p-tolylsulfone.
Obtained. The total yield was 57%.
【表】 〓元素分析【table】 〓Elemental analysis
Claims (1)
ドとを反応させて 一般式〔〕 CH3SCH2OCOR1 〔〕 〔式中R1は低級アルキル基を示す〕 で表わされるアシロキシメチルスルフイドを得、
ついで該化合物と 一般式〔〕 R2SO2M 〔〕 〔式中R2はアリール基を、Ｍはアルカリ金属
またはアルカリ土類金属を示す〕 で表わされるスルフイン酸塩とを、脂肪酸の共存
下に反応させることを特徴とする 一般式〔〕 CH3SCH2SO2R2 〔〕 〔式中R2はアリール基を示す〕 で表わされるメチルチオメチルアリールスルホン
の製造法。 ２ 一般式〔〕 CH3SCH2OCOR1 〔〕 〔式中R1は低級アルキル基を示す〕 で表わされるアシロキシメチルスルフイドと 一般式〔〕 R2SO2M 〔〕 〔式中R2はアリール基を、Ｍはアルカリ金属
またはアルカリ土類金属を示す〕 で表わされるスルフイン酸塩とを、脂肪酸の共存
下に反応させることを特徴とする 一般式〔〕 CH3SCH2SO2R2 〔〕 〔式中R2はアリール基を示す〕 で表わされるメチルチオメチルアリールスルホン
の製造法。[Claims] 1 A fatty acid anhydride represented by the general formula [] (R 1 CO) 2 O [] [in the formula, R 1 represents a lower alkyl group] is reacted with dimethyl sulfoxide to obtain the general formula [] Acyloxymethyl sulfide represented by CH 3 SCH 2 OCOR 1 [] [in the formula, R 1 represents a lower alkyl group] was obtained,
Then, the compound and a sulfinate represented by the general formula [] R 2 SO 2 M [] [wherein R 2 represents an aryl group and M represents an alkali metal or an alkaline earth metal] are combined in the presence of a fatty acid. A method for producing methylthiomethylarylsulfone represented by the general formula [] CH 3 SCH 2 SO 2 R 2 [] [In the formula, R 2 represents an aryl group]. 2 Acyloxymethyl sulfide represented by the general formula [] CH 3 SCH 2 OCOR 1 [] [in the formula, R 1 represents a lower alkyl group] and the general formula [] R 2 SO 2 M [] [in the formula R 2 represents an aryl group and M represents an alkali metal or alkaline earth metal] with a sulfinate represented by the following in the presence of a fatty acid: General formula [] CH 3 SCH 2 SO 2 R 2 [] [In the formula, R 2 represents an aryl group] A method for producing methylthiomethylarylsulfone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57065387A JPS58183667A (en) | 1982-04-21 | 1982-04-21 | Preparation of methylthiomethyl aryl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57065387A JPS58183667A (en) | 1982-04-21 | 1982-04-21 | Preparation of methylthiomethyl aryl sulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58183667A JPS58183667A (en) | 1983-10-26 |
| JPH0328423B2 true JPH0328423B2 (en) | 1991-04-19 |
Family
ID=13285519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57065387A Granted JPS58183667A (en) | 1982-04-21 | 1982-04-21 | Preparation of methylthiomethyl aryl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58183667A (en) |
-
1982
- 1982-04-21 JP JP57065387A patent/JPS58183667A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58183667A (en) | 1983-10-26 |
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