JPH0377188B2 - - Google Patents
Info
- Publication number
- JPH0377188B2 JPH0377188B2 JP15801883A JP15801883A JPH0377188B2 JP H0377188 B2 JPH0377188 B2 JP H0377188B2 JP 15801883 A JP15801883 A JP 15801883A JP 15801883 A JP15801883 A JP 15801883A JP H0377188 B2 JPH0377188 B2 JP H0377188B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- reaction
- water
- red phosphorus
- present
- 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
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- 238000006243 chemical reaction Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000012442 inert solvent Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- HVJWKJKNDKUSLD-UHFFFAOYSA-N (4-chlorosulfonylphenyl) methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=C(S(Cl)(=O)=O)C=C1 HVJWKJKNDKUSLD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- IFIKILAPWJGSPO-UHFFFAOYSA-N (4-sulfanylphenyl) methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=C(S)C=C1 IFIKILAPWJGSPO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は式
（式中R1は低級アルキルを表わし、R2は水素、
低級アルキル又はハロゲンを表わす。）
で表わされる化合物をヨウ素系触媒の存在下に、
赤リン及び水と反応さて、
式
（式中R1，R2は前記と同じものを表わす。）
で表わされるアルキルスルホニルオキシベンゼン
チオール誘導体を製造する方法に関するものであ
る。
式（）で表わされる化合物は、殺菌剤及び殺
虫剤の中間体として極めて有用な化合物である。
従来、アルキルスルホニルオキシベンゼンチオ
ール誘導体の製造法としてはアルキルスルホニル
オキシベンゼンスルホニルクロライドをアルコー
ル溶媒中、亜鉛及び塩酸を用いて還元し対応する
チオフエノールを得る方法が知られているが、
（特開昭52−3829）工業的な製造法としては良い
方法とは言い難い。すなわちこの方法において、
高収率で目的物を得るためには、適当量のアルコ
ールが必要である。このアルコールを再使用する
ためには蒸留等により回収する必要があるので工
業的には有利な方法ではない。更に亜鉛還元反応
中、水素ガスの発生することも、安全上好ましい
ことではない。その上使用する亜鉛は、高収率で
目的物を得るためには通常理論量より過剰に用い
る必要があり、反応終了後、未反応の亜鉛を過
等により回収するが、回収した亜鉛は、表面が活
性化されているために空気中の酸素と反応し、発
熱更には発火の危険さえ伴なうものである。
本発明者らは、アルキルスルホニルオキシベン
ゼンチオール誘導体の製造法においてかかる欠点
のない方法について種々研究を重ね、本発明を完
成したものである、すなわち式（）で表わされ
る化合物と赤リン、水とをヨウ素系触媒の存在下
に作用させることにより高収率、高純度の式
（）で表わされるアルキルスルホニルオキシベ
ンゼンチオール誘導体を製造しうることをみい出
したものである。
本発明で用いる水としては、通常の水の他にス
ルホニルクロライド基の加水分解を最小限にする
ために酸を含有する水例えば希塩酸や濃塩酸を用
いることもできる。
本発明で用いる水の量は、式（）の化合物１
モルに対して、1.6〜4.5モル、好ましくは、2.4〜
3.5モルである。赤リンの使用量は多くなればな
るほど、反応速度、反応収率を、ともに高めるが
工業的製法としては、おのずと限度があり式
（）の化合物１モルあたり2.0〜3.0モルが好ま
しい。ただし過剰に用いた赤リンは過により容
易に回収でき、再使用が可能である。
本発明で用いるヨウ素系触媒としてはヨウ素、
ヨウ化水素酸水溶液、ヨウ化ナトリウム、ヨウ化
カリウムなどが挙げられる。触媒量は、１モルあ
たり0.01〜0.06モルが適切である。それ以上の使
用によつても大きな利点は得られない反応は、好
ましくは105゜〜130゜の温度で行われる、90゜以下で
はあきらかに反応速度が遅く、また150℃以上で
はスルホニル基の加水分解をはじめとする副反応
が伴なうために実用的でなない、反応時間、条件
により若干変動するが通常２〜６時間の範囲で行
われる。また本発明においては、さらに不活性溶
媒を用いると、反応温度のコントロール反応に伴
なう発泡の抑制等、操作を容易にするなど有利な
点がある。ここで用いられる不活性溶媒として
は、上記反応温度範囲附近に沸点を有するものが
特に好ましく、例えばトルエン、モノクロルベン
ゼン、キシレン、パークロルエチレン等が挙げら
れる。その使用量としては、式（）の化合物１
モルに対して、10〜200mlが好ましく、過度の使
用は経済的でないばかりでなく反応の速度を遅く
するため好ましくない。
本発明の実施例に際しては、赤リン、ヨウ素系
触媒、水必要ならさらに不活性溶媒の混合物を適
度に加熱した中に、式（）の化合物を添加して
もよいし、あるいは式（）の化合物、赤リン、
ヨウ素系触媒混合物を適度に加熱した中に、水必
要ならさらに不活性溶媒を添加してもよい。
以下、本発明の実施例をいくつかを記載して詳
しく説明するが、本発明はこれ等の実施のみに限
定されるものではない。
実施例 １
温度計、冷却管、撹拌器をつけた３４径フラ
スコに45mlのモノクロルベンゼン、6.64ｇのヨウ
化カリウム、129ｇの水、166ｇの赤リンを加え、
加熱し、還流する。
580ｇの４−メチルスルホニルオキシベンゼン
スルホニルクロライドを小量づつ加え105゜〜110
℃で６時間反応する、反応後未反応赤リンを別
し、水洗後溶媒を除去すると422ｇ（収率96.2％）
の淡黄色結晶の４−メチルスルホニルオキシベン
ゼンチオールを得る。mp67〜68℃。
実施例 ２
温度計、冷却管、撹拌器をつけた２４径フラ
スコに、74.4ｇの実施例１で別回収した赤リン
74.4ｇと６ｇのヨウ化ナトリウム、100mlのキシ
レン、270.5ｇの４−メチルスルホニルオキシベ
ンゼンスルホニルクロライドを加え、110〜115℃
に加熱する。ここに55ｇの濃塩酸を、少量づつ加
える。120〜130℃で６時間反応を続けた後、未反
応赤リンを別する。水洗後溶媒を除去すると
199.8ｇ（収率97.9％）の淡黄色結晶４−メチル
スルホニルオキシベンゼンチオールを得る。
実施例 ３〜７
実施例１と同様な操作により４−メチルスルホ
ニルオキシベンゼンスルホニルクロライドの代り
に代表的なアルキルスルホニルオキシベンゼンス
ルホニルクロライドを用いた場合の反応生成物の
収率及び物性を表に示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the formula (In the formula, R 1 represents lower alkyl, R 2 is hydrogen,
Represents lower alkyl or halogen. ) in the presence of an iodine catalyst,
Now reacting with red phosphorus and water, the formula The present invention relates to a method for producing an alkylsulfonyloxybenzenethiol derivative represented by the formula (wherein R 1 and R 2 are the same as defined above). The compound represented by formula () is an extremely useful compound as an intermediate for fungicides and insecticides. Conventionally, as a method for producing alkylsulfonyloxybenzenethiol derivatives, a method is known in which alkylsulfonyloxybenzenesulfonyl chloride is reduced using zinc and hydrochloric acid in an alcohol solvent to obtain the corresponding thiophenol.
(Japanese Patent Application Laid-open No. 52-3829) It is difficult to say that this is a good method as an industrial manufacturing method. That is, in this method,
An appropriate amount of alcohol is required to obtain the desired product in high yield. In order to reuse this alcohol, it is necessary to recover it by distillation or the like, so this method is not industrially advantageous. Furthermore, the generation of hydrogen gas during the zinc reduction reaction is also not desirable from a safety standpoint. Furthermore, in order to obtain the desired product in a high yield, it is usually necessary to use zinc in excess of the theoretical amount, and after the reaction is complete, unreacted zinc is recovered by filtration. Because the surface is activated, it reacts with oxygen in the air, causing heat generation and even the risk of ignition. The present inventors have conducted various studies on methods for producing alkylsulfonyloxybenzenethiol derivatives that do not have these drawbacks, and have completed the present invention. It has been found that an alkylsulfonyloxybenzenethiol derivative represented by the formula (2) can be produced in high yield and purity by reacting the above in the presence of an iodine catalyst. As the water used in the present invention, in addition to ordinary water, water containing an acid such as dilute hydrochloric acid or concentrated hydrochloric acid can also be used in order to minimize hydrolysis of the sulfonyl chloride group. The amount of water used in the present invention is determined by the amount of water used in the compound 1 of formula ()
1.6 to 4.5 moles, preferably 2.4 to 4.5 moles
It is 3.5 moles. The larger the amount of red phosphorus used, the higher the reaction rate and reaction yield. However, as an industrial production method, there is a natural limit, and it is preferably 2.0 to 3.0 moles per mole of the compound of formula (). However, excess red phosphorus can be easily recovered by filtration and can be reused. The iodine-based catalyst used in the present invention includes iodine,
Examples include an aqueous solution of hydroiodic acid, sodium iodide, and potassium iodide. The appropriate amount of catalyst is 0.01 to 0.06 mol per mol. Reactions for which no significant advantage can be obtained by using temperatures higher than this are preferably carried out at temperatures between 105° and 130°; below 90° the reaction rate is clearly slow, and above 150° the hydration of the sulfonyl group The reaction time is not practical because it involves side reactions such as decomposition, and is usually carried out for a period of 2 to 6 hours, although it varies slightly depending on the reaction time and conditions. Further, in the present invention, the use of an inert solvent has advantages such as controlling the reaction temperature, suppressing foaming accompanying the reaction, and facilitating operation. The inert solvent used here is particularly preferably one having a boiling point around the above reaction temperature range, such as toluene, monochlorobenzene, xylene, perchloroethylene and the like. The amount used is compound 1 of formula ()
The amount is preferably 10 to 200 ml per mole, and excessive use is not only uneconomical but also undesirable because it slows down the reaction rate. In the embodiments of the present invention, the compound of formula () may be added to a moderately heated mixture of red phosphorus, an iodine-based catalyst, water and an inert solvent if necessary, or compound, red phosphorus,
Water and, if necessary, an inert solvent may be added to the iodine-based catalyst mixture that is heated appropriately. Hereinafter, some embodiments of the present invention will be described in detail, but the present invention is not limited to these embodiments. Example 1 Add 45 ml of monochlorobenzene, 6.64 g of potassium iodide, 129 g of water, and 166 g of red phosphorus to a 34-diameter flask equipped with a thermometer, condenser, and stirrer.
Heat to reflux. Add 580 g of 4-methylsulfonyloxybenzenesulfonyl chloride little by little to 105° to 110°.
React at ℃ for 6 hours. After reaction, unreacted red phosphorus was separated, and after washing with water and removing the solvent, 422g (yield 96.2%) was obtained.
4-methylsulfonyloxybenzenethiol is obtained as pale yellow crystals. mp67~68℃. Example 2 Into a 24-diameter flask equipped with a thermometer, condenser, and stirrer, 74.4 g of the red phosphorus recovered separately in Example 1 was added.
Add 74.4 g, 6 g of sodium iodide, 100 ml of xylene, and 270.5 g of 4-methylsulfonyloxybenzenesulfonyl chloride, and heat to 110-115°C.
Heat to. Add 55g of concentrated hydrochloric acid little by little. After continuing the reaction at 120-130°C for 6 hours, unreacted red phosphorus is separated. After washing with water and removing the solvent
199.8 g (yield 97.9%) of pale yellow crystals of 4-methylsulfonyloxybenzenethiol were obtained. Examples 3 to 7 The yield and physical properties of the reaction product when a typical alkylsulfonyloxybenzenesulfonyl chloride was used instead of 4-methylsulfonyloxybenzenesulfonyl chloride in the same manner as in Example 1 are shown in the table. . 【table】
Claims (1)
低級アルキル又はハロゲンを表わす。） で表わされる化合物をヨウ素系触媒の存在下に、
赤リン及び水と反応させることを特徴とする式 （式中R1，R2は前記と同じものを表わす。） で表わされるアルキルスルホニルオキシベンゼン
チオール誘導体の製造法。[Claims] 1 formula (In the formula, R 1 represents lower alkyl, R 2 is hydrogen,
Represents lower alkyl or halogen. ) in the presence of an iodine catalyst,
Formula characterized by reaction with red phosphorus and water (In the formula, R 1 and R 2 are the same as above.) A method for producing an alkylsulfonyloxybenzenethiol derivative represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15801883A JPS6051167A (en) | 1983-08-31 | 1983-08-31 | Production of alkylsulfonyloxybenzenethiol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15801883A JPS6051167A (en) | 1983-08-31 | 1983-08-31 | Production of alkylsulfonyloxybenzenethiol derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6051167A JPS6051167A (en) | 1985-03-22 |
| JPH0377188B2 true JPH0377188B2 (en) | 1991-12-09 |
Family
ID=15662469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15801883A Granted JPS6051167A (en) | 1983-08-31 | 1983-08-31 | Production of alkylsulfonyloxybenzenethiol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6051167A (en) |
-
1983
- 1983-08-31 JP JP15801883A patent/JPS6051167A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6051167A (en) | 1985-03-22 |
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