JPH03181455A - Production of 4-halogenothiophenol - Google Patents
Production of 4-halogenothiophenolInfo
- Publication number
- JPH03181455A JPH03181455A JP32114389A JP32114389A JPH03181455A JP H03181455 A JPH03181455 A JP H03181455A JP 32114389 A JP32114389 A JP 32114389A JP 32114389 A JP32114389 A JP 32114389A JP H03181455 A JPH03181455 A JP H03181455A
- Authority
- JP
- Japan
- Prior art keywords
- chloride
- water
- organic solvent
- halogenothiophenol
- halogenobenzenesulfonyl
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 7
- 239000011707 mineral Substances 0.000 claims abstract description 7
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 238000005660 chlorination reaction Methods 0.000 claims abstract 3
- 238000006277 sulfonation reaction Methods 0.000 claims abstract 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical group ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical group BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 3
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 125000000532 dioxanyl group Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 4
- 239000003791 organic solvent mixture Substances 0.000 abstract 2
- 239000011541 reaction mixture Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 28
- 239000012044 organic layer Substances 0.000 description 15
- PWOBDMNCYMQTCE-UHFFFAOYSA-N 2-chlorobenzenethiol Chemical compound SC1=CC=CC=C1Cl PWOBDMNCYMQTCE-UHFFFAOYSA-N 0.000 description 13
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- YUQUNWNSQDULTI-UHFFFAOYSA-N 2-bromobenzenethiol Chemical compound SC1=CC=CC=C1Br YUQUNWNSQDULTI-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KMMHZIBWCXYAAH-UHFFFAOYSA-N 4-bromobenzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=C(Br)C=C1 KMMHZIBWCXYAAH-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- -1 chlorobenzene Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
- C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、医薬、農薬などの原料や、染料の中間体とし
て有用な４−ハロゲノチオフェノールの製造方法に関す
る。さらに詳しくは、異性体である２−ハロゲノチオフ
ェノールをほとんど含まない高純度の４−ハロゲノチオ
フェノールの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for producing 4-halogenothiophenol, which is useful as a raw material for medicines, agricultural chemicals, etc., and as an intermediate for dyes. More specifically, the present invention relates to a method for producing highly purified 4-halogenothiophenol containing almost no 2-halogenothiophenol, which is an isomer.
（従来の技術および解決すべき課題）
４−ハロゲノチオフェノールを医薬品用原料として用い
るためには、不純物をほとんど含まない高純度のものが
要求される。(Prior Art and Problems to be Solved) In order to use 4-halogenothiophenol as a raw material for pharmaceuticals, it is required to be highly pure and contain almost no impurities.
しかしながらモノクロロベンゼンやモノブロムベンゼン
等のハロゲノベンゼンをクロルスルホン酸等のスルホン
化剤でスルホン化し、次いで塩化チオニル等の塩素化剤
を用いて塩素化して得られた４−ハロゲノベンゼンスル
ホニルクロリドには、不純物として異性体である２−ハ
ロゲノベンゼンスルホニルクロリドが通常１〜３％含ま
れている。However, 4-halogenobenzenesulfonyl chloride obtained by sulfonating halogenobenzene such as monochlorobenzene or monobromobenzene with a sulfonating agent such as chlorosulfonic acid, and then chlorinating it using a chlorinating agent such as thionyl chloride, has the following properties: 2-halogenobenzenesulfonyl chloride, which is an isomer, is usually contained in an amount of 1 to 3% as an impurity.
この異性体を含む４−ハロゲノベンゼンスルホニルクロ
リドを亜鉛および／または錫と鉱酸で還元する場合には
、異性体も同様に還元されてしまい、還元して得られる
４−ハロゲノチオフェノールと２−ハロゲノチオフェノ
ールとを分離することは、極めて困難である。例えば、
４−クロロチオフェノールと２−クロロチオフェノール
とでは、両者は、沸点が２０５〜２０７℃、２０５〜２
０６℃と近似しておりこれを蒸留し、分離することは極
めて困難である。When 4-halogenobenzenesulfonyl chloride containing this isomer is reduced with zinc and/or tin and a mineral acid, the isomer is similarly reduced, and the resulting 4-halogenothiophenol and 2- It is extremely difficult to separate it from halogenothiophenol. for example,
4-chlorothiophenol and 2-chlorothiophenol have boiling points of 205-207°C and 205-207°C.
The temperature is close to 0.6°C, and it is extremely difficult to distill and separate it.
再結晶による４−クロロチオフェノールと２クロロチオ
フエノールの分離精製は、一般によく用いられる方法で
あるが、溶媒へのロスがあり有利な方法とは言えない。Separation and purification of 4-chlorothiophenol and 2-chlorothiophenol by recrystallization is a commonly used method, but it cannot be said to be an advantageous method due to loss to the solvent.
また製品の酸化による純度低下を防ぐため濾過、乾燥な
どは、不活性ガス雰囲気下で行わなければならない。４
−クロロチオフェノールの場合には、融点が５２〜５３
℃であり乾燥時に高い温度にすることができないため溶
媒を除去するのに長時間を要するなど工業的に有利では
ない。In addition, in order to prevent product purity from decreasing due to oxidation, filtration, drying, etc. must be performed under an inert gas atmosphere. 4
-In the case of chlorothiophenol, the melting point is 52-53
℃ and cannot be heated to a high temperature during drying, so it takes a long time to remove the solvent, which is not industrially advantageous.
これらのことから不純物として異性体をほとんど含まな
い４−ハロゲノチオフェノールを得るためには、その前
段階である還元反応に際し、原料である４−ハロゲノベ
ンゼンスルホニルクロリドとして異性体を含まないもの
を用いるのが得策である。From these facts, in order to obtain 4-halogenothiophenol that contains almost no isomers as impurities, it is necessary to use 4-halogenobenzenesulfonyl chloride that does not contain isomers as a raw material in the reduction reaction that is the preliminary step. It is a good idea to
４−ハａ）ｆノベンゼンスルホニルクロリドの精製方法
としては従来より、４−ハロゲノベンゼンスルホニルク
ロリドを含む反応液を水中に添加し、４−ハロゲノベン
ゼンスルホニルクロリドを晶析させる方法が知られてい
る。しかし、この方法では、未反応のスルホン酸および
過剰の塩素化剤、スルホン化剤等は、除去できるが、異
性体の除去はほとんど不可能である。また、これらを蒸
留によって分離精製することは、両者の沸点か近似して
いるために非常に困難である。4-ha a) f A conventionally known method for purifying nobenzenesulfonyl chloride is to add a reaction solution containing 4-halogenobenzenesulfonyl chloride to water and crystallize 4-halogenobenzenesulfonyl chloride. . However, although this method can remove unreacted sulfonic acid, excess chlorinating agent, sulfonating agent, etc., it is almost impossible to remove isomers. Furthermore, it is extremely difficult to separate and purify these by distillation because their boiling points are similar.
このような状況に鑑み、本発明者らは従来法の欠点を改
良し、異性体である２−ハロゲノチオフェノールをほと
んど含まない４−ハロゲノチオフェノールを高収率で製
造する方法について鋭意検討した。その結果、４−ハロ
ゲノベンゼンスルホニルクロリドを含む反応溶液を水た
けでなく有機溶剤を加えた混合溶夜中に添加し、晶析さ
せ、これを、濾取すれば、異性体である２−ハロゲノベ
ンゼンスルホニルクロリドの含量を著しく減少させるこ
とができ、これを還元すれば、２−ハロゲノチオフェノ
ールをほとんど含まない４−ハロゲノチオフェノールを
高収率で製造することかできることを見出し本発明に至
った。In view of this situation, the present inventors have conducted intensive studies on a method for improving the shortcomings of conventional methods and producing 4-halogenothiophenol containing almost no 2-halogenothiophenol, which is an isomer, in high yield. . As a result, if the reaction solution containing 4-halogenobenzene sulfonyl chloride was added to a mixed solution containing an organic solvent instead of a water tank and crystallized, and this was collected by filtration, 2-halogenobenzene, which is an isomer, was obtained. The inventors have discovered that the content of sulfonyl chloride can be significantly reduced, and by reducing it, 4-halogenothiophenol containing almost no 2-halogenothiophenol can be produced in high yield, leading to the present invention.
（課題を解決するための手段）
本発明は、ハロゲノベンゼンをスルホン化して４−ハロ
ゲンベンゼンスルホン酸とし、続いて塩素化して４−ハ
ロゲノベンゼンスルホニルクロリドとなし、亜鉛および
／または錫と鉱酸で還元して４−ハロゲノチオフェノー
ルを得るに際し、４−ハロゲノベンゼンスルホニルクロ
リドを含む反応液を水および有機溶剤の混合液中に添加
し、晶析させ、濾取した後、亜鉛および／または錫と鉱
酸で還元することを特徴とする高純度４−ハロゲノチオ
フェノールの製造方法を提供するものである。(Means for Solving the Problems) The present invention sulfonates halogenobenzene to form 4-halogenobenzenesulfonic acid, and then chlorinates it to form 4-halogenobenzenesulfonyl chloride, which is then treated with zinc and/or tin and a mineral acid. When reducing to obtain 4-halogenothiophenol, a reaction solution containing 4-halogenobenzenesulfonyl chloride is added to a mixture of water and an organic solvent, crystallized, filtered, and then treated with zinc and/or tin. The present invention provides a method for producing high-purity 4-halogenothiophenol, which is characterized by reduction with a mineral acid.
４−ハロゲノベンゼンスルホニルクロリドを含む反応液
を水中に添加しても、結晶は析出するが、この場合には
、粘性を有する凝集しやすい物となり、濾過性が悪く、
洗浄しても異性体の含量を減少させる効果は少ない。Even if a reaction solution containing 4-halogenobenzenesulfonyl chloride is added to water, crystals will precipitate, but in this case, the crystals will be viscous and easily aggregate, resulting in poor filterability.
Even washing has little effect on reducing the content of isomers.
本発明では４−ハロゲノベンゼンスルホニルクロリドを
含む反応液を水および有機溶剤の混合液中に添加するこ
とにより濾過性のよい結晶が得られるため、異性体の含
量の少ない４−ハロゲノベンゼンスルホニルクロリドの
結晶が得られる。このようにして得られた４−ハロゲノ
ベンゼンスルホニルクロリドを還元することにより異性
体の２−ハロゲノチオフェノールの含量が極めて少ない
４−ハロゲノチオフェノールを得ることが可能となる。In the present invention, crystals with good filterability can be obtained by adding a reaction solution containing 4-halogenobenzenesulfonyl chloride to a mixture of water and an organic solvent. Crystals are obtained. By reducing the 4-halogenobenzenesulfonyl chloride thus obtained, it becomes possible to obtain 4-halogenothiophenol having an extremely low content of isomer 2-halogenothiophenol.
有機溶剤としては、４−ハロゲノベンゼンスルホニルク
ロリドと反応しない有機溶剤は何でも使用することがで
きる。例えば、メタノール、エタノール、プロパノール
等のアルコール類、ジオキサン、テトラヒドロフラン等
のエーテル類、ヘキサン、ヘプタン等の脂肪族炭化水素
、トルエン、キシレン等の芳香族炭化水素、クロロベン
ゼン等のハロゲン化芳香族炭化水素等が用いられる。と
りわけ、メタノール、エタノール、プロパノール等のア
ルコール類、ヘキサン、ヘプタン等の脂肪族炭化水素を
用いた場合に、異性体の除去効果が大きく、回収率が高
く好結果が得られる。Any organic solvent that does not react with 4-halogenobenzenesulfonyl chloride can be used as the organic solvent. For example, alcohols such as methanol, ethanol and propanol, ethers such as dioxane and tetrahydrofuran, aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as toluene and xylene, halogenated aromatic hydrocarbons such as chlorobenzene, etc. is used. In particular, when alcohols such as methanol, ethanol, and propanol, and aliphatic hydrocarbons such as hexane and heptane are used, the isomer removal effect is large, and good results are obtained with a high recovery rate.
水と有機溶剤との混合Ｂ液に４−ハロゲノベンゼンスル
ホニルクロリドを含む反応溶液を添加するときの温度は
、０〜３０℃が好ましく、特に５〜１５℃が好ましい。The temperature when adding the reaction solution containing 4-halogenobenzenesulfonyl chloride to the mixture B of water and an organic solvent is preferably 0 to 30°C, particularly preferably 5 to 15°C.
温度が３０℃より高くなると４−ハロゲノベンゼンスル
ホニルクロリドが分解したり、濾液への溶解ロスか増加
するため回収率が低下する。When the temperature is higher than 30° C., the recovery rate decreases because 4-halogenobenzenesulfonyl chloride decomposes and dissolution loss to the filtrate increases.
水と有機溶剤との混合割合は、水１重量部に対して有機
溶剤が０．１〜３，０重量部、好ましくは０．５〜２
、 Ｏ重量部の割合で用いられる。Ｏ５１重量部より少
ない場合には有機溶剤を混合する効果が得られず、３．
０重量部より多い場合には、不純物である２−ハロゲノ
ベンゼンスルホニルクロリドの含量は減少するが、目的
物である４−ハロゲノベンゼンスルホニルクロリドの溶
酸への溶解が多くなり、収量が低下するので好ましくな
い。The mixing ratio of water and organic solvent is 0.1 to 3.0 parts by weight, preferably 0.5 to 2 parts by weight of organic solvent to 1 part by weight of water.
, O parts by weight. If the amount of O is less than 1 part by weight, the effect of mixing the organic solvent cannot be obtained; 3.
If it is more than 0 parts by weight, the content of 2-halogenobenzenesulfonyl chloride, which is an impurity, will decrease, but the target product, 4-halogenobenzenesulfonyl chloride, will be more dissolved in the molten acid, resulting in a lower yield. Undesirable.
４−ハロゲノベンゼンスルホニルクロリドの純度および
収量について好ましい結果を得るためには、水と有機溶
剤との混合割合は、上記した範囲のものを用いることが
必要である。In order to obtain favorable results regarding the purity and yield of 4-halogenobenzenesulfonyl chloride, it is necessary to use a mixing ratio of water and organic solvent within the range described above.
析出した４−ハロゲノベンゼンスルホニルクロリドは、
濾過性が良好であり、洗浄後乾燥せずに次工程の還元反
応に供することができる。The precipitated 4-halogenobenzenesulfonyl chloride is
It has good filterability and can be used in the next step of reduction reaction without drying after washing.
還元反応は、塩酸または硫酸等鉱酸の存在下、亜鉛およ
び／または錫を用いて行われる。好ましくは塩酸の存在
下、亜鉛を用いて行われる。The reduction reaction is carried out using zinc and/or tin in the presence of a mineral acid such as hydrochloric acid or sulfuric acid. It is preferably carried out using zinc in the presence of hydrochloric acid.
亜鉛を使用する場合、その使用量は、理論量の１．０５
倍で十分である。When using zinc, the amount used is 1.05 of the theoretical amount.
Double is enough.
還元反応は、通常、有機溶剤を添加して行われ、該有機
溶媒としては、トルエン、キシレン等芳香族炭化水素が
好適に用いられる。The reduction reaction is usually carried out by adding an organic solvent, and aromatic hydrocarbons such as toluene and xylene are preferably used as the organic solvent.
還元反応終了後、有機層と水層とに分離し、有機層を希
酸で洗浄して未反応金属を除去する。After the reduction reaction is completed, it is separated into an organic layer and an aqueous layer, and the organic layer is washed with dilute acid to remove unreacted metals.
有機層を水洗した後、蒸留することにより、不純物とし
て存在する２−ハロゲノチオフェノール以外の４．４゛
−ジハロゲノジフェニルスルホン、４．４°−ジハロゲ
ノジフエニルジスルフィド等はそれらが高沸点であるた
め容易に分離することができ、純度が９９．５％以上の
４−ハロゲノチオフェノールが得られる。After washing the organic layer with water, the organic layer is distilled to remove impurities other than 2-halogenothiophenol, such as 4.4'-dihalogenodiphenyl sulfone and 4.4°-dihalogenodiphenyl disulfide, which have high boiling points. Therefore, it can be easily separated, and 4-halogenothiophenol with a purity of 99.5% or more can be obtained.
この様に、酸化されやすい４−ハロゲノチオフェノール
の精製のためには、晶析、濾過、洗浄等繁雑な操作を必
要とする再結晶によるよりも前記した蒸留による精製の
方が得策である。このとき、蒸留液中に異性体の２−ハ
ロゲノチオフェノールが混入している場合には両者の沸
点が近似しているため、これらを分離することは極めて
困難であるが、本発明の方法では混入する２−ハロゲノ
チオフェノールか極めて少ないため、容易に高純度の４
−ハロゲノチオフェノールを得ることが可能となる。Thus, for purification of 4-halogenothiophenol which is easily oxidized, it is better to purify by distillation as described above than by recrystallization which requires complicated operations such as crystallization, filtration and washing. At this time, if the isomer of 2-halogenothiophenol is mixed in the distillate, the boiling points of the two are similar, so it is extremely difficult to separate them, but the method of the present invention Since there is very little 2-halogenothiophenol contaminating, it is easy to obtain high-purity 4.
- It becomes possible to obtain halogenothiophenol.
（実施例）
以下に実施例および比較例をあげて本発明を具体的に説
明するが、本発明は、これらにより限定されるものでは
ない。(Example) The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
製造例１
クロルスルホン酸６５２．０（５，６モル）に硫酸ナト
リウム３２．８９を添加し、５０℃に昇温した。これに
モノクロロベンゼン４５０．４９＜４．０モル）を３時
間で滴下した。７０℃まで１時間で昇温した後、塩化チ
オニル４９９．４９（４，２モル）を３時間で滴下し、
同温度で１時間保持した。得られた４−クロロベンゼン
スルホニルクロリドを含む反応液１０６９．６９を分割
して、以下の実施例１〜４および比較例１の原料液とし
て供した。Production Example 1 32.89 mol of sodium sulfate was added to 652.0 (5.6 mol) of chlorosulfonic acid, and the temperature was raised to 50°C. Monochlorobenzene (450.49<4.0 mol) was added dropwise to this over 3 hours. After raising the temperature to 70°C over 1 hour, 499.49 (4.2 mol) of thionyl chloride was added dropwise over 3 hours.
It was maintained at the same temperature for 1 hour. The resulting reaction solution containing 4-chlorobenzenesulfonyl chloride (1,069.69 g) was divided and used as a raw material solution for Examples 1 to 4 and Comparative Example 1 below.
実施例１
製造例１においてｌ、０モルに相当する４−クロロベン
ゼンスルホニルクロリドを含む反応液２６７．４９をメ
タノール２４０ｇ、水１６０ｇの混合溶液に２０分で滴
下した。この間、温度をｌ０℃に保った。同温度で２時
間撹拌した後、減圧濾過し、メタノール６０９および水
４０９の混合溶液で洗浄した。４−クロロベンゼンスル
ホニルクロリドの湿ケーキ２１９ｇをトルエン５０９お
よび濃塩酸６５７９（６，３モル）中に添加し、亜鉛１
９６．２９（３，０モル）を２０℃から８０℃に昇温し
ながら１時間で添加した。Example 1 In Production Example 1, 267.49 mol of the reaction solution containing 4-chlorobenzenesulfonyl chloride corresponding to 1,0 mol was added dropwise to a mixed solution of 240 g of methanol and 160 g of water over 20 minutes. During this time, the temperature was maintained at 10°C. After stirring at the same temperature for 2 hours, the mixture was filtered under reduced pressure and washed with a mixed solution of 609% methanol and 409% water. 219 g of wet cake of 4-chlorobenzenesulfonyl chloride are added to 509 toluene and 6579 (6,3 mol) of concentrated hydrochloric acid, and 1
96.29 (3.0 mol) was added over 1 hour while increasing the temperature from 20°C to 80°C.
８５℃で２時間保持した後、トルエン１５０ｇを添加し
、３０°Ｃに冷却した後、分離した。After being maintained at 85°C for 2 hours, 150g of toluene was added, and after cooling to 30°C, it was separated.
トルエン層を１０％塩酸１００ｇで洗浄した後、水１０
０９で水洗し、有機層３３０．６９を得た。After washing the toluene layer with 100 g of 10% hydrochloric acid, 10 g of water
The organic layer was washed with water at 0.09 to obtain an organic layer of 330.69.
４−クロロチオフェノールの生成率は、９０．８％で、
２−クロロチオフェノールの含量は、０．１２％であっ
た。The production rate of 4-chlorothiophenol was 90.8%,
The content of 2-chlorothiophenol was 0.12%.
有機層を減圧蒸留し、４−クロロチオフェノールとして
９４〜９７°Ｃ／ １５〜２０ｍｍＨｇ℃の留分、１２
７．１９を得た。The organic layer was distilled under reduced pressure to obtain 4-chlorothiophenol as a fraction at 94-97°C/15-20mmHg°C, 12
I got 7.19.
有姿収率は８７．９％（対クロロベンゼン）、純度は９
９．７％で、２−クロロチオフェノールの含量は００１
２％であった。Tangible yield is 87.9% (based on chlorobenzene), purity is 9
9.7%, the content of 2-chlorothiophenol is 001
It was 2%.
実施例２
製造例１において０．５モルに相当する４−クロロベン
ゼンスルホニルクロリドを含む反応液１３３．７９を２
−プロパノール８０９、水１２０９の混合溶液に１５分
で滴下した。この間、温度を１５℃に保った。同温度で
１時間４５分撹拌した後、減圧濾過し、２−プロパノー
ル２０ｇおよび水３０ｇの混合溶液で洗浄した。Example 2 In Production Example 1, 133.79 mol of the reaction solution containing 4-chlorobenzenesulfonyl chloride corresponding to 0.5 mol was added to 2
- It was dropped into a mixed solution of 809% of propanol and 120% of water over 15 minutes. During this time, the temperature was maintained at 15°C. After stirring at the same temperature for 1 hour and 45 minutes, the mixture was filtered under reduced pressure and washed with a mixed solution of 20 g of 2-propanol and 30 g of water.
４−クロロベンゼンスルホニルクロリドの湿ケーキ１１
３．５９をトルエン２５９および濃塩酸３３４９（３，
２モル）中に添加し、亜鉛９８．ＮＦ（１，５モル）を
、２０℃から８０°Ｃに昇温しながら３０分で添加した
。８５℃で１時間３０分保持した後、トルエン１００９
を添加し、３０℃に冷却し、ついで、分液した。Wet cake of 4-chlorobenzenesulfonyl chloride 11
3.59 to toluene 259 and concentrated hydrochloric acid 3349 (3,
2 mol) and zinc 98. NF (1.5 mol) was added over 30 minutes while increasing the temperature from 20°C to 80°C. After holding at 85℃ for 1 hour and 30 minutes, toluene 1009
was added, cooled to 30°C, and then separated.
トルエン層を１０％塩酸５０９で洗浄し、さらに水５０
ｇで洗浄して有機層１８６．７９を得た。The toluene layer was washed with 50% 10% hydrochloric acid, and then washed with 50% water.
The organic layer 186.79 was obtained by washing with g.
４−クロロチオフェノールの生成率は８８．３％であり
、２−クロロチオフェノールの含量は０．１１％であっ
た。有機層を実施例１と同様に蒸留し、純度９９．８％
の４−クロロチオフェノール６２．０９を得た。クロロ
ベンゼンに対する収率は８５８％であり、０．１１％の
２−クロロチオフェノールを含んでいた。The production rate of 4-chlorothiophenol was 88.3%, and the content of 2-chlorothiophenol was 0.11%. The organic layer was distilled in the same manner as in Example 1, and the purity was 99.8%.
62.09 of 4-chlorothiophenol was obtained. The yield based on chlorobenzene was 858% and contained 0.11% 2-chlorothiophenol.
実施例３
製造例１で得た４−クロロベンゼンスルホニルクロリド
を含む反応１ｆｆ１２６７．４９をｎ−ヘキサン２００
ｇおよび水２００９の混合溶液中に３０分で滴下した。Example 3 The reaction 1ff containing 4-chlorobenzenesulfonyl chloride obtained in Production Example 1 was mixed with 200 g of n-hexane.
g and water 2009 over 30 minutes.
この間、温度を１００ｃに保った。同温度で１時間３０
分撹拌した後、減圧濾過し、ｎ −ヘキサン５０ｇおよ
び水５０９で洗浄し、湿ケーキ１７７．０ｇを得た。以
下、実施例１と同様にトルエンおよび濃塩酸中に添加し
、還元反応を行った。During this time, the temperature was kept at 100c. 1 hour 30 at the same temperature
After stirring for several minutes, the mixture was filtered under reduced pressure and washed with 50 g of n-hexane and 509 g of water to obtain 177.0 g of a wet cake. Thereafter, in the same manner as in Example 1, it was added to toluene and concentrated hydrochloric acid to perform a reduction reaction.
４−クロロチオフェノールの生成率は８６．９％で、２
−クロロチオフェノールの含量は０．０４％であった。The production rate of 4-chlorothiophenol was 86.9%, and 2
-The content of chlorothiophenol was 0.04%.
実施例１と同様に蒸留し、純度９９．８％の４−クロロ
チオフェノール１２２．６ｇを得た。クロロベンゼンに
対する収率は８４．８％であり、０．０４％の２−クロ
ロチオフェノールを含んでいた。Distillation was carried out in the same manner as in Example 1 to obtain 122.6 g of 4-chlorothiophenol with a purity of 99.8%. The yield based on chlorobenzene was 84.8% and contained 0.04% 2-chlorothiophenol.
実施例４
製造例１で得た４−クロロベンゼンスルホニルクロリド
を含む反応液１３３．７９をジオキサン８０９および水
１２０ｇの混合溶液中に１５分で滴下した。この間、温
度を５℃に保った。同温度で１時間４５分撹拌した後、
減圧濾過し、ジオキサン２５９および水２５９で洗浄し
、湿ケーキ９３．９９を得た。Example 4 133.79 g of the reaction solution containing 4-chlorobenzenesulfonyl chloride obtained in Production Example 1 was dropped into a mixed solution of 809 g of dioxane and 120 g of water over 15 minutes. During this time, the temperature was maintained at 5°C. After stirring at the same temperature for 1 hour and 45 minutes,
Filtration under reduced pressure and washing with 259 parts of dioxane and 259 parts of water gave 93.99 parts of a wet cake.
以下、実施例２と同様にトルエンおよび譜塩酸中に添加
し、還元反応を行った。Thereafter, in the same manner as in Example 2, it was added to toluene and hydrochloric acid to perform a reduction reaction.
４−クロロチオフェノールの生成率は８７．５％で、２
−クロロチオフェノールの含量は０．１８％であった。The production rate of 4-chlorothiophenol was 87.5%, and 2
-The content of chlorothiophenol was 0.18%.
実施例２と同様に蒸留し、純度９９．６％の４−クロロ
チオフェノール６１．５９を得た。Distillation was carried out in the same manner as in Example 2 to obtain 61.59 4-chlorothiophenol with a purity of 99.6%.
クロロベンゼンに対する収率は８５．１％であり、０．
１８％の２−クロロチオフェノールを含んでいた。The yield based on chlorobenzene was 85.1% and 0.
It contained 18% 2-chlorothiophenol.
比較例１
製造例１において０．５モルに相当する４−クロロベン
ゼンスルホニルクロリドを含む反応液１３３．７９を水
２００９中に２０分で滴下した。Comparative Example 1 In Production Example 1, 133.79 mol of a reaction solution containing 4-chlorobenzenesulfonyl chloride corresponding to 0.5 mol was dropped into 2009 ml of water over 20 minutes.
この間、温度を１５℃に保った。同温度で１時間４５分
間撹拌し、減圧濾過し、水５０ｇで洗浄した。得られた
湿ケーキＩ １８．２ｇをトルエン２５Ｖ、濃塩酸３１
３ｇ（３，０モル）中に添加し、亜鉛９８．１９（１，
５モル）を２０℃から８０℃に昇温しながら、１時間で
添加した。８５℃で２時間保持した後、トルエン１００
９を添加し、３０℃に冷却し、ついで、分液した。トル
エン層を１０％塩酸５０ｇで洗浄した後、水５０ｇで水
洗して有機層１８８．５９を得た。４−クロロチオフェ
ノールの生成収率は８８．１％で、２−クロロチオフェ
ノールの含量は０．９２％であった。実施例２と同様に
蒸留し４−クロロチオフェノール６１．４ｇを得た。有
姿収率は８４．９％（対モノクロロベンゼン）、純度は
９８．９％で、２−クロロチオフェノールを０．９３％
含んでいた。During this time, the temperature was maintained at 15°C. The mixture was stirred at the same temperature for 1 hour and 45 minutes, filtered under reduced pressure, and washed with 50 g of water. 18.2 g of the obtained wet cake I was mixed with 25 V of toluene and 31 V of concentrated hydrochloric acid.
Zinc 98.19 (1,0 mol)
5 mol) was added over 1 hour while increasing the temperature from 20°C to 80°C. After holding at 85°C for 2 hours, toluene 100
9 was added, cooled to 30°C, and then separated. The toluene layer was washed with 50 g of 10% hydrochloric acid and then with 50 g of water to obtain an organic layer 188.59. The production yield of 4-chlorothiophenol was 88.1%, and the content of 2-chlorothiophenol was 0.92%. Distillation was carried out in the same manner as in Example 2 to obtain 61.4 g of 4-chlorothiophenol. The tangible yield was 84.9% (based on monochlorobenzene), the purity was 98.9%, and 2-chlorothiophenol was 0.93%.
It contained.
製造例２
クロルスルホン酸３２６．３ｙ（２，８モル）に無水硫
酸ナトリウム１６．４９を添加し、５０℃に昇温した。Production Example 2 16.49 y of anhydrous sodium sulfate was added to 326.3 y (2.8 mol) of chlorosulfonic acid, and the temperature was raised to 50°C.
これにモツプロムベンゼン３１４．０ｇ（２，０モル）
を３時間かけて滴下した。同温度で３０分保持した後８
０℃に昇温し、塩化チオニル２４９．８９（２，１モル
）を３時間で滴下した。滴下後、同温度で１時間保持し
、４−ブロムベンゼンスルホニルクロリドを含む反応液
６２２．０９を得た。この反応液を分割して以下の実施
例５および比較例２の原料液に供した。To this, 314.0 g (2.0 mol) of motuprombenzene
was added dropwise over 3 hours. After holding at the same temperature for 30 minutes8
The temperature was raised to 0°C, and 249.89 (2.1 mol) of thionyl chloride was added dropwise over 3 hours. After the dropwise addition, the mixture was maintained at the same temperature for 1 hour to obtain 622.09 of a reaction solution containing 4-bromobenzenesulfonyl chloride. This reaction solution was divided into portions and used as raw material solutions for Example 5 and Comparative Example 2 below.
実施例５
製造例２の反応液において１．０モルに相当する４−ブ
ロムベンゼンスルホニルクロリドを含む反応液３１１．
０９をメタノール２００ｇおよび水２００９の混合溶液
に１５分で滴下した。この間、温度を１５°Ｃに保った
。同温度で、１時間４５分撹拌した後、減圧濾過し、メ
タノール５０９および水５０ｇの混合溶液で洗浄した。Example 5 Reaction solution 311. containing 4-bromobenzenesulfonyl chloride equivalent to 1.0 mol in the reaction solution of Production Example 2.
09 was added dropwise to a mixed solution of 200 g of methanol and water 2009 over 15 minutes. During this time, the temperature was maintained at 15°C. After stirring at the same temperature for 1 hour and 45 minutes, the mixture was filtered under reduced pressure and washed with a mixed solution of 509 methanol and 50 g of water.
４−ブロムベンゼンスルホニルクロリドの湿ケーキ２６
３．０９をトルエン５０９およびａ塩酸６８９９（６，
６モル）中に添加し、亜鉛２０６．０９（３，１５モル
）を２０℃から８０℃に昇温しながら１時間で添加した
。８５℃で１時間保持した後、トルエン４００７を加え
、３０℃に冷却し、ついで、分液した。トルエン層を１
０％塩酸１００９で洗浄し、さらに水１００９で洗浄し
て有機層６１８．４ｇを得た。４−ブロムチオフェノー
ルの生成収率は９１．０％、２−ブロムチオフェノール
の含量は０．１１％であった。有機層を蒸留Ａ−一・ツ
’ｍｌ、−１−−ｊ−ｑ＋ノー＋＋、＋ＱＱＱｏ九偵た
。有姿収率は８８．１％（対ブロムベンゼン）、純度９
９．７％で、２−ブロムチオフェノールを０．１１％含
んでいた。Wet cake of 4-bromobenzenesulfonyl chloride 26
3.09 to toluene 509 and a hydrochloric acid 6899 (6,
206.09 (3.15 mol) of zinc was added over 1 hour while raising the temperature from 20°C to 80°C. After holding at 85°C for 1 hour, toluene 4007 was added, cooled to 30°C, and then separated. 1 toluene layer
The organic layer was washed with 1,009 ml of 0% hydrochloric acid and then with 1,009 ml of water to obtain 618.4 g of an organic layer. The production yield of 4-bromothiophenol was 91.0%, and the content of 2-bromothiophenol was 0.11%. The organic layer was distilled to 1 ml, -1 ml, -1 ml, +QQQo. Tangible yield: 88.1% (based on bromobenzene), purity: 9
9.7% and contained 0.11% 2-bromthiophenol.
比較例２
実施例５と同様に製造ＰＪ２で得た４−ブロムベンゼン
スルホニルクロリドを含む反応液３１１．０９をトルエ
ン５０ｇおよび濃塩酸６８９ｇ（６，６モル）中に添加
し、２０℃から８０℃に昇温しながら亜鉛２３５．４ｆ
（３，６モル）を添加した。添加に要した時間は１時間
であった。８５℃で１時間保持した後、トルエン４００
ｇを加え、３０’Ｃに冷却して分液した。トルエン層を
１０％塩酸で洗浄した後、水！００？で洗浄し、有機層
６１２．６２を得た。４−ブロムチオフェノールの生成
収率は８８．１％、２−ブロムチオフェノールの含量は
０．７６％であった。有機層を実施例５と同様に蒸留し
、４−ブロムチオフェノール１６３．７９を有姿収率８
６．６％（対ブロムベンゼン）で得た。Comparative Example 2 311.09 of the reaction solution containing 4-bromobenzenesulfonyl chloride produced in PJ2 was added to 50 g of toluene and 689 g (6.6 mol) of concentrated hydrochloric acid in the same manner as in Example 5, and heated from 20°C to 80°C. Zinc 235.4f while increasing temperature to
(3.6 mol) was added. The time required for the addition was 1 hour. After holding at 85℃ for 1 hour, toluene 400
g was added thereto, and the mixture was cooled to 30'C and separated. After washing the toluene layer with 10% hydrochloric acid, water! 00? The organic layer 612.62 was obtained. The production yield of 4-bromothiophenol was 88.1%, and the content of 2-bromothiophenol was 0.76%. The organic layer was distilled in the same manner as in Example 5 to obtain 163.79 4-bromothiophenol with a visible yield of 8.
6.6% (based on bromobenzene).
純度は９８．２％で０．９６％の２−プロムチオフェ）
＋＋Ｉえｂ！哨りふ、−−）イム−
を除去するため同量のヘキサンを用いて再結晶を行った
ところ２−ブロムチオフェノールの含量は０．２１％に
減少したが、回収率は８２％であった。Purity is 98.2% and 0.96% 2-promthiophene)
++Ieb! When recrystallization was performed using the same amount of hexane to remove the 2-bromothiophenol, the content of 2-bromothiophenol decreased to 0.21%, but the recovery rate was 82%. Ta.
（発明の効果）
本発明によれば、４−ハロゲノベンゼンスルホニルクロ
リドを含む反応液を水および有機溶媒の混合溶液に添加
し、晶析させ、これを濾取することにより異性体の２−
ハロゲノベンゼンスルホニルクロリドを除去することが
容易に出来、異性体をほとんど含まない４−ハロゲノベ
ンゼンスルホニルクロリドを得ることができる。ついで
、これを還元することにより、通常の方法では分離困難
な２−ハロゲノチオフェノールの含量が極めて少ない４
−ハロゲノチオフェノールをこれまでに無い高収率で得
ることができる。(Effects of the Invention) According to the present invention, a reaction solution containing 4-halogenobenzenesulfonyl chloride is added to a mixed solution of water and an organic solvent to cause crystallization, and this is collected by filtration to obtain a 2-isomer.
Halogenobenzenesulfonyl chloride can be easily removed and 4-halogenobenzenesulfonyl chloride containing almost no isomer can be obtained. Then, by reducing this, the content of 2-halogenothiophenol, which is difficult to separate using normal methods, is extremely low.
- Halogenothiophenol can be obtained in an unprecedentedly high yield.
Claims (10)
より誘導した４−ハロゲノベンゼンスルホニルクロリド
を亜鉛および／または錫と鉱酸とで還元して４−ハロゲ
ノチオフェノールを得るに際し、４−ハロゲノベンゼン
スルホニルクロリドを含む反応液を水および有機溶剤の
混合液中に添加し、晶析させ、濾取した後、亜鉛および
／または錫と鉱酸とで還元することを特徴とする４−ハ
ロゲノチオフェノールの製造方法。(1) When reducing 4-halogenobenzenesulfonyl chloride derived from halogenobenzene by sulfonation and chlorination with zinc and/or tin and mineral acid to obtain 4-halogenothiophenol, 4-halogenobenzenesulfonyl chloride is A method for producing 4-halogenothiophenol, which comprises adding a reaction solution containing the same to a mixed solution of water and an organic solvent, crystallizing it, collecting it by filtration, and then reducing it with zinc and/or tin and a mineral acid. .
１重量部に対して有機溶剤が０．１〜３．０重量部であ
る請求項（１）記載の方法。(2) The method according to claim 1, wherein the mixing ratio in the mixed solution of water and organic solvent is 0.1 to 3.0 parts by weight of the organic solvent to 1 part by weight of water.
の方法。(3) The method according to claim (1), wherein the organic solvent is an alcohol.
ノールからなる群から選ばれたものである請求項（３）
記載の方法。(4) Claim (3) wherein the alcohol is selected from the group consisting of methanol, ethanol, and propanol.
Method described.
記載の方法。(5) Claim (1) in which the organic solvent is an aliphatic hydrocarbon.
Method described.
る請求項（５）記載の方法。(6) The method according to claim (5), wherein the aliphatic hydrocarbon is hexane or heptane.
方法。(7) The method according to claim (1), wherein the organic solvent is an ether.
の方法。(8) The method according to claim (7), wherein the ether is dioxane.
求項（１）記載の方法。(9) The method according to claim (1), wherein the halogenobenzene is monochlorobenzene.
請求項（１）記載の方法。(10) The method according to claim (1), wherein the halogenobenzene is monobromobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32114389A JPH082864B2 (en) | 1989-12-11 | 1989-12-11 | Method for producing 4-halogenothiophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32114389A JPH082864B2 (en) | 1989-12-11 | 1989-12-11 | Method for producing 4-halogenothiophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03181455A true JPH03181455A (en) | 1991-08-07 |
| JPH082864B2 JPH082864B2 (en) | 1996-01-17 |
Family
ID=18129282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32114389A Expired - Fee Related JPH082864B2 (en) | 1989-12-11 | 1989-12-11 | Method for producing 4-halogenothiophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082864B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070680A1 (en) * | 2000-03-21 | 2001-09-27 | Sumitomo Seika Chemicals Co., Ltd. | Process for producing 4-bromothioanisole |
-
1989
- 1989-12-11 JP JP32114389A patent/JPH082864B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001070680A1 (en) * | 2000-03-21 | 2001-09-27 | Sumitomo Seika Chemicals Co., Ltd. | Process for producing 4-bromothioanisole |
| US7041853B2 (en) | 2000-03-21 | 2006-05-09 | Sumitomo Seika Chemicals Co., Ltd. | Process for producing 4-bromothioanisole |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082864B2 (en) | 1996-01-17 |
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