JPH0940636A - Production of halothiophenol - Google Patents
Production of halothiophenolInfo
- Publication number
- JPH0940636A JPH0940636A JP19637795A JP19637795A JPH0940636A JP H0940636 A JPH0940636 A JP H0940636A JP 19637795 A JP19637795 A JP 19637795A JP 19637795 A JP19637795 A JP 19637795A JP H0940636 A JPH0940636 A JP H0940636A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- represented
- halothiophenol
- reaction
- surfactant
- 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 description 6
- 150000005171 halobenzenes Chemical class 0.000 claims abstract description 16
- -1 alkali metal salt Chemical class 0.000 claims abstract description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 12
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- PWOBDMNCYMQTCE-UHFFFAOYSA-N 2-chlorobenzenethiol Chemical compound SC1=CC=CC=C1Cl PWOBDMNCYMQTCE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 230000002140 halogenating effect Effects 0.000 claims abstract description 6
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- YUQUNWNSQDULTI-UHFFFAOYSA-N 2-bromobenzenethiol Chemical compound SC1=CC=CC=C1Br YUQUNWNSQDULTI-UHFFFAOYSA-N 0.000 claims description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 3
- QIULLHZMZMGGFH-UHFFFAOYSA-N 2,5-dichlorobenzenethiol Chemical compound SC1=CC(Cl)=CC=C1Cl QIULLHZMZMGGFH-UHFFFAOYSA-N 0.000 claims description 2
- WRXIPCQPHZMXOO-UHFFFAOYSA-N 3,5-dichlorobenzenethiol Chemical compound SC1=CC(Cl)=CC(Cl)=C1 WRXIPCQPHZMXOO-UHFFFAOYSA-N 0.000 claims description 2
- FTBCOQFMQSTCQQ-UHFFFAOYSA-N 4-bromobenzenethiol Chemical compound SC1=CC=C(Br)C=C1 FTBCOQFMQSTCQQ-UHFFFAOYSA-N 0.000 claims description 2
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- 238000006177 thiolation reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052794 bromium Inorganic materials 0.000 abstract description 7
- 230000026030 halogenation Effects 0.000 abstract description 5
- 238000005658 halogenation reaction Methods 0.000 abstract description 5
- 229910052740 iodine Inorganic materials 0.000 abstract description 5
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007872 degassing Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- ALAQDUSTXPEHMH-UHFFFAOYSA-N 1-bromo-2-methylsulfanylbenzene Chemical compound CSC1=CC=CC=C1Br ALAQDUSTXPEHMH-UHFFFAOYSA-N 0.000 description 2
- IHLDFHCSSCVPQW-UHFFFAOYSA-N 1-chloro-2-methylsulfanylbenzene Chemical compound CSC1=CC=CC=C1Cl IHLDFHCSSCVPQW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- GMVJKSNPLYBFSO-UHFFFAOYSA-N 1,2,3-tribromobenzene Chemical compound BrC1=CC=CC(Br)=C1Br GMVJKSNPLYBFSO-UHFFFAOYSA-N 0.000 description 1
- FWAJPSIPOULHHH-UHFFFAOYSA-N 1,2,4-tribromobenzene Chemical compound BrC1=CC=C(Br)C(Br)=C1 FWAJPSIPOULHHH-UHFFFAOYSA-N 0.000 description 1
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 description 1
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 1
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 description 1
- ZPQOPVIELGIULI-UHFFFAOYSA-N 1,3-dichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1 ZPQOPVIELGIULI-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- ZUAMDMWZDFEYFG-UHFFFAOYSA-N 2,5-dibromobenzenethiol Chemical compound SC1=CC(Br)=CC=C1Br ZUAMDMWZDFEYFG-UHFFFAOYSA-N 0.000 description 1
- ZHJYYYKHRSMJJP-UHFFFAOYSA-N 2,6-dibromobenzenethiol Chemical compound SC1=C(Br)C=CC=C1Br ZHJYYYKHRSMJJP-UHFFFAOYSA-N 0.000 description 1
- JBISHCXLCGVPGW-UHFFFAOYSA-N 2,6-dichlorobenzenethiol Chemical compound SC1=C(Cl)C=CC=C1Cl JBISHCXLCGVPGW-UHFFFAOYSA-N 0.000 description 1
- MNURPFVONZPVLA-UHFFFAOYSA-N 2-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1Cl MNURPFVONZPVLA-UHFFFAOYSA-N 0.000 description 1
- KMVZDSQHLDGKGV-UHFFFAOYSA-N 2-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=CC=C1S(Cl)(=O)=O KMVZDSQHLDGKGV-UHFFFAOYSA-N 0.000 description 1
- IXOFPUCWZCAFJX-UHFFFAOYSA-N 2-phenylethanethioic s-acid Chemical compound SC(=O)CC1=CC=CC=C1 IXOFPUCWZCAFJX-UHFFFAOYSA-N 0.000 description 1
- AZVGHTVANGAGFT-UHFFFAOYSA-N 3,5-dibromobenzenethiol Chemical compound SC1=CC(Br)=CC(Br)=C1 AZVGHTVANGAGFT-UHFFFAOYSA-N 0.000 description 1
- HNGQQUDFJDROPY-UHFFFAOYSA-N 3-bromobenzenethiol Chemical compound SC1=CC=CC(Br)=C1 HNGQQUDFJDROPY-UHFFFAOYSA-N 0.000 description 1
- CQJDYPZUDYXHLM-UHFFFAOYSA-N 3-chlorobenzenethiol Chemical compound SC1=CC=CC(Cl)=C1 CQJDYPZUDYXHLM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ハロベンゼン類を
原料とする、ハロチオフェノール類の新規な製造方法に
関する。ハロチオフェノール類は、医薬、農薬、機能性
材料などの種々の用途に用いられている有用な化合物で
ある。TECHNICAL FIELD The present invention relates to a novel method for producing halothiophenols using halobenzenes as a raw material. Halothiophenols are useful compounds used in various applications such as medicines, agricultural chemicals, and functional materials.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】従来、ハ
ロチオフェノール類を合成する方法としては、いくつか
の方法が知られている。2. Description of the Related Art Conventionally, several methods are known as methods for synthesizing halothiophenols.
【０００３】例えば、チオフェノールを塩素化し、その
後、亜鉛などで還元する方法（ＵＳ３３３１２０５）、
フェニルチオ酢酸を塩素化後、酸化、還元する方法（Ｕ
Ｓ３２９６３０８）、クロロベンゼンスルホニルクロリ
ドを亜鉛等で還元する方法（ＵＳ３３２５９８１）、ク
ロロベンゼンスルホン酸をリンで還元する方法（ＤＥ１
９３９４６９）、ジクロロベンゼンを高温下で硫化水素
と反応させる方法（Ｚｈ．Ｏｒｇ．Ｋｈｉｍ．１１
（５）．１１３２（１９７５））等が知られている。For example, a method in which thiophenol is chlorinated and then reduced with zinc or the like (US3331205),
Method of oxidizing and reducing phenylthioacetic acid after chlorination (U
S3296308), a method of reducing chlorobenzenesulfonyl chloride with zinc or the like (US3323591), a method of reducing chlorobenzenesulfonic acid with phosphorus (DE1)
939469), a method of reacting dichlorobenzene with hydrogen sulfide at high temperature (Zh. Org. Khim. 11).
(5). 1132 (1975)) and the like are known.
【０００４】しかしながら、これらの方法は、塩素化後
に還元が必要なこと、反応条件が厳しいこと、収率、生
産効率が悪いこと等より、いずれも工業的に製造するに
は適した方法とは言い難い。However, these methods are not suitable for industrial production, because reduction is required after chlorination, reaction conditions are severe, yield and production efficiency are poor. Hard to say.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記欠点
を排除して、工業的に簡便かつ経済的に有利にハロチオ
フェノール類を製造する方法を提供すべく鋭意検討し
た。DISCLOSURE OF THE INVENTION The present inventors have earnestly studied to provide a method for producing a halothiophenol compound which eliminates the above-mentioned drawbacks and is industrially convenient and economically advantageous.
【０００６】その結果、工業的に安価に供給されている
ハロベンゼン類を出発原料に用い、メチルチオ化、ハロ
ゲン化、引き続き加水分解と言う簡便な方法で、ハロチ
オフェノール類が高収率で得られることを見出し、本発
明を完成するに至った。As a result, halothiophenols can be obtained in high yield by a simple method such as methylthiolation, halogenation and subsequent hydrolysis using halobenzenes which are industrially supplied at low cost. This has led to the completion of the present invention.
【０００７】すなわち、本発明は、一般式（Ｉ）で表わ
されるハロベンゼン類を、メチルメルカプチドアルカリ
金属塩により、一般式（ＩＩ）で表わされるメチルチオ
ハロベンゼン類とした後、ハロゲン化剤により一般式
（ＩＩＩ）で表わされるハロメチルチオハロベンゼン類
となし、加水分解することを特徴とする、一般式（Ｉ
Ｖ）で表わされるハロチオフェノール類の製造方法であ
る。That is, according to the present invention, a halobenzene represented by the general formula (I) is converted to a methylthiohalobenzene represented by the general formula (II) with an alkali metal salt of methyl mercaptide and then a halogenating agent is used. A halomethylthiohalobenzene represented by the formula (III), which is characterized by being hydrolyzed.
V) is a method for producing halothiophenols.
【化２】 Embedded image
【０００８】[0008]
【発明の実施の形態】以下、本願発明を順次、具体的に
説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described in order.
【０００９】一般式（Ｉ）で表わされるハロベンゼン類
に対するメチルメルカプチドアルカリ金属塩による求核
置換反応により、一般式（ＩＩ）で表わされるメチルチ
オハロベンゼン類が得られる。ここに、Ｘ１、Ｘ２、Ｘ
３で表わされるハロゲン原子は、Ｃｌ、Ｂｒ、Ｉを意味
し、Ｃｌ、Ｂｒである場合に、良好な結果が得られる。The nucleophilic substitution reaction of the halobenzenes represented by the general formula (I) with an alkali metal salt of methyl mercaptide gives the methylthiohalobenzenes represented by the general formula (II). Where X 1 , X 2 , X
The halogen atom represented by 3 means Cl, Br, I, and when Cl or Br, good results are obtained.
【００１０】一般式（Ｉ）で表わされる化合物として
は、具体的には、１，２−ジクロロベンゼン、１，３−
ジクロロベンゼン、１，４−ジクロロベンゼン、１，
２，３−トリクロロベンゼン、１，２，４−トリクロロ
ベンゼン、１，３，５−トリクロロベンゼン、１，２−
ジブロモベンゼン、１，３−ジブロモベンゼン、１，４
−ジブロモベンゼン、１，２，３−トリブロモベンゼ
ン、１，２，４−トリブロモベンゼン、１，３，５−ト
リブロモベンゼン等が挙げられる。Specific examples of the compound represented by the general formula (I) include 1,2-dichlorobenzene and 1,3-dichlorobenzene.
Dichlorobenzene, 1,4-dichlorobenzene, 1,
2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene, 1,2-
Dibromobenzene, 1,3-dibromobenzene, 1,4
-Dibromobenzene, 1,2,3-tribromobenzene, 1,2,4-tribromobenzene, 1,3,5-tribromobenzene and the like.
【００１１】反応に用いるメチルメルカプチドアルカリ
金属塩としては、ナトリウム塩、カリウム塩等を使用す
ることができるが、経済的見地からは、ナトリウム塩水
溶液が好ましく用いられる。As the methyl mercaptide alkali metal salt used in the reaction, sodium salt, potassium salt and the like can be used. From the economical point of view, an aqueous sodium salt solution is preferably used.
【００１２】メチルメルカプチドアルカリ金属塩の使用
量は、一般式（Ｉ）で表わされるハロベンゼン類に対し
て、通常０．１〜３倍モル、好ましくは０．２〜２倍モ
ルである。反応温度は、用いるハロベンゼン類により異
なり一概には言えないが、通常７０〜２００℃、好まし
くは１００〜１５０℃である。The amount of the methyl mercaptide alkali metal salt used is usually 0.1 to 3 times, preferably 0.2 to 2 times the mol of the halobenzenes represented by the general formula (I). The reaction temperature varies depending on the halobenzenes used and cannot be generally specified, but is usually 70 to 200 ° C, preferably 100 to 150 ° C.
【００１３】反応は、ハロベンゼン類とメチルメルカプ
チドアルカリ金属塩を混合して撹拌するだけでも進行す
るが、界面活性剤の存在下で行なうと、反応はさらに円
滑に進行する。界面活性剤としては、例えば、アルキル
硫酸塩、アルキルスルホン酸塩等の陰イオン界面活性
剤、高級アミンハロゲン酸塩、ハロゲン化アルキルピリ
ジニウム、４級アンモニウム塩等の陽イオン界面活性
剤、ポリエチレングリコール、ポリエチレングリコール
アルキルエーテル等の非イオン界面活性剤、アミノ酸等
の両性界面活性剤等が挙げられるが、中でもポリエチレ
ングリコール、４級アンモニウム塩が経済的見地から好
ましく用いられる。界面活性剤を用いる場合の使用量
は、ハロベンゼン類に対して、通常０．００１〜５倍重
量、好ましくは０．００５〜２倍重量の範囲である。界
面活性剤の使用量が、０．００１倍重量未満の場合に
は、効果が充分あらわれず、一方、５倍重量を超えて用
いても、それに見合う効果が得られず経済的に不利であ
る。The reaction proceeds only by mixing the halobenzenes and the methyl mercaptide alkali metal salt and stirring, but when the reaction is carried out in the presence of a surfactant, the reaction proceeds more smoothly. As the surfactant, for example, anionic surfactants such as alkyl sulfates and alkyl sulfonates, higher amine halides, cationic surfactants such as alkylpyridinium halides and quaternary ammonium salts, polyethylene glycol, Examples include nonionic surfactants such as polyethylene glycol alkyl ethers, and amphoteric surfactants such as amino acids. Among them, polyethylene glycol and quaternary ammonium salts are preferably used from an economic viewpoint. When a surfactant is used, the amount used is usually in the range of 0.001 to 5 times by weight, preferably 0.005 to 2 times the weight of the halobenzenes. When the amount of the surfactant used is less than 0.001 times by weight, the effect is not sufficiently exhibited, while even when it is used in excess of 5 times by weight, an effect commensurate with it is not obtained and it is economically disadvantageous. .
【００１４】さらに、メチルメルカプチドアルカリ金属
塩の水溶液を使用する場合、系内から水を除きながら行
なうと、さらに反応は円滑に進行する。反応時間は、用
いるハロベンゼン類により異なり一概には言えないが、
通常１〜２０時間、好ましくは３〜１０時間の範囲であ
る。Furthermore, when an aqueous solution of an alkali metal salt of methyl mercaptide is used, the reaction proceeds more smoothly if it is carried out while removing water from the system. The reaction time varies depending on the halobenzenes used and cannot be generally stated,
It is usually in the range of 1 to 20 hours, preferably 3 to 10 hours.
【００１５】溶媒は、特に限定されるものではなく、無
溶媒またはハロベンゼン類自身を溶媒として好んで用い
るが、例えば、ヘキサン、シクロヘキサン、ヘプタン等
の炭化水素類、ジクロロエタン、トリクロロエタン等の
ハロゲン化炭化水素類、ベンゼン、トルエン、キシレ
ン、クロロベンゼン等の芳香族炭化水素類を用いること
ができる。溶媒を用いる場合、その使用量は、特に限定
されるものではないが、通常、一般式（Ｉ）で表わされ
るハロベンゼン類に対して、０．１〜１０倍重量であ
る。The solvent is not particularly limited, and solvent-free or halobenzenes themselves are preferably used as the solvent. For example, hydrocarbons such as hexane, cyclohexane and heptane, halogenated hydrocarbons such as dichloroethane and trichloroethane. And aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene can be used. When a solvent is used, the amount used is not particularly limited, but is usually 0.1 to 10 times the weight of the halobenzenes represented by the general formula (I).
【００１６】このようにして得た、一般式（ＩＩ）で表
わされるメチルチオハロベンゼン類は、常法の蒸留など
により単離可能であるが、単離することなく、塩を取り
除いたのみの反応液を次のハロゲン化工程に用いること
も可能である。The methylthiohalobenzenes represented by the general formula (II) thus obtained can be isolated by a conventional method such as distillation, but the reaction is carried out by removing the salt without isolation. It is also possible to use the liquid for the next halogenation step.
【００１７】ハロゲン化工程に用いるハロゲン化剤とし
ては、塩素、塩化スルフリル、臭素、ヨウ素が挙げられ
る。塩素、臭素を用いた場合に、良好な結果が得られ
る。Examples of the halogenating agent used in the halogenation step include chlorine, sulfuryl chloride, bromine and iodine. Good results are obtained when chlorine or bromine is used.
【００１８】一般式（ＩＩＩ）で表わされるハロメチル
チオハロベンゼン類においては、ｎが１、２または３で
あるが、ｎが２、３またはこれらの混合物を用いると、
次工程の加水分解を円滑に進行させることができる。In the halomethylthiohalobenzenes represented by the general formula (III), n is 1, 2 or 3, but when n is 2, 3 or a mixture thereof,
The hydrolysis in the next step can proceed smoothly.
【００１９】したがって、ハロゲン化剤の使用量は、一
般式（ＩＩ）で表わされるメチルチオハロベンゼン類に
対して１〜１０倍モル、好ましくは２〜３倍モルであ
る。Therefore, the amount of the halogenating agent used is 1 to 10 times mol, preferably 2 to 3 times mol, of the methylthiohalobenzenes represented by the general formula (II).
【００２０】溶媒は、特に限定されるものではなく、無
溶媒反応も可能であるが、例えば、ヘキサン、シクロヘ
キサン、ヘプタン等の炭化水素類、ジクロロエタン、ジ
クロロメタン、クロロホルム等のハロゲン化炭化水素
類、ベンゼン、トルエン、キシレン、クロロベンゼン、
ジクロロベンゼン、トリクロロベンゼン等の芳香族炭化
水素類を用いることができる。溶媒を用いる場合、その
使用量は、特に限定されるものではないが、通常、一般
式（ＩＩ）で表わされるメチルチオハロベンゼン類に対
して、０．１〜１０倍重量である。The solvent is not particularly limited, and a solventless reaction is also possible. For example, hydrocarbons such as hexane, cyclohexane and heptane, halogenated hydrocarbons such as dichloroethane, dichloromethane and chloroform, and benzene. , Toluene, xylene, chlorobenzene,
Aromatic hydrocarbons such as dichlorobenzene and trichlorobenzene can be used. When a solvent is used, the amount used is not particularly limited, but is usually 0.1 to 10 times the weight of the methylthiohalobenzenes represented by the general formula (II).
【００２１】ハロゲン化の反応温度は、通常、約０〜１
２０℃、好ましくは約２０〜５０℃の範囲である。反応
温度が低すぎると反応速度が遅く、逆に高すぎると副反
応が起こり、収率低下の原因となり好ましくない。反応
時間は通常０．５〜２０時間の範囲である。The reaction temperature for halogenation is usually about 0 to 1.
It is in the range of 20 ° C, preferably about 20-50 ° C. If the reaction temperature is too low, the reaction rate will be slow, while if it is too high, side reactions will occur and this will cause a decrease in yield, which is not preferable. The reaction time is usually in the range of 0.5 to 20 hours.
【００２２】生成した一般式（ＩＩＩ）で表わされるハ
ロメチルチオハロベンゼン類も、常法の蒸留、晶析によ
り単離することができるが、単離することなく、ハロゲ
ン化の反応液のまま、次の加水分解反応に用いることも
可能である。The produced halomethylthiohalobenzenes represented by the general formula (III) can also be isolated by a conventional distillation or crystallization method. It can also be used in the next hydrolysis reaction.
【００２３】このようにして得た、一般式（ＩＩＩ）で
表わされるハロメチルチオハロベンゼン類を加水分解す
ることにより、一般式（ＩＶ）で表わされるハロチオフ
ェノール類が得られる。By hydrolyzing the halomethylthiohalobenzenes represented by the general formula (III) thus obtained, the halothiophenols represented by the general formula (IV) can be obtained.
【００２４】加水分解は、単に水を加えて加熱すること
によっても進行するが、酸の存在下に行なうと、反応は
円滑に進行する。酸としては、特に限定されるものでは
ないが、塩酸、硫酸、硝酸、リン酸等の鉱酸が経済的見
地から用いられる。塩酸、硫酸が特に好ましい。酸の使
用量は、用いる酸種により一概に言えないが、通常、一
般式（ＩＩＩ）で表わされるハロメチルチオハロベンゼ
ン類に対して０．０１〜１倍重量で充分である。Hydrolysis proceeds by simply adding water and heating, but when carried out in the presence of an acid, the reaction proceeds smoothly. The acid is not particularly limited, but mineral acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid are used from the economical point of view. Hydrochloric acid and sulfuric acid are particularly preferred. The amount of the acid to be used cannot be generally determined depending on the type of the acid used, but is usually 0.01 to 1 times the weight of the halomethylthiohalobenzenes represented by the general formula (III).
【００２５】また、加水分解にアルコールを添加するこ
とも有効である。特に低級アルコールを添加すると、加
水分解反応がより円滑に進行する。低級アルコールとし
ては、炭素数が１〜４の脂肪族アルコール、例えば、メ
タノール、エタノール、イソプロパノール、ｎ−プロパ
ノール、イソブタノール、ｎ−ブタノール、ｓｅｃ−ブ
タノール等を挙げることができる。中でもメタノールが
経済的見地から好ましく用いられる。アルコールの使用
量は、特に限定されるものではないが、通常、一般式
（ＩＩＩ）で表わされるハロメチルチオハロベンゼン類
に対して０．５〜１０倍重量である。It is also effective to add alcohol to the hydrolysis. Especially, when a lower alcohol is added, the hydrolysis reaction proceeds more smoothly. Examples of the lower alcohol include aliphatic alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, isopropanol, n-propanol, isobutanol, n-butanol and sec-butanol. Of these, methanol is preferably used from the economical point of view. The amount of alcohol used is not particularly limited, but is usually 0.5 to 10 times the weight of the halomethylthiohalobenzenes represented by the general formula (III).
【００２６】溶媒は、特に限定されるものではなく、無
溶媒反応も可能であるが、例えば、ヘキサン、シクロヘ
キサン、ヘプタン等の炭化水素類、ジクロロエタン、ジ
クロロメタン、クロロホルム等のハロゲン化炭化水素
類、ベンゼン、トルエン、キシレン、クロロベンゼン、
ジクロロベンゼン、トリクロロベンゼン等の芳香族炭化
水素類を用いることができる。溶媒を用いる場合、その
使用量は、特に限定されるものではないが、通常、一般
式（ＩＩＩ）で表わされるハロメチルチオハロベンゼン
類に対して、０．１〜１０倍重量である。The solvent is not particularly limited, and a solventless reaction is also possible. For example, hydrocarbons such as hexane, cyclohexane and heptane, halogenated hydrocarbons such as dichloroethane, dichloromethane and chloroform, benzene. , Toluene, xylene, chlorobenzene,
Aromatic hydrocarbons such as dichlorobenzene and trichlorobenzene can be used. When a solvent is used, the amount used is not particularly limited, but is usually 0.1 to 10 times the weight of the halomethylthiohalobenzenes represented by the general formula (III).
【００２７】反応温度は、通常、約３０〜２００℃、好
ましくは約６０〜１１０℃の範囲である。反応温度が低
すぎると反応速度が遅く、逆に高すぎると副反応が起こ
り、収率低下の原因となり好ましくない。反応時間は、
通常、約１〜１０時間の範囲である。The reaction temperature is usually in the range of about 30 to 200 ° C, preferably about 60 to 110 ° C. If the reaction temperature is too low, the reaction rate will be slow, while if it is too high, side reactions will occur and this will cause a decrease in yield, which is not preferable. The reaction time is
Usually, it is in the range of about 1 to 10 hours.
【００２８】このようにして、目的の一般式（ＩＶ）で
表わされるハロチオフェノール類が得られる。生成した
ハロチオフェノール類は、常法の抽出や晶析、蒸留等に
より単離することができる。Thus, the desired halothiophenol represented by the general formula (IV) is obtained. The produced halothiophenols can be isolated by a conventional method such as extraction, crystallization and distillation.
【００２９】本発明で得られるハロチオフェノール類と
しては、具体的には、２−クロロチオフェノール、３−
クロロチオフェノール、４−クロロチオフェノール、
２，５−ジクロロチオフェノール、３，５−ジクロロチ
オフェノール、２，６−ジクロロチオフェノール、２−
ブロモチオフェノール、３−ブロモチオフェノール、４
−ブロモチオフェノール、２，５−ジブロモチオフェノ
ール、３，５−ジブロモチオフェノール、２，６−ジブ
ロモチオフェノール等が挙げられる。Specific examples of the halothiophenols obtained in the present invention include 2-chlorothiophenol and 3-chlorothiophenol.
Chlorothiophenol, 4-chlorothiophenol,
2,5-dichlorothiophenol, 3,5-dichlorothiophenol, 2,6-dichlorothiophenol, 2-
Bromothiophenol, 3-bromothiophenol, 4
-Bromothiophenol, 2,5-dibromothiophenol, 3,5-dibromothiophenol, 2,6-dibromothiophenol and the like.
【００３０】[0030]
【実施例】以下に、実施例により本願発明をさらに詳し
く説明するが、本願発明はこれらの実施例に何等限定さ
れるものではない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００３１】実施例１ 撹拌機、温度計、滴下ロート、リービッヒ冷却器および
受器を備え付けた３００ｍｌ四つ口フラスコに、１，２
−ジクロロベンゼン１４７ｇ（１．００モル）、ポリエ
チレングリコール（平均分子量３００）２７ｇ（０．０
９モル）を仕込み、撹拌下約１３５℃で３０％メチルメ
ルカプチドナトリウム塩水溶液７０ｇ（０．３０モル）
を４時間かけて滴下した。この際、水４８ｇおよび１，
２−ジクロロベンゼン３７ｇが系外に留去された。さら
に１時間撹拌し、反応を終了した。水を添加して分液
し、粗２−メチルチオクロロベンゼンの１，２−ジクロ
ロベンゼン溶液を得た。この溶液に塩素ガス４２．６ｇ
（０．６モル）を約４０℃で２時間かけて吹き込み、さ
らに１時間撹拌した。窒素を吹き込むことにより溶存塩
素を脱気した後、メタノール６０ｇを加え、還流下で４
時間撹拌し、加水分解反応を終了した。水を加えて分液
した後、有機層からアルカリ水溶液で逆抽出し、酸性水
で中和し、オイル層として２−クロロチオフェノール３
０．５ｇを得た。メチルメルカプチドに対する収率は７
０．４％であった。 Example 1 A 300 ml four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, a Liebig condenser and a receiver was charged with 1, 2
-Dichlorobenzene 147 g (1.00 mol), polyethylene glycol (average molecular weight 300) 27 g (0.0
9 mol) and 70 g (0.30 mol) of 30% methylmercaptide sodium salt aqueous solution at about 135 ° C. with stirring.
Was added dropwise over 4 hours. At this time, 48 g of water and 1,
37 g of 2-dichlorobenzene was distilled out of the system. The mixture was further stirred for 1 hour to complete the reaction. Water was added and the layers were separated to obtain a crude solution of 2-methylthiochlorobenzene in 1,2-dichlorobenzene. 42.6 g of chlorine gas in this solution
(0.6 mol) was blown in at about 40 ° C. for 2 hours, and the mixture was further stirred for 1 hour. After degassing dissolved chlorine by blowing nitrogen, 60 g of methanol was added, and the mixture was refluxed under 4
After stirring for an hour, the hydrolysis reaction was completed. After water was added for liquid separation, the organic layer was back-extracted with an aqueous alkaline solution and neutralized with acidic water to give 2-chlorothiophenol 3 as an oil layer.
0.5 g was obtained. The yield based on methyl mercaptide is 7
0.4%.
【００３２】実施例２〜７ 原料を表１に示したハロベンゼン類に変える以外は実施
例１と同様の操作により、相当するハロチオフェノール
類を得た。 Examples 2 to 7 Corresponding halothiophenols were obtained by the same procedure as in Example 1 except that the raw materials were changed to the halobenzenes shown in Table 1.
【００３３】[0033]
【表１】 実施例８ 反応に添加するポリエチレングリコールの代わりにテト
ラ−ｎ−ブチルアンモニウムブロミド３．２ｇ（０．０
１モル）を用いた以外は実施例１と同様の操作により粗
２−メチルチオクロロベンゼンの１，２−ジクロロベン
ゼン溶液を得た。この溶液に塩素ガス４２．６ｇ（０．
６モル）を約４０℃で２時間かけて吹き込み、さらに１
時間撹拌した。溶存塩素を脱気した後、１０％塩酸水１
００ｇを加え、還流下で５時間撹拌し、加水分解反応を
終了した。分液後、有機層からアルカリ水溶液で逆抽出
し、酸性水で中和し、２−クロロチオフェノール２９．
８ｇを得た。メチルメルカプチドに対する収率は６８．
７％であった。[Table 1] Example 8 3.2 g (0.0) tetra-n-butylammonium bromide instead of polyethylene glycol added to the reaction
A 1,2-dichlorobenzene solution of crude 2-methylthiochlorobenzene was obtained by the same operation as in Example 1 except that 1 mol) was used. 42.6 g of chlorine gas (0.
6 mol) at about 40 ° C. for 2 hours and then 1 more
Stirred for hours. After degassing dissolved chlorine, 10% hydrochloric acid water 1
00 g was added, and the mixture was stirred under reflux for 5 hours to complete the hydrolysis reaction. After liquid separation, the organic layer was back-extracted with an alkaline aqueous solution and neutralized with acidic water to give 2-chlorothiophenol 29.
8 g was obtained. The yield based on methyl mercaptide is 68.
7%.
【００３４】実施例９ 撹拌機、温度計、滴下ロート、リービッヒ冷却器および
受器を備え付けた２００ｍｌ四つ口フラスコに、１，２
−ジブロモベンゼン４７．２ｇ（０．２００モル）、キ
シレン１００ｇ、ポリエチレングリコール（平均分子量
３００）６０ｇ（０．２０モル）を仕込み、撹拌下約１
３５℃で３０％メチルメルカプチドナトリウム塩水溶液
７４．７ｇ（０．３２０モル）を３時間かけて滴下し
た。この際、系外に留出したキシレンおよび１，２−ジ
ブロモベンゼンは適時系内に戻した。さらに２時間撹拌
し、反応を終了した。水を添加して分液し、粗２−メチ
ルチオブロモベンゼンを得た。減圧蒸留を行ない、２−
メチルチオブロモベンゼン２５．５ｇ（０．１２６モ
ル）を得た。このものにクロロベンゼン１００ｇを加
え、塩素ガス２２．４ｇ（０．３１５モル）を約４０℃
で２時間かけて吹き込み、さらに１時間撹拌した。溶存
塩素を脱気した後、１０％硫酸水５０ｇを加え、還流下
で６時間撹拌し、加水分解反応を終了した。分液後、有
機層からアルカリ水溶液で逆抽出し、さらに酸性水で中
和し、減圧蒸留して２−ブロモチオフェノール２２．３
ｇを得た。１，２−ジブロモベンゼンに対する収率は５
９．０％であった。 Example 9 In a 200 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel, Liebig condenser and receiver, 1, 2
-Prepare 47.2 g (0.200 mol) of dibromobenzene, 100 g of xylene, 60 g (0.20 mol) of polyethylene glycol (average molecular weight 300), and stir about 1 with stirring.
At 35 ° C., 74.7 g (0.320 mol) of 30% methylmercaptide sodium salt aqueous solution was added dropwise over 3 hours. At this time, xylene and 1,2-dibromobenzene distilled out of the system were returned to the system in a timely manner. The reaction was completed by stirring for another 2 hours. Water was added and the layers were separated to obtain crude 2-methylthiobromobenzene. Perform vacuum distillation, 2-
25.5 g (0.126 mol) of methylthiobromobenzene was obtained. 100g of chlorobenzene was added to this, and 22.4g (0.315mol) of chlorine gas was added at about 40 ° C.
It was blown in over 2 hours and stirred for 1 hour. After degassing the dissolved chlorine, 50 g of 10% sulfuric acid water was added, and the mixture was stirred under reflux for 6 hours to complete the hydrolysis reaction. After liquid separation, the organic layer was back-extracted with an aqueous alkaline solution, further neutralized with acidic water, and distilled under reduced pressure to give 2-bromothiophenol 22.3.
g was obtained. The yield based on 1,2-dibromobenzene is 5
It was 9.0%.
【００３５】[0035]
【発明の効果】本発明は、医薬、農薬、機能性材料など
の種々の用途に用いられるハロチオフェノール類の新規
な製造方法を提供するものである。本発明の方法を採用
すると、工業的に安価なハロベンゼン類を、メチルチオ
化、ハロゲン化、加水分解することにより、簡便なプロ
セスで目的物が得られる。したがって、経済的、工業的
価値が極めて大きい。INDUSTRIAL APPLICABILITY The present invention provides a novel method for producing halothiophenols used in various applications such as medicines, agricultural chemicals and functional materials. When the method of the present invention is employed, industrially inexpensive halobenzenes can be methylthiolated, halogenated, or hydrolyzed to obtain the desired product by a simple process. Therefore, it has great economic and industrial value.
Claims (11)
類を、メチルメルカプチドアルカリ金属塩により一般式
（ＩＩ）で表わされるメチルチオハロベンゼン類とな
し、さらにハロゲン化剤により一般式（ＩＩＩ）で表わ
されるハロメチルチオハロベンゼン類とした後、加水分
解することを特徴とする、一般式（ＩＶ）で表わされる
ハロチオフェノール類を製造する方法。 【化１】 1. A halobenzene represented by the general formula (I) is converted to a methylthiohalobenzene represented by the general formula (II) by a methyl mercaptide alkali metal salt, and further a halogenating agent is added by the general formula (III). A process for producing a halothiophenol represented by the general formula (IV), which comprises hydrolyzing the halomethylthiohalobenzene represented by the formula. Embedded image
るメチルチオ化を、界面活性剤の存在下に行なうことを
特徴とする請求項１に記載の方法。2. The method according to claim 1, wherein the methyl thiolation with a methyl mercaptide alkali metal salt is carried out in the presence of a surfactant.
ある請求項２に記載の方法。3. The method according to claim 2, wherein the surfactant is polyethylene glycol.
請求項２に記載の方法。4. The method according to claim 2, wherein the surfactant is a quaternary ammonium salt.
載の方法。5. The method according to claim 1, wherein the halogenating agent is chlorine.
る請求項１〜５のいずれか１項に記載の方法。6. The method according to claim 1, wherein n in the general formula (III) is 2 or 3.
する請求項１〜６のいずれか１項に記載の方法。7. The method according to claim 1, wherein the hydrolysis is carried out in the presence of an acid.
ことを特徴とする請求項１〜６のいずれか１項に記載の
方法。8. The method according to claim 1, wherein the hydrolysis is carried out in the presence of a lower alcohol.
フェノールまたは４−クロロチオフェノールである請求
項１〜８のいずれか１項に記載の方法。9. The method according to claim 1, wherein the halothiophenol is 2-chlorothiophenol or 4-chlorothiophenol.
オフェノールまたは４−ブロモチオフェノールである請
求項１〜８のいずれか１項に記載の方法。10. The method according to claim 1, wherein the halothiophenols are 2-bromothiophenol or 4-bromothiophenol.
ロロチオフェノールまたは３，５−ジクロロチオフェノ
ールである請求項１〜８のいずれか１項に記載の方法。11. The method according to claim 1, wherein the halothiophenols are 2,5-dichlorothiophenol or 3,5-dichlorothiophenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19637795A JP3743865B2 (en) | 1995-08-01 | 1995-08-01 | Method for producing halothiophenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19637795A JP3743865B2 (en) | 1995-08-01 | 1995-08-01 | Method for producing halothiophenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0940636A true JPH0940636A (en) | 1997-02-10 |
| JP3743865B2 JP3743865B2 (en) | 2006-02-08 |
Family
ID=16356861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19637795A Expired - Fee Related JP3743865B2 (en) | 1995-08-01 | 1995-08-01 | Method for producing halothiophenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3743865B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000014060A1 (en) * | 1998-09-09 | 2000-03-16 | Nippon Finechemical Co., Ltd. | Process for the preparation of aromatic sulfur compounds |
| WO2001081299A1 (en) * | 2000-04-26 | 2001-11-01 | Sumitomo Seika Chemicals Co., Ltd. | Process for producing bishalophenyl disulfide |
| JP2011213711A (en) * | 2010-03-19 | 2011-10-27 | Sumitomo Seika Chem Co Ltd | Method for producing dimercaptodiaryl sulfone compound |
| US9040724B2 (en) | 2010-03-18 | 2015-05-26 | Sumitomo Seika Chemicals Co., Ltd. | Diaryl sulfone compound, and manufacturing method for same |
| US9365507B2 (en) | 2010-03-18 | 2016-06-14 | Sumitomo Seika Chemicals Co., Ltd. | Diaryl sulfone compound, and manufacturing method for same |
-
1995
- 1995-08-01 JP JP19637795A patent/JP3743865B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000014060A1 (en) * | 1998-09-09 | 2000-03-16 | Nippon Finechemical Co., Ltd. | Process for the preparation of aromatic sulfur compounds |
| US6376716B1 (en) | 1998-09-09 | 2002-04-23 | Nippon Finechemical Co., Ltd. | Process for the preparation of aromatic sulfur compounds |
| WO2001081299A1 (en) * | 2000-04-26 | 2001-11-01 | Sumitomo Seika Chemicals Co., Ltd. | Process for producing bishalophenyl disulfide |
| US9040724B2 (en) | 2010-03-18 | 2015-05-26 | Sumitomo Seika Chemicals Co., Ltd. | Diaryl sulfone compound, and manufacturing method for same |
| US9365507B2 (en) | 2010-03-18 | 2016-06-14 | Sumitomo Seika Chemicals Co., Ltd. | Diaryl sulfone compound, and manufacturing method for same |
| JP2011213711A (en) * | 2010-03-19 | 2011-10-27 | Sumitomo Seika Chem Co Ltd | Method for producing dimercaptodiaryl sulfone compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3743865B2 (en) | 2006-02-08 |
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