JPS6267063A - Production of 2-alkoxybenzenethiol based compound - Google Patents
Production of 2-alkoxybenzenethiol based compoundInfo
- Publication number
- JPS6267063A JPS6267063A JP60207677A JP20767785A JPS6267063A JP S6267063 A JPS6267063 A JP S6267063A JP 60207677 A JP60207677 A JP 60207677A JP 20767785 A JP20767785 A JP 20767785A JP S6267063 A JPS6267063 A JP S6267063A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- general formula
- expressed
- alkyl group
- 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.)
- Pending
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005749 Copper compound Substances 0.000 claims abstract description 7
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 10
- -1 alkoxybenzene compound Chemical class 0.000 abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 7
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 150000001555 benzenes Chemical class 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical class SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 150000005224 alkoxybenzenes Chemical class 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- HAEQAUJYNHQVHV-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-phenylbenzamide Chemical compound NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2=CC=CC=C2)C=CC=1 HAEQAUJYNHQVHV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910017610 Cu(NO3) Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Chemical group CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- OVFCVRIJCCDFNQ-UHFFFAOYSA-N carbonic acid;copper Chemical compound [Cu].OC(O)=O OVFCVRIJCCDFNQ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229910000009 copper(II) carbonate Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 239000011646 cupric carbonate Substances 0.000 description 1
- 235000019854 cupric carbonate Nutrition 0.000 description 1
- 235000019855 cupric citrate Nutrition 0.000 description 1
- 239000011641 cupric citrate Substances 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001802 myricyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は２−アルコキシベンゼンチオール系化合物の製
造方法に関し、更に詳しくはアルコキシベンゼンを出発
原料としてポリスルフィドを経由して高収率に２−アル
コキシベンゼンチオール系化合物を製造する方法罠関、
する。Detailed Description of the Invention [Technical Field] The present invention relates to a method for producing a 2-alkoxybenzenethiol compound, and more specifically, a process for producing a 2-alkoxybenzenethiol compound in high yield using alkoxybenzene as a starting material via polysulfide. How to make a compound Traseki,
do.
２−フル：Ｉキシベンゼンチオール系化合物ハ写真用カ
プラーのパラスト成分、活性点置換成分などとして有用
な化合物である。この系の化合物については、例えば特
開昭５７−３５８５８号にベンゼン誘導体をクロルスル
ホン酸でスルホクロリドにした後、金属亜鉛あるいは金
属錫と酸で還元することによるベンゼンチオール系化合
物の製造方法が開示されている。2-Flu: I-xybenzenethiol compound C is a compound useful as a pallast component of a photographic coupler, an active point substitution component, and the like. Regarding this type of compound, for example, JP-A-57-35858 discloses a method for producing a benzenethiol type compound by converting a benzene derivative into a sulfochloride with chlorosulfonic acid and then reducing it with metal zinc or metal tin and an acid. has been done.
ＡｒＨｙ距４ＡｒＳＯ，（Ｊ ” ”” ” ” Ａｒ
５Ｈしかし上記特許の方法では、中間体のスルホクロリ
ドを還元する際に加水分解が避けられずスルホン酸系化
合物を副生ずる。この結果、目的とするベンゼンチオー
ル系化合物の分離・精製が困難となり、高純度のものが
得られず、かつ低収率となり製造コストの高いものとな
ってしまう。ArHy distance 4ArSO, (J ” ” ” ” Ar
5H However, in the method of the above-mentioned patent, hydrolysis is unavoidable when reducing the intermediate sulfochloride, and a sulfonic acid compound is produced as a by-product. As a result, it becomes difficult to separate and purify the target benzenethiol-based compound, making it impossible to obtain a highly pure compound, resulting in a low yield and high manufacturing cost.
従って、より工業化に適した２−アルコキシベンゼンチ
オール系化合物の製造方法、すなわち高純度かつ高収率
で２−アルコキシベンゼンチオール系化合物の合成法の
開発が要望されている。Therefore, there is a need to develop a method for producing 2-alkoxybenzenethiol compounds that is more suitable for industrialization, that is, a method for synthesizing 2-alkoxybenzenethiol compounds with high purity and high yield.
本発明の目的は上記問題点の解決にある。すなわち、精
製が容易で純度の高い２−アルコキシベンゼンチオール
系化合物な高収率（低コスト）で得る製造方法を提供す
ることにある。An object of the present invention is to solve the above problems. That is, it is an object of the present invention to provide a method for producing a 2-alkoxybenzenethiol compound that is easy to purify and has high purity at a high yield (low cost).
前記本発明の目的は、下記一般式ＣＩ）で示される化合
物と塩化硫黄（Ｓ２Ｃｌ２）を１価もしくは２価の銅化
合物の存在下に反応せしめて下記一般式〔ＩＩ〕で示さ
れる化合物を得、更にこれを還元することによる下記一
般式（ＩＩＩ）で示される２−アルコキシベンゼンチオ
ール系化合物の製造方法により達成された。The object of the present invention is to react a compound represented by the following general formula CI) with sulfur chloride (S2Cl2) in the presence of a monovalent or divalent copper compound to obtain a compound represented by the following general formula [II]. This was achieved by a method for producing a 2-alkoxybenzenethiol compound represented by the following general formula (III) by further reducing this.
一般式ＣＩ） 一般式ＣＩＩ）一般式（ＩＩ
Ｉ）
式中、Ｒ３はアルキル基、Ｒ２は水素またはアルキル基
を表し、Ｒ８はアルキル基またはアルコキシ基を表す。General formula CI) General formula CII) General formula (II)
I) In the formula, R3 represents an alkyl group, R2 represents hydrogen or an alkyl group, and R8 represents an alkyl group or an alkoxy group.
Ｘは２以上の整数を表す。X represents an integer of 2 or more.
本発明において出発原料として用いられる一般式ＣＩ）
で示されるアルコキシベンゼン化合物は、ジャーナル・
オブ・ザ・アメリカン・ケミカル・ソサイアティ（Ｊ、
Ａｍ、 Ｃｈｅｍ、 ５ｏｃ）、 １９３９年、６１
巻。General formula CI) used as starting material in the present invention
The alkoxybenzene compound represented by
of the American Chemical Society (J.
Am, Chem, 5oc), 1939, 61
roll.
１４６３頁にコル力（Ｋｏｌｋａ）等により、また同誌
１９３５年、５７巻、７０９頁にソワ（Ｓｏｗａ）等に
より、またブルチ７−オプ・ザ・ケミ−（Ｂｕｌｌ、
Ｓｏｃ、 Ｃｈｉｍ、 ） 。Kolka et al. on page 1463, Sowa et al. on page 709, volume 57, 1935, and Bull,
Soc, Chim, ).
１８８３年、４０巻（２）、 １０６頁にピンセント（
Ｖｉｎｃｅｎｔ）により報告されている方法およびその
他の方法により得ることができる。Pinsent (1883, vol. 40 (2), p. 106)
Vincent) and other methods.
本発明は、また下記工程（１）および（２）で示すこと
ができる。The present invention can also be demonstrated by the following steps (1) and (2).
一般式ＣＩ）、（ＩＩ）および〔■〕においてＲ１はア
ルキル基を表すが、Ｒ３で表されるアルキル基として好
ましくは炭素原子数１〜３０の直鎖または分岐のアルキ
ル基、例えばメチル、エチル、イソプロピル。In general formulas CI), (II) and [■], R1 represents an alkyl group, and the alkyl group represented by R3 is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl , isopropyl.
ブチル、ｔ−ブチル、オクチル、ドデシル、エイコシル
、トリアコンチル等の基を挙げることができる。Ｒ７は
水素またはアルキル基を表すが、Ｒ７で表されるアルキ
ル基として好ましくは前記Ｒ，で述べたものと同じ基を
挙げることができる。Ｒ５はアルキル基またはアルコキ
シ基を表すが、Ｒ３で表されるアルキル基としても好ま
しくは前記Ｒ３と同じ基が挙げられる。Ｒ１で表される
アルコキシ基として好ましくは炭素原子数１〜３０の直
鎖または分岐のアルコキシ基、具体的にはメトキシ、エ
トキシ、プロポキシ、 ５ｅｃ−ブトキシ、オクトキ
シ、ドデソキシ、エイコツキシ、トリアコントキシ等の
基を挙げることができる。Mention may be made of groups such as butyl, t-butyl, octyl, dodecyl, eicosyl, triacontyl and the like. R7 represents hydrogen or an alkyl group, and the alkyl group represented by R7 is preferably the same group as described for R above. R5 represents an alkyl group or an alkoxy group, and the alkyl group represented by R3 is preferably the same group as R3 above. The alkoxy group represented by R1 is preferably a straight chain or branched alkoxy group having 1 to 30 carbon atoms, specifically methoxy, ethoxy, propoxy, 5ec-butoxy, octoxy, dodesoxy, eicotoxy, triacontoxy, etc. The following groups can be mentioned.
アルコキシベンゼンを塩化硫黄と反応させるに際しては
、ニートまたは溶媒に溶解させる。用いられる溶媒とし
ては、エーテル類、・・ロゲン化炭化水素類、ベンゼン
類、ニトリル類等を挙げることができる。この中で好ま
しいのは・・ロゲン化炭化水素類、ベンゼン類であり特
にノ・ロゲン化炭化水素類が好ましい。When reacting alkoxybenzene with sulfur chloride, it is dissolved neat or in a solvent. Examples of the solvent that can be used include ethers, logenated hydrocarbons, benzenes, and nitriles. Preferred among these are halogenated hydrocarbons and benzenes, with halogenated hydrocarbons being particularly preferred.
塩化硫黄（Ｓ、Ｃｌ２）はゴムの加硫剤として広く知ら
れており、溶融硫黄中に塩素ガスを通じて合成される。Sulfur chloride (S, Cl2) is widely known as a rubber vulcanizing agent, and is synthesized by passing chlorine gas into molten sulfur.
不純物として５Ｃ１２，５Ｃ１４を含むが蒸留により除
去できる。工程（１）において、塩化硫黄はアルコキシ
ベンゼン化合物１モル当す０．１〜２モルの範囲で用い
られ、好ましくは０３〜０．７モルである。It contains 5C12 and 5C14 as impurities, but they can be removed by distillation. In step (1), sulfur chloride is used in an amount of 0.1 to 2 mol, preferably 0.3 to 0.7 mol, per 1 mol of the alkoxybenzene compound.
１価もしくは２価の銅化合物は触媒として作用する。１
価もしくは２価の銅化合物としては、具体的には酸化第
−鋼（Ｃｕ２０）、酸化第二銅（ＣｕＯ）、塩化第一銅
（０１１Ｃ４？） 、塩化第二銅（Ｃｕ ＣＣ２）、臭
化第一銅（ＣｕＢｒ）、臭化第二銅（ＣｕＢｒ２）、沃
化第一銅（ＣｕＩ）、沃化第二銅（Ｃｕ Ｉ２）、水酸
化第二銅ＣＣｕ（ＯＨ）ｚ）、炭酸鋼（ＣｕＣＯ３）、
硫酸銅（ＣｕＳＯ４）、硝酸鋼（Ｃｕ（ＮＯ３）ｚ）、
シアン化第−銅（ＯｕＣＮ）、燐酸第二銅（Ｃｕ３（Ｐ
Ｏ４）２）、ギ酸銅（Ｃｕ （Ｉ−ＩＣＯＯ）２）、酢
酸第二銅（Ｏｕ（ＣＩ−１３ＣＯＯ）２）、 クエン酸
第二銅（ＯｕＣ６Ｈ６０７） 、オレイン酸’Ａ （Ｃ
ｕ（Ｃ１，１−ｉ３３ＣＯＯ）２〕、銅（Ｉｌｌアセチ
ルアセテ−） （Ｃｕ （ＣＨ３ＣＯＣＨＣＯＣＩｈｈ
）等を挙げることができる。これらの中で好ましいの
は塩化第二銅、水酸化第二銅である。A monovalent or divalent copper compound acts as a catalyst. 1
Examples of valent or divalent copper compounds include steel oxide (Cu20), cupric oxide (CuO), cuprous chloride (011C4?), cupric chloride (Cu CC2), and bromide. Cuprous (CuBr), cupric bromide (CuBr2), cuprous iodide (CuI), cupric iodide (Cu I2), cupric hydroxide (CCu(OH)z), carbonate steel ( CuCO3),
Copper sulfate (CuSO4), nitrate steel (Cu(NO3)z),
Cupric cyanide (OuCN), cupric phosphate (Cu3(P)
O4)2), copper formate (Cu (I-ICOO)2), cupric acetate (Ou(CI-13COO)2), cupric citrate (OuC6H607), oleic acid 'A (C
u(C1,1-i33COO)2], copper (Ill acetylacetate) (Cu (CH3COCHCOCIhh
) etc. Among these, preferred are cupric chloride and cupric hydroxide.
１価もしくは２価の銅化合物は、アルコキシベンゼン１
モル当り０．００１〜１モルで用いられるのが好ましく
、より好ましくは０．００５〜０．１モルの範囲である
。The monovalent or divalent copper compound is alkoxybenzene 1
It is preferably used in an amount of 0.001 to 1 mol, more preferably in a range of 0.005 to 0.1 mol.
反応温度は０〜１５０”Ｃの範囲が好ましく、特に４０
〜８０゛Ｃが好ましい。The reaction temperature is preferably in the range of 0 to 150"C, especially 40"C.
~80°C is preferred.
次に本発明において一般式（ＩＩ）で示される化合物の
代表的具体例を以下に示すが、本発明はこれｎ−１ｎ−
２
１１−３ｎ−４
ＩＩ −５ＴＩ −６
１１−７ｍ−８
ＩＩ −９ＩＩ −１０
■−１１
工程（２）における一般式（Ｉｆ）で示されるスルフィ
ド化合物の還元は通常用いられる方法、例えばベルギー
特許６３５６３４号に記載の方法で行うことができる。Next, typical specific examples of the compound represented by the general formula (II) in the present invention are shown below.
2 11-3n-4 II -5TI -6 11-7m-8 II -9II -10 ■-11 The reduction of the sulfide compound represented by the general formula (If) in step (2) can be carried out by a commonly used method, for example, as described in the Belgian patent. It can be carried out by the method described in No. 635634.
還元は亜鉛と酸（酢酸、塩酸、硫酸等）により行われる
。反応溶媒としてはベンゼン類が用いられるが、上記酸
自身が溶媒を兼ねてもよい。Reduction is carried out with zinc and an acid (acetic acid, hydrochloric acid, sulfuric acid, etc.). Although benzenes are used as the reaction solvent, the acid itself may also serve as a solvent.
用いられる亜鉛の量は、スルフィド化合物１部当り重量
比で０．０１〜１００部、好ましくは０１〜１０部であ
る。反応溶媒量はスルフィド化合物１部当り重量比で１
〜１０００部、好ましくは１〜ｌＯ部が用いられる。The amount of zinc used is from 0.01 to 100 parts by weight, preferably from 01 to 10 parts by weight per part of the sulfide compound. The amount of reaction solvent is 1 part by weight per part of the sulfide compound.
~1000 parts, preferably 1 to 10 parts are used.
本発明において一般式（Ｉｎ）で示される化合物の代表
的具体例を以下に示すが、本発明はこれらに限定されな
い。In the present invention, typical examples of the compound represented by the general formula (In) are shown below, but the present invention is not limited thereto.
ＩＩＩ −３Ｌｌｌ −４
ＩＩＩ −５１１Ｉ −６
ＩＩＩ −７ｌｌｌ−８
１１１−９ＩＩＩ −１０
１１Ｔ −１１
〔実施例〕
以下に本発明の具体的実施例を記載するが本発明はこれ
に限定されない。III-3Lll-4 III-511I-6 III-7lll-8 111-9III-10 11T-11 [Examples] Specific examples of the present invention will be described below, but the present invention is not limited thereto.
合成例−１（例示化合物［−７の合成）２４．４９の４
−ブトキシ−ｔ−オクチルベンゼンと０．３０９の塩化
第二銅を２５０ ｍｉ！のクロロホルムに加え、還流下
に４．５ｍＱの塩化硫黄を添加する。添加後、更に２時
間還流を続ける。反応物はクロロホルムを減圧留去した
後、カラムクロマトグラフィで分離精製する。２４！！
のカラメル状物質を得た。Synthesis Example-1 (Synthesis of Exemplary Compound [-7) 24.49-4
-butoxy-t-octylbenzene and 0.309 cupric chloride at 250 mi! of chloroform and 4.5 mQ of sulfur chloride under reflux. After the addition, continue to reflux for an additional 2 hours. After chloroform is distilled off under reduced pressure, the reaction product is separated and purified by column chromatography. 24! !
A caramel-like substance was obtained.
例示化合物ｎ−７であることがＮＭＲにより確認された
。It was confirmed by NMR to be Exemplified Compound n-7.
次に２４９の例示化合物ｎ−７を１ｏｏｍＱのトルエン
に溶解し、６．５ｇの亜鉛を加える。還流下に２４．５
ｍＱの濃塩酸を添加した後、３時間反応を続ける。反応
液を濾過し過剰の亜鉛を除き水洗する。Next, exemplified compound n-7 of 249 is dissolved in 1 oomQ of toluene, and 6.5 g of zinc is added. 24.5 under reflux
After adding mQ of concentrated hydrochloric acid, the reaction is continued for 3 hours. The reaction solution was filtered to remove excess zinc and washed with water.
トルエンを減圧留去しカラムクロマトグラフィで分離精
製し、２０ ｇ（７９，０％）のオイル状目的物２−プ
トキシー５−１−オクチルベンゼンチオールを得た。Toluene was distilled off under reduced pressure and the residue was separated and purified by column chromatography to obtain 20 g (79.0%) of the target product in the form of an oil, 2-ptoxy-5-1-octylbenzenethiol.
Ｃ＋ｓ Ｈ２ＯＯＳとしての元素分析値計算値（チ）
Ｃニア３．４７ Ｈ：１０．２０ Ｓ：１０．８
９実測値（％） Ｃニア３．１０ Ｈ：１０．５０
８：１０．４４比較合成例（例示化合物層−７の合成
）２４．４９の４−ブトキシ−１−オクチルベンゼンを
２５０ ｍｅのクロロホルム中で還流下に４．５ｍＱの
塩化硫黄を添加する。添加後、更に５時間還流を続ける
。反応物はクロロホルムを留去後カラムクロマトグラフ
ィで精製し８１Ｉのカラメル状物質を得た。これを３Ｑ
ｍＱのトルエンに溶解し、２．１．９の亜鉛を加える
。還流下に８．０ｍＱの濃塩酸を添加した後、３時間反
応を続ける。反応後は濾過、水洗後、トルエンを減圧留
去しカラムクロマトグラフィで分離精製し、７．０ｇ（
２６，６％）のオイル状目的物を得た。元素分析値、Ｆ
Ｄマススペクトル値より例示化合物１−７であることが
確認されたが、合成例−１に比べ収率は３以下に低下し
た。Calculated elemental analysis value as C+s H2OOS (chi)
C near 3.47 H: 10.20 S: 10.8
9 Actual value (%) C near 3.10 H: 10.50
8:10.44 Comparative Synthesis Example (Synthesis of Exemplified Compound Layer-7) 24.49 of 4-butoxy-1-octylbenzene is refluxed in 250 me of chloroform, and 4.5 mQ of sulfur chloride is added thereto. After the addition, reflux is continued for an additional 5 hours. After chloroform was distilled off, the reaction product was purified by column chromatography to obtain a caramel-like substance of 81I. This is 3Q
Dissolve in mQ toluene and add 2.1.9 zinc. After adding 8.0 mQ of concentrated hydrochloric acid under reflux, the reaction is continued for 3 hours. After the reaction, 7.0 g (
26.6%) of the oily target product was obtained. Elemental analysis value, F
Although it was confirmed to be Exemplified Compound 1-7 from the D mass spectrum value, the yield was lower than 3 compared to Synthesis Example-1.
Claims (1)
２Ｃｌ＿２）を１価もしくは２価の銅化合物の存在下に
反応せしめて下記一般式〔II〕で示される化合物を得、
更にこれを還元することを特徴とする下記一般式〔III
〕で示される２−アルコキシベンゼンチオール系化合物
の製造方法。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１はアルキル基、Ｒ＿２は水素またはアル
キル基を表し、Ｒ＿３はアルキル基またはアルコキシ基
を表す。〕 一般式〔II〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１、Ｒ＿２およびＲ＿３は前記Ｒ＿１、Ｒ
＿２およびＲ＿３と同義であり、ｘは２以上の整数を表
す。〕一般式〔III〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１、Ｒ＿２およびＲ＿３は前記Ｒ＿１、Ｒ
＿２およびＲ３と同義である。〕[Claims] A compound represented by the following general formula [I] and sulfur chloride (S_
2Cl_2) in the presence of a monovalent or divalent copper compound to obtain a compound represented by the following general formula [II],
Furthermore, the following general formula [III
] A method for producing a 2-alkoxybenzenethiol compound. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 represents an alkyl group, R_2 represents hydrogen or an alkyl group, and R_3 represents an alkyl group or an alkoxy group. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2 and R_3 are the above-mentioned R_1, R
It is synonymous with _2 and R_3, and x represents an integer of 2 or more. ]General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2 and R_3 are the above R_1, R
Synonymous with _2 and R3. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60207677A JPS6267063A (en) | 1985-09-17 | 1985-09-17 | Production of 2-alkoxybenzenethiol based compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60207677A JPS6267063A (en) | 1985-09-17 | 1985-09-17 | Production of 2-alkoxybenzenethiol based compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6267063A true JPS6267063A (en) | 1987-03-26 |
Family
ID=16543739
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60207677A Pending JPS6267063A (en) | 1985-09-17 | 1985-09-17 | Production of 2-alkoxybenzenethiol based compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6267063A (en) |
-
1985
- 1985-09-17 JP JP60207677A patent/JPS6267063A/en active Pending
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