JPH0813797B2 - Process for producing 4-methyl-1,2-benzenedithiol - Google Patents
Process for producing 4-methyl-1,2-benzenedithiolInfo
- Publication number
- JPH0813797B2 JPH0813797B2 JP62014367A JP1436787A JPH0813797B2 JP H0813797 B2 JPH0813797 B2 JP H0813797B2 JP 62014367 A JP62014367 A JP 62014367A JP 1436787 A JP1436787 A JP 1436787A JP H0813797 B2 JPH0813797 B2 JP H0813797B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl
- benzenedithiol
- producing
- lewis acid
- disulfide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NIAAGQAEVGMHPM-UHFFFAOYSA-N 4-methylbenzene-1,2-dithiol Chemical compound CC1=CC=C(S)C(S)=C1 NIAAGQAEVGMHPM-UHFFFAOYSA-N 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000011968 lewis acid catalyst Substances 0.000 claims description 9
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 6
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- TZOVOULUMXXLOJ-UHFFFAOYSA-N 1-methyl-4-[(4-methylphenyl)disulfanyl]benzene Chemical compound C1=CC(C)=CC=C1SSC1=CC=C(C)C=C1 TZOVOULUMXXLOJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000008282 halocarbons Chemical class 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims 1
- 239000000126 substance Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- LTPSRQRIPCVMKQ-UHFFFAOYSA-N 2-amino-5-methylbenzenesulfonic acid Chemical compound CC1=CC=C(N)C(S(O)(=O)=O)=C1 LTPSRQRIPCVMKQ-UHFFFAOYSA-N 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 1
- RDUOAPKDKFEXDX-UHFFFAOYSA-N 4-methylbenzene-1,2-disulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(S(O)(=O)=O)=C1 RDUOAPKDKFEXDX-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- -1 benzenedithiol metal complex Chemical class 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は４−メチル−1,2−ベンゼンジチオールの製
造法に関する。TECHNICAL FIELD The present invention relates to a method for producing 4-methyl-1,2-benzenedithiol.
本発明で得られる化合物である４−メチル−1,2−ベ
ンゼンジチオールは、金属イオンと反応してベンゼンジ
チオール金属錯体を生成し、これらの錯体は近赤外領域
の赤外光を強く吸収する物性を有することが知られてお
り、〔ジャーナル・オブ・ジ・アメリカン・ケミカル・
ソサエティ（JOURNAL OF THE AMERICAN CHEMICAL SOCIE
TY）、第88巻、43〜50頁、1966年〕、このため４−メチ
ル−1,2−ベンゼンジチオールは光情報記録媒体である
近赤外吸収色素の中間体として有用である。The compound 4-methyl-1,2-benzenedithiol obtained in the present invention reacts with a metal ion to form a benzenedithiol metal complex, and these complexes strongly absorb infrared light in the near infrared region. Known to have physical properties, [Journal of the American Chemical
Society (JOURNAL OF THE AMERICAN CHEMICAL SOCIE
TY), 88, 43-50, 1966], and therefore 4-methyl-1,2-benzenedithiol is useful as an intermediate for near-infrared absorbing dyes which are optical information recording media.
（特開昭57−11090）。(JP-A-57-11090).
従って、本発明で得られる４−メチル−1,2−ベンゼ
ンジチオールは近赤外吸収色素の中間体としての用途が
期待できる有用な物質である。Therefore, 4-methyl-1,2-benzenedithiol obtained in the present invention is a useful substance which can be expected to be used as an intermediate of a near infrared absorbing dye.
（従来の技術） ４−メチル−1,2−ベンゼンジチオールの製造法とし
ては下式（１）のように５−メチル−２−アミノベンゼ
ンスルホン酸をジアゾ化した後、キサントゲン酸カリウ
ムを反応させ、加水分解後、過マンガン酸カリウムによ
り酸化させて４−メチル−1,2−ベンゼンジスルホン酸
を得て、これを塩素化、還元することにより４−メチル
−1,2−ベンゼンジチオールを製造する方法が知られて
いる。(Prior Art) As a method for producing 4-methyl-1,2-benzenedithiol, after diazotizing 5-methyl-2-aminobenzenesulfonic acid as shown in the following formula (1), potassium xanthate is reacted. After hydrolysis, it is oxidized with potassium permanganate to obtain 4-methyl-1,2-benzenedisulfonic acid, which is chlorinated and reduced to produce 4-methyl-1,2-benzenedithiol. The method is known.
〔ジャーナル・オブ・ケミカル・ソサエティ（JOURNAL
・OF・CHEMICAL・SOCIETY）第73巻、751頁1898年および
同誌、178頁、1935年〕 （発明が解決しようとする問題点） 上記の製造方法は工程も長く、５−メチル−２−アミ
ノベンゼンスルホン酸から４−メチル−1,2−ベンゼン
ジチオールの収率は８％程度とかなり低収率である。[Journal of Chemical Society (JOURNAL
・ OF ・ CHEMICAL ・ SOCIETY) 73, 751 1898, and 178, 1935) (Problems to be Solved by the Invention) The above production method has a long process, and the yield of 4-methyl-1,2-benzenedithiol from 5-methyl-2-aminobenzenesulfonic acid is about 8%, which is considerably low. The yield.
（問題点を解決するための手段） このような従来技術の欠点を改善し、４−メチル−1,
2−ベンゼンジチオールを工業的に製造するために、本
発明者らは鋭意検討した結果、４−メチルベンゼンチオ
ールまたはその酸化物であるジ（４−メチルフェニル）
ジスルフィドと一塩化硫黄をヨウ素またはルイス酸触媒
の存在下で反応させ、酸性中、亜鉛のごとき金属を用い
て還元することにより、比較的簡単な工程で目的物であ
る４−メチル−1,2−ベンゼンジチオールが収率よく得
られることを見出し、本発明に到達した。(Means for Solving Problems) By improving the above-mentioned drawbacks of the conventional technique, 4-methyl-1,
In order to industrially produce 2-benzenedithiol, the present inventors have conducted extensive studies and as a result, 4-methylbenzenethiol or its oxide di (4-methylphenyl)
By reacting disulfide with sulfur monochloride in the presence of iodine or a Lewis acid catalyst and reducing with a metal such as zinc in acid, 4-methyl-1,2 -The present invention has been achieved by finding that benzenedithiol can be obtained in good yield.
すなわち、本発明の要旨は、４−メチルベンゼンチオ
ールまたはその酸化物であるジ（４−メチルフェニル）
ジスルフィドと一塩化硫黄をヨウ素あるいはフリーデル
クラフト反応に用いるルイス酸触媒の存在下ハロゲン化
炭化水素溶媒中で反応させた後、酸性中で亜鉛、錫、鉄
から選ばれた少なくとも１種の金属で還元を行うことを
特徴とする４−メチル−1,2−ベンゼンジチオールの製
造方法である。That is, the gist of the present invention is di (4-methylphenyl) which is 4-methylbenzenethiol or its oxide.
After reacting disulfide and sulfur monochloride in a halogenated hydrocarbon solvent in the presence of iodine or a Lewis acid catalyst used for Friedel-Crafts reaction, at least one metal selected from zinc, tin, and iron in acid is used. A method for producing 4-methyl-1,2-benzenedithiol characterized by performing reduction.
本発明に用いる一塩化硫黄の使用量は４−メチルベン
ゼンチオールに対して0.5〜2.0倍モル、好ましくは0.55
〜1.1倍モルである。ジ（４−メチルフェニル）ジスル
フィドの場合、一塩化硫黄の使用量はこのジスルフィド
に対して１〜４倍モル、好ましくは1.1〜2.2倍モルであ
る。The amount of sulfur monochloride used in the present invention is 0.5 to 2.0 times mol with respect to 4-methylbenzenethiol, preferably 0.55.
~ 1.1 times the molar amount. In the case of di (4-methylphenyl) disulfide, the amount of sulfur monochloride used is 1 to 4 times mol, preferably 1.1 to 2.2 times mol, of the disulfide.
また、本発明に用いるルイス酸触媒としては、塩化亜
鉛、塩化第二鉄、塩化アルミニウム、塩化第二錫、三弗
化ホウ素、三塩化アンチモン、五塩化アンチモンから選
ばれと少なくとも１種であり、中でも塩化亜鉛を使用し
た場合に好ましい結果が得られる。これらルイス酸触媒
の使用量は、４−メチルベンゼンチオールに対して0.05
〜２倍モル、好ましくは0.1〜１倍モルでありジ（４−
メチルフェニル）ジスルフィドに対して0.1〜４倍モ
ル、好ましくは0.2〜２倍モルである。The Lewis acid catalyst used in the present invention is at least one selected from zinc chloride, ferric chloride, aluminum chloride, stannic chloride, boron trifluoride, antimony trichloride and antimony pentachloride, Above all, preferable results are obtained when zinc chloride is used. The amount of these Lewis acid catalysts used is 0.05 with respect to 4-methylbenzenethiol.
~ 2 times mol, preferably 0.1 to 1 times mol, and is di (4-
The amount is 0.1 to 4 times mol, preferably 0.2 to 2 times mol, of methylphenyl) disulfide.
また、ルイス酸触媒にかえてヨウ素を使用する場合に
は、４−メチルベンゼンチオールおよび、ジ（４−メチ
ルフェニル）ジスルフィドに対して0.1〜４倍モル、好
ましくは0.2〜２倍モルである。When iodine is used in place of the Lewis acid catalyst, it is 0.1 to 4 times mol, preferably 0.2 to 2 times mol, of 4-methylbenzenethiol and di (4-methylphenyl) disulfide.
本発明に用いるハロゲン化炭化水素溶媒としては、ク
ロロホルム、四塩化炭素、1,1,2−トリクロルエタン、
1,1,2,2−テトラクロルエタン、モノクロルベゼン、０
−ジクロルベンゼン、1,2,4−トリクロルベンゼンなど
があり、これらの中から少なくとも１種の溶媒を選定し
て使用すればよい。As the halogenated hydrocarbon solvent used in the present invention, chloroform, carbon tetrachloride, 1,1,2-trichloroethane,
1,1,2,2-tetrachloroethane, monochlorobenzene, 0
-Dichlorobenzene, 1,2,4-trichlorobenzene, etc., and at least one solvent may be selected and used from these.
反応温度は室温〜140℃であり、好ましくはヨウ素の
場合、室温〜40℃、ルイス酸触媒の場合、60〜100℃で
ある。The reaction temperature is room temperature to 140 ° C., preferably room temperature to 40 ° C. for iodine, and 60 to 100 ° C. for Lewis acid catalyst.
反応時間はヨウ素またはルイス酸触媒の添加量、反応
温度により異なるので一義的にはいえないが、通常12〜
72時間かけて反応させる。The reaction time varies depending on the amount of iodine or Lewis acid catalyst added and the reaction temperature, so it cannot be said uniquely.
Allow to react for 72 hours.
本発明の還元反応に用いる金属末または金属粒の使用
量は４−メチルベンゼンチオールに対して１〜10倍、好
ましくは３〜７倍、ジ（４−メチルフェニル）ジスルフ
ィドに対して２〜13倍、好ましくは４〜11倍である。The amount of metal powder or metal particles used in the reduction reaction of the present invention is 1 to 10 times, preferably 3 to 7 times that of 4-methylbenzenethiol, and 2 to 13 times that of di (4-methylphenyl) disulfide. Times, preferably 4 to 11 times.
また、本発明に用いる酸としては酢酸、塩酸、硫酸が
好ましく、金属末または金属粒としては、錫、亜鉛、鉄
が用いられる。The acid used in the present invention is preferably acetic acid, hydrochloric acid or sulfuric acid, and the metal powder or metal particles may be tin, zinc or iron.
還元反応温度は、金属末または金属粒および酸の添加
の際には、室温以下であり、その後は40〜80℃の温度に
維持する。反応時間は0.5〜３時間である。The reduction reaction temperature is not higher than room temperature when the metal powder or metal particles and the acid are added, and then maintained at a temperature of 40 to 80 ° C. The reaction time is 0.5 to 3 hours.
以下実施例により本発明を説明する。 The present invention will be described below with reference to examples.
実施例１ クロロホルム340gにジ（４−メチルフェニル）ジスル
フィド37g、ヨウ素8.5g、一塩化硫黄45gを加え、室温で
24時間反応させ、冷却しながら亜鉛64gと濃塩酸240gを
加え60℃で２時間反応させ、反応生成液をろ過し、クロ
ロホルムで抽出を行い、クロロホルムを留去し、減圧蒸
留して沸点125℃（4mmHg）、４−メチル−1,2−ベンゼ
ンジチオール17gを得た。（収率 35％） NMR、IRより同定を行った。Example 1 To 340 g of chloroform were added 37 g of di (4-methylphenyl) disulfide, 8.5 g of iodine and 45 g of sulfur monochloride, and the mixture was stirred at room temperature.
After reacting for 24 hours, while cooling, 64 g of zinc and 240 g of concentrated hydrochloric acid were added and reacted at 60 ° C for 2 hours, the reaction product solution was filtered, extracted with chloroform, chloroform was distilled off, and the residue was distilled under reduced pressure to obtain a boiling point of 125 ° C. (4 mmHg), 17 g of 4-methyl-1,2-benzenedithiol was obtained. (Yield 35%) Identification was performed by NMR and IR.
（沸点 135〜137℃、17mmHg） 実施例２ 1,1,2,2−テトラクロルエタン400gに４−メチルベン
ゼンチオール45g、塩化亜鉛5.6g、一塩化硫黄54gを加え
100℃で24時間反応させ、冷却しながら亜鉛103gと濃塩
酸327gを加え、60℃で２時間反応させ、実施例１と同様
に処理を行い、４−メチル−1,2−ベンゼンジチオール2
4gを得た。（収率40％） （発明の効果） 本発明によれば、非常に簡単な工程で４−メチル−1,
2−ベンゼンジチオールを製造できるので工業的に有利
である。(Boiling point 135 to 137 ° C., 17 mmHg) Example 2 To 400 g of 1,1,2,2-tetrachloroethane, 45 g of 4-methylbenzenethiol, 5.6 g of zinc chloride and 54 g of sulfur monochloride were added.
The mixture was reacted at 100 ° C. for 24 hours, 103 g of zinc and 327 g of concentrated hydrochloric acid were added while cooling, and the mixture was reacted at 60 ° C. for 2 hours and treated in the same manner as in Example 1 to give 4-methyl-1,2-benzenedithiol
I got 4g. (Yield 40%) (Effect of the invention) According to the present invention, 4-methyl-1,
Since 2-benzenedithiol can be produced, it is industrially advantageous.
この物質と、金属イオンを反応させて得られる金属錯
体は近赤外吸収色素としての用途があり、４−メチル−
1,2−ベンゼンジチオールはその金属錯体をつくるため
の中間体として有用である。The metal complex obtained by reacting this substance with a metal ion has a use as a near-infrared absorbing dye, and 4-methyl-
1,2-benzenedithiol is useful as an intermediate for making its metal complex.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高橋 正英 兵庫県加古郡播磨町宮西346番地の１ 製 鉄化学工業株式会社研究所内 (72)発明者 中山 和幸 兵庫県加古郡播磨町宮西346番地の１ 製 鉄化学工業株式会社研究所内 (56)参考文献 特開 昭50−24233（ＪＰ，Ａ) 特開 昭60−199871（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masahide Takahashi, No. 1 at 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Prefecture Inside the Iron and Steel Chemical Industry Co., Ltd. (1) Iron and Steel Chemical Industry Co., Ltd. (56) References JP-A-50-24233 (JP, A) JP-A-60-199871 (JP, A)
Claims (2)
（４−メチルフェニル）ジスルフィドと、一塩化硫黄を
ヨウ素またはルイス酸触媒の存在下、クロロホルム、四
塩化炭素、1,1,2−トリクロルエタン、1,1,2,2−テトラ
クロルエタン、モノクロルベンゼン、ｏ−ジクロルベン
ゼン、および、1,2,4−トリクロルベンゼンからなる群
より選ばれた少なくとも１種のハロゲン化炭化水素溶媒
中で反応させた後、酸性に保って、亜鉛、錫および鉄か
らなる群より選ばれた少なくとも１種の金属により還元
させることを特徴とする４−メチル−1,2−ベンゼンジ
チオールの製造方法。1. 4-Methylbenzenethiol or di (4-methylphenyl) disulfide and sulfur monochloride in the presence of iodine or a Lewis acid catalyst, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, 1 The reaction is carried out in at least one halogenated hydrocarbon solvent selected from the group consisting of 1,1,2,2-tetrachloroethane, monochlorobenzene, o-dichlorobenzene, and 1,2,4-trichlorobenzene. After that, it is kept acidic and is reduced with at least one metal selected from the group consisting of zinc, tin and iron, and a method for producing 4-methyl-1,2-benzenedithiol.
範囲第（Ｉ）項記載の方法。2. The method according to claim 1, wherein the Lewis acid catalyst is zinc chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62014367A JPH0813797B2 (en) | 1987-01-24 | 1987-01-24 | Process for producing 4-methyl-1,2-benzenedithiol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62014367A JPH0813797B2 (en) | 1987-01-24 | 1987-01-24 | Process for producing 4-methyl-1,2-benzenedithiol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63185955A JPS63185955A (en) | 1988-08-01 |
| JPH0813797B2 true JPH0813797B2 (en) | 1996-02-14 |
Family
ID=11859080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62014367A Expired - Lifetime JPH0813797B2 (en) | 1987-01-24 | 1987-01-24 | Process for producing 4-methyl-1,2-benzenedithiol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813797B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319386B (en) * | 2013-06-29 | 2016-04-20 | 乐平市赛复乐医药化工有限公司 | For the treatment of the synthetic method of two sulfydryl type sequestrants of heavy metal complex waste water |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2221445B1 (en) * | 1973-03-12 | 1979-04-20 | Crown Zellerbach Corp | |
| JPS60199871A (en) * | 1984-03-26 | 1985-10-09 | Nippon Kayaku Co Ltd | Production of thiophenols |
-
1987
- 1987-01-24 JP JP62014367A patent/JPH0813797B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63185955A (en) | 1988-08-01 |
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