JPH0684345B2 - Process for producing 4-tert-butyl-1,2-benzenedithiol - Google Patents
Process for producing 4-tert-butyl-1,2-benzenedithiolInfo
- Publication number
- JPH0684345B2 JPH0684345B2 JP62276584A JP27658487A JPH0684345B2 JP H0684345 B2 JPH0684345 B2 JP H0684345B2 JP 62276584 A JP62276584 A JP 62276584A JP 27658487 A JP27658487 A JP 27658487A JP H0684345 B2 JPH0684345 B2 JP H0684345B2
- Authority
- JP
- Japan
- Prior art keywords
- tert
- benzenedithiol
- butyl
- chloride
- producing
- 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 - Fee Related
Links
- RDLVSWJHDFENPL-UHFFFAOYSA-N 4-tert-butylbenzene-1,2-dithiol Chemical compound CC(C)(C)C1=CC=C(S)C(S)=C1 RDLVSWJHDFENPL-UHFFFAOYSA-N 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 5
- 239000002904 solvent Substances 0.000 claims description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- GNXBFFHXJDZGEK-UHFFFAOYSA-N 4-tert-butylbenzenethiol Chemical compound CC(C)(C)C1=CC=C(S)C=C1 GNXBFFHXJDZGEK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011968 lewis acid catalyst Substances 0.000 claims description 6
- JHJKMOPTKMUFOG-UHFFFAOYSA-N 1-tert-butyl-4-[(4-tert-butylphenyl)disulfanyl]benzene Chemical compound C1=CC(C(C)(C)C)=CC=C1SSC1=CC=C(C(C)(C)C)C=C1 JHJKMOPTKMUFOG-UHFFFAOYSA-N 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011630 iodine Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 235000005074 zinc chloride Nutrition 0.000 claims description 5
- 239000011592 zinc chloride Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- JRNVQLOKVMWBFR-UHFFFAOYSA-N 1,2-benzenedithiol Chemical compound SC1=CC=CC=C1S JRNVQLOKVMWBFR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- -1 dithiol Compounds Chemical class 0.000 description 5
- 150000004696 coordination complex Chemical class 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- AXWKRUFUAGYTHB-UHFFFAOYSA-N 2-butylbenzenethiol Chemical compound CCCCC1=CC=CC=C1S AXWKRUFUAGYTHB-UHFFFAOYSA-N 0.000 description 1
- MSSNSTXFTUNKQH-UHFFFAOYSA-N 3,4,5,6-tetrachlorobenzene-1,2-dithiol Chemical compound SC1=C(S)C(Cl)=C(Cl)C(Cl)=C1Cl MSSNSTXFTUNKQH-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 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
- 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
- 239000003054 catalyst Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- YFUYVQWZEJRMBK-UHFFFAOYSA-N nickel(2+);tetrabutylazanium Chemical compound [Ni+2].CCCC[N+](CCCC)(CCCC)CCCC YFUYVQWZEJRMBK-UHFFFAOYSA-N 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 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
- KBOPQCLKSDUBAZ-UHFFFAOYSA-M tetrabenzylazanium;bromide Chemical compound [Br-].C=1C=CC=CC=1C[N+](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 KBOPQCLKSDUBAZ-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- VJFXTJZJJIZRKP-UHFFFAOYSA-M tetraphenylazanium;bromide Chemical compound [Br-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 VJFXTJZJJIZRKP-UHFFFAOYSA-M 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は下式（Ｉ）の構造式で表わされる４−tert−ブ
チル−1,2−ベンゼンジチオールの製造方法に関する。
式（Ｉ）の化合物は下式（II）の構造式で表わされる４
−tert−ブチル−1,2−ベンゼンジチオールニッケル錯
体の製造に使用される。TECHNICAL FIELD The present invention relates to a method for producing 4-tert-butyl-1,2-benzenedithiol represented by the structural formula (I) below.
The compound of formula (I) is represented by the structural formula of the following formula (II) 4
Used in the preparation of -tert-butyl-1,2-benzenedithiol nickel complex.
（式中Ａ は第４級アンモニウム基を表す）ジチオール
化合物、例えば1,2−ベンゼンジチオール、4,5−ジメチ
ル−1,2−ベンゼンジチオール、1,2,3,4−テトラクロル
−5,6−ベンゼンジチオール、3,4,5,6−テトラメチル−
1,2−ベンゼンジチオールなどのオルソ−ベンゼンジチ
オール類は、金属イオンと反応してベンゼンジチオール
金属錯体を形成し、これらの錯体は近赤外領域の赤外光
線を強く吸収する物性を有することが知られている。
〔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 SOCIETY）
第88巻、43〜50頁および4870〜4875頁、1966年〕 この物性の故にオルソーベンゼンジチオール類は光情報
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。（特開昭57-11090、特開昭58-175693）従って本発
明の４−tert−ブチル−1,2−ベンゼンジチオールも近
赤外吸収色素の中間体として有用な物質であり、さらに
その金属錯体も従来公知の文献には記載の無い新規な化
合物である。 (A in the formula Represents a quaternary ammonium group) dithiol
Compounds such as 1,2-benzenedithiol, 4,5-dimethyl
Ru-1,2-benzenedithiol, 1,2,3,4-tetrachloro
-5,6-benzenedithiol, 3,4,5,6-tetramethyl-
Ortho-benzenedithione such as 1,2-benzenedithiol
Oles react with metal ions to react with benzenedithiol.
It forms metal complexes, and these complexes are infrared light in the near infrared region.
It is known to have the property of strongly absorbing rays.
[Journal of the American Chemical Society
Eti (JOURNAL OF THE AMERICAN CHEMICAL SOCIETY)
Vol. 88, pp. 43-50 and 4870-4875, 1966] Due to these physical properties, orthobenzenedithiols have optical
It is useful as an intermediate for near-infrared absorbing dyes that are recording media.
It (Japanese Patent Laid-Open Nos. 57-11090 and 58-175693)
The bright 4-tert-butyl-1,2-benzenedithiol is also close
It is a substance useful as an intermediate for infrared absorbing dyes.
The metal complex is also a novel compound that has not been described in any conventionally known literature.
It is a combination.
（問題点を解決するための手段） 本発明者らは４−tert−ブチル−1,2−ベンゼンジチオ
ールおよびそのニッケル錯体を工業的に製造する方法に
ついて鋭意検討した結果、チオール化合物またはその酸
化物を一方の原料とし、これと硫黄化合物とを所定条件
下に反応させ、反応生成物を還元すれば、４−tert−ブ
チル−1,2−ベンゼンジチオールが収率よく得られるこ
とを見出した。さらに４−tert−ブチル−1,2−ベンゼ
ンジチオールにニッケル塩、第４級アンモニウム塩を加
え、溶媒中空気を吹き込みながら反応させるとニッケル
錯体が得られることを見出し、本発明に到達した。(Means for Solving the Problems) The inventors of the present invention have diligently studied a method for industrially producing 4-tert-butyl-1,2-benzenedithiol and a nickel complex thereof, and as a result, a thiol compound or its oxide It was found that 4-tert-butyl-1,2-benzenedithiol can be obtained in good yield by reacting this with one of the starting materials with a sulfur compound under predetermined conditions and reducing the reaction product. Further, they have found that a nickel complex can be obtained by adding a nickel salt and a quaternary ammonium salt to 4-tert-butyl-1,2-benzenedithiol and reacting them while blowing air in a solvent, and arrived at the present invention.
すなわち本発明の要旨は下式（Ｉ） で表わされる４−tert−ブチル−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 the following formula (I). Is a method for producing 4-tert-butyl-1,2-benzenedithiol.
（式中のＡ は第４級アンモニウム基を示す） 式（II）で表わされる化合物の製造方法は、４−tert−
ブチルベンゼンチオールあるいは、ジ（４−tert−ブチ
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、溶媒中で反応させた後、亜
鉛、錫、鉄、から選ばれた少なくとも一種の金属粒また
は金属末で還元させて、４−tert−ブチル−1,2−ベン
ゼンジチオールを得、この４−tert−ブチル−1,2−ベ
ンゼンジチオールに塩化ニッケルと第４級アンモニウム
塩を加え、溶媒中で空気を吹き込みながら反応させて４
−tert−ブチル−1,2−ベンゼンジチオールニッケル錯
体が得られる。 (A in the formula Represents a quaternary ammonium group) The method for producing the compound represented by the formula (II) is
Butylbenzenethiol or di (4-tert-butyl)
Ruphenyl) disulfide and sulfur monochloride to iodine or
Is reacted in a solvent in the presence of a Lewis acid catalyst and then
At least one metal particle selected from lead, tin, and iron
Is reduced with metal powder to give 4-tert-butyl-1,2-ben
Zendithiol was obtained and the 4-tert-butyl-1,2-beta
Nickel dichloride and quaternary ammonium
Add salt and let it react in the solvent while blowing air.
-Tert-Butyl-1,2-benzenedithiol nickel complex
The body is obtained.
次に４−tert−ブチル−1,2−ベンゼンジチオールの製
造方法の具体的態様について述べる。Next, specific embodiments of the method for producing 4-tert-butyl-1,2-benzenedithiol will be described.
反応に用いる一塩化硫黄の使用量は４−tert−ブチルベ
ンゼンチオールに対して0.5〜2.0倍モル、好ましくは0.
55〜1.5倍モルである。The amount of sulfur monochloride used in the reaction is 0.5 to 2.0 times mol of 4-tert-butylbenzenethiol, preferably 0.
55 to 1.5 times the molar amount.
一方の原料にジ（４−tert−ブチルフェニル）ジスルフ
ィドを使用する場合は原料に対して１〜４倍モル、好ま
しくは1.1〜3.0倍モルの一塩化硫黄を使用する。When di (4-tert-butylphenyl) disulfide is used as one of the raw materials, 1 to 4 times mol, preferably 1.1 to 3.0 times mol of sulfur monochloride is used with respect to the raw materials.
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、五塩化アンチモンなどが挙げ
られ、中でも塩化亜鉛を用いると好結果が得られる。As the Lewis acid catalyst used in the present invention, zinc chloride,
Examples thereof include ferric chloride, aluminum chloride, stannic chloride, boron trifluoride, antimony trichloride, antimony pentachloride and the like. Among them, zinc chloride gives good results.
これらルイス酸触媒の使用量は、４−tert−ブチルベン
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−tert−ブチルフェニル）
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 amount of these Lewis acid catalysts to be used is 0.05 to 2 times mol, preferably 0.1 to 4-tert-butylbenzenethiol.
1 to 1 times mol, di (4-tert-butylphenyl)
0.1 to 4 times the molar amount of disulfide, preferably 0.2 to
It is twice the mole.
ヨウ素を使用した場合、４−tert−ブチルベンゼンチオ
ールおよびジ（４−tert−ブチルフェニル）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, it is 0.1 to 4 times mol, preferably 0.2 to 2 times mol, of 4-tert-butylbenzenethiol and di (4-tert-butylphenyl) disulfide.
反応に用いる溶媒としては、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、モノクロルベンゼン、０−ジクロルベンゼン、
1,2,4−トリクロルベンゼンなどのハロゲン化炭化水素
溶媒が好適である。As the solvent used in the reaction, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, monochlorobenzene, 0-dichlorobenzene,
Halogenated hydrocarbon solvents such as 1,2,4-trichlorobenzene are preferred.
反応は、室温から〜140℃の範囲に保持して行うことが
できるが、好ましくはヨウ素を使用した場合、室温〜40
℃、ルイス酸触媒を使用した場合には60〜100℃の温度
である。The reaction can be carried out while maintaining the temperature in the range of room temperature to 140 ° C., but preferably when iodine is used, the temperature is room temperature to 40 ° C.
C., 60 to 100.degree. C. when a Lewis acid catalyst is used.
反応時間は触媒の添加量、反応温度によりその最適条件
は異なるが、通常12〜72時間で行う。反応生成物は還元
することにより、本発明の目的物である４−tert−ブチ
ル−1,2−ベンゼンジチオールが得られる。The optimum reaction time varies depending on the amount of catalyst added and the reaction temperature, but is usually 12 to 72 hours. By reducing the reaction product, 4-tert-butyl-1,2-benzenedithiol, which is the object of the present invention, can be obtained.
還元反応の際に使用する金属粒または金属末の使用量は
４−tert−ブチルベンゼンチオールに対して１〜10倍モ
ル、好ましくは３〜７倍モル、ジ（４−tert−ブチルフ
ェニル）ジスルフィドに対して２〜13倍モル、好ましく
は４〜11倍モルである。還元に際して反応液を酸性に保
つため酸を添加するが、酸の種類としては、酢酸、塩
酸、硫酸から選ばれた１種を使用すればよい。還元の際
に用いる金属粒または金属末としては、亜鉛、錫、鉄等
がある。還元反応温度は、金属粒または金属末の添加お
よび酸の添加時には室温以下に保持し、その後は40〜80
℃に保持して行えばよい。また反応時間は通常0.5〜３
時間である。The amount of metal particles or metal powder used in the reduction reaction is 1 to 10 times mol, preferably 3 to 7 times mol, of 4-tert-butylbenzenethiol, di (4-tert-butylphenyl) disulfide. It is 2 to 13 times mol, preferably 4 to 11 times mol. An acid is added in order to keep the reaction solution acidic during the reduction, and as the type of acid, one selected from acetic acid, hydrochloric acid and sulfuric acid may be used. Examples of the metal particles or metal powder used in the reduction include zinc, tin, iron and the like. The reduction reaction temperature is kept at room temperature or below during the addition of metal particles or powder and the addition of acid, and then 40 to 80
It may be held at ℃. The reaction time is usually 0.5 to 3
It's time.
４−tert−1,2−ベンゼンジチオールからニッケル錯体
を製造するには、これに金属塩、第４級アンモニウム塩
を加えて溶媒中常温で反応させればよい。In order to produce a nickel complex from 4-tert-1,2-benzenedithiol, a metal salt and a quaternary ammonium salt may be added thereto and the reaction may be carried out in a solvent at room temperature.
金属塩として塩化ニッケル、硫酸ニッケル、硝酸ニッケ
ルなどを用いるが、その使用量は４−tert−ブチル−1,
2−ベンゼンジチオールに対して0.4〜1.0倍モルであ
る。この量以下では収率が向上せず、これ以上過剰に加
えても収率は向上しないので不経済である。Nickel chloride, nickel sulfate, nickel nitrate, etc. are used as the metal salt, and the amount used is 4-tert-butyl-1,
It is 0.4 to 1.0 times the molar amount of 2-benzenedithiol. If the amount is less than this amount, the yield is not improved, and the yield is not improved even if it is added in excess, which is uneconomical.
本発明で用いる第４級アンモニウム塩としては、テトラ
ｎ−ブチルアンモニウムブロマイドあるいはクロライ
ド、テトラエチルアンモニウムブロマイドあるいはクロ
ライド、テトラオクチルアンモニウムブロマイドあるい
はクロライド、テトラフェニルアンモニウムブロマイド
あるいはクロライド、テトラベンジルアンモニウムブロ
マイドあるいはクロライド、トリメチルベンジルアンモ
ニウムブロマイドあるいはクロライドなどが挙げられ
る。これらの第４級アンモニウム塩の使用量は、４−te
rt−ブチル−1,2−ベンゼンジチオールに対して通常0.4
〜1.0倍モル程度である。Examples of the quaternary ammonium salt used in the present invention include tetra-n-butylammonium bromide or chloride, tetraethylammonium bromide or chloride, tetraoctylammonium bromide or chloride, tetraphenylammonium bromide or chloride, tetrabenzylammonium bromide or chloride, trimethylbenzyl. Examples thereof include ammonium bromide and chloride. The amount of these quaternary ammonium salts used is 4-te.
Usually 0.4 for rt-butyl-1,2-benzenedithiol
~ 1.0 times the molar amount.
錯体を製造する反応で用いる溶媒としては、メタノー
ル、エタノール、イソプロパノール、tert−ブチルアル
コールなどのアルコール類が好適である。反応は室温付
近にて行えばよい。反応時間は15分から５時間で行うと
好結果が得られる。As the solvent used in the reaction for producing the complex, alcohols such as methanol, ethanol, isopropanol and tert-butyl alcohol are suitable. The reaction may be performed near room temperature. Good results are obtained when the reaction time is 15 minutes to 5 hours.
（実施例） 以下実施例により本発明を具体的に説明する。(Example) Hereinafter, the present invention will be specifically described with reference to examples.
実施例１ クロロホルム340gにジ（４−tert−ブチルフェニル）ジ
スルフィド50g、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を加え、更
に濃塩酸240gを加えて60℃で１時間反応させた。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−te
rt−ブチル−1,2−ベンゼンジチオール41gを得た。純度
は99.3％であり、収率は68％であった。Example 1 To 340 g of chloroform, 50 g of di (4-tert-butylphenyl) disulfide, 8.5 g of iodine and 45 g of sulfur monochloride were added, reacted at room temperature for 24 hours, added with 64 g of zinc while cooling, and further added with 240 g of concentrated hydrochloric acid. And reacted at 60 ° C. for 1 hour. The reaction product solution is filtered, extracted with chloroform, the chloroform is distilled off, and the residue is distilled under reduced pressure to give a boiling point of 125 ° C. (4 mmHg) and 4-te.
41 g of rt-butyl-1,2-benzenedithiol was obtained. The purity was 99.3% and the yield was 68%.
４−tert−ブチル−1,2−ベンゼンジチオールの沸点、
元素分析値、核磁気共鳴吸収スペクトルおよび赤外吸収
スペクトルは次の通りである。Boiling point of 4-tert-butyl-1,2-benzenedithiol,
The elemental analysis values, nuclear magnetic resonance absorption spectrum and infrared absorption spectrum are as follows.
沸点 132〜133℃（5mmHg） 元素分析値 Ｃ Ｈ Ｓ 計算値 60.56 7.11 32.33 測定値 60.66 7.12 32.23 核磁気共鳴吸収スペクトル（CDCl3溶媒、TMS内標準） δ 7.0〜7.4ppm（3H、ｍ） δ 3.76 ppm（1H、ｓ） δ 3.61 ppm（1H、ｓ） δ 1.27 ppm（9H、ｓ） 実施例２ 1,1,2,2−テトラクロルエタン400gに４−tert−ブチル
ベンゼンチオール60g、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、20℃以下にて亜
鉛103gと濃塩酸327gを加え、60℃で２時間反応させた。
実施例１と同様に処理を行い、４−tert−ブチル−1,2
−ベンゼンジチオール41gを得た。収率は56％であっ
た。Boiling point 132-133 ℃ (5mmHg) Elemental analysis value CHS calculated value 60.56 7.11 32.33 Measurement value 60.66 7.12 32.23 Nuclear magnetic resonance absorption spectrum (CDCl 3 solvent, TMS internal standard) δ 7.0-7.4ppm (3H, m) δ 3.76 ppm (1H, s) δ 3.61 ppm (1H, s) δ 1.27 ppm (9H, s) Example 2 400 g of 1,1,2,2-tetrachloroethane was added with 60 g of 4-tert-butylbenzenethiol, 5.6 g of zinc chloride and 54 g of sulfur monochloride, reacted at 100 ° C. for 24 hours and cooled to 20 ° C. or lower. Then, 103 g of zinc and 327 g of concentrated hydrochloric acid were added and reacted at 60 ° C. for 2 hours.
The same treatment as in Example 1 was carried out to give 4-tert-butyl-1,2
-41 g of benzenedithiol are obtained. The yield was 56%.
実施例３ 1,1,2,2−テトラクロルエタン200gに、ジ（４−tert−
ブチルフェニル）ジスルフィド30g、塩化亜鉛2.8g、一
塩化硫黄13.5gを加え100℃で24時間反応させ、冷却し、
20℃以下にて亜鉛47.6gと濃塩酸168gを加え、60℃で２
時間反応させた。実施例１と同様に処理を行い、４−te
rt−ブチル−1,2−ベンゼンジチオール19gを得た。収率
は53％であった。Example 3 200 g of 1,1,2,2-tetrachloroethane was mixed with di (4-tert-
(Butylphenyl) disulfide (30 g), zinc chloride (2.8 g), sulfur monochloride (13.5 g) were added, and the mixture was reacted at 100 ° C for 24 hours, cooled,
At 20 ℃ or below, add 47.6g of zinc and 168g of concentrated hydrochloric acid, and add 2 at 60 ℃.
Reacted for hours. The same treatment as in Example 1 was performed and 4-te
19 g of rt-butyl-1,2-benzenedithiol was obtained. The yield was 53%.
なお実施例２および３で得た物質の物性は実施例１で測
定した値とほぼ同じであった。The physical properties of the substances obtained in Examples 2 and 3 were almost the same as the values measured in Example 1.
参考例 実施例１で得た４−tert−ブチル1,2−ベンゼンジチオ
ールを用いてそのニッケル錯体であるビス（４−tert−
ブチル−1,2−ジチオフェノレート）ニッケルテトラ−
ｎ−ブチルアンモニウムを以下に述べる方法で合成し
た。Reference Example Using the 4-tert-butyl 1,2-benzenedithiol obtained in Example 1, its nickel complex bis (4-tert-
Butyl-1,2-dithiophenolate) nickel tetra-
n-Butyl ammonium was synthesized by the method described below.
すなわち、140gのメタノールに４−tert−ブチル−1,2
−ベンゼンジチオール2.5g、塩化ニッケル６水塩1.5g、
テトラーｎ−ブチルアンモニウムブロマイド2.2gを加
え、空気を吹き込みながら室温にて３時間反応させ、ろ
過乾燥して、上記金属錯体を2.9gを得た。この金属錯体
を塩化メチレン−エタノール混合溶媒から再結晶を行
い、深緑色針状結晶2.0gを得た。That is, 4-tert-butyl-1,2 was added to 140 g of methanol.
-2.5 g of benzenedithiol, 1.5 g of nickel chloride hexahydrate,
Tetra-n-butylammonium bromide (2.2 g) was added, the mixture was reacted at room temperature for 3 hours while blowing air, and filtered and dried to obtain 2.9 g of the above metal complex. The metal complex was recrystallized from a mixed solvent of methylene chloride and ethanol to obtain 2.0 g of dark green needle crystals.
この金属錯体の融点および近赤外吸収スペクトルは次の
通りであった。The melting point and near-infrared absorption spectrum of this metal complex were as follows.
融点 169〜170℃ 近赤外吸収スペクトル（溶媒：塩化メチレン） 極大吸収波長 925nm モル吸収係数 13080 赤外吸収スペクトル（KBr、cm-1） 2964、2872、1576、1480、1376、 1294、1242、1092、874、806、606 元素分析値 Ｃ Ｈ N S Ni 計算値 62.32 8.72 2.02 18.48 8.46 実測値 62.41 8.78 1.96 18.49 8.36 （発明の効果） 本発明の方法により、４−tert−ブチル−1,2−ベンゼ
ンジチオールを、工業的に安価に製造することができ
る。該物質のニッケル錯体は近赤外吸収色素およびその
中間体として有用である。Melting point 169-170 ° C Near infrared absorption spectrum (solvent: methylene chloride) Maximum absorption wavelength 925 nm Molar absorption coefficient 13080 Infrared absorption spectrum (KBr, cm -1 ) 2964, 2872, 1576, 1480, 1376, 1294, 1242, 1092 , 874, 806, 606 Elemental analysis value C H NS Ni calculated value 62.32 8.72 2.02 18.48 8.46 measured value 62.41 8.78 1.96 18.49 8.36 (Effect of the invention) According to the method of the present invention, 4-tert-butyl-1,2-benzenedithiol Can be industrially manufactured at low cost. The nickel complex of the substance is useful as a near infrared absorbing dye and its intermediate.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０７Ｂ 61/00 ３００ (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63−165392（ＪＰ，Ａ) 特開 昭62−223166（ＪＰ，Ａ)─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification number Internal reference number FI Technical indication C07B 61/00 300 (72) Inventor Masahide Takahashi 1 Steel at 346 Miyanishi, Harima-cho, Kako-gun, Hyogo Prefecture Chemical Industry Co., Ltd. Research Institute (72) Inventor Kazuyuki Nakayama 1 346, Miyanishi, Harima-cho, Kako-gun, Hyogo Iron Chemical Industry Co., Ltd. Research Institute (56) Sho 62-223166 (JP, A)
Claims (2)
はジ（４−tert−ブチルフェニル）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、溶媒中
で反応させた後、亜鉛、錫、鉄から選ばれた少なくとも
１種の金属で還元させることを特徴とする４−tert−ブ
チル−1,2−ベンゼンジチオールの製造方法。1. After reacting 4-tert-butylbenzenethiol or di (4-tert-butylphenyl) disulfide with sulfur monochloride in the presence of an iodine or Lewis acid catalyst in a solvent, zinc, tin, A method for producing 4-tert-butyl-1,2-benzenedithiol, which comprises reducing with at least one metal selected from iron.
範囲（１）記載の方法。2. The method according to claim 1, wherein the Lewis acid catalyst is zinc chloride.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62276584A JPH0684345B2 (en) | 1987-01-20 | 1987-10-30 | Process for producing 4-tert-butyl-1,2-benzenedithiol |
| US07/143,643 US4835317A (en) | 1987-01-20 | 1988-01-13 | 4-tert.-butyl-1,2-benzenedithiol, complex compounds derived therefrom, and a method of producing the same |
| DE8888100619T DE3870898D1 (en) | 1987-01-20 | 1988-01-18 | 4-TERT.-BUTYL-1,2-BENZOLEDITHIOL, COMPLEX COMPOUNDS DERIVED FROM IT AND METHOD FOR THE PRODUCTION THEREOF. |
| EP88100619A EP0278257B1 (en) | 1987-01-20 | 1988-01-18 | 4-tert.-butyl-1,2-benzenedithiol, complex compounds derived therefrom, and a method of producing the same |
| CA000556788A CA1274530A (en) | 1987-01-20 | 1988-01-19 | 4-tert.-butyl-1,2-benzenedithiol, complex compounds derived therefrom, and a method of producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-11928 | 1987-01-20 | ||
| JP1192887 | 1987-01-20 | ||
| JP62276584A JPH0684345B2 (en) | 1987-01-20 | 1987-10-30 | Process for producing 4-tert-butyl-1,2-benzenedithiol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63307853A JPS63307853A (en) | 1988-12-15 |
| JPH0684345B2 true JPH0684345B2 (en) | 1994-10-26 |
Family
ID=26347460
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62276584A Expired - Fee Related JPH0684345B2 (en) | 1987-01-20 | 1987-10-30 | Process for producing 4-tert-butyl-1,2-benzenedithiol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0684345B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62223166A (en) * | 1986-03-25 | 1987-10-01 | Ricoh Co Ltd | Near-infrared absorbing compound |
| JPH0749433B2 (en) * | 1986-12-27 | 1995-05-31 | 三井東圧化学株式会社 | Novel t-butyl-substituted benzenethiol nickel complex for near infrared absorber and plastic composition containing the complex |
-
1987
- 1987-10-30 JP JP62276584A patent/JPH0684345B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63307853A (en) | 1988-12-15 |
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