JPH0460992B2 - - Google Patents
Info
- Publication number
- JPH0460992B2 JPH0460992B2 JP12011783A JP12011783A JPH0460992B2 JP H0460992 B2 JPH0460992 B2 JP H0460992B2 JP 12011783 A JP12011783 A JP 12011783A JP 12011783 A JP12011783 A JP 12011783A JP H0460992 B2 JPH0460992 B2 JP H0460992B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- water
- acetone
- copper
- benzothiazolyl
- 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
Links
- 238000004519 manufacturing process Methods 0.000 claims description 7
- GWIKYPMLNBTJHR-UHFFFAOYSA-M thiosulfonate group Chemical group S(=S)(=O)[O-] GWIKYPMLNBTJHR-UHFFFAOYSA-M 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 6
- 125000001164 benzothiazolyl group Chemical group S1C(=NC2=C1C=CC=C2)* 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 29
- 150000001875 compounds Chemical class 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- -1 alkali metal salt Chemical class 0.000 description 15
- 239000002904 solvent Substances 0.000 description 13
- JHCPRMVDOCTAMG-UHFFFAOYSA-L copper;benzenesulfinate Chemical compound [Cu+2].[O-]S(=O)C1=CC=CC=C1.[O-]S(=O)C1=CC=CC=C1 JHCPRMVDOCTAMG-UHFFFAOYSA-L 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- SJIHLYOMBYTQHT-UHFFFAOYSA-N [2-(1,3-benzothiazol-2-yl)phenyl]-hydroxy-oxo-sulfanylidene-lambda6-sulfane Chemical compound C1=CC=C(C(=C1)C2=NC3=CC=CC=C3S2)S(=O)(=S)O SJIHLYOMBYTQHT-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HOHVUEGHUQRFNQ-UHFFFAOYSA-N 1,3-benzothiazol-2-yloxy-oxo-phenyl-sulfanylidene-$l^{6}-sulfane Chemical compound N=1C2=CC=CC=C2SC=1OS(=S)(=O)C1=CC=CC=C1 HOHVUEGHUQRFNQ-UHFFFAOYSA-N 0.000 description 2
- RWYJGJWCMWVUAB-UHFFFAOYSA-N CC1=CC=CC2=C1N=C(C(C=CC=C1)=C1S(O)(=O)=S)S2 Chemical compound CC1=CC=CC2=C1N=C(C(C=CC=C1)=C1S(O)(=O)=S)S2 RWYJGJWCMWVUAB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- GOSLZYRGUTVYOP-UHFFFAOYSA-N (5-methoxy-1,3-benzothiazol-2-yl)oxy-oxo-phenyl-sulfanylidene-$l^{6}-sulfane Chemical compound N=1C2=CC(OC)=CC=C2SC=1OS(=O)(=S)C1=CC=CC=C1 GOSLZYRGUTVYOP-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NEQIINRMDYNPTO-UHFFFAOYSA-N 1,3-benzothiazol-2-yloxy-(4-methylphenyl)-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound C1=CC(C)=CC=C1S(=O)(=S)OC1=NC2=CC=CC=C2S1 NEQIINRMDYNPTO-UHFFFAOYSA-N 0.000 description 1
- 125000001917 2,4-dinitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1*)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- 125000005809 3,4,5-trimethoxyphenyl group Chemical group [H]C1=C(OC([H])([H])[H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- SSQNKTBATJCFLF-UHFFFAOYSA-N 4-methyl-2-[(4-methyl-1,3-benzothiazol-2-yl)disulfanyl]-1,3-benzothiazole Chemical compound C1=CC=C2SC(SSC=3SC=4C=CC=C(C=4N=3)C)=NC2=C1C SSQNKTBATJCFLF-UHFFFAOYSA-N 0.000 description 1
- SRJKHNTVCHLOIA-UHFFFAOYSA-N 5-chloro-2-[(5-chloro-1,3-benzothiazol-2-yl)disulfanyl]-1,3-benzothiazole Chemical compound ClC1=CC=C2SC(SSC=3SC4=CC=C(C=C4N=3)Cl)=NC2=C1 SRJKHNTVCHLOIA-UHFFFAOYSA-N 0.000 description 1
- QSOHSUYZXBNXBQ-UHFFFAOYSA-N 5-methoxy-2-[(5-methoxy-1,3-benzothiazol-2-yl)disulfanyl]-1,3-benzothiazole Chemical compound COC1=CC=C2SC(SSC=3SC4=CC=C(C=C4N=3)OC)=NC2=C1 QSOHSUYZXBNXBQ-UHFFFAOYSA-N 0.000 description 1
- SKQWJYKBNFADLR-UHFFFAOYSA-N 6-methyl-2-[(6-methyl-1,3-benzothiazol-2-yl)disulfanyl]-1,3-benzothiazole Chemical compound C1=C(C)C=C2SC(SSC3=NC4=CC=C(C=C4S3)C)=NC2=C1 SKQWJYKBNFADLR-UHFFFAOYSA-N 0.000 description 1
- MFCGAIPEIISLHT-UHFFFAOYSA-N 6-nitro-2-[(6-nitro-1,3-benzothiazol-2-yl)disulfanyl]-1,3-benzothiazole Chemical compound C1=C([N+]([O-])=O)C=C2SC(SSC3=NC4=CC=C(C=C4S3)[N+](=O)[O-])=NC2=C1 MFCGAIPEIISLHT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical class [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- GHJRPPPCGWIZJZ-UHFFFAOYSA-N hydroxy-[2-(6-nitro-1,3-benzothiazol-2-yl)phenyl]-oxo-sulfanylidene-lambda6-sulfane Chemical compound C1=CC=C(C(=C1)C2=NC3=C(S2)C=C(C=C3)[N+](=O)[O-])S(=O)(=S)O GHJRPPPCGWIZJZ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- CPXGFFUFUXXZGC-UHFFFAOYSA-M silver;4-methylbenzenesulfinate Chemical compound [Ag+].CC1=CC=C(S([O-])=O)C=C1 CPXGFFUFUXXZGC-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】 本発明はチオスルホネートの製造法に関する。[Detailed description of the invention] The present invention relates to a method for producing thiosulfonates.
更に詳しくは、本発明は、一般式
R1SSO2R2 （）
〔式中、R1は置換または非置換のベンゾチアゾ
リル基を示す。R2は置換または非置換のフエニ
ル基を示す。〕で表わされるチオスルホネートの
新規製造法に関する。 More specifically, the present invention provides a compound having the general formula R 1 SSO 2 R 2 () [wherein R 1 represents a substituted or unsubstituted benzothiazolyl group]. R 2 represents a substituted or unsubstituted phenyl group. This invention relates to a new method for producing thiosulfonate represented by
一般式（）で表わされるチオスルホネート
は、各種の反応試薬やゴムの加硫促進剤として有
用な化合物である。一般式（）で表わされる化
合物の製造法としては、例えば米国特許第３，
786，063号に記載されている様に、式(1)で表され
る方法が知られている。 Thiosulfonate represented by the general formula () is a compound useful as a variety of reaction reagents and a vulcanization accelerator for rubber. As a method for producing the compound represented by the general formula (), for example, U.S. Patent No. 3,
As described in No. 786,063, the method represented by formula (1) is known.
R1SSR1Cl2
―――→
R1SClR2SO2Na
――――――→
R1SSO2R2 (1)
しかしこの方法は不安定なスルフエニルクロリ
ドを合成中間体に用いなければならないために微
妙な反応の制御をする必要があり、収率もあまり
良くない。そこで簡便でかつ高収率で化合物
（）を製造する方法を発明すべく、鋭意研究を
重ねた結果、本発明を完成するに到つたものであ
る。 R 1 SSR 1 Cl 2 ―――→ R 1 SClR 2 SO 2 Na ――――――→ R 1 SSO 2 R 2 (1) However, this method uses unstable sulfenyl chloride as a synthetic intermediate. Therefore, the reaction must be delicately controlled, and the yield is not very good. Therefore, in order to invent a method for producing compound (2) in a simple and high yield, the present invention was completed as a result of extensive research.
本発明の目的は上記一般式（）で表わされる
チオスルホネートを簡便な操作で高純度かつ高収
率で製造し得る方法を提供することにある。 An object of the present invention is to provide a method for producing a thiosulfonate represented by the above general formula () with high purity and high yield through simple operations.
即ち本発明は一般式
R1SSR1 （）
〔式中R1は前記に同じ。〕で表わされるジスルフ
イドを、一般式
Mn＋（SO2R2）o （）
〔式中、Ｍは重金属陽イオンであり、そしてｎは
この陽イオンの原子価を示す。R2は前記に同
じ。〕で表わされるスルフイン酸の重金属塩と反
応させて一般式（）で表わされるチオスルホネ
ートを製造する方法に係る。 That is, the present invention is based on the general formula R 1 SSR 1 () [wherein R 1 is the same as above]. A disulfide represented by the general formula M n +(SO 2 R 2 ) o ( ) [where M is a heavy metal cation and n represents the valence of this cation. R 2 is the same as above. ] This relates to a method for producing a thiosulfonate represented by the general formula () by reacting it with a heavy metal salt of sulfinic acid represented by the following.
本発明に係る上記方法は有機溶媒中で行なわ
れ、斯かる有機溶媒は化合物（）及び化合物
（）の両方を必ずしも完全に溶解させる必要は
なく、一部溶解させることができれば良い。ま
た、使用する有機溶媒が親水性有機溶媒の場合に
は水を加えて反応させることもできる。加える水
の量としては使用する有機溶媒に対して50％迄が
適当である。 The above method according to the present invention is carried out in an organic solvent, and the organic solvent does not necessarily need to completely dissolve both compound () and compound (), as long as it can partially dissolve them. Furthermore, when the organic solvent used is a hydrophilic organic solvent, water can be added to carry out the reaction. The appropriate amount of water to be added is up to 50% of the organic solvent used.
本発明に於て有機溶媒としては例えばアセト
ン、メチルエチルケトン、メチルイソブチルケト
ン等のケトン類、メタノール、エタノール、イソ
プロパノール等のアルコール類、ジクロルメタ
ン、ジクロルエタン、クロロホルム等のハロゲン
化炭化水素類などの中から選ばれる単独又は混合
溶媒が使用される。また反応時の化合物（）の
濃度は溶媒に対して１〜50％、好ましくは５〜30
％で行なうのが良い。化合物（）の使用量は化
合物（）に対して0.5〜３当量を用いるのが良
い。また、化合物（）は反応系中で調製して用
いることもできる。即ち化合物（）を用いるか
わりに相当するスルフイン酸アルカリ金属塩と重
金属塩を相当量加えた後化合物（）と反応させ
ることもできる。この場合には水を加えて反応さ
せることが好ましい。 In the present invention, the organic solvent is selected from ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohols such as methanol, ethanol, and isopropanol, and halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform. Single or mixed solvents may be used. In addition, the concentration of the compound () during the reaction is 1 to 50%, preferably 5 to 30%, relative to the solvent.
It is better to do it in %. The amount of compound () to be used is preferably 0.5 to 3 equivalents relative to compound (). Moreover, the compound () can also be prepared and used in the reaction system. That is, instead of using compound (), a corresponding alkali metal salt of sulfinate and heavy metal salt may be added in corresponding amounts and then reacted with compound (). In this case, it is preferable to add water for the reaction.
本発明の反応に用いる一般式（）の化合物
は、通常、R1が非置換ベンゾチアゾリル又はア
ルキル、アルコキシ、ニトロ又はハロゲン置換ベ
ンゾチアゾリルである化合物が用いられ、その好
ましい具体例として、ベンゾチアゾール−２−イ
ル、４−メチルベンゾチアゾール−２−イル、６
−メチルベンゾチアゾール−２−イル、４，６−
ジメチルベンゾチアゾール−２−イル、５−メト
キシベンゾチアゾール−２−イル、６−ニトロベ
ンゾチアゾール−２−イル、５−クロロベンゾチ
アゾール−２−イル、６−クロロベンゾチアゾー
ル−２−イル等をあげることができる。 The compound of general formula () used in the reaction of the present invention is usually a compound in which R 1 is unsubstituted benzothiazolyl or alkyl, alkoxy, nitro or halogen-substituted benzothiazolyl. Preferred specific examples thereof include benzothiazole-2- yl, 4-methylbenzothiazol-2-yl, 6
-methylbenzothiazol-2-yl, 4,6-
Dimethylbenzothiazol-2-yl, 5-methoxybenzothiazol-2-yl, 6-nitrobenzothiazol-2-yl, 5-chlorobenzothiazol-2-yl, 6-chlorobenzothiazol-2-yl, etc. be able to.
また一般式（）の化合物としては、通常R2
がフエニル又はアルキル、アルコキシ、ハロゲン
又はニトロ置換フエニルである化合物が用いられ
る。R2の具体例としては、フエニル、ｐ−トリ
ル、ｐ−ブロモフエニル、ｐ−クロロフエニル、
ｐ−ニトロフエニル、ｏ−ニトロフエニル、ｐ−
メトキシフエニル、３，４，５−トリメトキシフ
エニル、２，４−ジニトロフエニル、２，４，６
−トリメチルフエニル等をあげることができる。
Mn+の具体例としては銅（）、水銀（）、銀
（）等をあげることができる。 In addition, as a compound of general formula (), usually R 2
Compounds are used in which is phenyl or alkyl, alkoxy, halogen or nitro-substituted phenyl. Specific examples of R2 include phenyl, p-tolyl, p-bromophenyl, p-chlorophenyl,
p-nitrophenyl, o-nitrophenyl, p-
Methoxyphenyl, 3,4,5-trimethoxyphenyl, 2,4-dinitrophenyl, 2,4,6
-trimethylphenyl and the like.
Specific examples of M n+ include copper ( ), mercury ( ), silver ( ), and the like.
本発明を実施するに当り反応温度としては０℃
〜150℃の範囲が適当で、好ましくは室温〜使用
溶媒の還流温度の範囲で反応させるのが良い。反
応時間は反応温度によつて変化するが、通常0.5
〜10時間反応させる。 In carrying out the present invention, the reaction temperature is 0°C.
The reaction temperature is suitably in the range of 150°C to 150°C, preferably room temperature to the reflux temperature of the solvent used. The reaction time varies depending on the reaction temperature, but is usually 0.5
Let react for ~10 hours.
反応後の処理は、析出した重金属メルカプタイ
ドの沈殿を過あるいは遠心分離法により分離し
た後、液を濃縮して得られる結晶を別、乾燥
することにより化合物（）が高純度で得られ
る。 In the post-reaction treatment, the precipitated heavy metal mercaptide is separated by filtration or centrifugation, the liquid is concentrated, and the resulting crystals are separated and dried to obtain the compound () with high purity.
本発明の方法によれば、副生する重金属メルカ
プタイドは有機溶媒に不溶のため簡単な操作で分
離することができ、純度もほぼ100％の一般式
（）で表わされる。チオスルホネートを収率80
％以上で製造することができる。 According to the method of the present invention, the heavy metal mercaptide produced as a by-product is insoluble in organic solvents, so it can be separated by a simple operation, and the purity is approximately 100%, expressed by the general formula (). Thiosulfonate yield 80
% or more.
次に実施例をあげて本発明を具体的に説明す
る。 Next, the present invention will be specifically explained with reference to Examples.
実施例 １
ベンゾチアゾリルジスルフイド30ｇとベンゼン
スルフイン酸銅（）22ｇをフラスコにとり、ア
セトン600ml、水180mlを加えて撹拌しながら1.5
時間加熱還流する。室温迄放冷し、褐色沈殿を
別し、その沈殿はアセトンで洗浄する。このよう
にして得られた液及び洗液を減圧濃縮すると淡
黄色結晶が析出する。これを数回水洗した後、少
量のメタノールで洗浄し、減圧下乾燥するとベン
ゾチアゾリルベンゼンチオスルホネート26.8ｇが
得られる。Example 1 Put 30 g of benzothiazolyl disulfide and 22 g of copper benzenesulfinate () into a flask, add 600 ml of acetone and 180 ml of water, and add 1.5 g of benzothiazolyl disulfide while stirring.
Heat to reflux for an hour. Allow to cool to room temperature, separate brown precipitate, and wash the precipitate with acetone. When the liquid and washing liquid thus obtained are concentrated under reduced pressure, pale yellow crystals are precipitated. This is washed several times with water, then with a small amount of methanol, and dried under reduced pressure to obtain 26.8 g of benzothiazolylbenzenthiosulfonate.
核磁気共鳴スペクトル（CDCl3δ）
7.50〜8.20（ｍ）
実施例 ２
４−メチルベンゾチアゾリルジスルフイド32ｇ
とベンゼンスルフイン酸銅（）22ｇを原料とし
て、アセトン600ml、水180mlを溶媒として用いて
実施例１と同様の操作により、４−メチルベンゾ
チアゾリルベンゼンチオスルホネート27.4ｇが得
られる。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 7.50-8.20 (m) Example 2 32 g of 4-methylbenzothiazolyl disulfide
Using 22 g of copper benzenesulfinate as raw materials, 600 ml of acetone, and 180 ml of water as solvents, the same procedure as in Example 1 was carried out to obtain 27.4 g of 4-methylbenzothiazolylbenzenethiosulfonate.
核磁気共鳴スペクトル（CDCl3δ）
2.60（ｓ，3H）
7.10〜7.90（ｍ，8H）
実施例 ３
６−メチルベンゾチアゾリルジスルフイド32ｇ
とベンゼンスルフイン酸銅（）22ｇを原料とし
て、アセトン600ml、水180mlを溶媒として実施例
１と同様の操作により、４−メチルベンズチアゾ
リルベンゼンチオスルホネート28.0ｇが得られ
る。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 2.60 (s, 3H) 7.10-7.90 (m, 8H) Example 3 32 g of 6-methylbenzothiazolyl disulfide
Using 22 g of copper benzenesulfinate as raw materials, 600 ml of acetone, and 180 ml of water as solvents, the same procedure as in Example 1 was carried out to obtain 28.0 g of 4-methylbenzthiazolylbenzenethiosulfonate.
核磁気共鳴スペクトル（CDCl3δ）
2.49（ｓ，3H）
7.20−7.95（ｍ，8H）
実施例 ４
６−ニトロベンゾチアゾリルジスルフイド32ｇ
とベンゼンスルフイン酸銅（）23ｇを原料とし
て、アセトン600ml、水180mlを溶媒として実施例
１と同様の操作により、６−ニトロベンゾチアゾ
リルベンゼンチオスルホネート21.3ｇが得られ
る。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 2.49 (s, 3H) 7.20-7.95 (m, 8H) Example 4 32 g of 6-nitrobenzothiazolyl disulfide
Using 23 g of copper benzenesulfinate as raw materials, 600 ml of acetone, and 180 ml of water as solvents, the same procedure as in Example 1 was carried out to obtain 21.3 g of 6-nitrobenzothiazolylbenzenthiosulfonate.
核磁気共鳴スペクトル（CDCl3δ）
7.40〜7.95（ｍ，5H）
8.07（ｄ，1H）
8.35（dd，1H）
8.77（ｄ，1H）
実施例 ５
５−メトキシベンゾチアゾリルジスルフイド31
ｇとベンゼンスルフイン酸銅（）20ｇを原料と
して、アセトン600ml、水180mlを溶媒として実施
例１と同様の操作により、５−メトキシベンゾチ
アゾリルベンゼンチオスルホネート24.8ｇが得ら
れる。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 7.40-7.95 (m, 5H) 8.07 (d, 1H) 8.35 (dd, 1H) 8.77 (d, 1H) Example 5 5-Methoxybenzothiazolyl disulfide 31
24.8 g of 5-methoxybenzothiazolyl benzenethiosulfonate is obtained by the same procedure as in Example 1 using 20 g of copper benzenesulfinate (20 g) as raw materials, 600 ml of acetone, and 180 ml of water as solvents.
核磁気共鳴スペクトル（CDCl3δ）
3.85（ｓ，3H）
7.09（dd，1H）
7.30〜7.85（ｍ，7H）
実施例 ６
５−クロルベンゾチアゾリルジスルフイド30ｇ
とベンゼンスルフイン酸銅（）25ｇを原料とし
て、アセトン600ml、水180mlを溶媒として実施例
１と同様の操作により、５−クロルベンゾチアゾ
リルベンゼンチオスルホネート21.7ｇが得られ
る。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 3.85 (s, 3H) 7.09 (dd, 1H) 7.30-7.85 (m, 7H) Example 6 30 g of 5-chlorobenzothiazolyl disulfide
Using 25 g of copper benzenesulfinate as raw materials, 600 ml of acetone, and 180 ml of water as solvents, the same procedure as in Example 1 was carried out to obtain 21.7 g of 5-chlorobenzothiazolyl benzenethiosulfonate.
核磁気共鳴スペクトル（CDCl3δ）
7.25〜8.40（ｍ）
実施例 ７
ベンゾチアゾリルジスルフイド30ｇとｐ−ブロ
ムベンゼンスルフイン酸銅（）32ｇを原料とし
て、アセトン600ml、水180mlを溶媒として実施例
１と同様の操作により、ベンゾチアゾリルｐ−ブ
ロムベンゼンチオスルホネート30.7ｇが得られ
る。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 7.25-8.40 (m) Example 7 Using 30 g of benzothiazolyl disulfide and 32 g of copper p-bromobenzenesulfinate () as raw materials, 600 ml of acetone and 180 ml of water as solvents. By the same operation as in Example 1, 30.7 g of benzothiazolyl p-bromobenzenethiosulfonate is obtained.
核磁気共鳴スペクトル（CDCl3δ）
7.25〜8.15（ｍ）
実施例 ８
ベンゾチアゾリルジスフイド30ｇとｐ−トルエ
ンスルフイン酸銀67ｇをフラスコにとり、アセト
ン1000ml、水300mlを加えて室温にて４時間撹拌
する。淡黄色沈殿を別し、その沈殿はアセトン
で洗浄する。こうして得られた液及び洗液を減
圧濃縮すると、再度淡黄色沈殿が析出する。これ
を数回水洗した後、少量のメタノールで洗浄し、
減圧乾燥するとベンゾチアゾリルｐ−トルエンチ
オスルホネート23.0ｇが得られる。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 7.25-8.15 (m) Example 8 30 g of benzothiazolyl disulfide and 67 g of silver p-toluenesulfinate were placed in a flask, 1000 ml of acetone and 300 ml of water were added, and the mixture was heated at room temperature. Stir for an hour. Separate the pale yellow precipitate and wash it with acetone. When the liquid and washing liquid thus obtained are concentrated under reduced pressure, a pale yellow precipitate is deposited again. After washing this with water several times, wash it with a small amount of methanol,
Drying under reduced pressure yields 23.0 g of benzothiazolyl p-toluenethiosulfonate.
核磁気共鳴スペクトル（CDCl3δ）
2.45（ｓ，3H）
7.10〜8.00（ｍ，8H）
実施例 ９
ベンゾチアゾリルジスルフイド30ｇとベンゼン
スルフイン酸銅（）22ｇを原料とし、アセトン
600mlを溶媒として、実施例１と同様の操作によ
りベンゾチアゾリルベンゼンチオスルホネート
25.5ｇが得られる。 Nuclear magnetic resonance spectrum (CDCl 3 δ) 2.45 (s, 3H) 7.10-8.00 (m, 8H) Example 9 Using 30 g of benzothiazolyl disulfide and 22 g of copper benzenesulfinate as raw materials, acetone
Using 600ml as a solvent, benzothiazolylbenzenthiosulfonate was prepared in the same manner as in Example 1.
25.5g is obtained.
実施例 10
ベンゾチアゾリルジスルフイド30ｇとベンゼン
スルフイン酸銅（）22ｇを原料とし、メタノー
ル400ml、クロロホルム200mlを溶媒として実施例
１と同様の操作によりベンゾチアゾリルベンゼン
チオスルホネート22.2ｇが得られる。Example 10 Using 30 g of benzothiazolyl disulfide and 22 g of copper benzenesulfinate as raw materials, 22.2 g of benzothiazolyl benzenethiosulfonate was obtained by the same operation as in Example 1 using 400 ml of methanol and 200 ml of chloroform as solvents. can get.
実施例 11
ベンゾチアゾリルジスルフイド30ｇとベンゼン
スルフイン酸銅（）22ｇを原料とし、メタノー
ル600ml、水200mlを溶媒として、実施例１と同様
の操作によりベンゾチアゾリルベンゼンチオスル
ホネート23.7ｇが得られる。Example 11 Using 30 g of benzothiazolyl disulfide and 22 g of copper benzenesulfinate as raw materials, and using 600 ml of methanol and 200 ml of water as solvents, 23.7 g of benzothiazolyl benzenethiosulfonate was obtained by the same procedure as in Example 1. is obtained.
実施例 12
ベンゾチアゾリルジスルフイド30ｇとベンゼン
スルフイン酸銅（）22ｇを原料とし、アセトン
600ml、クロロホルム100ml、水50mlを溶媒とし
て、実施例１と同様の操作によりベンゾチアゾリ
ルベンゼンチオスルホネート19.7ｇが得られる。Example 12 Using 30g of benzothiazolyl disulfide and 22g of copper benzenesulfinate as raw materials, acetone
600 ml of chloroform, 100 ml of chloroform, and 50 ml of water were used as solvents to obtain 19.7 g of benzothiazolylbenzenthiosulfonate in the same manner as in Example 1.
実施例 13
ベンゾチアゾリルジスルフイド30ｇとベンゼン
スルフイン酸銅（）44ｇを原料とし、メチルエ
チルケトン600ml、水150mlを溶媒として３室温で
６時間反応させる。続いて実施例１と同様の後処
理によりベンゾチアゾリルベンゼンチオスルホネ
ート21.4ｇが得られる。Example 13 Using 30 g of benzothiazolyl disulfide and 44 g of copper benzenesulfinate as raw materials, 600 ml of methyl ethyl ketone and 150 ml of water were used as solvents, and the mixture was reacted for 3 hours at room temperature for 6 hours. Subsequently, 21.4 g of benzothiazolylbenzenthiosulfonate was obtained by the same post-treatment as in Example 1.
実施例 14
硫酸銅５水和物15ｇを150mlの水に溶かし、こ
れにベンゼルスルフイン酸ナトリウム２水和物
24.1ｇを加えて室温で30分間撹拌する。続いてア
セトン500mlを加え撹拌しながらベンゾチアゾリ
ルジスルフイド40ｇを加えて室温で５時間反応さ
せる。ついで実施例１と同様の後処理によりベン
ゾチアゾリルベンゼンチオスルホネート33.0ｇが
得られる。Example 14 Dissolve 15 g of copper sulfate pentahydrate in 150 ml of water, and add sodium benzyl sulfinate dihydrate to this.
Add 24.1g and stir at room temperature for 30 minutes. Subsequently, 500 ml of acetone was added, and while stirring, 40 g of benzothiazolyl disulfide was added and reacted at room temperature for 5 hours. Subsequently, 33.0 g of benzothiazolylbenzenthiosulfonate was obtained by the same post-treatment as in Example 1.
Claims (1)
リル基を示す。〕で表わされるジスルフイドを、
一般式 Mn＋（SO2R2）o （） 〔式中、Ｍは重金属陽イオンであり、そしてｎは
この陽イオンの原子価を示す。また、R2は置換
または非置換のフエニル基を示す。〕で表わされ
るスルフイン酸の重金属塩と反応させることを特
徴とする一般式 R1SSO2R2 （） 〔式中R1及びR2は前記に同じ。〕で表されるチオ
スルホネートの製造法。[Claims] 1 General formula R 1 SSR 1 () [In the formula, R 1 represents a substituted or unsubstituted benzothiazolyl group. ] The disulfide represented by
General formula M n +(SO 2 R 2 ) o () [wherein M is a heavy metal cation, and n indicates the valence of this cation. Moreover, R 2 represents a substituted or unsubstituted phenyl group. [In the formula, R 1 and R 2 are the same as above. ] A method for producing thiosulfonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12011783A JPS6011480A (en) | 1983-06-30 | 1983-06-30 | Preparation of thiosulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12011783A JPS6011480A (en) | 1983-06-30 | 1983-06-30 | Preparation of thiosulfonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6011480A JPS6011480A (en) | 1985-01-21 |
| JPH0460992B2 true JPH0460992B2 (en) | 1992-09-29 |
Family
ID=14778372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12011783A Granted JPS6011480A (en) | 1983-06-30 | 1983-06-30 | Preparation of thiosulfonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011480A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD868703S1 (en) | 2017-11-15 | 2019-12-03 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD868704S1 (en) | 2017-11-15 | 2019-12-03 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD879725S1 (en) | 2017-10-31 | 2020-03-31 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD883231S1 (en) | 2017-10-31 | 2020-05-05 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD942955S1 (en) | 2019-12-19 | 2022-02-08 | Corning Research & Development Corporation | Cap for an adapter |
-
1983
- 1983-06-30 JP JP12011783A patent/JPS6011480A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USD879725S1 (en) | 2017-10-31 | 2020-03-31 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD883231S1 (en) | 2017-10-31 | 2020-05-05 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD868703S1 (en) | 2017-11-15 | 2019-12-03 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD868704S1 (en) | 2017-11-15 | 2019-12-03 | Corning Research & Development Corporation | Cap for optical fiber connectors |
| USD942955S1 (en) | 2019-12-19 | 2022-02-08 | Corning Research & Development Corporation | Cap for an adapter |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6011480A (en) | 1985-01-21 |
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