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Method for Producing Vicinal Dithiol Verfahren Zur Herstellung Von Vicinalen Dithiolen Procédé Pour La Préparation De Thiols Vicinaux

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Method for Producing Vicinal Dithiol Verfahren Zur Herstellung Von Vicinalen Dithiolen Procédé Pour La Préparation De Thiols Vicinaux (19) & (11) EP 1 564 207 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07C 319/02 (2006.01) C07C 327/22 (2006.01) 02.06.2010 Bulletin 2010/22 (21) Application number: 05101082.5 (22) Date of filing: 14.02.2005 (54) Method for producing vicinal dithiol Verfahren zur Herstellung von vicinalen Dithiolen Procédé pour la préparation de thiols vicinaux (84) Designated Contracting States: (74) Representative: Gille Hrabal Struck Neidlein Prop DE FR GB Roos Patentanwälte (30) Priority: 17.02.2004 JP 2004040619 Brucknerstrasse 20 40593 Düsseldorf (DE) (43) Date of publication of application: 17.08.2005 Bulletin 2005/33 (56) References cited: US-A1- 2003 195 270 (73) Proprietor: MITSUBISHI GAS CHEMICAL COMPANY, INC. • DATABASE WPI Section Ch, Week 200441 Chiyoda-ku, Derwent Publications Ltd., London, GB; Class Tokyo (JP) A41, AN 2004-433442 XP002331198 & JP 2004 107278A (MITSUBISHI GAS CHEM CO INC) 8 April (72) Inventors: 2004 (2004-04-08) • KONDO, Mitsuteru Tokyo (JP) Remarks: • TAKEUCHI, Motoharu Thefile contains technical information submitted after Tokyo (JP) the application was filed and not included in this • JOHNO, Masahiro specification Tokyo (JP) • ISHII, Kenji Tokyo (JP) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 1 564 207 B1 Printed by Jouve, 75001 PARIS (FR) EP 1 564 207 B1 Description BACKGROUND OF THE INVENTION 5 1. Field of the Invention [0001] The present invention relates to a method for producing a vicinal dithiol which is useful for the production of optical materials such as plastic lenses, prisms, fiber optics, information recording media, filters and adhesives for optical devices. 10 2. Description of the Prior Art [0002] Cured materials produced by the polymerization of an episulfide compound added with a sulfur-containing compound such as thiol compounds are widely used at present in the applications for spectacle plastic lenses because 15 of their good balance between the refractive index and Abbe’s number. The vicinal dithiol, above all, has a high sulfur content and is extremely suitable for such applications because of the ability of increasing the refractive index of cured materials and the ability of increasing the crosslinking density of resultant polymers. [0003] In many of the proposed methods of producing the vicinal dithiol, a vicinal diol or a vicinal dihalide is reacted with thiourea. However, the proposed reactions involve side reactions such as polymerization, rearrangement, etc. and 20 the vicinal dithiol is produced in low yields. In other proposed methods, a compound having a thiirane ring is reacted with hydrogen sulfide or an alkali metal hydrogen sulfide. However, these proposed methods also involve undesirable polymerization, etc. and give the vicinal dithiol only in low yields. For example, the reaction of ethylene sulfide and hydrogen sulfide at room temperature provides ethanedithiol in 49% yield (E. M. J. Meade, et al., J. Chem. Soc., 1894 (1948)). The reaction of cyclohexene sulfide and potassium hydrogen sulfide provides cyclohexanedithiol in 38% yield 25 (C. C. J. Culvenor, et al., J. Chem. Soc., 282 (1949)). [0004] A process for the preparation of 3,3’-thiobis-(1,2-propanedithiol) is described in US 2003/0195270 A1, in this process (β-epithiopropyl)sulphide is reacted with hydrogen sulphide. The yield of the process is low. SUMMARY OF THE INVENTION 30 [0005] An object of the present invention is to develop a method for producing a vicinal dithiol in high yields. [0006] As a result of extensive research, the inventors have found that the vicinal dithiol is produced in high yields by the reaction of an episulfide compound having two thiirane rings in its molecule and a thiocarboxylic acidS- such as thioacetic S-acid. The present invention has been accomplished on the basis of this finding. 35 [0007] Thus, the invention provides a method for producing a vicinal dithiol comprising a step of reacting an episulfide compound having two thiirane rings in its molecule and a thiocarboxylic S-acid. DETAILED DESCRIPTION OF THE INVENTION 40 [0008] In view of the crosslinking ability of resultant vicinal dithiol and the refractive index of cured materials which are to be produced by the addition of the vicinal dithiol, the episulfide compound represented by the following formula 1 is the starting raw material: 45 50 1 6 wherein R to R are each independently hydrogen or C1-C10 hydrocarbon group, m is an integer from 0 to 6, and n is an integer from 0 to 4. [0009] Examples of the episulfide compounds include 1-(epithioethyl)-2-(γ-epithiobutylthio)ethane, 1-(epithioethyl)- 2-[2-(γ-epithiobutylthio)ethylthio]ethane, bis(β-epithiopropyl) sulfide, bis(β-epithiopropyl) disulfide, bis(β-epithiopzopyl) 55 trisulfide, bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane, 1,4- bis(β-epithiopropylthio)butane, 1,5-bis(β-epithiopropylthio)pentane, 1,6-bis(β-epithiopropylthio)hexane, 1-(β-epithiopro- pylthio)-2-[(2-β-epithiopropylthioethyl)thio]ethane, β1-(-epithiopropylthio)-2-[[2-(2-β-epithiopropylthioethyl)thioethyl] thio]ethane, 1,1,1-tris(β-epithiopropylthiomethyl)propane, and compounds derived from the preceding episulfide com- 2 EP 1 564 207 B1 pounds by substituting methyl group for at least one hydrogen of the epithio group, with bis( β-epithiopropyl) sulfide and bis(β-epithiopropyl) disulfide being preferred. [0010] The episulfide compound usable in the invention is not specifically limited to examples recited above, and the above compounds may be used alone or in combination of two or more. 5 [0011] The method of the invention comprises a first step of reacting the episulfide compound and the thiocarboxylic S-acid represented by the following formula 2: 10 wherein R7 is a hydrocarbon group having 1 to 7 carbon atoms, 15 in the presence of a base to produce a thiocarboxylic S-ester; a second step of hydrolyzing the thiocarboxylic S-ester in the presence of a base to produce a mercaptide; and a third step of converting the mercaptide into the vicinal dithiol in the presence of an acid. Example of the production scheme is shown below. First Step 20 [0012] 25 30 Second Step 35 [0013] 40 45 Third Step [0014] 50 55 3 EP 1 564 207 B1 wherein R1, R2, R3 and R7 are as defined above. [0015] In the first step, the thiirane ring of the episulfide compound is opened in the presence of the base to produce the thiocarboxylic S- ester. Examples of the thiocarboxylic S- acid of the formula 2 include thioacetic S- acid, thiopropionic S-acid, thiobutyric S-acid, thiobenzoic S-acid, etc., with thioacetic S- acid being particularly preferred. The thiocarboxylic 5 S-acid is used in an amount so as to regulate the ratio of the total molar number of the mercaptocarbonyl groups in the thiocarboxylic S-acid to the total molar number of thiirane rings in the episulfide compound within the range of preferably 0.1 to 10, more preferably 0.5 to 5, and still more preferably 0.9 to 2. [0016] The base is selected from the group consisting of ammonia, amines, phosphines, metal alcoholates, metal hydrides, metal hydroxides, metal carbonates and metal sulfides. The amount of the base to be used is preferably 0.0001 10 to 1 mol, more preferably 0.001 to 0.3 mol, and still more preferably 0.001 to 0.1 mol per one mole of the episulfide compound. [0017] Examples of the base are shown below. (1) Ammonia 15 (2) Amines: primary amines such as ethylamine, propylamine,n- see-propylamine, n-butylamine, sec-butylamine, iso- butylamine, tert-butylamine, pentylamine, hexylamine, heptylamine, octylamine, decylamine, laurylamine, myr- istylamine, 1,2-dimethylhexylamine, 3-pentylamine, 2-ethylhexylamine, allylamine, aminoethanol, 1-aminopro- 20 panol, 2-aminopropanol, aminobutanol, aminopentanol, aminohexanol, 3-ethoxypropylamine, 3-propoxypro- pylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 3-(2-ethylhexyloxy)pro- pylamine, aminocyclopentane, aminocyclohexane, aminonorbornene, aminomethylcyclohexane, aminoben- zene, benzylamine, phenetylamine, α-phenylethylamine, naphthylamine and furfurylamine; primary polyamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 25 1,3-diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-di- aminooctane, dimethylaminopropylamine, diethylaminopropylamine, bis(3-aminopropyl) ether, 1,2-bis(3-ami- nopropoxy)ethane, 1,3-bis(3-aminopropoxy)-2,2’-dimethylpropane, aminoethylethanolamine, 1,2-, 1,3- or 1,4- diaminocyclohexane, 1,3- or 1,4-bis(aminomethyl)cyclohexane, 1,3- or 1,4-bis(aminoethyl)cyclohexane, 1,3- or 1,4-bis(aminopropyl)cyclohexane, hydrogenated 4,4’-diaminodiphenylmethane, 2- or 4-aminopiperidine, 2- 30 or 4-aminomethylpiperidine, 2- or 4-aminoethylpiperidine, N-(aminoethyl) piperidine, N-(aminopropyl)piperidine, N-(aminoethyl)morpholine, N-(aminopropyl)morpholine, isophoronediamine, menthanediamine, 1,4- bis(amino- propyl)piperadine, o-, m- or p- phenylenediamine, 2,4- or 2,6-tolylenediamine, 2,4-toluenediamine, m-aminoben- zylamine, 4-chloro-o-phenylenediamine, tetrachloro-o-xylylenediamine, 4-methoxy-6-methyl-m-phenylenedi-
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