GB760181A - Improvements in the production of substitution products of 1.3.4-thiadiazole - Google Patents

Improvements in the production of substitution products of 1.3.4-thiadiazole

Info

Publication number
GB760181A
GB760181A GB23188/54A GB2318854A GB760181A GB 760181 A GB760181 A GB 760181A GB 23188/54 A GB23188/54 A GB 23188/54A GB 2318854 A GB2318854 A GB 2318854A GB 760181 A GB760181 A GB 760181A
Authority
GB
United Kingdom
Prior art keywords
thiadiazole
group
aliphatic hydrocarbon
hydrocarbon radical
saturated aliphatic
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
Application number
GB23188/54A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Badische Anilin and Sodafabrik AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE, Badische Anilin and Sodafabrik AG filed Critical BASF SE
Publication of GB760181A publication Critical patent/GB760181A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D285/00Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01Five-membered rings
    • C07D285/02Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/121,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/1251,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Abstract

Compounds of the general formula: <FORM:0760181/IV(a)/1> wherein X is a -CO-, -SO2-, or -CH2- group Y is a saturated aliphatic hydrocarbon radical containing from 5 to 18 carbon atoms and in which the free valency is satisfied by a hydrogen atom, a saturated aliphatic hydrocarbon radical, the group -CH2-COOH or -X-Y or another group <FORM:0760181/IV(a)/2> are used as plasticizers for polyvinyl chloride. The use of 2,5-di-(2-ethyl-n-hexyl-mercapto)-1,3,4-thiadiazole is specifically mentioned.ALSO:The invention comprises substituted 2 : 5-dimercapto-1 : 3 : 4-thiadiazoles containing the structure -S-(C2N2S)-S-X-Y, wherein X is a -CO-, -SO2- or -CH2- group, Y is a saturated aliphatic hydrocarbon radical containing from 5 to 18 carbon atoms, and in which the free valency is satisfied by a hydrogen atom, a saturated aliphatic hydrocarbon radical, the group -CH2COOH or -X-Y or another group -S-(C2N2S)-S-X-Y. The invention also comprises a process for the production of the compounds H-S-(C2N2S)-S-X-Y and Y-X-S-(C2N2S)-S-X-Y by reacting 2 : 5 - dimercapto - 1 : 3 : 4 - thiadiazole with either one or two molecular proportions of a compound Hal-X-Y, followed, if desired, by conversion of H-S-(C2N2S)-S-X-Y into a disulphide or by reaction of this compound with a compound Hal-CH2.COOH. The first reaction is carried out in weakly acid or, preferably, alkaline solution in the presence of diluents such as water, alcohols or mixtures thereof, alkaline solutions being prepared by the addition of caustic alkali, alkali metal carbonates, alcoholates or tertiary amines. Suitable reaction temperatures are in the range of - 10 DEG to 200 DEG C. The oxidation to disulphides may be effected with, for example, alcoholic iodine, hydrogen peroxide, bleaching powder or chlorine. In the examples, 1 mol. of 2 : 5-dimercapto - 1 : 3 : 4 - thiadiazole is reacted with 2 mols. of n-octyl chloride, 2-ethyl-n-hexyl bromide and dodecyl bromide to give respectively 2 : 5 - di - (n - octylmercapto) -, 2 : 5 - di - (2 - ethyl - n - hexylmercapto) - and 2 : 5 - di - (dodecylmercapto) - 1 : 3 : 4 - thiadiazole; 1 mol. of 2 : 5 - dimercapto - 1 : 3 : 4 - thiadiazole gives, with 1 mol. of n-octyl bromide or iodide, 2-(n-octylmercapto)-5-mercapto-1 : 3 : 4-thiadiazole which is then oxidized to 2 : 21-dithio-bis-(5-n-octylmercapto - 1 : 3 : 4 - thiadiazole); 2 - (2 - ethyl - n - hexylmercapto) -, 2 - dodecylmercapto - and 2 - octadecylmercapto - 5 - mercapto - 1 : 3 : 4 - thiadiazole and the corresponding disulphides are similarly prepared, and the cyclohexylamine salt of the first is also prepared; 2 : 5-dimercapto-1 : 3 : 4-thiadiazole is reacted with either one or two molecular proportions of 2-ethylhexanoyl chloride to give the appropriate mono- or di-substituted 1 : 3 : 4-thiadiazoles, and with 1 mol. of decyl sulphochloride to give 5-decylsulphonylmercapto-2-mercapto - 1 : 3 : 4 - thiadiazole; and 2 - (2 - ethyl - n - hexylmercapto) - 5 - mercapto - 1 : 3 : 4 - thiadiazole and monochloracetic acid react to give 2-(2-ethyl-n-hexylmercapto)-5 carboxymethylmercapto - 1 : 3 : 4 - thiadiazole. Other starting materials referred to include sperm oil chloride, sperm oil fatty acid chloride, 2-ethylheptanoyl chloride, decyl and undecyl sulphonic acid chloride and palmitic acid chloride or bromide. Starting material. 2,5-Dimercapto-1,3,4-thiadiazole is prepared from hydrazine in aqueous solution containing free alkali by treatment with carbon disulphide and acidification.ALSO:Compounds of the general formula:- <FORM:0760181/II/1> wherein X is a - CO -, - SO2 -, or - CH2 - group, Y is a saturated aliphatic hydrocarbon radical containing from 5 to 18 carbon atoms and in which the free valency is satisfied by a hydrogen atom, a saturated aliphatic hydrocarbon radical, the group - CH2 - COOH or - X - Y or another group Y - X - S - (C2N2S) - S - are added to alkaline cleaning agents containing phosphates to prevent the corrosion or tarnishing of metals.ALSO:Compounds of the general formula <FORM:0760181/V/1> where X is a -CO-, -SO2-, or -CH2- group, Y is a saturated aliphatic hydrocarbon radical containing from 5 to 18 carbon atoms and in which the free valency is satisfied by a hydrogen atom, a saturated aliphatic hydrocarbon radical, the group -CH2-, COOH or -X-Y or another group Y-X-S- (C2N2S)-S- are used as vulcanization accelerators. Examples are given specifying, as vulcanization accelerators of the above formula, 2, 21 dithio-bis (5n -octylmercapto-1, 3, 4 thiadiazole) and the cyclohexylamine salt of 2- (2-ethyl-n-hexthylmercapto)-5-mercapto-1, 3, 4-thiadiozole.ALSO:Compounds of the general formula <FORM:0760181/VI/1> wherein X is a -CO-, -SO2-, or -CH2- group, Y is a saturated aliphatic hydrocarbon radical containing from 5 to 18 carbon atoms and in which the free valency is satisfied by a hydrogen atom, a saturated aliphatic hydrocarbon radical, the group -CH2-COOH or -X-Y or another group Y-X-S-(C2N2S)-S- are used as light protective agents. The following compositions are referred to: 2.5-di-(n-octylmercapto)-1.3.4-thiadiazole as an alcoholic solution, an aqueous emulsion and a cream; 2.21-dithio - bis - (5 - n - octyl - mercapto-1.3.4-thiadiazole) as an alcoholic solution; and 2-(2-ethyl-n-hexylmercapto) -5-carboxymethyl-mercapto-1.3.4-thiadiazole as an aqueous emulsion. The use of 2.5-di-(dodecylmercapto)-1.3.4-thiadiazole and 2.21 - dithio - bis - (5 - (2 - ethyl - n-hexylmercapto)-1.3.4-thiadiazole) as sunburn preparations is also referred to.
GB23188/54A 1953-08-19 1954-08-10 Improvements in the production of substitution products of 1.3.4-thiadiazole Expired GB760181A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE760181X 1953-08-19

Publications (1)

Publication Number Publication Date
GB760181A true GB760181A (en) 1956-10-31

Family

ID=6661211

Family Applications (1)

Application Number Title Priority Date Filing Date
GB23188/54A Expired GB760181A (en) 1953-08-19 1954-08-10 Improvements in the production of substitution products of 1.3.4-thiadiazole

Country Status (1)

Country Link
GB (1) GB760181A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3223524A (en) * 1959-09-26 1965-12-14 Agfa Ag Process for the production of planographic printing plates having an aluminum support
US4174324A (en) * 1977-06-30 1979-11-13 Smithkline Corporation 3-(Carboxymethyl)thio-1H-1,2,4-triazol-5-thione
CN104387339A (en) * 2014-11-18 2015-03-04 天津理工大学 Thiadiazole derivative containing fatty chains and method for preparing thiadiazole derivative containing fatty chains

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3223524A (en) * 1959-09-26 1965-12-14 Agfa Ag Process for the production of planographic printing plates having an aluminum support
US4174324A (en) * 1977-06-30 1979-11-13 Smithkline Corporation 3-(Carboxymethyl)thio-1H-1,2,4-triazol-5-thione
CN104387339A (en) * 2014-11-18 2015-03-04 天津理工大学 Thiadiazole derivative containing fatty chains and method for preparing thiadiazole derivative containing fatty chains

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