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WO1993013084A1 - Procede de fabrication de benzothiazolyl-2-sulfenamides - Google Patents

Procede de fabrication de benzothiazolyl-2-sulfenamides Download PDF

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Publication number
WO1993013084A1
WO1993013084A1 PCT/EP1992/002917 EP9202917W WO9313084A1 WO 1993013084 A1 WO1993013084 A1 WO 1993013084A1 EP 9202917 W EP9202917 W EP 9202917W WO 9313084 A1 WO9313084 A1 WO 9313084A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydrogen peroxide
amine
mol
mercaptobenzothiazole
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.)
Ceased
Application number
PCT/EP1992/002917
Other languages
German (de)
English (en)
Inventor
Ludwig Eisenhuth
Manfred Bergfeld
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.)
Akzo NV
Akzo Nobel NV
Original Assignee
Akzo NV
Akzo Nobel NV
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 Akzo NV, Akzo Nobel NV filed Critical Akzo NV
Priority to US08/240,780 priority Critical patent/US5436346A/en
Priority to EP93901029A priority patent/EP0618911A1/fr
Publication of WO1993013084A1 publication Critical patent/WO1993013084A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/70—Sulfur atoms
    • C07D277/76—Sulfur atoms attached to a second hetero atom
    • C07D277/80—Sulfur atoms attached to a second hetero atom to a nitrogen atom

Definitions

  • the present invention relates to a process for the preparation of benzothiazolyl-2-sulfenamides from 2-mercapto-benzothiazoles and primary or secondary amines in the presence of an oxidizing agent.
  • Sulfenamides are used in large quantities as vulcanization accelerators.
  • the benzthiazolyl-2-sulfenamides are industrially prepared from the sodium salt of 2-mercaptobenzthiazole and the corresponding amine with sodium hypochlorite or chlorine.
  • the reaction is carried out according to the following reaction scheme (example preparation N-cyclohexyl-benzothiazolyl-2-sulfenamide):
  • DE-PS 33 25 724 describes a method in which according to the general reaction scheme
  • EP-A2-0 180 869 a process for the preparation of benzothiazolyl-2-sulfena ⁇ r ⁇ iden from 2-mercaptobenzthiazole or its salts and primary amines is described up to a conversion of only 95%, in which chlorine bleach, chlorine is preferred as the oxidizing agent and hydrogen peroxide come into consideration, the only test example relating to the use of hydrogen peroxide starting from the sodium salt of 2-mercaptobenzothiazole and the Prescription of addition of sulfuric acid and sodium hydroxide solution, so sodium sulfate is still formed as a by-product.
  • the prerequisite for an economical, environmentally friendly process is one without additional auxiliaries and without by-products polluting the wastewater with a sufficiently high yield. A specific reference to this cannot be found elsewhere in EP-A2-0 180 869.
  • This object is achieved by a process for the preparation of benzothiazolyl-2-sulfenamides by reacting a 2-mercaptobenzothiazole or dibenzthiazolyl-2,2'-disulfide with a primary or secondary aliphatic or cycloaliphatic amine in the presence of hydrogen peroxide as the oxidizing agent in aqueous medium, characterized in that to an aqueous suspension of the respective amine and the 2-mercaptobenzthiazole or dibenzthiazolyl-2,2'-disulfide in a ratio in the range between 1.0 to 1.5 mol of amine per mol of 2-mercaptobenzthiazole or equivalent of dibenzthiazolyl An aqueous hydrogen peroxide solution is metered in at a temperature in the range from 30 to 70 ° C.
  • 2-mercaptobenzthiazole or dibenzthiazolyl-2,2'-disulfide to be reacted as starting substance can be found, for example, in DE-PS 33 25 724 on page 3, lines 34 to 58, or page 3, line 64 to page 4, line 4 , mentioned connections.
  • the unsubstituted 2-mercaptobenzthiazole or dibenzthiazolyl-2,2'-disulfide is preferably used.
  • cyclohexylamine is preferably used.
  • both the amine and the hydrogen peroxide can be used in a very slight stoichiometric excess over the amount of 2-mercaptobenzothiazole or dibenzthiazolyl-2,2'-disulfide used.
  • a larger excess is possible, but for general economic considerations, but also to guarantee the desired higher selectivities, the amine excess should be below 50 mol% and the hydrogen peroxide excess should preferably be below 35 mol% and particularly preferably below 20 mol%. , each based on the amount of 2-mercaptobenzthiazole or dibenzthiazolyl-2,2'-disulfide used.
  • concentration of the aqueous hydrogen peroxide solution used in the process according to the invention can be varied within wide limits. It should not be too low so as not to reduce the yields by using relatively large amounts of water. Highly concentrated hydrogen peroxide solutions lead to losses in the product selectivity and should also be excluded for safety reasons. Concentrations to be used advantageously in the process according to the invention are therefore in the range from 5 to 30% by weight of hydrogen peroxide.
  • the time within which the aqueous hydrogen peroxide solution in the reaction approach is metered in the longer these metering times are selected, the higher the product yields. Dosing is preferably carried out within a time of at least 60 minutes and particularly preferably of at least 150 minutes. In this way, yields above 90%, based on the 2-mercapto-benzothiazole or dibenzthiazolyl-2,2'-disulfide used, are essentially achieved.
  • reaction temperature in the process according to the invention influences the selectivity. It is advantageously in the range from 30 ° C to 70 ° C; According to the invention, the best results are achieved at reaction temperatures in the range from 40 ° C. to 60 ° C. Poor product yields are obtained above 70 ° C and below 30 ° C, in the latter case surprisingly associated with increased by-product formation (e.g. sulfite, sulfate and sulfinic and sulfonic acids of 2-mercaptobenzothiazole).
  • by-product formation e.g. sulfite, sulfate and sulfinic and sulfonic acids of 2-mercaptobenzothiazole.
  • the method according to the invention can be carried out in a very simple manner. Auxiliaries such as catalysts or solvents are not required. Additions of water-miscible solvents, such as alcohols, may be advantageous, for example to improve the stirrability of the reaction mixture. However, preference is given to working without additional solvents and the amount of water being chosen such that a stirrable mixture of the starting compounds is formed in the form of a fine, homogeneous suspension, for example 2 parts by weight of water per 1 part by weight of 2-mercaptobenzothiazole / amine mixture.
  • the 2-mercaptobenzthiazole or dibenzthiazolyl-2,2'-disulfide and the amine are mixed and mixed together with water in a reaction vessel Reaction temperature, for example 50 ° C, heated.
  • a reaction vessel Reaction temperature for example 50 ° C
  • the salt formed from 2-mercaptobenzothiazole and the respective amine, in particular cyclohexylamine can also be introduced. In this latter case, only that amount of amine has to be added which is required for the stoichiometric excess desired in each case.
  • the aqueous hydrogen peroxide solution is then evenly metered into the stirred mixture, the contents of the reaction vessel being kept at the reaction temperature.
  • reaction mixture is then cooled to room temperature and the solid reaction product is filtered off and washed with water, optionally after washing with a mixture of the amine and water used in each case.
  • the amine can be recovered from the mother liquor by distillation, and possibly also unreacted 2-mercapto-benzothiazole or dibenzthiazolyl-2,2'-disulfide.
  • the purity is determined by titration, HPLC and the melting point.
  • the product obtainable with the method according to the invention without additional cleaning measures is characterized by high purity with values above 98%.
  • the process according to the invention fulfills essential criteria for an environmentally friendly and economical process for the preparation of N-cyclohexylbenzthiazolyl-2-sulfenamides:
  • a wastewater pollution is largely avoided, in particular due to the absence of by-products and Auxiliaries, such as catalysts and generally also solvents, an environmentally compatible oxidizing agent is used, simple chemical compounds in a small stoichiometric excess are used, and a simple, unpressurized reaction is a pure end product compared to the state of the art Technically superior high yield and high selectivity obtained.
  • the purity of the cyclohexylbenzthiazolylsulfenamide product is 99.1% (titration according to Lichty, J. Applied Chem., 2, 26, (1963)), the melting point 100-101 ° C.
  • dibenzthiazolyl-2,2'-disulfide is used instead of 2-mercaptobenzthiazole.
  • This example shows the strong influence of the amount of water on the product yield.
  • Example 1 from DE-A-31 27 193 was followed up: In a 250 ml glass reactor, 59.9 g of 50% aqueous cyclohexylamine and 0.1 mol of 2-mercaptobenzothiazole were heated to 85 ° C. with vigorous stirring, the temperature rising resulting 2-mercaptobenzothiazole cyclohexylamine salt largely dissolved. After cooling to 45 ° C., 92 g of 5% hydrogen peroxide (0.135 mol) were metered in over the course of 60 min with vigorous stirring. After stirring for 30 min at the same temperature, the mixture was cooled to room temperature and the precipitate was filtered off, washed with 10% cyclohexylamine solution and water and dried. Cyclohexylbenzthiazolylsulfenamide was thereby obtained in a yield of 75.6% of theory obtained (melting point 99-100 ° C; purity (titration according to Lichty) 97.6%).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Procédé de fabrication de benzothiazolyl-2-sulfénamides, consistant à faire réagir un 2-mercaptobenzothiazol ou un disulfure de 2,2'-dibenzothiazolyle avec une amine aliphatique ou cycloaliphatique primaire ou secondiare, en présence de peroxyde d'hydrogène comme oxydant, en milieu aqueux, caractérisé en ce qu'on ajoute, en quantités dosées, dans un intervalle de temps de 60 minutes au minimum, et à une température comprise entre 30 et 70 °C, à une suspension aqueuse renfermant respectivement l'amine et le 2-mercaptobenzothiazol ou le disulfure de 2,2'-dibenzothiazolyle, dans un rapport compris entre 1,0 et 1,5 mole d'amine par mole de 2-mercaptobenzothiazol ou l'équivalent de disulfure de 2,2'-dibenzothiazolyle, une solution aqueuse de peroxyde d'hydrogène, de préférence en une quantité inférieure à 1,35 mole par mole de 2-mercaptobenzothiazol ou par équivalent de disulfure de 2,2'-dibenzothiazolyle. La quantité d'eau dans le mélange réactionnel ne doit pas dépasser 1500 g mar mole de 2-mercaptobenzothiazol. On dispose ainsi d'un procédé économique, et ne nuisant pas à l'environnement, de fabrication de benzothiazolyl-2-sulfénamides, avec des rendements et une sélectivité élevés.
PCT/EP1992/002917 1991-12-21 1992-12-16 Procede de fabrication de benzothiazolyl-2-sulfenamides Ceased WO1993013084A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US08/240,780 US5436346A (en) 1991-12-21 1992-12-16 Process for the preparation of benzothiazolyl-2-sulphenamides
EP93901029A EP0618911A1 (fr) 1991-12-21 1992-12-16 Procede de fabrication de benzothiazolyl-2-sulfenamides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4142963.2 1991-12-21
DE4142963 1991-12-21

Publications (1)

Publication Number Publication Date
WO1993013084A1 true WO1993013084A1 (fr) 1993-07-08

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ID=6448128

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002917 Ceased WO1993013084A1 (fr) 1991-12-21 1992-12-16 Procede de fabrication de benzothiazolyl-2-sulfenamides

Country Status (3)

Country Link
EP (1) EP0618911A1 (fr)
CA (1) CA2126336A1 (fr)
WO (1) WO1993013084A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2122544C1 (ru) * 1997-12-19 1998-11-27 Общество с ограниченной ответственностью "Инкохим" Способ получения n-трет-бутил-2-бензтиазолсульфенамида
WO2003014096A1 (fr) * 2001-08-10 2003-02-20 Duslo, A.S. Procede et dispositif de production de n-alkyl-2-benzothiazolyl-sulfenimides, et leur procede de purification
EP1449837A1 (fr) * 2003-02-20 2004-08-25 Bayer Aktiengesellschaft Procédé de préparation des benzthiazolylsulfénamides par réaction de un amine primaire avec mercaptobenzthiazole en présence de peroxyde d'hydrogène et hypochlorite de metal alkali
CN100404518C (zh) * 2005-05-31 2008-07-23 中国石油天然气集团公司 一种制备2-苯并噻唑次磺酰胺的方法及装置
EP2272890A1 (fr) 2009-07-07 2011-01-12 Bayer MaterialScience AG Procédé de fabrication de polycarbonate
CN110627740A (zh) * 2019-09-30 2019-12-31 山东尚舜化工有限公司 一种不产生废盐废水的促进剂cbs的新型环保生产方法
CN116693468A (zh) * 2023-06-16 2023-09-05 天津大学 一种双氧水分步氧化合成橡胶促进剂cbs的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106699685A (zh) * 2016-12-22 2017-05-24 蔚林新材料科技股份有限公司 一种制备橡胶硫化促进剂n‑环己基‑2‑苯并噻唑次磺酰胺的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2053205A (en) * 1979-06-08 1981-02-04 Pennwalt Corp Manufacture of 2-benzothiazole sulphenamides
EP0180869A2 (fr) * 1984-11-08 1986-05-14 Bayer Ag Procédé de préparation de benzothiazole-sulfénamides stables au stockage

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2053205A (en) * 1979-06-08 1981-02-04 Pennwalt Corp Manufacture of 2-benzothiazole sulphenamides
EP0180869A2 (fr) * 1984-11-08 1986-05-14 Bayer Ag Procédé de préparation de benzothiazole-sulfénamides stables au stockage

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2122544C1 (ru) * 1997-12-19 1998-11-27 Общество с ограниченной ответственностью "Инкохим" Способ получения n-трет-бутил-2-бензтиазолсульфенамида
WO2003014096A1 (fr) * 2001-08-10 2003-02-20 Duslo, A.S. Procede et dispositif de production de n-alkyl-2-benzothiazolyl-sulfenimides, et leur procede de purification
EP1449837A1 (fr) * 2003-02-20 2004-08-25 Bayer Aktiengesellschaft Procédé de préparation des benzthiazolylsulfénamides par réaction de un amine primaire avec mercaptobenzthiazole en présence de peroxyde d'hydrogène et hypochlorite de metal alkali
CN100404518C (zh) * 2005-05-31 2008-07-23 中国石油天然气集团公司 一种制备2-苯并噻唑次磺酰胺的方法及装置
EP2272890A1 (fr) 2009-07-07 2011-01-12 Bayer MaterialScience AG Procédé de fabrication de polycarbonate
DE102009032020A1 (de) 2009-07-07 2011-01-13 Bayer Materialscience Ag Verfahren zur Herstellung von Polycarbonat
US8173762B2 (en) 2009-07-07 2012-05-08 Bayer Materialscience Ag Process for the preparation of polycarbonate
CN110627740A (zh) * 2019-09-30 2019-12-31 山东尚舜化工有限公司 一种不产生废盐废水的促进剂cbs的新型环保生产方法
CN116693468A (zh) * 2023-06-16 2023-09-05 天津大学 一种双氧水分步氧化合成橡胶促进剂cbs的方法

Also Published As

Publication number Publication date
EP0618911A1 (fr) 1994-10-12
CA2126336A1 (fr) 1993-07-08

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