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EP0000573B1 - Procédé de préparation de diamines contenant un groupe thioéther - Google Patents

Procédé de préparation de diamines contenant un groupe thioéther Download PDF

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Publication number
EP0000573B1
EP0000573B1 EP78100485A EP78100485A EP0000573B1 EP 0000573 B1 EP0000573 B1 EP 0000573B1 EP 78100485 A EP78100485 A EP 78100485A EP 78100485 A EP78100485 A EP 78100485A EP 0000573 B1 EP0000573 B1 EP 0000573B1
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EP
European Patent Office
Prior art keywords
parts
process according
carbon atoms
mole
benzothiazole
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
EP78100485A
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German (de)
English (en)
Other versions
EP0000573A1 (fr
Inventor
Paul Dr. Uhrhan
Jürgen Dr. Schwindt
Gerhard Dr. Grögler
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.)
Bayer AG
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Bayer AG
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Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000573A1 publication Critical patent/EP0000573A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C08G18/3863—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms
    • C08G18/3865—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms
    • C08G18/3868—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing groups having sulfur atoms between two carbon atoms, the sulfur atoms being directly linked to carbon atoms or other sulfur atoms containing groups having one sulfur atom between two carbon atoms the sulfur atom belonging to a sulfide group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates

Definitions

  • the present invention relates to an improved process for the preparation of diamines of the general formula (I)
  • A is a straight-chain or branched, divalent, aliphatic hydrocarbon radical having 2-20, preferably 2-12, particularly preferably 2-6 C atoms or an araliphatic hydrocarbon radical having 8 C atoms.
  • A represents an ethylene, 1,2 or 1,3-propylene, 1,2-butylene, 1,2-isobutylene, tetramethylene, 2,3-butylene, pentamethylene, 1,2 -Pentylene, 1,2-isopentylene, hexamethylene, 1,2-hexylene, isobutylethylene, octamethylene, dodecamethylene, xylylene or phenylethylene radical.
  • Haloalkylamines are generally known Compounds which can be easily prepared by methods familiar to the person skilled in the art. According to the invention, the haloalkylamine is used either as such or preferably in the form of the ammonium salt with an organic or preferably inorganic acid or in acylated form or as haloalkyl urethane. The acyl or urethane residue is split off hydrolytically in the course or at the end of the reaction according to the invention.
  • the acyl or urethane residues can easily be split off hydrolytically by known methods.
  • benzothiazole is first mixed with the stoichiometric amount or an excess (preferably 0 to 10% excess) of a strong aqueous base, preferably an alkali or alkaline earth solution (preferably sodium or potassium hydroxide solution, particularly preferably sodium hydroxide solution), the mixture is heated until a clear one solution is formed (this takes generally about 1/2 to 4 hours) and adds the haloalkylamine or its derivative followed by, preferably in the form of a solution in a suitable solvent to the reaction mixture added.
  • the reactants are preferably reacted with one another in stoichiometric amounts. However, you can also work with an up to 10-fold excess of benzothiazole.
  • This second stage of the reaction according to the invention takes (depending on the reaction temperature and reactivity of the haloalkyl amine) is about 1/2 to 10 hours.
  • 200 to 5000 ml of solvent are preferably used per mole of benzothiazole, particularly preferably 200 to 2000 ml of solvent.
  • the reaction temperature is in the range from 40 to 180 ° C., preferably between 50 and 140 ° C., the range from 70 to 120 ° C. being particularly preferred.
  • the total reaction time is generally about 1 hour to 10 hours, preferably 3 to 6 hours.
  • the reaction pressure is usually 1 bar to 10 bar. Is preferably carried out at normal pressure; however, in the case of slow-reacting haloalkylamines, it may also be advantageous to work at elevated pressure to achieve a higher reaction rate.
  • the 2- (co-aminoalkylthio) anilines separate as liquids after the reaction mixture has been made alkaline and can optionally be distilled in vacuo, although this is generally not necessary. Purification by converting the 2- (a) -aminoalkylthio) anilines into their hydrochlorides with HCl is also possible, but not necessary, since the free amines are obtained in high yields and surprisingly high purity (usually over 98%) by the process according to the invention. receives.
  • the compounds of the general formula (I) accessible according to the invention are valuable intermediates in the known production of polyurethane plastics from polyisocyanates, higher molecular weight polyhydroxyl compounds and diamines as chain extenders.
  • those diamines accessible according to the invention in which the aliphatic amino groups are separated from the sulfur atom by at least 3 carbon atoms are particularly suitable as chain extenders.
  • these diamines are distinguished by a very different reactivity of the aromatic and aliphatic amino group (see Example 6), which is particularly advantageous when building up a polyurethane urea an intermediate product with terminal amino groups is to be produced, the polyisocyanate being intended to react only with one of the two amino groups of the chain extender.
  • R represents an optionally branched divalent aliphatic radical with 3 to 20, preferably 3 to 12, particularly preferably 3 to 6 carbon atoms, with the proviso that the aliphatic amino group is separated from the sulfur atom by at least 3 carbon atoms, or a divalent araliphatic radical with 8 carbon atoms.
  • R particularly preferably represents a linear alkyl radical having 3 to 6 carbon atoms.
  • a prepolymer (NCO content: 3.6% by weight), made from a linear polypropylene glycol (molecular weight: 2000; OH- Number: 56) and 2,4-tolylene diisocyanate with an equivalent ratio of NCO: NH z of 1.1: 1 with 6.5 to 8.65 parts of the araliphatic sulfur-containing diamines obtained according to Examples 1 to 4 are good within 30 seconds mixed, the reacting mixture placed in a preheated mold and the elastomer body heated at 110 ° C for 24 hours. Elastomer bodies of excellent mechanical value are obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (7)

1. Procédé de fabrication de diamines de formule générale:
Figure imgb0015
caractérisé en ce qu'on fait réagir 1 mole de benzothiazol à 40―180° C avec une quantité au moins équivalente d'une base aqueuse forte et ensuite, éventuellement par portions, avec 0,1 à 1 mole d'une halogénoalcoylamine de formule générale
Figure imgb0016
ou d'un sel, d'une amide ou d'un uréthane de l'halogénoalcoylamine et en ce qu'éventuellement on clive hydrolytiquement le groupe acyle ou uréthane du groupe aminé aliphatique,
A représentant un radical hydrocarboné aliphatique bivalent éventuellement ramifié ayant 2 à 20 atomes de carbone ou un radical hydrocarboné araliphatique ayant 8 atomes de carbone et
X représentant un atome d'halogène.
2. Procédé selon la revendication 1, caractérisé en ce que
A représente un radical hydrocarboné aliphatique ayant 2 à 12 atomes de carbone et
X du chlore ou du brome.
3. Procédé selon la revendication 1, caractérisé en ce que
A représente un radical hydrocarboné aliphatique ayant 2 à 6 atomes de carbone et
X du chlore.
4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce qu'on opère en présence de 0,2 à 5 litres d'un solvant pour 1 mole de benzothiazol.
5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'on utilise de l'eau, du méthanol, de l'éthanol, de l'isopropanol ou des mélanges de ceux-ci comme solvant.
6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce qu'on utilise le chlorhydrate ou l'uréthane de t-butyle de l'halogénoalcoylamine.
7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'on utilise 0,7 à 1 mole de l'halogénoalcoylamine ou de son dérivé pour 1 mole de benzothiazol.
EP78100485A 1977-07-30 1978-07-24 Procédé de préparation de diamines contenant un groupe thioéther Expired EP0000573B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2734575 1977-07-30
DE19772734575 DE2734575A1 (de) 1977-07-30 1977-07-30 Verfahren zur herstellung von diaminen

Publications (2)

Publication Number Publication Date
EP0000573A1 EP0000573A1 (fr) 1979-02-07
EP0000573B1 true EP0000573B1 (fr) 1981-03-18

Family

ID=6015333

Family Applications (1)

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EP78100485A Expired EP0000573B1 (fr) 1977-07-30 1978-07-24 Procédé de préparation de diamines contenant un groupe thioéther

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EP (1) EP0000573B1 (fr)
DE (2) DE2734575A1 (fr)
IT (1) IT7850522A0 (fr)

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1954706A (en) * 1930-08-30 1934-04-10 Du Pont Process of manufacturing aminoarylthioglycollic acids
GB404596A (en) * 1932-04-11 1934-01-18 Du Pont Preparation of arylamines
US2791612A (en) * 1955-10-10 1957-05-07 American Cyanamid Co Isolation process for 2-aminothiophenol
GB1161915A (en) * 1966-06-03 1969-08-20 Ciba Ltd Pharmaceutical Preparations comprising Sulphur-Containing Amino-Compounds for the Treatment of Depressive Conditions
US3950542A (en) * 1967-02-21 1976-04-13 L'oreal Cysteamine derivatives for oral treatment of seborrhea
US3789072A (en) * 1970-04-22 1974-01-29 Squibb & Sons Inc Carboxamides

Also Published As

Publication number Publication date
DE2860543D1 (en) 1981-04-16
EP0000573A1 (fr) 1979-02-07
IT7850522A0 (it) 1978-07-28
DE2734575A1 (de) 1979-02-08

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