EP0000573B1 - Process for the preparation of diamines containing a thioether group - Google Patents

Process for the preparation of diamines containing a thioether group 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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Prior art keywords
parts
process according
carbon atoms
mole
benzothiazole
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German (de)
French (fr)
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EP0000573A1 (en
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Paul Dr. Uhrhan
Jürgen Dr. Schwindt
Gerhard Dr. Grögler
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Bayer AG
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Bayer AG
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    • 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.

Description

Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung von Diaminen der allgemeinen Formel (I)The present invention relates to an improved process for the preparation of diamines of the general formula (I)

Figure imgb0001
Figure imgb0001

In dieser allgemeinen Formel (I) bedeutet A einen geradkettigen oder verzweigten, zweiwertigen, aliphatischen Kohlenwasserstoffrest mit 2-20, vorzugsweise 2-12, besonders bevorzugt 2-6 C-Atomen oder einen araliphatischen Kohlenwasserstoffrest mit 8 C-Atomen.In this 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.

Aus der Literatur (Farmaco Ed. Sci. 22 (7), 519-527 [1967]) ist ein Verfahren zur Herstellung von Verbindungen der Formel (I), in welcher A für einen gegebenenfalls methylsubstituierten Äthylenrest steht, bekanntgeworden, wobei man o-Aminothiophenol im alkalischen Milieu mit den entsprechenden ß-Halogenalkylaminen umsetzt. o-Aminothiophenol oder dessen Salze rufen jedoch auf der Haut empfindlicher Personen schwere Allergien hervor, was für ein technisches Herstellungsverfahren von großem Nachteil ist.From the literature (Farmaco Ed. Sci. 22 (7), 519-527 [1967]), a process for the preparation of compounds of the formula (I) in which A represents an optionally methyl-substituted ethylene radical has become known, where o- Aminothiophenol in an alkaline environment with the corresponding ß-haloalkylamines. However, o-aminothiophenol or its salts cause severe allergies on the skin of sensitive people, which is a great disadvantage for an industrial production process.

Gemäß US-Patent 3 789 072 werden Verbindungen analog zu jenen der obigen Formel (I), welche gegebenenfalls am aromatischen Ring substituiert sein können, die jedoch an der aliphatischen Aminogruppe alkyliert sind, durch Umsetzung eines o-Aminothiophenols mit einem N-alkylierten Halogenalkylamin in Gegenwart von NaNH2 hergestellt.According to US Pat. No. 3,789,072, compounds analogous to those of formula (I) above, which may optionally be substituted on the aromatic ring but are alkylated on the aliphatic amino group, are reacted by reacting an o-aminothiophenol with an N-alkylated haloalkylamine Presence of NaNH 2 produced.

Es wurde nun gefunden, daß man Verbindungen der allgemeinen Formel (I) auf einfache Weise und in hoher Ausbeute gefahrlos herstellen kann, indem man Benzothiazol in Gegenwart einer starken wäßrigen Base erhitzt und anschließend mit Halogenalkylaminen umsetzt. Es ist dabei als überraschend anzusehen, daß mit Hilfe des erfindungsgemäßen Verfahrens Produkte mit hohem Reinheitsgrad, d. h. ohne störende Nebenprodukte, erhalten werden, obwohl bekanntlich primäre und insbesondere primäre aliphatische Aminogruppen unter diesen Bedingungen leicht mit Verbindungen, die Alkylhalogenid-Strukturelemente aufweisen, unter N-Alkylierung reagieren.It has now been found that compounds of the general formula (I) can be prepared safely and in high yield in a simple manner by heating benzothiazole in the presence of a strong aqueous base and then reacting it with haloalkylamines. It is to be regarded as surprising that products with a high degree of purity, ie. H. without interfering by-products, although primary and especially primary aliphatic amino groups are known to react easily under these conditions with compounds having alkyl halide structural elements under N-alkylation.

Gegenstand der Erfindung ist ein Verfahren zur Herstellung von Diaminen der allgemeinen Formel

Figure imgb0002
welches dadurch gekennzeichnet ist, daß man 1 Mol Benzothiazol bei 40-180°C mit einer mindestens äquivalenten Menge einer starken wäßrigen Base und anschließend, gegebenenfalls portionsweise, mit 0,1 bis 1 Mol, vorzugsweise 0,7 bis 1 Mol, besonders bevorzugt 1 Mol, eines Halogenalkylamins der allgemeinen Formel
Figure imgb0003
bzw. eines Salzes, eines Amids oder Urethans des Halogenalkylamins umsetzt und gegebenenfalls anschließend die Acyl- bzw. Urethangruppe von der aliphatischen Aminogruppe hydrolytisch abspaltet, wobei

  • A einen gegebenenfalls verzweigten, zweiwertigen, aliphatischen Kohlenwasserstoffrest mit 2-20, vorzugsweise 2-12, besonders bevorzugt 2-6 C-Atomen oder einen araliphatischen Kohlenwasserstoffrest mit 8 C-Atomen darstellt und
  • X für ein Halogenatom, vorzugsweise Chlor oder Brom, besonders bevorzugt Chlor, steht.
The invention relates to a process for the preparation of diamines of the general formula
Figure imgb0002
 which is characterized in that 1 mol of benzothiazole at 40-180 ° C with an at least equivalent amount of a strong aqueous base and then, optionally in portions, with 0.1 to 1 mol, preferably 0.7 to 1 mol, particularly preferably 1 Mol, a haloalkylamine of the general formula
Figure imgb0003
 or a salt, an amide or urethane of the haloalkylamine and optionally subsequently hydrolytically cleaving the acyl or urethane group from the aliphatic amino group, where
  • A represents an optionally branched, divalent, aliphatic hydrocarbon radical with 2-20, preferably 2-12, particularly preferably 2-6 C atoms or an araliphatic hydrocarbon radical with 8 C atoms and
  • X represents a halogen atom, preferably chlorine or bromine, particularly preferably chlorine.

Beispielsweise steht A für einen Äthylen-, 1,2-oder 1,3-Propylen-, 1,2-Butylen-, 1,2-Isobutylen-, Tetramethylen-, 2,3-Butylen-, Pentamethylen-, 1,2-Pentylen-, 1,2-lsopentylen-, Hexamethylen-, 1,2-Hexylen-, Isobutyläthylen-, Octamethylen-, Dodekamethylen-, Xylylen- oder Phenyläthylen-Rest.For example, 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.

Verbindungen der obigen allgemeinen Formel (I), welche nach dem erfindungsgemäßen Verfahren erhältlich und zum Teil neu sind, sind z. B. die folgenden:

  • 2-(2-Aminoäthylthio)-anilin,
  • 2-(2-Aminopropylthio)-anilin,
  • 2-(3-Aminopropylthio)-anilin,
  • 2-(2-Amino-2,2-dimethyl-äthylthio)-anilin,
  • 2-(4-Aminobutylthio)-anilin,
  • 2-(2-Amino-1,2-dimethyl-äthylthio)-anilin,
  • 2-(5-Aminopentylthio)-anilin,
  • 2-(6-Aminohexylthio)-anilin,
  • 2-(5-Aminohexylthio)-anilin,
  • 2-(2-Aminoisobutylthio)-anilin,
  • 2-(12-Aminododecylthio)-anilin und
  • 2-(2-Aminophenyläthylthio)-anilin.
Compounds of the general formula (I) above, which are obtainable by the process according to the invention and some of which are new are e.g. B. the following:
  • 2- (2-aminoethylthio) aniline,
  • 2- (2-aminopropylthio) aniline,
  • 2- (3-aminopropylthio) aniline,
  • 2- (2-amino-2,2-dimethyl-ethylthio) aniline,
  • 2- (4-aminobutylthio) aniline,
  • 2- (2-amino-1,2-dimethyl-ethylthio) aniline,
  • 2- (5-aminopentylthio) aniline,
  • 2- (6-aminohexylthio) aniline,
  • 2- (5-aminohexylthio) aniline,
  • 2- (2-aminoisobutylthio) aniline,
  • 2- (12-aminododecylthio) aniline and
  • 2- (2-aminophenylethylthio) aniline.

Im erfindungsgemäßen Verfahren werden Benzothiazol, sowie Halogenalkylamine der allgemeinen Formel

Figure imgb0004
bzw. Derivate davon als Ausgangsmaterialien eingesetzt.In the process according to the invention, benzothiazole and haloalkylamines of the general formula
Figure imgb0004
 or derivatives thereof used as starting materials.

Halogenalkylamine sind allgemein bekannte Verbindungen, welche sich nach dem Fachmann geläufigen Verfahren leicht darstellen lassen. Erfindungsgemäß wird das Halogenalkylamin entweder als solches oder vorzugsweise in Form des Ammoniumsalzes mit einer organischen oder vorzugsweise anorganischen Säure oder in acylierter Form bzw. als Halogenalkylurethan eingesetzt. Der Acyl- bzw. Urethan-Rest wird im Verlauf bzw. am Ende der erfindungsgemäßen Umsetzung hydrolytisch abgespalten.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.

Bevorzugte Ammoniumsalze der Halogenalkylamine sind deren Hydrochloride. Geeignete Acyl-Reste sind geradkettige oder verzweigte aliphatische Acyl-Reste mit 1-18 C-Atomen oder aromatische Acyl-Reste mit 6-10 C-Atomen, wobei der Acetyl-Rest bevorzugt ist. Geeignete Urethane entsprechen der allgemeinen Formel

Figure imgb0005
in der

  • R einen geradkettigen oder verzweigten aliphatischen Rest mit 1-12 C-Atomen oder einen gegebenenfalls durch Halogen-Atome und/oder Alkyl-Gruppen (C1-C4) substituierten aromatischen Rest mit 6-10 C-Atomen bedeutet. Vorzugsweise steht R für den tert.-Butyl-Rest.
Preferred ammonium salts of the haloalkylamines are their hydrochlorides. Suitable acyl residues are straight-chain or branched aliphatic acyl residues with 1-18 C atoms or aromatic acyl residues with 6-10 C atoms, the acetyl residue being preferred. Suitable urethanes correspond to the general formula
Figure imgb0005
 in the
  • R denotes a straight-chain or branched aliphatic radical with 1-12 C atoms or an aromatic radical with 6-10 C atoms optionally substituted by halogen atoms and / or alkyl groups (C 1 -C 4 ). R is preferably the tert-butyl radical.

Im Anschluß an die erfindungsgemäße Reaktion können die Acyl- bzw. Urethanreste auf einfache Weise nach bekannten Verfahren hydrolytisch abgespalten werden.Following the reaction according to the invention, the acyl or urethane residues can easily be split off hydrolytically by known methods.

Erfindungsgemäß versetzt man zunächst Benzothiazol mit der stöchiometrischen Menge oder einem Überschuß (vorzugsweise 0 bis 10% Überschuß) einer starken wäßrigen Base, bevorzugt einer Alkali- oder Erdalkalilauge (vorzugsweise Natron- oder Kalilauge, besonders bevorzugt Natronlauge), erhitzt die Mischung, bis eine klare Lösung entstanden ist (dies dauert im allgemeinen etwa 1/2 bis 4 Stunden) und fügt das Halogenalkylamin bzw. dessen Derivat anschließend, vorzugsweise in Form einer Lösung in einem geeigneten Lösungsmittel, zu dem Reaktionsansatz hinzu. Die Reaktionspartner werden vorzugsweise in stöchiometrischen Mengen miteinander umgesetzt. Man kann jedoch auch mit einem bis zu 10fachen Überschuß an Benzothiazol arbeiten. Diese zweite Stufe der erfindungsgemäßen Reaktion dauert (je nach Reaktionstemperatur und Reaktivität des Halogenalkylamins) ca. 1/2 bis 10 h.According to the invention, 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.

Als Lösungsmittel können bei dem erfindungsgemäßen Verfahren beispielsweise die folgenden eingesetzt werden:

  • Wasser, Alkohole wie z. B. Methylalkohol, Äthylalkohol, Propylalkohol, Isopropylalkohol und Butylalkohol, Ketone wie Aceton oder Methyläthylketon, Äthylenglykol und dessen Alkyläther, Diäthylenglykol und Triäthylenglykol, Dimethylformamid, Dimethylsulfoxid, Dioxan usw. Auch Mischungen solcher Lösungsmittel sind geeignet. Bevorzugte Lösungsmittel sind Wasser und niedere Alkohole; ganz besonders bevorzugt sind Wasser sowie Mischungen von Wasser mit Methyl-, Äthyl- oder Isopropylalkohol.
The following can, for example, be used as solvents in the process according to the invention:
  • Water, alcohols such as B. methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol and butyl alcohol, ketones such as acetone or methyl ethyl ketone, ethylene glycol and its alkyl ether, diethylene glycol and triethylene glycol, dimethylformamide, dimethyl sulfoxide, dioxane, etc. Mixtures of such solvents are also suitable. Preferred solvents are water and lower alcohols; water and mixtures of water with methyl, ethyl or isopropyl alcohol are very particularly preferred.

Pro Mol Benzothiazol verwendet man vorzugsweise 200 bis 5000 ml Lösungsmittel, besonders bevorzugt 200 bis 2000 ml Lösungsmittel.200 to 5000 ml of solvent are preferably used per mole of benzothiazole, particularly preferably 200 to 2000 ml of solvent.

Die Reaktionstemperatur liegt im Bereich von 40 bis 180°C, vorzugsweise zwischen 50 und 140°C, wobei der Bereich von 70 bis 120°C besonders bevorzugt ist.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.

Die Gesamtreaktionszeit beträgt im allgemeinen ca. 1 Stunde bis 10 Stunden, vorzugsweise 3 bis 6 Stunden.The total reaction time is generally about 1 hour to 10 hours, preferably 3 to 6 hours.

Der Reaktionsdruck beträgt in der Regel 1 bar bis 10 bar. Vorzugsweise wird bei Normaldruck gearbeitet; jedoch kann es bei träge reagierenden Halogenalkylaminen auch vorteilhaft sein, zur Erreichung einer größeren Reaktionsgeschwindigkeit bei erhöhtem Druck zu arbeiten.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.

Die 2-(co-Aminoalkylthio)-aniline scheiden sich nach dem Alkalischstellen des Reaktionsansatzes als Flüssigkeiten ab und können gegebenenfalls im Vakuum destilliert werden, wenngleich dies im allgemeinen nicht erforderlich ist. Auch die Reinigung durch Überführung der 2-(a)-Aminoalkylthio)-aniline in deren Hydrochloride mit HCI ist möglich aber nicht erforderlich, da man die freien Amine nach dem erfindungsgemäßen Verfahren in hohen Ausbeuten und in überraschend hoher Reinheit (meist über 98%) erhält.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.

Die erfindungsgemäß zugänglichen Verbindungen der allgemeinen Formel (I) sind wertvolle Zwischenprodukte bei der an sich bekannten Herstellung von Polyurethankunststoffen aus Polyisocyanaten, höhermolekularen Polyhydroxylverbindungen und Diaminen als Kettenverlängerungsmitteln.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.

Als Kettenverlängerungsmittel besonders gut geeignet sind in vielen Fällen jene erfindungsgemäß zugänglichen Diamine, bei welchen die aliphatische Aminogruppen durch mindestens 3 C-Atome vom Schwefelatom getrennt ist. Diese Diamine zeichnen sich gegenüber jenen mit nur 2 C-Atomen nur 2 C-Atomen zwischen Schwefelatom und Aminogruppe durch eine stark unterschiedliche Reaktivität von aromatischer und aliphatischer Aminogruppe aus (siehe Beispiel 6), was insbesondere dann von Vorteil ist, wenn beim Aufbau eines Polyurethanharnstoffs ein Zwischenprodukt mit endständigen Aminogruppen hergestellt werden soll, wobei das Polyisocyanat gezielt nur mit einer der beiden Aminogruppen des Kettenverlängerungsmittels reagieren soll. In diesen Diaminen, der allgemeinen Formel

Figure imgb0006
steht R für einen gegebenenfalls verzweigten zweiwertigen aliphatischen Rest mit 3 bis 20, vorzugsweise 3 bis 12, besonders bevorzugt 3 bis 6 C-Atomen, mit der Maßgabe, daß die aliphatische Aminogruppe vom Schwefelatom durch mindestens 3 C-Atome getrennt ist, oder einen zweiwertigen araliphatischen Rest mit 8 C-Atomen. Besonders bevorzugt stellt R einen linearen Alkylrest mit 3 bis 6 C-Atomen dar.In many cases, 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. Compared to those with only 2 carbon atoms and only 2 carbon atoms between the sulfur atom and the amino group, 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. In these diamines, the general formula
Figure imgb0006
 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.

Die nachfolgenden Beispiele dienen zur näheren Erläuterung der Erfindung. Alle Mengenangaben beziehen sich, wenn nicht anders vermerkt, auf Gewichtsteile. Die Struktur der Substanzen wurde durch ihre IR-, NMR- und Massenspektren sowie durch Elementaranalyse eindeutig gesichert.The following examples serve to explain the invention in more detail. Unless otherwise noted, all quantities refer to parts by weight. The structure of the substances was clearly confirmed by their IR, NMR and mass spectra as well as by elemental analysis.

Beispiel 1example 1 2-(2-Aminoäthylthio)-anilin2- (2-aminoethylthio) aniline

135 Teile Benzothiazol und 80 Teile Natriumhydroxid werden in 200 Teilen Wasser 3 Stunden unter Rückfluß gekocht. Nach dem Abkühlen auf 70°Cwerden 200Teile Methanol hinzugefügt und bei 70°C innerhalb von 2 Stunden eine Lösung von 116 Teilen Chloräthylamin-hydrochlorid in 200 Teilen Wasser in den Ansatz getropft. Man rührt weitere 3 Stunden unter Rückfluß, kühlt ab und versetzt die Mischung mit einer Lösung von 50 Teilen Natriumhydroxid in 100 Teilen Wasser. Dann wird die organische Phase abgetrennt und die wäßrige Phase zweimal mit je 100 Teilen Toluol extrahiert.135 parts of benzothiazole and 80 parts of sodium hydroxide are refluxed in 200 parts of water for 3 hours. After cooling to 70 ° C, 200 parts of methanol are added and a solution of 116 parts of chloroethylamine hydrochloride in 200 parts of water is added dropwise at 70 ° C in the course of 2 hours. The mixture is stirred under reflux for a further 3 hours, cooled and a solution of 50 parts of sodium hydroxide in 100 parts of water is added to the mixture. Then the organic phase is separated and the aqueous phase extracted twice with 100 parts of toluene.

Die vereinigten organischen Phasen werden eingedampft. Man erhält 156 Teile 2-(2-Amino- äthylthio)-anilin in Form einer gelblichen Flüssigkeit vom Siedepunkt 1520 C (0,08 mbar).

Figure imgb0007
The combined organic phases are evaporated. This gives 156 parts of 2- (2-amino-ethylthio) aniline (0.08 mbar) in the form of a yellowish liquid of boiling point 152 0 C.
Figure imgb0007

Beispiel 2Example 2 2-(3-Aminopropylthio)-anilin2- (3-aminopropylthio) aniline

270 Teile Benzothiazol und 180 Teile Natriumhydroxid werden in 400 Teilen Wasser 3 Stunden unter Rückfluß gekocht. Nach dem Abkühlen auf 70° C werden 250 Teile Methanol hinzugefügt und bei 70°C innerhalb von 2 Stunden eine Lösung von 260 Teilen 3-Chlorpropylamin-hydrochlorid in 500 Teilen Wasser in den Ansatz getropft. Nachdem man weitere 3 Stunden bei 100°C nachgerührt hat, wird abgekühlt und eine Lösung von 100 Teilen Natriumhydroxid in 200 Teilen Wasser hinzugefügt. Man trennt die organische Phase ab, wäscht die wäßrige Phase noch einmal mit je 200 Teilen Toluol und dampft die vereinigten organischen Phasen ein.270 parts of benzothiazole and 180 parts of sodium hydroxide are refluxed in 400 parts of water for 3 hours. After cooling to 70 ° C., 250 parts of methanol are added and a solution of 260 parts of 3-chloropropylamine hydrochloride in 500 parts of water is added dropwise at 70 ° C. in the course of 2 hours. After stirring for a further 3 hours at 100 ° C., the mixture is cooled and a solution of 100 parts of sodium hydroxide in 200 parts of water is added. The organic phase is separated off, the aqueous phase is washed again with 200 parts of toluene each time and the combined organic phases are evaporated.

Es verbleiben 346 Teile 2-(3-Aminopropylthio)-anilin als gelbliche Flüssigkeit vom Siedepunkt 130°C (0,053 mbar).

Figure imgb0008
There remain 346 parts of 2- (3-aminopropylthio) aniline as a yellowish liquid with a boiling point of 130 ° C. (0.053 mbar).
Figure imgb0008

Beispiel 3Example 3 2-(2-Aminopropylthio)-anilin2- (2-aminopropylthio) aniline

135 Teile Benzothiazol und 80 Teile Natriumhydroxid werden in 200 Teilen Wasser 3 Stunden unter Rückfluß gekocht. Nach dem Abkühlen auf 80° C fügt man 200 Teile Äthanol hinzu und tropft bei 80°C eine Lösung von 130 Teilen 2-Chlorpropylamin-hydrochlorid in 300 Teilen Wasser innerhalb von 2 Stunden in den Ansatz. Man rührt weitere 3 Stunden unter Rückfluß, kühlt ab und versetzt die Mischung mit einer Lösung von 50 Teilen Natriumhydroxid in 100 Teilen Wasser. Dann wird die organische Phase abgetrennt, die wäßrige Phase zweimal mit je 100 Teilen Toluol extrahiert und die vereinigten organischen Phasen eingedampft. Es verbleiben 170 Teile 2-(2-Aminopropylthio)-anilin als gelbliche Flüssigkeit vom Siedepunkt 137°C (0,08 mbar).135 parts of benzothiazole and 80 parts of sodium hydroxide are refluxed in 200 parts of water for 3 hours. After cooling to 80 ° C., 200 parts of ethanol are added and a solution of 130 parts of 2-chloropropylamine hydrochloride in 300 parts of water is added dropwise at 80 ° C. in the course of 2 hours. The mixture is stirred under reflux for a further 3 hours, cooled and a solution of 50 parts of sodium hydroxide in 100 parts of water is added to the mixture. The organic phase is then separated off, the aqueous phase is extracted twice with 100 parts of toluene and the combined organic phases are evaporated. There remain 170 parts of 2- (2-aminopropylthio) aniline as a yellowish liquid with a boiling point of 137 ° C. (0.08 mbar).

Figure imgb0009
Figure imgb0009

Beispiel 4Example 4 2-(6-Aminohexylthio)-anilin2- (6-aminohexylthio) aniline

135 Teile Benzothiazol und 80 Teile Natriumhydroxid werden in 200 Teilen Wasser 3 Stunden unter Rückfluß gekocht. Nach dem Abkühlen auf 60° C werden 600 Teile Methanol eingetragen und bei 70° C 224,7 Teile N-(6-Chlorhexyl)-O-tert.-butylurethan innerhalb von 2 Stunden zugetropft. Nachdem man weitere 3 Stunden bei 70° C nachgerührt hat, kühlt man ab und trennt die organische Phase ab. Die wäßrige Phase wird noch zweimal mit je 150 Teilen Toluol extrahiert und die vereinigten organischen Phasen anschließend eingedampft. Es verbleiben 308 Teile einer gelben, viskosen Flüssigkeit, die in 950 Teile konzentrierter Salzsäure eingerührt werden. Man kocht zwei Stunden unter Rückfluß, kühlt ab und macht mit Natronlauge alkalisch. Anschließend wird die organische Phase abgetrennt, die wäßrige Phase noch zweimal mit je 200 Teilen Toluol extrahiert und die vereinigten organischen Phasen eingedampft. Es verbleiben 210 Teile 2-(6-Aminohexylthio)-anilin als gelbliche Flüssigkeit vom Siedepunkt 145° C (0,053 mbar).135 parts of benzothiazole and 80 parts of sodium hydroxide are refluxed in 200 parts of water for 3 hours. After cooling to 60 ° C., 600 parts of methanol are introduced and 224.7 parts of N- (6-chlorohexyl) -O-tert-butyl urethane are added dropwise at 70 ° C. in the course of 2 hours. After stirring for a further 3 hours at 70 ° C., the mixture is cooled and the organic phase is separated off. The aqueous phase is extracted twice with 150 parts of toluene and the combined organic phases are then evaporated. There remain 308 parts of a yellow, viscous liquid which are stirred into 950 parts of concentrated hydrochloric acid. The mixture is boiled under reflux for two hours, cooled and made alkaline with sodium hydroxide solution. The organic phase is then separated off, the aqueous phase is extracted twice with 200 parts of toluene and the combined organic phases are evaporated. 210 parts of 2- (6-aminohexylthio) aniline remain as a yellowish liquid with a boiling point of 145 ° C. (0.053 mbar).

Figure imgb0010
Figure imgb0010

Beispiel 5Example 5 Verwendung der nach dem erfindungsgemäßen Verfahren erhaltenen Diamine zur HerstellungUse of the diamines obtained by the process according to the invention for the preparation elastischer Polyurethankunststoffeelastic polyurethane plastics

100 Teile eines Präpolymeren (NCO-Gehalt: 3,6 Gew.-%), hergestellt aus einem linearen Polypropylenglykol (Molekulargewicht: 2000; OH-Zahl: 56) und 2,4-Toluylen-diisocyanat werden bei einem Äquivalentverhältnis NCO : NHz von 1,1 : 1 mit 6,5 bis 8,65 Teilen der nach Beispiel 1 bis 4 gewonnenen araliphatischen schwefelhaltigen Diamine innerhalb von 30 Sekunden gut vermischt, das reagierende Gemisch in eine vorgeheizte Form gegeben und der Elastomerkörper bei 110°C 24 Stunden lang ausgeheizt. Man erhält Elastomerkörper von ausgezeichnetem mechanischen Werteniveau.100 parts of 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.

Beispiel 6Example 6 Untersuchung der ReaktivitätInvestigation of reactivity von Diaminen gemäß Beispiel 1, und 4of diamines according to Example 1 and 4 gegenüber Isocyanatentowards isocyanates

  • a) in eine Lösung von 0,1 Mol 2(2-Aminoäthyl- thio)-anilin in 50 g Chlorbenzol werden bei 10°C 17,0 g (0,2 Mol) Propylisocyanat gegeben. Der NCO-Gehalt der Lösung beträgt 9,3%. Das Reaktionsgemisch erwärmt sich auf 63°C. Eine nach 30 Sekunden durchgeführte NCO-Bestimmung ergibt 4,12% NCO. Nach weiteren 10 Minuten können noch 1,8% NCO nachgewiesen werden.a) in a solution of 0.1 mol of 2 (2-aminoethylthio) aniline in 50 g of chlorobenzene, 17.0 g (0.2 mol) of propyl isocyanate are added at 10 ° C. The NCO content of the solution is 9.3%. The reaction mixture warms to 63 ° C. An NCO determination carried out after 30 seconds gives 4.12% NCO. After another 10 minutes, 1.8% NCO can still be detected.
  • b) Analog wie unter a) beschrieben, werden 0,1 Mol 2-(3-Aminopropylthio)-anilin und 0,2 Mol Propylisocyanat umgesetzt. Der Anfangsgehalt an NCO-Gruppen beträgt 9,1%; das Reaktionsgemisch erwärmt sich auf 60°C. Nach 30 Sekunden sind noch 4,0% NCO, nach 15 Minuten noch 3,95% NCO und nach 45 Minuten 3,6% NCO durch Titration nachzuweisen.b) Analogously as described under a), 0.1 mol of 2- (3-aminopropylthio) aniline and 0.2 mol of propyl isocyanate are reacted. The initial content of NCO groups is 9.1%; the reaction mixture warms to 60 ° C. After 30 seconds, 4.0% NCO can still be detected, after 15 minutes 3.95% NCO and after 45 minutes 3.6% NCO by titration.
  • c) Analog wie unter a) beschrieben, werden 0,1 Mol 2-(6-Aminohexylthio)-anilin und 0,2 Mol Propylisocyanat umgesetzt. Der Anfangs-NCO-Gehalt beträgt 8,65%. Das Reaktionsgemisch erwärmt sich nach Zugabe des Isocyanats auf 62° C. Nach 30 Sekunden sind noch 4,1% NCO, nach 15 Minuten 3,8% und nach 105 Minuten noch 3,4% an NCO-Gruppen nachzuweisen.c) Analogously to that described under a), 0.1 mol of 2- (6-aminohexylthio) aniline and 0.2 mol of propyl isocyanate are reacted. The initial NCO content is 8.65%. After the addition of the isocyanate, the reaction mixture warms to 62 ° C. After 30 seconds, 4.1% NCO, 3.8% after 15 minutes and 3.4% after 105 minutes can still be detected.

Die Versuche zeigen, daß bei den erfindungsgemäßen Diaminen aus Beispiel 2 und 4 die aromatische Aminogruppe gegenüber Isocyanaten wesentlich weniger reaktiv ist als die aliphatische.The experiments show that in the diamines according to the invention from Examples 2 and 4 the aromatic amino group is significantly less reactive towards isocyanates than the aliphatic one.

Claims (7)

1. A process for the production of diamines of the general formula
Figure imgb0013
characterised in that 1 mole of benzothiazole is reacted, at from 40 to 180°C, with an at least equivalent quantity of a strong aqueous base and then, optionally in portions, with from 0.1 to 1 mole of a halogen alkylamine of the general formula:
Figure imgb0014
or of a salt, an amide or a urethane of the halogen alkylamine, and the acyl or urethane group is optionally split off hydrolytically from the aliphatic amino group; in the above formulae:
A represents an optionally branched, difunctional aliphatic hydrocarbon radical containing from 2 to 20 carbon atoms or an araliphatic hydrocarbon radical containing 8 carbon atoms; and
X represents a halogen atom.
2. A process according to claim 1, characterised in that
A represents an aliphatic hydrocarbon radical containing from 2 to 12 carbon atoms; and
X represents chlorine or bromine.
3. A process according to claim 1, characterised in that
A represents an aliphatic hydrocarbon radical containing from 2 to 6 carbon atoms; and
X represents chlorine.
4. A process according to claim 1 to 3, characterised in that the reaction is carried out in the presence of from 0.2 to 5 litres of a solvent, based on 1 mole of benzothiazole.
5. A process according to claim 1 to 4, characterised in that water, methanol, ethanol, isopropanol or mixtures thereof are used as solvent.
6. A process according to claim 1 to 5, characterised in that the hydrochloride or the tert.-butyl urethane of the halogen alkylamine is used.
7. A process according to claim 1 to 6, characterised in that from 0.7 to 1 mole of the halogen alkylamine or its derivative is used per mole of benzothiazole.
EP78100485A 1977-07-30 1978-07-24 Process for the preparation of diamines containing a thioether group Expired EP0000573B1 (en)

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US1954706A (en) * 1930-08-30 1934-04-10 Du Pont Process of manufacturing aminoarylthioglycollic acids
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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
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