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DE4322053A1 - Process for the preparation of amino-substituted thioethers - Google Patents

Process for the preparation of amino-substituted thioethers

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Publication number
DE4322053A1
DE4322053A1 DE19934322053 DE4322053A DE4322053A1 DE 4322053 A1 DE4322053 A1 DE 4322053A1 DE 19934322053 DE19934322053 DE 19934322053 DE 4322053 A DE4322053 A DE 4322053A DE 4322053 A1 DE4322053 A1 DE 4322053A1
Authority
DE
Germany
Prior art keywords
phenyl
methyl
oxazolidine
oxo
mercaptoethanol
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.)
Withdrawn
Application number
DE19934322053
Other languages
German (de)
Inventor
Klaus Dipl Chem Dr Kunde
Karl Josef Dipl Chem Dr Herd
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
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Priority to DE19934322053 priority Critical patent/DE4322053A1/en
Priority to TW083105060A priority patent/TW280812B/zh
Priority to EP94109543A priority patent/EP0632022B1/en
Priority to DE59401383T priority patent/DE59401383D1/en
Priority to US08/265,525 priority patent/US5410081A/en
Priority to JP6165760A priority patent/JPH0717946A/en
Priority to KR1019940015725A priority patent/KR100286845B1/en
Priority to CN94108118A priority patent/CN1038127C/en
Publication of DE4322053A1 publication Critical patent/DE4322053A1/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)

Abstract

Compounds of the formula (I) <IMAGE> are prepared by reacting 2-mercaptoethanol with compounds of the general formula (II) <IMAGE> in which the substituents are as defined in the description.-

Description

Die Erfindung betrifft ein neues Verfahren zur Herstellung von aminosubstituierten Thioethern. Derartige Verbindungen und ihre Herstellung sind grundsätzlich bekannt aus Journal of Medicinal and Chemistry, 1977, Vol. 20, Soloway, Chemo-Imuno- Therapie of Cancer, S. 1357 f. Aus J.Org. Chem. 1992, 57, Poindexter, S. 6257-6265 ist weiterhin die Verwendung von 2-Oxazolidinonen zur Aminoethylierung aromati­ scher Verbindungen bekannt.The invention relates to a new process for the preparation of amino-substituted Thioethers. Such connections and their production are known in principle from Journal of Medicinal and Chemistry, 1977, Vol. 20, Soloway, Chemo-Imuno- Therapy of Cancer, p. 1357 f. From J.Org. Chem. 1992, 57, Poindexter, pp. 6257-6265 is also the use of 2-oxazolidinones for aminoethylation aromati known connections.

Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (I)The present invention relates to a method for producing compounds of the general formula (I)

worin
R, R¹-R⁴ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl, mit OH, C₁-C₄- Alkoxy oder SO₃H-substituiertes C₁-C₄-Alkyl, Phenyl, Benzyl, mit Halogen, C₁-C₄-Alkoxy oder SO₃H-substituiertes Phenyl oder Benzyl bedeuten,
dadurch gekennzeichnet, daß man von 2-Mercaptoethanol mit Verbindungen der allgemeinen Formel (II)
wherein
R, R¹-R⁴ independently of one another hydrogen, C₁-C₄-alkyl, with OH, C₁-C₄- alkoxy or SO₃H-substituted C₁-C₄-alkyl, phenyl, benzyl, with halogen, C₁-C₄-alkoxy or SO₃H-substituted phenyl or benzyl,
characterized in that 2-mercaptoethanol with compounds of the general formula (II)

worin
R und R¹-R⁴ die oben angegebene Bedeutung besitzen, umsetzt.
wherein
R and R¹-R⁴ have the meaning given above, implemented.

Die Umsetzung erfolgt vorzugsweise bei Temperaturen zwischen 100°C und 250°C, vorzugsweise zwischen 150°C und 200°C.The reaction is preferably carried out at temperatures between 100 ° C and 250 ° C, preferably between 150 ° C and 200 ° C.

Bevorzugt wird das Verfahren zur Herstellung von Verbindungen der Formel (I), worin
R = Wasserstoff, Methyl, Ethyl, Phenyl, Benzyl,
R¹-R⁴ = unabhängig voneinander Wasserstoff, Methyl, Phenyl ist.
Preferred is the process for the preparation of compounds of formula (I), wherein
R = hydrogen, methyl, ethyl, phenyl, benzyl,
R¹-R⁴ = independently of one another is hydrogen, methyl, phenyl.

In einer besonders bevorzugten Ausführungsform haben R¹-R⁴ die gleiche Bedeutung.In a particularly preferred embodiment, R¹-R⁴ have the same Meaning.

Die Umsetzung wird in einem Lösungsmittel, bevorzugt aber ohne Lösemittel, durchgeführt.The reaction is carried out in a solvent, but preferably without a solvent, carried out.

Die Umsetzung von 2-Oxazolidinonen mit Thiophenolen ist zwar bekannt, mit Alkyl­ mercaptanen ist dagegen keine Umsetzung zu den 2-(Alkylmercapto)-ethylaminen gelungen (G.S. Poindexter et al., J. Org. Chem. 1992, 57, 6257-6265).The reaction of 2-oxazolidinones with thiophenols is known, with alkyl In contrast, mercaptans is not a conversion to the 2- (alkylmercapto) ethylamines succeeded (G.S. Poindexter et al., J. Org. Chem. 1992, 57, 6257-6265).

Die Verbindungen der Formel (II) sind z. T. bekannt, ihre Herstellung erfolgt nach Verfahren, wie sie beschrieben sind in Houben-Weyl, Bd. E4 (1983) S. 192-211. The compounds of formula (II) are e.g. T. known, their manufacture takes place after Methods as described in Houben-Weyl, Vol. E4 (1983) pp. 192-211.  

Geeignet sind z. B.:
1-Oxo-1,3-oxazolidin (2-Oxazolidinon),
5-Methyl-2-oxo-1,3-oxazolidin,
3-Methyl-2-oxo-1,3-oxazolidin,
3-Phenyl-2-oxo-1,3-oxazolidin,
3-Benzyl-2-oxo-1,3-oxazolidin,
4-Phenyl-2-oxo-1,3-oxazolidin,
5-Phenyl-2-oxo-1,3-oxazolidin,
3,4-Diphenyl-2-oxo-1,3-oxazolidin ,
3,5-Diphenyl-2-oxo-1,3-oxazolidin,
3,4-Dimethy1-5-phenyl-2-oxo-1,3-oxazolidin,
3-Phenyl-4-hydroxymethyl-2-oxo-1,3-oxazolidin,
3,5-Dimethyl-2-oxo-1,3-oxazolidin
3-Ethyl-2-oxo-1,3-oxazolidin,
4-Ethyl-2-oxo-1,3-oxazolidin.
Are suitable for. B .:
1-oxo-1,3-oxazolidine (2-oxazolidinone),
5-methyl-2-oxo-1,3-oxazolidine,
3-methyl-2-oxo-1,3-oxazolidine,
3-phenyl-2-oxo-1,3-oxazolidine,
3-benzyl-2-oxo-1,3-oxazolidine,
4-phenyl-2-oxo-1,3-oxazolidine,
5-phenyl-2-oxo-1,3-oxazolidine,
3,4-diphenyl-2-oxo-1,3-oxazolidine,
3,5-diphenyl-2-oxo-1,3-oxazolidine,
3,4-dimethy1-5-phenyl-2-oxo-1,3-oxazolidine,
3-phenyl-4-hydroxymethyl-2-oxo-1,3-oxazolidine,
3,5-dimethyl-2-oxo-1,3-oxazolidine
3-ethyl-2-oxo-1,3-oxazolidine,
4-ethyl-2-oxo-1,3-oxazolidine.

Als Lösemittel können alle die verwendet werden, deren pKS-Wert deutlich geringer ist als der des 2-Mercaptoethanols, und die nicht selbst mit 2-Mercaptoethanol reagieren, z. B. Kohlenwasserstoffe, Ether, Alkohole, Carbonsäureamide, Sulfoxide, Sulfone, ausgenommen sind Amine.As solvents, all of which are used whose pK is much lower than that of the 2-mercaptoethanol, and do not themselves react with 2-mercaptoethanol, z. B. hydrocarbons, ethers, alcohols, carboxamides, sulfoxides, sulfones, except amines.

Solche Lösemittel sind z. B. Mesitylen, Naphthalin, 1-Methylnaphthalin, 2-Methyl­ naphthalin, Dekalin, Tetralin, o-Dichlorbenzol, Nitrobenzol, Biphenyl, Diphenylether, 1-Hexanol, 1-Heptanol, 1-Octanol, 2-Octanol, Ethylenglykol, Diethylenglykol, Diethylenglykolmonomethylether, Diethylenglykolmonoethylether, Glyzerin, N- Methyl-pyrrolidon, Caprolactam, N-Methylcaprolactam, Cyclohexanol, Dimethylsulf­ oxid, Dimethylsulfon, Sulfolan.Such solvents are e.g. B. mesitylene, naphthalene, 1-methylnaphthalene, 2-methyl naphthalene, decalin, tetralin, o-dichlorobenzene, nitrobenzene, biphenyl, diphenyl ether, 1-hexanol, 1-heptanol, 1-octanol, 2-octanol, ethylene glycol, diethylene glycol, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycerin, N- Methyl pyrrolidone, caprolactam, N-methyl caprolactam, cyclohexanol, dimethyl sulfate oxide, dimethyl sulfone, sulfolane.

Die erfindungsgemäß hergestellten 2-(2′-Aminoethylmercapto)-ethanole können verwendet werden als Zwischenprodukte für Pharmazeutika, Pestizide, insbesondere aber für Farbstoffe.The 2- (2'-aminoethylmercapto) ethanols prepared according to the invention can are used as intermediates for pharmaceuticals, pesticides, in particular but for dyes.

Beispiel 1example 1

78, 1 g 2-Mercaptoethanol und 163 g 3-Phenyl-2-oxazolidinon werden unter N₂ 5 Stunden auf 160°C erhitzt. Man erhält 2-(2′-Phenylaminoethylmercapto)-ethanol in fast quantitativer Ausbeute als schwach gelbliches Öl, dessen H-NMR-Spektrum folgende Signale aufweisen: (Lösemittel D₆-DMSO)
δ 2,58-2,75 ppm, 6H, m, δ 3,22 ppm, 2H, t, δ 4,80 ppm, 1H, s; δ 6,50-6,61 ppm, 3H, m; δ 7,05 ppm, 2H, d.
78, 1 g of 2-mercaptoethanol and 163 g of 3-phenyl-2-oxazolidinone are heated to 160 ° C. under N₂ for 5 hours. 2- (2′-Phenylaminoethylmercapto) ethanol is obtained in almost quantitative yield as a slightly yellowish oil, the H-NMR spectrum of which shows the following signals: (solvent D₆-DMSO)
δ 2.58-2.75 ppm, 6H, m, δ 3.22 ppm, 2H, t, δ 4.80 ppm, 1H, s; δ 6.50-6.61 ppm, 3H, m; δ 7.05 ppm, 2H, d.

Beispiel 2Example 2

156,2 g 2-Mercaptoethanol und 202 g 3-Methyl-2-oxazolidinon werden unter N₂ 5 Stunden auf 160°C erhitzt. Das 2-(2′-Methylaminoethylmercapto)-ethanol wird unter vermindertem Druck destilliert. Man erhält ein farbloses Öl; Kp 5-6,5 mm = 124°C bis 130°C.156.2 g of 2-mercaptoethanol and 202 g of 3-methyl-2-oxazolidinone are under N₂ 5th Heated to 160 ° C for hours. The 2- (2'-methylaminoethylmercapto) ethanol is under distilled under reduced pressure. A colorless oil is obtained; Kp 5-6.5 mm = 124 ° C to 130 ° C.

Beispiel 3Example 3

78, 1 g 2-Mercaptoethanol und 87 g 2-Oxazolidinon werden in 100 ml Diethylen­ glykolmonometyhlether 5 Stunden zum Sieden erhitzt. Man destilliert zunächst das Lösemittel und dann das 2-(2′-Aminoethylmercapto)-ethanol unter vermindertem Druck; Kp 3 mm = 117°C bis 119°C.78, 1 g of 2-mercaptoethanol and 87 g of 2-oxazolidinone are in 100 ml of diethylene glycol monomethyl ether heated to boiling for 5 hours. You distill that first Solvent and then the 2- (2'-aminoethylmercapto) ethanol under reduced Print; Kp 3 mm = 117 ° C to 119 ° C.

Claims (5)

1. Verfahren zur Herstellung von Verbindungen der allgemeinen Formel (1) worin
R, R¹-R⁴ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl, mit OH, C₁-C₄- Alkoxy oder SO₃H-substituiertes C₁-C₄-Alkyl, Phenyl, Benzyl, mit Halogen, C₁-C₄-Alkoxy oder SO₃H-substituiertes Phenyl oder Benzyl bedeuten,
dadurch gekennzeichnet, daß man 2-Mercaptoethanol mit Verbindungen der allgemeinen Formel (II) worin
R und R¹-R⁴ die oben angegebene Bedeutung besitzen, umsetzt.
1. Process for the preparation of compounds of the general formula (1) wherein
R, R¹-R⁴ independently of one another hydrogen, C₁-C₄-alkyl, with OH, C₁-C₄- alkoxy or SO₃H-substituted C₁-C₄-alkyl, phenyl, benzyl, with halogen, C₁-C₄-alkoxy or SO₃H-substituted phenyl or benzyl,
characterized in that 2-mercaptoethanol with compounds of the general formula (II) wherein
R and R¹-R⁴ have the meaning given above, implemented.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß
R = Wasserstoff, Methyl, Ethyl, Phenyl, Benzyl,
R¹-R⁴ = unabhängig voneinander Wasserstoff, Methyl, Phenyl ist.
2. The method according to claim 1, characterized in that
R = hydrogen, methyl, ethyl, phenyl, benzyl,
R¹-R⁴ = independently of one another is hydrogen, methyl, phenyl.
3. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Substituenten R¹ und R⁴ die gleich Bedeutung haben. 3. The method according to at least one of the preceding claims, characterized characterized in that the substituents R¹ and R⁴ have the same meaning.   4. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die Umsetzung zwischen 100°C und 250°C erfolgt.4. The method according to at least one of the preceding claims, characterized characterized in that the reaction takes place between 100 ° C and 250 ° C. 5. Verfahren nach wenigstens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß 2-Mercaptoethanol mit 3-Phenyl-2-oxazolidinon, 3- Methyl-2-oxazolidinon oder 2-Oxazolidinon umgesetzt wird.5. The method according to at least one of the preceding claims, characterized characterized in that 2-mercaptoethanol with 3-phenyl-2-oxazolidinone, 3- Methyl-2-oxazolidinone or 2-oxazolidinone is implemented.
DE19934322053 1993-07-02 1993-07-02 Process for the preparation of amino-substituted thioethers Withdrawn DE4322053A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
DE19934322053 DE4322053A1 (en) 1993-07-02 1993-07-02 Process for the preparation of amino-substituted thioethers
TW083105060A TW280812B (en) 1993-07-02 1994-06-03
EP94109543A EP0632022B1 (en) 1993-07-02 1994-06-21 Process for the preparation of amino-substituted thioethers
DE59401383T DE59401383D1 (en) 1993-07-02 1994-06-21 Process for the preparation of amino substituted thioethers
US08/265,525 US5410081A (en) 1993-07-02 1994-06-24 Process for the preparation of amino-substituted thioethers
JP6165760A JPH0717946A (en) 1993-07-02 1994-06-27 Preparation of amino-substituted thioether
KR1019940015725A KR100286845B1 (en) 1993-07-02 1994-07-01 Process for preparing amino-substituted thioether
CN94108118A CN1038127C (en) 1993-07-02 1994-07-02 Process for the preparation of amino-substituted thioethers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19934322053 DE4322053A1 (en) 1993-07-02 1993-07-02 Process for the preparation of amino-substituted thioethers

Publications (1)

Publication Number Publication Date
DE4322053A1 true DE4322053A1 (en) 1995-01-12

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Family Applications (1)

Application Number Title Priority Date Filing Date
DE19934322053 Withdrawn DE4322053A1 (en) 1993-07-02 1993-07-02 Process for the preparation of amino-substituted thioethers

Country Status (1)

Country Link
DE (1) DE4322053A1 (en)

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