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Title:
PROCESS FOR THE PREPARATION OF THIOALKYLAMINE DERIVATIVES
Document Type and Number:
WIPO Patent Application WO/2003/099777
Kind Code:
A1
Abstract:
The present invention relates to a novel process for the preparation of compounds of the formula (I) (I)by reacting in a first step amino alcohols of the formula (II) (II)with oleum to give sulphuric acid esters of the general formula (III) (III)and by reacting these sulphuric acid esters in a second step with mercaptans or salts thereof of the general formula (IV) (IV)in each formula, where applicable, R1, R2, R3, R4, R5, R6, R, n and M have the meanings given in the description,in the presence of a diluent and in the presence of a base.

Inventors:
STOELTING JOERN (DE)
Application Number:
PCT/EP2003/004911
Publication Date:
December 04, 2003
Filing Date:
May 12, 2003
Export Citation:
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Assignee:
BAYER CROPSCIENCE AG (DE)
STOELTING JOERN (DE)
International Classes:
C07C303/24; C07C305/06; C07C319/14; C07C323/25; C07D277/36; C07D277/74; (IPC1-7): C07C319/14; C07C323/25; C07D277/74; C07C303/24; C07C305/06
Domestic Patent References:
WO2001023350A12001-04-05
Foreign References:
US5507840A1996-04-16
US2689867A1954-09-21
Other References:
S. FRÄNKEL ET AL, BERICHTE DER DEUTSCHEN CHEMISCHEN GESELLSCHAFT, vol. 51, 1918, pages 1654 - 1662, XP002256757
Attorney, Agent or Firm:
BAYER CROPSCIENCE AG (Patents and Licensing, Leverkusen, DE)
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Claims:
Patent Claims
1. Process for preparing compounds of the formula (I) in which R1 and R2 in each case independently of one another represent hydrogen, C1 C4alkyl, C3C8cycloalkyl, C3C8cycloalkylClC4alkyl, hydroxyC1 C4alkyl; unsubstituted or monoto pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of halogen, cyano, nitro, ClC4alkyl, C3C8cycloalkyl, C1 C4alkoxy, C1C4alkylthio, C1C4alkylsulfinyl, C1C4alkylsulfonyl, carboxyl, ClC4alkoxycarbonyl, C1C4alkoxyC1C4alkyl, ClC4 alkylcarbonyl, haloClC4alkyl, haloClC4alkoxy, haloClC4alkyl thio, haloCiC4alkylsulfmyl, haloClC4alkylsulfonyl, haloClC4 alkylcarbonyl, phenylcarbonyl, phenoxycarbonyl, amino, ClC4alkyl amino and di(C1C4alkyl)amino (where the alkyl groups can be identical or different); phenyl, which is substituted at two adjacent carbon atoms by C3C4alkylene or C1C2alkylenedioxy ; unsubstituted or monoto pentasubstituted phenylClC4alkyl, where the substitu ents are identical or different and are selected from the group con sisting of halogen, cyano, nitro, C1C4alkyl, C3C8cycloalkyl, CiC4 alkoxy, C1C4alkylthio, C1C4aslkylsulfinyl, C1C4alkylsulfonyl, haloC1C4alkyl, haloC1C4alkoxy, haloC1C4alkylthio, haloCl C4alkylsulfinyl and haloClC4alkylsulfonyl ; R3 and R independently of one another represent hydrogen or C1C4alkyl, R5 and R6 independently of one another represent hydrogen, ClC4alkyl, unsubstituted or monoto pentasubstituted phenyl, where the substi tuents are identical or different and are selected from the group consisting of halogen, cyano, nitro, C1C4alkyl, C3C8cycloalkyl, C1 C4alkoxy, C1C4alkylthio, ClC4alkylsulfinyl, ClC4alkylsulfonyl, haloC1C4alkyl, haloClC4alkoxy, haloCIC4alkylthio, haloCl C4alkylsulfinyl and haloC1C4alkylsulfonyl ; unsubstituted or mono to pentasubstituted phenylC1C4alkyl, where the substituents are identical or different and are selected from the group consisting of halogen, cyano, nitro, ClC4alkyl, C3C8cycloalkyl, ClC4alkoxy, ClC4alkylthio, ClC4alkylsulfinyl, ClC4alkylsulfonyl, haloClC4 alkyl, haloClC4alkoxy, haloClC4alkylthio, haloClC4alkylsulfi nyl and haloClC4alkylsulfonyl, R represents unsubstituted or monoor polysubstituted C1C12alkyl, where the substituents are identical or different and are selected from the group consisting of halogen, hydroxy, ClC4alkoxy, haloClC4 alkoxy, C1C4alkylthio, C1C4alkylsulfinyl, and ClC4alkylsulfonyl ; unsubstituted or monoor polysubstituted C3Cscycloalkyl or C3C8 cycloalkylClC4alkyl, where the substituents are identical or different and are selected from the group consisting of halogen, C1C4 alkyl and ClC4alkoxy ; unsubstituted or monoto pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of halogen, C1C6alkyl, C3C8 cycloalkyl, C1C4alkoxy, haloClC4alkyl, haloClC4alkoxy ; un substituted or monoto pentasubstituted phenylClC4alkyl, where the substituents are identical or different and are selected from the group consisting of halogen and ClC4alkyl ; naphthyl; unsubstituted or monoor polysubstituted heteroaryl, where the substituents are identical or different and are selected from the group consisting of halogen, C1C4alkyl, ClC4alkoxy, unsubstituted or monoto pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of halogen and Cl C4alkyl, n represents 1,2, 3,4, 5,6, 7 or 8, where the group C (Rl) R2 may be identical or different, when n is greater than 1, and when n represents 1, R1 and R2 furthermore together represent C2C5alkylene, R1 furthermore represents together with R3 or Rs C3C5alkylene, R3 and R4 furthermore together represent C4C6alkylene, R3 and R furthermore together represent C2C4alkylene, RS and R6 furthermore together represent C4C6alkylene, characterized in that in a first step amino alcohols of the formula (II) in which R1,R2,R3,R4,R5,R6 and n have the above given meanings, are reacted with oleum to give sulphuric acid esters of the general formula (III) in which Ru, R2, R3, R4, R5, R6 and n have the above given meanings, and that these sulphuric acid esters in a second step are reacted with mercaptans or salts thereof of the general formula (IV) RSM (IV) in which R has the above given meanings, and Mrepresents hydrogen, ammonium or an alkali metal atom, in the presence of a base and preferably in the presence of a diluent.
2. Process according to Claim 1, characterized in that a compound of the formula (II), in which R1 and R2 in each case independently of one another represent hydrogen, C1 C4alkyl, C3C6cycloalkyl, C3C6cycloalkylC1C2alkyl, hydroxyCl C4alkyl ; unsubstituted or monoto pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, ClC4 alkyl, C3C6cycloalkyl, C1C4alkoxy, ClC4alkylthio, C1C4alkyl sulfinyl, C1C4alkylsulfonyl, carboxyl, C1C4alkoxycarbonyl, C1C4 alkoxyClC4alkyl, C1C4aslkylcarbonyl, haloCzC4alkyl, haloC1 C4alkoxy, haloClC4alkylthio, haloCzC4alkylsulfinyl, haloClC4 alkylsulfonyl, haloCzC4alkylcarbonyl, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms, phenylcarbonyl, phenoxycarbonyl, amino, C1C4alkylamino and di(CIC4alkyl) amino (where the alkyl groups can be identical or different); phenyl, which is substituted at two adjacent carbon atoms by C3C4alkylene or ClC2alkylenedioxy ; unsubstituted or monoto pentasubstituted phenylClC2alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, C1C4alkyl, C3C6cycloalkyl, ClC4 alkoxy, C1C4aslkylthio, C1C4alkylsulfinyl, C1C4alkylsulfonyl, haloClC4alkyl, haloCiC4alkoxy, haloClC4alkylthio, haloCl C4alkylsulfinyl and haloC1C4alkylsulfonyl, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms; R3 and R4 independently of one another represent hydrogen or ClC4alkyl, Rs and R6 independently of one another represent hydrogen, C1C4alkyl, unsubstituted or monoto pentasubstituted phenyl, where the substitu ents are identical or different and are selected from the group consist ing of fluorine, chlorine, bromine, iodine, cyano, nitro, C1C4alkyl, C3C6cycloalkyl, CiC4alkoxy, C1C4alkylthio, CiC4alkylsulfinyl, C1C4aslkylsulfonyl, haloClC4alkyl, haloClC4alkoxy, haloClC4 alkylthio, haloClC4alkylsulfmyl and haloClC4alkylsulfonyl, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms; unsubstituted or monoto pentasubstituted phenylC1C2alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, ClC4alkyl, C3C8cycloalkyl, ClC4alkoxy, ClC4alkylthio, C1C4alkylsulfinyl, C1C4alkylsulfonyl, haloCzC4alkyl, haloCl C4alkoxy, haloClC4alkylthio, haloClC4alkylsulfinyl and halo ClC4alkylsulfonyl, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms; n represents 1, 2,3, 4,5 or 6, where the group C (RI) R2 may be identical or different, when n is greater than 1, and when n represents 1, R1 and R2 furthermore together represent C2C5alkylene, R1 furthermore represents together with R3 or Rs C3C5alkylene, R3 and R4 furthermore together represent C4C6alkylene, R3 and RS furthermore together represent C2C4alkylene, Rs and R6 furthermore together represent C4C6alkylene, is used.
3. Process according to either Claim 1 or Claim 2, characterized in that a compound of the formula (IV), in which R represents unsubstituted or monoor polysubstituted ClCi2alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, ClC4alkoxy, haloClC4alkoxy having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms, ClC4alkylthio, ClC4alkyl sulfinyl and ClC4alkylsulfonyl ; unsubstituted or monoor polysub stituted C3C6cycloalkyl or C3C6cycloalkylClC2alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, ClC4alkyl and C1 C4alkoxy; unsubstituted or monoto pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, ClC4alkyl, C3C6cycloalkyl, ClC4alkoxy, haloClC4alkyl, haloClC4alkoxy, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms; unsubstituted or monoto pentasubstituted phenylCl C2alkyl, where the substituents are identical or different and are se lected from the group consisting of fluorine, chlorine, bromine, iodine and ClC4alkyl ; naphthyl; unsubstituted or monoor polysubstituted heteroaryl (preferably furyl, thienyl, pyrrolyl, oxazolyl, oxazolinyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2, 4oxadi azolyl, 1,3, 4oxadiazolyl, 1,2, 4thiadiazolyl, 1,3, 4thiadiazolyl, 1,2, 3 thiadiazolyl, 1,2, 5thiadiazolyl, 1,2, 3triazolyl, 1,2, 4triazolyl, tetrazo lyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl), where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, ClC4alkyl, ClC4 alkoxy, unsubstituted or monoto pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine and ClC4alkyl, M represents hydrogen, ammonium or an alkali metal atom (preferably sodium, potassium, lithium and caesium), is used.
4. Process according to any one of Claims 1 to 3, characterized in that the oleum contains between 1 % and 70 % S03.
5. Process according to any one of Claims 1 to 4, characterized in that the first step of the reaction is carried out at a temperature of between 50°C and 200°C.
6. Process according to any one of Claims 1 to 5, characterized in that within the first step per mol amino alcohol of formula (g) between 0.01 and 6 mol of S03, which is applied as solution in sulphuric acid (i. e. oleum) are used.
7. Process according to any one of Claims 1 to 6, characterized in that the sulphuric acid esters of formula (are used without isolation.
8. Process according to any one of Claims 1 to 7, characterized in that the base employed in the second step of the process is selected from the group consisting of alkali metal and alkaline earth metal hydroxides, alkali metal carbonates or hydrogencarbonates.
Description:
Process for the preparation of thioalkylamine derivatives The present invention relates to a novel process for the preparation of known thio- alkylamine derivatives.

Because of their chemical structure thioalkylamine derivatives can be divided into two groups, thiols and sulphides. For the preparation of both classes the methods discussed below have been described.

A first method for the preparation of thiols is based on the hydrolytic cleavage of thiazolin or thiazolidinone derivatives (cf. e. g. J. Med. Chem. 1965, 8, 762 ; JP 59- 231064, Bull. Soc. Chim. Fr. 1967, 3637). As thiazolin or thiazolidinone derivatives have to be prepared first via several reaction steps the overall yield of this method is very low.

Thiols can be obtained furthermore by a process comprising reacting sulphates of amino alcohols with ammonium sulphide (cf. e. g. Nihon Kagaku Kaishi 1979, 149).

This method requires long reactions times in a sealed reaction vessel, which causes high costs because of the required production plants having low productivity.

The reaction of oxazoline-or oxazolidinone derivatives with thiols is a method for the preparation of sulphides (cf. e. g. J. Org. Chem. 1992, 57,6257 ; J. Med. Chem.

1984, 27, 1354). A hydrolytic process is required to obtain reaction products as amides according to this method. However, no reaction is observed, if the oxazoli- dine ring of the starting compounds is e. g. alkyl substituted. Furthermore, only aro- matic sulphides can be prepared using this method because of the acidity of the mercaptans.

The hydrolytic cleavage of amides, which can be obtained by reaction of amino alcohols with mercaptans in the presence of carboxylic acids, also furnishes sulphides (cf. e. g. DE-OS 14 93 534). This method has to be carried out at high temperature and under pressure using long reaction times and is therefore restricted to the

synthesis of sulphides. Additionally a hydrolytic step is required to obtain the reaction products from amides.

The reaction of aziridines with sulphur compounds like mercaptans represents a me- thod for preparing of sulphides and thiols (cf. e. g. Tetrahedron 1992, 48,2359 ; Tetra- hedron Lett. 1983, 24, 2131). High demands on safety requirements have to be made for industrial scale production using this method, because highly toxic and possibly instable aziridines have to be prepared and isolated.

A method for the conversion of thioalkylalcohols into thioalkylamines is represented by the Ritter reaction with subsequent hydrolytic cleavage (cf. e. g. DE-OS 20 45 905). This method employs hydrocyanic acid in excess, which must be handled with the utmost caution. In the case that nitriles which can be easily handled are employed the hydrolytic process causes problems.

A further method for the preparation of thioalkylamine derivatives uses as starting material amino alcohols which are reacted with sulphuric acid to give the correspond- ing esters in a first step (cf. WO 01/23350). After evaporation to dryness this esters are further converted by reaction with mercaptans. The required evaporation after the first reaction step causes problems when this process is employed to a large scale production.

We have now found that compounds of the formula (1) in which R1 and R2 in each case independently of one another represent hydrogen, Cl-C4-alkyl, C3-Cg-cycloalkyl, C3-C8-cycloalkyl-Cl-C4-alkyl, hydroxy-Cl-C4-alkyl ; unsub- stituted or mono-to pentasubstituted phenyl, where the substituents are iden- tical or different and are selected from the group consisting of halogen, cyano,

nitro, C1-C4-alkyl, C3-c8-cycloalkyl, C1-C4-alkoxy, Cl-C4-alkylthio, C1-C4- alkylsulfinyl, Cl-C4-alkylsulfonyl, carboxyl, Cl-C4-alkoxycarbonyl, Cl-C4- alkoxy-C1-C4-alkyl, C1-C4-alkylcarbonyl, halo-Cl-C4-alkyl, halo-Cl-C4-alk- oxy, halo-Cl-C4-alkylthio, halo-Cl-C4-alkylsulfinyl, halo-C1-C4-alkylsulfonyl, halo-C,-C4-alkylcarbonyl, phenylcarbonyl, phenoxycarbonyl, amino, Cl-C4- alkylamino and di-(C1-C4-alkyl)-amino (where the alkyl groups can be identi- cal or different) ; phenyl, which is substituted at two adjacent carbon atoms by C3-C4-alkylene or C1-C2-alkylenedioxy; unsubstituted or mono-to pentasub- stituted phenyl-Cl-C4-alkyl, where the substituents are identical or different and are selected from the group consisting of halogen, cyano, nitro, C1-C4- alkyl, C3-C8-cycloalkyl, Cl-C4-alkoxy, Cl-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, halo-Cl-C4-alkyl, halo-Cl-C4-alkoxy, halo-Cl-C4-alkyl- thio, halo-C1-C4-alkylsulfinyl and halo-Cl-C4-alkylsulfonyl ; R3 and R4 independently of one another represent hydrogen or C1-C4-alkyl, and R6 independently of one another represent hydrogen, C1-C4-alkyl, unsubsti- tuted or mono-to pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of halogen, cyano, nitro, C1-C4-alkyl, C3-C8-cycloalkyl, Cl-C4-alkoxy, C1-C4-alkylthio, Cl-C4- alkylsulfinyl, C1-C4-alkylsulfonyl, halo-Cl-C4-alkyl, halo-Cl-C4-alkoxy, halo- C1-C4-alkylthio, halo-Cl-C4-alkylsulfinyl and halo-Cl-C4-alkylsulfonyl ; un- substituted or mono-to pentasubstituted phenyl-C1-C4-alkyl, where the substi- tuents are identical or different and are selected from the group consisting of halogen, cyano, nitro, C1-C4-alkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, Cl-C4- alkylthio, Cl-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, halo-Cl-C4-alkyl, halo-Cl- C4-alkoxy, halo-Cl-C4-alkylthio, halo-Cl-C4-alkylsulfinyl and halo-Cl-C4- alkylsulfonyl, R represents unsubstituted or mono-or polysubstituted Cl-C12-alkyl, where the substituents are identical or different and are selected from the group consist- ing of halogen, hydroxy, C1-C4j-alkoxy, halo-Cl-C4-alkoxy, C1-C4-alkylthio,

Cl-C4-alkylsulfinyl and Cl-C4-alkylsulfonyl ; unsubstituted or mono-or poly- substituted C3-Cs-cycloalkyl or C3-C8-cycloalkyl-C1-c4-alkyl, where the sub- stituents are identical or different and are selected from the group consisting of halogen, Cl-C4-alkyl and Cl-C4-alkoxy ; unsubstituted or mono-to penta- substituted phenyl, where the substituents are identical or different and are selected from the group consisting of halogen, Cl-C6-alkyl, C3-C8-cycloalkyl, Cl-C4-alkoxy, halo-Cl-C4-alkyl, halo-Cl-C4-alkoxy ; unsubstituted or mono- to pentasubstituted phenyl-Cl-C4-alkyl, where the substituents are identical or different and are selected from the group consisting of halogen and Cl-C4- alkyl ; naphthyl ; unsubstituted or mono-or polysubstituted heteroaryl, where the substituents are identical or different and are selected from the group consisting of halogen, Cl-C4-alkyl, Cl-C4-alkoxy, unsubstituted or mono-to pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of halogen and Cl-C4-alkyl, n represents 1,2, 3,4, 5,6, 7 or 8, where the group C (R') R may be identical or different, when n is greater than 1, and when n represents 1, R1 and R2 furthermore together represent C2-C5-alkylene, R1 furthermore represents together with R3 or R C3-C5-alkylene, R3 and R4 furthermore together represent C4-C6-alkylene, R3 and R furthermore together represent C2-C4-alkylene, R5 and R6 furthermore together represent C4-C6-alkylene, are obtained by reacting in a first step amino alcohols of the formula (IT) in which

Ru, R2, R3, R4, R5, R6 and n have the above given meanings, with oleum to give sulphuric acid esters of the general formula (III) in which Ru, R2, R3, R4, R5, R6 and n have the above given meanings, and by reacting these sulphuric acid esters in a second step with mercaptans or salts thereof of the general formula (IV) RSM (IV) in which R has the above given meanings, and M represents hydrogen, ammonium or an alkali metal atom, in the presence of a base and preferably in the presence of a diluent.

Surprisingly, using the process according to the invention, the tbioalkylamines of the formula (1) can be obtained in a simple manner in a very good space-time yield.

The reaction according to the invention therefore has the advantage of an increased reaction rate. This leads to the technical advantage of a high space-time yield. The process according to the invention has the further advantage that the solution of the intermediates of formula (hui) need not to be evaporated to dryness. The reaction mixture can be stirred at any time of the process which decreases the risk of a breaking reaction vessel in industrial plants.

Detailed description of the process according to the invention The course of the reaction of the process according to the invention can be outlined by the following general reaction scheme: NR'R'HN-'R5R6 NR5R6 (CR R Oleum CR R2 Base (CR R) n---- n -n CR3R4 CR3R4 RSM (IV) CR3R4 OH OS03 SR (n) (no (9 The formula (II) provides a general definition of the amino alcohols required as starting materials for carrying out the first step of the process according to the invention.

Preferred as starting material are amino alcohols of the formula (IT), in which Rl and R2 in each case independently of one another represent hydrogen, Cl-C4-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C2-alkyl, hydroxy-Cl-C4-alkyl ; unsub- stituted or mono-to pentasubstituted phenyl, where the substituents are iden- tical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C4-alkyl, C3-C6-cycloalkyl, Cl-C4- alkoxy, C1-C4-alkylthio, Cl-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, carboxyl, C1-C4-alkoxycarbonyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylcarbonyl, halo- Cl-C4-alkyl, halo-Cl-C4-alkoxy, halo-Cl-C4-alkylthio, halo-Cl-C4-alkylsulfi- nyl, halo-Cl-C4-alkylsulfonyl, halo-Cl-C4-alkylcarbonyl, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms, phenylcarbonyl, phenoxycarbonyl, amino, C1-C4-alkylamino and di- (Cl-C4-alkyl)-amino (where the alkyl groups can be identical or different); phenyl, which is substi- tuted at two adjacent carbon atoms by C3-C4-alkylene or Cl-C2-alkylenedioxy ; unsubstituted or mono-to pentasubstituted phenyl-C1-C2-alkyl, where the substituents are identical or different and are selected from the group consist- ing of fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C4-alkyl, C3-C6-

cycloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, C1-C4-alkyl- sulfonyl, halo-Cz-C4-alkyl, halo-C1-C4-alkoxy, halo-Cl-C4-allcylthio, halo-Cl- C4-alkylsulfinyl and halo-Cl-C4-alkylsulfonyl, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms; R3 and R4 independently of one another represent hydrogen or C1-C4-alkyl, R5 and R6 independently of one another represent hydrogen, C1-C4-alkyl, unsubsti- tuted or mono-to pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, Cl-C4-alkyl, C3-C6-cycloalkyl, Cl-C4-alkoxy, C1-C4-alkylthio, C1-C4-aslkylsulfinyl, Cl-C4-alkylsulfonyl, halo-C1-C4-alkyl, halo-Cl-C4-alkoxy, halo-C1-C4-alkylthio, halo-C1-C4-alkylsulfinyl and halo- Cl-C4-alkylsulfonyl, each having 1 to 9 identical or different fluorine, chlor- ine and/or bromine atoms; unsubstituted or mono-to pentasubstituted phenyl- Cl-C2-alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, C1-C4-aslkyl, C3-C8-cycloalkyl, C1-C4-alkoxy, C1-C4-alkylthio, C1-C4-alkyl- sulfinyl, C1-C4-alkylsulfonyl, halo-Cl-C4-alkyl, halo-Cl-C4-alkoxy, halo-Cl- C4-alkylthio, halo-Cl-C4-alkylsulfinyl and halo-Cl-C4-alkylsulfonyl, each having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms; n represents 1,2, 3,4, 5 or 6, where the group C (R') R2 may be identical or different, when n is greater than 1, and when n represents 1, R1 and R2 furthermore together represent C2-C5-alkylene, R1 furthermore represents together with R3 or R C3-C5-alkylene, R3 and R furthermore together represent C4-C6-alkylene, R3 and RS furthermore together represent C2-C4-alkylene, Rs and r6 furthermore together represent C4-C6-alkylene.

Particularly preferred as starting material are amino alcohols of the formula (fizz in which R1 and R2 in each case independently of one another represent hydrogen, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclo- hexylmethyl, cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexyl- ethyl, hydroxymethyl, hydroxyethyl; unsubstituted or mono-to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclobutyl, cyclo- pentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s-, t-butylthio, methylsulfmyl, ethylsulfinyl, n-, i-propylsulfinyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl, difluorochloromethyl, fluorodichloromethyl, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, difluorochloromethoxy, fluorodichloromethoxy, trifluor- methylthio, trichloromethylthio, difluoromethylthio, dichloromethylthio, di- fluorochloromethylthio, fluorodichloromethylthio, trifluoromethylsulfinyl, tri- chloromethylsulfinyl, difluoromethylsulfinyl, dichloromethylsulfinyl, di- fluorochloromethylsulfinyl, fluorodichloromethylsulfinyl, trifluoromethylsul- fonyl, trichloromethylsulfonyl, difluoromethylsulfonyl, dichloromethylsul- fonyl, difluorochloromethylsulfonyl, fluorodichloromethylsulfonyl, trifluoro- methylcarbonyl, carboxyl, methoxycarbonyl, ethoxycarbonyl, methoxymethyl, ethoxyethyl, methoxyethyl, ethoxymethyl, methylcarbonyl, ethylcarbonyl, phenylcarbonyl, phenoxycarbonyl, amino, methylamino, ethylamino, propyl- amino, dimethylamino, diethylamino; phenyl, which is substituted at two ad- jacent carbon atoms by-(CH2) 3-,-(CH2) 4-,-OCH20-,-O (CH2) 20- ; in each case unsubstituted or mono-to trisubstituted benzyl or phenylethyl, where in each case the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl,

ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfmyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl, difluorochloromethyl, fluorodichloromethyl, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, di- fluorochloromethoxy, fluorodichloromethoxy, trifluoromethylthio, trichloro- methylthio, difluoromethylthio, dichloromethylthio, difluorochloromethyl- thio, fluorodichloromethylthio, trifluoromethylsulfinyl, trichloromethylsul- finyl, difluoromethylsulfinyl, dichloromethylsulfmyl, difluorochloromethyl- sulfinyl, fluorodichloromethylsulfinyl, trifluoromethylsulfonyl, trichlorome- thylsulfonyl, difluoromethylsulfonyl, dichloromethylsulfonyl, difluorochloro- methylsulfonyl, fluorodichloromethylsulfonyl ; R3 and R4 independently of one another represent hydrogen, methyl, ethyl, n-, i-pro- pyl, n-, i-, s-, t-butyl, and R6 independently of one another represent hydrogen, methyl, ethyl, n-, i-pro- pyl, n-, i-, s-, t-butyl, unsubstituted or mono-to trisubstituted phenyl, where the substituents are identical or different and are selected from the group con- sisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfmyl, n-, i-propyl- sulfmyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-pro- pylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, trichloromethyl, di- fluoromethyl, dichloromethyl, difluorochloromethyl, fluorodichloromethyl, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, di- fluorochloromethoxy, fluorodichloromethoxy, trifluoromethylthio, trichloro- methylthio, difluoromethylthio, dichloromethylthio, difluorochloromethyl- thio, fluorodichloromethylthio, trifluoromethylsulfinyl, trichloromethylsulfi-

nyl, difluoromethylsulfinyl, dichloromethylsulfinyl, difluorochloromethylsul- finyl, fluorodichloromethylsulfinyl, trifluoromethylsulfonyl, trichloromethyl- sulfonyl, difluoromethylsulfonyl, dichloromethylsulfonyl, difluorochlorome- thylsulfonyl and fluorodichloromethylsulfonyl ; in each case unsubstituted or mono-to trisubstituted benzyl or phenylethyl, where in each case the substitu- ents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-propyl- thio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfinyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, trichloromethyl, difluoromethyl, di- chloromethyl, difluorochloromethyl, fluorodichloromethyl, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, difluorochloro- methoxy, fluorodichloromethoxy, trifluoromethylthio, trichloromethylthio, di- fluoromethylthio, dichloromethylthio, difluorochloromethylthio, fluorodi- chloromethylthio, trifluoromethylsulfinyl, trichloromethylsulfinyl, difluor- methylsulfinyl, dichloromethylsulfinyl, difluorochloromethylsulfinyl, fluoro- dichloromethylsulfmyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, di- fluoromethylsulfonyl, dichloromethylsulfonyl, difluorochloromethylsulfonyl, fluorodichloromethylsulfonyl, n represents 1,2, 3,4, 5 or 6, where the group C (R I) R2 may be identical or different, when n is greater than 1, and when n represents 1, R1 and R2 furthermore together represent- (CH2) 2-,- (CH2) 3-,- (CH2) 4-,- (CH2) 5-, R1 furthermore represents together with R3 or R5- (CH2) 3-,- (CH2) 4-,- (CH2) 5-, R3 and R4 furthermore together represent- (CH2) 4-,- (CH2) 5-,- (CH2) 6-, R3 and R furthermore together represent- (CH2) 2-,- (CH2) 3-,- (CH2) 4-, RS and R6 furthermore together represent -(CH2)4-, -(CH2)5-, -(CH2)6-.

Very particularly preferred as starting material are amino alcohols of the formula, in which R I and R in each case independently of one another represent hydrogen, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, hydroxymethyl, hydroxyethyl; unsubstituted or mono-to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consist- ing of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-pro- pylthio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfmyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylsulfmyl, trifluoromethylsulfonyl, trifluor- methylcarbonyl, carboxyl, methoxycarbonyl, methoxymethyl, ethoxyethyl, methoxyethyl, ethoxymethyl, methylcarbonyl, ethylcarbonyl, phenylcarbonyl, phenoxycarbonyl, amino, methylamino, ethylamino, propylamino, dimethyl- amino, diethylamino; phenyl, which is substituted at two adjacent carbon atoms by-(CH2) 3-,-(CH2) 4-,-OCH20-,-O (CH2) 20- ; unsubstituted or mono- to trisubstituted benzyl, where the substituents are identical or different and are selected from the group consisting of halogen, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-pro- pylthio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfinyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylsulfinyl, trifluoromethylsulfonyl ; R3 and R4 independently of one another represent hydrogen, methyl, ethyl, n-, i-pro- pyl, n-, i-, s-, t-butyl,

R and R independently of one another represent hydrogen, methyl, ethyl, n-, i-pro- pyl, n-, i-, s-, t-butyl, unsubstituted or mono-to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-propyl- thio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfinyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluoromethylsulfinyl, trifluoromethylsulfonyl ; unsubstitu- ted or mono-to trisubstituted benzyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, methylthio, ethylthio, n-, i-propylthio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfinyl, n-, i-, s-, t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy, trifluor- methylsulfinyl, trifluoromethylsulfonyl, n represents 1, 2,3 or 4, where the group C (RI) R2 may be identical or different, when n is greater than 1, and when n represents 1, R1 and R2 furthermore together represent-(CH2) 2-,-(CH2) 3-,-(CH2) 4-,-(CH2) s-, R1 furthermore represents together with R3 or Rus- (CH2)3-, -(CH2)4-, -(CH2)5-, R3 and R4 furthermore together represent- (CH2) 4-,- (CH2) 5-,- (CH2) 6-, R3 and Rs furthermore together represent- (CH2) 2-,- (CH2) 3-,- (CH2) 4-, R and R6 furthermore together represent- (CH2) 4-,- (CH2) 5-,- (CH2) 6-.

Amino alcohols of the formula (I are widely known and/or can be prepared according to known methods.

The formula (IV) provides a general definition of the mercaptans or salts thereof required as starting materials for carrying out the second step of the process according to the invention.

Preferred as starting material are mercaptans or salts thereof of the formula (IV), in which R represents unsubstituted or mono-or polysubstituted Cl-Cl2-aLkyl, where the substituents are identical or different and are selected from the group consist- ing of fluorine, chlorine, bromine, iodine, hydroxy, Cl-C4-alkoxy, halo-Cl-C4- alkoxy having 1 to 9 identical or different fluorine, chlorine and/or bromine atoms, Cl-C4-alkylthio, Cl-C4-alkylsulfinyl and Cl-C4-alkylsulfonyl ; unsub- stituted or mono-or polysubstituted C3-C6-cycloalkyl or C3-C6-cycloalkyl-Cl- C2-alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, Cl-C4-alkyl and Cl-C4-alkoxy ; unsubstituted or mono-to pentasubstituted phenyl, where the substituents are identical or different and are selected from the group con- sisting of fluorine, chlorine, bromine, iodine, Cl-C4-alkyl, C3-C6-cycloalkyl, Cl-C4-alkoxy, halo-Cl-C4-alkyl, halo-Cl-C4-alkoxy, each having 1 to 9 iden- tical or different fluorine, chlorine and/or bromine atoms; unsubstituted or mono-to pentasubstituted phenyl-Cl-C2-alkyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine and Cl-C4-alkyl ; naphthyl; unsubstituted or mono- or polysubstituted heteroaryl (preferably furyl, thienyl, pyrrolyl, oxazolyl, oxazolinyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2, 4- oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 3- thiadiazolyl, 1,2, 5-thiadiazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl), where the substitu- ents are identical or different and are selected from the group consisting of

fluorine, chlorine, bromine, iodine, Cl-C4-alkyl, Cl-C4-alloxy, unsubstituted or mono-to pentasubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine and Cl-C4-alkyl, M represents hydrogen, ammonium or an alkali metal atom (preferably sodium, potassium, lithium and caesium).

Particularly preferred as starting material are mercaptans or salts thereof of the formula (IV), in which R represents in each case unsubstituted or mono-or polysubstituted methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, in each case the isomeric pentyls, hexyl, octyl, decyls and dodecyls, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, trifluoro- methoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, difluor- chloromethoxy, fluorodichloromethoxy, methylthio, ethylthio, n-, i-propyl- thio, n-, i-, s-, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfinyl, n-, i-, s-, t-butylsulfmyl, methylsulfonyl, ethylsulfonyl, n-, i-propylsulfonyl, n-, i-, s-, t-butylsulfonyl ; in each case unsubstituted or mono-or polysub- stituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropyhnethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylethyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy ; unsubstituted or mono-to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclobutyl, cyclo- pentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, tri- fluoromethyl, trichloromethyl, difluoromethyl, dichloromethyl, difluor-

chloromethyl, fluorodichloromethyl, trifluoromethoxy, trichloromethoxy, difluoromethoxy, dichloromethoxy, difluorochloromethoxy, fluorodichloro- methoxy; in each case unsubstituted or mono-to trisubstituted benzyl or phenylethyl, where in each case the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine and methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl; naphthyl; in each case unsubstituted or mono-or polysubstituted furyl, thienyl, pyrrolyl, oxazolyl, oxazolinyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, 1,2, 4- oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 4-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,2, 3- thiadiazolyl, 1,2, 5-thiadiazolyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, tetrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, where in each case the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, unsubstituted or mono-to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine and methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, M represents hydrogen, ammonium, sodium, potassium, lithium and caesium.

Very particularly preferred as starting material are mercaptans or salts thereof of the formula (IV), in which R represents in each case unsubstituted or mono-or polysubstituted methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, in each case the isomeric pentyls, hexyl, octyl, decyls and dodecyls, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, hydroxy, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, trifluor- methoxy, trichloromethoxy, methylthio, ethylthio, n-, i-propylthio, t-butylthio, methylsulfinyl, ethylsulfinyl, n-, i-propylsulfinyl, t-butylsulfinyl, methylsulfo- nyl, ethylsulfonyl, n-, i-propylsulfonyl, t-butylsulfonyl ; in each case unsubsti- tuted or mono-or polysubstituted cyclopropyl, cyclopentyl, cyclohexyl, cyclo-

propylmethyl, cyclopentylmethyl, cyclohexylmethyl, where the substituents are identical or different and are selected from the group consisting of fluo- rine, chlorine, bromine, iodine, methyl, ethyl, n-, i-propyl, t-butyl, methoxy, ethoxy, n-, i-propoxy, t-butoxy; unsubstituted or mono-to trisubstituted phenyl, where the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, iodine, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy; unsubstituted or mono-to trisubstituted benzyl, where the substituents are identical or different and are selected from the group consist- ing of fluorine, chlorine, bromine, iodine and methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl; naphthyl; in each case unsubstituted or mono-or polysubstituted furyl, thienyl, pyrrolyl, oxazolyl, oxazolinyl, isoxazolyl, thiazolyl, isothiazo- lyl, imidazolyl, pyrazolyl, 1,2, 4-oxadiazolyl, 1,3, 4-oxadiazolyl, 1,2, 4-thiadi- azolyl, 1,3, 4-thiadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,2, 3-triazo- lyl, 1,2, 4-triazolyl, tetrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, where in each case the substituents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine, methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, methoxy, ethoxy, n-, i-propoxy, n-, i-, s-, t-butoxy, unsubstituted or mono-to trisubstituted phenyl, where the substi- tuents are identical or different and are selected from the group consisting of fluorine, chlorine, bromine and methyl, ethyl, n-, i-propyl, n-, i-, s-, t-butyl, M represents hydrogen, ammonium, sodium and potassium.

Mercaptans or salts thereof of the formula (IV) are widely known and/or can be prepared according to known methods.

Saturated or unsaturated hydrocarbon radicals, e. g. alkyl and alkenyl, can in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, e. g. in alkoxy.

Optionally substituted radicals may be mono-or polysubstituted, where in the case of polysubstitution the substituents may be identical or different.

Radicals subsituted by halogen, e. g. haloalkyl, are mono-or polysubsituted up to perhalogenation. In the case of multiple halogenation the halogen atoms may be identical or different. Halogen represents fluorine, chlorine, bromine or iodine.

However, it is also possible to combine the above-mentioned general or preferred radical definitions or illustrations with one another as desired, i. e. between the respective ranges and preferred ranges. The definitions apply both to the end products and, correspondingly, to the precursors and intermediates.

The first step of the reaction according to the invention can be carried out by addition of the amino alcohols of the formula (In into the oleum. This procedure is preferably carried out with mechanical stirring in that way, that the added amino alcohol does not touch the glass surface of the reaction vessel.

The addition of the amino alcohol of the formula (II) into the oleum is preferably done with cooling to keep the temperature below 150°C, while a temperature range between 80°C and 90°C is particularly preferred. In general a carbonization will not be observed even if higher substituted amino alcohols are employed.

The amino alcohols are applied in liquid form. Solutions with up to 15 % water may also be used.

According to the invention oleum means a solution of sulphur trioxide (S03) in sulphuric acid. The content of S03 can be varied in a broad range. In general between 1 % and 70 % S03 are used. Preferably the reaction is carried out using between 15 % and 60 %, particularly preferably 15 % and 30 %, very particularly preferably 20 % S03. For example, 40 % oleum means that 100 g of this solution contains 40 g of S03.

The reaction temperatures employed to the first step of the reaction according to the invention may be varied over a broad range. In general the reaction is carried out between 50°C and 200°C, preferably between 70°C and 180°C, particularly pref- erably between 80°C and 130°C.

The first step of the reaction is expediently carried out under atmospheric pressure, although it is also possible to work under reduced or elevated pressure. Particular preference is given to carrying out the reaction under atmospheric pressure.

The reaction time can be different depending on the scale of the reaction and may vary between 10 min and 4 hours.

The first step of the process is carried out in practice by reacting, for example, 1 mol of an amino alcohol of formula (II) with between 0.01 and 6 mol, preferably between 0.05 and 3 mol, particularly preferably between 0.1 and 1 mol, very particularly between 0.2 and 0.8 mol, especially preferably 0.6 mol of S03, which is applied as solution in sulphuric acid (i. e. oleum, see above).

The sulphuric acid esters of the formula (E) may be isolated. Preferably these esters of formula (hui) are used without isolation for the conversion in the second step of the process according to the invention.

The second step of the reaction according to the invention can be carried out by addition of the mercaptans or salts thereof of formula (IV), if as salt, then preferably in form of an aqueous solution of said mercaptan salt, into of the sulphuric acid ester of formula (m). Before this addition the reaction mixture is diluted with water and neutralized with a base. The reaction mixture may be neutralized directly when the reaction is carried out in small scale, for example in laboratory scale. The addition of the mercaptans or salts thereof of formula (IV) is done between 10 min up to 24 h, depending on the scale of the reaction, preferably between 20 min and 12 h, particularly preferably between 30 min and 6 h.

The second step of the process is carried out in the presence of a base. Examples which may be mentioned are: alkali metal and alkaline earth metal hydroxides, such as NaOH, KOH, Ca (OH) 2, alkali metal carbonates or hydrogencarbonates, such as Na2CO3, Li2C03, K2CO3, Cs2CO3 or NaHCO3 and KHCO3. Preference is given to Na2C03, KOH, NaOH and NaHC03, in particular NaOH.

The reaction temperatures employed to the second step of the reaction according to the invention may be varied over a broad range. In general the reaction is carried out between 30°C and 150°C, preferably between 50°C and 120°C, particularly preferably between 60'C and 80°C.

The second step of the reaction is expediently carried out under atmospheric pressure, although it is also possible to work under reduced or elevated pressure.

Particular preference is given to carrying out the reaction under atmospheric pressure.

The second step of the reaction according to the invention may be carried out in the presence of a further diluent, where all customary inert organic solvents apply.

Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methyl- cyclohexane, benzene, toluene, xylene or decaline; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichlorethane or trichloroethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert. -butyl ether, methyl tert- amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, n-or isobutyronitrile or benzo- nitrile; amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- formanilide, N-methylpyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, or sulphones, such as sulpholane.

The second step of the process is carried out in practice by reacting, for example, 1 mol of an sulphuric acid ester of formula (m) with between 1 and 10 mol, preferably between 1 and 5 mol, particularly preferably between 1 and 3 mol of an

mercaptan or salt thereof of formula (IV) in the presence of a base, to keep the pH value in general between pH 11 and 12.

The end-product can be isolated using standard procedures, e. g. cristallization, chromatography, extraction and distillation.

The process according to the invention is illustrated by the preparation examples given below. Preparation Examples Example 1

The oleum (120.1 g of 20 % S03 in H2SO4, i. e. 0.3 mol = 0.6 eq. S03) is placed in an 1 1 flat-bottomed flask with flat-flange joint and the 2-amino-2-methyl-1-propanol (46.9 g, 0.5 mol = 1 eq. , 95 %) is added slowly with mechanical stirring directly into the oleum so that 2-arnino-2-methyl-1-propanol touches the glass surface of the flask. The temperature is maintained by cooling between 85°C and 90°C. Stirring of the reaction mixture at 90°C is continued for additional 30 min. After cooling to room temperature the mixture is first diluted with 200 ml of water and then 45 % sodium hydroxide solution in water is added. The temperature in both procedures should not exceed 30°C. Under cooling the methyl mercaptane sodium salt solution (183.6 g, 0.5 mol = 1 eq. , 19.1 % in water) is added and then stirring is continued at 60 to 65°C for 6 h.

The mixture is cooled to 32°C and all the following procedures are performed at this temperature. 100 ml methyl tert. -butyl ether is added, the mixture is stirred and the organic layer is separated. The aqueous layer is extracted with two 100 ml portions of tert. -butyl ether. The combined organic layers were dried over anhydrous sodium sulfate. After filtration the solvent was removed at 20°C and under 150 mbar reduced pressure.

Yield: 62.7 g (crude product, purity according to internal standard: 68. 8 %, i. e. 72 % of the theory) of 2-methyl-1-methylthio-2-propanamine.

HNMR (d6-DMSO) : 6= 1. 04 (s, 6H), 1.44 (broad, 2H), 2.10 (s, 3H), 2.48 (s, 2H) ppm.

GC/MS-coupling: m/z (%) = 104 (3) [M-15] +, 58 (100), 42 (11), 41 (8), 31 (5).

Example 2

The oleum (91.4 g of 20 % S03 in H2SO4, i. e. 0.23 mol = 0.7 eq. S03) is placed in an 11 flat-bottomed flask with flat-flange joint and the 2-aminopropanol (25.0 g, 0.33 mol= 1 eq. ) is added slowly with mechanical stirring directly into the oleum.

The temperature is maintained by cooling slightly below 80°C. Stirring of the reaction mixture without heating is continued for additional 30 min. After cooling to room temperature the mixture is first diluted with 70 ml of water and then slowly 45 % sodium hydroxide solution in water is added until a pH value of 11 is reached.

The temperature in both procedures should not exceed 30°C. Under cooling the methyl mercaptane sodium salt solution (82.2 g, 0.33 mol = 1 eq. , 19.1 % in water) is added and then stirring is continued at 60°C for 12 h.

The mixture is cooled to 32°C and all following procedures are performed at this temperature. 75 ml methyl tert. -butyl ether is added, the mixture is stirred and the organic layer is separated. The aqueous layer is extracted with two 75 ml portions of methyl tert. -butyl ether. The combined organic layers were dried over anhydrous sodium sulfate. After filtration the solvent was removed at 20°C and under 150 mbar reduced pressure.

Yield: 23. 3 g (62.2 %, crude product, yield according to GC-purity) of 1-methylthio- 2-propanamine.

H NMR (d6-DMSO): 6 = 1.01 (d, 3H), 1. 48 (broad, 2H), 2.04 (s, 3H), 2.38 (m, 2H), 2.90 (m, 1H) ppm.

GC/MS-coupling : m/z (%) = 105 (4) [M] +, 61 (5), 44 (100), 42 (12), 41 (5), 28 (4).

Example 3

The oleum (45.4 g of 20 % S03 in H2SO4, i. e. 0. 114 mol = 0.7 eq. S03) is placed in an 1 1 flat-bottomed flask with flat-flange joint and the 3- (isopropylamino)-l-propan- ol (19. 0 g, 0.16 mol = 1 eq. ) is added slowly with mechanical stirring directly into the oleum. The temperature is maintained by cooling slightly below 80°C. Stirring is continued for additional 60 min. After cooling to room temperature the mixture is first diluted under cooling with 70 ml of water and then slowly 45 % sodium hydroxide solution in water is added until a pH value of 11 is reached. The tempera- ture in both procedures should not exceed 30°C. Under cooling the methyl mercaptane sodium salt solution (59.5 g, 0.16 mol = 1 eq. , 19.1 % in water) is added and then stirring is continued at 60°C for 12 h.

The mixture is cooled to 32°C and all following procedures are performed at this temperature. 75 ml methyl tert.-butyl ether is added, the mixture is stirred and the organic layer is separated. The aqueous layer is extracted with two 75 ml portions of methyl tert. -butyl ether. The combined organic layers were dried over anhydrous sodium sulfate. After filtration the solvent was removed at 20°C and under 150 mbar reduced pressure.

Yield: 12.6 g (48. 5 %, crude product, yield according to GC-purity) of N-isopropyl- 3-methylthio-1-propanamine.

HNMR (d6-DMSO): 8 = 0. 95 (d, 6H), 1.63 (m, 2H), 2.03 (s, 3H), 2.52 (m, 4H), 2.66 (m, 1H) ppm.

GC/MS-coupling : m/z (%) = 147 (17) [M] +, 132 (36), 89 (48), 72 (100), 58 (40), 30 (60)..

Example 4

The oleum (28. 4 g of 20 % S03 in H2SO4, i. e. 0. 07 mol = 0.7 eq. S03) is placed in an 11 flat-bottomed flask with flat-flange joint and the 2-amino-2-methylpropanol (9.4 g, 0.10 mol = 1 eq. ) is added slowly with mechanical stirring directly into the oleum. The temperature is maintained by cooling slightly below 80°C. Stirring with- out heating is continued for additional 30 min. After cooling to room temperature the mixture is first diluted with 30 ml of water and then slowly 45 % sodium hydroxide solution in water is added until a pH value of 11 is reached. The temperature in both procedures should not exceed 30°C. Under cooling the 4-methyl thiophenol (12.4 g, 0.1 mol = 1 eq. ) is added and then stirring is continued at 60°C for 12 h.

The mixture is diluted with 100 ml water, then 100 ml ethylacetate is added, the mixture is stirred and the organic layer is separated. The organic layer is washed twice with 50 ml portions of water. The organic layer is dried over anhydrous sodium sulfate. After filtration the solvent is removed at 20°C and under 150 mbar reduced pressure.

Yield: 15.4 g (57.3 %, crude product, yield according to GC-purity of 72.6 %) of 2-methyl-1- [ (4-methylphenyl) thio]-2-propanamine.

GC/MS-coupling: m/z (%) = 195 (1) [M] +, 138 (16), 58 (100).

Example 5

Applying the procedure according to example 4 the compound 1- (1, 3-benzothiazol-2- ylthio)-2-methyl-2-propanamine is obtained.

Yield: 37.9 % (according to GC-purity of 37.8 %).

GC/MS-coupling : m/z (%) = 238 (2) [M] +, 181 (6), 148 (5), 108 (4), 58 (100), 28 (9).

Example 6 Applying the procedure according to example 4 the compound 2- [ (2-amino-2- methylpropyl) thio] ethanol is obtained.

Yield: 24. 8 % (according to GC-purity of 74.0 %).

GC/MS-coupling : m/z (%) = 134 (2) [M-15] 88 (3), 58 (100), 42 (7).

Example 7 Applying the procedure according to example 4 the compound 3-[(2-amino-2- methylpropyl) thio]-l-propanol is obtained.

Yield: 57.9 % (according to GC-purity of 71. 6 %).

GC/MS-coupling : m/z (%) = 163 (1) [M] +, 148 (1) [M+-15], 58 (100), 42 (6).

Example 8 Applying the procedure according to example 4 the compound 6- [ (2-amino-2- methylpropyl) thio]-l-hexanol is obtained.

Yield: 40.7 % (according to GC-purity of 61. 9 %).

GC/MS-coupling: m/z (%) = 205 (1) [M] +, 190 (2) [M-15] +, 58 (100), 41 (7).