Hydrophilic and Difficultly Volatile Biocidal Triorganometallic Compounds

Triorganotin and triorgano-lead compounds are valuable biocides. However, the widely used compounds, for example bis(tri-n-butylin)oxide (TBTO) or triphenyl-lead acetat (TPLA), are highly hydrophobic in accordance with their chemical constitution. Their low water-solubility (that of TBTO is only 20 ppm) severely limits their field of use. It is extremely difficult to manufacture aqueous disinfectant solutions with them or to add them to disperse paints. The frequently used admixture with emulsifiers, for example, in the form of the commercial product "METATIN R 5710" (based on TBTO), is a long way from being able to satisfy all the requirements of practice because these emulsions have only limited durability. A further disadvantage, of the trialkyl tin compounds is their volatility. This volatility is the cause, for example, of the rapid loss of effectiveness of TBTO and its derivatives in many practical applications.

All tributyltin carboxylates, sulphonates, and salts with inorganic acids (chloride, sulphate, nitrate, perchlorate etc.) undergo hydrolysis on contact with water and consequently reconversion into volatile TBTO. Even more marked is the volatility in compounds with smaller organic radicals, especially the trimethyltin derivatives. However, these compounds are of considerable commercial interest because the biocidal activity spectrum in the triorganotin series is highly specific as to structure.

This invention therefore has for its object to develop biocidal triorganometallic compounds with hydrophilic properties which are soluble in water, or at least are readily compatible with or form stable emulsions with water, and which still continue to possess only a slight volatility. The surprising discovery has been made that it is possible to effect the hydrophilic modification and reduction of the volatility with a single structural principle. The hydrophilic solubilising groups which impart the water-solubility (compatibility) and simultaneously also lower the volatility, are bonded through the mercapto-sulphur to the triorganometallic radicals. Only this bond ensures a hydrolysis-resistant fixing of the solubilising groups mentioned.

A number of triorganometallic mercaptides with biocidal activity have already been proposed. For example, tributyltin-2-diethylaminoethyl mercaptide ##EQU1## IS CLAIMED AS FUNGICIDE IN French Pat. No. 1.533.524.

Through the diethylamino group this compound does have a slight hydrophily, but for practical purposes this is far from being sufficient. An even more serious disadvantage is its volatility. These disadvantages only disappear if this compound -- as shown in this invention -- is converted into an ammonium salt.

The same applies to the tributyl-tin-mercapto-pyridine described in Belgian Pat. No. 707.519 ##SPC1##

Here too only the salt formation leads to a product with hydrophilic properties which are useful for practical purposes.

Tributyl-tin-.beta.-hydroxyethyl mercaptide

is cited in U.S. Pat. No. 3.382.264. This compound contains a free hydroxy group. But this is still not sufficient for the hydrophilic solubilising of the tributyltin group necessary for practical purposes. A satisfactory hydrophily is obtained only with two or more free hydroxyl groups, e.g. in the form of the monomercaptoglyceride.

Japanese Pat. No. 1977/67 claims organotin sulphaminates with a certain water-solubility. However, verification has shown that, for example, the tributyltin sulphaminate is hydrolytically split off in water at once and passes over into TBTO. As further investigations have shown, only the mercapto compound (apart from the carbon bond) is able to prevent this hydrolysis.

The invention therefore provides hydrophilic, difficultly volatile biocidal compounds of the formula I ##EQU2## wherein M represents tin or lead and R.sub.1, R.sub.2, and R.sub.3 each independently represents a linear or branched aliphatic group with 1 to 16 carbon atoms which can be saturated or singly olefinically unsaturated, the cyclopentyl, cyclohexyl, or phenyl group, the sum of the carbon atoms of the substituents R.sub.1, R.sub.2, and R.sub.3 being altogether at most 18, and A represents a strongly hydrophilic group with polyol, polyether, carboxylate, sulphonate, carboxylic acid ester, carboxylic acid amide, and/or ammonium salt function.

The application also provides a process for the manufacture of compounds of the general formula I, wherein a triorganometallic compound of the general formula II ##EQU3## in which M, R.sub.1, R.sub.2, and R.sub.3 have the same meaning as in formula I and X represents OH, O.sub.1/2, chlorine, bromine, iodine, or acetate, is condensed in known manner with a mercapto compound of the general formula III.

in which A has the same meaning as in formula I, optionally in the presence of a basic compound, accompanied by the elimination of HX.

As triorganometallic compounds of the formula II there are used especially triorganometallic hydroxides or triorganometallic oxides.

The symbol M in formula I preferably represents tin and R.sub.1, R.sub.2, and R.sub.3 represents a linear or branched alkyl or alkenyl group with 1 to 4 carbon atoms, the cyclohexyl- or the phenyl group.

Preferably two or all three of the groups R.sub.1, R.sub.2, and R.sub.3 are the same. If two alkyl groups are the same, these are preferably methyl groups.

Exemplary of R.sub.1, R.sub.2, and R.sub.3 in the general formula I are n-amyl, 2-methylbutyl, 3-methylbutyl, neopentyl, pentenyl-3, pentenyl-4, 3-methyl-butenyl-3, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, cyclopentyl, but preferably methyl, ethyl, vinyl, n-propyl, i-propyl, n-butyl, i-butyl, butenyl-3, cyclohexyl, or phenyl.

Preferred triorganometallic groups are: tri-n-butyltin, triphenyltin, tricyclohexyltin, octyl-dimethyltin cyclohexyldimethyltin, phenyl-dimethyltin, and triphenylead.

A represents in detail:

1. The radical of a polyol with 2 to 6 hydroxyl groups which can also be substituted by an aldehyde group, or of a polyethylene oxide with 2 to 15, preferably 8 to 11, ethylene oxide units.

2. A hydrocarbon radical with carboxylate or sulphonate function, of the formula ##EQU4## wherein Q represents hydrogen or the hydroxyl group, p is a whole number from 1 to 6X represents --CO.sub.2 -- or --SO.sub.3 --, Y represents a counterion which is positively charged once or twice, with q = 1 in the first case and q = l/2 in the second. Y is preferably sodium or the ammonium group

Where p is O, the group X can also be ##EQU5## ##SPC2## or

3. A hydrocarbon radical with carboxylic acid amide or, in particular, carboxylic acid ester, function, of the formula ##EQU6## wherein Q and p have the meanings given hereinbefore, Q is preferably hydrogen and p is preferably 1 or 2, X is --CO-- and q is 1. Y is preferably a polyethylene oxide radical of the formula

in which n is 2 to 15, especially 8 to 11, a polyhydroxyalkyl radical of the formula ##EQU7## in which m is 2 to 6, or the polyhydroxyalkyl radicals which derive from pentaerythritol, dipentaerythritol, and trismethylol propane ##EQU8## Y is also the radical of primary or secondary amine-polyethylene oxide adducts of the formula ##EQU9## wherein r and s are numbers which are the same or different. The sum of r+s is 2 to 15, preferably 2.

The values for m, n, r, and s in the radicals cited hereinbefore can also be rational numbers for mean values of the chain length of the given radicals. 4. A hydrocarbon radical with an ammonium salt function, of the formula ##EQU10## wherein Q and p have the meanings given hereinbefore and p is preferably 2, X in its turn corresponds to the formula ##EQU11## where Q and p have the meanings given hereinbefore and p is preferably 2, X in its turn corresponds to the formula -NZ.sub.3.sup.+, and Z represents lower alkyl groups which are the same or different, polyethylene oxide radicals with 2 to 6 ethylene oxide units, and/or hydrogen, but preferably .beta.-hydroxyethyl.

The group X can also be ##EQU12## Where p is O, X can also be ##SPC3## ##EQU13## and Y represents a monovalent or divalent negative counterion, wherein in the first case of = 1 and in the second q = 1/2.

In the formula I -S-A preferably represents the radical of a salt of an aliphatic mercaptocarboxylic acid with at most 8, but above all at most 5, carbon atoms, and, in particular, represents the 2-mercaptopropionate or mercapto-acetate radical, wherein sodium, potassium or the triethanolamine group is preferred as cation, and very preferably -S-A is the radical of the triethanolamine salt of thioglycolic acid. In addition -S-A is preferably the radical of an ester of an aliphatic mercaptocarboxylic acid with up to 8, especially up to 5, carbon atoms, in particular of 2-mercaptopropionic acid, and polyethylene oxides with 2 to 15 ethylene oxide units, and is furthermore preferably the radical of the salt of a mercaptoalkanesulphonic acid with at most 6 carbon atoms, in particular the 3-mercaptopropionsulphonate radical. Preferably -S-A is also the radical of 1-mercaptoglycerol. Examples of the group A are ad 1. Polyol or polyethylene oxide radicals ##EQU14## (n is 2 to 15, preferably 8 to 10)

Examples of the group ##EQU15## are ad 2. Carboxylate or sulphonate radicals ##EQU16## ad 3. Carboxylic acid ester or carboxylic acid amide radicals

Examples of --X-- as --NZ.sub.3 -- group are ad 4.

(n is 1 to 6)

Examples of the group -Y are ad 2. A counterion which is positively charged once or twice

The triorganotin or triorganolead polyolmercaptides are manufactured by reacting the free mercaptans with a triorganotin or triorgano-lead oxide or hydroxide, for example ##EQU21##

The synthesis can also be carried out starting from triorganometallic halide in the presence of alkali lye, carbonate, or bicarbonate solution on the lines of a SCHOTTEN-BAUMANN reaction, e.g. ##EQU22##

The polyol-mercaptans themselves are obtainable by known methods.

The mercapto-polyglycols and mercapto-polyethylene oxides are obtained by the addition of polyethylene oxide to hydrogen sulphide ##EQU23##

The manufacture of the triorganotin or triorgano-lead mercaptoalkylsulphonates of the formula ##EQU24## can be carried out, for example, in the following way ##EQU25##

Using an ion exchanger (AT) it is possible to obtain therefrom the free sulphonic acid

which can be converted with the bases Y. OH into other salts,

with the equation

The reaction with a triorgano-tin or triorgano-lead oxide or hydroxide takes place subsequently, for example

The other mercaptoalkylsulphonic acids can be manufactured from the corresponding haloalkylsulphonic acids in known manner, for example via the isothiuronium halides ##EQU26##

The direct reaction with, for example, potassium hydrosulfide, leads to the same result. Finally, the .beta.-mercaptoethanesulphonic acid can also be obtained by starting from the carbyl sulphate.

The mercaptohydroxyalkylsulphonic acids can be easily obtained via the corresponding epoxides, e.g. ##EQU27##

The synthesis route to the analogous triorganotin or triorganolead mercaptocarboxylic acid salts also proceeds via the corresponding mercaptocarboxylic acids, for which there are a number of known methods of manufacture.

The reaction (neutralisation of the carboxyl group) with the base Y is carried out advantgeously after the linkage with the triorganotin or triorganolead group in accordance with the equation ##EQU28##

The corresponding mercapto-hydroxyalkylcarboxylic acids can also be obtained via the epoxycarboxylic acids by known methods.

Triorganotin or triorganolead derivatives which carry a hydrophilic carboxylic acid ester function are manufactured in two steps.

The reaction with a triorganotin or triorganolead oxide or hydroxide is performed after the esterification of the mercaptocarboxylic acid with a hydroxyl group of the polyol. The monoesterification with respect to a chemically unitary polyolmonoester is as a rule only possible with a substantial excess of polyol. The separation of excess (non-reacted) polyol is effected in these cases very smoothly at the end stage after the combination with the triorganotin or triorganolead group, on the basis of differing solubility properties, principally in chloroform or methylene chloride. However, the polyol esterification can also be carried out under stoichiometric conditions for the monoesterification. The products which are formed under these conditions do constitute statistical mixtures, but -- since the monoester derivative predominates -- are sufficiently hydrophilic.

If the polyol is obtainable as epoxide compound, the esterification can be effected also by the indirect route, in which case unitary polyol monoesters are also formed. It is advantageous in this case to effect the linkage of the mercaptocarboxylic acid with the triorganotin or triorganolead group beforehand. ##EQU29##

In obtaining the triorganotin or triorganolead mercaptocarboxylic acid polyethylene oxide esters the esterification is carried out first, as with the polyol esters ##EQU30##

Since these polyethylene oxides -- also called polyglycols -- are mostly mixtures, the triorganotin or triorganolead compounds resulting therefrom are not unitary products. Their commercial value is not thereby impaired.

The triorganotin or triorganolead mercaptocarboxylic acid amides with hydrophilic amide component can be readily manufactured from the corresponding triorganotin or triorganolead mercaptocarboxylic acid esters, preferably from the methyl esters, on the lines of an ester-amide exchange reaction, for example ##EQU31##

If amines which are polyethylene oxide adducts, and therefore constitute mostly mixtures, are used, then corresponding mixtures are also obtained as end product. This is not prejudical to the use of these products. Trioganotin or triorganolead derivatives with ammonium salt function of the formula ##EQU32## are easily manufactured. When n is 2, a .beta.-mercaptoethylamine is used as starting product

which in its turn can be obtained by addition of the amine HNZ.sub.2 to ethylene sulphide. It is possible to manufacture other mercapto amines in known manner by addition of hydrogen sulphide to amines with unsaturated ligands.

The conversion into the ammonium salt takes place advantageously after the reaction with the triorganotin or triorganolead compound. This is effected either with acid, preferably mineral acid, but more preferably by alkylating agents, for example dimethyl sulphate, p-toluenesulphonic acid esters, or alkyl nitrates, e.g.

Finally, mercapto-hydroxyalkylammonium salts can be obtained from the readily accessible epoxides, for example from glycidyltrimethylammonium chloride. ##EQU34##

Triorganotin or triorganolead compounds with aromatic ligands can be readily manufactured from the known mercaptoamines, some of which are obtainable commercially. The most important reaction step for one example of a pyridinium salt is ##SPC4##

Examples of compounds according to the invention are listed hereinbelow.

The following abbreviations are used: Me = methyl, Pr = propyl, Bu - butyl, Am = amyl, Hex = hexyl, Oc = octyl, Ph = phenyl. ##EQU35##

Preferred compounds are: ##EQU36##

The substance of the present invention possess marked hydrophilic properties. Moreover, they simultaneously fulfill the requirement of slight volatility.

By appropriate choice of the group A it is possible to attain substantial gradations of these properties for particular applications. Thus it is possible to obtain from one and the same triorganometallic group derivatives which are miscible with water to a practically unlimited extent, while others display good emulsiying properties.

The solubilising effect of a particular hydrophilic group naturally depends also on the triorganotin or triorganolead species itself. Large organic radicals (e.g. amyl or phenyl) require for a specific water-solubility of the resulting compound stronger solubilising groups than small organic radicals (e.g. methyl).

The quarternary ammonium group produces a very strong (already extreme) solubilising effect. The triorganotin or triorganolead compounds provided therewith -- they are almost always honey -or wax-like substances-- are in most cases miscible with water in any proportion. Very marked is also the solubilising effect of the sulphonate group in the form of the alkali salts. These substances display the typical behaviour of tensides (soaps), i.e. they form mostly micellar solutions and thereby also lower the surface tension of the water. The influence of the counterion is here more marked than in the caase of the ammonium salts. Coupled with the strongly hydrophilic quaternary ammonium ions -- for example with the tetra-(.beta.-hydroxyethyl)-ammonium group -- it is possible to obtain extremely good water-solubility.

With the corresponding carboxylates the water-solubility is reduced somewhat under otherwise comparable structural prerequisites. Substances with the typical behaviour of soaps are also available in the form of alkali salts. The aqueous solutions also display the alkaline reaction which is typical of alkali carboxylate soaps, and like these they form very stable emulsions.

Very similar are the solubility properties of the trioganotin or triorganolead arboxylic acid esters and amides (with hydrophilic alcohol or amine moiety). It can be said that there is a direct connection between the hydrophily and consequently of the water-solubility on the one hand, and the number of the hydroxyl groups and the length of the polyethylene oxide radicals on the other. The same applies also to the pure polyol and polyethylene oxide derivatives. All these products have a honey- or wax-like consistency.

In the compounds according to the invention the triorganotin or triogano lead bond is completely stable to hydrolysis in neutral medium. Only in a strongly acid or alkaline pH range does cleavage slowly commence.

The compounds of this invention are outstanding biocides. With them it is possible to manufacture aqueous disinfectant solutions which can be used with complete success in human and veterinary medicine. The disinfecting of seeds and wood conservation -- also from aqueous liquor -- are other fields of application for these substances. They can also be used with particular advantage as additives for pigment dye dispersions and disperse paints, both in respect of storage and of the long-lasting protective action of the coating. Furthermore these substances can be used in antifouling paints, whereby they prevent both the harmful growth of sea organisms and improve -- as a result of the hydrophilic radical -- the hydrodynamic properties on the ships's stern.

A further field of application for these substances is mucilage control in paper manufacture, thereby also simultaneously ensuring paper conservation.

Certain thermoplasts and elastomers, in particular PVC with plasticiser content, can be effectively protected by the substances against attack by microbes. An antistatic finish is thereby simultaneously provided.

The substances of the present invention are also valuable herbicides for various cultivated plants. In cotton growing they can be used as defoliants and desiccants.

In many cases the phytotoxicity of the triorganometallic compounds according to the invention is distinctly lower than of the corresponding known compounds, thereby ensuring their favourable use in plant protection. Their activity against phytopathogenic fungi in cereal disinfection extends, for example, over Fusarium nivale, Tilletia caries, Helminthosporium gramineum, Septoria nodorum. The activity against soil fungi comprises, for example, Fusarium oxysporum, Pythium debarynum, hizoctonia solani, Verticileum albo atrum. In fungoid leaf infections the following species, for example, are attacked and destroyed: Botrytis cinerea, rust fungi, e.g. Cloromyces and puccinia, powdery mildews, e.g Phytophthora and Plasmopara, Pseudoperonospera.

Total activity was observed e.g. against the following leaf fungi: Botrytis cinerea in Vicia faba, Plasmopora viticola (Bert, et Curt.), (Berl. et de Toni) on vines; in the disinfectant test against Fusarium nivale and Tilletia caries. This statement, however, does not constitute any limitation.

In the test for microbiocidal activity the compounds listed hereinbelow yielded the values indicated in the following Table:

Results of the test of growth resistance in the beer bottling plant of a brewery:

1. white pigmented disperse paint based on a finely dispersed polyvinylpropionate copolymer finished with

2. White pigmented disperse paint based on a finely dispersed styrene-butadiene copolymer finished with

The tin and lead compounds are used in these experiments in the same molar ratio.

Example i: s-tri-n-butyl-tin-thioglycolic acid polyethylene glycol ester (C.sub.4 H.sub.9).sub.3 Sn.S--CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n --H (n.about.9)

80 parts of polyethylene glycol (MG.about.400), 18,4 parts of thioglycolic acid, and 100 parts of toluene are heated under reflux with stirring until the water of reaction is removed by circulation. Subsequently 60 parts of bis-(tri-n-butyl-tin)-oxide are added and the water of reaction is once more removed by circulation. The solvent is then distilled off under reduced pressure.

Yield: 151 parts (99% of theory); colourless liquid; Sn calc. 15,5%, found 15,6%.

Example II: S-tri-n-butyl-tin-thioglycolic acid-polyethylene glycol ester (C.sub.4 H.sub.9).sub.3 Sn.S--CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n --H (n.about.4.5)

The synthesis is carried out under the conditions described in Example I.

Batch:

20 parts of polyethylene glycol (MG.about.200)

9.2 parts of thioglycolic acid

30 parts of bis-(tri-n-butyl-tin)-oxide

100 parts of toluene

Yield: 54 parts (97,5% of theory); colourless liquid: n.sub.D.sup.20 : 1.5012. Sn calc. 21,4%, found 20,9%.

Example III: S-tri-n-butyl-tin-.beta.-mercaptopropionic acid polyethylene glycol ester (C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O--).sub.n --H (n.about.9)

The synthesis is carried out under the conditions described in Example 1.

Batch:

80 parts of polyethylene glycol (MG.about.400)

21.2 parts of .beta.-mercaptopropionic acid

60 parts of bis-(tri-n-butyl-tin)-oxide

100 parts of toluene

Yield: 154 parts (99% of theory); yellowish liquid; n.sub.D.sup.20 : 1.4921 Sn calc. 15,3%, found 15,2%.

Example IV: S-tri-butyl-tin-.beta.-mercaptopropionic acid polyethylene glycol ester (C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n --H (n.about.4,5)

The synthesis is carried out under the conditions described in Example I.

Batch:

20 parts of polyethylene glycol (MG.about.200)

10.6 parts of .beta.-mercaptopropionic acid

30 parts of bis-(tri-n-butyl-tin)-oxide

100 parts of toluene

The reaction product was filtered over a filter aid.

Yield: 51 parts (88% of theory); colourless liquid; n.sub.D.sup.20 : 1.4990. Sn calc. 20.6%, found 20.2%.

Example V: S-tri-n-butyl-tin-mercaptosuccinic acid-bis-polyethylene glycol ester ##EQU37##

The synthesis is carried out under the conditions described in Example I.

Batch:

40 parts of polyethylene glycol (MG.about.200)

15 parts of thiosuccinic acid

30 parts of bis-(tri-n-butyl-tin)-oxide

100 parts of toluene

The reaction product was filtered over a filter aid.

Yield: 79 parts (98,5% of theory); colourless liquid; n.sub.D.sup.20 : 1.5000. Sn calc. 14.8, found 14,7%.

Example VI: S-triphenyl-tin-.beta.-mercaptopropionic acid-polyethylene glycol ester Ph.sub.3 Sn--S--CH.sub.2 --CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n H (n.about.9)

The synthesis is carried out under the conditions described in Example I.

Batch:

26,5 parts of .beta.-mercaptopropionic acid

100.0 parts of polyethylene glycol (MG.about.400)

99.0 parts of triphenyl tin hydroxide

200.0 parts of toluene

Yield: 202 parts (97% of theory); yellow viscous liquid; n.sub.D.sup.20 : 1.5584 Sn calc. 14.2%, found 14.5%.

Example VII: S-triphenyl lead-.beta.-mercaptopropionic acidpolyethylene glycol ester Ph.sub.3 Pb--S--CH.sub.2 --CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n H (N.about.9)

While stirring, 100 parts of polyethylene glycol (MG.about.400), 26.5 parts of .beta.-mercaptopropionic acid, and 200 parts of toluente are heated under reflux until the water of reaction has been quantitatively removed by circulation. A solution of 27 parts of sodium carbonate in 50 parts of water and 140 parts of triphenyl lead acetate are subsequently added and the batch is stirred for 30 minutes at the same temperature. Undissolved material is then filtered off, the filtrate dried over sodium sulphate, and the solvent distilled off under reduced pressure.

Yield: 183 parts (80% of theory); yellow oil. Pb calc. 21.4%, found 21.0%.

Example VIII: 1-(S-trimethyl tin)-mercapto-polyethylene oxide (CH.sub.3).sub.3 Sn--S--(CH.sub.2 --CH.sub.2 --O)-H (n.about.10)

While stirring, 47 parts of 1-mercapto-polyethylene oxide [HS--(CH.sub.2 --CH.sub.2 --O)-H; n.about.10], 18 parts of trimethyl tin hydroxide and 100 parts of toluene are heated under reflux until the water of reaction has been quantitatively removed by circulation The solvent is then distilled off under reduced pressure.

Yield: 61 parts (96% of theory); yellowish viscous liquid. Sn calc. 19.6%, found 18.4% S calc. 5,0%, found 4.8%.

Example IX: 1-(S-trivinyl tin)-mercapto-polyethylene oxide (CH.sub.2 =CH).sub.3 Sn--S--(CH.sub.2 --CH.sub.2 --O).sub.n H (n.about.8)

The synthesis is carried out under the conditions described in Example VIII.

Batch:

36 parts of 1-mercapto-polyethylene oxide (n.about.8)

22 parts of trivinyl tin hydroxide

100 parts of toluene

Yield: 54 parts (96% of theory); yellowish viscous liquid; Sn calc. 21,2%, found 21,2% S calc. 5,7%, found 5.55%.

Example X: 1-(S-tri-n-butyl tin)-mercapto-polyethylene oxide (C.sub.4 H.sub.9).sub.3 Sn--S--(CH.sub.2 --CH.sub.2 --O).sub.n --H (n.about.14)

The synthesis is carried out under the conditions described in Example VIII.

Batch:

62 parts of 1-mercapto-polyethylene oxide (n.about.14)

30 parts of bis-(tri-n-butyl tin)-oxide

100 parts of toluene

Yield: 90 parts (98% of theory); yellowish viscous liquid. Sn calc. 13.1%, found 12.9% S calc. 3,5%, found 3.4%.

Example XI: S-tri-n-butyl tin-mercaptodiethanol (C.sub.4 H.sub.9).sub.3 Sn--S--(CH.sub.2 --CH.sub.2 --O).sub.2 --H

While stirring, a mixture of 60 parts of bis-(tri-n-butyl tin)-oxide, 24.4 parts of mercaptodiethanol, and 100 parts of toluene is stirred under reflux until the water of reaction is quantitatively removed by circulation. The solvent is subsequently distilled off in vacuo.

Yield: 81 parts (99% of theory); colourless liquid; n.sub.D.sup.20 :1.5168. Sn calc. 28.9%, found 28.8%.

Example XII: S-tri-butyl tin-thioglycerol (C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CH (OH)--CH.sub.2 --OH

The synthesis is carried out under the conditions described in Example XI.

Batch:

30 parts of bis-(tri-n-butyl tin)-oxide

10.8 parts of thioglycerol

100 parts of toluene

Yield: 39 parts (98,3% of theory); colourless liquid; n.sub.D.sup.20 : 1.5178. Sn calc. 29,8%, found 30.1%.

Example XIII: 1-(S-triphenyl lead)-mercaptosorbitol ##EQU38##

The synthesis is carried out under the conditions described in Example XI.

Batch:

20 parts of -mercapto-sorbitol

45.5 parts of triphenyl lead hydroxide

100 parts of toluene

Yield: 63 parts (99% of theory); white powder; m.p. 210.degree.C (with decomp.) Pb calc. 32,7%, found 32.4%; S calc. 5,0%, found 5.1%.

Example XIV: .beta.-(S-tri-i-butyl tin)-mercaptopropionic acid-1, 1,1-trismethylolpropane monoester ##EQU39##

While stirring, 107.2 parts of 1,1,1-tris-(hydroxymethyl)-propane, 21.2 parts of .beta.-mercaptopropionic acid, and 250 parts of toluene are heated under reflux until the water of reaction has been quantitatively removed by circulation. Subsequently 60 parts of bis-(tri-i-butyl tin)-oxide are added and the water of reaction is once more removed by circulation. The solvent is then distilled off under reduced pressure, and subsequently excess tris-(hydroxymethyl)-propane is distilled off in an oil pump vacuum.

Yield: 101 parts (99% of theory); honey-like consistency. Sn calc. 23.2%, found 23.0%; S calc. 6,3%, found 6.0%.

Example XV: sodium S-tri-n-butyl tin-thioglycolate (C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CO.sub.2.Na

While stirring, 29.8 parts of bis-(tri-n-butyl tin)-oxide, 10.1 parts of thioglycolic acid, and 100 parts of toluene are heated under reflux until the water of reaction has been quantitatively removed by circulation. A solution of 4.4 parts of sodium hydroxide in 50 parts of methanol is subsequently added, the batch is heated under reflux for 10 minutes, and the solvent distilled off under reduced pressure.

Yield: 39.1 parts (97% of theory); wax-like substance. Sn calc. 29.45%, found 29.2%.

Example XVI: calcium .beta.-(S-tri-n-butyl tin).alpha.-hydroxy-propionate [(C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CH(OH)--CO.sub.2 ].sub.2 Ca

The synthesis is carried out under the conditions described in Example XV.

Batch:

59,6 parts of bis-(tri-n-butyl tin)-oxide

26.4 parts of 1-hydroxy-2-mercaptopropionic acid

200 parts of toluene

5.6 parts of calcium oxide

Yield: 93 parts (98% of theory); whit powder; m.p. 230.degree.-20.degree.C (with decomp.) Sn calc. 25.0%, found 24.8%; S calc. 6.7%, found 6.5%.

Example XVII: sodium S-tri-n-propyl-mercaptosuccinate ##EQU40##

The synthesis is carried out under the conditions described in Example XV.

Batch:

25.6 parts of bis-(tri-n-propyl tin)oxide

15.0 parts of thiosuccinic acid

100 parts of toluene

8.8 parts of sodium hydroxide

100 parts of methanol

Yield: 44 parts (100% of theory); soap-like consistency. Sn calc. 26.9%, found 26.4%; S calc. 7.3%, found 7.2%.

Example XVIII: potassium S-triphenyl tin-.omega.-mercaptoheptanoate Ph.sub.3 Sn--S--CH.sub.2 -CH.sub.2).sub.4 CH.sub.2 --COO.K

The synthesis is carried out under the conditions described in Example XV.

Batch:

36.7 parts of triphenyl tin hydroxide

16.2 parts of .omega.-mercaptoheptanoic acid

100 parts of toluene

6.2 parts of potassium hydroxide

50 parts of methanol

Yield: 54 parts (98% of theory): wax-like consistency Sn calc. 21.6%, found 21.1%; S calc. 5.8%, found 5.8%.

Example XIX: sodium S-tri-n-butyl tin-.gamma.-mercaptopropanesulphonate (C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CH.sub.2 --CH.sub.2 --SO.sub.3.Na

A solution of 60 g of bis-(tri-n-butyl tin)-oxide in 100 parts of toluene is added dropwise to a solution of 39 parts of sodium .gamma.-mercaptopropanesulphonate and 50 parts of water. While stirring under reflux the water is removed by circulation and the solvent is subsequently distilled off under reduced pressure.

Yield: 87 parts (93,1 of theory); colourless powder; m.p. 260.degree.-263.degree.C. Sn calc. 25.4%, found 25.0%; S calc. 13.7%, found 14.0%.

Example XX: sodium S-triphenyl tin-.gamma.-mercaptopropanesulphonate Ph.sub.3 Sn--S--CH.sub.2 --CH.sub.2 --CH.sub.2 --SO.sub.3.Na

While stirring, 36.7 parts of triphenyl tin hydroxide, 19.5 parts of sodium .gamma.-mercaptopropanesulphonate, and 300 parts of methanol are heated for 2 hours under reflux. The undissolved portion (7.5 parts) is filtered off and the filtrate is concentrated in vacuo.

Yield: 45 parts (85.4% of theory).

The product is purified by dissolving it in chloroform and then precipitating it with diethyl ether; m.p. 283.degree.-285.degree.C. Sn calc. 22.5%, found 21.9%; S calc. 12.2%, found 12.1%.

Example XXI: triethylammonium S-tri-n-butyl tin-thioglycolate (.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --COOH.N(--CH.sub.2 CH.sub.2 OH).sub.3

To a solution of 46 parts of thioglycolic acid, 74.6 parts of triethanolamine and 100 parts of toluene are added 59.6 parts of bis-(tri-n-butyl tin)-oxide and the water of reaction is quantitatively removed by circulation while stirring. The solvent is subsequently distilled off in vacuo and the residue us recrystallised from acetonitrile.

Yield: 76,4 parts (72% of theory); colourless crystals; m.p. 64.degree.-67.degree.C. Sn calc. 22.4%, found 22.3%.

Example XXII: triethanolammonium S-tri-n-butyl tin-.beta.-mercaptopropionate (C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CH.sub.2 --COOH.N (--CH.sub.2 --CH.sub.2 --OH).sub.3

The synthesis is carried out under the conditions described in Example XXI.

Batch:

53 parts of .beta.-mercaptopropionic acid

74 parts of triethanolamine

149 parts of bis-(tri-n-butyl tin)-oxide

150 parts of toluene

Yield: 266 parts (98% of theory); yellow viscous liquid; n.sub.D.sup.20 : 1.5182; Sn calc. 21.8%, found 21.5%.

Example XXIII: triethanolammonium S-triphenyl tin-thioglycolate Ph.sub.3 Sn--S--CH.sub.2 COOH.N(--CH.sub.2 --CH.sub.2 --OH).sub.3

36,7 parts of triphenyl tin hydroxide are added to a solution of 9.2 parts of thioglycolic acid, 14,9 parts of triethanolamine, and 100 parts of tetrahydrofuran and the batch is stirred for 1 hour under reflux. The reaction mixture is subsequently cooled to 0.degree.C and the precipitated product is filtered with suction and dried.

Yield: 41.4 parts (84% of theory); colourless crystals; m.p. 116.degree.-118.degree.C. Sn calc. 20.1%, found 20.2%; SH calc. 5.6% found 5.4%.

Example XXIV: triethanolammonium S-triphenyl lead-thioglycolate Ph.sub.3 Pb--S--CH.sub.2 --COOH.N(--CH.sub.2 --CH.sub.2 --OH).sub.3

The synthesis is carried out under the conditions described in Example XXIII.

Batch:

43.9 parts (65% of theory); crystalline powder;

m.p. 108.degree.-110.degree.C (with decomp.).

Pb calc. 30,5%, found 30.4%

N calc. 2.1%, found 2.1%

Example XXV: S-tri-n-butyl tin-thioglycolic acid diethanolamide (C.sub.4 H.sub.9).sub.3 Sn--S--CH.sub.2 --CO.N(--CH.sub.2 --CH.sub.2 --OH).sub.2

While stirring, 39.5 parts of tri-n-butyl tin-thioglycolic acid methyl ester, 12.5 parts of diethanolamine, and 0.5 part of ammonium carbonate are heated in vacuo until no more methanol is distilled off.

Yield: 46,7 parts (96% of theory); colourless liquid; n.sub.D.sup.20 :1.5252 -SH calc. 6.8%, found 6.5%; Sn calc. 24.4%, found 24.1%.

Example XXVI: .beta.-(S-triphenyl lead)-.alpha.-amino-propionic acid (S-triphenyl lead cystein) ##EQU41##

While stirring, 45.5 parts of triphenyl lead hydroxide, 12.1 parts of cystein, and 200 parts of methanol are heated under reflux for 30 minutes. The solvent is subsequently distilled off in vacuo and the reaction product is recrystallised from tetrahydrofuran/water.

Yield: 48 parts (86% of theory); crystalline powder; m.p. 140.degree.-148.degree.C (with decom.) Pb calc. 37.1%, found 36.9%; S calc. 5.7%, found 6.1%; N calc. 2.5%, found 2.4%.

Example XXVII: .beta.-(S-tri-n-butyl tin)-mercaptoethyl-diethylmethylammonium-methylsulphate ##EQU42##

While stirring, 13.3 parts of diethylamino-ethane thiol, 100 parts of toluene, and 26.8 parts of bis-(tri-n-butyl tin)-oxide are heated under reflux until the water of reaction has been quantitatively removed by circulation. The solvent is subsequently distilled off in vacuo and the residue is treated with 100 parts of methanol and 12.6 parts of dimethyl sulphate. The batch is then heated under reflux for 20 minutes while stirring, then cooled and the solvent is distilled off under reduced pressure.

Yield: 48 parts (97% of theory); soap-like consistency. Sn calc. 21.7%, found 20.9%.

Example XXVIII: .beta.-(S-triphenyl tin)-mercaptoethyl-diethylmethylammonium-methylsulphate ##EQU43##

The synthesis is carried out under the conditions described in Example XXVII.

Batch:

13.3 parts of diethylamino-ethane thiol

33.0 parts of triphenyl tin hydroxide

100 parts of toluene

100 parts of methanol

12.6 parts of dimethyl sulphate.

Yield: 50 parts (97% of theory); yellow resin. Sn calc. 20.75%, found 20.5%.

Example XXIX: S-tri-vinyl tin-thioglycolic acid-polyethylene glycol ester (CH.sub.2 =CH).sub.3 Sn--S--CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n --H (N.about.4.5)

The synthesis is carried out under the conditions described in Example I.

Batch:

20.0 parts of polyethylene glycol (MG.about.200)

9.2 parts of thioglycolic acid

21.7 parts of tri-vinyl tin hydroxide

100 parts of toluene

Yield: 46 parts (97.5% of theory); colourless liquid. Sn calc. 25.1%, found 25.0%

Example XXX: S-tri-n-propyl tin-.beta.-mercaptopropionic acidpolyethylene glycol ester (C.sub.3 H.sub.7).sub.3 Sn--S--CH.sub.2 --CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n --H (n.about.9)

The synthesis is carried out under the conditions described in Example I.

Batch:

40.0 parts of polyethylene glycol (MG.about.400)

10.6 parts of .beta.-mercaptopropionic acid

25.6 parts of bis-(tripropyl tin)-oxide

100 parts of toluene

Yield: 71 parts (97% of theory); yellowish liquid; n.sub.D.sup.20 : 1.4946; Sn calc. 16.15%, found 16.0%.

Example XXXI: S-tri-n-pentyl tin-.beta.-mercaptopropionic acidpolyethylene glycol ester (C.sub.5 H.sub.11).sub.3 Sn--S--CH.sub.2 --CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n --H (n.about.9)

The synthesis is carried out under the conditions described in Example I.

Batch:

80.0 parts of polyethylene glycol (MG.about.400)

21.2 parts of .beta.-mercaptopropionic acid

68.0 parts of bis-(tri-n-pentyl tin)-oxide

100.0 parts of toluene

Yield: 159 parts (97% of theory); yellow liquid; n.sub.D.sup.20 : 1.4895 Sn calc. 14.5%, found 14.4%.

Example XXXII: potassium S-tri-methyl tin-.gamma.-mercapto-propanesulphonate (CH.sub.3).sub.3 Sn--S--CH.sub.2 --CH.sub.2 --CH.sub.2 --SO.sub.3.K

The synthesis is carried out under the conditions described in Example XIX.

Batch:

19.4 parts of potassium .gamma.-mercaptopropanesulphonate

50.0 parts of water

18.0 parts of tri-methyl tin hydroxide

100.0 parts of toluene

Yield: 34 parts (95% of theory); colourless powder; m.p.> 250.degree.C. Sn calc. 33.2%, found 32.9%.

Example XXXIII: magnesium S-tri-methyl tin-.beta.-mercaptopropionate [(CH.sub.3).sub.3 Sn.S--CH.sub.2 --CH.sub.2 --COO].sub.2.Mg

The synthesis is carried out under the conditions described in Example XV.

Batch:

21.2 parts of .beta.-mercaptopropionic acid

36.1 parts of tri-methyl tin hydroxide

100.0 parts of toluene

8.1 parts of magnesium oxide

50.0 parts of methanol.

Yield: 52 parts (98,5% of theory); white powder; m.p. > 240.degree.C. Sn calc. 22.5%, found 22.0%; Mg calc. 4.6%, found 5.0%.

Example XXXIV: S-tri-cyclohexyl tin-.beta.-mercaptopropionic acidpolyethylene glycol ester Cy.sub.3 Sn--S--CH.sub.2 --CH.sub.2 --COO--(CH.sub.2 --CH.sub.2 --O).sub.n --H (n.about.9)

The synthesis is carried out under the conditions described in Example I.

Batch:

40.0 parts of polyethylene glycol (MG 400)

10.6 parts of .beta.-mercaptopropionic acid

38.5 parts of tricyclohexyl tin hydroxide

100.0 parts of toluene

Yield: 84 parts (98% of theory); yellowish liquid; Sn calc. 13.88%, found 13.6%; S calc. 3.75%, found 3.8%.

Example XXXV: S-dimethyl-phenyl tin-thioglycerol ##EQU44##

A solution of 61 parts of dimethylphenyl tin bromide in 50 parts of methanol is treated with 10.8 parts of sodium methylate. The reaction mixture is stirred for 10 minutes at 30.degree.C and subsequently 50 parts of i-propanol and 21.6 parts of thioglycerol in the form of a solution are added dropwise. The sodium bromide is completely precipitated by adding 100 parts of diethyl ether. The undissolved substance is filtered off and the filtrate concentrated in a rotary evaporator. The remaining solvent is stripped off with an oil pump.

Yield: 62 parts (93% of theory); yellowish liquid: n.sub.D.sup.20 :1.6009 Sn calc. 35.65%, found 35.9%.

Example XXXVI: S-dimethyl-n-octyl tin-thioglycerol ##EQU45##

The synthesis is carried out under the conditions described in Example XXXV.

Batch:

68.2 parts of dimethyl-n-octyl tin-bromide

10.8 parts of sodium methylate

21.6 parts of thioglycerol

50.0 parts of i-propanol

50.0 parts of methanol

Yield: 73 parts (99% of theory); yellowish liquid; n.sub.D.sup.20 :1.5158 Sn calc. 32.16%, found 32.2%; S calc. 8.69%, found 8.5%.

Example XXXVII: S-dimethylphenyl tin-.beta.-mercaptopropionic acidpolyethylene glycol ester ##EQU46##

To a solution of 30.6 parts of dimethylphenyl tin bromide and 50 parts of methanol are added 5.4 parts of sodium methylate and the batch is stirred for 10 minutes at 30.degree.C. The reaction mixture is subsequently treated with 48.8 parts of .beta.-mercaptopropionic acid polyethylene glycol ester and 50 parts of i-propanol.

The clear solution is concentrated in a rotary evaporator, and the residue is taken up with chloroform and purified neutral on silica gel (hydrated with 5% water). Subsequently the solvent is stripped off from the eluate.

Yield: 63.5 parts (87% of theory); yellowish liquid; n.sub.D.sup.20 : 1.5326; Sn calc. 16.64%, found 16.9%; S calc. 4.50%, found 4.3%.

Example XXXVIII: S-dimethylcyclohexyl tin-.beta.-mercaptopropionic acid-polyethylene glycol ester ##EQU47##

The synthesis is carried out under the conditions described in Example XXXVIII.

Batch:

31.2 parts of dimethylcyclohexyl tin bromide

5.4 parts of sodium methylate

48.8 parts of .beta.-mercaptopropionic acid polyethylene glycol ester

50.0 parts of methanol

50.0 parts of i-propanol

Yield: 69.9 parts (97% of theory); yellowish liquid; Sn calc. 16.51%, found 16.2%; S calc. 4.46%, found 4.5%.

Example XXXIX: S-dimethyl-n-octyl tin-.beta.-mercaptopropionic acid-polyethylene glycol ester ##EQU48##

The synthesis is carried out under the conditions described in Example XXXVII.

Batch:

34.2 parts of dimethyl-n-octyl tin-bromide

5.4 parts of sodium methylate

48.8 parts of .beta.-mercaptopropionic acid polyethylene glycol ester

50.0 parts of methanol

50.0 parts of i-propanol

Yield: 61.3 parts (90% of theory); yellowish liquid; n.sub.D.sup.20 :1.4940 Sn calc. 15.85%, found 15.9%; S calc. 4.28%, found 4.1%.

Example XL: sodium S-dimethyl-n-octyl tin-.gamma.-mercaptopropanesulphonate ##EQU49##

A solution of 51.3 parts of dimethyl-n-octyl tin bromide in 150 parts of methanol is treated with 8.1 parts of sodium methylate. The reaction mixture is stirred for 10 minutes at 30.degree.C and subsequently 26.7 parts of sodium .gamma.-mercaptopropanesulphonate dissolved in 40 parts of water are added dropwise. The clear solution is treated with chloroform and purified neutral on silica gel. The eluate is concentrated in a rotary evaporator and the residual solvent is distilled off in an oil pump.

Yield: 63 parts (96% of theory); semisolid mass; Sn calc. 27.03%, found 26.2%.

Example XLI: S-dimethyl-n-butyl tin-.beta.-mercaptopropionic acid polyethylene glycol ester ##EQU50##

The synthesis is carried out under the conditions described in Example XXXVII.

Batch:

42.8 parts of dimethyl-n-butyl tin bromide

8.1 parts of sodiummethylate

43.2 parts of .beta.-mercaptopropionic acid polyethylene glycol ester

75.0 parts of methanol

75.0 parts of i-propanol

Yield: 69 parts (93% of theory); colourless liquid; Sn calc. 24.08%, found 23.6%; S calc. 6.50%, found 6.3%.

Example XLII: .beta.-(S-dimethyl-n-dodecyl)-mercaptoethyl-diethylmethylammonium-methylsu lphate ##EQU51##

The synthesis is carried out under the conditions described in Example XXXVII.

Batch:

13.3 parts of diethylamino-ethane diol

33.5 parts of dimethyl-n-dodecylhydroxide

100.0 parts of toluene

12.6 parts of dimethyl sulphate

100.0 parts of methanol

Yield: 57 parts (99% of theory); soap-like consistency. Sn calc. 20.59%, found 19.9%; S calc. 11.12%, found 11.3%.