DE1593732A1 - Process for the preparation of organotin derivatives - Google Patents

Description

Yissum Research Development Company, Administration Bldg. _% Hebrew University »Jerusalem / Israel '

"Process for the preparation of organotin derivatives"

The invention relates to a process for the preparation of organotin derivatives, natural or synthetic Polymers or their derivatives have hydroxyl, carboxyl, acid anhydride or sulfonic acid groups. According to the invention uses the organotin radical as a substituent group (not as part of the polymeric chain) through the hydroxyl, carboxyl, acid anhydride or sulfonic acid groups an ether or ester compound bound to the polymer, where the attached organotin groups have the general formula

-O-Stf

have, in which R ₁ , R ₂ , R-, identical or different substituted or unsubstituted alkyl, aryl or aralkyl groups with 1 to 10 carbon atoms,

Ether derivatives χ

The process for the preparation of the organonin ether derivatives of the polyhydroxy polymers is based on the reaction of (1). an alkali metal alkoxy derivative of the polyhydroxy polymer with (2 ). an organonin compound of the general formula

: SnX,

R * * ^ ~ We / Cl / Wf

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009822/1864

where R., R ₂ and R, represent the above-mentioned groups and X (a) an inorganic anion such as a halide, sulfate, nitrate or (b) an organic anion derived from acids with a pK value not higher than 4.8 such as acetate or formate represents. The reaction of the hydroxy polymer and the organotin compound is as follows:

P <~ OH * -Ρ "~ 0" M ⁺

MX + ₁₂₃ ,

where P represents the polyhydroxy polymer, M an alkali metal cation and X has the above-mentioned composition. The reaction is preferably carried out in a suitable aprotic solution such as dioxane, tetrahydrofuran, dimethyl sulfoxide or dimethylformamide.

The present invention is concerned with the production of organoζin ethers of a large number of natural such as also synthetic polyhydroxy polymers and their derivatives. The natural polyhydroxy polymers also include cellulose, Starch and 'polysaccharides. The invention is further concerned with the production of Organonζinnäthern of cellulose derivatives, especially organic cellulose esters such as acetyl cellulose. The cellulose esters are very close large number of connections. The examples include the esters of mono- and dicarboxylic acids having 2-20 carbon atoms in branched and straight chain, both aliphatic and aromatic structure and mixtures from both. Examples of the acids include ant, propionic, butter, benzene ant, amber, palmitic and arachidic acids and the mixtures thereof. Short chain Monocarboxylic acids such as formic acid are preferred.

The invention is also concerned with the production of Organonζinnäther derivatives of ether derivatives of cellulose, as well as with the production of alkyl cellulose ethers such as methyl, ethyl or hexyl cellulose, in which the alkyl, group contains 1-6 carbon atoms.

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The process for the production of organotin ether derivatives of hydroxyalkyl cellulose ethers is of particular importance to the present invention. The ethers having 2-4 carbon atoms in the hydroxyalkyl group are particularly important, although not limited to there is a certain length of the carbon chain. as Examples are hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

The invention is also concerned with the production of alkyl ethers such as benzyl cellulose, also inorganic ones Esters, especially nitrocellulose.

The polyhydroxy polymers # that make up the Organoζinnäther are not limited to cellulose derivatives such as the aforementioned esters and ethers, but concern also starch derivatives. Since starch is a natural polyhydroxy polymer, those applied to cellulose concern Modifications also the strength.

The synthetic polyhydroxy polymers are also important, in particular polyvinyl alcohol, as well as partially hydrolyzed esters, such as partially hydrolyzed polyvinyl acetate (10-90 days hydrolysis).

The invention also includes the production of acetals of polyvinyl alcohols, the free hydroxyl groups have for alkoxide formation. These acetals are made from polyvinyl alcohol and aldehydes with 1-7 carbon atoms both aliphatic and aromatic in nature. The examples include polyvinyl butyral.

Likewise is the production of organotin ether derivatives the hydroxyl-containing polyglycol ethers included, likewise the production of organonin ether derivatives en of synthetic graft polymers of vinyl monomers on natural and synthetic polyhydroxy polymers, as well as epoxides on such polyhydroxy polymers.

Examples of the above are polystyrene cellulose, polymethyl methacrylate starch, polyacrylonitrile cellulose acetate and polyethylene oxide cellulose.

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The polymers are made by first doing the Hydroxyl containing polymer is converted to an alkoxide. In principle, it can contain any hydroxyl group Polymer that can be converted into alkoxides can be used for the production of OrganoζinnSthern.

The conversion of free hydroxyl groups of natural polyhydroxy compounds such as starch and cellulose into the corresponding alkali metal alkoxide derivatives has already been extensively researched. The reaction between concentrated alkali metal hydroxide solutions and cellulose is known to give alkali metal oxide cellulose with a known metal content and known structure (O.Champetler and 0. Yovanovitch, J. Chim.Phys .., BH, 587 (1951); S. Bleshinski and S. Lozitskaya, Trudy Khim, Inst. Kirgis Filial Akad Nauk USSR No. H. 73 (195Di KN Gaver, ER Lasure and DV Tieszen US Patent 2,572,923 Oct. 30, 1951) Alkali metal oxide cellulose is also obtained by reacting cellulose with alkali metal in liquid ammonia .

<These general processes for the preparation of alkoxide derivatives have some disadvantages in the preparation of Organotin ether derivatives of polyhydroxy polymers. So becomes excess alkali with the organotin reagent R ^ RgR-Sn X react.

The preparation of alkali metal alkoxide derivatives in liquid ammonia also has certain disadvantages. In the case of acetyl cellulose and nitrocellulose, a reduction in the polymers is found due to a reduction (Audrieth and Kleinberg "Non-Aqueous Solvents ¹¹ , Wiley and Snns, New York, 1952, p. 111). The ammonia present then causes side reactions and can also split off the not very stable CO-Sn bond, which means that all the solvent (liquid ammonia) must be completely evaporated before this reaction can be carried out.

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009822/1864

Because of these disadvantages, the invention Polymer alkoxide according to the In the Israeli patent Ν, ο. 19 379 of June 10, 1963 described method Tetrahydrofuran, dimethylformamide, dimethylsulfoxide, xether, etc. soluble derivatives, the polyhydroxy compound either in suspension or, better still, in solution with a compound of an alkali metal with a polynuclear aromatic hydrocarbon such as naphthalene, Anthracene, etc., reacted in a suitable solvent. This reaction proceeds as follows from: (Paul, Llpkin and Weissmtnn, J.Am. Chem. Soc, Ji (1956):

Na ⁺ - * ~ 2P-ONa ⁺ * fY} + l ^ vSft

If the polyhydroxy compound is a solution, the reaction is almost instantaneous.

In addition, this method of preparation has those used in the process of the present invention Alkali metal oxide derivatives have the following advantages:

1 · The alkali metal additive compounds are colored, and the end of the reaction is easy to disappear the color · It is therefore possible to let the product react directly, because there are no residue compounds that could cause side reactions can·

2, The by-products of the reaction are only polynuclear hydrocarbons and their dihydro-derivatives, which do not affect the subsequent reactions

3 · It is possible to have a certain precisely defined faction of the hydroxyl groups of the polyhydroxy polymer by adding a calculated amount of the polynuclear alkali metal hydrocarbon, d & measured from a solution

Q09822 / 1864

BATH ORIGINAL

and standardized by acid-base titration was to transform «and it is also suitable for the To regulate the amount of organotin ether to be added to the polyhydroxy compound »

Ester derivatives

The present invention also relates to a process for preparing the organotin esters of the polymers the polycarboxylic acid, which is based on the reaction of the polymers containing carboxyl groups with organotin hydroxides or oxides based. The reaction formula is:

P-COOH + R ₁ R ₂ R ₃ Sn-OH or (R ₁ R ₂ R ₃ Sn) ₂ O

H ₂ O,

where ^R ₁ Rp ^R 3 have ^the above-mentioned composition.

These organic tin esters can also be prepared by heating the metal salt of the polymer with organic tin halides, sulfates, nitrates, and so on. The reaction equation is:

P ~ COONa + R ₁ R ₂ R ₃ SrJ-Cl - * - NaCl + P ~ C00Sr> ^R i ^R 2 ^R 3.

Another method of making them is by reacting the carboxyl group of the polymer with organotin hydrides or Organotin sulfides. However, the former is preferred.

The reaction is carried out by dissolving or suspending the polycarboxy polymer in a suitable solution such as dimethylformamide, benzene or toluene and heating the same carried out with the organic oil hydroxide or oxide. This in The water resulting from the reaction is treated with conventional means, e.g. 9. driven off by azeotropic distillation.

The polycarboxy polymers according to the invention include natural and synthetic polymers and their derivatives with carboxyl or anhydride groups. Among the natural

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BATH ORIGINAL

Polymers would be pectic and algae acid, carboxyalkyl cellulose ethers, wherein the carboxyalkyl groups 2-6 Carbon atoms such as carboxymethyl cellulose and carboxypropyl cellulose included, to name. Also included are cellulose esters of dicarboxylic acids 2 τ 20 carbon atoms in a branched or straight chain, aliphatic or aromatic type and mixtures thereof, the other carboxyl group being free. Examples of this Acids include maleic, succinic, phthalic, glutaric, and sebacic acids.

Also included are such partially esterified polymers, for example partially esterified carboxymethyl cellulose with free carboxyl groups that can be converted into organic tin esters.

The polycarboxy polymers are not limited to the aforementioned cellulose derivatives, so are the corresponding Starch derivatives fall under the present invention.

The synthetic polymers include polyacrylic acid, crosslinked poly & acrylic acid, polystyrene with substituted carboxyl groups and the like, it does not matter whether the polymers are linear or cross-linked are, as well as copolymers such as copolymers of acrylic and methacrylic acid, of styrene maleic anhydride, Maleic acid vinyl acetate and acrylic acid methyl methyl acrylate.

/ + With reference to polyacrylic acid, however, it must be stated that the same polymers apply to other Way of Marinelli and Montermoso (U.S.P. 3 012 018 and 3 016 369). The method based on these patents includes however, the polymerization of the monomeric tin esters of acrylic acid. The distillation point the resulting polymers are low and the tin content is constant and unchangeable.

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BATH ORIGINAL

The invention also relates to synthetic, partially hydrolyzed polyesters such as polyacrylates and Methacrylates with 1-90 hydrolysis of the ester groups "

According to the invention, the preparation of organotin esters of sulfonic acids is carried out in the same range as that of the organotin carboxyl esters described above.

The polymer containing sulfonic groups is with Organotin oxide or hydroxide of the general formula

R ₁ R ₂ RS ^ OH or ( ^R i ^R 2 ^R 3 ^S $ p2 ° ^{heated and the} resulting water expelled.

These organotin esters can also be produced by heating of the metal salt of the polymer with the organotin halides, sulfates, nitrates, etc. are produced:

+ R ₁ R ₂ R ₃ S ^ OH

₂ R ₃ S ^

Examples of the polysulfonic acids are polyvinyl sulfonic acid and sulfonated polystyrene called·

The organotin containing polymers are new plastic materials. Through their organotin groups they are also effective as microbicidal, insecticidal and antifeed compounds.

Films made from organotin polyesters have antifungal properties and are water repellent. They are used to impregnate fibers and yarns to make them antifungal and preventive To give properties.

The method according to the invention is to be described below with the aid of some exemplary embodiments, without thereby limiting the scope of the inventive concept.

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BATH

009822/1864

example 1 Tri-n-butyllaine ether derivatives of starch

- (A) 0.96N potassium naphthalene solution in tetrahydrofuran (21.7 ml x »20.8 mol) was added dry starch (2 g) dissolved in dimethyl sulfoxide (50 ml) with stirring. The color of the potassium naphthalene disappeared when the alcoholate derivative was formed. Tri-n-butyltin chloride (6.77 g »20.8 moles) was added in an argon atmosphere. The stirring was continued for four hours and the reaction mixture was left to stand overnight. With the addition of dry Xther (1000 ml) the tributyltin ether derivative of the starch was precipitated and the precipitate was filtered under dry argon, with a yield of 4.3 g of a hygroscopic product. 0.86 g of potassium chloride (determined by Volhard titration of the chloride) was added to the crude derivative. It contained 25.5 % Sn (based on the crude derivative). The product is soluble in water, swells in dimethylformamide and is insoluble in ethanol, dioxane, butyl acetate, chloroform, CCl _1. , Acetone, benzene and propylene glycol.

(B) Dry soluble starch (2.76 g) was dissolved in dimethyl sulfoxide (50 ml) and dissolved 1.16 N potassium naphthalene solution in tetrahydrofuran (15 ml, 17.4 mmol) with stirring admitted. After the color had disappeared and the alcoholate had formed, a solution of tributyl acetate (6.07 g) in Tetrahydrofuran added. The viscosity of the solution decreased. The solution was stirred for eighteen hours. The polymer was precipitated by dry ether (1 1) and the precipitate filtered under dry argon, whereby a yield of 5 * 46 g of a hygroscopic white Powder revealed.

Example 2 Tri-n-butyltin ether derivative of hydroxyethyl cellulose.

Dry hydroxyethyl cellulose dissolved in dimethyl sulfoxide (75 ml) (2 g) was stirred with potassium naphthalene

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009822/18 6 4

reacted in tetrahydrofuran (10 ml of a 1.06 N solution, 10.6 mmol). The alkoxide derivative formed was tributyltin (3, ¹ J? G, 10.6 mmol) was added. The viscosity of the solution decreased. The reaction mixture was stirred for two hours and then poured into dry ether (11). The tri-n-butyltin ether of the hydroxyethyl cellulose was filtered under dry conditions and washed with dioxane and ether, after which the yield was 3 g. 0.44 g of potassium chloride (determined by Volhard titration) was added to the derivative. It contained 7 »1 % Sn.

Example 3

Tri-n-butyltin ether derivative of methyl cellulose (colloresin)

Methyl cellulose (0.767 g) (methoxyl content: 24.6 %) was dissolved in dimethyl sulfoxide (50 ml), and a 0.96 N solution of potassium naphthalene in tetrahydrofuran (5-52 ml, 5.3 mmol) was added under argon. The color of the potassium naphthalene disappeared and the solution became very viscous due to the alcoholate formed. Tri-n-butyltin chloride (1.43 ml; 1.72 g; 5.3 mmol) was then added, and the reaction mixture was stirred for five hours and left to stand overnight. The tri-n-butyltin ether derivative of methyl cellulose was precipitated by dry ether (500 ml) with a yield of 1.35 g. 0.355 g of potassium chloride were added to the crude product. It contained 21.3 % Sn.

Example 4 Tri-n-butyltin ether derivative of polyvinyl alcohol.

A polyvinyl alcohol solution? (3g) in dimethyl sulfoxide (50 ml) was a 1.07 N solution of potassium naphthalene in tetrahydrofuran (30 mlj 32.1 mmol) under strong magnetic force Stirring added; then tri-n-butyltin chloride (8.7 ml; 10.4 g; 32.1 mmol) was added and more

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stirred for two hours. The reaction mixture was left to stand overnight; then dry ether (700 ml) was added and the precipitated ether derivative was filtered in an argon atmosphere. The yield was 8.25 g. The crude derivative contained 1.9 ¹ J g of potassium chloride, the end product 33 »4 % Sn.

Example 5 Triphenyltin derivative of hydroxyethyl cellulose.

Dry hydroxyethyl cellulose (0.5 g) was dissolved in dimethyl sulfoxide (44 ml) and potassium naphthalene in tetrahydrofuran (3.23 ml of a 0.57 N solution; 1.84 mmol) was added. Triphenyltin chloride (0.706 gj 1.84 mmol) dissolved in dioxane (10 ml) was added to the resulting alkoxide derivative with vigorous stirring, the reaction mixture was stirred for six hours and the triphenyltin derivative of hydroxyethyl cellulose was precipitated with dry ether (400 ml), left to stand overnight and filtered . The yield of the crude polymer was 0.75 g. 0.06 g of potassium chloride was added; the tin content was 3 »8 %,

Example 6

Tri-n-butyltin ether of nitrocellulose .

Nitrocellulose (0.5 g) was dissolved in tetrahydrofuran (50 ml) under argon; to this solution was added a solution of 0.57 N potassium naphthalene (1.4 ml; 0.8 mmol). After the color of the potassium naphthalene disappeared , tri-n-butyltin chloride (0.26 g; 0.8 mmol) was added and the reaction mixture was stirred for five hours. The tri-n-butyltin ether derivative of nitrocellulose was precipitated by petroleum ether (400 ml), filtered under dry argon and dried. The yield was 0.51 g. Potassium chloride (Q, 03 g) was added to the product; it contained 2 % Sn.

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BATH ORIGINAL

Example 7 Tri-n-butyltin ether of acetyl cellulose.

Acetyl cellulose (1 g) (acetyl content: 36 %) was dissolved in dioxane (50 ml) and a 1.04 N solution of potassium naphthalene (3 »2 mlj 3 | 31 mmol) was added with stirring. The color of the potassium naphthalene disappeared and the viscosity of the solution increased. Tri-n-butyltin chloride (0.9 ml; 1.07 g; 3 * 31 mmol) was added, the reaction mixture was stirred for two hours and left to stand overnight. The polymer was precipitated through petroleum ether (300 ml) and filtered in an argon atmosphere. The yield was 1.31 g. The tri-n-butyltin ether of the acetyl cellulose formed was mixed with 0.21 g of potassium chloride (determined by Volhard titration). The product contained 15.8 % Sn and was soluble in dioxane, dimethyl sulfoxide, tetrahydrofuran and acetone, insoluble in petroleum ether, ether, toluene and propylene glycol, Von. Tetrahydrofuran and acetone solutions of this polymer can be used to make films.

Similar results were obtained when the reaction was carried out in tetrahydrofuran or dimethyl sulfoxide instead of Dioxane was carried out.

Example 8 Triphenyltin ether derivative of ethereal cellulose.

Acetyl cellulose (1 g) (acetyl content: 36 Jt) was dissolved in dry dioxane, and potassium naphthalene solution (3.31 mmol) was added. Triphenyltin chloride (1.27 g; 3.31 mmol) was added to the resulting alkoxide derivative, and the reaction mixture was stirred for two hours and left to stand overnight. The polymer was precipitated by adding petroleum ether (300 ml), filtered in an argon atmosphere and dried. The yield was 1.35 g. 2.1 g of potassium chloride were added to the ether derivative; the tin content was 11.3 %

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009822/186 A _{βΑΛ Λ}

SAi) ORIG »NAL

Example 9 Trl-n-butyl tin ester of carboxymethyl cellulose.

iarboxyraethyl cellulose (2 g) (containing 1.4 mmoles of free carboxyl groups per gram) and bis-tributyltin oxide (1 ml, 3.88 mmoles) in benzene (150 ml) were azeotropically distilled for eight hours. The ester was filtered and washed thoroughly with benzene and petroleum ether; the yield was 2.2 g. The ester contained 5.1 % Sn and was insoluble in water, bicarbonate solution or propylene glycol.

Example 1 0 Triphenyltin ester of carboxymethyl cellulose.

Sodium salt of carboxymethyl cellulose (9.5 g) and triphenyltin chloride (7.35 gj 19.1 mmol) were in Dimethylformamide refluxed for twenty hours. The reaction mixture was centrifuged and placed in the Centrifuge with dimethylformamide, then washed with petroleum ether. The yield was 10.85 g. The ester is in Insoluble in water, while the sodium salt of carboxymethyl cellulose easily dissolves in jelly with the formation of a gel Water dissolves.

Example 11 Tributyl tin ester of crosslinked polyacrylic acid.

Amberlite IRC 50 (cross-linked, 50 % moisture containing polymetracrylic acid (2 g)) was azeotropically distilled in toluene (250 g ml) with bis-tri-n-butyltin oxide (2.31 g; 7.76 mmol) for fifteen hours. The product was filtered, washed with toluene and dried, after which the yield gave 1.87 g of the tri-n-butyltin ester of the crosslinked polymeric acid. The / final product contained 9 »9 % Sn.

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Example 12

Tri-n-butyl tin ester of styrene maleic anhydride gopolymer.

(A) Styrene maleic anhydride copolymer (Ig) (containing 9.1 mmoles of carboxyl groups per gram) and bis-tri-n-butyltin oxide (2.95 g; 9.9 mmoles) were refluxed in benzene (250 ml) with stirring for ten hours held. The copolymer dissolved completely and the benzene was driven off in vacuo. Ethanol was added to the viscous residue; the residue then solidified to a white solid mass. The ester was filtered, washed with ethanol and dried for a yield of 2.43 g. The product contained 27.9 % Sn; (C, gHg2} O2jSrj ₂ ) theoretically requires 29.9 % Sn. The trin-butyltin ester is soluble in ether, petroleum ether, benzene and chloroform. It is insoluble in water, ethanol or propylene glycols. Films are made from the ethereal solutions of the polymer.

(B) It is also possible to produce partially esterified copolymers. For this purpose, 1 g of styrene maleic anhydride copolymer with tri-n-butyltin oxide (1 ml; 1> 155 gj 3.88 mmol) in benzene solution was refluxed for six hours. The polymer was filtered and washed with benzene, after which the yield was 0.37 g, which contained only 7.7 % Sn. The piltrate contains a polymer with a higher Sn content (18.6 % Sn), ie more carboxyl groups were esterified.

Example 13

Triphenyltin ester of styrene maleic anhydride copolymer .

Styrenic anhydride copolymer (1 g) (containing 9.1 mmol of carboxyl groups per gram) and triphenyltin hydroxide (356 g; 9.85 mmol) were azeotroped in benzene (250 ml) for fifteen hours. The solution was filtered and evaporated in vacuo. Ethanol was added and the triphenyl tin ester of the styrene maleic anhydride copolymer (2.21 g) was collected. It contained 23.4 % Sn. The polyester is soluble in benzene and dimethyl sulfoxide, but insoluble in alcohol, ether, water or propylene glycol. - -15-

009822/186 / »

example Ik Trl-n-butylzlnnester of acetallgeluloseuccinat.

Acetyl cellulose succinate (1 g) (DS0.2) (0.9 mmol free carboxyl groups per gram content) and bis-tri-n-butyltin oxide (1 ml; 3 * 88 mmol) in benzene (100 ml) became azeotropic for eight hours distilled. The solution was evaporated, petroleum ether was added to the residue and the whole was left to stand overnight. The tri-n-butylzinnester of the acetylcellulose succinate was filtered and washed with petroleum ether. The yield was 1.15 g of ester with a tin content of 8.8 % Sn (calculated were 8.4 % Sn). Films can be made from the benzene solutions of the polymer.

Example 1 5 Tri-n-butyltin ester of acetylcellulose phthalate.

Acet $ lcellulose phthalate (1 g) (DS 0.48) (which contains 2 mmoles of free carboxyl groups per gram) and bis-tri-n-butyltin oxide (2 ml; 7-76 mmoles) were azeotroped in benzene (100 ml) for eight hours. distilled. The homogeneous solution was evaporated to dryness. Petroleum ether was added to the residue and the whole was left to stand overnight. The polymer was filtered and washed thoroughly with petroleum ether. The yield was 1.25 g with a tin content of 13 »3 % . Films can be produced from benzene solutions of this polymer.

Example 16

Trl-n-butyltin ester of the cross-linked polystyrene sulfonic acid .

Dowex 5OW (cross-linked polystyrene sulfonic acid) (11.6 g with 50 % moisture) and bis-tri-n-butyltin oxide (13.8 g) were refluxed for four hours. The water was driven off by azeotropic distillation with benzene (150 ml) for three hours, during which time 6.5 ml of water was distilled from the wet polysulfone resin. The trin-butyltin ester of polysulfonic acid was filtered,

009822/1864

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CONSTRUCTION ORIGINAL

washed thoroughly with benzene and dried, yielding 7.52 g of 9 »3 % Sn resin.

Example 17

Tri-phenyl ester of cross-linked polystyrene sulfonic acid.

This ester was made by reacting the sodium salt of sulfonic acid with triphenyltin chloride. Dry Amberlite IR 120 (sodium salt of crosslinked polystyrene sulfonic acid) (6.97 g) was treated with triphenyltin chloride (6g) in dimethylformamide (150 ml) heated with stirring for twenty-one hours. The resin was • centrifuged and washed with dimethylformamide, then with petroleum ether, then thoroughly with ethanol and then washed with water and dried. The yield was 7.95 g »

The polymeric trialkyl and triaryl tin derivatives according to the invention are useful as antifungal agents as shown in the following examples :

Example 18

The fungicidal properties of the following were found polymeric tin derivatives examined:

Tributyltin ether derivative * des
Polyvinyl alcohols (SM 9)

Tributyltin ether derivative of
Hydroxyethyl cellulose (SM 11)

Tributyltin ether derivative of
Methyl cellulose (colloresin) (SM 13)

Tributyltin ether derivative of
Strength (SM 15)

Tributyltin ether derivative of
Acet ^ l cellulose (SM 17).

The polymeric tin derivatives were made in dimethyl sulfoxide dissolved and added to a solid nutrient medium.

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009822/1864

ßAD ORIGINAL

The effectiveness of the polymers was investigated on (1) Candida albieans and (2) Cryptococcus neoformans A. These mushrooms were allowed to grow for 48 hours at 28 ° C. on a 'Sabouraud dextrose culture medium (Difco) with the addition of 0.4 t of yeast extract. The mushrooms were added dropwise (0.02 ml) to the necks containing the nutrient medium. The quantities withdrawn were 1 10 and 1 10. Control experiments were made with Mycostatin (R) (Pa. Squibb), the lowest inhibition concentration (Minimal Inhibition Concentration = MJC) of which is known from the literature for Candida albieans with ~ 3 / ml and for Cryptococcus neoformans with ~ 2 <1 / ml.

Since the investigated compounds contained 9-25% potassium chloride, three control experiments were carried out: (1) solid nutrient medium alone, (2) solid nutrient medium with 1 ml dimethyl sulfoxide per 25 ml nutrient medium, (3) nutrient medium ■ with dimethyl sulfoxide and potassium chloride (25 %) “ The control experiments showed that the high concentration of potassium chloride did not affect the growth of the mushrooms.

All experiments were carried out in duplicate by two people working independently. The scored The results are shown in Table I.

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BATH ORIGINAL

009822/1864

Panel I.

link M.J.C. M.J.C. Crypbcpccus neoformans
1 χ 1O \ ι χ io ⁵ Candida albicans
1 χ ΙΟ ¹ *, Ι χ 100 SM9 ^a 30 f '/ ml " 10-30 // ml SMl l ^b > 100 // ml > 100 // ml SMl 3 > loo // ml > 100 // ml SM15 ^C 100 f / ϊΆΐ 100 // ml SMl 7 ^d 100 // ml 100 // ml Mycostatln ^x 100 <jVml ^xx 10 // ml ^XX

M.J.C. = Minimal Inhibition Concentration lowest Inhibition concentration

χ Added as a suspension in water

xx Lower concentrations were not investigated,

a Sn content of the compound

b Sn content dft. ¹ connection

c Sn ~ content; the VtifbiniJUKg

d Sn content of the compound

«25 * 3 %

* 7.1 %

'6 ₄ 6 pounds

= 15.8 JE

O CO OO M Ki

Example 19

The fungicidal properties of the following were found polymeric tin derivatives investigated;

Tributyl tin ester of carboxymethyl celluloae (SM 61)

Triphenyltin ester of styrene maleic anhydride copolymer (SM 69) Tri-n-butyltin ester of styrene maleic anhydride copolymer (SM 70).

The inhibitory effect of SM 61 _f SM 69 and SM 70 on the growth of Candida albicans and Cryptococcus neoformans was determined. The test conditions were the same as in Example 18 "KCi tmrde in the control tests" was not added, since the polymers investigated did not contain this chloride. The results obtained are shown in Table II.

BATH ORIGINAL

-19-

-19-panel II

Connection i-concentration

f-ion

SM-61

t!

If

LO // ml

30th

50

SM-6 ° to // ml 30 // ml

"50 // ml

"JOO f / ml

SM-70

η 30th «" / Ml π 50 // ml η 100 iVml

Candida albleans

Cr

ecus neoformans

no inhibition no-inhibition no inhibition no inhibition,

partially

Il ti Il

complete complete inhibition inhibition

"" complete inhibition

I! »

NIf

complete
inhibition

ksine inhibition partly partly

Inhibition inhibition

partially complete complete

Inhibition inhibition inhibition

complete inhibition

Il 11 If

complete

inhibition

i! ! 3 η

Il H Il

It Il Jf

Il It Il

If Il 11

no inhibition no inhibition no inhibition no

inhibition

MJIM

ti IS ti

f! tf «

η η ti

ti »η

!to do

ti Il Il

It ti ti

complete complete complete complete ^ Inhibition inhibition inhibition

CD CD CD OO KJ KJ

OO CJJ

Example S O:

It became the growth inhibiting properties of tributylin ester the carbojcymethyl cellulose (SM-61), from Triphenyltin ester of styrene maleic anhydride copolymer (SM-69) and of tri-n-butylzin ester of styrene maleic anhydride copolymer (SM-70) on Trichophyton mentagrophytes examined.

The experiments were carried out according to the auxonogram method. Trichophyton mentagrophytes were left on Sabouraud Grow nutrient media for four to five days at 28 ° C. After the ground was covered with hyphae, it became with

BAD ORIGINAL _üQpY -2o

-2ο-

Washed off 5 ml of saline, which resulted in a cloudy suspension, the spores but not contiguous Hyphae contained. 0.1 ml of this suspension were transferred to Sabouraud culture medium by the Drigalski method containing bowls sprayed. Small amounts of the substances tested were weighed and carefully weighed out Transfer four to five places on the bowls. The results showed that SM-βΙ six days after vaccination at 5 mg completely inhibits growth.

SM-69 and SM-70 partially ^{inhibit growth at 15 mg x.} ( ^x These were the lowest amounts possible under these confidence conditions).

Example 21

It was the growth inhibiting properties of tributyl tin ester of carboxymethyl cellulose (SM-6I) and · of triphenyltin ester of styrene maleic anhydride copolymer (SM-69) examined for Sclerotium rolfsii.

Sclerotlum rolfsii grows on a white hyphae "carpet" and forms black sclerotia there. Inoculation is carried out by transferring a few sclerotia to small plates of Sabouraud culture medium, where growth takes place for 24 to 28 hours at 28 ° C. Hyphae forms around the sclerotia, d4, e gradually cover the entire nutrient medium. In about ten to fourteen days new sclerotia appear on the Hyphae- ^{n H} carpet. They are white and gradually darken.

The substances examined, SM-61 and SM-69 »were in Suspended dimethyl sulfoxide and added to the Sabouraud culture medium. 3-4 sclerotia were on the bowls Transferred where they were grown. Dimethyl sulfoxide in the same concentration as in the growth experiments containing Sabouraud medium and simple Sabouraud medium were set up as control experiments. Ee

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BATH ORIGINAL

it turned out that, while the control experiments developed as usual, 30 // ml of the SM-61 prevented growth completely and that the inoculated sclerotia did not develop hyphae. SM-69 partially inhibited growth.

Table III summarizes the results of low concentrations of SM-61 and SM-69 on the growth of sclerotium rolfsii together.

SM-61 ' Plate III inhibition link Concentration/ // ml no SM-61 1 partially 5 partially 10 Completely 20th Completely 30th no SM-69 1 partially 5 partially 10 partially 20th partially 30th

It goes without saying that the person skilled in the art can easily make changes without thereby reducing the scope of protection of the present invention is departed so that the invention does not depend on the embodiments of the present Description is limited.

009822/186 4

BATH ORIGINAL

Claims (1)

-22- Pat entana preexe 1) Process for the production of organotin derivatives of natural or synthetic polymers or their derivatives with hydroxyl, carboxyl, acid anhydride or sulfonic acid groups, characterized in that the organotin * by de hydroxyl, carboxyl, acid anhydride or sulfonic acid groups via an ether - Or ester compound is bound to the polymers, the Organoζinngruppe having the general formula R ₁ R ₂ R Sh-O-, in which R ₁ F ₂ » ^R 3 are identical or different, substituted or unsubstituted alkyl, aryl or aralkyl groups with 1 to 10 carbon atoms (with the exception of organotin esters of soluble polymethacrylic acid). 2) Process for the production of organotin ether derivatives of natural and synthetic polyhydroxy polymers and their derivatives according to claim 1, characterized in that the hydroxyl groups of the polyhydroxy polymer are converted into alkali alkoxide groups and with an organotin compound of the general formula R ₁ RpR ₅ SbX are reacted, where R ₁ , Rg, R, are determined according to claim 1 and X are halides, sulfates, nitrates or other similar inorganic anions or other anions derived from acids with a pK _A value not exceeding 4.8, 3) Process for the preparation of organotin ether derivatives of polyhydroxy polymers according to claim 2, characterized in that the hydroxyl groups of the polyhydroxy compound by reaction with an additional compound of an alkali metal with a polycyclic aromatic hydrocarbons are converted into alkali alkoxide groups 4) Process for the preparation of organocarboxy ester derivatives of natural and synthetic polyhydroxy · Polymers and their derivatives with carboxyl groups according to Claim 1, (with the exception of organotin esters of 009822/1864 bad original ~ ²³ " Polyamic acid), which means that it is worthwhile because these polymers are organosense hydroxides or oxides brewed in reaction «to earth · 5) Process for the production of organosinnoarboxyester derivatives of natural and synthetic Polyhydroxy polyaers and their derivatives with car boxy! pits according to claim i (including the Organosense esters of soluble polymetacrylic acid), characterized in that metal salts of the polymers alt an organosin halide, sulfate, filtrate or other similar inorganic anions can be brewed in reaction 6) Process for the production of organotin sulfonic ester derivatives from polymers with sulfo groups according to claim I _9, characterized in that the polymers are brewed in reaction with organic tin hydroxides or oxides. 7) Process for the production of organo * innsulfonester-Oerivmten alt sulfo groups according to »claim 1, characterized by the fact that the polymers are completely neutral old organosinhalogenld, -sulphate, -ltrate or other similar inorganic anions are brought into reaction 8) The method according to claim 1, characterized in that organic oil derivatives of starch are produced. 9) The method according to claim I _{9 is} characterized by the fact that organosin derivatives of the starch derivatives are produced. 10) Method neon claim 1, characterized in that organosin derivative · des polyvinyl alcohols getting produced· 11) The method according to claim 1, characterized in that organosine derivatives of the polyvinyl alcohol derivatives are produced. -21- 009822/186 /, BAD OBIG'NAL 12) Process according to claim 1, characterized in that organo-indervers of the polyalkylene glycols and polyalkylene oxides are produced. 13) The method according to claim 1, characterized in that organocline derivatives of the cellulose ester how methyl cellulose are made. 1 * 1) Process according to claim 1, characterized in that organosin compounds of the hydroxyalkyl derivatives of starch and cellulose, such as hydroxyethylsellu are manufactured loosely. 15) The method according to claim 1, characterized in that organoxide derivatives of cellulose acetate are produced. 16) Method according to claim 1, characterized in that organosin derivatives of nitrocellulose getting produced. 17) Method according to claim 1, characterized in that Organoεinndtrirate the polyakryllsohen Stubborn be made. 18) The method according to claim 1, characterized in that organotin derivatives of the cross-linking * n FolyeetSikrylsture are produced. 19) The method according to claim I _9, characterized in that organotin derivatives of the partially hydrolyzed ester derivatives of polyacrylic and poly iiure are produced * 20) Method according to claim 1, characterized since organosin derivatives of carboytymethyl - \ - • are produced eldtlose. · ■ .. ^: *; - - ^: '·.''''' - _; '' · .. ■. · ' 81) The neon method of claim 1, characterized in that the organotin derivatives of Zelluloaeeater ■ with mono * and dicarboxylic acids or dicarboxylic acids, such as cellulose acetate phthalate, cellulose acetate succinate and cellulose esuocinate. -25- OO 9 8 2 2/1 8 6 o ^BATH 22) Method according to claim I _9, characterized in that organotin derivatives of polystyrene sulfonic acid are produced. Process according to Claim 1, characterized in that organotin derivatives of vinyl sulfonic acid are produced. , 24) The method according to claim 1, characterized in that Organoζinnabkömmlinge of styrene maleic acid or anhydride copolymers are produced. 25) The method according to claim 1, characterized in that biocides, bacterlocids or fungistatic susairane settlements are produced. 26) Method according to claim 1, characterized in that plastic compositions are produced. BATH ORIGINAL 009822 / 186A