DD148056A1 - METHOD FOR PRODUCING NEW TINNORGANIC COMPOUNDS - Google Patents

Abstract

The invention relates to processes for the preparation of novel organotin compounds of the general formulas R & ind 4-n! Sn (OCO (CH & ind 2!) & Ind m!) & Ind n! NR '& ind l! and R & ind 3! SN (OCO (CH & ind 2!) & ind m!) & ind n! NR '& ind l !, in which R uR' represent identical or different alkyl, aryl and cycloalkyl radicals, which may also be substituted, and m, n and l are integers, where in the case n = 2 m values of 0 nis 3 and l take the value 1, while in the case n = 3 m values of 1 to 3 and l take the value 0. The processes are characterized in that organotin oxides with nitrilotriacetic acids or N-alkyl (aryl) -iminodiacigsiguren or Organozinnhalogenide with the alkali salts of said acids at normal pressure at 50 to 150 degrees C in polar solvents such as alcohols, dimethylformamide, dimethyl sulfoxide or mixtures thereof approximately equimolar amounts are reacted.

Description

217666

a) Title

Process for the preparation of novel organotin compounds

b) Field of application of the invention

The invention relates to processes for the preparation of novel organotin compounds which have a variety of biological activity.

c) Characteristic of the known technical solutions

A variety of organotin compounds have heretofore been used as versatile bioactive agents. Their activities are variable in strength, and it has been found that essentially compounds of the type R.Sn-XR '(H: carbon-bonded radical, R': any radical, X: heteroatom, O, S, H) support of biological activity. The structure of the remainder X has little influence according to previous findings. In some cases, however, a certain effect enhancement was found by special groupings, which also Diorganozinnderivate are concerned, for example by fluorine, ethanolamine derivatives (DE-OS No. 2526711) or by using already recognized as biologically active compounds as the radical R ¹ ; For example, phenoxyacetic acid phosphoric esters, etc. In this connection, compounds with pentacoordination on the tin atom play a certain role, but this concept proved to be unsuccessful until now because the strength of the pentacoordination was obviously too low. For example, US Pat. No. 3,442,922 has described some organotin compounds which are derivatives of substituted iminodiacetic acids and ethylenediaminetetraacetic acids.

d) Object of the invention

The aim of the invention was to develop processes for the preparation of novel organotin compounds which have particularly stable pentacoordination.

e) Presentation of the essence of the invention

The technical object of the invention was the development of methods for the preparation of compounds of the type R ₄ _ _n Sa (OCO (OH ₂ V _n HIF ₁

and R ₃ S ₁ (OCO (CH ₂ ) _a j J _n IH-!

wherein R and R ^{1 represent} alkyl, aryl, cyclohexyl, which may also be substituted and n, m, 1 are numbers of о bia 3 and η may be 2 and 3. In the case of n =: 2, values of 1 to 3 and 1 take the value 1, in the case of ю «3, m values of 1 to 3 and 1 take the value о. Eb has been found that the new organotin compounds Bowohl from the corresponding Organozinnorxyden with Hitrilotrialkansäuren or ΪΓ-alkyl (aryl Hminodialkan acids and from the Organozinnhalogeniden and the sodium salts of the corresponding acids in high yields and in high purity can be, if the reaction In yields of 1-6, preferably 1-3 hours, at temperatures of 50-150 ⁰ C and yields about equimolar amounts of the obtained in a polar solvents and at elevated temperature Alcohols, dimethylformamide, dimethyl sulfoxide or mixtures thereof are particularly suitable as solvents. [0008] The invention relates to the preparation of diphenyltin compounds with aryl elimination of phenyltin derivatives, with longer reaction times of 20 to 40 hours being necessary.

The workup of the reaction mixtures is carried out in a known manner by separation of the by-products water or alkali metal salts and removal of the solvent *

217666

The invention will be explained below by way of examples.

example 1

DMF / toluene (Bu ₃ Sn) ₂ O + (Н000СН ₂ ) ₂ Ше ·> MeII (CH ₂ COOSnBu ₃ ) ₂

" ^N ° ° (D

20 g of tributyltin oxide (0.065 mol) and 4.79 g of H-Metbyliminodieseigsäure (0,032ffiol) are heated in a mixture of 150 ml of ИГО and 100 ml of toluene on a water. After completion of the water separation (about 1 h), the boesungsmittel is removed in vacuo and the residue umkrlstalliert from benzene. This gives 22 g (95 % of theory) of H-MethyliminodiessigsHure tributylstannylester (I).

Example 2

DMF / toluene (Cy ₂ SnO) + (HOOCOH ₂ CH ₂ ) ₂ HMe Cy ₂ Sn (OOOCHg) ₂ Me (II)

20 g Dicyclohexsrlzlnnoxid (0.0665 mol) and 14.4 g of H-butyliminodipropionic acid (0.0655 mol) are heated in 300 ml of BMF and 150 ml of toluene on a water. After completion of the water separation (about 2 h) and removal of the solvent, 30.5 g of (II) are obtained (91.7 % of theory).

Example 3

CH, 0H

EtoSilCl, + (HaOOCCH ₅ ) OKEt ί ► Et ₅ Sa (OOCCH,) "№t (III)

г. г ά г. _ _{2 HaC1} г. 2 2

20 g of diethyltin dichloride (0.08 mol) and the disodium salt of If-sthyliminodiacetic acid (16.56 g, 0.08 mol) are heated in methanol for 2 h at reflux. After removal of the HaCl, the solvent is removed in vacuo and the residue is recrystallized from water. 21 g of (III) are obtained (77.4 % of theory).

217666

Example 4

DMF / toluene BuSnOOH + (HOOCOHg) ₃ H ► BuSn (0OCOH _{2) 3} H (IV)

20 g Butylstaimonsäure (0.096 mol) and 18.30 g Hitriloessig acid are heated in 200 ml of ПЮ and 100 ml of toluene on a water. After completion of the separation of water, the solvent is removed in vacuo, giving 33 g of (IV) (94.7 % of theory).

Example 5

DMF / toluene

(Ph ₂ SnO) + (HOOCCH ₂ ) JJ. PhSn (0OCCH ₂ ) ₃ U (V)

-H ₂ O, -CgHg

20 g of diphenyltin oxide (0.069 mol) and 13.23 g of Hltrilosäasigsäure (0.069 mol) are heated in 300 ml of DMP and 150 ml of toluene for 30 hours on a water. Then we4 daa solvent is removed in vacuo and the residue recrystallized from water. This gives 24 g (?) (90 % of theory).

Example 6

Et ₃ SnCl + HaOOCCH ₂ CH ₂ IiEt ₂ * - - Et ₃ SnOOCCH ₂ OH ₂ HEt ₂ (VI)

20 g (0.083 mol) of triethyltin chloride and 12.85 g (O, 0S3 mol) of the tetrasodium salt of ß-H, -N-Diethylaminopropionsäure are heated in methanol for 2 hours at reflux. The NaCl wijd filtered off. The solvent is removed in vacuo and the residue is extracted with benzene. This gives 26 g (VI) (89.6 % of theory).

Example 7

DMP / benzene 2Cy ₃ SnOH + (HOOCCHg) ₂ HBu s- (Cy ₃ SnOOCCH ₂ ) ₂ ÄBu (VII)

30 g Trieyclohexylztanhydroxid (0.078 mol) and 7.37 g of H-butyliminodiacetic acid (0.039 mol) in 200 ml of DMP unil 100 ml

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Benzene heated at the water separator. After completion of the water separation (3 h), the solvent is removed in vacuo to give (VII) in 97-Ä.ger yield (35 e).

Example 8

ΟΗ, ΟΗ Eb ₃ SnCItHaOOOCH ₂ IT (OH ₂ OH ₂ OH) ₂ i_ Ph ₃ SnOOCCH ₂ Ii (OH ₂ OH ₂ OH) ₂ (VIII)

20 g of triphenyltin chloride (0.052 mol) and 9.6 g (0.052 mol) of the sodium salt of bis-.beta.-hydroxyethyl aminoacetic acid are refluxed in methanol for 2 hours. Make separation of the liaCl, the solvent is removed in vacuo and the residue extracted with benzene. Concentration of the benzoyl results (VIII) in 945% yield (25 g).

Example 9

DMF / benzene (Bu ₂ SnO) + (HOOCCH ₂ 1 ₂ Me ► Bu ₂ Sb (00CCH ₂ ) ₂ Ше (IZ)

Dibutyltin oxide and H-methyliminodiacetic acid are heated in 200 ml of BMF and 100 ml of benzene on a water separator (3 h). The mixture is then concentrated in vacuo to give (33) in 95jSiger yield.

The structure of all compounds was verified by elemental analysis and spectroscopy.

Claims (1)

21 7666 Go to the preparation of new organotin compounds of general mixtures in which R and R 'represent identical or different alkyl, cyclohexyl and aryl radicals, which may also be substituted and n, m, 1 represent numbers from O to 3, where in the case of n = 2 ra values of 1 to 3 and 1 the value 1, in the case n = 3 и values from 1 to 3 and 1 assumes the value O, characterized that organozlnnoxide with Hitrilotrialkansäuren or U-alkyl- (aryl) iniinodiessigsäuren or Organozinnhalogenide with alkali salts del corresponding acids at 50- 150 ⁰ G within 1 to 6 hours, preferably 1 to 3 hours at atmospheric pressure in polar solvents, preferably Alcohols, dimethyl sulfoxide, mmethylformamid or mixtures thereof are reacted, which can be used for the preparation of Monoorganostannylverbindungen diorganostannyl compounds as starting material, v / as longer reaction times of 20 to 40 hours required.