Substituted Organotin Compounds Research Articles

Novel diaminopropyl substituted organotin compounds

A novel synthetic pathway involving the desilylation of a tin trimethylsilyl species (Ph2Sn(SiMe3)2) towards nonprotected di(3-aminopropyl)tin dichloride ((H2N(CH2)3)2SnCl2) is described. Di(3-aminopropyl)tin dichloride is then converted to the respective dicarboxylates species (H2N(CH2)3)2Sn(OCOR)2 containing carboxylic acids of different lengths (R = –CH3, –(CH2)10CH3). Depending on the nature of R, discrete packing effects are observed in the solid state of di(3-aminopropyl)tin dicarboxylate derivatives. All the synthesized substances were characterized by 1H, 13C, and 119Sn nuclear magnetic resonance data and also single crystal X-ray analysis. These compounds are a promising class of substances for biological, pharmaceutical, and technical applications.

Novel amino propyl substituted organo tin compounds

In this work, a new synthetic pathway yielding unprotected amino propyl tin compounds is described. For this purpose, mono stannanes with different substitution patterns are used. In a first step, tin hydrides are deprotonated using lithium diisopropyl amide and mixed with an electrophile containing a protected amine in the ω-position. After deprotection via acidic hydrolysis, the desired amino propyl tin compounds are obtained in high yield and purity. The thermal reaction behavior of the amino propyl tin hydrohalide intermediates containing one aromatic residue at the central tin atom is also investigated. For this purpose, amino propyl tin hydrohalides are heated under vacuum until the aromatic hydrocarbon is liberated. This thermal treatment leads to so far unknown tin halides containing an amino propyl side chain. For all of these substances detailed liquid 1H, 13C, and 119Sn-nuclear magnetic resonance (NMR) data were obtained, and in one case solid state NMR is also conducted. Regarding solids, single crystal X-ray analysis is performed. Some derivatization reactions with these new substances are demonstrated, especially the synthesis of an amino propyl tin carboxylate, which might be very interesting for biological, pharmaceutical, or technical processes.

Sulphur substituted organotin compounds. Part 9. Crystal and molecular structure and reactions of [( p-chlorophenylthio)methyl]tricyclohexylstannane

The crystal and molecular structure of [( p-chlorophenylthio)methyl]tricyclohexylstannane ( II) has been determined. In the two independent molecules of monoclinic II there are slightly distorted tetrahedral geometries about tin with intramolecular SnS distances of 3.29(1) and 3.26(1) Å. Compound II reacts with N-bromosuccinimide, I 2, Pb(OAc) 4 or CF 3CO 2H to give XCH 2SC 6H 4Cl- p (X = Br, I, AcO or H) and the appropriate tricyclohexyltin species; II is less reactive than Cy 3SnCH 2SeC 6H 4Cl- p towards I 2. Oxidative cleavage of II by m-ClC 6H 4CO·O·OH provides mainly CH 3S(O)C 6H 4Cl- p. The absorption maximum for the charge transfer complex of II and (NC) 2CC(CN) 2 is reported.

ChemInform Abstract: Bromodestannylation Reactions of Some Functionally Substituted Organotin Compounds.

AbstractThe title reactions are reported for several organotin compounds such as (I) in CCl4 and MeCN as solvents.

Bromodestannylation reactions of some functionally substituted organotin compounds

Bromodestannylation reactions are reported for several functional substituted organotin compounds in carbon tetrachloride and acetonitrile as solvents. The reactions in carbon tetrachloride proceed with a high degree of retention of configuration at the carbon involved in the electrophilic substitution, while in a polar solvent there is an increase in the amount of inversion product formed. The electrophilic cleavage in the β-trialkylstannyl esters takes place with a complete reversal of the normal sequence of SnC bond cleavage by halogens; this is explained by tin assistance. The configuration of some 3-trialkylstannylpropanenitriles, β-bromonitriles and β-bromoesters are assigned. Full 1H, 13C and 119Sn NMR data are given.

Sulphur substituted organotin compounds : IX. Formation of [(3-chloro-4- o-nitrophenylthio)butyl]-triphenyltin, Ph 3SnCH 2CH 2CHClCH 2SC 6H 4NO 2- o, from reaction of 4-butenyltriphenyltin and o-nitrobenzenesulphenyl chloride

Reaction of the sulphenyl chloride, o-NO 2C 6H 4SCl, with Ph 3SnCH 2CH 2CHCH 2 occurs to give the adduct, Ph 3SnCH 2CH 2CHClCH 2SC 6H 4NO 2- o. In contrast, no adduct is formed with the more reactive, p-MeC 6H 4SCl. Instead, and as reported previously with Bu 3SnCH 2CH 2CHCH 2, the cyclopropylmethyl aryl sulphide is obtained. The adduct is thermally stable, and reacts with I 2 and HgCl 2 to give phenyld-tin cleaved products, Ph 2SnXCH 2CH 2CHClCH 2SC 6H 4NO 2- o (X = I or Cl).

Sulphur substituted organotin compounds : VII. Charge transfer interactions of arylthiomethyl(triphenyl)tin compounds with tetracyanoethylene

Charge-transfer interactions of Ph 3SnCH 2SC 6H 4X- p (X  MeO, Me, H, Cl or Br) with tetracyanoethylene are reported. Values of λ max, the absorption maxima, have been obtained and compared with the values for CH 3SC 6H 4X- p(CN) 2CC(CN) 2 interactions. The effect of the Ph 3Sn substituent is to shift λ max by 15–26 nm to longer wavelengths.

Organotin compounds : III. Organotin chlorohydride additions to methyl E-disubstituted propenoates

The syntheses of new functionally substituted organotin compounds are reported. The results indicate that the additions of di-n-butyltin and diphenyltin chlorohydrides to methyl E-disubstituted propenoates give high yields of organotin adducts and that the reactions are stereoselective. Evidence supporting a trans-stereospecific addition is discussed.

Sulphur substituted organotin compounds. Part 6. Reactions of mercaptomethyltin compounds with arenesulphenyl chlorides

Reactions between Ph 3SnCH 2SAr and 2-NO 2C 6H 4SCℓ lead to the formation of 2-(ArSCH 2-6-NO 2C 6H 3SSC 6H 4NO 2-2 via the [2,3]sigmatropic rearrangement of the S-arylthio-sulphonium ylides C H 2 S + (Ar)SC 6H 4NO 22.

Organotin hydride additions to E- And Z-trisubstituted ethylenes synthesis of some new functionally substituted organotin compounds

The syntheses of some new functionally substituted organotin compounds are reported. The results indicate that the additions of tri-n-butyltin and tri-phenyltin hydrides to trisubstituted ethylenes (where one substituent is either a carbomethoxy or a nitrile group) proceed smoothly to give high yields of organotin adducts and that the reactions are stereoselective. Evidence concerning the reversibility of the free radical forming step is presented.

Functionally substituted organotin compounds : I. Preparation and hydrostannation of stannylated allylic alcohols and related compounds

Hydrostannation of 1-alkynols leads to the formation of the corresponding triorganostannylalkenols in good yields. The main product is the trans-isomer, while cis-and α-products are formed in lower yields. In some cases the stannyl alkenols can be further hydrostannated to give distannyl alkanols. 13C and 119Sn NMR data for the organotin compounds are presented and discussed.

Functionally substituted organotin compounds : V. Beckmann rearrangement of oximes containing organotin substituents

The structures of the oximes formed from (4-oxopentyl)triphenyltin and (4-oxopentyl)diphenyltin chloride have been determined using IR, PMR and Mössbauer spectroscopy. Beckmann rearrangement of (4-oximinopentyl)diphenyltin chloride with phosphorus pentachloride gave the amide resulting from exchange of syn groups. Treatment of the second oxime with phosphorus pentachloride caused other reactions but the O-tosyl derivative was rearranged under mild conditions to give a mixture of amides.

Functionally substituted organotin compounds. Part IV. The use of protecting groups in the formation of 4-oxopentyltin compounds

Protection of the carbonyl group in 1-chloropentan-4-one by dioxolan formation has enabled preparation of a series of 4-oxopentyltin compounds via the Grignard reagent. I.r., n.m.r., and Mögssbauer spectroscopy have been used to aid structure assignments: in many of the-compounds the carbonyl group is intramolecularly co-ordinated to tin. Stereochemical assignments have been made for (4-oxopentyl)diphenyltin chloride and di(4-oxopentyl)tin dibromide.

Functionally substituted organotin compounds : III (Epoxyalkyl)tin compounds

Treatment of vinyltin and 3-butenyltin compounds with perbenzoic acid (or ?3-chloroperbenzoic acid) gave (epoxyalkyl)tin derivatives together with the organotin ?(3-chloro)benzoate. No epoxy derivative could be isolated from the corresponding ?allyltin compounds. Reduction of tributyl(3,4-epoxybutyl)tinn with lithium aluminium hydride gave tributyl(4-hydroxybutyl)tin.

Configurational stability of asymmetrically substituted organotin compounds. An example of optical activity at the tin centre

Chemical shift non-equivalence of diastereotopic groups has been studied for a series of organotin monohalides with organic groups of different sizes to test the stereochemical stability of the asymmetric tin centre. The mutually related effects of halogen intermolecular exchange, nature of tin–halogen bond, intrinsic asymmetry of the molecules, and the steric requirements of the organotin groups are discussed in the light of the experimental findings. The effect of the bulk of the organic groups on the intrinsic asymmetry of some organotin compounds with four carbon–tin bonds has also been studied. An optically active tetraorganotin compound has been obtained through asymmetric synthesis.

Functionally substituted organotin compounds : II. Reactions between (bromomethyl)tin compounds and sodium thiolates.

Compounds containing ▪ groups have been prepared by two routes: ▪ ▪ the former method is preferred. Reactions between RSNa and (BrCH 2) 2SnBr 2 give (RSCH 2) 2Sn(SR) 2. Properties, including the Mössbauer spectra, of these compounds are reported.

Functionally substituted organotin compounds I. Addition of thiols to alkenyltin compounds

3-(Trialkylstannyl)propyl aryl sulphides (R 3SnCH 2CH 2CH 2SR′; R = Me, Et, Bu; R′ = Ph, p-tolyl) were prepared by the addition of arenethiols to allyltrialkyltin compounds. Preferential cleavage of the allyl group by the reaction R 3SnCH 2CHCH 2+R′SH→R 3SnSR′+CH 3CHCH 2 occurred when R = R′ = Bu and R = R′ = Ph. Diallyltin dibromide and benzenethiol gave stannous bromide. Mössbauer parameters of the products are recorded.

Reformatsky-type reactions of α-functionally substituted organotin compounds

Reformatsky-type reactions of α-functionally substituted organotin compounds