Bis Tributyltin Oxide Research Articles

Utilization of Sugars in Organic Synthesis. Part XXV. Conversion of Thiocarbonyl into Carbonyl Group by O-S Exchange Reaction with Dibutyltin Oxide or Bistributyltin Oxide.

Cyclic thionocarbonates and thionolactones, when heated with 1.0-1.5 mol eq of dibutyltin oxide or bistributyltin oxide in dioxane, gave the corresponding carbonates and lactones in satisfactory yields, respectively.

119Sn-NMR Study on Bis(Tri-Butyltin)oxide Derivatives of Phenolic Compounds

Abstract 119Sn-NMR spectroscopy has been utilized in the characterization of various phenolics as their bis(tri-butyltin)oxide, TBTO, derivatives. The present method has been applied both for determination of simple model compounds and for characterization of complex biopolymeric material originating from spent bleach liquor fractionated by an ultrafiltration technique. Based on the large range of 119Sn-NMR chemical shifts of TBTO derivatives of the phenolic compounds and the similar relaxation properties of 119Sn nuclei located in those derivatives, both qualitative and quantitative analytical conclusions can be drawn.

ChemInform Abstract: Mild and Effective Cleavage of Esters with Bis(tributyltin) Oxide: A Useful Application in the Deprotection of Pom Penicillanate Esters.

AbstractThe pivaloyloxymethyl(Pom) penicillanates (I) are cleaved with bis(tributyltin) oxide to form the acids (II).

Inter-laboratory determination of bis(tributyltin) oxide in timber and timber-treatment solutions

Accurate analysis of timber preservatives in timber-treatment solutions and in treated timber is an essential aspect of quality control in the New Zealand wood preservation industry. The increasing use of light organic solvent preservatives in recent years has drawn attention to the need for dependable methods for the determination of bis(tributyltin) oxide (TBTO). As part of an on-going programme of timber preservative analyses at the Forest Research Institute the determination of TBTO was studied in detail by an inter-laboratory comparison between six laboratories. Significant differences between laboratories were found in the determination of TBTO (or tin) in timber preservative treatment solutions and preservative-treated timber. To rectify this situation, recommendations on the necessity to intensify quality assurance programmes are suggested.

Organotin derivatives of alkanedisulfonic acids

The preparation of dibutyltin and tributyltin alkanedisulfonates from alkyltin oxides and the corresponding alkanedisulfonic acids has been studied. The products, obtained in 56 – 74% yield, were tested as biocides against bacteria, yeasts, and moulds as well as fungicides against wood rot and their activity was compared with that of bis(tributyltin) oxide.

Catalytic Oxidation of Hydroquinones and Naphthalenediols to 1,4-Quinones with H2O2 in the Presence of Chromium(VI) Oxide-Bistributyltin Oxide and an Application to Vitamin K1 Synthesis

Abstract The oxidation of hydroquinones and naphthalenediols to 1,4-quinones was carried out in the presence of a chromium(VI) compound formed from chromium(VI) oxide and bistributyltin oxide with 30% aqueous H2O2 in benzene-isopropyl ether at 50 °C. The catalyst was fixed on charcoal and used for the oxidation of dihydrovitamin K1 to vitamin K1 in ethyl alcohol.

X-Ray crystal structure of an ionic trialkyldiaquotin(IV) cyclopentadiene derivative, [Bu3Sn(OH2)2]+[C5(CO2Me)5

Penta (methoxycarbonyl)cyclopentadiene reacts with bistributyltin oxide to give the salt [Bu3Sn(OH2)2]+[C5(CO2Me)5]–; X-ray analysis shows that the cation is trigonal bipyramidal, with apical water molecules.

A general route to dioxabicyclo [n.2.1]alkanes

6,7-Dioxabicyclo [3.2.1]octane has been prepared from its cis-8-bromo derivative by reduction with tributyltin hydride generated in situ from bis(tributyltin) oxide and polymethylhydrogen siloxane; analogous reactions have afforded 7,8-dioxabicyclo[4.2.1]nonane and 8,9-dioxabicyclo[5.2.1]decane.

Experimental Studies on the Organotin Poisoning (Report 39) : Enzymes in the Serum of Rabbits Administered with bis-Triphenyltin Oxide and bis-Tributyltin Oxide through Digestive Tract

Experimental Studies on the Organotin Poisoning (Report 39) : Enzymes in the Serum of Rabbits Administered with bis-Triphenyltin Oxide and bis-Tributyltin Oxide through Digestive Tract

A comparison of the half-life of inorganic and organic tin in the mouse

Tin-113-labeled bis-tributyltin oxide, TBTO, has been prepared from metallic 113Sn. The half-life of the organotin has been compared with inorganic tin in the mice using a whole-body counter. The biological half-life of inorganic tin, 29 days, was not changed by injection of an excess of unlabeled tin. During the first several days TBTO was cleared rapidly from the body of the mouse. At later times the turnover rate of TBTO in the mice appeared to become asymptotic to that of inorganic tin.

Behaviour of some lead(IV) and tin(IV) compounds in disulphoric acid

Lead and tin tetraacetates form H 2[Pb(HSO 4) 6] and H 2[Sn(HSO 4) 6] in disulphuric acid which behave as weak acids of the system. Tin tetraethoxide, tetraphenyl tin, triphenyl tin chloride and diphenyl tin dichloride are solvolysed. Tetraethyl and tetrapropyl tin form the corresponding trialkyl tin cations, whereas trimethyl, tripropyl tin chlorides and dipropyl and diethyl tin dichlorides have ionisable chloride ions. Tributyl tin chloride, bis-tributyl tin oxide and dipropyl tin oxide are also solvolysed but bis-tripropyl tin oxide forms stannonium ion.

Organometallic reactions. Part XVIII. The reactions of N-sulphinyltoluene-p-sulphonamide and of N-(2,2,2-trichloroethylidene)toluene-p-sulphonamide with some tributyltin–oxygen and –nitrogen compounds

The sulphonyl group in the structures p-MeC6H4·SO2·N:CH·CCl3 and p-MeC6H4·SO2·N:S:O activates the adjacent N:S or N:C double bond, so that both these compounds react very readily with a variety of tributyltin–oxygen and –nitrogen compounds. The adducts of N-sulphinyltoluene-p-sulphonamide with bistributyltin oxide and hexabutyl-N-phenyldistannazane readily eliminate NN-bistributylstannyltoluene-p-sulphonamide, which will react with toluene-p-sulphonamide itself to give N-tributylstannyltoluene-p-sulphonamide. N-(2,2,2-Trichloroethylidene)toluene-p-sulphonamide has acceptor properties similar to, but rather weaker than, those of chloral.

Determination of bis(tributyltin)oxide in air by atomic absorption spectroscopy or pyrolysis gas chromatography.

Determination of bis(tributyltin)oxide in air by atomic absorption spectroscopy or pyrolysis gas chromatography.

Organometallic reactions. Part XV. Addition–elimination reactions involving the Sn–O bond and the carbonyl group: a new route to trihalogenomethyltin compounds

Tributyltin methoxide and bistributyltin oxide displace a trihalogenomethyl group from a carbonyl centre by an addition–elimination mechanism, providing a route to tributyltrichloromethyltin and tributyltribromomethyltin. These compounds react with protolytic reagents, giving the corresponding halogenoforms. They decompose when they are heated to give the corresponding dibutyltin dihalides as a major product, and do not appear to be useful for transferring a dihalogenocarbene unit to an olefin.

Organometallic reactions. Part VII. Further addition reactions of tributyltin methoxide and of bistributyltin oxide

The addition of tributyltin methoxide and of biotributyltin oxide to the following acceptor molecules is described : isothiocyanates, trichloroacetonitrile, carbon disulphide, carbon dioxide, sulphur dioxide, and carbodi-imides. The corresponding phenoxide is generally less reactive than the methoxide. The initial product is always a 1 : 1 adduct, but in the reaction of bistributyltin oxide with isothiocyanates and with carbon disulphide, the nature of the ultimate product is determined by the elimination of bistributyltin sulphide. Many of the adducts dissociate when heated. Many react very readily with protic reagents, and consequently organotin compounds catalyse the addition of alcohols or of water to carbodi-imides.

Organometallic reactions. Part VI. The addition of the Sn–O bond to the carbonyl group

Tributyltin methoxide and bistributyltin oxide react at the carbonyl group of many aldehydes and of certain more reactive ketones to give the 1 : 1 adducts (A). In the case of chloral and of 1,1,3-trichloro-1,3,3-trifluoropropane-2-one, the n.m.r. spectra show that 1 : 2 adducts (B) can also be formed, and, with chloral, repetition of this process gives the polymer (C). R3Sn·OR[graphic omitted]R3Sn·O·CR″R″′·OR′[graphic omitted] (A) R3Sn·[O·CR″R″′]2·OR′[graphic omitted]R3Sn·[O·CR″R″′]a·OR′(B)(C) The 1 : 1 adduct (A) can alternatively react with other carbonyl compounds by a reversible exchange of the organotin reagent. Acetyl chloride or methanol similarly react by displacing the carbonyl compound OCR″R‴. If one or both of the groups R″ and R‴ is a trihalogenomethyl group, methanolysis can alternatively involve displacement of the carbonyl compound R″CO·OR′, liberating the haloform; in consequence, organotin compounds catalyse the methanolysis of hexachloroacetone to methyl trichloroacetate and chloroform. It is suggested that all these reactions proceed through a 6-membered cyclic transition state.

A Method for Determination of Organic Tin Compounds in Raw Starch

In Aichi prefecture diethyl benzyl tin hydroxide, one of organic tin compounds, added to raw starch as food additive was detected. Its content was about 5ppm. From the view of food hygiene, it is dangerous. This is the first case that diethyl benzyl tin hydroxide was used for the preservation of raw starch. Accordingly identification method of organic tin compound has not been found except for the method which is restricted to identify metallic tin.Of gas chromatography, infrared absorption spectrum, and thin layer chromatography, good results were obtained only by the latter method as follows: Not only diethyl benzyl tin hydroxide but tributyl tin acetate, triphenyl tin acetate and bis tributyl tin oxide were able to be identified by the “double T. L. C.” method. Linear calibration curve was obtained by each of them at the maximum absorption wave length by UV absorption method, which corresponded with the Beer's law, the quantitative analysis being found to be possible. Then we added diethyl benzyl tin hydroxide to raw starch produced in our laboratory and examined its recovery test. After the experience, their recoveries were 87.8-91.5%. From the above, this method seems to be excellent for detecting organic tin compounds.

Organometallic reactions. Part IV. The preparation of bistrialkyltin derivatives of ureas and biurets by the decarboxylation of bistrialkyltin oxide–isocyanate adducts

Under appropriate conditions of temperature and structure, bistributyltin oxide will react with isocyanates to yield carbon dioxide and the bistributylstannyl-NN′-dialkylureas; these ureas will react further with isocyanate giving bistributylstannyl-NN′N″-trialkylbiurets. By reactions of this type, mixed biurets of the composition RHN·CO·NR′·CO·NR″H have been prepared for the first time.