Tin preparation

Tin, If you should happen to run into a reduction using tin, prepare the following amalgam as follows. 

In the eleventh edition of this work, Lemery said that older writers believed bismuth to be a natural marcasite or an imperfect tin found in tin mines but tire modems, said he, believe with much likelihood that it is a regulus of tin prepared artificially by the English my thought on this subject is that there is natural bismuth, but that it is rare, and that... 

A white, granular, hygroscopic powder of alkaline reaction, soluble in 1 part of water, but insoluble in absolute alcohol. Tin- preparation should contain at least 99 per cent of K3(J(),. 

Trifluoromethyl)tributyl tin, prepared from (trifluoromethyl)trimethylsilane and bis(tributyltin) oxide, has been reported81 to react with disilyl sulphides to give the corresponding (trifluoromethyl)di- and (trifluoromethyl)trialkylsilanes. 

Blanda, M. T., Horner, J. H., Newcomb, M., Macrocycles containing tin - preparation of macrobicyclic Lewis acidic hosts containing 2 tin atoms and Sn-119 Nmr-studies of their chloride and bromide binding-properties in solution. J. Org. Chem. 1989,54,4626-4636. 

This is a fairly efficient method for the synthesis of 1,1-difluorocyclopropanes, the thermal variant requires an autoclave. Tributyl(trifluoromethyl)tin, prepared in situ, gave 9,9-di-fluorobicyclo[6.1.0]nonane (56%) with cyclooctene (Houben-Weyl, Vol. E19b, p 1471). 

Spiked aloes is frequently substituted for Barbadoes aloes in tins preparation, on account of the more ready solubility of the former. 

Usually prepared by the action of NaCN on benzaldehyde in dilute alcohol. It is oxidized by nitric acid to benzil, and reduced by sodium amalgam to hydrobenzoin PhCHOHCHOHPh by tin amalgam and hydrochloric acid to des-oxybenzoin, PhCH2COPh and by zinc amalgam to stilbene PhCH = CHPh. It gives an oxime, phenylhydrazone and ethanoyl derivative. The a-oxime is used under the name cupron for the estimation of copper and molybdenum. 

Tin IV) bromide, SnBr4. M.p. 33°C, b.p. 203 C, prepared from the elements. Fonns many complexes, including [SnBr ] ions. 

The greater metallic nature of tin is clearly indicated here for tin forms only one hydride, stannane, SnH4. It is best prepared by the... 

The precipitate obtained is in fact colloidal and has no definite composition. Careful drying of the precipitate gives the anhydrous oxide, SnO, which may also be prepared by heating tin(II) ethane-dioate (oxalate) ... 

Tin(IV) oxide occurs naturally, clearly indicating its high stability. It can be prepared either by heating tin in oxygen or by heating the... 

This chloride is prepared by dissolving tin in concentrated hydrochloric acid on cooling, the solution deposits crystals of hydrated tin(II) chloride. SnClj. 2H2O ("tin salt ). The anhydrous chloride is prepared by heating tin in a current of hydrogen chloride ... 

Stannic chloride is prepared by treating metallic tin with chlorine Sn + 2C1 SnCl4... 

Give brief experimental details to indicate how you could prepare in the laboratory a sample of either tin(IV) chloride or tin(IV) iodide. How far does the chemistry of the oxides and chlorides of carbon support the statement that the head element of a group in the Periodic Table is not typical of that group (JMB, A)... 

Uses of hydrogen chloride—Hydrogen chloride is sometimes used in the preparation of an ester, for example ethyl benzoate, where it acts as both an acid catalyst and a dehydrating agent. Hydrochloric acid is used primarily to produce chlorides, for example ammonium chloride. It is extensively used in the manufacture of anilme dyes, and for cleaning iron before galvanising and tin-plating. 

Arylamines are generally prepared by the reduction of nitro compounds. When only small quantities are to be reduced and the time element is important and cost is a secondary consideration, tin and hydrochloric acid may be employed, for example ... 

Secondary and tertiary amines are not generally prepared in the laboratory. On the technical scale methylaniline is prepared by heating a mixture of aniline hydrochloride (55 parts) and methyl alcohol (16 parts) at 120° in an autoclave. For dimethylaniline, aniline and methyl alcohol are mixed in the proportion of 80 78, 8 parts of concentrated sulphuric acid are added and the mixture heated in an autoclave at 230-235° and a pressure of 25-30 atmospheres. Ethyl- and diethyl-anihne are prepared similarly. One method of isolating pure methyl- or ethyl-aniline from the commercial product consists in converting it into the Y-nitroso derivative with nitrous acid, followed by reduction of the nitroso compound with tin and hydrochloric acid ... 

Note on the laboratory preparation of monoethylaniline. Although the laboratory preparation of monomethyl- or monoethyl-aniline is hardly worth whUe, the following experimental details may be useful to those who wish to prepare pure monoethylaniline directly from amline. In a flask, fitted with a double surface reflux condenser, place 50 g. (49 ml.) of aniline and 65 g. of ethyl bromide, and boU gently for 2 hours or until the mixture has almost entirely sohdified. Dissolve it in water and boil off the small quantity of unreacted ethyl bromide. Render the mixture alkaUne with concentrated sodium hydroxide solution, extract the precipitated bases with three 50 ml. portions of ether, and distil off the ether. The residual oil contains anihne, mono- and di-ethylaniline. Dissolve it in excess of dilute hydrochloric acid (say, 100 ml. of concentrated acid and 400 ml. of water), cool in ice, and add with stirring a solution of 37 g. of sodium nitrite in 100 ml. of water do not allow the temperature to rise above 10°. Tnis leads to the formation of a solution of phenyl diazonium chloride, of N-nitrosoethylaniline and of p-nitrosodiethylaniline. The nitrosoethylaniline separates as a dark coloured oil. Extract the oil with ether, distil off the ether, and reduce the nitrosoamine with tin and hydrochloric acid (see above). The yield of ethylaniline is 20 g. 

Compounds containing two primary amino groups attached to a benzene ring can be prepared by the reduction of dinitro compounds and of nitroanilines, usually with tin or stannous chloride and hydrochloric acid or with iron and very dilute hydrochloric acid. / ara-diamines may also be obtained by the reduction of aromatic amino-azo compounds (e.g., p-aminodimethylanihne from methyl orange, see Section IV,78). p-Phenylenediamine may also be prepared from p-nitroacetanilide reduction with iron and acid yields p-amino-acetaniUde,.which may be hydrolysed to the diamine. 

In a similar way HjC=C=C(0CH3)(SnBuj), n 1.4955 (undistilled) was prepared in almost quantitative yield from 0.12 mol of butyllithium in 75 ml of hexane and 75 ml of diethyl ether, 0.14 mol of methoxyallene and 0.10 mol of tributyl-tin chloride. The product contained 8-10% of an impurity, possibly Bu3Sn-CH2CEC-0CH3. 

Aldehydes can also be prepared by the carbonylation of aryl and alkenyl halides and triflate, and benzyl and allyl chlorides using tin hydride as a hydride source and Pd(PhjP)4 as a catalyst[377]. Hydrosilancs arc used as another hydride source[378]. The arenediazonium tetralluoroborate 515 is converted into a benzaldehyde derivative rapidly in a good yield by using Et ,SiH or PH MS as the hydride source[379]. 

Another preparative method for the enone 554 is the reaction of the enol acetate 553 with allyl methyl carbonate using a bimetallic catalyst of Pd and Tin methoxide[354,358]. The enone formation is competitive with the allylation reaction (see Section 2.4.1). MeCN as a solvent and a low Pd to ligand ratio favor enone formation. Two regioisomeric steroidal dienones, 558 and 559, are prepared regioselectively from the respective dienol acetates 556 and 557 formed from the steroidal a, /3-unsaturated ketone 555. Enone formation from both silyl enol ethers and enol acetates proceeds via 7r-allylpalladium enolates as common intermediates. 

A traditional method for such reductions involves the use of a reducing metal such as zinc or tin in acidic solution. Examples are the procedures for preparing l,2,3,4-tetrahydrocarbazole[l] or ethyl 2,3-dihydroindole-2-carbox-ylate[2] (Entry 3, Table 15.1), Reduction can also be carried out with acid-stable hydride donors such as acetoxyborane[4] or NaBHjCN in TFA[5] or HOAc[6]. Borane is an effective reductant of the indole ring when it can complex with a dialkylamino substituent in such a way that it can be delivered intramolecularly[7]. Both NaBH -HOAc and NaBHjCN-HOAc can lead to N-ethylation as well as reduction[8]. This reaction can be prevented by the use of NaBHjCN with temperature control. At 20"C only reduction occurs, but if the temperature is raised to 50°C N-ethylation occurs[9]. Silanes cun also be used as hydride donors under acidic conditions[10]. Even indoles with EW substituents, such as ethyl indole-2-carboxylate, can be reduced[ll,l2]. 

Nitro groups are readily reduced to primary amines by a variety of methods Cat alytic hydrogenation over platinum palladium or nickel is often used as is reduction by iron or tin m hydrochloric acid The ease with which nitro groups are reduced is especially useful m the preparation of arylamines where the sequence ArH ArN02 ArNH2 IS the standard route to these compounds... 

Reduction of aryl nitro compounds (Sec tion 22 9) The standard method for the preparation of an arylamine is by nitra tion of an aromatic ring followed by reduction of the nitro group Typical re ducing agents include iron or tin in hydro chloric acid or catalytic hydro genation... 

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