Carbonates with alcohols

Scheme 11.58 Furan formation of intramolecular reaction of propargylic carbonate with alcohol...

H. P. Luo, W. D. Xiao, K. H. Zhu, Isobaric Vapor-liquid Equilibria of Alkyl Carbonates with Alcohols, Fluid Phase Equilibria. 2000.175, 91 105. 

A number of nuclear alkylated naphthalenesulfonic adds has been prepared by treating the hydro carbon with alcohols in the presence of ehlorosulfonic add or oleum. Succesrive alkylation and sulfonation or the reverse has also been employed. Other procedures involve the ohloromethyl-ation of naphthalene before, during, or after the sulfonation, and the condensation of an unsatuiated alcohol or hydrocarbon with the sulfonated naphthalene. ... 

Luo, H.-P. Xiao, W.-D. Zhu, K.-H. Isobaric vapor-liquid equilibria of alkyl carbonates with alcohols. Fluid Phase Equilib. 2000, 175, 91-105. 

CO. Alkynes will react with carbon monoxide in the presence of a metal carbonyl (e.g. Ni(CO)4) and water to give prop>enoic acids (R-CH = CH-C02H), with alcohols (R OH) to give propenoic esters, RCH CHC02R and with amines (R NH2) to give propenoic amides RCHrCHCONHR. Using alternative catalysts, e.g. Fe(CO)5, alkynes and carbon monoxide will produce cyclopentadienones or hydroquinols. A commercially important variation of this reaction is hydroformyiation (the 0x0 reaction ). 

Cj jH,2N202. Used as its sodium salt, which is a white hygroscopic powder. Unstable, readily absorbing carbon dioxide and liberating phenytoin. Made by treating a-bromodi-phenylacetylurea with alcoholic ammonia. It has a mild hypnotic and strong anticonvulsant action, and is used in the treatment of grand-mal and focal epilepsy. 

I he methyl iodide is transferred quantitatively (by means of a stream of a carrier gas such as carbon dioxide) to an absorption vessel where it either reacts with alcoholic silver nitrate solution and is finally estimated gravimetrically as Agl, or it is absorbed in an acetic acid solution containing bromine. In the latter case, iodine monobromide is first formed, further oxidation yielding iodic acid, which on subsequent treatment with acid KI solution liberates iodine which is finally estimated with thiosulphate (c/. p. 501). The advantage of this latter method is that six times the original quantity of iodine is finally liberated. 

The sales brochures of the manufacturers describe the plasticizer range alcohols available on the merchant market (18). Typical properties of several commercial plasticizer range alcohols are presented in Table 8. Because in most cases these ate mixtures of isomers or alcohols with several carbon chains, the properties of a particular material can vary somewhat from manufacturer to manufacturer. Both odd and even carbon chain alcohols are available, in both linear and highly branched versions. Examples of the composition of several mixtures are given in Table 9. 

Hydrolysis of Peroxycarboxylic Systems. Peroxyacetic acid [79-21-0] is produced commercially by the controlled autoxidation of acetaldehyde (qv). Under hydrolytic conditions, it forms an equiHbrium mixture with acetic acid and hydrogen peroxide. The hydrogen peroxide can be recovered from the mixture by extractive distillation (89) or by precipitating as the calcium salt followed by carbonating with carbon dioxide. These methods are not practiced on a commercial scale. Alternatively, the peroxycarboxyHc acid and alcohols can be treated with an estetifying catalyst to form H2O2 and the corresponding ester (90,91) (see Peroxides and peroxy compounds). 

Lead Chloride. Lead dichloride, PbCl2, forms white, orthorhombic needles some physical properties are given in Table 1. Lead chloride is slightly soluble in dilute hydrochloric acid and ammonia and insoluble in alcohol. It is prepared by the reaction of lead monoxide or basic lead carbonate with hydrochloric acid, or by treating a solution of lead acetate with hydrochloric acid and allowing the precipitate to settle. It easily forms basic chlorides, such as PbCl Pb(OH)2 [15887-88 ] which is known as Pattinson s lead white, an artist s pigment. 

Lead Carbonate. Lead carbonate [598-63-0] PbCO, mol wt 267.22, d = 6.6g/cm, forms colorless orthorhombic crystals it decomposes at about 315°C. It is nearly insoluble in cold water (0.00011 g/100 mL at 20°C), but is transformed in hot water to the basic carbonate, 2PbC03 Pb(OH)2. Lead carbonate is soluble in acids and alkalies, but insoluble in alcohol and ammonia. It is prepared by passing CO2 iuto a cold dilute solution of lead acetate, or by shaking a suspension of a lead salt less soluble than the carbonate with ammonium carbonate at a low temperature to avoid formation of basic lead carbonate. 

Substitution Reactions on Side Chains. Because the benzyl carbon is the most reactive site on the propanoid side chain, many substitution reactions occur at this position. Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide stmeture. In a reversal of the ether cleavage reactions described, benzyl alcohols and ethers may be transformed to alkyl or aryl ethers by acid-catalyzed etherifications or transetherifications with alcohol or phenol. The conversion of a benzyl alcohol or ether to a sulfonic acid group is among the most important side chain modification reactions because it is essential to the solubilization of lignin in the sulfite pulping process (17). 

The reaction of phosgene with alcohols yields chloroformates, and with a basic catalyst present, carbonates ate formed ... 

The principal impurity in potassium metal is sodium. Potassium s purity can be accurately deterrnined by a melting point test (Fig. 2) or atomic absorption if necessary after quenching with alcohol and water. Traces of nonmetallic impurities such as oxygen, carbon, and hydrogen can be deterrnined by various chemical and physical methods (7,8). 

Bromine is soluble in nonpolar solvents and in certain polar solvents such as alcohol and sulfuric acid. It is miscible with alcohol, ether, carbon disulfide, and many halogenated solvents. Bromine reacts with some of these solvents under certain conditions. 

The reaction of phosgene (carbonic dichloride [75-44-5]) with alcohols gives two classes of compounds, carbonic esters and carbonochloridic esters, commonly referred to as carbonates and chloroformates. The carbonic acid esters (carbonates), R0C(0)0R, are the diesters of carbonic acid [463-79-6]. The carbonochloridic esters, also referred to as chloroformates or chlorocarbonates, C1C(0)0R, are esters of hypothetical chloroformic acid [463-73-0] CICOOH. 

---