Phenyl 0 carbon

Early Synthesis. Reported by Kolbe in 1859, the synthetic route for preparing the acid was by treating phenol with carbon dioxide in the presence of metallic sodium (6). During this early period, the only practical route for large quantities of sahcyhc acid was the saponification of methyl sahcylate obtained from the leaves of wintergreen or the bark of sweet bitch. The first suitable commercial synthetic process was introduced by Kolbe 15 years later in 1874 and is the route most commonly used in the 1990s. In this process, dry sodium phenate reacts with carbon dioxide under pressure at elevated (180—200°C) temperature (7). There were limitations, however not only was the reaction reversible, but the best possible yield of sahcyhc acid was 50%. An improvement by Schmitt was the control of temperature, and the separation of the reaction into two parts. At lower (120—140°C) temperatures and under pressures of 500—700 kPa (5—7 atm), the absorption of carbon dioxide forms the intermediate phenyl carbonate almost quantitatively (8,9). The sodium phenyl carbonate rearranges predominately to the ortho-isomer. sodium sahcylate (eq. 8). 

Carbonates are indexed in Chemicaly hstracts under carbonic acid, esters. Symmetrical diesters have the prefix di or bis. Unsymmetrical diesters are listed with the two radicals following each other. For example, ethyl phenyl carbonic diester is C2H OCOOC H. Table 6 Hsts commonly used carbonates, their Chemicaly hstracts Service Registry Number, and formulas. 

A number of less-hazardous reagents that can be substituted for tert-hutyl azidoformate in tert-butoxycarbonylation reactions are available including 2-(te/t-butoxycarbonyloxyimino)-2-phenylacetonitrile (Aldrich Chemical Company), 0-teri-hutyl N-phenyl thiocarbonate (Eastman Organic Chemicals), di-butyl dicarbonate and tert-butyl phenyl carbonate. ... 

In the case of partly modified polymers the spectra B, C and D show more complicated structures which can be presumably due to significant neighbouring-groups effects between phenyl carbonate groups and modified or unmodified groups linked to the next aliphatic methine carbon atoms. 

From these results it is reasonable to conclude that no inversion in the order of the chemical shifts of the tertiary carbon atoms belonging to the different triads occurs from the starting PV0CC1 to the poly(vinyl phenyl carbonate). Moreover the chemical modification of PV0CC1 by phenol does not induce any degradation of the polymer. 

Similarly, in the acetoxycarbene series, 87-OAc rearranges to 88-OAc with kc = 8.5 x 106 s-1, 265 times faster than 17-OAc ring expands to 23-OAc (3.2 x 104 s-1).81 These rapid and dominant phenyl carbon 1,2-C shifts of 87 to 88 (bond a), rather than benzyl carbon (bond b) 1,2-C shifts to 89, are attributed to tz orbital mediation by the phenyl group in effect an electrophilic attack of the carbenic carbon on the aromatic ring. Ab initio calculations support this view.114... 

A. t-Butyl phenyl carbonate. In a 2-1. round-bottomed flask fitted with thermometer, dropping funnel, and mechanical stirrer are placed 248 g. (3.35 moles) of /-butyl alcohol, 430 g. (3.33 moles) of quinoline, and 500 ml. of methylene dichloride (Note 1), The solution is stirred while 520 g. (3.32 moles) of phenyl chloro-formate (Note 2) is added dropwise over a period of 4 hours. 

Representative Procedure for Trityl Salt Promoted Clycosylation with Glycosyl Phenyl Carbonate Donors [360]... 

Ethyl phenyl carbonate, molecular formula, 6 305t... 

In this reaction, only the benzylic carbonate can react readily since cleavage of the benzylic carbon-oxygen bond leads to a stabilized carbocation while no such stabilization would exist for the hypothetical products which would be obtained by cleavage of the phenyl carbonate. The benzylic carbocation intermediate which is formed can either eliminate to the corresponding styrene 4 or recombine with the nucleophilic methanol which is formed by decarboxylation. It is the latter reaction which appears to prevail at room temperature as the ether 2 can be isolated in excellent yield. Subsequent heating in the presence of acid catalyst drives the reaction to the elimination product 6 and free methanol. 

The Arrhenius parameters and the thermochemical sum of the phenyl-carbon and phenyl-halogen bond dissociation energies are shown in Table 8. The extent of the diphenyl mercury decomposition was determined from the weight of mercury produced. It is the present author s opinion that in calculating the Arrhenius parameters for this compound Carter et al.81 gave too great a statistical... 

T. M. Kitson, The Action of Cytoplasmic Aldehyde Dehydrogenase on Methyl p-Nitro-phenyl Carbonate and p-Nitrophenyl Dimethylcarbamate , Biochem. J. 1989, 257, 579-584 T. M. Kitson, K. E. Kitson, A Comparison of Nitrophenyl Esters and Lactones as Substrates of Cytosolic Aldehyde Dehydrogenase , Biochem. J. 1996, 316, 225-232 T. M. Kitson, K. E. Kitson, Studies of the Esterase Activity of Cytosolic Aldehyde Dehydrogenase with Resorufin Acetate as Substrate , Biochem. J. 1997, 322, 701-708. 

This example documents the difficulty of rationalizing the results of in vivo investigations when competitive metabolic reactions are seen. In such cases, simpler in vitro systems may be more informative, as exemplified by the hydrolysis of alkyl phenyl carbonates (phenyl-O-CO-O-alkyl) catalyzed by pig pancreatic elastase (EC 3.4.21.36) [15]. The rate of hydrolysis was monitored by following C02 production as with the carbamates discussed above. Indeed, the enzyme-catalyzed hydrolysis yields the phenyl hemiester of carbonic acid (phenyl-O-COOH), which decomposes rapidly to produce C02 and phenol. With these carbonates, the rate of hydrolysis decreased in the series Bu > i-Bu > Et hexyl, the /-Hu and cyclohexyl derivatives being... 

Unsubstituted cycloamyloses have been used to catalyze a number of reactions in addition to acyl group transfer. Brass and Bender (8) showed that cycloamyloses promoted phenol release from diphenyl and bis(p-nitro-phenyl) carbonates and from diphenyl and bis(m-nitrophenyl)methyl phos-phonates. Breslow and Campbell (10,11) showed that the reaction of anisole with HOCL in aqueous solution is catalyzed by cyclohexaamylose and cycloheptaamylose. Anisole is bound by the cyclodextrins and is chlorinated exclusively in the para position while bound. Cycloheptaamylose has been used to promote regiospecific alkylation followed by the highly selective oxidation shown in reaction (3) (95). In addition cycloheptaamylose effec-... 

Kinetic studies of the reaction of Z-phenyl cyclopropanecarboxylates (1) with X-benzylamines (2) in acetonitrile at 55 °C have been carried out. The reaction proceeds by a stepwise mechanism in which the rate-determining step is the breakdown of the zwitterionic tetrahedral intermediate, T, with a hydrogen-bonded four-centre type transition state (3). The results of studies of the aminolysis reactions of ethyl Z-phenyl carbonates (4) with benzylamines (2) in acetonitrile at 25 °C were consistent with a four- (5) and a six-centred transition state (6) for the uncatalysed and catalysed path, respectively. The neutral hydrolysis of p-nitrophenyl trifluoroacetate in acetonitrile solvent has been studied by varying the molarities of water from 1.0 to 5.0 at 25 °C. The reaction was found to be third order in water. The kinetic solvent isotope effect was (A h2o/ D2o) = 2.90 0.12. Proton inventories at each molarity of water studied were consistent with an eight-membered cyclic transition state (7) model. 

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