Butyl methyl carbonate

Moreover, when the C-protonated ester mJz 117 is generated independently by El cleavage of tert-butyl methyl carbonate in the presence of CD3OD, mJz 73 and 76 are formed, as expected, from independent decarboxylation and condensation reactions (Scheme V). 

Fig. 6 Comparison of the carbonyl stretching region of the FT-IR spectra of (a) matrix-isolated pyrolysis products of di-tert-butyl-carbonate (, co-fragment isobutene) (b) carbonic acid vapor isolated in argon after sublimation of (a) P-H2CO3 and (b) a-H2C03-(c) matrix-isolated pyrolysis products of tert-butyl methyl carbonate (, co-fragment isobutene , traces of formaldehyde). Reprinted with permission from H. P. Reisenauer, J. P. Wagner and P. R. Schreiner, Angew. Chem., Int. Ed., 2014, 53,11766. Copyright 2014, Wiley.

Note 1,2-BC 1,2-dunethylethylene carbonate 1,3-DOL 1 -dioxolane AC acetonitrile A.N. acceptor number BC butylene carbonate BEC butyl ethyl carbonate BMC butyl methyl carbonate CF3-EC trifluoromethyl ethylene carbonate QEC chloroethylene carbonate DBC dibutyl carbonate DEC diethyl carbonate DEE 1,2-diethoxyethane DGM diethyleneglycol dimethyl ether DIPC di-isopropyl carbonate DMC dimethyl carbonate DME 1,2-dimethoxyethane DMSO dimethyl sulfoxide D.N. donor number DPC di-n-propyl carbonate EC ethylene carbonate EIPC ethyl isopropyl carbonate EMC ethyl methyl carbonate EPC ethyl propyl carbonate MeTHF 2-methyl tetrahydrofuran MIPC methyl isopropyl carbonate MFC methyl propyl carbonate PC propylene carbonate TEGM tetraethylene glycol dimethyl ether TGM triethylene glycol dimethyl ether TFIF tetrahydrofuran. 

The susceptibihty of dialkyl peroxides to acids and bases depends on peroxide stmcture and the type and strength of the acid or base. In dilute aqueous sulfuric acid (<50%) di-Z fZ-butyl peroxide is resistant to reaction whereas in concentrated sulfuric acid this peroxide gradually forms polyisobutylene. In 50 wt % methanolic sulfuric acid, Z fZ-butyl methyl ether is produced in high yield (66). In acidic environments, unsymmetrical acychc alkyl aralkyl peroxides undergo carbon—oxygen fission, forming acychc alkyl hydroperoxides and aralkyl carbonium ions. The latter react with nucleophiles,... 

Acetone with benzene, butyl acetate, butyl alcohol, carbon tetrachloride, chloroform, cyclohexane, ethanol, ethyl acetate, methyl acetate, acetonitrile, petroleum ether or water. 

In extreme cases, suitably bulky substituents at the radical center can render a radical persistent [e g. di-r-butyl methyl radical (32)].166 167 This radical (32) possesses no hydrogens on the rx-carbon and therefore cannot decay by the normal... 

Degradation of methyl terf-butyl ether by bifunctional aluminum in the presence of oxygen was investigated by Lien and Wilkin (2002). Bifunctional aluminum was synthesized by sulfating aluminum metal with sulfuric acid. When the initial methyl terf-butyl ether concentration was 14.4 mg/L, 90% of methyl ferf-butyl ether degraded within 24 h forming acetone, methyl acetate, tert-hniyX alcohol, and ferf-butyl formate. Carbon disulfide was tentatively identified as a reaction product by GC/MS. Product yields were 27.6% for acetone, 18.4% for methyl acetate, 21% for tert-hniyX alcohol, and 6.1% ferf-butyl formate. When the initial concentration of methyl tert-butyl ether was reduced to 1.4 mg/L, 99.5% of methyl terCbutyl ether reacted. Yields of acetone, methyl acetate, and /erf-butyl alcohol were 54.7,17.2, and 13.2, respectively. 

In an exploratory study, Cu-alkoxides were found to be superior to Zn-alkoxides, and tert-butyl cinnamyl carbonate superior to methyl cinnamyl carbonate, which underwent transesterificahon. Both, arylallyl and alkylallyl carbonates were successful as substrates. 

Eor ions of similar or identical stability, 1,2-shifts are also extremely rapid. Even at very low temperatures, the NMR spectrum of the 2,3,3-trimethyl-2-butyl cation 7 has only one signal, while the NMR shows two signals, one for the methyl carbons and one for the quaternary carbons. As shown in Scheme 1.1, these he almost exactly midway between those calculated for the static ion. A similar result is obtained for the 1,2-dimethylcyclopentyl cation 8, and other tertiary cations related by 1,2-shifts. Thus, even at very low temperatures, 1,2-shifts... 

Husson-Borg, P, Majer, V., and Gomes, M. F. G., Solubilities of oxygen and carbon dioxide in butyl methyl imidazolium tetrafluoroborate as a function of temperature and at pressures close to atmospheric pressure, /. Chem. Eng. Data, 48, 480, 2003. 

Is not known Thus it seems reasonable that one or more of the satellite peaks of the 1,4 peaks might arise from 1,2 methylene carbons as shown in VII and VIII. It is not certain what the multiple peaks near 35 ppm represent, but they probably arise from C-13c spin-spin coupling in oligomers with a DP of 2 or more The sharp peak at 29.70 is due to the methyl carbons of the reacted t-butyl group ... 

The synthetic utility of many of the substitution reactions described so far is limited because there are well-established thermal routes to the same products. However, a third group of photochemical nucleophilic substitutions involves aryl halides and nucleophiles based on sulfur, phosphorus or, of particular importance, carbon. Two examples are the reaction of bromobenzene with the anion of t-butyl methyl ketone 13.12), and the replacement of bromine by cyanomethyl in 2-bromopyridine (3.13). This type of reaction offers a clear advantage over lengthy thermal alternatives, and intramolecular versions have been used in the synthesis of indoles (e.g. 3.14) or benzofurans from o-iodoaniline or o-iodoanisole respectively. 

In the 13C-NMR spectra of the 2-alkyl-1,3,5,5-tetramethylhexahydropy-rimidines (328), the lower field absorption of the axial 5-methyl carbon in the 2-isopropyl and 2-tert-butyl derivatives than in 328 (R = Me or R = Et) has been interpreted in terms of flexible nonchair conformations for 328 (R = iPr and t-Bu).92... 

Butyl S-methylthiolcarbonate has been prepared from sodium /-butoxide, carbonyl sulfide, and methyl iodide 1 and from methyl chlorothiolformate and /-butyl alcohol.4 /-Butyl phenyl carbonate has been prepared from phenyl chloroformate and /-butyl alcohol.6 6... 

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