Ferf-Butyl formate

CASRN 637-92-3 molecular formula CeH O FW 102.17 Chemical/Physical The atmospheric oxidation of ethyl ferf-butyl ether by OH radicals in the presence of nitric oxide yielded ferf-butyl formate as the major product. Minor products included formaldehyde and nitrogen dioxide. In the absence of nitric oxide, 2-ethoxy-2-methylpropanal is likely to form (Wallington and Japar, 1991). 

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. 

Church, C.D., Pankow, J.F., and Tratnyek, P.G. Hydrolysis of ferf-butyl formate kinetics, products, and implications for the environmental impact of methyl ferf-butyl ether. Environ. Toxicol. Chem., 18(12) 2789-2796, 1999. 

Table VII-B-12. Rate coefficients (k, cm molecule s ) for reaction of chlorine atoms with ferf-butyl formate (ferf-C4H90CH0)...

Pimentel et al. (2010) studied the prcxiucts of the chlorine-atom- and OH-radical-initiated oxidation of ferf-butyl formate in 700 Torr of N2/O2 diluent with and without NOx. Photolysis of Cb-ferf-butyl formate-N2 mixtures with less than 200 m Torr CI2 showed no strong evidence for the formation of an acyl chloride, but instead led to large yields of CO2. The yield of CO2 at low CI2 was found to be 0.50 0.05. Pimentel et al. (2010) assigned this yield to the fraction of attack at the formyl group which is followed by decomposition of the resulting ferf-butoxycarbonyl radical. 

The functionalized allene, DIMETHYL 2,3-PENTADIENEDIOATE, the first in the series, is an intriguing substrate for various addition and cycloaddition reactions. Finally, a new reagent, DI-ferf-BUTYL DICARBONATE, for he formation of A-f-BOC derivatives which eliminates the use o the hazardous fert-BUTYL AZIDOFORMATE (WARNING) is intrqduced. 

Neopentyl alcohol has been made by lithium aluminum hydride reduction of trimethylacetic acid and by treating ferf-butyl-magnesium chloride with methyl formate. ... 

An unusual 1,4-migration of a trifluoromethyl group was observed when azomethine imines were synthesized from hexafluoroacetone azine and alkoxy-acetylenes The rearrangement, which occurs at temperatures as low as 0 "C, results in the formation of A-(perfluoro-ferf-butyl)pyrazoles [207] (equation 46)... 

During the course of the conversion of intermediate 18 into intermediate 16, the imposing ferf-butyl substituent at C-8 guides the formation of the adjacent stereocenter at C-9 and it is now called upon to guide, or at least influence in a favorable way, the stereo-... 

Another example has been provided by Ito et al., who described the use of methanofullerene derivatives as powerful and stable precursors for glycofullerenes.217 Their study was based on the use of [60]fullerenoacetyl chloride (227), obtained from the ferf-butyl [60]fullerenoacetate derivative 226, which had been prepared in 56% yield by treatment of corresponding stabilized sulfonium ylides 225 with C6o-218 Subsequent transformation with p-TsOH in toluene gave [60]full-erenoacetic acid, which was directly converted into the corresponding acyl chloride 227 by using thionyl chloride. Standard ester formation with methyl 2,3,4-tetra-O-benzyI -/<-d-gl ucopyranoside (228) and 4-(dimethylamino)pyridine (DMAP) afforded the desired hybrid derivative 229 in 66% yield. 

FIGURE 3.6 Deprotection of functional groups by acidolysis. Protonation followed by carbocation formation during the removal of ferf-butyl-based protectors by hydrogen chloride.8 One mechanism is involved in generating the ferf-butyl cation, which is the precursor of two other molecules. 

Lee and Meisel incorporated Py, at levels of 10 M or more, into 1200 EW acid form samples that were swollen with water and with ferf-butyl alcohol. It was concluded based on the /3//1 value for water swollen samples that the Py molecules were located in the water clusters and were most likely near fluorocarbon—water interfaces. It was also concluded, based on both absorption and emission spectra, that the probes had strong interactions with the SO3 groups that were exchanged with Ag+ and Pb + cations in the case of water containing samples. Likewise, the pyrene molecules were rationalized as being surrounded by terf-butanol molecules in that case. However, excimer formation (due to the presence of adjacent pyrene molecules) in the ferf-butyl alcohol system suggested the loss of cluster morphology-... 

AI3-00040, see Cyclohexanol AI3-00041, see Cyclohexanone AI3-00045, see Diacetone alcohol AI3-00046, see Isophorone AI3-00050, see 1,4-Dichlorobenzene AI3-00052, see Trichloroethylene AI3-00053, see 1,2-Dichlorobenzene AI3-00054, see Acrylonitrile AI3-00072, see Hydroquinone AI3-00075, see p-Chloro-rrr-cresol AI3-00078, see 2,4-Dichlorophenol AI3-00085, see 1-Naphthylamine AI3-00100, see Nitroethane AI3-00105, see Anthracene AI3-00109, see 2-Nitropropane AI3-00111, see Nitromethane AI3-00118, see ferf-Butylbenzene AI3-00119, see Butylbenzene AI3-00121, see sec-Butylbenzene AI3-00124, see 4-Aminobiphenyl AI3-00128, see Acenaphthene AI3-00134, see Pentachlorophenol AI3-00137, see 2-Methylphenol AI3-00140, see Benzidine AI3-00142, see 2,4,6-Trichlorophenol AI3-00150, see 4-Methylphenol AI3-00154, see 4,6-Dinitro-o-cresol AI3-00262, see Dimethyl phthalate AI3-00278, see Naphthalene AI3-00283, see Di-rj-butyl phthalate AI3-00327, see Acetonitrile AI3-00329, see Diethyl phthalate AI3-00399, see Tributyl phosphate AI3-00404, see Ethyl acetate AI3-00405, see 1-Butanol AI3-00406, see Butyl acetate AI3-00407, see Ethyl formate AI3-00408, see Methyl formate AI3-00409, see Methanol AI3-00520, see Tri-ocresyl phosphate AI3-00576, see Isoamyl acetate AI3-00633, see Hexachloroethane AI3-00635, see 4-Nitrobiphenyl AI3-00698, see IV-Nitrosodiphenylamine AI3-00710, see p-Phenylenediamine AI3-00749, see Phenyl ether AI3-00790, see Phenanthrene AI3-00808, see Benzene AI3-00867, see Chrysene AI3-00987, see Thiram AI3-01021, see 4-Chlorophenyl phenyl ether AI3-01055, see 1.4-Dioxane AI3-01171, see Furfuryl alcohol AI3-01229, see 4-Methyl-2-pentanone AI3-01230, see 2-Heptanone AI3-01231, see Morpholine AI3-01236, see 2-Ethoxyethanol AI3-01238, see Acetone AI3-01239, see Nitrobenzene AI3-01240, see I idine AI3-01256, see Decahydronaphthalene AI3-01288, see ferf-Butyl alcohol AI3-01445, see Bis(2-chloroethoxy)methane AI3-01501, see 2,4-Toluene diisocyanate AI3-01506, see p,p -DDT AI3-01535, see 2,4-Dinitrophenol AI3-01537, see 2-Chloronaphthalene... 

Chemical/Physical. tert-Butyl formate undergoes hydrolysis yielding ferf-butyl alcohol in stoichiometric amounts. At 22 °C, the estimated hydrolysis half-lives at pH 7 and pH 11 are 5 d and 8 min, respectively (Church et al, 1999). 

Marchand and co-workers reported a synthetic route to TNAZ (18) involving a novel electrophilic addition of NO+ NO2 across the highly strained C(3)-N bond of 3-(bromomethyl)-l-azabicyclo[1.1.0]butane (21), the latter prepared as a nonisolatable intermediate from the reaction of the bromide salt of tris(bromomethyl)methylamine (20) with aqueous sodium hydroxide under reduced pressure. The product of this reaction, A-nitroso-3-bromomethyl-3-nitroazetidine (22), is formed in 10% yield but is also accompanied by A-nitroso-3-bromomethyl-3-hydroxyazetidine as a by-product. Isolation of (22) from this mixture, followed by treatment with a solution of nitric acid in trifluoroacetic anhydride, leads to nitrolysis of the ferf-butyl group and yields (23). Treatment of (23) with sodium bicarbonate and sodium iodide in DMSO leads to hydrolysis of the bromomethyl group and the formation of (24). The synthesis of TNAZ (18) is completed by deformylation of (24), followed by oxidative nitration, both processes achieved in one pot with an alkaline solution of sodium nitrite, potassium ferricyanide and sodium persulfate. This route to TNAZ gives a low overall yield and is not suitable for large scale manufacture. 

Arnett and Moe studied the protodelithiation of organolithiums with isopropyl alcohol in hexane/ether mixtures. These authors found protodelithiation enthalpies for n- and iec-butyl lithium of —209.2 4.2 and —220.9 2.9, respectively. The difference between their enthalpies of reaction, and so of the enthalpies of formation of the two organolithiums, is 11.7 5.1 kJmor, about half the difference between these species as found in Table 1. The protodelithiation enthalpy of terf-butyl lithium is —237.7 7.5 kJmoP. From equation 10 with n-butyl lithium as the benchmark species, and the butane hydrocarbons in their liquid reference states, the derived enthalpy of formation of ferf-butyl lithium is —87.5 kJmoP, in good agreement with that found before by Hohn . 

---