Methyl formate, from alcohol oxidation

Sodamide should never be stored in a stoppered bottle from which samples are to be removed intermittently, since dangerous mixtures may result when the substance is exposed for 2-3 days to even limited amounts of air at the ordinary temperature. As a safe practice, sodamide should be used immediately after preparation, and should not be kept longer than 12-24 hours unless it be under an inert solvent. Even small amounts of unused sodamide should be removed from the apparatus in which it was made by washing with methyl or ethyl alcohol. In all cases where a yellowish or brownish colour develops, due to the formation of oxidation... 

From Boric Oxide and Alcohol. To avoid removing water, boric oxide, B2O3, can be used in place of boric acid. The water of reaction (eq. 4) is consumed by the oxide (eq. 5). Because boric acid reacts with borates at high temperatures, it is necessary to filter the reaction mixture prior to distillation of the product. Only 50% of the boron can be converted to ester by this method. In cases where this loss can be tolerated, the boric oxide method is convenient. This is particularly tme for methyl borate and ethyl borate preparation because formation of the undesirable azeotrope is avoided. 

The addition of Grignard reagents to aldehydes, ketones, and esters is the basis for the synthesis of a wide variety of alcohols, and several examples are given in Scheme 7.3. Primary alcohols can be made from formaldehyde (Entry 1) or, with addition of two carbons, from ethylene oxide (Entry 2). Secondary alcohols are obtained from aldehydes (Entries 3 to 6) or formate esters (Entry 7). Tertiary alcohols can be made from esters (Entries 8 and 9) or ketones (Entry 10). Lactones give diols (Entry 11). Aldehydes can be prepared from trialkyl orthoformate esters (Entries 12 and 13). Ketones can be made from nitriles (Entries 14 and 15), pyridine-2-thiol esters (Entry 16), N-methoxy-A-methyl carboxamides (Entries 17 and 18), or anhydrides (Entry 19). Carboxylic acids are available by reaction with C02 (Entries 20 to 22). Amines can be prepared from imines (Entry 23). Two-step procedures that involve formation and dehydration of alcohols provide routes to certain alkenes (Entries 24 and 25). 

Hydroboration occurred from the less hindered top face of rac-29 and resulted in the formation of alcohol rac-30. After a three-step sequence which included oxidation with tetrapropylammonium perruthenate (TPAP), methyl lithium addition and repeated oxidation with TPAP, ketone rac-31 was isolated. Finally, epimerization of the stereogenic center at C-7 to the correct configuration and methylenation with the Lombardo reagent led to the formation of racemic kelsoene (rac-1). 

The rate constants for oxidation of a series of cycloalkenes with ozone have been determined using a relative rate method. The effect of methyl substitution on the oxidation of cycloalkenes and formation of secondary organic aerosols has been analysed.155 Butadiene, styrene, cyclohexene, allyl acetate, methyl methacrylate, and allyl alcohol were epoxidized in a gas-phase reaction with ozone in the absence of a catalyst. With the exception of allyl alcohol, the yield of the corresponding epoxide ranged from 88 to 97%.156 Kinetic control of distereoselection in ozonolytic lactonization has been (g) reported in the reaction of prochiral alkenes.157... 

Fig. 18. Product formation during the oxidation of propane in the absence of pic d arret. Initial temperature = 430 °C initial pressure of propane = 60 torr initial pressure of oxygen = 240 torr. (b) Left ordinate +, methyl alcohol. Right ordinate X, isopropyl alcohol , ethyl alcohol o, n-propyl alcohol , allyl alcohol (xO.5). (c) Left ordinate +, hydrogen peroxide , formaldehyde. Right ordinate x, total aldehydes, (d) +, propene , methane , ethylene x, ethane. (From ref. 147.) References pp. 361—367...

Evidence for the formation of maleic anhydride only from the C-atoms of the aromatic ring has been obtained by Blanchard and Vanhove, who found no incorporation of radioactivity in the maleic anhydride formed from the oxidation of o-xy ene (methyl- C) or phthalic anhydride (- CO-) over V2O5 at 420-470 °C. A subsequent investigation by these authors was undertaken to elucidate the reaction pathways involved in the formation of the intermediates o-tolualdehyde, o-toluic acid and phthalide. A competitive oxidation of inactive o-methylbenzyl alcohol and o-xylene (methyl-... 

Competitive oxidation experiments were carried out in order to confirm this high selectivity towards primary alcohols. Thus, mixtures of benzyl alcohol with octan-2-ol or 1-phenylethanol were reacted and no carbonyl products resulting from the oxidation of the secondary alcohols were observed (Table XIV). This lack of reactivity of secondary alcohols may be explained by two factors affecting the catalytic cycle. (1) Steric effects between the methyl groups of TEMPO and the alkyl group of the secondary alcohol can hinder the formation of the active species III (Fig. 34a), crucial for the C-H abstraction. (2) In addition, in the case of primary alcohols, the... 

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