7214-65-5

Upstream product

• 585-71-7 (1-bromoethyl)benzne 
• 672-65-1 (1-chloroethyl)benzene 
• 100-42-5 styrene 
• 98-85-1 1-Phenylethanol 
• 4013-34-7 3-phenyl-2-oxabutane 
• 100-41-4 ethylbenzene 
• 10604-60-1 (1-iodoethyl)benzene 

Relevant academic research and scientific papers

Direct oxidative installation of nitrooxy group at benzylic positions and its transformation into various functionalities

C-H Nitrooxylation at benzylic positions has been achieved by employing the N-hydroxyphthalimide (NHPI) catalyst/cerium(IV) ammonium nitrate (CAN) reagent system. The nitrooxy groups were demonstrated to function as tentative hydroxy protecting groups, as well as excellent leaving groups for N- and C-substitution reactions. Hence, the present method offers a unique way to synthesize diverse O-, N-, or C-functionalized benzylic compounds from simple alkyl aromatics.

Oxidation of benzylic alcohols and ethers to carbonyl derivatives by nitric acid in dichloromethane

Nitric acid in dichloromethane may be successfully employed for the oxidation of benzylic alcohols and ethers to the corresponding carbonyl compounds. The proposed method proved to be of general applicability, affording very good yields of aldehydes and ketones and showing interesting chemoselectivity in many instances, allowing competitive aromatic nitration to be avoided, as well as - in the case of aldehydes - any further oxidation to carboxylic acids. The reaction probably proceeds by a radical mechanism, the active species in the oxidation process being NO2. Competitive formation of nitro esters was observed in some cases, whereas poor results were obtained with allylic and non-benzylic substrates. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

The nitration of styrenes by nitric acid in dichloromethane

Kinetics and products of reaction of 4-R-styrenes (R = Me, H, Cl, CF3, NO2) with nitric acid in dichloromethane are reported. Reaction occurs in the alkene group and aromatic nitration is insignificant. With increasingly electron-withdrawing substituents the reaction changes from one which is third order in nitric acid and gives rise to the 1-arylethyl nitrate, to one which is of higher order in nitric acid and gives rise to the 2-nitro-1-arylethyl nitrate (β-nitro-nitrate). Both reactions proceed through transition states with carbocation character, by initial β-addition of H+ and NO2+ respectively. The β-nitro-nitrate is formed in part also by a radical pathway, as are other minor products.

New one-pot synthesis of alkyl nitrates from alcohols

Treatment of alcohols with Ph3P-I2-imidazole followed by 'in situ' reaction of the generated iodides with AgNO3 allows the mild conversion of alcohols into alkyl nitrates. Unlike previous procedures, this one requires no electrophilic nitrating conditions.

Effect of Dimethyl Sulfoxide Solvent in the Thermolysis of Alkyl Nitrates Elucidated by the Temperature Dependence of a Kinetic Isotope Effect

The cyclic, bent TS* of gas-phase thermolytic decomposition of benzyl nitrate has been compared to the analogous thermal elimination of amine oxides in diglyme solution.The use of Me2SO solvent in amine oxide thermolysis has been shown to alter the TS* to one which accommodates linear H transfer.Me2SO solvent in the case of benzyl nitrate is now found to afford a nearly quantitative conversion to benzaldehyde.Other alkyl nitrates show a similarly facile reaction to produce good yields of the carbonyl product.However, through measurement of the temperature dependence of kH/kD with benzyl-α-d nitrate it is found that the TS* for decomposition is little altered by comparison with the gas-phase thermolysis reaction.The differences in behavior of the amine oxide and alkyl nitrate reactions in Me2SO and the possible origins of these differences are discussed briefly.

Mercury-assisted solvolyses of alkyl halides. Simple procedures for the preparation of nitrate esters, acetate esters, alcohols and ethers

The reactions of a wide variety of alkyl halides with mercury(I) and/or (II) nitrate in 1,2-dimethoxyethane, mercury(II) acetate in acetic acid, aqueous mercury(II) perchlorate, and mercury(II) perchlorate in alcohol solvents have been investigated; as a result, simple high yield procedures for the conversion of alkyl halides into the corresponding nitrate esters, acetate esters, alcohols and ethers have been developed.