Oxidation reactions with alcohols

The structural, spectroscopic and electrochemical properties of oxoruthenate (IV) complexes have been summarised, and a representative compilation of kinetic parameters for their oxidation reactions with alcohols, alkanes and alkenes presented [20],... 

Prepared by epoxidation of styrene with per-oxyelhanoic acid. Reactions are similar to those of aliphatic epoxides (s e, e.g. ethylene oxide). Reacts with alcohols to give mono-ethers, e g. PhCH(0Me)CH20H. Phenols give resins. 

Deoxygenative autoaromatization was reported to occur in the reaction of 3-amino-1,2,4-triazine 2-oxides 42 with alcohols in the presence of HCl or acetyl chloride. In this case the intermediate cr -adducts undergo elimination of water or acetic acid, resulting in 6-alkoxy-3-amino-l,2,4-triazines 75 (77JOC3498). 1,2,4-Triazine 1-oxides do not react with alcohols under these conditions (77JOC3498). 

The reaction between ethylene oxide and long-chain fatty alcohols or fatty acids is called ethoxylation. Ethoxylation of C10-C14 linear alcohols and linear alkylphenols produces nonionic detergents. The reaction with alcohols could be represented as ... 

Phosphine(s), chirality of, 314 Phosphite, DNA synthesis and, 1115 oxidation of, 1116 Phospholipid, 1066-1067 classification of, 1066 Phosphopantetheine, coenzyme A from. 817 structure of, 1127 Phosphoramidite, DNA synthesis and, 1115 Phosphoranc, 720 Phosphoric acid, pKa of, 51 Phosphoric acid anhydride, 1127 Phosphorus, hybridization of, 20 Phosphorus oxychloride, alcohol dehydration with. 620-622 Phosphorus tribromide, reaction with alcohols. 344. 618 Photochemical reaction, 1181 Photolithography, 505-506 resists for, 505-506 Photon, 419 energy- of. 420 Photosynthesis, 973-974 Phthalic acid, structure of, 753 Phthalimide, Gabriel amine synthesis and, 929... 

TS-1 is a material that perfectly fits the definition of single-site catalyst discussed in the previous Section. It is an active and selective catalyst in a number of low-temperature oxidation reactions with aqueous H2O2 as the oxidant. Such reactions include phenol hydroxylation [9,17], olefin epoxida-tion [9,10,14,17,40], alkane oxidation [11,17,20], oxidation of ammonia to hydroxylamine [14,17,18], cyclohexanone ammoximation [8,17,18,41], conversion of secondary amines to dialkylhydroxylamines [8,17], and conversion of secondary alcohols to ketones [9,17], (see Fig. 1). Few oxidation reactions with ozone and oxygen as oxidants have been investigated. 

NO Reactions. The most informative derivitization reaction of oxidized polyolefins that we have found for product identification is that with NO. The details of NO reactions with alcohols and hydroperoxides to give nitrites and nitrates respectively have been reported previously, and only the salient features are discussed here (23). The IR absorption bands of primary, secondary and tertiary nitrites and nitrates are shown in Table I. After NO treatment, y-oxidized LLDPE shows a sharp sym.-nitrate stretch at 1276 cm-1 and an antisym. stretch at 1631 cm-1 (Fig. 1), consistent with the IR spectra of model secondary nitrates. Only a small secondary or primary nitrite peak was formed at 778 cm-1. NO treatment of y-oxidized LLDPE which had been treated by iodometry (all -OOH converted to -OH) showed strong secondary nitrite absorptions, but only traces of primary nitrite, from primary alcohol groups (distinctive 1657 cm-1 absorption). However, primary products were more prominent in LLDPE after photo-oxidation. 

The theory of chain co-oxidation of binary mixtures of organic compounds was described in Chapter 5. The experimental study of co-oxidation of alcohols (HRiOH) and hydrocarbon R H opens the way to measure the rate constants of one chosen peroxyl radical R OO with several alcohols HRiOH and on the reverse, the chosen alcohol HR1 OH with several peroxyl radicals RiOO. The parameters of co-oxidation of alcohols and hydrocarbons are collected in Table 7.6. The absolute values of peroxyl radical reactions with alcohols were calculated from these data using the values of kp from Table 2.8 (see Table 7.7). 

Several examples have been reported of the use of palladium-mediated oxidation reactions of alcohols and alkyl halides. Palladium(II) acetate in the presence of iodobenzene converts primary and secondary alcohols into carbonyl compounds under solid-liquid two-phase conditions [20], However, other than there being no further oxidation to carboxylic acids, the procedure has little to commend it over other methods. It is relatively slow with reaction times in the order of 2 days needed to achieve yields of 55-100%. 

Table 2. Benzyl alcohol oxidation reaction with different catalytic systems ...

Carbinolamines, 87 Carbodiimides, 205-222 reaction with alcohols, 170 Carbon monoxide, as reducing agent, 336 a-Carbonyl azo compounds, 324, 326 Caro s add (permonosulfuric add), 408 oxidation with, 409 preparation of, 409 Chloramine T, 377 Chloroacetylenes 120-122 4-Chloro-l, 2-butadiene, 33 Chlorocyclohexenyl acetylene, 121 1 -Chloro-2-JV,N-diphenylaminoacetylene, 128-129... 

Cumylamine, oxidation of, 323 Cupferron ammonium salt, 447 reaction with Grignard reagents, 352 free acid, 402 Cyanamides, 161 reaction with alcohols, 174 Cyanoallene, 24... 

Ureas, 134-165 disubstituted, 148 monosubstituted, 148 0-alkylation, 178-179 prepared via oxidative carbamylation, 158 reaction with alcohols, 236-239 with amines, 135-138 tetrasubstituted, 145-146 Urethanes, see iV-Carbamates... 

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