Oxidation carboxylic acids from

Kunz, M. Schwarz, A. Kowalczyk, J. (Siidzucker AG), Process for continuous manufacture of di- and higher-oxidized carboxylic acids from carbohydrates, Ger. Offen. DE 19 542 287 (1996) Chem. Abstr., 1997, 127, 52504. 

Silverlsilver oxide Carboxylic acids from glycols s. 21,172... 

Silver/silver oxide Carboxylic acids from glycols Dicarboxylic acids from cyclic glycols... 

Catalytic oxidation Carboxylic acids from alcohols... 

Alkynes, like alkenes, can be cleaved by reaction with powerful oxidizing agents such as ozone or KMnC, although the reaction is of little value and we mention it only for completeness. A triple bond is generally less reactive than a double bond and yields of cleavage products are sometimes low. The products obtained from cleavage of an internal alkyne are carboxylic acids from a terminal alkyne, CO2 is formed as one product. 

All of the reactions discussed up till now involve the autoxidation of methylbenzenes to the corresponding carboxylic acids. From a practical viewpoint it would also be interesting to devise a process for the production of the corresponding aldehyde. Unfortunately, as noted earlier, the oxidizability of ArCHO is about four orders of magnitude higher than ArCH3 which essentially precludes the selective production of the aldehyde when O2 is the oxidant. With all other oxidants, on the other hand, the rate of oxidation of ArCHO is lower than that of ArCH3 (ref. 24) (Fig. 21). 

The chemical composition of B. papyrifera olibanum is markedly different from that of other Boswellia, with small amounts of monoterpenes and sesquiterpenes, large amounts of w-octanol (18) and -octy I acetate (40), with the latter being the major compound, and the presence of particular diterpenes [incensole (127), incen-sole acetate (129), incensole oxide (130) and incensole oxide acetate (131)] and the absence of both isoincensole and isoincensole acetate (128). Linear carboxylic acids from hexanoic acid (10) to lauric acid (93) were also identified in B. papyrifera olibanum exclusively. 

The fungal enzyme from R. praticola was able to catalyze the oxidative coupling of pentachlorophenol (PCP) and syringic acid, a representative of phenol carboxylic acids from lignin occurring in HS structures. 

Our observations are summarized as follows (1) no induction period, (2) fast alcohol oxidation in an oxygen-poor liquid phase, (3) no carboxylic acids from the higher alcohols, (4) slow oxidation of lauryl aldehyde to lauric acid in the presence of water, and (5) recovery of bromine in the organic phase on reaction completion. These data show that the reaction is not a radical chain process but rather a bromine oxidation in which the halogen is continuously regenerated, as shown in Reactions 1 through 7. 

Oxidation.1 Hydrated copper permanganate oxidizes alcohols in CH2C12 rapidly and in high yields. Ketones are obtained from secondary alcohols, and carboxylic acids from primary and benzylic alcohols. Primary or secondary allylic alcohols are also oxidized efficiently. Anhydrous reagent is much less active. 

The formation of a carboxylic acid from Baeyer-Villiger oxidation of an aldehyde requires hydrogen migration. 

Show how to synthesize carboxylic acids from oxidation of alcohols and aldehydes. Problems 20-36, 39, and 44 carboxylation of Grignard reagents, oxidative cleavage of alkenes and alkynes, hydrolysis of nitriles, and oxidation of alkylbenzenes. 

CARBOXYLIC ACIDS FROM OXIDATION OF TERMINAL ALKENES, 11... 

CARBOXYLIC ACIDS FROM THE OXIDATION OF TERMINAL ALKENES BY PERMANGANATE NONADECANOIC ACID... 

Cobalt(II) salts are effective catalysts for the oxidation of 1,2-glycols with molecular oxygen in aprotic polar solvents such as pyridine, 4-cyanopyridine, benzonitrile, DMF, anisole, chlorobenzene and sulfolane. Water, primary alcohols, fatty acids and nitrobenzene are not suitable as solvents. Aldehydic products are further oxidized under the reaction conditions. Thus, the oxidative fission of rram-cyclo-hexane-l,2-diol gives a mixture of aldehydes and acids. However, the method is of value in the preparation of carboxylic acids from vicinal diols on an industrial scale for example, decane-1,2-diol is cleaved by oxygen, catalyzed by cobalt(II) laurate, to produce nonanoic acid in 70% yield. ... 

Oxidation of aldehyde products produced from hydro-formylation is a major industrial route to carboxylic acids. The Hoechst-Celanese Corporation, for example, produces considerable quantities of linear C7 and C9 carboxylic acids from the Rh/PPh3-catalyzed hydroformylation of 1-hexene and 1-octene. 

Sodium periodate, used ong with catalytic amounts of osmium tetroxide, ruthenium dioxide or potassium permanganate, can also be employed to cleave carbon-double bonds. When used with osmium tetroxide, carbonyls are produced however, the presence of permanganate results in the formation of more highly oxidized products (carboxylic acids) from secondary carbons. 

Thietane 1-oxide may absorb carcinogens.The cyclic carbonate derived from bis(3,3-hydroxymethyl)thietane 1-oxide can be homo- or copolymerized to give high-molecular-weight solids.The sulfoxide of compound 52 is said to be useful in the preparation of pesticides, pharmaceuticals, and high-melting plastics. 3-aryloxythietane 1-oxides are claimed to be useful as herbicides, fungicides, insecticides, acaricides, antioxidants, stabilizers for plasticizers, and dye intermediates. Quinazoline derivatives of thietane 1-oxide carboxylic acids may be antihypertensive. 

Heumann s Synthesis, Phenyl Glycine Ortho-carboxylic Acid.—The synthesis that has resulted in placing synthetic indigo on the market is that of Heumann by the fusion of phenyl glycine ortho-carboxylic acid with caustic potash. The product of this fusion is indoxyl which by atmospheric oxygen is oxidized to indigo. The industrial success of this synthesis was achieved only when the preparation of the-phenyl glycine ortho-carboxylic acid from a cheap source was accomplished. 

N03)j, a newcomer to the arena of oxidants, is useful for the acetoxylation of aromatic side chains in benzylic positions [415, 416] and for the oxidation of methylene or methyl groups that are adjacent to aromatic rings to carbonyl groups [238, 415, 417]. The reagent also oxidizes alcohols to aldehydes [418, 419, 420, 421] and phenols to quinones [422, 423], cleaves vicinal diols to ketones and a-hydroxy ketones to acids [424, 425], and converts diaryl sulfides into sulfoxides [426]. A specialty of ammonium cerium nitrate is the oxidative recovery of carbonyl compounds from their oximes and semicarbazones [422, 427] and of carboxylic acids from their hydrazides [428] under mild conditions. 

Not very many other chromium compounds are suitable for the preparation of carboxylic acids from alcohols. One such compound is zinc dichromate, which oxidizes benzyl alcohol to benzoic acid in 90% yield in dichloromethane solution at room temperature [660]. 

Oxidations with peimanganates are suitable for the preparation of carboxylic acids from saturated and benzylic alcohols. Unsaturated alcohols may suffer cleavage of double bonds. Conventional oxidations are carried out in aqueous media, usually in the presence of alkali hydroxides. Thus... 

On the other hand, potassium permanganate is frequently used to prepare carboxylic acids from both aliphatic [86S] and aromatic aldehydes [555]. High yields of carboxylic acids are also obtained by oxidation with tetrabutylammonium permanganate [599] or benzyltriethylammonium permanganate [903] (equation 350). Recently, doubts about the safety of work with quaternary ammonium permanganates have been raised [967]. 

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