Acetates alicyclic

The effect of adding large quantities of acetic acid to the medium is more complicated. The acceleration of the oxidation rate of isopropanol was ascribed initially to a shift of the esterification equilibrium to the right (reaction 29). However, RoCek found that acceleration by acetic acid occurs for oxidations which cannot involve a pre-equilibrium esterification, e.g. those of aliphatic and alicyclic hydrocarbons. The obvious alternative, i.e. that acetic acid combines with chromic acid, viz. 

Acetone cyanohydrin nitrate, a reagent prepared by treating acetone cyanohydrin with nitric acid-acetic anhydride, has been used for the At-nitration of aliphatic and alicyclic secondary... 

A solution of fuming or absolute nitric acid in acetic anhydride is another commonly used reagent for the V-nitration of V-alkylamides. Curry and Mason used this reagent to synthesize a series of aliphatic and alicyclic V-nitro-V-alkylcarbamates from the corresponding V-alkylcarbamates. Aromatic ring nitration is observed if aryl groups are present in the carbamate substrate. 

Reiter et al. studied the condensations of 3-methylthio-AT and 3-morpholino-AT, respectively, with ethoxymethylene-cyanoacetate (and -malonitrile) in acetic acid or DMF (or mixtures) and isolated only the corresponding 7-amino-TP (87JHC1149). Analogous reactions of aliphatic (90M173) and alicyclic 3-ketocarbonic esters (87JHC1503 890PP163 91JHC721) always resulted in 7-oxo-TPs as the major products and 5-oxo-TPs as by-products. 

Some alicyclic alcohols are important as synthetic sandalwood fragrances. A few alicyclic aldehydes are valuable perfume materials and are obtained by Diels Alder reactions using terpenes and acrolein. Esters derived from hydrogenated aromatic compounds, such as /cr/-butylcyclohexyl and decahydro-/3-naphthyl acetates, are also used in large amounts as fragrance materials. 

The reaction is very general. The aldehyde or ketone may be aliphatic, alicyclic, or aromatic (including diaryl ketones) it may contain double or triple bonds it may contain various functional groups, such as OH, OR, NR2, aromatic nitro or halo, acetal, or even ester groups.643 Double or triple bonds conjugated with the carbonyl also do not interfere, the attack being at the 0=0 carbon. 

The hydroxyl group of a primary, secondary, or tertiary acyclic or alicyclic alcohol may be protected by conversion into (a) an ether, (b) a silyl ether, or (c) an ester. The most important method for the protection of a 1,2- or 1,3-diol is conversion into (d) a cyclic acetal. 

The most widely used protective groups for aliphatic and alicyclic aldehydes and ketones are (a) cyclic acetals and (b) cyclic dithioacetals and hemithio-acetals. The use of semicarbazones, oximes and 2,4-dinitrophenylhydrazones (for preparation see Section 9.6.13, p. 1257) is less common but has found application in certain instances where the more vigorous methods required for deprotection are not detrimental. 

The periodinane (10) may also be prepared from o-iodobenzoic acid by oxidation with potassium bromate and then treatment with acetic anhydride18 (see Expt 6.36 for detailed formulation). It should be noted that the organic derivatives of pentacoordinate iodine(v) are termed periodinanes.18b This compound (the systematic name is l,l,l-triacetoxy-2,l-benzoxiodol-3(3//)-one) has found use as an oxidant of primary alcohols to aldehydes and alicyclic ketones to secondary alcohols it is claimed to have advantages over the chromium-based oxidation reagents. 

The methods which are available for the protection of the aromatic carbonyl group are similar to those for the aliphatic and alicyclic analogues (Section 5.8.8, p. 623). It should be noted however, that when a cyclic acetal is used as the protecting group, a Birch reduction (Section 7.5) on the protected compound usually results in hydrogenolysis of the protecting acetal. 

DCA is the first bile acid whose inclusion ability was confirmed in the crystalline state. During the last century many research groups dealt with the inclusion compounds of DCA with various guest molecules, such as aliphatic, aromatic and alicyclic hydrocarbons, alcohols, ketones, fatty acids, esters, ethers, nitriles, peroxides and amines, and so on [2], In 1972, Craven and DeTitta first reported the exact crystal structure of DCA with acetic acid [3], Subsequent crystallographic studies made clear that most of DCA inclusion crystals have bilayer... 

Alicyclic enol acetates can lead to the corresponding enones by anodic oxidation. The electrolysis of d-menthenyl acetate 74 in an AcOH—Et4NOTs—(C) system by passing 2.5 F/mol of electricity provides the d-menthenone 75, a precursor for d-menthone 76 and /-citronellol 54 syntheses, in 97% yield (Scheme 3-28)76a). 

Acyloins have also been employed extensively as starting materials for the synthesis of imidazoles, usually in the presence of added aldehyde (or acid) and using ammoniacal cupric acetate to oxidize the acyloin to the corresponding a-dicarbonyl compound.24 Alicyclic and aromatic ketols and ketol acetates in an alcoholic solution of cupric acetate and ammonia undergo ring closure to the corresponding 2-imidazoyl ketones. Hence, benzoyl carbinol refluxed for 1 hour in... 

Aliphatic and alicyclic carbamates are nitrated smoothly and in excellent yields by a nitric acid-acetic anhydride mixture (4). Similarity, we have found that treating an acyl aliphatic amine and a urethane with one equivalent of nitronium tetrafluoroborate in acetonitrile at —30° C. gave the corresponding N-nitro derivatives in good to excellent yields. However, diacylamines are more difficult to nitrate, and Kauffman and Burger (9) have reported that nitrating succinimide required 13 hours... 

Alicyclic, aromatic, aliphatic, steroidal and triterpenoid 1,2-diols are cleaved by iodine triacetate and iodine(I) acetate to generate carbonyl compounds. Aldehydic products are not further oxidized. Iodine triacetate is prepared from iodine trichloride and silver(I) acetate, whereas iodine(I) acetate is prepared from iotUne and silver(I) acetate. Reactions occur in acetic acid at room temperature under nitrogen, and a radical pathway involving a hypoiodite is suggested. The cost and the availability of these reagents are probable reasons for their unpopularity. 

Hayashi, Y. and Sakaguchi, I. (1982). Stable dioxazine violet pigment production from metastable form—by heating aqueous suspension with aliphatic or alicyclic ketone or acetate. Sunmitomo Chem. Co. Ltd Patent DE 3 211 607 AL [260t]... 

The reaction of aliphatic, alicyclic, and aromatic aldehydes and ketones with cyanoacetic ester, NCCHjCOjCjH, is general. The products are 0L,/3-olefinic cyanoacetates. The aldehydes are condensed with the ester in the presence of amines or with sodium cyanoacetate in the presence of sodium hydroxide, Similarly, cyanoacetic ester is condensed with ketones by catalysts such as acetamide or the acetates... 

Although aliphatic and alicyclic hydrocarbons react with most sul-fonating agents, the reactions are not suitable for the preparation of the pure sulfonic acids. " Certain olefins react with sulfur dioxide-dloxane complex to give olefinic sulfonic acids In this way, cyclohexene is converted to l-cyclohexene-3-sulfonic acid, whereas with concentrated sulfuric acid in a mixture of acetic acid and acetic anhydride the main product is 2-hydroxycyclohexanesuIfonic acld. 1-Propene-l-sulfonic acid is obtained in low yield by the action of oleum on n- or isopxopyl alcohol. ... 

Carbohydrate chemistry is especially rich in examples of ring structures formed by reversible reactions, such as glycosides and cyclic acetals, and provides a more convenient field for examining the factors governing the stability of rings than does alicyclic chemistry, in which ring closures are usually irreversible. Furthermore, the prominent reversible reactions... 

Nearly all common mono- and disubstituted acetic acids, including several functionally substituted examples, have been reported to metalate. Unsaturated as well as saturated alicyclic carboxylic acids form dianions, but cyclopropane carboxylic acid is exceptional. Low yields of alkylated products are produced,14,20 suggesting incomplete dianion formation. 

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