Acid chlorides alicyclic

Triazolium salts (49 Scheme 23), prepared from an acid chloride and the thiohydrazo compound (48), have been reduced to the hydro compound (50) and then hydrolyzed in dilute sulfuric acid to the aldehyde. - Overall yields of aldehyde are reported to be 46-90% and a variety of other functional groups can be supported such as alkene, halogen, nitro, ketone and ester there can be one or two side chains on the a-carbon or it can be part of an alicyclic system. 

Weissman and Brown found that, in contrast to alkyl esters, which are inert to the reagent, phenyl esters of aliphatic and alicyclic adds react to form aldehydes. However, since the phenyl esters are generally prepared from the acid chlorides, it is preferable to proceed through the acid chloride directly. 

Aliphatic, alicyclic, and aromatic acid chlorides are reduced in variable yields to the corresponding aldehydes by the readily prepared copper(i) tetrahydroborate (10)-, ... 

Esterification with alicyclic alcohols proceeds best when the alcohol is saturated with hydrogen chloride and treated with an excess of the carboxylic acid (the Fischer-Speier method) a very impure ester results if sulphuric acid is used as the catalyst. 

A convenient method for preparing alicyclic or aromatic methyl ketones consists in the acylation of the ethoxymagnesium derivative of diethyl malonate with the appropriate acyl chloride, followed by acid hydrolysis and decarboxylation of the resulting /3-keto diester. The last step is Carried out like the ketonic cleavage of /3-keto esters. The over-all yields are 60-85%. 

Hexafluoroacetone has been a popular compound for further photochemical study" " Majer et al. have reported on the photolysis of alicyclic perfluoroketones and of chloropentafluoroacetone other work on fluorinated ketones has been reported by Pritchard et a/. - , by Phillips and Trotman-Dickenson , and by Schuster and Patel . Intramolecular elimination reactions in the photolysis of fluoroaldehydes have been discussed by Morris and Thynne and by Pritchard and Perona . Photolytic studies on other oxygen-containing halogen compounds have included chloroacetic acids , acetyl chloride , perfluoroacyl fluorides , CF3OF and CF3OOCF3 . 

A significant number of works are concerned with the development of new membranes for the separation of mixtures of aromatic/alicyclic hydrocarbons [10,11,77-109]. For example, the following works can be mentioned. A mixture of cellulose ester and polyphosphonate ester (50 wt%) was used for benzene/cyclohexane separation [113]. High values of the separation factor and flux were achieved (up to 2 kg/m h). In order to achieve better fluxes and separation factors the attention was shifted to the modification of polymers by grafting technique. Grafted membranes were made of polyvinylidene fluoride with 4-vinyl pyridine or acrylic acid by irradiation [83]. 2-Hydroxy-3-(diethyl-amino) propyl methacrylate-styrene copolymer membranes with cyanuric chloride were prepared, which exhibited a superior separation factor /3p= 190 for a feed aromatic component concentration of 20 wt%. Graft copolymer membranes based on 2-hydroxyethyl methylacrylate-methylacrylate with thickness 10 pm were prepared [85]. The membranes yielded a flux of 0.7 kg/m h (for feed with 50 wt% of benzene) and excellent selectivity. Benzene concentration in permeate was about 100 wt%. A membrane based on polyvinyl alcohol and polyallyl amine was prepared [87]. For a feed containing 10 wt% of benzene the blend membrane yielded a flux of 1-3 kg/m h and a separation factor of 62. 

The polyformals which were obtained in this manner from the alicyclic diols were highly colored, and their inherent viscosities were below 0.4 (determined using 60/40 phenol-tetrachloroethane mixture as solvent). Catalysts which were used were ferric chloride, methanedisulfonic acid, camphorsulfonic acid, antimony trifluoride, and titanium tetrafluoride. Polymers were not obtained with the latter two. 

Thorough kinetics studies of the chlorination of aliphatic, alicyclic, and arylalkyl ketones with CBT were carried out by Indian workers (82PIA921). Kinetic measurements were performed using aqueous acetic acid and the addition of HC104 and NaCl. In the presence of mineral acid the reaction is first order in ketone and acid and zero order in CBT. A large kinetic isotopic effect was observed (for acetone kHlkD = 6.6). Addition of chloride ion causes some changes in the reaction order they become first order in CBT, 0.6 in ketone, and 0.2 in chloride ion. The rate constant for chlorination of substituted acetophenones correlate with a constants for substituents in the aryl ring (p is -0.57). On the basis of these data the mechanism in the absence and in the presence of chloride ion was developed. 

A noteworthy route to highly substituted ketones involves the acylation of or-anions of carboxylic acid salts with acyl chlorides. Symmetrical and unsym-metrical, alicyclic, aliphatic, and aromatic ketones may be prepared in this manner (Scheme 6). ... 

In compositions based on the copolymer of vinyl chloride with vinylacetate, three series of alicyclic epojg compounds have been tested 3,4-epoxycyclohexylmethyl esters of lauric, palmitic, 9,10-epoxystearic, 9,10,12,13-diepoxystearic, oxalic, maleic, terephthalic, sebacic, and other acids of the general formula... 

---