Fluorinated compounds reactions

Chloroacetate esters are usually made by removing water from a mixture of chloroacetic acid and the corresponding alcohol. Reaction of alcohol with chloroacetyl chloride is an anhydrous process which Hberates HCl. Chloroacetic acid will react with olefins in the presence of a catalyst to yield chloroacetate esters. Dichloroacetic and trichloroacetic acid esters are also known. These esters are usehil in synthesis. They are more reactive than the parent acids. Ethyl chloroacetate can be converted to sodium fluoroacetate by reaction with potassium fluoride (see Fluorine compounds, organic). Both methyl and ethyl chloroacetate are used as agricultural and pharmaceutical intermediates, specialty solvents, flavors, and fragrances. Methyl chloroacetate and P ionone undergo a Dar2ens reaction to form an intermediate in the synthesis of Vitamin A. Reaction of methyl chloroacetate with ammonia produces chloroacetamide [79-07-2] C2H ClNO (53). 

Nonmeta.ls, Sulfur reacts with fluorine to yield the remarkably stable sulfur hexafluoride, SF. Operating conditions must be controlled because a mixture of the lower fluorides such as disulfur difluoride [13709-35-8] 2 2 disulfur decafluoride [5714-22-7] 2 10 sulfur tetrafluoride [7783-60-0] SF4, may also be formed. When this reaction is carried out between 310 and 340°C, SF is primarily obtained and essentially no SF and only trace amounts of lower fluorides. Below 300°C, and preferably at ca 275°C, SF is the primary product. At 450—500°C, a mixture comprising ca 50% SF and the lower sulfur fluorides is formed (see Fluorine compounds, inorganic-sulfur). 

Organic fluorine compounds were first prepared in the latter part of the nineteenth century. Pioneer work by the Belgian chemist, F. Swarts, led to observations that antimony(Ill) fluoride reacts with organic compounds having activated carbon—chlorine bonds to form the corresponding carbon—fluorine bonds. Preparation of fluorinated compounds was faciUtated by fluorinations with antimony(Ill) fluoride containing antimony(V) haUdes as a reaction catalyst. 

The fluorination reaction is best described as a radical-chain process involving fluorine atoms (19) and hydrogen abstraction as the initiation step. If the molecule contains unsaturation, addition of fluorine also takes place (17). Gomplete fluorination of complex molecules can be conducted using this method (see Fluorine compounds, organic-direct fluorination). 

Direct Fluorination. This is a more recently developed method for the synthesis of perfluorinated compounds. In this process, fluorine gas is passed through a solution or suspension of the reactant in a nonreactive solvent such as trichlorotrifluoroethane (CFC-113). Sodium fluoride may also be present in the reaction medium to remove the coproduct hydrogen fluoride. There has been enormous interest in this area since the early 1980s resulting in numerous journal pubHcations and patents (7—9) (see Fluorine compounds, organic-direct fluorination). Direct fluorination is especially useful for the preparation of perfluoroethers. 

Gaseous hydcofluoiic acid is generally made by the reaction of acid-grade fluorspar [14542-23-5] Cap2, with sulfuric acid (see Fluorine compounds, inorganic)... 

The breadth of reactions catalyzed by cobalt compounds is large. Some types of reactions are hydrotreating petroleum (qv), hydrogenation, dehydrogenation, hydrodenitrification, hydrodesulfurization, selective oxidations, ammonoxidations, complete oxidations, hydroformylations, polymerizations, selective decompositions, ammonia (qv) synthesis, and fluorocarbon synthesis (see Fluorine compounds, organic). 

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