Sodium amide fluoride

Tertiary benzylic nitriles are useful synthetic intermediates, and have been used for the preparation of amidines, lactones, primary amines, pyridines, aldehydes, carboxylic acids, and esters. The general synthetic pathway to this class of compounds relies on the displacement of an activated benzylic alcohol or benzylic halide with a cyanide source followed by double alkylation under basic conditions. For instance, 2-(2-methoxyphenyl)-2-methylpropionitrile has been prepared by methylation of (2-methoxyphenyl)acetonitrile using sodium amide and iodomethane. In the course of the preparation of a drug candidate, the submitters discovered that the nucleophilic aromatic substitution of aryl fluorides with the anion of a secondary nitrile is an effective method for the preparation of these compounds. The reaction was studied using isobutyronitrile and 2-fluoroanisole. The submitters first showed that KHMDS was the superior base for the process when carried out in either THF or toluene (Table I). For example, they found that the preparation of 2-(2-methoxyphenyl)-2-methylpropionitrile could be accomplished h... 

A detailed study of the conversion of 3,4-dichloro-l,2,5-thiadiazole into 3,4-diamino-l,2,5-thia-diazole has been carried out <76JHC13>. Reaction with lithium or sodium amide produces only 4% of the diamine together with cyano-containing by-products, a consequence of direct attack on sulfur. Use of a less powerful nucleophile, ammonia or potassium phthalimide, resulted in an increased attack on carbon and produced the diamine in 24% and 66% yields, respectively. Secondary amines, e.g. morpholine <76JOC3l2l> and dimethylamine <72JMC315>, produce the normal displacement products. The reaction of dichlorothiadiazole with potassium fluoride in sulfolane gives a mixture of 3-chloro-4-fluoro and 3,4-difluoro-l,2,5-thiadiazole <82CB2135>. 

Compound Name Oil Mineral Seal Ethyl Silicate Trichlorosilane Fluosilicic Acid Silicon Tetrachloride Dimethyl Polysiloxahe Silicon Tetrachloride Silver Acetate Silver Carbonate Silver Fluoride Silver Iodate Silver Fluoride Silver Nitrate Silver Oxide Silver Sulfate Cacodylic Acid Calcium Hydroxide Oil Road Sodium Amide Sodium... 

The preferential syn elimination of hydrogen fluoride from r/ am-l -bromo-2-fluorocyclohexane (trans-40) to give 1-bromocyclohexene (42) is achieved only when a strong base such as sodium amide is used.81-82 Potassium lerl-butoxide treatment results in elimination of hydrogen bromide to form 3-fluorocyclohexene (43).82... 

Due to the presence of silicon which stabilizes the a-carbanion, strong bases such as butyllithium and sodium amide are able to give an ylid from silylmethylammonium halides. Fluoride ion-assisted desilylation of these salts represents another means to create an ylid. These ylids are prone to rearrange and the results differ upon the nature of... 

Dehydrohalogenation Alumina, see Sulfur tetrafluoride. Alumina-Potassium hydroxide. Cesium fluoride. l,5-Diazabicyclo[4.3.0]nonene-5. l,4-Diazabicyclo[2.2.2]octane. 1,5-Diazabicyclo[5.4.0]undecene-5. Dimethylaminotrimethylstannane. Dimethyl sulfoxide. Hexamethylphosphoric triamide. Lithium chloride. Lithium dicyclohexylamide. Magnesium oxide. Potassium r-butoxide. Potassium fluoride. Potassium triethylmethoxide. Pyridine, see Nitrosyl chloride. Silver fluoride. Silver nitrate. Sodium amide. Sodium bicarbonate, see Nitryl iodide. Sodium isopropoxide. Triethylamine, see Sulfur dioxide. 

SODIUM ACID FLUORIDE (1333-83-1) NaHFj Dry material reacts, possibly violently, withchromyl chloride, diethylzinc, dimethyl sulfoxide, lead dioxide, nitric acid, redphosphoras, potassium, sodium peroxide. Incompatible with hexafluoroisopropylidene-aminolithium. Reacts with water releasing heat and, forming a highly acidic solution. Incompatible with sulfuric acid, bases, caustics, ammonia, amines, amides, organic... 

Several fluoro analogs of ketoses have been reported 1,6-dideoxy-1,6-difluoro-D-fructose was readily obtained from 2,3-O-isopropyli-dene-l,6-di-0-p-tolylsulfonyl-)3-D-fructofuranose by treatment with potassium fluoride in 1,2-ethanediol under a stream of carbon dioxide.96 Surprisingly, although the 6-sulfonyloxy group would be expected to be more reactive than the 1-sulfonyloxy group,97-99 no selectivity was observed. The failure to obtain 1-deoxy-l-fluoro-D-fructopyranose96 from 2,3 4,5-di-0-isopropylidene-l-0-(methylsulfonyl) (or p-nitro-phenylsulfonyl)-/3-D-fructopyranose or phenyl 3,4,5-tri-O-acetyl-l-O-(methylsulfonyl)-/3-D-fructopyranoside by treatment with potassium or sodium fluoride in 1,2-ethanediol, N,N-dimethylformamide, or form-amide at elevated temperatures may be attributed to the fact that nu-... 

Class B Fluoroacetic acid and salts, e.g. sodium fluoroacetate, triethyl-lead fluoroacetate all simple esters of fluoroacetic acid fluoroacetamide and substituted amides fluoroacetamidine hydrochloride fluoroacetyl chloride and fluoride fluoro-ethanol and its simple esters fluoroacetaldehyde. 

Von Runge and Triebs used a solution of dinitrogen pentoxide in chloroform for the N-nitration of both amides and imides. Solutions of dinitrogen pentoxide in chlorinated solvents are not neutral nitrating agents when amides and imides are nitrated - the presence of acidic N-H protons in these substrates leads to the formation of nitric acid. Sodium fluoride acts like a base towards nitric acid and so its addition to these reactions can increase product yield. Sodium acetate has been used for the same purpose during the nitration of n-butyl-V, V -dimethylurea. The effectiveness of dinitrogen pentoxide for the V-nitration of ureas is further illustrated by its use in the conversion of 2-imidazolidinone to N, V -dinitro-2-imidazolidinone in 90 % yield. In the presence of sodium fluoride the yield for this reaction exceeds 90 %. 

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