From inorganic halides preparation

Dialkylamino derivatives of elements located in the periodic table to the left or below those listed above cannot be prepared by the above method due to either the ionic character of some of the inorganic halides or the formation of stable metal halide-amine addition products. Therefore, other methods must be applied. Dialkylamino derivatives of tin7 and antimony8 are conveniently obtained by reaction of the corresponding halides with lithium dialkylamides. Others, such as the dialkylamino derivatives of aluminum,9 are made by the interaction of the hydride with dialkylamines. Dialkylamino derivatives of beryllium10 or lithium11 result from the reaction of the respective alkyl derivative with a dialkylamine. 

Fig. 5.32. Alkylation and GC of aqueous inorganic halides. A, authentic salts B, solution prepared on a cation-exchange column. Peaks 1 = methylfluoride 2 = water 3 = methyl chloride 4 = methyl bromide 5 = trimethylamine 6 = methyl iodide. Conditions stainless-steel column, 10 ft. x 1/4 in. O.D., Chromosorb 101 (80-100 mesh) helium flow-rate, 75 ml/min column temperature, 125°C injection port temperature, 360°C 6 til of an aqueous solution of tetramethylammonium halides (0.25 M each) injected. (Reproduced from Anal. Chem., 42 (1970) 1672, by courtesy of J. MacGee and the American Chemical Society.)...

The traditional technique for sulphonylation with sulphonyl chlorides uses at least one mole of Friedel-Crafts halide per mole of sulphonyl chloride and it was realised that this would lead to difficulties in isolating polymers free from inorganic contaminants. However, the preparation of monomeric sulphones using catalytic quantities of FeCl had been reported in a war-time German patent [12] and we applied this procedure to reactions (1). Polymers of high molecular weight (reduced viscosity, RV, up to 1.2 for 1% solutions of polymer in dimethyl formamide at 25 C) were obtained... 

Strictly speaking the alkyl halides are esters of the halogen acids, but since they enter into many reactions (t.g., formation of Grignard reagents, reaction with potassium cyanide to yield nitriles, etc.) which cannot be brought about by the other eaters, the alkyl halides are usually distinguished from the esters of the other inorganic acids. The preparation of a number of these is described below. 

These reactions are most important for the preparation of acyl fluorides. " Acyl chlorides and anhydrides can be converted to acyl fluorides by treatment with polyhydrogen fluoride-pyridine solution" or with liquid HF at — 10°C. Formyl fluoride, which is a stable compound, was prepared by the latter procedure from the mixed anhydride of formic and acetic acids. Acyl fluorides can also be obtained by reaction of acyl chlorides with KF in acetic acid or with DAST. Carboxylic esters and anhydrides can be converted to acyl halides other than fluorides by the inorganic acid halides mentioned in 10-77, as well as with PhsPXa (X = Cl or but this is seldom done. Halide exchange can be carried out in a... 

Halides are often prepared in a single step from alcohols through use of the Appel reaction. The reagents in this synthesis are tri-phenylphasphine and a halogen species such as tetrachloromethane, hexachloroacetone, or iodine. In place of the Appel reaction it is often possible to use inorganic acid chlorides, including phosphorus tribromide or thionyl chloride (see Chapter 16). 

These two complex hydrides have been used also in inorganic syntheses. Lithium aluminum hydride may be used to prepare unstable hydrides in ether at low temperatures from the appropriate halides cadmium hydride and mercury hydride (Chap. 2) have been so prepared. A number of additional borohydrides, aluminum hydrides, and even a gallohydride (LiGaH4) have been reported. 

Silver oxide, Ag20, easily prepared by basic precipitation from solutions containing the silver ion, is a convenient reagent, both in organic and inorganic chemistry, for preparing soluble hydroxides from the corresponding halides since the silver halide formed at the same time may be con-... 

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