Carbonyl hydrides, sodium salts

A. SODIUM SALT OF IRON CARBONYL HYDRIDE Sodium Tetracarbonylferrate(-II))... 

Aziridinyl ketones can be synthesized from unsaturated carbonyls using a series of other methods. For example, azabicyclo[4.1.0]heptanone 27 was obtained from cyclohexenone 25 in its reaction with TV-bromotoluenesulfona-mide sodium salt 33 [49] (Scheme 1.10). The reaction of chalcone with N-chlorotoluenesulfonamide in the presence of silver nitrite is described in [50]. Trans-Aziridinyl ketone 18 was synthesized by reacting chalcone 22 with N,N-diamino-l,4-diazoniabicyclo[2.2.2.]octane dinitrate 34 and sodium hydride in 2-propanol [30, 51]. Aziridinyl ketones can be obtained in the reaction of a -unsaturated ketones with A,A-dichlorosulfonamines [52] and with amines in the presence of lead tetraacetate and trifluoroacetic acid [53] or in the presence of triethylammonium acetate under electrochemical reaction conditions [54]. 

The chemistry of the metal carbonyl hydrides and metal carbonylates remained the principal research topic for Hieber until the 1960s. He mentioned in his account [25], that it was a particular pleasure for him that in his laboratory the first hydrido carbonyl complexes of the manganese group, HMn(CO)5 and HRe(CO)5, were prepared by careful addition of concentrated phosphoric acid to solid samples of the sodium salts of the [M(CO)5] anions, giving the highly volatile hydrido derivatives in nearly quantitative yield [45, 46]. In contrast to HCo(CO)4 and its rhodium and iridium analogues, the pentacarbonyl hydrido compounds of manganese and rhenium are thermally remarkably stable, and in... 

Many methods have been devised for the /V-alkylation of isatins. These derivatives are commonly synthesized from the reaction of the sodium salt of isatin with alkyl halides or sulphates . Various methods for the preparation of this salt have been reported, and include the reaction of isatin with sodium hydride, either in toluene under reflux74 or in DMF75. Other methods include the use of potassium carbonate in DMF76,77 or in acetone78. In the latter case an aldol reaction of the solvent also occurs with the C-3 carbonyl of the isatin derivative. 

Uninegative cobalt is found in sodium tetracarbonylcobaltate(—I), NaCo(CO)4, which is a typical salt with the anion [ 0(00)4] This and the corresponding salts of potassium and calcium are related to cobalt carbonyl hydride (p, 303). 

In general the complexes are mild reducing agents and in solution will reduce silver nitrate to silver (86). The hydrides are not acidic in solution, nor will they form sodium salts analogous to those of the carbonyl hydrides... 

Sodium salts of carbonyl hydrides prepared in ethereal media, synthesis 53... 

According to the proposed mechanism (see Scheme 21), the reaction of CL with sodium dialkoxyaluminum hydride gives rise to the sodium lactamate and dialkoxyaluminum hydride AIH(OR)2 [78]. Then, the reduction of the carbonyl function by the latter produces the sodium salt of 2-(dialkoxyaluminoxy)-l-azacycloheptane (41) [79]. The... 

Previous difficulties in the generation of the ylide from the spiro-phos-phonium salt (3) have been overcome by treating the salt with sodium hydride in DMSO in the presence of a carbonyl compound or by refluxing... 

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