Organosilazane compounds

William S. HeinamanJ has called attention to the fact that the sulfuric acid added in the preparation of silica gel, synthesis 26 of Volume II,1 should be 6 M rather than 6 N to be consistent with the submitter s statement that twice the theoretical amount of acid is employed.  

The preparation1 and properties2 of a great many organo-silicon compounds have been described. However, a relatively small amount of work has been done in the field of silazane chemistry, i.e., the chemistry of compounds which contain at least one silicon-nitrogen bond.3-8 In general, this group of compounds has been found to be extremely sensitive to hydrolysis. The hydrolytic reaction forms the appropriate amine or ammonia and a silanol and/or a siloxane. 

It is of interest to observe that the only tertiary amine containing three Si-N bonds that has been isolated to date is trisilylamine, (H3Si)3N, which was prepared by Stock and Somieski9 by treating the vapor of chlorosilane with ammonia. 

The following syntheses of specific compounds represent general procedures of preparation. 

---

Organic coordination groups, nomenclature of, 2 267 Organogermanium compounds, 5 64 nomenclature of, 5 64 Organosilazane compounds, 5 55, 62 Organosilicon compounds, 3 50 nomenclature of, 2 266 3 55 Orthite, extraction of, 2 44 Orthoboric acid, esters of, 6 29 Orthoperiodic acid (HsICh), 1 172, 173... 

Anhydrous lanthanon nitrates, synthesis 11 Cyanogen, synthesis 12 Allophanyl hydrazide, synthesis 13 Urazole, synthesis 14 Organosilazane compounds, synthesis 16 IV-Nitrosohydroxyla-mine-iV-sulfonates, synthesis 31 Hydroxylamine-O-sul-fonic acid, synthesis 32... 

Organosilazanes (i.e. bis(triorganosilyl)amines) are stable compounds. They can be distilled or melted without decomposition. They are slowly hydrolysed in a neutral or... 

Organocyclosilazanes may be prepared in several ways, including the reaction of dihalodiorganosilanes with ammonia [389] (Eq. 3.197), dilithiumalkylamides [390] (Eq. 3.198) or with A,A -dilithium-JV,7V -diorganohydrazo compounds [391] (Eq. 3.199). They may also be made by pyrolysis of bis(alkylamino)diorganosilanes [392] (Eq. 3.200) or by the reaction of open-chained organosilazanes with potassium hydrazide [393] (Eq. 3.201). 

---