Borazine reactions

This works well for all nido- and arachno-boranes but not for the c/o o-dianions, which are much less reactive. Reactions of B2H6 with NH3 are complex and, depending on the conditions, yield aminodiborane, H2B(/r-H)(/r-NH2)BH2, or the diammoniate of diborane, [BH2(NH3)2]-[BH4] (p. 165) at higher temperatures the benzene analogue borazine, (HNBH)3, results (see p. 210). 

Numerous other reactions have been documented, most of which are initiated by nucleophilic attack on B. There is no evidence that electrophilic substitution of the borazine ring occurs and conditions required for such reactions in benzenoid systems disrupt the borazine ring by oxidation or solvolysis. However, it is known that the less-reactive hexamethyl derivative B3N3Mee (which can be heated to 460° for 3 h without significant decomposition)... 

IV-substituted and B-substituted borazines are readily prepared by suitable choice of amine and borane starting materials or by subsequent reaction of other borazines with Grignard reagents, etc. Thermolysis of monocyclic borazines leads to polymeric materials and to polyborazine analogues of naphthalene, biphenyl, etc. ... 

Another useful deposition reaction is the decomposition of borazine. This is a condensation reaction which produces an amorphous BN with residual hydrogen incorporation ]... 

The cyclic dimeric borazine derivatives 2 and 3 can be prepared by reaction of 2,4-dichloro-l,3,5,6-tetramethylborazine with aromatic 1,3-dihydroxy and l-amino-3-hydroxy compounds (Fig. 2). The products are obtained in yields... 

By reaction of 2-alkyl-4,6-dichloro-l,3,5-trimethylborazines (alkyl = methyl, ethyl, i-propyl) with bis(trimethylsilyl)amine the tetrameric borazine ring systems 4-6 are produced (Fig. 2) they can be purified by several successive vacuum sublimations (yields 4-60%). If the borazines carry n-propyl and tert-butyl groups in the 2-position or if methylbis(trimethylsilyl)amine is used to bridge the borazine molecules, the macrocyclic ring formation is inhibited [17, 18]. 

Though borazine itself gives no stable complexes, alkyl substituted derivatives are formed by the reaction of borazines with LjMfCO), (L = nitrile) (Table 1,... 

Equation (aj) also allows the synthesis of unsymmetrieally substituted borazines, e.g., (EtBMe2B2NjMe3)Cr(CO)3 or (PhBMe2B2N3Me3)Cr(CO)3 . The reactions take place in dioxane at 30-40°C with reduced pressure to pump off eliminated nitrile. The dioxane complexes (C4Hg02)2M2(C0)5 are intermediates. If liquid borazines are used additional solvent becomes unnecessary. 

The introduction of small amounts of boron into precursors that produce silicon nitride have been known to improve the ceramic yields of silicon nitride and Si—B—C—N ceramics as first reported in 1986.110 Several reports have appeared in the past couple of years alone that utilize borazine precursors such as 2,4-diethylb-orazine and other cyclic boron precursors, such as pinacolborane, 1,3-dimethyl-1, 3-diaza-2-boracyclopentane, for their reactions with silanes, polysilazanes, and polysilylcarbodiimides for the high-yield production of Si—B—N—C ceramics.111... 

Polymer 1 is decomposed by reaction with ammonia, yielding methylamine and the intermediate A-trimethyl-.8-tri(amino)borazine 2, which was partially sublimed resulting in a major loss of fiber integrity (scheme 2). 

We have reported that the reaction of 2,4,6-tri(chloro)borazine CI3B3N3H3 with three equivalents of tris(isopropylamino)borane B(NHPr )3 led to the formation of 2,4,6-tri[bis(isopropylamino)boryl(isopropyl)amino]borazine 11 [Fig. 5(a)] in quantitative yield.26,27 The subsequent polycondensation carried out in vacuo up to 150°C, led to the formation of the polymer 12 containing B3N3 rings linked either through direct B—N interring bonds (minor pathway) or three-atoms —N—B—N— bridges... 

The original method1 reported for the preparation of trichloroborazine involves the use of borazine. However, this procedure is not recommended because of the difficulty of preparing this heterocycle and its hydrolytic instability. More recently, this trichloroborazine has been prepared directly from ammonium chloride and boron trichloride at elevated temperatures with or without a solvent.2-8 Ammonium chloride may be replaced by a primary aliphatic or aromatic amine or its hydrochloride, and organodihaloboranes can be used in place of the boron trichloride to give the respective N- and B-substituted borazines.6 Boron tribromide has been used in analogous reactions to yield -B,/ , .B"-tribromoborazines.6... 

Borazine originally was obtained by the reaction of ammonia with diborane.1 Mixtures of lithium or sodium tetrahydro-borate with ammonium chloride also have been pyrolyzed to yield this product.2 More recently, the reduction of B,B, B"-trichloroborazine with alkali metal hydroborates has proved to be a convenient laboratory-scale method for the preparation of this compound.3-7 The procedure described herein is a variation of the last method as reported by Dahl and Schaeffer.7 This method is effective for the synthesis of iV-substituted alkyl- and arylborazines, i.e., compounds of the formula (HBNR)3 where R is CH3, C2H6, C6H , C6H5, p-C6H4CH3, or p-C6H4OCH3.5... 

Compounds belonging to the borazine structural class which is based on a six-membered ring of alternating boron and nitrogen atoms are readily prepared by a number of reactions including... 

Borazine can also be prepared directly by the reaction of diborane with ammonia. 

An unusual type of product known as a borazine is produced by the reaction of BC13 with NH4C1. 

Borazine was first prepared in 1926 by the reaction of B2H6 with NH3, which can be shown as... 

On a larger scale, the reaction of (NH2)2CO with B(OH)3 at high temperature in an atmosphere of ammonia is used to produce borazine. Trichloroborazine, B3N3CI3H3, has the structure... 

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