The Chemistry of Borazene. I. The Reaction of B-Trichloro-N-trimethylborazene with Grignard Reagents¹

Abstract

Septa 5, 1958 REACTION OF B-T RICHLORO-N-TRIMETHYLBORAZENE WITH GRIGNARD RE.4GENTS 4515 boron in the chains. Characterizationz3 of the phase as a solid solution of carbon in boron is consistent with the experimental absencez4 of extrema in physical properties a t any stoichiometric composition throughout the entire range. (Although it is not a system in which one imagines that complete (23) F . W. Glaser, D. Moskowitz and B . Post, J . A p p . Phys., 24, (24) Cf., P . J. Bray, Atomic Energy Commission Report N Y O -731 (1953). 7624.thermodynamic equilibrium, involving the reconstitution and sorting of chains, will be readily attained.)Acknowledgments.-We wish to thank Dr. H. A. Weakliem, Jr., for expert aid in carrying out some of the computations and the Cornel1 Computing Center for allowing us the necessary time on IBM equipment. RECEIVED JANUARY 13, 1958B-Trichloro-N-trimethylborazene reacts smoothly with Grignard reagents t o give B-alkyl derivatives. B-Triethyl-N-B-Di-(n-butyl)-B-chloroand trimethyl-, B-triallyl-N-trimethyl-and B-tri-(n-butyl)-N-trimethylborazene were prepared. B-n-butyl-B-dichloro-N-trimethylborazene were prepared using a deficiency of Grignard reagents.

Synthesis and Reactions of Borazines

“…107 In contrast substitution reactions with in situ generated Grignard reagent generated from alkyl or aryl bromides and magnesium turnings only required heating of the reaction to the reflux temperature of diethyl ether to afford the product. 106 Scheme 61 Reaction of B-trichloro-N-trimethylborazine with Grignard reagents 106 Interestingly, the reaction of B-trichloroborazine with either 1 or 2 equiv of Grignard reagent leads selectively to monoalkylated or bis(alkylated) borazines. 106 This is an important method for preparing unsymmetrically functionalized borazines.…”

“…106 Scheme 61 Reaction of B-trichloro-N-trimethylborazine with Grignard reagents 106 Interestingly, the reaction of B-trichloroborazine with either 1 or 2 equiv of Grignard reagent leads selectively to monoalkylated or bis(alkylated) borazines. 106 This is an important method for preparing unsymmetrically functionalized borazines. This chlorine-for-carbon substitution strategy has even been adapted to access other allyl-and alken-ylborazines, such as B-triallyl-N-triphenylborazine, and Btrivinyl-N-triphenylborazine.…”

“…Another important type of substitution reaction of B -trichloroborazine involves the alkylation or arylation of boron by Grignard or lithium reagents. 91 106 107 These reactions provide access to various kinds of B -trialkylborazines and B -triarylborazines from B -trichloroborazines. Typically, the B -trichloroborazine reacted with freshly prepared Grignard reagent or lithium reagent (3 equiv to 4 equiv) in dry diethyl ether to give the corresponding B -functionalized borazines 117 and 82 (Schemes 61 and 62).…”

“…107 In contrast substitution reactions with in situ generated Grignard reagent generated from alkyl or aryl bromides and magnesium turnings only required heating of the reaction to the reflux temperature of diethyl ether to afford the product. 106…”

Notes: Inhibition of the Nitrostyrene Condensation in Acetic Acid by Traces of Water

“…Chem, Soc., 78, 2284, 6425 (1956). (7) In one experiment, Schiff base was substituted for piperonal. The deviation of the point at 0.021 Schiff base in Fig.…”