Synthesis Of2,3-bis(Hydroxymethyl)-2,3-dinitro-1,4-butanediol And Its Derivatives

2,3-Bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol is a kind of nitroalcohols which arecommon organic intermediates. Its nitration product is a new kind of energetic material, andcould be used as melt-castable explosive.In the article,2,3-bis(hydroxymethyl)-2,3-dinitro-1,4-butanediol was synthesizedthrough the condensation of nitromethane with formaldehyde, hydroxyl-protection,oxidative coupling, and deketalisation. Tris(hydroxymethyl)nitromethane (TN) wasobtained by the the condensation of nitromethane and formaldehyde in the catalysis ofcalcium hydroxide with the yield of62%. In the presence of BF3·Et2O, the reaction of TNand acetone gave2,2-dimethyl-5-hydroxymethyl-5-nitro-1,3-dioxane (DHND) in the yieldof73%. The coupling of DHND in the oxidation of sodium persulfate afforded2,2,2’,2’-tetramethyl-5,5’-dinitro-5,5’-bis(1,3-dioxane)(BDND) in57%yield. And thereaction of BDND with concentrated hydrochloric acid produced2,3-bis(hydroxyl-methyl)-2,3-dinitro-1,4-butanediol (BHDB) in92%yield.This paper studied the chlorination, p-toluenesulfonation of BHDB, etc. The expectedchlorinated product was not obtained when BHDB was chlorinated by thionyl chloride inthe presence of pyridine, and a new cyclic sulfite was obtained in75%yield. When thethionyl chloride was switched to sulfonyl chloride and the chlorination was runned inacetone, two different of ketals, one was seven-membered heterocyclic compound and theother was BDND, were obtained. The structures of two new heterocyclic compounds werecharacterized by optical sptectra, and undoubtedly confirmed by their single-crystaldeterminations. Dichloro substituted product was produced by the chlorination of BDNDwith sulfonyl chloride in acetonitrile. In the catalysis of pyridine, the reaction of BHDB andp-toluenesulfonyl chloride gave the corresponding product in5.6%yield. Besides, reactionof BHDB with different amines was also explored.