The Reduction of Urethans With Lithium Aluminum Hydride

Abstract

The reduction of urethans with lithium aluminum hydride has not been reported but appears to be a promising method of synthesis of amines of unusual structure. Successful reductions of amides of fatty acids to amines have already been obtained (1). The use of urethans is of interest from two standpoints: first, urethans can usually be prepared more easily than formamides as intermediates SUMMARY The reduction of urethans with lithium aluminum hydride is an excellent method of synthesis of methylamines in yields of 80 % or better. No evidence of unalkylated amine could be found in the reduction products.Cleveland 6, Ohio

Electronic control of stereoselectivity. 9. The stereochemical course of electrophilic additions to aryl-substituted benzobicyclo[2.2.2]octadienes

“…Completion of the sequence involved formation of the AUV-diurethane,22 N-methylation23 of 17b to give 18, and reduction with LiAlH4. 24 In our hands, repetition of an earlier procedure25 for obtaining 2,3-dimethoxybenzoquinone ( 22) which involved nitration of pyrogallol 1,2-dimethyl ether, reduction to the amino compound, and oxidation with ferric chloride proved problematical. The direct oxidation26 of pyrogallol dimethyl ether with Fremy's salt also met with serious complications.…”

New Prophosphatranes: Novel intermediates to five‐coordinate phosphatranes

“…Using a standard procedure [4], 7 (tren) was converted to 9 in two steps peak at 113.8 ppm (17) and the slower growth of the peak at 120.8 ppm corresponding to 4 (at the expense of the absorption for 17) the decline of the 115.2 ppm peak (18) and the eventual disappearance of the peak at 122.0ppm for the starting material P(NMe,),. Although neither 17 nor 18 have been isolated pure, the lH and I3C n.m.r.…”

2,6‐Diisopropoxyphenyl(dicyclohexyl)phosphine: A New Ligand for Palladium‐Catalyzed Amination Reactions of Aryl Chlorides with Potassium Hydroxide as the Base

“…The reaction of 1d (11.25 g, 0.1 mol), 2a (12.84 g, 0.12 mol), Pd(OAc) 2 (0.0562 g, 0.25 mmol), L2 ⋅ HBF 4 (0.179 g, 0.375 mmol), and KOH (11.22 g, 0.2 mol) in 50 mL of toluene at 110 °C under nitrogen afforded 3h 35 (purified by distillation at 113–114 °C/1 mmHg, lit: 148–149 °C/12 mmHg); yield: 14.291 g (78%). 1 H NMR (300 MHz, CDCl 3 ): δ =7.31–7.20 (m, 4 H), 7.05–6.99 (m, 4 H), 6.99–6.91 (m, 2 H), 3.31 (s, 3 H); 13 C NMR (75 MHz, CDCl 3 ): δ =149.0, 129.1, 121.2, 120.4, 40.2.…”