Displacement of an alkyl group from quaternary ammonium chlorides by certain neutral nucleophiles

Abstract

Lane and SpeierLithium in Ammonia Reduction of 1-Bromonorbornane with Inverse Addition. A solution of 134.8 mg (19.5 mmol) of lithium metal in 60 ml of twice-distilled ammonia3I was added dropwise to a rapidly stirred solution of 351.1 mg (2.00 mmol) of 1-bromonorbornane in 50 ml of doubly-distilled ammonia and 10 ml of dry diethyl ether. The characteristic blue color of lithium in ammonia was immediately discharged upon addition to the halide solution. Following the addition, excess lithium was destroyed with solid ammonium chloride as described above. GLC analysis of the ethereal residue revealed 90.6% norbornane and 9.4% 1,l'-binorbornane.Lithium in Ammonia Reduction of 1-Bromonorbornane at High Dilution. A solution of 500 mg (2.86 mmol) of 1-bromonorbornane in 50 ml of dry diethyl ether was diluted with 150 ml of twice-distilled ammonia31 and added dropwise to a rapidly stirred solution of 250 ml(35.7 mmol) of lithium in a mixture consisting of 500 ml of twice-distilled ammonia3I and 100 ml of dry diethyl ether at reflux. Following the addition, the reaction mixture was allowed to stir for 1 h a t reflux and was then quenched with solid ammonium chloride as described above. GLC analysis of the ethereal residue revealed 99.2% norbornane and 0.8% 1,l'-binorbornane.Registry No.--4, 59219-48-6; ciscyclopentane-1,3-dicarboxylic acid, 876-05-1; cis-cyclopentane-1,3-dicarboxylic acid chloride, 59219-49-7; cis-cyclopentane-l,3-bis(N,N-dimethylcarboxamide), 59219-50-0; trans-cyclopentane-l,3-bis(N,N-dimethylcarboxamide), 59219-51-1; 1,3-bis(dimethylamino)cyclopentane, 59219-52-2; Nmethyl-N-(1-norbornylmethyl)formamide, 59219-53-3; lithium, 7439-93-2; ammonia, 7664-41-7.

Amine Substitution Reactions of Brominated Poly(isobutylene-co-isoprene): New Chemical Modification and Cure Chemistry

“…Tong et al have demonstrated that a carboxylate anion can act as a nucleophile in an exchange reaction with onium ions at 140 °C, and alkyl group displacements from quaternary ammonium halides by amine nucleophiles have been well documented . We have similarly observed the ability of amines to participate in alkyl exchange with BPMN-derived compounds.…”

“…Tong et al have demonstrated that a carboxylate anion can act as a nucleophile in an exchange reaction with onium ions at 140 °C, 11 and alkyl group displacements from quaternary ammonium halides by amine nucleophiles have been well documented. 12 We have similarly observed the ability of amines to participate in alkyl exchange with BPMN-derived compounds. Upon heating a solution of 5a with approximately 0.25 equiv of octylamine to 100 °C for 2 h and washing with base, 1 H NMR revealed the presence of residual 5a along with the single N-alkylation product 6c (Figure 2b).…”

2-Alkylidene-4-oxothiazolidine Vinyl Bromides: Versatile Precursors for C(5) Functionalization via Pyridine-Assisted Bromine Transfer

“…A couple of examples involving nucleophilic displacements with pyridine as a leaving group has been reported so far. 26,27 However, Katritzky et al 28 reported in a series of papers the substitution of 2,4,6-triphenylpyridine by neutral and anionic nucleophiles from various N-substituted 2,4,6-triphenylpyridinium cations. Within this context, the reaction of unsubstituted pyridinium salts 7a and 7b with neutral nucleophiles, such as morpholine, aniline and methanol, forming the substitution products 9-11 in good to excellent yields (Table 2), represents an extension of the pyridinium salt chemistry.…”