Trimethylamine chlorination

Trimethylamine replaces PH3 quantitatively in BH3 PH3 to give BH3 N(CH3)3. Liquid or gaseous ammonia also replaces phosphine in the compound BH3 PH3 to the extent of 52-58% or up to 75%, respectively. The hydrogen atoms bonded to boron are partially, or completely, replaced by chlorine on treatment with hydrogen chloride, depending on the reaction conditions. The first stage of the reaction with hydrogen chloride is the formation of the colourless, viscous liquid BHjCl PH3 (see below). 

CH3)3N A1H2C1 was first prepared by Wiberg, who allowed a stoichiometric amount of hydrogen chloride gas to react with an ethereal solution of aluminiun hydride. The product was isolated by the addition of trimethylamine to the reaction mixture. A more convenient preparation consists of the chlorination of (CH3)3N-A1H3 by mercury (II) chloride. All degrees of chlorination are possible in this... 

Preparation. DISN is formed in 96% yield by base-catalyzed addition of hydrogen cyanide to cyanogen at —40°. It can also be prepared by passing chlorine into a toluene solution of HCN and trimethylamine at — 15° (65 % yield). 

A novel preparation of racemic and enantiopure forms of phosphocarnitine (348) from easily available 3-chloro-2-oxopropylphosphonate (349) has been accomplished. The Baker s yeast catalysed reduction of (349) followed by kinetic resolution of the reduction product using AFl-S AMNO lipase-catalysed acylation and finally standard exchange of chlorine atom for trimethylamine group are the key steps in the synthesis of enantiomers of phosphocarnitine (Figure 56). ... 

The reaction of dichlorocarbene with triethylamine resulted in a - S elimination of ethylene and the formation of diethylformamide after hydrolysis 124>. When trimethylamine was treated with dichlorocarbene, no normal Stevens rearrangement products were observed and the major product isolated was a, a, (3-trichloroethylamine. The presence of this extra chlorine atom in the product is unexpected and a satisfactory mechanism has not been proposed for its formation. 

Displacement of halides can be catalysed by amines - trimethylamine, pyridine and DABCO have been used. Mechanistically, the catalysis involves formation of an intermediate quaternary ammonium salt that is more reactive towards nucleophiles than the starting halide. The intermediate quaternary salts can be isolated, if required. Trimethylamine gives the most reactive quaternary salt, but DABCO can be more convenient. The relative reactivities for nucleophilic displacement at C-6 are trimethylamine DABCO chlorine = 100 10 1. Cyano and fluorine are amongst the groups that have been introduced in this way. 

Masuda, M., Suzuki, T., Friesen, M.D., Ravanat, J.L., Cadet, J., Pignatelli, B., Nishino, H., and Ohshima, H. (2001) Chlorination of guanosine and other nucleosides by hypochlorous acid and myeloperoxidase of activated human neutrophils. Catalysis by nicotine and trimethylamine. /. Biol. Chem., 276, 40486-40496. 

AA, aromatic amine TMA, trimethylamine CINA, chloronitroanilina ClAA, chlorinated aromatic amine LMMA, low molecular mass amine HA, heterocyclic amine PE, polyethylene PS/DVB, polystyrene-divinylbenzene PDMS, polydimethylsiloxane PA, polyacrylate PAB, polyacrilonitrilbutadiene CW, carbowax TPR, templated resin F, food samples. 

Kunz and Kirschning developed a chemically functionalized monolithic material which is based on a glass/polymer composite [28,29] (refer to Sect. 3.1). This material is available in different shapes including rods, disks, and Raschig rings. The polymeric phase of this composite was chemically functionalized (e.g., substitution of the benzylic chlorine by trimethylamine or sulfonation). Rod-shaped objects were first embedded in a solvent-resistant and shrinkable PTFE tube. This was followed by encapsulation with a pressure-resistant fiber-reinforced epoxy resin housing with two standard HPLC fittings, which created... 

Subsequent reaction of 178 with alcohols, phenols, or mercapto compounds, in the presence of base and trimethyl-amine, gives the trisubstituted product 180. The chlorine atom of 178 is deactivated by the amino group and the trimethylamine is used to activate this position by the introduction of a trimethylammonium moiety which can be displaced by the O- or S-nucleophile <2000JHC583>. 

Fig. 9.9 The fragments of the crystal structures of tris(hydrido)-bis(trimethylamine)-aluminium left) and of trichloro-bis(trimethylamine)-aluminium(III) (right) black circles correspond to carbon atoms, green to chlorine atoms, grey to hydrogens, pink to aluminiums and blue to nitrogens, the structures taken from the Cambridge Structural Database [59]...

An important number of esters of long-chain alcohols and amino acids have been described in the literature. The permethylation of the amino function (Scheme 7) leads to the ammonium salts (7) showing generally interesting surfactant properties [30], We have chosen a similar pathway by reacting a perfluorinated fatty alcohol with chloroacetic acid the subsequent substitution of the chlorine atom by trimethylamine leads to the corresponding ammonium salt (8) [31]. The latter is water soluble, but the hydrolysis of the ester function is rather rapid (<6 h), which renders this type of compound less interesting for possible applications. 

A base related to choline is betaine trimethy lycocoll, isolated from beet-juice by C. Scheibler, who did not give its composition. Liebreich by the oxidation of choline obtained a base, the chlorine compound of which, N(CH,)3(CH2C02H)C1, he obtained by the action of chloracetic add oh trimethylamine. The free base, which he called oxyneurine, had the composition CsHii02N, i.e. the expected CgHisOsN, minus H2O. Scheibler then stated that the base he had discovered, which he now named betaine, when dried at ioo had the same composition, and that its hydrochloride is C5Hu02N,HCl. He and Liebreich then showed that oxyneurine and betdne are identical. 

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