Amine tertiaiy

Clearly, the tertiaiy nature of the chloride would make an Sn2 mechanism highly unlikely. Furthermore, the nitro substituent is essential to the success of these reactions. Cumyl chloride itself undergoes elimination of HCl on reaction with amines. 

Phosphonitrilic halides (continued) primary amines and, 1 360-362 secondary amines and, 1 350-362 tertiaiy amines and, 1 362-363 structural theory further aspects of, 1 375 structure, 1 365-366 high polymer and, 1 372 medium polymers and, 1 368-372 spectroscopic data and, 1 369-372 structural theory and, 1 372-375 tetrameric compounds and, 1 367-368 trimeric compounds and, 1 366-367 Phosphonium cations, 9 243-250 halogenated, 9 243-249 salts... 

Augustamine, [109]. The stannylated inline 353 utilised in the synthesis of (-)-amabiline (346) also served as the advanced intermediate for the preparation (Scheme 65) of (-)-augustamine (493) [93,94]. Thus, treatment of the mixture of the lithium salts 355 and 356 with iodomethane furnished a 43 1 mixture of the two tertiaiy amines 494 and 495 respectively. The cij-diol, obtained on acid hydrolysis of the former was converted into the ortho ester 496, which on exposure to methanesulphonic acid underwent cyclisation via the carbenium ion 497 to (-)-augustamine (493) in 76% yield. 

Apocyanine dyes of the acridine series are obtained by treating acridinium iodide [43] or acridinium chloride [44] with tertiaiy aromatic amines. The dyes can also be obtained by ipso substitution of acridinium iodide with 4-haloaryl-amines in dimethyl sulfoxide at room temperature [45],... 

We e already studied the tw(j most general reactions of amines—alkylation and acylation.. s we saw earlier in this chapter, primary, secondary, and tertiary amines can be alkylated by reaction with a primary alkyl halide. Alkylations of primary and secondary amines are difficult to control and often give mixtures of products, but tertiaiy amines are cleanly alkylated to give quaternary amnic-niiim salts. Primary and secondary (but not tertiary) amines can also be acylaled by nudeophilir acyl substitution reaction with an acid chloride or an acid anhydride to yield an amide (Sections 21.4 and 21.5). Note that ovcracylation of the nitrogen does not occur because the amide product is much less nucleophilic and less reactive than the starting amme. 

Ttw use o( vinyl chtoiofonnate lor N-deal lon of tertiaiy amines, protection o( amino groups, prolection of hydroxyl groups or formation o( Z-ketoimidazolas. Synthesis of vinyl carbonates by means of lluoro orchioroformates. 

Triethylamine (bp 89°) is another commonly used tertiary amine and is considerably more basic than pyridine. Along with all other aliphatic amines, it may be dried by heating to reflux with and distilling from barium oxide. Secondary amines are common impurities in tertiaiy amines and may be removed by heating the amine with a small amount of acetic anhydride. If the amine has a boiling point considerably different from that of acetic anhydride (bp 140°), it may be distilled directly from the reaction mixture. Otherwise, the reaction mixture should be shaken with 20 per cent potassium hydroxide solution, dried over potassium hydroxide, and distilled from barium oxide. 

Etepn with yields up to 96% using formalde-yde, 1-nitropropane and tertiaiy amines or alkali hydroxides. Medard (Ref 5) and Med-ard Thomas (Ref 6) detd its heats of combustion (703.7 kcal/m,C ) and formation. Medard also described Its prepn and properties... 

Atropine, benztropine, dicyclomine, scopolamine, and trihexyphenidyl are all tertiary compounds. Tertiaiy amines do not carry a charge at physiologic pH, and thus will cross into the CNS and placenta. 

The cyclisation to 1,2,3-triazoles 158 ocurred after treatment with tosyl azide in the presence of a tertiaiy amine. Following removal of solvents, the treatment of the resin-bound 1,2,3-triazoles 158 with 60% TFA in CHjClj afforded triazoles 159 as trifluoroacetates salts in good purities. The mild reaction conditions used in this protocol enabled its application to building blocks with a large number of different functionalities. Only when using electron rich benzylic amines in the enamine forming step, mixtures of products were obtained. 

Reaction vtith imiues. The reaction of some acid chlorides with an imine in the presence of a tertiaiy amine often leads to a lactam. The reaction of acetyl chloride, however, follows a different course, and an oxazinone (2) is... 

The propagation reactions in tertiaiy amine initiated polymerizations can be pictured as follows ... 

Secondary amines such as piperidine, diethanolamine and imidazole are better anionic curing agents than tertiaiy amines. They first undergo addition to the epoxy group by means of their active hydrogens, then act as anionic initiators by formation of a quaternary amine with the CHj group to which the epoxy oxygen is attached. 

The use of cyclo and tertiaiy amines, salts, and ammonia catalysts offers the opportunity to thesize phenolic resins with a high stereoselectivity for the ortho position [68,69]. The nature of the catalyst controls the ratio of the substitution reactions at the ortho and para position. Substitution at the ortho position is preferred when the relatively stable intermediates shown in Scheme 3 are formed. Ortho/para-substitution ratio decreases from 1.1 at pH 8.7 to 0.38 at... 

Jagirdar and Sharma have employed tertiaiy amine extractants to recover and fractionate among several carboxylic acids in aqueous solution by means of dissociation extraction, in which a stoichiometrically deficient amount of extractant is used. Comparative equilibria for different carboxylic acids also are given by Niitsu and Sekine for TOPO-based solvents and by Wardell and King d for TBP, TOPO, and amines. 

Holeman, JA. Danielson, N.D. Microbore liquid chromatography of tertiaiy amine anticholinergic pharmaceuticals with tris(2,2 -bipyridine)ruthenium(IID chemiluminescence detection. J.Chromatogr. ScL, 1995, 33, 297-302... 

Other Bifunctional Tertiaiy Amine Thio(ureas)... 

Basic Tertiaiy amine (L) Alamine 308 Chloride (U I)2[CoCl4] [10]... 

A study of the effects of melittin on phospholipid membranes that included time-resolved fluorescence anisotropy measurements of l,6-diphenyl-l,3,5-hexatriene (DPH, the parent compoimd of TMA-DPH) incorporated into the membranes is described in (20). (Note TMA-DPH is now the preferred of the two probes as its cationic tertiaiy amine helps to anchor one end of the probe molecule to the bilayer-water interfece.)... 

Deshpande MC, Garnett MC, Vamvakaki M, Bailey L, Armes SP, Stolnik S (2002) firfluence of polymer architecture on the structure of complexes formed by PEG-tertiaiy amine methacrylate copolymers and phosphorothioate oligonucleotide. J Control Release 81 185-199... 

Sorokin and Shode investigated the reaction of epoxy with phenol in the presence of tertiaiy amines. The epoxy studied was l,2-epo -3-phenojg ropane (EPP), which is a short-chain monofunctional a-epoxide. The experiments were performed in solvent at 50°C. 

The first observation made was of a chemical reaction between the epoxy and the tertiaiy amine. Sorokin and Shode observed the formation of a quaternary ammonium phenoxide in stoichiometric concentrations of epoxy and amine, which was due to the reaction of the epoxy with the tertiary amine. No product of the epoxyphenol reaction was noted ... 

Elemental analysis of extraction residue was used to identify reaction products. Nearly all of the tertiaiy amine was converted into the quaternaiy ammonium phenoxide in 90-95% yield (based on the amine) at amine concentrations lower than or equal to the epojqr concentration. The product of the reaction between epoxy and phenol, l,3-diphenojq -2-propanol, was formed only when the initial amine concentration was less than the epojqr concentration. The yield of l,3-dipheno3Q -2-propanol was dictated by the difference between the initial epojqr and amine concentrations. Thus, their results indicate that the reaction of epoxy with phenol in the presence of tertiaiy amines must initially go through the stage in which the... 

Analysis of the reaction products showed that the reaction of epojqr with the tertiaiy amine, Rxns. 7 8, is preferred over formation of l,3-diphenoxy-2-propanol, Rxns. 9 Sc 10. Moreover, only the reaction of epoxy with the tertiary amine occurs at... 

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