Triethylamine amines

Figure Bl.16.9. Background-free, pseudo-steady-state CIDNP spectra observed in the photoreaction of triethylamine with different sensitizers ((a), antliraquinone (b), xanthone, CIDNP net effect (c), xanthone, CIDNP multiplet effect, amplitudes multiplied by 1.75 relative to the centre trace) in acetonitrile-d3. The stmctiiral formulae of the most important products bearing polarizations (1, regenerated starting material 2, N,N-diethylvinylamine 3, combination product of amine and sensitizer) are given at the top R denotes the sensitizer moiety. The polarized resonances of these products are assigned in the spectra. Reprinted from [21].

Chapter IV. a-Chloromethylnaphthalene (IV,23) benzylamine (Gabriel synthesis) (IV,39) i r.N -dialkylanilines (from amines and trialkyl orthophosphates) (IV,42) a-naphthaldehyde (Sommelet reaction) (IV,120) a-phenyl-cinnamic acid (Perkin reaction using triethylamine) (IV,124) p-nitrostyrene (IV,129) p-bromonaphthalene and p naphthoic acid (from 2 naphthylamine-1 -sulphonic acid) (IV,62 and IV,164) diphenic acid (from phenanthrene) (IV,165). 

Note. 3. All glassware of the distillation apparatus must be rinsed before use with a dilute solution of triethylamine Or another volatile amine in diethyl ether. Traces of acid on the glass walls may cause isomerization to H2C=CH-C(OCH3)=C(CH3)(OC2H5). 

To illustrate the specific operations involved, the scheme below shows the first steps and the final detachment reaction of a peptide synthesis starting from the carboxyl terminal. N-Boc-glycine is attached to chloromethylated styrene-divinylbenzene copolymer resin. This polymer swells in organic solvents but is completely insoluble. ) Treatment with HCl in acetic acid removes the fert-butoxycarbonyl (Boc) group as isobutene and carbon dioxide. The resulting amine hydrochloride is neutralized with triethylamine in DMF. 

Carbonyl sulfonyl fluorides of the formula FC0(CF2) S02F have been prepared by electrochemical fluorination of hydrocarbon sultones (41,42). More commonly in a technology pioneered by Du Pont, perfluoroalkanecarbonyl sulfonyl fluorides are prepared by addition of SO to tetrafluoroethylene followed by isomerization with a tertiary amine such as triethylamine (43). 

N -Heterocyclic Sulfanilamides. The parent sulfanilamide is manufactured by the reaction of A/-acetylsulfanilyl chloride with excess concentrated aqueous ammonia, and hydrolysis of the product. Most heterocycHc amines are less reactive, and the condensation with the sulfonyl chloride is usually done in anhydrous media in the presence of an acid-binding agent. Use of anhydrous conditions avoids hydrolytic destmction of the sulfonyl chloride. The solvent and acid-binding functions are commonly filled by pyridine, or by mixtures of pyridine and acetone. Tertiary amines, such as triethylamine, may be substituted for pyridine. The majority of A/ -heterocycHc sulfanilamides are made by simple condensation with A/-acetylsulfanilyl chloride and hydrolysis. 

A variation of this procedure is used for sulfisomidine because of the different character of the amino group in the 4-position of a pyrimidine ring. Two moles of the sulfonyl chloride are condensed with one mole of 4-amino-2,6-dimethy1pyrimidine in the presence of triethylamine. The resulting bis(acetylsulfanilyl) derivative is readily hydrolyzed to the product. The formation of the bis(acetylsulfanilyl) derivative has also been employed for other heterocycHc amines, eg, for synthesis of sulfathiazole and sulfamoxole (44), but the 1 1 reaction is probably preferable. 

Reaction of ethyl chloride with an alcohoHc solution of ammonia yields ethylamine, diethylamine, triethylamine, and tetraethyl ammonium chloride (10,11) (see Amines, lower aliphatic). 

Benzyl chloride undergoes self-condensation relatively easily at high temperatures or in the presence of trace metallic impurities. The risk of decomposition during distillation is reduced by the use of various additives including lactams (43) and amines (44,45). Lime, sodium carbonate, and triethylamine are used as stabilizers during storage and shipment. Other soluble organic compounds that are reported to function as stabilizers in low concentration include DMF (46), arylamines (47), and triphenylphosphine (48). 

Ethylamines. Mono-, di-, and triethylamines, produced by catalytic reaction of ethanol with ammonia (330), are a significant outlet for ethanol. The vapor-phase continuous process takes place at 1.38 MPa (13.6 atm) and 150—220°C over a nickel catalyst supported on alumina, siUca, or sihca—alumina. In this reductive amination under a hydrogen atmosphere, the ratio of the mono-, di-, and triethylamine product can be controlled by recycling the unwanted products. Other catalysts used include phosphoric acid and derivatives, copper and iron chlorides, sulfates, and oxides in the presence of acids or alkaline salts (331). Piperidine can be ethylated with ethanol in the presence of Raney nickel catalyst at 200°C and 10.3 MPa (102 atm), to give W-ethylpiperidine [766-09-6] (332). 

Irradiation of 3,5-disubstituted isoxazoles in alcoholic solvents gave reaction products such as acetals incorporating the reaction solvent. The use of triethylamine in acetonitrile media produced ketene-aminals by reductive ring cleavage. The reductive ring cleavage product was also obtained by irradiation of the isoxazole in alcohol in the presence of copper(II) salts (Scheme 3) (76JCS(P1)783). 

The dibenzosuberyl ether is prepared from an alcohol and the suberyl chloride in the presence of triethylamine (CH2CI2, 20°, 3 h, 75% yield). It is cleaved by acidic hydrolysis (1 N HCl/dioxane, 20°, 6 h, 80% yield). This group has also been used to protect amines, thiols, and carboxylic acids. The alcohol derivative can be cleaved in the presence of a dibenzosuberylamine. ... 

CgFgOAc, DMF, 25°, 1-12 h, 78-91% yield. These conditions allow selective acylation of amines in the presence of alcohols. If triethylamine is used in place of DMF, alcohols are also acylated (75-85% yield). 

Tosylates are generally formed from an amine and tosyl chloride in an inert solvent such as CH2CI2 with an acid scavenger such as pyridine or triethylamine. 

The reaction times varied from 10 min to 18 hr. A=the correspondi ng phosphonii salt was used with the addition of two moles of triethyl amine. B=the corresponding phosphorane was used with the addition of one mole of triethylamine. 

Tertiary amines form a further important class of catalytic hardeners. For example, triethylamine has found use in adhesive formulations. Also of value are the aromatic substituted tertiary amines such as benzyldimethylamine and dimethyldiaminophenol. They have found uses in adhesive and coating applications. A long pot life may be achieved by the use of salts of the aromatic substituted amines. 

In recent years there has been some substitution of TDI by MDI derivatives. One-shot polyether processes became feasible with the advent of sufficiently powerful catalysts. For many years tertiary amines had been used with both polyesters and the newer polyethers. Examples included alkyl morpholines and triethylamine. Catalysts such as triethylenediamine ( Dabco ) and 4-dimethyla-minopyridine were rather more powerful but not satisfactory on their own. In the late 1950s organo-tin catalysts such as dibutyl tin dilaurate and stannous octoate were found to be powerful catalysts for the chain extension reactions. It was found that by use of varying combinations of a tin catayst with a tertiary amine... 

With more strongly basic tertiary amines such as triethylamine, another mechanism can come into play. It has been found that wften methanol deuterated on oxygen reacts with acyl chlorides in the presence of triethylamine, some deuterium is found a to the carbonyl group in the ester... 

Epichlorohydrin with bisphenol A. The curing agents may pose significant health hazards, e.g. amines (triethylamine, p-phenylenediamine, diethylenetriamine) or acid anhydrides (pyromellitic dianhydride)... 

A tertiary amine such as triethylamine is then added to the isocyanate-terminated prepolymer (containing carboxylic acid groups). The tertiary amine reacts with the pendant carboxylic acid groups, forming a carboxylic acid salt. The presence of this salt, together with adequate stirring, allows the dispersion of the prepolymer in water by the so-called melt dispersion process [57]. 

Chemical Designations - Synonyms 2,2 2"-Nitrilotriethanol Triethilolamine Trihydroxy-triethylamine Tris(hydroxyethy)amine Chemical Formula (HOCH2CH2)3N. 

The bases most commonly used to effect rearrangement are hydroxides, alkoxides, alcoholic sodium bicarbonate and, in some instances, amines. In the rearrangement of a series of l,l-dibromo-2-keto-alkanes, where a direct comparison has been made between triethylamine and sodium methoxide, the amine has given slightly better results ... 

Figure 3-14. Absorbance-time plots for the reaction of carbon suboxide and triethylamine in ether solution in the presence of acetic anhydride. The initial C3O2 concentration was 2.03 X I0 - M the amine concentrations were 3 X lO " M, 5 x 10 M, and 7 X lO " M.

Seyferth et al. (//O) have also synthesized N,N-diethyl-trichlorovinyl-amine (128, R CjHj) from the reaction of triethylamine and phenyl-(trichloromethyl)mercury (138). The best yield was 23 %, obtained when a benzene solution of the amine (45 mM) was added to a refluxing solution of phenyl(trichloromethyl)mercury (10 mM) in benzene. Although no mechanistic study was attempted because of the low yields and the intractable nature of the reaction mixture, the authors proposed the following mechanistic sequence ... 

Aliphatic sulfonyl chlorides that have a-hydrogen substituents, react with simple tertiary amines, such as trimethylamine, to generate sulfenes or perhaps their amine adducts 446). These species are suggested by the incorporation of one (but not more) deuterium atoms on reaction of sulfonyl chlorides with deuterated alcohols and triethylamine (447-450). A 2 1 adduct of sulfene and trimethylamine with proposed sulfonyl-sulfene structure could be isolated (451). 

The intramolecular variant, reported by Hegedus in 1976, expanded the scope to weakly nucleophilic amines. ort/io-Allylaniline 1 delivered 2-methyl indole in 84% yield using a stoichiometric amount of (CH3CN)2PdCl2 and triethylamine in THF via the intermediacy of 5. 

The synthesis of flavones has also seen modifications over the years. One of the primary modifications has been substituting the carboxylate salt for other bases. Kohn and Low showed that catalytic amounts of triethylamine allowed for the reaction to be run at 160 Looker and coworkers expanded on the Kohn and Low modification by using amines as the solvent, and thus reduced the reaction temperatures. They typically found that the reaction could be run at the refluxing temperatures of the amine. They showcased this modification by converting oi-methoxyphloroacetophenone (35) to the methyl ether of galangin (36) using a variety of amines in 60-75% yield with benzoic anhydride. 

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