Triethylamine.hydrochloride

The submitters report that both l,4-diazabicyclo[2.2.2]octane and triethylamine have been used to catalyze this decomposition. Tri-ethylamine was less satisfactory as a catalyst because of its relatively rapid reaction with the solvent, carbon tetrachloride, to form triethylamine hydrochloride and because of difficulty encountered in separating triethylamine from the dicarbonate pi oduct. The 1,4-diazabicyclo-[2.2.2]octane was efficiently separated from the dicarbonate product by the procedure described in which the crude product was washed with very dilute aqueous acid. 

During this time a heavy precipitate of triethylamine hydrochloride forms the mixture first becomes yellow and eventually brown in color. 

Acryloyl chloride (0.2 mol) in dry benzene (60 ml) was added over 0.5 hour with mechanical stirring to pentane-1,5-diol (0.1 mol), triethylamine (0.2 mol) and pyrogallol (0.1 g) in dry benzene (100 ml). Further dry benzene (ca 100 ml) was added followed by triethylamine (10 ml), and the mixture stirred at 50°C for 0.5 hour. The triethylamine hydrochloride was fii-tered off and the solvent removed In vacuo to leave a yellow oil which was distilled in the presence of a trace of p-methoxyphenol, excluding light, to give 1,5-pen tarn ethylene diacrylate (12.9g 61% BP90°to95°C/0,01 mm Hg),... 

A solution of 75 g (Mo mol) of 1,3-propanolamine and 202 g of triethylamine in 100 cc of absolute dioxane Is added dropwise at 25°C to 30°C while stirring well to a solution of 25.9 g (Vio mol) of N,N-bis-( -chloroethyl)-phosphorlc acid amide dichlorlde in 100 cc of absolute dioxane. After the reaction is complete, the product is separated from the precipitated triethylamine hydrochloride and the filtrate Is concentrated by evaporation In waterjet vacuum at 35°C. The residue Is dissolved in a large amount of ether and mixed to saturation with water. The N,N-bis-( -chloroethyl)-N,0-propylene phosphoric acid diamide crystallizes out of the ethereal solution, after it has stood for some time in a refrigerator, in the form of colorless water-soluble crystals. MP 48 C to 49°C. Yield 65% to 70% of the theoretical. 

Triethylamine hydrochloride is separated by filtration and the filter cake is washed with 100 cc of anhydrous ethyl alcohol. The alcohol and the excess of triethylamine is distilled off in a vacuum of a water pump. The residue represents a light-yellowish brown viscous oil which is extracted 3 times with 500 cc of anhydrous benzene each time with stirring at 40° to 60°C. The benzene is distilled off on a water bath at 60°C. Thus, an oil is obtained which solidifies to a hard mass after some hours. This mass is crushed and dried over PjOs in an exsiccator. The compound represents N,N -bis-(3-hydroxypropyl)homo-piperazine. Yield 128.5 grams. FP 46°-47°C BPo.o2mm 141°-142°C. 

To this acid was then added 1 g of 4-ethyl-2,3-dioxo-1-piperazinocarbonyl chloride (from the reaction of N-ethylethylenediamine and diethyl oxalate to give 2,3-dioxo-4-ethyl-piperazine which Is then reacted with phosgene) and the resulting mixture was reacted at 15°C to 20°C for 2 hours. After the reaction, a deposited triethylamine hydrochloride was separated by filtration, and the filtrate was incorporated with 0.4 g of n-butanol to deposit crystals. The deposited crystals were collected by filtration to obtain 1.25 g of white crystals of 6-[ D(—l-Ct-(4-ethyl-2,3-dioxo-1 -piperazinocarbonylaminolphenylacetamido] penicillanic acid. Into a solution of these crystals in 30 ml of tetrahydrofuran was dropped a solution of 0.38 g of a sodium salt of 2-ethyl-hexanoic acid in 10 ml of tetrahydrofuran, upon which white crystals were deposited. The deposited crystals were collected by filtration, sufficiently washed with tetrahydrofuran and then dried to obtain 1.25 g of sodium salt of 6-[D(—)-a-(4-ethyl-2,3-di-0X0-1-piperazinocarbonylaminolphenylacetamido] penicillanic acid, melting point 183°C to 185°C (decomposition), yield 90%. 

A 15.7 g (0.1 mol) of 2,6-dihydroxy methylpy rid in e hydrochloride are suspended in 176 ml of acetonitrile, and 20fi ml (0.15 mol) of triethylamine are added to the suspension. Thereafter 13 ml (0.22 mol) of methyl isocyanate are added dropwise to the reaction mixture at 20°C to 25°C. The reaction mixture is stirred at 20°C to 30°C for one hour, thereafter boiled for 3 hours, and finally the solvent is evaporated under reduced pressure. 35 to 40 g of a greyish, crystalline residue are obtained, which Is a mixture of 2,6-dihydroxymethylpyridine-bis-(N-methylcarbamate) and triethylamine hydrochloride. The obtained residue is dissolved in 80 ml of hot water, decolorized with 2 g of activated carbon when hot, and filtered after 30 minutes of stirring. The filtrate is cooled, the resulting crystal suspension is stirred at 0°C to 5°C for 3 hours, the solids are filtered off, and dried at 50°C to 60°C. 

A solution of 30.3 parts of triethylamine and 12.9 parts of ethylenimine in 180 parts of dry benzene is treated with a solution of 16.9 parts of thiophosphoryl chloride in 90 parts of dry benzene at 5°C to 10°C. Triethylamine hydrochloride is filtered off. The benzene solvent is distilled from the filtrate under reduced pressure and the resulting crude product is recrystallized from petroleum ether. The N,N, N"-triethylenethiophosphoramide had a melting point of 51.5°C. 

After the termination of the addition, the mixture is heated to boiling for another 6 hours. Thereafter, the reaction mixture is cooled down and allowed to stand overnight at about 0°C. The precipitated triethylamine hydrochloride is filtered off with suction. The resulting solution is evaporated, the residue (about 370 g) is triturated with about 3.2 liters of ether and is heated to boiling for a short period of time. 

The yield of triethylamine hydrochloride obtained in this and subsequent extractions amounts to over 96% of that expected. 

Merck s thienamycin synthesis commences with mono (V-silylation of dibenzyl aspartate (13, Scheme 2), the bis(benzyl) ester of aspartic acid (12). Thus, treatment of a cooled (0°C) solution of 13 in ether with trimethylsilyl chloride and triethylamine, followed by filtration to remove the triethylamine hydrochloride by-product, provides 11. When 11 is exposed to the action of one equivalent of tm-butylmagnesium chloride, the active hydrogen attached to nitrogen is removed, and the resultant anion spontaneously condenses with the electrophilic ester carbonyl four atoms away. After hydrolysis of the reaction mixture with 2 n HC1 saturated with ammonium chloride, enantiomerically pure azetidinone ester 10 is formed in 65-70% yield from 13. Although it is conceivable that... 

Aminobenzenethiol undergoes a Michael reaction with methyl 5,5-dimethyl-2-oxo-2,5-dihyd-rofuran-3-carboXylate (4) to give the adduct 5, which cyclizes to the tricyclic benzothiazepinone 6 under the influence of triethylamine hydrochloride.426... 

Example 17. Poly(m-phenylene isophthalamide) in solution.14 To a well-dried 250-mL four-necked straight-wall flange flask with nitrogen inlet/outlet, dropping funnel, and magnetic stirrer (Fig. 3.18a). 2.163 g of 1,3-phenylenediamine, 5.62 g of triethylamine, 5.506 g of triethylamine hydrochloride, and 36 mL of dry chloroform are added. Isophthaloyl chloride (4.06 g) in 14 mL of chloroform is then added through the dropping funnel over a 15-min period at 30° C with slow... 

To mention a few synthetic appHcations of trialkylsilanols, trimethylsilanol 4 adds readily to 2-chloroacrylonitrile in diethyl ether in the presence of triethylamine as triethylammonium trimethylsilanolate followed by ehmination of triethylamine hydrochloride to give 99 [32] (cf. discussion of the strongly nucleophihc properties of ammonium trimethylsilanolate 155 in Section 4.2.1). The stable potassium trimethylsilanolate 97 has also been used for the saponification of esters (Section 4.7). Dimethylphenylsilanol 100 adds readily to a,y9-unsaturated carbonyl compounds such as methyl vinyl ketone 764 in the presence of Pd(OAc)2 in a Heck-Suzuki-type reaction to give the sihcon-free /9-phenylmethylvinylketone 101 [33]. 

Ammonium molybdate 2076 reacts with TCS 14 in 1,2-dimethoxyethane at room temperature to give hexachloromolybdenium, which reacts in situ with amines such as aniline, ammonia or teit-butylamine in the presence of triethyla-mine to give chloroimino molybdates such as 2077, HMDSO 7, and triethylamine hydrochloride [9] (Scheme 13.3). 

Sulfonyl chlorides are added in the presence of copper(I)- or copper(II)-chloride exclusively however, mostly in the further presence of triethylamine hydrochloride especially in additions to conjugated systems . ... 

B. Mixed benzoic-carbonic anhydride (Note 7). In a 500-ml. threenecked flask, equipped with a low-temperature thermometer, an efficient sealed stirrer, and an adaptive joint carrying a drying tube and a dropping funnel, is placed a solution of 24.4 g. (0.2 mole) of benzoic acid (Note 8) and 20.2 g. (0.2 mole) of triethylamine (Note 9) in 200 ml. of dry toluene. The solution is cooled below 0° by means of an ice-salt mixture, and 21.7 g. (0.2 mole) of ethyl chlorocarbonate (Note 10) is added at such a rate that the temperature does not rise above 0° (approximate time for addition is 25-30 minutes). Triethylamine hydrochloride precipitates both during the addition and while the mixture is stirred for 15-25 minutes thereafter. 

In a 500-ml. three-necked flask equipped with a mechanical stirrer, a dropping funnel, and a reflux condenser fitted with a potassium hydroxide drying tube are placed 7.0 g. (0.069 mole) of triethylamine (Note 1) and a solution of 3.15 g. (0.075 mole) of diazomethane in 200 ml. of ether (Note 2). The flask is cooled in an ice bath, and a solution of 13.0 g. (0.052 mole) of D-cam-phor-10-sulfonyl chloride (Note 3) in 75 ml. of anhydrous ether is added dropwise over a period of 1 hour. Triethylamine hydrochloride slowly precipitates. The reaction mixture is stirred for an additional 30 minutes and then concentrated to ca. 150 ml. under reduced pressure (water aspirator) with continued stirring to remove the excess of diazomethane. The mixture is filtered under reduced pressure the precipitate is washed with 50 ml. of... 

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