Triethylamine, purification

Triethylamine purification - if a blank absorbance is >0.01, reflux 100 mL ET3N with 20 mL HjO and 2 g Na hydrosulfite at least 8 hours. Wash with HjO, dry by distilling into a Dean-Stark trap, then distill, collecting the first 75 mL. Store over anhydrous Na2C03 or K2CO3. 

Triethylamine from Eastman Organic Chemicals was used without further purification. 

Intermediate 37 can be transformed into ( )-thienamycin [( )-1)] through a sequence of reactions nearly identical to that presented in Scheme 3 (see 22— 1). Thus, exposure of /(-keto ester 37 to tosyl azide and triethylamine results in the facile formation of pure, crystalline diazo keto ester 4 in 65 % yield from 36 (see Scheme 5). Rhodium(n) acetate catalyzed decomposition of 4, followed by intramolecular insertion of the resultant carbene 3 into the proximal N-H bond, affords [3.2.0] bicyclic keto ester 2. Without purification, 2 is converted into enol phosphate 42 and thence into vinyl sulfide 23 (76% yield from 4).18 Finally, catalytic hydrogenation of 23 proceeds smoothly (90%) to afford ( )-thienamycin... 

A solution of 1 equivalent of the oxazolidinone in diethyl ether is cooled to —78 C. To the resultant suspension are added 1.4 equivalents of triethylamine. followed by 1.1 equivalents of dibutylboryl triflate. The cooling bath is removed and the reaction mixture is stirred at 25 °C for 1.5 h. The resultant two-phase mixture is cooled to — 78 "C with vigorous stirring. After 1 equivalent of aldehyde is added, the reaction is stirred at —78 °C Tor 0.5 h, and 0 "C for 1 to 2 h. The solution is diluted with diethyl ether, washed with 1 N aq sodium bisulfate, and concentrated. Following oxidation with 30% aq hydrogen peroxide (10 equivalents, 1 1 methanol/water, 0 C. 1 h), extractive workup and chromatographic purification, the aldol adduct is obtained with >99% diastcrcomeric purity. 

A solution of 4.5 g (19.9 mmol) 4-(fm-butyldimethylsilyloxy)-2-cyclohexenone and 452 mg (1 mmol) of mercury(II) iodide is stirred at r.t. for 15 min and then cooled to — 78 °C. 5.03 g (24.8 mmol) of 1-ethoxy-1-(tm-bulyl(iimethylsilyloxy)ethene are added dropwise during 15 min. The mixture is stirred at — 78 °C for 2 h, quenched with 302 mg (3 mmol) of triethylamine and allowed to warm to r.t. The mixture is filtered through a short (3 cm) column of silica gel (deactivated with a 5% triethylamine solution in hexane/ethyl acetate, 10 1) eluting with hexane/ethyl acetate (10 1) and concentrated in vacuo. Purification of the crude material by flash chromatography (silica gel, hcxanc/cthyl acetate 30 1) gave the adduct as a colorless oil yield 7.98 g (18.7 mmol, 94%) d.r. (cisjtrans) 95.2 4.8. 

The peptide is removed from the resin by treating the peptide-containing resin with triethylamine in methanol for a longer time. Extensive column chromatography purification, however, is necessary in each case. 

In a typical procedure61144 the sulfonyl chloride in ether is added to an etheral solution of the diazoalkane and triethylamine. Filtration and evaporation gives the relatively pure thiirane dioxide. Further purification can be easily achieved by recrystallizations preferentially below room temperature in order to avoid fragmentation of the product into sulfur dioxide and the olefin. In general, when the temperature of the above reaction is lowered, the yields are improved without a drastic decrease in reactivity144. Many thiirane dioxides have been successfully synthesized through this method and a detailed list of them can be found elsewhere2. 

Hexen-l-ol and triethylamine were purchased from Acros Organics and used without further purification. Alternatively, 5-hexen-l-ol may be prepared from 2-(chloromethyl)tetrahydropyran according to the literature procedure for the preparation of 4-penten-l-ol (Brooks, L. A. Snyder, H. R. Org. Synth. Coll. Vol. Ill 1955, 698). Dichloromethane (certified ACS) was purchased from Fisher Scientific and was used as received. 

The alkanephosphonic acid dichlorides obtained by these methods are converted with amines, with all reactions carried out in solvents such as acetone, benzene, or diethyl ether at 10°C with triethylamine as HC1 captor. The conversion runs quantitatively followed by a purification with the help of column chromatography with chloroform/methanol in a ratio of 9 1 as mobile phase. The alkanephosphonic acid bisdiethanolamides could be obtained as pure substances with alkane residues of C8, C10, C12, and Ci4. The N-(2-hydroxyethane) alkanephosphonic acid 0,0-diethanolamide esters were also prepared in high purity. The obtained surfactants are generally stable up to 100°C. Only the alkanephosphonic acid bismonomethylamides are decomposed beneath this temperature forming cyclic compounds. 

Glycine ethyl ester hydrochloride, methyl formate, and triethylamine were purchased from Aldrich Chemical Company, Inc., and were used without purification. 

TLC has been traditionally regarded as a simple, rapid, and inexpensive separation method, currently used mainly for preliminary examinations to give an indication of the number and variety of pigments present and help in the selection of suitable separation and purification procedures for further analysis. To avoid epoxy-furanoid rearrangements caused by inherent silica gel acidify, one pellet of a strong alkali such as KOH or NaOH should be added to the water used to make the thin layer, or in case of ready commercial plates, 0.1% triethylamine (TEA) should be added to the mobile phase. 

Materials and Purification. Chemicals were purchased from Aldrich chemical company and used as received unless otherwise noted 1,1,1,3,3,3-hexamethyl disilazane, ethylene glycol, triphosgene, poly(ethylene oxide) (MW = 600), poly(tetramethylene oxide) (MW = 1000), poly(caprolactonediol) (MW = 530), toluene diisocyanate (TDI), anhydrous ethanol (Barker Analyzed), L-lysine monohydride (Sigma) and methylene bis-4-phenyl isocyanate (MDI) (Kodak). Ethyl ether (Barker Analyzer), triethylamine and dimethyl acetamide were respectively dried with sodium, calcium hydride and barium oxide overnight, and then distilled. Thionyl chloride and diethylphosphite were distilled before use. 

Both diastereomers are relatively reactive, complicating their isolation and purification. The half-lives of anti-and syn-BPDE in water at pH 7 are 2 hr and 30 min., respectively. Although they tend to decompose on chromatographic absorbants, these diol epoxides can be purified by rapid chromatography on low activity alumina columns or by HPLC in the presence of triethylamine as a stabilizer. 

The groups of Giacomelli and Taddei have developed a rapid solution-phase protocol for the synthesis of 1,4,5-trisubstituted pyrazole libraries (Scheme 6.194) [356]. The transformations involved the cyclization of a monosubstituted hydrazine with an enamino-/8-ketoester derived from a /8-ketoester and N,N-dimethylformamide dimethyl acetal (DMFDMA). The sites for molecular diversity in this approach are the substituents on the hydrazine (R3) and on the starting j3-keto ester (R1, R2). Subjecting a solution of the /8-keto ester in DMFDMA as solvent to 5 min of microwave irradiation (domestic oven) led to full and clean conversion to the corresponding enamine. After evaporation of the excess DMFDMA, ethanol was added to the crude reaction mixture followed by 1 equivalent of the hydrazine hydrochloride and 1.5 equivalents of triethylamine base. Further microwave irradiation for 8 min provided - after purification by filtration through a short silica gel column - the desired pyrazoles in >90% purity. 

Almqvist and coworkers have developed a two-step synthesis of optically active 2-pyridones via thiazolines (Scheme 6.216) [388]. Thus, heating a suspension of (R)-cysteine methyl ester hydrochloride with 2 equivalents of an imino ether and 2 equivalents of triethylamine base in 1,2-dichloroethane at 140 °C for 3 min furnished the desired thiazolines in near quantitative yield with limited racemization. Purification by filtration through a short silica gel column and concentration of the filtrate gave a crude product, which was used directly in the next step. Thus, after... 

In a separate study, Ohberg and Westman applied the same PS-DMAP in a one-pot microwave-induced base-catalyzed reaction of N-aryl and N-alkyl amino acids (or esters) and thioisocyanates for the library synthesis of thiohydantoins (Scheme 7.115) [136]. Thiohydantoins are of interest due to their ease of preparation and the range of biological properties associated with this heterocyclic ring system. The use of PS-DMAP as the base in this reaction gave slightly lower yields compared to when triethylamine (TEA) was used, but it resulted in a cleaner reaction mixture and an easier purification procedure. Cyclizations of a number of N-substituted... 

Triethylamine was obtained from Fisher Scientific Company and used without further purification. Acryloyl chloride was purchased from Aldrich Chemical Company and used without further purification. 

Triethylamine (puriss. p.a.) was purchased from Fluka A.G. and used without any purification. 

The methanol-triethylamine reagent is superior to the previously used methanolic sodium methoxide, and the crude 2-methoxycyclooctanone oxime thus obtained can be used for the Beckmann fission reaction without further purification. However, it is easily purified by distillation, b.p. 101° (0.7 mm.). 

Figure 13 Purification of pravastatin sodium by preparative liquid chromatography. Reprinted from [12], copyright 2001, with permission from Elsevier. (Column 125 X 4.6 mm i.d. 3 pm Hypersil ODS mobile-phase gradient methanol water triethylamine acetic acid 45 54.8 0.1 0.1 for 13 min, to 99.8 0 0.1 0.1 over 9 min flow rate 1.2 ml/min detector UV 235 nm.)...

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