Dimethylaminopyridine and

Dimethylaminopyridine and triethylamine were obtained from the Aldrich Chemical Company, Inc., and used without further purification. If 4-dimethylaminopyridine is omitted, the level of impurities rises.2... 

The molecular structures of [Cu(dipic)(4dmapy)] (where 4dmapy = 4-dimethylaminopyridine) and [Cu(dipic)(nmim)(H20)o 5] (where mnim = N-methylimidazole) are shown in Figure The structure of... 

The second protonation of dimethylaminopyridines and their N-oxides, all weak bases whose pK determination involves acidity function theory, yield o values in good agreement with previous values, affording thereby a check on the validity of the acidity function procedure. 

MHz of the MTPA ester that was prepared as follows The sample alcohol (0.1 mmol) was placed in a vial along with a solution of (+)-a-methoxy-a-trifluoromethylphenylacetyl chloride (0.15 mmol) in 1 mL of dichloromethane, triethylamine (0.15 mmol), and a crystal of 4-dimethylaminopyridine, and stirred at room temperature overnight. The excess acid chloride was treated with dimethylaminopropylamine (0.1 mmol). The MTPA ester was isolated in pure form after passing the mixture through a 5-g plug of silica gel and elution with 4 1 hexanes ethyl acetate. 

Catalytic amounts of 4-dimethylaminopyridine and a solution of 21.3 mmol of l-hydroxy-3-[(l-methyl-lH-imidazol-5-yl)methyl]-propan-2-one in 80 ml of CH2CI2 are added to a solution of 26.44 mmol of 2-diethylphosphonobutyric acid in 40 ml of purified CH2CI2. After cooling to 0°-5°C, a solution of 23.5 mmol of dicyclohexylcarbodiimide in 60 ml of CH2CI2 is added dropwise and the mixture is stirred for 1 h at 0°-5°C and for 2 h at 20°C. The crystallized... 

A solution of 15.7 g (92 mmol) of 2-isopropyl-4-(((N-methyl)amino)-methyl)thiazole in 200 ml of THF was combined with a solution of 20.5 g (69 mmol) of N-(((4-nitrophenyl)oxy)carbonyl)-L-valine methyl ester. The resulting solution was treated with 1.6 g of 4-dimethylaminopyridine and 12.9 ml (92 mmol) of triethylamine, heated at reflux for 2 h, allowed to cool, and concentrated in vacuo. The residue was taken up in CH2CI2, washed extensively with 5% aqueous K2C03, dried over Na2S04, and concentrated in vacuo. The resulting product mixture was purified by silica gel chromatography using chloroform as an eluent to provide 16.3 g (54%) of the desired compound. 

To a stirred suspension of 4.6 g (13.8 mmoles) of the (S)-3-(2-hydroxyethyl)-5-(2-oxo-l,3-oxazolidin-4- ylmethyl)-lH-indol-2-carboxylic acid ethyl ester in 42 ml of dichloromethane were added 4.2 ml of pyridine, 3.9 g (20.7 mmoles) oftosyl chloride and 170 mg (1.38 mmoles) of dimethylaminopyridine and the stirring continued at room temperature for 20 hours. The reaction mixture was poured over 20 ml of 3 N, HCI precooled to 0°C and extracted twice with dichlormethane. The organic phases were washed with brine, dried on anhydrous sodium sulphate and the solvent evaporated to dryness. The evaporated solid was crystallised with isopropyl alcohol to give 6.4 g (95%) of the title compound as a white crystalline solid. Melting point 166.4°-168.2°C. 

Such ionic species could also be detected in solution by 29Si NMR spectroscopy. Nucleophiles like TV-methylimidazole, pA M-dimethylaminopyridine and HMPA showed the strongest coordinating effects110. Mixtures of electrophilic trimethylsilyl compounds and nucleophiles(L), such as amines and amides, are common silylation agents111 and salts Me3SiL+X have been discussed as the active silylation species112. 

Bromination of 2-aminopyridine, 2-)V,)V-dimethylaminopyridine, and their 5-substituted derivatives (9.95) has been studied in detail [70J-CS(B)117]. All react as the free bases and logarithms of the true second-order rate coefficients (corrected to take account of the equilibrium con-... 

The entire Step 1 product was mixed with 4-dimethylaminopyridine and 239 g of methanol and then refluxed 20 hours. After cooling the mixture was neutralized with glacial acetic acid (0.133 mol) and precipitated in water. The precipitate was dissolved in acetone and then re-precipitated in water, the process being repeated three times. The precipitate was dried, and 102.8 g of polymer product were isolated, consisting of 70% p-hydroxystyrene and 30% 2-ethyl-2-adamantyl methacrylate with a of 8200 daltons and polydispersity of 1.68. 

Although strictly outside the remit of this chapter, it is appropriate to note continued activity in the chemistry of c X -p -bonded phosphorus compounds that do not possess a lone pair of electrons at phosphorus. A monomeric metaphosphonate species (262, X=0) has been stabilised by coordination via the P=0 bond), and Harger s group has provided evidence of the intermediacy of metathiophosphonates (262, X=S) in the reactions of phosphonami-dothioic acids with alcohols.The cation (263) has been stabilised by coordination at phosphorus with 4-dimethylaminopyridine and the reactivity of bis(methylene)phosphoranes (264) and related phosphoranylidene car-benoids has been investigated. ... 

It was decided that the most efficient method of identification was to couple succinic anhydride with the drug substance and isolate the peak of interest by preparative-scale HPLC. A solution of the drug substance was treated with dimethylaminopyridine and succinic anhydride. The resultant solution was stirred at room temperature for 48 hours. The reaction mixture was partitioned between ethyl acetate and water, and the aqueous layer was then treated with IN HC1. The two layers were shaken well, and the aqueous layer was removed. The organic layer was then washed with water, saturated sodium chloride solution, dried with magnesium sulfate, and concentrated by evaporation to afford a clear colorless oil (1.81 g). A suitable preparative HPLC method using a volatile mobile phase of 0.1% formic acid in water/ methanol was developed, and the crude reaction mixture was purified by preparative-scale HPLC. The solution was concentrated by evaporation and the water was removed from this solution by freeze-drying to afford a white lyophilate (40 mg). 

The effect of a halogen atom on the ring of 4-dimethylaminopyridine has been described. Amination of 3-bromo-4-dimethylaminopyridine with potassium amide under homogeneous conditions in liquid ammonia and without an oxidant afforded a 10% yield of 2-amino-5-bromo-4-dimethylaminopyridine and 3-amino-4-dimethylaminopyridine (32%) (87H2905). 

The report made in connection with a reaction between 1-dimethylaminoisoquinoline and Mel at 20° invites speculation. Quater-nization of the annular nitrogen atom results. This contrasts with reaction at the side chain of both 2-dimethylaminopyridine and 2-dimethylamiHoquinoline under similar conditions. Perhaps the neighboring peri-hydrogen causes the dimethylamino group to adopt a conformation that minimizes its steric effect and thereby allows the isoquinoline to react at the annular position. 

To a round bottom flask equipped with a modified Dean Stark trap, condenser, mechanical stirrer and nitrogen inlet, were added equimolar quantities of diamine and dianhydride as well as 0.5 wt % 4-N,N-dimethylaminopyridine and enough ODCB to provide an initial mixture containing 10% solids. The contents were heated for 6 hours at 180°C with azeotropic removal of water and distillation of ODCB such that the final polymer solution had a concentration of 20 to 25% solids. The polymer solution was cooled and precipitated twice into methanol, dried under vacuum (30 min) at 80°C for 12 hours and 170°C for 2 hours. 

Sample preparation Urine. Place 1 mL 100 ng/mL digitoxin in isopropanol in a tube and evaporate. Add 1 mL urine + 2 mL dichloromethane, shake by hand 4 times, centrifuge 1650 g. Remove organic layer and wash it twice wilii 2 mL 5% sodium bicarbonate solution, evaporate under nitrogen at 50°. Add 25 mg 4-dimethylaminopyridine and 10 p,L... 

Resorcinol monomethyl ether (3-methoxyphenol) upon treatment initially at 0°C with dichlorophenylborane, triethylamine and 4-dimethylaminopyridine, and then with propanal afforded after reaction during one and a half hours a 98% yield of the... 

AT-Alkylations can be conducted in strongly basic,or phase-transfer conditions" or in the presence of 4-dimethylaminopyridine," and it seems likely that under these conditions it is the pyrazolyl anion (section 22.4.1) which is alkylated. The use of sodium hydrogen carbonate, without solvent, but with microwave heating is highly recommended." ... 

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