2-Bromo-4-dimethylaminopyridine

Preparation 72 2-Bromo-N.N-dimethylpyridin-4-amine To a solution of 12.6 mL (125 mmol) of N, N-dimethylethanolamine in 160 mL of anhydrous hexane are added, under an argon atmosphere, at -5 C., over 2 hours 30 minutes, 100 mL (250 mmol) of 2.5 M n-butyllithium in hexane, and the reaction medium is then stirred for 30 minutes at 0 C., followed by addition of 7.6 g (62.5 mmol) of 4-dimethylaminopyridine. After stirring for 1 hour at 0 C., the reaction medium is cooled to -78 C. and 51.8 g (156.2 mmol) of carbon tetrabromide dissolved in 250 mL of anhydrous hexane are added over 2 hours 30 minutes at -78 C. The temperature is allowed to rise to 0 C. and stirring is then continued for 1 hour 30 minutes.The medium is then hydrolysed with water (400 mL) and subsequently extracted with Et2O (400 mL) and DCM (2*400 mL). The combined organic phases are dried over Na2SO4, filtered and concentrated under reduced pressure. 6.4 g of Compounds of Formula VI can be synthesized in two steps, as shown in Scheme I below. As indicated, 2.00 g (9.95 mmol) of 16 To a suspension of the compound 87-la (38 mg, 0.132 mmol, 1.3 eq) and the compound 1 (40 mg, 0.101 mmol, 1 eq) in mix solvent of H20 (0.1 mL) and dioxane (1 mL) were added Pd(dppf)Cl2 (7 mg, 10 umol, 0.1 eq) and Na2C03 (38 mg, 0.355 mmol, 3.5 eq) in one portion under N2. The mixture was stirred at 80 C for 16 h. LCMS showed the starting material was consumed completely and one main peak with desired MS was detected. The reaction mixture was diluted with water (10 mL) and extracted with EA (10 mL * 3). The combined organic layers were concentrated under reduced pressure to give a residue. The residue was purified by prep-HPLC. LCMS and XH NMR confirmed the Compound 87 (5.88 mg, 15 umol, 14.9% yield). LCMS (ESI): RT = 0.642 min, mass calcd. For C20H28N4O2S, 388.19 m/z found 389.1 [M+H]+. lH NMR (400MHz, CDC13) delta 8.60 (br d, J = 6.00 Hz, 1H), 8.22 (d, J = 6.00 Hz, 1H), 7.90 (d, J = 2.00 Hz, 1H), 7.63 (dd, J= 2.40, 8.80 Hz, 1H), 6.77 (d, J = 2.40 Hz, 1H), 6.71 (d, J = 8.80 Hz, 1H), 6.48 (dd, J= 2.40, 6.00 Hz, 1H), 4.40 - 4.27 (m, 1H), 3.49 - 3.35 (m, 1H), 3.07 (s, 6H), 2.60 (d, J = 5.60 Hz, 3H), 2.06 - 1.99 (m, 2H), 1.81 - 1.71 (m, 2H), 1.62 - 1.57 (m, 1H), 1.49 - 1.31 (m, 5H).1.0 equivalent of Intermediate A3, 1.0 equivalent of To a vial containing

Molecular Weight:201.06
XLogP3:2
Hydrogen Bond Acceptor Count:2
Rotatable Bond Count:1
Exact Mass:199.99491
Monoisotopic Mass:199.99491
Topological Polar Surface Area:16.1
Heavy Atom Count:10
Complexity:106
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes