Diisopropylethylamine → S-Isopropyl 4-(3-bromoimidazo[1,2-b]pyridazin-6-yl)piperazine-1-carbothioate

HRID 870757Notes

Reaction equation

HRID 870757 reaction equation
CCN(C(C)C)C(C)C.[C:10](=[O:16])(Cl)[S:11][CH:12]([CH3:14])[CH3:13].[Br:17][C:18]1[N:22]2[N:23]=[C:24]([N:27]3[CH2:32][CH2:31][NH:30][CH2:29][CH2:28]3)[CH:25]=[CH:26][C:21]2=[N:20][CH:19]=1>C(OCC)(=O)C>[Br:17][C:18]1[N:22]2[N:23]=[C:24]([N:27]3[CH2:28][CH2:29][N:30]([C:10](=[O:16])[S:11][CH:12]([CH3:14])[CH3:13])[CH2:31][CH2:32]3)[CH:25]=[CH:26][C:21]2=[N:20][CH:19]=1

Participants

5

Reactant 3

HCID 81531DiisopropylethylamineHCID 13279441S-Isopropyl chlorothioformateHCID 866964323-Bromo-6-piperazin-1-yl-imidazo[1,2-b]pyridazine

Product 1

HCID 86696466S-Isopropyl 4-(3-bromoimidazo[1,2-b]pyridazin-6-yl)piperazine-1-carbothioateYield 78.5%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

Hunig's base [7087-68-5] (0.4 mL, 2.4 mmol), then S-isopropyl carbonochloridothioate [13889-93-5] (0.2 mL, 1.6 mmol) were added to a stirred, ambient temperature solution of 3-bromo-6-piperazin-1-yl-imidazo[1,2-b]pyridazine (450.0 mg, 1.6 mmol) in ethyl acetate (30 mL). Then rapidly formed suspension was stirred overnight, under N2 blanket, then washed with brine, dried (MgSO4), evaporated, and crystallized from ethyl acetate/heptane to afford 482.9 mg of white powder, mp. 186-187° C. 1H NMR (400 MHz, DMSO-d6) δ ppm 1.30 (d, J=6.82 Hz, 6H) 2.51 (dt, J=3.60, 1.86 Hz, 1H) 3.49-3.59 (m, 1H) 3.59-3.71 (m, 7H) 7.58 (d, J=9.85 Hz, 1H) 8.09-8.13 (m, 2H). 13C NMR (100 MHz, DMSO-d6) δ ppm 23.22, 35.48, 44.71, 101.63, 110.84, 113.71, 114.69, 116.58, 119.46, 123.56, 126.04, 134.22, 155.61, 157.77, 158.15, 158.53, 158.90, 166.18. LRMS (ESI) m/z 384.0/386.0 [(M+H)]+, calc'd for C14H15BrN6OS: 384.30.

Workup

  1. washwashed with brine
  2. dry with materialdried (MgSO4)
  3. customevaporated
  4. customcrystallized from ethyl acetate/heptane

Sources & evidence

ORD record
ord-f3fabef5445a4afe9f7f8e00209290c1
Source dataset
uspto-grants-2015_03
Patent number
US08969565B2

Reaction notes

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