Acetonitrile → Diisopropylethylamine

HRID 251092Notes

Reaction equation

HRID 251092 reaction equation
[CH3:1][C:2]1[C:3]([CH2:8][NH:9][CH2:10][C:11]2[C:16]([CH3:17])=[CH:15][CH:14]=[CH:13][N:12]=2)=[N:4][CH:5]=[CH:6][CH:7]=1.[C:18]([O:22][C:23](=[O:30])[NH:24][CH2:25]/[CH:26]=[CH:27]\[CH2:28]Cl)([CH3:21])([CH3:20])[CH3:19].[CH3:31]C#N>>[CH3:18][CH2:19][N:12]([CH:11]([CH3:10])[CH3:16])[CH:13]([CH3:14])[CH3:31].[C:18]([O:22][C:23](=[O:30])[NH:24][CH2:25]/[CH:26]=[CH:27]\[CH2:28][N:9]([CH2:10][C:11]1[C:16]([CH3:17])=[CH:15][CH:14]=[CH:13][N:12]=1)[CH2:8][C:3]1[C:2]([CH3:1])=[CH:7][CH:6]=[CH:5][N:4]=1)([CH3:21])([CH3:20])[CH3:19]

Participants

5

Reactant 3

HCID 6342AcetonitrileHCID 14395669t-butyl [(2Z)-4-chloro-2-buten-1-yl]carbamateHCID 45098010Bis-(3-methyl-pyridin-2-ylmethyl)-amine

Product 2

HCID 81531DiisopropylethylamineHCID 67272352{4-[Bis-(3-methyl-pyridin-2-ylmethyl)-amino]-cis-but-2-enyl}-carbamic acid tert-butyl ester

Procedure

Using General Procedure A: Reaction of bis-(3-methyl-pyridin-2-ylmethyl)-amine, (4-chloro-cis-but-2-enyl)-carbamic acid tert-butyl ester (Casara, P et al, J. Am. Chem. Soc. 1989, 111, 9111-9113), KI in anhydrous CH3CN and DIPEA gave {4-[Bis-(3-methyl-pyridin-2-ylmethyl)-amino]-cis-but-2-enyl}-carbamic acid tert-butyl ester. 1H NMR (CDCl3) δ 1.46 (s, 9H), 2.13 (s, 6H), 3.18 (d, 2H, J=6.0 Hz), 3.63 (t, 2H, J=6.0 Hz), 3.74 (s, 4H), 5.69 (br, 2H), 5.80 (br, 1H, (NH)), 7.08 (m, 2H), 7.39 (d, 2H, J=6.0 Hz), 8.38 (d, 2H, J=3.6 Hz). Conversion to the HBr salt using General Procedure D gave COMPOUND 234 (56 mg) as a light beige solid. 1H NMR (D2O) δ 2.49 (s, 6H), 3.45 (d, 2H, J=6.9 Hz), 3.59 (d, 2H, J=6.9 Hz), 4.31 (s, 4H), 5.69 (m, 1H), 5.94 (m, 1H), 7.85 (t, 2H, J=6.9 Hz), 8.36 (d, 2H, J=7.8 Hz), 8.59 (d, 2H, J=5.4 Hz). 13C NMR (D2O) δ 17.37 (2C), 36.60, 51.89, 54.10 (2C), 125.93, 126.18 (2C), 130.97, 137.94 (2C), 138.86 (2C), 148.65 (2C), 150.66 (2C). ES-MS m/z 297 (M+H). Anal. Calcd. for C18H24N4.3.4HBr.1.9H2O.0.2C4H10O: C, 36.39; H, 5.39; N, 9.03; Br, 43.78. Found: C, 36.61; H, 5.26; N, 9.00; Br, 43.49.

Sources & evidence

ORD record
ord-d2b49c37052a4d35ae3ace3793f3e299
Source dataset
uspto-grants-2011_01
Patent number
US07863293B2

Reaction notes

Loading…