Aniline → Benzenamine, N-propyl-

HRID 741634

Reaction equation

[NH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[C:8](OC(=O)CC)(=O)[CH2:9][CH3:10].[CH2:17]([N:20]1[C@H:25]([CH3:26])[CH2:24][N:23]([C@H:27]([C:42]2[CH:43]=[C:44]([CH:48]=[CH:49][CH:50]=2)[C:45](Cl)=[O:46])[C:28]2[CH:33]=[CH:32][CH:31]=[C:30]([O:34][Si](C(C)(C)C)(C)C)[CH:29]=2)[C@@H:22]([CH3:51])[CH2:21]1)[CH:18]=[CH2:19]>>[CH2:8]([NH:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH2:9][CH3:10].[CH2:17]([N:20]1[C@H:25]([CH3:26])[CH2:24][N:23]([C@H:27]([C:42]2[CH:43]=[C:44]([CH:48]=[CH:49][CH:50]=2)[C:45]([N:1]([C:2]2[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=2)[CH2:8][CH2:9][CH3:10])=[O:46])[C:28]2[CH:33]=[CH:32][CH:31]=[C:30]([OH:34])[CH:29]=2)[C@@H:22]([CH3:51])[CH2:21]1)[CH:18]=[CH2:19]

Participants

Reactant 3

HCID 6115Aniline

HCID 31263Propionic anhydride

HCID 111350383-((alphaR)-alpha-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-(tert-butyldimethylsilyloxy)benzyl)benzoyl chloride

Product 2

HCID 12153Benzenamine, N-propyl-

HCID 11005571(+)-3-((alphaR)-alpha-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-hydroxybenzyl)-N-phenyl-N-propylbenzamide

Procedure

N-Propylaniline was prepared from aniline and propionic anhydride, coupled with 3-((αR)-α-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-(tert-butyldimethylsilyloxy)benzyl)benzoyl chloride, deprotected and purified by the methods described in Example 10 to give (+)-3-((αR)-α-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-hydroxybenzyl)-N-phenyl-N-propylbenzamide as a light yellow solid. NMR (200 MHz, DMSO-d6): δ0.87 (t, J=7.4 Hz, 3H); 0.91 (d, J=5.9 Hz, 3H); 0.98 (d, J=6.0 Hz, 3H); 1.51 (m, 2H); 1.69 (dd, J1 =7.2 Hz, J2 =10.9 Hz, 1H); 2.06 (dd, J1 =7.0 Hz, J2 =10.5 Hz, 1H); 2.30 (d, J=10.3 Hz, 1H); 2.39-2.54 (m, 2H); 2.65 (br d, J=10.3 Hz, 1H); 2.85 (dd, J1 =7.4 Hz, J2 =14.5 Hz, 1H); 3.16 (dd, J1 =5.1 Hz. J2 =14.2 Hz, 1H); 3.79 (t, J=7.6 Hz, 2H); 4.77 (s, 1H); 5.12 (d, J=10.2 Hz, 1H); 5.18 (d, J=16.0 Hz, 1H); 5.71-5.84 (m, 1H); 6.43 (d, J=7.6 Hz, 1H); 6.57 (s, 1H); 6.64 (d, J=8.0 Hz, 1H); 7.02-7.33 (m, 10H); 9.32 (s, 1H). Mass spectrum (CI--CH4) m/e: 498 (M+1,100%), 344 (23%), 153 (80%), [α]D20 =+8.9° (ethanol, c=1.1). The free amine (0.585 g) was dissolved in ethanol and titrated with ethanolic hydrogen chloride to pH 4.0 followed by precipitation with diethyl ether from dichloromethane to give 0.479 g of the monohydrochloride salt as a hygroscopic off-white powder. Calc. for C32H39N3O2HCl 0.75 H2O: C, 70.18; H, 7.64; N, 7.67; Cl, 6.47. Found: C, 70.16; H, 7.73; N, 7.59; Cl, 6.51.

Workup

custompurified by the methods

Sources & evidence

ORD record: ord-178d6a68b2104e9282b54325948f5d6b
Source dataset: uspto-grants-1996_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05552404

Linked notes

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