1,2-Dichloroethane → Hydrochloric Acid

HRID 1984570Notes

Reaction equation

HRID 1984570 reaction equation
[O:1]=[C:2]1[C:7]([C:8]([NH:10][CH2:11][C:12]2[S:13][C:14]([S:17]([N:20]3[CH2:25][CH2:24][C:23](=O)[CH2:22][CH2:21]3)(=[O:19])=[O:18])=[CH:15][CH:16]=2)=[O:9])=[CH:6][CH:5]=[CH:4][NH:3]1.[F:27][C:28]([F:38])([F:37])[C:29]1[CH:36]=[CH:35][C:32]([CH2:33][NH2:34])=[CH:31][CH:30]=1.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].[Cl:53]CCCl>C(Cl)Cl>[O:1]=[C:2]1[C:7]([C:8]([NH:10][CH2:11][C:12]2[S:13][C:14]([S:17]([N:20]3[CH2:25][CH2:24][CH:23]([NH:34][CH2:33][C:32]4[CH:31]=[CH:30][C:29]([C:28]([F:27])([F:37])[F:38])=[CH:36][CH:35]=4)[CH2:22][CH2:21]3)(=[O:19])=[O:18])=[CH:15][CH:16]=2)=[O:9])=[CH:6][CH:5]=[CH:4][NH:3]1.[ClH:53]

Participants

7

Reactant 4

HCID 111,2-DichloroethaneHCID 768044-(Trifluoromethyl)benzylamineHCID 5049666Sodium triacetoxyborohydrideHCID 68998531HCID 68998531, compound

Product 2

HCID 313Hydrochloric AcidHCID 68659108HCID 68659108, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A suspension of the ketone 198b (2.33 g, 5.89 mmol, 1.0 eq), 4-(trifluoromethyl)benzylamine (0.98 g, 5.59 mmol, 0.95 eq) and NaBH(OAc)3 (1.62 g, 7.66 mmol, 1.3 eq) in 1,2-dichloroethane (70 ml) was stirred for at r.t. After 3 days, it was poured in CH2Cl2 (600 ml), rinsed with sat. aq. NaHCO3 (100 ml), dried (MgSO4), and concentrated. The colourless oily crude was dissolved in MeOH (100 ml) and treated with 2 ml fuming HCl (pre-diluted with 20 ml MeOH). After 30 seconds, a white precipitate started appearing. This was collected after 10 minutes by filtration to give the desired product as its HCl salt, and in excellent purity (1.6 g, 47% yield). Concentration of the filtrate to 10 ml afforded more precipitate (0.6 g, 17% yield). Mp=288-289° C., 1H NMR (DMSO-d6) δ 12.5 (s, 1H), 10.38 (t, J=6.0 Hz, 1H), 9.90-9.70 (br.s, 1.5H), 8.37 (dd, J=7.2 & 2.1 Hz, 1H), 7.85-7.70 (m, 5H), 7.48 (d, J=3.7 Hz, 1H), 7.16 (d, J=3.8 Hz, 1H), 6.49 (t, J=6.8 Hz, 1H), 4.73 (d, J=5.8 Hz, 2H), 4.24-4.16 (br s, 2H), 3.66 (d, J=11.7 Hz, 2H), 3.20-3.05 (br. m, 1H), 2.39 (t, J=11.3 Hz, 2H), 2.19 (d, J=10.7 Hz, 2H), 1.76 (qd, J=11.5, 3.2 Hz, 2H). 19F NMR (DMSO-d6)−61.64.

Workup

  1. washrinsed with sat. aq. NaHCO3 (100 ml)
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated
  4. dissolutionThe colourless oily crude was dissolved in MeOH (100 ml)
  5. additiontreated with 2 ml fuming HCl (pre-diluted with 20 ml MeOH)
  6. waitAfter 30 seconds
  7. filtrationThis was collected after 10 minutes by filtration

Sources & evidence

ORD record
ord-56263f811fec485da42768b0692d0dfe
Source dataset
uspto-grants-2009_06
Patent number
US07544700B2

Reaction notes

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