1,2-Dichloroethane → tert-Butyl 2,2-dimethyl-5-((4-octylphenylamino)methyl)-1,3-dioxan-5-ylcarbamate

HRID 717619Notes

Reaction equation

HRID 717619 reaction equation
[CH2:1]([C:9]1[CH:15]=[CH:14][C:12]([NH2:13])=[CH:11][CH:10]=1)[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8].[CH:16]([C:18]1([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])[CH2:23][O:22][C:21]([CH3:25])([CH3:24])[O:20][CH2:19]1)=O.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].ClCCCl>CCOCC>[CH3:24][C:21]1([CH3:25])[O:20][CH2:19][C:18]([NH:26][C:27](=[O:33])[O:28][C:29]([CH3:32])([CH3:31])[CH3:30])([CH2:16][NH:13][C:12]2[CH:11]=[CH:10][C:9]([CH2:1][CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH3:8])=[CH:15][CH:14]=2)[CH2:23][O:22]1

Participants

6

Reactant 4

HCID 111,2-DichloroethaneHCID 853464-OctylanilineHCID 5049666Sodium triacetoxyborohydrideHCID 24754730Tert-butyl (5-formyl-2,2-dimethyl-1,3-dioxan-5-yl)carbamate

Product 1

HCID 66726563tert-Butyl 2,2-dimethyl-5-((4-octylphenylamino)methyl)-1,3-dioxan-5-ylcarbamateYield 71.3%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

To a mixture of 4-n-octylaniline (0.21 g; 1 mmol), tert-butyl 5-formyl-2,2-dimethyl-1,3-dioxan-5-ylcarbamate (Ooii et al, J. Org. Chem., 2004, 69, 7765; 0.26 g; 1 mmol) and NaBH(OAc)3 (0.3 g; 1.4 mmol) in 1,2-dichloroethane (3.5 ml) AcOH (0.06 ml; 1 mmol) was added at room temperature with stirring under N2. After stirring for 2 h, the mixture was diluted to 20 ml with Et2O, washed with 1.M NaOH (2×5 ml), brine and dried over anhydrous MgSO4 and filtered. The filtrate was evaporated to dryness under reduced pressure. The residue was dissolved in hexane (5 ml) and kept in the freezer (−18° C.) overnight. The crystals formed were filtered off, washed with small volume of hexane and dried to give the title compound (0.32 g; 71%), as colourless crystals. 1H-NMR (CDCl3) 6.96 (d, 2H, J=8.4 Hz); 6.58 (d, 2H, J=8.4 Hz); 4.84 (broad s, 1H); 4.01 (d, 2H, J=11.9); 3.85 (broad s, 1H); 3.8 (d, 2H, J=11.9 Hz); 3.44 (s, 2H); 2.46 (t, 2H, J=7.9 Hz); 1.5 (m, 2H); 1.45 (s, 3H); 1.43 (s, 9H); 1.42 (s, 3H); 1.26 (m, 10H); 0.86 (t, 2H, J=6.95 Hz).

Workup

  1. additionwas added at room temperature
  2. stirringAfter stirring for 2 h
  3. washwashed with 1.M NaOH (2×5 ml), brine
  4. dry with materialdried over anhydrous MgSO4
  5. filtrationfiltered
  6. customThe filtrate was evaporated to dryness under reduced pressure
  7. dissolutionThe residue was dissolved in hexane (5 ml)
  8. customkept in the freezer (−18° C.) overnight
  9. customThe crystals formed
  10. filtrationwere filtered off
  11. washwashed with small volume of hexane
  12. customdried

Sources & evidence

ORD record
ord-4d04086a581947df8cd7b30130cf04ae
Source dataset
uspto-grants-2015_11
Patent number
US09193716B2

Reaction notes

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