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

HRID 710279Notes

Reaction equation

HRID 710279 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>C(OCC)C>[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) acetic acid (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 diethyl ether (Et2O), washed with 1.M NaOH (2×5 ml), brine and dried over anhydrous MgSC4 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 pure title compound (0.32 g; 71%), as colourless crystals. 1H-NMR (CDCl3) 0.86 (tr, 2H, J=6.95 Hz); 1.26 (m, 10H, 1.42, (s, 3H); 1.43 (s, 9H); 1.45 (s, 3H); 1.5 (m, 2H); 2.46 (tr, 2H, J=7.9 Hz); 3.44 (5, 2H); 3.8 (d, 2H, J=11.9 Hz); 3.85 (broad s, 1H); 4.01 (d, 2H, J=11.9); 4.84 (broad s, 1H); 6.58 (d, 2H, J=8.4 Hz); 6.96 (d, 2H, J=8.4 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 MgSC4
  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-2e306b33bc9a44e6b3a270bdbc1255a5
Source dataset
uspto-grants-2015_11
Patent number
US09181182B2

Reaction notes

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