1,1-Dichloroethane → HCID 178455055, compound

HRID 1007968Notes

Reaction equation

HRID 1007968 reaction equation
[Si:1]([O:8][C:9]1[CH:14]=[C:13]([O:15][Si:16]([C:19]([CH3:22])([CH3:21])[CH3:20])([CH3:18])[CH3:17])[CH:12]=[CH:11][C:10]=1[C@H:23]1[CH2:28][CH2:27][C@H:26]([NH2:29])[CH2:25][CH2:24]1)([C:4]([CH3:7])([CH3:6])[CH3:5])([CH3:3])[CH3:2].ClC(Cl)C.C(N(CC)CC)C.[N+:41]([C:44]1[CH:45]=[C:46]([CH:50]=[CH:51][CH:52]=1)[C:47](Cl)=[O:48])([O-:43])=[O:42]>O1CCCC1.ClCCl.CN(C)C1C=CN=CC=1.ClCCl.[OH-].[Na+]>[Si:1]([O:8][C:9]1[CH:14]=[C:13]([O:15][Si:16]([C:19]([CH3:20])([CH3:21])[CH3:22])([CH3:18])[CH3:17])[CH:12]=[CH:11][C:10]=1[C@H:23]1[CH2:24][CH2:25][C@H:26]([NH:29][C:47](=[O:48])[C:46]2[CH:50]=[CH:51][CH:52]=[C:44]([N+:41]([O-:43])=[O:42])[CH:45]=2)[CH2:27][CH2:28]1)([C:4]([CH3:5])([CH3:6])[CH3:7])([CH3:3])[CH3:2]

Participants

9

Reactant 4

HCID 63651,1-DichloroethaneHCID 8471TriethylamineHCID 8495Benzoyl chloride, 3-nitro-HCID 178455052HCID 178455052, compound

Product 1

HCID 178455055HCID 178455055, compoundYield 49%

Reagents, catalysts & solvents 4

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolventHCID 14798Sodium HydroxideSolventHCID 21919333Tetrahydrofurane dichloromethaneSolvent

Conditions

Temperature
40 °C

Procedure

To a round bottomed flask was added trans-4-(2,4-bis{[tert-butyl(dimethyl)silyl]oxy}phenyl)cyclohexylamine (80 mg) and dichloroethane (7 ml), and the reaction mixture heated to 40° C. To the stirred solution was added triethylamine (100 μl), a solution of 3-nitrobenzoyl chloride (101 mg) in tetrahydrofuran/dichloromethane (6 ml, 1:1 v/v) and 4-dimethylamino pyridine (catalytic). The reaction mixture was heated at 40° C. for 24 hr, and then room temperature for 24 hr. The reaction mixture was diluted with dichloromethane (20 ml) and aqueous sodium hydroxide (16 ml, 0.5M) was added. After stirring for 0.2 hr, the layers were separated and the aqueous layer extracted with dichloromethane (2×10 ml). The combined organic phases were washed with saturated sodium hydrogen carbonate solution (15 ml) and brine (16 ml), dried over magnesium sulfate, filtered and concentrated in vacuo. Purification via flash chromatography (SiO2, ethyl acetate/petroleum ether, gradient elution using 1:10, 1:8, 1:5, then 1:4, v/v) furnished the title compound (52 mg, 49%) as a colourless gum. δ6H (CDCl3): 0.18 (6H, s), 0.24 (6H, s), 0.97 (9H, s), 1.03 (9H, s), 1.34-1.61 (4H, m), 1.87-1.96 (2H, m), 2.17-2.27 (2H, m), 2.88 (1H, tt), 4.01-4.13 (1H, m), 6.08 (1H, d), 6.29 (1H, d), 6.43 (1H, dd), 6.97 (1H, d), 7.65 (1H, t), 8.18 (1H, d), 8.35 (1H, d), 8.57 (1H, s).

Workup

  1. temperatureThe reaction mixture was heated at 40° C. for 24 hr
  2. additionwas added
  3. customthe layers were separated
  4. extractionthe aqueous layer extracted with dichloromethane (2×10 ml)
  5. washThe combined organic phases were washed with saturated sodium hydrogen carbonate solution (15 ml) and brine (16 ml)
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customPurification via flash chromatography (
  10. washSiO2, ethyl acetate/petroleum ether, gradient elution

Sources & evidence

ORD record
ord-bf13119d0cf6450b97066dd7d1e572fc
Source dataset
uspto-grants-2004_09
Patent number
US06797731B2

Reaction notes

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