Dichloromethane → HCID 68775436, compound

HRID 1176962Notes

Reaction equation

HRID 1176962 reaction equation
[CH2:1]([O:13][C:14]1[CH:15]=[C:16]([C:33]2([CH:39]([C:41]3[CH:46]=[CH:45][C:44]([Br:47])=[CH:43][CH:42]=3)[OH:40])SCCCS2)[CH:17]=[CH:18][C:19]=1[O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12].BrN1C(=[O:54])CCC1=O.ClCCl>CC(C)=O.O.CC(C)=O>[CH2:1]([O:13][C:14]1[CH:15]=[C:16]([C:33](=[O:54])[C:39]([C:41]2[CH:46]=[CH:45][C:44]([Br:47])=[CH:43][CH:42]=2)=[O:40])[CH:17]=[CH:18][C:19]=1[O:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][CH3:32])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH3:12]

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 67184N-bromobutanimideHCID 86620323HCID 86620323, compound

Product 1

HCID 68775436HCID 68775436, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 18366337Propan-2-one--water (1/1)Solvent

Conditions

Temperature
0 °C

Procedure

A solution of [2-(3,4-bis-dodecyloxy-phenyl)-[1,3]dithian-2-yl]-(4-bromo-phenyl)-methanol (JYC-I-049-A). (10.99 g, 0.015 mol) in 400 mL of acetone was added dropwise to a solution of N-bromosuccinimide (NBS) (45.4 g, 0.255 mol) in 300 mL of 3% water/acetone (v/v) at 0° C. in an ice bath. The reaction mixture was stirred at 0° C. and gradually warmed up to room temperature over 30 min. The mixture was then poured into a saturated aqueous NaSO3 solution (400 mL) and dichloromethane (400 mL). The mixture was stirred for an additional 10 min. The organic layer was washed with water several times and dried over anhydrous MgSO4. The solvent was removed under reduced pressure to give a pale yellow solid. Purification was carried out by first recrystallization from hexanes, followed by column chromatography (silica gel, hexanes:dichloromethane=1:1 (v/v)) to afford two products. The major product, 1-(3,4-bis-dodecyloxy-phenyl)-2-(4-bromo-phenyl)-ethane-1,2-dione (JYC-I-053-B), was isolated as a yellow solid. (3.21 g, 33%). 1H NMR (200 MHz, CDCl3, δ): 7.81 (d, J=8.7 Hz, 2H), 7.62 (d, J=8.7 Hz, 2H), 7.54 (d, J=2.0 Hz, 1H), 7.39 (dd, J=2.0 Hz, 8.4 Hz, 1H), 6.83 (d, J=8.4 Hz, 1H), 4.04 (t, J=6.6 Hz, 2H), 4.03 (t, J=6.6 Hz, 2H), 1.82 (m, 4H), 1.20-1.52 (m, 40H), 0.85 (t, J=6.2 Hz, 6H). 13C{(H} NMR (50 MHz, CDCl3, δ): 193.60, 192.64, 155.37, 149.46, 132.30, 132.08, 131.24, 130.17, 126.22, 125.60, 112.13, 111.58, 69.23, 69.15, 31.91, 29.61, 29.36, 29.03, 28.88, 25.97, 25.90, 22.68, 14.10. HRMS-FAB (m/z): [M+H]+ calcd for C38H58BrO4, 657.3518; found, 657.3515. Anal. Calcd for C39H57BrO4: C, 69.39; H, 8.73. Found: C, 69.27; H, 8.71. The minor product, 1-(2-bromo-4,5-bis-dodecyloxy-phenyl)-2-(4-bromo-phenyl)-ethane-1,2-dione (JYC-I-053-A), was isolated as a white solid (0.31 g). 1H NMR (200 MHz, CDCl3, δ): 7.85 (d, J=8.6 Hz, 2H), 7.65 (d, J=8.6 Hz, 2H), 7.39 (s, 1H), 6.98 (s, 1H), 4.02 (t, J=6.6 Hz, 2H), 4.01 (t, J=6.6 Hz, 2H), 1.82 (m, 4H), 1.20-1.52 (m, 36H), 0.86 (t, J=6.4 Hz, 6H). HRMS-FAB (m/z): [M+H]+ calcd for C38H57Br2O4, 735.2624; found, 735.2638.

Workup

  1. temperaturegradually warmed up to room temperature over 30 min
  2. stirringThe mixture was stirred for an additional 10 min
  3. washThe organic layer was washed with water several times
  4. dry with materialdried over anhydrous MgSO4
  5. customThe solvent was removed under reduced pressure
  6. customto give a pale yellow solid
  7. customPurification
  8. customwas carried out by first recrystallization from hexanes
  9. customto afford two products

Sources & evidence

ORD record
ord-bc7d24ad755c4c07a9eced06fbb50a37
Source dataset
uspto-grants-2010_11
Patent number
US07842830B2

Reaction notes

Loading…