Carbon tetrabromide → HCID 58610149, compound

HRID 1592831Notes

Reaction equation

HRID 1592831 reaction equation
C(Br)(Br)(Br)[Br:2].[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([C@H:13]([C@@H:15]2[O:20][CH2:19][CH2:18][N:17]([CH2:21][C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)[CH2:16]2)O)=[CH:9][CH:8]=1.[Cl:28][C:29]1[CH:34]=[CH:33][C:32]([C@@H:35]([C@H:37]2[O:42][CH2:41][CH2:40][N:39]([CH2:43][C:44]3[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=3)[CH2:38]2)O)=[CH:31][CH:30]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>ClCCl>[Br:2][C@@H:13]([C:10]1[CH:11]=[CH:12][C:7]([Cl:6])=[CH:8][CH:9]=1)[C@@H:15]1[O:20][CH2:19][CH2:18][N:17]([CH2:21][C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)[CH2:16]1.[Br:2][C@H:35]([C:32]1[CH:33]=[CH:34][C:29]([Cl:28])=[CH:30][CH:31]=1)[C@H:37]1[O:42][CH2:41][CH2:40][N:39]([CH2:43][C:44]2[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=2)[CH2:38]1

Participants

7

Reactant 4

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 58610165HCID 58610165, compoundHCID 58610166HCID 58610166, compound

Product 2

HCID 58610149HCID 58610149, compoundHCID 58610170HCID 58610170, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A solution of carbon tetrabromide (2.82 g, 8.5 mmol) in dichloromethane (3 ml) was added dropwise over 10 min to a stirred solution of (R)-[4-chlorophenyl][(2R)-4-benzylmorpholin-2-yl]methanol and (S)-[4-chlorophenyl][(2S)-4-benzylmorpholin-2-yl]methanol (1.80 g, 5.67 mmol) and triphenylphosphine (2.23 g, 8.5 mmol) in dichloromethane (40 ml) at room temperature under nitrogen. After 30 min, the reaction solution was washed with saturated aqueous sodium bicarbonate (50 ml). The dichloromethane layer was dried, filtered and evaporated to a red liquid (8.5 g). Trituration with diethyl ether (20 ml) crystallised triphenylphoshine oxide that was then removed by filtration. The filtrate was evaporated to a yellow oil and was purified by chromatography on silica eluting with ethyl acetate:hexane 20:80 to give a colourless oil of (2R)-2-[(S)-bromo(4-chlorophenyl)methyl]-4-benzylmorpholine and (2S)-2-[(R)-bromo(4-chlorophenyl)methyl]-4-benzylmorpholine (1.17 g) that crystallised to a pink solid on standing.

Workup

  1. washthe reaction solution was washed with saturated aqueous sodium bicarbonate (50 ml)
  2. dry with materialThe dichloromethane layer was dried
  3. filtrationfiltered
  4. customevaporated to a red liquid (8.5 g)
  5. customTrituration with diethyl ether (20 ml) crystallised triphenylphoshine oxide that
  6. customwas then removed by filtration
  7. customThe filtrate was evaporated to a yellow oil
  8. customwas purified by chromatography on silica eluting with ethyl acetate:hexane 20:80

Sources & evidence

ORD record
ord-2969099119ed4978bd457deb7f1e3e96
Source dataset
uspto-grants-2007_11
Patent number
US07294623B2

Reaction notes

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