Benzyl Alcohol → HCID 14654377, compound

HRID 981028Notes

Reaction equation

HRID 981028 reaction equation
[Br:1][CH:2]1[CH2:8][CH:7]([Br:9])[C:6](=[O:10])[O:5][C:3]1=[O:4].[CH2:11]([OH:18])[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1.C(Cl)(=O)C(Cl)=O.[C:25](O)([CH3:28])([CH3:27])[CH3:26].C(N(CC)CC)C>C1C=CC=CC=1.CN(C)C1C=CN=CC=1.C(Cl)Cl.CN(C=O)C.C(Cl)(Cl)Cl>[Br:9][CH:7]([CH2:8][CH:2]([Br:1])[C:3]([O:5][C:25]([CH3:28])([CH3:27])[CH3:26])=[O:4])[C:6]([O:18][CH2:11][C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1)=[O:10]

Participants

11

Reactant 5

HCID 244Benzyl AlcoholHCID 6386tert-ButanolHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 14654375HCID 14654375, compound

Product 1

HCID 14654377HCID 14654377, compoundYield 76%

Reagents, catalysts & solvents 5

HCID 142844-(Dimethylamino)pyridineCatalystHCID 241BenzeneSolvent2×HCID 6212ChloroformSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

2.18 g (8 mmol) of 2,4-dibromoglutaric anhydride, 0.83 ml (8 mmol) of benzyl alcohol, and 2 ml of chloroform are stirred for 1 hour at room temperature and for another hour under reflux. 20 ml of benzene and 0.1 ml of DMF are added, the solution is cooled in an ice bath, and 1.05 ml (12 mmol) of oxalyl chloride in 5 ml of benzene is added dropwise. Stirring is continued for 40 min. at 0° C. and 70 min. at room temperature, after which time gas evolution has virtually ceased. Volatiles are evaporated in vacuo, and the residue is taken up in 5 ml of CH2Cl2. This solution is added dropwise with ice cooling to a solution of 1.4 ml (15 mmol) of tert.-butanol, 1.4 ml (10 mmol) of triethylamine, and 19.5 mg (0.16 mmol) of 4-dimethylaminopyridine in 15 ml of CH2Cl2 . After stirring at 0° C. and room temperature for 20 min. each, the mixture is washed with aqueous KHSO4 solution, dried over MgSO4, evaporated, and filtered over silica gel to afford 2.65 g (76%) of benzyl t-butyl 2,4-dibromoglutarate. 1H NMR (CDCl3): δ7.37 (br. s., 5H), 5.22 (2 narrow AB systems, 2H), 1.48 (s, 9H); dl isomer: δ4.54 (t, 1H, J=7.5), 4.39 (t, 1H, J=7.5), 2.63 (t, 2H, J=7.5); meso isomer: δ4.44 (t, 1H, J=7.5), 4.26 (t, 1H, J=7.5), 2.83 (dt, 1H, J=7.5 (t), 15 (d)), 2.59 (dt, 1H, J=7.5 (t), 15 (d)); dl/meso=1:2. IR (neat): 2980, 1736, 1456, 1370, 1266, 1148, 843, 752, 696 cm- 1.

Workup

  1. temperatureunder reflux
  2. temperaturethe solution is cooled in an ice bath
  3. customVolatiles are evaporated in vacuo
  4. stirringAfter stirring at 0° C. and room temperature for 20 min. each, the mixture
  5. washis washed with aqueous KHSO4 solution
  6. dry with materialdried over MgSO4
  7. customevaporated
  8. filtrationfiltered over silica gel

Sources & evidence

ORD record
ord-29b0e92f502a4ac2a839e9f3b1168572
Source dataset
uspto-grants-1991_02
Patent number
US04990504

Reaction notes

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