Oxalyl chloride → HCID 86584593, compound

HRID 1356950Notes

Reaction equation

HRID 1356950 reaction equation
[C:1]([O:12][CH:13]1[CH:18]([CH:19]([CH3:21])[CH3:20])[CH2:17][CH2:16][CH:15]([CH3:22])[CH2:14]1)(=[O:11])[C:2]1[C:3](=[CH:7][CH:8]=[CH:9][CH:10]=1)[C:4]([O-])=[O:5].C(Cl)(=O)C(Cl)=O>>[OH:5][CH2:4][C:3]1[CH:7]=[CH:8][CH:9]=[CH:10][C:2]=1[C:1]([O:12][C@H:13]1[C@H:18]([CH:19]([CH3:21])[CH3:20])[CH2:17][CH2:16][C@@H:15]([CH3:22])[CH2:14]1)=[O:11]

Participants

3

Reactant 2

HCID 65578Oxalyl chlorideHCID 53249597HCID 53249597, compound

Product 1

HCID 86584593HCID 86584593, compoundYield 55%

Procedure

3.78 g (12.4 mmol) monomenthyl (−)-phthalate (Fluka) was heated at reflux in 19 ml oxalyl chloride (18 eq.) for 1.5 h. The excess oxalyl chloride was distilled under vacuum. 2.75 g crude acid chloride was then diluted in 5 ml THF cooled to −80 under argon, and 0.97 g (3 eq.) NABH4 was added. The reaction mixture was maintained under stirring at 0° for 10 min and at ambient temperature for 30 min. The mixture was then poured over cold 5% KHSO4 then extracted using diethyl ether. Chromatography of the crude product over silica gel (93:7 toluene/ether) yielded 1.85 g (55%) pure (1R,3R,4S)-3-p-menthanyl 2-hydroxymethylbenzoate in the form of a colourless oil.

Workup

  1. distillationThe excess oxalyl chloride was distilled under vacuum
  2. addition2.75 g crude acid chloride was then diluted in 5 ml THF
  3. temperaturecooled to −80 under argon
  4. addition0.97 g (3 eq.) NABH4 was added
  5. temperatureThe reaction mixture was maintained
  6. additionThe mixture was then poured over cold 5% KHSO4
  7. extractionthen extracted

Sources & evidence

ORD record
ord-060a984fa2614adbaa248e6b8c8725bb
Source dataset
uspto-grants-2003_07
Patent number
US06589921B2

Reaction notes

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