Benzaldehyde → Dalosirvat

HRID 1913483Notes

Reaction equation

C(N(CC)CC)C.[CH:8](=[O:15])[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[O:16]1[CH2:21][CH2:20][O:19][C:18]2[CH:22]=[C:23]([C:26](=[O:32])[CH2:27][CH2:28]N(C)C)[CH:24]=[CH:25][C:17]1=2>O1CCOCC1.[Br-].C([N+]1C(C)=C(CCO)SC=1)C>[O:16]1[CH2:21][CH2:20][O:19][C:18]2[CH:22]=[C:23]([C:26](=[O:32])[CH2:27][CH2:28][C:8]([C:9]3[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=3)=[O:15])[CH:24]=[CH:25][C:17]1=2

Participants

Conditions

Temperature: 95 °C

Procedure

Triethylamine (3.61 mmol) and benzaldehyde (4.3 mmol) in dry dioxane (10 mL) was added to a solution of 1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-(dimethylamino)propan-1-one (XVI) (5.4 mmol) and 3-ethyl-5-(2-hydroxyethyl)-4-methylthiazolium bromide (0.43 mmol) in dioxane heated at 95° C. under nitrogen. The solution was further heated overnight at 95° C. The solution was cooled and excess solvent was evaporated under vacuum. The residue was partitioned between CH2Cl2 and water. The organic phase was dried over MgSO4, filtered and concentrated. The residue was purified by flash chromatography eluting with ethyl acetate in hexane gradient to yield 1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-4-phenylbutane-1,4-dione 1 as a white solid (12% yield). 1H NMR (DMSO-d6, 400 MHz): δ ppm 3.33-3.37 (m, 4H), 4.29 (m, 2H), 4.34 (m, 2H), 6.98 (m, 1H), 7.48 (m, 1H), 7.55 (m, 3H), 7.64 (m, 1H), 8.00-8.02 (m, 2H); ESIMS found C18H16O4 m/z 297 (M+H).

Workup

temperatureThe solution was cooled
customexcess solvent was evaporated under vacuum
customThe residue was partitioned between CH2Cl2 and water
dry with materialThe organic phase was dried over MgSO4
filtrationfiltered
concentrationconcentrated
customThe residue was purified by flash chromatography
washeluting with ethyl acetate in hexane gradient

Sources & evidence

ORD record: ord-c032c9320e204b84bb64d908f5b04de4
Source dataset: uspto-grants-2013_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08609717B2

Reaction notes

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