Dichloromethane → HCID 86617517, compound

HRID 2367130Notes

Reaction equation

[N+:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][C:11]=1[N+:12]([O-:14])=[O:13])[CH:7]=O)([O-:3])=[O:2].C(OC1(O[Si](C)(C)C)CC1)C.[N+]([C:29]1[CH:30]=[C:31]([CH:38]2[O:42]C(=O)C[CH2:39]2)C=CC=1[N+]([O-])=O)([O-])=O.[Cl:44]CCl>[Ti](Cl)(Cl)(Cl)Cl>[CH2:30]([CH2:31][C:38](=[O:42])[CH2:39][CH:7]([Cl:44])[C:6]1[CH:9]=[CH:10][C:11]([N+:12]([O-:14])=[O:13])=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)[CH3:29]

Participants

Conditions

Temperature: 0 °C

Procedure

3,4-Dinitrobenzaldehyde (634.5 mg, 3.24 mmol.) was taken into dichloromethane (20 mL) and the resulting solution was cooled to 0° C. under a nitrogen atmosphere. [(1-Ethoxycyclopropyl)oxy]trimethylsilane (0.85 mL, 4.21 mmol.) was added by syringe followed by addition of titanium tetrachloride (0.4 mL, 3.56 mmol.) and the resulting mixture was allowed to slowly warm to room temperature over 12 hours then stirred an additional 3 days. The solution was partitioned with water and the organic layer was dried over anhydrous sodium sulfate. Filtration and concentration followed by purification of the residue using silica gel flash chromatography (1:1 to 3:1 ethyl acetate:hexane eluent) gave a less polar fraction ethyl 4-chloro-4-(3,4-dinitrophenyl)butanone (379 mg, 37% yield) as an amorphous residue and 5-(3,4-dinitrophenyl)dihydrofuran-2(3H)-one as a more polar fraction (338 mg, 41% yield). 1H NMR (400 MHz, CDCl3): 7.98 (d, 1H), 7.96 (d, 1H), 7.80 (dd, 1H), 5.11 (dd, 1H), 4.15 (q, 2H), 2.66-2.50 (m, 2H), 2.42-2.28 (m, 2H), 1.27 (tr, 3H).

Workup

temperatureto slowly warm to room temperature over 12 hours
customThe solution was partitioned with water
dry with materialthe organic layer was dried over anhydrous sodium sulfate
filtrationFiltration and concentration
customfollowed by purification of the residue

Sources & evidence

ORD record: ord-19d285adaeb449ec8533c27567456d7d
Source dataset: uspto-grants-2014_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08697737B2

Reaction notes

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