Triethyl orthoacetate → HCID 58525654, compound

HRID 1962414Notes

Reaction equation

HRID 1962414 reaction equation
[F:1][C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:11]=1[C:10](=[O:12])[O:9][C:8](=[O:13])[CH2:7]2.[C:14](OCC)(OCC)([O:16][CH2:17][CH3:18])[CH3:15]>>[CH2:14]([O:16]/[C:17](=[C:7]1/[C:8](=[O:13])[O:9][C:10](=[O:12])[C:11]2[C:6]/1=[CH:5][CH:4]=[CH:3][C:2]=2[F:1])/[CH3:18])[CH3:15]

Participants

3

Reactant 2

HCID 66221Triethyl orthoacetateHCID 577334018-Fluoro-isochroman-1,3-dione

Product 1

HCID 58525654HCID 58525654, compoundYield 53.5%

Procedure

A suspension of 8-fluoro-isochroman-1,3-dione (7.125 g, 39.55 mmol) and triethyl orthoacetate (50.0 mL, 273 mmol) was heated to a gentle reflux during 5 min and reflux continued for 10 min. It was allowed to cool to r.t. with formation of crystalline product. It was cooled further on dry ice-EtOH bath, filtered, washed with cold ethanol (3×15 ml) and dried in vacuo (50° C., 30 min) to give 4.600 g of the title compound as a pink solid. The supernatant was evaporated and the purple oil residue was quenched with ethanol (20 ml) with formation of crystalline product, separated by filtration to give 693 mg more of the title product, total yield 53.5%. LC-MS (m/z) 251.2 (MH+), tR=1.05. 1H NMR (500 MHz, DMSO-d6): 1.41 (t, J=7.0 Hz, 3H, Me of Et), 2.68 (s, 3H, Me), 4.46 (q, J=7.0 Hz, 2H, CH2 of Et), 7.21 (dd, J=8.5 Hz, 10.7 Hz, 1H, C(7)-H), 7.72 (dt, J(d)=5.9 Hz, J(t)=8.3 Hz, 1H, C(6)-H), 8.08 (d, J=8.3 Hz, 1H, C(5)-H). 19F NMR (470.59 MHz): −110.2 ppm (dd, J=5.9 Hz, 10.7 Hz). 13C APT (125.76 MHz, DMSO-d6=39.89 ppm): 14.8 (CH3 of Et), 17.97 (CH3), 66.79 (CH2), 99.71 (C4), 109.04 (d, J=7.9 Hz, C9), 114.04 (d, J=20.6 Hz, CH, C7), 123.43 (d, J=3.3 Hz, CH, C5), 136.28 (d, J=10.5 Hz, CH, C6), 137.43 (s, C3=O), 157.22 (d, J=4.3 Hz, C1=O), 161.77 (C), 162.19 (d, J=262 Hz, C8), 178.45 (═C-OEt).

Workup

  1. temperaturewas heated to
  2. temperaturea gentle reflux during 5 min
  3. temperaturereflux
  4. temperatureIt was cooled further on dry ice-EtOH bath
  5. filtrationfiltered
  6. washwashed with cold ethanol (3×15 ml)
  7. customdried in vacuo (50° C., 30 min)

Sources & evidence

ORD record
ord-ff432374d34c44f3a0c736cedf28ac44
Source dataset
uspto-grants-2013_04
Patent number
US08415373B2

Reaction notes

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