Dichloromethane → HCID 18687729, compound

HRID 1872877Notes

Reaction equation

HRID 1872877 reaction equation
C[O:2][C:3]1[CH:4]=[CH:5][C:6]2[S:7][C:8]3[C:13]([O:14][C:15]=2[CH:16]=1)=[CH:12][CH:11]=[CH:10][CH:9]=3.C(Cl)Cl.B(Br)(Br)Br>CO>[CH:5]1[C:6]2[S:7][C:8]3[C:13](=[CH:12][CH:11]=[CH:10][CH:9]=3)[O:14][C:15]=2[CH:16]=[C:3]([OH:2])[CH:4]=1

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 25134Boron tribromideHCID 18687730HCID 18687730, compound

Product 1

HCID 18687729HCID 18687729, compoundYield 91.9%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

A stirred 3-methoxyphenoxathiin (3.00, 13.03 mmol) 25 ml CH2Cl2 was cooled to -70° C. under N2 and BBr3 (45.6 ml, 45.6 mmol, 1.0 M in CH2Cl2) was added dropwise over 1 h. The resulting bright, blue, heterogeneous mixture was allowed to warm to room temperature and stirred overnight. After 21 h the yellow homogeneous reaction is cooled to -60° C. and poured onto 300 mL MeOH at -60° C. After warming to room temperature the solution was concentrated in vacuo to a dark yellow oil which was purified by column chromatography (CH2Cl2 /hexane, gradient elution, 50:50 to 100:00) to give 2.59 g (91%) 3-phenoxathiinol as a white solid. TLC (CH2Cl2 /hexane 50:50) Rf =0.14; HPLC (Tr =14.2), 1H-NMR (CDCl3) δ 4.78 (s, 1H, --OH), δ 6.52 (d, J=8 Hz, 1H, C2 --H), δ 6.56 (s, 1H, C4 --H), δ 6.92-7.14 (m, 5H); MS m/z (relative intensity) 217 (MH+, 100).

Workup

  1. customAfter 21 h the yellow homogeneous reaction
  2. temperatureis cooled to -60° C.
  3. temperatureAfter warming to room temperature the solution
  4. concentrationwas concentrated in vacuo to a dark yellow oil which
  5. customwas purified by column chromatography (CH2Cl2 /hexane, gradient elution, 50:50 to 100:00)

Sources & evidence

ORD record
ord-441399dfac454256a3e145d5a0ae2a6f
Source dataset
uspto-grants-2000_08
Patent number
US06110961

Reaction notes

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