Pyridine → 3-Phenylthio-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic Acid, Diphenylmethyl Ester

HRID 2164581Notes

Reaction equation

HRID 2164581 reaction equation
[C:1]1([S:7][CH:8]2[CH2:14][CH:13]3[CH:10]([C:11](=[O:15])[CH2:12]3)[CH:9]2[C:16]([O:18][CH:19]([C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)=[O:17])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.N1C=CC=CC=1.S(Cl)(Cl)(=O)=O>C(Cl)Cl>[C:1]1([S:7][C:8]2[CH2:14][CH:13]3[CH:10]([C:11](=[O:15])[CH2:12]3)[C:9]=2[C:16]([O:18][CH:19]([C:26]2[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=2)[C:20]2[CH:21]=[CH:22][CH:23]=[CH:24][CH:25]=2)=[O:17])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 24648Sulfuryl chlorideHCID 134769543-Phenylthio-7-oxobicyclo[3.2.0]heptan-2-carboxylic acid, diphenylmethyl ester

Product 1

HCID 134769553-Phenylthio-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic Acid, Diphenylmethyl Ester

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A 500 mL, 3-neck flask fitted with an argon inlet, septum cap, thermometer, and stir bar was charged with 7.2 g of 3-phenylthio-7-oxobicyclo[3.2.0]heptan-2-carboxylic acid, diphenylmethyl ester, prepared by the procedure of Paragraph A, dissolved in 200 mL of methylene chloride. To this rapidly stirred solution at -65° was added 5.7 mL of pyridine in one portion, then 1.85 mL of sulfonyl chloride dropwise, slowly. This solution was stirred between -60° and -55° C. for 30 min and then it was poured onto water. The organic phase was washed again with water, then with brine dried over sodium sulfate and evaporated to dryness. The two major components of this mixture was separated on a Waters prep LC/System 500 liquid chromatograph by elution on 2 silica gel cartridges with methylene chloride. The second major component to be eluted was 3-phenylthio-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid, diphenylmether ester, 3.46 g (48.3%) as a colorless solid: NMR (220 MHz; CDCl3): δ 2.27 (1 H, dd, J=17, 3.5), 2.6-3.0 (3H, m), 3.18 (1H, ddd, J=17, 8, 4), 4.57 (1H, m), 6.84 (1H, s), and 7.0-7.5 (15H, m). The analytical sample, mp 148° to 150°, was prepared by recrystallization from benzene-ether.

Workup

  1. customA 500 mL, 3-neck flask fitted with an argon inlet
  2. customseptum cap
  3. customprepared by the procedure of Paragraph A
  4. stirringThis solution was stirred between -60° and -55° C. for 30 min
  5. additionit was poured onto water
  6. washThe organic phase was washed again with water
  7. dry with materialwith brine dried over sodium sulfate
  8. customevaporated to dryness
  9. customThe two major components of this mixture was separated on a Waters prep LC/System 500 liquid chromatograph by elution on 2 silica gel cartridges with methylene chloride
  10. washThe second major component to be eluted
  11. customThe analytical sample, mp 148° to 150°, was prepared by recrystallization from benzene-ether

Sources & evidence

ORD record
ord-afb19d467f4e4b69bf6c07ca55b7147a
Source dataset
uspto-grants-1985_03
Patent number
US04505905

Reaction notes

Loading…