1,1'-(Diazomethylene)bis(benzene) → 6,6-Dichloro-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid diphenylmethyl ester

HRID 2164578Notes

Reaction equation

HRID 2164578 reaction equation
[Cl:1][C:2]1([Cl:13])[C:8](=[O:9])[CH:7]2[CH:3]1[CH2:4][CH:5]=[C:6]2[C:10]([OH:12])=[O:11].[C:14]1([C:20]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[N+]=[N-])[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1>C(OCC)(=O)C>[C:14]1([CH:20]([O:11][C:10]([C:6]2[CH:7]3[CH:3]([CH2:4][CH:5]=2)[C:2]([Cl:13])([Cl:1])[C:8]3=[O:9])=[O:12])[C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

4

Reactant 2

HCID 612301,1'-(Diazomethylene)bis(benzene)HCID 134769516,6-Dichloro-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid

Product 1

HCID 134769526,6-Dichloro-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid diphenylmethyl esterYield 72%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

The crude 6,6-dichloro-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid (61 g) from Example 3 was stirred as a suspension in 300 mL of ethyl acetate and treated portionwise with 57 g of diphenyldiazomethane over a 45 min period. The resulting solution was stirred at room temperature for 1 hr. Evaporation of the solvent and trituration with ether afforded 76.9 g (71.9%) of 6,6-dichloro-7-oxobicyclo[3.2.0]hept-2-en-2-carboxylic acid diphenylmethyl ester. Material prepared by essentially the same procedure had the following characteristics: IR (Nujol mull): 1625, 1730, 1800 cm-1 ; NMR (CDCl3): δ 3.07 (1H, dddd, J=20, 8, 2, 2), 3.20 (1H, broad d, J=20), 3.64 (1H, ddd, J=8, 8, 2), 4.89 (1H, ddd, J=8, 4, 2), 6.86 (1H, s), 6.95 (1H, dd, J=4, 2), and 7.2-7.5 (10H, m). HRMS: Calcd for C21H16O3Cl2, 386.0475; found, 386.0495.

Workup

  1. customEvaporation of the solvent and trituration with ether

Sources & evidence

ORD record
ord-7c2584d145e648e690bf1e9a8243ee09
Source dataset
uspto-grants-1985_03
Patent number
US04505905

Reaction notes

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