Pyridine → HCID 131719381, compound

HRID 1720945Notes

Reaction equation

HRID 1720945 reaction equation
O=[C:2]1[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH:3]1[CH2:14][CH2:15][C:16]([O:18][CH3:19])=[O:17].Cl.[CH2:21]([O:28][NH2:29])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.N1C=CC=CC=1>CCOCC>[CH2:21]([O:28][N:29]=[C:2]1[CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH:3]1[CH2:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

Participants

5

Reactant 3

HCID 1049PyridineHCID 102312Benzyloxyamine hydrochlorideHCID 588910HCID 588910, compound

Product 1

HCID 131719381HCID 131719381, compoundYield 92.4%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
140 °C

Procedure

A heavy walled reaction tube was charged with 3-(2-oxocyclododecyl)-propionic acid, methyl ester (6.0 g, 22.3 mmol), benzyloxyamine hydrochloride (3.99 g, 25 mmol), and pyridine (30 mL). The tube was sealed and heated in an oil bath at 140° C. for 2 hours. Upon cooling, the reaction mixture was diluted with ether (1L) and extracted with 2NN HCl until the aqueous layer was acidic, followed by extraction with water (2×50 mL). The organic phase was dried over magnesium sulfate, filtered through a silica gel plug, and the solvent removed in vacuo to afford 8.1 g (97%) of a crude oil. Purification by flash column chromatography on silica gel (100:1 ratio) and by elution with hexane/ethyl acetate (95/5) afforded 7.7 g (92% yield) of the title compound as a colorless oil with a 4:1 (E/Z) isomer ratio. 1H NMR (CDCl3, 400 Mhz) δ: 7.23-7.36 (m, 5H), 5.03 (s, 2H, (E) major isomer), 5.02 (s, 2H, (Z) minor isomer), 3.63 (s, 2.4H, (E) major isomer), 3.61 (s, 0.6H, (Z) minor isomer), 2.63 (ddd, J=13.3, 9.8, 4.8 hz, 1H), 2.36 (m, 1H), 2.24 (m, 2H), 2.05 (m, 1H), 1.75 -1.84 (m, 2H), 1.69 (m, 2H), 1.52-1.62 (m, 1H), 1.40-1.51 (m, 1H), 1.26 (m, 14H)

Workup

  1. customThe tube was sealed
  2. temperatureUpon cooling
  3. extractionextracted with 2NN HCl until the aqueous layer
  4. extractionfollowed by extraction with water (2×50 mL)
  5. dry with materialThe organic phase was dried over magnesium sulfate
  6. filtrationfiltered through a silica gel plug
  7. customthe solvent removed in vacuo
  8. customto afford 8.1 g (97%) of a crude oil
  9. customPurification by flash column chromatography on silica gel (100:1 ratio)
  10. washby elution with hexane/ethyl acetate (95/5)

Sources & evidence

ORD record
ord-db901785554d4a23802daf06686af5ef
Source dataset
uspto-grants-1996_04
Patent number
US05508302

Reaction notes

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