Benzyl Alcohol → HCID 11392118, compound

HRID 712095Notes

Reaction equation

HRID 712095 reaction equation
[CH3:1][O:2][C:3]([C@@H:5]1[C@H:10](C(O)=O)[CH2:9][CH:8]=[CH:7][CH2:6]1)=[O:4].C([N:16]([CH2:19]C)CC)C.C1C=CC([O:27]P(OC2C=CC=CC=2)(N=[N+]=[N-])=O)=CC=1.[CH2:40]([OH:47])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1>C1(C)C=CC=CC=1.CCOC(C)=O>[CH2:40]([O:47][C:19]([NH:16][C@H:10]1[C@@H:5]([C:3]([O:2][CH3:1])=[O:4])[CH2:6][CH:7]=[CH:8][CH2:9]1)=[O:27])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1

Participants

7

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 123414Diphenylphosphoryl azideHCID 53259071-Methyl (1S,2R)-4-cyclohexene-1,2-dicarboxylate

Product 1

HCID 11392118HCID 11392118, compoundYield 99.8%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

To a solution of (1R,6S)-6-(methoxycarbonyl)cyclohex-3-ene-1-carboxylic acid (5.0 g, 27 mmol) (from Alfa Aesar) in toluene (50.0 mL) stirring under N2 was added triethylamine (9.1 mL, 65 mmol) followed by diphenylphosphonic azide (5.85 mL, 27.1 mmol). The resulting mixture was stirred at 85° C. overnight (18 h). Benzyl alcohol (2.81 mL, 27.1 mmol) was added and the mixture heated to reflux (135° C.) and stirred overnight. After cooling, the mixture was diluted with EtOAc and then washed with sat. NaHCO3 (2×), water and brine. The organic layer was dried (Na2SO4), filtered, and concentrated. The residue was dried in vacuo to give 7.8 g of yellow oil. LCMS calculated for C16H20NO4 (M+H)+: m/z=290.1. Found: 290.0. 1H NMR (300 MHz, CDCl3) δ 7.38-7.27 (m, 5H), 5.62 (q, J=10.1 Hz, 2H), 5.39 (d, J=8.9 Hz, 1H), 5.07 (s, 2H), 4.28-4.19 (m, 1H), 3.66 (s, 3H), 2.81 (d, J=3.2 Hz, 1H), 2.56-2.12 (m, 4H) ppm.

Workup

  1. temperaturethe mixture heated
  2. temperatureto reflux (135° C.)
  3. stirringstirred overnight
  4. temperatureAfter cooling
  5. washwashed with sat. NaHCO3 (2×), water and brine
  6. dry with materialThe organic layer was dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was dried in vacuo

Sources & evidence

ORD record
ord-688b3712b8854b94a28ab48b7d61451a
Source dataset
uspto-grants-2015_11
Patent number
US09181271B2

Reaction notes

Loading…