3-Fluorophenol → HCID 13039288, compound

HRID 1106343Notes

Reaction equation

HRID 1106343 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:11][CH2:10][C@@H:9]([OH:12])[C@H:8]([C:13]2[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=2)[CH2:7]1)=[O:5])[CH3:2].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[F:38][C:39]1[CH:40]=[C:41](O)[CH:42]=[CH:43][CH:44]=1.N(C(OCC)=O)=NC(OCC)=O>C1C=CC=CC=1.CCOCC>[CH2:1]([O:3][C:4]([N:6]1[CH2:11][CH2:10][C@H:9]([O:12][C:43]2[CH:42]=[CH:41][CH:40]=[C:39]([F:38])[CH:44]=2)[C@H:8]([C:13]2[CH:14]=[CH:15][CH:16]=[CH:17][CH:18]=2)[CH2:7]1)=[O:5])[CH3:2]

Participants

7

Reactant 4

HCID 97433-FluorophenolHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 13039299HCID 13039299, compound

Product 1

HCID 13039288HCID 13039288, compound

Reagents, catalysts & solvents 2

HCID 241BenzeneSolvent2×HCID 3283Diethyl EtherSolvent

Procedure

To a mixture of 6.23 g of trans-1-ethoxycarbonyl-3-phenyl-4-piperidinol, 7.21 g of triphenylphosphine and 2.49 ml of m-fluorophenol in 250 ml of anhydrous benzene is added dropwise under nitrogen at 5° C. over a 90 minute period a solution of 4.79 g of diethyl azodicarboxylate in 250 ml of benzene. After the addition is complete the mixture is stirred overnight at room temperature. The solid is filtered, washed with benzene, and the filtrate is concentrated in vacuo to a gum. The gum is triturated overnight in a stoppered flask with 250 ml of hexane. The solid is filtered and washed with hexane. The filtrate is washed with 10% aqueous sodium hydroxide solution (3×75 ml), water (2×100 ml), saturated sodium chloride solution (100 ml) and dried overnight over anhydrous sodium sulfate. Filtration and concentration in vacuo affords a light yellow oil. Chromatography of the oil on 430 g of silica gel, using 2:1 (petroleum ether:ether), affords a colorless, cloudy gum. Trituration of the gum with petroleum ether yields product as a colorless crystalline solid, mp 74°-76.5° C.

Workup

  1. additionAfter the addition
  2. filtrationThe solid is filtered
  3. washwashed with benzene
  4. concentrationthe filtrate is concentrated in vacuo to a gum
  5. customThe gum is triturated overnight in a stoppered flask with 250 ml of hexane
  6. filtrationThe solid is filtered
  7. washwashed with hexane
  8. washThe filtrate is washed with 10% aqueous sodium hydroxide solution (3×75 ml), water (2×100 ml), saturated sodium chloride solution (100 ml)
  9. dry with materialdried overnight over anhydrous sodium sulfate
  10. filtrationFiltration and concentration in vacuo
  11. customaffords a light yellow oil
  12. customaffords a colorless, cloudy gum

Sources & evidence

ORD record
ord-c73dc3b3f0854aedb272caa72e3dd8c3
Source dataset
uspto-grants-1982_01
Patent number
US04312876

Reaction notes

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