Triphenylphosphine → HCID 178469088, compound

HRID 1035717Notes

Reaction equation

HRID 1035717 reaction equation
[OH:1][C@H:2]1[CH2:7][CH2:6][C@H:5]([C:8]([O:10][C:11]([CH3:14])([CH3:13])[CH3:12])=[O:9])[CH2:4][CH2:3]1.O[C:16]1[CH:26]=[CH:25][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:18][N:17]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>O1CCCC1>[C:11]([O:10][C:8]([C@@H:5]1[CH2:4][CH2:3][C@H:2]([O:1][C:16]2[CH:26]=[CH:25][C:19]([C:20]([O:22][CH2:23][CH3:24])=[O:21])=[CH:18][N:17]=2)[CH2:7][CH2:6]1)=[O:9])([CH3:14])([CH3:13])[CH3:12]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 178451169HCID 178451169, compoundHCID 178469094HCID 178469094, compound

Product 1

HCID 178469088HCID 178469088, compoundYield 45.7%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

1.63 g of tert-butyl trans-4-hydroxycyclohexanecarboxylate (8.14 mmol, 1 eq.) and 1.62 g of ethyl 6-hydroxynicotinate (10.58 mmol, 1.3 eq.) are placed in 24 mL of tetrahydrofuran at room temperature. 3.20 g of triphenylphosphine (12.21 mmol, 1.5 eq.) are added, followed by dropwise addition of 2.37 mL of diisopropyl azodicarboxylate (12.21 mmol, 1.5 eq.) to the reaction medium with stirring. After 1 hour at room temperature, the medium is concentrated to dryness and taken up in diethyl ether. The triphenylphosphine oxide is filtered off. The organic phase is washed successively with sodium hydroxide solution and than with water, dried over magnesium sulfate, filtered and evaporated to give a residue. This residue is chromatographed on silica gel, eluting with a gradient of ethyl acetate in heptane ranging from 3% to 30%. 1.3 g of ethyl cis-6-(4-tert-butoxycarbonylcyclohexyloxy)-nicotinate are obtained.

Workup

  1. concentrationthe medium is concentrated to dryness
  2. filtrationThe triphenylphosphine oxide is filtered off
  3. washThe organic phase is washed successively with sodium hydroxide solution and than with water
  4. dry with materialdried over magnesium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customto give a residue
  8. customThis residue is chromatographed on silica gel
  9. washeluting with a gradient of ethyl acetate in heptane ranging from 3% to 30%

Sources & evidence

ORD record
ord-77da375d2854454881ed7c089820d10b
Source dataset
uspto-grants-2013_10
Patent number
US08546391B2

Reaction notes

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