Citric Acid → HCID 86749456, compound

HRID 1721419Notes

Reaction equation

HRID 1721419 reaction equation
C(O[C:5]([NH:7]C[C@H]1CC[C@H](C(O)=O)CC1)=[O:6])C=C.[CH2:18]([N:20]([CH2:23][CH3:24])[CH2:21][CH3:22])[CH3:19].C1(P([N:39]=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[CH3:42][C:43]([CH3:46])([O-:45])[CH3:44].[Li+].C[C:49](C)([O-:51])C.[C:53](O)(=O)[CH2:54][C:55]([CH2:60][C:61](O)=O)(C(O)=O)O>C1C=CC=CC=1.C1COCC1>[C:43]([O:45][C:49]([NH:39][C@H:22]1[CH2:21][N:20]([CH2:23][CH:24]2[CH2:53][CH2:54][CH2:55][CH2:60][CH2:61]2)[C@H:18]([C:5]([NH2:7])=[O:6])[CH2:19]1)=[O:51])([CH3:46])([CH3:44])[CH3:42]

Participants

9

Reactant 6

HCID 311Citric AcidHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 45749132-Methylpropan-2-olateHCID 236647642-Propanol, 2-methyl-, lithium salt (1:1)HCID 178459855HCID 178459855, compound

Product 1

HCID 86749456HCID 86749456, compoundYield 82%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
45 °C

Procedure

A stirred solution of 15.0 g (62.2 mmol) of trans-4-allyloxycarbonylaminomethylcyclohexanecarboxylic acid in 550 mL of benzene and 9.1 mL (65.3 mmol) of triethylamine was heated to 45° C under Ar. Diphenylphosphoryl azide (14.1 mL, 65.3 mmol, Aldrich) was added in one portion, and the solution stirred for 24 h at 45° C. The solution was cooled to 10° C. and 65 mL of a 1.0M solution of lithium tbutoxide in THF (Aldrich) was added such that the reaction temperature remained between 8°-10° C. A second 65 mL portion of t-butoxide solution was added, and the solution stirred for 45° C at 8°-12° C. This solution was then poured into a rapidly stirred mixture of 1M aq. citric acid and ice, and the resulting mixture stirred for 1 h. This mixture was extracted with 2 portions of ethyl acetate, the combined organic layers washed with 2×10% Na2CO3, brine, and dried over Na2SO4. This solution was poured through a pad of 150 g of silica gel, and the pad washed with 2×300 mL of ethyl acetate. Evaporation of the filtrate gave 15.9 g (82%) of the title compound as a solid.

Workup

  1. temperatureThe solution was cooled to 10° C.
  2. customremained between 8°-10° C
  3. stirringthe solution stirred for 45° C at 8°-12° C
  4. stirringthe resulting mixture stirred for 1 h
  5. extractionThis mixture was extracted with 2 portions of ethyl acetate
  6. washthe combined organic layers washed with 2×10% Na2CO3, brine
  7. dry with materialdried over Na2SO4
  8. additionThis solution was poured through a pad of 150 g of silica gel
  9. washthe pad washed with 2×300 mL of ethyl acetate
  10. customEvaporation of the filtrate

Sources & evidence

ORD record
ord-cb817052c3754ae3b979be94861909fb
Source dataset
uspto-grants-1996_04
Patent number
US05510369

Reaction notes

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