4-Hydroxybenzoic Acid → HCID 21249025, compound

HRID 1194939Notes

Reaction equation

HRID 1194939 reaction equation
C(N(CC)CC)C.[N+:8]([C:11]1[CH:25]=[CH:24][C:14]([CH2:15][O:16][C:17]([NH:19][CH2:20][C:21]([OH:23])=[O:22])=[O:18])=[CH:13][CH:12]=1)([O-:10])=[O:9].ClC(OCC)=O.O[C:33]1[CH:41]=[CH:40][C:36]([C:37]([OH:39])=[O:38])=[CH:35][CH:34]=1>ClCCl>[N+:8]([C:11]1[CH:12]=[CH:13][C:14]([CH2:15][O:16][C:17]([NH:19][CH2:20][C:21]([O:23][C:33]2[CH:41]=[CH:40][C:36]([C:37]([OH:39])=[O:38])=[CH:35][CH:34]=2)=[O:22])=[O:18])=[CH:24][CH:25]=1)([O-:10])=[O:9]

Participants

6

Reactant 4

HCID 1354-Hydroxybenzoic AcidHCID 8471Triethylamine2×HCID 10928Ethyl chloroformateHCID 12187147N-(p-nitrobenzyloxycarbonyl)glycine

Product 1

HCID 21249025HCID 21249025, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Triethylamine (4 ml) was added to a suspension of N-(4-nitrobenzyloxycarbonyl)glycine (7.25 g) in dry dichloromethane at -20° C. Ethyl chloroformate (2.75 ml) was added to the resultant solution and the mixture stirred at -20° to -10° C. for 20 mins. A solution of 4-hydroxybenzoic acid (3.94 g) and triethylamine (4 ml) in dichloromethane (50 ml) was added dropwise, and stirring continued for 2.5 h after addition. The mixture was filtered, the filtrate washed with 10% aqueous citric acid (20 ml), water (20 ml), and brine (20 ml), and dried (MgSO4). Evaporation under reduced pressure afforded the crude product, 4-[N-(4-nitrobenzyloxycarbonyl)glycyloxy]benzoic acid as a pale yellow foam. Without further purification, 4-[N-(4-nitrobenzyloxycarbonyl)glycyloxy]benzoic acid was treated with chloromethylchlorosulphate (5.77 g) under the conditions described in Example 55b. After work-up and chromatography as described therein, the title compound was obtained as a white crystalline solid (1.81 g), m.p. 119°-120° C. (ethylacetate/hexane); νmax (CH2Cl2) 3450, 1780, 1740, 1610, and 1520 cm-1 ; δH (CDCl3) 4.33 (2H, d, J 6 Hz), 5.33 (2H, s), 5.72 (1H, br t, J 6 Hz), 6.03 (2H, s), 7.23-7.70 (4H, m), and 8.18-8.40 (4H, m).

Workup

  1. stirringstirring
  2. waitcontinued for 2.5 h
  3. additionafter addition
  4. filtrationThe mixture was filtered
  5. washthe filtrate washed with 10% aqueous citric acid (20 ml), water (20 ml), and brine (20 ml)
  6. dry with materialdried (MgSO4)
  7. customEvaporation under reduced pressure

Sources & evidence

ORD record
ord-9124b7cb67994230afb88cb68c97be96
Source dataset
uspto-grants-1989_03
Patent number
US04816452

Reaction notes

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