Triethylamine → HCID 86639776, compound

HRID 2095215Notes

Reaction equation

HRID 2095215 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][C:18]1[CH:23]=[CH:22][C:21]([OH:24])=[C:20]([CH:25]=[O:26])[CH:19]=1)[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(N(CC)CC)C.[P:34](Cl)([O:39][CH2:40][CH3:41])([O:36][CH2:37][CH3:38])=[O:35]>ClCCl>[CH2:1]([O:8][C:9]([NH:11][C@@H:12]([CH2:17][C:18]1[CH:23]=[CH:22][C:21]([O:24][P:34]([O:39][CH2:40][CH3:41])([O:36][CH2:37][CH3:38])=[O:35])=[C:20]([CH:25]=[O:26])[CH:19]=1)[C:13]([O:15][CH3:16])=[O:14])=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 13139Diethyl chlorophosphateHCID 11068278HCID 11068278, compound

Product 1

HCID 86639776HCID 86639776, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of 1.03 g 3C in 20 mL anhydrous dichloromethane in an ice-water bath were added 0.60 ml triethylamine and 0.48 mL diethyl chlorophosphate. The mixture was kept in the ice-water bath for 1 hour and then kept at room temperature overnight. After wash with water, with brine and drying with anhydrous sodium sulfate, the mixture was concentrated to an oily liquid and then purified by flash column chromatography (0.1% Et3N/20% EtOAc/CH2Cl2). The desired orthoformylated phosphotyrosine (3D) was obtained as colorless oil (1.21 g, 85%). 1H NMR (CDCl3, 200 MHz): δ 10.37 (s, 1H), 7.64 (s, 1H), 7.43-7.31 (m, 7H), 5.28 (d, J=7.7 Hz, 1H), 5.11 (s, 2H), 4.66 (m, 1H), 4.33-4.18 (m, 4H), 3.75 (s, 3H), 3.21 (dd, J1=14.1 Hz, J2=5.6 Hz, 1H), 3.09 (dd, J1=14.1 Hz, J2=6.1 Hz, 1H), 1.37 (m, 6H). 13C NMR (CDCl3, 50 MHz): δ 188.3, 171.4, 155.5, 152.0 (d), 136.5, 136.1, 133.4, 129.3, 128.6, 128.3, 128.1, 127.2 (d), 121.3, 67.1, 65.2 (d), 54.7, 52.6, 37.4, 16.1 (d). 31P NMR (CDCl3, 81 MHz): δ −6.4.

Workup

  1. washAfter wash with water, with brine
  2. dry with materialdrying with anhydrous sodium sulfate
  3. concentrationthe mixture was concentrated to an oily liquid
  4. custompurified by flash column chromatography (0.1% Et3N/20% EtOAc/CH2Cl2)

Sources & evidence

ORD record
ord-99908a4ed04b41deba4d365dcd2deb91
Source dataset
uspto-grants-2013_05
Patent number
US08445706B2

Reaction notes

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