Phosphorus oxychloride → HCID 67103715, compound

HRID 2080750Notes

Reaction equation

HRID 2080750 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][C:5]=1[NH2:14].[C:16]([O:20][C:21]([NH:23][CH2:24][CH2:25][CH2:26][CH:27]([NH:31][C:32]([O:34][CH2:35][CH:36]1[C:48]2[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=2[C:42]2[C:37]1=[CH:38][CH:39]=[CH:40][CH:41]=2)=[O:33])[C:28](O)=[O:29])=[O:22])([CH3:19])([CH3:18])[CH3:17].P(Cl)(Cl)(Cl)=O>N1C=CC=CC=1>[CH3:1][O:2][C:3](=[O:15])[C:4]1[CH:13]=[CH:12][C:7]([C:8]([O:10][CH3:11])=[O:9])=[CH:6][C:5]=1[NH:14][C:28](=[O:29])[CH:27]([NH:31][C:32]([O:34][CH2:35][CH:36]1[C:37]2[CH:38]=[CH:39][CH:40]=[CH:41][C:42]=2[C:43]2[C:48]1=[CH:47][CH:46]=[CH:45][CH:44]=2)=[O:33])[CH2:26][CH2:25][CH2:24][NH:23][C:21]([O:20][C:16]([CH3:19])([CH3:18])[CH3:17])=[O:22]

Participants

5

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 79336Dimethyl aminoterephthalateHCID 4276179HCID 4276179, compound

Product 1

HCID 67103715HCID 67103715, compoundYield 73.9%

Reagents, catalysts & solvents 1

HCID 1049PyridineSolvent

Conditions

Temperature
-15 °C

Procedure

In anhydrous pyridine (30 ml), 2-amino-terephthalic acid dimethyl ester (manufactured by Merck Ltd.) (1.46 g) and 5-t-butoxycarbonylamino-2-(9H-fluoren-9-ylmethoxycarbonylamino)-valeric acid (manufactured by Watanabe Chemical Industries, Ltd.) (3.18 g) were dissolved. The whole was cooled to −15° C. and added with phosphorus oxychloride (0.718 ml), followed by stirring at room temperature for 1 hour. After completion of the reaction, the whole was poured in ice-cold water and subjected to extraction with ethyl acetate. The extract was washed with a saturated aqueous sodium hydrogen carbonate solution and a saturated saline solution and dried with magnesium sulfate. After the solvent was distilled off, the resultant was subjected to azeotropic distillation with toluene. The residue was purified through silica gel column chromatography (chloroform/ethyl acetate), thereby obtaining the subject compound (3.33 g) as a white crystal.

Workup

  1. customAfter completion of the reaction
  2. additionthe whole was poured in ice-cold water
  3. extractionsubjected to extraction with ethyl acetate
  4. washThe extract was washed with a saturated aqueous sodium hydrogen carbonate solution
  5. dry with materiala saturated saline solution and dried with magnesium sulfate
  6. distillationAfter the solvent was distilled off
  7. distillationthe resultant was subjected to azeotropic distillation with toluene
  8. customThe residue was purified through silica gel column chromatography (chloroform/ethyl acetate)

Sources & evidence

ORD record
ord-466f3e1f59ec40b197af33a0d3f34951
Source dataset
uspto-grants-2011_04
Patent number
US07932281B2

Reaction notes

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