2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 178471561, compound

HRID 2230922Notes

Reaction equation

HRID 2230922 reaction equation
[CH3:1][C:2]([CH3:41])([CH3:40])[C:3]([NH:5][C:6]1[NH:7][C:8](=[O:39])[C:9]2[CH2:15][CH:14]([CH2:16][CH2:17][C:18]3[S:22][C:21]([C:23]([NH:25][C@H:26]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH2:27][CH2:28][C:29]([O:31][CH2:32][CH3:33])=[O:30])=[O:24])=[CH:20][CH:19]=3)[CH2:13][NH:12][C:10]=2[N:11]=1)=[O:4].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>ClCCl>[CH3:41][C:2]([CH3:1])([CH3:40])[C:3]([NH:5][C:6]1[NH:11][C:10]2[N:12]=[CH:13][C:14]([CH2:16][CH2:17][C:18]3[S:22][C:21]([C:23]([NH:25][C@H:26]([C:34]([O:36][CH2:37][CH3:38])=[O:35])[CH2:27][CH2:28][C:29]([O:31][CH2:32][CH3:33])=[O:30])=[O:24])=[CH:20][CH:19]=3)=[CH:15][C:9]=2[C:8](=[O:39])[N:7]=1)=[O:4]

Participants

4

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 135487828HCID 135487828, compound

Product 1

HCID 178471561HCID 178471561, compoundYield 87.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Dichloromethane (350 mL) was added to the 2:3 mixture of R-L and S-L diastereomers of N-[[5-[2-[2-[(2,2-dimethyl-1-oxopropyl)amino)-3,4,5,6,7,8-hexahydro-4-oxopyrido-(2,3-d)-pyrimidin-6-yl]ethyl]-2-thienyl]carbonyl]-L-glutamic acid, diethyl ester (17.0 g, 28.9 mmole) from Preparation 9 and stirred 30 minutes until a light yellow solution formed. As a solid, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) (13.4 g, 59.2 mmol) was added. The solution initially turned purple, then with 30 minutes stirring at room temperature it transitioned to a light pink mixture. A pink solid was removed by filtration, washing three times with dichloromethane (25 mL). The filtrate was stirred three times for 30 minutes with a saturated solution of sodium bicarbonate (200 mL) and separated. The final organic layer was stirred for 30 minutes with sodium bicarbonate (100 mL) and water (100 mL) then separated. The organic layer was washed with brine (100 mL) and dried over magnesium sulfate. Removal of the solvent at reduced pressure gave 14.7 g (87.1%) of the title compound. mp 57° C.-87° C. IR(CHCl3): 3690-3025, 2978, 3000, 1736, 1677, 1629, 1558, 1449, 1245, 1147, 1022, 811 cm−1. MS(HR) calculated for C28H35N5O7S: 586.234100. Found: 586.233546.

Workup

  1. customfrom Preparation 9
  2. customformed
  3. stirringThe solution initially turned purple, then with 30 minutes stirring at room temperature it
  4. customA pink solid was removed by filtration
  5. washwashing three times with dichloromethane (25 mL)
  6. stirringThe filtrate was stirred three times for 30 minutes with a saturated solution of sodium bicarbonate (200 mL)
  7. customseparated
  8. stirringThe final organic layer was stirred for 30 minutes with sodium bicarbonate (100 mL) and water (100 mL)
  9. customthen separated
  10. washThe organic layer was washed with brine (100 mL)
  11. dry with materialdried over magnesium sulfate
  12. customRemoval of the solvent at reduced pressure

Sources & evidence

ORD record
ord-fdab5e06a8d749fc91dd8df03083642b
Source dataset
uspto-grants-2002_07
Patent number
US06426417B1

Reaction notes

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