Triethylamine → HCID 53752614, compound

HRID 1284895Notes

Reaction equation

HRID 1284895 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[N:7]=[CH:8][C:9]2[NH:10][C:11]3[CH:12]=[CH:13][C:14](I)=[CH:15][C:16]=3[C:17]=2[N:18]=1)=[O:5])[CH3:2].[P:20]([O-:27])(OCC)OCC.[CH2:28](N(CC)CC)[CH3:29].CN1CC[CH2:38][C:37]1=O>C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[CH2:1]([O:3][C:4]([C:6]1[N:7]=[CH:8][C:9]2[NH:10][C:11]3[CH:12]=[CH:13][C:14]([P:20]([CH2:37][CH3:38])([CH2:28][CH3:29])=[O:27])=[CH:15][C:16]=3[C:17]=2[N:18]=1)=[O:5])[CH3:2]

Participants

6

Reactant 4

HCID 8471Triethylamine2×HCID 13387N-methyl-2-pyrrolidoneHCID 3780918Diethylphosphite2×HCID 13321946HCID 13321946, compound

Product 1

HCID 53752614HCID 53752614, compound

Reagents, catalysts & solvents 1

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst2×

Conditions

Temperature
90 °C

Procedure

510 mg of 8-iodo-5H-pyrimido[5,4-b]indole-2-carboxylic acid ethyl ester (Example 13) is added to a mixture of 0.22 ml of diethyl phosphite, 0.22 ml of triethylamine, 120 mg of palladium tetrakis(triphenylphosphine) in 25 ml of N-methylpyrrolidone, and stirred under argon at 90° C. for 4 hours. After adding 0.22 ml of diethyl phosphite, 0.22 ml of triethylamine, and 120 mg of palladium tetrakis(triphenylphosphine), the mixture is once again heated for 3 hours to 90° C. After concentration at a bath temperature of 80° C. (oil pump), the residue is chromatographed over silica gel with the use of methylene chloride/ethanol=10:1 as the eluent. Recrystallization of the corresponding fractions from ethyl acetate/diisopropyl ether yields 131 mg of 8-diethylphosphoryl-5H-pyrimido[5,4-b]indole-2-carboxylic acid ethyl ester, mp 195°-197° C.

Workup

  1. temperaturethe mixture is once again heated for 3 hours to 90° C
  2. concentrationAfter concentration at a bath temperature of 80° C. (oil pump)
  3. customthe residue is chromatographed over silica gel with the use of methylene chloride/ethanol=10:1 as the eluent
  4. customRecrystallization of the corresponding fractions from ethyl acetate/diisopropyl ether

Sources & evidence

ORD record
ord-ace5dd2a39b44f42b7d666d56a0fbe60
Source dataset
uspto-grants-1986_01
Patent number
US04564610

Reaction notes

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