Dimethylformamide → HCID 86745912, compound

HRID 893024Notes

Reaction equation

HRID 893024 reaction equation
[C:1](Cl)(=O)[C:2](Cl)=O.[CH3:7][N:8](C=O)C.[C:12]([O:15][C:16]1[C:17]([CH3:32])=[C:18]2[C:23](=[C:24]([CH3:27])[C:25]=1[CH3:26])[O:22][C:21]([CH3:31])([C:28]([OH:30])=[O:29])[CH2:20][CH2:19]2)(=[O:14])[CH3:13].OCCN(C)[C:37]1[CH:42]=[C:41]([N:43]2[CH2:47][CH2:46][CH2:45][CH2:44]2)[N:40]=[C:39]([N:48]2[CH2:52][CH2:51][CH2:50][CH2:49]2)[N:38]=1>C(#N)C.N1C=CC=CC=1.C(Cl)Cl>[N:48]1([C:39]2[N:38]=[C:37]([CH2:7][NH:8][CH2:1][CH2:2][O:29][C:28]([C:21]3([CH3:31])[CH2:20][CH2:19][C:18]4[C:17]([CH3:32])=[C:16]([O:15][C:12](=[O:14])[CH3:13])[C:25]([CH3:26])=[C:24]([CH3:27])[C:23]=4[O:22]3)=[O:30])[CH:42]=[C:41]([N:43]3[CH2:44][CH2:45][CH2:46][CH2:47]3)[N:40]=2)[CH2:49][CH2:50][CH2:51][CH2:52]1

Participants

8

Reactant 4

HCID 6228DimethylformamideHCID 65578Oxalyl chlorideHCID 10334479HCID 10334479, compoundHCID 10469565HCID 10469565, compound

Product 1

HCID 86745912HCID 86745912, compound

Reagents, catalysts & solvents 3

HCID 1049PyridineSolventHCID 6342AcetonitrileSolvent3×HCID 6344DichloromethaneSolvent

Procedure

A solution of oxalyl chloride (0.4 ml) in acetonitrile (0.4 ml) is added dropwise to a solution of 1 ml of DMF and 2.4 ml of acetonitrile. The mixture is stirred (mechanically) for 15 minutes at -20° and a precipitate separates. Powdered 6-acetoxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (1.169 g, 4 mmol) is added, the mixture is stirred 20 minutes at -20°, 20 minutes at 0° and then is recooled to -20°. A solution of 1.165 g (4 mmol) of N-(2-hydroxyethyl)-N-methyl-[2,6-bis(1-pyrrolidinyl)]-4-pyrimidinamine in 1 ml of pyridine and a total of 4 ml of acetonitrile is added. The mixture is allowed to warm and stand overnight at 20°-25° and then is diluted with methylene chloride. The solution is washed with water, aqueous potassium bicarbonate and water, then dried and concentrated to give a foam. Chromatography on silica gel and elution with acetone/methylene chloride (10/90) gives the title compound. NMR 4.70, 4.27, 3.9-3.2, 2.85, 2.58, 2.32, 2.17, 2.16, 2.02, 1.9 and 1.58 δ; m.p. 69.5°-76°.

Workup

  1. stirringthe mixture is stirred 20 minutes at -20°, 20 minutes at 0°
  2. customis recooled to -20°
  3. temperatureto warm
  4. waitstand overnight at 20°-25°
  5. washThe solution is washed with water, aqueous potassium bicarbonate and water
  6. customdried
  7. concentrationconcentrated
  8. customto give a foam
  9. washChromatography on silica gel and elution with acetone/methylene chloride (10/90)

Sources & evidence

ORD record
ord-0218f38a32004a33add56953442ce5d2
Source dataset
uspto-grants-1992_06
Patent number
US05120843

Reaction notes

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