Triethylamine → trans-4-(2-cyanoiminopyrrolidin-1-yl)-3,4-dihydro-2,2-dimethyl-3-hydroxy-2H-1-benzopyran-6-carbonitrile

HRID 1030220Notes

Reaction equation

HRID 1030220 reaction equation
[NH2:1][C@@H:2]1[C:7]2[CH:8]=[C:9]([C:12]#[N:13])[CH:10]=[CH:11][C:6]=2[O:5][C:4]([CH3:15])([CH3:14])[C@H:3]1[OH:16].[C:17]([N:19]=[C:20](OC)[CH2:21][CH2:22][CH2:23]Cl)#[N:18].C(N(CC)CC)C>C1(C)C=CC=CC=1>[C:17]([N:19]=[C:20]1[CH2:21][CH2:22][CH2:23][N:1]1[C@@H:2]1[C:7]2[CH:8]=[C:9]([C:12]#[N:13])[CH:10]=[CH:11][C:6]=2[O:5][C:4]([CH3:14])([CH3:15])[C@H:3]1[OH:16])#[N:18]

Participants

5

Reactant 3

HCID 8471TriethylamineHCID 10943936(3S,4R)-4-amino-3-hydroxy-2,2-dimethyl-chroman-6-carbonitrileHCID 15734837methyl N-cyano-4-chlorobutyrimidate

Product 1

HCID 86745669trans-4-(2-cyanoiminopyrrolidin-1-yl)-3,4-dihydro-2,2-dimethyl-3-hydroxy-2H-1-benzopyran-6-carbonitrileYield 12.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of trans-4-amino-3,4-dihydro-2,2-dimethyl-3-hydroxy-2H-1-benzopyran-6-carbonitrile (5.0 g), methyl N-cyano-4-chlorobutyrimidate (7.36 g), triethylamine (4.8 ml), and toluene (12 ml) was stirred at 100° C. for 2 days. After being cooled to room temperature, the reaction mixture was concentrated. The residue was taken up in ethyl acetate and washed with brine, dried over anhydrous magnesium sulfate, and concentrated. After purification by column chromatography on silica gel (elution with chloroform-methanol 25:1), the crude product was further purified by recrystallization from ethyl acetate to give trans-4-(2-cyanoiminopyrrolidin-1-yl)-3,4-dihydro-2,2-dimethyl-3-hydroxy-2H-1-benzopyran-6-carbonitrile (0.87 g).

Workup

  1. concentrationthe reaction mixture was concentrated
  2. washwashed with brine
  3. dry with materialdried over anhydrous magnesium sulfate
  4. concentrationconcentrated
  5. customAfter purification by column chromatography on silica gel (elution with chloroform-methanol 25:1)
  6. customthe crude product was further purified by recrystallization from ethyl acetate

Sources & evidence

ORD record
ord-ba0e5e1b36e54c72b32547748385fdf9
Source dataset
uspto-grants-1992_04
Patent number
US05104890

Reaction notes

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