Dimethylcyanamide → HCID 58609529, compound

HRID 502924Notes

Reaction equation

HRID 502924 reaction equation
C(#N)N(C)C.[CH3:6][O:7][C:8]([CH:10]1[CH2:16][CH:15]2[C:17](Br)=[CH:18][CH:11]1[C:12](=[O:33])[CH:13]([C:21]([C:23]1[C:24]([CH3:32])=[N:25][C:26]([CH:29]([F:31])[F:30])=[CH:27][CH:28]=1)=[O:22])[C:14]2=[O:20])=[O:9].C[Si]([SiH]([Si](C)(C)C)[Si](C)(C)C)(C)C>C1(C)C=CC=CC=1>[CH3:6][O:7][C:8]([CH:10]1[CH2:16][CH:15]2[CH:17]=[CH:18][CH:11]1[C:12](=[O:33])[CH:13]([C:21]([C:23]1[C:24]([CH3:32])=[N:25][C:26]([CH:29]([F:30])[F:31])=[CH:27][CH:28]=1)=[O:22])[C:14]2=[O:20])=[O:9]

Participants

5

Reactant 3

HCID 15112Dimethylcyanamide2×HCID 123134Tris(trimethylsilyl)silaneHCID 684648458-Bromo-3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester

Product 1

HCID 58609529HCID 58609529, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Conditions

Temperature
80 °C

Procedure

Catalytic amounts (10 mg) of azaisobutyronitrile are added to a solution of 0.10 g (0.24 mmol) of 8-bromo-3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester (Example 1.1155) and 0.149 ml (0.48 mmol) of tris(trimethylsilyl)silane in 3.5 ml of toluene and the reaction mixture is stirred at a temperature of 80° C. 5 mg portions of fresh azaisobutyronitrile dissolved in a small amount of toluene are then added four times until, after 6 days, the reaction has come to a complete standstill (LC-MS monitoring). The solvent is then removed under reduced pressure and the residue is purified by silica gel chromatography (eluant: gradient mixture of ethyl acetate/tetrahydrofuran/hexane and 3% triethylamine). After removal of the solvents the triethyl-ammonium salt of 3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester is obtained.

Workup

  1. additionare then added four times until, after 6 days
  2. customThe solvent is then removed under reduced pressure
  3. customthe residue is purified by silica gel chromatography (eluant: gradient mixture of ethyl acetate/tetrahydrofuran/hexane and 3% triethylamine)
  4. customAfter removal of the solvents the triethyl-ammonium salt of 3-(2-methyl-6-difluoromethyl-pyridine-3-carbonyl)-2,4-dioxo-bicyclo-[3.2.2]non-8-ene-6-carboxylic acid methyl ester
  5. customis obtained

Sources & evidence

ORD record
ord-07f5b8e71611457e973359c6169c23f7
Source dataset
uspto-grants-2010_08
Patent number
US07776888B2

Reaction notes

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