Dimethyl Sulfate → HCID 131724334, compound

HRID 2119783Notes

Reaction equation

HRID 2119783 reaction equation
[C:1]([CH:5]([OH:28])[C@H:6]1[O:10][C@@H:9]([N:11]2[C:20]3[C:14]([C:15]([N:17]=[CH:18][N:19]=3)=[NH:16])=[N:13][C:12]2=[SiH2:21])[C@H:8]([OH:22])[C@@H:7]1[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:4])([CH3:3])[CH3:2].[CH3:29]OS(OC)(=O)=O.[H-].[Na+]>CN1CCCC1=O.CN(C=O)C.C1(C)C=CC=CC=1>[C:1]([CH:5]([OH:28])[C@H:6]1[O:10][C@@H:9]([N:11]2[C:20]3[C:14]([C:15]([N:17]=[CH:18][N:19]=3)=[NH:16])=[N:13][C:12]2=[SiH2:21])[C@H:8]([O:22][CH3:29])[C@@H:7]1[O:23][C:24]([CH3:27])([CH3:26])[CH3:25])([CH3:4])([CH3:2])[CH3:3]

Participants

7

Reactant 3

HCID 6497Dimethyl SulfateHCID 24758Sodium hydrideHCID 131724335HCID 131724335, compound

Product 1

HCID 131724334HCID 131724334, compoundYield 60%

Reagents, catalysts & solvents 3

HCID 1140TolueneSolvent2×HCID 6228DimethylformamideSolventHCID 13387N-methyl-2-pyrrolidoneSolvent

Conditions

Temperature
-35 °C

Procedure

Compound (72) (35.9 g, 88.1 mmol) was dissolved in mixture of 1-methyl-2-pyrrolidinone (60 ml) and DMF (240 ml) at 80° C. The resulting solution was cooled to −35° C. and dimethylsulfate (20.9 ml, 220.4 mmol) was added. Sodium hydride (5.99 g as 60% suspension in mineral oil, 149.8 mmol) was washed with ca. 75 ml of toluene and then suspended in toluene (approximately 15 ml). The resulting suspension was added to the reaction mixture dropwise via syringe while stirring. The reaction was allowed to proceed at −35° C. until nearly all starting material was consumed (about 4 h). The reaction was quenched by careful addition of methanol (200 ml) followed by water (100 ml). The resulting suspension was stirred 30 min at −20-−30° C. The precipitate of (73) was filtered out and washed with methanol twice on filter bed and then dried in vacuo to give 28.1 g of crude (73) having about 85% of purity. Yield 60-65%.

Workup

  1. additionThe resulting suspension was added to the reaction mixture dropwise via syringe
  2. customto proceed at −35° C.
  3. customwas consumed (about 4 h)
  4. customThe reaction was quenched by careful addition of methanol (200 ml)
  5. stirringThe resulting suspension was stirred 30 min at −20-−30° C
  6. filtrationThe precipitate of (73) was filtered out
  7. washwashed with methanol twice
  8. filtrationon filter bed
  9. customdried in vacuo

Sources & evidence

ORD record
ord-578b41f7787e4ebebdc314f01bfa8c56
Source dataset
uspto-grants-2004_02
Patent number
US06686463B2

Reaction notes

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