5-Bromo-2-(methylsulfanyl)pyrimidine → HCID 67729129, compound

HRID 1450041Notes

Reaction equation

HRID 1450041 reaction equation
Br[C:2]1[CH:3]=[N:4][C:5]([S:8][CH3:9])=[N:6][CH:7]=1.C([Li])CCC.[CH3:15][S:16][C:17]1[C:28]2[O:27][C:26]([CH3:30])([CH3:29])[O:25][C:24]=2[C:23]([C:31]([C:33]2[C:43]3[O:44][C:45]([CH3:48])([CH3:47])[O:46][C:42]=3[C:41]([S:49][CH3:50])=[C:35]3[O:36][C:37]([CH3:40])([CH3:39])[O:38][C:34]=23)=[O:32])=[C:22]2[C:18]=1[O:19][C:20]([CH3:52])([CH3:51])[O:21]2>C1COCC1.C(OCC)C>[CH3:50][S:49][C:41]1[C:35]2[O:36][C:37]([CH3:39])([CH3:40])[O:38][C:34]=2[C:33]([C:31]([C:23]2[C:22]3[O:21][C:20]([CH3:52])([CH3:51])[O:19][C:18]=3[C:17]([S:16][CH3:15])=[C:28]3[O:27][C:26]([CH3:30])([CH3:29])[O:25][C:24]=23)([C:2]2[CH:3]=[N:4][C:5]([S:8][CH3:9])=[N:6][CH:7]=2)[OH:32])=[C:43]2[C:42]=1[O:46][C:45]([CH3:48])([CH3:47])[O:44]2

Participants

6

Reactant 3

HCID 47385645-Bromo-2-(methylsulfanyl)pyrimidineHCID 18943064HCID 18943064, compoundHCID 178418339Butyllithium

Product 1

HCID 67729129HCID 67729129, compound

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-75 °C

Procedure

5-Bromo-2-methylthio-pyrimidine (0.250 g, 1.2195 mmol) was dissolved in THF (50 mL, sodium benzophenone ketyl) and cooled to -105° C. n-Butyl lithium (0.455 ml in toluene, 1.2195 ml) was added and the temperature was increased to -75° C. for 15 minutes and thereafter reduced to -105° C. Bis(8-methylthio-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d']-bis(1,3)dioxole-4-yl)ketone (0.63146 g, 1.1236 mmol, Example 59) was added in solid form and the temperature was gradually increased to room temperature (removal of cooling bath). The mixture was stirred overnight, NaCl (15 mL, sat.) and diethyl ether (40 mL) were added and the phases separated after 5 minutes stirring. The organic phase was dried (MgSO4) and evaporated yielding 0.59 crude product. Pure product was obtained by crystallization in diethyl ether followed by a second crystallization in diisopropyl ether. Yield 0.115 g (0.1669 mmol, 14.9%).

Workup

  1. additionwas added
  2. customreduced to -105° C
  3. temperaturethe temperature was gradually increased to room temperature
  4. custom(removal of cooling bath)
  5. additionNaCl (15 mL, sat.) and diethyl ether (40 mL) were added
  6. customthe phases separated after 5 minutes
  7. stirringstirring
  8. dry with materialThe organic phase was dried (MgSO4)
  9. customevaporated
  10. customyielding 0.59 crude product
  11. customfollowed by a second crystallization in diisopropyl ether

Sources & evidence

ORD record
ord-fcab5744a91b4399b9b0d76e53f96b19
Source dataset
uspto-grants-1997_02
Patent number
US05599522

Reaction notes

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