Hydrochloric Acid → HCID 23227005, compound

HRID 1956187Notes

Reaction equation

HRID 1956187 reaction equation
C(S[C:9]1[C:14]([CH:15]2[C:23]3[C:18](=[CH:19][CH:20]=[CH:21][CH:22]=3)[CH2:17][C:16]2([CH3:25])[CH3:24])=[CH:13][N:12]=[CH:11][N:10]=1)C1C=CC=CC=1.Cl.Cl[O-].[Na+].[S:30](=[O:33])(O)[O-:31].[Na+].CN.[OH-].[Na+].C(Cl)C1C=CC=CC=1.Cl[C:48]1C(C2C3C(=CC=CC=3)CC2(C)C)=CN=C[N:49]=1>ClCCl.O.O1CCCC1>[CH3:24][C:16]1([CH3:25])[CH2:17][C:18]2[C:23](=[CH:22][CH:21]=[CH:20][CH:19]=2)[CH:15]1[C:14]1[C:13]([S:30]([NH:49][CH3:48])(=[O:33])=[O:31])=[N:12][CH:11]=[N:10][CH:9]=1

Participants

12

Reactant 8

HCID 313Hydrochloric AcidHCID 6329MethylamineHCID 7503Benzyl ChlorideHCID 14798Sodium HydroxideHCID 18662969HCID 18662969, compoundHCID 23226996HCID 23226996, compoundHCID 23665760Sodium HypochloriteHCID 23665763Sodium Bisulfite

Product 1

HCID 23227005HCID 23227005, compoundYield 26%

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
5 °C

Procedure

A 3.0 g (8.7 mmol) sample of 4-benzylthio-5-(2,2-dimethylindan-1-yl)pyrimidine was dissolved in 100 mL of dichloromethane and 50 mL of water and 4.2 g of concentrated aqueous hydrochloric acid were added. The resulting mixture was cooled to 5° C. and 60 mL of commercial bleach (5.25 percent sodium hypochlorite solution) was added dropwise with stirring and cooling over a 12-min period. The mixture was then stirred for 30 min at 5°-6° C. A solution of 1.5 g of sodium bisulfite in 15 mL of water was added with stirring and then 10 mL of 2M (20 mmol) methylamine in tetrahydrofuran was added with stirring and cooling. The pH of the mixture was adjusted to 9-10 by the addition of 2N aqueous sodium hydroxide. After 1 hour gas-liquid chromatographic analysis of the product indicated it was about 29 percent benzyl chloride, 21 percent 4-chloro-5-(2,2-dimethylindan-1-yl)pyrimidine, and 26 percent desired product. An additional 100 mL of dichloromethane and 100 mL of water were added. The organic phase was recovered, washed with 100 mL of water, dried over sodium sulfate, and concentrated by evaporation under reduced pressure. The residual oil was dissolved in a minimum amount of dichloromethane and chromatographed on dry flask grade silica gel, eluting initially with a 50:50 by volume mixture of dichloromethane and hexane and then with dichloromethane in 150 mL fractions. Fractions 15-25 were combined and concentrated by evaporation under reduced pressure. The solid residue was extracted with hexane and then rechromatographed on silica gel eluting with a 20:80 by volume mixture of ethyl acetate and hexane. The resulting white solid was impure title compound melting at 152°-160° C.

Workup

  1. temperaturecooling over a 12-min period
  2. stirringThe mixture was then stirred for 30 min at 5°-6° C
  3. stirringwith stirring
  4. stirringwith stirring
  5. temperaturecooling

Sources & evidence

ORD record
ord-56e68ff472df462fbb83d01e944e6191
Source dataset
uspto-grants-1998_07
Patent number
US05780465

Reaction notes

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