Hydrochloric Acid → 2,4-Diamino-6-methyl-5-[3-(2,5-dichlorophenyl)-2-butenyl]pyrimidine

HRID 54246Notes

Reaction equation

HRID 54246 reaction equation
Cl.[NH2:2][C:3]1[N:8]2N=N[N:11]=[C:7]2[C:6]([CH2:12][CH:13]=[C:14]([C:16]2[CH:21]=[C:20]([Cl:22])[CH:19]=[CH:18][C:17]=2[Cl:23])[CH3:15])=[C:5]([CH3:24])[N:4]=1.O>C(O)(=O)C.[Zn]>[NH2:2][C:3]1[N:8]=[C:7]([NH2:11])[C:6]([CH2:12][CH:13]=[C:14]([C:16]2[CH:21]=[C:20]([Cl:22])[CH:19]=[CH:18][C:17]=2[Cl:23])[CH3:15])=[C:5]([CH3:24])[N:4]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 962WaterHCID 536571025-Amino-7-methyl-8-[3-(2,5-dichlorophenyl)-2-butenyl]tetrazolo[1,5-c]pyrimidine

Product 1

HCID 538750882,4-Diamino-6-methyl-5-[3-(2,5-dichlorophenyl)-2-butenyl]pyrimidineYield 30.9%

Reagents, catalysts & solvents 2

HCID 23994ZincCatalyst2×HCID 176Acetic AcidSolvent

Conditions

Temperature
80 °C

Procedure

Zinc is activated by treating 2.5 grams (excess) of it with aqueous 10% hydrochloric acid for two minutes. The activated zinc is collected by filtration, washed with water then acetone, and dried in a vacuum oven for one hour. A solution of 1.5 grams (0.004 mole) of 5-amino-7-methyl-8-[3-(2,5-dichlorophenyl)-2-butenyl]tetrazolo[1,5-c]pyrimidine in 35 mL of acetic acid is stirred, and the activated zinc is added portionwise during a 20 minute period. Upon completion of addition, the reaction mixture is warmed to about 80° C. where it is stirred for about 18 hours. After this time, the reaction mixture is stirred with 50 mL of water. The mixture is then extracted with three 30 mL portions of methylene chloride. The combined extracts are washed with two 10 mL portions of an aqueous solution saturated with sodium bicarbonate. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residue. The residue is subjected to column chromatography on silica gel, using 15% methanol in methylene chloride as the eluant. The product-containing fractions are combined and concentrated under reduced pressure, yielding 0.4 gram of 2,4-diamino-6-methyl-5-[3-(2,5-dichlorophenyl)-2-butenyl]pyrimidine; mp 172°-174° C. The NMR spectrum is consistent with the proposed structure.

Workup

  1. filtrationThe activated zinc is collected by filtration
  2. washwashed with water
  3. dry with materialacetone, and dried in a vacuum oven for one hour
  4. additionUpon completion of addition
  5. extractionThe mixture is then extracted with three 30 mL portions of methylene chloride
  6. washThe combined extracts are washed with two 10 mL portions of an aqueous solution saturated with sodium bicarbonate
  7. dry with materialThe organic layer is dried with magnesium sulfate
  8. filtrationfiltered
  9. concentrationThe filtrate is concentrated under reduced pressure to a residue
  10. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b4a708c8e5c34ab5997623dea6bff47e
Source dataset
uspto-grants-1997_04
Patent number
US05622954

Reaction notes

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