Nitric Acid → HCID 11608651, compound

HRID 2105961Notes

Reaction equation

HRID 2105961 reaction equation
[N+:1]([O-:4])([OH:3])=[O:2].S(=O)(=O)(O)O.[CH3:10][C:11]1[N:12]=[C:13]([C:19]2[CH:20]=[N:21][CH:22]=[CH:23][CH:24]=2)[S:14][C:15]=1[CH2:16][CH2:17]O.[OH-].[Na+]>O>[CH3:10][C:11]1[N:12]=[C:13]([C:19]2[CH:20]=[N:21][CH:22]=[CH:23][CH:24]=2)[S:14][C:15]=1[CH2:16][CH2:17][O:2][N+:1]([O-:4])=[O:3]

Participants

6

Reactant 4

HCID 944Nitric AcidHCID 1118Sulfuric AcidHCID 14798Sodium HydroxideHCID 18440833HCID 18440833, compound

Product 1

HCID 11608651HCID 11608651, compoundYield 41%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Conditions

Temperature
2.5 °C

Procedure

3-[4-Methyl-5-(2-nitrooxy-ethyl)-thiazole-2-yl]-pyridine was prepared by drop-wise addition of 1.145 gr. of nitric acid (70%) to 1.78 grams of cooled sulfuric acid (95-98%) at 0-5° C., followed by addition of 4 grams (0.0181 moles) 2-(4-methyl-2-pyridin-3-yl-thiazole-5-yl)-ethanol over a time period of 30 minutes at 0-5° C. After the addition was completed the reaction mixture was stirred for 30 minutes at 0-5° C., and for one additional hour at room temperature. The reaction mixture was then added carefully to 25 ml of cold water. The water solution was turned basic with an aqueous 20% solution of sodium hydroxide and the aqueous phase was extracted with three portions of 75 grams of dichloromethane. The extracts were combined, dried over sodium sulfate, filtered and evaporated to dryness under vacuum. The nitration step was confirmed initially by thin-layer chromatography stained with diphenylamine as a marker for the nitrate ester moiety (FIG. 1). Chromatography of the crude product on silica gel (using ethyl acetate as eluent) gave 1.5 grams (41% yield) of Pet-12 as a pale yellow liquid having a purity of 99% as determined by HPLC.

Workup

  1. additionAfter the addition
  2. customat room temperature
  3. extractionthe aqueous phase was extracted with three portions of 75 grams of dichloromethane
  4. dry with materialdried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated to dryness under vacuum

Sources & evidence

ORD record
ord-490e9098503a424abf14cc469d7cc80b
Source dataset
uspto-grants-2009_08
Patent number
US07579477B2

Reaction notes

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