Nitric Acid → 4,9-Dihydroxydiamantane

HRID 1021185Notes

Reaction equation

HRID 1021185 reaction equation
[CH2:1]1[CH:6]2[CH:7]3[CH:13]4[CH2:14][CH:2]1[CH2:3][CH:4]1[CH:12]4[CH2:11][CH:9]([CH2:10][CH:5]12)[CH2:8]3.C(Cl)Cl.[N+]([O-])(O)=[O:19].OS(O)(=O)=O.[OH2:27]>CO>[CH2:14]1[C:2]2([OH:27])[CH2:1][CH:6]3[CH:5]4[CH2:10][C:9]5([OH:19])[CH2:11][CH:12]([CH:4]4[CH2:3]2)[CH:13]1[CH:7]3[CH2:8]5

Participants

7

Reactant 5

HCID 944Nitric AcidHCID 962WaterHCID 1118Sulfuric AcidHCID 6344DichloromethaneHCID 123154Congressane

Product 1

HCID 130222964,9-DihydroxydiamantaneYield 65%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
25 °C

Procedure

Diamantane 1 (1.28 g, 0.149 mol), CH2Cl2 (250 mL) and 100% HNO3 (90 mL, 2.13 mol) are mixed at 0° C., stirred for 2 h at 25° C. and subsequently diluted with water (180 mL). The CH2Cl2 is removed and the reaction mixture 26 is refluxed for 1.5 h. Removal of the water in the vacuum yielded a mixture of different oligohydroxydes 20 as a remainder. These 20 are added to 200 mL of 96% H2SO4 and stirred for 2 h at room temperature. Subsequently, the reaction mixture is poured onto 300 g ice and filtered. Extraction of the filtrate with one or several organic solvents (typically diethylether) yields 21.3 g (0.097 mmol, 65%) 4.9-dihydroxydiamantane (2, m=0) as white solid, mp. 291-293° C. (from methanol, literature 290-292° C.).

Workup

  1. customThe CH2Cl2 is removed
  2. temperaturethe reaction mixture 26 is refluxed for 1.5 h
  3. customRemoval of the water in the vacuum
  4. customyielded
  5. additiona mixture of different oligohydroxydes 20 as a remainder
  6. stirringstirred for 2 h at room temperature
  7. filtrationfiltered
  8. extractionExtraction of the filtrate with one or several organic solvents (typically diethylether)

Sources & evidence

ORD record
ord-e85d64f6ebfa4daf833e07983cdad2e0
Source dataset
uspto-grants-2014_05
Patent number
US08716539B2

Reaction notes

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