Sodium Hydroxide → 1H-Indene-5-carbonitrile, 2,3-dihydro-1,1,2,3,3,6-hexamethyl-

HRID 328659Notes

Reaction equation

HRID 328659 reaction equation
[CH3:1][C:2]1([CH3:18])[C:10]2[C:5](=[CH:6][C:7]([CH3:14])=[C:8]([C:11]([NH2:13])=O)[CH:9]=2)[C:4]([CH3:16])([CH3:15])[CH:3]1[CH3:17].S(Cl)(Cl)=O.[OH-].[Na+]>C1C=CC=CC=1>[CH3:1][C:2]1([CH3:18])[C:10]2[C:5](=[CH:6][C:7]([CH3:14])=[C:8]([C:11]#[N:13])[CH:9]=2)[C:4]([CH3:16])([CH3:15])[CH:3]1[CH3:17]

Participants

5

Reactant 3

HCID 14798Sodium HydroxideHCID 24386Thionyl ChlorideHCID 21439677HCID 21439677, compound

Product 1

HCID 1125521H-Indene-5-carbonitrile, 2,3-dihydro-1,1,2,3,3,6-hexamethyl-

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

The crude product from Step III was dissolved in 250 ml. of benzene in a 50-ml. flask equipped with mechanical stirrer, cooling bath, thermometer, addition funnel, condenser, and static nitrogen head. Thionyl chloride (72 ml.) was added gradually with cooling over six mimutes at 24° to 30° C. The mixture was then heated to reflux for about 4 hours, and after cooling, 150 ml. of 5% sodium hydroxide solution was added at between 32° and 50° C., with cooling, over 16 minutes. The entire contents of the reaction flask were transferred to a separatory funnel and washed twice with 500 ml. of 5% sodium hydroxide solution. The washings were extracted in succession with 50 ml. of benzene. The organic phases were combined and flash evaporated on a rotary evaporator for one hour at 50° C. 10 mm. Hg to yiedl 30.6 g. of crude nitrile. The infrared spectrum (mineral oil mull) showed a medium intensity nitrile band at 2400 cm-1. The crude nitrile was taken up in 100 ml. of benzene and run onto a 1 1/8 inch by 35 inch chromatography column (wet-packed with 400 g. of MCB grade 923 silica gel using benzene as packing solvent). Pure nitrile was collected after 525 ml. of benzene were eluted from the column. A 5 g. portion of the chromatographed nitrile was recrystallized from hexane. The recrystallized nitrile was dissolved in 30 ml. of methanol, 2 g. of Draco K-9 activated carbon added, and the slurry filtered. After repeating the carbon treatment, the product was again recrystallized from hexane. The recrystallized product melted at 70.2° to 72.8° C. NMR spectrum (CDCl3 with TMS reference):

Workup

  1. customflask equipped with mechanical stirrer
  2. temperaturecooling bath
  3. additionthermometer, addition funnel, condenser
  4. temperaturewith cooling over six mimutes at 24° to 30° C
  5. temperatureThe mixture was then heated
  6. temperatureto reflux for about 4 hours
  7. temperatureafter cooling
  8. temperaturewith cooling, over 16 minutes
  9. customThe entire contents of the reaction flask were transferred to a separatory funnel
  10. washwashed twice with 500 ml
  11. extractionThe washings were extracted in succession with 50 ml
  12. customflash evaporated on a rotary evaporator for one hour at 50° C
  13. customPure nitrile was collected after 525 ml
  14. washof benzene were eluted from the column
  15. customportion of the chromatographed nitrile was recrystallized from hexane
  16. dissolutionThe recrystallized nitrile was dissolved in 30 ml
  17. additionadded
  18. filtrationthe slurry filtered
  19. customthe product was again recrystallized from hexane

Sources & evidence

ORD record
ord-85c81dcf929d4ad2b3d0a7c11ca45862
Source dataset
uspto-grants-1977_04
Patent number
US04018719

Reaction notes

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