Acrylonitrile → HCID 12361859, compound

HRID 128127Notes

Reaction equation

HRID 128127 reaction equation
CN(C)C1CC2C3C(=CC=CC=3)NC=2CC1.C(#N)C=C.[OH-].C([N+](C)(C)C)C1C=CC=CC=1.CN(C)C1CC2C3C(=CC=CC=3)N(CCC#N)C=2CC1.[OH-].[K+].Cl.[CH3:56][N:57]([CH3:76])[CH:58]1[CH2:70][C:69]2[C:68]3[C:63](=[CH:64][CH:65]=[CH:66][CH:67]=3)[N:62]([CH2:71][CH2:72][C:73]([OH:75])=[O:74])[C:61]=2[CH2:60][CH2:59]1>CO.C(O)C.C1C=CC=CC=1>[CH3:76][N:57]([CH3:56])[CH:58]1[CH2:70][C:69]2[C:68]3[C:63](=[CH:64][CH:65]=[CH:66][CH:67]=3)[N:62]([CH2:71][CH2:72][C:73]([OH:75])=[O:74])[C:61]=2[CH2:60][CH2:59]1

Participants

10

Reactant 6

HCID 7855AcrylonitrileHCID 14797Potassium HydroxideHCID 36082CyclindoleHCID 66854Benzyltrimethylammonium hydroxideHCID 12361860HCID 12361860, compoundHCID 12891876HCID 12891876, compound2×

Product 1

HCID 12361859HCID 12361859, compound

Reagents, catalysts & solvents 3

HCID 241BenzeneSolventHCID 702EthanolSolventHCID 887MethanolSolvent

Procedure

To a solution of 17.1 g. of 3-(dimethylamino)-1,2,3,4-tetrahydrocarbazole in 150 ml. of benzene was added 10.6 g. of acrylonitrile followed by 1 ml. of 35% benzyltrimethylammonium hydroxide in methyl alcohol. The solution was heated under reflux for one hour and fifteen minutes, cooled to room temperature, filtered, and evaporated to dryness. The residue was treated with hot hexane and then hot heptane (total volume 3.3 liters), both solutions being decanted from insoluble gum. The combined hexane-heptane solution was cooled and filtered to give a solid which, on recrystallization from hexane, yielded 8.6 g. of 3-(dimethylamino)-9-(2-cyanoethyl)-1,2,3,4-tetrahydrocarbazole, m.p. 106°-108° C. A solution of 13 g. of 3-(dimethylamino)-9-(2-cyanoethyl)-1,2,3,4-tetrahydrocarbazole in 125 ml. of ethyl alcohol and 150 ml. of 10% potassium hydroxide solution was heated under reflux for three hours, cooled, and the ethyl alcohol was removed under reduced pressure. The resulting aqueous solution was extracted with benzene, and the aqueous layer was separated and treated with acid to pH 7, cooled, and filtered to give 5.6 g. of solid material. The filtrate was acidified to pH 6 and the resulting crystals were collected by filtration. The filtrate was evaporated to dryness under reduced pressure and the solid residue was slurried in water and collected by filtration. The above three crops of solids were combined, dissolved in ethyl alcohol and treated with hydrogen chloride in ethyl alcohol to give, on filtration and recrystallization from ethyl alcohol, 11.4 g. of 3-(dimethylamino)-1,2,3,4-tetrahydrocarbazole-9-propionic acid hydrochloride, m.p. 304°-305° C.

Workup

  1. temperatureThe solution was heated
  2. temperatureunder reflux for one hour and fifteen minutes
  3. filtrationfiltered
  4. customevaporated to dryness
  5. additionThe residue was treated with hot hexane
  6. customhot heptane (total volume 3.3 liters), both solutions being decanted from insoluble gum
  7. temperatureThe combined hexane-heptane solution was cooled
  8. filtrationfiltered
  9. customto give a solid which
  10. customon recrystallization from hexane
  11. customyielded 8.6 g
  12. temperatureunder reflux for three hours
  13. temperaturecooled
  14. customthe ethyl alcohol was removed under reduced pressure
  15. extractionThe resulting aqueous solution was extracted with benzene
  16. customthe aqueous layer was separated
  17. additiontreated with acid to pH 7
  18. temperaturecooled
  19. filtrationfiltered
  20. customto give 5.6 g
  21. filtrationthe resulting crystals were collected by filtration
  22. customThe filtrate was evaporated to dryness under reduced pressure
  23. filtrationcollected by filtration
  24. dissolutiondissolved in ethyl alcohol
  25. additiontreated with hydrogen chloride in ethyl alcohol
  26. customto give, on filtration and recrystallization from ethyl alcohol, 11.4 g

Sources & evidence

ORD record
ord-7c6f7bc81d754cfb9afc18c89275c73f
Source dataset
uspto-grants-1981_03
Patent number
US04257952

Reaction notes

Loading…