Tetrahydrofuran → HCID 21412133, compound

HRID 2071714Notes

Reaction equation

HRID 2071714 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[C:7]([CH2:9][CH:10]=[C:11]1[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=2[CH:15]=[CH:14][C:13]2[CH:22]=[CH:23][CH:24]=[CH:25][C:12]1=2)#[N:8].O1CCCC1.[OH-].[Na+]>O>[NH2:8][CH2:7][CH2:9][CH:10]=[C:11]1[C:12]2[CH:25]=[CH:24][CH:23]=[CH:22][C:13]=2[CH:14]=[CH:15][C:16]2[CH:21]=[CH:20][CH:19]=[CH:18][C:17]1=2

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 14798Sodium HydroxideHCID 21226445Aluminium lithium hydrideHCID 21412086HCID 21412086, compound

Product 1

HCID 21412133HCID 21412133, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent2×

Procedure

In a system protected by a drying tube and in which a nitrogen atmosphere is maintained, lithium aluminum hydride (380 mg., 0.01 mole) is suspended in 15 ml. of dry, peroxide-free tetrahydrofuran. The mixture is stirred and heated to refluxing for 4 hours. After cooling in an ice-bath, the mixture is stirred while a solution of 5-(2-cyanoethylidene)-5H-dibenzo[a,d]cycloheptene (1.21 g., 0.005 mole) in 20 ml. of tetrahydrofuran is added dropwise over 20 minutes. The deep red solution is stirred for 1 hour in the cold and then hydrolyzed by the successive dropwise addition of water, 0.4 ml., 20% sodium hydroxide, 0.4 ml., and water, 1.0 ml. The granular precipitate is filtered and washed with absolute ether. The combined filtrate and washings are evaporated to dryness under reduced pressure. The residual yellow oily base is dissolved in absolute alcohol and treated with a solution of maleic acid in absolute alcohol. Dilution with ether precipitates the hydrogen maleate as white crystals, m.p. 171°-173° C., dec. The yield of 5-(3-aminopropylidene)-5H-dibenzo[a,d]cycloheptene hydrogen maleate is 0.45 g. (25%). Repeated crystallizations from mixtures of absolute alcohol-absolute ether gave an analytical sample melting at 176.5°-177.5° C., dec.

Workup

  1. customIn a system protected by a drying tube and in which
  2. temperaturea nitrogen atmosphere is maintained
  3. customof dry
  4. temperatureheated
  5. temperatureto refluxing for 4 hours
  6. temperatureAfter cooling in an ice-bath
  7. stirringThe deep red solution is stirred for 1 hour in the cold and
  8. filtrationThe granular precipitate is filtered
  9. washwashed with absolute ether
  10. customThe combined filtrate and washings are evaporated to dryness under reduced pressure
  11. dissolutionThe residual yellow oily base is dissolved in absolute alcohol
  12. additiontreated with a solution of maleic acid in absolute alcohol
  13. customDilution with ether precipitates the hydrogen maleate as white crystals, m.p. 171°-173° C., dec
  14. customcrystallizations from mixtures of absolute alcohol-absolute ether
  15. customgave an analytical sample melting at 176.5°-177.5° C., dec.

Sources & evidence

ORD record
ord-ec3263424f294071a8bdc32999132057
Source dataset
uspto-grants-1977_09
Patent number
US04048223

Reaction notes

Loading…