Benzyl Alcohol → HCID 178469798, compound

HRID 2419150Notes

Reaction equation

HRID 2419150 reaction equation
[C:1]([CH:6]1[C@@H:15]2[C:16]3[C:21]([C@H:8]([C:9]4[CH:10]=[CH:11][CH:12]=[CH:13][C:14]=42)[CH:7]1C(O)=O)=[CH:20][CH:19]=[CH:18][CH:17]=3)([O:3][CH2:4][CH3:5])=[O:2].ClC(OCC)=O.[N-:31]=[N+]=[N-].[Na+].N(C1[C@H]2C3C=CC=CC=3[C@@H](C3C2=CC=CC=3)C1C(OCC)=O)=[N+]=[N-].[N-]=[N+]=[N-].C(O)C1C=CC=CC=1.C(NC1[C@H]2C3C=CC=CC=3[C@@H](C3C2=CC=CC=3)C1C(OCC)=O)(OCC1C=CC=CC=1)=O.[H][H]>[Pd].C(OCC)C.C(OCC)(=O)C.C1(C)C=CC=CC=1.O.CC(C)=O>[NH2:31][CH:7]1[C@H:8]2[C:21]3[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=3[C@@H:15]([C:14]3[C:9]2=[CH:10][CH:11]=[CH:12][CH:13]=3)[CH:6]1[C:1]([O:3][CH2:4][CH3:5])=[O:2]

Participants

15

Reactant 8

HCID 244Benzyl AlcoholHCID 10928Ethyl chloroformateHCID 33557Sodium AzideHCID 33558AzideHCID 178418361HCID 178418361, compound2×HCID 178469382HCID 178469382, compoundHCID 178469859HCID 178469859, compoundHCID 178470006HCID 178470006, compound

Product 1

HCID 178469798HCID 178469798, compound

Reagents, catalysts & solvents 6

HCID 23938PalladiumCatalystHCID 180AcetoneSolvent2×HCID 962WaterSolvent2×HCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

A solution of trans-12-carboethoxy-11-carboxy-9,10-dihydro-9,10-ethanoanthracene prepared as set forth in Example 1 (19.3 g., 60 mmoles) in 11 ml. of water and 100 ml. of acetone is cooled to 0° C. Ethyl chloroformate (8.6 g., 79 mmoles) in 30 ml. of acetone is added dropwise at 0° C., then the mixture is stirred at 0° C. for about 30 minutes. Sodium azide (6.2 g., 94 mmoles) in 20 ml. of water is added at 0° C., and the mixture is stirred at 0° C. for 1 hour, then poured into 500 ml. of ice water. The product is extracted twice with diethyl ether, the ether layers are washed with saturated sodium chloride solution, then dried over anhydrous magnesium sulfate. Evaporation under vacuum gives 19.7 g. of a white solid, trans-11-azido-12-carboethoxy-9,10-dihydro-9,10-ethanoanthracene. The infrared spectral analysis of this compound is in agreement with the assigned structure. The solid azide is dissolved in 75 ml. of dry toluene and heated on a steam bath until the evolution of nitrogen stops. The toluene is removed by evaporation under vacuum to provide 16.9 g. of a yellow oil. The oil is treated with 17.2 g. of benzyl alcohol, and the mixture is heated on a steam bath for 2 hours. The excess benzyl alcohol is removed by evaporation under vacuum leaving 22.7 g. of a yellow oil, trans-11-(N-carbobenzyloxyamino)-12-carboethoxy-9,10-dihydro-9,10-ethanoanthracene. The oil is dissolved in 100 ml. of ethyl acetate, 5.0 g. of palladium on charcoal are added and the mixture is treated with hydrogen gas at about 45 psi on a Parr apparatus until uptake of hydrogen stops. The mixture is filtered, the filtrate is evaporated under vacuum, and the residue is dissolved in diethyl ether. The ether solution is washed with saturated sodium bicarbonate solution and saturated sodium chloride solution, then dried over anhydrous magnesium sulfate to give 20.7 g. of an oil. The oil is dissolved in diethyl ether and extracted with 5 percent hydrochloric acid. The acid extracts are neutralized with sodium bicarbonate. The aqueous solution is extracted with diethyl ether, and the ether layer is dried over magnesium sulfate. The ether is removed by evaporation under vacuum to provide a solid residue which is recrystallized from a benzene-hexane mixture to provide trans-11-amino-12-carboethoxy-9,10-dihydro-9,10-ethanoanthracene, m.p. 118°-121° C.

Workup

  1. stirringthe mixture is stirred at 0° C. for 1 hour
  2. additionpoured into 500 ml
  3. extractionThe product is extracted twice with diethyl ether
  4. washthe ether layers are washed with saturated sodium chloride solution
  5. dry with materialdried over anhydrous magnesium sulfate
  6. customEvaporation under vacuum
  7. customgives 19.7 g
  8. customThe toluene is removed by evaporation under vacuum
  9. customto provide 16.9 g
  10. additionThe oil is treated with 17.2 g
  11. customThe excess benzyl alcohol is removed by evaporation under vacuum
  12. customleaving 22.7 g
  13. dissolutionThe oil is dissolved in 100 ml
  14. filtrationThe mixture is filtered
  15. customthe filtrate is evaporated under vacuum
  16. dissolutionthe residue is dissolved in diethyl ether
  17. washThe ether solution is washed with saturated sodium bicarbonate solution and saturated sodium chloride solution
  18. dry with materialdried over anhydrous magnesium sulfate
  19. customto give 20.7 g
  20. extractionextracted with 5 percent hydrochloric acid
  21. extractionThe aqueous solution is extracted with diethyl ether
  22. dry with materialthe ether layer is dried over magnesium sulfate
  23. customThe ether is removed by evaporation under vacuum
  24. customto provide a solid residue which
  25. customis recrystallized from a benzene-hexane mixture

Sources & evidence

ORD record
ord-af471dfe28884e38934fac787539c6d3
Source dataset
uspto-grants-1978_08
Patent number
US04104475

Reaction notes

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