Hydrazine → HCID 22335636, compound

HRID 586634Notes

Reaction equation

HRID 586634 reaction equation
[C:1](Cl)(=[O:5])[C:2](Cl)=O.[Cl:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[C:15]([C:22]3[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=3)=[CH:16][N:17]3[C:21]=2[CH2:20][CH2:19][CH2:18]3)=[CH:10][CH:9]=1.NN.[OH-:30].[K+]>C1COCC1.O.C(O)COCCO>[Cl:7][C:8]1[CH:9]=[CH:10][C:11]([C:14]2[C:15]([C:22]3[CH:23]=[CH:24][CH:25]=[CH:26][CH:27]=3)=[C:16]([CH2:2][C:1]([OH:5])=[O:30])[N:17]3[C:21]=2[CH2:20][CH2:19][CH2:18]3)=[CH:12][CH:13]=1

Participants

8

Reactant 4

HCID 9321Hydrazine2×HCID 14797Potassium HydroxideHCID 65578Oxalyl chlorideHCID 14855804HCID 14855804, compound

Product 1

HCID 22335636HCID 22335636, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8117Diethylene GlycolSolvent

Conditions

Temperature
60 °C

Procedure

Oxalyl dichloride (5.6 g, 0.044 mol) is added dropwise at 0-10° C. to an ice-cold solution of 7-(4-chlorophenyl)-6-phenyl-2,3-dihydro-1H-pyrrolizine (9.2 g, 0.031 mol) in THF (100 ml). After addition is complete, the mixture is stirred for 15 min and the excess of acid chloride is then cautiously decomposed (gas and foam formation!) with ice water (12 ml). Hydrazine (18 ml, 80%, about 0.3 mol) is added dropwise, the mixture is stirred for 30 min and diethylene glycol (36 ml) is poured in. THF and water are distilled off under atmospheric pressure at a bath temperature of 100-110° C. (foam formation at 105° C.!). The mixture is cooled to 60° C. and potassium hydroxide (15.7 g of KOH 85%, 0.238 mol) is added in portions and the temperature in the bottom is increased to 140° C. (foam formation!), and water, hydrazine and residual solvents are distilled off. This temperature is maintained in the bottom for 1 h and the mixture is allowed to cool. The mixture cooled to 60° C. is treated with water (200 ml) and acidified to pH 2-3 with conc. HCl in an ice bath (temp. <10° C.). The depositing carboxylic acid is extracted with ethyl acetate (300 ml), and the EA extract is washed with water until neutral, dried using Na2SO4 sicc. and concentrated in the presence of heat (45° C.) until the start of crystallization and placed in the cold. The crystal mass deposited at 5° C. is filtered off with suction and washed with cold ethyl acetate and dried.

Workup

  1. additionAfter addition
  2. stirringthe mixture is stirred for 30 min
  3. distillationTHF and water are distilled off under atmospheric pressure at a bath temperature of 100-110° C. (foam formation at 105° C.!)
  4. distillationare distilled off
  5. temperatureThis temperature is maintained in the bottom for 1 h
  6. temperatureto cool
  7. temperatureThe mixture cooled to 60° C.
  8. additionis treated with water (200 ml)
  9. customacidified to pH 2-3 with conc. HCl in an ice bath
  10. custom(temp. <10° C.)
  11. extractionThe depositing carboxylic acid is extracted with ethyl acetate (300 ml)
  12. extractionthe EA extract
  13. washis washed with water until neutral,
  14. customdried
  15. concentrationand concentrated in the presence
  16. temperatureof heat (45° C.)
  17. customuntil the start of crystallization
  18. customdeposited at 5° C.
  19. filtrationis filtered off with suction
  20. washwashed with cold ethyl acetate
  21. customdried

Sources & evidence

ORD record
ord-a88575d6a61c4576a5e12f3e92c818f8
Source dataset
uspto-grants-2005_08
Patent number
US06936632B2

Reaction notes

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