N,N-Dimethylaniline → 6-(1-Pyrrolidinyl)-3-pyridazinamine

HRID 2419016Notes

Reaction equation

HRID 2419016 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5](N)([N:8]2[CH2:12][CH2:11][CH2:10][CH2:9]2)[NH:4][N:3]=1.NC1N=NC(Cl)=CC=1.N1CCCC1.CN(C)C1C=CC=CC=1>[Cu].C(O)(C)C>[NH2:1][C:2]1[N:3]=[N:4][C:5]([N:8]2[CH2:12][CH2:11][CH2:10][CH2:9]2)=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 949N,N-Dimethylaniline2×HCID 216436-Amino-3-chloropyridazineHCID 31268Pyrrolidine2×HCID 20316830HCID 20316830, compound

Product 1

HCID 201959516-(1-Pyrrolidinyl)-3-pyridazinamineYield 76%

Reagents, catalysts & solvents 2

HCID 23978CopperCatalyst2×HCID 3776IsopropanolSolvent

Conditions

Temperature
30 °C

Procedure

A better procedure for preparing 3-amino-6-amino-6-(1-pyrrolidinyl)pyridazine is given as follows: a mixture containing 80 g. of 3-amino-6-chloropyridazine, 105 ml. of pyrrolidine, 1.2 liters of N,N-dimethylaniline and 1 g. of copper bronze powder was heated with stirring at 130°-135° C. for 18 hours. When a TLC test indicated that starting material was still present, an additional 50 ml. portion of pyrrolidine in 200 ml. of N,N-dimethylaniline was added to the reaction mixture followed by more copper bronze powder and the reaction mixture was heated for an additional 24 hours. The reaction mixture was cooled to 30° C. and filtered. The filtrate was concentrated under oil pump vacuum to leave a crystalline solid. The solid was slurried with isopropyl alcohol while chilling the mixture in an ice bath. The solid was collected, washed with a small amount of cold isopropyl alcohol and dried in a vacuum oven at 60° C. to produce 53 g. (76% yield) of 3-amino-6-(1-pyrrolidinyl)-pyridazine, m.p. 209°-211° C. A TLC check of the filtrate indicated that it contained more of the product, which was not isolated. The intermediate 3-amino-6-(1-pyrrolidinyl)pyridazine prepared by said better procedure was used in the preparation of the final product as described in the second paragraph of (Example D-4) described hereinbelow.

Workup

  1. additiona mixture containing 80 g
  2. temperaturethe reaction mixture was heated for an additional 24 hours
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated under oil pump vacuum
  5. customto leave a crystalline solid
  6. temperaturewhile chilling the mixture in an ice bath
  7. customThe solid was collected
  8. washwashed with a small amount of cold isopropyl alcohol
  9. customdried in a vacuum oven at 60° C.
  10. customto produce 53 g

Sources & evidence

ORD record
ord-e2ec533b031841fb895a2ca09d34e254
Source dataset
uspto-grants-1978_08
Patent number
US04104385

Reaction notes

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