Hydrochloric Acid → HCID 14373418, compound

HRID 255448Notes

Reaction equation

HRID 255448 reaction equation
[C:1](ON=O)([CH3:4])(C)[CH3:2].[F:8][CH:9]([F:29])[C:10]1[N:15]=[C:14]([C:16]([F:19])([F:18])[F:17])[C:13]([C:20](=[O:23])[S:21][CH3:22])=[C:12]([NH2:24])[C:11]=1[C:25](=[O:28])[S:26][CH3:27].N#N.Cl.ClC1C=CN=CC=1.C(N(CC)CC)C.C1(N)CC1>CC#N.CN(C=O)C.O.CCOCC>[F:29][CH:9]([F:8])[C:10]1[N:15]=[C:14]([C:16]([F:19])([F:17])[F:18])[C:13]([C:20](=[O:23])[S:21][CH3:22])=[C:12]([NH:24][CH:4]2[CH2:1][CH2:2]2)[C:11]=1[C:25](=[O:28])[S:26][CH3:27]

Participants

12

Reactant 7

HCID 313Hydrochloric AcidHCID 947NitrogenHCID 8471TriethylamineHCID 10906Tert-Butyl nitriteHCID 122884-ChloropyridineHCID 69828CyclopropylamineHCID 14373417HCID 14373417, compound

Product 1

HCID 14373418HCID 14373418, compoundYield 63.8%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 3283Diethyl EtherSolventHCID 6228DimethylformamideSolventHCID 6342AcetonitrileSolvent

Procedure

To a mechanically stirred mixture of 0.78 g (0.006 mol) of CuCl2, and 0.75 g (0.007 mol) of t-butylnitrite in 40 ml of CH3CN at 25° C. was added dropwise a solution of 1.7 g (0.0047 mol) of product of Example 191 in 10 ml of CHhd 3CN. Evolution of N2 was observed and reaction mixture was stirred for 18 hours. The crude mixture was poured into 3.7% HCl(aq), and extracted with diethyl ether. The ether phase was washed with H2O and dried (MgSO4). The dry ether phase was concentrated in vacuo to 1.55 g (0.004 mol) of the 4-chloropyridine as a yellow solid. To a magnetically stirred solution of 1.55 g (0.004 mol) of this yellow solid, and 0.50 g (0.005 mol) of triethylamine in 40 ml of DMF at 25° C. was added dropwise 0.28 g (0.005 mol) of cyclopropylamine. After 18 hours the reaction mixture was poured into H2O, and extracted with diethyl ether. The ether phace was washed with H2O, dried (MgSO4), and concentrated in vacuo affording 1.2 g of a brown solid. The crude was purified by preparatory centrifugally-accelerated radical thin-layer chromatography in 10% EtOAc/cyclohexane yielding 0.4 g (25%) of product as a yellow solid; mp 85°-86° C.

Workup

  1. customreaction mixture
  2. extractionextracted with diethyl ether
  3. washThe ether phase was washed with H2O
  4. dry with materialdried (MgSO4)
  5. extractionextracted with diethyl ether
  6. washThe ether phace was washed with H2O
  7. dry with materialdried (MgSO4)
  8. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-09272e79bcd4439786d6aacf9d3ec022
Source dataset
uspto-grants-1987_10
Patent number
US04698093

Reaction notes

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