Propargyl alcohol → HCID 9951891, compound

HRID 1168186Notes

Reaction equation

HRID 1168186 reaction equation
[Cl:1][C:2]1[CH:24]=[CH:23][C:5]([CH2:6][NH:7][C:8]([C:10]2[C:19](=[O:20])[C:18]3[C:13](=[CH:14][CH:15]=[C:16](I)[CH:17]=3)[N:12]([CH3:22])[N:11]=2)=[O:9])=[CH:4][CH:3]=1.[CH2:25]([OH:28])[C:26]#[CH:27]>C(NCC)C.[Cu]I.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[Cl:1][C:2]1[CH:24]=[CH:23][C:5]([CH2:6][NH:7][C:8]([C:10]2[C:19](=[O:20])[C:18]3[C:13](=[CH:14][CH:15]=[C:16]([C:27]#[C:26][CH2:25][OH:28])[CH:17]=3)[N:12]([CH3:22])[N:11]=2)=[O:9])=[CH:4][CH:3]=1

Participants

6

Reactant 2

HCID 7859Propargyl alcoholHCID 9955567HCID 9955567, compound

Product 1

HCID 9951891HCID 9951891, compoundYield 85%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418476HCID 178418476, compoundCatalystHCID 8021DiethylamineSolvent

Procedure

A suspension of N-(4-chlorobenzyl)-6-iodo-1-methyl-4-oxo-1,4-dihydro-3-cinnolinecarboxamide; (Ex. 1, 0.13 g), propargyl alcohol (0.035 mL), CuI (0.028 g), and Pd(PPh3)2Cl2 (0.013 g) in 11 mL diethylamine is stirred at room temperature for 18 h. The solid in the reaction is filtered, washed with water, and dried. The solid is dissolved in CH2Cl2 and adsorbed onto silica. Purification by chromatography (eluent CH2Cl2 (1L), 1% MeOH/CH2Cl2 (1L), 2% MeOH/CH2Cl2 (1L), 3% MeOH/CH2Cl2 (1L), 5% MeOH/CH2Cl2 (1L)) affords the desired product as a tan solid (0.094 g, 85%). Physical characteristics are as follows: m.p. 229-231° C.; 1H NMR (300 MHz, DMSO-d6) δ9.92, 8.19, 7.96, 7.40, 5.45, 4.55, 4.36, 4.24; IR (drift) 3365, 3273, 1656, 1598, 1551, 1479, 1410, 1351, 1284, 1034, 1028, 821, 812, 671, 646 cm−1; MS (ESI) m/z 382.1 (M+H)+; HRMS (FAB) calcd for C20H16ClN3O3+H1 382.0958, found 382.0963.

Workup

  1. filtrationThe solid in the reaction is filtered
  2. washwashed with water
  3. customdried
  4. dissolutionThe solid is dissolved in CH2Cl2
  5. customPurification by chromatography (eluent CH2Cl2 (1L), 1% MeOH/CH2Cl2 (1L), 2% MeOH/CH2Cl2 (1L), 3% MeOH/CH2Cl2 (1L), 5% MeOH/CH2Cl2 (1L))

Sources & evidence

ORD record
ord-dc8215d90e474895a53aefa26223087b
Source dataset
uspto-grants-2003_09
Patent number
US06624160B2

Reaction notes

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