Ethylene Glycol → HCID 18001580, compound

HRID 478321Notes

Reaction equation

HRID 478321 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1B(O)O.C(O)CO.Cl[C:17]1[N:25]=[CH:24][N:23]=[C:22]2[C:18]=1[N:19]=[C:20]([CH2:33][CH3:34])[N:21]2[CH:26]([CH2:31][CH3:32])[CH2:27][CH2:28][CH2:29][CH3:30].C(=O)([O-])[O-].[Tl+2]>C1C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[Cl:1][C:2]1[CH:7]=[C:6]([Cl:8])[CH:5]=[CH:4][C:3]=1[C:17]1[N:25]=[CH:24][N:23]=[C:22]2[C:18]=1[N:19]=[C:20]([CH2:33][CH3:34])[N:21]2[CH:26]([CH2:31][CH3:32])[CH2:27][CH2:28][CH2:29][CH3:30]

Participants

8

Reactant 4

HCID 174Ethylene GlycolHCID 2734659(2,4-Dichlorophenyl)boronic acidHCID 18001491HCID 18001491, compoundHCID 178526101HCID 178526101, compound

Product 1

HCID 18001580HCID 18001580, compoundYield 68%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

A solution of 2,4-dichlorobenzeneboronic acid (572 mg, 3.00 mmol) and ethylene glycol (205 mg, 3.30 mmol) in benzene (20 mL) was heated to reflux with azeotropic removal of water for a period of 8 h. The resulting solution was cooled, and treated with 6-chloro-8-ethyl-9-(1-ethylpentyl)purine (see Example 2, Part C above; 562 mg, 2.00 mmol), thallium carbonate (1.03 g, 2.20 mmol) and tetrakis(triphenylphosphine)palladium (116 mg, 0.10 mmol). The resulting mixture was heated to reflux with stirring for 12 h, then cooled, filtered through celite and evaporated. The resulting residue was separated by column chromatography (silica gel, 10:90 ethyl acetate-hexane) to afford the title compound as a viscous oil (530 mg, 1.35 mmol, 68%). TLC RF 0.31 (20:80 ethyl acetate-hexane). 1H NMR (300 MHz, CDCl3): d 8.94 (1H, s), 7.71 (1H, d, J=8.4 Hz), 7.58 (1H, d, J=1.8 Hz), 7.41 (1H, dd, J=8.4, 1.8 Hz), 4.27 (1H, br), 2.95 (2H, q, J=7.3 Hz), 2.41 (2H, br), 2.11-1.98 (2H, br), 1.42 (3H, t, J=7.3 Hz), 1.37-1.20 (3H, m), 1.09-0.99 (1H, m), 0.84 (3H, t, J=7.7 Hz), 0.82 (3H, t, J=7.7 Hz). MS (NH3—CI): m/e calc'd for C20H25NCl2: 391.1456, found 391.1458; 395 (11), 394 (14), 393 (71), 392 (29), 391 (100).

Workup

  1. temperatureThe resulting solution was cooled
  2. temperatureThe resulting mixture was heated
  3. temperatureto reflux
  4. temperaturecooled
  5. filtrationfiltered through celite
  6. customevaporated
  7. customThe resulting residue was separated by column chromatography (silica gel, 10:90 ethyl acetate-hexane)

Sources & evidence

ORD record
ord-d513bb0cd8b3403594416e8815e2665e
Source dataset
uspto-grants-2003_11
Patent number
US06642230B2

Reaction notes

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