Potassium Carbonate → HCID 86595087, compound

HRID 2219110Notes

Reaction equation

HRID 2219110 reaction equation
[CH2:1]([O:3][P:4]([N:9]1[CH2:22][CH2:21][CH2:20][N:19](P(OCC)(OCC)=O)[CH2:18][CH2:17][N:16](P(OCC)(OCC)=O)[CH2:15][CH2:14][CH2:13][NH:12][CH2:11][CH2:10]1)([O:6][CH2:7][CH3:8])=[O:5])[CH3:2].C([O-])([O-])=O.[K+].[K+].BrCC1C=CC(CBr)=CC=1>CC#N>[CH2:7]([O:6][P:4]([N:9]1[CH2:22][CH2:21][CH2:20][NH:19][CH2:18][CH2:17][NH:16][CH2:15][CH2:14][CH2:13][NH:12][CH2:11][CH2:10]1)([O:3][CH2:1][CH3:2])=[O:5])[CH3:8]

Participants

5

Reactant 3

HCID 11430Potassium CarbonateHCID 693351,4-Bis(bromomethyl)benzeneHCID 15203124HCID 15203124, compound

Product 1

HCID 86595087HCID 86595087, compoundYield 139.7%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
70 °C

Procedure

To a stirred solution of 4,8,11-Tris(diethoxyphosphoryl)-1,4,8,11-tetraazacyclotetradecane (See Bridger et al. J Med. Chem. 1995, 38, 366-378) (6.1 g, 0.01 mol) and K2CO3 (1.89 g, 0.013 mol) in CH3CN (150 ml) was added α,α′-dibromo-p-xylene (13.2 g, 0.05 mol) and the reaction mixture stirred at 70° C. for 1 hour. The solution was cooled to room temperature and the solvent removed under reduced pressure. The residue was partitioned between brine (50 ml) and CH2Cl2 (100 ml). The organic phase was separated, dried (Na2SO4) and concentrated to a minimum volume. The solid was filtered off and the solvent evaporated under reduced pressure to give the crude product as a pale yellow oil. Purification by column chromatography in silica gel (CH2Cl2\CH3OH, 25:1) gave 1-[1-methylene-4-(bromomethylene)phenylene]-4,8,11-tris(diethoxyphosphoryl-1,4,8,11-tetraazacyclotetra-decane (4.7 g, 59%) as a pale yellow oil. 1H NMR (CDCl3) δ 1.21-1.37 (m, 18H), 1.66-1.74 (m, 2H), 1.82-1.91 (m, 2H), 2.30-2.35 (m, 2H), 2.58-2.63 (m, 2H), 2.99-3.16 (m, 12H), 3.48 (s, 2H), 3.95-4.07 (m, 12H), 4.48 (s, 2H), 7.21-7.35 (4H).

Workup

  1. temperatureThe solution was cooled to room temperature
  2. customthe solvent removed under reduced pressure
  3. customThe residue was partitioned between brine (50 ml) and CH2Cl2 (100 ml)
  4. customThe organic phase was separated
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated to a minimum volume
  7. filtrationThe solid was filtered off
  8. customthe solvent evaporated under reduced pressure
  9. customto give the crude product as a pale yellow oil
  10. customPurification by column chromatography in silica gel (CH2Cl2\CH3OH, 25:1)

Sources & evidence

ORD record
ord-eac5a30c22344d7a92a73086310ae001
Source dataset
uspto-grants-2008_08
Patent number
US07414065B2

Reaction notes

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