Tetraethyl [[1,1'-biphenyl]-4,4'-diylbis(methylene)]bis(phosphonate) → HCID 67429829, compound

HRID 1660682Notes

Reaction equation

HRID 1660682 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].[C:7]1([N:13]2[C:26]3[CH:25]=[CH:24][C:23]([CH:27]=O)=[CH:22][C:21]=3[S:20](=[O:30])(=[O:29])[C:19]3[C:14]2=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C(OP([CH2:39][C:40]1[CH:45]=[CH:44][C:43]([C:46]2[CH:51]=[CH:50][C:49]([CH2:52]P(OCC)(OCC)=O)=[CH:48][CH:47]=2)=[CH:42][CH:41]=1)(=O)OCC)C>CS(C)=O.C(Cl)Cl>[C:7]1([N:13]2[C:26]3[CH:25]=[CH:3][C:2]([CH:5]=[CH:52][C:49]4[CH:48]=[CH:47][C:46]([C:43]5[CH:42]=[CH:41][C:40]([CH:39]=[CH:27][C:23]6[CH:24]=[CH:25][C:26]7[N:13]([C:7]8[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=8)[C:14]8[C:19]([S:20](=[O:30])(=[O:29])[C:21]=7[CH:22]=6)=[CH:18][CH:17]=[CH:16][CH:15]=8)=[CH:45][CH:44]=5)=[CH:51][CH:50]=4)=[CH:1][C:21]=3[S:20](=[O:30])(=[O:29])[C:19]3[C:14]2=[CH:15][CH:16]=[CH:17][CH:18]=3)[CH:8]=[CH:9][CH:10]=[CH:11][CH:12]=1

Participants

6

Reactant 3

HCID 635132Tetraethyl [[1,1'-biphenyl]-4,4'-diylbis(methylene)]bis(phosphonate)HCID 23665647Potassium tert-butoxideHCID 59609624HCID 59609624, compound

Product 1

HCID 67429829HCID 67429829, compound

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolventHCID 6344DichloromethaneSolvent

Procedure

2.28 g (19.9 mmol) of potassium tert-butoxide and then 5.90 g (17.6 mmol) of 10-phenyl-5,5-dioxophenothiazine-3-carbaldehyde (Example 21) were added under nitrogen at room temperature with stirring to a solution of 4.00 g (8.80 mmol) of diethyl[4′-(diethoxyphosphorylmethyl)biphenyl-4-ylmethyl]phosphonate in 45 ml of dimethyl sulfoxide dried over molecular sieve. After stirring at room temperature for 72 h, the reaction solution was diluted with 200 ml of methanol and stirred for a further 1 h. The precipitate was filtered off, washed with 500 ml of methanol and dried at 80° C. under reduced pressure. The crude product (5.44 g) was recrystallized in 250 ml of o-dichlorobenzene. The crystals were filtered off with suction, washed successively with o-dichlorobenzene and ethanol, filtered off with suction and dried at 80° C. under reduced pressure. After solvent residues had been removed in high vacuum (2×10−5 mbar) at 250° C., 4.35 g (60% of theory) of yellow microcrystals having a melting point of 392° C. were obtained, whose solution in methylene chloride fluoresced at λ=456 nm.

Workup

  1. customdried over molecular sieve
  2. additionthe reaction solution was diluted with 200 ml of methanol
  3. stirringstirred for a further 1 h
  4. filtrationThe precipitate was filtered off
  5. washwashed with 500 ml of methanol
  6. customdried at 80° C. under reduced pressure
  7. customThe crude product (5.44 g) was recrystallized in 250 ml of o-dichlorobenzene
  8. filtrationThe crystals were filtered off with suction
  9. washwashed successively with o-dichlorobenzene and ethanol
  10. filtrationfiltered off with suction
  11. customdried at 80° C. under reduced pressure
  12. customAfter solvent residues had been removed in high vacuum (2×10−5 mbar) at 250° C.
  13. customwere obtained

Sources & evidence

ORD record
ord-b2856ae2c79a46d18317ca78fc89ea34
Source dataset
uspto-grants-2011_10
Patent number
US08029919B2

Reaction notes

Loading…