Tetraethyl [[1,1'-biphenyl]-4,4'-diylbis(methylene)]bis(phosphonate) → HCID 72337841, compound

HRID 1660690Notes

Reaction equation

HRID 1660690 reaction equation
[CH3:1][C:2]([CH3:5])([O-])[CH3:3].[K+].[C:7]1([CH3:33])[CH:12]=[C:11]([CH3:13])[CH:10]=[C:9]([CH3:14])[C:8]=1[N:15]1[C:28]2[CH:27]=[CH:26][C:25]([CH:29]=O)=[CH:24][C:23]=2[S:22](=[O:32])(=[O:31])[C:21]2[C:16]1=[CH:17][CH:18]=[CH:19][CH:20]=2.C(OP([CH2:42][C:43]1[CH:48]=[CH:47][C:46]([C:49]2[CH:54]=[CH:53][C:52]([CH2:55]P(OCC)(OCC)=O)=[CH:51][CH:50]=2)=[CH:45][CH:44]=1)(=O)OCC)C>C(Cl)(Cl)Cl>[C:7]1([CH3:33])[CH:12]=[C:11]([CH3:13])[CH:10]=[C:9]([CH3:14])[C:8]=1[N:15]1[C:28]2[CH:27]=[CH:26][C:25]([CH:29]=[CH:55][C:52]3[CH:51]=[CH:50][C:49]([C:46]4[CH:45]=[CH:44][C:43]([CH:42]=[CH:1][C:2]5[CH:5]=[CH:27][C:28]6[N:15]([C:8]7[C:7]([CH3:33])=[CH:12][C:11]([CH3:13])=[CH:10][C:9]=7[CH3:14])[C:16]7[C:21]([S:22](=[O:32])(=[O:31])[C:23]=6[CH:3]=5)=[CH:20][CH:19]=[CH:18][CH:17]=7)=[CH:48][CH:47]=4)=[CH:54][CH:53]=3)=[CH:24][C:23]=2[S:22](=[O:32])(=[O:31])[C:21]2[C:16]1=[CH:17][CH:18]=[CH:19][CH:20]=2

Participants

5

Reactant 3

HCID 635132Tetraethyl [[1,1'-biphenyl]-4,4'-diylbis(methylene)]bis(phosphonate)HCID 23665647Potassium tert-butoxideHCID 86648279HCID 86648279, compound

Product 1

HCID 72337841HCID 72337841, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

0.93 g (8.1 mmol) of potassium tert-butoxide and then 2.70 g (7.16 mmol) of 10-mesityl-5,5-dioxophenothiazine-3-carbaldehyde (example 35b) were added at room temperature with stirring under nitrogen to a solution of 1.63 g (3.58 mmol) of diethyl[4′-(diethoxyphosphorylmethyl)biphenyl-4-ylmethyl]phosphonate (U.S. Pat. No. 3,984,399, example 2, column 29, lines 58-66) in 40 ml of dimethyl sulfoxide which has been dried over a molecular sieve. After stirring at room temperature for 4 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 100 ml of methanol, stirred up again in 300 ml of methanol, filtered again and dried at 35° C. under reduced pressure. The crude product (2.90 g) was recrystallized twice from dimethylformamide and once from chlorobenzene. The crystals were filtered off with suction, washed successively with chlorobenzene and ethanol, filtered off with suction and dried at 80° C. under reduced pressure. After the removal of solvent residues under high vacuum (2×10−5 mbar) at 250° C., 0.98 g (30% of theory) of analytically pure luminous yellow microcrystals having an m.p. of >350° C. were obtained, whose solution in chloroform fluoresced at λ=456, 485 (S), 522 (S) nm.

Workup

  1. dry with material3,984,399, example 2, column 29, lines 58-66) in 40 ml of dimethyl sulfoxide which has been dried over a 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 100 ml of methanol
  6. stirringstirred up again in 300 ml of methanol
  7. filtrationfiltered again
  8. customdried at 35° C. under reduced pressure
  9. customThe crude product (2.90 g) was recrystallized twice from dimethylformamide and once from chlorobenzene
  10. filtrationThe crystals were filtered off with suction
  11. washwashed successively with chlorobenzene and ethanol
  12. filtrationfiltered off with suction
  13. customdried at 80° C. under reduced pressure
  14. customAfter the removal of solvent residues under high vacuum (2×10−5 mbar) at 250° C.
  15. customwere obtained

Sources & evidence

ORD record
ord-37baab55a49a4176b9597daed0f71b67
Source dataset
uspto-grants-2011_10
Patent number
US08029919B2

Reaction notes

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