Water → HCID 19033956, compound

HRID 1647966Notes

Reaction equation

HRID 1647966 reaction equation
C([O:3][P:4]([C:9]([P:30](=[O:37])([O:34]CC)[O:31]CC)=[CH:10][C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[C:17]#[C:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])(=[O:8])[O:5]CC)C.C[Si](Br)(C)C.O1CCCC1.O>C(Cl)Cl.[2H]C([2H])(Cl)Cl>[C:17]([C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=1[CH:10]=[C:9]([P:30](=[O:31])([OH:34])[OH:37])[P:4](=[O:3])([OH:5])[OH:8])#[C:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29]

Participants

6

Reactant 4

HCID 962WaterHCID 8028TetrahydrofuranHCID 76113Bromotrimethylsilane2×HCID 54279876HCID 54279876, compound

Product 1

HCID 19033956HCID 19033956, compoundYield 78.5%

Reagents, catalysts & solvents 1

HCID 131719048HCID 131719048, compoundSolvent

Procedure

Tetraethyl[2-[2-(1-tridecynyl)phenyl]ethenylidene]bisphosphonate (1.26 g, 2.28 mmol) prepared according to Example 9 was dissolved in a mixture of CH2Cl2 -CD2Cl2 (12 ml, 1.73:1). Trimethylsilyl bromide (1.3 ml, 9.85 mmol) was added, and the reaction was stirred for 5 hours. At this time additional trimethylsilyl bromide (0.2 ml, 1.5 mmol) was added. The progress of the reaction was monitored by 1H and 31P NMR, until no additional change occurred. 1H NMR was more useful in this regard, particularly the low field doublet of doublets. At the end of 8 hours, the solvent was removed under reduced pressure and the resulting oil was placed on the vacuum line. Tetrahydrofuran (10 ml) and water (0.25 ml, 13.9 mmol) were added and stirred for 20 hours, then removed under reduced pressure. NMR showed at least two species to be present, so the tetrahydrofuran-water treatment was repeated. After stripping, the residue was recrystallized from heptane as a white solid, 0.793 g, 1.79 mmol, 78.5% yield; mp 141°-142° C.; 1H NMR (CD3OD) ∂ 0.89 (m, 3H), 1.20 to 1.55 (m, 16H), 1.63 (quintet, J=7.4 Hz, 2H), 2.46 (t, J=7.1 Hz, 2H), 7.24 to 7.42 (m, 3H), 7.98 (m, 1H), 8.42 (dd, J=46.4, 29.0 Hz, 1H); FAB mass spectrum m/z 443 (M+H)+.

Workup

  1. customAt the end of 8 hours, the solvent was removed under reduced pressure
  2. stirringstirred for 20 hours
  3. customremoved under reduced pressure
  4. customthe residue was recrystallized from heptane as a white solid, 0.793 g, 1.79 mmol, 78.5% yield

Sources & evidence

ORD record
ord-843fc970fc64451ba75af35e8044b380
Source dataset
uspto-grants-1995_07
Patent number
US05434288

Reaction notes

Loading…