Bromotrimethylsilane → Phosphonic acid, (p-hydroxyphenyl)-

HRID 889679Notes

Reaction equation

HRID 889679 reaction equation
Br[Si](C)(C)C.C([O:8][P:9]([C:14]1[CH:19]=[CH:18][C:17]([OH:20])=[CH:16][CH:15]=1)([O:11]CC)=[O:10])C>C(#N)C>[OH:10][P:9]([C:14]1[CH:15]=[CH:16][C:17]([OH:20])=[CH:18][CH:19]=1)([OH:11])=[O:8]

Participants

4

Reactant 2

HCID 76113BromotrimethylsilaneHCID 2773718p-Diethoxyphosphorylphenol

Product 1

HCID 214694Phosphonic acid, (p-hydroxyphenyl)-

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

Bromotrimethylsilane (1 ml) was added to 24 (0.5 g) in dry acetonitrile (10 ml) and the solution was refluxed for 24 h. The volatiles were removed under reduced pressure and acetonitrile (20 ml) was added to the residue and the solution stirred for 1 hour. The volatiles were removed under reduced pressure to yield 25 in quantitative yield, which was used without further purification in the next step. 1H NMR (DMSO-d6, 25° C., 500 MHz) δ 8.6 (br s, 3H, COH/POH), 7.49 (dd, 2H, ArH, J=12.5/8.5 Hz), 6.81 (dd, 2H, ArH, J=8.5/3.0 Hz); 13C NMR (DMSO-d6, 25° C., 126 MHz) δ 159.82 (d, 4JP-C=3.3 Hz), 132.52 (d, 2JP-C=11.3 Hz), 123.47 (d, 1JP-C=189.4 Hz), 114.92 (d, 3JP-C=15.3 Hz); 31P NMR (DMSO-d6, 25° C., 243 MHz) δ 14.69. Crystal/refinement details for 25a: C10H15O4P, M=230.19, F (000)=488 e, monoclinic, P21/n (No. 14), Z=4, T=100(2) K, a=8.5520(3), b=15.5263(4), c=8.6384(2) Å, β=92.433(2)°, V=1145.98(6) Å3, Dc=1.334 gcm−3, μMo=0.232 mm−1, sin θ/λmax=0.7035, N (unique)=3340 (merged from 13120, Rint=0.0303, Rsig=0.0306), No (I>2σ(I))=2694, R=0.0350, wR2=0.0948 (A, B=0.06, 0.1), GOF=1.003, |Δρmax|=0.41(6) e Å−3.

Workup

  1. temperaturethe solution was refluxed for 24 h
  2. customThe volatiles were removed under reduced pressure and acetonitrile (20 ml)
  3. additionwas added to the residue
  4. customThe volatiles were removed under reduced pressure

Sources & evidence

ORD record
ord-9f214753304a471ca01b2193366016ac
Source dataset
uspto-grants-2012_08
Patent number
US08252954B2

Reaction notes

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