Triphenylphosphine → Triphenyl(3-pyridylmethyl)phosphonium chloride

HRID 2119296Notes

Reaction equation

HRID 2119296 reaction equation
Cl.[Cl:2][CH2:3][C:4]1[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=1.[C:10]1([P:16]([C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)[C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH:15]=[CH:14][CH:13]=[CH:12][CH:11]=1>O.C1(C)C=CC=CC=1>[Cl-:2].[C:23]1([P+:16]([C:10]2[CH:11]=[CH:12][CH:13]=[CH:14][CH:15]=2)([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)[CH2:3][C:4]2[CH:5]=[N:6][CH:7]=[CH:8][CH:9]=2)[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1

Participants

5

Reactant 2

HCID 11776TriphenylphosphineHCID 233943-(Chloromethyl)pyridine hydrochloride

Product 1

HCID 22325077Triphenyl(3-pyridylmethyl)phosphonium chloride

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
0 °C

Procedure

To an ice-cooled 2-phase mixture of 55.8 g (195 mmol) Na2CO3·10 H2O in 200 ml water and 100 ml toluene, 21.3 g (133 mmol) 3-chloromethylpyridine hydrochloride is added in portions. The mixture is stirred at 0° C. until a clear solution is obtained, the aqueous phase separated off, and the mixture extracted twice with 50 ml toluene. The toluene phases are dried (Na2SO4) and evaporated in the RE (10 mbar, 30° C.) to about half its original volume. To the yellowish solution, 68.1 g (259 mmol) triphenylphosphine is added and the mixture stirred for several days under a N2 atmosphere at 70° C. The title compound is precipitated off in the process. It is filtered off and washed with toluene and hexane; 1H-NMR (DMSO-d6) 8.47 (m, 1HPy), 8.18 (sb, 1HPy), 7.91 (m, 3H), 7.72 (m, 12H), 7.37 (m, 1HPy), 7.26 (m, 1HPy), 5.33 (d, J=15 Hz, H2C); FAB-MS (M−Cl)+=354; an. calc. (C24H21NClP·0.17 H2O) C, 73.36%; H, 5.47%; N, 3.56%; Cl, 9.02%; P, 7.88%; H2O, 0.78%; meas. C, 73.11%; H, 5.43%; N, 3.82%; Cl, 9.49%; P, 7.98%; H2O, 0.77%.

Workup

  1. additionis added in portions
  2. customis obtained
  3. customthe aqueous phase separated off
  4. extractionthe mixture extracted twice with 50 ml toluene
  5. dry with materialThe toluene phases are dried (Na2SO4)
  6. customevaporated in the RE (10 mbar, 30° C.) to about half its original volume
  7. stirringthe mixture stirred for several days under a N2 atmosphere at 70° C
  8. customThe title compound is precipitated off in the process
  9. filtrationIt is filtered off
  10. washwashed with toluene and hexane

Sources & evidence

ORD record
ord-4bf57f1e54dd49aa84d60fadbd61d9ea
Source dataset
uspto-grants-2004_02
Patent number
US06686347B2

Reaction notes

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