Chlorodicyclohexylphosphine → HCID 21183118, compound

HRID 1386832Notes

Reaction equation

HRID 1386832 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[O:12][CH2:11][CH2:10][O:9]2)=[CH:4][CH:3]=1.C([Li])(C)(C)C.Cl[P:19]([CH:26]1[CH2:31][CH2:30][CH2:29][CH2:28][CH2:27]1)[CH:20]1[CH2:25][CH2:24][CH2:23][CH2:22][CH2:21]1>C(OCC)C>[CH:26]1([P:19]([CH:20]2[CH2:21][CH2:22][CH2:23][CH2:24][CH2:25]2)[C:2]2[CH:7]=[CH:6][C:5]([CH:8]3[O:12][CH2:11][CH2:10][O:9]3)=[CH:4][CH:3]=2)[CH2:27][CH2:28][CH2:29][CH2:30][CH2:31]1

Participants

5

Reactant 3

HCID 2734135ChlorodicyclohexylphosphineHCID 27738422-(4-Bromophenyl)-1,3-dioxolaneHCID 178418306HCID 178418306, compound

Product 1

HCID 21183118HCID 21183118, compound

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

This is an example of synthesis of ligand 2. 2-(4′-Dicyclohexylphosphinophenyl)-1,3-dioxolane (Ligand 2): Part I. A solution of 4-bromobenzaldehyde (5 g, 0.027 mol), ethylene glycol (7.0 g, 0.11 mmol), and p-toluenesulfonic acid (0.1 g, 0.5 mmol) in benzene was heated at reflux for 24 h using a Dean-Stark setup to remove water. The reaction was taken up in diethyl ether (100 mL) and washed with water (5×30 mL) and brine (30 mL). The organic phase was dried over magnesium sulfate and concentrated under vacuum to afford 2-(4′-bromophenyl)-1,3-dioxolane (5.95 g). Part II. 2-(4′-bromophenyl)-1,3-dioxolane (1.0 g, 4.4 mmol) was dissolved in anhydrous diethyl ether (30 mL) and the solution was cooled to −78° C. t-Butyllithium (5.14 mL, 1.7 M solution in pentane, 8.8 mmol) was added dropwise with stirring. The reaction was stirred for 2 h at −78 ° C. Chlorodicyclohexylphosphine (1.13 g, 4.8 mmol) was added dropwise via a syringe at −78 ° C. with stirring. The reaction mixture was allowed to warm up to room temperature and stirred for an additional 18 h. To the reaction mixture was added argon purged water (25 mL) slowly. The organic phase was separated under argon and the aqueous phase was washed with diethyl ether (20 mL). The combined organic phase was concentrated under vacuum to afford a colorless oil, which was crystallized from methanol to afford ligand 2 as a white crystalline solid having the structure shown below (yield: 1.4 g, 92%). 31P{1H} NMR (CDCl3): δ2.4.

Workup

  1. additionwas added dropwise
  2. stirringThe reaction was stirred for 2 h at −78 ° C
  3. stirringwith stirring
  4. stirringstirred for an additional 18 h
  5. additionTo the reaction mixture was added argon
  6. custompurged water (25 mL) slowly
  7. customThe organic phase was separated under argon
  8. washthe aqueous phase was washed with diethyl ether (20 mL)
  9. concentrationThe combined organic phase was concentrated under vacuum
  10. customto afford a colorless oil, which
  11. customwas crystallized from methanol

Sources & evidence

ORD record
ord-a239f245856b4bc3a86587d669928196
Source dataset
uspto-grants-2001_07
Patent number
US06265601B1

Reaction notes

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