Phosphonium, (2-methoxy-2-oxoethyl)triphenyl-, bromide (1:1)

white powder

General procedure: To a stirred solution of PPh3 (1.7 g, 6.7 mmol) in ethylacetate, a solution of methyl 2-bromoacetate (0.62 μL, 6.5 mmol) in ethyl acetate was added at room temperature.After 17 h, a white precipitate was collectedby filtration, washed three times with ether and driedin air to furnish (2-methoxy-2-oxoethyl)triphenylphosphoniumbromide (4, 2.49 g) as a white solid in almostquantitative yield. The phosphonium bromide 4 (2.0 g, 4.81 mmol) was added to a suspension of sodium ethoxide(340 mg) in ethanol (10 mL) followed by the additionof 3a (1.15 g, 4.75 mmol) at room temperature for 25 min.The mixture was stirred at 50–55°C for 1 h. The progressof the reaction was monitored via TLC. After completionof the reaction, water (10 mL) was added to the reactionmixture, and the product was extracted four timeswith diethyl ether (20 mL). The organic layers were combined, dried over anhydrous sodium sulfate and evaporatedunder reduced pressure to furnish a solid residue.Further purification by column chromatography (ethylacetate : hexane 3 : 7) afforded two methyl cinnamatederivatives as a 3.5 : 1 mixture of E- and Z-isomers, respectively.(1) Synthesis of phosphorus salt (0.09 mol) of KI in 200 ml of water was added to toluene and 44.4 g (0.29 mol) of 2-bromoacetic acid (0.29 mol) was added to a solution of 888 (0.29111001) triphenylphosphine, Methyl ester. Nitrogen protection down to 65 ~ 75 ° C, insulation 20h. After the end of the insulation, cool to 50 ~ 60 ° C, add 350ml of water, phase separation. The water was incubated at 40 ° C and slowly added 268.4 g of 10percent sodium hydroxide solution. After incubation for 30 min, the filter was filtered and the filter cake was rinsed with 40 ml of n-heptane and dried at 50 ° C under reduced pressure to give a yellow solid. G, the yield of 90percent.To a solution of triphenylphosphine (942 mg, 3.6 mmol) in dry THF (3 mL) was added methyl 2-bromoacetate (500 mg, 3.27 mmol) and the mixture was stirred at rt for 3h. The product was filtered, washed with THF and dried under reduced pressure to give a colourless solid 57 (1.20 g, 89percent). HPLC: 4.91 min (99percent).A mixture of 9-formyl-8-hydroxyjulolidine (1.00 g, 4.60 mmol), (carbomethoxymethyl)triphenylphosphonium bromide (2.29 g, 5.51 mmol) and DBU (0.820 mL, 5.47 mmol) was refluxed in DMSO (20 mL) for 20 min. After cooling to room temperature, water (20 mL) was added and the mixture was extracted with DCM (5×30 mL) then washed with water (2×30 mL) and dried over MgSO4. After evaporation of the solvent, the crude product was purified by column chromatography (hexanes/EtOAc : 3/1 ' 1/1) to give 12 (694 mg, 63percent) as yellow solid. 1H-NMR (CDCl3, 250 MHz): delta = 1.96 (m, 4H); 2.74 (t, 2H, J = 6.5 Hz); 2.87 (t, 2H, J = 6.3 Hz); 3.24 (m, 4H); 5.97 (d, 1H, J = 9.2 Hz); 6.83 (s, 1H); 7.45 (d, 1H, J = 9.16 Hz). 13C-NMR (CDCl3, 62.5 MHz): delta = 20.2; 20.5; 21.4; 27.4; 49.6; 50.0; 106.7; 108.2; 108.3; 118.2; 124.9; 144.0; 145.9; 151.7; 162.7.

Molecular Weight:415.3
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:6
Exact Mass:414.03843
Monoisotopic Mass:414.03843
Topological Polar Surface Area:26.3
Heavy Atom Count:25
Complexity:345
Covalently-Bonded Unit Count:2
Compound Is Canonicalized:Yes