Purity | Size | Price | VIP Price | USA Stock *0-1 Day | Global Stock *5-7 Days | Quantity | ||||||
{[ item.p_purity ]} | {[ item.pr_size ]} | Inquiry |
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price) ]} {[ getRatePrice(item.pr_usd,item.pr_rate,1,item.pr_is_large_size_no_price) ]} |
{[ getRatePrice(item.pr_usd, 1,1,item.pr_is_large_size_no_price) ]} | Inquiry {[ getRatePrice(item.pr_usd,item.pr_rate,item.mem_rate,item.pr_is_large_size_no_price) ]} {[ getRatePrice(item.pr_usd,1,item.mem_rate,item.pr_is_large_size_no_price) ]} | {[ item.pr_usastock ]} | in stock Inquiry - | {[ item.pr_chinastock ]} | {[ item.pr_remark ]} in stock Inquiry - | Login | Inquiry |
Please Login or Create an Account to: See VIP prices and availability
CAS No. : | 4009-98-7 | MDL No. : | MFCD00011800 |
Formula : | C20H20ClOP | Boiling Point : | - |
Linear Structure Formula : | [(C6H5)3PCH2OCH3]Cl | InChI Key : | SJFNDMHZXCUXSA-UHFFFAOYSA-M |
M.W : | 342.80 | Pubchem ID : | 2723798 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P501-P270-P264-P280-P337+P313-P301+P312+P330 | UN#: | N/A |
Hazard Statements: | H302-H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Preparation Example 267 To a suspension of (methoxymethyl)(triphenyl)phosphonium chloride (164.57 g) which had been cooled in a dry ice-acetone bath in THF (500 ml) was added dropwise a solution of n-butyllithium in hexane (concentration 1.65 M, 281.3 ml) at -55C or lower under a nitrogen air flow. Then, the mixed reaction liquid was warmed, followed by stirring at room temperature for 1 hour. After stirring, the mixed reaction liquid was cooled under ice, and a solution of <strong>[17429-02-6]4-hydroxy-4-methylcyclohexanone</strong> (20.51 g) in THF (205 ml) was added dropwise thereto. After dropwise addition, the mixed reaction liquid was warmed to room temperature, followed by stirring for 15 hours. To the mixed reaction liquid were sequentially added water and EtOAc, followed by stirring, and then the organic layer was collected by separation. The aqueous layer was further extracted with EtOAc, and the organic layer was combined, washed with saturated brine, and dried over anhydrous sodium sulfate. After the desiccant was removed, the solvent was evaporated under reduced pressure. The residue was purified by silica gel flash column chromatography (hexane-EtOAc) to obtain 4-(methoxymethylene)-1-methylcyclohexanol (21.37 g). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
820 mg (71%) | With sodium hexamethyldisilazane; In tetrahydrofuran; | Step A 2-[4-[(E)-2-methoxyethenyl]phenyl]-pyrazine Sodium hexamethyldisilazide (10.80 mL, 10.80 mmol, 11.0M in THF) was added to a suspension of methoxymethyltriphenylphosphonium chloride (3.72 g, 10.80 mmol) in THF (20 mL) at -10 C., and the red-orange mixture was stirred for 15 min at -10 C. A solution of 4-pyrazinylbenzaldehyde (1.00 g, 5.43 mmol) prepared as described in reference example 17) in THF (3 mL) was added dropwise, and stirring was continued at -10 C. for 1 h. The reaction mixture was quenched with sat. aq. NH4Cl, extracted with ethyl acetate, the organic layer dried with Na2SO4, and concentrated in vacuo. Purification by medium pressure liquid chromatography (SiO2, 3:1 hexane/ethyl acetate) yielded 820 mg (71%) of the title compound (E:Z=1:1). MS 213 (M+H)+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With selenium(IV) oxide; potassium tert-butylate; In hexane; | EXAMPLE 3 This Example illustrates an alternative synthesis of (E)-methyl 3-methoxy-2-[2-(3-methylphenoxy)phenyl]propenoate. A mixture of methyl ortho-bromophenylacetate (4.10 g, prepared as described in Example 1) and selenium dioxide (4.92 g) was stirred for 25 hours at 190 C. After cooling, the mixture was diluted with dichloromethane (100 ml) then filtered through `Supercel`. The filtrate was washed successively with saturated aqueous sodium bicarbonate (*2) and brine, then dried and concentrated to give a yellow liquid (3.60 g) containing (52% by GC-MS) <strong>[122394-38-1]methyl (2-bromobenzoyl)formate</strong> and unreacted methyl ortho-bromophenylacetate. Potassium tert-butoxide (2.33 g) was added to a vigorously-stirred suspension of (methoxymethyl)triphenylphosphonium chloride (7.90 g) in ether (80 ml) at room temperature. After 15 minutes, a solution of the crude <strong>[122394-38-1]methyl (2-bromobenzoyl)formate</strong> (3.60 g) in ether (10 ml) was added in a single portion. After a further 15 minutes, the reaction mixture was poured into water (150 ml), the aqueous and organic layers were separated, and the former was extracted with a further portion of ether (100 ml). The combined ether layers were washed successively with water (*2) and brine, then dried and concentrated to give a yellow oil (5.81 g) containing, in a ratio of about 6:5, the (E)- and (Z)-isomers respectively of methyl 2-(2-bromophenyl)-3-methoxypropenoate. Chromatography using ether:hexane (1:1) as eluant allowed the pure (Z)-isomer (0.450 g) to be isolated as a pale yellow oil, IR (film) 1712, 1638 cm-1, 1 H n.m.r delta 3.71 (3H, s), 3.95 (3H, s), 6.57 (1H, s) p.p.m. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride; In tetrahydrofuran; at 0 - 20℃; for 13h;Heating / reflux; | Example 3 : rralphaw.s'-2-(ammome1hyl)-5-(5'-fluoro-2'-methoxybenzyl)tetrahydrofuran[0195] S-Fluoro-2-methoxyphenacetaldehyde:; To a suspension of methoxymethyltriphenylphosphonium chloride (10.0 g, 30.0 mmol) in THF (30 mL) under Ar(g) was added NaH (60% in mineral oil, 1.2 g, 30 mmol) and the mixture thus obtained was heated to reflux for 1 h. The orange suspension thus obtained was cooled to O0C and 5- fluoro-2-methoxybenzaldehyde (4.2 g, 26.0 mmol) was added and the reaction was continued for 12 h while warmed to room temperature. The reaction mixture was poured in to a separatory funnel containing ammonium chloride aqueous solution (sat. NH4Cl: H2O=I :1, 100 mL). The organic fraction was extracted with ethyl acetate (3 x 80 mL) and the combined organic layers were washed with brine (60 mL) and dried over sodium sulfate. The solvent was then removed in vacuo and crude product thus obtained was dissolved in acetone (50 mL) and H2SO4 (1 M, 1.5 mL) was added and the mixture thus obtained was heated to reflux for 6 h. It was then cooled to room temperature and the crude product obtained after the removal of the solvent was purified by flash column chromatography (10% ethyl acetate in hexane, Rf = 0.15) to give the product (2.63 g, 66%) as an oil.; [0287] 5-Fluoro~2-methoxyphenylacetaldehyde (2a): To a suspension of methoxymethyltriphenylphosphonium chloride (10.0 g, 30.0 mmol) in THF (30 niL) under Ar was added NaH (60% in mineral oil, 1.2 g, 30 mmol) and then heated to reflux for 1 h. The orange colored suspension was cooled to 0C and <strong>[19415-51-1]5-fluoro-2-methoxybenzaldehyde</strong> (4.2 g, 26.0 mmol) was added and the mixture was stirred for 12 h at room temperature. The reaction mixture was then poured into a separatory funnel containing ammonium chloride aqueous solution (sat. NH4C1/H20, 1:1, v:v, 100 niL). The organic material was extracted with ethyl acetate (3 x 80 mL) and the combined organic layers were washed with brine (60 mL) and dried over Na2SO4. The solvent was then removed in vacuo and the crude product (2a) obtained was dissolved in acetone (50 mL). H2SO4 (1 M, 1.5 mL) was then added and the mixture obtained was heated to reflux for 6 h while stirring. The reaction was then cooled to room temperature and the solvent was removed in vacuo to obtain the crude product that was then purified by flash column chromatography (Rf = 0.15, EtOAc/Hexane, 10:90, v:v) to afford the product (2.63 g, 66%) as an oil: 1H NMR (CDCl3, 500 MHz): delta 9.68 (s, 1 H), 6.97 (dt, J= 3.1, 8.7 Hz, 1 H), 6.89 (dd, J= 3.1, 8.7 Hz, 1 H), 6.83 (dd, J= 4.3, 8.7 Hz, 1 H), 3.80 (s, 3 H), 3.63 (d, J= 1.7 Hz, 2 H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
34% | Step 1 : Potassium tert-butoxide (4.49 mL, IM in THF) was added over about5 minutes to (methoxymethyl) triphenylphosphonium chloride (1.42 g, 4.15 mmol) suspended in anhydrous THF (25 mL) at O0C. The resulting suspension was stirred at about this temperature for about 45 minutes at which time, tert-butyl 2-benzyl-4-oxopiperidine-l- <n="111"/>carboxylate (1.Og, 3.46 mmol) dissolved in THF (5 niL) was added. The reaction mixture was allowed to warm to ambient and stir for another 6h. The reaction was quenched by the addition of ammonium chloride solution and then taken up in EtOAc. After washing twice with water and once with brine, the organic portion was dried over magnesium sulfate, filtered and concentrated. The resulting semi-solid residue was purified via silica gel chromatography to give (Z)-tert-butyl 2-benzyl-4-(methoxymethylene)piperidine-l- carboxylate (375 mg, 34%). LCMS (APCI+) m/z 218.1 [M+H]+; Rt = 4.51 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
660 mg (1.9 mmol) of methoxymethyl-triphenylphosphonium chloride was dissolved in 10 ml of tetrahydrofuran, then n-butyl lithium was added to the resulting at - 78C. After 30 minutes, the reaction was heated to 0C and 2 ml of hexamethylphosphoamide was added thereto, then 220 mg (1.3 mmol) of 1-phenyl-lH- pyrrazole-3-carbaldehyde dissolved in 3 ml of tetrahydrofuran was further added thereto. After stirring for 1 hour, ethylacetate was added, followed by washing with ammonium chloride solution. The organic solution thus obtained was dried over anhydrous ammonium sulfate, the residue was purified by column chromatography to obtain 3- (2- methoxy-vinyl)-1-phenyl-lH-pyrazole. This compound was dissolved in a mixture of 3 ml of 3 N hydrogen chloride solution and 20 ml of tetrahydrofuran, then the resulting solution was stirred with heating for 2 hours. Ethylacetate was added thereto and the resulting solution was washed with water, then the organic solution thus obtained was dried over anhydrous magnesium sulfate, and the residue was purified by column chromatography to obtain 130 mg of the title compound in a yield of 36%. Mass (EI) 187 (M++1) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Synthesis of Intermediate 1-46To a solution of (methoxymethyl)triphenylphosphonium chloride (160 mg, 0.466 mmol) in THF (4.7 mL) at 0C was added dropwise KfBuO (57 mg, 0.508 mmol) in THF (1 mL). The mixture was stirred at RT for 30 min. A solution of 8- bromoquinoline-2-carbaldehyde (100 mg, 0.424 mmol) in THF (1 mL) was added dropwise to the generated ylide at RT and the reaction mixture was stirred at RT for 16 h. More ylide (1.1 eq) was added, and the reaction mixture was stirred at RT for 19 h, heated at 50C for 6 h, and then refluxed for 16 h. More ylide (1.1 eq) was added and the reaction was heated at 50C for 3 days. On cooling, the mixture was evaporated. The residue was triturated from Et20 and filtered. The filtrate was evaporated and the residue was purified by column chromatography (Biotage, MeOH:DCM, 0:100 to 6:94) to give Intermediate I-46 (23 mg, 21%) (mixture of E and Z isomers) as yellow solid.HPLC-MS (method 4): Rt =4.3, [M+H]+ 264. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | LiHMDS (53 mL, 1 .0 N, 53 mmol) was added to a stirred suspension of KR-Si(7.20 g, 35 mmol) in THE (120 mL) at -20C over a period of 20 mm undernitrogen. The resulting solution was stirred at -10C for 1 hr, and thenmethoxymethyl(triphenyl)phosphonium;chloride (i8.i3 g, 53 mmol) in THE (10 mL) was added over a period of 15 mm under nitrogen. The resulting solution was stirred at room temperature for 15 hrs. The reaction was quenched aq.NH4CI and then extracted with EtOAc (200 mL). The combinedorganic phase was washed with saturated brine (100 mL), dried over anhydrous Na2SO4, filtered and concentrated in vacuo. The residue was purified by column to give the pure reagent R-32a(4.6i g, 56% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | To a stirring solution of (methoxymethyl)triphenylphosphonium chloride (3.74 g, 10.91 mmol) in THF (16 mL) was added potassium tert-butoxide (1.224 g, 10.91 mmol) portionwise. The solution was stirred at room temperature for 50 min then a solution of <strong>[56309-94-5]4-(1,4-dioxaspiro[4.5]decan-8-yl)cyclohexanone</strong> (2 g, 8.39 mmol) in THF (16 mL) was added slowly. The reaction mixture was stirred for 3.5 h. The solvent was removed under vacuum. The residue was treated with Et2O (44 mL) and stirred for 1 h. The mixture was filtered, washed with Et2O (2 x 50 mL) and the filtrate was evaporated. The crude product was purified by column chromatography (EA/Iso- hexane) to afford 1.8 g (76percent) of 8-(4-(methoxymethylene)cyclohexyl)-l ,4- dioxaspiro[4.5]decane as a colourless oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Step 1 : To a solution of (methoxymethyl)triphenylphosphonium chloride (1.5 equiv.) in THF (0.3 M) at 0 C was added NaHMDS (1M in THF, 1.55 equiv.) and the red solution was stirred in the cold bath for 30 min at which point 5-bromo-2- methoxynicotinaldehyde (1.0 equiv.) was added. After stirring in the cold bash for 30 min, the solution was allowed to warm to rt, stirred for 2 hours, then partitioned between ethyl acetate and sat. sodium bicarbonate. The layers were mixed, separated, the organic phase was washed with brine, dried over magnesium sulfate, filtered and concentrated. The residue was purified via siiica gel chromatography (0-30% ethyl aeetate/n-heptanes) to yield 5-bromo-2- methoxy-3-(2-methoxyvinyl)pyridine contaminated with the starting aldehyde. This mixture was dissolved in methanol and 0.5 equiv. of sodium borohydride were added. After stirring at rt for 10 min, the volatiles were removed in vacuo and the residue was partitioned between ethyl acetate and brine. The organic phase was dried over magnesium sulfate, filtered and concentrated. Purification via silica gel chromatography (ISCO, 0-15% ethyl acetate/n- heptanes) afforded 5-bromo-2-methoxy-3-(2-methoxyvinyl)pyridine in 11% yield as a mixture of enol ethers isomers. LCMS (m/z) (M+H) - 244.0/246.0, Rt = 0.97 and 1.01 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | To a stirred suspension of (melhoxymethyi)triphenyiphosphonium chloride (17.0 g, 49.6 mrnol)) in THF (41 mL)was added slowly a solution of potassium 2-methyipropan-2-olate (41 niL, 41 mniol) at 0C via cannula under nitrogen. The resulting cherry-red solution was stirred at 0 C for I h. A solution of 2-chioro- 7.8-dihydroquinoiin-5(6H)-one (3.00 g, 16.5 mmoi) in THF (10.0 mL) was added dropwaise. The reaction mixture was stirred at r.t. for I h. The reaction quenched with water (5 mL). It was concentrated at 35 C to about 40 rnL, then aqueous30% H2S04(15 mL) was added at ri. and it was stirred al 50 C for 16 h. The reaction mixture was gradually poured into saturated sodium carbonate solution (70 mL) and ethyl acetate (100 mL). The aqueous layer was extracted with ethyl acetate (2x30 mL). The combined organic phases were washed with brine and dried over anhydrous Mg504. After concentration the residue was loaded on a 80gISC() Gold column and eluted with 0 % to 9() % F:tOAc /hexane to provide the title compound (3.0 g. 15.3mmol. 93% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To a solution of (methoxymethyl)triphenylphosphonium chloride (2.92 g, 8.52 mmol) in THF (20 mL) was added dropwise LDA (4.47 ml, 8.95 mmol, 1.0 M in THF) over 20 mm under N2 at 0 °C. The reaction mixture was stirred at room temperature for 2 h. Then a solution of tertbutyl 6-oxo-2-azaspiro[3.3jheptane-2-carboxylate (900 mg, 4.26 mmol) in THF (10 mL) was added dropwise to the mixture. The reaction mixture was stirred at 60 °C for 3 h, thenquenched with water (30 mL) and extracted with ethyl acetate (20 mL x 3). The combined organic layers were washed with water (40 mL) and brine (40 mL), dried over anhydrous MgSO4 and filtered. The filtrate was concentrated under reduced pressure. The resulting residue was purified by column chromatography on silica gel eluted with PE / EtOAc (50:1- 20: 1, v/v) to give the title compound. ?H NMR (400 MI-Tz, CDC13): oe = 5.81 (s, 1H), 3.93(s, 4H), 3.56 (s, 3H), 2.87 (s, 2H), 2.79 (s, 2H), 1.44 (s, 12H). |