甘罗溴铵EP杂质H

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Potassium tert-butoxide (9.52 g) was added in a single portion to a stirred suspension of (methoxymethyl)-triphenylphosphonium chloride (34.3 g) in dry ether (300 ml). After 45 minutes, the resulting red suspension was treated with a solution of methyl benzoylformate (8.20 g) in dry ether (100 ml) (colour lightens; exotherm). After 3 hours, the mixture was diluted with water, treated with magnesium sulphate and charcoal, then concentrated under reduced pressure to give the crude product (36.39 g) as a yellow oil which partially crystallised on standing. This was flushed through silica gel using dichloromethane, then carefully chromatographed using dichloromethane: petrol (2:1) to give E-methyl 3-methoxy-2-phenylpropenoate (4.83 g, 50% yield) as a pale yellow oil, eluted first, infrared (film): 1710, 1630 cm−1, 1H nmr (CDCl3): delta 7.55 (s, olefinic proton), and Z-methyl 3-methoxy-2-phenylpropenoate (3.43 g, 36% yield) as a pale yellow oil, eluted second, infrared (film): 1715, 1630 cm−1, 1H nmr (CDCl3): delta 3.76 (3H,s), 3.90 (3H,s), 6.65 (1H,s), 7.28 (5H,s) ppm. After 3 hours concentrated under reduced pressure to give the crude product (36.39 g) as a yellow oil which partially crystallised This was flushed through silica gel carefully chromatographed

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 41.0 g (0.25 mol) of methyl phenylglyoxalate are dissolved in 300 ml of pyridine. 19.1 g (0.27 mol) of hydroxylammonium hydrochloride are added in portions to this solution. When the addition is complete, the reaction mixture is stirred at room temperature for 20 hours. After addition of ethyl acetate and water, the organic layer is separated, washed with diluted HCl and water and dried over magnesium sulfate. Evaporation of the solvent gives 45 g (100%) of crude methyl α-(hydroxyimino)-2-phenylacetate as a slightly brownish liquid. This compound is used without further purification in the next reaction step. 1H-NMR (CDCl3), δ [ppm]:7.55-7.30 (m, 5 aromatic H); 3.96 and 3.87 (s, 3H, CH3O of the trans and cis isomers). The trans/cis isomer ratio is approximately 3:1. When the addition the organic layer is separated washed with diluted HCl and water dried over magnesium sulfate Evaporation of the solvent

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 16.42 g (0.1 mol) of methyl phenylglyoxalate is transesterified as described in example 1.1, using 1-hexanol instead of methoxyethanol. 21.33 g (87%) hexyl phenylglyoxalate are obtained as a colorless liquid.

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Using the same method as described for (1) of example 3, raw materials at equal weight were added successively. The difference was using a reaction temperature of -10-6° C. during dropuise addition of the toluene solution of 82 g of methyl phenylglyoxylate to cyclopentadiene Grignard reagent. 90 g of methyl 2-phenyl-2-cyclopentyl-2-hydroxy-acetate was obtained in 76.9% yield, nD25 1.5203, boiling point 82-5° C./0.03 mmHg. Silicagel GF 254 thin layer plate; developer: 1,2-dichloroethane, ultraviolet 254 nm fluorescence localization, main spot: Rf=0.72, without impurity spot. were added successively a reaction temperature of -10-6° C.

反应条件: temp:60.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To an ice cooled, stirred solution of dibenzyl sulfide (2.14 g, 0.01 m) in dried N,N-dimethylformamide was added sodium hydride (0.88 g, 0.022 mmol of a 60% suspension in mineral oil). The mixture was gradually heated to 60° C. (bath temperature), kept 2 hours and allowed to cool. Methyl benzoylformate (1.42 ml, 0.01 mmol) was then added and the mixture heated at 60° C. for 1 hour, cooled, added to a stirred ice-dilute hydrochloric acid-ether mixture, separated, the aqueous layer re-extracted 1 time with ether, and the combined organic layer washed 2 times with water, dried over sodium sulfate, filtered and concentrated to a residue. Chromatography on silica gel (1 time flush with 10% ethyl acetate/hexane followed by a careful chromatography with a methylene chloride/hexane mixture) yielded 50 mg. of product compound as a pale yellow-white crystalline material. M.S.: M+ =328; NMR: consistent, identical to the nmr spectrum of material prepared from α-phenylcinnamic acid and α-mercaptophenylacetic acid via Michael addition and ring closure. ##STR28## to cool the mixture heated at 60° C. for 1 hour cooled separated the aqueous layer re-extracted 1 time with ether the combined organic layer washed 2 times with water dried over sodium sulfate filtered concentrated to a residue Chromatography on silica gel (1 time flush with 10% ethyl acetate/hexane yielded 50 mg

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Lithium ribbon (1.0% Na content) 6.9 g., 1.0 g. at.) was cut into strips (1.0 cm.=0.089 g.), degreased in hexane and cut into thin strips into ether (200 ml.) under helium. The reaction flask was equipped with dry-ice condenser and trans-propenyl chloride (25.5 g., 0.30 mole) was introduced dropwise during 60 minutes to the rapidly stirred suspension. The reaction was exothermic and was controlled by the addition of the halide. After addition the mixture was stirred for an additional 60 minutes. The trans-propenyllithium slurry was subsequently siphoned (in spurts during 30 minutes by He.pressure) into a stirred solution containing methyl phenylglyoxylate (55.0 g., 0.3 mole) in ether which was cooled to -78°. After 30 minutes of additional stirring, the reaction was warmed to -10° and poured onto 30 ml. of concentrated HCl and ca. 200 g. of ice. The ether layer was separated and the aqueous layer was further extracted with 3×50 ml. of ether. All ether layers were combined and dried over Drierite for 18 hours. After the solvent was stripped, the crude product weighting 58.1 g. (94%) was obtained which on distillation afforded 35 g. (57%) of pure material, b.p. 100° (0.05 mm.). The reaction flask was equipped with dry-ice condenser After addition the mixture (in spurts during 30 minutes by He.pressure) was cooled to -78° After 30 minutes of additional stirring the reaction was warmed to -10° poured onto 30 ml The ether layer was separated the aqueous layer was further extracted with 3×50 ml dried over Drierite for 18 hours (94%) was obtained which on distillation afforded 35 g

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 1-Propynylmagnesium bromide (0.2 mole) was made from magnesium (4.8 g., 0.2 g. atom) ethyl bromide (21.8 g., 0.2 mole) and excess propyne gas in 400 ml. of THF. The Grignard reagent then was siphoned under nitrogen into an addition funnel and added dropwise over a 40 minute period to a cooled solution of methyl phenylglyoxylate (32.8 g., 0.2 mole) in 200 ml. of THF. A slight temperature rise took place. The reaction mixture was stirred for 24 hours, and then poured onto a slurry of ice and 25 ml. conc. HCl. Ether was added, and the layers were separated. Several more ether extracts were made and the organic extracts combined and dried. The volatile components were stripped subsequently in vacuo and the residue distilled to yield 13.1 g. (32%) of the product, b.p. 109°-12° (0.2 mm.). The oil solidified on standing and melted at 64°-65° after recrystallization from 20°-40° petroleum ether. poured onto a slurry of ice and 25 ml the layers were separated dried the residue distilled to yield 13.1 g melted at 64°-65° after recrystallization from 20°-40° petroleum ether

反应条件: temp:0.00; pressure:0.00; stir: