chloromethyl benzoate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture containing 0.79 g (0.01 mol) pyridine and 1.7 g (0.01 mol) chloromethyl benzoate was allowed to react at ambient temperature for 24 hr. Trituration in anhydrous ether followed by filtration under nitrogen gave 1.2 g (0.005 mol), 50%, 29, mp 197°-199° (dec); ir (KBr) 3440, 3020, 1710, 1610, 1475, 1265, 1150, 1085, 870 and 700 cm-1 ; pmr (D2O) δ 7.0-10.0 (m, 10H) and 6.6 (s, 2H) ppm. to react at ambient temperature for 24 hr Trituration in anhydrous ether followed by filtration under nitrogen gave 1.2 g (0.005 mol), 50%, 29, mp 197°-199° (dec)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mixture of 3.00 g (0.02 mol) ethyl nicotinate and 3.50 g (0.02 mol) chloromethyl benzoate was heated at 70° under nitrogen for 10 hrs. Trituration in anhydrous ether and recrystallization from ethanol-ether gave 2.18 g (0.007 mol), 35%, 1-benzoyloxymethyl-3-carboethoxypyridinium chloride, mp 138°-141°; ir (KBr) 1730 cm-1 ; pmr (CDCl3) δ 1.43 (t, 3H), 4.47 (q, 2H), 7.7-7.3 (m, 5H), 8.2-7.95 (m, 2H), 9.17-8.50 (m, 4), 10.0 (bs, 1H) and 10.2 (bd, 1H) ppm. was heated at 70° under nitrogen for 10 hrs Trituration in anhydrous ether and recrystallization from ethanol-ether

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Para-formaldehyde (4.5 g) and zinc chloride (catalytic amount) were mixed together at 0° C. Benzoyl chloride (0.142 mole, 20 g) was added dropwise over 1 hour. The reaction was warmed to ambient temperature, then was heated to 55° C. for 10 hours. The progress of the reaction was followed by TLC (silica gel, 5/95, ethyl acetate/hexane). Since the starting material was still seen, an additional 1 g para-formaldehyde was added. The reaction was continued stirring at 55° C. for an additional 10 hours, cooled and flash chromatographed on 500 g silica gel, eluting with a solvent mixture of 2% ethyl acetate and 98% hexane. The solvent was evaporated in vacuo. Since the product had a low boiling point, the rotovapor bath temperature was not above 35° C. The desired product, 11.82 g (49%) was obtained as clear oil. MS (ES+): m/e 171 (M+H). was heated to 55° C. for 10 hours cooled flash chromatographed on 500 g silica gel eluting with a solvent mixture of 2% ethyl acetate and 98% hexane The solvent was evaporated in vacuo was not above 35° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Para-formaldehyde (4.5 g) and zinc chloride (catalytic amount) were mixed together at 0° C. Benzoyl chloride (0.142 mole, 20 g) was added dropwise over 1 hour. The reaction was warmed to ambient temperature, then was heated to 55° C. for 10 hours. The progress of the reaction was followed by TLC (silica gel, 5/95, ethyl acetate/hexane). Since the starting material was still seen, an additional 1 g para-formaldehyde was added. The reaction was continued stirring at 55° C. for an additional 10 hours, cooled and flash chromatographed on 500 g silica gel, eluting with a solvent mixture of 2% ethyl acetate and 98% hexane. The solvent was evaporated in vacuo. Since the product had a low boiling point, the rotovapor bath temperature was not above 35° C. The desired product, 11.82 g (49%) was obtained as clear oil. MS (ES+): m/e 171 (M+H). was heated to 55° C. for 10 hours cooled flash chromatographed on 500 g silica gel eluting with a solvent mixture of 2% ethyl acetate and 98% hexane The solvent was evaporated in vacuo was not above 35° C

反応条件: temp:65.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A solution of [2-(8,9-dioxo-2,6-diazabicyclo[5.2.0]non-1(7)-en-2-yl)ethyl]phosphonic acid (20.16 mmol, 5.25 g) in dry DMF (120 mL) was treated with N,N-diisopropylethylamine (80.64 mmol, 14 ml) for ½ hour at ambient temperature. Benzoic acid chloromethyl ester (60.49 mmol, 10.32 g, synthesis described below) was added at ambient temperature under exclusion of moisture. The reaction mixture was heated to 65° C. for 20 hours. The temperature was then raised to 72° C. and stirred at 72° C. for 16 hours after which the reaction was completed. The mixture was cooled to room temperature and partitioned between 10% sodium bicarbonate and ethyl acetate. After separation of the layers the aqueous phase was again extracted with ethyl acetate (6×) until there was no more product in the water phase (by silica gel TLC, 7% 2M ammonia in methanol and 93% chloroform). The combined organic layers were washed with brine, dried over magnesium sulfate, filtered and evaporated to dryness. The residue was flash chromatographed on 400 g silica gel using a solvent mixture of 1% 2M ammonia in methanol and 99% chloroform. Gradually the percentage of ammonia in methanol was increased to 7% and 93% chloroform. The solvent was evaporated in vacuo to yield the desired product (10.5 g, 99%; glass like material). MS (ES−): m/e 527 (M−H). The temperature was then raised to 72° C. The mixture was cooled to room temperature partitioned between 10% sodium bicarbonate and ethyl acetate After separation of the layers the aqueous phase was again extracted with ethyl acetate (6×) until there The combined organic layers were washed with brine dried over magnesium sulfate filtered evaporated to dryness chromatographed on 400 g silica gel using a solvent mixture of 1% 2M ammonia in methanol and 99% chloroform Gradually the percentage of ammonia in methanol was increased to 7% and 93% chloroform The solvent was evaporated in vacuo

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 1-acetoxy-1-bromoacetone was extremely difficult or impossible to make by the standard preparation of 1-acyloxyalkyl bromide compounds, since the standard route would require preparation of pure anhydrous pyruvaldehyde, CH3COCHO, to be reacted with acetyl bromide. Anhydrous pyruvaldehyde is extremely hygroscopic, unstable, and prone to polymerization. All the above preparations of 1-acyloxyalkyl halides carried out with trimethylsilyl bromide and a catalytic quantity of anhydrous zinc chloride at room temperature overnight; if the starting 1,1-diester was solid, a chlorinated solvent (CH2Cl2, CHCl3, or CCl4) was added to make a homogeneous reaction mixture. Products were characterized by boiling point, NMR, and halide titration. Different Lewis acids were tested in the case of methylene dibenzoate. ZnCl2, ZnI2, ZrCl4, and SnCl4 all proved effective, AlCl3 less so. BF3.Et2O and Cu2Br2 were ineffective. 1-acyloxyalkyl chlorides can also be obtained by this general procedure, though more vigorous conditions are required and lower yields result. Thus C6H5COOCH2OCOC6H5 and Me3SiCl reacted in CCl4 with AlCl3 catalysis at 100° (sealed vessel) for 60 hrs. and gave a 35% yield of C6H5COOCH2Cl. lower yields result (sealed vessel) for 60 hrs