* 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.
Reference：
[1] Monatsberichte der Deutschen Akademie der Wissenschaften zu Berlin, 1959, vol. 1, p. 180,181
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[ 38843-85-5 ]
[ 93-61-8 ]
[ 53581-81-0 ]
Reference：
[1] Journal of Medicinal Chemistry, 1974, vol. 17, p. 1100 - 1111
[2] Journal of Medicinal Chemistry, 1975, vol. 18, # 12, p. 1201 - 1204
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[ 93-61-8 ]
[ 150-78-7 ]
[ 5312-97-0 ]
Yield
Reaction Conditions
Operation in experiment
71%
Stage #1: at 0℃; for 0.5 h; Stage #2: at 100℃; for 10 h; Stage #3: With ammonia; iodine In tetrahydrofuran; water; N,N-dimethyl-formamide at 20℃; for 3 h;
General procedure: To an ice cooled solution of N-methylformanilide (2.2 mmol) was added dropwise diphosphoryl chloride (2.2 mmol). The solution was stirred for 30 min at 0 °C, and then 1,2-dimethoxybenzene (276.3 mg, 2 mmol) in DMF (1.0 mL) was added dropwise. After being stirred for 10 h at 100 °C, I2 (1015.2 mg, 4 mmol), aq NH3 (4 mL, 28-30percent) and THF (1 mL) were added to the reaction mixture. The obtained mixture was stirred for 3 h at rt. After the reaction, the mixture was poured into aq satd Na2SO3 solution and extracted with CHCl3 (3.x.20 mL). The organic layer was dried over Na2SO4, filtered, and evaporated. The product was purified by flash short column chromatography (Hexane:AcOEt=3:1) to afford 3,4-dimethoxybenzonitrile as a white solid in 92percent yield.
EXAMPLE 1 This Example illustrates the preparation of 4-[2-(5-n-butylthiophen-2-yl)-trans-cyclopropylmethyl]-2,6-cis-dimethylmorpholine (Compound No. 8 in Table I). Phosphorus oxychloride (12.02 g, 0.078 mol) was added dropwise to N-methylformanilide (10.62 g, 0.079 mol) and a yellow solid was produced. This was cooled to 0 C. for 1/2 hour, then <strong>[1455-20-5]2-<strong>[1455-20-5]n-butylthiophene</strong></strong> (10 g, 0.071 mol) was added dropwise and the mixture stirred at room temperature for 3 hours. The mixture was poured into ice/water, neutralised with sodium carbonate and extracted into diethyl ether. The ethereal extracts were washed with water, dried over anhydrous sodium sulphate and the solvent removed to give a brown oil. Purification by column chromatography (silica eluted with petroleum ether/ethyl acetate 9:1) gave 5-n-butyl-2-thiophenecarboxaldehyde (11.8 g, 99%).
With water; In N,N-dimethyl-formamide; at 110℃; for 6h;Schlenk technique;
General procedure: A 25 mL oven-dried Schlenk tube was sequentially added N-methylaniline 1 or aniline 4 (0.2 mmol), Ethyl Bromodifluoroacetate 2a (81.2 mg, 0.4 mmol), DMF (1ml) and H2O (1 mL) was added under air. The reaction mixture was stirred for 6 h at 110. The solution was then diluted with ethyl acetate (20 mL), washed with brine (10 mL), extracted with ethyl acetate (3*5 mL), dried over anhydrous Na2SO4, filtered and evaporated under vacuum. The crude reaction mixture was purified by column chromatography (silica gel, ethyl acetate/petroleum ether) yielded the desired product 3 or 5.
With thionyl chloride; In toluene; at 20℃; for 19.5h;
General procedure: 33.8 g (0.25 mol) of N-methylformylaniline, 12.5 g of toluene, and 1.65 g (0.01 mol) of ethyl paraaminobenzoate were added to the reaction device. After stirring and dissolving, 29.8 g of sulfoxide was added dropwise. (0.25 mol), after stirring (about 70 min), continue stirring for 20 min.Then add 225g of toluene, and then add 39.6g (0.24mol) of ethyl p-aminobenzoate step by step. After the addition (about 90min), stir at room temperature for 18h.The material was orange-yellow, and the purity of UV-1 was 93.0% by sampling (HPLC, the same below). The material liquid was heated to 55 ± 1 C and kept for 7 hours. The material liquid was yellow. The purity of UV-1 was 97.3%. Continue heating the material liquid to 90 ± 1 , stop heating, and recover sulfoxide. Cool the recovered sulfoxide to 35 ± 1 , neutralize it with 10wt% sodium carbonate aqueous solution to pH = 6, and control the temperature below 35 . After neutralization, let it stand and separate layers, and layer Desolvation of the organic layer,68.3 g of ultraviolet absorber UV-1 is obtained,The yield was 96.7% and the purity was 99.6%.
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