Amines are absorbed on the silica gel by mixing with dry silica gel (dried for 24 h at 450°C). The silica gel (ca 30 g) containing the amine (0.1-0.2 wt/wt%) was cooled to -78°C and a stream of 3% of ozone inoxygen passed through it. By this procedure, nitro compounds are obtained in 60-70% yield 2. 1-Nitroadamantane is prepared by oxidation of 1-aminoadamantane with peracetic acid and ozone in 95% yield. 3
非均相的催化体系与均相催化体系相比有很多优点，比如催化剂的回收利用以及产物的后处理更加便捷。如催化剂chromium-containingmedium-pore molecular sieve (Si:Cr > 140:1), CrS-2和70% t-butylhydroperoxide(TBHP)都能够有效地催化和提高各种伯胺氧化成硝基化合物的反应。4
n-butylamine (0.052 g, 0.7 mmol) in 5 ml of acetone is treated with 95 ml of dimethyldioxirane in acetone solution (0.05 M). The solution is kept at room temperature for 30 min with the exclusion of light.5
A solution of 1,3,4,6-tetra-O-acetyl-2-amino-2-deoxy-β-D-glucopyranose (1 mmol) in CHCl3(20 mL) and solid Na2SO4 (2 g) was heated under reflux with stirring, and m-CPBA (Aldrich 57-86%) (2 g) was added. The suspension was stirred until completion of the reaction (TLC) (1-2 h). It was then left to cool to room temperature and diluted with CH2Cl2. The organic phase was washed successively with 0.1 M aqueous Na2CO3 and water, then dried (Na2SO4), and concentrated to give a crude product (essentially desired compound): yield 85%.8
To a well-stirred suspension of 650 g (4.11 mol) of potassium permanganate in 3 L of water, contained in a 5-L, three-necked flask fitted with a reflux condenser, a mechanical stirrer, a thermometer, and a 250-mL dropping funnel, is added, dropwise and with stirring over a 10- minute period,100 g. (1.37 mol) of tert-butylamine. When the addition is complete, the reaction mixture is heated to 55°C over a period of approximately 2 hours, and maintained at 55°C with continuous stirring for 3 hours. The dropping funnel and reflux condenser are replaced with a stopper and a still head fitted for steam distillation, and the product is steam distilled from the reactionmixture. The liquid product is separated from the denser water layer, diluted with 250 mL of diethyl ether, and washed successively with two 50-mL portions of 2 M hydrochloric acid and 50 ml. of water. After the ethereal solution has been dried over anhydrous magnesium sulfate, the solution is fractionally distilled at atmospheric pressure, removing the ether. The residual crude product totals 106–128 g. and is sufficiently pure for use in the next step. Ina typical run, distillation of 124 g of the crude product affords 110 g (78%) of the pure 2-methyl-2-nitropropane as a colorless liquid.9
A solution of the amine (10.0 mmol) in dry CH2Cl2(20 mL) was treated successively with freshly activated powdered molecular sieves (3 Å, 1.5 g) and Zr(O t-Bu)4 (0.4 mL, 1.0 mmol). After stirring for 30 min, a solution of TBHP in CH2Cl2 (c =3.66 mol/L, 16.0 mL, 59 mmol) was added within 2-5 min. After complete consumption of the starting material (GC control, 1.5 h) the reaction was quenched by addition of water (10-20 mL). The mixture was filtered and the molecular sieves washed carefully with CH2Cl2 (50 mL).The organic phase was stirred overnight in presence of a Na2SO3 solution (5%, 50 mL) to reduce the excessive TBHP. The organic phase wasseparated, dried (Na2SO4) and purified by column chromatography on silica gel followed by bulb-tobulb destillation to give nitrocompound with 70% yield. 10
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