* 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.
(a) 3,4-Dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene 3,4-Dichloro-alpha,alpha,alpha-trifluorotoluene (862 g. 4.0 mols) is added to a stirred mixture of concentrated sulfuric acid (4400 g.) and nitric acid (3400 g.) at 35 C. The mixture is stirred 70 minutes at 95 C. and allowed to separate. The oil layer is washed once with water and twice with 5% sodium carbonate solution, dried, and fractionally distilled to give 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 18%) b.p. 115-118 C./15 mm, 88% pure.
18%
With sulfuric acid; nitric acid;
a. 3.4-Dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene 3,4-Dichloro-alpha,alpha,alpha-trifluorotoluene (862 g. 4.0 mols) is added to a stirred mixture of concentrated sulfuric acid (4400 g.) and nitric acid (3400 g.) at 35 C. The mixture is stirred 70 minutes at 95 C. and allowed to separate. The oil layer is washed once with water and twice with 5% sodium carbonate solution, dried, and fractionally distilled to give 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 18%) b.p. 115-118 C./15 mm, 88% pure.
18%
With sulfuric acid; nitric acid;
a. 3,4-Dichloro-5-nitro-alpha,alpha,alpha -trifluorotoluene 3,4-Dichloro-alpha,alpha,alpha-trifluorotoluene (862 g. 4.0 mols) is added to a stirred mixture of concentrated sulfuric acid (4400 g.) and nitric acid (3400 g.) at 35 C. The mixture is stirred 70 minutes at 95 C, and allowed to separate. The oil layer is washed once with water and twice with 5% sodium carbonate solution, dried, and fractionally distilled to give 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 18%) b.p. 115-118 C./15 mm, 88% pure.
18%
With sulfuric acid; nitric acid;
a. 3,4-Dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene 3,4-Dichloro-alpha,alpha,alpha-trifluorotoluene (862 g. 4.0 mols) is added to a stirred mixture of concentrated sulfuric acid (4400 g.) and nitric acid (3400 g.) at 35 C. The mixture is stirred 70 minutes at 95 C. and allowed to separate. The oil layer is washed once with water and twice with 5% sodium carbonate solution, dried, and fractionally distilled to give 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 18%) b.p. 115-118 C./15 mm, 88% pure.
18%
With sulfuric acid; nitric acid;
a. 3,4-Dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene 3,4-Dichloro-alpha,alpha,alpha-trifluorotoluene (862 g. 4.0 mols) is added to a stirred mixture of concentrated sulfuric acid (4400 g.) and nitric acid (3400 g.) at 35 C. The mixture is stirred 70 minutes at 95 C. and allowed to separate. The oil layer is washed once with water and twice with 5% sodium carbonate solution, dried, and fractionally distilled to give 3,4dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 18%) b.p. 115-118 C./15 mm, 88% pure.
(b) 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene 500 ml. of an ethanolic solution containing 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 0.72 mol), and platinum oxide (Adam's catalyst) (0.2 g.) is reduced at room temperature in a low pressure hydrogenation apparatus to give 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene (129.9 g. 78%) b.p. 65-70 C./1-2 mm.
78%
(b) 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene 600 ml. of an ethanolic solution containing 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 0.72 mol), and platinum oxide (Adam's catalyst) (0.2 g.) is reduced at room temperature in a low pressure hydrogenation apparatus to give 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene (129.9 g. 78%) b.p. 65-70 C./1-2 mm.
78%
(b) 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene 500 ml. of an ethanolic solution containing 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 0.72 mol), and platinum oxide (Adam's catalyst) (0.2 g.) is reduced at room temperature in a low pressure hydrogenation apparatus to give 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene (129.9 g. 78% b.p. 65-70 C./1-2 mm.
78%
b. 5-Amino-3,4-dichloro-alpha,alpha,alpha -trifluorotoluene 500 ml. of an ethanolic solution containing 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 0.72 mol), and platinum oxide (Adam's catalyst) (0.2 g.) is reduced at room temperature in a low pressure hydrogenation apparatus to give 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene (129.9 g. 78%) b.p. 65-70 C./1-2 mm.
78%
b. 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene 500 ml. of an ethanolic solution containing 3,4-dichloro-5-nitro-alpha,alpha,alpha-trifluorotoluene (188 g. 0.72 mol), and platinum oxide (Adam's catalyst) (0.2 g.) is reduced at room temperature in a low pressure hydrogenation apparatus to give 5-Amino-3,4-dichloro-alpha,alpha,alpha-trifluorotoluene (129.9 g. 78%) b.p. 65-70 C./1-2 mm.
With potassium fluoride; tetramethlyammonium chloride;
(B) The 3-chloro-4-fluoro-5-nitrobenzotrifluoride starting reactant employed in the above example was prepared in the follow manner. A mixture of 52 parts of <strong>[657-02-3]3,4-dichloro-5-nitrobenzotrifluoride</strong>, 16.2 parts of anhydrous potassium fluoride and 2.5 parts of tetramethylammonium chloride was heated and maintained at about 120 to 140 C. for about 7 hours. The mixture was then cooled to room temperature, diluted with methylene chloride, and filtered. The filtrate was distilled to yield 35.2 parts (67% yield) of 3-chloro-4-fluoro-5-nitrobenzotrifluoride. The structure of the product was confirmed by gas chromatography-mass spectrum analysis.
2-chloro-α,α,α-trifluoro-6-nitro-p-tolylphenyl ether[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With potassium hydroxide; In sulfolane; water;
b. 2-Chloro-alpha,alpha,alpha-trifluoro-6-nitro-p-tolylphenyl ether A solution of potassium hydroxide (43.2 g. of 86% pure, 0.665 moles) in water (20 ml.) was added slowly to a mixture of phenol (62.5 g., 0.665 mole) and the product from (a) above 450 g. total, equivalent to 0.665 mole of 3,4-dichloro-alpha,alpha,alpha-trifluoro-5-nitro toluene) in sulfolane (300 ml.) at 30-68 C. with stirring. After stirring at 42-68 C for a total of one hour the mixture was diluted with hexane (400 ml.) and water (600 ml.). The resulting layers were separated and the aqueous phase extracted once with hexane. The combined organic phases were washed with water and dilute caustic soda solution, dried and the solvent removed. The residue (471.3 g.) was distilled through a vacuum jacketed Vigreux column. No. 1 (272.2 g.) bp < 100 C/0.2 mm. consisted essentially of unreacted 3,4-dichloro-alpha,alpha,alpha-trifluoro-6-nitrotoluene. No. 2 (196.2 g.) b.p. 109-119 C/0.2 mm. was essentially pure desired diphenylether. A small residue (3.5 g.) was discarded. No. 2 crystallized and was recrystallized from 2-propanol (600 ml.) at 0 C. to give 2-chloro-alpha,alpha,alpha-trifluoro-6-nitro-p-tolylphenyl ether (144 g. 68%) m.p. 57-61 C.
With potassium hydroxide; In sulfolane; water;
b. 2-Chloro-alpha,alpha,alpha-trifluoro-6-nitro-p-tolylphenyl ether A solution of potassium hydroxide (43.2 g. of 86% pure, 0.665 moles) in water (20 ml.) was added slowly to a mixture of phenol (62.5 g., 0.665 mole) and the product from (a) above 450 g. total, equivalent to 0.665 mole of 3,4-dichloro-alpha,alpha,alpha-trifluoro-5-nitro toluene) in sulfolane (300 ml.) at 30-68 C. with stirring. After stirring at 42-68 C. for a total of one hour the mixture was diluted with hexane (400 ml.) and water (600 ml.). The resulting layers were separated and the aqueous phase extracted once with hexane. The combined organic phases were washed with water and dilute caustic soda solution, dried and the solvent removed. The residue (471.3 g.) was distilled through a vacuum jacketed Vigreux column. No. 1 (272.2 g.) bp<100 C./0.2 mm. consisted essentially of unreacted 3,4-dichloro-alpha,alpha,alpha-trifluoro-6-nitrotoluene. No. 2 (196.2 g.) b.p. 109-119 C./0.2 mm. was essentially pure desired diphenylether. A small residue (3.5 g.) was discarded. No. 2 crystallized and was recrystallized from 2-propanol (600 ml.) at 0 C. to give 2-chloro-alpha,alpha,alpha-trifluoro-6-nitro-p-tolylphenyl ether (144 g. 68%) m.p. 57-61 C.
EXAMPLE 3 50 g of 3,4-dichloro-5-nitro-benzotrifluoride and 5 g of benzyltriethylammonium bromide are initially introduced into 150 ml of methanol, and 100 g of 50% strength sodium hydroxide solution are added dropwise at 25 to 30 C. The mixture is then stirred at 65 C. for a further 4 hours and cooled, 100 ml of water are added and the mixture is rendered acid with sulphuric acid. The crude product is extracted with methylene chloride, the solution is dried and the methylene chloride is distilled off. The residue is subjected to fractional distillation and 35 g of 2-chloro-4-trifluoromethyl-6-nitrophenol with a boiling point of 74 to 76 C. under 0.25 mm are obtained. Melting point: 33-34 C. from hexane. Yield: 77% of theory.
To the reactor was added <strong>[657-02-3]3,4-dichloro-5-nitrobenzotrifluoride</strong> 600Kg, airtight reactor, nitrogen substitution, open stirring, gradually warmed to 200 C, gradually through the ammonia gas,To pass into the amount of 125Kg, the sampling tube sampling and detection of <strong>[657-02-3]3,4-dichloro-5-nitrobenzotrifluoride</strong> 0.3%, cooled to below 80 C, venting ammonia gas to the tail gas recovery unit, the kettle 200Kg * 2 washing,The organic layer was washed with saturated brine and dehydrated under reduced pressure to obtain 544 kg of the obtained product (yield: 99.1%, water: 0.5%, yield: 98.1%).
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
