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With chlorine;pelletized catalyst TOSOH HSZ-690 HOD (SAR 203) with a silica binder; at 350℃;Gas phase;Product distribution / selectivity;
Example 2; The pelletized catalyst, TOSOH HSZ-690 HOD (SAR 203) with a silica binder, was ground to a coarse powder and screened to obtain a uniform size of 1-2 mm in diameter. A weight of 0.26 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. Operating at a chlorine feed of 5 cc/min, a beta-picoline feed rate of 0.13 mg/min (10 cc/min N2 with a chiller temperature of 10 C.), the reagents were fed to the reactor at an initial temperature of 250 C. The system was initially ramped up to 325 C. and allowed to stablize. Under these conditions the product gases were 18.5% 3-trichloromethylpyridine (beta-tri ) and 65.4% beta-2-tet. When the system was allowed to stabilized at 350 C. the amount of beta-tri in the product gases was reduced to 2.6% and the conversion to beta-2-tet increased to 68.6% (see Table 2).; Example 3; The catalyst, TOSOH HSZ-690 HOD (SAR 203) with the silica binder, was sized to a uniform particle size of 1-2 mm in diameter. A weight of 0.26 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. The reactor temperature was initially set to 250 C. prior to flowing chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.13 mg/min (N2 flow 10 cc/min, chiller at 10 C.), while the reactor oven was ramped up to 350 C. over a one hour time period. At 350 C. the amount of beta-2-tet observed in the product gases was 65.6% (see Table 2).; Example 4; The catalyst, TOSOH HSZ-690 HOD (SAR 203) with the silica binder, was sized to a uniform particle size of 1-2 mm in diameter. A weight of 0.51 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. The reactor temperature was initially set to 250 C. prior to flowing chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.13 mg/min (chiller at 10 C.), with a nitrogen flow of 10 cc/min, while the reactor oven was ramped up to 350 C. over 2 hours. When the system had stabilized at 350 C. the amount of beta-2-tet observed in the product gases was 71.7% (see Table 2).; Example 5; The catalyst, TOSOH HSZ-690 HOD (SAR 203) with the silica binder, was sized to a uniform particle size of 1-2 mm. A weight of 0.51 g of catalyst was charged into the reactor tube and glass wool (Pyrex) was used to secure it in place. The reactor temperature was initially set to 250 C. prior to flowing chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.25 mg/min (N2 at 10 cc/min, chiller at 20 C.), while the reactor oven was slowly ramped up to 350 C. over 2 hours. When the system had stabilized at 350 C. the amount of beta-2-tet observed in the product gases was 66.9% (see Table 2).
With chlorine; at 400℃;Gas phase;Product distribution / selectivity;
Example A; This is the control run where the reactor contained glass wool (Pyrex) plugs and no catalyst. The reactor temperature was initially set to 350 C. prior to feeding chlorine at a rate of 5 cc/min. The beta-picoline feed rate was set to 0.25 mg/min (N2 at 10 cc/min, chiller at 20 C.) at the oven temperature of 350 C. When the system had stabilized the amount of beta-2-tet was only 8.7%, with the majority of the conversion going to beta-tri (65.4%). When the temperature was increased to 400 C. the amount of beta-2-tet increased to 46.1% with a reduction in beta-tri (21.5%). A fair amount of over chlorinated 2,6-dichloro-3-trichloromethylpyridine (beta-2,6-penta,12.2%) was also observed (see Table 2).
The liquid was found to contain 17 ppm tungsten. The solid (1.4 grams) was used to catalyze the chlorination of 187.6 grams of 2-chloro-5-trichloromethylpyridine at 200 C. and ambient pressure. In 98 hours, 77.5 weight percent of 2,3-dichloro-5-trichloromethylpyridine was obtained.
With phosphorus pentachloride; at 210℃; for 16h;Autoclave;
EXAMPLE 9 Preparation of 2,3-dichloro-5-(trichloromethyl)pyridine from various compounds of the formula [I]. The starting material of formula [I] (50 mmole) and PCI5 (1 or 2 eq.) was mixed in a 50 ml teflon autoclave. The autoclave was closed and heated in a 210 C warm metal block. After 16 hours the autoclave was cooled to 25 C and opened. The resulting solution was analysed by GC with results according to table 5. (trichloromethyl)pyridine In comparison, starting with the compound 2-chloro-5- (trichloromethyl)pyridine only very low conversion to the compound [II] is observed.
With phosphorus pentachloride; at 175℃; under 18751.9 - 30003 Torr; for 96h;Autoclave;
EXAMPLE 5 Conversion of Nicotinic acid to 2,3-dichloro-5-(trichloromethyl)pyridine. Using a similar setup as described in example 1, a series of experiments were carried out with 4 molar eq. of PCI5 at various temperatures and a pressure reaching between 25 and 40 bar after completion. Results are provided in table 2.
With phosphorus pentachloride; at 185℃; under 18751.9 - 30003 Torr; for 72h;Autoclave;
EXAMPLE 5 Conversion of Nicotinic acid to 2,3-dichloro-5-(trichloromethyl)pyridine. Using a similar setup as described in example 1, a series of experiments were carried out with 4 molar eq. of PCI5 at various temperatures and a pressure reaching between 25 and 40 bar after completion. Results are provided in table 2.
With phosphorus pentachloride; at 185℃; under 18751.9 - 30003 Torr; for 64h;Autoclave;
EXAMPLE 6 Conversion of Nicotinic acid to 2,3-dichloro-5-(trichloromethyl)pyridine. Using a similar setup as described in example 1, a series of experiments were carried out using various amounts of PCI5, at a temperature set at 210C, and at pressure reaching between 25 and 40 bar after completion. Results in accordance with the below table 3.
With phosphorus pentachloride; at 210℃; under 1500.15 - 27752.8 Torr; for 14h;Autoclave;
EXAMPLE 7 Conversion of Nicotinic acid to a mixture of 2-chloro-5- (trichloromethyl)pyridine and 2,3-dichloro-5-(trichloromethyl)pyridine. To a 250 ml Berghof autoclave with PTFE lining was added Nicotinic acid (20g, 162 mmole) and phosphorous pentachloride (139 g, 668 mmole). The autoclave was closed and heated to 210 C for 14 hours. During the heating an exotherm was observed around a temperature of 130 C bringing the temperature to 190 C and a pressure increase from 2 bar to 8 bar within 2 minutes. The heating was continued to 210 C. After the 14 hours the pressure had increased to 37 Bar. The autoclave was cooled to room temperature, ventilated to a scrubber, opened and quantified by GC indicating a yield of 2- chloro-5-(trichloromethyl)pyridine of 33% compared to the Nicotinic acid starting material and a yield of 2,3-dichloro-5-(trichloromethyl)pyridine 60%.
The obtained 2-chloro-5-trichloromethylpyridine 46.2 g,After adding the catalyst, the temperature is raised to 150-160C.Slowly dry the chlorine gas for heavy chlorination.After 6 hours of reaction, dilute the reaction solution with benzene, wash with water and dry the organic phase.After evaporating the benzene under reduced pressure,After distillation, 50.3 g of oily product was obtained.That is the intermediate 2,3-dichloro-5-trichloromethylpyridine,The yield was 90% and the content was 95%.
With chlorine; at 130 - 180℃; for 100h;Large scale;
2000 kg of 2-chloro-5-trichloromethylpyridine was placed in a glass-lined chlorination kettle.Then adding catalyst to the reactorThe 150kg reactor is heated with a heat transfer oil.When the temperature rises to 130 C, chlorine gas is introduced into the reactor to control the amount of chlorine.The reaction temperature was controlled at 180 C. The reaction time is usually 100 hours.After the reaction is completed, the temperature is lowered to 50 C, and the catalyst is filtered off.After the 2,3-dichloro-5-trichloromethylpyridine was metered, it was fluorinated in a fluorination kettle.
With tetrachloromethane; at 200 - 350℃; for 0.00305556h;Molecular sieve; Inert atmosphere;
40 G ZSM - 5 molecular sieve (silicon-aluminum ratio 200, strip (1 - 2 mm)) by adding [...] 60 cm, diameter of 2.4 cm cylindrical quartz tube, the upper end of the catalyst filling 10 g of inert ceramic ball (diameter 4 mm), the quartz tube using the resistance wire heating. The constant pressure in the funnel 8 g 3 - methyl pyridine and 70 g CCl4[...] 200 C flask, 2 h the raw materials of the completion of the dropping, of the 3 - methyl pyridine with CCl4The steam is N2The carrier gas to the quartz tube, N2The flow rate control in 250 ml/min. Cl2In order to 300 ml/min flow rate individually to the quartz tube with the raw material of the steam in the catalyst bed on the reaction, the reaction temperature is 350 C, time is 11 s. The reaction mixture through the receiving flask condensation, GC normalized 3 - methyl pyridine totally transformed, 3 - dichloro pyridine and isomer 47%, 2 - chloro -5 - trichloromethyl pyridine 27%, 2 - chloro -3 - trichloromethyl pyridine 4.8%, 2, 3 - dichloro -5 - trichloromethyl pyridine 11%. The purity of the purification after rectification>99% of 2 - chloro -5 - trichloromethyl pyridine, the yield of 21%.
With chlorine; In tetrachloromethane; at 400℃; for 4h;
10 g of catalyst B was taken into a cylindrical fixed bed reactor with an inner diameter of 25 mm, and the plunger pump was pumped into a solution of 3-methylpyridine in carbon tetrachloride. The mass ratio of 3- methylpyridine to carbon tetrachloride was 1: The weight hourly space velocity of 10,3-methylpyridine is 6h, the chlorine gas flow rate is 2L/min, and the 3-methylpyridine and chlorine gas are vaporized by the preheating tube and then passed into the fixed bed reactor. The fixed bed reactor is used. The temperature was 400 C, the reaction was carried out for 4 h, the reaction product was passed through a condenser, and 2987 g of the reaction product mixture was obtained in a receiving tank. The ammonia solution was added to adjust to neutrality, and the pear-shaped funnel was separated to obtain an organic phase. 30 g of anhydrous sulfuric acid was added to the organic phase. Magnesium is dehydrated, suction filtered, and then rotary evaporated to remove carbon tetrachloride to give a pale yellow liquid. After analysis and detection, the product is a mixture of 2-chloro-5-trichloromethylpyridine, 2,3-dichloro-5-trichloromethylpyridine and 2,3,6-trichloropyridine, respectively. 77%, 16%, 7%. It is indicated that it is difficult to remove trichloromethyl group under the reaction conditions in the absence of water
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