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CAS No. : | 69045-83-6 | MDL No. : | MFCD03701543 |
Formula : | C6H2Cl5N | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | XVBWGQSXLITICX-UHFFFAOYSA-N |
M.W : | 265.35 | Pubchem ID : | 94647 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With acetic acid; zinc; In methanol; at -5℃; for 4h; | 2, 3-dichloro-5-trichloromethylpyridine (36.60 g, 0.139 mol) was added to a flask containing acetic acid (53.50 g, 0.892 mol) and methanol (200 mL). The mixture was cooled to-5 C, and zinc dust (20.01 g, 0.308 mol) was added in small portions at 10 minute intervals. The mixture was stirred mechanically for 4 hours, filtered, and concentrated in vacuo. The residue was dissolved in dichloromethane and washed with brine, followed by saturated aqueous sodium bicarbonate, followed by a second brine wash. The organic phase was dried over magnesium sulfate and concentrated in vacuo to yield 21.55 g (79%) of Preparatory Compound P, 2, 3-DICHLORO-5- (CHLOROMETHYL) pyridine, as a yellow liquid (about 65% PURITY). 1H NMR No. 8.31 (d, 1H, J=2.3 Hz), 7.85 (q, 1H, J=0.4 Hz and J=2.2 Hz), 4.56 (s, 2H). MS (ESI) NIZ 199 ([M+4] +, 8), 197 ([M+2]+, 27), 195 ([M]+, 28), 164 (11), 162 (66), 160 (100), 124 (19) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
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). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
(c) Preparation of 2,3-dichloro-5-trichloromethylpyridine The product from (b) (64 g) in dry carbon tetrachloride (650 ml) was treated with dry hydrogen chloride. The precipitate was broken up and the suspension heated under reflux while dry chlorine was bubbled into the mixture, with illumination from an ultra-violet light source. After 41/2 hours, the mixture was cooled, filtered, and the filtrate evaporated to give the required 2,3-dichloro-5-trichloromethylpyridine. The mass spectrum was consistent with the structure assigned to this compound. | ||
(c) Preparation of 2,3-dichloro-5-trichloromethylpyridine The product from (b) (64 g) in dry carbon tetrachloride (650 ml) was treated with dry hydrogen chloride. The precipitate was broken up and the suspension heated under reflux while dry chlorine was bubbled into the mixture, with illumination from an ultra-violet light source. After 41/2 hours, the mixture was cooled, filtered, and the filtrate evaporated to give the required 2,3-dichloro-5-trichloromethylpyridine. The mass spectrum was consistent with the structure assigned to this compound. | ||
(c) Preparation of 2,3-dichloro-5-trichloromethylpyridine The product from (b) (64 g) in dry carbon tetrachloride (650 ml) was treated with dry hydrogen chloride. The precipitate was broken up and the suspension heated under reflux while dry chlorine was bubbled into the mixture, with illumination from an ultra-violet light source. After 41/2 hours, the mixture was cooled, filtered, and the filtrate evaporated to give the required 2,3-dichloro-5-trichloromethylpyridine. The mass spectrum was consistent with the structure assigned to this compound. |
The product from paragraph (i) (2.9 g) in dry carbon tetrachloride (250 ml) was treated with dry hydrogen chloride to convert it to the hydrochloride. Chlorine was passed through the suspension which was kept at 80 C. and illuminated by an ultra-violet lamp inside the reaction flask. After three hours the solvent was removed, leaving a residue of 2,3-dichloro-5-trichloromethylpyridine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With phosphorus pentachloride; | EXAMPLE III Preparation of 2,3-dichloro-5-(trichloromethyl)pyridine STR5 To a 5-liter flask equipped with an air stirrer, thermometer, and condenser was added 1000 grams (5.13 m) of phenylphosphonic dichloride. Thereafter, 383 g (2.707 m) of 5-chloro-6-hydroxynicotinic acid (prepared by bubbling chlorine into a stirred aqueous suspension of 6-hydroxynicotinic acid) was added. The mixture was slowly heated and stirred over a 20 minute period, with the temperature rising to 73 C. The mixture was in the form of a thick paste. To this mixture was slowly added 1755 g (8.4 m) of phosphorus pentachloride over a 45 minute period. The hydrogen chloride by-product which formed was continuously removed and the heat was adjusted to maintain the temperature in the range of 83-108 C. After the phosphorus pentachloride addition was complete, the mixture was heated to reflux and some of the phosphorus oxychloride by-product which formed was allowed to distill off. After a period of about 70 minutes, the temperature had exothermically risen to 169 C. and the temperature was held in the range of 162-180 C. for 53/4 hours. During the above time additional phosphorus oxychloride was intermittently removed. The mixture was allowed to stand overnight and then poured over cracked ice, neutralized with 50 percent sodium hydroxide solution and the product extracted with hexane. The solvent was removed by evaporation under reduced pressure leaving 567 g of crude 2,3-dichloro-5-(trichloromethyl)pyridine. The crude product was placed on a 15 tray vacuum jacketed Oldershaw distillation column and the light ends removed. The pot material was transferred to a Vigreux Claisen still and flash distilled to yield of 518 g (88.5 percent of theoretical) of a colorless oil which analyzed as 99 percent pure 2,3-dichloro-5-(trichloromethyl)pyridine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With antimonypentachloride; | EXAMPLE 8 This Example further illustrates the preparation of 2,3-dichloro-5-trifluoromethylpyridine. Antimony trifluoride (61 g) was melted under a vacuum to remove moisture. The cooled material was broken up and heated to 65-70 while antimony pentachloride (6.6 g) was added dropwise with stirring. 2,3-Dichloro-5-trichloromethylpyridine (40 g) was then added dropwise to the mixture and the whole heated to 160 over 45 minutes. The mixture was cooled and steam distilled. The oil which distilled over was extracted with ether (2*100 ml). The ether extract was washed with tartaric acid solution then water, sodium bicarbonate, and water, and dried. The remaining oil was distilled. The fraction boiling at 71-80/18 Torr was identified as the required pyridine derivative. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
copper(I) chloride; In tantalum; diethyl ether; acetonitrile; | EXAMPLE 5 Single-step preparation of 2,3-dichloro-5-trichloromethylpyridine 23 g of pentachloropropionaldehyde, 8 g of acrylonitrile, 0.5 g of copper(I) chloride and 40 ml of acetonitrile are heated in a tantalum autoclave for 3 hours to 170 C. After they have cooled, the contents of the autoclave are taken up in 50 ml of diethyl ether and the ethereal solution is filtered. The filtrate is evaporated to dryness in vacuo and the residue is rectified. 2,3-Dichloro-5-trichloromethylpyridine is collected in a receiver (yield: 17.49 g). Boiling point: 147-149 C./1700 Pa. IR spectrum (KBr) in cm-1: 3050, 1590, 1555, 1430, 1380, 1180, 1049. 1 H-NMR spectrum (100 MHz in CDCl3) in ppm: 8.85 (d, J=5 Hz), 8.25 (d. J=5 Hz). Elemental analysis for C6 H2 Cl5 N (mol.wt. 265.35): calculated C 27.15%, H 0.75%, N 5.27%, Cl 66.80%; found C 27.1%, H 0.9%, N 5.3%, Cl 66.4%. |