2-Chloro-5-methylthiazole

72 g (0.6 mol) of t-butyl sulfonitrile was dissolved in dry acetonitrile (1.5 L) to prepare a solution.The reactor was purged with nitrogen, then 65 g (0.48 mol) of dry anhydrous copper (II) chloride was added, and the prepared t-butyl sulfonitrile solution was added to the reaction vessel under vigorous stirring and nitrogen protection, and then kept. 2-Amino-5-methylthiazole (45.6 g, 0.40 mol) was added portionwise over a period of 40 min at 25 °C.The reaction mixture was reacted at 25 ° C for 2 h.Then 20percent hydrochloric acid solution was added.The solvent was distilled off under reduced pressure, and then 300 ml of chloroform was added thereto, and 100 mL × 3 was washed with brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 49.7 g of 2-chloro-5-methylthiazole, yield 93percent;(1) Preparation of 2-chloro-5-methylthiazole:72 g (0.6 mol) of t-butyl sulfonitrile was dissolved in dry acetonitrile (1.5 L) to prepare a solution.Nitrogen gas was introduced into the reaction vessel, followed by the addition of dry anhydrous copper (II) chloride (65 g (0.48 mol)).The formulated t-butyl sulfonitrile solution was added to the reaction vessel under vigorous stirring and nitrogen protection.Then, at 25 ° C, 2-amino-5-methylthiazole (45.6 g, 0.40 mol) was added portionwise over a period of about 40 min.The reaction mixture was reacted at 25 ° C for 2 h.Then 20percent hydrochloric acid solution was added. The solvent was distilled off under reduced pressure.300 ml of chloroform was added, and 100 mL × 3 was washed with saturated brine.Drying with anhydrous magnesium sulfate and distilling off the solvent under reduced pressure.49.7 g of 2-chloro-5-methylthiazole were obtained.Yield 93percent;In the reaction vessel was added 2-amino-5-methylthiazole (2) 0.23mol, mass fraction of 60percent o-chlorotoluene solution 0.29mol, cuprous chloride 0.31mol, mass fraction of 45percent hexane 310ml, stirred for control speed 170rpm, temperature of the solution is reduced to 6 , reaction 8h, the solution temperature rises to 65 , the reaction was continued 7h, reducing the solution temperature to 15 , mass fraction of 65percent acetonitrile extraction seven times the mass fraction of 75percent isopropyl washed with alcohol, isopropyl alcohol was distilled off under reduced pressure, the temperature of the solution is reduced to 7 , allowed to stand for 35h, the precipitated solid was filtered, washed with sodium sulfate solution, the mass fraction of 85percent ethyl acetate and washed, in the mass fraction of 95percent triacetate recrystallization amines crystals of 2-chloro-5-methylthiazole 24.96g, yield 81percent.Comparative Comparative Example 3 Comparative Example P2a) Preparation of 5-bromomethyl-2-chloro-thiazole: 1.0 g of 72 g (0.6 mol) of t-butyl sulfonitrile was dissolved in dry acetonitrile (1.5 L) to prepare a solution.The reactor was purged with nitrogen, then 65 g (0.48 mol) of dry anhydrous copper (II) chloride was added, and the prepared t-butyl sulfonitrile solution was added to the reaction vessel under vigorous stirring and nitrogen protection, and then kept. 2-Amino-5-methylthiazole (45.6 g, 0.40 mol) was added portionwise over a period of 40 min at 25 C.The reaction mixture was reacted at 25 C for 2 h.Then 20% hydrochloric acid solution was added.The solvent was distilled off under reduced pressure, and then 300 ml of chloroform was added thereto, and 100 mL × 3 was washed with brine, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure to give 49.7 g of (1) Preparation of In the reaction vessel was added 2-amino-5-methylthiazole (2) 0.23mol, mass fraction of 60% o-chlorotoluene solution 0.29mol, cuprous chloride 0.31mol, mass fraction of 45% hexane 310ml, stirred for control speed 170rpm, temperature of the solution is reduced to 6 , reaction 8h, the solution temperature rises to 65 , the reaction was continued 7h, reducing the solution temperature to 15 , mass fraction of 65% acetonitrile extraction seven times the mass fraction of 75% isopropyl washed with alcohol, isopropyl alcohol was distilled off under reduced pressure, the temperature of the solution is reduced to 7 , allowed to stand for 35h, the precipitated solid was filtered, washed with sodium sulfate solution, the mass fraction of 85% ethyl acetate and washed, in the mass fraction of 95% triacetate recrystallization amines crystals of Synthesis of Comparative Synthesis of Comparative Example 3 Synthesis of Comparative Synthesis of 5-methylthiazol-2-amine (2.0 g, 17.5 mmol, 1.0 equiv) was taken in con. HCI (35%) (9 ml) and cooled in ice-salt mixture (- 5C). A solution of NaN02 (1.33 g, 19.2 mmol, 1.1 equiv) in water (10 ml) was added drop wise over 15 min and stirred for 1 h at 0C and slowly warmed to room temperature. Reaction mixture was heated to 60C and stirred for about 2h. Reaction mixture was monitored by TLC and LCMS. After consumption of starting material reaction mixture was diluted with ice water and extracted with DCM (3 x 50 mL). Combined organic layers were washed with water and brine solution, dried over Na2S04, filtered and concentrated to get crude product as black oil, yield (1.3g, 75%). LC- MS (ES) m/z = 134.1 [M+H]+. H NMR (400 MHz, DMSOcfe) delta ppm 2.40 (s, 3 H), 7.38 (s, 1 H).49.7 g (0.372 mol)2-Chloro-5-methylthiazole was dissolved in 100 ml of chloroform, and an equimolar amount of N-chlorosuccinimide was added.After warming to 50 C and reacting for 5 h under light, 150 ml of water was added to the reactor to remove the succinimide. After the organic layer was desolved, 40.65 g of 2-chloro-5-chloromethylthiazole was obtained in a yield of 65%(2) Preparation of 2-chloro-5-chloromethylthiazole:49.7 g (0.372 mol) of 5 mg of dibenzoyl peroxide in portions and then 155 mg of N-chlorosuccinimide are added at room temperature and with stirring to a solution of 124 mg of

Used as pesticide intermediate

Molecular Weight:133.60
XLogP3:2.3
Hydrogen Bond Acceptor Count:2
Exact Mass:132.9752980
Monoisotopic Mass:132.9752980
Topological Polar Surface Area:41.1
Heavy Atom Count:7
Complexity:68.7
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes