Preparation method for 4-(4-cyclopropyl-naphthalene-1-yl)-5-thio-[1,2,4]triazolidine-3-ketone and intermediate 4-cyclopropyl-naphthalene-1-yl-ethyl carbamate
An intermediate, cyclopropyl technology, which is applied in the field of intermediate (4-cyclopropylnaphthalen-1-yl)-ethyl carbamate and its preparation, can solve the problem of long synthetic route, large environmental impact and difficult operation. Convenience and other issues
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Examples
Embodiment 1
[0022] Example 1: Preparation of (4-cyclopropylnaphthalen-1-yl)-urethane
[0023] Weigh (17.5 g; 197 mmol) ethyl carbamate, (58.6 g; 236 mmol) 4-cyclopropyl-1-bromonaphthalene, (6.2 g; 10% mmol) CuI 2 , (81.6 g; 3 eq) K 2 CO 3 , (5.7 g; 20% mmol) 8-hydroxyquinoline was added to a 500 mL three-necked flask, 140 mL of toluene was added, under nitrogen protection, the temperature was raised to reflux, and the reaction was tracked by LC. The raw material was less than 3% in about 18 h, and the reaction liquid was cooled to about 30 °C, filter out the insoluble matter, transfer the filtrate to a 1000 mL three-neck flask, drop the reaction solution into 10 °C, add 400 mL of purified water, stir at 10 °C for 1.5 h, filter with suction, wash with 200 mL of purified water for two Once, dried in vacuo at 80 ℃ to obtain 32.7 g of off-white solid with a yield of 65%.
Embodiment 2
[0024] Example 2: Preparation of 4-(4-cyclopropylnaphthalen-1-yl)-5-thio-[1,2,4]triazolidin-3-one
[0025] Weigh (5.2 g; 20 mmol) (4-cyclopropylnaphthalen-1-yl)-urethane, (7.6 g; 100 mmol) CS 2 , (6.1 g; 3eq) TEA was added to a 100 mL single-necked bottle, 50 mL of toluene was added, and the reaction was stirred at 35-40 °C. After LC tracking, the raw material was completely converted in about 24 h, filtered with suction, washed twice with 25 mL of toluene, 35 Vacuum-dry at ℃ for 2 hours, take out the solid, put all into a 100 mL single-necked bottle, add (2.1 g; 20 mmol) hydrazine dihydrochloride, (10.3 g; 5 eq) diethylenetriamine, wash the hydrazine dihydrochloride completely with 50 mL toluene Add in, heat up to 80 °C, stir for 4 h, cool the reaction solution to 10 °C, add 30 mL of 1N hydrochloric acid dropwise, stir for 5 h, filter with suction, wash 3 times with 50 mL of purified water, and vacuum-dry at 80 °C to obtain an off-white solid 4.5 g, yield 85%.
Embodiment 3
[0026] Example 3: Preparation of 4-(4-cyclopropylnaphthalen-1-yl)-5-thio-[1,2,4]triazolidin-3-one
[0027] Weigh (5.2 g; 20 mmol) (4-cyclopropylnaphthalen-1-yl)-urethane, (3.8 g; 50 mmol) CS 2 , (6.1 g; 3eq) TEA was added to a 100 mL single-necked bottle, 50 mL of toluene was added, and the reaction was stirred at 35-40 °C. After LC tracking, the raw material was completely converted in about 24 h, filtered with suction, washed twice with 25 mL of toluene, 35 Vacuum-dry at ℃ for 2 hours, take out the solid, put all into a 100 mL single-necked bottle, add (2.1 g; 20 mmol) hydrazine dihydrochloride, (10.3 g; 5 eq) diethylenetriamine, wash the hydrazine dihydrochloride completely with 50 mL toluene Add in, heat up to 80 °C, stir for 4 h, cool the reaction solution to 10 °C, add 30 mL of 1N hydrochloric acid dropwise, stir for 5 h, filter with suction, wash 3 times with 50 mL of purified water, and vacuum-dry at 80 °C to obtain an off-white solid 2.2 g, yield 40%.
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