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CAS No. : | 1030613-07-0 | MDL No. : | MFCD12165919 |
Formula : | C5H5BrN2O2S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KDZLTNORBKZJKE-UHFFFAOYSA-N |
M.W : | 237.07 | Pubchem ID : | 52987824 |
Synonyms : |
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Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H332-H335 | Packing Group: | N/A |
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 |
---|---|---|
87.4% | With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 20 - 60℃; for 1.33333h; | To a stirred solution of compound 59 (21 g, 121.38 mmol) in ACN (400 mL), CuBr2 (53.3 g, 239.01 mmol) was added and stirred at room temperature for 15 min. To this solution, tert- butyl nitrite (24.65 g, 239.04 mmol) was added drop wise over a period of 20 min. The resulting reaction mixture was stirred at room temperature for 30 min. and then heated at 60 C for 30 min. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water; ethyl acetate and filtered through Celite bed. The organic layer was separated; washed with brine; dried over anhydrous sodium sulfate, filtered and concentrated in vacuo to afford the title compound 60 (25 g, 87.40percent) as a yellow solid. TLC: 20percent EtOAc/hexane (Rf: 0.7); 1H NMR (400 MHz, DMSO-d6): delta 4.45-4.40 (m, 2H), 1.34 (t, J= 6.8 Hz, 3H). |
82% | With hydrogen bromide; copper(I) bromide; sodium nitrite; In water; at 3 - 20℃; for 2.75h; | A 500 mL (three neck) round-bottom flask with a stir bar, needle inlet, and a gas outlet to a trap containing a 10percent solution of Na2S203 was charged with CuBr (1.24g, 8.67 mmol, 0.1 equiv.) and HBr (48percent aqueous solution, 108 mL). The purple solution was cooled to 3°C (internal, ice bath), to which was added portion- wise a solid mixture of 5-amino-[l,3,4]thiadiazole-2-carboxylic acid ethyl ester (15.0 g, 86.6 mmol) and sodium nitrite (27.0 g, 391.3 mmol, 4.5 equiv.) over the course of 30 min. The reaction mixture was allowed to warm to room temperature for 2 h 15 min. The reaction mixture was diluted with CH2C12 and 10percent aqueous Na2S203 and the layers were separated. The aqueous layer was extracted 3 times with CH2C12. The combined organic layers were washed with Brine, dried over MgS04, and concentrated. The crude product was purified by column chromatography (ISCO XL, 330g Si02 column, 20-25percent EtOAc/Hexanes) to provide an off-white solid that was triturated with 5percent EtOAc/Hexanes. Filtration provided 5-bromo-[l ,3,4]thiadiazole-2-carboxylic acid ethyl ester (14.5 g, 71percent) as white needles. Concentration and trituration of the mother liquor provided an additional product (2.3 g, 11percent). |
79% | Step l:5-Bromo-[l,3,4]thiadiazole-2-carboxylic acid ethyl ester (3_39_2) [00332] CuBr2 (18.06 g, 80.1 mmol) was added to a suspension of 5-amino- [l,3,4]thiadiazole-2-carboxylic acid ethyl ester 3_39_1 (7 g, 40.5 mmol) in 150 mL of acetonitrile, the mixture was stirred for 15 min, t-BuONO (9.6 mL, 80.1 mmol) was added over 20 min., and the mixture was heated at 60°C for 0.5 h. Water and ethyl acetate were added, the mixture was stirred until the dark color disappeared and filtered through celite, and the organic layer was washed with brine, dried over Na2S04, filtrated and concentrated to give compound 3_39_2 (7.56 g, 79 percent yield) as a yellow solid. [00333] NMR (400 MHz, DMSO-d6): delta = 1.32 (t, J = 7.14 Hz, 3 H), 4.41 (q, J = 7.30 Hz, 2 H); |
74% | With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 20 - 60℃; for 0.666667h; | Step 2: ethyl 5-bromo-l,3,4-thiadiazole-2-carboxylate ter-BuONOTo a stirred solution of ethyl 5-amino-l,3,4-thiadiazole-2-carboxylate (3.1 g, 17.8 mmol) in acetonitrile (50 mL) at room temperature was added copper (II) bromide (7.95 g, 35.6 mmol) and the mixture was stirred for 20 min. Tertiary butyl nitrite (3.67 g, 35.63 mmol) was then added drop wise for 10 min, and the reaction mixture was heated to 60°C for 30 min. The reaction mixture was concentrated under reduced pressure, diluted with water (300 mL), and then extracted with ethyl acetate (500 m:). The organic layer was separated and dried over anhydrous sodium sulphate, and evaporated to afford ethyl 5-bromo-l,3,4-thiadiazole-2-carboxylate as a brown solid (3.0 g, 74percent yield). XH NMR (400 MHz, CDC13): ? 4.53-4.51 (m, 2H), 1.45-1.43 (m, 3H); LC-MS m/z calcd for [M+H]+ 238.92, found 238.9. |
With tert.-butylnitrite; copper(ll) bromide; In acetonitrile; at 20 - 60℃; for 1.08333h; | Step 1: Ethyl 5-bromo-1,3,4-thiadiazole-2-carboxylate To a suspension of <strong>[64837-53-2]ethyl 5-amino-1,3,4-thiadiazole-2-carboxylate</strong> (10 g, 58 mmol) in CH3CN (180 mL) was added CuBr2 (25.7 g, 115 mmol). The mixture turned dark green and was further stirred for 15 min at room temperature. t-BuONO, 90percent (13.8 mL, 115 mmol) was added dropwise over 15-20 min. The mixture became slightly warm and gas was evolved after 5 min and then throughout the addition. After completion of the addition and gas evolution subsided, the mixture was heated at 60° C. for 30 min. Solvent was then evaporated in vacuo. Water and EtOAc were added and the mixture was agitated in the flask until the dark green color disappeared. The organic phase became light brown and the aqueous was green with insoluble material. The whole mixture was filtered through celite and washed with EtOAc. The EtOAc layer was separated, washed with dilute brine solution, dried (Na2SO4) and concentrated to give the title compound. 1H NMR (400 MHz, acetone-d6): delta4.52 (q, 2H), 1.43 (t, 3H). | |
To a suspension of ethyl 5-amino-l,3,4- thiadiazole-2-carboxylate in CH3CN (0.32 M) was added CuBr2 (2 equiv). The mixture turned dark green and was stirred for 15 min at room temperature. t-BuONO, 90percent (2 equiv) was added dropwise over 15 - 20 min. The mixture became slightly warm and gas evolved after about 5 min and then throughout the addition. After completion of the addition and after gas evolution subsided, the mixture was heated at 60 °C for 30 min. Solvent was then evaporated in vacuo. Water and EtOAc were added and the mixture was stirred until the dark green color disappeared. The organic phase became light brown and the aqueous phase was green with insoluble material. The entire mixture was filtered through Celite.(TM). and washed with EtOAc. The EtOAc layer was separated, washed with diluted brine, dried (Na2SO4) and concentrated to give the title compound. lH NMR (400 MHz, acetone-^): delta 4.52 (q, 2H), 1.43 (t, 3H). | ||
To a suspension of ethyl 5-amino- l,3,4-thiadiazole-2-carboxylate in CH3CN (0.32 M) was added CuBr2 (2 equiv). The mixture turned dark green and was stirred for 15 min at room temperature. Then /-BuONO (2 equiv, 90percent) was added dropwise over 15 - 20 min. The mixture became slightly warm and gas evolved after about 5 min and then throughout the addition. After completion of the addition and after gas evolution subsided, the mixture was heated at 60 °C for 30 min. Solvent was then evaporated in vacuo. Water and EtOAc were added and the mixture was stirred until the dark green color disappeared. The mixture was filtered through Celite.(TM). and washed with EtOAc. The EtOAc layer was separated, washed with diluted brine, dried (Na2SO4) and concentrated to give the title compound. lH NMR (400 MHz, acetone-t/6): delta 4.52 (q, 2H), 1.43 (t, 3H). | ||
Step 1 Ethyl 5-bromo-l ,3,4-thiadiazole-2-carboxylateTo a suspension of ethyl 5-ammo-l ,3,4-thiadiazole-2-carboxylate in CH3CN (0 32 M) was added CuBr2 (2 equiv) The mixture turned dark green and was stirred for 15 mm at room temperature ^-BuONO, 90percent (2 equiv) was added dropwise over 15 - 20 mm The mixture became slightly warm and gas was evolved after about 5 min and then throughout the addition After completion of the addition and gas evolution subsided, the mixture was heated at 60 0C for 30 mm Solvent was then evaporated under diminished pressure Water and EtOAc were added and the mixture was stirred until the dark green color disappeared The organic phase became light brown and the aqueous phase was green with insoluble material The entire mixture was filtered through celite and washed with EtOAc The EtOAc layer was separated, washed with diluted bpine, dpied (Na2SO4) and concentrated to give the title compound lH NMR (400 MHz, acetone-d) delta 4 52 (q, 2H), 1 43 (t, 3H) |
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