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CAS No. : | 64837-49-6 | MDL No. : | MFCD11112114 |
Formula : | C5H5ClN2O2S | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | YQWCUJDSRXQJRN-UHFFFAOYSA-N |
M.W : | 192.62 | Pubchem ID : | 12348753 |
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 |
---|---|---|
In acetonitrile; at 0 - 20℃; | Ethyl diazoacetate (1, 10 g, 87.6 mmol) was taken up in acetonitrile (50 mL) and the resultant mixture cooled to 0 C. Thiophosgene (3.4 mL, 43.8 mmo.) was added to the mixture dropwise and the mixture was then stirred at room temperature for 20 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the solvent was evaporated from the reaction mixture under reduced pressure. The resultant crude product was purified by column chromatography using 10% EtOAc-hexane to afford ethyl 5-chloro-l ,3,4-thiadiazole-2-carboxylate (2, 3, 4 g, 25%). NMR (400 MHz, CDCI3): delta 4.57 (q, 2H), 1.42 (t, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In DMF (N,N-dimethyl-formamide); at 70 - 80℃; for 18.0h; | Synthesis of 5-(7-Chloro-quinolin-4-yloxy)-[1,3,4]thiadiazole-2-carboxylic Acid Ethyl Ester [CHEMMOL-00141] [0176] NaH (0.022 mg, 0.5 mmol) was added in portions to a solution of 7-chloro-4-hydroxyquinoline (0.093 mg, 0.5 mmol) in DMF (6 ml) at room temperature and the mixture stirred at room temperature for 20 min. 2-Chloro-[1,3,4]thiadiazole derivative (0.097 mg, 0.5 mmol) was then added in one portion and the mixture heated at 70-80 C. (oil bath temperature) for 18 h. The reaction mixture was allowed to cool to room temperature and water (15-30 ml) was added. The precipitate was separated by filtration, washed several times with cold water, then with Et2O and dried to afford the product (0.081 mg, 47% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In DMF (N,N-dimethyl-formamide); at 80℃; for 18.0h; | Synthesis of 5-Chloro-[1,3,4]thiadiazole-2-carboxylic Acid (7-chloro-quinolin-4-yl)-amide [CHEMMOL-00146] [0186] NaH (0.023 g, 0.58 mmol) was added in portions to a solution of 4-amino-7-chloro-quinoline (0.1 g, 0.56 mmol) in DMF (6 ml) at room temperature and the mixture was stirred for 20 min. 5-Chloro-[1,3,4]thiadiazole derivative (0.108 g, 0.56 mmol) was then added in one portion and the mixture heated at 80 C. (oil bath temperature) for 18 h. The reaction mixture was allowed to cool to room temperature and water (15 ml) was added. The precipitate was separated by filtration, washed with Et2O and dried to afford the product (0.08 g, 60% yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With sodium borohydrid; In methanol; | Preparation 39 Synthesis of (5-chloro-1,3,4-thiadiazol-2-yl)methanol To a solution of <strong>[64837-49-6]ethyl 5-chloro-1,3,4-thiadiazole-2-carboxylate</strong> (0.51 g, 2.60 mmol) in anhydrous methanol (5.00 mL) was added sodium borohydride (0.30 g, 7.99 mmol) at 0 C. The reaction mixture was stirred at ambient temperature for 16 h, diluted with acetic acid (3.00 mL) and extracted with ethyl acetate (2*150 mL). The combined organics was washed with aqueous saturated sodium bicarbonate (3*25.0 mL) and aqueous saturated sodium chloride (2*25.0 mL). The organic layer was dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to dryness to give the title compound (0.30 g, 75%) as a light yellow semi-solid: 1H NMR (300 MHz, CDCl3) delta 5.04 (s, 2H), 2.80 (br, 1H); MS (ES+) 151.1 (M+1), 153.1 (M+1). |
75% | With sodium tetrahydroborate; In methanol; at 0 - 20℃; for 16.0h; | To a a solution of <strong>[64837-49-6]ethyl 5-chloro-1 ,3,4-thiadiazole-2-carboxylate</strong> (0.51 g, 2.60 mmol) in anhydrous methanol (5.00 mL) was added sodium borohydride (0.30 g, 7.99 mmol) at 0 0C. The reaction mixture was stirred at ambient temperature for 16 h, diluted with acetic acid (3.00 mL) and extracted with ethyl acetate (2 x 150 mL). The combined organics was washed with aqueous saturated sodium bicarbonate (3 x 25.0 mL) and aqueous saturated sodium chloride (2 x 25.0 mL). The organic layer was dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated in vacuo to dryness to give the title compound (0.30 g, 75%) as a light yellow semi-solid: 1H NMR (300 MHz, CDCI3) delta 5.04 (s, 2H), 2.80 (br, 1 H); MS (ES+) 151.1 (M + 1), 153.1 (M + 1). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | With toluene-4-sulfonic acid; In Isopropyl acetate; at 80℃; | Ethyl 5-chloro-l ,3,4-thiadiazole-2 -carboxylate (3, 3 g, 15.7 mmol), 2-methoxy-4-(4-methyl piperazin-l -yl)aniline (4, 3.4 g, 15.7 mmol) and p-TSA (3 g, 15.7 mmol) were taken up in IPA (25 mL) and the resultant mixture was stirred at 80 C overnight. The progress of the reaction was monitored by TLC. After completion of the reaction, the solvent was evaporated from the reaction mixture under reduced pressure, and the resultant residue was basified using aq. NaHC03 solution and extracted with ethyl acetate. The organic extract was dried over anhydrous sodium sulfate and evaporated under reduced pressure. The resultant crude product was purified by columnchromatography using 5% MeOH-DCM to afford ethyl 5-((2-methoxy-4-(4-methylpiperazin-l - yl)phenyl)amino)-l ,3,4-thiadiazole-2-carboxylate (5, 1 .5 g, 25%). NMR (400 MHz, CDC13): delta 7.90 (bs, 1 H), 7.43 (d, 1 H), 6.59-6.55 (m, 2H), 4.50 (q, 2H), 3.90 (s, 3H), 3.25-3.22 (m, 4H), 2.65- l .60 (m, 4H), 2.40 (s, 3H), 1.42 (t, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With potassium carbonate; In N,N-dimethyl-formamide; at 40℃; for 3.0h; | Step 1. General procedure for preparation of Intermediate 8. 8 A solution of ethyl 5-chloro-l,3,4-thiadiazole-2-carboxylate (60 g, 0.313 mol), K2CO3 (130 g, 0.94 mol) and methyl piperazine in DMF (300 mL) was stirred at 40 C for 3 h. TLC Rf 0.5 (petroleum ether/EtOAc, 10/1) showed the reaction was complete. The reaction mixture was poured into water and extracted with. CH2CI2. The organic layer was washed with water, dried over Na2S04, and concentrated to give Intermediate 8 (58.5 g, 73%) as a yellow solid. 1H NMR (400 MHz, CDCI3) delta 1.35-1.47 (m, 3H), 2.34 (s, 3H), 2.47-2.60 (m, 4H), 3.60-3.71 (m, 4H), 4.37-4.47 (m, 2H), 5.30 (s, 1H). |
73% | With potassium carbonate; In N,N-dimethyl-formamide; at 40℃; for 3.0h; | A solution of compound 7A (60 g, 0.313 mol), K2C03 (130 g, 0.94 mol), and methyl piperazine in DMF (300 mL) was stirred at 40 C for 3 h. The reaction mixture was poured into water and extracted with CH2C12. The organic layer was washed with water, dried over Na2S04, and concentrated to give compound 7B (58.5 g, 73%) as a yellow solid. 1H NMR (400 MHz, CDC13) delta 4.37-4.47 (m, 2H), 3.60-3.71 (m, 4H), 2.47-2.60 (m, 4H), 2.34 (s, 3H), 1.35- 1.47 (m, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
44% | With toluene-4-sulfonic acid; In ethanol;Reflux; | [0192] Step 3. A mixture of Compound 6-D (4.1 g, 0.015 mol), Compound 6-E (2.33 g, 0.0 13 mol) and p-toluenesulfonic acid (2.85 g, 0.0 15 mol) in ethanol (70 mL) was refluxed overnight. Monitoring by thin layer chromatography (petrol ether: ethyl acetate=2: 1 and Rf at 0.5) showed the reaction was complete. The mixture was partitioned between saturated aqueous NaHCO3 (100 mL) and ethyl acetate (100 mL) and extracted with ethyl acetate (100 mL x 2). The combined organic layers were dried and concentrated. The residue was recrystallized with ethyl acetate to give Compound 6-F (2.8 g, 44%) as light brown solid.?H NMR (400 MHz, MeOH) oe 1.37-1.41 (m, 3H), 4.40-4.48 (m, 2H), 7.42-7.47 (m, 2H), 7.78-7.87 (m, 4H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
0.95 g | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine; at 20℃; for 7.5h;Inert atmosphere; | Reference Production Example 2 (0648) 5-Chloro-1,3,4-thiadiazole-2-carboxylic acid ethyl ester (1.00 g, 5.19 mmol), 1-pentyne (530 mg, 7.79 mmol), triethylamine (2.9 mL, 20.8 mmol), copper iodide (20 mg, 0.10 mmol) and dichlorobis(triphenylphosphine)palladium (73 mg, 0.10 mmol) were added, and the mixture was stirred at room temperature for 7 hours and 30 minutes, under a nitrogen atmosphere. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was sequentially washed with aqueous ammonia, 1.5% hydrochloric acid and saturated saline water, and then dried over anhydrous sodium sulfate. The residue was applied to a silica gel column chromatography to obtain 0.95 g of ethyl 5-pent-1-ynyl-1,3,4-thiadiazole-2-carboxylate represented by the following formula. 1H-NMR(CDCl3, TMS)delta(ppm) :1.07(t, 3H), 1.46(t, 3H), 1.70(m, 2H), 2.51(t, 2H), 4.52(q, 2H) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; | To a stirred solution of <strong>[64837-49-6]ethyl 5-chloro-1 ,3,4-thiadiazole-2-carboxylate</strong> (0.25 g, 1 .29mmol) in dry DMF (2.5 mL), K2C03 (0.54 g, 3.89 mmol) and Intermediate 30 (0.59 g,1 .93 mmol) were added at rt. The reaction mixture was stirred overnight at 80 C. It was then concentrated under vacuum. EtOAc (10 mL) was added and the resulting solution was washed with water (10 mL), brine (10 mL), dried over anhydrous Na2SO4 and concentrated. The crude product was purified by flash chromatography to afford thetitle compound. Yield: 51% (0.26 g, off white solid). 1H NMR (400 MHz, DMSO-d6): 67.15 (d, J= 7.60 Hz, IH), 6.75 (d, J= 7.60 Hz, IH), 6.71 (s, IH), 4.50 (t, J= 8.80 Hz,2H), 4.33 (q, J = 6.80 Hz, 2H), 3.54 (t, J= 5.20 Hz, 4H), 3.43-3.41 (m, IH), 3.13 (t, J=8.40 Hz, 2H), 2.45-2.32 (m, 4H), 1.31-1.27 (m, 6H). LCMS: (Method A) 389.2 (M+H),Rt. 2.88mm, 95.7% (Max). HPLC: (Method A) Rt2.8lmin, 96.5% (Max). |
0.26 g | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; | To a stirred solution of <strong>[64837-49-6]ethyl 5-chloro-1,3,4-thiadiazole-2-carboxylate</strong> (0.25 g, 1.29 mmol) in dry DMF (2.5 mL), K2CO3 (0.54 g, 3.89 mmol) and Example 8 (0.59 g, 1.93 mmol) were added at rt. The reaction mixture was stirred overnight at 80 C It was then concentrated under vacuum. EtOAc (10 mL) was added and the resulting solution was washed with water (10 mL), brine(10 mL), dried over anhydrous Na2SO4 and concentrated. The crude product was purified by flash chromatography to afford the title compound. Yield: 51% (0.26 g, off white solid). 1H NMR (400 MHz, DMSO-d6): delta 7.15 (d, J = 7.60 Hz, 1H), 6.75 (d, J = 7.60 Hz, 1H), 6.71 (s, 1H), 4.50 (t, J = 8.80 Hz, 2H), 4.33 (q, J = 6.80 Hz, 2H), 3.54 (t, J= 5.20 Hz, 4H), 3.43-3.41 (m, 1H), 3.13 (t, J= 8.40Hz, 2H), 2.45-2.32 (m, 4H), 1.31-1.27 (m, 6H). LCMS: (Method A) 389.2(M+H), Rt. 2.88min, 95.7% (Max). HPLC: (Method A) Rt 2.81min, 96.5% (Max). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; | To a stirred solution of <strong>[64837-49-6]ethyl 5-chloro-1 ,3,4-thiadiazole-2-carboxylate</strong> (0.25 g, 1 .29 mmol) in dry DMF (2.5 mL), K2C03 (0.54 g, 3.89 mmol) and Intermediate 13 (0.59 g, 1.93 mmol)were added at rt. The reaction mixture was stirred overnight at 80 C. It was then concentrated under vacuum. EtOAc (10 mL) was added and the resulting solution waswashed with water (10 mL), brine (10 mL), dried over anhydrous Na2SO4 and concentrated.The crude product was purified by flash chromatography to afford the title compound.Yield: 51% (0.26 g, off white solid). 1H NMR (400 MHz, DMSO-d6): 6 7.15 (d, J = 7.60 Hz,IH), 6.75 (d, J = 7.60 Hz, IH), 6.71 (5, IH), 4.50 (t, J = 8.80 Hz, 2H), 4.33 (q, J = 6.80 Hz,2H), 3.54 (t, J = 5.20 Hz, 4H), 3.43-3.41 (m, IH), 3.13 (t, J = 8.40 Hz, 2H), 2.45-2.32 (m,4H), 1.31-1.27 (m, 6H). LCMS: (Method A) 389.2 (M+H), Rt. 2.88mm, 95.7% (Max). HPLC:(Method A) Rt 2.81 mm, 96.5% (Max). |
51% | With potassium carbonate; In N,N-dimethyl-formamide; at 80℃; | To a stirred solution of <strong>[64837-49-6]ethyl 5-chloro-1,3,4-thiadiazole-2-carboxylate</strong> (0.25 g, 1.29 mmol) in dry DMF (2.5 mL), K2CO3 (0.54 g, 3.89 mmol) and Intermediate 13 (0.59 g, 1.93 mmol) were added at rt. The reaction mixture was stirred overnight at 80 C. It was then concentrated under vacuum. EtOAc (10 mL) was added and the resulting solution was washed with water (10 mL), brine (10 mL), dried over anhydrous Na2S04 and concentrated. The crude product was purified by flash chromatography to afford the title compound. Yield: 51 % (0.26 g, off white solid). 1H NMR (400 MHz, DMSO-d6): delta 7.15 (d, J = 7.60 Hz, 1 H), 6.75 (d, J = 7.60 Hz, 1 H), 6.71 (s, 1 H), 4.50 (t, J = 8.80 Hz, 2H), 4.33 (q, J = 6.80 Hz, 2H), 3.54 (t, J = 5.20 Hz, 4H), 3.43-3.41 (m, 1 H), 3.13 (t, J = 8.40 Hz, 2H), 2.45-2.32 (m, 4H), 1.31 -1.27 (m, 6H). LCMS: (Method A) 389.2 (M+H), Rt. 2.88min, 95.7% (Max). HPLC: (Method A) Rt 2.81 min, 96.5% (Max). |
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