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Chemical Structure| 1393128-21-6 Chemical Structure| 1393128-21-6

Structure of 1393128-21-6

Chemical Structure| 1393128-21-6

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Product Details of [ 1393128-21-6 ]

CAS No. :1393128-21-6
Formula : C4H6N2S
M.W : 114.17
SMILES Code : CSC1=CNN=C1
MDL No. :MFCD28680871
InChI Key :VQRKUUUHFSFKAB-UHFFFAOYSA-N
Pubchem ID :20784854

Safety of [ 1393128-21-6 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 1393128-21-6 ]

* 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.

  • Downstream synthetic route of [ 1393128-21-6 ]

[ 1393128-21-6 ] Synthesis Path-Downstream   1~10

  • 1
  • [ 1393125-43-3 ]
  • [ 1393128-21-6 ]
  • C22H24N2O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate;copper(l) iodide; 8-quinolinol; In dimethyl sulfoxide; at 120℃; for 12h;Inert atmosphere; Example 20 (+/-)-3-(4-(1-(4-(4-(methylthio)-1H-pyrazol-1-yl)phenoxy)butyl)benzamido)propanoic acid Copper iodide (1.31 g, 6.87 mmol), quinolin-8-ol (1.00 g, 6.87 mmol), and potassium carbonate (10.5 g, 76.0 mmol) were combined and pulverized. 78 mg of this mixture was added to <strong>[1393128-21-6]4-(methylthio)-1H-pyrazole</strong> (0.400 mmol) in a two dram vial. A solution of Intermediate (27) (123 mg, 0.300 mmol) in dimethylsulfoxide (0.500 mL) was added to the vial under a stream of dry nitrogen. The vial was capped and agitated on an orbital shaker at 120 C. for 12 hours. The reaction mixture was concentrated in vacuo. To the crude residue was added methanol (2.0 mL), tetrahydrofuran (1.0 mL), and aqueous lithium hydroxide (2.0 M, 2.0 mL). The reaction was agitated on an orbital shaker at 60 C. for 12 hours. The reaction mixture was concentrated in vacuo and the remaining crude residue was carefully acidified with 1.0M aqueous hydrochloric acid (5.0 mL). The resulting acidified mixture was concentrated in vacuo. A mixture of tert-butyl 3-aminopropanoate hydrochloride (12.3 g, 67.7 mmol), 1-hydroxybenzotriazole (6.89 g, 45 mmol) and 1-ethyl-3-(3-dimethylamino propyl)carbodiimide hydrochloride (12.9 g, 67.3 mmol) was suspended in tetrahydrofuran (450 mL). A 3.0 mL aliquot of this solution was transferred to the crude acid from the previous transformation. Triethylamine (0.167 mL, 1.20 mmol) was added and the mixture was agitated on an orbital shaker overnight. The reaction mixture was treated with Si-diamine scavenger (ca. 5.0 eq) and was agitated for 12 hours on an orbital shaker. The reaction was filtered through a silica gel plug, washing with tetrahydrofuran (three times). The combined organic filtrate was concentrated in vacuo. To the crude residue was added dichloromethane (4.0 mL), followed by trifluoroacetic acid (2.0 mL). The reaction was agitated on an orbital shaker for 12 hours. The reaction mixture was concentrated in vacuo. Purification by reversed-phase HPLC on a Waters Sunfire C18 19*100 mm, 0.005 mm column eluting with a gradient of water in acetonitrile (0.05% trifluoroacetic acid modifier) gave (+/-)-3-(4-(1-(4-(4-(methylthio)-1H-pyrazol-1-yl)phenoxy)butyl)benzamido)propanoic acid (39.7 mg, 23% over 4 steps).
  • 2
  • [ 1393128-21-6 ]
  • [ 590-17-0 ]
  • 2-(4-(methylthio)-1H-pyrazol-1-yl)acetonitrile [ No CAS ]
YieldReaction ConditionsOperation in experiment
72.54% With sodium hydride; In tetrahydrofuran; at 0 - 20℃;Inert atmosphere; Step 2: 2-(4-(Methylthio)-1 H-pyrazol-1-yl)acetonitrile Sodium hydride (631 mg, 16 mmol) was added to a solution of 4-(methylthio)-1 H- pyrazole (1500 mg, 13.14 mmol) in anhydrous tetrahydrofuran (30 mL) under nitrogen at 0C. The reaction mixture was stirred at 0C until gas evolution was no longer observed. Bromoacetonitrile (1.005 mL, 14.43 mmol) was added dropwise and the reaction mixture was stirred at room temperature for 18 h. The mixture was poured into a solution of aqueous ammonium chloride (30 mL) and was extracted with ethyl acetate (60 mL x 3). The combined organics were dried over sodium sulfate. The residue was filtered through a plug of silica gel which was eluted with ethyl acetate and the filtrate was concentrated under reduced pressure. The crude material was purified via flash chromatography (0-50% ethyl acetate in heptanes) to afford 2-(4-(methylthio)-1 H- pyrazol-1-yl)acetonitrile (1460 mg, 72.54 %). MS (ES+) (M+H) 154.1 ; LCMS retention time 0.40 min (Method N).
  • 3
  • [ 2075-45-8 ]
  • [ 624-92-0 ]
  • [ 1393128-21-6 ]
YieldReaction ConditionsOperation in experiment
3300 mg Step 1 : 4-(Methylthio)-1H-pyrazole A suspension of 4-bromopyrazole (4 g, 27 mmol) in tetrahydrofuran (68 mL) was cooled to 0C and n-butyllithium (2.5 M in hexanes, 35.9 mL, 90 mmol) was added dropwise over a period of 20 min. The reaction mixture was stirred at room temperature for 1 h and then was cooled to 0C. 1 ,2-Dimethyldisulfide (2.66 mL, 30.0 mmol) was added dropwise. The reaction mixture was stirred at 0C for 1.5 h. The reaction mixture was poured into water (150 mL) and then it was acidified to pH~8 with a saturated aqueous solution of ammonium chloride and a solution of aqueous hydrochloric acid (1 N). The mixture was extracted with ethyl acetate (150 mL x 3) and the combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure to afford 4-(methylthio)-1 H-pyrazole (3300 mg). 1H NMR (500 MHz, CDCI3) delta 2.36 (s, 3H), 7.63 (s, 2H).
To a solution of 4-bromo-lH-pyrazole (200 mg, 1.361 mmol) in anhydrous THF (5 mL) was added n-BuLi (2.5 M, 1.8 mL, 4.5 mmol) at 0C. The solution was stirred at room temperature for 1 hour. The MeSSMe (128 mg, 0.12 mL, 1.361 mmol) was added at 0C and reaction solution was stirred at room temperature for 2 hours. The reaction was poured into ethyl acetate (50 mL) and water (50 mL). The separated organic layer was washed brine (50 mL), dried over magnesium sulfate and concentrated in vacuo. Due to its smell, the crude product was used in next oxidation reaction without further purification
  • 4
  • [ 1393128-21-6 ]
  • [ 1430065-01-2 ]
  • C25H37FN2O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With potassium carbonate; In N,N-dimethyl-formamide; at 19℃; for 16h; To a solution of SB-FF (100 mg, 0.24 mmol) in DMF (2 mL) was added Al (55 mg, 0.48 mmol) and K2CO3 (100 mg, 0.72 mmol) at 19C. The reaction was stirred at 19C for 16 h. The resulting mixture was poured into water (3 ml). The mixture was extracted with EtOAc (2 mL x 3). The combined organic layers was washed with brine (5 mL), dried over Na2S04 and concentrated in vacuum. The residue was purified by silica gel column (Petroleum ether/ethyl acetate = 10/1 to 3/1) to give SB-14 (80 mg, yield: 74%) as a pink solid. 1H NMR: (400 MHz, CDC13) delta 7.53 (s, 1H), 7.43 (s, 1H), 4.79-4.97 (m, 2H), 4.47-4.65 (m, 1H), 2.56-2.63 (m, 1H), 2.35 (s, 3H), 2.19-2.26 (m, 1H), 2.00-2.08 (m, 2H), 1.63-1.92 (m, 5H), 1.35-1.57 (m, 5H), 1.20-1.1.32 (m, 5H), 1.07-1.18 (m, 5H), 0.75-0.91 (m, 1H), 0.71 (s, 3H). LCMS: rt = 1.25 mm, m/z = 449.2 [M+H]+
  • 5
  • [ 1393128-21-6 ]
  • 4-methylsulfonyl-1H-pyrazole [ No CAS ]
YieldReaction ConditionsOperation in experiment
51 mg With 3-chloro-benzenecarboperoxoic acid; trifluoroacetic acid; In dichloromethane; at 0 - 20℃; To a solution of the crude reactant (155.4 mg, 1.361 mmol, theoretical amount) in dichloromethane (2.7 mL) was added trifluoroacetic acid (0.1 mL) at 0C. Then 3-chloroperbenzoic acid (m-CPBA, 85% wt, 863 mg, 4.25 mmol) was added in portions and the solution was stirred at room temperature overnight. The solution was diluted with ethyl acetate (100 mL) and the resulting solution was washed with sat. Na2C03 solution (3x50 mL) followed by brine (50 mL), dried over magnesium sulfate and concentrated in vacuo. The crude product was purified by silica gel chromatography ( ethyl acetate to ethyl acetate: methanol =10: 1) to afford product (51 mg, 0.349 mmol, Yield=26% (2 steps)) as pale yellow thick oil. 1HNMR (500 MHz, CDC13) 5(ppm): 8.04 (2H, s), 3.14 (3H, s)
  • 6
  • [ 1393128-21-6 ]
  • [ 1430063-93-6 ]
  • C25H38N2O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
76% With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 18h;Inert atmosphere; To a mixture of SA (200 mg, 0.50 mmol) and K2CO? (138.2 mg, 1.00 mmol) in 5 mL dry DMF was added 4-(methylthio)-lH-pyrazole (1 14.2 mg, 1.00 mmol) under N2 at room temperature (25C). The reaction mixture was stirred at the same temperature for 18 h. The reaction mixture was poured into water and extracted with EtOAc (50 mLx2). The organic layers were washed with brine, dried over Na2S04, filtered and concentrated in vacuum. The residue was purified by silica gel column (Petroleum ether/ ethyl acetatelO/1 to 2/1) to give Compound SA-18 (165 mg, yield: 76%) as white powder. 1H NMR: (400 MHz, CDC13) delta 7.53 (s, 1H), 7.42 (s, 1H), 4.94-4.80 (m, 2H), 2.60-2.56 (m, 1H), 2.34 (s, 3H), 2.23-2.16 (m, 1H), 2.06-2.02 (m, 1H), 1.87-1.58 (m, 12H, contained H20), 1.49-1.27 (m, 14H), 1.15-1.07 (m, 2H), 0.67 (s, 3H). LCMS: rt = 1.32 mm, m/z = 431.2 [M+H]+
  • 7
  • [ 1393128-21-6 ]
  • 4-(methylthio)-1H-pyrazol-1-amine [ No CAS ]
  • 8
  • [ 1393128-21-6 ]
  • 2-bromo-1-((3R,5R,8R,9S,10S,13S,14S,17S)-3-hydroxy-3,10,13-trimethylhexadecahydro-1H-cyclopenta[a]phenanthren-17-yl)ethanone [ No CAS ]
  • C26H40N2O2S [ No CAS ]
YieldReaction ConditionsOperation in experiment
With potassium carbonate; In acetone; at 40℃; for 16h; To a solution of A26 (300mg, 0.729 mmol) in acetone (2 mL) was added 4-(methylthio)-1H-py(247 mg,2.17 mmol), followed by K2CO3 (200 mg, 1.45mmol). The resulting reaction mixture was stirred at 40 oC for 16 hours, at which point LCMS indicated the starting material was consumed completely. The mixture was diluted with water (10 mL) and then extracted with EtOAc (8 mL*3). The combined organic phases were concentrated to give a residue, which was purified by HPLC.
  • 9
  • [ 1393128-21-6 ]
  • C23H37BrO3 [ No CAS ]
  • C27H42N2O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
75% With potassium carbonate; In acetone; at 25℃; for 4h; To a solution of CI (300 mg, 0.679 mmol) in acetone (6 mL) was added K2C03 (280 mg) and 4-(methylthio)- lH-pyrazole (115 mg, 1.01 mmol). The mixture was stirred at 25C for 4 hrs. The solvent was removed by rotary evaporator. To the mixture was added water (6 mL) and EtOAc (8 mL). The organic layer was separated. The aqueous phase was extracted with EtOAc (2 x 8 mL). The combined organic layers was washed with brine (10 mL), dried over Na2S04, filtered and evaporated to give a residue, which was purified by preparative HPLC to afford compound 21 (30.3 mg, 75%). [349] 21: (400 MHz, CDC13) delta 7.53 (s, IH), 7.41 (s, IH), 4.94- 4.87 (m, IH), 4.86-4.78 (m, IH), 3.53 (d, = 9.0 Hz, IH), 3.32 (s, 3H), 3.18 (d, = 9.0 Hz, IH), 2.61-2.52 (m, IH), 2.34 (s, 3H), 2.24-2.13 (m, IH), 2.08-1.99 (m, IH), 1.96-1.86 (m, 2H), 1.79-1.61 (m, 8H), 1.52-1.35 (m, 5H), 1.27 (s, 9H), 0.66 (s, 3H). LCMS Rt = 0.900 min in 1.5 min chromatography, MS ESI calcd. for C27H42N203SNa [M+Na]+ 497, found 497
  • 10
  • [ 1393128-21-6 ]
  • C23H37BrO3 [ No CAS ]
  • C27H42N2O3S [ No CAS ]
YieldReaction ConditionsOperation in experiment
36% With potassium carbonate; In acetone; at 25℃; for 4h; To a solution of Al (300 mg, 0.679 mmol) in acetone (6 mL) was added K2CO3 (280 mg, 2.03 mmol) and 4-(methylthio)-lH-pyrazole (115 mg, 1.01 mmol). The mixture was stirred at 25C for 4 hrs. The solvent was removed by rotary evaporator. To the mixture was added water (6 mL) and EtOAc (8 mL). The organic layer was separated. The aqueous phase was extracted with EtOAc (2 x 8 mL). The combined organic layers was washed with brine (10 mL), dried over Na2S04, filtered and evaporated to afford a crude product, which was purified by preparative HPLC to give compound 34 (120 mg, 36%). [373] 34: 1H NMR (400 MHz, CDC13) delta 7.52 (s, 1H), 7.41 (s, 1H), 4.95-4.77 (m, 2H), 3.49- 3.43 (m, 1H), 3.40-3.34 (m, 1H), 3.28 (s, 3H), 2.58 (t, J = 8.7 Hz, 1H), 2.34 (s, 3H), 2.26-2.14 (m, 1H), 2.07- 1.98 (m, 2H), 1.77-1.63 (m, 4H), 1.57- 1.44 (m, 5H), 1.41-0.79 (m, 14H), 0.69 (s, 3H). LCMS Rt = 0.927 min in 1.5 min chromatography, MS ESI calcd. for C27H42N203SNa [M+Na]+ 497, found 497.
 

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