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[ CAS No. 1009071-34-4 ]

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Chemical Structure| 1009071-34-4
Chemical Structure| 1009071-34-4
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Product Details of [ 1009071-34-4 ]

CAS No. :1009071-34-4 MDL No. :MFCD12407274
Formula : C15H25BN2O4 Boiling Point : 404.9±47.0°C at 760 mmHg
Linear Structure Formula :- InChI Key :-
M.W :308.18 g/mol Pubchem ID :-
Synonyms :

Safety of [ 1009071-34-4 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 1009071-34-4 ]

  • Downstream synthetic route of [ 1009071-34-4 ]

[ 1009071-34-4 ] Synthesis Path-Downstream   1~16

  • 1
  • 1-[3-bromo-5-(trifluoromethyl)phenyl]sulfonyl}-4-({2-[4-(trifluoromethyl)phenyl]cyclopropyl}-carbonyl)piperazine [ No CAS ]
  • [ 1009071-34-4 ]
  • 1-[3-(3-methyl-1H-pyrazol-4-yl)-5-(trifluoromethyl)phenyl]sulfonyl}-4-({2-[4-(trifluoromethy)phenyl]cyclopropyl}carbonyl)piperazine [ No CAS ]
YieldReaction ConditionsOperation in experiment
Stage #1: 1-[3-bromo-5-(trifluoromethyl)phenyl]sulfonyl}-4-({2-[4-(trifluoromethyl)phenyl]cyclopropyl}-carbonyl)piperazine; tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate With sodium carbonate In 1-methyl-pyrrolidin-2-one; water; isopropyl alcohol for 0.333333h; Stage #2: With tetrakis(triphenylphosphine) palladium(0) In 1-methyl-pyrrolidin-2-one; water at 100℃; for 3h; 147 To a solution of l-[3-bromo-5- (trifluoromethyl)phenyl]sulfonyl} -4-( {2-[4-(trifluoromethyl)phenyl]cyclopropyl} - carbonyl)piperazine (80mg, 0.14 mmol, prepared by the method described in Example 5 substituting l-(4-trifluoromethylphenylacetyl)piperazine for 1-benzoylpiperazine and 3-bromo-5- trifluoromethylphenylsulfonyl chloride for 3,5-bis(trifluoromethyl)phenylsulfonyl chloride) in N- methyl-2-pyrrolidone (2 mL) are sequentially added water (2 mL), isopropyl alcohol (ImL), 1- (erf-butyloxycarbonyl)-3-methyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxoboralan-2-yl)-pyrazole (100 mg, 0.32 mmol) and sodium carbonate (21 mg, 0.20 mmol). The reaction mixture is degassed with nitrogen for 20 min after which tetrakis(triphenylphosphine)palladium is added. The reaction mixture is heated to 1000C for 3h and then cooled to ambient temperature, concentrated and purified using mass triggered preparative reverse phase ηPLC system (Method C). The reaction is purified using the preparative ηPLC. LCMS (Method B) m/z (MH)+ = 587 (at) 2.19 min.
  • 2
  • [ 936250-20-3 ]
  • [ 24424-99-5 ]
  • [ 1009071-34-4 ]
YieldReaction ConditionsOperation in experiment
59% With triethylamine; In 1,4-dioxane; at 20℃; for 48h; C. tert-Butyl 3-methyl-4-(4,4,5,5-tetramethyI-l,3,2-dioxaboroIan-2-yl)- lH-pyrazole-1-carboxylate. 3-Methyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)- lH-pyrazole (0.2 g, 0.96 mmol), di-t-butyldicarbonate (0.4 g, 1.8 mmol) and triethylamine (0.18 g, 1.79 mmol) were placed in 1 ,4-dioxane (5 mL) and stirred, under nitrogen, at rt for two days. The solvent was removed and the desired product isolated using silica gel chromatography (25 % ethyl acetate in hexanes) to afford the title compound (0.175 g, 59 % yield). MS (ESI) m/z 309.4 [M+l]+.
  • 3
  • [ 1009071-34-4 ]
  • [ 1021918-82-0 ]
  • [ 1021917-07-6 ]
YieldReaction ConditionsOperation in experiment
22% With potassium phosphate In water; N,N-dimethyl-formamide at 100℃; 5.1.141.D C. tert-Butyl 3-methyl-4-(4,4,5,5-tetramethyI-l,3,2-dioxaboroIan-2-yl)- lH-pyrazole-1-carboxylate. 3-Methyl-4-(4,4,5,5-tetramethyl-l,3,2-dioxaborolan-2-yl)- lH-pyrazole (0.2 g, 0.96 mmol), di-t-butyldicarbonate (0.4 g, 1.8 mmol) and triethylamine (0.18 g, 1.79 mmol) were placed in 1 ,4-dioxane (5 mL) and stirred, under nitrogen, at rt for two days. The solvent was removed and the desired product isolated using silica gel chromatography (25 % ethyl acetate in hexanes) to afford the title compound (0.175 g, 59 % yield). MS (ESI) m/z 309.4 [M+l]+. [00614] D. 6-(3-Methyl-lH-pyrazol-4-yl)-l-((tetrahydro-2H-pyran-4-yl)methyl)- lH-imidazo[4,5-b]pyrazin-2(3H)-one. 6-Bromo- 1 -((tetrahydro-2H-pyran-4-yl)methyl)- lH-imidazo[4,5-b]pyrazin-2(3H)-one (See Example 101. B) (0.16 g, 0.51 mmol), tert-butyl 3-methyl-4-(4,4,5 ,5-tetramethyl- 1 ,3 ,2-dioxaborolan-2-yl)- 1 H-pyrazole- 1 -carboxylate (0.175 g, 0.56 mmol), dichloro[l,r-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.04 g, 0.05 mmol) and potassium phosphate (0.43 g, 2.05 mmol) were combined in DMF (3 mL) and water (0.2 mL), the mixture purged with nitrogen and heated in a sealed tube at 100 °C overnight. The solvent was removed and the crude purified on silica gel chromatography (100 % ethyl acetate) to afford the title compound as a white solid (0.036 g, 22% yield). 1H NMR (400 MHz, DMSO-J6) δ 12.77 (s, IH), 1 1.87 (s, IH), 8.17 (s,lH), 7.92 (s,lH), 3.82 (d, J= 12, 2H),3.72 (d, J=7.2, 2H), 3.23 (t, J= 10, 2H), 2.54 (s, 3H), 2.13 (m, IH), 1.54 (d, J=72, 2H), 1.26(m, 2H); MS (ESI) m/z 315.1 [M+l]+; mp 222-224 °C.
  • 4
  • [ 1021919-24-3 ]
  • [ 73183-34-3 ]
  • [ 1009071-34-4 ]
YieldReaction ConditionsOperation in experiment
With potassium acetate In dimethyl sulfoxide at 20 - 80℃; for 5.08333h; 35.B Step B: N-Boc-3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-pyrazole. To the product of Step A (3.30 g 12.6 mmol) was added bis(pinacolato)diboron (3.53 g, 13.9 mmol), potassium acetate (3.72 g, 37.9 mmol), 1,1'-bis(diphenylphosphino)ferrocenedichloropalladium (II) (0.457 g, 0.632 mmol) and DMSO (15 mL). The reaction vessel was purged with N2 for 5 min at rt prior to heating to 80° C. for about 5 hours. The reaction was cooled to rt, diluted with EtOAc and filtered through Celite. The solution was then washed with brine 5 times and concentrated. The residue was purified by flash chromatography on silica gel gradient eluted with 0-21% EtOAc in hexane affording the title compound. HPLC/MS: 309.3 (M+1); Rt=3.48 min.
With potassium acetate In 1,2-dimethoxyethane at 90℃; Inert atmosphere; 108.3 A mixture of tert-butyl 4-bromo-3-methyl-lH-pyrazole- 1-carboxylate (9.2 g, 35.2 mmol), 4, 4, 4' , 4' , 5, 5, 5' , 5' - octamethyl-2, 2' -bi-1, 3, 2-dioxaborolane (9.39 g, 37.0 mmol), potassium acetate (10.4 g, 106 mmol) and 1,2-dimethoxyethane (100 itiL) was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (2.88 g, 3.52 mmol) was added, and the mixture was purged with argon again. The mixture was stirred at 900C overnight. After cooled to room temperature, the mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was suspended in 1:1 EtOAc/hexane and filtered. The filtrate was concentrated under reduced pressure. The residue was purified by column chromatography (Purif, silica gel, hexane to 70:30 hexane/EtOAc) to afford the crude title compound (7.0 g, 65%) as a colorless oil:1H NMR (300 MHz, CDCl3) δ 1.32 (12H, s) , 1.62 (9H, s) , 2.42 (3H, s), 8.26 (IH, s) . This material included some impurities and was used in next reaction without further purification
  • 5
  • [ 1009071-34-4 ]
  • [ 1072708-49-6 ]
  • [ 1072709-38-6 ]
YieldReaction ConditionsOperation in experiment
With sodium carbonate In 1-methyl-pyrrolidin-2-one; water; iso-butanol at 100℃; for 4h; 3 6-[2-chloro-4-(3-methyl-1H-pyrazol-4-yl)phenyl]-5-(4-chlorophenyl)-2-(2,2-dimethylpropanoyl)furo[2,3-b]pyridine-3-carboxamide. To the product of Reference Example 8 (4.34 g, 7.95 mmol) was added the product of Reference Example 35 (4.41 g, 14.30 mmol), tetrakis(triphenylphosphine)palladium (0) (413 mg, 0.358 mmol), NMP (40 mL), water (3.2 mL) 2-butanol (30 mL) and aq Na2CO3 (2 M, 6.75 mL). The reaction vessel was purged with N2 for 4 min at rt prior to heating to 100° C. for about 4 hours. The reaction was cooled and then concentrated. The residue was dissolved in EtOAc and washed with saturated aqueous NaHCO3. Brine has been used instead of NaHCO3. The concentrated residue was purified by flash chromatography on silica gel gradient eluted with 0-60% EtOAc in hexane. Further purification was achieved by suspension of the product in 2-propanol (heated to 80° C.), followed by filtration of the cooled mixture to afford the title compound.HPLC/MS: 547.0 (M+1), 549.0 (M+3); Rt=3.73 min. 1H NMR (500 MHz, DMSO-d6): δ 12.73 (bd, J=33.27 Hz, 1H); 8.36 (s, 1H); 8.21 (s, 1H); 8.11 (bs, 0.4H); 7.92 (s, 1H); 7.81 (bs, 0.6H); 7.50-7.42 (m, 3H); 7.36 (d, J=8.38 Hz, 2H); 7.26 (d, J=8.37 Hz, 2H); 2.38 (s, 3H); 1.38 (s, 9H).
  • 6
  • [ 1009071-34-4 ]
  • [ 1244027-58-4 ]
  • [ 1244027-03-9 ]
YieldReaction ConditionsOperation in experiment
60% Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; 6-bromo-2,2-dimethyl-2,3-dihydrothieno[3,2-d]pyrimidin-4(1H)-one With caesium carbonate In 1,2-dimethoxyethane; water for 2h; Inert atmosphere; Reflux; Stage #2: With water; sodium hydroxide In 1,2-dimethoxyethane for 3h; 108.4 A mixture of 6-bromo-2,2-dimethyl-2, 3- dihydrothieno [3, 2-d]pyrimidin-4 (IH) -one (522 mg, 2 mmol) , tert-butyl 3-methyl-4- (4, 4, 5, 5-tetramethyl-l, 3, 2- dioxaborolan-2-yl) -lH-pyrazole-1-carboxylate (1.85 g, 6.00 mmol), cesium carbonate (3.26 g, 10.0 mmol), 1,2- dimethoxyethane (20 itiL) and water (5 mL) was purged with argon. Then, 1, lf -bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (163 mg, 0.20 mmol) was added, and the mixture was purged with argon again. The mixture was refluxed for 2 h. Then, sodium carbonate (636 mg, 6.00 mmol) was added. After 30 min, 8 M NaOH (1.5 mL, 12 mmol) was added. After 3 h, the mixture was cooled to room temperature, and poured into water (100 mL) and EtOAc (200 mL) . The insoluble materials were filtered off, and the organic layer was collected from the filtrate. This organic layer was washed with brine, dried over MgSO4, filtered and concentrated under reduced pressure. The residual oil was purified by column chromatography (Purif, silica gel, 95:5 hexane/EtOAc to EtOAc) , then triturated with EtOAc, and the precipitate was collected by filtration to afford the title compound (312 mg, 60%) as a pale yellow solid: 1H NMR (300 MHz, DMSO-d6) δ 1.40 (6H, s) , 2.37 (3H, br s) , 6.53 (IH, s), 6.96 (IH, br s) , 7.34 (IH, br s) , 7.70 (0.6H, br s), 8.06 (0.4H, br s) , 12.85 (IH, m) .
  • 7
  • [ 1009071-34-4 ]
  • [ 1244027-69-7 ]
  • [ 1244026-99-0 ]
YieldReaction ConditionsOperation in experiment
50% Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; 6-bromo-1,2-dimethyl-2-(2,2,2-trifluoroethyl)-2,3-dihydrothieno[3,2-d]pyrimidin-4(1H)-one With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 2h; Inert atmosphere; Stage #2: With water; sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 1h; 104.2 A flask was charged with 6-bromo-l, 2-dimethyl-2-(2, 2, 2-trifluoroethyl) -2, 3-dihydrothieno [3, 2-d]pyrimidin- 4 (IH) -one (420 mg, 1.22 mmol) , tert-butyl 3-methyl-4- (4,4,5, 5-tetramethyl-l, 3, 2-dioxaborolan-2-yl) -lH-pyrazole-1- carboxylate (1.13 g, 3.7 mmol), sodium carbonate (366 mg, 6.1 mmol), 1, 2-dimethoxyethane (6 mL) and water (3 ml). The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (98 mg, 0.12 mmol) was added to the mixture. The flask was purged with argon again. After stirring at 1000C for 2 h, 8 M aqueous NaOH (1 mL) was added. After stirring at 1000C for 1 h, the organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 80:20 hexane/EtOAc to EtOAc) , then crystallized from MeOH/EtOAc/heptane) to give the title compound (212 mg, 50%) as a pale yellow solid:1H NMR (300 MHz, DMSO-d6) δ 1.59 (3H, s) , 2.40 (3H, br s), 2.55-2.79 (IH, m) , 2.84-3.06 (IH, m) , 2.93 (3H, s) , 6.88 (IH, s), 7.71 (IH, s), 7.79 (0.6H, br s) , 8.12 (0.4H, br s) , 12.87 (IH, br s) .
  • 8
  • [ 1009071-34-4 ]
  • [ 1244027-80-2 ]
  • [ 1244027-04-0 ]
YieldReaction ConditionsOperation in experiment
54% Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; 6'-bromo-1'-ethyl-1'H-spiro[cyclopentane-1,2'-thieno[3,2-d]pyrimidin]-4'(3'H)-one With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 1h; Inert atmosphere; Stage #2: With water; sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 1h; 109.4 A flask was charged with 6' -bromo-1' -ethyl-1'H- spiro[cyclopentane-l,2f -thieno [3, 2-d]pyrimidin] -4' (3'H) -one (158 mg, 0.50 mmol), tert-butyl 3-methyl-4- (4, 4, 5, 5- tetramethyl-1, 3, 2-dioxaborolan-2-yl) -lH-pyrazole-1- carboxylate (463 mg, 1.5 mmol), sodium carbonate (150 mg, 2.5 mmol), 1,2-dimethoxyethane (3.0 mL) and water (1.5 mL) . The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (41 mg, 0.050 mmol) was added to the mixture. The flask was purged with argon again. After stirring at 1000C for 1 h, 8 M aqueous NaOH (0.5 mL) was added. After stirring at 1000C for 1 h, organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 50:50 hexane/EtOAc to EtOAc) , then crystallized from MeOH/EtOAc/hexane to give the title compound (86 mg, 54%) as a yellow solid:1H NMR (300 MHz, DMSO-d6) δ 1.13 (3H, t, J = 7.0 Hz), 1.54- 1.79 (4H, m) , 1.79-2.03 (4H, m) , 2.40 (3H, br s) , 3.30 (2H, q, J = 7.0 Hz), 6.85 (IH, s) , 7.60 (IH, s) , 7.79 (0.6H, br s), 8.13 (0.4H, br s) , 12.85 (IH, br s) .
  • 9
  • [ 1009071-34-4 ]
  • C11H12BrF3N2OS [ No CAS ]
  • [ 1244027-05-1 ]
YieldReaction ConditionsOperation in experiment
With sodium carbonate In 1,2-dimethoxyethane; water at 110℃; for 6h; Inert atmosphere; 110 A mixture of 5-bromo-3- (ethylamino) thiophene-2- carboxamide (250 mg, 1.0 mmol) , 4, 4, 4-trifluorobutan-2-one (1.0 mL), CSA (23 mg, 0.10 mmol), MgSO4 (192 mg, 2.0 mmol) and DMA (0.5 mL) was microwave-irradiated at 1500C for 1 h. The mixture was poured into saturated aqueous NaHCO3. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 90:10 hexane/EtOAc to 50:50 hexane/EtOAc) to give a brown crystalline solid. A flask was charged with this solid, 1, 2-dimethoxyethane (3 mL) , tert- butyl 3-methyl-4- (4,4,5, 5-tetramethyl-l, 3, 2-dioxaborolan-2- yl) -lH-pyrazole-1-carboxylate (555 mg, 1.8 mmol), sodium carbonate (180 mg, 3.0 mmol) and water (1.5 mL) . The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (49 mg, 0.060 mmol) was added to the mixture. The flask was purged with argon again. After stirring at 1000C for 6 h, organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 50:50 hexane/EtOAc to EtOAc) , then crystallized from MeOH/EtOAc/heptane) to give the title compound (37 mg, 10%) as a pale brown solid:1H NMR (300 MHz, DMSO-d6) δ 1.16 (3H, t, J = 7.0 Hz), 1.69 (3H, s), 2.40 (3H, br s) , 2.53-2.71 (IH, m) , 2.74-3.00 (IH, m) , 3.32-3.50 (2H, m) , 6.83 (IH, s) , 7.66 (IH, s) , 7.80 (0.6H, br s), 8.14 (0.4H, br s) , 12.85 (IH, br s) .
  • 10
  • [ 1009071-34-4 ]
  • C10H11BrF2N2OS [ No CAS ]
  • [ 1244027-10-8 ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; C10H11BrF2N2OS With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 2h; Inert atmosphere; Stage #2: With water; sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 1h; 115.3 A mixture of 5-bromo-3- [ (2, 2- difluoroethyl) amino] thiophene-2-carboxamide (130 mg, 0.456 mmol), 2, 2-dimethoxypropane (1 mL) , CSA (11 mg, 0.046 mmol), MgSO4 (110 mg, 0.912 itimol) and DMA (1 mL) was stirred at 90°C for 2 h. Then, saturated aqueous NaHCC>;3 and EtOAc were added to quench the reaction. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, a colorless crystalline solid was obtained. A flask was charged with the solid, 1,2- dimethoxyethane (3.0 mL) , tert-butyl 3-methyl-4- (4, 4, 5, 5- tetramethyl-1, 3, 2-dioxaborolan-2-yl) -lH-pyrazole-1- carboxylate (422 mg, 1.37 mmol) , sodium carbonate (137 mg, 2.28 mmol) and water (1.5 mL) . The flask was purged with argon. Then, 1, 1' -bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (37 mg, 0.046 mmol) was added to the mixture. The flask was purged with argon. After stirring at 1000C for 2 h, 8 M aqueous NaOH (0.5 mL) was added. After stirring at 1000C for 1 h, the organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 80:20 hexane/EtOAc to EtOAc), then crystallized from EtOAc/hexane to give the title compound (78 mg, 52%) as a yellow solid: 1H NMR (300 MHz, DMSO-d6) 6 1.44 (6H, s) , 2.39 (3H, br s) , 3.78 (2H, td, J = 15.1, 3.8 Hz), 5.95-6.44 (IH, m) , 6.88 (IH, s), 7.58 (IH, s), 7.78 (0.6H, br s) , 8.11 (0.4H, br s), 12.88 (IH, br s)
  • 11
  • [ 1009071-34-4 ]
  • C15H14BrN3O3S [ No CAS ]
  • [ 1244027-14-2 ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; C15H14BrN3O3S With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 2h; Inert atmosphere; Stage #2: With sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 2h; 119.3 A mixture of 5-bromo-3- [ (3- nitrobenzyl) amino] thiophene-2-carboxamide (260 mg, 0.730 mmol), 2,2-dimethoxypropane (2.0 mL) , CSA (17 mg, 0.073 mmol), MgSO4 (200 mg) and DMA (2 mL) was microwave-irradiated at 1200C for 1 h. Then, saturated aqueous sodium hydrogen carbonate was added to quench the reaction. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, a yellow crystalline solid was obtained. A flask was charged with this solid, 1, 2-dimethoxyethane (4 mL) , tert-butyl 3- methyl-4- (4, 4, 5, 5-tetramethyl-l, 3, 2-dioxaborolan-2-yl) -IH- pyrazole-1-carboxylate (675 mg, 2.19 mmol), sodium carbonate (219 mg, 3.65 mmol) and water (2 mL) . The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (60 mg, 0.073 mmol) was added to the mixture. The flask was purged with argon again. After stirring at 1000C for 2 h, 8 M aqueous NaOH (1.0 mL) was added. After stirring at 1000C for 1 h, the organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 80:20 hexane/EtOAc to EtOAc), then crystallized from MeOH/EtOAc/hexane to give the title compound (124 mg, 43%) as a yellow solid:1H NMR (300 MHz, DMSO-d6) δ 1.45 (6H, s) , 2.30 (3H, br s) , 4.74 (2H, s), 6.70 (IH, s) , 7.54-7.77 (2.6H, m) , 7.81 (IH, d, J = 7.9 Hz), 8.01 (0.4H, br s) , 8.13 (IH, d, J = 7.9 Hz),8.20 (IH, s), 12.85 (IH, br s) .
  • 12
  • [ 1009071-34-4 ]
  • C10H13BrN2O2S [ No CAS ]
  • [ 1244027-18-6 ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; C10H13BrN2O2S With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 1h; Inert atmosphere; Stage #2: With water; sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 1.5h; 123.2 A mixture of 5-bromo-3- [ (2- hydroxyethyl) amino] thiophene-2-carboxamide (100 mg, 0.377 mmol), acetone (1.0 mL) , PTSA (6.5 mg, 0.038 mmol) and acetic acid (1.0 mL) was stirred at 700C for 1 h. The mixture was poured into saturated aqueous NaHCC>;3. The organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, a pale brown amorphous solid was obtained. A flask was charged with the amorphous, 1,2-dimethoxyethane (3.0 mL) , tert-butyl 3-methyl-4- (4, 4, 5, 5-tetramethyl-l, 3, 2- dioxaborolan-2-yl) -lH-pyrazole-1-carboxylate (349 mg, 1.13 mmol), sodium carbonate (113 mg, 1.89 mmol) and water (1.5 mL) . The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (31 mg, 0.038 mmol) was added to the mixture. The flask was purged with argon. After stirring at 1000C for 1 h, 8 M aqueous NaOH (1.0 mL) was added. After stirring at 1000C for 1.5 h, the organic materials were extracted with EtOAc/THF. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 90:10 hexane/EtOAc to EtOAc then to 90:10 EtOAc/MeOH) , then crystallized from MeOH/EtOAc/hexane) to give the title compound (40 mg, 35%) as a pale brown solid:1H NMR (300 MHz, DMSO-d6) δ 1.43 (6H, s) , 2.29-2.45 (3H, m) , 3.24-3.40 (2H, m) , 3.45-3.62 (2H, m) , 4.80 (IH, t, J = 5.6 Hz), 6.79 (IH, s), 7.40 (IH, s) , 7.75 (0.6H, br s) , 8.09 (0.4H, br s), 12.55-13.06 (IH, m) .
  • 13
  • [ 1009071-34-4 ]
  • [ 1244028-01-0 ]
  • [ 1244027-19-7 ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; C12H13BrF2N2OS With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 2h; Inert atmosphere; Stage #2: With water; sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 0.5h; 124 A mixture of 5-bromo-3- [ (2, 2- difluoroethyl) amino] thiophene-2-carboxamide (150 mg, 0.53 mmol) , cyclopentanone (2.0 mL) , CSA (12 mg, 0.053 mmol) , MgSO4 (100 mg) and DMA (1 mL) was stirred at 1100C for 20 h. The mixture was poured into saturated aqueous NaHCU3. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, hexane to 80:20 hexane/EtOAc) to give a brown crystalline solid. A flask was charged with this solid, 1,2-dimethoxyethane (4 mL) , tert-butyl 3-methyl-4- (4, 4, 5, 5- tetramethyl-1, 3, 2-dioxaborolan-2-yl) -lH-pyrazole-1- carboxylate (370 mg, 1.20 mmol), sodium carbonate (120 mg, 2.00 mmol) and water (2 mL) . The flask was purged with argon. Then, 1, 1' -bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (33 mg, 0.040 mmol) was added to the mixture. The flask was purged with argon. After stirring at 1000C for 2 h, 8 M aqueous NaOH (1.0 mL) was added. After stirring at 1000C for 30 min, organic materials were extracted with EtOAc. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 80:20 hexane/EtOAc to EtOAc), then crystallized from heptanes/EtOAc to give the title compound (29 mg, 16%) as a yellow solid: 1H NMR (300 MHz, DMSO-d6) δ 1.54-2.06 (8H, m) , 2.41 (3H, br s), 3.63-3.84 (2H, m) , 5.91-6.41 (IH, m) , 6.93 (IH, s) , 7.68-7.89 (1.6H, m) , 8.11 (0.4H, br s) , 12.88 (IH, br s) .
  • 14
  • [ 1009071-34-4 ]
  • [ 1244028-04-3 ]
  • [ 1244027-22-2 ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; C14H14BrN3OS With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 0.5h; Inert atmosphere; Stage #2: With sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 1h; 127.3 Preparation of 2 , 2 -dimethyl- 6- (5-methyl-lH-pyrazol-4-yl) -1- (pyridin-2-ylmethyl) -2 , 3-dihydrothieno [3 , 2-d] pyrimidin- 4 (IH) -one A mixture of 5-bromo-3- [ (pyridin-2- ylmethyl) amino] thiophene-2-carboxamide (160 mg, 0.51 mmol) , 2,2-dimethoxypropane (1.5 mL) , CSA (12 mg, 0.051 mmol), MgSO4 (150 mg) and DMA (1.5 mL) was microwave-irradiated at 1200C for 1 h. The mixture was poured into saturated aqueous NaHCC>;3. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, a brown solid was obtained. A flask was charged with this solid, 1,2-dimethoxyethane (5 mL) , tert- butyl 3-methyl-4- (4,4,5, 5-tetramethyl-l, 3, 2-dioxaborolan-2- yl) -lH-pyrazole-1-carboxylate (472 mg, 1.53 mmol), sodium carbonate (153 mg, 2.55 mmol) and water (2.5 mL) . The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (42 mg, 0.051 mmol) was added to the mixture. The flask was purged with argon. After stirring at 1000C for 0.5 h, 8 M aqueous NaOH (1.0 mL) was added. After stirring at 1000C for 1 h, the organic materials were extracted with EtOAc/THF. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 80:20 hexane/EtOAc to EtOAc then to 90:10 EtOAc/MeOH), then crystallized from MeOH/EtOAc) to give the title compound (59 mg, 33%) as a pale yellow solid: 1H NMR (300 MHz, DMSO-d6) δ 1.44 (6H, s) , 2.31 (3H, br s) , 4.64 (2H, s), 6.72 (IH, br s) , 7.23-7.33 (IH, m) , 7.39 (IH, d, J = 7.7 Hz), 7.56 (IH, s) , 7.67 (0.6H, br s) , 7.73-7.83 (IH, m), 8.03 (0.4H, br s) , 8.50-8.61 (IH, in), 12.59-13.16 (IH, m) .
  • 15
  • [ 1009071-34-4 ]
  • [ 1244028-07-6 ]
  • [ 1244027-23-3 ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; C14H14BrN3OS With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 1h; Inert atmosphere; Stage #2: With sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 1h; 128.3 A mixture of 5-bromo-3- [ (pyridin-3- ylmethyl) amino] thiophene-2-carboxamide (175 mg, 0.56 mmol) , 2,2-dimethoxypropane (1.5 mL) , CSA (13 mg, 0.056 mmol), MgSO4 (150 mg) and DMA (1.5 mL) was microwave-irradiated at 1200C for 1 h. The mixture was poured into saturated aqueous NaHCO3. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, a brown solid was obtained. A flask was charged with this solid, 1, 2-dimethoxyethane (5.0 mL) , tert- butyl 3-methyl-4- (4,4,5, 5-tetramethyl-l, 3, 2-dioxaborolan-2- yl) -lH-pyrazole-1-carboxylate (518 mg, 1.68 mmol), sodium carbonate (168 mg, 2.80 mmol) and water (2.5 mL) . The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (41 mg, 0.056 mmol) was added to the mixture. The flask was purged with argon. After stirring at 1000C for 1 h, 8 M aqueous NaOH (1.0 mL) was added. After stirring at 1000C for 1 h, the organic materials were extracted with EtOAc/THF. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 80:20 hexane/EtOAc to EtOAc then to 90:10 EtOAc/MeOH), then crystallized from MeOH/EtOAc) to give the title compound (64 mg, 32%, 3 steps) as a pale yellow solid:1H NMR (300 MHz, DMSO-d6) δ 1.44 (6H, s) , 2.31 (3H, br s), 4.63 (2H, s), 6.72 (IH, br s) , 7.33-7.43 (IH, m) , 7.58 (IH, s), 7.63-7.78 (1.6H, m) , 8.04 (0.4H, br s) , 8.41-8.51 (IH, m) , 8.58 (IH, d, J = 2.1 Hz), 12.85 (IH, br s) .
  • 16
  • [ 1009071-34-4 ]
  • [ 1244028-10-1 ]
  • [ 1244027-24-4 ]
YieldReaction ConditionsOperation in experiment
Stage #1: tert-butyl 3-methyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-pyrazole-1-carboxylate; C14H14BrN3OS With sodium carbonate In 1,2-dimethoxyethane; water at 100℃; for 0.5h; Inert atmosphere; Stage #2: With sodium hydroxide In 1,2-dimethoxyethane at 100℃; for 1h; 129.3 A mixture of 5-bromo-3- [ (pyridin-4- ylmethyl) amino] thiophene-2-carboxamide (167 mg, 0.53 mmol), 2,2-dimethoxypropane (1.5 mL) , CSA (12 mg, 0.053 mmol), MgSO4 (150 mg) and DMA (1.5 mL) was microwave-irradiated at 1200C for 1 h. The mixture was poured into saturated aqueous NaHCθ3. The organic materials were extracted with EtOAc. The combined extracts were washed with water and brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, a brown solid was obtained. A flask was charged with the solid, 1,2-dimethoxyethane (5 mL) , tert- butyl 3-methyl-4- (4,4,5, 5-tetramethyl-l, 3, 2-dioxaborolan-2- yl) -lH-pyrazole-1-carboxylate (490 mg, 1.59 iranol) , sodium carbonate (159 mg, 2.65 iranol) and water (2.5 mL) . The flask was purged with argon. Then, 1,1'- bis (diphenylphosphino) ferrocenepalladium (II) dichloride dichloromethane adduct (43 mg, 0.053 mmol) was added to the mixture. The flask was purged with argon again. After stirring at 1000C for 0.5 h, 8 M aqueous NaOH (1.0 mL) was added. After stirring at 1000C for 1 h, the organic materials were extracted with EtOAc/THF. The combined extracts were washed with brine, dried over Na2SO4 and filtered. After removal of the solvent at reduced pressure, the residue was purified by column chromatography (Purif, silica gel, 80:20 hexane/EtOAc to EtOAc then to 90:10 EtOAc/MeOH) , then crystallized from MeOH/EtOAc) to give the title compound (38 mg, 20%) as a pale yellow solid: 1H NMR (300 MHz, DMSO-d6) δ 1.43 (6H, s) , 2.16-2.38 (3H, m) , 4.62 (2H, br s) , 6.56-6.71 (IH, m) , 7.34 (2H, d, J = 5.9 Hz), 7.60 (IH, s), 7.66 (0.6H, br s) , 8.02 (0.4H, br s) , 8.52 (2H, d, J = 5.9 Hz), 12.71-12.93 (IH, m) .
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