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[ CAS No. 288-13-1 ]

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Chemical Structure| 288-13-1
Chemical Structure| 288-13-1
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Product Details of [ 288-13-1 ]

CAS No. :288-13-1MDL No. :MFCD00005234
Formula : C3H4N2 Boiling Point : 187°C at 760 mmHg
Linear Structure Formula :-InChI Key :-
M.W :68.08Pubchem ID :1048
Synonyms :

Computed Properties of [ 288-13-1 ]

TPSA : 28.7 H-Bond Acceptor Count : 1
XLogP3 : - H-Bond Donor Count : 1
SP3 : 0.00 Rotatable Bond Count : 0

Safety of [ 288-13-1 ]

Signal Word:WarningClass:N/A
Precautionary Statements:P261-P273-P305+P351+P338UN#:N/A
Hazard Statements:H302-H315-H319-H335-H412Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 288-13-1 ]

  • Upstream synthesis route of [ 288-13-1 ]
  • Downstream synthetic route of [ 288-13-1 ]

[ 288-13-1 ] Synthesis Path-Upstream   1~13

  • 1
  • [ 1134-81-2 ]
  • [ 288-13-1 ]
  • [ 13036-57-2 ]
  • [ 4472-44-0 ]
  • [ 14164-34-2 ]
Reference: [1] Journal of the Chemical Society - Perkin Transactions 1, 1997, # 24, p. 3581 - 3585
  • 2
  • [ 288-13-1 ]
  • [ 67-56-1 ]
  • [ 1120-82-7 ]
YieldReaction ConditionsOperation in experiment
90% With formaldehyd In water at 25℃; for 4 h; A roundbottom flask comprising pyrazole (144 mmol, 100 g) and methanol (about 200 mL) was charged with formaldehyde (131 g, 37percent aq. solution). The reaction mixture was stirred at 25 °C for 4 hours to give a (0193) homogenous solution. The solvent was removed under reduced pressure and dried in vacuo hours, yielding the title compound (127 g, 90percent).
Reference: [1] Patent: WO2016/191677, 2016, A1, . Location in patent: Paragraph 0110
  • 3
  • [ 288-13-1 ]
  • [ 50-00-0 ]
  • [ 1120-82-7 ]
YieldReaction ConditionsOperation in experiment
98% for 120 h; Reflux The 1H-pyrazolyl-1-methanol as starting material were preparedin processes described in literature [1]. The CH2Cl2 solution(100 mL) of pyrazole (20.4 g, 0.30 mol) was added a CH2Cl2 solution(100 mL) of para-formaldehyde (9.00 g, 0.30 mol). The solutionwas reflux for 5 days and the filtrate solvent was removedunder reduced pressure to give white powder (28.5 g, 98.0percent). 1HNMR (CDCl3, 400 MHz) for 1H-pyrazolyl-1-methanol: d 7.71 (s,1H), 7.59 (d, 1H, J = 2.24 Hz), 7.56 (d, 1H, J = 1.48 Hz), 6.29 (t, 1H,J = 1.8 Hz), 5.51 (s, 2H).
96.6% at 60℃; for 4 h; After dissolving 20.4 g (0.300 mol) of pyrazole and 9.0 g (0.300 mol) of para-formaldehyde in 400 mL of methylene chloride, the reaction was carried out at 60 ° C. for 4 days using a reflux condenser . The reaction mixture was dried under reduced pressure, and the reaction mixture obtained after the removal was washed with 100 ml of hexane three times, followed by vacuum drying under reduced pressure.The yield of (1H-1-pyrazolyl-1-methanol) obtained was 34.8 g (96.6percent).
Reference: [1] Polyhedron, 2012, vol. 42, # 1, p. 135 - 141
[2] Journal of Molecular Structure, 2014, vol. 1063, # 1, p. 70 - 76
[3] Inorganica Chimica Acta, 2015, vol. 428, p. 193 - 202
[4] Recueil: Journal of the Royal Netherlands Chemical Society, 1982, vol. 101, # 12, p. 441 - 443
[5] Applied Organometallic Chemistry, 2014, vol. 28, # 6, p. 445 - 453
[6] Patent: KR2017/51867, 2017, A, . Location in patent: Paragraph 0078; 0079
[7] Medicinal Chemistry Research, 2012, vol. 21, # 10, p. 3035 - 3042,8
[8] Heterocycles, 1986, vol. 24, # 8, p. 2233 - 2237
[9] Chemische Berichte, 1952, vol. 85, p. 820,823
[10] Chemische Berichte, 1952, vol. 85, p. 820,823
[11] Patent: EP1710234, 2006, A1, . Location in patent: Page/Page column 40-41
[12] Patent: EP1422228, 2004, A1, . Location in patent: Page 223
[13] Dalton Transactions, 2009, # 35, p. 7029 - 7038
[14] Patent: WO2010/132999, 2010, A1, . Location in patent: Page/Page column 138
[15] European Journal of Medicinal Chemistry, 2014, vol. 73, p. 83 - 96
[16] Inorganic Chemistry, 2014, vol. 53, # 8, p. 4192 - 4201
[17] RSC Advances, 2015, vol. 5, # 41, p. 32369 - 32375
[18] Medicinal Chemistry, 2016, vol. 12, # 1, p. 83 - 89
  • 4
  • [ 288-13-1 ]
  • [ 529-28-2 ]
  • [ 102908-37-2 ]
YieldReaction ConditionsOperation in experiment
82% With (N,N'-bis(salicylidenate)cyclohexane-1,2-diamine)copper(II); sodium hydroxide In dimethyl sulfoxide at 100℃; for 12 h; Sealed tube General procedure: Complex 2 (0.05 mmol) was added to a 5 mL of a sealed tube containing the aryl iodide or bromide (0.5 mmol), 1H-pyrazole (0.75 mmol), NaOH (1 mmol), and DMSO (1 mL). The mixture was stirred at 100 °C for 12 h. After being cooled to room temperature, the mixture was quenched with 10 mL H2O and extracted with EtOAc(3 × 20 mL). The combined EtOAc extracts were dried with anhydrous Na2SO4, filtered and the solvent was removed under reduced pressure.The residue was purified by flash column chromatography on silicagel with PE/EtOAc (from 10:1 to 5:1) as the eluent to afford the pure products. All N-aryl pyrazoles reported here are known products and were characterised by 1H NMR, and GC-MS.
68% With bis(1-dodecylimidazole)cupronium dichlorocuprate; tetrabutylammomium bromide; potassium carbonate In water at 80℃; for 15 h; Green chemistry General procedure: At first [Cu(Im12)2]CuCl2 (0.5 mmol, 0.305 g) was added to a 25 mL round bottom flask containing water (4 mL), indole (0.117 g, 1 mmol) and iodobenzene (0.203 g, 1 mmol).K2CO3 (0.276 g, 2 mmol) and TBAB (0.322 g, 1 mmol) was added and the reaction stirred at 80 °C for 12 h. The reaction progress was monitored by TLC(EtOAc/n-hexane; 1:3 v/v) and after completion, the organic phase was extracted from the ionic liquid with EtOAc (2 8 mL) and concentrated in vacuo. The promoter was used directly for the next run. The product was purified by silica gel column chromatography (EtOAc/n-hexane; 1:3 v/v). The isolated product was dried under vacuum overnight to give a yield of 92percent. All products are known in the literature and were identified by comparison of their FT-IR, 1H, and 13C NMR spectra with the literature data.
54% With copper diacetate; sodium hydroxide; 3-(diphenylphosphino)propionic acid In 1,4-dioxane at 100℃; for 24 h; Sealed tube General procedure: Cu(OAc)2 (0.03mmol), L2 (0.06mmol), aryl idione or bromide (0.5mmol), 1H-pyrazole (0.75mmol), NaOH (1mmol), and 1,4-dioxane (1mL) was added into a 5mL tube, then sealed. The mixture was stirred at 100°C for certain time. After cooling to room temperature, the mixture was quenched with 10mL H2O and extracted with EtOAc (3×20mL). The combined EtOAc extracts were dried with anhydrous Na2SO4 and filtrated and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel with PE/EtOAc, as the eluent, to afford the desired products.
30% With copper(l) iodide; manganese(II) fluoride; (1R,2R)-1,2-diaminocyclohexane; potassium hydroxide In water at 60℃; for 24 h; General procedure: The N-nucleophile (1.47 mmol), CuI (Sigma-Aldrich, 99.999percent purity, 0.147 mmol), MnF2 (Sigma-Aldrich, 98percent purity, 0.441 mmol), KOH (2.94 mmol), the aryl halide (2.21 mmol), trans-1,2-diaminocyclohexane (0.294 mmol) and water (0.75 mL) were added to a reaction vial and a screw cap was fitted to it. The reaction mixture was stirred under air in a closed system at 60C for 24 h. After cooling to room temperature, the mixture was diluted with dichloromethane and filtered through a pad of Celite. The combined organic extracts were dried with anhydrous Na2SO4 and the solvent was removed under reduced pressure. The crude product was purified by silica-gel column chromatography to afford the N-arylated product. The identity and purity of known products was confirmed by 1H and 13C NMR spectroscopic analysis.

Reference: [1] Advanced Synthesis and Catalysis, 2007, vol. 349, # 17-18, p. 2673 - 2676
[2] Journal of Chemical Research, 2013, vol. 37, # 10, p. 636 - 637
[3] Tetrahedron Letters, 2015, vol. 56, # 46, p. 6360 - 6363
[4] Chinese Chemical Letters, 2014, vol. 25, # 5, p. 775 - 778
[5] Advanced Synthesis and Catalysis, 2009, vol. 351, # 5, p. 720 - 724
[6] Advanced Synthesis and Catalysis, 2010, vol. 352, # 18, p. 3241 - 3245
[7] Angewandte Chemie - International Edition, 2007, vol. 46, # 46, p. 8862 - 8865
[8] Journal of Organic Chemistry, 2009, vol. 74, # 19, p. 7514 - 7517
[9] Chemistry - A European Journal, 2009, vol. 15, # 13, p. 3072 - 3075
[10] Tetrahedron Letters, 2011, vol. 52, # 52, p. 7171 - 7174
[11] Chemical Communications, 2009, # 41, p. 6258 - 6260
  • 5
  • [ 288-13-1 ]
  • [ 578-57-4 ]
  • [ 102908-37-2 ]
YieldReaction ConditionsOperation in experiment
51% With copper diacetate; sodium hydroxide; 3-(diphenylphosphino)propionic acid In 1,4-dioxane at 120℃; for 36 h; Sealed tube General procedure: Cu(OAc)2 (0.03mmol), L2 (0.06mmol), aryl idione or bromide (0.5mmol), 1H-pyrazole (0.75mmol), NaOH (1mmol), and 1,4-dioxane (1mL) was added into a 5mL tube, then sealed. The mixture was stirred at 100°C for certain time. After cooling to room temperature, the mixture was quenched with 10mL H2O and extracted with EtOAc (3×20mL). The combined EtOAc extracts were dried with anhydrous Na2SO4 and filtrated and the solvent was removed under reduced pressure. The residue was purified by flash column chromatography on silica gel with PE/EtOAc, as the eluent, to afford the desired products.
Reference: [1] Advanced Synthesis and Catalysis, 2007, vol. 349, # 17-18, p. 2673 - 2676
[2] Chinese Chemical Letters, 2014, vol. 25, # 5, p. 775 - 778
  • 6
  • [ 288-13-1 ]
  • [ 100-66-3 ]
  • [ 102908-37-2 ]
  • [ 35715-67-4 ]
Reference: [1] Science, 2015, vol. 349, # 6254, p. 1326 - 1330
[2] Patent: WO2016/196816, 2016, A1, . Location in patent: Paragraph 00324; 00370
[3] Chemistry - A European Journal, 2017, vol. 23, # 72, p. 18161 - 18165
  • 7
  • [ 288-13-1 ]
  • [ 5720-06-9 ]
  • [ 102908-37-2 ]
Reference: [1] Helvetica Chimica Acta, 2010, vol. 93, # 5, p. 974 - 979
  • 8
  • [ 67129-08-2 ]
  • [ 288-13-1 ]
  • [ 1131-01-7 ]
Reference: [1] Bulletin des Societes Chimiques Belges, 1989, vol. 98, # 5, p. 319 - 326
  • 9
  • [ 67129-08-2 ]
  • [ 288-13-1 ]
  • [ 4073-98-7 ]
  • [ 1131-01-7 ]
Reference: [1] Bulletin des Societes Chimiques Belges, 1989, vol. 98, # 5, p. 319 - 326
  • 10
  • [ 288-13-1 ]
  • [ 100-11-8 ]
  • [ 110525-57-0 ]
YieldReaction ConditionsOperation in experiment
76% With potassium carbonate In acetonitrile at 20℃; A mixture of 4-nitrobenzyl bromide (0.500 g, 2.31 mmol), lH-pyrazole (0.362 g, 5.23 mmol), and potassium carbonate (0.704 g, 5.09 mmol) in acetonitrile (30 mL) was stirred at rt overnight. After this time, the mixture was diluted with water and extracted with ethyl acetate. The combined organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated. The residue was purified by column chromatography (silica, hexanes/ethyl acetate) to afford the title compound (0.380 g, 76percent) as a white solid. MW = 203.20. ]H NMR (CDC13, 500 MHz) δ 8.21-8.19 (m, 1H), 8.19-8.16 (m, 1H),7.61- 7.57 (m, 1H), 7.48-7.44 (m, 1H), 7.32-7.28 (m, 2H), 6.35 (t, / = 2.1 Hz, 1H), 5.44 (s, 2H); APCI MS m/z 204 [M + H]+.
Reference: [1] Organic Preparations and Procedures International, 2000, vol. 32, # 4, p. 385 - 390
[2] Patent: WO2014/66659, 2014, A1, . Location in patent: Paragraph 0824
  • 11
  • [ 288-13-1 ]
  • [ 100-14-1 ]
  • [ 110525-57-0 ]
Reference: [1] Tetrahedron Letters, 1986, vol. 27, # 51, p. 6209 - 6212
[2] Farmaco, 1992, vol. 47, # 3, p. 335 - 344
  • 12
  • [ 288-13-1 ]
  • [ 13360-57-1 ]
  • [ 133228-21-4 ]
YieldReaction ConditionsOperation in experiment
91% With 1,4-diaza-bicyclo[2.2.2]octane In acetonitrile at 20℃; for 18 h; EXAMPLE 802- Amino- 1 -(4-chloro-phenyD- 1 - [4-(3 -ethyl- 1 H-pyrazol-4-y D-phenyl] -ethanol8OA. Pyrazole-1-sulphonic acid dimethylamide; 1,4-Diazabicyclo[2.2.2]octane (DABCO, 10. Ig, 90.3mmol) and dimethylsulphamoylchloride (8.8ml, 82.9mmol) were added sequentially to a solution of pyrazole (4.8g, 81.9mmol) in EPO <DP n="192"/>acetonitrile (125ml) whilst stirring at room temperature. After 18 hours, the reaction was concentrated in vacuo and wet with water and ethyl acetate. The organic layer was removed and washed with hydrochloric acid (2N) and then brine before drying (MgSO^ and concentrating in vacuo to furnish the title compound as a colourless oil (13. Ig, 91percent). LC/MS (PS-A2) Rt 2.16 [M+H]+176
91% With 1,4-diaza-bicyclo[2.2.2]octane In acetonitrile at 20℃; for 18 h; Jl. Pyrazole-1-sulphonic acid dimethylamide1,4-Diazabicyclo[2.2.2]octane (DABCO, lO.lg, 90.3 mmol) and dimethylsulphamoylchloride (8.8 ml, 82.9 mmol) were added sequentially to a solution of pyrazole (4.8g, 81.9 mmol) in acetonitrile (125 ml) whilst stirring at room temperature. After 18 hours, the reaction mixture was concentrated in vacuo and partitioned between water and ethyl acetate. The organic layer was removed and washed with hydrochloric acid (2N) and then brine before drying (MgSO^ and concentrating in vacuo to furnish the title compound as a colourless oil (13. Ig, 91percent).
82%
Stage #1: With sodium hydride In tetrahydrofuran at 0℃; for 0.333333 h;
Stage #2: at 0 - 20℃; for 2 h;
To a stirred solution of pyrazole (12 g, 176 mmol) in THF (200 mL) was added portionwise sodium hydride (50percent, 8.46 g, 212 mmol) at 00C. After 20 min, dimethylsulfamoyl chloride (17 mL, 157 mmol) was added dropwise, and the stirring was continued for 1 h at the same temperature. Then, the mixture was allowed to room temperature for 1 h. The mixture was poured into saturated aqueous NaHCO3 (400 mL) and extracted with EtOAc (400 mL) , and the extract was dried over MgSO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (Purif, silica gel, hexane to 50:50 hexane/EtOAc) to afford the title compound (25.3 g, 82percent) as a colorless oil: 1H NMR (300 MHz, CDCl3) δ 2.95 (6H, s) , 6.40 (IH, m) , 7.75 (IH, m) , 7.99 (IH, d, J = 2.7 Hz).
75%
Stage #1: With sodium hydride In tetrahydrofuran; mineral oil at 0℃; for 1 h;
Stage #2: at 0 - 20℃; for 2 h;
A solution of lH-pyrazole (30 g, 440 mmol) in tetrahydrofuran (500 mL) was treated with sodium hydride (26 g, 648 mmol, 60percent) at 0 °C, and then stirred for 1 h at 0 °C. N,N-Dimethylsulfamoyl chloride (95 g, 661 mmol) was added dropwise at 0 °C. The resulting solution was stirred for additional 2 h at room temperature and then quenched by water. The resulting solution was extracted with dichloromethane and concentrated in vacuo. The residue was purified by flash chromatography on silica gel eluting with ethyl acetate/petroleum ether (1/6) to afford to N,N-dimethyl-lH-pyrazole-l -sulfonamide ( 58 g, 75percent) as colorless oil. LCMS (ESI): M+H+ = 175.0.
6.24 g With triethylamine In toluene at 10 - 35℃; for 18 h; To a solution of 1H-pyrazole (5.00 g) in toluene (67.0 mL) were added dimethylsulfamoyl chloride (7.89 mL) and triethylamine (13.3 mL) at room temperature, and the reaction mixture was stirred at room temperature for 18 hr. The resulting solid was removed by filtration, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/hexane) to give the title compound (6.24 g). 1H NMR (400 MHz, CDCl3) δ 2.91 (6H, s), 6.38 (1H, dd, J = 2.6, 1.8 Hz), 7.72 (1H, d, J = 1.2 Hz), 7.96 (1H, d, J = 2.4 Hz)

Reference: [1] Synthesis, 2006, # 5, p. 793 - 798
[2] Chemistry - An Asian Journal, 2015, vol. 10, # 8, p. 1626 - 1630
[3] Advanced Synthesis and Catalysis, 2014, vol. 356, # 7, p. 1555 - 1561
[4] Patent: WO2006/136830, 2006, A1, . Location in patent: Page/Page column 190-191
[5] Patent: WO2006/136829, 2006, A2, . Location in patent: Page/Page column 129
[6] Patent: WO2010/101302, 2010, A1, . Location in patent: Page/Page column 209-210
[7] Patent: WO2015/52226, 2015, A1, . Location in patent: Paragraph 0498
[8] Chemische Berichte, 1991, vol. 124, p. 1639 - 1650
[9] Patent: WO2007/43677, 2007, A1, . Location in patent: Page/Page column 487
[10] Patent: WO2008/91594, 2008, A2, . Location in patent: Page/Page column 87
[11] Patent: WO2010/132999, 2010, A1, . Location in patent: Page/Page column 183-184
[12] Patent: EP2540728, 2013, A1, . Location in patent: Page/Page column 53
[13] Patent: EP2818473, 2014, A1, . Location in patent: Paragraph 0581
[14] Patent: WO2008/130021, 2008, A2, . Location in patent: Page/Page column 389-390
[15] Patent: WO2007/14290, 2007, A2, . Location in patent: Page/Page column 70
  • 13
  • [ 288-13-1 ]
  • [ 411235-57-9 ]
  • [ 1151814-36-6 ]
Reference: [1] Patent: JP5668756, 2015, B2, . Location in patent: Paragraph 0147
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