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Structure of 141459-53-2

Chemical Structure| 141459-53-2

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Product Details of [ 141459-53-2 ]

CAS No. :141459-53-2
Formula : C8H15N3
M.W : 153.22
SMILES Code : NC1=CC(C)=NN1C(C)(C)C
MDL No. :MFCD00122731
InChI Key :CMPRMWFPGYBHTQ-UHFFFAOYSA-N
Pubchem ID :737200

Safety of [ 141459-53-2 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H317-H319
Precautionary Statements:P280-P305+P351+P338

Application In Synthesis of [ 141459-53-2 ]

* 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 [ 141459-53-2 ]

[ 141459-53-2 ] Synthesis Path-Downstream   1~35

  • 1
  • [ 108-24-7 ]
  • [ 141459-53-2 ]
  • [ 154910-87-9 ]
YieldReaction ConditionsOperation in experiment
at 20 - 35℃; Step (ii): Preparation of N-(l-(tert-Butyl)-3-methyl-lH-pyrazol-5-yl)acetamideTo l-(tert-butyl)-3-methyl-lH-pyrazol-5-amine (110 g, 0.71 mol), acetic anhydride (73 ml, 0.71 mol) was added dropwise with stirring. The reaction mixture was stirred for 1-2 h at 20-35 C. Thereafter the reaction mixture was washed with excess of hexane and filtered to obtain the title compound as a yellow solid. MP: 118-120C.1H NMR (400 MHz, CDC13) δ 7.27,(bs, 1H), 6.003 (s, 1H), 2.17 (s, 3H), 1.62 (s, 9H). MS (m/z): 196 (M++l , 70%).
  • 2
  • [ 98-88-4 ]
  • [ 141459-53-2 ]
  • [ 154910-89-1 ]
  • 3
  • [ 141459-53-2 ]
  • [ 103-80-0 ]
  • [ 154910-88-0 ]
  • 4
  • [ 106-31-0 ]
  • [ 141459-53-2 ]
  • [ 161153-61-3 ]
  • 5
  • [ 1118-61-2 ]
  • [ 32064-67-8 ]
  • [ 141459-53-2 ]
YieldReaction ConditionsOperation in experiment
In pentan-1-ol; for 20h;Heating / reflux; To a solution of 16.4 g (0.2 mol) of 3-aminocrotononitrile in 100 cm3 of n-pentanol were added 19.4 g (0.22 mol) of tert-butylhydrazine. This solution was heated at reflux for 20 hours. The n-pentanol was subsequently distilled off under reduced pressure. A pale yellow solid was obtained, which was taken up in 100 cm3 of isopropyl ether at room temperature and filtered on a sinter funnel. After drying under vacuum at 40 C., 18 g of the expected product were obtained in the form of a pale yellow solid, the melting point of which was from 172 to 175 C.
With triethylamine; In ethanol;Reflux; Step (i): Preparation of l-(tert-Butyl)-3-methyl-lH-pyrazol-5-amineTo a mixture of 3-aminobut-2-enenitrile (60 g, 731 mmol) and tert-butylhydrazine (96 g, 731.1 mmol) in ethanol (35 ml), triethylamine (220 ml, 2195 mmol) was added. The mixture was refluxed for 12-16 h. The reaction mixture was then concentrated under reduced pressure. The concentrate was extracted with water (100 ml) and ethylacetate (700 ml). The organic layer was washed with brine and dried over Na2SC>4 and concentrated under reduced pressure to obtain the title product..Η ΝΜΡν (400 MHz, CDC13) δ 5.37 (s, 1H), 3.51 (bs, 2H), 2.14 (s, 3H), 1.61 (s, 9H). MS (m/z): 154 (M++l, 100%).
  • 6
  • [ 122-01-0 ]
  • [ 141459-53-2 ]
  • [ 161153-63-5 ]
  • 7
  • [ 123-62-6 ]
  • [ 141459-53-2 ]
  • [ 161153-60-2 ]
  • 8
  • [ 586-75-4 ]
  • [ 141459-53-2 ]
  • [ 161153-62-4 ]
  • 9
  • [ 141459-53-2 ]
  • [ 407-25-0 ]
  • [ 442850-65-9 ]
  • 10
  • [ 141459-53-2 ]
  • [ 442850-75-1 ]
  • 11
  • [ 141459-53-2 ]
  • 1-<i>tert</i>-butyl-3-methyl-6-trifluoromethyl-1<i>H</i>-pyrazolo[3,4-<i>d</i>][1,3]thiazine-4-thione [ No CAS ]
  • 12
  • [ 141459-53-2 ]
  • [ 161153-64-6 ]
  • 13
  • [ 141459-53-2 ]
  • [ 161153-65-7 ]
  • 14
  • [ 141459-53-2 ]
  • [ 161153-67-9 ]
  • 15
  • [ 141459-53-2 ]
  • [ 161153-66-8 ]
  • 16
  • [ 141459-53-2 ]
  • [ 154910-96-0 ]
  • 17
  • [ 141459-53-2 ]
  • [ 154911-06-5 ]
  • 18
  • [ 141459-53-2 ]
  • [ 154910-98-2 ]
  • 19
  • [ 141459-53-2 ]
  • [ 154910-97-1 ]
  • 20
  • [ 141459-53-2 ]
  • [ 154911-08-7 ]
  • 21
  • [ 141459-53-2 ]
  • [ 154911-07-6 ]
  • 22
  • [ 141459-53-2 ]
  • [ 184172-90-5 ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride; isopentyl nitrite; In ethanol; water; at 0 - 20℃; for 4h; To a solution of 15.3 g (0.1 mol) of 5-amino-3-methyl-1-tert-butylpyrazole, obtained in the above step, in 200 cm3 of absolute ethanol were added dropwise 0.5 cm3 of 12 N hydrochloric acid and then 13.5 cm3 (0.1 mol) of isoamyl nitrite, at 0 C. The solution was subsequently warmed to and left at room temperature for 4 hours. The ethanol was evaporated off under a pressure of 175 mbar, at 40 C. An orange-coloured solid was crystallized from heptane at 0 C. and then filtered off on a sinter funnel. After drying under vacuum at room temperature, 11 g of the expected product were obtained in the form of an orange-coloured solid, the melting point of which was 120 C.
  • 23
  • 4-bromo-2-(2-methoxyethyl)-2H-phthalazin-1-one [ No CAS ]
  • [ 141459-53-2 ]
  • 4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(2-methoxy-ethyl)-2H-phthalazin-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 130℃; for 8h; Typical procedure for the Buchwald reaction with l-(terf-butyl)-3-methyl-lff- pyrazol- 5 -ylamine:4-(2-teft-Butyl-5-methyl-2JJ-pyrazol-3-ylamino)-2-(2-methoxy-ethyl)-2J- phthalazin-1-one4-Bromo-2-(2-methoxyethyl)-4-bromo-2H-phthalazin-l-one (0.57g, 2.0mmol), 1- (tert-butyl)-3-methyl-lH-pyrazol-5-ylamine (0.46g, 3.0mmol), Cs2CO3 (0.98mg, 3.0mmol), tris(dibenzylideneacetone)-dipalladium (0) (0.092g, O.lmmol) and 4,5- bis(diphenylphosphino)-9,9-dimethylxanthene (0.17mg, 0.3mmol) were dissolved in degassed dioxane (10ml). The reaction mixture was heated with stirring to 13O0C for 8 hours and then cooled to room temperature. H2O (100ml) was added and the precipitated solid was filtered and washed with ethyl acetate and H2O. The raw product was purified over silica gel (ethyl acetate:heptane 0%-60% ethyl acetate) to give the title compound (0.46g, 65% yield). EPO <DP n="189"/>1H-NMR: (400 MHz, D6-DMSO) 8.22-8.31 (3H, m), 7.95 (IH, t), 7.86 (IH, t), 5.91 (IH, s), 4.05 (IH, t),3.55 (IH, t), 3.17 (3H, s), 2.14 (3H, s), 1.54 (9H, s); MS (ESI+) = 356.3 (M+H)+.
  • 24
  • 4-Bromo-2-(4-chloro-phenyl)-2H-phthalazin-1-one [ No CAS ]
  • [ 141459-53-2 ]
  • 4-(2-tert-Butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-chloro-phenyl)-2H-phthalazin-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
74% With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 18h; Example V-I: 4-f5-Methyl-2H-pyrazol-3-ylaminoV2-f4-piperidin-l-yl-phenylV2H-phthalazin- 1-one4-(2-tert-Butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-chloro-phenyl)-2H- phthalazin- 1-one200 mg 4-Bromo-2-(4-chloro-phenyl)-2H-phthalazin-l-one (prepared as described in Method R), 91 mg l-tert.-butyl-3-methyl-lH-pyrazol-5-ylamine, 310 mg cesium carbonate, 21 mg 4,5-bis(diphenylphosphmo)-9,9-dimethylxanthene and 16.4 mg tris-(dibenzylideneacetone)-dipalladium in 2 ml dry dioxane were stirred under nitrogen at 100 C for 18 hrs. The solvent was removed under vacuum and the residue stirred with 50 ml water. The crude product was isolated by filtration, washed with water and purified by chromatography on silica, eluting sequentially with heptane, dichloromethane and finally dichloromethane / methanol 60:1.Yield 180 mg (74%) of the title product.
74% With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃; for 18h; 4-(2-tert-Butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-chloro-phenyl)-2H-phthalazin-1-one: 200 mg 4-Bromo-2-(4-chloro-phenyl)-2H-phthalazin-1-one (prepared as described in Method R), 91 mg 1-tert.-butyl-3-methyl-1H-pyrazol-5-ylamine, 310 mg cesium carbonate, 21 mg 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene and 16.4 mg tris-(di-benzylideneacetone)-dipalladium in 2 ml dry dioxane were stirred under nitrogen at 100 C. for 18 hrs. The solvent was removed under vacuum and the residue stirred with 50 ml water. The crude product was isolated by filtration, washed with water and purified by chromatography on silica, eluting sequentially with heptane, DCM and finally DCM/MeOH 60:1. Yield 180 mg (74%) of the title product.
  • 25
  • 4,6-dibromo-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one [ No CAS ]
  • [ 141459-53-2 ]
  • [ 880488-73-3 ]
YieldReaction ConditionsOperation in experiment
With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); at 100℃; for 20h; Example ZB-6: 6-Bromo-2-(4-tert-butyl-phenyl)-4-(5-methyl-2H-pyrazol-3- ylamino)-2H-phthalazin- 1 -one6-Bromo-4-(2-tert-butyl-5-methyl-2H-pyrazol~3-ylamino)-2~(4-tert-butyl- phenyl) -2H-phthalazin-l -one11 mg 4,6-Dibromo-2-(4-tert-butyl-phenyl)-2H-phthalazin-l-one (preparation see ZA-I) were reacted with 39.0 mg l-tert.-butyl-3-methyl-lH-pyrazol-5-ylamine, 132 mg cesium carbonate, 7.0 mg tris-(dibenzylideneacetone)-dipalladium and 8.8 mg 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene were stirred under argon at 100 0C. for 20 hrs until HPLC indicated complete conversion. The solvent was removed under vacuum, the residue was taken up in dichloromethane and washed dilute HCl. Removal of the dichloromethane and chromatography on silica in first heptane and then heptan / ethyl acetate 8:2 yielded 25 mg of the title product.
With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); at 100℃; for 20h; 6-Bromo-4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one: 11 mg 4,6-Dibromo-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one (preparation see ZA-1) were reacted with 39.0 mg 1-tert.-butyl-3-methyl-1H-pyrazol-5-ylamine, 132 mg cesium carbonate, 7.0 mg tris-(dibenzylideneacetone)-dipalladium and 8.8 mg 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene were stirred under argon at 100 C. for 20 hrs until HPLC indicated complete conversion. The solvent was removed under vacuum, the residue was taken up in DCM and washed dilute HCl. Removal of the DCM and chromatography on silica in first heptane and then heptan/EtOAc 8:2 yielded 25 mg of the title product.
  • 26
  • 4-bromo-2-(4-tert-butyl-phenyl)-7-nitro-2H-phthalazin-1-one [ No CAS ]
  • 4-bromo-2-(4-tert-butyl-phenyl)-6-nitro-2H-phthalazin-1-one [ No CAS ]
  • [ 141459-53-2 ]
  • [ 880488-64-2 ]
  • [ 880488-65-3 ]
YieldReaction ConditionsOperation in experiment
With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 80℃; for 2h; 6-Nitro-4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-tert-butyl-phenyl)-2H-phthalazin-l-one and 7-Nitro-4-(2-tert-butyl-5-methyl-2H-pyrazol-3- ylamino)-2-(4-tert-butyl-phenyl)-2H-phthalazin-l-one4.56 g of a 1:1 mixture of 4-Bromo-2-(4-tert-butyl-phenyl)-6-nitro-2H-phthalazin-1-one and 4-Bromo-2-(4-tert-butyl-phenyl)-7-nitro-2H-phfhalazin-l-one in 45 ml dry dioxane were reacted with 2.605 g l-(tert. butyl)-3-methyl-lH-pyrazole-5- ylamine, 5.526 g cesium carbonate, 311 mg tris-(dibenzylideneacetone)- EPO <DP n="211"/>dipalladium and 393 mg 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene under nitrogen at 80 C. After 2 hrs HPLC indicated complete conversion and the mixture was cooled to room temperature, diluted with 150 ml dichloromethane and washed twice with diluted HCl. The organic phase was dried and evaporated and the residue chromatographed on silica eluting first heptane and subsequently with heptane / ethyl acetate 8:2. The first eluting product was the 6-nitro isomer (1.82 g), the second eluting product was the 7-nitro isomer (2.05 g).
With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 80℃; for 2h; 6-Nitro-4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one and 7-Nitro-4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one: 4.56 g of a 1:1 mixture of 4-Bromo-2-(4-tert-butyl-phenyl)-6-nitro-2H-phthalazin-1-one and 4-Bromo-2-(4-tert-butyl-phenyl)-7-nitro-2H-phthalazin-1-one in 45 ml dry dioxane were reacted with 2.605 g 1-(tert.butyl)-3-methyl-1H-pyrazole-5-ylamine, 5.526 g cesium carbonate, 311 mg tris-(dibenzylideneacetone)-dipalladium and 393 mg 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene under nitrogen at 80 C. After 2 hrs HPLC indicated complete conversion and the mixture was cooled to RT, diluted with 150 ml DCM and washed twice with diluted HCl. The organic phase was dried and evaporated and the residue chromatographed on silica eluting first heptane and subsequently with heptane/EtOAc 8:2. The first eluting product was the 6-nitro isomer (1.82 g), the second eluting product was the 7-nitro isomer (2.05 g).
  • 27
  • [ 141459-53-2 ]
  • [ 110-46-3 ]
  • [ 184172-90-5 ]
YieldReaction ConditionsOperation in experiment
With hydrogenchloride; In ethanol; b) Preparation of 5-amino-3-methyl-4-nitroso-1-tert-butylpyrazole To a solution of 15.3 g (0.1 mol) of 5-amino-3-methyl-1-tert-butylpyrazole, obtained in the above step, in 200 cm3 of absolute ethanol were added dropwise 0.5 cm3 of 12N hydrochloric acid and then 13.5 cm3 (0.1 mol) of isoamyl nitrite, at 0 C. The solution was subsequently warmed to and left at room temperature for 4 hours. The ethanol was evaporated off under a pressure of 175 mbar, at 40 C. An orange-coloured solid was crystallized from heptane at 0 C. and then filtered off on a sinter funnel. After drying under vacuum at room temperature, 11 g of the expected product were obtained in the form of an orange-coloured solid, the melting point of which was 120 C.
  • 28
  • 4-bromo-2-(2-methoxyethyl)-4-bromo-2H-phthalazin-1-one [ No CAS ]
  • [ 141459-53-2 ]
  • 4-(2-tert-butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(2-methoxy-ethyl)-2H-phthalazin-1-one [ No CAS ]
YieldReaction ConditionsOperation in experiment
65% With caesium carbonate; 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 130℃; for 8h; 4-(2-tert-Butyl-5-methyl-2H-pyrazol-3-ylamino)-2-(2-methoxy-ethyl)-2H-phthalazin-1-one (Typical Procedure for Buchwald Reaction): 4-Bromo-2-(2-methoxyethyl)-4-bromo-2H-phthalazin-1-one (0.57 g, 2.0 mmol), 1-(tert-butyl)-3-methyl-1H-pyrazol-5-ylamine (0.46 g, 3.0 mmol), Cs2CO3 (0.98 mg, 3.0 mmol), tris(dibenzylideneacetone)-dipalladium (0) (0.092 g, 0.1 mmol) and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.17 mg, 0.3 mmol) were dissolved in degassed dioxane (10 ml). The reaction mixture was heated with stirring to 130 C. for 8 hours and then cooled to RT. H2O (100 ml) was added and the precipitated solid was filtered and washed with EtOAc and H2O. The raw product was purified over silica gel (EtOAc:heptane 0%-60% EtOAc) to give the title compound (0.46 g, 65% yield).1H-NMR: (400 MHz, D6-DMSO) 8.22-8.31 (3H, m), 7.95 (1H, t), 7.86 (1H, t), 5.91 (1H, s), 4.05 (1H, t),3.55 (1H, t), 3.17 (3H, s), 2.14 (3H, s), 1.54 (9H, s); MS (ESI+)=356.3 (M+H)+.
  • 29
  • [ 120-92-3 ]
  • [ 141459-53-2 ]
  • [ 1069085-25-1 ]
  • 30
  • [ 141459-53-2 ]
  • tetrahydrothiophen-3-one-4-carboxylic acid ester [ No CAS ]
  • [ 1069084-88-3 ]
  • 31
  • [ 141459-53-2 ]
  • [ 1360058-40-7 ]
  • 32
  • [ 141459-53-2 ]
  • [ 1360058-41-8 ]
  • 33
  • [ 141459-53-2 ]
  • [ 1360058-42-9 ]
  • 34
  • [ 141459-53-2 ]
  • [ 1360058-43-0 ]
  • 35
  • [ 141459-53-2 ]
  • [ 1354822-82-4 ]
 

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Technical Information

Categories

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[ 141459-53-2 ]

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