141459-53-2|1-(tert-Butyl)-3-methyl-1H-pyrazol-5-amine| Ambeed

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Quality Control of [ 141459-53-2 ] Purity: 98% SDS Specification

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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 1~41

1
[ 108-24-7 ]
[ 141459-53-2 ]
[ 154910-87-9 ]

Yield	Reaction Conditions	Operation 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%).

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.
[2]Patent: WO2013/46045,2013,A1 .Location in patent: Page/Page column 22.

2
[ 98-88-4 ]
[ 141459-53-2 ]
[ 154910-89-1 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

3
[ 141459-53-2 ]
[ 103-80-0 ]
[ 154910-88-0 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

4
[ 106-31-0 ]
[ 141459-53-2 ]
[ 161153-61-3 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

5
[ 1118-61-2 ]
[ 32064-67-8 ]
[ 141459-53-2 ]

Yield	Reaction Conditions	Operation 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%).

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.
[2]Patent: US6338741,2002,B1 .Location in patent: Page column 21.
[3]Journal of Combinatorial Chemistry,2010,vol. 12,p. 510 - 517.
[4]Patent: WO2013/46045,2013,A1 .Location in patent: Page/Page column 21.

6
[ 122-01-0 ]
[ 141459-53-2 ]
[ 161153-63-5 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

7
[ 123-62-6 ]
[ 141459-53-2 ]
[ 161153-60-2 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

8
[ 586-75-4 ]
[ 141459-53-2 ]
[ 161153-62-4 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

9
[ 141459-53-2 ]
[ 407-25-0 ]
[ 442850-65-9 ]

References: [1]Journal of Agricultural and Food Chemistry,2002,vol. 50,p. 4839 - 4845.

10
[ 141459-53-2 ]
[ 442850-75-1 ]

References: [1]Journal of Agricultural and Food Chemistry,2002,vol. 50,p. 4839 - 4845.

11
[ 141459-53-2 ]
1-tert-butyl-3-methyl-6-trifluoromethyl-1H-pyrazolo[3,4-d][1,3]thiazine-4-thione [ No CAS ]

References: [1]Journal of Agricultural and Food Chemistry,2002,vol. 50,p. 4839 - 4845.

12
[ 141459-53-2 ]
[ 161153-64-6 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

13
[ 141459-53-2 ]
[ 161153-65-7 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

14
[ 141459-53-2 ]
[ 161153-67-9 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

15
[ 141459-53-2 ]
[ 161153-66-8 ]

References: [1]Journal of Heterocyclic Chemistry,1994,vol. 31,p. 1477 - 1480.

16
[ 141459-53-2 ]
[ 154910-96-0 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

17
[ 141459-53-2 ]
[ 154911-06-5 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

18
[ 141459-53-2 ]
[ 154910-98-2 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

19
[ 141459-53-2 ]
[ 154910-97-1 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

20
[ 141459-53-2 ]
[ 154911-08-7 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

21
[ 141459-53-2 ]
[ 154911-07-6 ]

References: [1]Heterocycles,1993,vol. 36,p. 2291 - 2302.

22
[ 141459-53-2 ]
[ 184172-90-5 ]

Yield	Reaction Conditions	Operation 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.

References: [1]Patent: US6338741,2002,B1 .Location in patent: Page column 21-22.

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 ]

Yield	Reaction Conditions	Operation 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)+.

References: [1]Patent: WO2006/32518,2006,A1 .Location in patent: Page/Page column 187; 188.

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 ]

Yield	Reaction Conditions	Operation 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.

References: [1]Patent: WO2006/32518,2006,A1 .Location in patent: Page/Page column 198.
[2]Patent: US2007/219195,2007,A1 .Location in patent: Page/Page column 55.

25
4,6-dibromo-2-(4-tert-butyl-phenyl)-2H-phthalazin-1-one [ No CAS ]
[ 141459-53-2 ]
[ 880488-73-3 ]

Yield	Reaction Conditions	Operation 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.

References: [1]Patent: WO2006/32518,2006,A1 .Location in patent: Page/Page column 213.
[2]Patent: US2007/219195,2007,A1 .Location in patent: Page/Page column 60.

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 ]

Yield	Reaction Conditions	Operation 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).

References: [1]Patent: WO2006/32518,2006,A1 .Location in patent: Page/Page column 209; 210.
[2]Patent: US2007/219195,2007,A1 .Location in patent: Page/Page column 59.

27
[ 141459-53-2 ]
[ 110-46-3 ]
[ 184172-90-5 ]

Yield	Reaction Conditions	Operation 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.

References: [1]Patent: US6099592,2000,A .

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 ]

Yield	Reaction Conditions	Operation 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)+.

References: [1]Patent: US2007/219195,2007,A1 .Location in patent: Page/Page column 51.

29
[ 120-92-3 ]
[ 141459-53-2 ]
[ 1069085-25-1 ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 5126 - 5129.

30
[ 141459-53-2 ]
tetrahydrothiophen-3-one-4-carboxylic acid ester [ No CAS ]
[ 1069084-88-3 ]

References: [1]Bioorganic and Medicinal Chemistry Letters,2008,vol. 18,p. 5126 - 5129.

31
[ 141459-53-2 ]
[ 1360058-40-7 ]

References: [1]Patent: WO2012/19954,2012,A1 .

32
[ 141459-53-2 ]
[ 1360058-41-8 ]

References: [1]Patent: WO2012/19954,2012,A1 .

33
[ 141459-53-2 ]
[ 1360058-42-9 ]

References: [1]Patent: WO2012/19954,2012,A1 .

34
[ 141459-53-2 ]
[ 1360058-43-0 ]

References: [1]Patent: WO2012/19954,2012,A1 .

35
[ 141459-53-2 ]
[ 1354822-82-4 ]

References: [1]Patent: WO2012/19954,2012,A1 .

36
[ 141459-53-2 ]
sodium 1,4-diethoxy-1,4-dioxobut-2-en-2-olate [ No CAS ]
[ 1354822-18-6 ]

Yield	Reaction Conditions	Operation in experiment
53%	With acetic acid; In water; at 80℃; for 4h;	A stirred solution of diethyl oxalacetate sodium salt (504 mg, 2.4 mmol) and l-tert-butyl-3- methyl pyrazol-5-ylamine (250 mg, 1.63 mmol) in a mixture of acetic acid / water (0.3 mL, 6 mL), was heated at 80 C for 4 h. The reaction mixture was cooled to room temperature and the solid precipitate was filtered off then washed with water (50 mL). The solid was dissolved in ethyl acetate (50 mL) and dried over sodium sulfate. The organic layer was evaporated in vacuo to afford the title compound as a pale yellow solid (240 mg, 53%). HPLC-MS (Method A): MH+ requires m/z=278; Found m/z=278, Rt 3.63 min (100%). 1H MR (300 MHz, CDC13) δ 9.46 (br, 1H), 6.78 (s, 1H), 4.47-4.40 (q, 2H), 2.49 (s, 3H), 1.72 (s, 9H) and 1.44- 1.40 (t, 3H).

References: [1]Patent: WO2012/19954,2012,A1 .Location in patent: Page/Page column 27-28.

37
[ 1229236-85-4 ]
[ 141459-53-2 ]
[ 1346221-91-7 ]
C₃₅H₄₇FN₁₀O [ No CAS ]

References: [1]Organic Process Research and Development,2012,vol. 16,p. 70 - 81.

38
[ 1118-61-2 ]
[ 7400-27-3 ]
[ 141459-53-2 ]

Yield	Reaction Conditions	Operation in experiment
92%	With sodium hydroxide; In water; at 90℃; for 18h;	Intermediate P : 1 -tert-Butyl-3-methyl-1 H-pyrazol-5-amine tert- Butylhydrazine hydrochloride (15.2 g, 122 mmol) was added to the aqueous solution of sodium hydroxide (60 mL, 2M, 122 mmol) and stirred until dissolution of a solid. To the mixture 3-aminobut-2-enenitrile (10 g, 122 mmol) was added. The reaction mixture was stirred while heating at 90C for 18 hours, then cooled to room temperature and extracted with dichloromethane (3 χ 50 mL). Organic layers were combined, washed with brine, dried (Na2S04) and concentrated under reduced pressure to obtain title product as a white, amorphous solid with the yield of 92% (17.2 g, 1 12 mmol). 1H NMR (500 MHz, CDCl3) δ 7.25 (t, J=8.3 Hz, 1 H), 6.50 (d, J=8.3 Hz, 2H), 3.88 (s, 6H).

References: [1]Patent: WO2014/20531,2014,A1 .Location in patent: Page/Page column 14.
[2]Organic Syntheses,2012,vol. 89,p. 537 - 548.
[3]Organic Process Research and Development,2012,vol. 16,p. 70 - 81.
[4]ACS Chemical Neuroscience,2017,vol. 8,p. 1873 - 1879.

39
[ 87650-63-3 ]
[ 141459-53-2 ]
[ 1401688-61-6 ]

References: [1]Journal of Medicinal Chemistry,2012,vol. 55,p. 8582 - 8587,6.

40
[ 141459-53-2 ]
[ 609-09-6 ]
[ 1354822-18-6 ]

Yield	Reaction Conditions	Operation in experiment
70%		Intermediate 3Ethyl l-(l,l-dimethylethyl)-6-hydroxy-3-methyl-lH-pyrazolo[3,4-6]pyridine-4- carboxylatel-(l,l-Dimethylethyl)-3 -methyl- lH-pyrazol-5 -amine (5 g, 32.6 mmol), diethyl 2- oxobutanedione (6.14 g, 32.6 mmol) and toluene (100 mL) were heated at 70 C for 16 hours. The solvent was removed in vacuo, the crude residue dissolved in acetic acid (100 mL), and heated at reflux for 4 hours. The solvent was removed in vacuo, and the crude product purified via silica gel chromatography (eluent: gradient of 0 to 10%EtOAc/Hexanes). The product was collected as a solid, 6.32 g (70%). LCMS E-S (M+H) = 278.4. 1H NMR (400 MHz, DMSO-d6) ? ppm 11.39 (s, 1H), 6.82 (s, 1H), 4.36 (q, 2H, j = 7.2 Hz), 2.45 (s, 3H), 1.69 (s, 9H), 1.32 (t, 3H, j = 7.2 Hz).

References: [1]Patent: WO2013/39988,2013,A1 .Location in patent: Page/Page column 47.

41
[ 1354822-96-0 ]
[ 141459-53-2 ]
ethyl 6-cyclopropyl-1-(1,1-dimethylethyl)-3-methyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
278 mg	With acetic acid; for 2h;Reflux;	Example 1356-cyclopropyl- 1-(1 , l-dimethylethyl)-3-methyl- V- [(6-methyl-2-oxo-4-propyl- 1 ,2- dihydro-3-pyridinyl)methyl]-lH-pyrazolo[3,4-6]pyridine-4-carboxamidea) Ethyl 6-cyclopropyl-l-(l,l-dimethylethyl)-3-methyl-lH-pyrazolo[3,4- b] pyridine-4-carboxylate1 -(l,l-dimethylethyl)-3 -methyl- lH-pyrazol-5 -amine (166 mg, 1.086 mmol), ethyl (3Z)-4- cyclopropyl-4-hydroxy-2-oxo-3-butenoate (200 mg, 1.086 mmol) and acetic acid (10 mL) were heated to reflux for 2 hours. The solvent was removed in vacuo and the residue purified by silica gel chromatography (eluent: 0% to 7 % EtOAc:Hex). The product was collected as 278 mg. 1H NMR (400 MHz, CHLOROFORM-d) δ ppm 1.07 (dt, 2 H), 1.13 - 1.20 (m, 2 H), 1.46 (t, J=7.20 Hz, 3 H), 1.78 (s, 9 H), 2.18 (m, J=7.99, 7.99, 4.74, 4.55 Hz, 1 H), 2.65 (s, 3 H), 4.47 (q, J=7.07 Hz, 2 H), 7.43 (s, 1 H). LCMS(ES) [M+H]+ 302.2

References: [1]Patent: WO2013/39988,2013,A1 .Location in patent: Page/Page column 201.

Historical Records

Technical Information

• Buchwald-Hartwig C-N Bond and C-O Bond Formation Reactions • Chan-Lam Coupling Reaction • Hydride Reductions • Leuckart-Wallach Reaction • Mannich Reaction • Petasis Reaction • Preparation of Amines • Reactions of Amines • Specialized Acylation Reagents-Vilsmeier Reagent • Ugi Reaction

Related Functional Groups of
[ 141459-53-2 ]

Amines

A898285 [1124-16-9]

5-Amino-1-isopropyl-3-methylpyrazole

Similarity: 1.00

A336430 [3524-33-2]

1-Ethyl-3-methyl-1H-pyrazol-5-amine

Similarity: 0.93

A561916 [90206-23-8]

1-(Sec-butyl)-3-methyl-1H-pyrazol-5-amine

Similarity: 0.92

A222439 [874136-23-9]

3-(tert-Butyl)-1-isopropyl-1H-pyrazol-5-amine

Similarity: 0.91

A661718 [1015845-99-4]

3-Methyl-1-(pentan-3-yl)-1H-pyrazol-5-amine

Similarity: 0.91

Related Parent Nucleus of
[ 141459-53-2 ]

Pyrazoles

A898285 [1124-16-9]

5-Amino-1-isopropyl-3-methylpyrazole

Similarity: 1.00

A336430 [3524-33-2]

1-Ethyl-3-methyl-1H-pyrazol-5-amine

Similarity: 0.93

A561916 [90206-23-8]

1-(Sec-butyl)-3-methyl-1H-pyrazol-5-amine

Similarity: 0.92

A222439 [874136-23-9]

3-(tert-Butyl)-1-isopropyl-1H-pyrazol-5-amine

Similarity: 0.91

A661718 [1015845-99-4]

3-Methyl-1-(pentan-3-yl)-1H-pyrazol-5-amine

Similarity: 0.91

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CAS No.: 141459-53-2

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