[ CAS No. 86-92-0 ] {[proInfo.proName]}

Name: 86-92-0|3-Methyl-1-p-tolyl-5-pyrazolone|97%
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SKU: A474101
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Quality Control of [ 86-92-0 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 86-92-0 ]

Product Details of [ 86-92-0 ]

CAS No. :	86-92-0	MDL No. :	MFCD00035708
Formula :	C₁₁H₁₂N₂O	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	IOQOLGUXWSBWHR-UHFFFAOYSA-N
M.W :	188.23	Pubchem ID :	66591
Synonyms :

Calculated chemistry of [ 86-92-0 ] Expand+

Physicochemical Properties

Num. heavy atoms :	14
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.27
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	0.0
Molar Refractivity :	63.26
TPSA :	32.67 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	Yes
P-gp substrate :	No
CYP1A2 inhibitor :	Yes
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-6.29 cm/s

Lipophilicity

Log Po/w (iLOGP) :	2.34
Log Po/w (XLOGP3) :	1.63
Log Po/w (WLOGP) :	1.35
Log Po/w (MLOGP) :	1.89
Log Po/w (SILICOS-IT) :	2.66
Consensus Log Po/w :	1.97

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.55

Water Solubility

Log S (ESOL) :	-2.29
Solubility :	0.976 mg/ml ; 0.00519 mol/l
Class :	Soluble
Log S (Ali) :	-1.93
Solubility :	2.22 mg/ml ; 0.0118 mol/l
Class :	Very soluble
Log S (SILICOS-IT) :	-3.26
Solubility :	0.103 mg/ml ; 0.000547 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	0.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	2.27

Safety of [ 86-92-0 ]

Signal Word:	Warning	Class:	N/A
Precautionary Statements:	P261-P280-P301+P312-P302+P352-P305+P351+P338	UN#:	N/A
Hazard Statements:	H302	Packing Group:	N/A
GHS Pictogram:

Application In Synthesis of [ 86-92-0 ]

* 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 [ 86-92-0 ]

[ 86-92-0 ] Synthesis Path-Downstream 1~65

1
[ 86-92-0 ]
[ 4857-47-0 ]
3-hydroxy-4-[N'-(3-methyl-5-oxo-1-p-tolyl-1,5-dihydro-pyrazol-4-ylidene)-hydrazino]-naphthalene-1-sulfonic acid [ No CAS ]

Reference： [1]Journal of Medicinal Chemistry,2001,vol. 44,p. 3730 - 3745

2
[ 94205-62-6 ]
[ 86-92-0 ]
2-{4-[N'-(3-methyl-5-oxo-1-p-tolyl-1,5-dihydro-pyrazol-4-ylidene)-hydrazino]-phenyl}-quinoline-4-carboxylic acid [ No CAS ]

Reference： [1]Doklady Chemistry,2002,vol. 383,p. 72 - 74

3
[ 5464-79-9 ]
[ 86-92-0 ]
(4-methoxy-benzothiazol-2-yl)-(5-methyl-2-p-tolyl-2,4-dihydro-pyrazol-3-ylidene)-amine [ No CAS ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2005,vol. 44,p. 1452 - 1455

4
[ 22307-44-4 ]
[ 86-92-0 ]
N-[2-(5-methyl-2-p-tolyl-2,4-dihydro-pyrazol-3-ylideneamino)-benzothiazol-6-yl]-acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	In methanol for 0.0416667h; microwave irradiation;

Reference： [1]Mistry, Ketan; Desai [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2005, vol. 44, # 7, p. 1452 - 1455]

5
[ 6973-51-9 ]
[ 86-92-0 ]
(5-methyl-2-p-tolyl-2,4-dihydro-pyrazol-3-ylidene)-(4-nitro-benzothiazol-2-yl)-amine [ No CAS ]

Reference： [1]Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry,2005,vol. 44,p. 1452 - 1455

6
[ 21951-32-6 ]
[ 86-92-0 ]
2-(5-methyl-2-p-tolyl-2,4-dihydro-pyrazol-3-ylideneamino)-benzothiazole-6-sulfonic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
87%	In methanol for 1.45h; microwave irradiation;

Reference： [1]Mistry, Ketan; Desai [Indian Journal of Chemistry - Section B Organic and Medicinal Chemistry, 2005, vol. 44, # 7, p. 1452 - 1455]

7
[ 141-97-9 ]
[ 539-44-6 ]
[ 86-92-0 ]

Yield	Reaction Conditions	Operation in experiment
83%	With acetic acid; at 100℃; for 1h;	General procedure: To a neat solution containing 1,3-ketoester (2.84 mmol) and hydrazines (2.84mmol) was added glacialacetic acid (0.05 mL). The reaction mixture was stirred at 100 oil-bath for 1h. After the reaction was completed, the solution was cooled down to room temperature and then diluted with Et2O (2 mL)and stirred vigorously for 2h. The resultant solid was filtrated off, washed with Et2O (1 mL), driedunder vacuum at 50 for 6h to give pure pyrazolones 2 as white to light yellow crystal or powder in70-97.7% yield
	In ethanol; water; at 60℃;	General procedure: The intermediate 5-chloro-1-aryl-3-methyl-1H-pyrazole-4-carboxylic acids 1a-1d were synthesized as the following: para-substituted phenylhydrazines (0.025 mol) were reacted with ethyl acetoacetate (0.025 mol) in anhydrous ethanol to form a solid, which was then dissolved in a cold mixed solution of DMF (20 mL) and POCl3 (16 mL), and stirred at 50-60 C. The resulting mixture was poured into ice-cold water, a saturated solution of sodium hydroxide was added to neutralize the mixture, and the solid precipitate was filtered, and washed with water. Then above product was oxidized by KMnO4 solution, stirred at 70-80 C. After cooling to room temperature the pH of the reaction mixture wasadjusted to pH 7-8 by the dropwise addition of KOH solution, and the solution was filtered, HCl solution was added to the solution and solid 1a-1d eventually separated out. The crude product obtained was recrystallized from DMF to afford the pure product. All the reactions were monitored by TLC.
61 mg	With acetic acid; at 120℃; for 0.75h;Inert atmosphere; Glovebox;	General procedure: In an inert atmosphere glovebox, [Pd(cinnamyl)Cl]2 (typically 2.5 mol%) and Mor-DalPhos(typically 7.5 mol%) were added to a vial sealed with a cap containing a PTFE septum and stirred in toluene for 5 min, then NaOtBu (2.1 equiv.) was added along with the aryl chloride substrate (1 equiv., [ArCl] = 0.1 M) if it was a solid. After removing the vial from the glovebox the aryl chloride was added via a syringe if it was a liquid, along with hydrazine hydrate (2.0 equiv.). The reaction was stirred at the desired temperature for 0.5-2 h. Generally, after a short period of time, reactions were observed to darken and considerable black precipitate was formed.After completion of the reaction was observed by thin layer chromatography (TLC) or GC methods, the solution was allowed to cool and filtered through a short plug of neutral alumina, which was washed with CH2Cl2/MeOH (25:1). The resulting eluent solution was concentrated and charged with ethyl acetoacetate (1 equiv., [ethyl acetoacetate] = 0.125 M) and glacial acetic acid. The solution was heated at reflux for 0.5-3 h, and the reaction progress was monitored by use of TLC or GC methods. After complete consumption of the aryl hydrazine, the reaction was cooled, diluted with EtOAc (40 mL) and washed with H2O (60 mL) followed by 1:1 water/brine (60 mL). The organic fractions were dried over Na2SO4, filtered and concentrated to afford crude product which was purified by column chromatography. Typical reaction scales were 0.4 -1.0 mmol. Aryl hydrazines were stored at -4 C for no longer than 12 hours before reacting with ethyl acetate.

	In ethanol; at 70 - 80℃; for 5h;	General procedure: Para-substituted phenyl hydrazine (0.025 mol)was dissolved in anhydrous ethanol, ethyl acetoacetate(0.025 mol) was slowly added and stirred at 70-80 8C for 5 h,then the anhydrous ethanol was removed under reduced pressureto form a solid, which was dissolved in DMF (20 mL) andphosphorus oxychloride (16 mL) of cold mixed solution andstirred at 80-85 8C for 5 h. The resulting mixture was poured intoice-cold water, the resulting solid was separated by filtration togive the light yellow solid.
	In ethanol; water; for 5h;Heating;	General procedure: para-Substituted phenyl hydrazine (25 mmol) was dissolved inanhydrous ethanol, ethyl acetoacetate (25 mmol) was slowlyadded and stirred at 70-80C for 5 h, then the anhydrousethanol was removed under reduced pressure to form a solid,which was dissolved in DMF (20 mL) and phosphorus oxychloride(16 mL) of cold mixed solution and stirred at 90Cfor 1h. The resulting mixture was poured into ice-cold water,the resulting solid was separated by filtration to give the lightyellow solid. Then above product was oxidized by 5.0 mol/LKMnO4 solution, stirred at 70-80C. After cooling to roomtemperature the pH of the reaction mixture was adjusted topH 7-8 by the dropwise addition of 3.0 mol/L KOH solution,and the solution was filtered, 6.0 mol/L HCl solution wasadded to the solution and solid 2a-2d eventually separatedout. The crude product obtained was recrystallized from anhydrousethanol to afford the pure product.
		The hydrazine is then condensed with a beta-keto ester such as ethyl acetoacetate, compound (h), in an appropriate solvent such as acetic acid or ethanol at an appropriate temperature typically 0-100 to give the corresponding pyrazole, compound (I) as described herein.
	In ethanol; water; at 60℃; for 5h;	General procedure: Intermediates 2a-d were obtained from Reference [30]. Dissolve para-substituted phenylhydrazine (0.025 mol) with anhydrous ethanol ethyl acetoacetate (0.025 mol) was added portionwise, stirred, and refluxed for 5 h, then the solution was rotary evaporated to form a solid, whichwas dissolved in DMF (25 mL) and phosphorus oxychloride (20 mL) of cold mixed solution andstirred at 85 C for 2 h. The resulting product was poured into ice-cold water and the solid wasisolated by filtration to give a yellow solid, which was oxidized by KMnO4 solution and stirred at70-80 C. After cooling to room temperature, the pH was adjusted to alkaline by the addition of 10%NaOH solution, and the solution was filtered, HCl solution was added to the solution and solid 2a-deventually separated out. The resulting crude product was recrystallized from anhydrous ethanol togive the pure product.

Reference： [1]Synlett,2016,vol. 27,p. 1983 - 1988
[2]Journal of Chemical Research,2012,vol. 36,p. 691 - 696
[3]Bioorganic and Medicinal Chemistry,2008,vol. 16,p. 8587 - 8591
[4]Journal of Heterocyclic Chemistry,2012,vol. 49,p. 1169 - 1178
[5]Molecules,2015,vol. 20,p. 807 - 821
[6]Bioorganic and Medicinal Chemistry Letters,2016,vol. 26,p. 100 - 104
[7]European Journal of Medicinal Chemistry,2016,vol. 116,p. 147 - 155
[8]Chinese Chemical Letters,2017,vol. 28,p. 377 - 382
[9]Organic Letters,2017,vol. 19,p. 662 - 665
[10]Chemical and Pharmaceutical Bulletin,2018,vol. 66,p. 358 - 362
[11]European Journal of Organic Chemistry,2018,vol. 2018,p. 4723 - 4730
[12]Patent: US6670387,2003,B1 .Location in patent: Page column 12
[13]Molecules,2019,vol. 24
[14]Organic and Biomolecular Chemistry,2019,vol. 17,p. 7552 - 7557
[15]Journal of Organic Chemistry,2019,vol. 84,p. 9138 - 9150

8
[ 68-12-2 ]
[ 86-92-0 ]
[ 350997-70-5 ]

Yield	Reaction Conditions	Operation in experiment
	With trichlorophosphate; at 50 - 60℃;	General procedure: The intermediate 5-chloro-1-aryl-3-methyl-1H-pyrazole-4-carboxylic acids 1a-1d were synthesized as the following: para-substituted phenylhydrazines (0.025 mol) were reacted with ethyl acetoacetate (0.025 mol) in anhydrous ethanol to form a solid, which was then dissolved in a cold mixed solution of DMF (20 mL) and POCl3 (16 mL), and stirred at 50-60 C. The resulting mixture was poured into ice-cold water, a saturated solution of sodium hydroxide was added to neutralize the mixture, and the solid precipitate was filtered, and washed with water. Then above product was oxidized by KMnO4 solution, stirred at 70-80 C. After cooling to room temperature the pH of the reaction mixture wasadjusted to pH 7-8 by the dropwise addition of KOH solution, and the solution was filtered, HCl solution was added to the solution and solid 1a-1d eventually separated out. The crude product obtained was recrystallized from DMF to afford the pure product. All the reactions were monitored by TLC.
	With trichlorophosphate; at 80 - 85℃; for 5h;	General procedure: Para-substituted phenyl hydrazine (0.025 mol)was dissolved in anhydrous ethanol, ethyl acetoacetate(0.025 mol) was slowly added and stirred at 70-80 8C for 5 h,then the anhydrous ethanol was removed under reduced pressureto form a solid, which was dissolved in DMF (20 mL) andphosphorus oxychloride (16 mL) of cold mixed solution andstirred at 80-85 8C for 5 h. The resulting mixture was poured intoice-cold water, the resulting solid was separated by filtration togive the light yellow solid.
	With trichlorophosphate; at 90℃;Cooling;	General procedure: para-Substituted phenyl hydrazine (25 mmol) was dissolved inanhydrous ethanol, ethyl acetoacetate (25 mmol) was slowlyadded and stirred at 70-80C for 5 h, then the anhydrousethanol was removed under reduced pressure to form a solid,which was dissolved in DMF (20 mL) and phosphorus oxychloride(16 mL) of cold mixed solution and stirred at 90Cfor 1h. The resulting mixture was poured into ice-cold water,the resulting solid was separated by filtration to give the lightyellow solid. Then above product was oxidized by 5.0 mol/LKMnO4 solution, stirred at 70-80C. After cooling to roomtemperature the pH of the reaction mixture was adjusted topH 7-8 by the dropwise addition of 3.0 mol/L KOH solution,and the solution was filtered, 6.0 mol/L HCl solution wasadded to the solution and solid 2a-2d eventually separatedout. The crude product obtained was recrystallized from anhydrousethanol to afford the pure product.

With trichlorophosphate;

General procedure: Intermediates 2a-d were obtained from Reference [30]. Dissolve para-substituted phenylhydrazine (0.025 mol) with anhydrous ethanol ethyl acetoacetate (0.025 mol) was added portionwise, stirred, and refluxed for 5 h, then the solution was rotary evaporated to form a solid, whichwas dissolved in DMF (25 mL) and phosphorus oxychloride (20 mL) of cold mixed solution andstirred at 85 C for 2 h. The resulting product was poured into ice-cold water and the solid wasisolated by filtration to give a yellow solid, which was oxidized by KMnO4 solution and stirred at70-80 C. After cooling to room temperature, the pH was adjusted to alkaline by the addition of 10%NaOH solution, and the solution was filtered, HCl solution was added to the solution and solid 2a-deventually separated out. The resulting crude product was recrystallized from anhydrous ethanol togive the pure product.

Reference： [1]Journal of Agricultural and Food Chemistry,2008,vol. 56,p. 10160 - 10167
[2]Central European Journal of Chemistry,2011,vol. 9,p. 635 - 647
[3]Journal of the Serbian Chemical Society,2012,vol. 77,p. 1165 - 1174
[4]Journal of Heterocyclic Chemistry,2012,vol. 49,p. 1169 - 1178
[5]European Journal of Medicinal Chemistry,2014,vol. 76,p. 549 - 557
[6]Molecules,2015,vol. 20,p. 807 - 821
[7]Research on Chemical Intermediates,2016,vol. 42,p. 2101 - 2117
[8]Chinese Chemical Letters,2017,vol. 28,p. 377 - 382
[9]Chemical and Pharmaceutical Bulletin,2018,vol. 66,p. 358 - 362
[10]Molecules,2019,vol. 24

9
[ 1310735-98-8 ]
[ 86-92-0 ]
C₂₉H₂₈N₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With tetra(n-butyl)ammonium hydrogensulfate; In acetonitrile; for 10h;Reflux;	General procedure: A mixture of aldehydes 3a-d (2 mmol), pyrazolones 4a-d (2 mmol) and catalyst TBA-HS (25 mol %) was stirred under the refluxing xylene (when R = H) or acetonitrile (when R = CH3) for a specified time shown in Table 2. After complete conversion, as indicated by the TLC, the mixture was cooled and subjected to reduced pressure to remove solvent. The residue 7a-p were washed with an appropriate solvent such as xylene or acetonitrile to remove any residual starting material and dried in vacuo. The products were obtained in 68-88% yields. Analytically pure sample was obtained by preparative TLC using ethyl acetate/hexane (3:7) as an eluent.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2853 - 2856

10
[ 1310736-16-3 ]
[ 86-92-0 ]
C₂₉H₂₇ClN₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
83%	With tetra(n-butyl)ammonium hydrogensulfate; In acetonitrile; for 9h;Reflux;	General procedure: A mixture of aldehydes 3a-d (2 mmol), pyrazolones 4a-d (2 mmol) and catalyst TBA-HS (25 mol %) was stirred under the refluxing xylene (when R = H) or acetonitrile (when R = CH3) for a specified time shown in Table 2. After complete conversion, as indicated by the TLC, the mixture was cooled and subjected to reduced pressure to remove solvent. The residue 7a-p were washed with an appropriate solvent such as xylene or acetonitrile to remove any residual starting material and dried in vacuo. The products were obtained in 68-88% yields. Analytically pure sample was obtained by preparative TLC using ethyl acetate/hexane (3:7) as an eluent.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2853 - 2856

11
[ 1310735-97-7 ]
[ 86-92-0 ]
C₂₇H₂₄N₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%	With tetra(n-butyl)ammonium hydrogensulfate; In 5,5-dimethyl-1,3-cyclohexadiene; for 8h;Reflux;	General procedure: A mixture of aldehydes 3a-d (2 mmol), pyrazolones 4a-d (2 mmol) and catalyst TBA-HS (25 mol %) was stirred under the refluxing xylene (when R = H) or acetonitrile (when R = CH3) for a specified time shown in Table 2. After complete conversion, as indicated by the TLC, the mixture was cooled and subjected to reduced pressure to remove solvent. The residue 7a-p were washed with an appropriate solvent such as xylene or acetonitrile to remove any residual starting material and dried in vacuo. The products were obtained in 68-88% yields. Analytically pure sample was obtained by preparative TLC using ethyl acetate/hexane (3:7) as an eluent.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2853 - 2856

12
[ 1310736-15-2 ]
[ 86-92-0 ]
C₂₇H₂₃ClN₄O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
80%	With tetra(n-butyl)ammonium hydrogensulfate; In 5,5-dimethyl-1,3-cyclohexadiene; for 7h;Reflux;	General procedure: A mixture of aldehydes 3a-d (2 mmol), pyrazolones 4a-d (2 mmol) and catalyst TBA-HS (25 mol %) was stirred under the refluxing xylene (when R = H) or acetonitrile (when R = CH3) for a specified time shown in Table 2. After complete conversion, as indicated by the TLC, the mixture was cooled and subjected to reduced pressure to remove solvent. The residue 7a-p were washed with an appropriate solvent such as xylene or acetonitrile to remove any residual starting material and dried in vacuo. The products were obtained in 68-88% yields. Analytically pure sample was obtained by preparative TLC using ethyl acetate/hexane (3:7) as an eluent.

Reference： [1]Tetrahedron Letters,2011,vol. 52,p. 2853 - 2856

13
[ 5765-63-9 ]
[ 86-92-0 ]
[ 1312921-08-6 ]

Yield	Reaction Conditions	Operation in experiment
72%		Example 16; 4-(4-hvdroxymorpholin-3-yl)-3-methyl-1 -p-tolyl-1 /-/-pyrazol-5(4/-/)-one:; A mixture of N-hydroxymorpholine (1 .03 g, 10 mmol), azodicarbonamide (1 .39 g, 12 mmol) and methanol (10 ml) was heated to reflux for 50 minutes. During this period the solid, initially orange in colour, changed into a whitish precipitate. After cooling to ambient temperature, said precipitate was separated by suction and washed twice with methanol (2 x 5 ml). All the methanol fractions were combined and under agitation 3-methyl-1 -p-tolyl-1 /-/-pyrazol-5(4H)-one (10 mmol) was added. After 10 minutes, the methanol was removed under vacuum (water bath temperature 50QC) to give a compound of formula (16).Yield: 72% after grinding with diethyl etherFormula: Ci4Hi9N303 MW: 289.33 g/mol
72%		A mixture of N-hydroxymorpholine (1.03 g, 10 mmol), azodicarbonamide (1.39 g, 12 mmol) and methanol (10 ml) was heated to reflux for 50 minutes. During this period the solid, initially orange in colour, changed into a whitish precipitate. After cooling to ambient temperature, said precipitate was separated by suction and washed twice with methanol (2 x 5 ml). All the methanol fractions were combined and under agitation 3-methyl-1-p-tolyl-1H-pyrazol-5(4H)-one (10 mmol) was added. After 10 minutes, the methanol was removed under vacuum (water bath temperature 50ºC) to give a compound of formula (16). Yield: 72% after grinding with diethyl ether Formula: C14H19N3O3 MW: 289.33 g/mol

Reference： [1]Patent: WO2011/76930,2011,A1 .Location in patent: Page/Page column 34-35
[2]Patent: EP2345639,2011,A1 .Location in patent: Page/Page column 29

14
[ 358-23-6 ]
[ 86-92-0 ]
[ 1373936-54-9 ]

Reference： [1]Organic Letters,2012,vol. 14,p. 2544 - 2547

15
[ 1354703-76-6 ]
[ 86-92-0 ]
[ 1354703-86-8 ]

Reference： [1]Dyes and Pigments,2012,vol. 95,p. 142 - 148
[2]Research on Chemical Intermediates,2012,vol. 38,p. 885 - 901

16
[ 850427-85-9 ]
[ 86-92-0 ]
(5aRS,11bSR)-1,11b-dimethyl-3-(4-methylphenyl)-10-nitro-3,5a,6,11b-tetrahydro-5Hchromeno[4',3':4,5]pyrano[2,3-c]pyrazole [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2012,p. 5953 - 5964,12
[2]Molecular Diversity,2017,vol. 21,p. 339 - 354

17
[ 1417703-64-0 ]
[ 86-92-0 ]
(5aRS,11bSR)-1,5,5,11b-tetramethyl-3-(4-methylphenyl)-10-nitro-3,5a,6,11b-tetrahydro-5Hchromeno[4',3':4,5]pyrano[2,3-c]pyrazole [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2012,p. 5953 - 5964,12
[2]Molecular Diversity,2017,vol. 21,p. 339 - 354

18
[ 1417703-65-1 ]
[ 86-92-0 ]
(5aRS,11bSR)-1,5,5,11b-tetramethyl-3-(4-methylphenyl)-8-nitro-3,5a,6,11b-tetrahydro-5H-chromeno[4',3':4,5]pyrano[2,3-c] pyrazole [ No CAS ]

Reference： [1]European Journal of Organic Chemistry,2012,p. 5953 - 5964,12
[2]Molecular Diversity,2017,vol. 21,p. 339 - 354

19
[ 637-60-5 ]
[ 141-97-9 ]
[ 86-92-0 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In ethanol; at 60℃; for 24h;Reflux;	General procedure: To a stirred solution of aryl hydrazine hydrochloride (10 mmol) and Et3N (1.52 g, 15 mmol) in EtOH (30 mL) at 60 oC, ethyl acetoacetate (1.30 g, 10 mmol) was added and stirred at reflux for 24h. After the reaction was completed, the solvent was removed under reduced pressure. The crude salt was solved in EtOAc/H2O 30:70 and stirred for 2h. Then the organic phase was separated, dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure after filtration. After recrystallization from EtOH, pure pyrazolones were obtained as white or pink solid.The pyrazolones were solved in Ac2O (20 mL) and stirred at room temperature for 12h. After the reaction was completed, the solution was diluted with H2O (200 mL) and stirred for another 2h. Then the aqueous phase was extracted with EtOAc (3×30 mL). The combined organic phases were washed with H2O (2×100 mL), dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure after filtration. The residue was purified by flash chromatography on silica gel (eluent: petroleum ether/ethyl acetate 10:1-6:1) to afford the desired products 1 in 54-83% yield.
	With sodium acetate; In acetic acid;Reflux; Inert atmosphere;	General procedure: Acetylacetic ether or trifluoroacetyl ethyl acetate (25 mmol) were added to a mixture solution of 5a-g (25 mmol) and sodium acetate (26 mmol) in acetic acid (20 mL). The reaction mixture was stirred at reflux temperature for 5-10 h. After cooling, the mixture was added to a saturated solution of NaHCO3 until its pH value is adjusted to 7 and extracted with ethyl acetate for three times. The combined organic layer was then dried, filtered, concentrated and the residue was purified by column chromatography (PE/EtOAc = 6:1, v/v) to give light yellow solid 6a-g and 7a-g in 50-70% yield.

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 6650 - 6653
[2]Bioorganic and Medicinal Chemistry Letters,2015,vol. 25,p. 3535 - 3540
[3]Organic and Biomolecular Chemistry,2017,vol. 15,p. 7267 - 7271
[4]Bioorganic and Medicinal Chemistry Letters,2018,vol. 28,p. 3526 - 3528
[5]Angewandte Chemie - International Edition,2019,vol. 58,p. 4710 - 4713
Angew. Chem.,2019,vol. 131,p. 4758 - 4761,4

20
[ 108-24-7 ]
[ 86-92-0 ]
[ 1002547-93-4 ]

Yield	Reaction Conditions	Operation in experiment
72%	at 20℃; for 12h;	General procedure: To a stirred solution of aryl hydrazine hydrochloride (10 mmol) and Et3N (1.52 g, 15 mmol) in EtOH (30 mL) at 60 oC, ethyl acetoacetate (1.30 g, 10 mmol) was added and stirred at reflux for 24h. After the reaction was completed, the solvent was removed under reduced pressure. The crude salt was solved in EtOAc/H2O 30:70 and stirred for 2h. Then the organic phase was separated, dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure after filtration. After recrystallization from EtOH, pure pyrazolones were obtained as white or pink solid.The pyrazolones were solved in Ac2O (20 mL) and stirred at room temperature for 12h. After the reaction was completed, the solution was diluted with H2O (200 mL) and stirred for another 2h. Then the aqueous phase was extracted with EtOAc (3×30 mL). The combined organic phases were washed with H2O (2×100 mL), dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure after filtration. The residue was purified by flash chromatography on silica gel (eluent: petroleum ether/ethyl acetate 10:1-6:1) to afford the desired products 1 in 54-83% yield.

Reference： [1]Tetrahedron Letters,2012,vol. 53,p. 6650 - 6653

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