[ CAS No. 60481-51-8 ] {[proInfo.proName]}

Name: 60481-51-8|(3,4-Dimethylphenyl)hydrazine hydrochloride|97%
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SKU: A149620
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Quality Control of [ 60481-51-8 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

Alternatived Products of [ 60481-51-8 ]

Product Details of [ 60481-51-8 ]

CAS No. :	60481-51-8	MDL No. :	MFCD00052270
Formula :	C₈H₁₃ClN₂	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	YYMIOVAEQIEPET-UHFFFAOYSA-N
M.W :	172.66	Pubchem ID :	173740
Synonyms :

Calculated chemistry of [ 60481-51-8 ]

Physicochemical Properties

Num. heavy atoms :	11
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.25
Num. rotatable bonds :	1
Num. H-bond acceptors :	1.0
Num. H-bond donors :	2.0
Molar Refractivity :	49.43
TPSA :	38.05 Å²

Pharmacokinetics

GI absorption :	Low
BBB permeant :	No
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.54 cm/s

Lipophilicity

Log Po/w (iLOGP) :	0.0
Log Po/w (XLOGP3) :	2.56
Log Po/w (WLOGP) :	-1.49
Log Po/w (MLOGP) :	2.34
Log Po/w (SILICOS-IT) :	1.25
Consensus Log Po/w :	0.93

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.56

Water Solubility

Log S (ESOL) :	-2.86
Solubility :	0.238 mg/ml ; 0.00138 mol/l
Class :	Soluble
Log S (Ali) :	-3.01
Solubility :	0.17 mg/ml ; 0.000985 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-2.83
Solubility :	0.254 mg/ml ; 0.00147 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.34

Safety of [ 60481-51-8 ]

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

Application In Synthesis of [ 60481-51-8 ]

* 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.

Upstream synthesis route of [ 60481-51-8 ]
Downstream synthetic route of [ 60481-51-8 ]

[ 60481-51-8 ] Synthesis Path-Upstream 1~4

1
[ 141-97-9 ]
[ 60481-51-8 ]
[ 18048-64-1 ]

Yield	Reaction Conditions	Operation in experiment
82%	With potassium acetate; acetic acid In water at 120℃; for 7 h;	3,4-dimethylphenylhydrazine hydrochloride (8.7g, 50m mol), was dissolved in 100mlof glacial acetic acid, ethyl acetoacetate (6.5g, 50m mol) and sodium acetate (4.1g,50m mol) , 120 reflux reaction 7h, TLC detection of raw materials reaction completely.Evaporated under reduced pressureglacial acetic acid, was added 100ml of water, 100ml of ethyl acetate 4 times the combined ethyl acetatelayer was not over anhydrous sodium sulfate, and concentrated under reduced pressure to give 1- (3,4-dimethylphenyl) - 3- methyl-1hydrogen - pyrazol-5 (4 hydrogen) -one (8.3g, 82percent yield)

Reference： [1] Patent: CN103360317, 2016, B, . Location in patent: Paragraph 0095; 0105; 0106; 0108

2
[ 583-71-1 ]
[ 60481-51-8 ]

Yield	Reaction Conditions	Operation in experiment
52%	Stage #1: With potassium phosphate; N,N'-bis(2,5-dimethylpyrrol-1-yl)oxalamide; cetyltrimethylammonim bromide; copper(I) bromide In water at 80℃; for 0.166667 h; Sealed tube; Inert atmosphere Stage #2: With hydrazine hydrate In water at 80℃; for 2 h; Sealed tube; Inert atmosphere Stage #3: With hydrogenchloride In dichloromethane; water	General procedure: CuBr (36 mg, 0.25 mmol, 2.5 mol percent), L3 (110 mg, 0.4 mmol,4 mol percent), H2O (0.5 mL), and K3PO4 (254 mg, 1.2 mmol) were mixedin a 15 mL screw cap test tube. After STAC (110 mg, 0.3 mmol,3 mol percent) and aryl bromide (10 mmol) were added, the resulting mixture was stirred at 80-110° C (bath temperature) for 10 min.Then K3PO4 (2.29 g, 10.8 mmol) and N2H4*H2O (1 g, 20 mmol) were added and argon (flow rate 5-7 mL/min) was bubbled through thereaction mixture for 5 min.28 The reaction mixture was stirred ina closed test tube at 80-110° C (bath temperature) for 1-2 h until complete consumption of starting material was observed as monitoredby TLC (eluentehexane), then cooled to room temperatureand diluted with SH2Cl2 (50 mL). The resulting solutionwas filteredand washed with brine (225 mL). Aq HCl (37percent) was added to the CH2Cl2 solution dropwise until pH 3-4. The formed precipitate was filtered, washed with SH2Cl2 (15 mL) and dried atroom temperature. NMR spectra of certain synthesized aryl hydrazine hydrochlorides showed that they contained 1-5 mol percent of the corresponding aniline hydrochlorides as impurities (see Supplementary data). Analytical samples of aryl hydrazine hydrochlorides were purified via precipitation from methanol solution by adding 2-3 volumes of diethyl ether.

Reference： [1] Chinese Journal of Chemistry, 2018, vol. 36, # 11, p. 1003 - 1006
[2] Tetrahedron, 2014, vol. 70, # 26, p. 4043 - 4048

3
[ 95-64-7 ]
[ 60481-51-8 ]

Yield	Reaction Conditions	Operation in experiment
11.8 g	Stage #1: With hydrogenchloride; sodium nitrite In water at 0℃; for 0.5 h; Stage #2: With hydrogenchloride; tin(ll) chloride In water	3,4-dimethyl aniline (12.2g, 0.1mol) in 50ml and 20ml of concentrated hydrochloric acidmixed uniformly in water, cooling to below 0 , with mechanical stirring, to which the solution of sodium nitriteaqueous solution (7.6g, 0.11 mol), maintaining the reaction temperature at 0 , stirring was continued for 0.5h,and thereto was added stannous chloride (56.5g, 0.25mol) in concentrated hydrochloric acid (20ml),naturally to room temperature, TLC monitored the reaction was complete feed.Suction filtration, the filter cake dried to give 3,4-dimethylphenylhydrazine hydrochloride (11.8g).

Reference： [1] Angewandte Chemie - International Edition, 2013, vol. 52, # 47, p. 12426 - 12429[2] Angew. Chem., 2013, vol. 125, # 47, p. 12652 - 12656,4
[3] Patent: CN103360317, 2016, B, . Location in patent: Paragraph 0095; 0105; 0106; 0107

4
[ 141-97-9 ]
[ 60481-51-8 ]
[ 277299-70-4 ]

Yield	Reaction Conditions	Operation in experiment
76%	With sodium bicarbonate; sodium acetate In diethyl ether; acetic acid	f 1-(3,4-Dimethylphenyl)-3-methyl-3-pyrazolin-5-one A solution of 3,4-dimethylphenylhydrazine hydrochloride (17.7 g; 0.1 mol.), ethyl acetoacetate (13.0 g; 0.1 mol.) and sodium acetate (8.2 g; 0.1 mol.) in glacial acetic acid (250 mL) was stirred and heated under reflux for 24 h. The mixture was cooled and evaporated and the residue dissolved in diethyl ether (IL) and carefully washed with sat. aqu. sodium hydrogen carbonate (5*200 mL). The ethereal layer was evaporated to afford the title compound (15.4 g; 76percent). ¹H NMR (300 MHz, d₆-DMSO) δ11.30 (br s, 1H), 7.49 (d, J=1.4 Hz, 1H), 7.43 (dd, J=8.2 Hz, 1H), 7.14 (d, J=8.2 Hz, 1H), 5.31 (s, 1H), 2.20 (s, 3H), 2.22 (s, 3H), 2.08 (s, 3H); MS(ES) m/z 203 [M+H].
76%	With sodium acetate In acetic acid for 24 h; Heating / reflux	A solution of 3,4-dimethylphenylhydrazine hydrochloride (17.7 g; 0.1 mol.), ethyl acetoacetate (13.0 g; 0.1 mol.) and sodium acetate (8.2 g; 0.1 mol.) in glacial acetic acid; (250 mL) was stirred and heated under reflux for 24 h. [0378] The mixture was cooled and evaporated and the residue dissolved in diethyl ether (1L) and carefully washed with sat. aqu. sodium hydrogen carbonate (5.x.200 mL). The ethereal layer was evaporated to afford the title compound (15.4 g; 76percent). 1H NMR (300 MHz, d6-DMSO) δ 11.30 (br s, 1H), 7.49 (d, J=1.4 Hz, 1H), 7.43 (dd, J=8.2 Hz, 1H), 7.14 (d, J=8.2 Hz, 1H), 5.31 (s, 1H), 2.20 (s, 3H), 2.22 (s, 3H), 2.08 (s, 3H); MS(ES) m/z 203 [M+H].
76%	for 24 h; Reflux	A solution of 3,4-dimethylphenylhydrazine hydrochloride (17.7 g; 0.1 mol.), ethyl acetoacetate (13.0 g; 0.1 mol.) and sodium acetate (8.2 g; 0.1 mol.) in glacial acetic acid; (250 mL) was stirred and heated under reflux for 24h. The mixture was cooled and evaporated and the residue dissolved in diethyl ether (1L) and carefully washed with saturated aqueous sodium hydrogen carbonate (5 x 200 mL). The ethereal layer was evaporated to afford the title compound (15.4 g; 76percent).

Reference： [1] Patent: US2004/53299, 2004, A1,
[2] Patent: US2004/19190, 2004, A1, . Location in patent: Page 17
[3] Patent: WO2016/35018, 2016, A1, . Location in patent: Page/Page column 13

[ 60481-51-8 ] Synthesis Path-Downstream 1~88

1
[ 583-71-1 ]
[ 60481-51-8 ]
[ 4920-95-0 ]

Reference： [1]Bulletin of the Chemical Society of Japan,1983,vol. 56,p. 1113 - 1115

2
[ 60481-51-8 ]
3-[3-(2-chlorophenyl)-5-methyl-4-isoxazolylcarbonylamino]-5,6-dimethyl-2-phenyl-1H-indole [ No CAS ]

Reference： [1]Chemistry of Heterocyclic Compounds,2003,vol. 39,p. 161 - 167

3
[ 60481-51-8 ]
3-[3-(2-chlorophenyl)-5-methyl-4-isoxazolylcarbonylamino]-4,5-dimethyl-2-phenyl-1H-indole [ No CAS ]

Reference： [1]Chemistry of Heterocyclic Compounds,2003,vol. 39,p. 161 - 167

4
[ 60481-51-8 ]
[ 374924-93-3 ]

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

5
[ 60481-51-8 ]
4-{<i>N</i>'-[1-(3,4-dimethyl-phenyl)-5-oxo-1,5-dihydro-pyrazol-4-ylidene]-hydrazino}-3-hydroxy-naphthalene-1-sulfonic acid [ No CAS ]

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

6
[ 87-13-8 ]
[ 60481-51-8 ]
[ 376593-74-7 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In ethanol; for 3h;Heating / reflux;	A suspension of <strong>[60481-51-8]3,4-dimethylphenylhydrazine hydrochloride</strong> (2.0 g; 0.012 mol.) and potassium carbonate (3.2 g; 0.023 mol.) in anhydrous ethanol (40.0 mL) was treated dropwise with diethyl(ethoxymethylene)malonate (2.5 g; 0.012 mol.) and the mixture stirred and heated under reflux for 3 h. After cooling the mixture was evaporated and the residue suspended in water and acid;ified to pH 2 followed by extraction with ethyl acetate. After drying and evaporation the resulting intermediate 1-(3,4-dimethyl-phenyl)-3-oxo-2,3-dihydro-1H-pyrazole-4-carboxylic acid; ethyl ester was dissolved in methanol (10.0 mL) and 10percent aqueous sodium hydroxide (10.0 mL) and stirred at room temperature for 3 h and then heated under reflux to effect hydrolysis. The solution was cooled and acid;ified to pH 4 with 3M aqu. hydrochloric acid; and stirred at room temperature for 2 h to effect decarboxylation. The mixture was extracted with ethyl acetate, dried and evaporated to give the title compound (87percent) as a yellow solid. 1H NMR (300 MHz, CDCl3) delta 7.61 (d, J=2.3 Hz, 1H), 7.55 (dd, J=8.2 and 2.3 Hz, 1H), 7.48 (t, J=1.3 Hz, 1H), 1.16 (d, J=8.2 Hz, 1H), 3.50 (d, J=1.3 Hz, 2H)

Reference： [1]Patent: US2004/19190,2004,A1 .Location in patent: Page 44

7
4-dimethylaminocyclohexanone hydrochloride [ No CAS ]
[ 60481-51-8 ]
[ 60481-52-9 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium hydroxide; In methanol; ethanol; hexane;	EXAMPLE 242 3-(Dimethylamino)-6,7-dimethyl-1,2,3,4-tetrahydrocarbazole A solution of 11.5 g. of 4-dimethylaminocyclohexanone hydrochloride and 11 g. of <strong>[60481-51-8]3,4-dimethylphenylhydrazine hydrochloride</strong> in 200 ml. of absolute ethyl alcohol was heated under reflux for 6 hours, cooled, filtered, and the filtrate was diluted with ether. The oily precipitate, which was collected by decantation and solidified on standing, was suspended in boiling isopropyl alcohol, filtered and dissolved in methyl alcohol. This solution was diluted with isopropyl alcohol and the methyl alcohol was removed by distillation. The cooled mixture was filtered to give 9.2 g. of a solid which was suspended in ether and treated with dilute potassium hydroxide. The ether extract was evaporated to dryness and the residue was suspended and boiled in hexane and filtered to give 3.2 g. of 3-(dimethylamino)-6,7-dimethyl-1,2,3,4-tetrahydrocarbazole, m.p. 183°-187°C.
	With potassium hydroxide; In methanol; ethanol; hexane;	EXAMPLE 242 3-(Dimethylamino)-6,7-dimethyl-1,2,3,4-tetrahydrocarbazole A solution of 11.5 g. of 4-dimethylaminocyclohexanone hydrochloride and 11 g. of <strong>[60481-51-8]3,4-dimethylphenylhydrazine hydrochloride</strong> in 200 ml. of absolute ethyl alcohol was heated under reflux for 6 hours, cooled, filtered, and the filtrate was diluted with ether. The oily precipitate, which was collected by decantation and solidified on standing, was suspended in boiling isopropyl alcohol, filtered and dissolved in methyl alcohol. This solution was diluted with isopropyl alcohol and the methyl alcohol was removed by distillation. The cooled mixture was filtered to give 9.2 g. of a solid which was suspended in ether and treated with dilute potassium hydroxide. The ether extract was evaporated to dryness and the residue was suspended and boiled in hexane and filtered to give 3.2 g. of 3-(dimethylamino)-6,7-dimethyl-1,2,3,4-tetrahydrocarbazole, m.p. 183°-187° C.

Reference： [1]Patent: US3959309,1976,A
[2]Patent: US4062864,1977,A

8
[ 41979-39-9 ]
[ 60481-51-8 ]
8,9-dimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole [ No CAS ]
7,8-Dimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	In ethanol; water; at 75℃; for 3h;	Example 8 7,8-Dimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole; To a solution of 1-<strong>[60481-51-8](3,4-dimethylphenyl)hydrazine hydrochloride</strong> (3.7 g, 21.5 mmol) and 4-piperidone hydrochloride monohydrate (3.3 g, 21.5 mmol) in EtOH (63.2 mL) was added 12 N HCl (5.4 ml, 64.5 mmol) at 75° C. The reaction mixture was stirred at 75° C. for 3 h, filtered and rinsed with cold EtOH to a 3:1 mixture of the title compound and its regio-isomer, (4.8 g, 17.6 mmol). The mixture (15 mg) was purified via HPLC (10-20percent CH3CN/H2O), to obtain the title compound (3.3 mg, 0.012 mmol): MS (ES) 201.22 (M+H).; Example 9 8,9-Dimethyl-2,3,4,5-tetrahydro-1H-pyrido[4,3-b]indole; The title compound was obtained as a minor product from the synthesis of example 8: MS (ES) 201.22 (M+H).

Reference： [1]Patent: US2007/27178,2007,A1 .Location in patent: Page/Page column 19-20

9
[ 1058738-02-5 ]
[ 60481-51-8 ]
[ 1083098-22-9 ]

Reference： [1]Heterocyclic Communications,2007,vol. 13,p. 359 - 366

10
[ 141-97-9 ]
[ 60481-51-8 ]
[ 925633-57-4 ]

Yield	Reaction Conditions	Operation in experiment
73%		Example 1; Preparation of 4-[2-(3-cyclohexyl-2-hydroxyphenyl)hydrazin-1-ylidene]-1-(3,4-dimethylphenyl)-3-methyl-4,5-dihydro-1H-pyrazol-5-one; Step 1:; Compound 1a (<strong>[60481-51-8]3,4-dimethylphenylhydrazine hydrochloride</strong>, Acros Catalog Number 408510250) (0.50 g, 2.9 mmol), ethyl acetoacetate (0.38 g, 2.9 mmol), and sodium acetate (0.24 g, 2.9 mmol) were heated in acetic acid (8 mL) to reflux at an oil bath temperature of 155 deg C. for 12 hours. The dark brown solution was allowed to cool, and the solvent was removed under reduced pressure. The brown residue was dissolved in ethyl ether (100 mL), washed sequentially with saturated sodium bicarbonate (3.x.10 mL), and saturated sodium chloride (3.x.10 mL) and dried over sodium sulfate. The solvent was removed under reduced pressure. The mixture was purified by silica gel chromatography with 40percent ethyl acetate-hexanes as eluant to afford Compound 1b as a brown oil which solidified upon standing (0.43 g, 73percent) (i.e., compound (v) in U.S. Pat. No. 7,160,870 B2 herein incorporated by reference in its entirety). 1H NMR (400 MHz, DMSO-d6) delta 11.24 (1H, s), 7.46 (1H, s), 7.39 (1H, dd, J=8.0, 2.0 Hz), 7.15 (1H, d, J=8.0 Hz), 5.34 (1H, s), 2.24 (3H, s), 2.21 (3H, s), 2.09 (3H, s).
71%	With sodium acetate; acetic acid; at 118℃; for 24h;	2-(3,4-Dimethylphenyl)hydrazinium chloride (900 g, 5.21 mol), ethyl acetoacetate (678 g, 5.21 mol), sodium acetate (428 g, 5.21 mol) and glacial acetic acid (10 L) were stirred at 118° C. for about 24 hours. The resulting mixture was cooled and concentrated, and the residue was dissolved in dichloromethane (10 L) and carefully washed with saturated sodium bicarbonate (3.x.3 L). The organic layer was concentrated to afford a solid. The solid was dissolved in ethanol (450 mL) under reflux. Petroleum ether (7.2 L) was slowly added, and the resulting mixture was cooled and filtered to afford the title compound (748 g, 71percent). PXRD analysis provided the diffractogram as shown in FIG. 31.

Reference： [1]Patent: US2008/139621,2008,A1 .Location in patent: Page/Page column 36
[2]Patent: US2010/256212,2010,A1 .Location in patent: Page/Page column 16

11
[ 60481-51-8 ]
[ 42837-61-6 ]
[ 1252577-81-3 ]

Reference： [1]Tetrahedron,2010,vol. 66,p. 5442 - 5450

12
[ 59997-51-2 ]
[ 60481-51-8 ]
[ 1025893-78-0 ]

Yield	Reaction Conditions	Operation in experiment
90%	In ethanol; for 5h;Reflux;	a. 5-tert-Butyl-2-(3,4-dimethyl-phenyl)-2H-pyrazol-3-ylamine (Intermediate Ja) A black solution of <strong>[60481-51-8]3,4-dimethylphenyl hydrazine hydrochloride</strong> (Apollo, 1.73 g, 10.0 mmol) and 4,4-dimethyl-3-oxopentanenitrile (1.38 g, 11.0 mmol) in EtOH (20 mL) was stirred at reflux for 5 h. The cooled solution was concentrated in vacuo, redissolved in diethyl ether (20 mL) and washed with aqueous NaOH solution (1M, 20 mL). The aqueous was extracted with diethyl ether (2*20 mL), then the combined organics washed with brine (20 mL), dried (Na2SO4), filtered and concentrated in vacuo to leave the title compound (2.18 g, 90percent). LCMS (Method 3): Rt 2.75 min, m/z 244 [MH+].
90%	In ethanol; for 5h;Reflux;	A black solution of <strong>[60481-51-8]3,4-dimethylphenyl hydrazine hydrochloride</strong> (Apollo, 1.73 g, 10.0 mmol) and 4,4-dimethyl-3-oxopentanenitrile (1.38 g, 11.0 mmol) in EtOH (20 mL) was stirred at reflux for 5 h. The cooled solution was concentrated in vacuo, redissolved in diethyl ether (20 mL) and washed with aqueous NaOH solution (1M, 20 mL). The aqueous was extracted with diethyl ether (2 x 20 mL), then the combined organics washed with brine (20 mL), dried (Na2S04), filtered and concentrated in vacuo to leave the title compound (2.18 g, 90percent). LCMS (Method 3): Rt 2.75 min, m/z 244 [MH+].
490 mg	With triethylamine; In toluene; for 5h;Reflux;	Example 62 3-(tert-butyl)-1-(3,4-dimethylphenyl)-1H-pyrazol-5-amine To a solution of pivaloylacetonitrile (400 mg) in toluene (10 mL) were added <strong>[60481-51-8]3,4-dimethylphenylhydrazine hydrochloride</strong> (520 mg) and triethylamine (0.4 mL) and refluxed with heating for 5 hours. The reaction mixture was added with a saturated sodium hydrogen carbonate aqueous solution. The obtained organic layer was washed with a saturated sodium chloride aqueous solution. The obtained organic layer was dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The obtained residue was purified on silica gel column chromatography (hexane : ethyl acetate = 4 : 1) to give the titled compound (490 mg) having the following physical data. TCL : Rf 0.41 (Hexane : Ethyl Acetate = 4 : 1).

Reference： [1]Organic Process Research and Development,2010,vol. 14,p. 650 - 656
[2]Patent: US2014/364412,2014,A1 .Location in patent: Paragraph 0495; 0496
[3]Patent: WO2014/195402,2014,A1 .Location in patent: Page/Page column 106
[4]Organic Process Research and Development,2011,vol. 15,p. 841 - 854
[5]Patent: EP2842955,2015,A1 .Location in patent: Paragraph 0260

13
C₁₆H₂₅NO [ No CAS ]
[ 60481-51-8 ]
1-(3,4-dimethylphenyl)-5-(2,6,6-trimethyl-2-cyclohex-1-yl)ethenyl-1H-pyrazole [ No CAS ]
1-(3,4-dimethylphenyl)-3-(2,6,6-trimethyl-2-cyclohex-1-yl)ethenyl-1H-pyrazole [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
60%; 15%	In ethanol; at 50℃; for 1h;	General procedure: The hydrazines (method 2) or hydrazine hydrochlorides (2 mmol) (method 1) were added in one portion to a stirred solution of enammines (2 mmol) in acidified ethanol (10 mL containing 0.17 mL of HCl 37percent) (method 2) or ethanol (10 mL) (method 1). The resulting solution was stirred for different time at different temperatures. After cooling, several compounds were collected from the reaction mixture by filtration and then crystallized; other compounds were obtained by silica gel chromatography of the residue after removal of the solvent.

Reference： [1]European Journal of Medicinal Chemistry,2011,vol. 46,p. 5293 - 5309

14
[ 3949-36-8 ]
[ 60481-51-8 ]
[ 1448308-25-5 ]

Yield	Reaction Conditions	Operation in experiment
82%	With acetic acid; In methanol; water; at 60℃; for 0.5h;	General procedure: Phenylhydrazine hydrochloride 6a (0.160 g,1.1 mmol) in mixture of H2O and AcOH was added to a stirred solution of 4-chloro-2-oxo-2H-chromene-3-carbaldehyde 5a (0.208 g,1.0 mmol) in methanol at 60 °C and the reaction was continued for another 30 min at same temperature. The reactionwas monitored by TLC and an orangeered precipitate formation was observed. After completion of the reaction, the reaction mixture was cooled to room temperature, precipitate was filtered off, and the resulted precipitate was dissolved in ethyl acetate and washed with cold water to remove the acetic acid. The organic layer was separated and dried over Na2SO4, solvent was removed under reduced pressure afforded (E)-4-chloro-3-((2-phenylhydrazono)methyl)-2H-chromen-2-one (7a, 0.275 g) as orange color sold in 92percent yield.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 65,p. 389 - 402

15
[ 60481-51-8 ]
[ 1450908-84-5 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 4524 - 4527

16
[ 924-44-7 ]
[ 60481-51-8 ]
[ 1450909-04-2 ]

Reference： [1]Organic Letters,2013,vol. 15,p. 4524 - 4527

17
[ 1149371-93-6 ]
[ 60481-51-8 ]
C₃₁H₄₆N₂O₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium acetate; In ethanol; at 78℃;	General procedure: A mixture of compound 5 (0.360 g, 1 mmol) and various phenylhydrazines 6a-6ad (0.145-0.225 g,1 mmol) in dry EtOH (10 mL) were stirred at 78°C in the presence of CH3COONa (0.099 g,1.2 mmol). After completion of the reaction monitored by TLC, the solution was then poured into water (10 mL), the white precipitate was filtered and washed with water and dried. The crude product was recrystallized from ethyl acetate/light petroleum ether to give compounds 7a-7ad. Then to a solution of compounds 7a-7ad(0.450-0.529 g, 1 mmol) in toluene (5 mL), 48percent BF3*OEt2 (48percent solution in Et2O, 0.05 mL, 0.17 mmol) was added dropwise and the mixture was heated under a nitrogen atmosphere at 118°C. After completion of the reaction monitored by TLC, water (10 mL) was added to the mixture, which was next neutralized with NaHCO3, and the organic phase was separated and dried over Na2SO4. After evaporation in vacuo, the crude product was purified by column chromatography to give product 9a-9ad.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 65,p. 70 - 82

18
C₂₃H₃₄O₄ [ No CAS ]
[ 60481-51-8 ]
[ 1448583-07-0 ]

Yield	Reaction Conditions	Operation in experiment
59%	In isopropyl alcohol;Reflux;	General procedure: A mixture of compound 10 (0.376 g, 1 mmol) and various phenylhydrazines 6a-6ad (0.145-0.225 g, 1 mmol) in isopropanol (10 mL) were stirred under reflux. After completion of the reaction monitored by TLC, the reaction mixture was concentrated under vacuum, and extracted with CH3CO2C2H5 and H2O. At last the organic layer was washed with saturated NaCl aqueous solution, dried with Na2SO4 and concentrated under vacuum. The residue was purified by column chromatography on silica to give product 11a-11ad.

Reference： [1]European Journal of Medicinal Chemistry,2013,vol. 65,p. 70 - 82

19
[ 95-64-7 ]
[ 60481-51-8 ]

Yield	Reaction Conditions	Operation in experiment
63%		3,4-dimethylaniline (3 kg, 24.75 mol) was added to 19 L of water, heated to 40-50°C to dissolve, and cooled to room temperature.Add 9.3L concentrated hydrochloric acid and continue to cool down to 0-5 °C.Slowly add NaNO2 solution (1.8kg NaNO2 dissolved in 2.7L water),Control temperature does not exceed 10°C; after the dropwise addition, the reaction was carried out at 0-5 ° C for 1 h to form a diazonium salt solution; dissolve Na2SO3 (7.8kg, 61.89mol) in 33L water, warm to 70 ° C, add NaOH solution (1.2kg NaOH dissolved in 12L water), slowly add diazonium salt solution, adjust pH to 6-7 after adding.The reaction was carried out at 70 ° C for 2-3 hours; 150 g of zinc powder was added, and the reaction was continued at 70°C for 1 h, 12 L of concentrated hydrochloric acid was added, and the mixture was heated to 80-85 ° C for 1 h.The mixture was decanted to room temperature, and the crude product was filtered. The crude product was then taken to 30L of ethyl acetate for 3h, filtered, and the filter cake was collected and dried at 40 ° C to obtain about 2.7 kg of product in a yield of about 63percent.
11.8 g		3,4-dimethyl aniline (12.2g, 0.1mol) in 50ml and 20ml of concentrated hydrochloric acidmixed uniformly in water, cooling to below 0 , with mechanical stirring, to which the solution of sodium nitriteaqueous solution (7.6g, 0.11 mol), maintaining the reaction temperature at 0 , stirring was continued for 0.5h,and thereto was added stannous chloride (56.5g, 0.25mol) in concentrated hydrochloric acid (20ml),naturally to room temperature, TLC monitored the reaction was complete feed.Suction filtration, the filter cake dried to give 3,4-dimethylphenylhydrazine hydrochloride (11.8g).

Reference： [1]Patent: CN109438359,2019,A .Location in patent: Paragraph 0020; 0028; 0029
[2]Angewandte Chemie - International Edition,2013,vol. 52,p. 12426 - 12429
Angew. Chem.,2013,vol. 125,p. 12652 - 12656,4
[3]Patent: CN103360317,2016,B .Location in patent: Paragraph 0095; 0105; 0106; 0107

20
[ 60481-51-8 ]
[ 38829-72-0 ]

Reference： [1]Angewandte Chemie - International Edition,2013,vol. 52,p. 12426 - 12429
Angew. Chem.,2013,vol. 125,p. 12652 - 12656,4

21
[ 108-24-7 ]
[ 60481-51-8 ]
[ 374924-94-4 ]

Reference： [1]Angewandte Chemie - International Edition,2013,vol. 52,p. 12426 - 12429
Angew. Chem.,2013,vol. 125,p. 12652 - 12656,4
[2]Organic and Biomolecular Chemistry,2014,vol. 12,p. 5469 - 5476

22
[ 29509-06-6 ]
[ 60481-51-8 ]
[ 1226269-75-5 ]

Yield	Reaction Conditions	Operation in experiment
67%	With hydrogenchloride; In ethanol; for 18h;Reflux;	Intermediate A18: 1-(3,4-Dimethylphenyl)-3-isopropyl-1 H-pyrazol-5-amine. Intermediate A18 To a solution of <strong>[60481-51-8](3,4-dimethylphenyl)hydrazine hydrochloride</strong> (3.0 g, 17 mmol) and 4-methyl- 3-oxopentanenitrile (2.3 mL, 19 mmol) in EtOH (20 mL) was added concentrated hydrochloric acid (1.7 mL, 12 M, 20 mmol). The reaction mixture was heated to reflux for 18 hr and was then cooled to RT and evaporated in vacuo. The residue was partitioned between DCM (50 mL) and water (20 mL). The aq phase was separated and was extracted with DCM (2 x 50 mL). The combined organic extracts were dried and evaporated in vacuo and the residue was purified by flash column chromatography (Si02, 80 g, 0-100percent Et20 in isohexane, gradient elution) to afford the title compound, Intermediate A18 as an orange oil (2.69 g, 67percent); Rl 1.49 min (Method 2 acidic); m/z 230 (M+H)+, (ES+).

Reference： [1]Patent: WO2014/27209,2014,A1 .Location in patent: Page/Page column 60

23
[ 1384519-04-3 ]
[ 60481-51-8 ]
[ 1583273-10-2 ]

Yield	Reaction Conditions	Operation in experiment
66%	With acetic acid; In ethanol; at 20℃;Reflux;	General procedure: Compound (E)-ethyl 3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylate (3a, 100 mg, 0.4 mmol) was dissolved in absolute ethanol (3 mL), phenylhydrazine hydrochloride (5a, 62 mg,0.4 mmol) and acetic acid (0.06 mL, 0.06 mmol) were added atroom temperature, and the resulting mixture was refluxed for 4 h.The reaction was monitored by TLC and after completion of thereaction (TLC), the reaction mixture was brought to room temperatureand solvent was removed under reduced pressure; diluted with water and extracted with ethyl acetate. The organic layer wasdried over Na2SO4, solvent was removed under reduced pressure,and the residue was purified by column chromatography usingsilica gel (hexane/ethyl acetate) provided 6a in 80percent yield. Similarlyother benzoxepinopyrazolones 6b-t were prepared from corresponding3-oxo-2,3-dihydrobenzo[b]oxepine-4-carboxylates 3bed with substituted phenylhydrazine hydrochlorides 5b-k.

Reference： [1]European Journal of Medicinal Chemistry,2014,vol. 76,p. 460 - 469

24
[ 126443-11-6 ]
[ 60481-51-8 ]
[ 1607062-44-1 ]

Yield	Reaction Conditions	Operation in experiment
85%		General procedure: For the synthesis of compounds (1b?12b), 25mL of acetic acid solution of the respective 4-alkoxychalcone (0.01mol) (1a?12a) containing a few drops of hydrochloric acid was heated at 60?65°C for 30min with constant stirring in a round bottom flask. (3,4-Dimethylphenyl)hydrazine hydrochloride (3.45g, 0.02mol) was then added to the reaction flask and the reaction mixture was heated to reflux for 5?6h. After that, the reaction mixture was cooled to room temperature and poured onto the crushed ice. The precipitates thus formed, were filtered, washed with distilled water and dried. The crude products were further purified by silica gel column chromatography using petroleum ether/ethyl acetate (4:1) as the mobile phase to get pure compounds 1b?12b in excellent yields for spectral characterization and fluorescence properties.