97-36-9

Basic information

• Product Name: 2',4'-Dimethylacetoacetanilide
• Synonyms: 2',4'-ACETOACETOXYLIDIDE;2',4'-DIMETHYLACETOACETANILIDE;AAMX;ACETOACETIC ACID-M-XYLIDID-2,4;ACETOACET-M-XYLIDIDE;ACETO ACET M-XYLIDINE;ACETOACET-2,4-XYLIDIDE;LABOTEST-BB LT01274614
• CAS NO: 97-36-9
• Molecular Formula: C₁₂H₁₅NO₂
• Molecular Weight: 205.25
• EINECS: 202-576-0
• Product Categories: Intermediates of Dyes and Pigments;Aromatic amine products
• Mol File: 97-36-9.mol
• Article Data: 9

Chemical Properties

• Melting Point: 88-91 °C(lit.)
• Boiling Point: 343.93°C (rough estimate)
• Flash Point: 171 °C
• Appearance: White to off white powder
• Density: 1.24
• Vapor Pressure: 1.57E-05mmHg at 25°C
• Refractive Index: 1.5160 (estimate)
• Storage Temp.: 2-8°C
• Solubility: Chloroform (Slightly), Methanol (Slightly)
• PKA: 11.33±0.46(Predicted)
• CAS DataBase Reference: 2',4'-Dimethylacetoacetanilide(CAS DataBase Reference)
• NIST Chemistry Reference: 2',4'-Dimethylacetoacetanilide(97-36-9)
• EPA Substance Registry System: 2',4'-Dimethylacetoacetanilide(97-36-9)

Safety Data

• Hazard Codes: Xn
• Statements: 22
• Safety Statements: 24/25
• WGK Germany: 1
• RTECS: AK4585000
• Hazardous Substances Data: 97-36-9(Hazardous Substances Data)

Usage

Chemical Properties

White to off-white powder

Uses

2',4'-DiMethylacetoacetanilide is used as intermediate for the manufacture of organic pigments.

InChI:InChI=1/C12H15NO2/c1-8-4-5-11(9(2)6-8)13-12(15)7-10(3)14/h4-6H,7H2,1-3H3,(H,13,15)

Synthetic route

4-methyleneoxetan-2-one (674-82-8) + 2,4-Xylidine (95-68-1) → m-acetoacetoxylidide (97-36-9)

Conditions	Yield
In ethanol at 23 - 40℃; for 4.5h; Temperature; Solvent; Inert atmosphere; Autoclave; Large scale;	98%
With benzene
In water at 73 - 81℃; under 18.7519 - 277.528 Torr; Product distribution / selectivity; Heating / reflux;
In benzene Heating;

ethyl acetoacetate (141-97-9) + 2,4-Xylidine (95-68-1) → m-acetoacetoxylidide (97-36-9)

Conditions	Yield
With sodium hydroxide In water; toluene for 12h; Reflux;	78%

3-(2,4-dimethylphenylamino)-2-[(2,4-dimethylphenylimino)methyl]-acrylonitrile (1352630-25-1) + 2,2,6-trimethyl-4H-1,3-dioxin-4-one (5394-63-8) → m-acetoacetoxylidide (97-36-9) + 5-acetyl-1-(2,4-dimethylphenyl)-6-oxo-1,6-dihydropyridine-3-carbonitrile (1352630-37-5)

Conditions	Yield
In toluene at 110℃; for 0.333333h; Inert atmosphere;	A n/a B 78%

2,4-Xylidine (95-68-1) → m-acetoacetoxylidide (97-36-9)

m-acetoacetoxylidide (97-36-9) → N-(2,4-dimethylphenyl)-2-fluoro-3-oxobutanamide (1371607-83-8)

Conditions	Yield
With Selectfluor In PEG-400 at 60℃; for 5h;	99%
With Selectfluor In water; acetonitrile at 20℃; for 4h; Schlenk technique; Sealed tube; chemoselective reaction;	90%

m-acetoacetoxylidide (97-36-9) → N-(2,4-dimethylphenyl)-2,2-difluoro-3-oxobutanamide (1439365-70-4)

Conditions	Yield
With 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2 2 2]octane bis(tetrafluoroborate); potassium carbonate In water at 20℃; for 29h;	99%
With Selectfluor In water; acetonitrile at 20℃; for 16h; Schlenk technique; Sealed tube; chemoselective reaction;	88%

3,3'-dichlorobenzidine (91-94-1) + m-acetoacetoxylidide (97-36-9) → pigment yellow 13

Conditions	Yield
With hydrogenchloride; sodium nitrite In water at 20℃; for 0.333333h; Green chemistry;	99%

1,4-dibromo-butane (110-52-1) + m-acetoacetoxylidide (97-36-9) → 1-acetyl-N-(2,4-dimethylphenyl)cyclopentanecarboxamide

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide	96%
With potassium carbonate In N,N-dimethyl-formamide at 20℃;
Stage #1: m-acetoacetoxylidide With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 1,4-dibromo-butane In N,N-dimethyl-formamide at 20℃;

m-acetoacetoxylidide (97-36-9) + 1,3-dibromo-propane (109-64-8) → 1-[6-(2,4-dimethylphenylamino)-3,4-dihydro-2H-pyran-5-yl]ethanone (958650-22-1)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 7h;	95%

3-bromo-4H-chromen-4-one (49619-82-1) + m-acetoacetoxylidide (97-36-9) → 1-{2-[(2,4-dimethylphenyl)amino]-5-[(2-hydroxyphenyl)carbonyl]furan-3-yl}ethan-1-one

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In 1,4-dioxane at 20℃; regioselective reaction;	93%

m-acetoacetoxylidide (97-36-9) → C24H26N2O2 (1182302-49-3)

Conditions	Yield
With N,N,N',N'-tetramethylchlorformamidinium chloride; triethylamine In N,N-dimethyl-formamide at 20℃; for 0.25h;	92%

carbon disulfide (75-15-0) + ethyl bromide (74-96-4) + m-acetoacetoxylidide (97-36-9) → 2-(bis(ethylthio)methylene)-N-(2,4-dimethylphenyl)-3-oxobutanamide

Conditions	Yield
Stage #1: carbon disulfide; m-acetoacetoxylidide With potassium carbonate In N,N-dimethyl-formamide at 0℃; for 0.5h; Stage #2: ethyl bromide In N,N-dimethyl-formamide at 20℃; for 24h;	92%
Stage #1: m-acetoacetoxylidide With potassium carbonate In N,N-dimethyl-formamide Stage #2: carbon disulfide In N,N-dimethyl-formamide Stage #3: ethyl bromide In N,N-dimethyl-formamide at 20℃;

10-ethyl-10H-phenothiazine-3-carbaldehyde (18413-61-1) + m-acetoacetoxylidide (97-36-9) + urea (57-13-6) → C28H28N4O2S

Conditions	Yield
With toluene-4-sulfonic acid In ethanol for 12h; Reflux;	92%

m-acetoacetoxylidide (97-36-9) + benzohydroximoyl chloride (698-16-8) → N-(2,4-dimethylphenyl)-5-methyl-3-phenylisoxazole-4-carboxamide

Conditions	Yield
With triethylamine; N,N,N',N'-tetramethylguanidine In methanol at 80℃; for 48h; regioselective reaction;	91%

m-acetoacetoxylidide (97-36-9) + malononitrile (109-77-3) → 1-(2,4-dimethyl-phenyl)-2-imino-4-methyl-6-oxo-1,2,5,6-tetrahydro-pyridine-3-carbonitrile

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 4h;	91%

m-acetoacetoxylidide (97-36-9) + phenyl isothiocyanate (103-72-0) → 3-anilino-N-(2,4-dimethylphenyl)-3-thioxopropanamide (1149748-02-6)

Conditions	Yield
Stage #1: m-acetoacetoxylidide With potassium carbonate In ethanol at 20℃; Stage #2: phenyl isothiocyanate In ethanol for 1.7h; Reflux;	90%

m-acetoacetoxylidide (97-36-9) + indole-2,3-dione (91-56-5) → 4,4'-((2-oxoindoline-3,3-diyl)bis(methylene))bis(2-(2,4-dimethylphenyl)-1H-pyrrolo[3,4-c]quinoline-1,3(2H)-dione)

Conditions	Yield
With toluene-4-sulfonic acid In ethanol at 80℃;	90%

Phenylpropargyl aldehyde (2579-22-8) + m-acetoacetoxylidide (97-36-9) → 3-acetyl-1-(2,4-dimethylphenyl)-4-phenylpyridin-2(1H)-one

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 65℃; for 10h; Green chemistry; regioselective reaction;	89%

m-acetoacetoxylidide (97-36-9) + 4-chlorobenzaldehyde (104-88-1) + dimedone (126-81-8) → 4-(4-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylic acid 2,4-dimethylphenylamide (1276306-85-4)

Conditions	Yield
With ammonium acetate at 150 - 160℃;	87%

m-acetoacetoxylidide (97-36-9) + salicylaldehyde (90-02-8) + urea (57-13-6) → N-(2,4-dimethylphenyl)-2-methyl-4-oxo-3,4,5,6-tetrahydro-2H-2,6-methano-1,3,5-benzoxadiazocine-11-carboxamide

Conditions	Yield
With sodium hydrogen sulfate In ethanol for 1h; Reflux;	87%

m-acetoacetoxylidide (97-36-9) + Phenyl azide (622-37-7) → N-(2,4-dimethylphenyl)-5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxamide (866871-73-0)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In chloroform at 20℃; for 24h; regioselective reaction;	86%
With 1,8-diazabicyclo[5.4.0]undec-7-ene In chloroform at 20℃; for 24h; Inert atmosphere;	86%

m-acetoacetoxylidide (97-36-9) + dimethyl(prop-2-yn-1-yl)sulfonium bromide (23451-62-9) → 1-{2-[(2,4-dimethylphenyl)amino]-4-methylfuran-3-yl}ethanone

Conditions	Yield
With caesium carbonate In N,N-dimethyl-formamide at 20℃; for 0.75h; chemoselective reaction;	86%

m-acetoacetoxylidide (97-36-9) + cyanomethyl bromide (590-17-0) → 2-(cyanomethyl)-N-(2,4-dimethylphenyl)-3-oxobutanamide

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide	85%

m-acetoacetoxylidide (97-36-9) + L-proline (147-85-3) → N-(2,4-dimethylphenyl)pyrrolidine-1-carboxamide (35938-97-7)

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; for 3h;	85%

m-acetoacetoxylidide (97-36-9) + 3,4-dimethoxy-benzaldehyde (120-14-9) + 5-amino-1H-pyrazole-4-carboxylic acid amide (5334-31-6) → 5-(3,4-dimethoxyphenyl)-N6-(2,4-dimethylphenyl)-7-hydroxy-7-methyl-4,5,6,7-tetrahydropyrazolo[1,5-a]pyrimidine-3,6-dicarboxamide

Conditions	Yield
In ethanol at 25℃; for 1.5h; Sonication;	85%

m-acetoacetoxylidide (97-36-9) + 2,6-di-tert-butyl-4-(2-hydroxybenzylidene)-2,5-cyclohexadiene-1-one → C33H43NO4

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In dichloromethane at 20℃; for 48h; Inert atmosphere;	85%

10-ethyl-10H-phenothiazine-3-carbaldehyde (18413-61-1) + m-acetoacetoxylidide (97-36-9) → C39H40N4O2S

Conditions	Yield
With ammonium acetate; toluene-4-sulfonic acid In ethanol Reflux;	84%

3-amino-5-tert-butylisoxazole (55809-36-4) + m-acetoacetoxylidide (97-36-9) → 2-(2-(5-tert-butylisoxazol-3-yl)hydrazono)-N-(2,4-dimethylphenyl)-3-oxobutanamide

Conditions	Yield
Stage #1: 3-amino-5-tert-butylisoxazole With phosphoric acid; sodium nitrite In water at -5 - 5℃; for 2h; Stage #2: m-acetoacetoxylidide With sodium hydroxide In water at -5 - 20℃; pH=8 - 10; Further stages.;	83.5%

m-acetoacetoxylidide (97-36-9) → 5-methyl-2-(2,4-dimethylphenyl)isoxazole-3(2H)-one (1417647-06-3)

Conditions	Yield
With [bis(acetoxy)iodo]benzene; zinc(II) oxide In 1,4-dioxane at 100℃; for 5h; Schlenk technique;	83%

5-methoxyisatine (39755-95-8) + m-acetoacetoxylidide (97-36-9) → 4,4'-((5-methoxy-2-oxoindoline-3,3-diyl)bis(methylene)) bis(2-(2,4-dimethylphenyl)-8-methoxy-1H-pyrrolo[3,4-c] quinoline-1,3(2H)-dione)

Conditions	Yield
With toluene-4-sulfonic acid In ethanol at 80℃;	82%

Upstream product

• 141-97-9 ethyl acetoacetate 
• 95-68-1 2,4-Xylidine 
• 1352630-25-1 3-(2,4-dimethylphenylamino)-2-[(2,4-dimethylphenylimino)methyl]-acrylonitrile 
• 5394-63-8 2,2,6-trimethyl-4H-1,3-dioxin-4-one 
• 674-82-8 4-methyleneoxetan-2-one 

Downstream Products

• 13888-26-1 2-(o-Tolyloxyimino-carbonyl)-acetessigsaeure-(2,4-dimethylanilid) 
• 958650-22-1 1-[6-(2,4-dimethylphenylamino)-3,4-dihydro-2H-pyran-5-yl]ethanone 
• 1092368-99-4 2-((dimethylamino)methylene)-N-(2,4-dimethylphenyl)-3-oxobutanamide 
• 124236-34-6 C₃₆H₃₃Cl₃N₆O₆ 
• 455927-05-6 N-(2,4-dimethylphenyl)-4-methyl-6-phenyl-2-thioxo-1,2,3,6-tetrahydropyrimidine-5-carboxamide 
• 681472-85-5 4-methyl-N-(2,4-dimethylphenyl)-2-oxo-6-phenyl-1,2,3,6-tetrahydropyrimidine-5-carboxamide 
• 1349163-31-0 7-(3,4-dimethoxyphenyl)-N₆-(2,4-dimethylphenyl)-5-methyl-4,7-dihydropyrazolo[1,5-a]pyrimidine-3,6-dicarboxamide 
• 1276306-85-4 4-(4-chlorophenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylic acid 2,4-dimethylphenylamide 
• 1282955-27-4 2,7,7-trimethyl-4-(3-nitrophenyl)-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylic acid 2,4-dimethylphenylamide 
• 1282452-28-1 2,7,7-trimethyl-4-(4-nitrophenyl)-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylic acid 2,4-dimethylphenylamide 
• 1285112-70-0 4-(4-methoxyphenyl)-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylic acid 2,4-dimethylphenylamide 
• 1371607-83-8 N-(2,4-dimethylphenyl)-2-fluoro-3-oxobutanamide 
• 1393729-25-3 N,1-bis(2,4-dimethylphenyl)-2,6-dimethyl-4-oxo-1,4-dihydropyridine-3-carboxamide 

Relevant articles and documents

Phenothiazine and amide-ornamented novel nitrogen heterocyclic hybrids: synthesis, biological and molecular docking studies

The synthesis of novel hybrids, namely, phenothiazine and amide-ornamented nitrogen heterocycles (25-34) has been accomplished utilizing a multi-step synthetic protocol and the structures have been established based on physical and spectral techniques. Of these, the hybrids possessing meta-nitro (26), para-fluoro (28), meta- and para-methyl (31), ortho-bromo (33) and ortho- and para-dimethyl (34) phenyl carboxamide scaffolds exhibited superior anti-inflammatory profiles over the standard diclofenac sodium. A hybrid integrated with a para-fluorophenyl carboxamide moiety (28) showed the highest DPPH radical scavenging activity among the chemical entities synthesized. Furthermore, the results of anticancer evaluations implied that the hybrid tethered with a phenyl carboxamide structural unit (29) exerted superior activity when compared with other hybrids against the pancreatic cancer cells SW1990 and AsPC1. Molecular docking between the hybrid 29 and B-cell lymphoma 2 reflects its appreciable binding affinity (-8.84 kcal mol-1). The results revealed that these chemical entities can serve as potent biological agents and/or efficient intermediates for the construction of potent biological agents.

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The invention provides a preparation method of an acetoacetanilide compound. The method comprises the steps of performing diacetylation reaction on aniline compounds and diketene in an organic solvent under anaerobic conditions to obtain the acetoacetanilide compound. The acetoacetanilide compound is prepared under the anaerobic conditions; the acetoacetanilide compound prepared by using the method has a relatively high melting point, thereby being beneficial for applications of the acetoacetanilide compound. In addition, the acetoacetanilide compound prepared by using the method provided by the invention is not easy to agglomerate, and the preparation method of the acetoacetanilide compound, provided by the invention, is relatively low in energy consumption. Experimental results show that the melting point of the acetoacetanilide compound prepared by using the method provided by the invention is 82.5-103 DEG C.

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