537-92-8

Basic information

• Product Name: 3'-Methylacetanilide
• Synonyms: m-Methyl Acetanilide m-Acetotoluidide;ACETYL-META-TOLUIDINE;N-ACETYL-META-TOLUIDINE;3-METHYLACETANILIDE / M-ACETOTOLUIDIDE;3-METHYLACETANILIDE 98%;3-Acetaminotoluene;N-Acetyltoluidine;N-Acetotoluidine
• CAS NO: 537-92-8
• Molecular Formula: C₉H₁₁NO
• Molecular Weight: 149.19
• EINECS: 208-678-1
• Product Categories: Anilines, Amides & Amines;Aromatics;Mutagenesis Research Chemicals
• Mol File: 537-92-8.mol
• Article Data: 133

Chemical Properties

• Melting Point: 65-67 °C(lit.)
• Boiling Point: 303 °C(lit.)
• Flash Point: 175.156 °C
• Appearance: white crystalline solid
• Density: 1.1410
• Vapor Pressure: 16 mm Hg ( 163 °C)
• Refractive Index: 1.5279 (estimate)
• Storage Temp.: Inert atmosphere,Room Temperature
• Solubility: alcohol: freely soluble(lit.)
• PKA: 15.12±0.70(Predicted)
• Stability: Stable. Incompatible with strong oxidizing agents.
• Merck: 14,74
• CAS DataBase Reference: 3'-Methylacetanilide(CAS DataBase Reference)
• NIST Chemistry Reference: 3'-Methylacetanilide(537-92-8)
• EPA Substance Registry System: 3'-Methylacetanilide(537-92-8)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 22-36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• RTECS: AN2875000
• Hazardous Substances Data: 537-92-8(Hazardous Substances Data)

Usage

Chemical Properties

white crystalline solid

General Description

White solid.

Air & Water Reactions

Water insoluble.

Reactivity Profile

3'-Methylacetanilide is an amide. Flammable gases are formed by the reaction of organic amides with strong reducing agents. Amides are very weak bases (weaker than water). Imides are less basic yet and in fact react with strong bases to form salts. That is, they can react as acids. Mixing amides with dehydrating agents such as P2O5 or SOCl2 generates the corresponding nitrile. The combustion of these compounds generates mixed oxides of nitrogen (NOx).

Health Hazard

ACUTE/CHRONIC HAZARDS: When heated to decomposition 3'-Methylacetanilide emits toxic fumes of nitrogen oxides.

Fire Hazard

Flash point data for 3'-Methylacetanilide are not available; however, 3'-Methylacetanilide is probably combustible.

Safety Profile

Moderately toxic by ingestion. Seealso p-ACETOTOLUIDIDE. When heated todecomposition it emits toxic fumes of NOx.

Purification Methods

Crystallise the toluidide from H2O, EtOH, aqueous EtOH or Et2O/pet ether (m 66o). UV: max 245nm (EtOH). [Beilstein 12 H 860, 12 I 400, 12 II 468, 12 III 1962, 12 IV 1823.]

Synthetic route

acetic anhydride (108-24-7) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In dichloromethane at 20℃; Inert atmosphere;	100%
With cadmium(II) oxide at 80℃; for 0.166667h; Neat (no solvent); Microwave irradiation;	97%
With pyridine; aluminum oxide at 129 - 131℃; for 2h; microwave irradiation;	96%

acetyl chloride (75-36-5) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In dichloromethane at 0 - 20℃;	100%
With hydroxyapatite supported copper(I) oxide In acetonitrile at 50℃; for 0.116667h;	92%
With triethylamine In dichloromethane at 0 - 25℃;	92%

1-methyl-3-nitrobenzene (99-08-1) + acetic anhydride (108-24-7) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With indium; acetic acid In methanol at 20℃; for 1h;	99%
Stage #1: 1-methyl-3-nitrobenzene With sodium tetrahydroborate In water at 60 - 70℃; Green chemistry; Stage #2: acetic anhydride In water at 60 - 70℃; Green chemistry;	94%
Stage #1: 1-methyl-3-nitrobenzene In water for 0.0833333h; Stage #2: With sodium tetrahydroborate In water at 65℃; for 0.05h; Stage #3: acetic anhydride In water at 65℃; for 0.0333333h; Catalytic behavior;	93%

1-acetyl-2,3,4,6,7,8-hexahydropyrrolo[1,2-a]pyrimidinium tetraphenylborate (1363906-80-2) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In acetonitrile at 80℃; for 24h; Inert atmosphere;	99%

tungsten hexacarbonyl (14040-11-0) + 1-methyl-3-nitrobenzene (99-08-1) + carbonic acid dimethyl ester (616-38-6) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With di(rhodium)tetracarbonyl dichloride; 1,3-bis-(diphenylphosphino)propane; sodium phosphate; sodium iodide In water at 120℃; for 24h; Inert atmosphere; Sealed tube;	99%

formaldehyd (50-00-0) + N,N'-Bis(3-methylphenyl)guanidine (51131-78-3) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With platinum(II) acetylacetonate; 1-carboxyethyl-3-methylimidazolium hydrogen bisulfate; zinc diacetate; copper(II) bis(trifluoromethanesulfonate) at 60℃; for 7h; Reagent/catalyst;	97.1%

3-methylbenzenediazonium tetrafluoroborate (1422-76-0) + acetonitrile (75-05-8) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
Stage #1: 3-methylbenzenediazonium tetrafluoroborate; acetonitrile for 0.0166667h; Microwave irradiation; Stage #2: With water In diethyl ether	97%

1-amino-3-methylbenzene (108-44-1) + potassium thioacetate (10387-40-3) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With tetrabutylammonium tetrafluoroborate In ethyl acetate at 20℃; for 24h; Electrochemical reaction;	97%
With tris(2,2'-bipyridyl)ruthenium dichloride In acetonitrile at 20℃; Irradiation;	89%
With copper(II) acetate monohydrate In acetonitrile at 80℃; for 18h; Temperature; Reagent/catalyst; Sealed tube;	73%

N,N-dimethyl acetamide (127-19-5) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With potassium tert-butylate at 130℃; for 0.5h; Inert atmosphere; Microwave irradiation;	96%
With Imidazole hydrochloride at 150℃; for 3h; Sealed tube;	90%
Stage #1: N,N-dimethyl acetamide With 1,1'-carbonyldiimidazole at 120 - 125℃; for 0.5h; Inert atmosphere; Stage #2: 1-amino-3-methylbenzene at 60 - 65℃; for 1.5h; Inert atmosphere;	86%

2,4,6-triacetyloxy-1,3,5-triazine (13483-16-4) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
at 25℃; for 0.0833333h; neat (no solvent);	95%

acetic acid (64-19-7) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
at 150℃; microwave irradiation;	94%
With hydrazine hydrate for 3h; Heating;	91%
With 1-methyl-3-(4-sulfonylbutyl)-1H-imidazol-3-ium trifluoromethanesulfonate at 96 - 100℃; for 5h; Temperature; chemoselective reaction;	90%

3-Methylacetophenone (585-74-0) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With O-trifluorobenzenesulfonyl-acetohydroxamic acid ethyl ester; toluene-4-sulfonic acid In water; acetonitrile at 20℃; Beckmann Rearrangement; Inert atmosphere;	93%
With O-benzenesulfonyl-acetohydroxamic acid ethyl ester; toluene-4-sulfonic acid In water; acetonitrile at 23℃; for 24h; Inert atmosphere;	93%
With nitromethane; trifluoromethylsulfonic anhydride; acetic acid In formic acid at 80 - 120℃;	34%
With Mexican Bentonite; hydroxylamine hydrochloride for 0.25h; Irradiation;	10.9%

1-amino-3-methylbenzene (108-44-1) + acetonitrile (75-05-8) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With tert.-butylnitrite; tetrabutylammomium bromide; water; toluene-4-sulfonic acid at 60℃; for 23h;	91%
With tert.-butylnitrite; trifluorormethanesulfonic acid; water at 60℃; for 24h;	59%

1-m-tolyl-ethanone oxime (23040-54-2) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With 10-methyl-9-phenylacridin-10-ium perchlorate In 1,2-dichloro-ethane at 20℃; for 5h; Beckmann Rearrangement; Irradiation; Sealed tube;	91%
With carbon tetrabromide; triphenylphosphine In toluene at 80℃; for 0.5h; Beckmann Rearrangement; Inert atmosphere;	81%
With tris(2,2'-bipyridyl)ruthenium dichloride; carbon tetrabromide; N,N-dimethyl-formamide at 50℃; under 2250.23 Torr; for 0.833333h; Beckmann Rearrangement; Flow reactor;	76%

ethanol (64-17-5) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With oxygen; sodium hydroxide In water at 40℃; for 24h;	88%

1-amino-3-methylbenzene (108-44-1) + thioacetic acid (507-09-5) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With 10-methyl-9-(2,4,6-trimethylphenyl) acridinium tetrafluoroborate In acetonitrile at 20℃; for 5h; Irradiation;	88%
With 10-methyl-9-(2,4,6-trimethylphenyl) acridinium tetrafluoroborate In acetonitrile at 20℃; for 5h; Irradiation;	88%

1-methyl-3-nitrobenzene (99-08-1) + potassium thioacetate (10387-40-3) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In N,N-dimethyl-formamide at 130℃; for 2h;	86%
In N,N-dimethyl-formamide at 130℃; for 2h; Product distribution / selectivity;	86%
Triton-X 405 at 130℃; for 2h; Product distribution / selectivity;	73%

1-amino-3-methylbenzene (108-44-1) + acetylacetone (123-54-6) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With dihydrogen peroxide In water at 25℃; for 8h; Green chemistry;	86%
With 2,2'-azobis(isobutyronitrile); oxygen In acetonitrile at 80℃; for 24h; Sealed tube;	86%
With iodine; toluene-4-sulfonic acid In 1,4-dioxane at 140℃; for 24h; Schlenk technique;	63%

[bis(acetoxy)iodo]benzene (3240-34-4) + N-tert-butyl-3-methylbenzenecarboximidamide (1321176-77-5) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In toluene at 80℃; for 5h; Sealed tube; Inert atmosphere;	86%

N-acetyl-4,6-dimethylpyrimidine-2-thione + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8) + 4,6-dimethyl-pyrimidine-2-thione (22325-27-5)

Conditions	Yield
In chloroform for 0.15h;	A 83% B n/a

4-bromo-3-methylacetanilide (90914-81-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With (4,4'-di-tert-butyl-2,2'-dipyridyl)-bis-(2-phenylpyridine(-1H))-iridium(III) hexafluorophosphate; tris-(trimethylsilyl)silane; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 10h; Irradiation;	83%

1-(m-tolyl)ethanone oxime (251113-21-0) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol; tetrabutylammonium tetrafluoroborate; water In 1,2-dichloro-ethane at 20℃; for 0.733333h; Beckmann Rearrangement; Electrochemical reaction;	83%

1-amino-3-methylbenzene (108-44-1) + polymer-bound acetic dithiocarbamic anhydride → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In chloroform for 1h;	77%

acetamide (60-35-5) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With [Mn((N'1E,N'2E)-N'1,N'2-bis(phenyl(pyridin-2-yl)methylene)oxalohydrazide(-H))(OAc)(H2O)]2*6H2O In neat (no solvent) at 120℃; for 24h;	77%
In 1,4-dioxane at 20℃; for 0.5h; Microwave irradiation; Sealed tube;	74%
With C28H26ClN3ORuS In 1,4-dioxane at 100℃; for 8h; Sealed tube; Inert atmosphere;	70%
With H-β-zeolite In neat (no solvent) at 130℃; for 24h; Green chemistry;	63%

3-Iodotoluene (625-95-6) + acetonitrile (75-05-8) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With copper(l) iodide; water; caesium carbonate; potassium hydroxide; N,N`-dimethylethylenediamine at 100℃; for 15h; Inert atmosphere; Schlenk technique;	74%

m-toluamide (618-47-3) + I,I-bis(acetoxy)iodobenzene → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In 1,2-dichloro-ethane at 100℃; for 24h;	70%

[bis(acetoxy)iodo]benzene (3240-34-4) + N-benzyl-3-methylbenzenecarboximidamide → 3-Methylacetanilide (537-92-8)

Conditions	Yield
In toluene at 100℃; for 15h; Sealed tube; Inert atmosphere;	66%

ethyl acetate (141-78-6) + 1-amino-3-methylbenzene (108-44-1) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With ytterbium(III) triflate for 5h; Heating;	65%

1-ethynyl-3-methyl-benzene (766-82-5) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With trimethylsilylazide; silver carbonate; trifluoroacetic acid In water; 1,2-dichloro-ethane at 60℃; for 12h; Schlenk technique; Inert atmosphere;	63%
With (triphenylphosphine)gold(I) chloride; trimethylsilylazide; water; silver carbonate; trifluoroacetic acid In 1,2-dichloro-ethane at 60℃; Schlenk technique; Inert atmosphere;	59%

Ketene (463-51-4) + 3-methylcyclohex-2-enone oxime (58367-95-6) → 3-Methylacetanilide (537-92-8)

Conditions	Yield
With toluene-4-sulfonic acid In acetonitrile at 70 - 80℃;	61%

Upstream product

• 463-51-4 Ketene 
• 58367-95-6 3-methylcyclohex-2-enone oxime 
• 99-08-1 1-methyl-3-nitrobenzene 
• 108-24-7 acetic anhydride 
• 99848-91-6 N-chloro-3'-methylacetanilide 
• 7647-01-0 hydrogenchloride 
• 64-17-5 ethanol 
• 64-19-7 acetic acid 
• 141-78-6 ethyl acetate 
• 108-44-1 1-amino-3-methylbenzene 
• 1422-76-0 3-methylbenzenediazonium tetrafluoroborate 
• 75-05-8 acetonitrile 
• 13483-16-4 2,4,6-triacetyloxy-1,3,5-triazine 
• 625-95-6 3-Iodotoluene 

Downstream Products

• 62121-57-7 4-methyl-N-(3-methylphenyl)aniline 
• 615-59-8 1,4-dibromo-2-methylbenzene 
• 35274-16-9 m-thioacetotoluidide 
• 611-05-2 4-nitro-3-methylaniline 
• 578-46-1 5-methyl-2-nitroaniline 
• 587-48-4 3-acetylaminobenzoic acid 
• 51366-39-3 4-acetamido-2-methylnitrobenzene 
• 7418-36-2 N-(5-methyl-2-nitrophenyl)acetamide 
• 4949-69-3 4-iodo-3-methylaniline 
• 90914-81-1 4-bromo-3-methylacetanilide 
• 860741-16-8 acetic acid-(2,3-dibromo-5-methyl-anilide) 
• 103752-65-4 acetic acid-(5-methyl-2,4-dinitro-anilide) 
• 103753-97-5 2,6-dinitro-3-acetamidotoluene 
• 6933-10-4 amino-5-bromo-2-toluene 

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