70977-72-9

Basic information

• Product Name: 3-Amino-2-hydroxyacetophenone
• Synonyms: 3-Amino-2-Hydroxy Acetophenone 3'-Amino-2'-Hydroxy Acetophenone;Ethanone, 1-(3-amino-2-hydroxyphenyl)- (9CI);3amino-2hydroxyacetophenone (intermediate of pranlukast);3-Amino-2-hydroxyacetophenone;2'-Hydroxy-3'-aminoacetophenone;1-(3-aMinophenyl)-2-hydroxyethan-1-one;Ethanone, 1-(3-aMino-2-hydroxyphenyl)-;3'-Amino-2'-hydroxyacetophenone (Pranlukast)
• CAS NO: 70977-72-9
• Molecular Formula: C₈H₉NO₂
• Molecular Weight: 151.16256
• EINECS: 1592732-453-0
• Product Categories: ACETYLGROUP;(intermediate of pranlukast)
• Mol File: 70977-72-9.mol
• Article Data: 8

Chemical Properties

• Melting Point: 95-96 °C
• Boiling Point: 287.2 °C at 760 mmHg
• Flash Point: 127.5 °C
• Appearance: /
• Density: 1.242 g/cm³
• Vapor Pressure: 0.00146mmHg at 25°C
• Refractive Index: 1.613
• Storage Temp.: under inert gas (nitrogen or Argon) at 2–8 °C
• PKA: 9.95±0.10(Predicted)
• CAS DataBase Reference: 3-Amino-2-hydroxyacetophenone(CAS DataBase Reference)
• NIST Chemistry Reference: 3-Amino-2-hydroxyacetophenone(70977-72-9)
• EPA Substance Registry System: 3-Amino-2-hydroxyacetophenone(70977-72-9)

Safety Data

• Hazardous Substances Data: 70977-72-9(Hazardous Substances Data)

Usage

Chemical Properties

Yellow crystalline powder

InChI:InChI=1/C8H9NO2/c1-5(10)6-3-2-4-7(9)8(6)11/h2-4,11H,9H2,1H3

Synthetic route

1-(2-hydroxy-3-amino-5-bromophenyl)ethan-1-one (70977-85-4) → 3'-Amino-2'-hydroxyacetophenone (70977-72-9)

Conditions	Yield
With palladium on activated charcoal; hydrogen In ethanol under 15001.5 Torr; for 8h; Reflux; Large scale;	91%

3-acetamido-4-acetoxybenzenesulfonic acid (123687-02-5) → 3'-Amino-2'-hydroxyacetophenone (70977-72-9)

Conditions	Yield
Stage #1: 3-acetamido-4-acetoxybenzenesulfonic acid With aluminum (III) chloride In nitrobenzene for 5h; Reflux; Stage #2: With hydrogenchloride In water at 20℃; for 6h; pH=9 - 10; Cooling with ice; Reflux;	87%
Stage #1: 3-acetamido-4-acetoxybenzenesulfonic acid With aluminum (III) chloride In chloroform for 5h; Reflux; Stage #2: With hydrogenchloride In chloroform; water at 20℃; for 6h; Reflux;	87%

2-acetamidophenyl acetate (5467-64-1) → 3'-Amino-2'-hydroxyacetophenone (70977-72-9)

Conditions	Yield
With titanium tetrachloride In 1-methyl-pyrrolidin-2-one at 120℃; for 3h; Catalytic behavior; Concentration; Fries Phenol Ester Rearrangement; Large scale;	87%

2-hydroxy-3-nitroacetophenone (28177-69-7) → 3'-Amino-2'-hydroxyacetophenone (70977-72-9)

Conditions	Yield
With hydrogenchloride; tin(ll) chloride
In diethyl ether; ethanol
With hydrogenchloride; tin In water; ethyl acetate Heating / reflux;
With hydrogenchloride; tin

5'-bromo-2'-hydroxy-3'-nitroacetophenone (70978-54-0) → 3'-Amino-2'-hydroxyacetophenone (70977-72-9)

Conditions	Yield
In methanol; dichloromethane

2-(acetylamino)phenol (614-80-2) → 3'-Amino-2'-hydroxyacetophenone (70977-72-9)

Conditions	Yield
Multi-step reaction with 3 steps 1: N-Bromosuccinimide / dichloromethane / 3 h / 0 - 20 °C / Large scale 2: zinc(II) chloride; hydrogenchloride / acetonitrile / 20 h / 50 °C / Large scale 3: palladium on activated charcoal; hydrogen / ethanol / 8 h / 15001.5 Torr / Reflux; Large scale View Scheme

2-amino-phenol (95-55-6) → 3'-Amino-2'-hydroxyacetophenone (70977-72-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: water / 2 h / 20 °C / Cooling with ice; Large scale 2: N-Bromosuccinimide / dichloromethane / 3 h / 0 - 20 °C / Large scale 3: zinc(II) chloride; hydrogenchloride / acetonitrile / 20 h / 50 °C / Large scale 4: palladium on activated charcoal; hydrogen / ethanol / 8 h / 15001.5 Torr / Reflux; Large scale View Scheme

trifluoromethyl trifluoromethanesulfonate (3582-05-6) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 7-acetylbenzo[d]oxazol-2(3H)-one

Conditions	Yield
In acetonitrile at 20℃; for 1h; Sealed tube;	99%

4-(4-phenyl-1-butoxy)benzoic acid (30131-16-9) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 3-[4-(4-phenyl-1-butoxy)benzoyl]amino-2-hydroxyacetophenone (136450-06-1)

Conditions	Yield
With phosphotungstic acid at 140℃; for 8h; Temperature; Time; Inert atmosphere;	98.36%
Stage #1: 4-(4-phenyl-1-butoxy)benzoic acid With thionyl chloride at 50℃; for 3h; Stage #2: 3'-Amino-2'-hydroxyacetophenone With pyridine In dichloromethane at 10℃; for 2h; Inert atmosphere;	84%

2-(benzyloxymethyl)benzofuran-5-carboxylic acid + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → N-(3-acetyl-2-hydroxyphenyl)-2-(benzyloxymethyl)benzofuran-5-carboxamide

Conditions	Yield
	98%

3-ethoxysalicylaldehyde (492-88-6) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 1-(3-((3-ethoxy-2-hydroxybenzylidene)amino)-2-hydroxyphenyl)ethanone

Conditions	Yield
In ethanol for 2h; Reflux;	97%
In ethanol for 2h; Reflux;
In ethanol for 2h; Reflux;
In ethanol for 2h; Reflux;
With acetic acid In methanol at 60℃; for 1.5h;

3,5-Dibromosalicylaldehyde (90-59-5) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 1-(3-((3,5-dibromo-2-hydroxybenzylidene)amino)-2-hydroxyphenyl)ethanone

Conditions	Yield
In ethanol for 2h; Reflux;	96%
In ethanol for 2h; Reflux;
With acetic acid In methanol at 70℃; for 1.5h; Temperature;

3'-Amino-2'-hydroxyacetophenone (70977-72-9) + 3,5-dichlorosalicyclaldehyde (90-60-8) → 1-(3-((3,5-dichloro-2-hydroxybenzylidene)amino)-2-hydroxyphenyl)ethanone

Conditions	Yield
In ethanol for 2h; Reflux;	96%
In ethanol for 2h; Reflux;
for 2h; Reflux;

3'-Amino-2'-hydroxyacetophenone (70977-72-9) + 5-bromosalicyclaldehyde (1761-61-1) → 1-(3-((5-bromo-2-hydroxybenzylidene)amino)-2-hydroxyphenyl)ethan-1-one

Conditions	Yield
In ethanol at 49.84℃; for 2h;	96%
In ethanol for 2h; Reflux;

3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 1-(3-azido-2-hydroxyphenyl)ethan-1-one

Conditions	Yield
Stage #1: 3'-Amino-2'-hydroxyacetophenone With hydrogenchloride In water at 0℃; for 0.166667h; Stage #2: With sodium nitrite In water at 5℃; for 0.5h; Stage #3: With sodium azide In water at 20℃; for 1h;	95%

4-chloro-2-(3-phenylpropyl)-2,3-dihydrobenzofuran-5-carboxylic acid + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → N-(3-acetyl-2-hydroxyphenyl)-4-chloro-2-(3-phenylpropyl)-2,3-dihydrobenzofuran-5-carboxamide

Conditions	Yield
	93%

3'-Amino-2'-hydroxyacetophenone (70977-72-9) + potassium ethyl xanthogenate (140-89-6) → 7-acetyl-2-mercaptobenzooxazole

Conditions	Yield
With hydrogenchloride In ethanol; water	92%

3'-Amino-2'-hydroxyacetophenone (70977-72-9) + 3-cyclohexyl-7-hydrazinyl-5-(propylthio)-3H-[1,2,3]triazolo[4,5-d]pyrimidine → 2-amino-6-(1-(2-(3-cyclohexyl-5-(propylthio)-3H-[1,2,3]triazolo[4,5-d]pyrimidin-7-yl)hydrazono)ethyl)phenol

Conditions	Yield
In ethanol Reflux;	88%

3'-Amino-2'-hydroxyacetophenone (70977-72-9) + 2,4,6-triphenylpyrylium tetrafluoroborate (448-61-3) → C31H24NO2(1+)*BF4(1-)

Conditions	Yield
In ethanol for 12h; Reflux;	88%

3'-Amino-2'-hydroxyacetophenone (70977-72-9) + chloroacetyl chloride (79-04-9) → 8-acetyl-2H-benzo[b][1,4]oxazin-3(4H)-one

Conditions	Yield
Stage #1: 3'-Amino-2'-hydroxyacetophenone; chloroacetyl chloride With sodium hydrogencarbonate In N,N-dimethyl-formamide for 2h; Inert atmosphere; Stage #2: With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 20h; Inert atmosphere;	84%
Stage #1: 3'-Amino-2'-hydroxyacetophenone; chloroacetyl chloride With sodium hydrogencarbonate In N,N-dimethyl-formamide for 2h; Stage #2: With caesium carbonate In N,N-dimethyl-formamide at 100℃; for 20h;	84%

2,6-diisopropylbenzenamine (24544-04-5) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → C21H24F3NO

Conditions	Yield
With toluene-4-sulfonic acid In neat (no solvent) at 150℃; for 36h;	81%

3-(morpholinosulfonyl)benzohydrazide + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → (E)-N'-(1-(3-amino-2-hydroxyphenyl)ethylidene)-3-(morpholinosulfonyl)benzohydrazide

Conditions	Yield
In ethanol Reflux;	74%

2-bromo-3,3,3-trifluoropropene (1514-82-5) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 1-(2-(2,2,2-trifluoroethyl)benzoxazol-7-yl)ethanone

Conditions	Yield
With sulfur; 2,2'-azobis-(2,4-dimethylvaleronitrile); sodium hydrogencarbonate; bis(pinacol)diborane In N,N-dimethyl-formamide at 100℃; for 15h; Reagent/catalyst; Solvent; Inert atmosphere;	73%

Conditions	Yield
With pyridine In oxalyl dichloride; dichloromethane; chloroform; nitrogen	72%

3'-Amino-2'-hydroxyacetophenone + sodium chlorodifluoroacetate (1895-39-2) → 1-(3-(difluoromethyl)-2-thioxo-2,3-dihydrobenzo[d]oxazol-7-yl)ethanone

Conditions	Yield
With sulfur; 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium hydroxide In N,N-dimethyl-formamide at 70℃; for 3h; Molecular sieve; Inert atmosphere;	72%

4-(4-phenyl-1-butoxy)benzoyl chloride (108807-05-2) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 2-[(E)-3-oxo-3-(2-hydroxy-3-(4-(4-phenylbutoxy)benzamido)phenyl)-1-propenyl]imidazole

Conditions	Yield
With potassium carbonate In acetone	70%

3'-Amino-2'-hydroxyacetophenone (70977-72-9) + 2-(((1R,2S)-2-(3,4-difluorophenyl)cyclopropyl)amino)acetohydrazide → N'-((E)-1-(3,-amino-2-hydroxyphenyl)ethylidene)-2-(((1R,2S)-2-(3,4-difluorophenyl)cyclopropyl)amino)acetohydrazide

Conditions	Yield
In ethanol Reflux;	70%

4-(4-phenylbutoxy)iodobenzene (203311-23-3) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 3-[4-(4-phenyl-1-butoxy)benzoyl]amino-2-hydroxyacetophenone (136450-06-1)

Conditions	Yield
	68%

3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 1-(2-(2,2,2-trifluoroethyl)benzoxazol-7-yl)ethanone

Conditions	Yield
With 2,2'-azobis-(2,4-dimethylvaleronitrile); sodium hydrogencarbonate; sulfur; bis(pinacol)diborane In N,N-dimethyl-formamide at 100℃; for 15h; Inert atmosphere;	63%

2-(3-phenylpropyl)-2,3-dihydrobenzofuran-5-carboxylic acid (197506-30-2) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → N-(3-Acetyl-2-hydroxyphenyl)-2-(3-phenylpropyl)2,3-dihydrobenzofuran-5-carboxamide

Conditions	Yield
	60%

2‐[O‐(1‐ethyloxyamide)]oxime‐6‐methoxyphenol (844644-77-5) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 6-amino-6'-methoxy-2,2'-[1,1'-(ethylenedioxy)(nitrilomethylidyne)(nitriloethylidyne)]bisphenol

Conditions	Yield
In methanol at 80℃; for 24h;	52.2%
In ethanol at 55 - 60℃; for 24h;	50%
In ethanol at 55 - 60℃; for 24h;	25%

2-(3-phenylpropyl)-6-chromanecarboxylic acid (197506-16-4) + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 3E N-(3-Acetyl-2-hydroxyphenyl)-2-(3-phenylpropyl)-chromane-6-carboxamide

Conditions	Yield
	45%

6-chloro-2-(3-phenylpropyl)-2,3-dihydrobenzofuran-5-carboxylic acid + 3'-Amino-2'-hydroxyacetophenone (70977-72-9) → N-(3-acetyl-2-hydroxyphenyl)-6-chloro-2-(3-phenylpropyl)-2,3-dihydrobenzofuran-5-carboxamide

Conditions	Yield
	42%

3'-Amino-2'-hydroxyacetophenone (70977-72-9) → 3’-bromo-2’-hydroxylacetophenone (1836-05-1)

Conditions	Yield
Stage #1: 3'-Amino-2'-hydroxyacetophenone With cis-nitrous acid Sandmeyer Reaction; Stage #2: With copper(I) bromide	25%
With cis-nitrous acid; copper(I) bromide Sandmeyer Reaction;	25%

Upstream product

• 28177-69-7 2-hydroxy-3-nitroacetophenone 
• 70978-54-0 5'-bromo-2'-hydroxy-3'-nitroacetophenone 
• 123687-02-5 3-acetamido-4-acetoxybenzenesulfonic acid 
• 614-80-2 2-(acetylamino)phenol 
• 70977-85-4 1-(2-hydroxy-3-amino-5-bromophenyl)ethan-1-one 
• 95-55-6 2-amino-phenol 
• 5467-64-1 2-acetamidophenyl acetate 

Downstream Products

• 70978-25-5 3-Acetyl-2-hydroxy-cyanoformanilid 
• 100245-22-5 1-(4-Methoxy-benzyl)-1H-tetrazole-5-carboxylic acid (3-acetyl-2-hydroxy-phenyl)-amide 
• 70977-58-1 N-(3-acetyl-2-hydroxyphenyl)-1H-tetrazole-5-carboxamide 
• 136450-06-1 3-[4-(4-phenyl-1-butoxy)benzoyl]amino-2-hydroxyacetophenone 
• 70977-75-2 1-benzyl-1H-tetrazole-5-carboxylic acid 3-acetyl-2-hydroxy-anilide 
• 1836-05-1 3’-bromo-2’-hydroxylacetophenone 
• 1202860-29-4 N-(3-acetyl-2-hydroxyphenyl)-4-nitro-benzamide 
• 1202860-30-7 N-(3-acetyl-2-hydroxyphenyl)-4-chloro-benzamide 
• 1202860-32-9 N-(3-acetyl-2-hydroxyphenyl)-2-nitro-benzamide 
• 1202860-27-2 N-(3-acetyl-2-hydroxyphenyl)-3-methylbenzamide 
• 1202860-33-0 N-(3-acetyl-2-hydroxyphenyl)-3-nitro-benzamide 
• 1202860-31-8 N-(3-acetyl-2-hydroxyphenyl)-propionamide 
• 1202860-28-3 pyridine-2-carboxylic acid (3-acetyl-2-hydroxyphenyl)-amide 

Relevant articles and documents

Novel preparation method of 3-amino-2-hydroxyacetophenone

The invention provides a novel preparation method of 3-amino-2-hydroxyacetophenone. The novel preparation method comprises the following steps of using 2-aminophenol as an initial raw material; enabling the 2-aminophenol and acetic anhydride to synthesize 2-acetamidophenol acetate in a polar solvent under the alkaline or acid catalyzing condition; then, performing Fries rearrangement on the 2-acetamidophenol acetate in an aprotic solvent under the catalyzing action of anhydrous titanium tetrachloride, and adopting an acid hydrolysis one-pot method, so as to synthesize the 3-amino-2-hydroxyacetophenone. The novel preparation method has the advantages that the price of the used raw materials is low, the obtaining is easy, and the selection of the raw materials is diversified; the implementing of the production technology is easy, the management and control are easy, the purity of a final product is high, the dangerous technology is avoided, the equipment is simple, the synthesizing route is novel and short, the production capacity is increased, and the production and processing cost is reduced.

New preparation method of Pranlukast

The invention provides a new preparation method of drug Pranlukast for treating asthma. The new preparation method includes the specific steps that with 2-aminophenol-4-sulfonic acid as a starting material, a key intermediate 3-amino-2-hydroxyacetophenone is prepared by means of acylation, Fries rearrangement and deprotection, then reacts with 4-(phenylbutoxy)benzoic acid, and then is subjected to condensation with ethyl 1H-tetrazole-5-acetate, and finally preparation is achieved through ring closing under the acidic condition. Compared with the prior art, the raw material used for the new preparation method is low in price and easy to obtain, industrialization of a process can be achieved easily, and the obtained final product is high in purity; and no dangerous process exists, equipment is simple, and the route is novel.

N-sulfamoyl-N'-benzopyranpiperidine compounds and uses thereof

N-sulfamoyl-N′-benzopyranpiperidine compounds of formula I and their physiologically acceptable acid addition salts, pharmaceutical compositions comprising them, processes for their preparation, and their use for the treatment and/or inhibition of glaucoma, epilepsy, bipolar disorders, migraine, neuropathic pain, obesity, type II diabetes, metabolic syndrome, alcohol dependence, and/or cancer, and related concomitant and/or secondary diseases or conditions.