616-82-0

Basic information

• Product Name: 4-Hydroxy-3-nitrobenzoic acid
• Synonyms: NHB;RARECHEM AL BO 1164;4-HYDROXY-3-NITROBENZOIC ACID;3-NITRO-4-HYDROXYBENZOIC ACID;2-NITRO-4-CYANOPHENOL;LABOTEST-BB LT00452849;3,4-Nitrohydroxybenzoic acid;Benzoic acid, 4-hydroxy-3-nitro-
• CAS NO: 616-82-0
• Molecular Formula: C₇H₅NO₅
• Molecular Weight: 183.12
• EINECS: 210-494-1
• Product Categories: Aromatic Carboxylic Acids, Amides, Anilides, Anhydrides & Salts;Organic acids;C7;Carbonyl Compounds;Carboxylic Acids
• Mol File: 616-82-0.mol

Chemical Properties

• Melting Point: 183-186 °C(lit.)
• Boiling Point: 316.77°C (rough estimate)
• Flash Point: 162.528 °C
• Appearance: yellow to light brown powder
• Density: 1.6074 (rough estimate)
• Vapor Pressure: 1.24E-05mmHg at 25°C
• Refractive Index: 1.6280 (estimate)
• Storage Temp.: -20°C
• Solubility: Acetonitrile (Slightly), DMSO (Slightly), Methanol (Slightly)
• PKA: 3.94±0.10(Predicted)
• BRN: 2213134
• CAS DataBase Reference: 4-Hydroxy-3-nitrobenzoic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Hydroxy-3-nitrobenzoic acid(616-82-0)
• EPA Substance Registry System: 4-Hydroxy-3-nitrobenzoic acid(616-82-0)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 36/37/38
• Safety Statements: 26-37/39-24/25-36
• WGK Germany: 3
• TSCA: T
• HazardClass: IRRITANT
• Hazardous Substances Data: 616-82-0(Hazardous Substances Data)

Usage

Chemical Properties

yellow to light brown powder

Uses

Standard in chymotrypsin assays

General Description

4-Hydroxy-3-nitrobenzoic acid was coupled to ionic liquid-immobilized o-phenylenediamine to form benzimidazole derivatives.

InChI:InChI=1/C7H5NO5/c9-6-2-1-4(7(10)11)3-5(6)8(12)13/h1-3,9H,(H,10,11)/p-2

Synthetic route

4-hydroxy-benzoic acid (99-96-7) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With magnesium(II) nitrate hexahydrate; AMA at 20℃; for 1.5h; Neat (no solvent); regioselective reaction;	98%
With dimethylbromosulphonium bromide; tetrabutylammonium nitrite In acetonitrile at 20℃; for 2h; regioselective reaction;	93%
With trichloroisocyanuric acid; silica gel; sodium nitrite In dichloromethane at 20℃; for 0.333333h;	87%

4-chloro-3-nitrobenzoate (96-99-1) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With water; sodium hydroxide at 100℃;	98%
With sodium hydroxide In water at 95℃; for 10h;	91.83%
With sodium hydroxide In water	430 g (90 %)

3-nitro-4-fluorobenzoic acid (453-71-4) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With acetylhydroxamic acid; potassium carbonate In dimethyl sulfoxide at 80℃; for 1h; Sealed tube;	93%

4-hydroxy-benzoic acid (99-96-7) → 4-nitro-phenol (100-02-7) + 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With ammonium cerium(IV) nitrate In acetonitrile at 20℃; for 0.333333h;	A 10% B 84%

4-hydroxy-benzoic acid (99-96-7) → 2,4-Dinitrophenol (51-28-5) + 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With ammonium cerium(IV) nitrate In acetonitrile at 60 - 70℃; for 0.25h;	A 45% B 50%
With ammonium cerium(IV) nitrate In acetonitrile at 60 - 70℃; for 0.25h;	A 50% B 50%
With chloroform; nitric acid

p-hydroxybenzamide (619-57-8) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + 2-nitro-4-hydroxybenzoic acid (74230-08-3) + 4-hydroxy-benzoic acid (99-96-7)

Conditions	Yield
With acetic acid; isopentyl nitrite at 80℃; for 21h; Inert atmosphere;	A 39% B 43% C 13%

3,4-Dihydroxybenzoic acid (99-50-3) → 2,4-Dinitrophenol (51-28-5) + 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With diethyl ether; cis-nitrous acid

1-methyl-4-nitrosobenzene (623-11-0) + 3,4-dinitrobenzoic acid (528-45-0) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

1-methyl-4-nitrosobenzene (623-11-0) + (4-methoxycarbonyl-2-nitro-phenoxy)-acetic acid → 3-nitro-4-hydroxybenzoic acid (616-82-0)

1-methyl-4-nitrosobenzene (623-11-0) + 4-methoxycarbonylmethoxy-3-nitro-benzoic acid (476313-40-3) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

1-methyl-4-nitrosobenzene (623-11-0) + 2-(4'-methoxy-3'-nitro-α'-oxo-bibenzyl-α-ylmercapto)-benzoic acid (855469-12-4) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + 2-(benzylthio)benzoic acid (1531-80-2)

4-hydroxymethyl-2-nitrophenol (41833-13-0) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With alkaline permanganate at 90 - 100℃;

2,5-dihydroxy-3,6-bis(4-hydroxyphenyl)cyclohexa-2,5-diene-1,4-dione (519-67-5) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With nitric acid

4-carboxymethoxy-3-nitro-benzoic acid (25253-99-0) + furan-2,3,5(4H)-trione pyridine (1:1) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

4-carboxymethoxy-3-nitro-benzoic acid (25253-99-0) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With sodium hydroxide

methyl 4-(2-methoxy-2-oxo-ethoxy)-3-nitrobenzoate (83785-14-2) + furan-2,3,5(4H)-trione pyridine (1:1) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + 4-carboxymethoxy-3-nitro-benzoic acid (25253-99-0)

4-amino-benzoic acid (150-13-0) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With chloroform; sulfur dioxide; nitric acid

p-carboxybenzene diazonium nitrate + toluene (108-88-3) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

4-amino-3-nitrobenzoic acid (1588-83-6) → 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With potassium hydroxide

4-carboxy-2-nitrophenyl heptanoate (43049-38-3) → oenanthic acid (111-14-8) + 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin, var. conc. of α- and β-cyclodextrin;

4-(acetyloxy)-3-nitrobenzoic acid (1210-97-5) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + acetic acid (64-19-7)

Conditions	Yield
1,3-dimethyl-1H-imidazol-3-ium bromide In ethanol at 23.9℃; Rate constant; var. catalyst - imidazolium salts, var. pH, var. composition of solvent, var. conc. of catalyst;
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin;

4-carboxy-2-nitrophenyl butanoate (56003-42-0) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + butyric acid (107-92-6)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin, var. conc. of α-cyclodextrin;

3-nitro-4-hexanoyloxybenzoic acid (65293-27-8) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + hexanoic acid (142-62-1)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin, var. conc. of α- and β-cyclodextrin;

3-nitro-4-propionyloxybenzoic acid (86868-06-6) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + propionic acid (802294-64-0)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin, var. conc. of α-cyclodextrin;

4-carboxy-2-nitrophenyl pentanoate (67880-44-8) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + valeric acid (109-52-4)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin, var. conc. of α-cyclodextrin;

4-carboxy-2-nitrophenyl 4-methylpentanoate (137363-37-2) → 4-Methylpentanoic acid (646-07-1) + 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin;

4-carboxy-2-nitrophenyl 2-ethylhexanoate (137363-36-1) → 2-Ethylhexanoic acid (149-57-5) + 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin;

3-nitro-4-(octanoyloxy)benzoic acid (113894-26-1) → Octanoic acid (124-07-2) + 3-nitro-4-hydroxybenzoic acid (616-82-0)

Conditions	Yield
With phosphate buffer; alpha cyclodextrin at 25℃; Rate constant; also in the presence of β-cyclodextrin, var. conc. of α- and β-cyclodextrin;
With Tris-HCl buffer; water; calcium(II) ion; sodium chloride; Agkistrodon piscivorus piscivorus In acetonitrile at 37℃; Rate constant; pH = 8.0;

4-carboxy-2-nitrophenyl 4-t-butylbenzoate (143671-56-1) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + 4-(1,1-dimethylethyl)benzoic acid (98-73-7)

Conditions	Yield
With phosphate buffer; β‐cyclodextrin; sodium chloride In acetonitrile at 25℃; Rate constant; pH 7.65; also with ether CD or PEI alone;

C25H20N2O10 (143671-58-3) → 3-nitro-4-hydroxybenzoic acid (616-82-0) + 4-(1,1-dimethylethyl)benzoic acid (98-73-7)

Conditions	Yield
With phosphate buffer; β‐cyclodextrin; sodium chloride In acetonitrile at 25℃; Rate constant; pH 7.65; also with ether CD or PEI alone;

3-nitro-4-hydroxybenzoic acid (616-82-0) → 4-hydroxymethyl-2-nitrophenol (41833-13-0)

Conditions	Yield
With borane-THF; boron trifluoride diethyl etherate In tetrahydrofuran for 18h;	100%
With borane-THF; boron trifluoride diethyl etherate In tetrahydrofuran at 20℃; for 18h;	93%
With borane-THF In tetrahydrofuran at 0 - 20℃; for 20h; Inert atmosphere;	91%

methanol (67-56-1) + 3-nitro-4-hydroxybenzoic acid (616-82-0) → methyl (4-hydroxy-3-nitro)benzoate (99-42-3)

Conditions	Yield
With sulfuric acid for 12h; Inert atmosphere; Schlenk technique; Reflux;	98%
With sulfuric acid for 16h; Heating;	93%
With Amberlite IR-120(H+) for 168h;	93%

3-nitro-4-hydroxybenzoic acid (616-82-0) → 3-amino-4-hydroxybenzoic acid (1571-72-8)

Conditions	Yield
With hydrogenchloride; tin(ll) chloride at 0℃; for 1h; Reflux;	98%
With hydrogenchloride; tin(ll) chloride In tetrahydrofuran; water at 0℃; for 1h;	98%
With hydrogenchloride; tin(ll) chloride In water at 0℃; for 1h; Reflux;	98%

3-nitro-4-hydroxybenzoic acid (616-82-0) → 4-Hydroxy-3-nitrobenzoyl chloride

Conditions	Yield
	97.6%
With pyridine; thionyl chloride for 1.5h; Reflux;
With thionyl chloride In 1,2-dimethoxyethane at 80℃;

ethanol (64-17-5) + 3-nitro-4-hydroxybenzoic acid (616-82-0) → ethyl 4-hydroxy-3-nitrobenzoate (19013-10-6)

Conditions	Yield
With sulfuric acid for 72h; Fischer esterification; Reflux;	97%
With sulfuric acid for 12h; Reflux;	96%
With hydrogenchloride at 20℃;	95%

methanol (67-56-1) + 3-nitro-4-hydroxybenzoic acid (616-82-0) → methyl 3-amino-4-hydroxybenzoate (536-25-4)

Conditions	Yield
With thionyl chloride at 20℃; for 16h;	95%

pentan-1-ol (71-41-0) + 3-nitro-4-hydroxybenzoic acid (616-82-0) → pentyl 4-hydroxy-3-nitrobenzoate

Conditions	Yield
With sulfuric acid for 72h; Fischer esterification; Reflux;	95%

3-nitro-4-hydroxybenzoic acid (616-82-0) + ethyl iodide (75-03-6) → ethyl 4-ethoxy-3-nitrobenzoate (937625-32-6)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 50℃; for 72h; Inert atmosphere;	94%
With potassium carbonate In DMF (N,N-dimethyl-formamide) at 90℃;

3-nitro-4-hydroxybenzoic acid (616-82-0) + phenol (108-95-2) → phenyl 4-hydroxy-3-nitrobenzoate (1089331-13-4)

Conditions	Yield
With dmap; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride In dichloromethane at 20℃; for 1.5h;	92%

3-nitro-4-hydroxybenzoic acid (616-82-0) + benzyl bromide (100-39-0) → 4-(benzyloxy)-3-nitrobenzoic acid (17903-89-8)

Conditions	Yield
Stage #1: 3-nitro-4-hydroxybenzoic acid; benzyl bromide With potassium carbonate In acetone Heating; Stage #2: With sodium hydroxide In methanol at 20℃; for 3h; Further stages.;	91.5%

3-nitro-4-hydroxybenzoic acid (616-82-0) + isopropyl alcohol (67-63-0) → isopropyl 4-hydroxy-3-nitrobenzoate (52791-72-7)

Conditions	Yield
With sulfuric acid at 170℃; for 8h;	91%
With sulfuric acid for 48h; Inert atmosphere; Reflux;	2.11 g

3-nitro-4-hydroxybenzoic acid (616-82-0) → 2-hydroxynitrobenzene (88-75-5)

Conditions	Yield
With sulfolane; sodium hydrogencarbonate at 200℃; for 2h;	91%

3-nitro-4-hydroxybenzoic acid (616-82-0) → tert-butyl 4-hydroxy-3-nitrobenzoate (273939-22-3)

Conditions	Yield
With sodium bicarbonate; sulfuric acid; magnesium sulfate In dichloromethane; tert-butyl alcohol	90%

3-nitro-4-hydroxybenzoic acid (616-82-0) → C7H7NO3*H3O4P

Conditions	Yield
With phosphoric acid; palladium on activated carbon; hydrogen at 95℃; under 7500.75 - 10501.1 Torr; for 5h; Autoclave;	88.5%

3-nitro-4-hydroxybenzoic acid (616-82-0) + methyl chloroformate (79-22-1) → 4-methoxycarbonyloxy-3-nitrobenzoic acid

Conditions	Yield
With sodium hydroxide In water	86%
With sodium hydroxide In water

chloro-trimethyl-silane (75-77-4) + 3-nitro-4-hydroxybenzoic acid (616-82-0) → 3-nitro-4-trimethylsiloxybenzoic acid trimethylsilyl ester (79302-41-3)

Conditions	Yield
With triethylamine In toluene for 2h; Heating;	84%

3-nitro-4-hydroxybenzoic acid (616-82-0) + trimethoxonium tetrafluoroborate (420-37-1) → methyl (4-hydroxy-3-nitro)benzoate (99-42-3)

Conditions	Yield
With diisopropylamine In dichloromethane	82%

n-Dodecylamine (124-22-1) + 3-nitro-4-hydroxybenzoic acid (616-82-0) → N-dodecyl-4-hydroxy-3-nitrobenzamide (70382-09-1)

Conditions	Yield
Stage #1: n-Dodecylamine; 3-nitro-4-hydroxybenzoic acid With benzotriazol-1-ol In N,N-dimethyl-formamide at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 0 - 20℃; for 5h; Inert atmosphere;	80%
Stage #1: n-Dodecylamine; 3-nitro-4-hydroxybenzoic acid With benzotriazol-1-ol In N,N-dimethyl-formamide at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: With 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 20℃; for 5h; Inert atmosphere;	80%

3-nitro-4-hydroxybenzoic acid (616-82-0) + bis-[(trifluoroacetoxy)iodo]benzene (2712-78-9) → phenyliodine(III) bis(4-hydroxy-3-nitrobenzoate) (89563-20-2)

Conditions	Yield
In acetonitrile	74%

3-nitro-4-hydroxybenzoic acid (616-82-0) + acetic anhydride (108-24-7) → 4-(acetyloxy)-3-nitrobenzoic acid (1210-97-5)

Conditions	Yield
With sodium hydroxide for 0.0333333h;	70%
With sodium hydroxide
With triethylamine In N,N-dimethyl-formamide
With pyridine at 25℃; for 3h;
With pyridine at 20℃; for 65h;

3-nitro-4-hydroxybenzoic acid (616-82-0) + acryloyl chloride (814-68-6) → 4-carboxy-2-nitrophenylacrylate

Conditions	Yield
With triethylamine In acetonitrile Ambient temperature;	70%

3-nitro-4-hydroxybenzoic acid (616-82-0) + isobutylamine (78-81-9) → 4-hydroxy-N-isobutyl-3-nitro-benzamide (909255-49-8)

Conditions	Yield
With benzotriazol-1-ol; N-(3-dimethylaminopropyl)-N-ethylcarbodiimide In dichloromethane at 5 - 20℃; for 9h;	70%

3-nitro-4-hydroxybenzoic acid (616-82-0) + sodium hydrogencarbonate (144-55-8) → methyl (4-hydroxy-3-nitro)benzoate (99-42-3)

Conditions	Yield
With sulfuric acid In methanol; 1,2-dichloro-ethane	68%

3-nitro-4-hydroxybenzoic acid (616-82-0) + 4-methylbenzenesulfonic acid n-hexylester (3839-35-8) → hexyl 4-hydroxy-3-nitrobenzoate (885620-29-1)

Conditions	Yield
Stage #1: 3-nitro-4-hydroxybenzoic acid With sodium hydrogencarbonate In N,N-dimethyl acetamide Heating; Stage #2: 4-methylbenzenesulfonic acid n-hexylester In N,N-dimethyl acetamide for 1h; Heating;	67%

3-nitro-4-hydroxybenzoic acid (616-82-0) + benzyl bromide (100-39-0) → C21H17NO5 (79520-01-7)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 20℃;	64%

n-hexanoic anhydride (2051-49-2) + 3-nitro-4-hydroxybenzoic acid (616-82-0) → 3-nitro-4-hexanoyloxybenzoic acid (65293-27-8)

Conditions	Yield
With sulfuric acid In ethyl acetate at 65℃; for 0.25h;	62%
With sulfuric acid at 85 - 90℃; for 4h;

Upstream product

• 99-50-3 3,4-Dihydroxybenzoic acid 
• 143671-58-3 C₂₅H₂₀N₂O₁₀ 
• 7697-37-2 nitric acid 
• 99-96-7 4-hydroxy-benzoic acid 
• 7664-93-9 sulfuric acid 
• 96-99-1 4-chloro-3-nitrobenzoate 
• 41833-13-0 4-hydroxymethyl-2-nitrophenol 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 855469-12-4 2-(4'-methoxy-3'-nitro-α'-oxo-bibenzyl-α-ylmercapto)-benzoic acid 
• 476313-40-3 4-methoxycarbonylmethoxy-3-nitro-benzoic acid 
• 528-45-0 3,4-dinitrobenzoic acid 
• 453-71-4 3-nitro-4-fluorobenzoic acid 
• 74-11-3 para-chlorobenzoic acid 
• 619-57-8 p-hydroxybenzamide 

Downstream Products

• 43049-38-3 4-carboxy-2-nitrophenyl heptanoate 
• 137363-37-2 4-carboxy-2-nitrophenyl 4-methylpentanoate 
• 65293-27-8 4-carboxy-2-nitrophenyl hexanoate 
• 86868-06-6 4-carboxy-2-nitrophenyl propanoate 
• 41833-13-0 4-hydroxymethyl-2-nitrophenol 
• 317352-21-9 4-[1-[3-methoxy-4-[N'-(2-methylphenyl)ureido]phenylacetyl]-2-pyrrolidinylmethoxy]-3-nitrobenzoic Acid 
• 273939-22-3 tert-butyl 4-hydroxy-3-nitrobenzoate 
• 99-42-3 methyl (4-hydroxy-3-nitro)benzoate 
• 85136-67-0 4-Hydroxy-3-nitrobenzoyl chloride 
• 79302-41-3 3-nitro-4-trimethylsiloxybenzoic acid trimethylsilyl ester 
• 56003-42-0 4-carboxy-2-nitrophenyl butanoate 
• 52791-73-8 4-hydroxy-3-nitro-benzoic acid butyl ester 
• 35288-44-9 3-nitro-4-propoxybenzoic acid 
• 861306-34-5 4-ethoxycarbonyloxy-3-nitro-benzoic acid 

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Nitrophenols were obtained via direct nitration of phenols with tetrabutylammonium nitrite in the presence of bromodimethylsulfonium bromide at room temperature in high yields under aprotic conditions. TUeBITAK.

AI203/MeS03H (AMA) as a novel heterogeneous system for the nitration of aromatic compounds by magnesium nitrate hexahydrate

Mg(NO3)2-6H2O was an efficient nitrating agent in the presence of a mixture of AI2O3/MeSO 3H (AMA) as a novel heterogeneous system for the nitration of aromatic compounds without use of any organic solvents and with high selectivity. The reaction proceeds at room temperature for the nitration of highly reactive aromatic compounds such as phenols and anilines.

PEG-N2O4: An efficient nitrating agent for the selective mono- and dinitration of phenols under mild conditions

N2O4 was easily impregnated on polyethyleneglycol to give a stable reagent. The polyethyleneglycol-N2O4 (PEG-N2O4) system was used as an effective nitrating agent for the nitration of phenols. Mono- and dinitrophenols can be obtained via direct nitration of phenols in the presence of PEG-N2O4 at room temperature in moderate to high yields. Copyright Taylor & Francis Group, LLC.