74-11-3

Basic information

• Product Name: 4-Chlorobenzoic acid
• Synonyms: 'LGC' (4004);LABOTEST-BB LT00776185;CHLORODRACYLIC ACID;4-CHLOROBENZOIC ACID;AKOS 92635;AKOS BBS-00003713;RARECHEM AL BO 0054;PCBA
• CAS NO: 74-11-3
• Molecular Formula: C₇H₅ClO₂
• Molecular Weight: 156.5664
• EINECS: 200-805-9
• Product Categories: Benzoic acid;Organic acids;Absolute Configuration Determination (Exciton Chirality CD Method);Analytical Chemistry;Enantiomer Excess & Absolute Configuration Determination;Exciton Chirality CD Method (for Hydroxyl Groups);Alpha sort;C;CAlphabetic;CH;Pesticides&Metabolites;C7;Carbonyl Compounds;Carboxylic Acids;Aromatics;Intermediates;carboxylic acid| alkyl chloride;Pyridines
• Mol File: 74-11-3.mol
• Article Data: 778

Chemical Properties

• Melting Point: 238-241 °C(lit.)
• Boiling Point: 274-276 °C
• Flash Point: 238 °C
• Appearance: White to yellow/Crystalline Powder
• Density: 1.540
• Vapor Pressure: 0.00117mmHg at 25°C
• Refractive Index: 1.5812 (estimate)
• Storage Temp.: room temp
• Solubility: methanol: soluble1%, clear, colorless to faintly yellow
• PKA: 3.98(at 25℃)
• Water Solubility: soluble in hot water
• Stability: Stable. Combustible. Incompatible with bases, strong oxidizing agents.
• Merck: 14,2125
• BRN: 907196
• CAS DataBase Reference: 4-Chlorobenzoic acid(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Chlorobenzoic acid(74-11-3)
• EPA Substance Registry System: 4-Chlorobenzoic acid(74-11-3)

Safety Data

• Hazard Codes: Xn
• Statements: 22-36/37/38
• Safety Statements: 26-36-37/39
• WGK Germany: 2
• RTECS: DG4976010
• TSCA: Yes
• Hazardous Substances Data: 74-11-3(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powder. Soluble in methanol, anhydrous ethanol and ether, very slightly soluble in water, toluene and 95% ethanol.

Uses

Different sources of media describe the Uses of 74-11-3 differently. You can refer to the following data:
1. 4-Chlorobenzoic acid is a benzoic acid analogue that showed antifungal activity against strains of Aspergillus flavus, Aspergillus fumigatus and Aspergillus terreus, causative agents of human aspergillosis, in in vitro bioas says. It is used as a preservative.P-chlorobenzoic acid is the intermediate of fungicide dimethomorph, rodenticide Warfarin, Coumatetralyl and insecticide flumethrin, and also the intermediate of dye and medicine.
2. 4-Chlorobenzoic acid can be used:As a ligand to synthesize luminescent lanthanide complexes for bio-labeling or fiber communication applications.To prepare organotin(IV) chlorobenzoates exhibiting anticorrosion properties.As a ligand to synthesize di-n-butyl(4-chlorobenzoxy)(4-chlorobenzohydroxamato)tin(IV).

Preparation

4-Chlorobenzoic acid is obtained by oxidation of p-chlorotoluene: add potassium permanganate solution to the mixture of p-chlorotoluene and water in stages. The reaction is refluxed under stirring for 5-6h, then acidified with hydrochloric acid to pH 2, filtered to obtain the crude product, and recrystallized with ethanol to obtain the finished product.

Definition

ChEBI: 4-chlorobenzoic acid is a monochlorobenzoic acid carrying a chloro substituent at position 4. It has a role as a bacterial xenobiotic metabolite. It derives from a benzoic acid. It is a conjugate acid of a 4-chlorobenzoate.

Synthesis Reference(s)

Organic Syntheses, Coll. Vol. 2, p. 135, 1943Synthetic Communications, 25, p. 3695, 1995 DOI: 10.1080/00397919508015507Tetrahedron Letters, 22, p. 1013, 1981 DOI: 10.1016/S0040-4039(01)82853-7

General Description

Triclinic crystals or light fluffy white powder.4-Chlorobenzoic acid is a degradation product of indomethacin. It is degraded by Acinetobacter sp. strain ST-1 and causes its dehalogenation to yield 4-hydroxybenzoic acid under both aerobic and anaerobic conditions.

Air & Water Reactions

Insoluble in water.

Reactivity Profile

4-Chlorobenzoic acid is incompatible with strong oxidizing agents and strong bases.

Fire Hazard

Flash point data for 4-Chlorobenzoic acid are not available; however, 4-Chlorobenzoic acid is probably combustible.

Purification Methods

Purify it as for m-chlorobenzoic acid. It has also been crystallised from hot water, and from EtOH. [Beilstein 9 IV 973.]

InChI:InChI=1/C7H5ClO2/c8-6-3-1-5(2-4-6)7(9)10/h1-4H,(H,9,10)/p-1

Synthetic route

4-chlorobenzaldehyde (104-88-1) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With sodium perborate In acetic acid for 1.5h; steam bath;	100%
With hydrogen bromide; oxygen In acetonitrile at 20℃; for 5h; UV-irradiation;	100%
With C4H11FeMo6NO24(3-)*3C16H36N(1+); water; oxygen; sodium carbonate at 50℃; under 760.051 Torr; for 8h; Green chemistry;	99%

benzyl p-chlorobenzoate (67483-73-2) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With hydrogen In ethyl acetate at 60℃; for 24h; Reagent/catalyst;	100%
With methanol; sodium tetrahydroborate; nickel(II) chloride hexahydrate at 20℃; for 0.0833333h; chemoselective reaction;	87%
With ammonium cerium(IV) nitrate In water; acetonitrile for 6h; Mechanism; Heating; other esters react in the same way;	65%

allyl 4-chlorobenzoate (15784-28-8) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With formic acid; triethylamine In acetonitrile at 80℃; for 1h; Inert atmosphere;	100%
With toluene-4-sulfonic acid for 0.0666667h; microwave irradiation;	86%
With iodine; dimethyl sulfoxide for 0.2h; Heating;	76%
With ammonium cerium(IV) nitrate In water; acetonitrile for 6h; Mechanism; Heating; other esters react in the same way;	74%

para-Chlorobenzyl alcohol (873-76-7) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With bromine; oxygen In acetonitrile for 10h; Irradiation;	100%
With periodic acid; tripropylammonium fluorochromate (VI) In acetonitrile at 0℃;	99%
With silica-supported Jones reagent In dichloromethane for 0.035h;	99.4%

4-chlorobenzoic anhydride (790-41-0) → para-Chlorobenzyl alcohol (873-76-7) + para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With methanol; sodium tetrahydroborate In tetrahydrofuran for 1h; Ambient temperature;	A 94% B 100%

4-chloro-N,N-diisopropylbenzamide (79606-45-4) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With hydrogenchloride; zinc(II) chloride at 160℃; for 72h;	100%

para-chlorotoluene (106-43-4) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With Oxone; potassium bromide In dichloromethane; water at 20℃; for 24h; visible light irradiation;	99%
With ruthenium trichloride; sodium hypochlorite; tetrabutylammomium bromide In 1,2-dichloro-ethane at 25℃; for 2h;	98%
With ruthenium trichloride; sodium hypochlorite; tetrabutylammomium bromide In 1,2-dichloro-ethane at 25℃; for 2h; Rate constant; Mechanism; pH 9: other methylbenzenes; var. concentration of aq. NaOCl, ruthenium and tetrabutylammonium bromide;	98%

Methyl 4-chlorobenzoate (1126-46-1) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With iodine; aluminium In acetonitrile at 80℃; for 18h;	99%
With potassium hydroxide In toluene at 150℃; for 0.166667h; microwave irradiation;	94%
With sodium hydroxide In N,N-dimethyl-formamide for 0.5h; Ambient temperature;	93%

1-Chloro-4-iodobenzene (637-87-6) + carbon monoxide (201230-82-2) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With amphiphilic resin-supported phosphine-palladium; water; potassium carbonate at 25℃; under 760 Torr; for 12h; hydroxycarbonylation;	99%
With dichloro bis(acetonitrile) palladium(II); potassium hydroxide; sodium dodecyl-sulfate In water; butan-1-ol at 70℃; under 760 Torr; for 4h;	94%
With potassium carbonate; palladium diacetate In water; N,N-dimethyl-formamide at 25℃; under 760 Torr; for 2h;	92%

cobalt (II) acetate·4 H2O + para-chlorotoluene (106-43-4) + 1N,3N,5N-trihydroxy-1,3,5-triazin-2,4,6[1H,3H,5H]-trione (143435-52-3) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With acetic acid	99%

4-chlorobenzyl azide (27032-10-6) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With tert.-butylhydroperoxide; vanadia In water at 100℃; for 6h;	99%

1-chloro-4-{[(phenylmethyl)oxy]methyl}benzene (3395-72-0) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With Oxone; potassium bromide In acetonitrile at 0 - 30℃; for 24.5h; Green chemistry;	99%

2-(4-Chlorophenyl)ethanol (1875-88-3) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With oxygen; sodium t-butanolate In tetrahydrofuran at 20℃; under 750.075 Torr; for 17h; chemoselective reaction;	99%

bromochlorobenzene (106-39-8) + carbon monoxide (201230-82-2) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With tetrabutylammomium bromide; dicobalt octacarbonyl In sodium hydroxide; benzene at 65℃; for 1h; Irradiation;	98%
With sodium hydroxide; tetrabutylammomium bromide; dicobalt octacarbonyl In water; benzene at 65℃; under 760 Torr; for 1h; Irradiation;	98%

ethyl 4-chlorobenzoate (7335-27-5) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
Stage #1: ethyl 4-chlorobenzoate With iron(III) chloride In tetrachloromethane at 85℃; for 24h; Inert atmosphere; Stage #2: With hydrogenchloride; water In tetrachloromethane Inert atmosphere;	98%
With potassium hydroxide In methanol at 35℃; for 0.333333h;	89%
With ammonium cerium(IV) nitrate In water; acetonitrile for 6h; Mechanism; Heating; other esters react in the same way;	58%
Stage #1: ethyl 4-chlorobenzoate With sodium hydroxide In water at 20℃; Stage #2: With hydrogenchloride In water
With water; lithium hydroxide In tetrahydrofuran at 25℃; for 6h; Reagent/catalyst; Solvent;	92 %Chromat.

p-chlorobenzoylmethanesulfonic acid (98554-12-2) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With water; sodium hydroxide for 5h; Heating;	98%

para-chloroacetophenone (99-91-2) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With 1,10-Phenanthroline; oxygen; copper diacetate; potassium hydroxide In dimethyl sulfoxide at 130℃; under 3000.3 Torr; for 12h; Autoclave;	97%
Stage #1: para-chloroacetophenone With tert.-butylhydroperoxide; sodium hydroxide; tungsten(VI) oxide In water at 80℃; for 8h; Stage #2: With hydrogenchloride In water	94%
With copper(II) nitrate trihydrate; oxygen In acetonitrile at 120℃; under 4500.45 Torr; for 10h; Autoclave;	93%

4-amino-benzoic acid (150-13-0) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With t-butyl thionitrite; copper dichloride In acetonitrile at 25℃; for 0.0333333h;	97%
Stage #1: 4-amino-benzoic acid With tert.-butylnitrite In acetonitrile at 20℃; Sandmeyer Reaction; Flow reactor; Stage #2: With copper dichloride In ethylene glycol; acetonitrile at 82℃; Sandmeyer Reaction; Flow reactor;	50%
With hydrogenchloride; potassium nitrite; dimethyl sulfoxide; copper(l) chloride In water at 35℃; for 0.5h;	77 % Chromat.

4-chloro-benzoic acid 3-methyl-but-2-enyl ester → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With Montmorillonite K-10 clay; toluene for 0.333333h; Dealkylation; Microwave irradiation;	97%
With toluene-4-sulfonic acid for 0.0666667h; microwave irradiation;	84%

benzyl p-chlorobenzoate (67483-73-2) + toluene (108-88-3) → 1-methyl-3-(phenylmethyl)-benzene (620-47-3) + 1-methyl-4-(phenylmethyl)benzene (620-83-7) + 2-benzyltoluene (713-36-0) + para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With boron trifluoride diethyl etherate; water at 80℃; for 2h; regioselective reaction;	A n/a B n/a C n/a D 97%

1-Chloro-4-(chloromethyl)benzene (104-83-6) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With sodium hydroxide In water; tert-butyl alcohol at 70℃; Ni-anode, 16 mA/cm2;	96%

4-chlorobenzyl bromide (622-95-7) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With Oxone In water; acetonitrile for 9h; Reflux;	96%
With sodium periodate; sulfuric acid In water at 95℃; for 12h;	79%
With tert.-butylhydroperoxide In water at 80℃; for 12h; Green chemistry;
Multi-step reaction with 2 steps 1: silver(I) nitrite / diethyl ether / 5 h / 0 °C / Reflux 2: tetra-(n-butyl)ammonium iodide; zinc diacetate; water / 24 h / 80 °C View Scheme

para-chlorotoluene (106-43-4) → N-acetoxy-1,8-naphthalenedicarboximide + para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With acetic acid In titanium	A n/a B 96%

1-(p-chlorophenyl)ethyl alcohol (3391-10-4) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With sodium nitrate; water; oxygen In dimethyl sulfoxide at 130℃; for 24h;	96%
With 1,10-Phenanthroline; oxygen; copper diacetate; potassium hydroxide In dimethyl sulfoxide at 130℃; under 3000.3 Torr; for 12h; Autoclave;	93%
With iron(III) chloride; cerium(III) chloride; tetrabutyl-ammonium chloride; oxygen In acetonitrile at 20℃; under 760.051 Torr; for 24h; Schlenk technique; Irradiation;	90%

para-chlorotoluene (106-43-4) → 4-chlorobenzaldehyde (104-88-1) + para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With hydrogenchloride; oxygen; 9-(2-mesityl)-10-methylacridinium perchlorate In acetonitrile at 4.84℃; for 12h; Irradiation;	A 5% B 95%
With N-hydroxyphthalimide; oxygen; cobalt(II) acetate In acetic acid at 25℃; under 760 Torr; for 20h;	A 3% B 67%
With sulfuric acid bei der elektrolytischen Oxydation;

para-dichlorobenzene (106-46-7) + carbon dioxide (124-38-9) → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With magnesium In tetrahydrofuran for 0.5h; Heating;	95%
With Al-anode In N,N-dimethyl-formamide at 20℃; electrocarboxylation;	78%
With tetrabutylammonium tetrafluoroborate In N,N-dimethyl-formamide at 20℃; under 760.051 Torr; for 4h; Electrolysis;	66%
Stage #1: para-dichlorobenzene With bis(cyclopentadienyl)titanium dichloride; butyl magnesium bromide In tetrahydrofuran at 40℃; for 6h; Inert atmosphere; Schlenk technique; Stage #2: carbon dioxide In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; Schlenk technique;	44%

4-chlorobenzaldehyde (104-88-1) → para-Chlorobenzyl alcohol (873-76-7) + para-chlorobenzoic acid (74-11-3)

Conditions	Yield
Stage #1: 4-chlorobenzaldehyde With potassium hydroxide for 0.0833333h; Cannizzaro Reaction; Milling; Inert atmosphere; Sealed tube; Green chemistry; Stage #2: With hydrogenchloride In water Green chemistry;	A 95% B 95%
With sodium hydroxide In water at 20℃; for 3.5h; Cannizzaro Reaction;	A n/a B 89%
With TEA; magnesium bromide In dichloromethane at 20℃; for 48h; Cannizzaro reaction;	A 88% B n/a

cinnamyl 4-chlorobenzoate → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With Montmorillonite K-10 clay; methoxybenzene for 0.333333h; Dealkylation; Microwave irradiation;	95%
With methoxybenzene In toluene for 15h; Heating;	5%

4-chlorophenyl trifluoromethanesulfonate (29540-84-9) + molybdenum hexacarbonyl → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With pyridine; 1,1'-bis-(diphenylphosphino)ferrocene; palladium diacetate at 150℃; for 0.333333h; microwave irradiation;	95%

C16H25ClO2Si → para-chlorobenzoic acid (74-11-3)

Conditions	Yield
With water; N,N-dimethyl-formamide at 70℃; for 1h; Green chemistry; chemoselective reaction;	95%

methanol (67-56-1) + para-chlorobenzoic acid (74-11-3) → Methyl 4-chlorobenzoate (1126-46-1)

Conditions	Yield
With sulfuric acid for 4h; Reflux;	100%
With sulfuric acid Fischer-Speier esterification method; Reflux;	100%
With di(methoxycarbonyl)methylene tri-n-butylphosphorane In toluene at 70℃; for 24h;	98%

para-chlorobenzoic acid (74-11-3) → 4-chloro-benzoyl chloride (122-01-0)

Conditions	Yield
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃;	100%
With thionyl chloride for 2h; Reflux;	100%
With oxalyl dichloride; N,N-dimethyl-formamide In dichloromethane at 20℃; for 2h; Reflux;	100%

para-chlorobenzoic acid (74-11-3) → para-Chlorobenzyl alcohol (873-76-7)

Conditions	Yield
With C25H42N6Rh(1+)*CF3O3S(1-); phenylsilane In tetrahydrofuran at 30℃; for 20h; Inert atmosphere;	100%
With samarium diiodide; benzaldehyde; samarium(III) trifluoromethanesulfonate In tetrahydrofuran; methanol; water at 20℃; for 0.0166667h; Reduction;	99%
With samarium diiodide; phosphoric acid In tetrahydrofuran for 0.000833333h; Ambient temperature;	94%

benzyl alcohol (100-51-6) + para-chlorobenzoic acid (74-11-3) → benzyl p-chlorobenzoate (67483-73-2)

Conditions	Yield
With N,N-bis[2-oxo-3-oxazolidinyl]phosphorodiamidic chloride In acetonitrile for 1.5h; Heating;	100%
Stage #1: para-chlorobenzoic acid With 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In neat (no solvent) at 20℃; for 0.0166667h; Stage #2: benzyl alcohol In neat (no solvent) at 20℃; for 0.216667h;	90%
Stage #1: para-chlorobenzoic acid With N-chlorobenzotriazole; triphenylphosphine In dichloromethane for 0.25h; Cooling; Stage #2: benzyl alcohol With triethylamine In dichloromethane at 20℃; for 0.583333h;	85%
With 2-butyl-1,3-diphenyl-1,3,2-diazaphospholidine; 1,1'-azodicarbonyl-dipiperidine In 1,2-dichloro-ethane at 40℃; under 760.051 Torr; Mitsunobu Displacement;	85%

para-chlorobenzoic acid (74-11-3) → benzoic acid (65-85-0)

Conditions	Yield
Stage #1: para-chlorobenzoic acid With palladium/alumina; hydrogen; potassium carbonate In water at 60℃; Stage #2: With hydrogenchloride In water	100%
With hydrogen; triethylamine; palladium on activated charcoal In methanol at 20℃; for 6h;	99%
With ammonium formate In water; isopropyl alcohol at 20℃; for 3h;	99%

4-(2-AMINOETHYL)MORPHOLINE (2038-03-1) + para-chlorobenzoic acid (74-11-3) → moclobemide (71320-77-9)

Conditions	Yield
With tetramethylorthosilicate In toluene at 110℃; for 1h; Inert atmosphere;	100%
With zirconocene dichloride In toluene at 110℃; for 24h; Inert atmosphere; sealed tube;	86%
With [((CH3)5Cp)2Zr(H2O)2OSO2C8F17]+[OSO2C8F17]-*THF In tetrahydrofuran at 100℃; for 12h; Catalytic behavior; Reagent/catalyst; Temperature;	85%

n-heptan1ol (111-70-6) + para-chlorobenzoic acid (74-11-3) → heptyl 4-chlorobenzoate (97222-05-4)

Conditions	Yield
With Candida antarctica lipase B immobilised in a macroporous DVB crosslinked polymer (Novozym 435) In cyclohexane at 80℃; for 24h; Enzymatic reaction;	100%

propargyl bromide (106-96-7) + para-chlorobenzoic acid (74-11-3) → prop-2-yn-1-yl 4-chlorobenzoate (79318-18-6)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene for 5h;	100%

ethanol (64-17-5) + para-chlorobenzoic acid (74-11-3) → ethyl 4-chlorobenzoate (7335-27-5)

Conditions	Yield
With sulfuric acid for 0.666667h; Reflux;	99.7%
With sulfuric acid for 5h; Reflux;	93.4%
With sulfuric acid for 3h; Heating;	87%

4-(diazomethyl)-7-methoxycoumarin (84471-16-9) + para-chlorobenzoic acid (74-11-3) → 4-Chloro-benzoic acid 7-methoxy-2-oxo-2H-chromen-4-ylmethyl ester (76196-61-7)

Conditions	Yield
In acetonitrile at 80℃; for 1h;	99.7%

aniline (62-53-3) + para-chlorobenzoic acid (74-11-3) → 4-chlorobenzanilide (6833-15-4)

Conditions	Yield
With fluorosulfonyl fluoride; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 5h;	99%
With nano sulfated-TiO2 at 115℃; under 760.051 Torr; for 4h; Neat (no solvent);	98%
With triethylamine; Phenyl N-phenylphosphoramidochloridate In dichloromethane for 0.333333h; Ambient temperature;	93%

para-chlorobenzoic acid (74-11-3) → 4-chlorobenzoic anhydride (790-41-0)

Conditions	Yield
With iodine; triethylamine; triphenylphosphine In dichloromethane at 0 - 20℃;	99%
With N,N-bis[2-oxo-3-oxazolidinyl]phosphorodiamidic chloride; tributyl-amine In acetonitrile at 20℃; for 0.5h;	97%
With thionyl chloride In dichloromethane at 22 - 25℃; for 1h;	96.9%

benzylamine (100-46-9) + para-chlorobenzoic acid (74-11-3) → N-benzyl-p-chlorobenzamide (7461-34-9)

Conditions	Yield
With Bromotrichloromethane; 4-(diphenylphosphino)-benzyltrimethylammonium bromide; triethylamine In tetrahydrofuran at 60℃; for 6h; Inert atmosphere;	99%
With borane-ammonia complex In 5,5-dimethyl-1,3-cyclohexadiene for 6h; Reflux;	99%
With nickel ferrite nanoparticle In neat (no solvent) for 0.166667h; Irradiation; Sealed tube;	92%

thiophene (188290-36-0) + para-chlorobenzoic acid (74-11-3) → 2-(4-chlorobenzoyl)thiophene (4153-45-1)

Conditions	Yield
With pyridin-2-yl trifluoromethanesulfonate; trifluoroacetic acid for 4h; Heating;	99%
With phosphoric acid; trifluoroacetic anhydride In water at 20℃; for 2h;	87%

benzyl bromide (100-39-0) + para-chlorobenzoic acid (74-11-3) → benzyl p-chlorobenzoate (67483-73-2)

Conditions	Yield
With N(Et)4(1+)*(2-pyrrolidone-anion) In N,N-dimethyl-formamide for 1h; Ambient temperature;	99%

N,O-dimethylhydroxylamine*hydrochloride (6638-79-5) + para-chlorobenzoic acid (74-11-3) → 4-chloro-N-methoxy-N-methylbenzamide (122334-37-6)

Conditions	Yield
With 4-methyl-morpholine; 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride In methanol at 20℃; for 0.5h;	99%
Stage #1: para-chlorobenzoic acid With 1,1'-carbonyldiimidazole In dichloromethane at 0℃; for 0.5h; Stage #2: N,O-dimethylhydroxylamine*hydrochloride With triethylamine In dichloromethane at 0 - 20℃;	99%
Stage #1: para-chlorobenzoic acid With triethylamine; trichloromethyl chloroformate In dichloromethane at 0℃; Stage #2: N,O-dimethylhydroxylamine*hydrochloride In dichloromethane at 25℃; for 1h;	96%

N,0-dimethylhydroxylamine (1117-97-1) + para-chlorobenzoic acid (74-11-3) → 4-chloro-N-methoxy-N-methylbenzamide (122334-37-6)

Conditions	Yield
Stage #1: N,0-dimethylhydroxylamine; para-chlorobenzoic acid In toluene at 0℃; for 0.166667h; Stage #2: With phosphorus trichloride In toluene at 20 - 60℃; for 0.5h;	99%
With 1,1'-carbonyldiimidazole
With triethylamine; 1,1'-carbonyldiimidazole

Boc-Apns-Dmt-NHtBu (159000-71-2) + para-chlorobenzoic acid (74-11-3) → (1S,2S)-2-[(tert-butoxycarbonyl)amino]-1-({(4R)-4-[(tert-butylamino)carbonyl]-5,5-dimethyl-1,3-thiazolan-3-yl}carbonyl)-3-phenylpropyl 4-chlorobenzoate

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In dichloromethane at 0 - 20℃;	99%
With dmap; dicyclohexyl-carbodiimide In dichloromethane at 20℃;

sodium cyanide (143-33-9) + para-chlorobenzoic acid (74-11-3) → 4-cyanobenzoic Acid (619-65-8)

Conditions	Yield
With nickel dibromide In 1-methyl-pyrrolidin-2-one at 200℃; under 10343 Torr; for 0.166667h; microwave irradiation;	99%

para-chlorobenzoic acid (74-11-3) + phenylboronic acid (98-80-6) → biphenyl-4-carboxylic acid (92-92-2)

Conditions	Yield
With potassium hydroxide In water at 80℃; for 2h; Suzuki Coupling; Green chemistry;	99%
With glucosamine-based dicyclohexylarylphosphine; sodium carbonate; palladium diacetate In ethanol; water; toluene at 80℃; Suzuki-Miyaura cross coupling reaction;	97%
With sodium hydroxide; polyaniline-supported palladium In water at 80℃; for 4h; Suzuki coupling;	97%

3-Carboxyphenylboronic acid (25487-66-5) + para-chlorobenzoic acid (74-11-3) → biphenyl-3,4′-dicarboxylic acid (92152-01-7)

Conditions	Yield
With sodium 2'‐(dicyclohexylphosphaneyl)‐2,6‐diisopropyl‐[1,1'‐biphenyl]‐3‐sulfonate; palladium diacetate; potassium carbonate In water at 50℃; for 8h; Suzuki-Miyaura coupling;	99%

Upstream product

• 623-03-0 4-Cyanochlorobenzene 
• 106-39-8 bromochlorobenzene 
• 109-72-8 n-butyllithium 
• 22711-23-5 4-chlorobenzil 
• 912-17-4 1,2-diphenyl-1,2-bis-(4-chlorophenyl)-ethanediol 
• 103-71-9 phenyl isocyanate 
• 98-59-9 p-toluenesulfonyl chloride 
• 860537-22-0 2-(N-ethyl-p-toluidino)-1-(4-chloro-phenyl)-ethanone 
• 622-57-1 N-ethyl-p-tolylamine 
• 13450-77-6 4-chlorohippuric acid 
• 50-00-0 formaldehyd 
• 65599-34-0 1-(4-chloro-phenyl)-3-(2-hydroxy-phenyl)-propane-1,3-dione 
• 1875-88-3 2-(4-Chlorophenyl)ethanol 
• 10570-46-4 (4-chloro-benzoyl)-phosphonic acid diethyl ester 

Downstream Products

• 19048-85-2 (4'-chlorobenzyl) 4-chlorobenzoate 
• 6961-42-8 4-chlorophenyl 4-chlorobenzoate 
• 4347-67-5 2-([1,1'-biphenyl]-4-yl)-2-oxoethyl 4-chlorobenzoate 
• 92425-06-4 4-chloro-benzoic acid-(4-bromo-phenacyl ester) 
• 5395-79-9 4'-methyl-4-chlorobenzophenone 
• 3857-70-3 4-chloro-benzoic acid octadecylamide 
• 7561-01-5 vinyl 4-chlorobenzoate 
• 20461-80-7 1-(4-chlorophenyl)-2-diazo-propan-1-one 
• 7461-33-8 4-Chloro-N-isobutyl-benzamid 
• 86026-65-5 (4-Chloro-phenyl)-{2-[2-(4-chloro-phenylsulfanyl)-ethyl]-pyrrolidin-1-yl}-methanone 
• 96145-18-5 2-Methyl-quinolin-4-ylamine; compound with 4-chloro-benzoic acid 
• 7455-77-8 2-(4-chlorophenyl)-4(3H)-quinazolinone 
• 53144-72-2 (4-chlorobenzyl)diphenylphosphine oxide 
• 54797-45-4 2-oxo-2-phenylethyl-4-chlorobenzoate 

Relevant articles and documents

A novel immobilised cobalt(III) oxidation catalyst

A complex form of cobalt(III) has been successfully immobilised on a chemically modified silica and proven to be an active catalyst for the selective oxidation of alkylaromatics using air as the source of oxygen and in the absence of solvent.

EVIDENCE D'UN MECANISME DE CATALYSE PAR TRANSFERT MONOELECTRONIQUE (ETC) POUR LA REACTION DE CANNIZZARO, EN PHASE HETEROGENE, EN CONDITIONS SONOCHIMIQUES

Additional evidence about an Electron Transfer Catalysis Mechanism (ETC) in the Cannizzaro reaction, catalyzed by solid bases under sonochemical conditions is shown.The reducing sites of basic solids and the ultrasound act in the first step of the ETC mechanism.

Gram-scale synthesis of carboxylic acids via catalytic acceptorless dehydrogenative coupling of alcohols and hydroxides at an ultralow Ru loading

Acceptorless dehydrogenative coupling (ADC) of alcohols and water/hydroxides is an emergent and graceful approach to produce carboxylic acids. Therefore, it is of high demand to develop active and practical catalysts/catalytic systems for this attractive transformation. Herein, we designed and fabricated a series of cyclometallated N-heterocyclic carbene-Ru (NHC-Ru) complexes via ligand tuning of [Ru-1], the superior complex in our previous work. Gratifyingly, gram-scale synthesis of carboxylic acids was efficiently enabled at an ultralow Ru loading (62.5 ppm) in open air. Moreover, effects of distinct ancillary NHC ligands and other parameters on this catalytic process were thoroughly studied, while further systematic studies were carried out to provide rationales for the activity trend of [Ru-1]-[Ru-7]. Finally, determination of quantitative green metrics illustrated that the present work exhibited superiority over representative literature reports. Hopefully, this study could provide valuable input for researchers who are engaging in metal-catalyzed ADC reactions.

Hydrolysis of amides to carboxylic acids catalyzed by Nb2O5

Hydrolysis of amides to carboxylic acids is an industrially important reaction but is challenging due to the difficulty of cleaving the resonance stabilized amidic C-N bond. Twenty-three heterogeneous and homogenous catalysts were examined in the hydrolysis of acetamide. Results showed that Nb2O5was the most effective heterogeneous catalyst with the greatest yield of acetic acid. A series of Nb2O5catalysts calcined at various temperatures were characterized and tested in the hydrolysis of acetamide to determine the effects of crystal phase and surface properties of Nb2O5on catalytic performance. The high catalytic performance observed was attributed mainly to the facile activation of the carbonyl bond by Lewis acid sites that function even in the presence of basic inhibitors (NH3and H2O). The catalytic studies showed the synthetic advantages of the present method, such as simple operation, catalyst recyclability, additive free, solvent free, and wide substrate scope (>40 examples; up to 95% isolated yield).