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106-48-9 Usage

Chemical Properties

Different sources of media describe the Chemical Properties of 106-48-9 differently. You can refer to the following data:
1. off-white to light tan crystals or powder
2. All isomers have a characteristic odor.

Uses

Different sources of media describe the Uses of 106-48-9 differently. You can refer to the following data:
1. Intermediates of Liquid Crystals
2. antineoplastic
3. Biocide; disinfectant for home, hospital and farm.
4. It is used as main raw material of compounding for medicine, dye, plastic and other industries. 4-Chlorophenol was used in visible-light-induced degradation of 4-chlorophenol in aqueous suspension of pure TiO2.

Definition

ChEBI: A monochlorophenol substituted at the pare position by a chlorine atom.

Synthesis Reference(s)

The Journal of Organic Chemistry, 50, p. 2145, 1985 DOI: 10.1021/jo00212a029Tetrahedron Letters, 24, p. 3117, 1983 DOI: 10.1016/S0040-4039(00)88111-3

General Description

White crystals with a strong phenol odor Slightly soluble to soluble in water, depending on the isomer, and denser than water. Noncombustible. Used as an intermediate in organic synthesis of dyes and drugs.

Air & Water Reactions

Slightly soluble to soluble in water.

Reactivity Profile

CHLOROPHENOLS, SOLID are incompatible with acid chlorides, acid anhydrides and oxidizing agents. Also incompatible with iron . Liquefy and darken in color at temperatures above 108°F.

Hazard

Toxic by skin absorption, inhalation, or ingestion; strong irritant to tissue.

Health Hazard

Inhalation causes headache, dizziness, weak pulse. Ingestion causes irritation of mouth and stomach; headache, dizziness, weak pulse. Contact with eyes causes severe irritation and burning. Contact with skin causes irritation and burn; if absorbed, causes same symptoms as inhalation.

Fire Hazard

Special Hazards of Combustion Products: Toxic and irritating hydrogen chloride and chlorine gases may form in fires.

Flammability and Explosibility

Notclassified

Safety Profile

Poison by inhalation and intraperitoneal routes. Moderately toxic by ingestion, skin contact, and subcutaneous routes. A severe skin and eye irritant. Human systemic effects by inhalation: excitement, irritability. Mutation data reported. Combustible when exposed to heat or flame. To fight fire, use water, spray, mist, fog, foam, dry chemical. When heated to decomposition it emits toxic fumes of Cl-. See also CHLOROPHENOLS and CHLORIDES.

Potential Exposure

Monochlorophenols are used in the manufacture of fungicides, slimicides, bactericides, pesticides, herbicides, disinfectants, wood and glue preservatives; in the production of phenolic resins; in the extraction of certain minerals from coal; as a denaturant for ethanol; as an antiseptic; as a disinfectant, and others.

Shipping

UN 2020 (solid); UN2021 (liquid) Chlorophenols, solid and liquid, Hazard Class: 6.1; Labels: 6.1-Poisonous materials.

Purification Methods

Distil the phenol, then crystallise it from pet ether (b 40-60o) or hexane, and dry it under vacuum over P2O5 at room temperature. [Bernasconi & Paschalis J Am Chem Soc 108 2969 1986, Beilstein 6 IV 820.]

Incompatibilities

May form explosive mixture with air. Contact with oxidizing agents can cause fire and explosion hazard. Heat produces hydrogen chloride and chlorine. Corrosive to aluminum, copper and other chemically active metals.

Waste Disposal

Incinerate in admixture with flammable solvent in furnace equipped with afterburner and scrubber.

Check Digit Verification of cas no

The CAS Registry Mumber 106-48-9 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,0 and 6 respectively; the second part has 2 digits, 4 and 8 respectively.
Calculate Digit Verification of CAS Registry Number 106-48:
(5*1)+(4*0)+(3*6)+(2*4)+(1*8)=39
39 % 10 = 9
So 106-48-9 is a valid CAS Registry Number.
InChI:InChI=1/C8H9ClO/c1-2-10-8-5-3-7(9)4-6-8/h3-6H,2H2,1H3

106-48-9 Well-known Company Product Price

  • Brand
  • (Code)Product description
  • CAS number
  • Packaging
  • Price
  • Detail
  • Alfa Aesar

  • (A15602)  4-Chlorophenol, 99%   

  • 106-48-9

  • 100g

  • 281.0CNY

  • Detail
  • Alfa Aesar

  • (A15602)  4-Chlorophenol, 99%   

  • 106-48-9

  • 250g

  • 460.0CNY

  • Detail
  • Alfa Aesar

  • (A15602)  4-Chlorophenol, 99%   

  • 106-48-9

  • 1000g

  • 1482.0CNY

  • Detail
  • Alfa Aesar

  • (A15602)  4-Chlorophenol, 99%   

  • 106-48-9

  • 5000g

  • 2602.0CNY

  • Detail
  • Sigma-Aldrich

  • (35826)  4-Chlorophenol  PESTANAL®, analytical standard

  • 106-48-9

  • 35826-1G

  • 179.01CNY

  • Detail
  • USP

  • (1496802)  Parachlorophenol  United States Pharmacopeia (USP) Reference Standard

  • 106-48-9

  • 1496802-500MG

  • 4,588.74CNY

  • Detail
  • Sigma-Aldrich

  • (25865)  4-Chlorophenolsolution  725 mg/L in H2O, for AOX determination (according to DIN 38409-H14)

  • 106-48-9

  • 25865-50ML

  • 403.65CNY

  • Detail

106-48-9SDS

SAFETY DATA SHEETS

According to Globally Harmonized System of Classification and Labelling of Chemicals (GHS) - Sixth revised edition

Version: 1.0

Creation Date: Aug 10, 2017

Revision Date: Aug 10, 2017

1.Identification

1.1 GHS Product identifier

Product name 4-chlorophenol

1.2 Other means of identification

Product number -
Other names p-Chlorophenol

1.3 Recommended use of the chemical and restrictions on use

Identified uses For industry use only.
Uses advised against no data available

1.4 Supplier's details

1.5 Emergency phone number

Emergency phone number -
Service hours Monday to Friday, 9am-5pm (Standard time zone: UTC/GMT +8 hours).

More Details:106-48-9 SDS

106-48-9Synthetic route

4-chloromethoxybenzene
623-12-1

4-chloromethoxybenzene

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With sodium; diphenyldisulfane In 1-methyl-pyrrolidin-2-one for 0.5h; Heating;100%
With calcium hydride; diphenyldisulfane In 1-methyl-pyrrolidin-2-one at 220℃; for 0.5h;99%
With copper(I) oxide; sodium methylate In methanol at 185℃; for 12h; Autoclave;96%
n-butyllithium
109-72-8, 29786-93-4

n-butyllithium

(4-Chlorophenoxy)dimethylsulfoxonium Tetrafluoroborate
73040-88-7

(4-Chlorophenoxy)dimethylsulfoxonium Tetrafluoroborate

A

n-butyl 4-chlorophenyl ether
51241-35-1

n-butyl 4-chlorophenyl ether

B

[(18)O]dimethyl sulfone

[(18)O]dimethyl sulfone

C

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With 18O-labeled water In 1,2-dimethoxyethane at -11 - 25℃; Product distribution; Mechanism;A 5%
B 100%
C 79%
1,1'-sulfinylbisbenzene
945-51-7

1,1'-sulfinylbisbenzene

A

2-monochlorophenol
95-57-8

2-monochlorophenol

B

diphenyl sulfide
139-66-2

diphenyl sulfide

C

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With hydrogenchloride; phenol In dichloromethane at 0 - 25℃;A n/a
B 100%
C n/a
1-methoxyl-4-(phenylsulfinyl)benzene
951-92-8

1-methoxyl-4-(phenylsulfinyl)benzene

A

2-monochlorophenol
95-57-8

2-monochlorophenol

B

1-methoxy-4-(phenylsulfanyl)benzene
5633-57-8

1-methoxy-4-(phenylsulfanyl)benzene

C

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With hydrogenchloride; phenol In dichloromethane at 0 - 25℃;A n/a
B 100%
C n/a
ammonium thiocyanate

ammonium thiocyanate

4-chlorophenyl 1-chloroethylcarbonate
117971-97-8

4-chlorophenyl 1-chloroethylcarbonate

A

4-chlorophenyl 1-thiocyanoethylcarbonate
117972-05-1

4-chlorophenyl 1-thiocyanoethylcarbonate

B

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
In formamide at 50℃; for 20h;A 100%
B n/a
1-<(tert-butyldimethylsilyl)oxy>-4-chlorobenzene
126644-72-2

1-<(tert-butyldimethylsilyl)oxy>-4-chlorobenzene

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With potassium hydroxide In ethanol at 20℃; for 0.3h;99%
With sodium phosphate dodecahydrate In N,N-dimethyl-formamide at 20℃; for 0.3h;98%
With hafnium tetrakis(trifluoromethanesulfonate) In methanol at 20℃; for 8h;96%
With P(MeNCH2CH2)3N In dimethyl sulfoxide at 80℃; for 24h; desilylation;94%
4-Chlorophenylboronic acid
1679-18-1

4-Chlorophenylboronic acid

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With 2,5-dimethylfuran; zinc(II) phthalocyanine; oxygen In tetrahydrofuran at 25℃; under 760.051 Torr; for 1.5h; Irradiation; Sealed tube; Schlenk technique;99%
With water In tetrahydrofuran at 100℃; for 12h;99%
With dihydrogen peroxide In acetonitrile at 30 - 35℃; for 0.0833333h; Schlenk technique;98%
4-chlorophenoxytrimethylsilane
17005-59-3

4-chlorophenoxytrimethylsilane

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With bismuth(lll) trifluoromethanesulfonate In methanol at 20℃; for 0.0333333h;99%
With nano magnetic sulfated zirconia (Fe3O4 at ZrO2/SO42-) In neat (no solvent) at 20℃; for 0.75h; Green chemistry;91%
With K5 In acetonitrile at 20℃; for 1.25h;5 % Chromat.
With (NH4)8[CeW10O36]*20H2O In acetonitrile at 20℃; for 0.5h;55 %Chromat.
1-<(tert-butyldimethylsilyl)oxy>-4-chlorobenzene
126644-72-2

1-<(tert-butyldimethylsilyl)oxy>-4-chlorobenzene

Cs2CO3

Cs2CO3

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
In water; N,N-dimethyl-formamide at 20℃; for 1h;99%
1-Chloro-4-iodobenzene
637-87-6

1-Chloro-4-iodobenzene

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With glycolic Acid; copper hydroxide; sodium hydroxide In water; dimethyl sulfoxide at 120℃; for 6h; Inert atmosphere; Schlenk technique;99%
Stage #1: 1-Chloro-4-iodobenzene With copper(l) iodide; cesiumhydroxide monohydrate; 1,3-diphenylpropanedione In water; dimethyl sulfoxide at 130℃; for 36h; Inert atmosphere;
Stage #2: With hydrogenchloride In dichloromethane; water; dimethyl sulfoxide at 20℃; Inert atmosphere; chemoselective reaction;
95%
With copper(l) iodide; potassium hydroxide In water at 100℃; Inert atmosphere;94%
potassium (4-chlorophenyl)trifluoroborate

potassium (4-chlorophenyl)trifluoroborate

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With Oxone; water In acetone at 20℃; for 0.0333333h;99%
With rose bengal; triethylamine In ethanol at 25℃; for 12h; Schlenk technique; Irradiation;60%
2-(4-chlorophenoxy)ethanol
1892-43-9

2-(4-chlorophenoxy)ethanol

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With potassium hydroxide In dimethyl sulfoxide at 100℃; for 3h; Schlenk technique;99%
1,2,3-Benzotriazole
95-14-7

1,2,3-Benzotriazole

p-chlorophenyl 2-benzoxazolyl ether
50798-82-8

p-chlorophenyl 2-benzoxazolyl ether

A

4-chloro-phenol
106-48-9

4-chloro-phenol

B

1-(2-benzoxazolyl)-1H-benzotriazole
25124-80-5

1-(2-benzoxazolyl)-1H-benzotriazole

Conditions
ConditionsYield
With hydridotetakis(triphenylphosphine)rhodium(I); o-phenylenebis(diphenylphosphine) In chlorobenzene for 5h; Inert atmosphere; Reflux;A 95%
B 99%
4-chlorophenyl acetate
876-27-7

4-chlorophenyl acetate

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
silica gel; toluene-4-sulfonic acid In water; benzene at 80℃; for 40h;98%
With sodium tetrahydroborate; cobalt(II) chloride In ethanol at 0 - 25℃; for 10h;97%
With sodium hydrogencarbonate In water at 20℃; for 4h;97%
1-allyloxy-4-chlorobenzene
13997-70-1

1-allyloxy-4-chlorobenzene

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With chloro-trimethyl-silane; sodium iodide In acetonitrile for 0.0333333h;98%
With iodine at 20℃; Reagent/catalyst;96%
With sodium tetrahydroborate; nickel(II) chloride hexahydrate In methanol at 0℃;90%
4-chloro-N-[2,2-dichloro-1-(4-chlorophenoxy)-2-phenylethyl]benzenesulfonamide
1329689-03-3

4-chloro-N-[2,2-dichloro-1-(4-chlorophenoxy)-2-phenylethyl]benzenesulfonamide

A

4-chloro-phenol
106-48-9

4-chloro-phenol

B

4-chloro-N-(2,2-dichloro-1-hydroxy-2-phenylethyl)benzenesulfonamide
360564-14-3

4-chloro-N-(2,2-dichloro-1-hydroxy-2-phenylethyl)benzenesulfonamide

Conditions
ConditionsYield
With waterA n/a
B 98%
4-Chlorophenylboronic acid
1679-18-1

4-Chlorophenylboronic acid

dihydrogen peroxide
7722-84-1

dihydrogen peroxide

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With ammonium bicarbonate In water at 20℃; for 2h; Schlenk technique;98%
sulfur bis(trifluoromethyl)amide chloride
1768-32-7

sulfur bis(trifluoromethyl)amide chloride

phenol
108-95-2

phenol

A

sulfur bis{bis(trifluoromethyl)amide}
1913-85-5

sulfur bis{bis(trifluoromethyl)amide}

B

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
In diethyl ether at 20℃; for 24h;A 95%
B 97%
4-chlorophenyl tetrahydro-2H-pyran-2-yl ether
20443-90-7

4-chlorophenyl tetrahydro-2H-pyran-2-yl ether

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With methanol at 20℃; for 0.5h;97%
With aluminium(III) iodide; N,N-dimethyl-formamide dimethyl acetal In acetonitrile at 80℃; for 18h;96%
With aluminium(III) iodide; N,N-dimethyl-formamide dimethyl acetal In acetonitrile at 80℃;96%
phenol
108-95-2

phenol

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With N-chloro-succinimide; 2C5HN10(3-)*2Mn(2+)*Cu(2+)*5H2O In acetonitrile at 90℃; for 6h; Catalytic behavior; Reagent/catalyst; Solvent; Temperature; regioselective reaction;95%
With chloro(dimethyl)sulfonium chloride In dichloromethane at -25℃; for 4h;84%
Stage #1: phenol In acetonitrile at 80℃; for 0.166667h;
Stage #2: With N-chloro-succinimide In acetonitrile at 80℃; for 8h; regioselective reaction;
77%
di(p-tolyl) sulfoxide
1774-35-2

di(p-tolyl) sulfoxide

A

di-(p-tolyl)sulfane
620-94-0

di-(p-tolyl)sulfane

B

2-monochlorophenol
95-57-8

2-monochlorophenol

C

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With hydrogenchloride; phenol In dichloromethane at 0 - 25℃;A 95%
B n/a
C n/a
Z-L-Phe p-chlorophenyl ester
3272-95-5

Z-L-Phe p-chlorophenyl ester

H-Gly-NH2
598-41-4

H-Gly-NH2

A

Z-L-phenylalanylglycinamide
17187-05-2

Z-L-phenylalanylglycinamide

B

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With thiolsubtilisin In water; N,N-dimethyl-formamide Ambient temperature; pH 8.0 phosphate buffer containing PhB(OH)2 traces;A 95%
B n/a
With thiolsubtilisin In water; N,N-dimethyl-formamide Ambient temperature; further acyl donors and acyl acceptors; method for enzymic peptid segment coupling;A 95%
B n/a
4-chlorophenyl benzoate
2005-08-5

4-chlorophenyl benzoate

2-amino-benzenethiol
137-07-5

2-amino-benzenethiol

A

2-Phenylbenzothiazole
883-93-2

2-Phenylbenzothiazole

B

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With 1-methyl-pyrrolidin-2-one; potassium carbonate at 100℃; for 0.75h; Hydrolysis; cyclization; debenzoylation;A n/a
B 95%
4-Chlorophenylboronic acid
1679-18-1

4-Chlorophenylboronic acid

acetonitrile complex of hypofluorous acid

acetonitrile complex of hypofluorous acid

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
In dichloromethane at 20℃;95%
4-Chlorophenylboronic acid
1679-18-1

4-Chlorophenylboronic acid

oxygen
80937-33-3

oxygen

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With triethanolamine In water at 20℃; for 18h; Sonication; Irradiation; Green chemistry;95%
With methylene blue; N-ethyl-N,N-diisopropylamine In water; acetonitrile at 20℃; for 7h; Schlenk technique; Irradiation;
(5‐chloro‐2‐hydroxyphenyl)boronic acid
89488-25-5

(5‐chloro‐2‐hydroxyphenyl)boronic acid

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
In dimethyl sulfoxide at 120℃; for 18h;95%
3-(4-chlorophenoxy)-1-propanol
18673-04-6

3-(4-chlorophenoxy)-1-propanol

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With potassium hydroxide In dimethyl sulfoxide at 100℃; for 3h; Schlenk technique;95%
1-chloro-4-((2-methoxyethoxy)methoxy)benzene

1-chloro-4-((2-methoxyethoxy)methoxy)benzene

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With aluminium(III) iodide; N,N-dimethyl-formamide dimethyl acetal In acetonitrile at 80℃; for 18h;94%
With aluminium(III) iodide; N,N-dimethyl-formamide dimethyl acetal In acetonitrile at 80℃; for 18h;94%
bis(4-chlorophenyl)sulfoxide
3085-42-5

bis(4-chlorophenyl)sulfoxide

A

bis(4-chlorophenyl)sulfide
5181-10-2

bis(4-chlorophenyl)sulfide

B

2-monochlorophenol
95-57-8

2-monochlorophenol

C

4-chloro-phenol
106-48-9

4-chloro-phenol

Conditions
ConditionsYield
With hydrogenchloride; phenol In dichloromethane at 0 - 25℃;A 93%
B n/a
C n/a
acetic anhydride
108-24-7

acetic anhydride

4-chloro-phenol
106-48-9

4-chloro-phenol

4-chlorophenyl acetate
876-27-7

4-chlorophenyl acetate

Conditions
ConditionsYield
K5 In acetonitrile at 20℃; for 0.25h;100%
With magnesium(II) perchlorate at 80℃; for 0.25h;100%
With sodium hydroxide for 0.0125h; microwave irradiation;99%
4-chloro-phenol
106-48-9

4-chloro-phenol

4-Fluoronitrobenzene
350-46-9

4-Fluoronitrobenzene

4-(4-chlorophenoxy)nitrobenzene
1836-74-4

4-(4-chlorophenoxy)nitrobenzene

Conditions
ConditionsYield
With cesium fluoride/clinoptilolite In dimethyl sulfoxide at 110℃; for 0.15h; Ullmann Condensation;100%
With potassium fluoride supported on Clinoptilolite In dimethyl sulfoxide at 110 - 115℃; for 1.66667h;95%
With potassium carbonate In dimethyl sulfoxide at 70℃;92%
4-chloro-phenol
106-48-9

4-chloro-phenol

4-chloro-2,6-dinitrophenol
88-87-9

4-chloro-2,6-dinitrophenol

Conditions
ConditionsYield
With dinitrogen tetraoxide; ferric nitrate In ethyl acetate for 0.0833333h; Heating;100%
With chromium(III) nitrate; dinitrogen tetraoxide In ethyl acetate for 0.166667h; Nitration; reflux;98%
With Tetraethylene glycol; silica gel; dinitrogen tetraoxide In ethyl acetate for 0.833333h; Heating;98%
4-chloro-phenol
106-48-9

4-chloro-phenol

1,1,1,3,3,3-hexamethyl-disilazane
999-97-3

1,1,1,3,3,3-hexamethyl-disilazane

4-chlorophenoxytrimethylsilane
17005-59-3

4-chlorophenoxytrimethylsilane

Conditions
ConditionsYield
With aluminum potassium sulfate dodecahydrate In acetonitrile at 20℃; for 0.333333h;100%
With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione at 20℃; for 0.25h;98%
With melamine-N2,N4,N6-trisulfonic acid at 20℃; for 0.166667h; neat (no solvent); chemoselective reaction;98%
tert-butyldimethylsilyl chloride
18162-48-6

tert-butyldimethylsilyl chloride

4-chloro-phenol
106-48-9

4-chloro-phenol

1-<(tert-butyldimethylsilyl)oxy>-4-chlorobenzene
126644-72-2

1-<(tert-butyldimethylsilyl)oxy>-4-chlorobenzene

Conditions
ConditionsYield
With 1H-imidazole In N,N-dimethyl-formamide at 20℃;100%
With dmap; triethylamine In [D3]acetonitrile at 25℃; for 0.2h;99%
With triethylamine at 20℃; for 0.166667h; Inert atmosphere;95%
dichloromethane
75-09-2

dichloromethane

4-chloro-phenol
106-48-9

4-chloro-phenol

bis(p-chlorophenoxy)methane
555-89-5

bis(p-chlorophenoxy)methane

Conditions
ConditionsYield
With potassium hydroxide; benzyltrimethylammonium chloride In water at 40℃; for 72h;100%
With potassium hydroxide; benzyltrimethylammonium chloride In dichloromethane at 40℃; for 72h;100%
Stage #1: 4-chloro-phenol With sodium hydride In 1-methyl-pyrrolidin-2-one
Stage #2: dichloromethane In 1-methyl-pyrrolidin-2-one at 40℃; for 9h;
98%
With 1-methyl-pyrrolidin-2-one; sodium hydride at 40℃; for 9h;98%
With sodium hydroxide; Amberlite IRA-400 (Cl-) 2.) reflux, 15 h; Yield given. Multistep reaction;
dabsyl chloride
56512-49-3

dabsyl chloride

4-chloro-phenol
106-48-9

4-chloro-phenol

4-(4-Dimethylamino-phenylazo)-benzenesulfonic acid 4-chloro-phenyl ester
146303-65-3

4-(4-Dimethylamino-phenylazo)-benzenesulfonic acid 4-chloro-phenyl ester

Conditions
ConditionsYield
With carbonate-bicarbonate In acetone; acetonitrile for 0.25h; Product distribution; other (mono-, di- and trihydric) phenols; effect of reaction time, pH, molar ratio, concentration;100%
With carbonate-bicarbonate buffer In acetone; acetonitrile 1.) 15 min, 2.) reflux;100%
With carbonate-bicarbonate buffer In acetone for 0.5h; Heating;
4-chloro-phenol
106-48-9

4-chloro-phenol

1,1,3,3-tetramethyldisilazane
15933-59-2

1,1,3,3-tetramethyldisilazane

(4-Chloro-phenoxy)-dimethyl-silane
30342-25-7

(4-Chloro-phenoxy)-dimethyl-silane

Conditions
ConditionsYield
100%
at 20 - 160℃; for 2h; Inert atmosphere;
4-chloro-phenol
106-48-9

4-chloro-phenol

phenol
108-95-2

phenol

Conditions
ConditionsYield
With hydrogen; sodium hydroxide In water under 760.051 Torr; for 0.833333h; Kinetics; Reagent/catalyst; Solvent; Green chemistry;100%
With hydrogen; sodium hydroxide In water at 20℃; for 2h; Kinetics; Catalytic behavior; Solvent; Reagent/catalyst;99.1%
With hydrogen; sodium hydroxide In water at 25℃; under 760.051 Torr; for 2h; Reagent/catalyst; Solvent;99.9%
3,5-dinitrobenzotrifluoride
401-99-0

3,5-dinitrobenzotrifluoride

4-chloro-phenol
106-48-9

4-chloro-phenol

1-(4-chlorophenoxy)-3-nitro-5-trifluoromethylbenzene

1-(4-chlorophenoxy)-3-nitro-5-trifluoromethylbenzene

Conditions
ConditionsYield
With potassium carbonate In N,N-dimethyl-formamide at 98℃; for 3h;100%
With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 3h; Activation energy; Inert atmosphere;54%
With potassium carbonate In N,N-dimethyl-formamide
4-fluorobenzonitrile
1194-02-1

4-fluorobenzonitrile

4-chloro-phenol
106-48-9

4-chloro-phenol

4-(4'-chlorophenoxy)benzonitrile
74448-92-3

4-(4'-chlorophenoxy)benzonitrile

Conditions
ConditionsYield
With sodium carbonate In N,N-dimethyl-formamide for 24h; Reflux;100%
With potassium carbonate In N,N-dimethyl-formamide Reflux;96%
With sodium carbonate In N,N-dimethyl-formamide for 24h; Reflux;95%
bisphenol AF bisoxalyl chloride adduct
335148-89-5

bisphenol AF bisoxalyl chloride adduct

4-chloro-phenol
106-48-9

4-chloro-phenol

bisphenol-AF bis(4-chlorophenyl oxalate)

bisphenol-AF bis(4-chlorophenyl oxalate)

Conditions
ConditionsYield
In dichloromethane at -20℃; Heating / reflux;100%
{Ni(Al(O-i-Pr)4)2}

{Ni(Al(O-i-Pr)4)2}

4-chloro-phenol
106-48-9

4-chloro-phenol

{Ni(Al(O-i-Pr)(p-ClC6H4O)3)2}

{Ni(Al(O-i-Pr)(p-ClC6H4O)3)2}

Conditions
ConditionsYield
In benzene byproducts: isopropanol; anhyd. conditions; Ni(Al(OC3H7)4)2 : p-chlorophenol = 1 : 6; refluxed (4 h); solvent removed (reduced pressure);100%
{Co(Al(O-i-Pr)4)2}

{Co(Al(O-i-Pr)4)2}

4-chloro-phenol
106-48-9

4-chloro-phenol

{Co(Al(O-i-Pr)2(p-ClC6H4O)2)2}

{Co(Al(O-i-Pr)2(p-ClC6H4O)2)2}

Conditions
ConditionsYield
In benzene byproducts: isopropanol; anhyd. conditions; Co(Al(OC3H7)4)2 : p-chlorophenol = 1 : 4; refluxed (2 h); solvent removed (reduced pressure); elem.anal.;100%
2-Iodobenzyl bromide
40400-13-3

2-Iodobenzyl bromide

4-chloro-phenol
106-48-9

4-chloro-phenol

4-(2-iodobenzyloxy)-1-chlorobenzene
1332326-20-1

4-(2-iodobenzyloxy)-1-chlorobenzene

Conditions
ConditionsYield
With potassium carbonate In acetone at 50℃;100%
4-chloro-phenol
106-48-9

4-chloro-phenol

2,4-dinitrophenyl benzoate
1523-15-5

2,4-dinitrophenyl benzoate

A

4-chlorophenyl benzoate
2005-08-5

4-chlorophenyl benzoate

B

potassium 2,4-dinitrophenolate
14314-69-3

potassium 2,4-dinitrophenolate

Conditions
ConditionsYield
With potassium hydrogencarbonate In N,N-dimethyl-formamide at 25℃; for 5h;A 100%
B n/a
ethyl 3-(chloromethyl)-4-methoxybenzoate
858124-04-6

ethyl 3-(chloromethyl)-4-methoxybenzoate

4-chloro-phenol
106-48-9

4-chloro-phenol

ethyl 3-[(4-chlorophenoxy)methyl]-4-methoxybenzoate
1360060-15-6

ethyl 3-[(4-chlorophenoxy)methyl]-4-methoxybenzoate

Conditions
ConditionsYield
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 13h;100%
5-methyl-3,4-hexadien-1-ol
54795-27-6

5-methyl-3,4-hexadien-1-ol

4-chloro-phenol
106-48-9

4-chloro-phenol

1-chloro-4-(5-methylhexa-3,4-dienyloxy)benzene
1376520-79-4

1-chloro-4-(5-methylhexa-3,4-dienyloxy)benzene

Conditions
ConditionsYield
With di-isopropyl azodicarboxylate; triphenylphosphine In tetrahydrofuran at 0 - 20℃; Inert atmosphere;100%
4-chloro-phenol
106-48-9

4-chloro-phenol

dimethylamino sulfonyl chloride
13360-57-1

dimethylamino sulfonyl chloride

4-chlorophenyl N,N-dimethylsulfamate
1135-05-3

4-chlorophenyl N,N-dimethylsulfamate

Conditions
ConditionsYield
Stage #1: 4-chloro-phenol With sodium hydride In 1,2-dimethoxyethane; mineral oil at 0 - 20℃; for 0.166667h;
Stage #2: dimethylamino sulfonyl chloride In 1,2-dimethoxyethane; mineral oil at 0 - 20℃; for 16h;
100%
Stage #1: 4-chloro-phenol With sodium hydride In 1,2-dimethoxyethane; mineral oil at 0 - 20℃; for 10h;
Stage #2: dimethylamino sulfonyl chloride In 1,2-dimethoxyethane; mineral oil at 0 - 20℃;
83%
2-methylbenzoic acid 2-pyridinyl ester
73686-46-1

2-methylbenzoic acid 2-pyridinyl ester

4-chloro-phenol
106-48-9

4-chloro-phenol

2-methyl-benzoic acid-(4-chloro-phenyl ester)
500285-59-6

2-methyl-benzoic acid-(4-chloro-phenyl ester)

Conditions
ConditionsYield
With potassium carbonate In 1,4-dioxane at 60℃; for 48h; Green chemistry;100%
2,3-dichloropyrazine
4858-85-9

2,3-dichloropyrazine

4-chloro-phenol
106-48-9

4-chloro-phenol

C9H5Cl2N3O

C9H5Cl2N3O

Conditions
ConditionsYield
With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 15h;100%
2,3-dichloropyrazine
4858-85-9

2,3-dichloropyrazine

4-chloro-phenol
106-48-9

4-chloro-phenol

2-chloro-3-(4-chlorophenoxy)pyrazine

2-chloro-3-(4-chlorophenoxy)pyrazine

Conditions
ConditionsYield
With potassium carbonate In N,N-dimethyl-formamide at 90℃; for 15h;100%
3-chloro-4-fluoronitrobenzene
350-30-1

3-chloro-4-fluoronitrobenzene

4-chloro-phenol
106-48-9

4-chloro-phenol

4-(4'-chlorophenoxy)-3-chloronitrobenzene
22544-07-6

4-(4'-chlorophenoxy)-3-chloronitrobenzene

Conditions
ConditionsYield
With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 17h;100%
With caesium carbonate In dimethyl sulfoxide for 4h;
C16H11I

C16H11I

4-chloro-phenol
106-48-9

4-chloro-phenol

C22H15ClO

C22H15ClO

Conditions
ConditionsYield
Stage #1: 4-chloro-phenol With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.0833333h;
Stage #2: C16H11I In N,N-dimethyl-formamide; mineral oil at 0 - 20℃; for 12h;
100%
fluoroformyl chloride
353-49-1

fluoroformyl chloride

4-chloro-phenol
106-48-9

4-chloro-phenol

4-chlorophenyl fluoroformate
1644-73-1

4-chlorophenyl fluoroformate

Conditions
ConditionsYield
With triethylamine In toluene at 60℃;99.8%

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106-48-9Relevant articles and documents

Photodegradation of Azole Fungicide Triadimefon

Nag, Subir K.,Dureja, Prem

, p. 294 - 298 (1997)

To examine the photostability of the fungicide triadimefon [1-(4-chlorophenoxy)-3,3-dimethyl-1H-(1,2,4-triazol-1-yl)butan-2-one] in the field, model experiments with organic solvents were performed. Photolysis in methanol, hexane, and acetone resulted in considerable formation of 1-(4-chlorophenoxy)-3,3-dimethylbutan-2-one, 1-[(4-chlorophenoxy)methyl]-1H-1,2,4-triazole, 1H-(1,2,4-triazol-1-yl)-3,3-dimethylbutan-2-one, and 1-phenoxy-3,3-dimethyl-1H-(1,2,4-triazol-1-yl)butan-2-one. The rate of photodegradation in different solvents followed first-order rate kinetics with a significant correlation coefficient.

Regioselective chlorination of phenols in the presence of tetrahydrothiopyran derivatives

Smith, Keith,Williams, Des,El-Hiti, Gamal A.

, p. 529 - 538 (2019)

Four six-membered cyclic sulfides, namely tetrahydrothiopyran, 3-methyltetrahydrothiopyran, 4-methyltetrahydrothiopyran and 4,4-dimethyltetrahyrdrothiopyran have been used as moderators in chlorination reactions of various phenols with sulfuryl chloride in the presence of aluminum or ferric chloride. On chlorination of phenol, ortho-cresol and meta-cresol the para/ortho chlorination ratios and yields of the para-chloro isomers are higher than when no cyclic sulfide is used for all of the cyclic sulfides, but chlorination of meta-xylenol is less consistent, with some cyclic sulfides producing higher p/o ratios and others producing lower ratios than reactions having no sulfide present.

Regiospecific Chlorination of Aromatic Substrates using Donor-Acceptor and Hydrogen Bonding Interactions

Guy, Alain,Lemaire, Marc,Guette, Jean-Paul

, p. 8 - 9 (1980)

The chlorination of aromatic substances has been achieved with good regioselectivity using 2,3,4,4,5,6-hexachlorocyclohexa-2,5-dien-1-one and 2,3,4,5,6,6-hexachlorocyclohexa-2,4-dien-1-one as chlorinating agents.

Kinetics and mechanism of the reaction of α-phenoxypropanoic acids with sodium salt of N-chlorobenzene-sulphonamide: EDTA catalysis

Meenakshisundaram, Subbiah,Selvaraju

, p. 27 - 33 (2002)

EDTA smoothly catalyses the oxidation cum chlorination of some 17 α-phenoxypropanoic acids with sodium salt of N-chlorobenzenesulphonamide in acidic solution. A ternary intermediate can be envisaged for describing the enhanced reactivity. Imperfections are observed in the linear Hammett relationship in the case of-NO2 substituents, irrespective of the position. The susceptibility constant, p(≈ + 1) indicates the development of an electron-rich transition state.

Hydroxylation of Benzene with Dinitrogen Monoxide over H-ZSM-5 Zeolite

Suzuki, Eiichi,Nakashiro, Katsumi,Ono, Yoshio

, p. 953 - 956 (1988)

Phenol was obtained from benzene and dinitrogen monoxide over H-ZSM-5-zeolite at 603 K, a phenol yield on a benzene basis being 8.1percent at partial pressures of benzene and dinitrogen monoxide of 6.9 kPa and 51 kpa, respectively.Neither CO nor CO2 was detected in the product.

-

Goldsmith,Endres,Dirsch

, p. 577 (1925)

-

Pd-Fe/SiO2 and Pd-Fe/Al2O3 catalysts for selective hydrodechlorination of 2,4-dichlorophenol into phenol

Witońska, Izabela A.,Walock, Michael J.,Binczarski, Micha?,Lesiak, Magdalena,Stanishevsky, Andrei V.,Karski, Stanis?aw

, p. 248 - 256 (2014)

The effect of iron introduction on the activity and selectivity of chemically precipitated supported palladium catalysts in the hydrodechlorination of 2,4-dichlorophenol in liquid phase at room temperature was studied. Bimetallic Pd-Fe catalysts supported

N-Chloro-2,3,4,4,5,6-hexachlorocyclohexa-2,5-dienylideneamine as a mild and highly regioselective chlorinating reagent

Mamaghani,Zolfigol,Shojaei

, p. 735 - 740 (2002)

N-Chloro-2,3,4,4,5,6-hexachlorocyclohexa-2,5-dienylideneamine was used as a new, mild and highly regioselective chlorinating reagent in the chlorination of phenol and o-cresol in CCl4, DMF and CH3CN. The effects of C2H5OH, C5H5N, DMF and Et3N on the regioselectivity in CCl4 have also been examined.

Enhanced dechlorination performance of 2,4-dichlorophenol by vermiculite supported iron nanoparticles doped with palladium

Wu, Pingxiao,Liu, Chongmin,Huang, Zhujian,Wang, Wanmu

, p. 25580 - 25587 (2014)

In this study, environment-friendly vermiculite (VMT) was used to support nanoscale zero-valent iron (nZVI) and nZVI doped with palladium (abbreviated as Fe-VMT and Pd/Fe-VMT, respectively). The physicochemical properties of the products obtained were analyzed by X-ray diffraction (XRD), specific surface area (BET), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results showed that the BET surface areas of Fe-VMT and Pd/Fe-VMT were 39.5 m2 g-1 and 59.1 m2 g-1, and 18.9 m2 g-1 for unsupported nZVI nanoparticles. The presence of vermiculite led to a decrease in the aggregation of nZVI and Pd/Fe as observed by SEM and TEM. Batch experiments were conducted to investigate the catalytic performance of nZVI, Pd/Fe, VMT, Fe-VMT and Pd/Fe-VMT via the dechlorination reaction of 2,4-dichlorophenol (2,4-DCP). The dechlorination rates of 2,4-DCP by Pd/Fe-VMT (by adding Pd) were greater than that achieved by Fe-VMT. Additionally, the dechlorination of 2,4-DCP by Pd/Fe-VMT would be influenced by temperature, initial pH values, Pd loading, initial concentration of 2,4-DCP and the dosage of materials. It was confirmed that the ultimate reduction product of 2,4-DCP was phenol. Overall, Pd/Fe-VMT is a promising material for the dechlorination of 2,4-DCP. the Partner Organisations 2014.

Effect of β-cyclodextrin on the hydrolysis of trifluoroacetate esters

Fernandez,De Rossi,Cervello, Enric,Jaime, Carlos

, p. 4399 - 4404 (2001)

The hydrolysis of p-F, p-Cl, and m-Cl phenyl trifluoracetates was studied in the presence of β-cyclodextrin (β-CD). The reactions are inhibited by β-CD at pH 6 while they are catalyzed in alkaline solution. MM3 calculations reproduce some of the experimen

An experimental and numerical study of the thermal oxidation of chlorobenzene

Higgins, Brian,Thomson, Murray J.,Lucas, Donald,Koshland, Catherine P.,Sawyer, Robert F.

, p. 703 - 717 (2001)

A combustion-driven flow reactor was used to examine the formation of chlorinated and non-chlorinated species from the thermal oxidation of chlorobenzene under post-flame conditions. Temperature varied from 725 to 1000 K, while the equivalence ratio was held constant at 0.5. Significant quantities of chlorinated intermediates, vinyl chloride and chlorophenol, were measured. A dominant C-Cl scission destruction pathway seen in pyrolytic studies was not observed. Instead, hydrogen-abstraction reactions prevailed, leading to high concentrations of chlorinated byproducts. The thermal oxidation of benzene was also investigated for comparison. Chemical kinetic modeling of benzene and chlorobenzene was used to explore reaction pathways. Two chlorobenzene models were developed to test the hypothesis that chlorobenzene oxidation follows a CO-expulsion breakdown pathway similar to that of benzene. For the temperatures and equivalence ratio studied, hydrogen abstraction by hydroxyl radicals dominates the initial destruction of both benzene and chlorobenzene. Chlorinated byproducts (i.e., chlorophenol and vinyl chloride) were formed from chlorobenzene oxidation in similar quantities and at similar temperatures to their respective analogue formed during benzene oxidation (i.e., phenol and ethylene).

Improving the Dakin reaction by using an ionic liquid solvent

Zambrano, Jorge L.,Dortab, Romano

, p. 1545 - 1546 (2003)

The oxidation of aromatic aldehydes to phenols (Dakin reaction) has been demonstrated to proceed readily on both activated and non-activated aldehydes in the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF6], 1) with high selectivity, easy product separation and excellent chemical yields.

Correlating the Surface Basicity of Metal Oxides with Photocatalytic Hydroxylation of Boronic Acids to Alcohols

Leow, Wan Ru,Yu, Jiancan,Li, Bin,Hu, Benhui,Li, Wei,Chen, Xiaodong

, p. 9780 - 9784 (2018)

Photoredox catalysis provides opportunities in harnessing clean and green resources such as sunlight and O2, while the acid and base surface sites of metal oxides are critical for industrial catalysis such as oil cracking. The contribution of metal oxide surfaces towards photocatalytic aerobic reactions was elucidated, as demonstrated through the hydroxylation of boronic acids to alcohols. The strength and proximity of the surface base sites appeared to be two key factors in driving the reaction; basic and amphoteric oxides such as MgO, TiO2, ZnO, and Al2O3 enabled high alcohol yields, while acidic oxides such as SiO2 and B2O3 gave only low yields. The reaction is tunable to different irradiation sources by merely selecting photosensitizers of compatible excitation wavelengths. Such surface complexation mechanisms between reactants and earth abundant materials can be effectively utilized to achieve a wider range of photoredox reactions.

Hydrodechlorination of chlorophenols at low temperature on a novel Pd catalyst

Jin, Zhonghao,Yu, Chao,Wang, Xingyi,Wan, Ying,Li, Dao,Lu, Guanzhong

, p. 4438 - 4440 (2009)

Pd/mesoporous silica-carbon nanocomposites with 3.2 nm Pd particles, prepared by a simple wetness impregnation method, have demonstrated high activity at 258 K for the hydrodechlorination of chlorophenols with a high selectivity. The Royal Society of Chemistry 2009.

Photosensitization of crystalline and amorphous titanium dioxide by platinum(IV) chloride surface complexes

Macyk, Wojciech,Kisch, Horst

, p. 1862 - 1867 (2001)

Anatase, rutile, and amorphous titania powders were surface-modified by grinding with PtCl4 and H2[PtCl6]. Only the anatase modification afforded hybrid photocatalysts capable of degradation of 4-chlorophenol (4-CP) with visible light, with sufficient stability towards decomplexation. Grinding with K2[PtCl4] produced materials of only low photocatalytic activity. Most efficient photocatalysts contained up to 2 wt % of PtIV. At higher surface loading the excess fraction of the complex is desorbed into the aqueous solution. Scavenging experiments with benzoic acid and tetranitromethane revealed that hydroxyl radicals are produced by the primary reduction of oxygen by conduction band electrons generated through electron injection from a postulated surface platinum(III) complex. It is proposed that the latter is formed from a charge-transfer ligand-to-metal (CTLM) excited state through homolysis of the Pt-Cl bond. Accordingly, the primary oxidation of 4-CP may occur by adsorbed chlorine atoms, the intermediary existence of which was demonstrated by scavenging experiments with phenol.

Non-Innocent Role of the Ceria Support in Pd-Catalyzed Halophenol Hydrodehalogenation

An, Yeongseo,Freppon, Daniel,Masching, Hayley,Naik, Pranjali J.,Sedinkin, Sergey L.,Slowing, Igor I.,Smith, Emily A.,Venditti, Vincenzo

, p. 10553 - 10564 (2021)

The hydrodehalogenation (HDH) of halophenols is efficiently catalyzed by palladium supported on high-surface ceria (Pd/CeO2) under mild conditions (35 °C, 1 atm H2). A combination of NMR, diffuse reflectance infrared Fourier transform spectroscopy, Raman spectroscopy, and XPS studies and HDH kinetics of substituted halobenzenes suggests that the reaction proceeds mainly via a sequence of dissociative adsorption of phenolic hydroxyl onto the support, oxidative addition of the C-halogen bond to Pd, and reductive elimination to give phenol and hydrogen halide. The dissociative adsorption of the -OH group onto oxygen vacancies of the ceria support results in an electron-rich intermediate that facilitates the turnover-limiting reductive elimination step. In contrast, the direct pathway catalyzed by Pd without dissociative adsorption of the reactants on the support takes place at a slower rate. The mechanistic insights gained in this study were used to modify the reaction conditions for enabling HDH of recalcitrant halides such as fluorides and iodides.

Selective water-based oxychlorination of phenol with hydrogen peroxide catalyzed by manganous sulfate

Xin, Hongchuan,Yang, Shilei,An, Baigang,An, Zengjian

, p. 13467 - 13472 (2017)

An efficient method for the selective oxychlorination of phenol to 2,4-dichlorophenol catalyzed by manganous(ii) sulfate is developed using hydrogen chloride as a chlorinating source, hydrogen peroxide as an oxidant and water as a solvent. The catalyst has high activity and selectivity under mild conditions. The products are automatically isolated from aqueous solution, which also contains the catalyst at the end of the reaction, and hence product separation and catalyst recycling are both simple in this system. The performance of manganous(ii) sulfate with the oxidative chlorinating system HCl/H2O2 indicates that this is a promising synthetic method for the manufacture of various 2,4-dichlorophenol derivatives.

Mechanistic and computational study of a palladacycle-catalyzed decomposition of a series of neutral phosphorothioate triesters in methanol

Liu, C. Tony,Maxwell, Christopher I.,Edwards, David R.,Neverov, Alexei A.,Mosey, Nicholas J.,Brown, R. Stan

, p. 16599 - 16609 (2010)

The methanolytic cleavage of a series of O,O-dimethyl O-aryl phosphorothioates (1a-g) catalyzed by a C,N-palladacycle, (2-[N,N- dimethylamino(methyl)phenyl]-C1,N)(pyridine) palladium(II) triflate (3), at 25 °C and sspH 11.7 in methanol is reported, along with data for the methanolytic cleavage of 1a-g. The methoxide reaction gives a linear log k2-OMe vs sspKa (phenol leaving group) Bronsted plot having a gradient of βlg = -0.47 ± 0.03, suggesting about 34% cleavage of the P-OAr bond in the transition state. On the other hand, the 3-catalyzed cleavage of 1 gives a Bronsted plot with a downward break at sspKa (phenol) ~ 13, signifying a change in the rate-limiting step in the catalyzed reaction, with the two wings having βlg values of 0.0 ± 0.03 and -1.93 ± 0.06. The rate-limiting step for good substrates with low leaving group sspKa values is proposed to be substrate/pyridine exchange on the palladacycle, while for substrates with poor leaving groups, the rate-limiting step is a chemical one with extensive cleavage of the P-OAr bond. DFT calculations support this process and also identify two intermediates, namely, one where substrate/pyridine interchange has occurred to give the palladacycle coordinated to substrate through the S - P linkage and to methoxide (6) and another where intramolecular methoxide attack has occurred on the P - S unit to give a five-coordinate phosphorane (7) doubly coordinated to Pd via the S- and through a bridging methoxide linked to P and Pd. Attempts to identify the existence of the phosphorane by 31P NMR in a d4-methanol solution containing 10 mM each of 3, trimethyl phosphorothioate (a very slow cleaving substrate), and methoxide proved unsuccessful, instead showing that the phosphorothioate was slowly converted to trimethyl phosphate, with the palladacycle decomposing to Pd0 and free pyridine. These results provide the first reported example where a palladacycle-promoted solvolysis reaction exhibits a break in the Bronsted plot signifying at least one intermediate, while the DFT calculations provide further insight into a more complex mechanism involving two intermediates.

Regioselective synthesis of important chlorophenols in the presence of methylthioalkanes with remote SMe, OMe or OH substituents

Smith, Keith,Al-Zuhairi, Ali J.,Elliott, Mark. C.,El-Hiti, Gamal A.

, p. 607 - 621 (2018)

Various methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes have been used as regioselectivity modifiers in the chlorination reactions of various phenols at room temperature. The process involves the use of a slight excess of sulfuryl chloride in the presence of aluminum or ferric chloride as an activator. Methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 2 and 3 methylene groups as a spacer were found to be good for the para-selective chlorination of o-cresol and phenol. On the other hand, methylthio alcohols, methoxy(methylthio)alkanes and bis(methylthio)alkanes having 6 and 9 methylene groups were found to be good for the selective para-chlorination of m-xylenol and m-cresol. Calculations using density functional theory on bis(methylthio)alkanes have suggested two different types of stable chlorinated intermediates depending on the number of methylene units as a spacer.

Active-alkali metal-promoted reductive cleavage of chlorinated phenols

Azzena, Ugo,Dettori, Giovanna,Pisano, Luisa,Pittalis, Mario,Mangano, Giuseppe,Petretto, Giacomo,Pintore, Giorgio

, p. 601 - 605 (2012)

We investigated the degradation of chlorinated phenols under reductive electron transfer reaction conditions. Although Li and Na metal proved useless, activated forms of these metals, either their soluble naphthalene radical anions or 1,2-diarylethane dianions, promoted the degradation of the starting materials to various extents. Additionally, efficient dehalogenation of the sodium salts of several mono-, di-, and tri-chlorophenols was obtained by their reduction with an excess of Na metal and a catalytic amount of naphthalene. Springer-Verlag 2012.

The influence of triethylamine on the hydrodechlorination reactivity of chlorophenols over Raney Ni catalyst

Ma, Xuanxuan,Zhou, Shiwei,Yang, Cuiyun,Liu, Sujing,Bi, Xiaoli,Xia, Chuanhai

, p. 282 - 285 (2010)

The hydrodechlorination (HDCl) of 2,4-dichlorophenol (2,4-DCP), 2-chlorophenol (2-CP) and 4-chlorophenol (4-CP) over Raney Ni in liquid phase with triethylamine (Et3N) under mild conditions was studied. The results showed that Et3N together with solvents significantly affected the HDCl reactivity or selectivity, in which ortho-positioned Cl of chlorophenols (CPs) was easier to be dechlorinated in methanol (MeOH) and ethanol (EtOH), whereas para-positioned Cl was preferentially dechlorinated in water. Different species and action mechanisms of Et3N in water and organic solvents possibly affected the HDCl reactivity or selectivity of CPs over Raney Ni.

Adsorption-driven photocatalytic activity of mesoporous titanium dioxide

Shiraishi, Yasuhiro,Saito, Naoya,Hirai, Takayuki

, p. 12820 - 12822 (2005)

Titanium dioxide with a mesoporous structure, when photoactivated in water, demonstrates an unprecedented photocatalytic activity, driven strongly by an adsorption degree of molecules onto the catalyst surface, which promotes a preferential conversion of a well-adsorbed molecule. This catalyzes a selective transformation of a well-adsorbed molecule into a less-adsorbed molecule, so-labeled "stick-and-leave" transformation, which promotes a direct hydroxylation of benzene to phenol, one of the most difficult synthetic reactions, with very high selectivity (> 80%) and using water as a source of oxidant. Copyright

Hydroxyl radical reactions with 2-chlorophenol as a model for oxidation in supercritical water

Zhang, Jiaming,Ma, Chunyuan,Sun, Youmin,Ren, Xiaohua

, p. 973 - 990 (2014)

To determine the detailed mechanism of 2-chlorophenol (2-CP) oxidation in supercritical water, both the experiments and theoretical calculations were conducted in this paper. A set of experiments was performed to oxidize 2-CP in supercritical water under temperatures of 380-420 °C, pressure of 25 MPa, residence times of 0-60 s, and H2O2 as oxidant. By determining the molar yields of products, the primary single-ring products were identified as chlorohydroquinone, 2,4-dichlorophenol (2,4-DCP), 2,6-DCP, and 4-CP. The trends for the molar yields of the four products were analyzed at various temperatures and residence times. And built upon the trends, the possible reaction pathways were conjectured. Subsequently, the reaction mechanism was further verified by theoretical calculations, in which density functional theory was adopted as the computational method. The calculated results have well illustrated the experimental results and ascertained the reaction paths we proposed. Springer Science+Business Media Dordrecht 2013.

Vapour-phase Chemistry of Arenes. Part 11. Autoxidation of Chlorobenzene between 500-1100 K. Mechanisms of Formation of Chlorophenols and Phenol

Mulder, Peter,Louw, Robert

, p. 1541 - 1550 (1986)

Slow combustion of chlorobenzene (1) has been studied at low degrees of conversion (tOOH, cyclohexane, nitroethane, and hydrogen peroxide, forming .OH in situ by thermolysis or autoxidation, has been used to induce the reaction of (1).The change in product composition (2,3) with temperature revealed a major change in mechanism of hydroxylation between 600-700 K.Above ca. 600 K, H-abstraction (1) + .OH -> o/m/p-ClC6H4. .OH -> Cl. + (3)> is followed by rapid addition of O2 (step 4) to give C6H4OO. radicals (v).At moderate temperatures (v) reacts bimolecularly, with itself or with HO2., leading to ClC6H4O. (iv) and therefrom to (2).Thermokinetic analysis emphasises that at elevated temperatures (v) decomposes into (iv) and O(3P).The latter species adds to (1) and forms (2) rather efficiently, with an isomer distribution different from that associated with the pathway Ar. -> ArO2. -> ArOH.Data on model runs, including kinetic isotope effect measurements on p-DC6H4Cl and C6H6/C6D6 support our mechanistic interpretation.

Helical Carbenium Ion: A Versatile Organic Photoredox Catalyst for Red-Light-Mediated Reactions

Mei, Liangyong,Veleta, José M.,Gianetti, Thomas L.

, p. 12056 - 12061 (2020)

Red light has the advantages of low energy, less health risks, and high penetration depth through various media. Herein, a helical carbenium ion (N,N′-di-n-propyl-1,13-dimethoxyquinacridinium (nPr-DMQA+) tetrafluoroborate) has been used as an organic photoredox catalyst for photoreductions and photooxidations in the presence of red light (λmax = 640 nm). It has catalyzed red-light-mediated dual transition-metal/photo-redox-catalyzed C-H arylation and intermolecular atom-transfer radical addition through oxidative quenching. Moreover, its potential in photooxidation catalysis has also been demonstrated by successful applications in red-light-induced aerobic oxidative hydroxylation of arylboronic acids and benzylic C(sp3)-H oxygenation through reductive quenching. Thus, a versatile organic photoredox catalyst (helical carbenium ion) for red-light-mediated photoredox reactions has been developed.

Imidazolium-urea low transition temperature mixtures for the UHP-promoted oxidation of boron compounds

Martos, Mario,Pastor, Isidro M.

, (2022/01/03)

Different carboxy-functionalized imidazolium salts have been considered as components of low transition temperature mixtures (LTTMs) in combination with urea. Among them, a novel LTTM based on 1-(methoxycarbonyl)methyl-3-methylimidazolium chloride and urea has been prepared and characterized by differential scanning calorimetry throughout its entire composition range. This LTTM has been employed for the oxidation of boron reagents using urea-hydrogen peroxide adduct (UHP) as the oxidizer, thus avoiding the use of aqueous H2O2, which is dangerous to handle. This metal-free protocol affords the corresponding alcohols in good to quantitative yields in up to 5 mmol scale without the need of further purification. The broad composition range of the LTTM allows for the reaction to be carried out up to three consecutive times with a single imidazolium salt loading offering remarkable sustainability with an E-factor of 7.9, which can be reduced to 3.2 by the threefold reuse of the system.

Light-Induced Efficient Hydroxylation of Benzene to Phenol by Quinolinium and Polyoxovanadate-Based Supramolecular Catalysts

Gu, Yaqi,Huang, Yichao,Li, Qi,Wei, Yongge,Yu, Han,Zang, Dejin

, p. 13310 - 13316 (2020/10/19)

Direct Hydroxylation of benzene to phenol with high yield and selectivity has been the goal of phenol industrial production. Photocatalysis can serve as a competitive method to realize the hydroxylation of benzene to phenol owing to its cost-effective and environmental friendliness, however it is still a forbidding challenge to obtain good yield, high selectivity and high atom availability meanwhile. Here we show a series of supramolecular catalysts based on alkoxohexavanadate anions and quinolinium ions for the photocatalytic hydroxylation of benzene to phenol under UV irradiation. We demonstrate that polyoxoalkoxovanadates can serve as efficient catalysts which can not only stabilize quinolinium radicals but also reuse H2O2 produced by quinolinium ions under light irradiation to obtain excellent synergistic effect, including competitive good yield (50.1 %), high selectivity (>99 %) and high atom availability.

Isotruxene-based porous polymers as efficient and recyclable photocatalysts for visible-light induced metal-free oxidative organic transformations

Zhang, Haowen,Zhang, Xiao,Zheng, Ying,Zhou, Cen

supporting information, p. 8878 - 8885 (2021/11/27)

Two new isotruxene-based porous polymers were prepared and demonstrated to be highly efficient, metal-free heterogeneous photocatalysts for oxidative transformations using air as the mild oxidant under visible-light irradiation. Both catalysts show excellent recyclability. In addition, the reactions can be performed in water, further indicating the greenness of this method. This journal is

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