611-19-8

Basic information

• Product Name: 2-Chlorobenzyl chloride
• Synonyms: ,2-Dichlorotoluene;1-chloro-2-(chloromethyl)-benzen;alpha,o-dichloro-toluen;Benzene,1-chloro-2-(chloromethyl)-;o,alpha-dichlorotoluene;Ortho-alpha-dichlorotoluene;Toluene, o,alpha-dichloro-;O-CHLOROBENZYL CHLORIDE
• CAS NO: 611-19-8
• Molecular Formula: C₇H₆Cl₂
• Molecular Weight: 161.03
• EINECS: 210-258-8
• Product Categories: Pesticides intermediate
• Mol File: 611-19-8.mol
• Article Data: 13

Chemical Properties

• Melting Point: -13 °C
• Boiling Point: 213-214 °C(lit.)
• Flash Point: 180 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 1.274 g/mL at 25 °C(lit.)
• Vapor Density: 5.5 (vs air)
• Vapor Pressure: 3 mm Hg ( 84 °C)
• Refractive Index: n20/D 1.559(lit.)
• Storage Temp.: 2-8°C
• Explosive Limit: 1.5-7.8%(V)
• Water Solubility: insoluble
• BRN: 471700
• CAS DataBase Reference: 2-Chlorobenzyl chloride(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Chlorobenzyl chloride(611-19-8)
• EPA Substance Registry System: 2-Chlorobenzyl chloride(611-19-8)

Safety Data

• Hazard Codes: C,N
• Statements: 34-43-50/53-20/21/22
• Safety Statements: 26-36/37/39-45-29
• RIDADR: UN 2235 6.1/PG 3
• WGK Germany: 3
• RTECS: CZ0195000
• F: 19-21
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: III
• Hazardous Substances Data: 611-19-8(Hazardous Substances Data)

Usage

Chemical Properties

Colorless to light yellow liqui

Uses

Different sources of media describe the Uses of 611-19-8 differently. You can refer to the following data:
1. 2-Chlorobenzyl chloride was used as a sensory irritant to evaluate the characteristic modifications of the normal breathing pattern of exposed mice.
2. 2-Chlorobenzyl chloride was used as a sensory irritant to evaluate the characteristic modifications of the normal breathing pattern of exposed mice. It is used as an intermediate for organic chemicals, pharmaceuticals, and dyes.

InChI:InChI=1/C7H6Cl2/c8-5-6-3-1-2-4-7(6)9/h1-4H,5H2

Synthetic route

2-chloro-benzaldehyde (89-98-5) → 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With dichloromethylsilane; iron(III) chloride In 1,2-dimethoxyethane for 4h; Heating;	93%

2-methylchlorobenzene (95-49-8) → 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With N-chloro-succinimide; N-hydroxyphthalimide; 2,3-dicyano-5,6-dichloro-p-benzoquinone In acetonitrile at 80℃; for 3h; Sealed tube; Inert atmosphere;	91%
With hydrogenchloride; potassium chloride; tetrabutyl-ammonium chloride In water at 20℃; Irradiation; Green chemistry;	90%
With 2,2'-azobis(isobutyronitrile); benzyl(trimethyl)ammonium tetrachloroiodate In tetrachloromethane for 5h; Heating;	80%

C7H6Cl2S (81067-96-1) → 1,2-bis(2-chlorobenzyl)disulfane (5219-70-5) + 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With triethylamine In dichloromethane; pentane at 20 - 23℃; for 24h;	A 81% B 10%

2-chloro-benzaldehyde (89-98-5) → 2,2'-(oxybis(methylene))bis(chlorobenzene) (56427-98-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With chloro-trimethyl-silane; thionyl chloride; 1,1,3,3-Tetramethyldisiloxane; zinc(II) iodide at 70℃; for 1h;	A 45% B 55%

2-Chlorobenzyl alcohol (17849-38-6) → 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With pyridine; thionyl chloride
With phosphorus pentachloride at 100℃;
With phosphorus pentachloride
With thionyl chloride In pyridine Ambient temperature;

N,N-bis-(2-chloro-benzyl)-benzamide → 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With phosphorus pentachloride durch Schmelzen;

benzyl chloride (100-44-7) → 1-Chloro-4-(chloromethyl)benzene (104-83-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With iodine at 30 - 40℃; beim Chlorieren;

Toluene-2-sulfonyl chloride (133-59-5) → 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
With chlorine; phosphorus trichloride at 110 - 130℃;

1-chloro-1-(4-methylphenyl)-2,2,2-trifluoroethane (708-65-6) + C7H6Cl(1+) → C9H8F3(1+) (128408-26-4) + 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
at 69.85℃; Thermodynamic data; chloride-transfer;

1-(1-Chloro-2,2,2-trifluoro-ethyl)-3,5-dimethyl-benzene (191402-57-0) + C7H6Cl(1+) → C10H10F3(1+) (128408-30-0) + 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
at 69.85℃; Thermodynamic data; chloride-transfer;

iodine (7553-56-2) + benzyl chloride (100-44-7) → 1-Chloro-4-(chloromethyl)benzene (104-83-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
at 30 - 40℃; beim Chlorieren;

iodine (7553-56-2) + benzyl chloride (100-44-7) → 2,3,4-trichlorobenzyl chloride (13911-02-9) + 1,2,3,4-Tetrachloro-5-chloromethyl-benzene (13911-07-4) + 1-Chloro-4-(chloromethyl)benzene (104-83-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
Chlorierung;

antimonypentachloride (7647-18-9) + benzyl chloride (100-44-7) → 1-Chloro-4-(chloromethyl)benzene (104-83-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8) + 2,3-dichlorobenzyl chloride (3290-01-5)

Conditions	Yield
Chlorierung;

chlorine (7782-50-5) + phosphorus trichloride (7719-12-2, 52843-90-0) + Toluene-2-sulfonyl chloride (133-59-5) → 2-methylchlorobenzene (95-49-8) + 1-chloro-2-(chloromethyl)benzene (611-19-8) + α-chloro-toluene-sulfonyl chloride-(2)

Conditions	Yield
at 110 - 130℃;

sulfuryl dichloride (7791-25-5) + 2-methylphenyl bromide (95-46-5) + dibenzoyl peroxide (94-36-0) → 2-methylchlorobenzene (95-49-8) + 1-chloro-2-(chloromethyl)benzene (611-19-8) + 2-bromobenzylchloride (578-51-8) + 1-Bromo-2-bromomethyl-benzene (3433-80-5)

Conditions	Yield
at 110℃;

phosphorus pentachloride (10026-13-8, 874483-75-7) + N,N-bis-(2-chloro-benzyl)-benzamide → 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
Destillieren im Vakuum;

2-Chlorobenzyl alcohol (17849-38-6) + o-chlorobenzoyl chloride (609-65-4) → 1-chloro-2-(chloromethyl)benzene (611-19-8) + (2'-chlorobenzyl) 2-chlorobenzoate

Conditions	Yield
In dichloromethane at 20℃; for 12h;

toluene (108-88-3) → 1-chloro-2-(chloromethyl)benzene (611-19-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: N-hydroxyphthalimide; trichloroisocyanuric acid; cobalt(II) diacetate tetrahydrate / dichloromethane; methanol / 19 h / 25 °C 2: N-hydroxyphthalimide; trichloroisocyanuric acid; copper(II) acetate monohydrate; carbon tetrabromide / dichloromethane / 40 h / 25 °C View Scheme

4-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester (64276-62-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 1-(2-Chloro-benzyl)-4-phenyl-1H-pyrrole-3-carboxylic acid ethyl ester (131924-82-8)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 90℃;	100%

7-Chloro-4-(3,5-dimethylpyrazol-1-yl)imidazo<4,5-d>pyridazine-2-thiol (85732-80-5) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 7-Chloro-4-(3,5-dimethylpyrazol-1-yl)-2-(2-chlorobenzylthio)imidazo<4,5-d>pyridazine (85732-84-9)

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 50℃; for 4h;	100%

phenyltellurotrimethylsilane (73296-31-8) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → o-chlorobenzyl phenyl telluride

Conditions	Yield
at 20℃; for 0.5h;	100%
In acetonitrile at 20℃; for 0.5h;	100 % Spectr.

8-benzyloxy-2,2-dimethyl-benzo[1,3]dioxin-4-one (533897-45-9) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → C17H15ClO4 (533890-66-3)

Conditions	Yield
With potassium carbonate; tetra-(n-butyl)ammonium iodide In DMF (N,N-dimethyl-formamide) at 20 - 50℃; for 2h;	100%

C8H7BrO4 (533897-87-9) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → C22H17BrCl2O4 (533897-89-1)

Conditions	Yield
With potassium carbonate; tetra-(n-butyl)ammonium iodide In DMF (N,N-dimethyl-formamide) at 60℃; for 4h;	100%

p-hydroxyphenethyl alcohol (501-94-0) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-(4-(2-chlorobenzyloxy)phenyl)ethanol (1228930-61-7)

Conditions	Yield
With potassium carbonate In acetone for 24h; Reflux;	100%

1-chloro-2-(chloromethyl)benzene (611-19-8) → (2-chlorobenzyl)magnesium chloride (29874-00-8)

Conditions	Yield
Stage #1: 1-chloro-2-(chloromethyl)benzene With magnesium; ethylene dibromide In dibutyl ether at 20 - 30℃; for 0.166667h; Inert atmosphere; Stage #2: 1-chloro-2-(chloromethyl)benzene In dibutyl ether; cyclohexane at -5 - 5℃; for 4h; Solvent; Temperature;	99.5%

concentrated ammonium chloride + 1-chloro-2-(chloromethyl)benzene (611-19-8) + p-chlorophenacyl chloride (937-20-2) → 1-chloro-2-(4-chlorophenyl)-3-(2-chlorophenyl)propan-2-ol (133001-02-2)

Conditions	Yield
With magnesium In toluene	99%

5,6-bis-O-isopropylidene-α-D-glucofuranose + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 5,6-di-O-isopropylidene-3-O-(2'-chlorobenzyl)-α-D-glucofuranose

Conditions	Yield
With sodium chloride; tetra-(n-butyl)ammonium iodide In tetrahydrofuran; ethanol; dichloromethane; water; mineral oil	99%

3,5-dimethyl-1H-pyrazole (67-51-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 1-(2-chlorobenzyl)-3,5-dimethyl-1H-pyrazole (908228-44-4)

Conditions	Yield
With potassium hydroxide In dimethyl sulfoxide	99%
Stage #1: 3,5-dimethyl-1H-pyrazole With potassium hydroxide In dimethyl sulfoxide at 80℃; for 1.5h; Stage #2: 1-chloro-2-(chloromethyl)benzene In dimethyl sulfoxide for 1.75h;	99%
Stage #1: 3,5-dimethyl-1H-pyrazole With potassium hydroxide In dimethyl sulfoxide at 80℃; for 1.5h; Inert atmosphere; Stage #2: 1-chloro-2-(chloromethyl)benzene In dimethyl sulfoxide at 20℃; for 1.25h; Inert atmosphere;	99%

1-carbomethoxy-3,5-dihydroxybenzene (2150-44-9) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → C22H18Cl2O4

Conditions	Yield
With potassium carbonate; potassium iodide In acetone Reflux;	99%

phenoxyacetylene (4279-76-9) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → C15H12ClN3O

Conditions	Yield
Stage #1: 1-chloro-2-(chloromethyl)benzene With sodium azide In methanol at 20℃; Green chemistry; Stage #2: phenoxyacetylene In methanol at 20℃; Green chemistry;	99%

morpholine (110-91-8) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-(morpholinomethyl)chlorobenzene (415932-72-8)

Conditions	Yield
With sodium hydroxide In toluene for 16h; Heating / reflux;	98.9%
With sodium hydroxide In water; toluene Solvent; Reflux;

1-chloro-2-(chloromethyl)benzene (611-19-8) + dimethyl amine (124-40-3) → 1-(2-chlorophenyl)-N,N-dimethylmethanamine (10175-31-2)

Conditions	Yield
With sodium hydroxide In water at -10 - 40℃; for 13.17h; Solvent; Large scale;	98.4%
In water at 140℃; for 0.5h; Time; Temperature; Autoclave;	95.4%
at 100℃;

1,2,3-Benzotriazole (95-14-7) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 1-(2-chlorobenzyl)-1H-benzo[d][1,2,3]triazole (30516-22-4)

Conditions	Yield
In toluene for 24h; Heating;	98%

1-chloro-2-(chloromethyl)benzene (611-19-8) + ethyl 6,7,8-trifluoro-4-oxo-1,4-dihydroquinoline-3-carboxylate (79660-46-1) → 1-(2-Chloro-benzyl)-6,7,8-trifluoro-4-oxo-1,4-dihydro-quinoline-3-carboxylic acid ethyl ester (214602-33-2)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 90 - 100℃; for 12h;	98%

4-nitro-phenol (100-02-7) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-chlorobenzyl-4-nitrophenyl ether (56532-65-1)

Conditions	Yield
With potassium carbonate In ethanol at 78℃; for 5h;	98%
With potassium carbonate; sodium iodide In acetone at 50℃;

N-allylbenzotriazole (52298-91-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 1-{1-[(2-chlorophenyl)methyl]prop-2-enyl}-1H-1,2,3-benzotriazole (305861-94-3)

Conditions	Yield
Stage #1: N-allylbenzotriazole With n-butyllithium In tetrahydrofuran at -78℃; for 0.333333h; Stage #2: 1-chloro-2-(chloromethyl)benzene In tetrahydrofuran Further stages.;	98%

4-morpholinecarboxaldehyde (4394-85-8) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-(morpholinomethyl)chlorobenzene (415932-72-8)

Conditions	Yield
With NHC-Pd(II)-Im; sodium hydroxide In water at 50℃; for 3h; Inert atmosphere; Schlenk technique;	98%
With potassium hydroxide In water at 50℃; for 3h; Green chemistry;	96%

diphenylmaleimide (31295-36-0) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 1-(2-chlorobenzyl)-3,4-diphenyl-1H-pyrrole-2,5-dione

Conditions	Yield
Stage #1: diphenylmaleimide With potassium tert-butylate In ethanol at 90℃; for 0.333333h; Microwave irradiation; Stage #2: 1-chloro-2-(chloromethyl)benzene In acetonitrile at 90℃; for 0.25h; Solvent; Temperature; Reagent/catalyst; Microwave irradiation;	98%

N-tosyl-4-iodoaniline (158268-30-5) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → N-[4-(2-chlorobenzyl)-phenyl]-4-methylbenzenesulfonamide

Conditions	Yield
Stage #1: 1-chloro-2-(chloromethyl)benzene With chloro-trimethyl-silane; ethylene dibromide; lithium chloride; zinc In tetrahydrofuran at 25℃; for 24h; Inert atmosphere; Stage #2: N-tosyl-4-iodoaniline With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; palladium diacetate In tetrahydrofuran at 25℃; Negishi Coupling; Inert atmosphere;	98%

1-chloro-2-(chloromethyl)benzene (611-19-8) + acetone oxime (127-06-0) → O-(o-chlorobenzyl)acetoxime

Conditions	Yield
Stage #1: acetone oxime With potassium hydroxide; lithium hydroxide In N,N-dimethyl acetamide; water at 53℃; Stage #2: 1-chloro-2-(chloromethyl)benzene In N,N-dimethyl acetamide; water at 65℃; for 2.16667h;	97.11%

p-cresol (106-44-5) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → (2-chloro-benzyl)-p-tolyl ether

Conditions	Yield
With potassium carbonate In ethanol at 78℃; for 5h;	97%
With sodium hydroxide

4-(3,5-dimethylpyrazol-1-yl)imidazo<4,5-d>pyridazine-2-thiol (85732-81-6) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 4-(3,5-Dimethylpyrazol-1-yl)-2-(2-chlorobenzylthio)imidazo<4,5-d>pyridazine (85732-93-0)

Conditions	Yield
With potassium hydroxide at 45℃; for 5h;	97%

1-chloro-2-(chloromethyl)benzene (611-19-8) + C7H6Cl2Zn → 2',3-dichloro-2-methyldiphenylmethane

Conditions	Yield
bis-triphenylphosphine-palladium(II) chloride In tetrahydrofuran at 50℃; for 1h;	97%

1-chloro-2-(chloromethyl)benzene (611-19-8) → Sodium 2-chlorobenzylsulphonate (41345-36-2)

Conditions	Yield
With sodium sulfite In water at 100℃; for 5h;	97%
With copper; sodium sulfite In ethanol; water for 1h; Reflux;	92.1%
With sodium sulphite-heptahydrate; tetrabutylammomium bromide In water at 80℃; for 6h;

4-iodobenzoic acid ethyl ester (51934-41-9) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → ethyl 4-(2-chlorobenzyl)benzoate (1013931-12-8)

Conditions	Yield
Stage #1: 1-chloro-2-(chloromethyl)benzene With chloro-trimethyl-silane; ethylene dibromide; lithium chloride; zinc In tetrahydrofuran at 0 - 25℃; for 2h; Inert atmosphere; Stage #2: 4-iodobenzoic acid ethyl ester With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 60℃; for 5h; Negishi cross-coupling reaction; Inert atmosphere;	97%

1,2,3,4-tetrahydroisoquinoline (91-21-4) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-(2-chlorobenzyl)-1,2,3,4-tetrahydroisoquinoline (72809-43-9)

Conditions	Yield
In acetonitrile at 20℃;	97%

6-chloroisoquinoline (62882-02-4) + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-(2-chlorobenzyl)-isoquinolinium chloride

Conditions	Yield
In acetonitrile at 20℃;	97%

1α,2β,3β-trihydroxy-11-oxo-18β-olean-12-en-30-oic acid + 1-chloro-2-(chloromethyl)benzene (611-19-8) → 2-chlorobenzyl 1α,2β,3β-trihydroxy-11-oxo-18β-olean-12-en-30-oate

Conditions	Yield
Stage #1: 1α,2β,3β-trihydroxy-11-oxo-18β-olean-12-en-30-oic acid With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 0.333333h; Stage #2: 1-chloro-2-(chloromethyl)benzene In N,N-dimethyl-formamide at 20℃; for 4h;	97%

Upstream product

• 95-49-8 2-methylchlorobenzene 
• 17849-38-6 2-Chlorobenzyl alcohol 
• 100-44-7 benzyl chloride 
• 133-59-5 Toluene-2-sulfonyl chloride 
• 89-98-5 2-chloro-benzaldehyde 
• 81067-96-1 C₇H₆Cl₂S 
• 708-65-6 1-chloro-1-(4-methylphenyl)-2,2,2-trifluoroethane 
• 108-88-3 toluene 
• 609-65-4 o-chlorobenzoyl chloride 
• 10026-13-8 phosphorus pentachloride 
• 7791-25-5 sulfuryl dichloride 
• 95-46-5 2-methylphenyl bromide 
• 94-36-0 dibenzoyl peroxide 
• 7782-50-5 chlorine 

Downstream Products

• 17532-19-3 1-(2-chloro-benzyl)-piperazine 
• 36995-37-6 2-(2-chlorobenzyl)pyridine 
• 134642-52-7 N-(2-chlorobenzyl)pyridinium bromide 
• 117877-50-6 1-(2-chloro-benzyl)-3-hydroxy-pyridinium; chloride 
• 79147-00-5 (2-chloro-benzyl)-thiazol-2-yl-amine 
• 109846-79-9 1-(2-chloro-benzyl)-3-methoxy-pyridinium; chloride 
• 5363-23-5 2-(2-chloro-benzyl)-2H-indazole 
• 112746-31-3 4-(2-chloro-benzyl)-4-decyl-morpholinium; chloride 
• 70627-21-3 4-((2-chlorobenzyl)oxy)benzaldehyde 
• 122119-90-8 4-(2-chloro-benzyl)-4-hexadecyl-morpholinium; chloride 
• 52844-77-6 {[(Z)-2,4-Dimethyl-phenylimino]-methyl}-methyl-dithiocarbamic acid 2-chloro-benzyl ester 
• 52804-96-3 {[(Z)-4-Chloro-2-methyl-phenylimino]-methyl}-methyl-dithiocarbamic acid 2-chloro-benzyl ester 
• 52805-15-9 Methyl-[(Z)-o-tolylimino-methyl]-dithiocarbamic acid 2-chloro-benzyl ester 
• 52805-23-9 {[(Z)-2-Chloro-6-methyl-phenylimino]-methyl}-methyl-dithiocarbamic acid 2-chloro-benzyl ester 

Relevant articles and documents

N -Hydroxyphthalimide/benzoquinone-catalyzed chlorination of hydrocarbon C-H bond using N -chlorosuccinimide

The direct chlorination of C-H bonds has received considerable attention in recent years. In this work, a metal-free protocol for hydrocarbon C-H bond chlorination with commercially available N-chlorosuccinimide (NCS) catalyzed by N-hydroxyphthalimide (NHPI) with 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) functioning as an external radical initiator is presented. Aliphatic and benzylic substituents and also heteroaromatic ones were found to be well tolerated. Both the experiments and theoretical analysis indicate that the reaction goes through a process wherein NHPI functions as a catalyst rather than as an initiator. On the other hand, the hydrogen abstraction of the C-H bond conducted by a PINO species rather than the highly reactive N-centered radicals rationalizes the high chemoselectivity of the monochlorination obtained by this protocol as the latter is reactive towards the C(sp3)-H bonds of the monochlorides. The present results could hold promise for further development of a nitroxy-radical system for the highly selective functionalization of the aliphatic and benzylic hydrocarbon C-H.

Mild Aliphatic and Benzylic Hydrocarbon C-H Bond Chlorination Using Trichloroisocyanuric Acid

We present the controlled monochlorination of aliphatic and benzylic hydrocarbons with only 1 equiv of substrate at 25-30 °C using N-hydroxyphthalimide (NHPI) as radical initiator and commercially available trichloroisocyanuric acid (TCCA) as the chlorine source. Catalytic amounts of CBr4 reduced the reaction times considerably due to the formation of chain-carrying ·CBr3 radicals. Benzylic C-H chlorination affords moderate to good yields for arenes carrying electron-withdrawing (50-85%) or weakly electron-donating groups (31-73%); cyclic aliphatic substrates provide low yields (24-38%). The products could be synthesized on a gram scale followed by simple purification via distillation. We report the first direct side-chain chlorination of 3-methylbenzoate affording methyl 3-(chloromethyl)benzoate, which is an important building block for the synthesis of vasodilator taprostene.

Ferric chloride-catalyzed deoxygenattve chlorination of carbonyl compounds to halides

-