626-16-4

Basic information

• Product Name: 1,3-Bis(chloromethyl)benzene
• Synonyms: 1,3-Bis(chloroethyl)benzene;1,3-bis(chloromethyl)-benzen;alpha,alpha’-dichloro-m-xylen;benzene,1,3-bis(chloromethyl)-;m-Bis(chloromethyl)benzene;m-Dichloroxylene;m-Xylene, alpha,alpha'-dichloro-;α,α’-dichloro-m-xylene
• CAS NO: 626-16-4
• Molecular Formula: C₈H₈Cl₂
• Molecular Weight: 175.06
• EINECS: 210-932-1
• Product Categories: Intermediates of Dyes and Pigments;Aryl;Building Blocks;C8;Chemical Synthesis;Halogenated Hydrocarbons;Organic Building Blocks
• Mol File: 626-16-4.mol
• Article Data: 5

Chemical Properties

• Melting Point: 33-35 °C(lit.)
• Boiling Point: 250-255 °C(lit.)
• Flash Point: >230 °F
• Appearance: Colorless to light yellow liquid
• Density: 1.202 g/mL at 25 °C(lit.)
• Refractive Index: 1.5544 (estimate)
• Storage Temp.: Store at
• Solubility: methanol: soluble1g/10 mL, clear, colorless
• Water Solubility: hydrolysis
• BRN: 2079898
• CAS DataBase Reference: 1,3-Bis(chloromethyl)benzene(CAS DataBase Reference)
• NIST Chemistry Reference: 1,3-Bis(chloromethyl)benzene(626-16-4)
• EPA Substance Registry System: 1,3-Bis(chloromethyl)benzene(626-16-4)

Safety Data

• Hazard Codes: Xn,Xi,C
• Statements: 22-36/37/38-36-34
• Safety Statements: 26-24/25-45-36/37/39-27
• RIDADR: UN 2811 6.1/PG 2
• WGK Germany: 3
• RTECS: ZE4070000
• F: 19
• TSCA: Yes
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 626-16-4(Hazardous Substances Data)

Usage

Chemical Properties

Colorless to light yellow liqui

Uses

m-Xylene Dichloride is used in ionic liquids to increase their thermal stability as well as used as a reagent in C2-Symmetric Small Molecule Inhibitors.

Synthetic route

m-xylene (108-38-3) → 3-(chloromethyl)benzyl chloride (626-16-4)

Conditions	Yield
With chlorine; 1-butyl-3-methylimidazolium chloride at 58℃; for 3h; Reagent/catalyst; Temperature; Irradiation; Ionic liquid;	99.18%
With chlorine Sonnenlicht;
With phosphorus pentachloride at 190℃;

1,3-dimethanol benzene (626-18-6) → 3-(chloromethyl)benzyl chloride (626-16-4)

Conditions	Yield
With oxalyl dichloride; Tropone In dichloromethane at 20℃; for 0.416667h; Inert atmosphere;	76%
With hydrogenchloride

N-chloro-succinimide (128-09-6) + m-xylene (108-38-3) → 1-chloromethyl-3-methyl-benzene (620-19-9) + 3-(chloromethyl)benzyl chloride (626-16-4)

Conditions	Yield
Irradiation.UV-Licht;

N-chloro-succinimide (128-09-6) + m-xylene (108-38-3) → 3-(chloromethyl)benzyl chloride (626-16-4)

Conditions	Yield
Irradiation.UV-Licht;

dimethyl Isophthalate (1459-93-4) → 3-(chloromethyl)benzyl chloride (626-16-4)

Conditions	Yield
With lithium aluminium tetrahydride; diethyl ether anschliessend Behandeln des Reaktionsprodukts mit konz. wss. Salzsaeure;

formaldehyd (50-00-0) + benzyl chloride (100-44-7) → 3-(chloromethyl)benzyl chloride (626-16-4)

Conditions	Yield
With aluminium trichloride; 1,2-dichloro-ethane; zinc(II) chloride at 50℃; Einleiten von HCl;

m-xylene (108-38-3) → 1-chloromethyl-3-methyl-benzene (620-19-9) + 3-(chloromethyl)benzyl chloride (626-16-4) + m-chloromethylbenzylidene chloride (30220-25-8) + α,α-dichloro-m-xylene (2719-42-8) + α,α,α',α'-Tetrachloro-m-xylene (30430-40-1)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); chlorine at 70℃; for 1.2h; Product distribution; various educt-reagent ratio, various time;

hydrogenchloride (7647-01-0) + formaldehyd (50-00-0) + aluminium trichloride (7446-70-0) + benzyl chloride (100-44-7) + ZnCl2 → 4,4'-bis(chloromethyl)diphenylmethane (14568-83-3) + o-Xylylene dichloride (612-12-4) + 3-(chloromethyl)benzyl chloride (626-16-4) + p-Xylylene dichloride (623-25-6)

Conditions	Yield
at 50℃; Verb. 5: 1.2-Dichlor-aethan;

...Expand

m-xylene (108-38-3) → 1-chloromethyl-3-methyl-benzene (620-19-9) + 3-(chloromethyl)benzyl chloride (626-16-4)

Conditions	Yield
With 2,2'-azobis(isobutyronitrile); 1,3,4,6-tetrachloro-3α,6α-diphenyl glycoluril In tetrachloromethane at 81℃; for 2h; Inert atmosphere;	A 52 %Chromat. B 16 %Chromat.

3-(chloromethyl)benzyl chloride (626-16-4) + N1-(2,6-diisopropylphenyl)-N2-methylethane-1,2-diamine → C38H58N4

Conditions	Yield
With potassium carbonate In ethanol for 96h; Reflux;	99%

3-(chloromethyl)benzyl chloride (626-16-4) → 1,3-Bis-benzene (17604-82-9)

Conditions	Yield
With N-benzyl-N,N,N-triethylammonium chloride; potassium acetate In acetone; toluene	98.7%

1H-imidazole (288-32-4) + 3-(chloromethyl)benzyl chloride (626-16-4) → 1,3-bis(imidazol-1-ylmethyl)benzene (69506-92-9)

Conditions	Yield
With sodium hydride In 1,2-dimethoxyethane; mineral oil at 0 - 20℃; for 15h;	98%
Stage #1: 1H-imidazole With potassium hydroxide In acetonitrile at 20℃; for 1h; Stage #2: 3-(chloromethyl)benzyl chloride In acetonitrile at 20℃; for 6h;	73%
With potassium hydroxide In acetonitrile at 20℃;

N-Ethylimidazole (7098-07-9) + 3-(chloromethyl)benzyl chloride (626-16-4) → [(1,3-phenylene)bis(methylene)]bis(1-ethyl-imidazolium) dichloride

Conditions	Yield
Stage #1: N-Ethylimidazole; 3-(chloromethyl)benzyl chloride at 135℃; for 0.166667h; Stage #2: Inert atmosphere;	98%

para-xylene (106-42-3) + 3-(chloromethyl)benzyl chloride (626-16-4) → C24H26

Conditions	Yield
With silica gel; zinc(II) chloride at 30℃; for 0.5h;	97%

3-(chloromethyl)benzyl chloride (626-16-4) + phenylacetylene (536-74-3) → 1,1'-(m-phenylenedimethylene)bis<4-phenyl-1H-1,2,3-triazole> (137959-34-3)

Conditions	Yield
With copper(l) iodide; sodium azide In water at 100℃; for 10h;	97%
With sodium azide In water at 70℃; for 7h; Huisgen Cycloaddition; Green chemistry; regioselective reaction;	88%

3-(chloromethyl)benzyl chloride (626-16-4) + phenylboronic acid (98-80-6) → 1,3-dibenzylbenzene (15180-20-8)

Conditions	Yield
With potassium phosphate; SP-4-[1,3-bis[2,6-diisopropylphenyl]-1,3-dihydro-2H-imidazol-2-ylidene]chloro[2-(1-methyl-1H-imidazol-2-yl-κN3)phenyl-κC]palladium(II) In ethanol at 60℃; for 3h; Suzuki-Miyaura Coupling; Inert atmosphere;	97%

3-(chloromethyl)benzyl chloride (626-16-4) + 2-methylpropan-2-thiol (75-66-1) → 1,3-bis(t-butylthiomethyl)benzene (70606-45-0)

Conditions	Yield
Stage #1: 2-methylpropan-2-thiol With sodium hydride In tetrahydrofuran at 20℃; for 0.166667h; Inert atmosphere; Schlenk technique; Stage #2: 3-(chloromethyl)benzyl chloride In tetrahydrofuran for 5h; Inert atmosphere; Schlenk technique;	97%

1-methyl-1-propanethiol (513-53-1) + 3-(chloromethyl)benzyl chloride (626-16-4) → C16H26S2

Conditions	Yield
Stage #1: 1-methyl-1-propanethiol With sodium hydride In tetrahydrofuran at 20℃; for 0.166667h; Inert atmosphere; Schlenk technique; Stage #2: 3-(chloromethyl)benzyl chloride In tetrahydrofuran for 5h; Inert atmosphere; Schlenk technique;	97%

3-(chloromethyl)benzyl chloride (626-16-4) + mercaptoacetic acid (68-11-1) → 1,3-xylylenedimercaptoacetic acid (122591-10-0)

Conditions	Yield
With sodium hydroxide In methanol for 6h; Heating;	96%

3-(chloromethyl)benzyl chloride (626-16-4) + diphenylphosphane (829-85-6) → 1,3-bis(diphenylphosphinomethyl)benzene (89756-88-7)

Conditions	Yield
Stage #1: diphenylphosphane With n-butyllithium In tetrahydrofuran; hexane at -40 - 0℃; Metallation; Stage #2: 3-(chloromethyl)benzyl chloride In tetrahydrofuran; hexane at 20℃; Condensation; Heating; Further stages.;	96%
With n-butyllithium In tetrahydrofuran; hexane at -40℃; for 2h;

1-methyl-1H-imidazole (616-47-7) + 3-(chloromethyl)benzyl chloride (626-16-4) → 3,3'-dimethyl-1,1’-(1,3-phenylenedimethylene)-bis(1H-imidazolium) dichloride

Conditions	Yield
In N,N-dimethyl-formamide at 100℃; for 0.05h; Microwave irradiation;	96%
at 60℃; for 2h;	91.4%
at 135℃; for 10h;	91%
In toluene for 16h; Reflux;	70%

4,4'-Dihydroxybiphenyl (92-88-6) + 3-(chloromethyl)benzyl chloride (626-16-4) → 1,3-bis[4-(4-hydroxyphenyl)phenoxymethyl]benzene (815600-60-3)

Conditions	Yield
Stage #1: 4,4'-Dihydroxybiphenyl With sodium hydroxide In water; dimethyl sulfoxide at 80℃; Stage #2: 3-(chloromethyl)benzyl chloride In water; dimethyl sulfoxide at 80 - 120℃; for 2h;	96%

4-(2,6-dimethylphenyl)-1,2,4-4H-triazole (1245737-20-5) + 3-(chloromethyl)benzyl chloride (626-16-4) → 1-[1-(3-chloromethyl)phenyl(methyl)]-4-[2,6-dimethylphenyl]-1,2,4-4H-triazol-1-ium chloride (1429043-31-1)

Conditions	Yield
In neat (no solvent) at 120℃; for 2h;	96%

3-(chloromethyl)benzyl chloride (626-16-4) + bis(pinacol)diborane (73183-34-3) → 1,3-bis((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)benzene

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 20℃; for 18h;	96%

3-(chloromethyl)benzyl chloride (626-16-4) + ephedrine (299-42-3) → C28H36N2O2 (191990-87-1)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃;	95%

3-(chloromethyl)benzyl chloride (626-16-4) + 2-Phenylphenol (90-43-7) → 1,3-bis(([1,1'-biphenyl]-2-yloxy)methyl)benzene (1409952-66-4)

Conditions	Yield
Stage #1: 2-Phenylphenol With potassium hydroxide In dimethyl sulfoxide at 35℃; for 0.75h; Inert atmosphere; Stage #2: 3-(chloromethyl)benzyl chloride In dimethyl sulfoxide at 35 - 50℃; for 3.41667h;	95%

N1-(2,6-dimethylphenyl)-N2-methylethane-1,2-diamine + 3-(chloromethyl)benzyl chloride (626-16-4) → C30H42N4

Conditions	Yield
With potassium carbonate In ethanol for 96h; Reflux;	95%

4-(2-benzylthiophenyl)-4H-1,2,4-triazole (1245737-22-7) + 3-(chloromethyl)benzyl chloride (626-16-4) → 1,1'-[1,3-phenylenedi(methylene)]bis[4-((2-benzylthio)phenyl)-4H-1,2,4-triazol-1-ium] dichloride

Conditions	Yield
at 130℃; for 2h; neat (no solvent);	94%

2-methylpropanethiol-1 (513-44-0) + 3-(chloromethyl)benzyl chloride (626-16-4) → C16H26S2

Conditions	Yield
Stage #1: 2-methylpropanethiol-1 With sodium hydride In tetrahydrofuran at 20℃; for 0.166667h; Inert atmosphere; Schlenk technique; Stage #2: 3-(chloromethyl)benzyl chloride In tetrahydrofuran for 5h; Inert atmosphere; Schlenk technique;	94%

3,4-dimethyl-7-hydroxycoumarin (2107-78-0) + 3-(chloromethyl)benzyl chloride (626-16-4) → 7-{[3-(chloromethyl)benzyl]oxy}-3,4-dimethyl-2H-chromen-2-one

Conditions	Yield
With potassium carbonate; potassium iodide In acetone at 130℃; for 0.5h; Microwave irradiation;	94%
With potassium carbonate In acetonitrile for 8h; Reflux;	65%

N,N,N',N'-tetramethyl-1,4-butanediamine (111-51-3) + 3-(chloromethyl)benzyl chloride (626-16-4) → C16H28N2(2+)*2Cl(1-)

Conditions	Yield
In acetonitrile for 24h; Alkylation; Cyclization; Heating;	93%

3-(chloromethyl)benzyl chloride (626-16-4) + diphenylthioselenophosphinic acid sodium salt (35351-90-7) → Se-prop-2-en-1-yl diphenylthioselenophosphinate (1427544-16-8)

Conditions	Yield
In ethanol at 40 - 43℃; for 0.166667h; Inert atmosphere;	93%

3-(chloromethyl)benzyl chloride (626-16-4) + 4,5-dihydro-1-[3-(triethoxysilyl)propyl]imidazole → 1,1’-[1,3-phenylenebis(methylene)]bis{3-[3-(triethoxysilyl)propyl]-4,5-dihydro-1H-imidazol-3-ium} chloride

Conditions	Yield
In toluene for 48h; Inert atmosphere; Reflux;	92%

2,3-benzocarbazole (243-28-7) + 3-(chloromethyl)benzyl chloride (626-16-4) → 1,3-bis(benzo[b]carbazol-9-ylmethyl)benzene

Conditions	Yield
With 1-methyl-pyrrolidin-2-one; potassium hydroxide at 80℃; for 10h;	91%
With potassium hydroxide 1.) DMSO, 50 deg C, 1 h, 2.) DMSO, 90 deg C, 1 h; Yield given. Multistep reaction;

2-(2-hydroxy-phenoxy)-ethanol (4792-78-3) + 3-(chloromethyl)benzyl chloride (626-16-4) → m-bis(2-ethoxyphenyloxy)xylene (1012793-41-7)

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 120℃; for 7h;	91%

3-(chloromethyl)benzyl chloride (626-16-4) + potassium diphenylphosphine (15475-27-1, 4346-39-8) → 1,3-bis(diphenylphosphinomethyl)benzene (89756-88-7)

Conditions	Yield
In tetrahydrofuran at 20℃; for 6.16667h; Inert atmosphere;	90.1%

methanol (67-56-1) + carbon monoxide (201230-82-2) + 3-(chloromethyl)benzyl chloride (626-16-4) → dimethyl 2,2'-(1,3-phenylene)diacetate (36076-19-4)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); N-ethyl-N,N-diisopropylamine at 80℃; under 15514.9 Torr; for 8h;	90%
With tetrakis(triphenylphosphine) palladium(0); N-ethyl-N,N-diisopropylamine at 80℃; for 8h; Autoclave;	90%
With calcium oxide; methyl iodide; dicobalt octacarbonyl at 65℃; under 760 Torr; for 10h;	77%

3-(chloromethyl)benzyl chloride (626-16-4) → 1,3-bis(mercaptomethyl)benzene (41563-69-3)

Conditions	Yield
With thiourea In ethanol for 2h; Heating;	90%
With sodium hydroxide; thiourea In water 1.) reflux, 2 h, 2.) reflux, 5 h;
Stage #1: 3-(chloromethyl)benzyl chloride With thiourea In water for 2.5h; Inert atmosphere; Reflux; Stage #2: With water; sodium hydroxide at 40 - 70℃; for 2h; Temperature; Inert atmosphere;	55 g

Upstream product

• 128-09-6 N-chloro-succinimide 
• 108-38-3 m-xylene 
• 626-18-6 1,3-dimethanol benzene 
• 1459-93-4 dimethyl Isophthalate 
• 50-00-0 formaldehyd 
• 100-44-7 benzyl chloride 
• 7647-01-0 hydrogenchloride 
• 7446-70-0 aluminium trichloride 

Downstream Products

• 626-18-6 1,3-dimethanol benzene 
• 23189-85-7 1,3-Bis-<2,2-dicarbethoxy-penten-(4)-yl>-benzol 
• 6047-59-2 1,3-Bis-(3-methyl-3-butenyl)-benzol 
• 69909-20-2 4,7,13,15-tetraoxa-1,10-diaza-14(1,2),19(1,3)-dibenzena-bicyclo[8.7.3]eicosaphane-11,17-dione 
• 36076-19-4 dimethyl 2,2'-(1,3-phenylene)diacetate 
• 19806-17-8 1,3-benzenediacetic acid 
• 85894-48-0 C₂₈H₂₄N₄⁽²⁺⁾*2Cl^(1-) 
• 18412-15-2 1,3-bis[(trimethylsilyl)methyl]benzene 
• 82005-93-4 1,3-bis[(chlorodimethylsilyl)methyl]benzene 
• 155106-81-3 1-(3-Chloromethyl-benzyl)-4-(2-isopropoxy-phenyl)-piperazine 
• 41563-69-3 1,3-bis(mercaptomethyl)benzene 
• 51744-98-0 [2.2]Metacyclophan 
• 4662-96-8 1,2-di-m-tolylethane 
• 14553-78-7 <2.2.2.2>metacyclophane 

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