4885-02-3

Basic information

• Product Name: 1,1-Dichlorodimethyl ether
• Synonyms: a,a-Dichloromethyl methyl ether;α,α-Dichloromethyl methyl ether, 1,1-Dichlorodimethyl ether;alpha,alpha-Dichloromethyl methyl ether,97%;DICHLOROMETHYL METHYL ETHER FOR SYNTHESI;DichloroMethyl Methyl ether 98%;DichloroMethyl Methyl Ether, 97.0%(GC);alpha,alpha-Dichloromethyl ether;alpha,alpha-dichloromethylether
• CAS NO: 4885-02-3
• Molecular Formula: C₂H₄Cl₂O
• Molecular Weight: 114.96
• EINECS: 225-498-9
• Product Categories: Alcohol& Phenol& Ethers;Chlorination;Halogenation;Synthetic Organic Chemistry;Pyrimidines;BUILDING BLOCKS
• Mol File: 4885-02-3.mol
• Article Data: 8

Chemical Properties

• Melting Point: 85 C
• Boiling Point: 85 °C(lit.)
• Flash Point: 108 °F
• Appearance: Clear colorless to light yellow/Liquid
• Density: 1.271 g/mL at 25 °C(lit.)
• Vapor Pressure: 79mmHg at 25°C
• Refractive Index: n20/D 1.431(lit.)
• Storage Temp.: 2-8°C
• BRN: 1900293
• CAS DataBase Reference: 1,1-Dichlorodimethyl ether(CAS DataBase Reference)
• NIST Chemistry Reference: 1,1-Dichlorodimethyl ether(4885-02-3)
• EPA Substance Registry System: 1,1-Dichlorodimethyl ether(4885-02-3)

Safety Data

• Hazard Codes: C,T,F
• Statements: 10-20/22-34-37-33-23/24-40-36-23/24/25
• Safety Statements: 26-36/37/39-45-24/25-16-27-7/9
• RIDADR: UN 2924 3/PG 2
• WGK Germany: 3
• RTECS: KN8150000
• F: 21
• HazardClass: 6.1(a)
• PackingGroup: I
• Hazardous Substances Data: 4885-02-3(Hazardous Substances Data)

Usage

Chemical Properties

Colorless liquid

Uses

Common formylating reagent for aromatic compounds, chlorinating agent for carboxylic acids, and reactant with borinic esters for the preparation of alkenones.

InChI:InChI=1/C2H4Cl2O/c1-5-2(3)4/h2H,1H3

Synthetic route

oxalyl dichloride (79-37-8) + Methyl formate (107-31-3) → Dichloromethyl methyl ether (4885-02-3)

Conditions	Yield
With N-methyl-N-phenylformamide at 25 - 30℃; for 31h;	71%

Methyl formate (107-31-3) → Dichloromethyl methyl ether (4885-02-3)

Conditions	Yield
With phosphorus pentachloride
With phosphorus pentachloride Chlorination;
With oxalyl dichloride; N-methyl-N-phenylformamide at 30℃; for 9h;
With oxalyl dichloride; N-methyl-N-phenylformamide

3-chloro-3-methoxy-diazirine (4222-27-9) → Dichloromethyl methyl ether (4885-02-3) + methoxychlorocarbene (67894-87-5)

Conditions	Yield
With hydrogenchloride Irradiation; Yield given. Yields of byproduct given;

chlorine (7782-50-5) + chloromethyl methyl ether (107-30-2) → trichloromethyl ether (20524-84-9) + 1,1,1,1'-Tetrachlor-dimethylaether (20524-85-0) + Dichloromethyl methyl ether (4885-02-3)

Conditions	Yield
unbekannte Halogenstellung;

phosgene (75-44-5) + Methyl formate (107-31-3) → Dichloromethyl methyl ether (4885-02-3)

Conditions	Yield
With triphenylphosphine In 1,2-dichloro-benzene

Dichloromethyl methyl ether (4885-02-3) + 2,6-dimethoxytoluene (5673-07-4) → 2,4-dimethoxy-3-methylbenzaldehyde (7149-92-0)

Conditions	Yield
Stage #1: 2,6-dimethoxytoluene With tin(IV) chloride In dichloromethane at 0℃; for 1h; Inert atmosphere; Stage #2: Dichloromethyl methyl ether In dichloromethane at 0℃; for 1h; Inert atmosphere;	100%
With titanium tetrachloride In dichloromethane at 0 - 20℃; for 2h;	98%
With titanium tetrachloride In dichloromethane	95.8%

Dichloromethyl methyl ether (4885-02-3) + <25>(1,2,3,4,5)cyclophane (70759-58-9) → 4-formyl<25>(1,2,3,4,5)cyclophane (79539-21-2)

Conditions	Yield
With tin(IV) chloride In dichloromethane 1.) 0 deg C, 24 h, 2.) room temperature, 4 d;	100%

Dichloromethyl methyl ether (4885-02-3) + 25,27-dihydroxy-26,28-dipropoxycalix[4]arene (143406-35-3) → 26,28-dihydroxy-25,27-dipropoxycalix[4]arene-5,11-dicarbaldehyde (143433-59-4)

Conditions	Yield
With tin(IV) chloride In chloroform at -15 - 20℃; for 2h;	100%
With tin(IV) chloride In chloroform for 0.5h; Ambient temperature;	95%
With tin(IV) chloride In chloroform at -15℃; Inert atmosphere;	95%

Dichloromethyl methyl ether (4885-02-3) + 2-(3,4,5-Trimethoxy-benzyl)-malonic acid bis-(2,2,2-trichloro-ethyl) ester (149296-17-3) → 2-(2-Formyl-3,4,5-trimethoxy-benzyl)-malonic acid bis-(2,2,2-trichloro-ethyl) ester (149296-18-4)

Conditions	Yield
With tin(IV) chloride In dichloromethane a) -78 deg C, 30 min, b) to r.t., 20 min;	100%

Dichloromethyl methyl ether (4885-02-3) + colchicine (64-86-8) → 4-Formylcolchicine (2730-82-7)

Conditions	Yield
With tin(IV) chloride In dichloromethane	100%
With tin(IV) chloride In dichloromethane at 20℃; for 13h; Cooling with ice; Inert atmosphere;	100%
With tin(IV) chloride In dichloromethane 0 deg C, 30 min., r.t. 15 h;	90%
With tin(IV) chloride In dichloromethane at 20℃;

Dichloromethyl methyl ether (4885-02-3) + 1,10,12-trimethoxy-8-methyl-6H-dibenzo[c,h]chromen-6-one (185103-21-3) → 1,10,12-Trimethoxy-8-methyl-6-oxo-6H-dibenzo[c,h]chromene-4-carbaldehyde (185103-22-4)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0℃; for 0.5h;	100%

Dichloromethyl methyl ether (4885-02-3) + 3-(4-methoxy-phenyl)-propionic acid 2,2,2-trichloro-ethyl ester (377777-84-9) → 3-(3-formyl-4-methoxy-phenyl)-propionic acid 2,2,2-trichloro-ethyl ester (377777-85-0)

Conditions	Yield
With tin(IV) chloride In dichloromethane for 2h;	100%

Dichloromethyl methyl ether (4885-02-3) + ethyl 2-[1-(4-methoxyphenyl)methyl]butyrate (378232-17-8) → ethyl 2-ethyl-3-(3-formyl-4-methoxyphenyl)propanoate (378232-23-6)

Conditions	Yield
Stage #1: Dichloromethyl methyl ether; ethyl 2-[1-(4-methoxyphenyl)methyl]butyrate With titanium tetrachloride In dichloromethane at -20℃; Stage #2: With hydrogenchloride In dichloromethane Further stages.;	100%
Stage #1: Dichloromethyl methyl ether; ethyl 2-[1-(4-methoxyphenyl)methyl]butyrate With titanium tetrachloride In dichloromethane at -20℃; for 6h; Inert atmosphere; Stage #2: With hydrogenchloride; water In tetrahydrofuran	100%
Stage #1: Dichloromethyl methyl ether; ethyl 2-[1-(4-methoxyphenyl)methyl]butyrate With titanium tetrachloride In dichloromethane at -20℃; for 6h; Stage #2: With hydrogenchloride In dichloromethane	97%
With hydrogenchloride; titanium chloride In dichloromethane	10.9 g (97%)
With titanium tetrachloride In dichloromethane

6-methoxy-2,2,7,8-tetramethylchroman (66259-78-7) + Dichloromethyl methyl ether (4885-02-3) → 3,4-dihydro-6-methoxy-2,2,7,8-tetramethyl-2H-benzopyran-5-carboxaldehyde (389633-98-1)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 20℃; for 2h;	100%

Dichloromethyl methyl ether (4885-02-3) + 2-dodecyl-6-methoxy-2,7,8-trimethylchroman (389634-29-1) → 3,4-dihydro-2-dodecyl-6-methoxy-2,7,8-trimethyl-2H-benzopyran-5-carboxaldehyde (389634-00-8)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 20℃; for 2h;	100%

Dichloromethyl methyl ether (4885-02-3) + 1,4-dimethoxybezene (150-78-7) → 2,5-dimethoxybenzaldehyde (93-02-7)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0℃;	100%
With titanium tetrachloride In dichloromethane at -5 - 20℃; for 1.5h; Reagent/catalyst; Temperature; Inert atmosphere;	97.6%
With titanium tetrachloride In dichloromethane at 20℃; for 0.25h;

Dichloromethyl methyl ether (4885-02-3) + 4-methoxyphenyl methyl carbonate (22159-41-7) → 3-formyl-4-methoxyphenylmethylcarbonate (1296133-11-3)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0 - 20℃; for 1h;	100%

Dichloromethyl methyl ether (4885-02-3) + 2-Bromo-6-methoxynaphthalene (5111-65-9) → 6-bromo-2-methoxynaphthalene-1-carbaldehyde (247174-18-1)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 40℃; for 2h;	100%
With titanium tetrachloride In dichloromethane at 0 - 20℃;	100%
With titanium tetrachloride In dichloromethane at 0 - 20℃;	100%

5-methoxy-1-methyl-1-trifluoromethyl-1,3-dihydroisobenzofuran + Dichloromethyl methyl ether (4885-02-3) → 3-methyl-3-trifluoromethyl-6-methoxy-1,3-dihydroisobenzofuran-5-carbaldehyde

Conditions	Yield
Stage #1: 5-methoxy-1-methyl-1-trifluoromethyl-1,3-dihydroisobenzofuran With titanium tetrachloride In dichloromethane at -78℃; for 0.25h; Stage #2: Dichloromethyl methyl ether In dichloromethane at -78℃; for 1.5h;	100%

Dichloromethyl methyl ether (4885-02-3) + 2-methyl-1-((4-nitrophenyl)sulfonyl)-1H-indole (1181669-81-7) → 2-methyl-1-(4-nitrobenzenesulfonyl)-1H-indole-3-carbaldehyde (1181669-84-0)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0 - 20℃; Inert atmosphere;	100%

Dichloromethyl methyl ether (4885-02-3) + (4-dodecylthiophen-2-ylmethyl)phosphonic acid diethyl ether (1316844-61-7) → (4-dodecyl-5-formylthiophen-2-ylmethyl)phosphonic acid diethyl ester (1316844-58-2)

Conditions	Yield
With titanium tetrachloride	100%

Dichloromethyl methyl ether (4885-02-3) + 2,4-dimethoxy-3-methylphenyl methanesulfonate (1402887-46-0) → 5-formyl-2,4-dimethoxy-3-methylphenyl methanesulfonate (1402887-47-1)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0 - 20℃; for 2h;	100%

Dichloromethyl methyl ether (4885-02-3) + Coarannulen (5821-51-2) → 2-dibenzo[ghi,mno]fluoranthenecarbaldehyde (695179-12-5)

Conditions	Yield
With titanium tetrachloride	100%
With titanium tetrachloride In dichloromethane at 0 - 20℃; for 21h; Rieche Formylation; Inert atmosphere;	95%
With titanium tetrachloride In dichloromethane at 0 - 20℃; for 21h; Inert atmosphere;	93%

Dichloromethyl methyl ether (4885-02-3) + 5-methyl-9-(2-methylpyridin-3-yl)spiro[benzo[f]pyrrolo[1,2-a][1,4]diazepine-6,1'-cyclopropan]-4(5H)-one → 5-methyl-9-(2-methylpyridin-3-yl)-4-oxo-4,5-dihydrospiro[benzo[f]pyrrolo[1,2-a][1,4]diazepine-6,1'-cyclopropane]-2-carbaldehyde

Conditions	Yield
With aluminum (III) chloride In nitromethane; 1,2-dichloro-ethane at 0 - 20℃;	100%

Dichloromethyl methyl ether (4885-02-3) + C24H28S3 + tin(IV) chloride (7646-78-8) → C25H27S3(1+)*0.5Cl6Sn(2-)

Conditions	Yield
In 1,2-dichloro-ethane for 24h; Reflux; Inert atmosphere;	100%

6-bromo-3,4-dihydro-2H-1-benzopyran-2-carboxylic acid + Dichloromethyl methyl ether (4885-02-3) → 6-bromo-8-formyl-3,4-dihydro-2H-1-benzopyran-2-carboxylic acid

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0℃; for 2h; Inert atmosphere;	100%

Dichloromethyl methyl ether (4885-02-3) + 1,3-bis(4-methoxyphenyl)propane (4741-73-5) → 1,3-bis(3-formyl-4-methoxyphenyl)propane

Conditions	Yield
With titanium tetrachloride In dichloromethane at 20℃; for 3h;	99.6%

N-phenylsulfonylpyrrole (16851-82-4) + Dichloromethyl methyl ether (4885-02-3) → 1-benzenesulfonyl-2-formylpyrrole (86688-93-9)

Conditions	Yield
With aluminium trichloride In 1,2-dichloro-ethane at 0℃; for 3h;	99%
With aluminum (III) chloride In 1,2-dichloro-ethane at 0℃; for 5h; Inert atmosphere;	83%

Dichloromethyl methyl ether (4885-02-3) + [2.2]Paracyclophan (1633-22-3) → 4-formyl[2.2]paracyclophane (36325-27-6, 37044-38-5, 729-30-6, 147127-97-7)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 20℃; for 6h; Rieche formylation;	99%
With titanium tetrachloride In dichloromethane; water at 0 - 20℃; for 8h;	99%
Stage #1: Dichloromethyl methyl ether; [2.2]Paracyclophan With titanium tetrachloride In dichloromethane at 0 - 20℃; for 6h; Rieche Formylation; Inert atmosphere; Stage #2: With water for 2h;	99%

Dichloromethyl methyl ether (4885-02-3) + 1-phenyladamantane (780-68-7) → 4-(adamantan-1-yl)benzaldehyde (67116-18-1)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0℃; for 1h;	99%

Dichloromethyl methyl ether (4885-02-3) + 2-methoxyphenyl triflate (59099-58-0) → 4-methoxy-3-trifluoromethanesulfonyloxybenzaldehyde (157790-73-3)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0 - 20℃; for 5h;	99%

Dichloromethyl methyl ether (4885-02-3) + ethyl 4-benzyl-2-[(ethoxycarbonyl)methyl]-9-methyl-2,3,4,9-tetrahydro[1,4]oxazino[3,2-g]indole-8-carboxylate (462117-35-7) → 6-benzyl-8-ethoxycarbonylmethyl-3-formyl-1-methyl-1,6,7,8-tetrahydro-9-oxa-1,6-diaza-cyclopenta[a]naphthalene-2-carboxylic acid ethyl ester (497945-84-3)

Conditions	Yield
Stage #1: ethyl 4-benzyl-2-[(ethoxycarbonyl)methyl]-9-methyl-2,3,4,9-tetrahydro[1,4]oxazino[3,2-g]indole-8-carboxylate With aluminium trichloride In dichloromethane at 0℃; for 0.05h; Stage #2: Dichloromethyl methyl ether In dichloromethane at 0℃; for 1h; Rieche reaction;	99%

Dichloromethyl methyl ether (4885-02-3) + C48H42O6 (90507-93-0) → C54H42O12

Conditions	Yield
With titanium tetrachloride In dichloromethane at -5 - 20℃;	99%

Dichloromethyl methyl ether (4885-02-3) + 1-bromo-4-butoxybenzene (39969-57-8) → 5-bromo-2-butoxybenzaldehyde (515148-88-6)

Conditions	Yield
With titanium tetrachloride In dichloromethane at -78℃;	99%

Dichloromethyl methyl ether (4885-02-3) + 4-methoxylbiphenyl (613-37-6) → C15H12O3 (1258238-47-9)

Conditions	Yield
With titanium tetrachloride In dichloromethane at 0 - 20℃; Inert atmosphere;	99%

Upstream product

• 7782-50-5 chlorine 
• 107-30-2 chloromethyl methyl ether 
• 79-37-8 oxalyl dichloride 
• 107-31-3 Methyl formate 
• 75-44-5 phosgene 
• 4222-27-9 3-chloro-3-methoxy-diazirine 

Downstream Products

• 122-04-3 4-nitro-benzoyl chloride 
• 4451-35-8 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl chloride 
• 2548-87-0 (E)-2-Octenal 
• 22859-16-1 tris(phenylselanyl)methane 
• 40611-79-8 methyl 4-formyl-1H-pyrrole-2-carboxylate 
• 1126-18-7 2-butylcyclohexanone 
• 589-57-1 diethyl phosphorylchloridite 
• 75-00-3 chloroethane 
• 107-31-3 Methyl formate 
• 109-94-4 formic acid ethyl ester 
• 83681-56-5 (1R,2R)-(-)-trans-2-methylcyclohexyl-n-pentyl ketone 
• 928-80-3 decan-3-one 
• 629-23-2 tetradecan-3-one 
• 88939-66-6 1-<(p-methoxyphenyl)sulfonyl>-3-methyl-2-formylindole 

Relevant articles and documents

On the Stereochemistry of 2,6-Dichloro-4-methoxy-heptanes

2,6-Dichloro-4-methoxy-heptanes may exist as 2 optical active isomers and 2 meso compounds.By double addition of α,α-dichloro-dimethylether to propene a mixture of these stereoisomers was obtained.They were separated by HPLC.Using 1H- and 13C-NMR-spectroscopy their configuration could be established. - Keywords: 2,6-Dichloro-4-methoxy-heptanes; Stereoisomers; NMR-Spectroscopy; Configurational assignment

Convenient preparation of dichloromethyl alkyl ethers

Dichloromethyl alkyl ethers have been synthesized from alkyl formates (C1–C4) and oxalyl chloride in the presence of catalytic amount of N-methylformanilide. N,N-Dimethylformamide is not suitable for the reaction. The method has the advantages of simple experimental procedure, which is applicable to large scale synthesis, without use of harmful reagents.

Process for the preparation of methyl 1,1-dichloromethyl ether or of ethyl 1,1-dichloromethyl ether

The invention relates to a process for the preparation of methyl 1,1-dichloromethyl ether or of ethyl 1,1-dichloromethyl ether, according to which methyl formate or ethyl formate is reacted with phosgene, diphosgene, triphosgene or oxalyl chloride or one of their mixtures, at a temperature of between 40° C. and 100° C., in the presence of a catalyst chosen from the group consisting of trisubstituted phosphine oxides and sulphides, trisubstituted phosphine dichlorides, formamides, the products of reaction of formamides with chlorinating agents and mixtures thereof. The 1,1-dichloromethyl ethers are obtained in a high purity. They are useful especially for performing the formylation of aromatic compounds.