78-71-7

Basic information

• Product Name: 3,3-Dichloromethyloxolane
• Synonyms: 3,3-Bis(chloromethyl)-1-oxacyclobutane;3,3-Bis(chloromethyl)oxacyclobutane;NSC 650608
• CAS NO: 78-71-7
• Molecular Formula: C₅H₈Cl₂O
• Molecular Weight: 155.03
• EINECS: 201-136-5
• Mol File: 78-71-7.mol
• Article Data: 3

Chemical Properties

• Boiling Point: 208.9 °C at 760 mmHg
• Flash Point: 115.8 °C
• Appearance: /
• Density: 1.236 g/cm³
• Refractive Index: 1.474
• CAS DataBase Reference: 3,3-Dichloromethyloxolane(CAS DataBase Reference)
• NIST Chemistry Reference: 3,3-Dichloromethyloxolane(78-71-7)
• EPA Substance Registry System: 3,3-Dichloromethyloxolane(78-71-7)

Safety Data

• Hazardous Substances Data: 78-71-7(Hazardous Substances Data)

Usage

General Description

3,3-Dichloromethyloxolane, also known as DCMO, is an organic compound with the chemical formula C5H8Cl2O. It is a colorless liquid with a slightly sweet, chloroform-like odor. DCMO is a highly reactive compound and is commonly used as an intermediate in the synthesis of pharmaceuticals and agrochemicals. It is also used in the preparation of specialty chemicals and as a solvent in various industrial processes. DCMO is considered to be a hazardous substance and should be handled with care, as prolonged or repeated exposure can cause irritation to the eyes, skin, and respiratory system. It is important to follow proper safety precautions when working with DCMO, including wearing protective equipment and ensuring adequate ventilation.

InChI:InChI=1/C6H10Cl2O2/c7-4-9-6(10-5-8)2-1-3-6/h1-5H2

Synthetic route

3-chloro-(2,2-chloromethyl)propan-1-ol (813-99-0) → 3,3-bis(chloromethyl)oxetane (78-71-7)

Conditions	Yield
With potassium hydroxide In ethanol for 72h; Heating / reflux;	80%
With potassium hydroxide In ethanol for 0.5h; Reflux;	74%
With potassium hydroxide

acetic acid-(3-chloro-2,2-bis-chloromethyl-propyl ester) (13103-49-6) → 3,3-bis(chloromethyl)oxetane (78-71-7)

Conditions	Yield
With potassium hydroxide; benzene
With alkaline solution

Pentaerythritol (115-77-5) + copper → 3,3-bis(chloromethyl)oxetane (78-71-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: SOCl2, pyridine / 14 h / Heating 2: KOH / ethanol / 5 h / Heating View Scheme

Pentaerythritol (115-77-5) → 3,3-bis(chloromethyl)oxetane (78-71-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: concentrated aqueous hydrochloric acid / 185 °C 2: ethanolic KOH-solution View Scheme
Multi-step reaction with 2 steps 1: water; hydrochloric acid / 185 °C 2: ethanolic KOH-solution View Scheme
Multi-step reaction with 2 steps 1: pyridine; thionyl chloride 2: ethanolic NaOH-solution View Scheme
Multi-step reaction with 2 steps 1: pyridine; thionyl chloride / 22 h / 65 - 130 °C 2: potassium hydroxide / ethanol / 0.5 h / Reflux View Scheme

3,3-bis(chloromethyl)oxetane (78-71-7) → 3,3-bis(azidomethyl)-oxetane (17607-20-4)

Conditions	Yield
With sodium hydroxide; tetrabutylammomium bromide In water	99.5%
With sodium azide In N,N-dimethyl-formamide at 90 - 100℃; for 2h;	76%
With sodium azide In N,N-dimethyl-formamide at 90 - 100℃; for 2h;	76%
With sodium azide In dimethyl sulfoxide at 65℃;

3,3-bis(chloromethyl)oxetane (78-71-7) + trimethylsilyl bromide (2857-97-8) → 2,2-Bis-3-bromo-1-trimethylsiloxypropane (79271-75-3)

Conditions	Yield
at 100℃; for 2h;	93%

3,3-bis(chloromethyl)oxetane (78-71-7) + paraformaldehyde → 5,5-bis(chloromethyl)-1,3-dioxane (61729-08-6)

Conditions	Yield
With sulfuric acid In toluene at 100℃; for 4.5h;	84%

3,3-bis(chloromethyl)oxetane (78-71-7) + sodium methylate (124-41-4) → 3,3-di(methoxymethyl)oxetane (10404-84-9)

Conditions	Yield
In methanol at 80℃; for 240h;	82%

3,3-bis(chloromethyl)oxetane (78-71-7) + p-nitrobenzenesulfonamide (6325-93-5) → C11H12N2O5S

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 80℃; for 18h;	82%

3,3-bis(chloromethyl)oxetane (78-71-7) + 1H,1H,2H,2H-tridecafluoro-n-octanol (647-42-7) → 3-chloromethyl-3-(1,1,2,2-tetrahydro-perfluoro-octyloxy)methyl oxetane + 3,3-Bis-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyloxymethyl)-oxetane

Conditions	Yield
With sodium hydroxide; tetra(n-butyl)ammonium hydrogensulfate at 70℃; for 10h;	A 80% B 16%

3,3-bis(chloromethyl)oxetane (78-71-7) → 3,3-Bis(iodomethyl)oxacyclobutane (2402-82-6)

Conditions	Yield
With sodium iodide In acetone for 52h; Heating;	75%
With sodium iodide In acetone for 56h; Heating;	75%
With butanone; sodium iodide

3,3-bis(chloromethyl)oxetane (78-71-7) + sodium ethanolate (141-52-6) → 3,3-di(ethoxymethyl)oxetane (10404-85-0)

Conditions	Yield
In ethanol at 90℃; for 330h;	75%

3,3-bis(chloromethyl)oxetane (78-71-7) + 1,1-dimethylhydrazine (57-14-7) → 3-(1,1-dimethylhydraziniomethyl)-3-(chloromethyl)oxetane chloride

Conditions	Yield
Alkylation;	75%

3,3-bis(chloromethyl)oxetane (78-71-7) → 2,2-bis(chloromethyl)propane-1,3-diol dinitrate (107149-26-8)

Conditions	Yield
With sulfuric acid; nitric acid at 0 - 15℃; for 5h;	73%

3,3-bis(chloromethyl)oxetane (78-71-7) + 2-Nitrobenzenesulfonamide (5455-59-4) → C11H12N2O5S

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 80℃; for 18h;	73%

3,3-bis(chloromethyl)oxetane (78-71-7) + formaldehyd (50-00-0) → 5,5-bis(chloromethyl)-1,3-dioxane (61729-08-6)

Conditions	Yield
With sulfuric acid In 1,4-dioxane at 90 - 100℃; for 5h;	70%
With sulfuric acid In 1,4-dioxane for 5h; Heating;

3,3-bis(chloromethyl)oxetane (78-71-7) + sodium butanolate (2372-45-4) → 3,3-bis-butoxymethyl-oxetane (1522-91-4)

Conditions	Yield
In butan-1-ol at 105℃; for 270h;	68%

3,3-bis(chloromethyl)oxetane (78-71-7) + benzaldehyde (100-52-7) → 2-phenyl-5,5-bis(chloromethyl)-1,3-dioxane (6103-09-9)

Conditions	Yield
With sulfuric acid In toluene at 110℃; for 4.5h;	68%
With sulfuric acid In 1,4-dioxane for 5h; Heating;

3,3-bis(chloromethyl)oxetane (78-71-7) → 2-oxa-6,7-ditelluraspiro<3.4>octane (125906-12-9)

Conditions	Yield
With potassium tellurocyanate In dimethyl sulfoxide	65%

3,3-bis(chloromethyl)oxetane (78-71-7) + diisopropyl malonate (13195-64-7) → diisopropyl 2-oxaspiro[3.3]heptane-6,6-dicarboxylate (1023817-50-6)

Conditions	Yield
Stage #1: diisopropyl malonate With sodium hydride In N,N-dimethyl-formamide for 3h; Inert atmosphere; Stage #2: 3,3-bis(chloromethyl)oxetane With potassium iodide at 140℃; for 10h; Reflux; Inert atmosphere;	64%

3,3-bis(chloromethyl)oxetane (78-71-7) + N-(but-2-yn-1-yl)-2-ethynyl-N-methylaniline → 5-{2-[but-2-yn-1-yl(methyl)amino]phenyl}-2,2-bis(chloromethyl)pent-4-yn-1-ol

Conditions	Yield
Stage #1: N-(but-2-yn-1-yl)-2-ethynyl-N-methylaniline With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: With boron trifluoride diethyl etherate In tetrahydrofuran; hexane at -78℃; for 0.0833333h; Inert atmosphere; Stage #3: 3,3-bis(chloromethyl)oxetane In tetrahydrofuran; hexane at -78℃; Inert atmosphere;	63%

3,3-bis(chloromethyl)oxetane (78-71-7) + paracetaldehyde (123-63-7) → 2-methyl-5,5-bis(chloromethyl)-1,3-dioxane (13727-37-2)

Conditions	Yield
With sulfuric acid In toluene at 60℃; for 4.5h;	62%

1,3-dioxolane-4-methanol (5464-28-8) + 3,3-bis(chloromethyl)oxetane (78-71-7) → 4-(3-Chloromethyl-oxetan-3-ylmethoxymethyl)-[1,3]dioxolane (127719-58-8)

Conditions	Yield
With potassium hydroxide; 18-crown-6 ether for 4h; Ambient temperature;	60%

3,3-bis(chloromethyl)oxetane (78-71-7) + benzylamine (100-46-9) → 2-benzyl-6-oxa-2-azaspiro[3.3]-heptane (46246-91-7)

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 100℃; for 18h;	57%

3,3-bis(chloromethyl)oxetane (78-71-7) + indole (120-72-9) → 3,3-bis(indol-1-ylmethyl)oxetane (1314235-53-4)

Conditions	Yield
Stage #1: 3,3-bis(chloromethyl)oxetane; indole In butanone Reflux; Stage #2: With tetra(n-butyl)ammonium hydrogensulfate; potassium carbonate; potassium hydroxide In butanone for 48h; Reflux;	53%

3,3-bis(chloromethyl)oxetane (78-71-7) → 3-(Iodomethyl)-3-(chloromethyl)oxetane (35842-61-6)

Conditions	Yield
With sodium iodide In acetone for 6h; Heating;	52%
With sodium iodide In acetone for 6h; Heating;	52%
With sodium iodide In acetone for 6.5h; Product distribution; Heating; oth. time;	1.23 g

3,3-bis(chloromethyl)oxetane (78-71-7) → 2,2-bis(chloromethyl)-1,3-diacetoxypropane (3296-86-4) + 5,5-bis-chloromethyl-[1,3,2]dioxaphosphinane 2-oxide (69213-72-5)

Conditions	Yield
With phosphonic Acid; acetic anhydride In 1,4-dioxane for 2h; Heating; Title compound not separated from byproducts;	A n/a B 47.9%

3,3-bis(chloromethyl)oxetane (78-71-7) + cyclohexylamine (108-91-8) → 6-Cyclohexyl-2-oxa-6-azaspiro<3.3>heptane (97401-34-8)

Conditions	Yield
With sodium hydroxide at 120℃; for 0.666667h;	45%

3,3-bis(chloromethyl)oxetane (78-71-7) + 4-methoxy-benzylamine (2393-23-9) → 6-(4-methoxybenzyl)-2-oxa-6-azaspiro[3.3]heptane

Conditions	Yield
With 1,8-diazabicyclo[5.4.0]undec-7-ene In N,N-dimethyl-formamide at 80℃; for 18h;	45%

3,3-bis(chloromethyl)oxetane (78-71-7) + acetic acid (64-19-7) → 2,2-Bis(chloromethyl)propyl acetate (13431-60-2)

Conditions	Yield
With potassium iodide; zinc at 120℃; for 10h;	36%

3,3-bis(chloromethyl)oxetane (78-71-7) → 3,3-bis-fluoromethyl-oxetane (338-61-4) + 3-Chloromethyl-3-fluoromethyl-oxetane (74465-76-2)

Conditions	Yield
With potassium fluoride; 18-crown-6 ether at 100℃; for 23h;	A 18% B 35%

1,3-dioxolane-4-methanol (5464-28-8) + 3,3-bis(chloromethyl)oxetane (78-71-7) → C13H22O7 (127719-61-3)

Conditions	Yield
With potassium hydroxide; 18-crown-6 ether for 4h; Ambient temperature;	30%

3,3-bis(chloromethyl)oxetane (78-71-7) → 2,2-bis(chloromethyl)-1,3-propanediol (2209-86-1)

Conditions	Yield
With sulfuric acid In water	28%

Upstream product

• 813-99-0 3-chloro-(2,2-chloromethyl)propan-1-ol 
• 13103-49-6 acetic acid-(3-chloro-2,2-bis-chloromethyl-propyl ester) 
• 115-77-5 Pentaerythritol 

Downstream Products

• 61729-08-6 5,5-dichloromethyl-1,3-dioxane 
• 1522-91-4 3,3-Bis-butyloxymethyl-oxacyclobutan 
• 24043-70-7 1-{2-[3-(2-Acetyl-phenoxymethyl)-oxetan-3-ylmethoxy]-phenyl}-ethanone 
• 97401-34-8 6-Cyclohexyl-2-oxa-6-azaspiro<3.3>heptane 
• 97401-35-9 3,3-Bis(cyclohexylaminomethyl)oxetane 
• 6103-09-9 2-phenyl-5,5-bis(chloromethyl)-1,3-dioxane 
• 338-61-4 3,3-bis-fluoromethyl-oxetane 
• 74465-76-2 3-Chloromethyl-3-fluoromethyl-oxetane 
• 2209-86-1 2,2-bis(chloromethyl)-1,3-propanediol 
• 35842-61-6 3-(Iodomethyl)-3-(chloromethyl)oxetane 
• 174-80-1 2-oxa-6-thiaspiro[3.3]heptane 
• 2402-82-6 3,3-Bis(iodomethyl)oxacyclobutane 
• 96915-41-2 tris<2,2,2-(azidomethyl)ethyl> 1,3,5-benzenetricarboxylate 
• 822-48-0 3-chloromethyl-3-methyl oxetane 

Relevant articles and documents

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