4360-63-8

Basic information

• Product Name: 2-Bromomethyl-1,3-dioxolane
• Synonyms: 2-(bromomethyl)-3-dioxolane;2-(BROMOMETHYL)-1,3-DIOXOLANE/BROMOACETALDEHYDE ETHYLENE ACETAL;2-Bromomethyl-1,3-dioxolane, 97 %;2-Brommethyl-,1,3-dioxolane;2-BroMoMethyl-1,3-dioxolane, 97% 25ML;2-(Bromomethyl)-1,3-dioxolane 98+%;Bromoacetaldehyde ethylene acetal, (1,3-Dioxolan-2-yl)methyl bromide;2-Bromomethyl-1,3-dioxolane 96%
• CAS NO: 4360-63-8
• Molecular Formula: C₄H₇BrO₂
• Molecular Weight: 167.00118
• EINECS: 224-443-6
• Product Categories: Miscellaneous;Dioxanes & Dioxolanes;Dioxolanes;Acetals/Ketals/Ortho Esters;Building Blocks;Chemical Synthesis;Organic Building Blocks;Oxygen Compounds;Halogenated Heterocycles
• Mol File: 4360-63-8.mol
• Article Data: 12

Chemical Properties

• Boiling Point: 80-82 °C27 mm Hg(lit.)
• Flash Point: 145 °F
• Appearance: Clear colorless/Liquid
• Density: 1.613 g/mL at 25 °C(lit.)
• Vapor Pressure: 1.32mmHg at 25°C
• Refractive Index: n20/D 1.482(lit.)
• Storage Temp.: Store below +30°C.
• Solubility: Chloroform, Ethyl Acetate (Slightly)
• Water Solubility: Immiscible with water.
• Sensitive: Moisture Sensitive
• BRN: 103309
• CAS DataBase Reference: 2-Bromomethyl-1,3-dioxolane(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Bromomethyl-1,3-dioxolane(4360-63-8)
• EPA Substance Registry System: 2-Bromomethyl-1,3-dioxolane(4360-63-8)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-24/25
• WGK Germany: 3
• TSCA: Yes
• Hazardous Substances Data: 4360-63-8(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless liquid

Uses

Different sources of media describe the Uses of 4360-63-8 differently. You can refer to the following data:
1. 2-Bromomethyl-1,3-dioxolane is used in the preparation of alfa, beta-unsaturated aldehyde and 1, 4-two aldehyde monoacetals synthesis of monomers.
2. 2-Bromomethyl-1,3-dioxolane was used in the synthesis of 1,4-benzoxazepine (BZO) compounds.

InChI:InChI=1/C4H7BrO2/c5-3-4-6-1-2-7-4/h4H,1-3H2

Synthetic route

2-methyl-1,3-dioxolane (497-26-7) → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Conditions	Yield
With bromine; di-tert-butyldicyclohexano-18-crown-18 In benzene at 20℃; for 0.166667h; Bromination;	96%
With 1,4-Dioxane Dibromide In tetrachloromethane at 29.9℃; Rate constant; Thermodynamic data; Mechanism; ΔH(excit.), ΔS(excit.), ΔG(excit.), lg A; further temp., kinetics;

1-bromo-2,2-dimethoxyethane (7252-83-7) + ethylene glycol (107-21-1) → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Conditions	Yield
With Dowex 50(H+) at 120℃; for 1h;	94%
With Dowex-x8 (H+) resin	75%
With sulfuric acid
With potassium bisulfite; methoxybenzene at 140℃;	15 g
at 150℃;

ethylene glycol (107-21-1) + Bromoacetaldehyde diethyl acetal (2032-35-1) → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Conditions	Yield
With toluene-4-sulfonic acid at 110℃; for 2h;	87%
With sulfuric acid
at 150℃;

ethylene glycol (107-21-1) + acetaldehyde (75-07-0) → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Conditions	Yield
Stage #1: ethylene glycol; acetaldehyde at 20℃; for 0.5h; Large scale; Stage #2: With bromine at 0 - 3℃; for 3.5h; Temperature; Large scale;	79.2%

2-methyl-1,3-dioxolane (497-26-7) → 2-bromomethyl-1,3-dioxolane (4360-63-8) + bromoethyl acetate (927-68-4)

Conditions	Yield
With bromine In tetrachloromethane at 60 - 70℃;	A 45% B 45%
With N-Bromosuccinimide; di-tert-butylcyclohexano-18-crown-6 In benzene Ambient temperature;	A 32 % Chromat. B 68 % Chromat.

vinyl acetate (108-05-4) + ethylene glycol (107-21-1) → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Conditions	Yield
With bromine

bis-(1,2-dibromo-ethyl) ether (6304-35-4) + ethylene glycol (107-21-1) → 2-bromomethyl-1,3-dioxolane (4360-63-8) + 2-bromoethanol (540-51-2)

ethylene glycol (107-21-1) + bromoacetaldehyde (17157-48-1) → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Bromoacetaldehyde diethyl acetal (2032-35-1) → 2-bromomethyl-1,3-dioxolane (4360-63-8)

ethylene glycol (107-21-1) + ω.ω'-dibromo-paraldehyde → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Conditions	Yield
With sulfuric acid

ethylene glycol (107-21-1) + tribromoparaldehyde → 2-bromomethyl-1,3-dioxolane (4360-63-8)

Conditions	Yield
With sulfuric acid at 100℃;

2-bromomethyl-1,3-dioxolane (4360-63-8) + tributylphosphine (998-40-3) → (1,3-dioxolan-2-ylmethyl)tributylphosphonium bromide (115754-62-6)

Conditions	Yield
at 90℃; for 96h;	100%
at 90℃; for 72h; Yield given;

2-bromomethyl-1,3-dioxolane (4360-63-8) → 2-(azidomethyl)-1,3-dioxolane

Conditions	Yield
With sodium azide In dimethyl sulfoxide at 100℃; for 0.5h;	100%
With sodium azide In dimethyl sulfoxide at 70℃;	93%
With sodium azide In dimethyl sulfoxide Inert atmosphere;	83%

2-bromomethyl-1,3-dioxolane (4360-63-8) → sodium S-((1,3-dioxolan-2-yl)methyl) thiosulfate

Conditions	Yield
With Sodium thiosulfate pentahydrate In methanol; water for 24h; Reflux;	100%

2-bromomethyl-1,3-dioxolane (4360-63-8) + triphenylphosphine (603-35-0) → (1,3-dioxolan-2-yl-methyl)triphenylphosphonium bromide (52509-14-5)

Conditions	Yield
In isopropyl alcohol at 60 - 65℃; for 3h; Inert atmosphere; Green chemistry;	99.1%
In toluene for 24h; Heating / reflux;	54%
at 120℃; for 24h;

2-bromomethyl-1,3-dioxolane (4360-63-8) + tris-n-propylphosphine (2234-97-1) → C13H28O2P(1+)*Br(1-)

Conditions	Yield
With sodium iodide In 1,4-dioxane for 24h; Heating;	97%

2-bromomethyl-1,3-dioxolane (4360-63-8) + 2-methoxy-phenol (90-05-1) → 2-[(2-methoxyphenoxy)methyl]-1,3-dioxolane (1160183-64-1)

Conditions	Yield
With potassium carbonate In 1-methyl-pyrrolidin-2-one at 135℃; for 10h; Product distribution / selectivity;	91.15%
With potassium carbonate In 2-methoxy-ethanol at 125 - 126℃; for 17h; Product distribution / selectivity;	88.59%
With potassium carbonate In ethylene glycol at 132℃; for 20h; Product distribution / selectivity;	80.6%

2-bromomethyl-1,3-dioxolane (4360-63-8) + dimethyl methylphosphonite (20278-51-7) → C6H13O4P

Conditions	Yield
at 120℃; for 5h; Inert atmosphere;	91.1%

2-bromomethyl-1,3-dioxolane (4360-63-8) + N,N-diethyl-2-propynylamine (4079-68-9) + 2-(vinyloxy)ethyl isothiocyanate (59565-09-2) → 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl]-1-[2-(ethenyloxy)ethyl]-N,N-diethyl-1H-pyrrol-2-amine

Conditions	Yield
Stage #1: N,N-diethyl-2-propynylamine With n-butyllithium In tetrahydrofuran; hexane at -60℃; Inert atmosphere; Stage #2: 2-(vinyloxy)ethyl isothiocyanate In tetrahydrofuran; hexane at 0 - 45℃; for 0.0833333h; Inert atmosphere; Stage #3: 2-bromomethyl-1,3-dioxolane Further stages;	91%

2-bromomethyl-1,3-dioxolane (4360-63-8) + N-9-fluorenylisovaleraldehyde imine → N-(1-(1,3-dioxolan-2-yl)-4-methylpentan-2-yl)-9H-fluoren-9-imine

Conditions	Yield
Stage #1: 2-bromomethyl-1,3-dioxolane; N-9-fluorenylisovaleraldehyde imine With cobalt(II) bromide In diethyl ether at 25℃; for 0.166667h; Sealed tube; Stage #2: With lithium hexamethyldisilazane In diethyl ether at -20 - 25℃; for 2.16667h; Catalytic behavior; Reagent/catalyst; Solvent; Sealed tube; regioselective reaction;	91%

2-bromomethyl-1,3-dioxolane (4360-63-8) + epichlorohydrin (106-89-8) → (2R,2S)-(3,4-epoxy)butyl-1,3-dioxolane

Conditions	Yield
Stage #1: 2-bromomethyl-1,3-dioxolane With iodine; magnesium In tetrahydrofuran at 30 - 40℃; for 3h; Inert atmosphere; Stage #2: epichlorohydrin In tetrahydrofuran at 0 - 15℃; for 4h;	90.6%

2-bromomethyl-1,3-dioxolane (4360-63-8) + theophylline (58-55-9) → doxofylline (69975-86-6)

Conditions	Yield
With tetrabutylammomium bromide; sodium hydroxide In acetone for 6.3h; Reagent/catalyst; Solvent; Reflux; Large scale;	90%
With sodium carbonate In N,N-dimethyl-formamide at 120℃;	7 g
With potassium carbonate; potassium iodide In N,N-dimethyl-formamide for 12h; Large scale;

2-bromomethyl-1,3-dioxolane (4360-63-8) + 5-methoxy-2-phenylindole (5883-96-5) → 8-methoxy-1H-benzocarbazole

Conditions	Yield
With bismuth(III) chloride In acetonitrile at 80℃; for 7h;	90%

2-bromomethyl-1,3-dioxolane (4360-63-8) + methyl 3-amino-3-iminopropanoate → 2-amino-3-pyrrolecarboxylate methyl ester

Conditions	Yield
Stage #1: 2-bromomethyl-1,3-dioxolane With hydrogenchloride In water; ethyl acetate at 10℃; for 0.333333h; Stage #2: methyl 3-amino-3-iminopropanoate In water; ethyl acetate at 100℃; for 3h;	89.3%

2-bromomethyl-1,3-dioxolane (4360-63-8) + ethyl-3-hydroxybenzoate (7781-98-8) → ethyl 3-((1,3-dioxolan-2-yl)methoxy)benzoate

Conditions	Yield
With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 120℃; for 18h;	89%
With potassium carbonate; sodium iodide In N,N-dimethyl-formamide at 120℃;	88%

2-bromomethyl-1,3-dioxolane (4360-63-8) + 5-[1-(4-chlorophenylsulfonyl)-3-piperidinyl]-1,3,4-oxadiazole-2-thiol → 5-[1-[(4-chlorophenyl)sulfonyl]-3-piperidinyl]-1,3,4-oxadiazole-2-yl 1,3-dioxolan-2-ylmethyl sulfide

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide	89%

2-bromomethyl-1,3-dioxolane (4360-63-8) + 1,4,7,10-tetraazacyclododecan (294-90-6) → 1-(1,3-Dioxolan-2-ylmethyl)-1,4,7,10-tetraazacyclododecane (141794-32-3)

Conditions	Yield
In acetonitrile for 1h; Heating;	88%

2-bromomethyl-1,3-dioxolane (4360-63-8) + 5-methoxylindole (1006-94-6) + acetoacetic acid methyl ester (105-45-3) → methyl 6-methoxy-1-methyl-9H-carbazole-2-carboxylate

Conditions	Yield
With bismuth(III) chloride In acetonitrile at 80℃; for 2h;	88%

2-bromomethyl-1,3-dioxolane (4360-63-8) → 2-(iodomethyl)-1,3-dioxolane (41031-93-0)

Conditions	Yield
With sodium iodide In acetone for 24h; Reflux;	87%
With sodium iodide In acetone at 25 - 120℃; for 8h; Inert atmosphere;	85%
With sodium iodide In various solvent(s) for 24h; Heating;	78%

2-bromomethyl-1,3-dioxolane (4360-63-8) + 5-Hydroxy-2-methylpyridine (1121-78-4) → 5-(1,3-dioxolan-2-ylmethoxy)-2-methylpyridine (494776-68-0)

Conditions	Yield
Stage #1: 5-Hydroxy-2-methylpyridine With sodium hydride In DMF (N,N-dimethyl-formamide) at 25℃; for 0.166667h; Stage #2: 2-bromomethyl-1,3-dioxolane In DMF (N,N-dimethyl-formamide) at 100℃; for 12h;	87%

Upstream product

• 108-05-4 vinyl acetate 
• 107-21-1 ethylene glycol 
• 7252-83-7 1-bromo-2,2-dimethoxyethane 
• 6304-35-4 bis-(1,2-dibromo-ethyl) ether 
• 2032-35-1 Bromoacetaldehyde diethyl acetal 
• 17157-48-1 bromoacetaldehyde 
• 497-26-7 2-methyl-1,3-dioxolane 
• 75-07-0 acetaldehyde 

Downstream Products

• 927-68-4 bromoethyl acetate 
• 4070-51-3 Bromessigsaeure-monoglykolester 
• 115754-62-6 (1,3-dioxolan-2-ylmethyl)tributylphosphonium bromide 
• 100157-42-4 1-cyano-1-<2-(1,1-ethylendioxyethyl)>diphenylmethane 
• 130220-08-5 2-(4-Chloro-2-methyl-phenylsulfanylmethyl)-[1,3]dioxolane 
• 107535-97-7 2-[2-Methylsulfanyl-2-(toluene-4-sulfonyl)-ethyl]-[1,3]dioxolane 
• 344439-21-0 N-(4-Bromo-phenyl)-N-[1,3]dioxolan-2-ylmethyl-methanesulfonamide 
• 117013-72-6 2-<(4-acetamido-3-nitro-phenoxy)-methyl>-1,3-dioxolane 
• 114614-55-0 4-Amino-5-chloro-N-(2-diethylamino-ethyl)-2-([1,3]dioxolan-2-ylmethoxy)-benzamide 
• 125228-46-8 (3R,8aR)-5-[1,3]Dioxolan-2-ylmethyl-3-phenyl-hexahydro-oxazolo[3,2-a]pyridine-5-carbonitrile 
• 71516-48-8 2-((benzyloxy)methyl)-1,3-dioxolane 
• 73785-78-1 allyl<2,2-(ethylenedioxy)ethyl>diphenylphosphonium bromide 
• 179669-44-4 dioxolanne de l'α-phenylthioacetaldehyde 
• 764-48-7 ethyleneglycol vinyl ether 

Relevant articles and documents

Electron Spin Resonance Spectra of Free Radicals. Part 2. Radicals formed by Hydrogen Abstraction from Cyclic and Acyclic Fluoro-acetals

Free radicals formed during the photolysis of solutions containing di-t-butyl peroxide and fluoro-acetals such as 1,1-diethoxy-2-fluoroethane and substituted 1,3-dioxolanes, have been studied by e.s.r. spectroscopy.Only the radicals formed initially by hydrogen abstraction were detected, although product analysis by g.c.-m.s. indicated that certain of the cyclic radicals rearranged to acyclic species.The e.s.r. parameters are discussed in relation to the preferred conformations of the radicals.

Kinetics and mechanism of bromination of cyclic acetals with 1,4-dioxane dibromide

It is shown that the reactivities of cyclic formals in the case of bromination with dioxane dibromide increase in the order 1,3-dioxepane > 1,3-dioxalane ? 1,3-dioxane, which is explained not only by steric factors but also by the ease of cleavage of the C4-O3 bond of the dioxacyclane ring. The bromination of cyclic acetals takes place through prior enolization of the cyclic acetal with subsequent electrophilic addition of bromine to the double bond.

Preparation method of doxofylline

The invention provides a preparation method of doxofylline and particularly relates to a synthetic method of bromoacetaldehyde ethylene acetal represented as the formula II and the doxofylline. The method includes the steps of preparing the side-chain bromoacetaldehyde ethylene acetal represented as the formula II through a one-pot reaction of acetaldehyde, ethylene glycol and bromine, and then carrying out a N-alkylation reaction to the compound represented as the formula II with theophylline to prepare the doxofylline. The synthetic method is carried out with easy-to-obtain raw materials, is low in cost, is high in yield, is simple in processes, is economical and environment-friendly, and is beneficial to industrial scale-up production of the drug.

Catalytic Effect of Crown Ethers in the Bromination of 2-Alkyl-substituted 1,3-Dioxacyclanes

Bromination of 2-alkyl-1,3-dioxacyclanes with molecular bromine in the presence of crown ethers in benzene (chloroform) results, regardless of the acetal ring size, in exclusive formation of 2-(1-bromoalkyl)-1,3-dioxacyclanes in near-quantitative yields. The use of crown ethers allows the bromination to be accomplished at room temperature.