2402-83-7

Basic information

• Product Name: 3,3-BIS(BROMOMETHYL)OXETANE
• Synonyms: 3,3-BIS(BROMOMETHYL)OXETANE;Oxetane, 3,3-bis(broMoMethyl)-;BBMO;NSC 281665;3,3-Bis-brommethyl-oxetan
• CAS NO: 2402-83-7
• Molecular Formula: C₅H₈Br₂O
• Molecular Weight: 243.92
• Mol File: 2402-83-7.mol
• Article Data: 8

Chemical Properties

• Melting Point: 25℃
• Boiling Point: 125℃ (23 Torr)
• Flash Point: 98 °C
• Appearance: /
• Density: 1.891 g/cm³
• Vapor Pressure: 0.0363mmHg at 25°C
• Refractive Index: 1.535
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• Solubility: Chloroform (Sparingly), Methanol (Slightly)
• Stability: Hygroscopic
• CAS DataBase Reference: 3,3-BIS(BROMOMETHYL)OXETANE(CAS DataBase Reference)
• NIST Chemistry Reference: 3,3-BIS(BROMOMETHYL)OXETANE(2402-83-7)
• EPA Substance Registry System: 3,3-BIS(BROMOMETHYL)OXETANE(2402-83-7)

Safety Data

• Hazard Codes: Xn
• Statements: 34-22
• Safety Statements: 26-36/37/39
• RIDADR: 3265
• WGK Germany: 3
• Hazardous Substances Data: 2402-83-7(Hazardous Substances Data)

Usage

General Description

3,3-Bis(bromomethyl)oxetane is a chemical compound with the formula C6H8Br2O2. It is a brominated oxetane, which is a type of cyclic ether. 3,3-BIS(BROMOMETHYL)OXETANE is used as a monomer in the synthesis of poly(3,3-bis(bromomethyl)oxetane) (PBMO) through a ring-opening polymerization process. PBMO has potential applications in the development of high-performance materials and composites due to its high thermal stability and flame retardant properties. 3,3-Bis(bromomethyl)oxetane is known for its ability to improve the fire safety performance of various materials, making it a valuable compound in the field of polymer science and materials engineering.

InChI:InChI=1/C5H8Br2O/c6-1-5(2-7)3-8-4-5/h1-4H2

Synthetic route

(C4H9)3SnOCH2C(CH2Br)3 → 3,3-bis(bromomethyl)oxetane (2402-83-7) + tributyltin bromide (1461-23-0)

Conditions	Yield
decompn. at 160°C (0.5 h);	A 94% B n/a
decompn. at 160°C (0.5 h);	A 94% B n/a

2,2-bis(bromomethyl)-3-bromo-propan-1-ol (1522-92-5) → 3,3-bis(bromomethyl)oxetane (2402-83-7)

Conditions	Yield
With sodium ethanolate In ethanol at 20 - 76℃; for 3.16667h;	85%
With sodium ethanolate In ethanol at 80℃; for 2.5h;	62%
With potassium hydroxide
With potassium hydroxide
With tetra(n-butyl)ammonium hydrogensulfate; sodium hydroxide In water; toluene at 23℃; for 23h; Inert atmosphere; Industrial scale;

3-bromo-2,2-bis(bromomethyl)propyl acetate (3580-97-0) → 3,3-bis(bromomethyl)oxetane (2402-83-7)

Conditions	Yield
With alkaline solution

2,2-bis(bromomethyl)-3-bromo-propan-1-ol (1522-92-5) → 2,6-Dioxa-spiro<3.3>heptan (174-79-8) + 3,3-bis(bromomethyl)oxetane (2402-83-7) + [3-(bromomethyl)oxetan-3-yl]methanol (22633-44-9)

Conditions	Yield
In water at 70℃; pH=7.06; Kinetics; Further Variations:; Temperatures; pH-values;

Pentaerythritol (115-77-5) → 3,3-bis(bromomethyl)oxetane (2402-83-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: HBr 2: ethanolic KOH-solution View Scheme
Stage #1: Pentaerythritol With sulfuric acid; hydrogen bromide; acetic acid In water for 10h; Reflux; Stage #2: With tetrabutylammomium bromide; sodium hydroxide In water at 60℃; for 1h;

3,3-bis(bromomethyl)oxetane (2402-83-7) → 3,3-bis(azidomethyl)-oxetane (17607-20-4)

Conditions	Yield
With sodium azide; tetrabutylammomium bromide In water for 2h; Heating;	92%
With sodium azide; tetrabutylammomium bromide In water at 70℃;
With sodium azide; tetrabutylammomium bromide In water at 70℃;

3,3-bis(bromomethyl)oxetane (2402-83-7) + NH-pyrazole (288-13-1) → 3,3-bis(pyrazol-1-ylmethyl)oxetane (208105-64-0)

Conditions	Yield
With potassium tert-butylate In tetrahydrofuran for 12h; Heating;	90%

3,3-bis(bromomethyl)oxetane (2402-83-7) + octreotide → C54H74N10O11S2

Conditions	Yield
Stage #1: octreotide With tris(2-carboxyethyl)phosphine; potassium carbonate In water at 20℃; for 1h; Stage #2: 3,3-bis(bromomethyl)oxetane In water; N,N-dimethyl-formamide for 12h;	81%

3,3-bis(bromomethyl)oxetane (2402-83-7) + 9-chloro-7-methoxy-1H,2H,3H-cyclopenta[b]quinolin-6-ol → 6-{[3-(bromomethyl)oxetan-3-yl]methoxy}-9-chloro-7-methoxy-1H,2H,3H-cyclopenta[b]quinoline

Conditions	Yield
With caesium carbonate In acetonitrile at 70℃; for 2.5h; Sealed tube;	81%

3,3-bis(bromomethyl)oxetane (2402-83-7) + Methyl phenyldiazoacetate (22979-35-7) → C14H16Br2O3

Conditions	Yield
In chloroform for 3h; Irradiation;	79%

3,3-bis(bromomethyl)oxetane (2402-83-7) + cyclohex-3-enylmethanol (72581-32-9, 1679-51-2) → 3,3-bis[(3-cyclohexen-1-ylmethoxy)methyl]oxetane

Conditions	Yield
With potassium tert-butylate In N,N-dimethyl-formamide at 5 - 20℃; for 14h;	78.1%

3,3-bis(bromomethyl)oxetane (2402-83-7) + somatostatin → C81H112N18O20S2

Conditions	Yield
Stage #1: somatostatin With tris(2-carboxyethyl)phosphine; potassium carbonate In water at 20℃; for 1h; Stage #2: 3,3-bis(bromomethyl)oxetane In water; N,N-dimethyl-formamide for 12h;	76%

3,3-bis(bromomethyl)oxetane (2402-83-7) + CAAAC → C22H36N6O7S2

Conditions	Yield
Stage #1: CAAAC With tris(2-carboxyethyl)phosphine; potassium carbonate In N,N-dimethyl-formamide at 20℃; for 1h; Stage #2: 3,3-bis(bromomethyl)oxetane In N,N-dimethyl-formamide for 12h;	75%

3,3-bis(bromomethyl)oxetane (2402-83-7) + 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 60℃; for 18h; Temperature; Reagent/catalyst; Solvent;	70%
With tetra(n-butyl)ammonium hydrogensulfate; sodium hydroxide In water; toluene at 83℃; for 20h; Industrial scale;

3,3-bis(bromomethyl)oxetane (2402-83-7) + 7-tert-butyl-1-ethyl 3-oxo-2H,5H,6H,8H-imidazo[1,5-a]pyrazine-1,7-dicarboxylate → 7-tert-butyl 1-ethyl 2-[[3-(bromomethyl)oxetan-3-yl]methyl]-3-oxo-5H,6H,8H-imidazo[1,5-a]pyrazine-1,7-dicarboxylate

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 60℃; for 4h;	65%

3,3-bis(bromomethyl)oxetane (2402-83-7) + 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 60℃; for 21h;	51%

3,3-bis(bromomethyl)oxetane (2402-83-7) + rac-(4bR,5R,6R,7S,7aR)-5-(aminomethyl)-7a-(4-bromophenyl)-6-(hydroxymethyl)-4-methoxy-7-phenyl-5,6,7,7a-tetrahydro-4bH-cyclopenta[4,5]furo[2,3-c]pyridin-4b-ol → rac-(4bR,5R,6R,7S,7aR)-5-((2-oxa-6-azaspiro[3.3]heptan-6-yl)methyl)-7a-(4-bromophenyl)-6-(hydroxymethyl)-4-methoxy-7-phenyl-5,6,7,7a-tetrahydro-4bH-cyclopenta[4,5]furo[2,3-c]pyridin-4b-ol trifluoroacetic acid

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 80℃; for 4.5h;	45%

3,3-bis(bromomethyl)oxetane (2402-83-7) → 2-oxa-6-thiaspiro[3.3]heptane (174-80-1)

Conditions	Yield
With sodiumsulfide nonahydrate In N,N-dimethyl-formamide at 50℃; for 6.5h; Inert atmosphere;	44%

3,3-bis(bromomethyl)oxetane (2402-83-7) + 3-(5-(((1S,2S)-2-aminocyclopentyl)oxy)-1-oxoisoindolin-2-yl)piperidine-2,6-dione → 3-(5-(((1S,2S)-2-(2-oxa-6-azaspiro[3.3]heptan-6-yl)cyclopentyl)oxy)-1-oxoisoindolin-2-yl)piperidine-2,6-dione

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In acetonitrile at 80℃; for 120h;	32%

3,3-bis(bromomethyl)oxetane (2402-83-7) + benzyl 5-(4-methoxybenzyl)-3,6-dioxo-1,2,3,4,5,6,7,8-octahydropyrazolo[4,3-c]azepin-7-ylcarbamate → benzyl (10'-(4-methoxybenzyl)-9'-oxo-8',9',10',11'-tetrahydro-2'H,4'H,7'H-spiro[oxetane-3,3'-[1,3]oxazino[3',2':1,5]pyrazolo[4,3-c]azepin]-8'-yl)carbamate

Conditions	Yield
With potassium carbonate In N,N-dimethyl-formamide at 80℃; for 3h;	30%

3,3-bis(bromomethyl)oxetane (2402-83-7) + 4-fluorophenylsulphonamide (402-46-0) → 2-(4-fluoro-benzenesulfonyl)-2-aza-spiro[3.3]heptane

Conditions	Yield
Stage #1: 4-fluorophenylsulphonamide With sodium hydride In N,N-dimethyl-formamide; mineral oil at 0℃; for 0.166667h; Stage #2: 3,3-bis(bromomethyl)oxetane In N,N-dimethyl-formamide; mineral oil at 20℃; Stage #3: With hydrogenchloride In water; N,N-dimethyl-formamide; mineral oil	26%

3,3-bis(bromomethyl)oxetane (2402-83-7) + 3-(5-(((1S,2S)-2-aminocyclohexyl)oxy)-1-oxoisoindolin-2-yl)piperidine-2,6-dione → 3-(5-(((1S,2S)-2-(2-oxa-6-azaspiro[3.3]heptan-6-yl)cyclohexyl)oxy)-1-oxoisoindolin-2-yl)piperidine-2,6-dione

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In N,N-dimethyl-formamide at 60℃; for 40h; Microwave irradiation;	9%

3,3-bis(bromomethyl)oxetane (2402-83-7) + Benzoyl bromide (618-32-6) → benzoic acid-(3-bromo-2,2-bis-bromomethyl-propyl ester) (100119-07-1)

3,3-bis(bromomethyl)oxetane (2402-83-7) + sodium cyanide (143-33-9) → 3,3-bis-cyanomethyl-oxetane (22030-97-3)

Conditions	Yield
With ethanol

3,3-bis(bromomethyl)oxetane (2402-83-7) + diethylamine (109-89-7) → 3,3-bis-diethylaminomethyl-oxetane (208105-67-3)

3,3-bis(bromomethyl)oxetane (2402-83-7) + trimethylamine (75-50-3) → (3-bromomethyl-oxetan-3-ylmethyl)-trimethyl-ammonium; bromide

Conditions	Yield
With water

3,3-bis(bromomethyl)oxetane (2402-83-7) + trimethylamine (75-50-3) → 3,3-bis-trimethylammoniomethyl-oxetane; dibromide

Conditions	Yield
With water at 120℃;

3,3-bis(bromomethyl)oxetane (2402-83-7) → 3,3-bis-fluoromethyl-oxetane (338-61-4)

Conditions	Yield
With potassium fluoride; ethylene glycol

3,3-bis(bromomethyl)oxetane (2402-83-7) → 3,3-Bis(iodomethyl)oxacyclobutane (2402-82-6)

Conditions	Yield
With acetone; sodium iodide

3,3-bis(bromomethyl)oxetane (2402-83-7) → 3,3-Bis-(aminomethyl)-oxetane (23500-57-4)

Conditions	Yield
With ammonia
With ammonium hydroxide
Multi-step reaction with 2 steps 1: sodium azide; tetrabutylammomium bromide / water / 70 °C 2: hydrogen; palladium 10% on activated carbon / methanol / 5 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: sodium azide; tetrabutylammomium bromide / water / 70 °C 2: 20% palladium hydroxide-activated charcoal; hydrogen / methanol / 5 h / 20 °C View Scheme

3,3-bis(bromomethyl)oxetane (2402-83-7) → 2,2-bis-bromomethyl-3-chloro-propan-1-ol (137530-33-7)

Conditions	Yield
With hydrogenchloride; water

3,3-bis(bromomethyl)oxetane (2402-83-7) → 2,2-bis-bromomethyl-3-iodo-propan-1-ol

Conditions	Yield
With water; hydrogen iodide

3,3-bis(bromomethyl)oxetane (2402-83-7) → 3-amino-2,2-bis(aminomethyl)-1-propanol (120844-28-2)

Conditions	Yield
With ammonia; water at 200℃;
With ethanol; ammonia; water at 200℃;
Multi-step reaction with 2 steps 1: aq.-ethanolic ammonia 2: water; ethanol; NH3 / 200 °C View Scheme

Upstream product

• 115-77-5 Pentaerythritol 
• 1522-92-5 2,2-bis(bromomethyl)-3-bromo-propan-1-ol 
• 3580-97-0 3-bromo-2,2-bis(bromomethyl)propyl acetate 

Downstream Products

• 100119-07-1 benzoic acid-(3-bromo-2,2-bis-bromomethyl-propyl ester) 
• 22030-97-3 3,3-bis-cyanomethyl-oxetane 
• 338-61-4 3,3-bis-fluoromethyl-oxetane 
• 2402-82-6 3,3-Bis(iodomethyl)oxacyclobutane 
• 872805-46-4 6-sulfanilyl-2-oxa-6-aza-spiro[3.3]heptane 
• 174-80-1 2-oxa-6-thiaspiro[3.3]heptane 
• 1045709-32-7 2-oxa-6-azaspiro[3.3]heptane 0.5 oxalic acid salt 
• 1159599-99-1 2-oxa-6-azaspiro[3.3]heptan-6-ium carboxyformate 

Relevant articles and documents

Synthesis and copolymerization of azidomethyl-substituted oxetanes: the morphology of statistical block copolymers

[Figure not available: see fulltext.] 3,3-Bis(azidomethyl)oxetane and 3-azidomethyl-3-methyloxetane were obtained by bromination of pentaerythritol and metriol with a mixture of hydrobromic, acetic, and sulfuric acids, followed by cyclization in the presence of a phase-transfer catalyst TBAB, with the formation of oxetane ring and replacement of bromide substituents with azide ions. The copolymerization reaction of 3,3-bis-(azidomethyl)oxetane and 3-azidomethyl-3-methyloxetane was performed in the presence of a catalytic system prepared from triisobutylaluminum and water. The methods of small-angle and wide-angle X-ray diffraction analysis were used to determine the amorphous-crystalline and domain structures of the synthesized copolymers. We also present data about conformational and relaxation transitions in these statistical copolymers.

The Development of a Manufacturing Route to an MCHr1 Antagonist

Process development work to provide an efficient manufacturing route to a MCHr1 antagonist is presented herewith. Features of this development work include a scalable manufacturing route to the useful 6-oxa-2-azaspiro[3.3]heptane building block and the use of a (soluble) alternative to sodium triacetoxyborohydride.

Chemical transformation of 3-bromo-2,2-bis(bromomethyl)-propanol under basic conditions

The mechanism of the spontaneous decomposition of 3-bromo-2,2- bis(bromomethyl)propanol (TBNPA) and the kinetics of the reaction of the parent compound and two subsequent products were determined in aqueous solution at temperatures from 30 to 70 °C and pH from 7.0 to 9.5. TBNPA is decomposed by a sequence of reactions that form 3,3-bis(bromomethyl)oxetane (BBMO), 3-bromomethyl-3-hydroxymethyloxetane (BMHMO), and 2,6-dioxaspiro[3.3]-heptane (DOH), releasing one bromide ion at each stage. The pseudo-first-order rate constant of the decomposition of TBNPA increases linearly with the pH. The apparent activation energy of this transformation (98 ± 2 KJ/mol) was calculated from the change of the effective second-order rate constant with temperature. The pseudoactivation energies of BBMO and BMHMO were estimated to be 109 and 151 KJ/mol, respectively. Good agreement was found between the rate coefficients derived from changes in the organic molecules concentrations and those determined from the changes in the Br- concentrations. TBNPA is the most abundant semivolatile organic pollutant in the aquitard studied, and together with its byproducts they posess an environmental hazard. TBNPA half-life is estimated to be about 100 years. This implies that high concentrations of TBNPA will persist in the aquifer long after the elimination of all its sources.