22612-89-1

Basic information

• Product Name: 1,1,3,3-TETRABROMOACETONE
• Synonyms: 1,1,3,3-TETRABROMO-2-PROPANONE;1,1,3,3-TETRABROMOACETONE;Tetrabromoacetone;1,1,3,3-TETRABROMOACETONE 95+%;1,1,3,3-tetrabroMopropan-2-one;1,1,3,3-Tetrabromopropanone;alpha,alpha,alpha',alpha'-Tetrabromoacetone
• CAS NO: 22612-89-1
• Molecular Formula: C₃H₂Br₄O
• Molecular Weight: 373.66
• Product Categories: Carbonyl Compounds;Halides
• Mol File: 22612-89-1.mol
• Article Data: 5

Chemical Properties

• Melting Point: 36°C
• Boiling Point: 311.4°C at 760 mmHg
• Flash Point: 125.3°C
• Appearance: /
• Density: 2.904g/cm³
• Vapor Pressure: 0.000566mmHg at 25°C
• Refractive Index: 1.648
• Storage Temp.: Refrigerator
• Solubility: Chloroform, Dichloromethane, Ethyl Acetate, Methanol
• Stability: Temperature Sensitive
• CAS DataBase Reference: 1,1,3,3-TETRABROMOACETONE(CAS DataBase Reference)
• NIST Chemistry Reference: 1,1,3,3-TETRABROMOACETONE(22612-89-1)
• EPA Substance Registry System: 1,1,3,3-TETRABROMOACETONE(22612-89-1)

Safety Data

• Statements: 36/37/38
• Safety Statements: 26-36/37/39
• Hazardous Substances Data: 22612-89-1(Hazardous Substances Data)

Usage

Uses

1,1,3,3-Tetrabromoacetone is an intermediate in the synthesis of 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone-13C5, which is an isotope labelled Mutagen X (MX) is a chlorinated furanone that accounts for more of the mutagenic activity of drinking water than any other disinfection byproduct. DNA damages provoked by the six mutagens (furylframide, MX, 4-nitroquinoline N-oxide, sodium azide, 1-nitropyrene, and captan) used in the present study have been known to subject to the nucleotide excision repair system.

InChI:InChI=1/C3H2Br4O/c4-2(5)1(8)3(6)7/h2-3H

Synthetic route

acetone (67-64-1) → 1,1,3,3-tetrabromoacetone (22612-89-1)

Conditions	Yield
With hydrogen bromide; bromine In water for 240h; Bromination;	89%
With hydrogen bromide; bromine In water at 0 - 20℃; for 78h; Inert atmosphere;	70%
With bromine Acidic conditions;
With hydrogen bromide; bromine

acetonedicarboxylic acid (542-05-2) → 1,1,3,3-tetrabromoacetone (22612-89-1)

Conditions	Yield
With bromine

water (7732-18-5) + bromine (7726-95-6) + acetone (67-64-1) + acid → 1,3-dibromoroacetone (816-39-7) + 1,1,3-tribromoacetone (3475-39-6) + 1,1,3,3-tetrabromoacetone (22612-89-1)

acetonedicarboxylic acid (542-05-2) + water (7732-18-5) + bromine (7726-95-6) → pentabromoacetone (79-49-2) + 1,1,3,3-tetrabromoacetone (22612-89-1)

acetone (67-64-1) → 1,1,3-tribromoacetone (3475-39-6) + 1,1,3,3-tetrabromoacetone (22612-89-1)

Conditions	Yield
With hydrogen bromide; bromine In water at 0 - 23℃; for 212h; Inert atmosphere; Overall yield = 85 g;

methanol (67-56-1) + 1,1,3,3-tetrabromoacetone (22612-89-1) → 3,3-dibromopropenoic acid methyl ester (66656-00-6)

Conditions	Yield
With sulfuric acid for 12h; Inert atmosphere; Reflux;	96%

1,1,3,3-tetrabromoacetone (22612-89-1) + 9-methylanthracene (779-02-2) → 11,13-dibromo-9,10-dihydro-9-methyl-9,10-propanoanthracen-12-one (143331-53-7)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; ultrasonication;	71%

1,1,3,3-tetrabromoacetone (22612-89-1) + 9-vinylanthracene (2444-68-0) → 11,13-dibromo-9,10-dihydro-9-vinyl-9,10-propanoanthracen-12-one (143331-54-8)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; Product distribution; ultrasonication; other 9,10-dihydro-9,10-propanoanthracen-12-ones, other polybromo ketones, stereoselectivity;	71%
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; ultrasonication;	71%

1,1,3,3-tetrabromoacetone (22612-89-1) + 9-(but-3-en-1-yl)anthracene (97451-55-3) → 9-(3-butenyl)-11,13-dibromo-9,10-dihydro-9,10-propanoanthracen-12-one (143331-56-0)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; ultrasonication;	70%

1,1,3,3-tetrabromoacetone (22612-89-1) → 3,3-dibromopropenoic acid (1578-21-8)

Conditions	Yield
With sodium hydrogencarbonate at 20℃; Favorski rearrangement;	67%
With sodium hydrogencarbonate In water at 20℃; for 48h; Inert atmosphere;	62%
With sodium carbonate

1,1,3,3-tetrabromoacetone (22612-89-1) + 9-β-propenylanthracene (23707-65-5) → 11,13-dibromo-9,10-dihydro-9-(2-propenyl)-9,10-propanoanthracen-12-one (143331-55-9)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; ultrasonication;	67%
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane; water at 15 - 20℃; Sonication;

2-benzyloxymethylfuran (16361-14-1) + 1,1,3,3-tetrabromoacetone (22612-89-1) → (1RS,2RS,4SR,5RS)-1-[(benzyloxy)methyl]-2-endo,4-endo-dibromo-8-oxabicyclo[3.2.1]oct-6-en-3-one

Conditions	Yield
With diethylzinc In toluene 1.) 0 deg C, 3 h, 2.) 20 deg C, 3 h;	65%
With diethylzinc In toluene at 0 - 20℃; for 3h;

1,1,3,3-tetrabromoacetone (22612-89-1) + tert-butyl(furan-2-ylmethoxy)dimethylsilane (121389-55-7) → (1S,2S,4R,5S)-2,4-Dibromo-1-(tert-butyl-dimethyl-silanyloxymethyl)-8-oxa-bicyclo[3.2.1]oct-6-en-3-one

Conditions	Yield
With diethylzinc In toluene 1.) 0 deg C, 3 h, 2.) 20 deg C, 3 h;	65%

1,1,3,3-tetrabromoacetone (22612-89-1) + 9-methoxyanthracene (2395-96-2) → 11,13-dibromo-9,10-dihydro-9-methoxy-9,10-propanoanthracen-12-one (143345-14-6)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; ultrasonication;	64%

furan (110-00-9) + 1,1,3,3-tetrabromoacetone (22612-89-1) → 2,4-dibromo-8-oxabicyclo<3.2.1>oct-6-en-3-one (55076-42-1, 55122-61-7, 67773-46-0)

Conditions	Yield
With diiron nonacarbonyl for 48h; Heating;	63%
With zinc/copper couple; 1,1-dibromomethane In acetonitrile at 20℃; for 1h; ultrasonification;
With ethylene dibromide In acetonitrile at 25℃; Sonication; Inert atmosphere;
With triethyl borate; zinc In tetrahydrofuran at 25℃; for 17h; Darkness;

1,1,3,3-tetrabromoacetone (22612-89-1) + 3-cyclopropyl-1-(4-(trifluoromethyl)phenylsulfonyl)-1H-pyrrole (1215184-06-7) → 2,4-dibromo-6-cyclopropyl-8-(4-(trifluoromethyl)phenylsulfonyl)-8-azabicyclo[3.2.1]oct-6-en-3-one (1215184-07-8)

Conditions	Yield
With diethylzinc In hexane; toluene at -10 - 20℃; for 17h;	62%

N-p-toluenesulfonylpyrrole (17639-64-4) + 1,1,3,3-tetrabromoacetone (22612-89-1) → 8-(toluene-4-sulfonyl)-8-aza-bicyclo[3.2.1]oct-6-en-3-one (646036-43-3)

Conditions	Yield
With diethylzinc In toluene at -12 - 20℃; for 18h;	60%

1,1,3,3-tetrabromoacetone (22612-89-1) + 1-benzyloxycarbonyl pyrrole (56857-08-0) → 3-oxo-8-aza-bicyclo[3.2.1]oct-6-ene-8-carboxylic acid benzyl ester (446873-84-3)

Conditions	Yield
With diethylzinc In toluene at -12 - 20℃; for 18h;	57%

furan (110-00-9) + 1,1,3,3-tetrabromoacetone (22612-89-1) → (1α,2β,4β,5α)-2,4-dibromo-8-oxabicyclo<3.2.1>oct-6-en-3-one (55076-42-1)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; ultrasonication;	56%

furan (110-00-9) + 1,1,3,3-tetrabromoacetone (22612-89-1) → meso-8-oxabicyclo[3.2.1]oct-6-en-3-one (40458-77-3)

Conditions	Yield
Stage #1: furan; 1,1,3,3-tetrabromoacetone With triethyl borate; zinc In tetrahydrofuran Cycloaddition; Heating; Stage #2: With copper; ammonium chloride; zinc In methanol at -78 - 10℃; for 1h; Reduction; Further stages.;	56%
Stage #1: furan; 1,1,3,3-tetrabromoacetone With triethyl borate; bromine; zinc In tetrahydrofuran at 20℃; for 2h; Inert atmosphere; Reflux; Stage #2: With zinc/copper couple; ammonium chloride In methanol at 0 - 20℃; for 1.5h; Inert atmosphere;	43%
With triethyl borate; copper; ammonium chloride; zinc Multistep reaction;
Cycloaddition;

1,1,3,3-tetrabromoacetone (22612-89-1) + 9,10-dimethoxyanthracene (2395-97-3) → 9,10-dimethoxy-9,10-propanoanthracen-12-one

Conditions	Yield
With copper(l) chloride; zinc In 1,4-dioxane at 20 - 50℃; for 9h; Cycloaddition; sonication;	56%

furfurylacetate (623-17-6) + 1,1,3,3-tetrabromoacetone (22612-89-1) → (1S*,2R*,4S*,5R*)-1-acetoxymethyl-2,4-dibromo-8-oxabicyclo<3.2.1>oct-6-en-3-one

Conditions	Yield
With silver; zinc In tetrahydrofuran at 20℃; for 12h;	52%

3-furan-2-yl-propan-1-ol (26908-23-6) + 1,1,3,3-tetrabromoacetone (22612-89-1) → 2,4-Dibromo-1-(3-hydroxy-propyl)-8-oxa-bicyclo[3.2.1]oct-6-en-3-one

Conditions	Yield
With diethylzinc In hexane; benzene at 0 - 20℃; for 5h;	51%

1,1,3,3-tetrabromoacetone (22612-89-1) + 2,5-furandimethanol dimethyl ether (18801-76-8) → 1,5-bis-methoxymethyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-one (257860-37-0)

Conditions	Yield
Stage #1: 1,1,3,3-tetrabromoacetone; 2,5-furandimethanol dimethyl ether With triethyl borate; zinc In tetrahydrofuran at 20℃; for 18.25h; Stage #2: With ammonium chloride; copper(l) chloride In methanol at 20℃; for 16h;	51%

2-furoic acid methyl ester (611-13-2) + 1,1,3,3-tetrabromoacetone (22612-89-1) → (1R,2R,4S,5R)-2,4-Dibromo-3-oxo-8-oxa-bicyclo[3.2.1]oct-6-ene-1-carboxylic acid methyl ester

Conditions	Yield
With diethylzinc In toluene 1.) 0 deg C, 3 h, 2.) 20 deg C, 3 h;	50%

methyl 1H-pyrrole-1-carboxylate (4277-63-8) + 1,1,3,3-tetrabromoacetone (22612-89-1) → methyl 3-oxo-8-azabicyclo<3.2.1>oct-6-ene-8-carboxylate (53416-89-0)

Conditions	Yield
With diethylzinc In toluene at -12 - 20℃; for 18h;	40%
With diiron nonacarbonyl; copper; ammonium chloride; zinc 1.) benzene, 50 deg C, 72 h; 2.) CH2Cl2/MeOH, r.t., 3 h; Yield given. Multistep reaction;

di-furan-2-yl-methanone (17920-86-4) + 1,1,3,3-tetrabromoacetone (22612-89-1) → (1SR,5RS)-1-(2-furoyl)-8-oxabicyclo[3.2.1]oct-6-en-3-one

Conditions	Yield
With diethylzinc In hexane; benzene at 20℃;	40%

methyl 1H-pyrrole-1-carboxylate (4277-63-8) + 1,1,3,3-tetrabromoacetone (22612-89-1) → methyl (1RS,5SR)-3-oxo-8-azabicyclo[3.2.1]oct-6-ene-8-carboxylate

Conditions	Yield
Stage #1: methyl 1H-pyrrole-1-carboxylate; 1,1,3,3-tetrabromoacetone With zinc/copper couple; triethyl borate; bromine In hexane; toluene at 0 - 20℃; for 24h; Inert atmosphere; Stage #2: With ammonium chloride; zinc In methanol at 20℃; for 2.5h;	40%
Stage #1: methyl 1H-pyrrole-1-carboxylate; 1,1,3,3-tetrabromoacetone With diethylzinc Stage #2:
Stage #1: methyl 1H-pyrrole-1-carboxylate; 1,1,3,3-tetrabromoacetone With diethylzinc Stage #2:

1,1,3,3-tetrabromoacetone (22612-89-1) + {[5-(but-3-en-1-yloxy)furan-2-yl]methoxy}(tert-butyl)dimethylsilane (1337876-93-3) → (1RS,5SR)-1-(but-3-en-1-yloxy)-5-{[(tert-butyldimethylsilyl)oxy]methyl}-8-oxabicyclo[3.2.1]oct-6-en-3-one

Conditions	Yield
Stage #1: 1,1,3,3-tetrabromoacetone; {[5-(but-3-en-1-yloxy)furan-2-yl]methoxy}(tert-butyl)dimethylsilane With diethylzinc In hexane; toluene at 0 - 20℃; Inert atmosphere; Stage #2: With zinc/copper couple; ammonium chloride In methanol at 20℃; for 1h; Inert atmosphere;	38%

1,1,3,3-tetrabromoacetone (22612-89-1) + 6-acetoxyfulvene (699-15-0) → C11H12O3

Conditions	Yield
With zinc/copper couple; 1,1-dibromomethane In acetonitrile at 23℃; for 1.58333h; Inert atmosphere; Sonication;	27%

1,1,3,3-tetrabromoacetone (22612-89-1) + 9-cyclopropylanthracene (26979-34-0) → 9-cyclopropyl-9,10-dihydro-9,10-propanoanthracen-12-one (143331-57-1)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 15 - 20℃; for 8h; ultrasonication;	26.5%

1,1,3,3-tetrabromoacetone (22612-89-1) + 1-benzyloxycarbonyl pyrrole (56857-08-0) → 3-oxo-8-azabicyclo[3.2.1]oct-6-ene-8-carboxylic acid phenylmethyl ester

Conditions	Yield
Stage #1: 1,1,3,3-tetrabromoacetone; 1-benzyloxycarbonyl pyrrole With diethylzinc In toluene at -12 - 20℃; for 20h; Inert atmosphere; Schlenk technique; Stage #2: With zinc/copper couple; ammonium chloride at 0℃; for 1h; Inert atmosphere; Schlenk technique;	24%

1,1,3,3-tetrabromoacetone (22612-89-1) + anthracene (120-12-7) → 9,10-dihydro-9,10-propanoanthracen-12-one (143331-52-6)

Conditions	Yield
With chloro-trimethyl-silane; copper(l) chloride; zinc In 1,4-dioxane at 80℃; for 6h;	22%

1,1,3,3-tetrabromoacetone (22612-89-1) + 3-(5-(4-ethylphenyl)pentyl)furan → 6-(5-(4-ethylphenyl)pentyl)-8-oxabicyclo[3.2.1]oct-6-en-3-one

Conditions	Yield
With copper; diiron nonacarbonyl In benzene at 60℃; for 2.5h;	17%

Upstream product

• 67-64-1 acetone 
• 542-05-2 acetonedicarboxylic acid 
• 7732-18-5 water 
• 7726-95-6 bromine 

Downstream Products

• 185099-67-6 N-Boc-nortropinone 
• 66656-00-6 3,3-dibromopropenoic acid methyl ester 
• 1215184-07-8 2,4-dibromo-6-cyclopropyl-8-(4-(trifluoromethyl)phenylsulfonyl)-8-azabicyclo[3.2.1]oct-6-en-3-one 
• 446873-84-3 3-oxo-8-aza-bicyclo[3.2.1]oct-6-ene-8-carboxylic acid benzyl ester 
• 646036-43-3 8-(toluene-4-sulfonyl)-8-aza-bicyclo[3.2.1]oct-6-en-3-one 
• 75-25-2 Bromoform 
• 40458-77-3 meso-8-oxabicyclo[3.2.1]oct-6-en-3-one 
• 3721-60-6 bicyclo<3.2.1>oct-6-en-3-one 
• 53416-89-0 methyl 3-oxo-8-azabicyclo<3.2.1>oct-6-ene-8-carboxylate 
• 695182-98-0 methyl 2-ethyl-3-oxo-8-azabicyclo<3.2.1>oct-6-ene-8-carboxylate 
• 89920-06-9 1-Phenyl-8-oxa-bicyclo[3.2.1]oct-6-en-3-one 
• 77745-32-5 (1α-H,5α-H)-8-Oxabicyclo<3.2.1>octan-3-on 
• 40458-77-3 8-oxabicyclo[3.2.1]oct-6-en-3-one 
• 141938-48-9 2-ethyl-8-oxabicyclo<3.2.1>oct-6-en-3-one 

Relevant articles and documents

Synthesis of tetrahydrofuran-based natural products and their carba analogs via stereoselective enzyme mediated Baeyer–Villiger oxidation

In this work we present efficient formal syntheses of several biologically interesting natural products (showdomycin, goniofufurone, trans-kumausyne) and their novel carba analogs by applying different Baeyer–Villiger monooxygenases. This strategy provides access to tetrahydrofuran-based natural products, C-nucleosides and both antipodes of the corresponding carba analogs in high optical purities (up to >95% ee) starting from simple achiral and commercially available building blocks (tetrabromoacetone, furan and cyclopentadiene). The striking key features of this chemo-enzymatic approach are the introduction of four stereogenic centers in as few as three reaction steps within a desymmetrization approach and the short-cut of several reaction sequences by the implementation of a biocatalytic step.

A Desymmetrization-Based Total Synthesis of Reserpine

Reported herein is a desymmetrization-based synthetic approach to the fused polycyclic indole alkaloid reserpine. The centerpiece of the developed strategy features an internal desymmetrization process that enabled the use of a readily accessible and nonstereogenic reserpine E-ring precursor, in contrast to the synthesis-intensive and stereodefined E-ring intermediates employed in all past reserpine syntheses. Utilization of inexpensive reagents through an orchestrated sequence of carefully selected chemical transformations further highlight the overall effectiveness of the developed pathway.

Synthesis of the C38-C44 segment of altohyrtin A - with an addendum on the preparation of 8-oxabicyclo[3,2.1]oct-6-en-3-one

The densely funtionalized C38-C44 segment F of altohyrtin A with its five contiguous stereogenic centers was prepared in 10 steps and in 28% overall yield (two steps per stereogenic center), from 8- oxabicyclo[3.2.1]oct-6-en-3-one as a template. The preparation of the title compound 1, m.p. 38 °C, is described on a 0.5 m scale in a three-step-two- stage reaction from acetone anti furan. The oxacycle was stored without change at room temperature.