3240-34-4

Basic information

• Product Name: (Diacetoxyiodo)benzene
• Synonyms: PHENYLIODINE DIACETATE;PIA;AURORA KA-6690;(DIACETOXYIODO)BENZENE;DIACETOXYIODOSOBENZENE;DAIB;LABOTEST-BB LT00847235;IODOBENZENE I,I-DIACETATE
• CAS NO: 3240-34-4
• Molecular Formula: C₁₀H₁₁IO₄
• Molecular Weight: 322.1
• EINECS: 221-808-1
• Product Categories: Benzene derivatives;APIs;Hypervalent Iodine Compounds;Oxidation;Synthetic Organic Chemistry
• Mol File: 3240-34-4.mol
• Article Data: 44

Chemical Properties

• Melting Point: 161-163 °C(lit.)
• Boiling Point: 456.8ºC at 760 mmHg
• Flash Point: 230.1ºC
• Appearance: Clear to cloudy colorless to yellow/Solution
• Density: 1.6865 (estimate)
• Vapor Pressure: 3.87E-09mmHg at 25°C
• Refractive Index: n/D 1.444
• Storage Temp.: -20°C
• Solubility: INSOLUBLE
• Water Solubility: INSOLUBLE
• Sensitive: Light Sensitive
• Stability: Light and Moisture sensitive
• BRN: 1879369
• CAS DataBase Reference: (Diacetoxyiodo)benzene(CAS DataBase Reference)
• NIST Chemistry Reference: (Diacetoxyiodo)benzene(3240-34-4)
• EPA Substance Registry System: (Diacetoxyiodo)benzene(3240-34-4)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 22-24/25-37/39-26-36/37/39-27
• RIDADR: 1479
• WGK Germany: 3
• RTECS: DA3525000
• F: 4.10-8
• TSCA: Yes
• HazardClass: 6.1(b)
• PackingGroup: III
• Hazardous Substances Data: 3240-34-4(Hazardous Substances Data)

Usage

Chemical Properties

white to light yellow crystal powder

Uses

Different sources of media describe the Uses of 3240-34-4 differently. You can refer to the following data:
1. (Diacetoxyiodo)benzene is a hypervalent iodine reagent that is used in conjunction with catalytic amount of sodium azide in acetonitrile, which enables oxidative decarboxylation of 2-aryl carboxylic a cid into the corresponding aldehydes, ketones and nitriles.
2. (Diacetoxyiodo)benzene is a hypervalent iodine reagent that is used in conjunction with catalytic amount of sodium azide in acetonitrile, which enables oxidative decarboxylation of 2-aryl carboxylic acid into the corresponding aldehydes, ketones and nitriles.

Purification Methods

The purity of diacetoxyiodobenzene can be checked by treatment with H2SO4 then KI and the liberated I2 is estimated with standard thiosulfate. It has been recrystallised from 5M acetic acid and dried overnight in a vacuum desiccator over CaCl2. The surface of the crystals may become slightly yellow but this does not affect its usefulness. [Sharefkin & Saltzman Org Synth Coll Vol V 600 1973, Beilstein 5 IV 693.]

InChI:InChI=1/C6H5I.2C2H4O2/c7-6-4-2-1-3-5-6;2*1-2(3)4/h1-5H;2*1H3,(H,3,4)

Synthetic route

trimethylsilyl acetate (2754-27-0) + iodosylbenzene (536-80-1) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
In dichloromethane Ambient temperature;	100%

iodobenzene (591-50-4) + acetic acid (64-19-7) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
With sodium perborate; trifluorormethanesulfonic acid at 40 - 45℃; for 3h;	99%
With dipotassium peroxodisulfate; sulfuric acid at 25℃; for 2h;	95.7%
With lithium perchlorate In 2,2,2-trifluoroethanol at 20℃; for 7.5h; Electrochemical reaction;	94%

iodosylbenzene (536-80-1) + acetic acid (64-19-7) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
at 23℃; for 1h;	99%

iodobenzene (591-50-4) + acetaldehyde (75-07-0) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
With N-hydroxyphthalimide; cobalt(II) diacetate tetrahydrate; acetic acid at 20℃; for 1.5h; Reagent/catalyst; Time;	99%
With cobalt(II) chloride hexahydrate; oxygen; acetic acid at 23℃; under 760.051 Torr; for 5h; Reagent/catalyst; Sealed tube;	92%
With cobalt(II) chloride hexahydrate; oxygen In acetic acid at 23℃; under 760.051 Torr; for 5h; Solvent; Reagent/catalyst;	92%
With cobalt(II) chloride hexahydrate; oxygen In 1,2-dichloro-ethane at 23℃; under 760.051 Torr; for 1h; Kinetics; Solvent; Reagent/catalyst;

peracetic acid (79-21-0) + iodobenzene (591-50-4) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
With acetic acid for 4h;	92%
With acetic acid at 23℃; for 7h;	92%
With sulfuric acid; dihydrogen peroxide; acetic acid In water 1.) 29-31 deg C, 65 min; 2.) 0 deg C, 75 min;	88.8%
With acetic acid at 20℃;

iodobenzene (591-50-4) + acetic anhydride (108-24-7) + acetic acid (64-19-7) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
With sodium peroxoborate tetrahydrate at 45℃;	91%
Stage #1: iodobenzene; acetic anhydride; acetic acid at 50℃; Stage #2: With sodium perborate tetrahydrate at 50℃; for 24.17h;
at 115 - 125℃; for 4h; Inert atmosphere;

[N-(p-tolylsulfonyl)imino]phenyliodinane (55962-05-5) + acetic acid (64-19-7) → [bis(acetoxy)iodo]benzene (3240-34-4) + toluene-4-sulfonamide (70-55-3)

Conditions	Yield
at 70℃; for 5h;	A 88% B 88%

iodobenzene (591-50-4) + acetic anhydride (108-24-7) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
Stage #1: acetic anhydride With dihydrogen peroxide In water at 40℃; for 4h; Stage #2: iodobenzene at 20 - 40℃;	83%
With sodium percarbonate; acetic acid In dichloromethane at 25 - 40℃; for 6.5h;	79%
With sodium periodate; sodium acetate In acetic acid for 2h; Heating;	73%

phenylbis(2,2,2-trifluoroethoxy)- λ3-iodane + acetic acid (64-19-7) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
at 20℃; Flow reactor;	78%

acetic acid (64-19-7) + benzene (71-43-2) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
With dipotassium peroxodisulfate; sulfuric acid; iodine In dichloromethane at 40℃; for 20h;	73%
With dipotassium peroxodisulfate; sulfuric acid; iodine In 1,2-dichloro-ethane at 40℃; for 20h;	73%
Stage #1: acetic acid; benzene With sulfuric acid; iodine In 1,2-dichloro-ethane at 40℃; for 0.25h; Green chemistry; Stage #2: With dipotassium peroxodisulfate In 1,2-dichloro-ethane for 0.166667h; Green chemistry;

acetic acid (64-19-7) + benzene (71-43-2) → iodobenzene (591-50-4) + [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
With dipotassium peroxodisulfate; sulfuric acid; iodine In 1,2-dichloro-ethane at 40℃; for 20h;	A 66% B 21%

iodobenzene (591-50-4) → [bis(acetoxy)iodo]benzene (3240-34-4)

Conditions	Yield
With peracetic acid In acetic acid	30%
Multi-step reaction with 2 steps 1: tetrabutylammonium tetrafluoroborate / Electrolysis; Flow reactor 2: 20 °C / Flow reactor View Scheme

4-acetoxy-4-tert-butyl-2,5-cyclohexadienone → [bis(acetoxy)iodo]benzene (3240-34-4) + hydroquinone monoacetate (3233-32-7) + hydroquinone (123-31-9) + p-benzoquinone (106-51-4)

Conditions	Yield
With perchloric acid In water; acetonitrile at 30℃; pH=1.0; Kinetics; Further Variations:; pH-values; Reagents; Temperatures;

bis(trifluoromethanesulfonyl)methane (428-76-2) + [bis(acetoxy)iodo]benzene (3240-34-4) → phenyliodonium bis(trifluoromethylsulfonyl)methylide (132273-36-0)

Conditions	Yield
In dichloromethane at 20℃;	100%
In dichloromethane at 20℃; for 24h;	80%
In dichloromethane at 20℃; for 2h; Inert atmosphere;	73%
In dichloromethane for 24h; Ambient temperature;	71%
In dichloromethane at 20℃;

[bis(acetoxy)iodo]benzene (3240-34-4) + dimedone (126-81-8) → (4,4-dimethyl-2,6-dioxo-cyclohexyl)-phenyl-iodonium betaine (35024-12-5)

Conditions	Yield
With potassium hydroxide In methanol at 20℃; for 2h;	100%
In dichloromethane at 20℃; for 1.5h;	95%
In dichloromethane at 20℃; for 2h;	92%

[bis(acetoxy)iodo]benzene (3240-34-4) + toluene-4-sulfonic acid (104-15-4) → [hydroxy(tosyloxy)iodo]benzene (27126-76-7)

Conditions	Yield
In acetonitrile	100%
for 0.166667h;	97%
In acetonitrile at 20℃;	94%

[bis(acetoxy)iodo]benzene (3240-34-4) + 1,3-diphenylpropanedione (120-46-7) → 1,3-diphenyl-2-(phenyliodaneylidene)propane-1,3-dione (128753-03-7)

Conditions	Yield
Stage #1: 1,3-diphenylpropanedione With potassium hydroxide In acetonitrile at 0℃; for 0.0833333h; Inert atmosphere; Stage #2: [bis(acetoxy)iodo]benzene In acetonitrile at 0℃; for 0.333333h; Inert atmosphere; Stage #3: With water In acetonitrile for 0.0166667h; Inert atmosphere;	100%
With potassium hydroxide In methanol at 0℃; for 0.5h;	44%
With potassium hydroxide In methanol

4-nitro-phenol (100-02-7) + [bis(acetoxy)iodo]benzene (3240-34-4) → 2-hydroxy-5-nitrodiphenyliodonium ylide (72212-81-8)

Conditions	Yield
In methanol at 20℃; Inert atmosphere;	100%
In acetic acid

2-Hydroxy-1,4-naphthoquinone (83-72-7) + [bis(acetoxy)iodo]benzene (3240-34-4) → 3-phenyliodonio-1,2,4-trioxo-1,2,3,4-tetrahydronaphthalenide (117560-06-2)

Conditions	Yield
In dichloromethane at 10 - 20℃; for 1h; Inert atmosphere;	100%
In chloroform at 20℃; for 5h;	91%
In chloroform at 0 - 20℃; for 5h;	89%

[bis(acetoxy)iodo]benzene (3240-34-4) + triphenylphosphine (603-35-0) + benzylamine (100-46-9) → N-(phenylmethyl)acetamide (588-46-5) + Triphenylphosphine oxide (791-28-6)

Conditions	Yield
Stage #1: [bis(acetoxy)iodo]benzene; triphenylphosphine In chloroform for 1h; Heating; Stage #2: benzylamine In chloroform for 0.166667h;	A 94% B 100%

dimesylamine (5347-82-0) + [bis(acetoxy)iodo]benzene (3240-34-4) → acetoxy((N-mesyl)methanesulfonamidyl)iodosobenzene (1345824-07-8)

Conditions	Yield
In chlorobenzene at 55℃;	100%
In chlorobenzene at 55℃;	100%
In chlorobenzene at 55℃;	92%

[bis(acetoxy)iodo]benzene (3240-34-4) + di(4-tosyl)amine (3695-00-9) → ((4-methyl-N-tosylphenyl)sulfonamido)(phenyl)-λ3-iodanyl acetate (1345824-06-7)

Conditions	Yield
In dichloromethane at 20℃; for 0.5h;	100%
In dichloromethane at 20℃; for 0.5h;	100%
In dichloromethane at 25℃; for 3h;	93%
In dichloromethane at 20℃; for 0.5h;	92%

[bis(acetoxy)iodo]benzene (3240-34-4) + methyl (E)-4-bromocinnamate (3650-78-0, 84878-00-2, 71205-17-9) + acetic anhydride (108-24-7) + acetic acid (64-19-7) → syn-3-methoxy-3-oxo-1-(4-bromophenyl)propane-1,2-diyl diacetate

Conditions	Yield
Stage #1: [bis(acetoxy)iodo]benzene; methyl (E)-4-bromocinnamate; acetic acid With boron trifluoride diethyl etherate In water at 20℃; for 20h; Stage #2: acetic anhydride In water at 20℃; optical yield given as %de; diastereoselective reaction;	100%

[bis(acetoxy)iodo]benzene (3240-34-4) + di(4-tosyl)amine (3695-00-9) → μ-oxo-bis[(4-methyl)-N-tosylbenzenesulfonamidyl(phenyl)iodine] (1414869-21-8)

Conditions	Yield
In chloroform; water at 20℃; for 4h;	100%
In chloroform; water at 25℃; for 2h;	90%

[bis(acetoxy)iodo]benzene (3240-34-4) + 1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one (35896-48-1) → 1-phenyl-2-(phenyl-λ3-iodaneylidene)-2-((trifluoromethyl)sulfonyl)ethan-1-one (1443036-49-4)

Conditions	Yield
In acetonitrile at 0℃; for 2h; Inert atmosphere;	100%

1,2-bis(prop-2-ynyloxy)benzene (5651-91-2) + [bis(acetoxy)iodo]benzene (3240-34-4) → 3,3'-(1,2-phenylenebis(oxy))bis(2-oxopropane-3,1-diyl)diacetate (1443212-46-1)

Conditions	Yield
With silver(I) acetate In acetonitrile at 25℃; for 26h;	100%

2-Iodobenzoic acid (88-67-5) + [bis(acetoxy)iodo]benzene (3240-34-4) → 1-acetoxy-1,2-benziodoxol-3-one (1829-26-1)

Conditions	Yield
With boron trifluoride diethyl etherate In dichloromethane at 20℃; for 4h; Inert atmosphere;	100%
Stage #1: 2-Iodobenzoic acid; [bis(acetoxy)iodo]benzene In chloroform-d1 at 20℃; for 18h; Stage #2: With boron trifluoride diethyl etherate In chloroform-d1 at 20℃; for 67h;

[bis(acetoxy)iodo]benzene (3240-34-4) + methyl 4-hydroxylbenzoate (99-76-3) → C14H11IO3

Conditions	Yield
In methanol at 20℃; Inert atmosphere;	100%

methyl 4-hydroxy-2-methoxybenzoate (28478-46-8) + [bis(acetoxy)iodo]benzene (3240-34-4) → C15H13IO4

Conditions	Yield
In methanol at 20℃; Inert atmosphere;	100%

[bis(acetoxy)iodo]benzene (3240-34-4) + acetic acid (64-19-7) + methyl 3-aminocrotonate (14205-39-1) → C13H16INO4

Conditions	Yield
In 2,2,2-trifluoroethanol at 20℃; for 0.0833333h;	100%

[bis(acetoxy)iodo]benzene (3240-34-4) + 9-(5-O-benzyl-3-deoxy-3-fluoro-β-D-ribofuranosyl)-6-chloro-2-(tritylamino)purine → 9-(5-O-benzyl-3-deoxy-3-fluoro-2-oxo-β-D-ribofuranosyl)-6-chloro-2-(tritylamino)purine

Conditions	Yield
With 2,2,6,6-tetramethyl-piperidine-N-oxyl In dichloromethane; acetic acid at 20℃; for 16h;	100%

pent-4-enoic acid (591-80-0) + [bis(acetoxy)iodo]benzene (3240-34-4) → (5-oxotetrahydrofuran-2-yl)methyl acetate (5904-80-3, 79580-69-1, 112607-21-3, 112709-12-3)

Conditions	Yield
With trifluorormethanesulfonic acid In acetic acid at 80℃; for 17h;	99%
With tetrafluoroboric acid In acetic acid for 1h; Ambient temperature;	73%

[bis(acetoxy)iodo]benzene (3240-34-4) + para-methylacetophenone (122-00-9) → 2-oxo-2-(4-tolyl)ethyl acetate (65143-37-5)

Conditions	Yield
With acetic acid; scandium tris(trifluoromethanesulfonate) at 50℃; for 48h;	99%
With acetic anhydride; acetic acid

[bis(acetoxy)iodo]benzene (3240-34-4) + benzophenone hydrazone (5350-57-2) → benzhydryl acetate (954-67-6)

Conditions	Yield
	99%

[bis(acetoxy)iodo]benzene (3240-34-4) + 2-(trimethylsilyl)ethanesulfonamide (125486-96-6) → 2-(trimethylsilyl)-N-(phenyl-λ3-iodanylidene)-ethanesulfonamide (236122-13-7)

Conditions	Yield
With potassium hydroxide In methanol 1.) 0 deg C, 30 min, 2.) 20 deg C, 3 h;	99%

[bis(acetoxy)iodo]benzene (3240-34-4) + N-benzyl-3-(4-hydroxy-3-methoxyphenyl)-propionamide (391609-32-8) → 6-acetoxy-4-(2-benzylcarbamoyl-ethyl)-6-methoxycyclohexa-2,4-dienone (391609-36-2)

Conditions	Yield
In dichloromethane at -78℃; for 1h;	99%

[bis(acetoxy)iodo]benzene (3240-34-4) + 4-phenylpent-4-enoic acid (5747-06-8) → acetic acid 2-benzyl-5-oxo-tetrahydrofuran-2-yl ester

Conditions	Yield
With trifluorormethanesulfonic acid In dichloromethane at 20℃; for 1h;	99%
In dichloromethane	87%

[bis(acetoxy)iodo]benzene (3240-34-4) + R,S,R,S-[iron(II)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)(OTf)](OTf) (1070239-37-0, 854159-07-2, 551938-25-1) + acetonitrile (75-05-8) → acetonitrile(oxido)(1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)iron(IV) bis(trifluoromethanesulfonate)

Conditions	Yield
With NBu4BF4 In acetonitrile react. of Fe(II) complex with PhI(OAc)2 (1 equiv.) in CH3CN in the presence of NBu4BF4;	99%

[bis(acetoxy)iodo]benzene (3240-34-4) + para-chlorobenzoic acid (74-11-3) → [bis-(p-chlorobenzoyloxy)iodo]benzene (65037-30-1)

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene Inert atmosphere;	99%
In methanol at 45℃; for 0.5h;	79%
In methanol at 45℃; for 0.5h;

[bis(acetoxy)iodo]benzene (3240-34-4) + 2,5-dimethyl-1-tosylindolin-3-one (1253203-13-2) → 2,5-dimethyl-3-oxo-1-tosylindolin-2-yl acetate (1253203-05-2)

Conditions	Yield
With tetra-(n-butyl)ammonium iodide In 1,4-dioxane at 25℃;	99%

Upstream product

• 79-21-0 peracetic acid 
• 591-50-4 iodobenzene 
• 2754-27-0 trimethylsilyl acetate 
• 536-80-1 iodosylbenzene 
• 64-19-7 acetic acid 
• 75-07-0 acetaldehyde 
• 108-24-7 acetic anhydride 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 
• 71-43-2 benzene 
• 873-49-4 cyclopropylbenzene 

Downstream Products

• 632-92-8 2,4-dimethyl-1,3,5-trinitrobenzene 
• 17348-69-5 5-chlorobenzofurazan-1-oxide 
• 1227476-15-4 Azobenzene 
• 92387-00-3 2,5-di-p-phenetidino-[1,4]benzoquinone-bis-(4-ethoxy-phenylimine) 
• 6597-18-8 (dibenzoyloxyiodo)benzene 
• 584-90-7 trans-di-o-tolyl-diazene 
• 66166-42-5 2-iodo-4-nitro-1-phenoxybenzene 
• 99971-04-7 4-Nitro-3-(4-nitro-phenoxy)-phenol 
• 29478-23-7 (E)-β-iodo-α-phenylstyryl acetate 
• 30030-31-0 [di(4-nitrobenzoyloxy)iodo]benzene 
• 57357-25-2 benzene 
• 86396-03-4 (2,6-dioxo-4-methylcyclohexyl)phenyliodonium inner salt 
• 87301-29-9 N-(phenylsulfonylimino)-phenyl-λ³-iodane 
• 1283-97-2 phenyliodonium betaine of 1,3-indanedione 

Relevant articles and documents

Synthesis of Diverse Aryliodine(III) Reagents by Anodic Oxidation?

An anodic oxidation enabled synthesis of hypervalent iodine(III) reagents from aryl iodides is demonstrated. Under mild electrochemical conditions, a range of aryliodine(III) reagents including iodosylarenes, (difunctionaliodo)arenes, benziodoxoles and diaryliodonium salts can be efficiently synthesized and derivatized in good to excellent yields with high selectivity. As only electrons serve as the oxidation reagents, this method offers a more straightforward and sustainable manner avoiding the use of expensive or hazardous chemical oxidants.

Preparation and Synthetic Applicability of Imidazole-Containing Cyclic Iodonium Salts

A novel approach to the preparation of imidazole-substituted cyclic iodonium salts has been developed via the oxidative cyclization of 1-phenyl-5-iodoimidazole using a cheap and available Oxone/H2SO4 oxidative system. The structure of the new polycyclic heteroarenes has been confirmed by single-crystal X-ray diffractometry, revealing the characteristic structure features for cyclic iodonium salts. The newly produced imidazole-flanked cyclic iodonium compounds were found to readily engage in a heterocyclization reaction with elemental sulfur, affording benzo[5,1-b]imidazothiazoles in good yields.

A trivalent hypervalent iodine compound using hypochlorite (by machine translation)

[A] used in the prior art organic salt, toxic chlorine gas, organic peroxides can be used without the novel trivalent hypervalent iodine compound production. Furthermore, the acyloxy groups other than the trivalent hypervalent iodine compounds having a ligand manufacturing method. (1) Formula [solution](In the formula, R1 Substituted/unsubstituted aromatic group, aliphatic group or the like. N is an integer of 1 or more. ) Represented by the iodine compound, carboxylic acid, carboxylic acid anhydride, a sulfonic acid or sulfonic acid anhydride with at least one organic acid selected from the group consisting of, a hypochlorite mixing, trivalent hypervalent iodine compound. [Drawing] no (by machine translation)