14268-66-7

Basic information

• Product Name: 3,4-(Methylenedioxy)aniline
• Synonyms: benzo[d][1,3]dioxol-5-amine;5-Amino-1,3-benzodioxole 98%;1,3-Benzodioxol-5-amine, 3,4-(Methylenedioxy)aniline;3,4-(Methylenedioxy)aniline, 97% 10GR;3,4-(Methylenedioxy)aniline, 97% 50GR;5-Amino-1,3-benzodioxole 4-Amino-1,2-methylenedioxybenzene;3,4-METHYLENEDIOXYANILINE (STABILISED WI;4-aMino-1,3-benzodioxole
• CAS NO: 14268-66-7
• Molecular Formula: C₇H₇NO₂
• Molecular Weight: 137.14
• EINECS: 238-161-6
• Product Categories: Anilines, Aromatic Amines and Nitro Compounds
• Mol File: 14268-66-7.mol
• Article Data: 40

Chemical Properties

• Melting Point: 39-41 °C(lit.)
• Boiling Point: 144 °C16 mm Hg(lit.)
• Flash Point: 289 °F
• Appearance: Dark brown to black/Low Melting Solid
• Density: 1.2528 (rough estimate)
• Vapor Pressure: 0.00795mmHg at 25°C
• Refractive Index: 1.5030 (estimate)
• Storage Temp.: Store below +30°C.
• PKA: 4.78±0.20(Predicted)
• Water Solubility: slightly soluble
• Sensitive: Air & Light Sensitive
• BRN: 4919
• CAS DataBase Reference: 3,4-(Methylenedioxy)aniline(CAS DataBase Reference)
• NIST Chemistry Reference: 3,4-(Methylenedioxy)aniline(14268-66-7)
• EPA Substance Registry System: 3,4-(Methylenedioxy)aniline(14268-66-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36
• WGK Germany: 3
• TSCA: Yes
• HazardClass: 6.1
• Hazardous Substances Data: 14268-66-7(Hazardous Substances Data)

Usage

Chemical Properties

dark brown to black low melting solid

Uses

3,4-(Methylenedioxy)aniline is an pharmaceutically important aniline derivative. It undergoes N-alkylation with cyclic secondary alkylamines in the presence of Shvo catalyst to yield N-arylpyrrolidines. 3,4-(Methylenedioxy)aniline was used in the synthesis of γ-glutamylanilides.

General Description

3,4-(Methylenedioxy)aniline is an pharmaceutically important aniline derivative. It undergoes N-alkylation with cyclic secondary alkylamines in the presence of Shvo catalyst to yield N-arylpyrrolidines.

Purification Methods

Crystallise the base from pet ether and/or distil it in a vacuum. The hydrochloride has m 198o(dec). [Sonn & Benirschke Chem Ber 54 1734 1921, Beilstein 19 H 328, 19 II 341, 19 III/IV 4056.]

InChI:InChI=1/C7H7NO2/c8-5-1-2-6-7(3-5)10-4-9-6/h1-3H,4,8H2

Synthetic route

N-(3,4-methylendioxyphenyl)-N-benzylamine (32932-20-0) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With formic acid; potassium hydroxide In ethanol at 70℃; for 1h; Catalytic behavior; Reagent/catalyst;	97%

5-nitro-1,3-benzodioxole (2620-44-2) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With C30H29BrMnNO2P2; hydrogen; potassium carbonate In toluene at 130℃; under 60006 Torr; for 24h; Glovebox; Autoclave; chemoselective reaction;	96%
With hydrogen; nickel In ethanol at 60℃; under 18751.9 Torr; for 2h; Solvent; Pressure; Concentration;	95.9%
With C36H56Cl3CrN2O; magnesium; 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane In tetrahydrofuran at 60℃; for 24h; Inert atmosphere;	85%

1,2-(methylenedioxy)-4-bromobenzene (2635-13-4) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With copper(I) oxide; ammonium hydroxide; C17H14N2O3; potassium hydroxide In ethanol at 60℃; for 24h; Schlenk technique; Inert atmosphere;	95%
With ammonium hydroxide; copper(l) iodide; N,N-dimethylethylenediamine In dimethyl sulfoxide at 130℃; for 18h; Reagent/catalyst; Time; Sealed tube; Inert atmosphere;	90%
With diethylenetriaminopentaacetic acid; ammonia; copper(II) oxide; potassium hydroxide In water at 100℃; for 12h;	73%
With ammonium hydroxide; diethylenetriaminopentaacetic acid; copper(II) oxide; potassium hydroxide In water at 100℃; for 12h; Sealed tube;	73%
Stage #1: 1,2-(methylenedioxy)-4-bromobenzene With magnesium In tetrahydrofuran Inert atmosphere; Stage #2: With C10H17NO In tetrahydrofuran; toluene at -78℃; for 2h; Inert atmosphere; Stage #3: With ammonium chloride In tetrahydrofuran; water; toluene Inert atmosphere;	66%

5-iodo-1,3-benzodioxole (5876-51-7) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With copper(I) oxide; ammonium hydroxide; N1-(furan-2-ylmethyl)-N2-(2-methylnaphthalen-1-yl)oxalamide; potassium hydroxide In ethanol at 80℃; for 24h; Schlenk technique; Inert atmosphere;	95%

C11H9NO4 → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With chloro-trimethyl-silane; cyclopentadienyl titanium(IV) trichloride; magnesium; triethylamine In tetrahydrofuran at 50℃; for 15h;	93%

3,4-(methylenedioxy)-benzeneboronic acid (94839-07-3) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With sodium hydroxide; hydroxylamine-O-sulfonic acid In acetonitrile at 20℃; for 16h;	90%

Methylenedioxybenzene (274-09-9) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With O-(4-nitrobenzoyl)hydroxylammonium trifluoromethanesulfonate; iron(II) bromide; silver(I) triflimide In 2,2,2-trifluoroethanol; water at 30℃; for 2h;	60%
Stage #1: Methylenedioxybenzene With sulfuric acid; hydroxylamine hydrochloride In acetonitrile at 25℃; for 0.166667h; Stage #2: With hydrogenchloride; titanium(III) chloride In water; acetonitrile at 25℃; Inert atmosphere; Sealed tube;	57%

1-(benzo[d][1,3]dioxole-5-carbonyl)piperidine-2,6-dione → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
Stage #1: 1-(benzo[d][1,3]dioxole-5-carbonyl)piperidine-2,6-dione With Benzophenone imine; 1,1'-bis-(diphenylphosphino)ferrocene; potassium phosphate; Ni(1,5-cyclooctadiene)2; lithium chloride In toluene at 170℃; Glovebox; Inert atmosphere; Sealed tube; Stage #2: With hydrogenchloride In tetrahydrofuran at 20℃;	55%

2-(benzo[d][1,3]dioxol-5-yloxy)propanamide (1181403-64-4) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With potassium hydroxide In dimethyl sulfoxide at 140℃; for 8h; Green chemistry;	48%

C20H15NO2 → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With hydrogenchloride In tetrahydrofuran at 20℃;	40%

3,4-methylenedioxybenzamide (4847-94-3) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With sodium hydroxide; alkaline aqueous sodium hypochlorite solution
With alkaline alkali hypobromite solution

Methylenedioxybenzene (274-09-9) → benzo[d][1,3]dioxol-4-amine (1668-84-4) + benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With sulfuric acid; hydroxylamine-O-sulfonic acid; iron(II) sulfate In water; N,N-dimethyl-formamide at 30 - 35℃; for 1h; Yield given. Yields of byproduct given;

2,4-dinitroso-2,4-diaza-glutaric acid diethyl ester (857829-30-2) + 4-amino-1.2-dioxy-benzene hydrochloride → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With potassium hydroxide; diethyl ether

4-nitro-pyrocatechol-methylene ether → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With hydrogenchloride; tin

3,4-methylenedioxybenzamide (4847-94-3) + potassium hypobromite → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
beim Erhitzen;

6-nitrobenzo[d][1,3]dioxole-5-carboxylic acid (716-32-5) → benzo[1,3]dioxolo-5-ylamine (14268-66-7) + 6-amino-piperonylic acid

Conditions	Yield
With hydrogenchloride; tin

2-benzo[1,3]dioxol-5-yl-1,1,1,3,3,3-hexamethyl-disilazane → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With hydrogenchloride In diethyl ether

1-(benzo[d][1,3]dioxol-5-yl)urea → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
With sulfuric acid In methanol; water at 80 - 90℃; Kinetics; Further Variations:; Temperatures;

piperonylonitrile (4421-09-4) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: hydrogen peroxide; KOH-solution 2: alkaline alkali hypobromite solution View Scheme

Piperonylic acid (94-53-1) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: hydrogen chloride 2: aqueous ammonia / 60 - 80 °C / im Rohr 3: alkaline alkali hypobromite solution View Scheme
Multi-step reaction with 3 steps 1.1: thionyl chloride / 2 h / Reflux 2.1: dmap; triethylamine / dichloromethane / 0 - 20 °C 3.1: Ni(1,5-cyclooctadiene)2; Benzophenone imine; 1,1'-bis-(diphenylphosphino)ferrocene; potassium phosphate; lithium chloride / toluene / 170 °C / Glovebox; Inert atmosphere; Sealed tube 3.2: 20 °C View Scheme

methyl 3,4-methylenedioxybenzoate (326-56-7) → benzo[1,3]dioxolo-5-ylamine (14268-66-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: aqueous ammonia / 60 - 80 °C / im Rohr 2: alkaline alkali hypobromite solution View Scheme

acetic anhydride (108-24-7) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → 3,4-methylenedioxyacetanilide (13067-19-1)

Conditions	Yield
In 1,4-dioxane at 0 - 20℃; for 1h;	100%
With triethylamine In dichloromethane at 0℃; for 0.5h;	97%
With acetic acid	95%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + diethyl 2-ethoxymethylenemalonate (87-13-8) → diethyl [[3,4-(methylenedioxy)phenylamino]methylene]malonate (17394-77-3)

Conditions	Yield
In ethanol at 90℃; for 18h;	100%
In benzene for 3.5h; Reflux;	96%
In benzene for 3.5h; Heating;	71%
In benzene for 3h; Reflux;

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + acetone (67-64-1) → N-isopropyl-3,4-(methylenedioxy)aniline (10368-14-6)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 17h;	100%
With sodium tris(acetoxy)borohydride; acetic acid In tetrahydrofuran for 15h; Ambient temperature;

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + 6,7-dimethoxy-4-(1-piperazinyl)quinazoline (21584-72-5) + 1,1'-carbonyldiimidazole (530-62-1) → 4-(6,7-dimethoxy-quinazolin-4-yl)-piperazine-1-carboxylic acid benzo[1,3]dioxol-5-ylamide

Conditions	Yield
Stage #1: benzo[1,3]dioxolo-5-ylamine; 1,1'-carbonyldiimidazole In dichloromethane at 20℃; for 4h; Stage #2: 6,7-dimethoxy-4-(1-piperazinyl)quinazoline In dichloromethane at 20℃; Further stages.;	100%

glyoxylic acid ethyl ester (924-44-7) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → ethyl 2-(benzo[1,3]dioxol-5-ylimino)acetate

Conditions	Yield
With magnesium sulfate In toluene at 25℃; for 0.5h;	100%
In toluene at 23℃; for 1h; Molecular sieve; Inert atmosphere;
In dichloromethane for 0.333333h; Inert atmosphere;

benzaldehyde (100-52-7) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → C14H11NO2 (32932-19-7)

Conditions	Yield
In ethanol for 1h; Sonication;	100%
In ethanol for 5h; Reflux;
In toluene for 6h; Reflux;
In neat (no solvent) at 20℃; for 0.5h; Schlenk technique; Molecular sieve; Inert atmosphere;

1,4-oxathiane-2,6-dione (3261-87-8) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → C11H11NO5S

Conditions	Yield
In dichloromethane at 20℃; for 24h;	100%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + p-toluenesulfonyl chloride (98-59-9) → N-(benzo[d][1,3]dioxol-5-yl)-4-methylbenzenesulfonamide

Conditions	Yield
With triethylamine In dichloromethane at 4℃;	100%
With pyridine at 0 - 20℃;	96%
With silica gel at 20℃;	92%

benzaldehyde (100-52-7) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → N-(3,4-methylendioxyphenyl)-N-benzylamine (32932-20-0)

Conditions	Yield
With sodium tris(acetoxy)borohydride In 1,2-dichloro-ethane at 20℃; for 17h;	100%
With tetra(n-butyl)ammonium hydrogensulfate; dimethyl sulfoxide at 20℃; for 5h; Electrolysis;	30%
With sodium triacetoxy borohydride; acetic acid In dichloromethane at 0 - 20℃;
Multi-step reaction with 2 steps 1: neat (no solvent) / 0.5 h / 20 °C / Schlenk technique; Molecular sieve; Inert atmosphere 2: 4,4,5,5-tetramethyl-[1,3,2]-dioxaboralane / neat (no solvent) / 24 h / 20 °C / Schlenk technique; Inert atmosphere View Scheme

1,3-cyclopentadione (3859-41-4) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → 3-(Benzo[1,3]dioxol-5-ylamino)-cyclopent-2-enone

Conditions	Yield
In 1,4-dioxane Ambient temperature;	99%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + diisopropylamine (108-18-9) → N-isopropyl-3,4-(methylenedioxy)aniline (10368-14-6)

Conditions	Yield
With μ-diiodo-di((η5-pentamethylcyclopentadienyl)(iodo)iridium) In 5,5-dimethyl-1,3-cyclohexadiene at 155℃; for 10h; Inert atmosphere;	99%

2-Hydroxy-1,4-naphthoquinone (83-72-7) + 4-methyl-benzaldehyde (104-87-0) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → 12-(4-methylphenyl)-5,10-dihydro-benzo[i][1,3]dioxolo[4,5-b]acridine-6,11-dione

Conditions	Yield
With L-proline In ethanol for 1h; Reflux; Green chemistry;	99%

ethanol (64-17-5) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → N-ethyl-3,4-(methylenedioxy)aniline (32953-14-3)

Conditions	Yield
With cesiumhydroxide monohydrate; (1,4-dimethyl-5,7-diphenyl-1,2,3,4-tetrahydro-6H-cyclopenta[b]pyrazin-6-one) irontricarbonyl complex3 at 110℃; Schlenk technique; Inert atmosphere;	99%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + 2-fluoro-4-methylbenzoic Acid (7697-23-6) → N-(benzo[d][1,3]dioxol-5-yl)-2-fluoro-4-methylbenzamide

Conditions	Yield
With triethylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate In N,N-dimethyl-formamide at 20℃; for 2h;	99%

5-methylene-4-phenyl-4-vinyl-1,3-dioxolan-2-one + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → 1-(benzo[d][1,3]dioxol-5-yl)-2-methyl-3-phenyl-1H-pyrrole

Conditions	Yield
With palladium(II) trifluoroacetate; trifuran-2-yl-phosphane In dichloromethane at 20℃; for 12h;	99%

[5-(3-methoxybenzyl)-3-methyl-6-oxo-6H-pyridazin-1-yl]acetic acid (1184304-26-4) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → N-(benzo[1,3]dioxol-5-yl)-2-[5-(3-methoxybenzyl)-3-methyl-6-oxo-6H-pyridazin-1-yl]-acetamide (1184304-64-0)

Conditions	Yield
Stage #1: [5-(3-methoxybenzyl)-3-methyl-6-oxo-6H-pyridazin-1-yl]acetic acid With triethylamine In tetrahydrofuran at -5 - 0℃; Stage #2: With chloroformic acid ethyl ester In tetrahydrofuran at 0℃; for 1h; Stage #3: benzo[1,3]dioxolo-5-ylamine In tetrahydrofuran at 20℃; for 12h;	98%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + 3-(2,2,2-trifluoroacetyl)-4H-chromen-4-one (160856-31-5) → 3-{[(1,3-benzodioxol-5-yl)amino]methylene}-2-hydroxy-2-(trifluoromethyl)chroman-4-one

Conditions	Yield
In N,N-dimethyl-formamide at 60℃;	98%

chloroformic acid ethyl ester (541-41-3) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → ethyl (1,3-benzodioxolan-5-yl)carbamate (165330-00-7)

Conditions	Yield
With triethylamine In tetrahydrofuran at 20℃; for 0.5h;	98%
With triethylamine In tetrahydrofuran at 20℃; for 4h;	85%
With triethylamine In tetrahydrofuran at 20℃; for 0.5h;
With triethylamine In tetrahydrofuran at 20℃; for 0.5h;

formaldehyd (50-00-0) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → N-methyl-3,4-(methylenedioxy)aniline (34060-22-5)

Conditions	Yield
Stage #1: formaldehyd; benzo[1,3]dioxolo-5-ylamine With sodium methylate In methanol at 20℃; for 24h; Stage #2: With methanol; sodium tetrahydroborate at 40℃; for 3h;	98%
Stage #1: formaldehyd; benzo[1,3]dioxolo-5-ylamine With sodium methylate In methanol at 20℃; for 18h; Stage #2: With sodium tetrahydroborate In methanol at 40℃; for 3h;	1.43 g

piperonal (120-57-0) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) + diallyl phosphite (23679-20-1) → diallyl (benzo[d][1,3]dioxol-5-yl(benzo[d][1,3]dioxol-5-ylamino)methyl)phosphonate (1449479-35-9)

Conditions	Yield
With Amberlite-IR 120 for 0.0166667h; Microwave irradiation;	98%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + methanesulfonyl chloride (124-63-0) → N-(benzo[d][1,3]dioxol-5-yl)methanesulfonamide

Conditions	Yield
With pyridine In dichloromethane at 0 - 20℃; for 12h;	98%
With silica gel at 20℃;	95%
Stage #1: benzo[1,3]dioxolo-5-ylamine With triethylamine In dichloromethane at 20℃; for 0.166667h; Stage #2: methanesulfonyl chloride In dichloromethane at 20℃; for 24h;	89.2%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + tetraacetoxysilane (562-90-3) → 3,4-methylenedioxyacetanilide (13067-19-1)

Conditions	Yield
In tetrahydrofuran at 20℃; for 4h;	98%

4-hydroxy-2(5H)-furanone (541-57-1) + 4-methoxy-benzaldehyde (123-11-5) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → 9-(4-methoxyphenyl)-6,9-dihydro-[1,3]dioxolo[4,5-g]furo[3,4-b]quinolin-8(5H)-one

Conditions	Yield
Inert atmosphere; Reflux;	97%

methanol (67-56-1) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → N-methyl-3,4-(methylenedioxy)aniline (34060-22-5)

Conditions	Yield
With cesiumhydroxide monohydrate; (1,4-dimethyl-5,7-diphenyl-1,2,3,4-tetrahydro-6H-cyclopenta[b]pyrazin-6-one) irontricarbonyl complex3 at 110℃; Schlenk technique; Inert atmosphere;	97%
With dimanganese decacarbonyl; potassium tert-butylate In toluene at 100℃; for 24h; Inert atmosphere; Sealed tube;	92%
With potassium tert-butylate; C38H37ClN2PRu(1+)*C32H12BF24(1-) In neat (no solvent) at 110℃; for 12h; Sealed tube; Inert atmosphere; Schlenk technique; Green chemistry;	92%

benzo[1,3]dioxolo-5-ylamine (14268-66-7) + benzyl alcohol (100-51-6) → N-(3,4-methylendioxyphenyl)-N-benzylamine (32932-20-0)

Conditions	Yield
With C50H38ClN3O2P2RuS; potassium hydroxide In toluene at 100℃; for 12h;	97%
With iron(III) oxide; potassium hydroxide In toluene at 135℃; for 24h; Inert atmosphere; Sealed tube;	80%
With zinc(II) nitrate hexahydrate; potassium tert-butylate In toluene at 140℃; for 36h; Sealed tube; Inert atmosphere; Schlenk technique;	72%

isatoic anhydride (118-48-9) + 2-Formylphenoxyacetic acid (6280-80-4) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → 2-(phenoxyacetic acid-2-yl)-3-(benzo[d]-[1,3]dioxol-5-yl)-2,3-dihydroquinazolin-4(1H)-one

Conditions	Yield
With ethylenediaminediacetic acid In water for 12h; Reflux;	96.4%

tetrahydrofuran-2,4-dione (4971-56-6) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) → 4-(benzo[d][1,3]dioxol-5-ylamino)furan-2(5H)-one (200053-21-0)

Conditions	Yield
In acetonitrile for 0.666667h; Microwave irradiation; Reflux;	96%
In 1,4-dioxane Product distribution; Ambient temperature; var. anilines;
In 1,4-dioxane Ambient temperature;

piperonal (120-57-0) + benzo[1,3]dioxolo-5-ylamine (14268-66-7) + mercaptoacetic acid (68-11-1) → C17H13NO5S (1129572-76-4)

Conditions	Yield
In water at 110℃; for 0.15h; Microwave irradiation; chemoselective reaction;	96%

Upstream product

• 2620-44-2 5-nitro-1,3-benzodioxole 
• 2635-13-4 1,2-(methylenedioxy)-4-bromobenzene 
• 533-31-3 Sesamol 
• 274-09-9 Methylenedioxybenzene 
• 4847-94-3 3,4-methylenedioxybenzamide 
• 119179-46-3 1-(benzo[d][1,3]dioxol-5-yl)urea 
• 6329-73-3 1-benzo[1,3]dioxol-5-yl-ethanol 
• 32932-19-7 C₁₄H₁₁NO₂ 
• 32932-20-0 N-(3,4-methylendioxyphenyl)-N-benzylamine 
• 3162-29-6 1-(benzo[d][1,3]dioxol-6-yl)ethanone 
• 709010-30-0 benzyl (1,3-benzodioxolan-5-yl)carbamate 
• 25054-53-9 3,4-(methylenedioxy)benzoyl chloride 
• 5876-51-7 5-iodo-1,3-benzodioxole 
• 94839-07-3 3,4-(methylenedioxy)-benzeneboronic acid 

Downstream Products

• 438590-28-4 dimethyl [1,3]dioxolo[4,5-g]quinoline-6,8-dicarboxylate 
• 69922-28-7 5-isocyanato-1,3-benzodioxole 
• 165459-70-1 3,4-(methylenedioxy)benzeneisonitrile 
• 133748-06-8 1-(3,4-Methylenedioxyphenyl)-5-oxo-3-pyrrolidinecarboxylic acid 
• 2620-44-2 5-nitro-1,3-benzodioxole 
• 17394-77-3 diethyl [[3,4-(methylenedioxy)phenylamino]methylene]malonate 
• 81329-90-0 4-(2,hydroxyethyl)amino-1,2-methylenedioxybenzene 
• 85575-56-0 N-Benzo[1,3]dioxol-5-yl-2,2,2-trifluoro-acetamide 
• 120959-23-1 N-(3,4-Methylenedioxyphenyl)-N'-[3-(3-piperidinomethylphenoxy)propyl]urea 
• 65069-55-8 1-(benzo[d][1,3]dioxol-5-yl)thiourea 
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• 128924-77-6 C₁₄H₁₁ClN₂O₅S 
• 138261-37-7 4'-O-demethyl-2'-chloro-4β-[3,4-(methylenedioxy)anilino]-4-desoxypodophyllotoxin 

Relevant articles and documents

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Chemoselective Hydrogenation of Nitroarenes Using an Air-Stable Base-Metal Catalyst

The reduction of nitroarenes to anilines as well as azobenzenes to hydrazobenzenes using a single base-metal catalyst is reported. The hydrogenation reactions are performed with an air-and moisture-stable manganese catalyst and proceed under relatively mild reaction conditions. The transformation tolerates a broad range of functional groups, affording aniline derivatives and hydrazobenzenes in high yields. Mechanistic studies suggest that the reaction proceeds via a bifunctional activation involving metal-ligand cooperative catalysis.

Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications

Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.

One-Pot Generation of Benzynes from Phenols: Formation of Primary Anilines by the Deoxyamination of Phenols

Benzynes were selectively generated in situ from phenols and trapped regioselectively with potassium hexamethyldisilazide to form primary anilines following acidic workup. The direct conversion of a phenolic hydroxyl group into a free amino group is a useful method for the preparation of primary aryl amines that are hard to synthesize by using coupling reactions involving phenol derivatives with ammonia. Whereas reactions of ortho- and meta-substituted phenols produced meta-substituted anilines exclusively, those of para-substituted phenols provided ortho-silylanilines.