6935-27-9

Basic information

• Product Name: 2-Benzylaminopyridine
• Synonyms: BENZYL-PYRIDIN-2-YL-AMINE;AURORA KA-4160;ALPHA-BENZYLAMINOPYRIDINE;2-BENZYLAMINOPYRIDINE;N-BENZYL-2-PYRIDYLAMINE;N-BENZYLPYRIDIN-2-AMINE;N-(2-PYRIDYL)BENZYLAMINE;N-(PHENYLMETHYL)-2-PYRIDINAMINE
• CAS NO: 6935-27-9
• Molecular Formula: C₁₂H₁₂N₂
• Molecular Weight: 184.24
• EINECS: 230-060-5
• Product Categories: Pyridines derivates;C9 to C46;Heterocyclic Building Blocks;Pyridines
• Mol File: 6935-27-9.mol
• Article Data: 165

Chemical Properties

• Melting Point: 95-97 °C(lit.)
• Boiling Point: 116-131 °C0.6 mm Hg(lit.)
• Flash Point: 182°C/12mm
• Appearance: white to off-white powder
• Density: 1.1160 (rough estimate)
• Vapor Pressure: 0.000291mmHg at 25°C
• Refractive Index: 1.6266 (estimate)
• Storage Temp.: Store below +30°C.
• PKA: 6.61±0.10(Predicted)
• BRN: 134309
• CAS DataBase Reference: 2-Benzylaminopyridine(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Benzylaminopyridine(6935-27-9)
• EPA Substance Registry System: 2-Benzylaminopyridine(6935-27-9)

Safety Data

• Hazard Codes: Xn,Xi
• Statements: 22-37/38-41-40-36/37/38-20/21/22
• Safety Statements: 26-39-36-22
• WGK Germany: 3
• RTECS: US2700000
• TSCA: Yes
• Hazardous Substances Data: 6935-27-9(Hazardous Substances Data)

Usage

Chemical Properties

white to off-white powder

Uses

2-(Benzylamino)pyridine is used as a reactant in the amination of aryl chlorides, bromides, and triflates catalyzed by palladium complexes.

Synthesis Reference(s)

Organic Syntheses, Coll. Vol. 4, p. 91, 1963The Journal of Organic Chemistry, 67, p. 4965, 2002 DOI: 10.1021/jo020057z

General Description

2-Benzylaminopyridine on reaction with BBr3 yields the corresponding amino or hydroxy substituted compounds. It forms 5- and 6-coordinated organometallic complexes of gallium(III) and indium(III).

InChI:InChI=1/C12H12N2/c1-2-6-11(7-3-1)10-14-12-8-4-5-9-13-12/h1-9H,10H2,(H,13,14)

Synthetic route

2-aminopyridine (504-29-0) + benzyl alcohol (100-51-6) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With dichloro-[1,3-bis(4-tert-butylbenzyl)perhydrobenzimidazol-2-ylidene](p-cymene)ruthenium(II); potassium tert-butylate at 120℃; for 24h; Reagent/catalyst; Inert atmosphere; Schlenk technique; Sealed tube;	100%
With potassium tert-butylate; copper diacetate In 1,4-dioxane at 130℃; for 24h;	99%
With potassium tert-butylate; copper diacetate In 1,4-dioxane at 130℃; for 24h; Inert atmosphere;	99%

2-chloropyridine (109-09-1) + benzylamine (100-46-9) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With sodium t-butanolate In toluene at 100 - 110℃; for 24h; Buchwald-Hartwig amination; Inert atmosphere; Sealed vial;	99%
With potassium phosphate In dimethyl sulfoxide at 80℃; UV-irradiation;	95%
With copper(l) iodide; C14H16N2O; caesium carbonate In N,N-dimethyl-formamide at 130℃; for 24h; Inert atmosphere; Sealed tube;	93%

2-iodopyridine (5029-67-4) + benzylamine (100-46-9) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With cesium acetate; copper In dimethyl sulfoxide at 90℃; for 24h; Inert atmosphere;	99%
With copper(l) iodide; 1-tetralone oxime; potassium hydroxide In water at 25℃; for 18h; Sealed tube; Inert atmosphere; Green chemistry;	93%
With tetra(n-butyl)ammonium hydroxide; copper(II) sulfate In water at 80℃; for 24h; Schlenk technique; Sealed tube; Inert atmosphere;	80%
With tetramethyl ammoniumhydroxide; ethyl 2-oxocyclohexane carboxylate; copper(l) chloride In dimethyl sulfoxide at 80℃; for 24h; Inert atmosphere;	72%

N-benzylidenepyridin-2-amine (1883-96-1, 82299-15-8, 88785-73-3) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With Triethoxysilane; [bis(2,6-diisopropylaniline)acenaphthene]Fe(η6-toluene) at 70℃; for 18h; Schlenk technique; Inert atmosphere; Glovebox; Sealed tube;	98%
With (4-Ph)Triaz(NHPiPr2)2Mn(CO)2Br; potassium tert-butylate; hydrogen In tetrahydrofuran at 50℃; under 15001.5 Torr; for 4h; Glovebox; Autoclave; Sealed tube; chemoselective reaction;	92%
With sodium tetrahydroborate In tetrahydrofuran at 25℃; for 4h;	40%
With sodium tetrahydroborate In methanol for 5h; Cooling;	19.09 g
With [MnBr(CO)3(2-(diphenylphosphinoamino)pyridine)]; potassium tert-butylate; hydrogen In ethanol at 80℃; for 48h; Autoclave;	50.7 mg

methyl benzylpyridin-2-ylcarbamate (1444866-70-9) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With water; sodium hydroxide In methanol for 3h; Reflux;	98%

benzyl-pyridin-2-yl-carbamic acid tert-butyl ester (442513-39-5) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With trifluoroacetic acid In dichloromethane; water	97%
With trifluoroacetic acid In dichloromethane; water at 25℃;

2-bromo-pyridine (109-04-6) + benzylamine (100-46-9) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With dibenzylphosphoramidous acid 1,1'-binaphthyl-2,2'-diyl ester; caesium carbonate; copper(I) bromide In N,N-dimethyl-formamide at 90℃; for 36h;	97%
With copper(l) iodide; 1-tetralone oxime; potassium hydroxide In water at 65℃; for 18h; Sealed tube; Inert atmosphere; Green chemistry;	95%
With cesium acetate; copper In dimethyl sulfoxide at 90℃; for 24h; Inert atmosphere;	92%

N-benzyl-N-(pyridin-2-yl)hydroxylamine (1335111-43-7) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In methanol at 20℃; under 760.051 Torr; for 0.5h; Inert atmosphere;	97%

2-nitropyridine (15009-91-3) + benzyl alcohol (100-51-6) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With [RuCl(CO)(PPh3)(PNS-Me)]; potassium hydroxide In toluene at 100℃; for 12h;	96%
With bis(5-chlorosalicylidene)hydrazone binuclear copper(I) complex; potassium hydroxide In toluene at 100℃; for 18h;	80%
With aluminum (III) chloride; water In acetonitrile at 20℃; Irradiation;	50%

2-aminopyridine (504-29-0) + benzaldehyde (100-52-7) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; silver trifluoromethanesulfonate In dichloromethane at 20℃; for 2h;	93%
With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate In neat (no solvent) at 150℃; for 0.25h;	92%
With diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate; thiourea In toluene at 70℃; for 24h;	91%

2-aminopyridine (504-29-0) + para-Chlorobenzyl alcohol (873-76-7) → N-benzylpyridin-2-amine (6935-27-9) + N-[(4-chlorophenyl)methyl]pyridin-2-amine (22881-33-0)

Conditions	Yield
With potassium tert-butylate; copper diacetate In 1,4-dioxane at 130℃; for 24h;	A 8% B 90%
With cesium hydroxide; palladium diacetate In toluene at 150℃; for 12h;	A 19% B 74%

N-(pyridin-2-yl)benzimidamide (4931-08-2) + benzyl alcohol (100-51-6) → N-benzylpyridin-2-amine (6935-27-9) + benzamide (55-21-0)

Conditions	Yield
With potassium hydroxide In toluene at 120℃; for 15h; Schlenk technique; Glovebox; Inert atmosphere; Sealed tube;	A 82% B 94 %Chromat.

N-benzyl-2,2-difluoro-2-(pyridin-2-ylsulfonyl)acetamide → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With sodium hydride In N,N-dimethyl-formamide at 0 - 60℃; for 3h; Julia-Kocienski Olefination;	80%

2-<α-(p-tolylthio)benzylamino>pyridine (78508-26-6) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With sodium tetrahydroborate In 1,2-dimethoxyethane for 1h; Heating;	75%

1-[benzyl(pyridin-2-yl)amino]pyridinium bromide → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With acetic acid; zinc at 20℃; for 29h; Reduction;	75%

2-aminopyridine (504-29-0) + N-butylamine (109-73-9) + benzyl alcohol (100-51-6) → N-benzylpyridin-2-amine (6935-27-9) + N-benzylidenebutan-1-amine (1077-18-5)

Conditions	Yield
With iron(II,III) oxide; potassium tert-butylate In 1,4-dioxane at 90℃; for 168h; Inert atmosphere;	A 74% B 26%

pyridine N-oxide (694-59-7) + benzylamine (100-46-9) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine; bromo-tris(1-pyrrolidinyl)phosphonium hexafluorophosphate In dichloromethane at 25℃; for 15h;	70%

2-aminopyridine (504-29-0) + benzyl bromide (100-39-0) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With oxygen; lithium carbonate; copper(II) bis(trifluoromethanesulfonate) In toluene at 100℃; under 760.051 Torr; for 12h; Schlenk technique;	62%
With sodium hydrogencarbonate In tetrahydrofuran at 20℃; Inert atmosphere;	56%

benzylamine (100-46-9) + pyridin-2-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate (202923-80-6) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
In dimethyl sulfoxide at 100℃; for 24h;	60%

2-aminopyridine (504-29-0) + benzylamine (100-46-9) → N-benzylpyridin-2-amine (6935-27-9) + tribenzylamine (620-40-6) + dibenzylamine (103-49-1)

Conditions	Yield
With C4F9SO3H at 200℃; for 42h; Yields of byproduct given;	A 54% B n/a C n/a

2-aminopyridine (504-29-0) + toluene (108-88-3) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With di-tert-butyl peroxide; copper In neat (no solvent) at 120℃; for 12h; Inert atmosphere; Schlenk technique;	51%

2-fluoropyridine (372-48-5) + benzylamine (100-46-9) → N-benzylpyridin-2-amine (6935-27-9)

Conditions	Yield
With cesium acetate; copper In dimethyl sulfoxide at 110℃; for 24h; Inert atmosphere;	50%
In 1-methyl-pyrrolidin-2-one at 150℃; for 0.25h; Flow reactor;

2-aminopyridine (504-29-0) + benzyl chloride (100-44-7) → N-benzylpyridin-2-amine (6935-27-9) + 2-Benzylamino-5-benzylpyridine (137002-80-3)

Conditions	Yield
1) 180 to 250 deg C, 3 h, 2) 250 deg C, 0.5 h;	A 20% B 41%

2-(Dimethylamino)pyridine (5683-33-0) + benzyl chloride (100-44-7) → N-benzylpyridin-2-amine (6935-27-9) + N-benzyl-N-methyl-N-(2-pyridyl)amine (20173-75-5) + 2-Benzylamino-5-benzylpyridine (137002-80-3) + 2-(N,N-dibenzylamino)pyridine (154424-43-8)

Conditions	Yield
at 250℃; for 4h;	A 15% B 21% C 4.7% D 19%

benzyl chloride (100-44-7) + dimethylamino-pyridine hydrochloride → N-benzylpyridin-2-amine (6935-27-9) + 2-amino-5-benzylpyridine (98477-40-8) + N-benzyl-N-methyl-N-(2-pyridyl)amine (20173-75-5) + 2-(N,N-dibenzylamino)pyridine (154424-43-8)

Conditions	Yield
at 250℃; for 4h; Further byproducts given;	A 17% B 4.3% C 20% D 14%

benzyl chloride (100-44-7) + dimethylamino-pyridine hydrochloride → N-benzylpyridin-2-amine (6935-27-9) + N-benzyl-N-methyl-N-(2-pyridyl)amine (20173-75-5) + 2-Benzylamino-5-benzylpyridine (137002-80-3) + 2-(N,N-dibenzylamino)pyridine (154424-43-8)

Conditions	Yield
at 250℃; for 4h; Further byproducts given;	A 17% B 20% C 14% D 12%

2-aminopyridine (504-29-0) + benzyl formate (104-57-4) → N-benzylpyridin-2-amine (6935-27-9)

2-aminopyridine (504-29-0) + benzoic acid benzyl ester (120-51-4) → N-benzyl-2-pyridone (1753-62-4) + N-benzylpyridin-2-amine (6935-27-9) + benzamide (55-21-0) + benzoic acid (65-85-0)

Conditions	Yield
at 190 - 200℃; anschliessend Behandeln mit wss. Salzsaeure;

2-aminopyridine (504-29-0) + formic acid (64-18-6) + benzaldehyde (100-52-7) → N-benzylpyridin-2-amine (6935-27-9)

bis(1,5-cyclooctadiene)diiridium(I) dichloride (12112-67-3) + N-benzylpyridin-2-amine (6935-27-9) → (2-benzylaminopyridine)chloro(1,5-cyclooctadiene)iridium(I)

Conditions	Yield
In tetrahydrofuran at 20℃; for 7h;	100%

N-benzylpyridin-2-amine (6935-27-9) + tetraacetatodiruthenium chloride → Ru(2+)*Ru(3+)*Cl(1-)*4C6H5CH2NC5H4N(1-)=Ru2(C6H5CH2NC5H4N)4Cl

Conditions	Yield
In neat (no solvent) stirring at 120°C, 16h; sublimating excess ligand; repeating heating with fresh benzylaminopyridine; collecting; washing (acetone, methanol, diethyl ether); drying (vac., 80°C); elem. anal.;	97%

N-benzylpyridin-2-amine (6935-27-9) → benzo[4,5]imidazo[1,2-a]pyridine (245-47-6)

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol; bis(tertbutylcarbonyloxy)iodobenzene at 25℃; for 7h; Reagent/catalyst; Solvent;	97%

N-benzylpyridin-2-amine (6935-27-9) + acetyl chloride (75-36-5) → N-benzyl-N-(pyridin-2-yl)acetamide

Conditions	Yield
Stage #1: N-benzylpyridin-2-amine With methylmagnesium chloride In tetrahydrofuran at 20℃; for 0.166667h; Stage #2: acetyl chloride In tetrahydrofuran at 20℃; for 1h;	94%

N-benzylpyridin-2-amine (6935-27-9) + S,S-diethyl 2-phenylpropanebis(thioate) → 1-benzyl-3-phenyl-4-oxo-4H-pyrido[1,2-a]pyrimidin-1-ium-2-olate

Conditions	Yield
In chlorobenzene for 3h; Reflux;	93%

N-benzylpyridin-2-amine (6935-27-9) + (butane-1-sulfenyl)-dipropyl-borane (2938-91-2) → (C3H7)2BN(CH2C6H5)(2-C5H4N) (64738-97-2)

Conditions	Yield
In dichloromethane byproducts: C4H9SH;	92%
In dichloromethane byproducts: C4H9SH;	92%

N-benzylpyridin-2-amine (6935-27-9) → benzyl(5-bromopyridin-2-yl)amine (280116-83-8)

Conditions	Yield
With dihydrogen peroxide; 1-butylpyridinium bromide; toluene-4-sulfonic acid In 1,2-dimethoxyethane at 80℃; for 24h; Reagent/catalyst; Schlenk technique; Inert atmosphere; Green chemistry; regioselective reaction;	91%

N-benzylpyridin-2-amine (6935-27-9) + bis(2,4,6-trichlorophenyl) ethylmalonate (15781-72-3) → anhydro-(1-benzyl-3-ethyl-4-oxo-2-hydroxypyrido[1,2-a]pyrimidinium hydroxide)

Conditions	Yield
at 180℃; for 0.0833333h; Cyclization;	86%
at 160℃; for 0.0666667h; Condensation;	70%

formaldehyd (50-00-0) + N-benzylpyridin-2-amine (6935-27-9) + diphenylphosphane (829-85-6) → 2-(N-diphenylphosphinomethyl-N-benzyl)aminopyridine (562108-07-0)

Conditions	Yield
With acetic acid In toluene at 70 - 80℃; for 6h;	86%

N-benzylpyridin-2-amine (6935-27-9) → 2-aminopyridine (504-29-0)

Conditions	Yield
With sulfuric acid for 24h; Ambient temperature;	85%
With 9,10-Dicyanoanthracene In water; acetonitrile Irradiation;	75%

N-benzylpyridin-2-amine (6935-27-9) + benzyl chloride (100-44-7) → 2-(N,N-dibenzylamino)pyridine (154424-43-8)

Conditions	Yield
With sodium amide In toluene	83%

N-benzylpyridin-2-amine (6935-27-9) + chlorocarbonyl-diazo-acetic acid ethyl ester (57072-87-4) → N-benzyl-N-(2-pyridinyl)-α-(ethoxycarbonyl)-α-diazoacetamide

Conditions	Yield
	83%

N-benzylpyridin-2-amine (6935-27-9) + N-(4-chlorobenzyl)-3-methylpyridin-2-amine → benzo[4,5]imidazo[1,2-a]pyridine (245-47-6) + 8-methyl-4-chloropyrido[1,2-a]benzimidazole (1445436-82-7)

Conditions	Yield
With 1,1,1,3',3',3'-hexafluoro-propanol; bis(tertbutylcarbonyloxy)iodobenzene at 25℃; for 7h;	A 83% B 79%

N-benzylpyridin-2-amine (6935-27-9) + (6R,8R)-(-)-2-chloro-5,6,7,8,-tetrahydro-7,7-dimethyl-[6,8-methanoquinoline] (304857-39-4) → (6R,8R)-(+)-benzyl-(5,6,7,8-tetrahydro-7,7-dimethyl-6,8-methanoquinolin-2-yl)-pyridin-2-yl-amine

Conditions	Yield
With 1,3-bis-(diphenylphosphino)propane; bis(dibenzylideneacetone)-palladium(0); sodium t-butanolate; tetrabutylammomium bromide In toluene at 100℃; Buchwald-Hartwig amination reaction;	81%

N-benzylpyridin-2-amine (6935-27-9) + phenylacetylene (536-74-3) → phenyl-(2-phenylimidazo[1,2-a]pyridin-3-yl)methanone (61122-85-8)

Conditions	Yield
With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; oxygen; lithium carbonate; copper(II) bis(trifluoromethanesulfonate) In toluene at 100℃; under 760.051 Torr; for 12h; Schlenk technique;	81%

N-benzylpyridin-2-amine (6935-27-9) + pivaloyl chloride (3282-30-2) → N-benzyl-N-(pyridin-2-yl)pivalamide (521300-02-7)

Conditions	Yield
Stage #1: N-benzylpyridin-2-amine With methylmagnesium chloride In tetrahydrofuran at 20℃; for 0.166667h; Stage #2: pivaloyl chloride In tetrahydrofuran at 20℃; for 1h;	79%

Upstream product

• 504-29-0 2-aminopyridine 
• 104-57-4 benzyl formate 
• 120-51-4 benzoic acid benzyl ester 
• 64-18-6 formic acid 
• 100-52-7 benzaldehyde 
• 100-44-7 benzyl chloride 
• 100-51-6 benzyl alcohol 
• 142-08-5 2-Pyridone 
• 100-46-9 benzylamine 
• 5683-33-0 2-(Dimethylamino)pyridine 
• 78508-26-6 2-<α-(p-tolylthio)benzylamino>pyridine 
• 1883-96-1 N-benzylidenepyridin-2-amine 
• 202923-80-6 pyridin-2-yl 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate 
• 109-09-1 2-chloropyridine 

Downstream Products

• 80095-92-7 2-benzyliminopiperidine 
• 102862-18-0 C₂₀H₁₅N₃O₃ 
• 137002-83-6 Bis-(2-benzylamino-5-pyridyl)phenylmethane 
• 504-29-0 2-aminopyridine 
• 98477-40-8 2-amino-5-benzylpyridine 
• 98477-41-9 Bis-(2-amino-5-pyridyl)phenylmethane 
• 137002-80-3 2-Benzylamino-5-benzylpyridine 
• 154424-43-8 2-(N,N-dibenzylamino)pyridine 
• 20173-75-5 N-benzyl-N-methyl-N-(2-pyridyl)amine 

Relevant articles and documents

[(PPh3)2NiCl2]-Catalyzed C-N bond formation reaction via borrowing hydrogen strategy: Access to diverse secondary amines and quinolines

Commercially available [(PPh3)2NiCl2] was found to be an efficient catalyst for the mono-N-alkylation of (hetero)- A romatic amines, employing alcohols to deliver diverse secondary amines, including the drug intermediates chloropyramine (5b) and mepyramine (5c), in excellent yields (up to 97%) via the borrowing hydrogen strategy. This method shows a superior activity (TON up to 10000) with a broad substrate scope at a low catalyst loading of 1 mol % and a short reaction time. Further, this strategy is also successful in accessing various quinoline derivatives following the acceptorless dehydrogenation pathway.

A Fe single atom on N,S-doped carbon catalyst for performing N-alkylation of aromatic amines under solvent-free conditions

A green and gram-scale strategy has been developed for the synthesis of Fe single atom/N,S-doped carbon catalyst (Fe20-SA@NSC) via the pyrolysis of polyaniline (PAN)-modified Fe,S-doped ZIFs, in which the synthesis of ZIFs can be accomplished in water at room temperature. The as-prepared catalyst exhibits superior activity in the N-alkylation of amines with alcohols via a borrowing strategy under solvent-free conditions (TOF up to 13.9 h-1). Based on the HAADF-STEM and XAFS results, Fe in this material is dispersed as the single-atom Fe1-N4S1 site. According to the experimental and theoretical calculation results, the Fe1-N4S1 site displays a better borrowing hydrogen ability than other Fe sites owing to its higher electron density. In addition, this catalyst has excellent stability and recyclability, and no obvious loss in activity is observed after 7 runs.

Water-promoted dehydrative coupling of 2-aminopyridines in heptane: Via a borrowing hydrogen strategy

A synthetic method for dehydrative N-benzylation promoted by water molecules in heptane using a π-benzylpalladium system has been developed. The presence of water significantly accelerates carbon-nitrogen bond formation, which is accomplished in an atom-economical process to afford the corresponding N-monobenzylated products. A crossover experiment afforded H/D scrambled products, which is consistent with a borrowing hydrogen mechanism. Kinetic isotope effect measurements revealed that benzylic carbon-hydrogen bond cleavage was the rate-determining step.