487-19-4

Basic information

• Product Name: B-NICOTYRINE
• Synonyms: 3-(1-methyl-2-pyrrolyl)pyridine;3,2’-nicotyrine;alpha-nicotyrine;B-NICOTYRINE;BETA-NICOTYRINE;3-(1-METHYL-1H-PYRROL-2-YL)PYRIDINE;(3-(1)-METHYLPYRROL-2-YL)-PYRIDINE;NICOTYRINE
• CAS NO: 487-19-4
• Molecular Formula: C₁₀H₁₀N₂
• Molecular Weight: 158.2
• EINECS: 207-651-1
• Product Categories: pharmacetical;Nicotine Derivatives;Heterocycles;Mutagenesis Research Chemicals
• Mol File: 487-19-4.mol
• Article Data: 30

Chemical Properties

• Melting Point: 168-169 °C
• Boiling Point: 78-80°C/0/15mm
• Flash Point: 124.8°C
• Appearance: /
• Density: 1.2410
• Vapor Pressure: 0.00561mmHg at 25°C
• Refractive Index: 1.6057 (estimate)
• Storage Temp.: -20°C Freezer, Under Inert Atmosphere
• Solubility: Chloroform (Slightly), Dichloromethane (Slightly), Ethyl Acetate (Slightly), Met
• PKA: pK1:4.76(+1) (25°C)
• Stability: Light, Air Sensitive
• CAS DataBase Reference: B-NICOTYRINE(CAS DataBase Reference)
• NIST Chemistry Reference: B-NICOTYRINE(487-19-4)
• EPA Substance Registry System: B-NICOTYRINE(487-19-4)

Safety Data

• Hazardous Substances Data: 487-19-4(Hazardous Substances Data)

Usage

Description

The occurrence of this alkaloid in the cigar type of tobacco has been reported by Wenusch and subsequently confirmed by Spath and Kesztler. It forms a colour_x0002_less oil when pure and yields crystalline salts and derivatives, e.g. the p1atinichloride, m.p. 158°C; picrate, m.p. 170-1 °c and the methiodide, m.p. 2l1-3°e. It may also be prepared from nicotine by oxidation with silver oxide, silver acetate or potassium ferricyanide. With Zn and HCI, the base is reduced to nicotine and 4:5-dihydronicotyrine, b.p. 244-6°C, yielding a dipicrate, m.p. l64°e. In the presence of prepared Pt02, the latter may be further reduced to dihydrometanicotine, the dipicrate of which has m.p. 161-2°C. Nicotyrine may be converted directly into nicotine in one operation by controlled hydrogenation in the presence on Pd-e

Chemical Properties

Clear Light Red-Brown Oil

Uses

Nicotryrine is an alkaloid derived from the dehydrogenation of nicotine and its analog, nornicotine. An alkaloid occurring in cigaret smoke.

Synthesis Reference(s)

The Journal of Organic Chemistry, 54, p. 2476, 1989 DOI: 10.1021/jo00271a052

References

Cahours, Etard., Bull. Soc. Chim. Fr., 34, 449 (1880)Pictet, Crepieux., Ber., 28, 1904 (1895)Pictet, Crepieux., ibid, 33, 2355 (1900)Wibaut, Oberhoff., Rec. trav. Chim., 47,935 (1928)Wenusch., Biochem. Zeit., 275,361 (1935)Spath, Kesztler., Ber., 70,2450 (1937)Spath, Wibaut, Kesztler., ibid, 71, 100 (1938)

InChI:InChI=1/C10H10N2/c1-12-7-3-5-10(12)9-4-2-6-11-8-9/h2-8H,1H3

Synthetic route

methylamine (74-89-5) + 4-Oxo-1-(3-pyridyl)-1-butanone (76014-80-7) → nicotirine (487-19-4)

Conditions	Yield
In methanol; dichloromethane at 20℃; for 1h;	98%
In water for 2.5h;	57%

bis-1-methyl-2-(3-pyridyl)pyrrol-3-yl disulphide (73671-58-6) → nicotirine (487-19-4)

Conditions	Yield
With sodium hydroxide; nickel In tetrahydrofuran for 2h; Heating;	87%

3-Bromopyridine (626-55-1) + 1-Methyl-2-pyrrolecarboxylic acid (6973-60-0) → nicotirine (487-19-4)

Conditions	Yield
With tetrabutyl-ammonium chloride; caesium carbonate; bis(tri-t-butylphosphine)palladium(0) In N,N-dimethyl-formamide at 170℃; for 0.133333h; microwave irradiation;	85%
With bis(tri-t-butylphosphine)palladium(0); tetrabutyl-ammonium chloride; caesium carbonate In N,N-dimethyl-formamide at 170℃; for 0.133333h; Microwave irradiation;	85%

nicotin (54-11-5) → nicotirine (487-19-4)

Conditions	Yield
With manganese(IV) oxide; silica gel for 0.05h; microwave irradiation;	75%
zirconium(IV) oxide In gaseous matrix at 500℃;	72.5%

N-Methylpyrrole (96-54-8) + 3-Bromopyridine (626-55-1) → nicotirine (487-19-4)

Conditions	Yield
With 9,10-Dicyanoanthracene; N-ethyl-N,N-diisopropylamine In acetonitrile at 20℃; for 48h; Inert atmosphere; Sealed tube; Irradiation;	68%
With rhodamine 6G; N-ethyl-N,N-diisopropylamine In dimethyl sulfoxide at 25℃; for 60h; Inert atmosphere; Irradiation;	59%
Stage #1: N-Methylpyrrole With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 0.5h; Stage #2: With tert.-butyl lithium; zinc(II) chloride In tetrahydrofuran at -78℃; for 0.5h; Stage #3: 3-Bromopyridine With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran at 20℃; for 11h;	56%
With tributyl-amine; (4s,6s)-2,4,5,6-tetra(9H-carbazol-9-yl)isophthalonitrile; N,N,N',N'-tetramethylguanidine In water; dimethyl sulfoxide at 20℃; for 16h; Irradiation;	38%
With ZnSe/CdS core/shell QDs; N-ethyl-N,N-diisopropylamine In hexane for 76h; Irradiation; Inert atmosphere;	42 %Chromat.

N-Methylpyrrole (96-54-8) + pyridine-3-diazonium o-benzenedisulfonimide → nicotirine (487-19-4)

Conditions	Yield
With copper(l) iodide; caesium carbonate at 22℃; for 1h; Gomberg-Bachmann-Hey Reaction;	67%

3-Bromopyridine (626-55-1) → nicotirine (487-19-4)

Conditions	Yield
With 2-(N-methylpyrrolyl)zinc chloride; [1,4-bis(diphenylphosphino)butane] palladium(ll) dichloride In tetrahydrofuran for 22h; Ambient temperature;	66%

3-Bromopyridine (626-55-1) + 1-methyl-2-pyrrolyllithium (31785-72-5) → nicotirine (487-19-4)

Conditions	Yield
With 1-ethyl-2-pyrrolidinone; dmap; phosphonic acid diethyl ester; nickel dichloride; zinc dibromide In tetrahydrofuran at 70℃; for 22h;	62%
Stage #1: 1-methyl-2-pyrrolyllithium With zinc dibromide In tetrahydrofuran Stage #2: 3-Bromopyridine With dmap; phosphonic acid diethyl ester; nickel dichloride In tetrahydrofuran at 70℃; for 22h; Negishi cross-coupling;	62%
Stage #1: 1-methyl-2-pyrrolyllithium With zinc dibromide In tetrahydrofuran; ethylpyrrolidin-2-one; 1- Inert atmosphere; Schlenk tube; Cooling; Stage #2: 3-Bromopyridine With dmap; phosphonic acid diethyl ester; nickel dichloride In tetrahydrofuran; ethylpyrrolidin-2-one; 1- at 70℃; for 22h; Schlenk tube; Inert atmosphere; Stage #3: With ammonium chloride In tetrahydrofuran; ethylpyrrolidin-2-one; 1- Product distribution / selectivity;	62%

N-methyl-β-nicotyrinium iodide (69047-35-4) → nicotirine (487-19-4) + Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8)

Conditions	Yield
With methylamine In water at 150℃; for 22h;	A n/a B 60%
With benzylamine In water at 150℃; for 22h; Yield given;	A 10% B n/a
With Dimethylammonium sulphite In water at 180℃; for 30h; Yield given;

N-ethyl-β-nicotyrinium iodide + Dimethylammonium sulphite (69639-75-4, 79461-73-7) → nicotirine (487-19-4) + Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8)

Conditions	Yield
In water at 150℃; for 30h;	A 14% B 57%

Dimethylammonium sulphite (69639-75-4, 79461-73-7) + N-benzyl-β-nicotyrinium iodide → nicotirine (487-19-4) + Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8)

Conditions	Yield
In water at 180℃; for 30h;	A 14% B 57%

N-ethyl-β-nicotyrinium iodide + methylamine (74-89-5) → nicotirine (487-19-4) + Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8)

Conditions	Yield
In water at 150℃; for 22h;	A 14% B 57%

N-benzyl-β-nicotyrinium iodide + methylamine (74-89-5) → nicotirine (487-19-4) + Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8)

Conditions	Yield
In water at 150℃; for 22h;	A 14% B 57%

N-ethyl-β-nicotyrinium iodide → nicotirine (487-19-4) + Ethyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine

Conditions	Yield
With ethylamine In water at 150℃; for 22h;	A n/a B 56%
With benzylamine In water at 150℃; for 22h; Yield given;	A 10% B n/a
With ethylammonium sulphite In water at 180℃; for 30h; Yield given;

N-Methylpyrrole (96-54-8) + 3-iodopyridine (1120-90-7) → nicotirine (487-19-4)

Conditions	Yield
With 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline bis[(2-diphenyl-phosphino)phenyl]ether copper(I) hexafluorophosphate; N,N-dicyclohexyl-2-methyl-1-propanamine; potassium carbonate In acetonitrile at 20℃; for 72h; Inert atmosphere; Sealed tube; UV-irradiation;	54%
With 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline bis[(2-diphenyl-phosphino)phenyl]ether copper(I) hexafluorophosphate; N,N-dicyclohexyl-2-methyl-1-propanamine; potassium carbonate In acetonitrile at 20℃; UV-irradiation;	54%

N-Methylpyrrole (96-54-8) + 3-Chloropyridine (626-60-8) → nicotirine (487-19-4)

Conditions	Yield
With 9-ethyl-N3,N3,N6,N6,-tetramethyl-9H-carbazole-3,6-diamine; N-ethyl-N,N-diisopropylamine In dimethyl sulfoxide at 23℃; for 36h; Inert atmosphere; UV-irradiation; Schlenk technique;	46%

N-methyl-β-nicotyrinium iodide (69047-35-4) + ethylammonium sulphite (69639-76-5, 79461-74-8) → nicotirine (487-19-4) + Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8) + Ethyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine

Conditions	Yield
In water at 150℃; for 40h;	A n/a B 13% C 45%

N-methyl-β-nicotyrinium iodide (69047-35-4) + ethylamine (75-04-7) → nicotirine (487-19-4) + Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8) + Ethyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine

Conditions	Yield
In water at 150℃; for 22h;	A n/a B 13% C 45%

N-benzyl-β-nicotyrinium iodide → nicotirine (487-19-4) + Benzyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine

Conditions	Yield
With benzylamine In water at 150℃; for 22h;	A n/a B 40%
With benzylammonium sulphite In water at 180℃; for 30h; Yield given;

N-Methylpyrrole (96-54-8) + Pyridine-3-sulfonyl chloride (16133-25-8) → nicotirine (487-19-4)

Conditions	Yield
With dichloro bis(acetonitrile) palladium(II); lithium carbonate In 1,4-dioxane at 140℃; for 24h; Schlenk technique; Inert atmosphere; chemoselective reaction;	31%

1-benzyl-3-(1-methylpyrrolidin-2-yl)piperidine (812648-74-1) → nicotirine (487-19-4)

Conditions	Yield
With selenium at 250 - 260℃; for 30h;	18%

Phenyl vinyl sulfoxide (20451-53-0) + M-methyl-1-(3-pyridyl)ethanimine N-oxide (119908-57-5) → nicotirine (487-19-4)

Conditions	Yield
In toluene for 6h; Heating;	14%

Phenyl vinyl sulfoxide (20451-53-0) + N-methyl-1-(3-pyridyl)ethanimine N-Oxide → nicotirine (487-19-4)

Conditions	Yield
In toluene	9.88%

N-methyl-β-nicotyrinium iodide (69047-35-4) → nicotirine (487-19-4) + C-(1-Methyl-1H-indol-7-yl)-methyleneamine

Conditions	Yield
With ammonium hydroxide at 180℃; for 40h;	A n/a B 6%

3-(1-methyl-pyrrolidin-2-yl)-pyridine (22083-74-5) → Myosmine (532-12-7) + N-methylmyosmine (525-74-6) + nicotirine (487-19-4) + cotinine (15569-85-4) + 3-(1-Methyl-2,3-dihydro-1H-pyrrol-2-yl)-pyridine

Conditions	Yield
With 9,10-Dicyanoanthracene; oxygen In acetonitrile for 22h; Mechanism; Irradiation; also TiO2 as electron acceptor, in absence of O2;	A 0.27% B n/a C 0.11% D 1.05% E n/a

tetrachloromethane (56-23-5) + 1-methyl-2-(3-pyridyl)-3-pyrroline (21446-40-2) + ethylene glycol (107-21-1) → nicotirine (487-19-4) + 3-(1-methyl-pyrrolidin-2-yl)-pyridine (22083-74-5)

1-methyl-2-(3-pyridyl)-3-pyrroline (21446-40-2) → nicotirine (487-19-4) + 3-(1-methyl-pyrrolidin-2-yl)-pyridine (22083-74-5)

3-(1-methyl-pyrrolidin-2-yl)-pyridine (22083-74-5) → 1-Methylpyrrolidine (120-94-5) + nicotirine (487-19-4)

Conditions	Yield
With water; silver(l) oxide

3-(1-methyl-pyrrolidin-2-yl)-pyridine (22083-74-5) → nicotirine (487-19-4)

Conditions	Yield
With magnesium hydrosilicate; palladium
With air; vanadia

3-(1-methyl-pyrrolidin-2-yl)-pyridine (22083-74-5) → nicotirine (487-19-4) + methyl-bis-(4-[3]pyridyl-butyl)-amine (111357-52-9)

Conditions	Yield
With magnesium hydrosilicate; palladium at 230 - 280℃;

nicotirine (487-19-4) + Dimethylphenylsilane (766-77-8) → 2-(dimethylphenylsilyl)-5-(1-methyl-1H-pyrrol-2-yl)pyridine

Conditions	Yield
With 2-methoxytetrahydropyran; tert-butylethylene; C78H70Al2Cl4N6P4Rh2 In dodecane at 150℃; for 6h; Glovebox;	75%

nicotirine (487-19-4) + PhMe2SiBpin → 2-(dimethylphenylsilyl)-5-(1-methyl-1H-pyrrol-2-yl)pyridine + 3-(1-methyl-1H-pyrrol-2-yl)-4-(dimethylphenylsilyl)pyridine + 2-(dimethylphenylsilyl)-3-(1-methyl-1H-pyrrol-2-yl)pyridine

Conditions	Yield
With potassium hexamethylsilazane In dodecane at 20℃; for 3h; Glovebox;	A 16% B n/a C n/a

nicotirine (487-19-4) + Dimethylammonium sulphite (69639-75-4, 79461-73-7) → Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8)

Conditions	Yield
In water at 180℃; for 60h;	15%

nicotirine (487-19-4) + methylamine (74-89-5) → Methyl-[1-(1-methyl-1H-indol-7-yl)-meth-(Z)-ylidene]-amine (163729-92-8)

Conditions	Yield
In water at 150℃; for 22h;	13%

nicotirine (487-19-4) + dimethyl acetylenedicarboxylate (762-42-5) → 9-(1-Methyl-1H-pyrrol-2-yl)-9aH-quinolizine-1,2,3,4-tetracarboxylic acid tetramethyl ester

Conditions	Yield
In acetonitrile at 0℃; for 4h;	6.3%

Upstream product

• 626-55-1 3-Bromopyridine 
• 20451-53-0 Phenyl vinyl sulfoxide 
• 119908-57-5 M-methyl-1-(3-pyridyl)ethanimine N-oxide 
• 69639-75-4 Dimethylammonium sulphite 
• 69047-35-4 N-methyl-β-nicotyrinium iodide 
• 75-04-7 ethylamine 
• 56-23-5 tetrachloromethane 
• 104-46-1 anethole 
• 54-11-5 nicotin 
• 7732-18-5 water 
• 31785-72-5 1-methyl-2-pyrrolyllithium 
• 96-54-8 N-Methylpyrrole 
• 22083-74-5 3-(1-methyl-pyrrolidin-2-yl)-pyridine 
• 626-60-8 3-Chloropyridine 

Downstream Products

• 22083-74-5 3-(1-methyl-pyrrolidin-2-yl)-pyridine 

Relevant articles and documents

An improved synthesis of β-Nicotyrine from the dehydrogenation of nicotine: Comparison of conventional and microwave-assisted reactions

β-Nicotyrine, a minor tobacco alkaloid, can be rapidly prepared in good yield from the dehydrogenation of S-(-)-nicotine over MnO2 with microwave irradiation. This method is superior to dehydrogenation reactions that utilize S-(-)-nicotine and MnO2 in a variety of solvents under reflux.

C2-Selective silylation of pyridines by a rhodium-aluminum complex

We have developed a C2-selective mono-silylation of a variety of pyridines using a Rh-Al complex. Both the site- and mono-selectivity are controlledviathe pyridine coordination to the Lewis-acidic Al center prior to the activation of the pyridine C(2)-H bond at the proximal Rh center. A reaction mechanism is proposed based on several mechanistic studies, including the isolation of a (2-pyridyl)silylrhodium intermediate.

A case of chain propagation: α-aminoalkyl radicals as initiators for aryl radical chemistry

The generation of aryl radicals from the corresponding halides by redox chemistry is generally considered a difficult task due to their highly negative reduction potentials. Here we demonstrate that α-aminoalkyl radicals can be used as both initiators and chain-carriers for the radical coupling of aryl halides with pyrrole derivatives, a transformation often employed to evaluate new highly reducing photocatalysts. This mode of reactivity obviates for the use of strong reducing species and was also competent in the formation of sp2 C-P bonds. Mechanistic studies have delineated some of the key features operating that trigger aryl radical generation and also propagate the chain process.