550-90-3

Basic information

• Product Name: lupanine
• Synonyms: lupanine;(7aβ,14aα)-Dodecahydro-7α,14α-methano-4H,6H-dipyrido[1,2-a:1',2'-e][1,5]diazocin-4-one;2-Oxosparteine;d-Lupanine;Lupanin;LUPANINE(SH)
• CAS NO: 550-90-3
• Molecular Formula: C15H24N2O
• Molecular Weight: 248.368
• Mol File: 550-90-3.mol
• Article Data: 11

Chemical Properties

• Melting Point: 40-44°
• Boiling Point: bp3 190-193°
• Flash Point: 172.7°C
• Appearance: /
• Density: 0.9789 (rough estimate)
• Vapor Pressure: 1.67E-06mmHg at 25°C
• Refractive Index: nD24 1.5444
• PKA: 9.47±0.20(Predicted)
• CAS DataBase Reference: lupanine(CAS DataBase Reference)
• NIST Chemistry Reference: lupanine(550-90-3)
• EPA Substance Registry System: lupanine(550-90-3)

Safety Data

• Hazardous Substances Data: 550-90-3(Hazardous Substances Data)

Usage

Uses

(+)-Lupanine is used in biological studies with quinolizidine alkaloids in seeds of lupin genotypes of different origins.

Definition

ChEBI: The delta-lactam obtained by formal oxidation at the 2-position of sparteine. The major alkaloid from the seeds of Lupinus exaltatus, L. mexicanus and L. rotundiflorus, it is among the most important of the tetracyc ic quinolizidine alkaloids.

InChI:InChI=1/C15H24N2O/c18-15-6-3-5-14-11-8-12(10-17(14)15)13-4-1-2-7-16(13)9-11/h11-14H,1-10H2/t11-,12-,13+,14-/m0/s1

Synthetic route

(1S,2R,9S,10S)-7,15-diazatetracyclo[7.7.1.02,7.010,15]heptadec-12-en-6-one → (+)-lupanine (550-90-3)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In methanol at 20℃; under 760.051 Torr; for 2.5h;	93%

L-(-)-lupanine D-tartrate salt → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	30%

D-(+)-lupanine-L-tartrate → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	19%

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → (+)-lupanine (550-90-3)

Conditions	Yield
With sodium tetrahydroborate; formic acid; sulfur dioxide Ambient temperature; other N-oxides of sparteine lactams;
With hydrogen; platinum(IV) oxide In acetic acid under 760 Torr; for 1h; Product distribution; other N-oxides of sparteine lactams; other times;

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → 17-hydroxylupanine + (+)-lupanine (550-90-3)

Conditions	Yield
With formic acid; sulfur dioxide for 0.5h; Mechanism; Product distribution; Ambient temperature; other N-oxides of sparteine lactams; other times;

5,6-dehydrolupanine (32101-29-4) → (+)-lupanine (550-90-3)

Conditions	Yield
With hydrogen; palladium on activated charcoal In ethanol	3.2 mg
With hydrogen; palladium on activated charcoal In ethanol Ambient temperature;

(+)-lupanine N-oxide → (+)-lupanine (550-90-3)

Conditions	Yield
With sulfur dioxide In methanol at 0℃; for 0.25h;	4 mg

hydrogen iodide (10034-85-2) + 13α-hydroxylupanine (15358-48-2) + red phosphorus → (+)-lupanine (550-90-3)

13α-hydroxylupanine (15358-48-2) + phosphorus pentoxide → water (7732-18-5) + (+)-lupanine (550-90-3)

Conditions	Yield
at 170℃; folgende Hydrierung;

6β-hydroxylupanine → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: CHCl3 / 12 h / Ambient temperature 2: 3.2 mg / H2 / 5percent Pd-C / ethanol View Scheme

(1S,2R,9S,10S)-7,15-diazatetracyclo[7.7.1.02,7.010,15]heptadec-12-en-6-one → (+)-lupanine (550-90-3)

Conditions	Yield
With palladium 10% on activated carbon; hydrogen In methanol at 20℃; under 760.051 Torr; for 2.5h;	93%

L-(-)-lupanine D-tartrate salt → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	30%

D-(+)-lupanine-L-tartrate → (+)-lupanine (550-90-3)

Conditions	Yield
With potassium hydroxide In water	19%

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → (+)-lupanine (550-90-3)

Conditions	Yield
With sodium tetrahydroborate; formic acid; sulfur dioxide Ambient temperature; other N-oxides of sparteine lactams;
With hydrogen; platinum(IV) oxide In acetic acid under 760 Torr; for 1h; Product distribution; other N-oxides of sparteine lactams; other times;

lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9) → 17-hydroxylupanine + (+)-lupanine (550-90-3)

Conditions	Yield
With formic acid; sulfur dioxide for 0.5h; Mechanism; Product distribution; Ambient temperature; other N-oxides of sparteine lactams; other times;

5,6-dehydrolupanine (32101-29-4) → (+)-lupanine (550-90-3)

Conditions	Yield
With hydrogen; palladium on activated charcoal In ethanol	3.2 mg
With hydrogen; palladium on activated charcoal In ethanol Ambient temperature;

(+)-lupanine N-oxide → (+)-lupanine (550-90-3)

Conditions	Yield
With sulfur dioxide In methanol at 0℃; for 0.25h;	4 mg

hydrogen iodide (10034-85-2) + 13α-hydroxylupanine (15358-48-2) + red phosphorus → (+)-lupanine (550-90-3)

13α-hydroxylupanine (15358-48-2) + phosphorus pentoxide → water (7732-18-5) + (+)-lupanine (550-90-3)

Conditions	Yield
at 170℃; folgende Hydrierung;

6β-hydroxylupanine → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: CHCl3 / 12 h / Ambient temperature 2: 3.2 mg / H2 / 5percent Pd-C / ethanol View Scheme

O,O'-dibenzoyl-D-tartaric acid (17026-42-5) + rac-lupanine (4356-43-8) → (-)-lupanine (+)-2,3-dibenzoyl-D-tartarate (1335287-92-7) + (+)-lupanine (550-90-3) + L-(-)-lupanine (486-88-4)

Conditions	Yield
In methanol Resolution of racemate; Heating; optical yield given as %ee;

L-Tartaric acid (87-69-4) + rac-lupanine (4356-43-8) → (+)-lupanine (550-90-3)

Conditions	Yield
Stage #1: L-Tartaric acid; rac-lupanine In acetone Resolution of racemate; Stage #2: With potassium hydroxide In water Resolution of racemate;	n/a

6-methyl-3,7-diazabicyclo[3.3.1]non-6-en-2-one → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 8 steps 1.1: triethylamine; dmap / dichloromethane / 20 h 2.1: triethylamine / tetrahydrofuran / 5 h / 20 °C 3.1: Adam’s catalyst; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 4.1: sodium tetrahydroborate / 2.5 h / 0 °C 4.2: 4 h / 0 - 20 °C 5.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 6.1: triethylamine / dichloromethane / 120 h 7.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 8.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

3-tert-butoxycarbonyl-6-methyl-3,7-diazabicyclo[3.3.1]non-6-en-2-one → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 7 steps 1.1: triethylamine / tetrahydrofuran / 5 h / 20 °C 2.1: Adam’s catalyst; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 3.1: sodium tetrahydroborate / 2.5 h / 0 °C 3.2: 4 h / 0 - 20 °C 4.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 5.1: triethylamine / dichloromethane / 120 h 6.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 7.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

11-tert-butoxycarbonyl-7,11-diazatricyclo[7.3.1.02,7]tridec-2,4-dien-6,10-dione → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: Adam’s catalyst; hydrogen / methanol / 4 h / 20 °C / 760.05 Torr 2.1: sodium tetrahydroborate / 2.5 h / 0 °C 2.2: 4 h / 0 - 20 °C 3.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 4.1: triethylamine / dichloromethane / 120 h 5.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 6.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(1S,2R,9S)-11-tert-butoxycarbonyl-7,11-diazatricyclo[7.3.1.02,7]tridecane-6,10-dione → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: sodium tetrahydroborate / 2.5 h / 0 °C 1.2: 4 h / 0 - 20 °C 2.1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 3.1: triethylamine / dichloromethane / 120 h 4.1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 5.1: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(1S,2R,9S)-11-tert-butoxycarbonyl-10-methoxy-7,11-diazatricyclo[7.3.1.02,7]tridecane-6-one → (+)-lupanine (550-90-3)

Conditions

Yield

Multi-step reaction with 4 steps 1: boron trifluoride diethyl etherate / dichloromethane / 17 h / 0 - 20 °C 2: triethylamine / dichloromethane / 120 h 3: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 4: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(-)-Angustifoline (550-43-6) → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: triethylamine / dichloromethane / 120 h 2: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 3: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(1S,2R,9S,10S)-10,11-diallyl-7,11-diazatricyclo[7.3.1.02,7]tridecane-6-one → (+)-lupanine (550-90-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: tricyclohexylphosphine[1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidine][benzylidene]ruthenium(II) dichloride / dichloromethane / 1 h / Reflux 2: palladium 10% on activated carbon; hydrogen / methanol / 2.5 h / 20 °C / 760.05 Torr View Scheme

(+)-lupanine (550-90-3) → lupanine N(16)-oxide (3019-47-4, 74183-21-4, 74183-22-5, 133163-04-9)

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 48h;	90%

(+)-lupanine (550-90-3) → (-)-sparteine (90-39-1)

Conditions	Yield
With lithium aluminium tetrahydride In tetrahydrofuran Heating;	85%
With lithium aluminium tetrahydride In tetrahydrofuran at 0℃; for 18h; Reflux;	84%
With hydrogenchloride; platinum Hydrogenation;
With lithium aluminium tetrahydride In diethyl ether for 5h; Heating;

(+)-lupanine (550-90-3) → (+)-lupanine N-oxide

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane	80%
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 6h; Ambient temperature;	71%

bromocyane (506-68-3) + (+)-lupanine (550-90-3) → (1S)-4c-(4-bromo-butyl)-8-oxo-(11ac)-octahydro-1r,5c-methano-pyrido[1,2-a][1,5]diazocine-3-carbonitrile (2584-20-5)

Conditions	Yield
With benzene

(+)-lupanine (550-90-3) + methyl iodide (74-88-4) → N-16-methyl-2-oxosparteine iodide (6080-95-1, 54815-53-1, 58846-15-4, 82978-45-8, 82978-46-9, 115113-81-0)

Conditions	Yield
at 110 - 120℃; im Rohr;
for 96h; Ambient temperature; Yield given;

(+)-lupanine (550-90-3) → (+)-2-Thionosparteine

Conditions	Yield
With tetraphosphorus decasulfide; potassium polysulfide; xylene

(+)-lupanine (550-90-3) → 17-hydroxylupanine (15043-17-1, 55732-48-4, 69427-33-4, 127515-92-8)

Conditions	Yield
With N-Bromosuccinimide; chloroform und anschliessenden Behandeln mit wss.NaOH;
With methanol; silver(l) oxide
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In 1,4-dioxane

(+)-lupanine (550-90-3) → (7S)-3,3-dichloro-(7at,14ac)-dodecahydro-7r,14c-methano-dipyrido[1,2-a;1',2'-e][1,5]diazocin-4-one

Conditions	Yield
With phosphorus pentachloride anschliessend Behandeln mit Eis;

(+)-lupanine (550-90-3) → (+)-2,17-dioxosparteine (4697-83-0)

Conditions	Yield
With potassium permanganate; acetic acid; acetone
With sodium hydroxide; potassium hexacyanoferrate(III)

(+)-lupanine (550-90-3) → 4-((1S)-(11at)-decahydro-1r,5c-methano-pyrido[1,2-a][1,5]diazocin-4t-yl)-butyric acid ; dihydrochloride (15333-74-1, 33964-84-0, 117895-46-2)

Conditions	Yield
With hydrogenchloride
With hydrogenchloride

iodomethane-d3 (865-50-9) + (+)-lupanine (550-90-3) → C16H24(2)H3N2O(1+)*I(1-)

Conditions	Yield
In acetone for 72h;

(+)-lupanine (550-90-3) → (+)-2,17-dioxosparteine (4697-83-0, 38485-03-9)

Conditions	Yield
With potassium permanganate

(+)-lupanine (550-90-3) → (2,2-2H2)sparteine (19879-75-5, 20210-08-6, 20210-10-0)

Conditions	Yield
With lithium aluminium deuteride In tetrahydrofuran for 1h; Heating;	50 mg

benzyl bromide (100-39-0) + (+)-lupanine (550-90-3) → (+)-lupanine-bromobenzylate

ethyl iodide (75-03-6) + (+)-lupanine (550-90-3) → (+)-lupanine hydriodide

ethanol (64-17-5) + ethyl iodide (75-03-6) + (+)-lupanine (550-90-3) → (+)-lupanine hydriodide

benzyl chloride (100-44-7) + (+)-lupanine (550-90-3) → (+)-lupanine hydrochloride

(+)-lupanine (550-90-3) + methyl iodide (74-88-4) → (+)-lupanine iodomethylate

Upstream product

• 3019-47-4 lupanine N⁽¹⁶⁾-oxide 
• 32101-29-4 5,6-dehydrolupanine 
• 10034-85-2 hydrogen iodide 
• 15358-48-2 13α-hydroxylupanine 
• 17026-42-5 O,O'-dibenzoyl-D-tartaric acid 
• 4356-43-8 rac-lupanine 
• 87-69-4 L-Tartaric acid 
• 550-43-6 (-)-Angustifoline 
• 1476-39-7 1,5-diaminopentane dihydrochloride 
• 90-39-1 (-)-sparteine 

Downstream Products

• 15043-17-1 17-hydroxylupanine 
• 4697-83-0 (+)-17-oxolupanine 
• 90-39-1 (-)-sparteine 
• 67528-17-0 (+)-2,3-Didehydrospartein 
• 106656-92-2 2-(p-tolyl)-2-dehydrosparteine 
• 4697-83-0 (+)-2,17-dioxosparteine 

Relevant articles and documents

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ALKALOIDS OF BOLUSANTHUS SPECIOSUS

Investigation of the alkaloids of Bolusanthus speciosus afforded a new quinolizidine alkaloid, 6β-hydroxylupanine.The structure of this alkaloid was assigned on the basis of spectroscopic methods and by chemical transformations.The other alkaloids isolated were cytisine, N-methylcytisine, 11α-allylcytisine, anagyrine, 13-hydroxyanagyrine, 5,6-dehydrolupanine, lupanine, sparteine and β-isoparteine.The biosynthetic significance of these finding is discussed briefly. Key Word Index - Bolusanthus speciosus; Leguminosae; ten quinolizidine alkaloids; novel 6β-hydroxylupanine.

Process for preparing enantiopure Lupanine and Sparteine

The present invention relates to processes for preparing enantiopure Lupanine and Sparteine.

Simple and highly efficient preparation and characterization of (-)-lupanine and (+)-sparteine

In a simple and convenient way, we have improved the non-chromatographic isolation of optically pure (-)-2-oxosparteine ((-)-lupanine) and (+)-sparteine. The fast and efficient method for the determination of the ee of bisquinolizidine alkaloids has been proposed. A relatively simple simple 1H NMR method has been applied for evaluation of the % ee of enantiomers of the lupanines and sparteines with the chiral dibenzoyltartaric acids as the shift reagents. The 1H NMR spectra of the bases and the new salts in polar solvents have been measured. The results are confirmed by chiral HPLC method. Additionally, for the first time X-ray analysis of the salt of (-)-lupanine has been performed. The improved method of purification of bisquinolizidine alkaloids will considerably facilitate the employment of these alkaloids as chiral ligands in asymmetric reactions and as pharmacological tools.