639-41-8

Basic information

• Product Name: crinamine
• Synonyms: crinamine;[5α,11R,13β,19α]-1,2-Didehydro-3α-methoxycrinan-11-ol
• CAS NO: 639-41-8
• Molecular Formula: C17H19NO4
• Molecular Weight: 301.33706
• Mol File: 639-41-8.mol
• Article Data: 1

Chemical Properties

• Boiling Point: 467.5°C at 760 mmHg
• Flash Point: 236.5°C
• Appearance: /
• Density: 1.42g/cm³
• Vapor Pressure: 1.53E-09mmHg at 25°C
• Refractive Index: 1.679
• CAS DataBase Reference: crinamine(CAS DataBase Reference)
• NIST Chemistry Reference: crinamine(639-41-8)
• EPA Substance Registry System: crinamine(639-41-8)

Safety Data

• Hazardous Substances Data: 639-41-8(Hazardous Substances Data)

Usage

General Description

Crinamine is a natural alkaloid chemical found in the plant species Crinum moorei. It is a biologically active compound with various pharmaceutical properties, including antitumor, anti-inflammatory, and antiviral activities. Crinamine has been studied for its potential use in cancer therapy, as it has been found to inhibit the growth of certain cancer cells. It has also shown promise in reducing inflammation and combating viral infections. Further research is being conducted to explore the potential therapeutic applications of crinamine, particularly in the field of oncology and infectious diseases.

InChI:InChI=1/C17H19NO4/c1-20-11-2-3-17-12-6-14-13(21-9-22-14)4-10(12)7-18(8-16(17)19)15(17)5-11/h2-4,6,11,15-16,19H,5,7-9H2,1H3/t11-,15-,16-,17-/m0/s1

Synthetic route

eschenmoser's salt (33797-51-2) + (3R,3aS,6R,7aS)-N-p-tolylsulfonyl-3-acetyloxy-3a-(3,4-methylenedioxyphenyl)-6-methoxy-2,3,3a,6,7,7a-hexahydroindole (215609-83-9) → (+)-crinamine (639-41-8)

Conditions	Yield
With Na*C10H8; potassium carbonate 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH; Yield given. Multistep reaction;

2-(3,4-methylenedioxyphenyl)-3-[(methoxycarbonyl)oxy]-1-cyclohexene (215609-74-8) → (+)-crinamine (639-41-8)

Conditions	Yield
Multi-step reaction with 7 steps 1: (S)-BINAPO / Pd2dba3*CHCl3 / tetrahydrofuran / 18 h / Ambient temperature 2: 83 percent / FeCl3*SiO2 / acetone / Ambient temperature 3: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 4: 98 percent / pyridine 5: 86 percent / SeO2 / dioxane / Heating 6: 1.) Ms2O, Et3N / 2.) 0 deg C 7: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme
Multi-step reaction with 7 steps 1: (S)-BINAPO / Pd2dba3*CHCl3 / tetrahydrofuran / 18 h / Ambient temperature 2: 83 percent / FeCl3*SiO2 / acetone / Ambient temperature 3: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 4: 98 percent / pyridine 5: 86 percent / SeO2 / dioxane / Heating 6: Montmorillonite K-10 / Heating 7: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme

2-(3,4-methylenedioxyphenyl)-3-[(diethylphosphoryl)oxy]-1-cyclohexene (215609-92-0) → (+)-crinamine (639-41-8)

Conditions	Yield
Multi-step reaction with 7 steps 1: NaH, (S)-BINAPO / Pd2dba3*CHCl3 / tetrahydrofuran / 48 h / -20 °C / other solvents 2: 83 percent / FeCl3*SiO2 / acetone / Ambient temperature 3: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 4: 98 percent / pyridine 5: 86 percent / SeO2 / dioxane / Heating 6: 1.) Ms2O, Et3N / 2.) 0 deg C 7: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme
Multi-step reaction with 7 steps 1: NaH, (S)-BINAPO / Pd2dba3*CHCl3 / tetrahydrofuran / 48 h / -20 °C / other solvents 2: 83 percent / FeCl3*SiO2 / acetone / Ambient temperature 3: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 4: 98 percent / pyridine 5: 86 percent / SeO2 / dioxane / Heating 6: Montmorillonite K-10 / Heating 7: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme

N-((S)-2-Benzo[1,3]dioxol-5-yl-cyclohex-2-enyl)-4-methyl-N-(2-oxo-ethyl)-benzenesulfonamide (215609-75-9) → (+)-crinamine (639-41-8)

Conditions	Yield
Multi-step reaction with 5 steps 1: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 2: 98 percent / pyridine 3: 86 percent / SeO2 / dioxane / Heating 4: 1.) Ms2O, Et3N / 2.) 0 deg C 5: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme
Multi-step reaction with 5 steps 1: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 2: 98 percent / pyridine 3: 86 percent / SeO2 / dioxane / Heating 4: Montmorillonite K-10 / Heating 5: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme

(3R,3aS,7aS)-N-p-tolylsulfonyl-3-hydroxy-3a-(3,4-methylenedioxyphenyl)-2,3,3a,6,7,7a-hexahydroindole (215609-76-0) → (+)-crinamine (639-41-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: 98 percent / pyridine 2: 86 percent / SeO2 / dioxane / Heating 3: 1.) Ms2O, Et3N / 2.) 0 deg C 4: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme
Multi-step reaction with 4 steps 1: 98 percent / pyridine 2: 86 percent / SeO2 / dioxane / Heating 3: Montmorillonite K-10 / Heating 4: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme

(3R,3aS,7aS)-N-p-tolylsulfonyl-3-acetyloxy-3a-(3,4-methylenedioxyphenyl)-2,3,3a,6,7,7a-hexahydroindole (215609-79-3) → (+)-crinamine (639-41-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: 86 percent / SeO2 / dioxane / Heating 2: 1.) Ms2O, Et3N / 2.) 0 deg C 3: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme
Multi-step reaction with 3 steps 1: 86 percent / SeO2 / dioxane / Heating 2: Montmorillonite K-10 / Heating 3: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme

(S)-2-(3,4-methylenedioxyphenyl)-3-[(N-p-tolylsulfonyl)-2,2-diethoxyethylamino]-1-cyclohexene (215609-78-2) → (+)-crinamine (639-41-8)

Conditions	Yield
Multi-step reaction with 6 steps 1: 83 percent / FeCl3*SiO2 / acetone / Ambient temperature 2: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 3: 98 percent / pyridine 4: 86 percent / SeO2 / dioxane / Heating 5: 1.) Ms2O, Et3N / 2.) 0 deg C 6: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme
Multi-step reaction with 6 steps 1: 83 percent / FeCl3*SiO2 / acetone / Ambient temperature 2: 59 percent / 4 Angstroem molecular sieves / 230 - 240 °C 3: 98 percent / pyridine 4: 86 percent / SeO2 / dioxane / Heating 5: Montmorillonite K-10 / Heating 6: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme

(3R,3aS,6R,7aS)-N-p-tolylsulfonyl-3-acetyloxy-3a-(3,4-methylenedioxyphenyl)-2,3,3a,6,7,7a-hexahydroindole (215609-81-7) → (+)-crinamine (639-41-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: 1.) Ms2O, Et3N / 2.) 0 deg C 2: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme
Multi-step reaction with 2 steps 1: Montmorillonite K-10 / Heating 2: 1.) Na*C10H8, 3.) K2CO3 / 1.) THF, -95 deg C, 2.) MeCN, reflux, 3.) MeOH View Scheme

acetic anhydride (108-24-7) + (+)-crinamine (639-41-8) → 11-O-acetoxycrinamine (106196-22-9)

Conditions	Yield
With pyridine; dmap In dichloromethane at 20℃; for 2h;	98%

4-methoxy-benzoyl chloride (100-07-2) + (+)-crinamine (639-41-8) → 11-O-(4-methoxybenzoyl)crinamine

Conditions	Yield
With pyridine; dmap In dichloromethane at 40℃; for 4h;	97%

sodium methylate (124-41-4) + (+)-crinamine (639-41-8) → (6R)-8c,9t-dimethoxy-(6at)-5,6a,7,8,9,11-hexahydro-6r,11c-methano-benzo[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepine (606-51-9, 109667-30-3, 109667-31-4, 109784-16-9, 144609-74-5)

Conditions	Yield
(i) MeSO2Cl, Py, (ii) /BRN= 3592982/, MeOH; Multistep reaction;

(+)-crinamine (639-41-8) → (6R)-8c-methoxy-(6at)-5,6a,7,8,9,11-hexahydro-6r,11c-methano-benzo[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepin-9c-ol (485-59-6)

Conditions	Yield
(i) MeSO2Cl, (ii) NaHCO3; Multistep reaction;
With methanesulfonyl chloride In pyridine

(+)-crinamine (639-41-8) → (6R)-8c-methoxy-(6at)-5,6a,7,8,9,11-hexahydro-6r,11c-methano-benzo[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepin-9t-ol (485-58-5)

Conditions	Yield
With methanesulfonyl chloride In pyridine

(+)-crinamine (639-41-8) → ent-3β-methoxy-crin-1-en-11-one (1797-92-8)

Conditions	Yield
With chromium(VI) oxide In pyridine

(+)-crinamine (639-41-8) → ent-(11S)-3β,11-epoxy-crin-1-ene (1472-72-6, 6900-81-8)

Conditions	Yield
With hydrogenchloride

(+)-crinamine (639-41-8) → (6S)-8c-methoxy-(6at,9at)-6a,7,8,9,9a,10-hexahydro-5H-6r,10c-ethano-cyclopenta[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepin-12anti-ol (67657-13-0)

Conditions	Yield
In methanol Irradiation;

(+)-crinamine (639-41-8) → (6S)-12anti-acetoxy-8c-methoxy-(6at,9at)-6a,7,8,9,9a,10-hexahydro-5H-6r,10c-ethano-cyclopenta[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepine (67657-14-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: methanol / Irradiation 2: (acetylation) View Scheme

(+)-crinamine (639-41-8) → (6R)-8c,9c-dimethoxy-(6at)-5,6a,7,8,9,11-hexahydro-6r,11c-methano-benzo[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepine (606-51-9, 109667-30-3, 109667-31-4, 109784-16-9, 144609-74-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: MeSO2Cl / pyridine 2: (i) K, benzene, (ii) /BRN= 609209/ View Scheme

(+)-crinamine (639-41-8) → (6R)-8c,9t-dimethoxy-(6at)-5,6a,7,8,9,11-hexahydro-6r,11c-methano-benzo[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepine (606-51-9, 109667-30-3, 109667-31-4, 109784-16-9, 144609-74-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: MeSO2Cl / pyridine 2: (i) K, benzene, (ii) /BRN= 609209/ View Scheme

(+)-crinamine (639-41-8) → (6R)-8c-methoxy-(6at)-5,7,8,11-tetrahydro-6aH-6r,11c-methano-benzo[b][1,3]dioxolo[4',5':4,5]benzo[1,2-e]azepin-9-one (111034-22-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: MeSO2Cl / pyridine 2: MnO2 View Scheme
Multi-step reaction with 2 steps 1: MeSO2Cl / pyridine 2: MnO2 View Scheme

(+)-crinamine (639-41-8) → ent-(11S)-3β,11-epoxy-crinane (1153-01-1, 41758-70-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: aq. HCl 2: H2 / PtO2 / 760 Torr View Scheme

Upstream product

• 33797-51-2 eschenmoser's salt 
• 215609-83-9 (3R,3aS,6R,7aS)-N-p-tolylsulfonyl-3-acetyloxy-3a-(3,4-methylenedioxyphenyl)-6-methoxy-2,3,3a,6,7,7a-hexahydroindole 
• 215609-74-8 2-(3,4-methylenedioxyphenyl)-3-[(methoxycarbonyl)oxy]-1-cyclohexene 
• 215609-92-0 2-(3,4-methylenedioxyphenyl)-3-[(diethylphosphoryl)oxy]-1-cyclohexene 
• 215609-75-9 N-((S)-2-Benzo[1,3]dioxol-5-yl-cyclohex-2-enyl)-4-methyl-N-(2-oxo-ethyl)-benzenesulfonamide 
• 215609-76-0 (3R,3aS,7aS)-N-p-tolylsulfonyl-3-hydroxy-3a-(3,4-methylenedioxyphenyl)-2,3,3a,6,7,7a-hexahydroindole 
• 215609-79-3 (3R,3aS,7aS)-N-p-tolylsulfonyl-3-acetyloxy-3a-(3,4-methylenedioxyphenyl)-2,3,3a,6,7,7a-hexahydroindole 
• 215609-78-2 (S)-2-(3,4-methylenedioxyphenyl)-3-[(N-p-tolylsulfonyl)-2,2-diethoxyethylamino]-1-cyclohexene 
• 215609-81-7 (3R,3aS,6R,7aS)-N-p-tolylsulfonyl-3-acetyloxy-3a-(3,4-methylenedioxyphenyl)-2,3,3a,6,7,7a-hexahydroindole 
• 67-56-1 methanol 
• 1472-75-9 Oxohaemanthamin 
• 466-75-1 haemanthamine 
• 466-75-1 haemanthamine 
• 35611-53-1 rac-(11Ξ)-3α-methoxy-2β-(toluene-4-sulfonyloxy)-crinan-11-ol 

Downstream Products

• 466-75-1 haemanthamine 
• 606-51-9 O-Methyl-α-isocrinamin 
• 606-51-9 O-Methyl-β-isocrinamin 
• 561-19-3 Haemultin 
• 35611-50-8 ent-(11S)-crin-2-en-11-ol 
• 1472-72-6 ent-(11S)-3β,11-epoxy-crin-1-ene 
• 1797-92-8 11-Oxo-crinamin 
• 485-59-6 β-Isocrinamin 
• 1472-75-9 Oxohaemanthamin 
• 1472-75-9 Oxohaemanthamin 
• 606-51-9 (-)-manthine 

Relevant articles and documents

First Asymmetric Total Syntheses of (+)-Crinamine, (-)-Haemanthidine, and (+)-Pretazettine

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