723-97-7

Basic information

• Product Name: 1-Methoxy-9H-carbazole-3-carbaldehyde
• Synonyms: 1-Methoxy-9H-carbazole-3-carbaldehyde;Murrayanine
• CAS NO: 723-97-7
• Molecular Formula: C₁₄H₁₁NO₂
• Molecular Weight: 225.24
• Mol File: 723-97-7.mol
• Article Data: 13

Chemical Properties

• Boiling Point: 466.4°C at 760 mmHg
• Flash Point: 235.9°C
• Appearance: /
• Density: 1.312g/cm³
• Vapor Pressure: 7.08E-09mmHg at 25°C
• Refractive Index: 1.748
• CAS DataBase Reference: 1-Methoxy-9H-carbazole-3-carbaldehyde(CAS DataBase Reference)
• NIST Chemistry Reference: 1-Methoxy-9H-carbazole-3-carbaldehyde(723-97-7)
• EPA Substance Registry System: 1-Methoxy-9H-carbazole-3-carbaldehyde(723-97-7)

Safety Data

• Hazardous Substances Data: 723-97-7(Hazardous Substances Data)

Usage

Description

This simple carbazole alkaloid is found in the stem bark of Mu"aya koenigii Spreng. It is best purified by sublimation of the crude base when it yields colour_x0002_less crystals. The ultraviolet spectrum in ethanol has absorption maxima at 238, 247,274,289 and 335 mJJ.. The structure has been shown to be 3-formyl-lmethoxycarbazole by spectroscopic methods and synthesis. It yields an oxime, m.p. l55-6°C; a picrate, m.p. 198-2000 C and the 2:4-dinitrophenylhydrazone, m.p. > 300°C. The N-methyl derivative forms colourless needles from C6H6- light petroleum, m.p. l48-9°C. When subjected to Wolff-Kishner reduction, the alkaline phase yields l-hydroxy-3-methyl-carbazole.

References

Chakraborty, Barman, Bose., Tetrahedron, 21, 681 (1965)Synthesis: Crum, Sprague., Chern. Cornrnun., 417 (1966)Chakraborty, Chowdhury., J. Org. Chern., 33, 1265 (1968)

InChI:InChI=1/C14H11NO2/c1-17-13-7-9(8-16)6-11-10-4-2-3-5-12(10)15-14(11)13/h2-8,15H,1H3

Synthetic route

koenoline (3909-78-2) → murrayanine (723-97-7)

Conditions	Yield
With manganese(IV) oxide In acetone at 20℃; for 12h;	98%
With manganese(IV) oxide In tetrachloromethane at 20℃; for 12h;	81%
for 144h; Ambient temperature;	10%
With manganese(IV) oxide In tetrachloromethane for 6h; Ambient temperature; Yield given;

1-methoxy-3-methylcarbazole (4532-33-6) → murrayanine (723-97-7)

Conditions	Yield
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In tetrahydrofuran; methanol; water at 20℃; for 0.5h;	95%
With 2,3-dicyano-5,6-dichloro-p-benzoquinone In benzene for 4h; Ambient temperature;	70%

1-bromo-9H-carbazole-3-carbaldehyde (1384959-52-7) + sodium methylate (124-41-4) → murrayanine (723-97-7)

Conditions	Yield
With methanol; copper(l) iodide In N,N-dimethyl-formamide at 120℃; for 5h; Inert atmosphere;	88%

4-[(2-bromophenyl)amino]-3-methoxybenzaldehyde (954378-08-6) → murrayanine (723-97-7)

Conditions	Yield
With sodium carbonate; lithium chloride; tetrakis(triphenylphosphine) palladium(0) In acetonitrile for 48h; Heating;	85%

3-methoxy-4-(phenylamino)benzaldehyde (808114-06-9) → murrayanine (723-97-7)

Conditions	Yield
With acetic acid; palladium diacetate at 160℃; for 12h;	73%
With copper diacetate; palladium diacetate; acetic acid at 110 - 130℃; Reagent/catalyst; Inert atmosphere;	68%
Stage #1: 3-methoxy-4-(phenylamino)benzaldehyde With palladium diacetate; potassium carbonate; Trimethylacetic acid at 115℃; for 12h; Stage #2: With sodium hydrogencarbonate	20%

2-methoxy-4-methylaniline (39538-68-6) + (η5-cyclohexadienyl)tricarbonyliron tetrafluoroborate → murrayanine (723-97-7)

Conditions	Yield
With manganese(IV) oxide 1.) MeCN, 25 deg C, 2.) toluene, 25 deg C; Multistep reaction;

2-methoxy-4-methylaniline (39538-68-6) + tricarbonyl<(1-5-η)-cyclohexadienylium>iron tetrafluoroborate → murrayanine (723-97-7)

Conditions	Yield
With manganese(IV) oxide 1) CH3CN, 46 h, RT, 2) toluene, RT 24 h and 2 d; Yield given. Multistep reaction;

methyl 3-methoxy-4-aminobenzoate (41608-64-4) + tricarbonyl<(1-5-η)-cyclohexadienylium>iron tetrafluoroborate → murrayanine (723-97-7)

Conditions	Yield
With manganese(IV) oxide; diisobutylaluminium hydride Yield given. Multistep reaction;

3-(2-bromophenyl)-2,3,4,5,6,7-hexahydro-2-oxobenzoxazol-6-carboxaldehyde (954378-09-7) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 4 steps 1: 65 percent / DDQ / benzene / 24 h / Heating 2: KOH / ethanol; H2O / 18 h / 20 °C 3: 0.24 g / K2CO3 / acetone / 12 h / Heating 4: 85 percent / Na2CO3; LiCl / [Pd(PPh3)4] / acetonitrile / 48 h / Heating View Scheme

3-(2-bromophenyl)-2,3-dihydro-2-oxobenzoxazol-6-carboxaldehyde (954378-10-0) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: KOH / ethanol; H2O / 18 h / 20 °C 2: 0.24 g / K2CO3 / acetone / 12 h / Heating 3: 85 percent / Na2CO3; LiCl / [Pd(PPh3)4] / acetonitrile / 48 h / Heating View Scheme

C13H10BrNO2 → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 0.24 g / K2CO3 / acetone / 12 h / Heating 2: 85 percent / Na2CO3; LiCl / [Pd(PPh3)4] / acetonitrile / 48 h / Heating View Scheme

3-(2-Bromo-phenyl)-4,5-dimethylene-oxazolidin-2-one (189953-32-0) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 5 steps 1: 90 percent / BF3*Et2O / CH2Cl2 / 0.42 h / -78 °C 2: 65 percent / DDQ / benzene / 24 h / Heating 3: KOH / ethanol; H2O / 18 h / 20 °C 4: 0.24 g / K2CO3 / acetone / 12 h / Heating 5: 85 percent / Na2CO3; LiCl / [Pd(PPh3)4] / acetonitrile / 48 h / Heating View Scheme

4,5-dimethylene-3-phenyl-1,3-oxazolidin-2-one (153897-88-2) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 5 steps 1: BF3*Et2O / CH2Cl2 / 2.5 h / 160 °C 2: 69 percent / DDQ / benzene / 24 h / Heating 3: 81 percent / aq. NaOH / ethanol / 1 h / 20 °C 4: 95 percent / K2CO3 / acetone / 3 h / 60 °C 5: 73 percent / glacial acetic acid / Pd(OAc)2 / 12 h / 160 °C View Scheme
Multi-step reaction with 5 steps 1: boron trifluoride diethyl etherate / dichloromethane / 0.25 h / -78 °C 2: 2,3-dicyano-5,6-dichloro-p-benzoquinone / dichloromethane / 12 h / 60 °C 3: sodium hydroxide / ethanol; water / 0.75 h / 60 °C 4: potassium carbonate / acetone / 0.75 h / 60 °C 5: palladium diacetate; acetic acid; copper diacetate / 110 - 130 °C / Inert atmosphere View Scheme

3-hydroxy-4-(phenylamino)benzaldehyde (808114-01-4) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 95 percent / K2CO3 / acetone / 3 h / 60 °C 2: 73 percent / glacial acetic acid / Pd(OAc)2 / 12 h / 160 °C View Scheme
Multi-step reaction with 2 steps 1: potassium carbonate / acetone / 0.75 h / 60 °C 2: palladium diacetate; acetic acid; copper diacetate / 110 - 130 °C / Inert atmosphere View Scheme

2,3-dihydro-2-oxo-3-phenylbenzo[d]oxazole-6-carbaldehyde (808114-05-8) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: 81 percent / aq. NaOH / ethanol / 1 h / 20 °C 2: 95 percent / K2CO3 / acetone / 3 h / 60 °C 3: 73 percent / glacial acetic acid / Pd(OAc)2 / 12 h / 160 °C View Scheme
Multi-step reaction with 3 steps 1: sodium hydroxide / ethanol; water / 0.75 h / 60 °C 2: potassium carbonate / acetone / 0.75 h / 60 °C 3: palladium diacetate; acetic acid; copper diacetate / 110 - 130 °C / Inert atmosphere View Scheme

2,3,4,5,6,7-hexahydro-2-oxo-3-phenylbenzo[d]oxazole-6-carbaldehyde (808113-99-7) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 4 steps 1: 69 percent / DDQ / benzene / 24 h / Heating 2: 81 percent / aq. NaOH / ethanol / 1 h / 20 °C 3: 95 percent / K2CO3 / acetone / 3 h / 60 °C 4: 73 percent / glacial acetic acid / Pd(OAc)2 / 12 h / 160 °C View Scheme
Multi-step reaction with 4 steps 1: 2,3-dicyano-5,6-dichloro-p-benzoquinone / dichloromethane / 12 h / 60 °C 2: sodium hydroxide / ethanol; water / 0.75 h / 60 °C 3: potassium carbonate / acetone / 0.75 h / 60 °C 4: palladium diacetate; acetic acid; copper diacetate / 110 - 130 °C / Inert atmosphere View Scheme

1-methoxy-3-methoxycarbonyl-9H-carbazole (23523-94-6) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 90 percent / DIBAH / diethyl ether; hexane / 3.5 h / -78 °C 2: MnO2 / CCl4 / 6 h / Ambient temperature View Scheme
Multi-step reaction with 2 steps 1: lithium aluminium tetrahydride / tetrahydrofuran / 4 h / 0 - 70 °C 2: manganese(IV) oxide / acetone / 12 h / 20 °C View Scheme
Multi-step reaction with 2 steps 1: diisobutylaluminium hydride / toluene; diethyl ether / 2 h / -78 °C / Inert atmosphere 2: manganese(IV) oxide / tetrachloromethane / 12 h / 20 °C View Scheme

methyl 1-hydroxy-9H-carbazole-3-carboxylate (182261-83-2) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: K2CO3 / acetone / 7 h / Heating 2: 90 percent / DIBAH / diethyl ether; hexane / 3.5 h / -78 °C 3: MnO2 / CCl4 / 6 h / Ambient temperature View Scheme
Multi-step reaction with 3 steps 1: methanol; diethyl ether / 12 h / 0 °C 2: lithium aluminium tetrahydride / tetrahydrofuran / 4 h / 0 - 70 °C 3: manganese(IV) oxide / acetone / 12 h / 20 °C View Scheme

3-methoxy-4-nitrotoluene (38512-82-2) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: 96 percent / hydrogen / 10percent Pd/C / ethanol / 912 Torr 2: 2) MnO2 / 1) CH3CN, 46 h, RT, 2) toluene, RT 24 h and 2 d View Scheme
Multi-step reaction with 2 steps 1: H2 / Pd/C / ethanol 2: 2.) MnO2 / 1.) MeCN, 25 deg C, 2.) toluene, 25 deg C View Scheme

4-hydroxy-9H-carbazole-3-carbaldehyde (1375487-97-0) → murrayanine (723-97-7)

Conditions

Yield

Multi-step reaction with 4 steps 1: N-Bromosuccinimide / N,N-dimethyl-formamide / 0.5 h / 20 °C / Inert atmosphere 2: triethylamine / dichloromethane / 2 h / 0 - 20 °C / Inert atmosphere 3: tetrakis(triphenylphosphine) palladium(0); tri-n-butyl-tin hydride / N,N-dimethyl-formamide / 0.75 h / 100 °C / Inert atmosphere 4: methanol; copper(l) iodide / N,N-dimethyl-formamide / 5 h / 120 °C / Inert atmosphere View Scheme

1-bromo-4-hydroxy-9H-carbazole-3-carbaldehyde (1375487-99-2) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: triethylamine / dichloromethane / 2 h / 0 - 20 °C / Inert atmosphere 2: tetrakis(triphenylphosphine) palladium(0); tri-n-butyl-tin hydride / N,N-dimethyl-formamide / 0.75 h / 100 °C / Inert atmosphere 3: methanol; copper(l) iodide / N,N-dimethyl-formamide / 5 h / 120 °C / Inert atmosphere View Scheme

1-bromo-3-formyl-9H-carbazol-4-yl trifluoromethanesulfonate (1384959-51-6) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: tetrakis(triphenylphosphine) palladium(0); tri-n-butyl-tin hydride / N,N-dimethyl-formamide / 0.75 h / 100 °C / Inert atmosphere 2: methanol; copper(l) iodide / N,N-dimethyl-formamide / 5 h / 120 °C / Inert atmosphere View Scheme

9H-carbazol-4-ol (52602-39-8) → murrayanine (723-97-7)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: trichlorophosphate / 10 - 20 °C / Inert atmosphere 1.2: 20 - 35 °C / Inert atmosphere 1.3: 20 - 30 °C / Inert atmosphere 2.1: N-Bromosuccinimide / N,N-dimethyl-formamide / 0.5 h / 20 °C / Inert atmosphere 3.1: triethylamine / dichloromethane / 2 h / 0 - 20 °C / Inert atmosphere 4.1: tetrakis(triphenylphosphine) palladium(0); tri-n-butyl-tin hydride / N,N-dimethyl-formamide / 0.75 h / 100 °C / Inert atmosphere 5.1: methanol; copper(l) iodide / N,N-dimethyl-formamide / 5 h / 120 °C / Inert atmosphere View Scheme

vanillin (121-33-5) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: pyridine / dichloromethane / 0.25 h / 20 °C 1.2: 1 h / -20 °C 2.1: caesium carbonate; palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl / toluene / 12 h / 96 °C 3.1: potassium carbonate; palladium diacetate; Trimethylacetic acid / 12 h / 115 °C View Scheme

vanillin triflate (194018-68-3) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: caesium carbonate; palladium diacetate; 2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl / toluene / 12 h / 96 °C 2: potassium carbonate; palladium diacetate; Trimethylacetic acid / 12 h / 115 °C View Scheme

(2-methoxy-4-methylphenyl)phenylamine (808114-08-1) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 2 steps 1: potassium carbonate; Trimethylacetic acid; palladium diacetate / 12 h / 110 °C 2: 2,3-dicyano-5,6-dichloro-p-benzoquinone / water; methanol; tetrahydrofuran / 0.5 h / 20 °C View Scheme

2-methoxy-4-methylaniline (39538-68-6) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: C19H19N5O; copper(l) iodide; potassium carbonate / water / 24 h / 100 °C / Green chemistry 2: potassium carbonate; Trimethylacetic acid; palladium diacetate / 12 h / 110 °C 3: 2,3-dicyano-5,6-dichloro-p-benzoquinone / water; methanol; tetrahydrofuran / 0.5 h / 20 °C View Scheme

iodobenzene (591-50-4) → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: C19H19N5O; copper(l) iodide; potassium carbonate / water / 24 h / 100 °C / Green chemistry 2: potassium carbonate; Trimethylacetic acid; palladium diacetate / 12 h / 110 °C 3: 2,3-dicyano-5,6-dichloro-p-benzoquinone / water; methanol; tetrahydrofuran / 0.5 h / 20 °C View Scheme

5-methoxy-2'-nitrobiphenyl-3-carboxylic acid methyl ester → murrayanine (723-97-7)

Conditions	Yield
Multi-step reaction with 3 steps 1: triphenylphosphine / 1,2-dichloro-benzene / 10 h / Reflux 2: diisobutylaluminium hydride / toluene; diethyl ether / 2 h / -78 °C / Inert atmosphere 3: manganese(IV) oxide / tetrachloromethane / 12 h / 20 °C View Scheme

murrayanine (723-97-7) → 3,3'-dihydroxy-1,1'-dimethoxy-4,4'-bis(9,9'H-carbazole)

Conditions	Yield
With potassium hydrogensulfate; dihydrogen peroxide In methanol at 20℃; for 1h; Dakin Phenol Oxidation; Inert atmosphere;	93%

murrayanine (723-97-7) → koenoline (3909-78-2)

Conditions	Yield
With potassium borohydride In methanol at 25℃; for 17h;	90%
With sodium tetrahydroborate In methanol at 0 - 20℃; for 0.75h;	90%
With potassium borohydride In methanol at 25℃; Yield given;
With sodium tetrahydroborate In methanol for 24h;	20 mg
With methanol; sodium tetrahydroborate at 20℃; for 24h;

murrayanine (723-97-7) → 1-hydroxy-9H-carbazole-3-carbaldehyde

Conditions	Yield
With boron tribromide In dichloromethane 1.) 0 deg C, 3 h, 2.) r.t., overnight;	90%
Stage #1: murrayanine With aluminum (III) chloride In benzene for 6h; Reflux; Stage #2: With hydrogenchloride In water

murrayanine (723-97-7) → 1-methoxy-9H-carbazol-3-yl formate

Conditions	Yield
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 0.333333h; Baeyer-Villiger Ketone Oxidation; Inert atmosphere;	65%

murrayanine (723-97-7) → 1-methoxy-3-methylcarbazole (4532-33-6) + koenoline (3909-78-2)

Conditions	Yield
With amalgamated zinc In ethanol Heating;

murrayanine (723-97-7) → koenoline acetate

Conditions	Yield
Multi-step reaction with 2 steps 1: 20 mg / NaBH4 / methanol / 24 h 2: 3 mg / pyridine / 120 h View Scheme

Upstream product

• 3909-78-2 koenoline 
• 4532-33-6 1-methoxy-3-methylcarbazole 
• 39538-68-6 2-methoxy-4-methylaniline 
• 41608-64-4 methyl 3-methoxy-4-aminobenzoate 
• 808114-06-9 3-methoxy-4-(phenylamino)benzaldehyde 
• 954378-08-6 4-[(2-bromophenyl)amino]-3-methoxybenzaldehyde 
• 954378-09-7 3-(2-bromophenyl)-2,3,4,5,6,7-hexahydro-2-oxobenzoxazol-6-carboxaldehyde 
• 954378-10-0 3-(2-bromophenyl)-2,3-dihydro-2-oxobenzoxazol-6-carboxaldehyde 
• 189953-32-0 3-(2-Bromo-phenyl)-4,5-dimethylene-oxazolidin-2-one 
• 153897-88-2 4,5-dimethylene-3-phenyl-1,3-oxazolidin-2-one 
• 808114-01-4 3-hydroxy-4-(phenylamino)benzaldehyde 
• 808114-05-8 2,3-dihydro-2-oxo-3-phenylbenzo[d]oxazole-6-carbaldehyde 
• 808113-99-7 2,3,4,5,6,7-hexahydro-2-oxo-3-phenylbenzo[d]oxazole-6-carbaldehyde 
• 23523-94-6 1-methoxy-3-methoxycarbonyl-9H-carbazole 

Downstream Products

• 4532-33-6 1-methoxy-3-methylcarbazole 
• 3909-78-2 koenoline 

Relevant articles and documents

KOENOLINE, A FURTHER CYTOTOXIC CARBAZOLE ALKALOID FROM MURRAYA KOENIGII

Koenoline, a carbazole alkaloid, has been isolated from the root bark of Murraya koenigii for the first time as a natural product.Its structure was established as 1-methoxy-3-hydroxymethylcarbazole by analysis of spectroscopic data and was confirmed by pa

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A Suzuki-Miyaura cross coupling, followed by triphenylphosphine mediated Cadogan reductive cyclization sequence provided efficient access to a series of carbazole alkaloids. In the present work, this approach was applied to the total synthesis of mukonine, clauszoline K, koenoline, murrayanine, murrayafoline A, mukoeic acid, glycoborine, glycozolicine, mukolidine, mukoline, glycozoline, 3-methoxy-9H-carbazole-1-carboxylic acid methyl ester, (3-methoxy-9H-carbazol-1-yl)-methanol, 3-methoxy-9H-carbazole-1-carbaldehyde, 3-methoxy-9H-carbazole-1-carboxylic acid, 2-methyl-9H-carbazole and nonsteroidal anti-inflammatory drug (NSAID) carprofen and its derivatives.

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