CN104529888A - Preparation method of quinoline compound - Google Patents

Preparation method of quinoline compound Download PDF

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Publication number
CN104529888A
CN104529888A CN201510028169.2A CN201510028169A CN104529888A CN 104529888 A CN104529888 A CN 104529888A CN 201510028169 A CN201510028169 A CN 201510028169A CN 104529888 A CN104529888 A CN 104529888A
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preparation
alcohol
additive
catalyzer
triphenylphosphine
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吴彦超
李惠静
朱帅
李峰
文迈
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Jiangsu Lan Jian Pharmaceutcal Corp Ltd
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Jiangsu Lan Jian Pharmaceutcal Corp Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D215/18—Halogen atoms or nitro radicals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a preparation method of a quinoline compound. The preparation method comprises a step of enabling 2-nitrobenzyl alcohol, alcohol, a catalyst and an additive to react at 110-180 DEG C for 1-24 hours. According to the preparation method, the quinoline compound is prepared through one step by taking 2-nitrobenzyl alcohol and alcohol as raw materials; and the preparation method has the characteristics of stable and easily-available raw materials, economy and environment-friendliness, good repeatability, suitability for industrial production and the like.

Description

A kind of preparation method of quinolines
Technical field
The present invention relates to a kind of with nitro alcohol and alcohol for the method for quinoline prepared by raw material.
Background technology
Chinoline backbone is extensively present in bioactive natural product (Nat.Prod.Rep.2007,24,223; Nat.Prod.Rep.2008,25,166.), functional materials (J.Am.Chem.Soc.2005,127,1614; Org.Lett.2012,14,1012) (Bioorg.Med.Chem.Lett.2012,22,1643 and in drug molecule; Eur.J.Med.Chem.2012,57,29; RSC Adv.2013,3,2942; Bioorg.Med.Chem.Lett.2014,24,1734; Org.Biomol.Chem.2014,12,255; Bioorg.Med.Chem.Lett.2014,24,1790), its synthesis is one of study hotspot of Synthetic Organic Chemistry circle (Curr.Org.Chem.2008,12,1116 always; Chem.Asian J.2009,4,1036; Chem.Rev.2009,109,2652; RSC Adv.2014,4,24463).In existing quinoline synthetic method, quinoline synthesis remains the simplest and the most direct method (Chem.Rev.2009,109,2652). raw material normally 2-amino benzaldehyde compound and the alpha-methylene aldehyde ketone (Chem.Rev.2009,109,2652) of quinoline synthesis.Easily there is self-condensation reaction in 2-amino benzaldehyde compound, limits the use range of quinoline synthesis and versatility (Chem.Rev.2009,109,2652).In order to overcome this intrinsic problem, 2-amino benzaldehyde compound is protected, deprotection again in reaction process, but such a process increases reactions steps (Tetrahedron Lett.2005,46,3493; Tetrahedron:Asymmetry 1995,6,1245).Another kind method is for raw material with 2-aminobenzyl alcohol compounds, in reaction process, oxidation generates 2-amino benzaldehyde compound, but this method needs extra oxygenant, do not meet Atom economy and green chemical concept (Chem.Commun.2001,2576; J.Org.Chem.2008,73,9778; J.Org.Chem.2008,73,8608; Eur.J.Org.Chem.2008,1625; J.Mol.Catal.A:Chem.2009,299,117.).
Summary of the invention
The object of the invention be to provide a kind of with nitro alcohol and alcohol for the method for quinoline prepared by raw material.The method obtains quinolines with nitro alcohol and alcohol for raw material one step, have that raw material stable is easy to get, economic environmental protection, reproducible, be applicable to the features such as suitability for industrialized production.
For achieving the above object, a kind of preparation method of the quinolines as shown in formula III, key step is:
Such as formula the nitro alcohol shown in I, such as formula the alcohol alcohol shown in II, catalyzer and additive react 1 ~ 24 hour at 110 ~ 180 DEG C of temperature, obtain quinolines;
Wherein R 1, R 2, R 3, R 4and R 5for hydrogen atom, alkyl, aryl, halogen, alkoxyl group, aryloxy, trifluoromethyl etc.; R 6and R 7for hydrogen atom, alkyl, aryl; R 1, R 2, R 3, R 4and R 5for same group or be selected from different groups.
Described catalyzer is two (diphenylphosphine) ferrocene of 1,1'-, triphenylphosphine ruthenium chloride, triphenylphosphine palladium chloride, triphenylphosphine iridium chloride, triphenylphosphine rhodium chloride, triphenylphosphine cuprous chloride.
Preferred catalyst is two (diphenylphosphine) ferrocene of 1,1'-.
Described additive is sodium carbonate, salt of wormwood, potassium hydroxide, sodium hydride, sodium ethylate, potassium tert.-butoxide.
Preferable additives is sodium carbonate.
Described is 1:2-1:4 such as formula the nitro alcohol shown in I with such as formula the mol ratio of the alcohol shown in II.
The described mol ratio such as formula the nitro alcohol shown in I and catalyzer is 1:0.01-1:0.10.
The described mol ratio such as formula the nitro alcohol shown in I and additive is 1:0.5-1:1.5.
Described preparation method carries out in toluene, chlorobenzene medium.
Described catalyzer is two (diphenylphosphine) ferrocene of 1,1'-, and the mol ratio such as formula the nitro alcohol shown in I and catalyzer is 1:0.05; Described additive is sodium carbonate, and the mol ratio such as formula the nitro alcohol shown in I and additive is 1:1; Reaction is carried out under toluene medium.
Preparation method provided by the invention, key step is: nitro alcohol, alcohol, and catalyzer and additive react 1 ~ 24 hour at 110 ~ 180 DEG C of temperature.Reaction terminates rear diatomite filtration, organic solvent washing, concentrated, and column chromatography is purified, and obtain quinolines, productive rate is 50 ~ 90%.Gained compound through nmr spectrum ( 1h-NMR and 13c-NMR) and infrared spectra confirm, high resolution is determined, structure is errorless.
The present invention adopts and replaces or do not replace nitro alcohol and alcohol compound can directly commercially.
Column chromatography of the present invention eluent used is sherwood oil or alkane etc.
Beneficial effect:
Consider that 2-amino benzaldehyde compound is prepared through nitroreduction etc. by ortho-nitrophenyl aldehyde compound usually, and alpha-methylene group compounds of aldehydes and ketones usually prepares (Org.Lett.2003,5,4257 by alcohol through alcohol oxidation; Org.Biomol.Chem.2007,5,61; Synthesis 2010,1678; J.Org.Chem. 2010,75,3488.).The present invention with nitro alcohol compounds and alcohol compound for raw material, in reaction process, alcohol compound is reduced into 2-amino benzaldehyde compound nitro alcohol compounds, and nitro alcohol compounds is oxidized to group compounds of aldehydes and ketones alcohol compound simultaneously, the 2-amino benzaldehyde compound of generation and group compounds of aldehydes and ketones pass through cyclization, generates quinolines.The method successfully avoid use instability and expensive ortho-nitrophenyl aldehyde compound is raw material, obtain quinolines with stable nitro alcohol compounds and the alcohol compound of being easy to get for raw material one step, have economic environmental protection, substituting group versatile and flexible, reproducible, be applicable to the features such as suitability for industrialized production.
Embodiment
Its reaction process is as follows:
Wherein R 1, R 2, R 3, R 4and R 5for hydrogen atom, alkyl, aryl, halogen, alkoxyl group, aryloxy, trifluoromethyl etc.; R 6and R 7for hydrogen atom, alkyl, aryl; R 1, R 2, R 3, R 4and R 5for same group or be selected from different groups;
Embodiment 1
0.5 mmole nitro alcohol, 1.1 mmole phenylethyl alcohols, 0.05 mmole 1, two (diphenylphosphine) ferrocene (catalyzer) of 1'-, 0.5 mmole sodium carbonate (additive) and 1 milliliter of toluene mix, abundant stirring reaction 24 hours (tube sealing reaction) at 150 DEG C of temperature.Reaction terminates rear diatomite filtration, organic solvent washing, concentrated, and column chromatography is purified, and obtain 2-phenylquinoline, yield is 70%.Fusing point is 82 ~ 84 DEG C (reference value is 81.9 ~ 83.6 DEG C, reference Org.Lett.2012,14,4818); Proton nmr spectra 1h NMR (Bruker AVANCE III 400MHz, CDCl 3) δ 8.26 – 8.16 (m, 4H), 7.88 (d, J=8.6Hz, 1H), 7.83 (d, J=8.1Hz, 1H), 7.74 (t, J=7.8Hz, 1H), 7.58 – 7.44 (m, 4H); Carbon-13 nmr spectra 13c NMR (Bruker AVANCE III 100MHz, CDCl 3) δ 157.3,148.1,139.4,136.9,129.7,129.6,129.4,128.8,127.6,127.4,127.2,126.3,119.0; Infrared spectra FTIR (Nicolet 380, film, 25 DEG C): 2922,2851,1598,1554,1493,1446,1423,1320,1285,1256,1177,1028,831,813,773. high resolution mass spectrum HRMS (Thermo Orbitrap, ESI) m/z:Calcd for C 15h 11nNa [M+Na] +: 228.0784.Found:228.0761.
Embodiment 2
0.5 mmole 5-fluorine nitro alcohol, 1.1 mmole 4-anisole ethanol, 0.05 mmole triphenylphosphine ruthenium chloride (catalyzer), 0.5 mmole salt of wormwood (additive) and 1 milliliter of chlorobenzene mix, abundant stirring reaction 24 hours (tube sealing reaction) at 110 DEG C of temperature.Reaction terminates rear diatomite filtration, organic solvent washing, concentrated, and column chromatography is purified, and obtain 2-(4-p-methoxy-phenyl) 6-fluorine quinoline, yield is 60%.Faint yellow solid; Fusing point is 111 – 113 DEG C; Proton nmr spectra 1h NMR (Bruker AVANCE III 400MHz, CDCl 3) δ 8.16 – 8.06 (m, 4H), 7.84 (d, J=8.1Hz, 1H), 7.77 (s, 1H), 7.64 (d, J=8.1Hz, 1H), 7.05 (d, J=7.2Hz, 2H), 3.89 (s, 3H); Carbon-13 nmr spectra 13c NMR (Bruker AVANCE III 100MHz, CDCl 3) δ 161.0,160.2 (d, 1j c-F=245.8Hz, 1C), 156.2 (d, 4j c-F=2.2Hz, 1C), 145.2,136.1 (d, 4j c-F=5.1Hz, 1C), 131.8 (d, 3j c-F=9.3Hz, 1C), 131.7,128.8,127.4 (d, 3j c-F=9.9Hz, 1C), 119.7 (d, 2j c-F=25.5Hz, 1C), 119.3,114.3,110.5 (d, 2j c-F=21.5Hz, 1C), 55.4; Infrared spectra FTIR (Nicolet380, film, 25 DEG C): 2920,2850,1600,1548,1498,1487,1468,1322,1288,1255,1177,1114,1028,886,871,849,832,813cm -1. high resolution mass spectrum HRMS (Thermo Orbitrap, ESI) m/z:Calcd for C 16h 12fNNaO [M+Na] +: 276.0795.Found:276.0778.
Embodiment 3
0.5 mmole O-Nitrophenylfluorone methylol, 1.1 mmole phenylethyl alcohols, 0.05 mmole triphenylphosphine iridium chloride (catalyzer), 1.0 mmole potassium hydroxide (additive) and 1 milliliter of toluene mix, abundant stirring reaction 1 hour (tube sealing reaction) at 180 DEG C of temperature.Reaction terminates rear diatomite filtration, organic solvent washing, concentrated, and column chromatography is purified, and obtain 2-phenyl-4-toluquinoline, yield is 90%.Faint yellow solid; Fusing point is 65 – 67 DEG C; Proton nmr spectra 1h NMR (Bruker AVANCE III 400MHz, CDCl 3) δ 8.24 (d, J=8.4Hz, 1H), 8.19 (d, J=7.2Hz, 2H), 7.97 (d, J=8.1Hz, 1H), 7.77 – 7.46 (m, 6H), 2.73 (s, 3H); Carbon-13 nmr spectra 13c NMR (Bruker AVANCE III 100MHz, CDCl 3) δ 157.0,148.1,144.7,139.8,130.3,129.2,129.1,128.7,127.5,127.2,125.9,123.5,119.6,18.9; Infrared spectra FTIR (Nicolet 380, film, 25 DEG C): 2922,2851,1597,1551,1509,1495,1451,1348,1079,1029,861,769,694cm -1. high resolution mass spectrum HRMS (Thermo Orbitrap, ESI) m/z:Calcd for C 16h 14n [M+H] +: 220.1121.Found:220.1120.
Embodiment 4
0.5 mmole nitro alcohol, 1.1 mmole 2-phenylethyl alcohols, 0.05 mmole triphenylphosphine rhodium chloride (catalyzer), 1.5 mmole potassium tert.-butoxide (additive) and 1 milliliter of toluene mix, abundant stirring reaction 12 hours (tube sealing reaction) at 150 DEG C of temperature.Reaction terminates rear diatomite filtration, organic solvent washing, concentrated, and column chromatography is purified, and obtain 3-phenylquinoline, yield is 68%.Faint yellow solid; Fusing point is 49 – 51 DEG C; Proton nmr spectra 1h NMR (Bruker AVANCE III 400MHz, CDCl 3) δ 9.07 (s, 1H), 8.18 (s, 1H), 8.06 (d, J=7.7Hz, 1H), 7.75 (d, J=7.3Hz, 1H), 7.61 – 7.30 (m, 7H); Carbon-13 nmr spectra 13c NMR (Bruker AVANCE III 100MHz, CDCl 3) δ 149.5,146.9,137.6,133.8,133.4,129.4,129.1,128.9,128.1,128.0,127.9,127.3,127.0; Infrared spectra FTIR (Nicolet 380, film, 25 DEG C): 2922,2851,1659,1633,1493,1469,1449,1412,1363,1341,1125,1077,1026,954,787,762,697cm -1. high resolution mass spectrum HRMS (Thermo Orbitrap, ESI) m/z:Calcd for C 15h 11nNa [M+Na] +: 228.0784.Found:228.0776.
Embodiment 5
0.5 mmole nitro alcohol, 1.1 mmole butanols, 0.05 mmole triphenylphosphine chlorination Asia-Pacific copper (catalyzer), 0.5 mmole sodium hydride (additive) and 1 milliliter of toluene mix, abundant stirring reaction 18 hours (tube sealing reaction) at 150 DEG C of temperature.Reaction terminates rear diatomite filtration, organic solvent washing, concentrated, and column chromatography is purified, and obtain 2-propyl group quinoline, yield is 61%.Colourless liquid; Proton nmr spectra 1h NMR (Bruker AVANCE III 400MHz, CDCl 3) δ 8.08 (d, J=8.3Hz, 1H), 8.06 (d, J=8.2Hz, 1H), 7.78 – 7.46 (m, 3H), 7.29 (d, J=8.4Hz, 1H), 2.96 (t, J=7.8Hz, 2H), 1.90 – 1.79 (m, 2H), 1.02 (t, J=7.3Hz, 3H); Carbon-13 nmr spectra 13c NMR (Bruker AVANCE III 100MHz, CDCl 3) δ 162.8,147.5,136.4,129.4,128.5,127.4,126.7,125.7,121.3,41.0,23.2,13.9; Infrared spectra FTIR (Nicolet 380, film, 25 DEG C): 2960,2929,2871,1618,1601,1561,1508,1464,1426,1310,1116,825,755cm -1. high resolution mass spectrum HRMS (Thermo Orbitrap, ESI) m/z:Calcd for C 12h 14n [M+H] +: 172.1121.Found:172.1113..

Claims (10)

1., such as formula a preparation method for the quinolines shown in I, key step is:
Nitro alcohol, alcohol, catalyzer and additive react 1 ~ 24 hour at 110 ~ 180 DEG C of temperature, obtain quinolines;
Wherein R 1, R 2, R 3, R 4and R 5for hydrogen atom, alkyl, aryl, halogen, alkoxyl group, aryloxy, trifluoromethyl etc.; R 6and R 7for hydrogen atom, alkyl, aryl; R 1, R 2, R 3, R 4and R 5for same group or be selected from different groups.
2. preparation method according to claim 1, is characterized in that: described catalyzer is two (diphenylphosphine) ferrocene of 1,1'-, triphenylphosphine ruthenium chloride, triphenylphosphine palladium chloride, triphenylphosphine iridium chloride, triphenylphosphine rhodium chloride, triphenylphosphine cuprous chloride.
3. preparation method according to claim 2, is characterized in that: described catalyzer is two (diphenylphosphine) ferrocene of 1,1'-.
4. preparation method according to claim 1, is characterized in that: described additive is sodium carbonate, salt of wormwood, potassium hydroxide, sodium hydride, sodium ethylate, potassium tert.-butoxide.
5. preparation method according to claim 4, is characterized in that: described additive is sodium carbonate.
6. preparation method according to claim 1, is characterized in that: described nitro alcohol and the mol ratio of alcohol are 1:2-1:4.
7. preparation method according to claim 1, is characterized in that: described nitro alcohol and the mol ratio of catalyzer are 1:0.01-1:0.10.
8. preparation method according to claim 1, is characterized in that: described nitro alcohol and the mol ratio of additive are 1:0.5-1:1.5.
9. preparation method according to claim 1, is characterized in that: described preparation method carries out in toluene, chlorobenzene medium.
10. preparation method according to claim 1, is characterized in that: described catalyzer is two (diphenylphosphine) ferrocene of 1,1'-, and the mol ratio of nitro alcohol and catalyzer is 1:0.05; Described additive is sodium carbonate, and the mol ratio of nitro alcohol and additive is 1:1; Reaction is carried out under toluene medium.
CN201510028169.2A 2015-01-20 2015-01-20 Preparation method of quinoline compound Pending CN104529888A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105001156A (en) * 2015-06-30 2015-10-28 李公元 Three-ingredient reaction system synthetic method of quinoline derivative

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102134219A (en) * 2010-12-31 2011-07-27 华东理工大学 Preparation method of quinoline derivative

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102134219A (en) * 2010-12-31 2011-07-27 华东理工大学 Preparation method of quinoline derivative

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
FENG XIE，ET AL.: "Convenient Synthesis of Quinolines from α-2-Nitroaryl Alcohols and Alcohols via a Ruthenium-catalyzed Hydrogen Transfer Strategy", 《CHEMCATCHEM》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105001156A (en) * 2015-06-30 2015-10-28 李公元 Three-ingredient reaction system synthetic method of quinoline derivative
CN105001156B (en) * 2015-06-30 2017-08-04 河南科技大学第一附属医院 A kind of three component reaction system synthetic methods of quinoline

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Application publication date: 20150422