CN105566218A - Palladium carbon catalyzed selective partial dehydrogenation method of tetrahydroisoquinoline - Google Patents

Palladium carbon catalyzed selective partial dehydrogenation method of tetrahydroisoquinoline Download PDF

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CN105566218A
CN105566218A CN201410539445.7A CN201410539445A CN105566218A CN 105566218 A CN105566218 A CN 105566218A CN 201410539445 A CN201410539445 A CN 201410539445A CN 105566218 A CN105566218 A CN 105566218A
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reaction
tetrahydroisoquinoline
palladium carbon
dehydrogenation
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周永贵
时磊
姬悦
陈木旺
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Dalian Institute of Chemical Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention relates to a method for synthesis of 1-substituted-3, 4-dihydroisoquinoline by palladium carbon catalyzed selective partial dehydrogenation of a 1-substituted-1, 2, 3, 4-tetrahydroisoquinoline compound. The reaction temperature is 0-80DEG C. For easily available cyclic amine compounds like tetrahydroisoquinoline, a corresponding imine compound can be obtained through selective dehydrogenation, the conversion rate is up to 99%, and the proportion of a partial dehydrogenation product and a complete dehydrogenation product is greater than 20:1. The method provided by the invention has simple and practical operation, the raw materials and catalyst are cheap and easily available, the reaction conditions are mild, and the catalyst can be recycled, thus greatly reducing the actual cost. In addition, the method for synthesis of 3, 4-dihydroisoquinoline through direct dehydrogenation of tetrahydroisoquinoline has the advantages of atom economy and environmental friendliness.

Description

The method of the tetrahydroisoquinoline selectivity partial of a kind of palladium carbon catalysis
Technical field
The present invention relates to a kind of method that selectivity partial by palladium carbon catalysis 1-replacement-1,2,3,4-tetrahydroisoquinolines synthesizes 1-replacement-3,4-tetrahydro isoquinoline compounds.
Background technology
Imines is with the most frequently used, the most important substrate of a class in Synthetic Organic Chemistry, as the addition reaction of cyclization, nucleophilic reagent.By the direct oxidation dehydrogenation synthesizing imine of amine, it is also the very important synthetic method of a class.But, often need the oxygenant or hydrogen acceptor (reference 1:(a) OritoK., HatakeyamaT., TakeoM., UchiitoS., TokudaM., the SuginomeH.Tetrahedron1998 that add equivalent, 54,8403; (b) AjzertK.I., Tak á csK.LiebigsAnn.Chem.1987,1061; (c) KhatriP.K., JainS.L., SivakumarK.L.N., SainB.Org.Biomol.Chem.2011,9,3370; (d) YaoW., ZhangY., JiaX., HuangZ.Angew.Chem.Int.Ed.2014,53,1390; (e) ChoiH., DoyleM.P.Chem.Commun.2007,745), as elemental iodine, sulphur, peroxy tert-butyl alcohol, tert-butyl vinyl etc.In addition, using trichloroisocyanuric acid or t-butyl hypochlorate as oxygenant (reference 2:(a) BolchiC., PallaviciniM., FumagalliL., StranieroV., ValotiE.Org.Process.Res.Dev.2013,17,432; (b) ScullyF.E., SchlagerJ.J.Heterocycles, 1982,19,653.), be oxidized through the form of nitrogen halogenation and dehydrochlorination two step, the synthesis of imines can be realized equally.And the dehydrogenation of transition metal-catalyzed organic compound provides, and one has Atom economy, eco-friendly synthesis strategy introduces unsaturated double-bond, as carbon-carbon double bond, carbon-to-nitrogen double bon, C=O bond (reference 3:ChoiJ., MacArthurA.H.R., BrookhartM., GoldmanA.S.ChemRev, 2011,111,1761; (b) EssweinA.J., NoceraD.G., Chem.Rev.2007,107,4022; (c) DobereinerG.E., CrabtreeR.H.Chem.Rev.2010,110,681.), successfully avoid adding of harmful equivalent oxygenant.In the past few decades, the dehydrogenation reaction of nitrogen heterocyclic has attracted broad interest (reference 4:LuS.-M., WangY.-Q., HanX.-W., ZhouY.-G.Chin.J.Catal.2005, the 26:287 of scientists equally; (b) WangD.-W., WangX.-B., WangD.-S., LuS.-M., ZhouY.-G., LiYX.J.Org.Chem.2009,74,2780.).
Relevant study mechanism shows the dehydrogenation of nitrogen heterocyclic through a high reactivity cyclic imide intermediate, subsequently further dehydroaromatizationof (reference 5:(a) LiH., JiangJ., LuG., HuangF., WangZ.X.Organometallics, 2011,30,3131; (b) ZhangX.-B., XiZ.Phys.Chem.Chem.Phys.2011,13,3997.).In theory, imine intermediate can be obtained by controlling nitrogen heterocyclic dehydrogenation reaction conditions.But, the fresh rare report obtaining the example of cyclic imide through partial.Up to date, Stahl group (reference 6:WendlandtA.E., StahlS.S.J.Am.Chem.Soc.2014,136,506.) aerobic oxidation that successfully reports the complex-catalyzed amine of a kind of zinc/quinone of difunctionalization obtains the reaction of imines, and achieve excellent yield.Turner group (reference 7:GhislieriD., GreenA.P., PontiniM., WilliesS.C., RowlesI., FrankA., GroganG., TurnerN.J.J.Am.Chem.Soc.2013,135,10863.) creatively ammonia oxidase MAO-ND11C is applied to the selective oxidation of amine.Nitrogen heterocyclic dehydrogenation reaction is more prone to be formed the product of the complete dehydrogenation with fragrant stability, and imine intermediate is a kind of transient state intermediate in certain embodiments.The dehydrogenation how highly selective realizes nitrogen heterocyclic remains one of challenging problem of this field most.The conclusive problem being badly in need of solving suppresses aromatization products, thus improve dehydrogenation selectivity.Consider that complete dehydrogenation product and partial product are all very important organic synthesis skeletons, so it is significant for developing a kind of efficient, controlled nitrogen heterocyclic dehydrogenation systems.
Heterogeneous catalyst Pd/C has catalytic dehydrogenation activity to tetrahydro isoquinoline compound, but reaction preference is poor, produces the aromatization products isoquinoline 99.9 of complete dehydrogenation simultaneously.By experiment, the selectivity (reference 8:JinQ., JiaG., ZhangY., LiC., Catal.Sci.Technol.2014,4,464.) that can significantly improve reaction is in the presence of an inorganic base found.Utilize this strategy, we successfully achieve the selectivity partial of 1,2,3,4-tetrahydroisoquinoline.The reaction path of this kind of easy, atom economy, high chemo-selective for partial of tetrahydroisoquinoline provides.In addition, repeatedly, activity and selectivity can keep all right recycling use of heterogeneous catalyst Pd/C substantially.
Summary of the invention
The object of the invention is the method that a kind of 1,2,3,4-tetrahydroisoquinoline selectivity partial by Pd/C catalysis of development synthesizes 3,4-dihydro-isoquinoline.
The present invention's practicality simple to operate, raw material and Pd/C catalyzer cheap and easy to get, and can catalyst recycling be realized.This reaction conditions is gentle, and by direct dehydrogenation synthesising target compound, thus reaction has green Atom economy.
For achieving the above object, the present invention using palladium carbon as dehydrogenation catalyst, three water potassiumphosphates as additive, to realize the selectivity partial of tetrahydroisoquinoline.
Technical scheme of the present invention is as follows:
The present invention is to provide a kind of method that 1,2,3,4-tetrahydroisoquinoline selectivity partial by Pd/C catalysis synthesizes 3,4-dihydro-isoquinoline, its synthetic route is as follows:
In formula:
Temperature: 0-80 DEG C;
Solvent: acetonitrile;
Time: 10-22 hour;
Catalyzer: palladium carbon;
Additive: alkali;
Described R 1, R 2for the alkyl of C1-C10, the alkoxyl group of C1-C10, the one in halogen (F, Cl, Br or I);
Described R 3for the alkyl of C1-C10, or phenyl and containing substituent phenyl ring, the substituting group on phenyl ring is F, Cl, CF 3, a kind of substituting group in Me, MeO or two kinds of substituting groups or three kinds of substituting groups;
Described additive is three water potassiumphosphates, sodium carbonate, cesium carbonate, salt of wormwood, the one in potassium tert.-butoxide;
Described palladium carbon to be commercial available quality mark be 5% palladium carbon;
Reactions steps is:
In oxygen atmosphere or air, to in the reaction flask filling the Pd/C 40mol% of substrate (in the formula 1) and three water the potassiumphosphates 20mol% of substrate (in the formula 1), add solvent, stirring at room temperature number minute, again substituted tetrahydroisoquinolicompounds is added reaction system, stirring reaction 12-22 hour at 0-80 DEG C.Filter palladium-carbon catalyst, direct column chromatography obtains corresponding partial product.And the palladium-carbon catalyst in reaction can realize recycle.
Described catalyzer is palladium carbon (massfraction is 5%PdonCarbon), for commercially available palladium carbon and without the need to carrying out any process.
Described additive is inorganic alkali compound.The mineral alkali reacting used is three water potassiumphosphates, sodium carbonate, cesium carbonate, salt of wormwood, potassium tert.-butoxide.In reaction, the mol ratio of usage quantity and substituted tetrahydroisoquinolicompounds is 1:5.
Described reaction solvent is one or both the mixing in acetonitrile, normal hexane, ether, methylene dichloride, toluene, Isosorbide-5-Nitrae-dioxane, methyl alcohol.
Described temperature of reaction is 0-80 DEG C.
The present invention has the following advantages
1. use comparatively cheap Pd/C as catalyzer, and can recycle.
2. reaction conditions is gentle, without the need to adding equivalent oxygenant.
3. the selectivity of product is good, can obtain partial product with high yield.
Formula 1 is Pd/C catalysis substituted tetrahydroisoquinolicompounds selective dehydrogenation synthetic compound 2.
Embodiment
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to following embodiment.
Embodiment 1
The optimization of condition:
In oxygen atmosphere or air, the acetonitrile of 3 milliliters is added in the reaction flask being added with the Pd/C 40mol% of substrate (in the formula 1), the three water potassiumphosphates 20mol% of substrate (in the formula 1), after stirring at room temperature number minute, add 1-phenyl-1 again, 2,3,4-tetrahydroisoquinoline (0.125mmol), and at 60 DEG C after stirring reaction 12-22 hour, filter Pd/C, concentrated, direct column chromatography (eluent: the volume ratio of sherwood oil and ethyl acetate is 5:1), obtain target product 1-phenyl-3,4-dihydro-isoquinoline.Its reaction formula is as follows:
Its transformation efficiency and two kinds of proportion of products are by reacting coarse product 1hNMR determines, refers to table 1.
The optimization of table 1.Pd/C catalysis substituted tetrahydroisoquinolicompounds selective dehydrogenation reaction conditions a
aConditions:1(0.125mmol),Pd/C(40mol％),K 3PO 4·3H 2O(20mol％),Solvents(3mL).
bDeterminedby 1HNMRspectroscopyanalysisofthecrudeproducts.
c.O 2balloon.
Embodiment 2
Palladium carbon catalytic selectivity partial synthesis 3,4-dihydro-isoquinoline product 2:
In oxygen atmosphere or air, the acetonitrile of 4 milliliters is added in the reaction flask being added with the Pd/C 40mol% of substrate (in the formula 1), the three water potassiumphosphates 20mol% of substrate (in the formula 1), after stirring at room temperature number minute, add 1-phenyl-1 again, 2,3,4-tetrahydroisoquinoline (0.3mmol), and at 60 DEG C after stirring reaction 12-22 hour, filter Pd/C, concentrated, direct column chromatography (eluent: the volume ratio of sherwood oil and ethyl acetate is 5:1), obtain target product 3,4-dihydro-isoquinoline compound.Reaction formula is as follows:
Productive rate is separation yield, and partial product and the completely ratio of dehydrogenation product are slightly composed by nuclear-magnetism and determined, in table 2.
Table 2.Pd/C catalysis substituted tetrahydroisoquinolicompounds selective dehydrogenation synthesis 2 a
aConditions:1(0.3mmol),Pd/C(40mol％),K 3PO 4·3H 2O(20mol％),CH 3CN(4mL).
bDeterminedby 1HNMRspectroscopyanalysisofthecrudeproducts.
c.Isolatedyield.
d.Pd/C(20mol％).
1-Phenyl-3,4-dihydroisoquinoline(2a):86％yield,knowncompound,yellow 47.7,26.3.
1-Phenylisoquinoline(3a):knowncompound,whitesolid,R f＝0.93(ethyl 127.2,126.9,120.1.
1-(4-Chlorophenyl)-3,4-dihydroisoquinoline(2b):84％yield,known
1-(4-Methoxyphenyl)-3,4-dihydroisoquinoline(2c):89％yield,known 55.3,47.5,26.4.
1-m-Tolyl-3,4-dihydroisoquinoline(2d):82％yield,knowncompound, 127.9,127.4,126.6,126.0,47.7,26.4,21.4.
1-p-Tolyl-3,4-dihydroisoquinoline(2e):84％yield,knowncompound,whitesolid,R f＝0.45(petroleumether/ethylacetate2/1).mp＝73-74℃. 1HNMR 127.4,126.5,47.6,26.4,21.4.
1-(4-(Trifluoromethyl)phenyl)-3,4-dihydroisoquinoline(2f):82％yield,knowncompound,paleyellowsolid,R f＝0.60 2H)； 13CNMR(100MHz,CDCl3)δ166.3,142.5,138.7,131.8,131.4,131.1,129.2,128.4,127.6,127.5,125.2(q,J＝3.7Hz),124.1(q,J＝271Hz),47.8,26.2；19FNMR(376MHz,CDCl3)δ-62.66.
1-(Furan-2-yl)-3,4-dihydroisoquinoline(2g):88％yield,knowncompound, 151.7,144.0,138.9,130.8,127.6,127.5,126.9,126.8,113.1,111.2,47.0,26.2.
7-Methyl-1-phenyl-3,4-dihydroisoquinoline(2h):79％yield,known 167.6,139.4,136.3,136.0,131.5,129.4,129.0,128.9,128.6,128.3,127.4,48.1,26.2,21.4.
7-Chloro-1-phenyl-3,4-dihydroisoquinoline(2i):76％yield,known 2H),2.77-2.74(m,2H). 13CNMR(100MHz,CDCl 3)δ166.2,138.4,137.1,132.3,130.5,130.1,129.6,128.7,128.7,128.4,127.8,47.6,25.7.
7-Methoxy-1-phenyl-3,4-dihydroisoquinoline(2j):74％yield,knowncompound,colorlessoil,R f＝0.74(ethylacetate). 1HNMR(400MHz, 2H)； 13CNMR(100MHz,CDCl 3)δ167.2,158.2,138.9,130.9,129.5,129.3,128.8,128.2,128.2,116.1,113.8,55.4,48.1,25.5.
7-Methoxy-1-phenylisoquinoline(3j):10％yield,knowncompound,yellow 140.5,139.9,132.5,129.6,128.6,128.5,128.4,127.8,122.9,119.7,105.3,55.4.
6,7-Dimethoxy-1-phenyl-3,4-dihydroisoquinoline(2k):84％yield,known 3.78(m,2H),3.72(d,J＝2.7Hz,3H),2.72(dd,J＝10.3,4.3Hz,2H)； 13CNMR(100MHz,CDCl 3)δ166.7,151.0,147.1,139.2,132.6,129.3,128.8,128.1,121.6,111.7,110.3,56.2,56.0,47.7,26.0.
6,7-Dimethoxy-1-phenylisoquinoline(3k):7％yield,knowncompound,colorlessoil,R f＝0.82(dichloromethane/methanol15/1). 1HNMR(400MHz, 150.1,141.4,140.1,133.8,129.6,128.4,122.6,118.7,105.7,105.0,56.1,55.9.
1-Cyclohexyl-3,4-dihydroisoquinoline(2l):51％yield,knowncompound, 13CNMR(100MHz,CDCl 3)δ170.8,138.3,130.1,128.9,127.6,126.8,124.6,46.8,42.1,31.3,26.6,26.4,26.3.
1-Cyclohexylisoquinoline(3l):10％yield,knowncompound,yellowoil,R f＝0.82(ethylacetate). 1HNMR(400MHz,CDCl 3)δ8.48(d,J＝5.7Hz,1H), MHz,CDCl 3)δ165.9,142.1,136.6,129.7,127.7,127.0,126.5,124.9,119.0,41.7,32.8,27.1,26.4.
1-Cyclohexylidene-1,2,3,4-tetrahydroisoquinoline(4l):27％yield,unknowncompound,yellowoil,R f＝0.95(ethylacetate). 1HNMR(400MHz,CDCl 3)δ CDCl 3)δ171.0,139.4,130.4,128.1,126.9,126.6,126.4,73.9,45.8,36.7,27.1,25.6,22.2；HRMS:m/z[M+H] +calculatedforC 15H 20N:214.1590；found:214.1586.
The present invention successfully achieves the selectivity partial that 1-replaces-1,2,3,4-tetrahydroisoquinolines.The palladium carbon that the method uses industry to be easy to get, as catalyzer, under the acting in conjunction of alkaline additive, can realize the conversion completely of raw material, the separation yield of the highest acquisition 89%.For cyclic amine compound simple and easy to get as tetrahydro isoquinoline compound, obtain corresponding group with imine moiety by selective dehydrogenation, its transformation efficiency is up to 99%, and partial product and complete dehydrogenation product ratio are greater than 20:1.The present invention is easy to operation, and raw material and catalyzer are all cheap and easy to get, and reaction conditions is gentle, and catalyzer can realize recycle, greatly reduces real cost.In addition, by the method for tetrahydroisoquinoline direct dehydrogenation synthesis 3,4-dihydro-isoquinoline, there is Atom economy, eco-friendly advantage.

Claims (8)

1. a 1-replaces the method for-1,2,3,4-tetrahydro isoquinoline compound selectivity partial, and this method adopts palladium carbon as catalyzer, alkali as additive, its reaction formula and condition as follows:
In formula:
Temperature: 0-80 DEG C;
Solvent: organic solvent;
Time: 10-22 hour;
Catalyzer: palladium carbon;
Additive: inorganic alkali compound;
Described R 1, R 2be respectively the alkyl of C1-C10, the alkoxyl group of C1-C10, the one in halogen (F, Cl, Br or I);
Described R is the alkyl of C1-C10, phenyl and containing substituent phenyl ring, and the substituting group on phenyl ring is F, Cl, CF 3, one in Me, MeO or two kinds of substituting groups or three kinds of substituting groups.
2. the method for claim 1, is characterized in that:
Reactions steps is: in one or both mixtures in oxygen or air, to in the reaction flask filling the Pd/C 40mol% of substrate consumption (in the formula 1) and the inorganic alkali compound 20mol% of substrate consumption (in the formula 1), add solvent, stirring at room temperature is after ten minutes, again 1-is replaced-1,2,3,4-tetrahydroisoquinoline adds reaction system, stirring reaction 12-22 hour at 0-80 DEG C; Filter palladium carbon, direct column chromatography obtains corresponding partial product; Palladium-carbon catalyst in reaction can be recycled.
3. the method for claim 1, is characterized in that: described catalyzer is palladium carbon (massfraction 5%PdonCarbon), and it is for commercially available palladium carbon and without the need to carrying out any process.
4. the method for claim 1, is characterized in that: described additive is inorganic alkali compound, and the mineral alkali reacting used is three water potassiumphosphates, sodium carbonate, cesium carbonate, salt of wormwood, one or two or more kinds in potassium tert.-butoxide.
5. the method as described in claim 1,3 or 4, is characterized in that: in reaction, substrate substituted tetrahydroisoquinolicompounds and molecular proportion of catalyst are 5:2, and the mol ratio of substituted tetrahydroisoquinolicompounds and mineral alkali usage quantity is 5:1.
6. synthetic method as claimed in claim 1, is characterized in that: the organic solvent reacting used is one or more the mixing in acetonitrile, normal hexane, ether, methylene dichloride, toluene, Isosorbide-5-Nitrae-dioxane, methyl alcohol.
7. the synthetic method as described in claim 1 or 6, is characterized in that: when tetrahydroisoquinoline substrate consumption is 0.3mmol, and reacting consumption of organic solvent used is 4mL.
8. method as claimed in claim 1 or 2, it is characterized in that: described reaction formula is for replacing-1 to 1-, 2,3,4-tetrahydroisoquinoline obtains corresponding partial product 1-and replaces-3,4-dihydro-isoquinoline compounds, alkaline additive is three water potassiumphosphates, solvent is acetonitrile, and when temperature is 60 DEG C, described result is best, and Reaction Separation yield can reach 89%.
CN201410539445.7A 2014-10-11 2014-10-11 Palladium carbon catalyzed selective partial dehydrogenation method of tetrahydroisoquinoline Pending CN105566218A (en)

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CN114195713A (en) * 2022-01-12 2022-03-18 西安石油大学 Method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline
CN114516835A (en) * 2022-03-07 2022-05-20 西安石油大学 Synthetic method of alpha, alpha-disubstituted tetrahydroisoquinoline compounds

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Publication number Priority date Publication date Assignee Title
CN113617354A (en) * 2021-07-08 2021-11-09 南京红太阳生物化学有限责任公司 3-methylpiperidine dehydrogenation catalyst, and preparation method and application thereof
CN113617354B (en) * 2021-07-08 2023-06-27 南京红太阳生物化学有限责任公司 3-methylpiperidine dehydrogenation catalyst and preparation method and application thereof
CN114195713A (en) * 2022-01-12 2022-03-18 西安石油大学 Method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline
CN114195713B (en) * 2022-01-12 2023-11-17 广东众源药业有限公司 Method for synthesizing dihydroisoquinoline by catalyzing selective dehydrogenation of tetrahydroisoquinoline
CN114516835A (en) * 2022-03-07 2022-05-20 西安石油大学 Synthetic method of alpha, alpha-disubstituted tetrahydroisoquinoline compounds
CN114516835B (en) * 2022-03-07 2023-08-15 西安石油大学 Synthesis method of alpha, alpha-disubstituted tetrahydroisoquinoline compound

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