CN102977007A - Method for synthesizing 3-aryl pyridine derivative - Google Patents
Method for synthesizing 3-aryl pyridine derivative Download PDFInfo
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- CN102977007A CN102977007A CN2012105663863A CN201210566386A CN102977007A CN 102977007 A CN102977007 A CN 102977007A CN 2012105663863 A CN2012105663863 A CN 2012105663863A CN 201210566386 A CN201210566386 A CN 201210566386A CN 102977007 A CN102977007 A CN 102977007A
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Abstract
The invention discloses a method for synthesizing a 3-aryl pyridine derivative. A palladium compound is used to catalyze substituted pyridine and p-toluenesulfonic acid aryl ester to generate the 3-aryl pyridine derivative. The method has the advantages of high product selectivity, high yield, low cost and mild reaction condition and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of method of synthetic 3-aryl pyridine derivative; Be specifically related to the method for a kind of palladium compound catalysis substituted pyridines and aryl sulfonic acid fat reaction generation 3-aryl pyridine derivative.Belong to metal catalytic, organic synthesis field.
Background technology
Pyridine ring is the natural product of existing discovery, medicine, most important heterocycle structure in material and the part.Pyridine and its derivatives is the very important fine chemical product of a class, and its purposes is very extensive, and especially purposes is more extensive in medicine, pesticide field.At pesticide field, pyridine structure almost spreads all over the agricultural chemicals of all categories.
Therefore, by No. 3 position hydrogen atoms of activation pyridine, the synthetic synthetic method that contains the compound of pyridine ring of exploitation has important practical value.At present No. 3 position hydrogen atoms of activation pyridine are synthetic contains the pyridine ring compound certain methods has been arranged.For example use zirconium, rhodium, ruthenium and iridium are that catalyzer has been obtained gratifying result at No. 3 position hydrogen of activation pyridine, Hiyama and Nakao efforts be made so that recently with metallic nickel be No. 3 position hydrogen of catalyst activation pyridine, also obtain also good result, but it's a pity that these catalyzer are higher to the requirement of substrate, the substrate scope that can select is narrow, is of limited application.
In sum, by the synthetic method that contains the pyridine ring compounds of No. 3 position hydrogen atoms of activation pyridine substrate is required height now, also higher to requirement for experiment condition, in industrial production, receive very large restriction.From the beginning of this year, the C-H activation of palladium catalysis has obtained remarkable progress, and Jin-Quan Yu in 2011 etc. have reported for the first time after adding certain part, by No. 3 position hydrogen of palladium catalytic activation pyridine, with fragrant iodide reaction, generate the method for the pyridine of No. 3 position replacements.But fragrant iodide are more expensive rare raw materials, at present, also do not utilize palladium catalyst both at home and abroad, use open source literature and the patent of pyridine and tosic acid phenolic ester reaction preparation 3-aryl-pyridine.
Summary of the invention
The object of the present invention is to provide a kind of highly selective, high yield, the method for synthetic 3-aryl pyridine derivative cheaply, the method reaction conditions is gentle, is applicable to suitability for industrialized production.
The invention provides a kind of method of synthetic 3-aryl pyridine derivative, the method is to generate the 3-aryl pyridine derivative with palladium compound catalysis substituted pyridines and the reaction of tosic acid aryl ester;
Described tosic acid aryl ester has formula 1 structure:
Formula 1
R
2Be selected from substituted-phenyl, substituted naphthyl, replacement phenanthryl or replace in the anthryl a kind of;
Described substituted pyridines has formula 2 structures:
Formula 2
R
1Be selected from hydrogen atom or C
1～4A kind of in the alkyl.
Described palladium compound comprises: Pd (OAc)
2Or PdCl
2In a kind of, be preferably Pd (OAc)
2
Preferred tosic acid aryl ester has formula 1 structure, R in its Chinese style 1
2Have in the following structural formula a kind of:
R wherein
3, R
4, R
5, R
6Or R
7Be selected from independently of one another C
1 ~ 5Alkyl, C
1 ~ 5Alkoxyl group, halogen atom, hydrogen atom or phenyl in a kind of.
Most preferred tosic acid aryl ester comprises: tosic acid 2-naphthalene ester, tosic acid 1-naphthalene ester, tosic acid 6-phenyl-2-naphthalene ester or tosic acid are to tertiary butyl phenyl ester.
Preferred substituted pyridines has formula 3 structures:
Formula 3
R
1Be selected from hydrogen atom or C
1 ~ 4Alkyl in a kind of.
Most preferred substituted pyridines has formula 3 structures, wherein R
1Be selected from hydrogen atom or the methyl a kind of.
Described reaction is best at 130 ~ 160 ℃ of lower reaction 40 ~ 60h at 150 ℃ of reaction 48h.
Described reaction is carried out under the protection of rare gas element.
Described 3-aryl pyridine derivative has formula 4 structures:
Formula 4
R
1Be selected from hydrogen atom or C
1 ~ 4Alkyl in a kind of;
R
2Be selected from substituted-phenyl, substituted naphthyl, replacement anthryl or replace in the phenanthryl a kind of.
Preferred 3-aryl pyridine derivative has formula 5 structures:
Formula 5
R
1Be selected from hydrogen atom or C
1～4Alkyl in a kind of;
R
2For a kind of in substituted-phenyl, substituted naphthyl, replacement anthryl or the replacement phenanthryl.
More preferably the 3-aryl pyridine derivative has formula 5 structures, wherein R
1Be selected from hydrogen atom or the methyl a kind of; R
2Be selected from substituted-phenyl, substituted naphthyl, replacement anthryl or replace in the phenanthryl a kind of.
Further preferred 3-aryl pyridine derivative has formula 5 structures, wherein R
1Be selected from hydrogen atom or the methyl a kind of; R
2Have in the following structural formula a kind of:
R wherein
3, R
4, R
5, R
6Or R
7Be selected from independently of one another C
1 ~ 5Alkyl, C
1 ~ 5Alkoxyl group, halogen atom, hydrogen atom or phenyl in a kind of.
Most preferred 3-aryl pyridine derivative comprises: the 3-(2-naphthyl) pyridine, 3-(1-naphthyl) pyridine, 3-methyl-5-(1-naphthyl) pyridine, 3-methyl-5-(2-naphthyl) pyridine, 3-(6-phenyl-2-naphthyl) pyridine, 3-methyl-5-(6-phenyl-2-naphthyl) pyridine or 3-be to the tert.-butylbenzene yl pyridines.
Add 1,10-phenanthroline in the described reaction or 1,10-phenanthroline derivative is part, be preferably 1,10-phenanthroline, the adding of part is used for increasing speed of reaction.
Also add metal base in the reaction, described basic metal comprises: K
3PO
4, Cs
2CO
3Or K
2CO
3In a kind of.
Preferred method is with the tosic acid aryl ester, Pd (OAc)
2, 1,10-phenanthroline and metal base, substituted pyridines mix; In nitrogen environment, 130 ~ 160 ℃ of lower reaction 40 ~ 60h, after reaction finishes, extraction, with the organic phase evaporate to dryness, residue obtains product through chromatographic separation.
The concrete building-up process of method of the synthetic 3-aryl pyridine derivative of the present invention: concrete synthetic with substrate tosic acid 2-aryl ester, catalyst P d (OAc)
2Or PdCl
2(Pd (OAc) preferably
2), part (being preferably 1,10-phenanthroline), metal base and pyridine add in the tube sealing under nitrogen environment; With tube sealing put into 130 ~ 160 ℃ of oil baths react 40 ~ 60h(at 150 ℃ of reaction 48h for best); Reaction is cooled to room temperature with reaction solution after finishing, and adds saturated aqueous common salt, use ethyl acetate extraction, with the organic layer anhydrous magnesium sulfate drying, filter, the filtrate decompression distillation separates (ethyl acetate/petroleum ether is made eluent) by silica gel column chromatography, gets the 3-aryl-pyridine.
Synthetic route is as follows:
Beneficial effect of the present invention: with simple palladium compound catalysis to after No. 3 positions of the pyridine hydrogen highly selective C-H activation, with be simple and easy to raw material tosic acid aryl ester react, obtain the product of highly selective, high yield, reduce the synthetic cost of 3-aryl pyridine derivative, be conducive to suitability for industrialized production.
Embodiment
The following example is to further specify of the present invention, rather than restriction the present invention.
Embodiment 1:3-(2-naphthyl) pyridine is synthetic
With substrate 147mg (0.5mmol) tosic acid beta naphthal ester, catalyzer 11mg (0.1mmol) Pd (OAc)
2, part 27mg (0.3mmol) 1,10-Phen, alkali 207mg (1.5mmol) K
2CO
3, and solvent 3ml pyridine adds in the 15ml tube sealing under nitrogen environment.Then tube sealing is put into 150 ℃ of oil baths and reacted 48h.Reaction is cooled to room temperature with reaction solution after finishing, and adds the 80ml saturated aqueous common salt, then uses the 100ml ethyl acetate extraction three times, merges organic layer.The organic layer anhydrous magnesium sulfate drying filters, and the filtrate decompression distillation separates (ethyl acetate/petroleum ether: 1/4 makees eluent) by silica gel column chromatography and gets the 66.7mg white solid, and productive rate is 65%.
1H?NMR(400MHz,CDCl
3):δ=8.99(d,J=1.4Hz1H),8.63(d,J=4.7Hz,1H),8.04(s,1H),8.01-7.81(m,,4H),7.71(d,J=8.5Hz,1H),7.65-7.50(m,2H),7.40(dd,J=4.9,7.8Hz,1H);
13C?NMR(100MHz,CDCl
3):δ=148.5,148.4,136.5,135.1,134.5,133.5,132.8,128.8,128.1,127.6,126.5,126.4,126.1,124.9,123.5;
LRMS:m/z:205。
Embodiment 2:3-(1-naphthyl) pyridine is synthetic
With substrate 147mg (0.5mmol) tosic acid 1-naphthol ester, catalyzer 11mg (0.1mmol) Pd (OAc)
2, part 27mg (0.3mmol) 1,10-Phen, alkali 207mg (1.5mmol) K
2CO
3, and solvent 3ml pyridine adds in the 15ml tube sealing under nitrogen environment.Then tube sealing is put into 150 ℃ of oil baths and reacted 48h.Reaction is cooled to room temperature with reaction solution after finishing, and adds the 80ml saturated aqueous common salt, then uses the 10ml ethyl acetate extraction three times, merges organic layer.The organic layer anhydrous magnesium sulfate drying filters, and the filtrate decompression distillation separates (ethyl acetate/petroleum ether: 1/4 makees eluent) by silica gel column chromatography and gets the 64.5mg white solid, and productive rate is 65%.
1H?NMR(400MHz,CDCl
3):δ8.75(s,1H),8.67(d,J=8.0Hz,1H),7.90-7.81(t,2H),7.79(s,1H),7.55(s,1H),7.55-7.39(m,5H);
13C?NMR(100MHz,CDCl
3):δ150.5,148.5,137.3,136.3,136.2,133.7,131.4,128.5,128.4,127.3,126.5,126.0,125.3,125.2,123.1;
LRMS:m/z:205。
Embodiment 3:3-methyl-5-(1-naphthyl) pyridine is synthetic
With substrate 147mg (0.5mmol) tosic acid 1-naphthol ester, catalyzer 16mg (0.15mmol) Pd (OAc)
2, part 40mg (0.45mmol) 1,10-Phen, alkali 207mg (1.5mmol) K
2CO
3, and solvent 3ml3-picoline adds in the 15ml tube sealing under nitrogen environment.Then tube sealing is put into 150 ℃ of oil baths and reacted 48h.Reaction is cooled to room temperature with reaction solution after finishing, and adds the 80ml saturated aqueous common salt, then uses the 100ml ethyl acetate extraction three times, merges organic layer.The organic layer anhydrous magnesium sulfate drying filters, and the filtrate decompression distillation separates (ethyl acetate/petroleum ether: 1/4 makees eluent) by silica gel column chromatography and gets the 61.5mg white solid, and productive rate is 57%.
1H?NMR(400MHz,CDCl
3):δ8.56(s,1H),8.51(s,1H),7.92-7.87(t,2H),7.81(d,J=8.0Hz1H),7.61(s,1H),7.55-7.43(m,3H),7.38(d,J=8.0Hz,1H),2.42(s,3H);
13C?NMR(100MHz,DMSO-d
6):δ149.0,147.7,137.8,136.4,135.8,133.7,132.6,131.4,128.4,128.3,127.2,126.4,126.0,125.3,125.5,18.4;
LRMS:m/z:219。
Embodiment 4:3-methyl-5-(2-naphthyl) pyridine is synthetic
With substrate 147mg (0.5mmol) tosic acid beta naphthal ester, catalyzer 16mg (0.15mmol) Pd (OAc)
2, part 40mg (0.45mmol) 1,10-Phen, alkali 207mg (1.5mmol) K
2CO
3, and solvent 3ml3-picoline adds in the 15ml tube sealing under nitrogen environment.Then tube sealing is put into 150 ℃ of oil baths and reacted 48h.Reaction is cooled to room temperature with reaction solution after finishing, and adds the 80ml saturated aqueous common salt, then uses the 100ml ethyl acetate extraction three times, merges organic layer.The organic layer anhydrous magnesium sulfate drying filters, and the filtrate decompression distillation separates (ethyl acetate/petroleum ether: 1/4 makees eluent) by silica gel column chromatography and gets the 64.6mg white solid, and productive rate is 59%.
1H?NMR(400MHz,CDCl
3):δ8.77(s,1H),8.45(s,1H),8.02(s,1H),7.83(s,1H),7.94(s,1H),7.91-7.85(m,2H),7.78(s,1H),7.70(d,J=8.0Hz,1H),7.52-7.49(m,2H),2.42(s,3H);
13C?NMR(100MHz,CDCl
3):δ149.0,145.7,136.0,135.2,135.1,133.5,133.0,132.8,128.7,128.1,127.6,126.5,126.3,126.0,125.0,18.5;
LRMS:m/z:219。
Embodiment 5:3-(6-phenyl-2-naphthyl) pyridine is synthetic:
With substrate 187mg (0.5mmol) tosic acid 6-phenyl beta naphthal ester, catalyzer 11mg (0.1mmol) Pd (OAc)
2, part 27mg (0.3mmol) 1,10-Phen, alkali 207mg (1.5mmol) K
2CO
3, and solvent 3ml pyridine adds in the 15ml tube sealing under nitrogen environment.Then tube sealing is put into 150 ℃ of oil baths and reacted 48h.Reaction is cooled to room temperature with reaction solution after finishing, and adds the 80ml saturated aqueous common salt, then uses the 100ml ethyl acetate extraction three times, merges organic layer.The organic layer anhydrous magnesium sulfate drying filters, and the filtrate decompression distillation separates (ethyl acetate/petroleum ether: 1/4 makees eluent) by silica gel column chromatography and gets the 81.8mg white solid, and productive rate is 58%.
1H?NMR(400MHz,CDCl
3):δ8.99(s,1H),8.63(d,J=8.0Hz,1H),8.07-7.80(m,5H),7.81-7.71(m,4H),7.48(t,J=8.8Hz,2H),7.41-7.38(m,2H);
13C?NMR(100MHz,CDCl
3):δ148.5,140.8,139.1,136.5,135.1,134.5,133.1,132.7,129.1,128.9,128.7,127.5,127.4,126.3,125.8,125.5,125.4,123.6;
LRMS:m/z:282。
Embodiment 6:3-methyl-5-(6-phenyl-2-naphthyl) pyridine is synthetic
With substrate 187mg (0.5mmol) tosic acid 6-phenyl beta naphthal ester, catalyzer 16mg (0.15mmol) Pd (OAc)
2, part 40mg (0.45mmol) 1,10-Phen, alkali 207mg (1.5mmol) K
2CO
3, and solvent 3ml3-picoline adds in the 15ml tube sealing under nitrogen environment.Then tube sealing is put into 150 ℃ of oil baths and reacted 48h.Reaction is cooled to room temperature with reaction solution after finishing, and adds the 80ml saturated aqueous common salt, then uses the 100ml ethyl acetate extraction three times, merges organic layer.The organic layer anhydrous magnesium sulfate drying filters, and the filtrate decompression distillation separates (ethyl acetate/petroleum ether: 1/4 makees eluent) by silica gel column chromatography and gets the 82.9mg white solid, and productive rate is 56%.
1H?NMR(400MHz,CDCl
3):δ8.79(s,1H),8.45(s,1H),8.06(s,1H),8.05(s,1H),7.97(m,3H),7.80-7.70(m,5H),7.71-7.41(m,2H),7.39(t,J=8.8Hz1H),2.43(s,3H);
13C?NMR(100MHz,CDCl
3):δ149.4,147.1,136.6,134.4,134.1,134.0,133.9,133.0,132.6,129.0,128.5,128.4,127.4,126.9,126.8,126.5,124.8,124.4,21.2;
LRMS:m/z:296
Embodiment 7:3-is synthetic to the tert.-butylbenzene yl pyridines
With substrate 153mg (0.5mmol) tosic acid p-tert-butylphenol ester, catalyzer 11mg (0.1mmol) Pd (OAc)
2, part 27mg (0.3mmol) 1,10-Phen, alkali 207mg (1.5mmol) K
2CO
3, and solvent 3ml pyridine adds in the 15ml tube sealing under nitrogen environment.Then tube sealing is put into 150 ℃ of oil baths and reacted 48h.Reaction is cooled to room temperature with reaction solution after finishing, and adds the 80ml saturated aqueous common salt, then uses the 100ml ethyl acetate extraction three times, merges organic layer.The organic layer anhydrous magnesium sulfate drying filters, and the filtrate decompression distillation separates (ethyl acetate/petroleum ether: 1/4 makees eluent) by silica gel column chromatography and gets the 52.8mg white solid, and productive rate is 50%.
1H?NMR(400MHz,CDCl
3):δ8.56(d,J=8.0Hz,1H),7.86(d,J=8.0Hz,1H),7.54-7.49(m,4H),7.35(m,1H),1.37(s,9H);
13C?NMR(100MHz,CDCl
3):δ151.2,148.2,148.1,136.5,134.9,134.1,126.8,126.0,123.5,34.6,31.3;
LRMS:m/z:211。
Claims (10)
1. the method for a synthetic 3-aryl pyridine derivative is characterized in that, generates the 3-aryl pyridine derivative with palladium compound catalysis substituted pyridines and the reaction of tosic acid aryl ester;
Described tosic acid aryl ester has formula 1 structure:
Formula 1
R
2Be selected from substituted-phenyl, substituted naphthyl, replacement phenanthryl or replace in the anthryl a kind of;
Described substituted pyridines has formula 2 structures:
Formula 2
R
1Be selected from hydrogen atom or C
1 ~ 4A kind of in the alkyl.
2. method according to claim 1 is characterized in that, described palladium compound comprises: Pd (OAc)
2Or PdCl
2In a kind of.
3. method according to claim 1 is characterized in that, described tosic acid aryl ester has formula 1 structure, R in its Chinese style 1
2Have in the following structural formula a kind of:
R wherein
3, R
4, R
5, R
6Or R
7Be selected from independently of one another C
1 ~ 5Alkyl, C
1 ~ 5Alkoxyl group, halogen atom, hydrogen atom or phenyl in a kind of.
4. method according to claim 3 is characterized in that, described tosic acid aryl ester comprises: tosic acid 2-naphthalene ester, tosic acid 1-naphthalene ester, tosic acid 6-phenyl-2-naphthalene ester or tosic acid are to tertiary butyl phenyl ester.
5. method according to claim 1 is characterized in that, described substituted pyridines has formula 3 structures:
Formula 3
R
1Be selected from hydrogen atom or C
1 ~ 4Alkyl in a kind of.
6. method according to claim 5 is characterized in that, described substituted pyridines has formula 3 structures, wherein R
1Be selected from hydrogen atom or the methyl a kind of.
7. method according to claim 1 is characterized in that, described reaction is at 130 ~ 160 ℃ of lower reaction 40 ~ 60h.
8. each described method is characterized in that according to claim 1 ~ 7, and described 3-aryl pyridine derivative has formula 4 structures:
Formula 4
R
1Be selected from hydrogen atom or C
1～4Alkyl in a kind of;
R
2Be selected from substituted-phenyl, substituted naphthyl, replacement anthryl or replace in the phenanthryl a kind of.
9. method according to claim 1 is characterized in that, adds 1,10-phenanthroline in the described reaction or 1,10-phenanthroline derivative is part.
10. according to claim 1 or 9 described methods, it is characterized in that also add metal base in the reaction, described basic metal comprises: K
3PO
4, Cs
2CO
3Or K
2CO
3In a kind of.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249483A (en) * | 2001-02-21 | 2002-09-06 | Koei Chem Co Ltd | Method of producing aryl substituted heterocyclic compound |
| CN1680325A (en) * | 2004-02-02 | 2005-10-12 | 三协化学株式会社 | Preparation of pyridine derivatives |
| JP2010184881A (en) * | 2009-02-10 | 2010-08-26 | Kyoto Univ | Method for producing aryl derivative using heterogeneous catalyst |
-
2012
- 2012-12-24 CN CN201210566386.3A patent/CN102977007B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002249483A (en) * | 2001-02-21 | 2002-09-06 | Koei Chem Co Ltd | Method of producing aryl substituted heterocyclic compound |
| CN1680325A (en) * | 2004-02-02 | 2005-10-12 | 三协化学株式会社 | Preparation of pyridine derivatives |
| JP2010184881A (en) * | 2009-02-10 | 2010-08-26 | Kyoto Univ | Method for producing aryl derivative using heterogeneous catalyst |
Non-Patent Citations (2)
| Title |
|---|
| LUTZ ACKERMANN，等: "Direct arylations of electron-deficient (hetero)arenes with aryl or alkenyl tosylates and mesylates", 《CHEM.COMM.》 * |
| MENGCHUN YE，等: "Ligand-Promoted C3-Selective Arylation of Pyridines with Pd Catalysts: Gram-Scale Synthesis of (±)-Preclamol", 《J. AM. CHEM. SOC.》 * |
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