CN104844503A - Pyridine derivative 6-[(6-methoxypyridyl-2-yl)methyl]-2,2'-pyridine and synthesis method thereof - Google Patents
Pyridine derivative 6-[(6-methoxypyridyl-2-yl)methyl]-2,2'-pyridine and synthesis method thereof Download PDFInfo
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- CN104844503A CN104844503A CN201510316443.6A CN201510316443A CN104844503A CN 104844503 A CN104844503 A CN 104844503A CN 201510316443 A CN201510316443 A CN 201510316443A CN 104844503 A CN104844503 A CN 104844503A
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- pyridine
- base
- methyl
- methoxypyridine
- ethyl acetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
Abstract
The invention discloses a pyridine derivative 6-[(6-methoxypyridyl-2-yl)methyl]-2,2'-pyridine and a synthesis method thereof. The method comprises the following steps: adding [2,2'-dipyridyl]-6-yl(6-methoxypyridyl-2-yl)ketone, sodium hydroxide, hydrazine hydrate (80%) and ethylene glycol into a three-neck flask, and stirring at 100 DEG C for 5 hours; adding water and a sodium hydroxide solution to regulate the alkality, extracting the solution 2-4 times; and merging the organic layer, drying the layer, carrying out centrifugal drying to remove the organic solvent, and passing through an aluminum oxide column to obtain a yellow liquid. In the method, an asymmetric pyridine compound is synthesized, and the methoxy group is introduced to the 6- site of the pyridine, thereby facilitating the conversion among functional groups, facilitating synthesis of the pyridine derivative containing hydroxy substituent group, and further synthesizing the metal organic complex with higher catalytic performance.
Description
Technical field
The present invention relates to a kind of pyridine derivatives and synthetic method thereof, be specifically related to a kind of novel pyridine compounds 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine and synthetic method thereof.
Background technology
Coordination chemistry is as an emerging cross discipline, its irreplaceable effect is played in crystal engineering field, and organic ligand and metal ion are under varying experimental conditions because of the uncertainty of interactional diversity and influence factor, ligand polymer is made to have abundant, novel molecular structure, pyridine derivatives is as the emerging part of a class, because of its can with many metal ion-chelants, form constitutionally stable compound, therefore become one of most widely used part in coordination chemistry.
Pyridine compounds and their has stronger coordination ability (having three haptos) and special molecular configuration, its can with some transition metal (Zn
2+, Fe
2+deng) construct the structure of linear, branch, the multiple different spaces skeleton such as netted.Simultaneously pyridine all has potential application prospect in multiple fields such as separating chiral and the identifications of catalysis nlo molecule due to the advantage such as diversity, Modulatory character, preferably thermostability of its structure, along with investigator is to the further research of this compounds, it must obtain more achievement in coordination chemistry field.
Summary of the invention
The object of this invention is to provide a kind of pyridine derivate 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine and synthetic method thereof.The method has synthesized a kind of asymmetric pyridine compounds, and introduce methoxyl group in pyridine 6-position, facilitate the conversion between functional group, so that the bipyridyliums derivative of synthesis containing substituted hydroxy group, thus a metal-organic complex that synthesis catalytic performance increases.
The object of the invention is to be achieved through the following technical solutions:
A kind of pyridine derivate 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine, its molecular structural formula is as follows:
The synthetic method of above-mentioned pyridine derivate 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine, concrete steps are as follows:
3.4mmol [2 is added in there-necked flask, 2 '-dipyridyl]-6-base (6-methoxypyridine-2-base) ketone (CN104628632A), 1.5g sodium hydroxide, 20mL hydrazine hydrate (80%), add 20mL ethylene glycol as solvent, 100 DEG C are stirred 5h; To add water and sodium hydroxide solution alkali tune (pH=9), aqueous layer with ethyl acetate or dichloromethane extraction two ~ tetra-times; Merge organic layer, organic solvent, after 1 ~ 3 hour, is spin-dried for by organic over anhydrous sodium sulfate or calcium chloride drying, crosses the pillar of one section of aluminum oxide, with sherwood oil: ethyl acetate=4: 1 (v/v) is elutriant, obtains yellow liquid.Reaction equation is as follows:
Tool of the present invention has the following advantages:
(1) operation is simple, and a step can obtain a kind of asymmetric pyridine compounds that is novel, that have no report.
(2) in compound, the introducing of methoxy group makes the synthesis of hydroxy functional group more simple and easy to get.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum resonance collection of illustrative plates of 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine that the present invention synthesizes;
Fig. 2 is the nuclear-magnetism carbon spectrum resonance collection of illustrative plates of 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine that the present invention synthesizes;
Fig. 3 is the high resolution mass spectrum collection of illustrative plates of 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine that the present invention synthesizes.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
The invention provides the synthetic method of a kind of pyridine derivate 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine, concrete synthesis step is as follows:
In there-necked flask, add 3.4mmol [2,2 '-dipyridyl]-6-base (6-methoxypyridine-2-base) ketone, 1.5g sodium hydroxide, 20mL hydrazine hydrate (80%), add 20mL ethylene glycol as solvent, 100 DEG C are stirred 5h; To add water and sodium hydroxide solution adjusts pH=9, aqueous layer with ethyl acetate or dichloromethane extraction three times; Merge organic layer, organic solvent, after dry 2 hours, is spin-dried for by organic over anhydrous sodium sulfate or calcium chloride, cross the pillar of one section of aluminum oxide, with sherwood oil: ethyl acetate=4: 1 (v/v) is elutriant, obtain yellow liquid (0.77g, 81%).As Figure 1-3,
1h NMR (400MHz, CDCl
3, ppm) and δ 8.67 (d, J=2Hz, 1H), δ 8.45 (d, J=8.0Hz, 1H), δ 8.24 (d, J=7.6Hz, 1H), δ 7.79 (t, J=7.8Hz, 1H), δ 7.72 (t, J=7.6Hz, 1H), δ 7.48 (t, J=7.8Hz, 1H), δ 7.30 (d, J=7.2Hz, 2H), δ 6.84 (d, J=7.2Hz, 1H), δ 6.58 (d, J=8.4Hz, 1H), δ 4.32 (s, 2H), δ 3.91 (s, 3H).
13c NMR (100MHz, CDCl
3, ppm) and δ 163.51,159.21,156.93,156.05,155.14,148.90,138.68,137.23,136.68,123.57,123.50,120.91,118.77,116.02,107.90,53.32,47.01.HRMS (ESI) m/z (%; MeOH solvent): calcd for [M+H+] 277.1215; Found:278.1300.
Claims (5)
1. pyridine derivate 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine, is characterized in that the molecular structural formula of described 6-[(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine is as follows:
2. the synthetic method of pyridine derivate 6-described in a claim 1 [(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine, is characterized in that described method concrete steps are as follows:
In there-necked flask, add 3.4mmol [2,2 '-dipyridyl]-6-base (6-methoxypyridine-2-base) ketone, 1.5g sodium hydroxide, 20mL hydrazine hydrate, add 20mL ethylene glycol as solvent, 100 DEG C are stirred 5h; To add water and sodium hydroxide solution alkali tune, aqueous layer with ethyl acetate or dichloromethane extraction two ~ tetra-times; Merge organic layer, organic solvent, after 1 ~ 3 hour, is spin-dried for by organic over anhydrous sodium sulfate or calcium chloride drying, crosses the pillar of one section of aluminum oxide, with the mixed solution of sherwood oil and ethyl acetate for elutriant, obtains yellow liquid.
3. the synthetic method of pyridine derivate 6-according to claim 2 [(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine, is characterized in that described alkaline pH=9.
4. pyridine derivate 6-according to claim 2 [(6-methoxypyridine-2-base) methyl]-2, the synthetic method of 2 '-pyridine, it is characterized in that in the mixed solution of described sherwood oil and ethyl acetate, sherwood oil: ethyl acetate=4: 1 (v/v).
5. the synthetic method of pyridine derivate 6-according to claim 2 [(6-methoxypyridine-2-base) methyl]-2,2 '-pyridine, is characterized in that the volumetric concentration of described hydrazine hydrate is 80%.
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| CN201510316443.6A CN104844503A (en) | 2015-06-10 | 2015-06-10 | Pyridine derivative 6-[(6-methoxypyridyl-2-yl)methyl]-2,2'-pyridine and synthesis method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914173A (en) * | 2003-12-12 | 2007-02-14 | 惠氏公司 | Quinolines useful in treating cardiovascular disease |
| CN1993347A (en) * | 2004-07-29 | 2007-07-04 | 默克公司 | Potassium channel inhibitors |
| WO2014177062A1 (en) * | 2013-04-30 | 2014-11-06 | 台湾立凯绿能移动股份有限公司 | Large-scale electric vehicle power architecture and battery pack rotating rest scheduling control method therefor |
-
2015
- 2015-06-10 CN CN201510316443.6A patent/CN104844503A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914173A (en) * | 2003-12-12 | 2007-02-14 | 惠氏公司 | Quinolines useful in treating cardiovascular disease |
| CN1993347A (en) * | 2004-07-29 | 2007-07-04 | 默克公司 | Potassium channel inhibitors |
| WO2014177062A1 (en) * | 2013-04-30 | 2014-11-06 | 台湾立凯绿能移动股份有限公司 | Large-scale electric vehicle power architecture and battery pack rotating rest scheduling control method therefor |
Non-Patent Citations (3)
| Title |
|---|
| BYUNG SUN PARK,等: "Synthesis and Photoluminescent Properties of New Ceramidine Derivatives", 《HETEROATOM CHEMISTRY》 * |
| CHRISTOPHER S. LETKO,等: "Influence of Second Coordination Sphere Hydroxyl Groups on the Reactivity of Copper(I) Complexes", 《INORG. CHEM.》 * |
| GERALD DYKER，等: "Synthesis of Methylene- and Methine-Bridged Oligopyridines", 《EUR. J. ORG. CHEM.》 * |
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