CN103183636A - New method for synthesizing 2, 2'-Bipyridyl-4, 4'-dicarboxylic acid - Google Patents
New method for synthesizing 2, 2'-Bipyridyl-4, 4'-dicarboxylic acid Download PDFInfo
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- CN103183636A CN103183636A CN2013101150798A CN201310115079A CN103183636A CN 103183636 A CN103183636 A CN 103183636A CN 2013101150798 A CN2013101150798 A CN 2013101150798A CN 201310115079 A CN201310115079 A CN 201310115079A CN 103183636 A CN103183636 A CN 103183636A
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Abstract
The invention discloses a new method for synthesizing 2, 2'-Bipyridyl-4, 4'-dicarboxylic acid. 2-Chloroisonicotinic Acid serves as the raw material, palladium on activated carbon serves as a catalyst, inorganic base and glycerine serve as reductant systems and water serves as solvent; the catalyst is subjected to ultrasonic dispersion pretreatment to be uniformly dispersed in a reaction system; then reductive coupling reaction occurs in a hydrothermal reaction kettle; after reaction, the catalyst in the product is separated to obtain a filtrate; and the pH value of the filtrate is regulated by a mineral acid to obtain the 2, 2'-Bipyridyl-4, 4'-dicarboxylic acid. The method provided by the invention greatly improves the reaction rate and the selectivity, reduces consumption of the catalyst, provides an operable synthetic route for industrial production of 2, 2'-Bipyridyl-4, 4'-dicarboxylic acid, has vary good practical significance and an economic value, and is very hopeful to be applied to mass production of DSSCs (Dye-sensitized solar cells).
Description
Technical field
The invention belongs to the synthetic field of Chemicals, be specifically related to a kind of 2,2 '-dipyridyl-4, the synthetic method of 4 '-dioctyl phthalate.
Technical background
Dipyridyl and derivative thereof are the important chemical synthetic intermediates, can form the metal complexes with conjugated electrons system with multiple metal, and present good light, electricity, heat, magnetics function and catalysis characteristics, thereby shown important value at photoelectrocatalysis and aspect such as photosensitive.Wherein 2,2 '-dipyridyl-4,4 '-dioctyl phthalate are star's dye molecule such as the N3 of synthetic dyestuff sensitization solar battery (DSSC), the important source material of N719 etc., in dye sensitization solar battery, play the part of important role, thereby causing investigator's extensive concern.
2,2 '-dipyridyl-4,4 '-dioctyl phthalate be generally by 4,4 '-dimethyl-2, and the direct oxidation of 2 '-dipyridyl forms, and oxygenant is generally the potassium permanganate of acid system or potassium bichromate etc.As Claudio Luis Donnici etc. (J. Braz. Chem. Soc., 1998,9,455-460) reported with potassium bichromate and vitriol oil system oxidation 4,4 '-dimethyl-2 2 '-dipyridyl and obtain product with higher yields.But these oxygenants are heavy metallic salt, and the addition in the reaction is bigger, be generally 4 times of stoichiometric number and more than, used a large amount of concentrated acids simultaneously, very big to environmental influence.And 4,4 '-dimethyl-2, the synthetic difficulty of 2 '-dipyridyl generally got from coupling by palladium carbon or nickel catalyzator by the 4-picoline, but the reaction times is longer, is generally 3 days even longer.And productive rate is very low, is generally 0.5% ~ 10%.Luke M.Neal etc. (Journal of Molecular Catalysis A:Chemical, 2008,284,141-148) reported that the palladium-carbon catalyst with 10% generally only can obtain 1.5 ~ 2.0g product/g catalyzer.Such synthesis route cost is very high, thereby has limited production greatly.
Summary of the invention
The objective of the invention is to synthesize 2,2 '-dipyridyl-4, the novel method of 4 '-dioctyl phthalate in order to provide a kind of.
For achieving the above object, the technical solution used in the present invention is: the present invention synthetic 2,2 '-dipyridyl-4, the method of 4 '-dioctyl phthalate comprises: be raw material with the 2-chloroisonicotinic acid, palladium carbon is catalyzer, mineral alkali and glycerol are the reductive agent system, water is solvent, earlier by the ultra-sonic dispersion pre-treatment described catalyzer is dispersed in the reaction system, reductive coupling reaction takes place in hydrothermal reaction kettle then, isolate the catalyzer in the product after reaction finishes and obtain filtrate, regulate the pH of filtrate and obtain product 2 with mineral acid, 2 '-dipyridyl-4,4 '-dioctyl phthalate.
Further, the quality percentage composition of the palladium in the palladium carbon of the present invention is 5% or 10%.
Further, mineral alkali of the present invention is NaOH or KOH.
Further, the mass ratio of 2-chloroisonicotinic acid of the present invention and palladium carbon is 5 ~ 20:1.
Further, the mass ratio of 2-chloroisonicotinic acid of the present invention and palladium carbon is 15:1.
Further, the temperature of reaction of reductive coupling reaction of the present invention is 50 ~ 100 ℃, and the reaction times is 5 ~ 12h.
Compared with prior art, the present invention major advantage be: in the methods of the invention, the active substance palladium in the palladium-carbon catalyst can be oxidized to Palladous chloride by the 2-chloroisonicotinic acid and lose activity; And utilize mineral alkali and glycerol to form novel reduction system, because the trivalent alcohol structure of glycerol uniqueness, can utilize a plurality of hydroxyls to come palladium catalyst oxidized in the reduction reaction, self but can not form reacting disadvantageous acetal, can make palladium catalyst fast restore oxidized in the linked reaction become the palladium of zeroth order and recover catalytic activity, improve speed of reaction and selectivity greatly, reduced the usage quantity of catalyzer, obtained unforeseeable effect.The present invention utilizes the ultra-sonic dispersion pretreating raw material can increase the contact area of catalyzer and raw material greatly, thereby the air that retains in the desolventizing simultaneously improves the catalytic activity of catalyst P d, has accelerated speed of reaction; In addition, ultrasonic pretreatment has improved the selectivity of reaction, and the dechlorination by product Yi Yansuan that obtains is less, and product purity is higher and reduced separation costs.And utilize solvent thermal method also to improve speed of reaction effectively, shortened the reaction times.On industrial production, the palladium-carbon catalyst after the filtration can activate the back and recycle, thereby greatly reduces production cost.The solvent that reaction is simultaneously used is very green solvent glycerol and water, and is very little to the influence of production and environment.As fully visible, the inventive method is 2,2 '-dipyridyl-4, and the suitability for industrialized production of 4 '-dioctyl phthalate provides an exercisable route of synthesis, has good realistic meaning and economic worth, is expected to very much be applied in the large-scale production and application of DSSC dyestuff.
Embodiment
Make with the present invention of embodiment below and further specifying.
Embodiment 1:
The massfraction that takes by weighing 0.3151g (2mmol) raw material 2-chloroisonicotinic acid, 0.6841g (10mmol) massfraction and be 82% KOH and 0.0210gPd is 5% Pd/C catalyzer, add in 5mL glycerol and the 15mL distilled water mixed solvent, then supersound process 10min.All reactant transfer are reacted 5h down at 70 ℃ in hydrothermal reaction kettle.Reaction is cooled to room temperature after finishing, and opens reactor, and the vacuum filtration reaction solution is isolated catalyst P d/C.Filtrate is adjusted to pH=1 with the hydrochloric acid of 0.1M, separates out white depositions.After the standing over night, vacuum filtration namely gets product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 0.2203g at 90 ℃ of following dry 12h in refrigerator.Yield is 90.21%.
Present embodiment products therefrom 2,2 '-dipyridyl-4, the physicochemical data of 4 '-dioctyl phthalate is as follows:
(molecular formula is C in ultimate analysis
12H
8N
2O
4): calculated value C, 59.02; H, 3.30; N, 11.47.Analytical value C, 58.79; H, 3.35; N, 11.27.
FT-IR（cm-1）KBr：ν3112.84，2431.86，1719.13，1460.77，1365.94，1292.99，1268.77，1243.72，765.60，682.19。
1H?NMR（d6-DMSO,400MHz）δ：8.92?(d,?2H,H6),?8.85?(s,?2H,?H3),?7.92?(d,?2H,H5)。
Comparative example 1:
The massfraction that takes by weighing 0.3151g (2mmol) raw material 2-chloroisonicotinic acid, 0.6841g (10mmol) massfraction and be 82% KOH and 0.0210gPd is 5% Pd/C catalyzer, add in 5mL methyl alcohol and the 15mL distilled water mixed solvent, then supersound process 10min.All reactant transfer are reacted 24h down at 100 ℃ in hydrothermal reaction kettle.Reaction is cooled to room temperature after finishing, and opens reactor, and the vacuum filtration reaction solution is isolated catalyst P d/C.Filtrate is adjusted to pH=1 with the hydrochloric acid of 0.1M, separates out white depositions.After the standing over night, vacuum filtration namely gets product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate 0.1236g at 90 ℃ of following dry 12h in refrigerator.Yield is 50.60%.
Comparative example 1 products therefrom 2,2 '-dipyridyl-4, the physicochemical data of 4 '-dioctyl phthalate is as follows:
(molecular formula is C in ultimate analysis
12H
8N
2O
4): calculated value C, 59.02; H, 3.30; N, 11.47.Analytical value C, 58.92; H, 3.39; N, 11.33.
FT-IR（cm-1）KBr：ν3113.39，2452.51，1719.22，1461.20，1366.31，1288.93，1268.43，1244.47，766.58，681.76。
1H?NMR（d6-DMSO,400MHz）δ：8.92?(d,?2H,H6),?8.84?(s,?2H,?H3),?7.91?(d,?2H,H5)。
Contrast as can be known with comparative example 1 by embodiment 1, glycerol is being brought into play irreplaceable effect in this reduction system.Glycerol is because its unique trivalent alcohol structure, reduction process that can accelerator activator, thereby make catalyzer rapidly regeneration shorten the reaction times greatly, obtain unforeseeable effect, and other alcohol (as methyl alcohol etc.) do not have so significant effect.
Comparative example 2:
The massfraction that takes by weighing 0.3151g (2mmol) raw material 2-chloroisonicotinic acid, 0.6841g (10mmol) massfraction and be 82% KOH and 0.0210gPd is 5% Pd/C catalyzer, add in 5mL ethanol and the 15mL distilled water mixed solvent, then supersound process 10min.All reactant transfer are reacted 36h down at 100 ℃ in hydrothermal reaction kettle.Reaction is cooled to room temperature after finishing, and opens reactor, and the vacuum filtration reaction solution is isolated catalyst P d/C.Filtrate is adjusted to pH=1 with the hydrochloric acid of 0.1M, and fails to separate out white depositions, namely and fail to obtain product 2,2 '-dipyridyl-4,4 '-dioctyl phthalate.
Contrast as can be known with comparative example 2 by embodiment 1, ethanol is when reducing oxidized palladium-carbon catalyst, self be oxidized to the aldehyde that contains α-hydrogen atom and aldol reaction has taken place, product is unfavorable for the carrying out of former reaction, even the raising temperature of reaction, the prolongation reaction times also can not get required product.Glycerol then can not be oxidized to the aldehyde that contains α-hydrogen atom, can guarantee efficiently carrying out of former reaction.
Comparative example 3:
The massfraction that takes by weighing 0.3151g (2mmol) raw material 2-chloroisonicotinic acid and 0.0210gPd is 5% Pd/C catalyzer, adds in 5mL glycerol and the 15mL distilled water mixed solvent, then supersound process 10min.All reactant transfer are reacted 24h down at 100 ℃ in hydrothermal reaction kettle.Reaction is cooled to room temperature after finishing, and opens reactor, and the vacuum filtration reaction solution is isolated catalyst P d/C.Filtrate is adjusted to pH=1 with the hydrochloric acid of 0.1M, separates out white depositions.After the standing over night, vacuum filtration namely gets product 2 at 90 ℃ of following dry 12h in refrigerator, 2 '-dipyridyl-4, and 4 '-dioctyl phthalate 0.0496g, yield are 20.31%.
This Comparative Examples products therefrom 2,2 '-dipyridyl-4, the physicochemical data of 4 '-dioctyl phthalate is as follows:
(molecular formula is C in ultimate analysis
12H
8N
2O
4): calculated value C, 59.02; H, 3.30; N, 11.47.Analytical value C, 58.96; H, 3.41; N, 11.29.
FT-IR（cm-1）KBr：ν3113.35，2456.11，1719.29，1460.96，1366.34，1288.88，1268.64，1243.77，765.83，681.97。
1H?NMR（d6-DMSO,400MHz）δ：8.92?(d,?2H,H6),?8.84?(s,?2H,?H3),?7.91?(d,?2H,H5)。
Contrast as can be known with comparative example 3 by embodiment 1, mineral alkali is being brought into play the effect that promotes pure reducing/regenerating catalyzer in reaction.
Embodiment 2:
The Pd/C catalyzer massfraction that suction filtration among the embodiment 1 is gone out is 2% NaOH solution activation, removes the NaOH solution on surface then with alcohol flushing.Pd/C catalyzer after the activation is all transferred to it in beaker, the massfraction that takes by weighing 0.3151g (2mmol) raw material 2-chloroisonicotinic acid, 0.6841g (10mmol) massfraction and be 82% KOH and 0.0210gPd is 5% Pd/C catalyzer, add in 5mL glycerol and the 15mL distilled water mixed solvent, then supersound process 10min.All reactant transfer are reacted 5h down at 70 ℃ in hydrothermal reaction kettle.Reaction is cooled to room temperature after finishing, and opens reactor, and the vacuum filtration reaction solution is isolated catalyst P d/C.Filtrate is adjusted to pH=1 with the hydrochloric acid of 0.1M, separates out white depositions.After the standing over night, vacuum filtration namely gets product 2 at 90 ℃ of following dry 12h in refrigerator, 2 '-dipyridyl-4, and 4 '-dioctyl phthalate 0.1973g, yield are 80.79%.
Present embodiment products therefrom 2,2 '-dipyridyl-4, the physicochemical data of 4 '-dioctyl phthalate is as follows:
(molecular formula is C in ultimate analysis
12H
8N
2O
4): calculated value C, 59.02; H, 3.30; N, 11.47.Analytical value C, 58.73; H, 3.38; N, 11.19.
FT-IR（cm-1）KBr：ν3112.55，2431.01，1719.05，1461.43，1366.27，1290.97，1268.59，1244.33，766.37，682.22。
1H?NMR（d6-DMSO,400MHz）δ：8.91?(d,?2H,H6),?8.84?(s,?2H,?H3),?7.92?(d,?2H,H5)。
By embodiment 2 as can be known: still can use efficiently after utilizing palladium-carbon catalyst that the inventive method reaction reclaims by simple activation, in industrial production, can reduce the cost of catalyzer greatly, this is because the ultra-sonic dispersion pre-treatment can make palladium-carbon catalyst be dispersed in the system, causes surface-area to reduce and inactivation thereby catalyzer is difficult for after reaction because reunite.Simultaneously, a plurality of hydroxyls of glycerol can become active palladium with the palladium fast restore of inactivation in the reaction, make a concentrated effort to finish catalyst regeneration process.
Embodiment 3:
Take by weighing 0.3151g (2mmol) raw material 2-chloroisonicotinic acid, 0.4001g (10mmol) NaOH and 0.0630g massfraction and be 10% Pd/C catalyzer, add in 5mL glycerol and the 15mL distilled water mixed solvent, then supersound process 10min.All reactant transfer are reacted 12h down at 50 ℃ in hydrothermal reaction kettle.Reaction is cooled to room temperature after finishing, and opens reactor, and the vacuum filtration reaction solution is isolated catalyst P d/C.Filtrate is adjusted to pH=1 with the hydrochloric acid of 0.1M, separates out white depositions.After the standing over night, vacuum filtration namely gets product 2 at 90 ℃ of following dry 12h in refrigerator, 2 '-dipyridyl-4, and 4 '-dioctyl phthalate 0.1950g, yield are 79.85%.
Present embodiment products therefrom 2,2 '-dipyridyl-4, the physicochemical data of 4 '-dioctyl phthalate is as follows:
(molecular formula is C in ultimate analysis
12H
8N
2O
4): calculated value C, 59.02; H, 3.30; N, 11.47.Analytical value C, 58.69; H, 3.33; N, 11.30.
FT-IR（cm-1）KBr：ν3112.64，2432.06，1719.56，1460.79，1364.12，1293.06，1268.32，1243.56，765.88，682.34。
1H?NMR（d6-DMSO,400MHz）δ：8.92?(d,?2H,H6),?8.84?(s,?2H,?H3),?7.92?(d,?2H,H5)。
Embodiment 4:
Take by weighing 0.3151g (2mmol) raw material 2-chloroisonicotinic acid, 0.4001g (10mmol) NaOH and 0.0158g massfraction and be 5% Pd/C catalyzer, add in 5mL glycerol and the 15mL distilled water mixed solvent, then supersound process 10min.All reactant transfer are reacted 10h down at 100 ℃ in hydrothermal reaction kettle.Reaction is cooled to room temperature after finishing, and opens reactor, and the vacuum filtration reaction solution is isolated catalyst P d/C.Filtrate is adjusted to pH=1 with the hydrochloric acid of 0.1M, separates out white depositions.After the standing over night, vacuum filtration namely gets product 2 at 90 ℃ of following dry 12h in refrigerator, 2 '-dipyridyl-4, and 4 '-dioctyl phthalate 0.1785g, yield are 73.11%.
Present embodiment products therefrom 2,2 '-dipyridyl-4, the physicochemical data of 4 '-dioctyl phthalate is as follows:
(molecular formula is C in ultimate analysis
12H
8N
2O
4): calculated value C, 59.02; H, 3.30; N, 11.47.Analytical value C, 59.01; H, 3.42; N, 11.20.
FT-IR（cm-1）KBr：ν3112.51，2448.99，1719.25，1461.22，1366.20，1290.42，1268.43，1244.55，766.23，682.06。
1H?NMR（d6-DMSO,400MHz）δ：8.92?(d,?2H,H6),?8.84?(s,?2H,?H3),?7.91?(d,?2H,H5)。
Claims (10)
1. one kind is synthesized 2,2 '-dipyridyl-4, and the method for 4 '-dioctyl phthalate is characterized in that, comprising:
Be that raw material, palladium carbon are that catalyzer, mineral alkali and glycerol are that reductive agent system, water are solvent with the 2-chloroisonicotinic acid, earlier by the ultra-sonic dispersion pre-treatment described catalyzer is dispersed in the reaction system, reductive coupling reaction takes place in hydrothermal reaction kettle then, isolate the catalyzer in the product after reaction finishes and obtain filtrate, regulate the pH of filtrate and obtain product 2 with mineral acid, 2 '-dipyridyl-4,4 '-dioctyl phthalate.
2. according to claim 1 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: described mineral alkali is NaOH or KOH.
3. according to claim 1 and 2 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the quality percentage composition of the palladium in the described palladium carbon is 5% or 10%.
4. according to claim 1 and 2 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the mass ratio of described 2-chloroisonicotinic acid and palladium carbon is 5 ~ 20:1.
5. according to claim 4 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the mass ratio of described 2-chloroisonicotinic acid and palladium carbon is 15:1.
6. according to claim 1 and 2 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the temperature of reaction of described reductive coupling reaction is 50 ~ 100 ℃, the reaction times is 5 ~ 12h.
7. according to claim 4 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the temperature of reaction of described reductive coupling reaction is 50 ~ 100 ℃, the reaction times is 5 ~ 12h.
8. according to claim 7 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the mass ratio of described 2-chloroisonicotinic acid and palladium carbon is 15:1.
9. according to claim 7 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the quality percentage composition of the palladium in the described palladium carbon is 5% or 10%.
10. according to claim 9 a kind of synthetic 2,2 '-dipyridyl-4, the method for 4 '-dioctyl phthalate is characterized in that: the mass ratio of described 2-chloroisonicotinic acid and palladium carbon is 15:1.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500956B1 (en) * | 1998-04-29 | 2002-12-31 | Axiva Gmbh | Method for the catalytic production of substituted bipyridyl derivatives |
| JP2006022012A (en) * | 2004-07-06 | 2006-01-26 | Koei Chem Co Ltd | Method for producing 4, 4'-dicarboxy-2, 2'-bipyridine |
| JP2006206516A (en) * | 2005-01-28 | 2006-08-10 | Koei Chem Co Ltd | Method for producing 4,4'-dicarboxy-2,2'-bipyridine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6500956B1 (en) * | 1998-04-29 | 2002-12-31 | Axiva Gmbh | Method for the catalytic production of substituted bipyridyl derivatives |
| JP2006022012A (en) * | 2004-07-06 | 2006-01-26 | Koei Chem Co Ltd | Method for producing 4, 4'-dicarboxy-2, 2'-bipyridine |
| JP2006206516A (en) * | 2005-01-28 | 2006-08-10 | Koei Chem Co Ltd | Method for producing 4,4'-dicarboxy-2,2'-bipyridine |
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Application publication date: 20130703 |