CN102070517B - 6-methyl-2,3,5-pyridine tricarboxylic acid and synthetic method thereof - Google Patents
6-methyl-2,3,5-pyridine tricarboxylic acid and synthetic method thereof Download PDFInfo
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- CN102070517B CN102070517B CN2011100334297A CN201110033429A CN102070517B CN 102070517 B CN102070517 B CN 102070517B CN 2011100334297 A CN2011100334297 A CN 2011100334297A CN 201110033429 A CN201110033429 A CN 201110033429A CN 102070517 B CN102070517 B CN 102070517B
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Abstract
The invention discloses 6-methyl-2,3,5-pyridine tricarboxylic acid and a synthetic method thereof. The 6-methyl-2,3,5-pyridine tricarboxylic acid is represented by a formula (I). The synthetic method has a low-toxicity reaction and belongs to environment-friendly synthesis; a raw material, namely potassium permanganate is cheap and readily available; the experimental operation is simple and reaction conditions are easy to control; and an obtained pyridine tricarboxylic acid ligand is low in structural symmetry and can construct complexes with novel structures and coordination modes and contributes to the research of coordination polymers.
Description
Technical field
The present invention relates to the polycarboxylic compound method of a kind of pyridine, particularly relate to a kind of 6-methyl-2,3,5-pyridine tricarboxylic acid (H
3Mptc) and compound method.
Background technology
6-methyl-2,3,5-pyridine tricarboxylic acid (H
3Mptc) be the assorted aromatic nucleus poly carboxylic acid part of a kind of N, have two kinds of ligating atoms of N and O, both can monodentate, the coordination of bidentate pattern, again can the coordination of bridging pattern, coordination mode is various, for the synthetic polynuclear coordination compound of assembling provides favourable condition.The poly carboxylic acid part is different according to the deprotonation degree, and what can be used as hydrogen bond gives body and acceptor, for the formation of hydrogen bond provides favourable condition; And itself contains pyridine ring, and making π-π interact becomes possibility, therefore makes up the supramolecular system that three-dimensional coordination polymer is expected to obtain special light, magnetic property with this organic polydentate ligand.It obtains extensive studies and application in the ambits such as reaction, biological chemistry simulator and analytical chemistry such as stereochemistry, structure, magnetic, spectrum kinetics and reaction mechanism and part.
Obtain that structure is abundant, the 6-methyl-2,3 of excellent performance, 5-pyridine tricarboxylic acid (H
3Mptc) title complex is the most basic will synthesize purified 6-methyl-2,3,5-pyridine tricarboxylic acid (H exactly
3Mptc).
Present 6-methyl-2,3,5-pyridine tricarboxylic acid (H
3Mptc) compound method is not seen bibliographical information, and people such as nineteen fifty-one E.M.BOTTORFF once reported 6-methyl-2,3; The compound method of 5-pyridine tricarboxylic acid triethyl, this method raw materials cost is higher, and reaction conditions is harsh; Wayward; And do not relate to about 6-methyl-2,3 5-pyridine tricarboxylic acid (H
3Mptc) compound method.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, propose 6-methyl-2,3, the 5-pyridine tricarboxylic acid.
Second purpose of the present invention provides 6-methyl-2,3, the compound method of 5-pyridine tricarboxylic acid.
Technical scheme of the present invention is summarized as follows:
6-methyl-2,3, the 5-pyridine tricarboxylic acid, represent with formula (I):
A kind of 6-methyl-2,3, the compound method of 5-pyridine tricarboxylic acid comprises the steps:
2,6-dimethyl--3, the hydrolysis under alkaline condition of 5-dinicotinic acid diethyl ester obtains 2,6-dimethyl--3,5-dinicotinic acid potassium; By 2,6-dimethyl--3,5-dinicotinic acid potassium is 1 with potassium permanganate amount of substance ratio: the ratio of 1.8-2.5, to said 2; 6-dimethyl--3, the adding massfraction is 3%～9% potassium permanganate solution in the 5-dinicotinic acid potassium pressed powder, stirring heating is at 70～75 ℃; Reaction 14～30h is cooled to room temperature, filters, and filtrating is regulated pH=0.5～1.5 with concentrated hydrochloric acid; The room temperature held is separated out colourless rectangle sheet crystal and is 6-methyl-2,3, the 5-pyridine tricarboxylic acid.
Preferably 2,6-dimethyl--3,5-dinicotinic acid potassium is 1: 2.1 with potassium permanganate amount of substance ratio.
Described KMnO
4Aqueous solution massfraction is 5.7%, said KMnO
4The adding of the aqueous solution divides 5-15 adding, is that purple with reaction soln takes off continued and adds the KMnO that next time adds
4The aqueous solution.
The temperature of said reaction is 72～74 ℃.
The said reaction times is 18～20h.
The pH=1 that described filtrating is regulated with concentrated hydrochloric acid.Regulate with concentrated hydrochloric acid, remove because of the relatively large and unnecessary concentrated hydrochloric acid of the solubleness under the Repone K room temperature that generates volatilizees easily.
The invention has the beneficial effects as follows: the reaction low toxicity; Belong to green synthetic; Raw material potassium permanganate is cheap and be easy to get; Simple and the easy control of reaction conditions of experimental implementation, the pyridinetricarboxylic acid part that the structural symmetry that obtains is low, can make up novel structure and coordination mode title complex helps the research of ligand polymer.
Description of drawings
Fig. 1 is the existing chemical reaction synoptic diagram relevant with the present invention.
Fig. 2 is a chemical reaction synoptic diagram of the present invention.
Fig. 3 is for being schematic flow sheet of the present invention.
Fig. 4 is a 6-methyl-2,3, the infrared spectrum of 5-pyridine tricarboxylic acid.
Fig. 5 is a 6-methyl-2,3, the thermogravimetric spectrogram of 5-pyridine tricarboxylic acid.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is described in further detail:
2,6-dimethyl--3, the hydrolysis under alkaline condition of 5-dinicotinic acid diethyl ester obtains 2,6-dimethyl--3,5-dinicotinic acid potassium.
Embodiment 1
Weighing 2,6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate; According to 2,6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate amount of substance ratio are to feed intake at 1: 2; Wherein potassium permanganate is that to use dissolved in distilled water to process massfraction be to add behind 5% the potassium permanganate solution; Stirring heating is 70～71 ℃ in temperature, and the potassium permanganate solution purple does not take off fully behind the reaction 20h.
Through measuring, the yield of the product that the method for present embodiment generates is low.
Embodiment 2
Weighing 2; 6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate are according to 2; 6-dimethyl--3; 5-dinicotinic acid potassium and potassium permanganate amount of substance ratio are to feed intake at 1: 2, and wherein potassium permanganate is that to use dissolved in distilled water to process massfraction be to divide 10 times behind 5% the potassium permanganate solution to add KMnO
4Each adding of the aqueous solution is to add after the purple of the reaction soln after adding with the last time takes off again, stirring heating, and at 72～74 ℃, reaction 20h; Be cooled to room temperature, filter, filtrating is adjusted to pH=1 with concentrated hydrochloric acid; The room temperature held is separated out colourless rectangle sheet crystal, and productive rate is 41.0%.Be 6-methyl-2,3,5-pyridine tricarboxylic acid (H through detecting
3Mptc) see Fig. 4, Fig. 5.Fig. 2, Fig. 3 (K are seen in reaction equation and technical process
2PT is 2,6-dimethyl--3,5-dinicotinic acid potassium).
Embodiment 3
Weighing 2; 6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate are according to 2; 6-dimethyl--3; 5-dinicotinic acid potassium and potassium permanganate amount of substance ratio are to feed intake at 1: 2.1, and wherein potassium permanganate is that to use dissolved in distilled water to process massfraction be to divide 10 times behind 5.7% the potassium permanganate solution to add, and take off continued with the purple of reaction soln and add the KMnO that next time adds
4The aqueous solution, stirring heating, at 72-74 ℃, reaction 20h is cooled to room temperature, filters, and filtrating is adjusted to pH=1 with concentrated hydrochloric acid, and the room temperature held is separated out H
3The colourless rectangle sheet of mptc crystal, productive rate is 49.8%.
Embodiment 4
Weighing 2; 6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate are according to 2; 6-dimethyl--3; 5-dinicotinic acid potassium and potassium permanganate amount of substance ratio are to feed intake at 1: 2.3, and wherein potassium permanganate is that to use dissolved in distilled water to process massfraction be to divide 10 times behind 5% the potassium permanganate solution to add, and are that purple with reaction soln takes off continued and adds the KMnO that next time adds
4The aqueous solution, stirring heating, at 72～74 ℃, reaction 20h is cooled to room temperature, filters, and filtrating is adjusted to pH=1 with concentrated hydrochloric acid, and the room temperature held is separated out H
3The colourless rectangle sheet of mptc crystal, productive rate is 39.0%.
Embodiment 5
Weighing 2; 6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate are according to 2; 6-dimethyl--3; 5-dinicotinic acid potassium and potassium permanganate amount of substance ratio are to feed intake at 1: 1.8, and wherein potassium permanganate is that to use dissolved in distilled water to process massfraction be to divide 5 times behind 3% the potassium permanganate solution to add, and are that purple with reaction soln takes off continued and adds the KMnO that next time adds
4The aqueous solution, stirring heating, at 73～75 ℃, reaction 14h is cooled to room temperature, filters, and filtrating is adjusted to pH=1 with concentrated hydrochloric acid, and the room temperature held is separated out H
3The colourless rectangle sheet of mptc crystal, productive rate is 30.0%.
Embodiment 6
Weighing 2; 6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate are according to 2; 6-dimethyl--3; 5-dinicotinic acid potassium and potassium permanganate amount of substance ratio are to feed intake at 1: 2.5, and wherein potassium permanganate is that to use dissolved in distilled water to process massfraction be to divide 15 times behind 9% the potassium permanganate solution to add, and are that purple with reaction soln takes off continued and adds the KMnO that next time adds
4The aqueous solution, stirring heating, at 72～74 ℃, reaction 30h is cooled to room temperature, filters, and filtrating is adjusted to pH=0.5 with concentrated hydrochloric acid, and the room temperature held is separated out H
3The colourless rectangle sheet of mptc crystal, productive rate is 40.0%.
Embodiment 7
Weighing 2; 6-dimethyl--3,5-dinicotinic acid potassium and potassium permanganate are according to 2; 6-dimethyl--3; 5-dinicotinic acid potassium and potassium permanganate amount of substance ratio are to feed intake at 1: 2.3, and wherein potassium permanganate is that to use dissolved in distilled water to process massfraction be to divide 10 times behind 5% the potassium permanganate solution to add, and are that purple with reaction soln takes off continued and adds the KMnO that next time adds
4The aqueous solution, stirring heating, at 72～74 ℃, reaction 20h is cooled to room temperature, filters, and filtrating is adjusted to pH=1.5 with concentrated hydrochloric acid, and the room temperature held is separated out H
3The colourless rectangle sheet of mptc crystal, productive rate is 35.0%.
Claims (6)
1. 6-methyl-2,3, the compound method of 5-pyridine tricarboxylic acid is characterized in that comprising the steps:
2,6-dimethyl--3, the hydrolysis under alkaline condition of 5-dinicotinic acid diethyl ester obtains 2,6-dimethyl--3,5-dinicotinic acid potassium; By 2,6-dimethyl--3,5-dinicotinic acid potassium is 1 with potassium permanganate amount of substance ratio: the ratio of 1.8-2.5, to said 2; 6-dimethyl--3, the adding massfraction is 3%～9% potassium permanganate solution in the 5-dinicotinic acid potassium pressed powder, stirring heating is at 70～75 ℃; Reaction 14～30h is cooled to room temperature, filters, and filtrating is regulated pH=0.5～1.5 with concentrated hydrochloric acid; The room temperature held is separated out colourless rectangle sheet crystal and is 6-methyl-2,3, the 5-pyridine tricarboxylic acid.
2. a kind of 6-methyl-2,3 according to claim 1, the compound method of 5-pyridine tricarboxylic acid, it is characterized in that said 2,6-dimethyl--3,5-dinicotinic acid potassium is 1: 2.1 with potassium permanganate amount of substance ratio.
3. a kind of 6-methyl-2,3 according to claim 1, the compound method of 5-pyridine tricarboxylic acid is characterized in that described KMnO
4Aqueous solution massfraction is 5.7%, said KMnO
4The adding of the aqueous solution divides 5-15 adding, is that purple with reaction soln takes off continued and adds the KMnO that next time adds
4The aqueous solution.
4. a kind of 6-methyl-2,3 according to claim 1, the compound method of 5-pyridine tricarboxylic acid, the temperature that it is characterized in that said reaction is 72～74 ℃.
5. a kind of 6-methyl-2,3 according to claim 1, the compound method of 5-pyridine tricarboxylic acid is characterized in that the said reaction times is 18～20h.
6. a kind of 6-methyl-2,3 according to claim 1, the compound method of 5-pyridine tricarboxylic acid is characterized in that the pH=1 that described filtrating is regulated with concentrated hydrochloric acid.
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