CN102532145A - Method for synthesizing hydrated dipyridino hexahydro triazine bromide salt - Google Patents
Method for synthesizing hydrated dipyridino hexahydro triazine bromide salt Download PDFInfo
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- CN102532145A CN102532145A CN2012100097332A CN201210009733A CN102532145A CN 102532145 A CN102532145 A CN 102532145A CN 2012100097332 A CN2012100097332 A CN 2012100097332A CN 201210009733 A CN201210009733 A CN 201210009733A CN 102532145 A CN102532145 A CN 102532145A
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- methylene bromide
- dipyridino
- aminopyridines
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Abstract
The invention discloses a method for synthesizing a hydrated dipyridino hexahydro triazine bromide salt. The method comprises the step of carrying out a reaction on 2-amino pyridine substances and dibromomethane under the reflux state so as to synthesize a series of nitrogen cyanine compounds. The nitrogen cyanine compounds synthesized by using the method can show absorption performance in an ultraviolet light-visible light region and have fluorescent properties. The method disclosed by the invention has the advantages of simple step and high yield, and is convenient.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly pyridines N heterocycle and methylene bromide synthetic technology, specifically a kind of method of synthetic hydration bromination two pyrido Hexahydrotriazine salt.
Background technology
The azacyanine compound is a triazine derivative, is specially 1,3,5-triazines, and s-triazine is a clear crystal, is produced by prussic acid and hcl reaction, can in industrial production such as papermaking, coating, use as sterilant.Cyanidin(e) is also very important in dyestuff and pharmaceutical industry, can be used as cancer therapy drug like tretamine.
Pyridine and pyridine growth exist reactive behavior very high because of the N element, in the organic synthesis field extensive use are arranged.Methylene halide also has high reaction activity and high; As reports such as Wamser utilize synthetic at normal temperatures and pressures dichloride 1,1 '-methylene radical two pyridines of pyridine and methylene dichloride (reference: J. Org. Chem. Vol. 75, No. 12; 2010,4292-4295).But pyridine and pyridine compounds and their and methylene bromide synthetic nitrogen cyanine compound rarely have report, and only report such as Haddadin utilizes 2-EL-970 and methylene iodide in acetonitrile solvent, to reflux and obtains azacyanine, and productive rate have only 25% (reference:
J. Org. Chem., Vol. 66, and No. 4,2001,1310-1315), methylene iodide not only costs an arm and a leg, and has stronger toxicity, and decomposes is emitted deleterious iodide flue gas; Be reflected in the acetonitrile solution and carry out, subsequent disposal is brought certain influence.
Summary of the invention
The compound method that the purpose of this invention is to provide a kind of hydration bromination two pyrido Hexahydrotriazine salt, this method utilize 2-aminopyridines and comparatively cheap methylene bromide under the condition of not having other solvent, to synthesize azacyanine, and product yield is higher.
The objective of the invention is to realize like this:
A kind of compound method of hydration bromination two pyrido Hexahydrotriazine salt may further comprise the steps:
A) in having the reaction vessel of reflux, add 2-aminopyridines and methylene bromide, reaction under 100 ℃ of-120 ℃ of oil baths;
B) during reaction was carried out, with wetting pH detection paper, if no ammonia produces, reaction finished;
C) after reaction finishes, be cooled to room temperature, resultant is separated out, and remaining methylene bromide is removed in underpressure distillation, gets said hydration bromination two pyrido Hexahydrotriazine salt; Wherein:
Said 2-aminopyridines and methylene bromide mol ratio are 0.05:1-2:1;
Said 2-aminopyridines is 2-EL-970,5-bromo-2-EL-970 or 3,5-two bromo-2-EL-970s.
Its reaction expression is:
In the formula: R
1=R
2=H, R
1=H, R
2=Br or R
1=R
2=Br.
Products therefrom through characterize after the drying or in methyl alcohol isopolarity solvent recrystallization obtain crystal.
The present invention utilizes 2-EL-970 and comparatively cheap methylene bromide under the condition of not having other solvent, to synthesize the bromination azacyanine, and product yield is high, can carry out suitability for industrialized production.Material of the present invention has important use in dyestuff and pharmaceutical industry, in industrial circles such as papermaking, coating, can be used as sterilant and use, also can be as pharmaceutical intermediate in pharmaceutical industries.
Description of drawings
Fig. 1 is the single crystal structure ellipsoid figure of product of the present invention; C1-C11 represents 11 carbon atoms among the figure, and N1-N3 represents 3 nitrogen-atoms, and O1-O3 represents 3 Sauerstoffatoms, and Br1 represents 1 bromine atoms, and 10 unblanketed circles are represented 10 Wasserstoffatomss on the azacyanine ring;
Fig. 2 is a product fluorescence excitation collection of illustrative plates of the present invention, under the 475nm emission wavelength excites, obtains, and the maximum excitation wavelength is 393.4nm;
Fig. 3 is a product fluorescent emission collection of illustrative plates of the present invention, under the 393nm excitation wavelength excites, obtains, and maximum emission wavelength is 477.6nm.
Embodiment
Embodiment 1
1.0002g the 2-EL-970 joins in the 100mL flask, and adds the 15.0mL methylene bromide, connects reflux, reaction is 3 hours in 110 ℃ of oil baths, and after reaction finished, the cooling flask was to room temperature.Remaining methylene bromide is removed in underpressure distillation, obtains the glassy yellow pressed powder, is dissolved in methyl alcohol, and recrystallization under the room temperature obtains light yellow crystal 1.5238g, and productive rate is 90.20%.
Embodiment 2
1.5332g 5-bromo-2-EL-970 joins in the 100mL flask, and adds the 10.0mL methylene bromide, connects reflux, reaction is 3 hours in 110 ℃ of oil baths, and after reaction finished, the cooling flask was to room temperature.Remaining methylene bromide is removed in underpressure distillation, after drying, obtains 1.8390g faint yellow solid powder, and productive rate is 87.25%.
Embodiment 3
2.0128g 3,5-two bromo-2-EL-970s join in the 100mL flask, and add the 5.0mL methylene bromide, connect reflux, reaction is 3 hours in 120 ℃ of oil baths, and after reaction finished, the cooling flask was to room temperature.Remaining methylene bromide is removed in underpressure distillation, after drying, obtains 2.0147g brown solid powder, and productive rate is 79.61%.
Claims (1)
1. the compound method of hydration bromination two pyrido Hexahydrotriazine salt is characterized in that this method comprises following concrete steps:
A) in having the reaction vessel of reflux, add 2-aminopyridines and methylene bromide, reaction under 100 ℃ of-120 ℃ of oil baths;
B) during reaction was carried out, with wetting pH detection paper, if no ammonia produces, reaction finished;
C) after reaction finishes, be cooled to room temperature, resultant is separated out, and remaining methylene bromide is removed in underpressure distillation, gets said hydration bromination two pyrido Hexahydrotriazine salt; Wherein:
Said 2-aminopyridines and methylene bromide mol ratio are 0.05:1-2:1;
Said 2-aminopyridines is 2-EL-970,5-bromo-2-EL-970 or 3,5-two bromo-2-EL-970s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100097332A CN102532145A (en) | 2012-01-13 | 2012-01-13 | Method for synthesizing hydrated dipyridino hexahydro triazine bromide salt |
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|---|---|---|---|
| CN2012100097332A CN102532145A (en) | 2012-01-13 | 2012-01-13 | Method for synthesizing hydrated dipyridino hexahydro triazine bromide salt |
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| CN2012100097332A Pending CN102532145A (en) | 2012-01-13 | 2012-01-13 | Method for synthesizing hydrated dipyridino hexahydro triazine bromide salt |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594413A (en) * | 1985-08-13 | 1986-06-10 | The United States Of America As Represented By The Secretary Of The Army | Preparation of N,N'-methylene-2,2'-azopyridocyanines |
| CN101107328A (en) * | 2005-01-25 | 2008-01-16 | 宝洁公司 | Dyeing agent containing cationic azacyanine dye |
-
2012
- 2012-01-13 CN CN2012100097332A patent/CN102532145A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4594413A (en) * | 1985-08-13 | 1986-06-10 | The United States Of America As Represented By The Secretary Of The Army | Preparation of N,N'-methylene-2,2'-azopyridocyanines |
| CN101107328A (en) * | 2005-01-25 | 2008-01-16 | 宝洁公司 | Dyeing agent containing cationic azacyanine dye |
Non-Patent Citations (2)
| Title |
|---|
| KEVIN S. HUANG，等: "Synthesis and Reactions of Some Heterocyclic Azacyanines", 《J. ORG. CHEM.》 * |
| S. MUNAVALLI，等: "One-step synthesis of N,N"-methylene-2,2"-azapyridocyanines", 《SYNTHESIS》 * |
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Application publication date: 20120704 |