CN101880279B - One-step synthetic method of symmetrical 1,10-phenanthroline derivatives - Google Patents
One-step synthetic method of symmetrical 1,10-phenanthroline derivatives Download PDFInfo
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Abstract
The invention relates to a one-step synthetic method of symmetrical 1,10-phenanthroline derivatives in the field of organic synthesis, in particular to a one-step synthetic method of symmetrical 1,10-phenanthroline derivatives shown as the formula I. The one-step synthetic method comprises the following steps of: adding components in the formula III in concentrated hydrochloric acid solutions in the formula II to react, and then carrying out one-step synthesis in the presence of mixed shrinking agents to obtain the symmetrical 1,10-phenanthroline derivatives, wherein the mixed shrinking agents are the mixtures of concentrated hydrochloric acid and organic acid. The organic acid has the functions of a phase transfer catalyst and a shrinking agent, and meanwhile, the organic acid as a buffering reagent reduces the polymerization of the components in the formula III to reduce the generation of side reaction and has the advantages of high purity, mild reaction and easy control. Because no pollutants are added and generated in the reaction, waste liquor can be safely discharged, a ketone solvent is adopted in the aftertreatment of the reaction so that a separation step is reduced, the losses of the products are reduced, the yield is improved, and the obtained phenanthroline derivatives can be applied in the fields of ion detection, luminescent materials and medicine.
Description
Technical field
The invention belongs to the organic synthesis field, it is efficiently synthetic symmetric 1 to relate to single stage method, and the method for the luxuriant and rich with fragrance network quinoline derivant of 10-can be applied it at ion detection, luminescent material, medical field.
Technical background
1,10-brown envelope morpholine compound is one of research and most widely used nitrogen heterocyclic ring sequestrant.As an important part, its a lot of complex compounds have all been brought into play important effect (P.G.Sammes, G.Yahioglu, Chem.Sov.Rev., 1994,23,327) in a lot of fields.With 1, the 10-phenanthroline derivative is that the complex compound of part has good optical character, can be used as photosensitizers and photocatalyst (R.Sahai, L.Morgan, D.P.Killema, Inorg.Chem., 1988,27,3495).Particularly symmetrical dibasic 1, the 10-phenanthroline derivative because this type of material can keep two portions symmetry of ligand, produces steric isomerism when can be good at avoiding with metal complex, therefore be one type of particularly important and the compound that is worth research.
2,9-dimethyl--4,7-phenylbenzene-1,10-phenanthroline, 4; 7-phenylbenzene-1,10-phenanthroline, 5,6-dimethyl--1,10-phenanthroline etc. is 1; Important compound in the 10-brown envelope morpholine verivate can be used for detecting metals ion, can also be used in the photovaltaic material aspect.2,9-dimethyl--4,7-phenylbenzene-1,10-phenanthroline are because of a plurality of benzene ring structures, and fusing point is up to 288 ℃, and therefore energy level 3.3eV is commonly used to as exciton/hole barrier materials in OLED.In addition, 2,9-dimethyl--4,7-phenylbenzene-1,10-phenanthroline, 4,7-phenylbenzene-1,10-phenanthroline sulphonate can be used in medical science (Mohindru, A., Fisher, J.M., Rabinovitz, M., Nature, 1983,303,64-65.).But the synthetic of these phenanthroline derivatives is not very desirable, and synthetic at present this type material mainly is Skraup and Doebner-von Miller synthesis method, need use arsenic acid or five arsenic oxide arsenoxides (Case F.H.; Brennan J.A., J.Org.Chem., 1954; 19,919.); Need three-step reaction, react very violent, productive rate has only percentum, is not suitable for industriallization.The shortcoming of these methods is that midbody is many, productive rate is extremely low, only prepares few products and will spend long time, and complicated steps, and is of poor benefits above the economic benefit angle.Czech patents CS146036 has proposed to come Synthetic 2 with single stage method, 9-dimethyl--4,7-phenylbenzene-1, the 10-phenanthroline, though synthetic route from three the step change a step into, saved great amount of manpower, remain arsenic as oxygenant, environmental pollution is also very heavy; And poor repeatability, aftertreatment is also very complicated, produces a large amount of industrial sewages, therefore needs to seek and does not use the synthetic route of arsenic compound as oxygenant.Mentioned among the Czech patents CS226921 with tetrachloro quinhydrones, DDQ etc. and synthesized 1 as oxygenant; 10-brown envelope morpholine verivate; Though this method has been broken away from the use of arsenic compound; But in course of industrialization, run into very big problem, the tetrachloro quinhydrones is insoluble to acidic solution and organic solvent after reaction, is difficult to handle; And can be lost at the aftertreatment large-tonnage product, productive rate is also only less than 10%, and it is very big that experiment is influenced by temperature of reaction, aftertreatment etc.According to the compound method of having reported at present, need seek not only environmental protection but also the high method of productive rate.
Summary of the invention
To the defective in the above-mentioned field, it is a kind of symmetric 1 that the present invention provides, the one-step method for synthesizing of the luxuriant and rich with fragrance network quinoline derivant of 10-, and this method is prone to control, environmental protection, and productive rate is high, and product purity is good.
Symmetric 1 suc as formula shown in the I, the luxuriant and rich with fragrance network quinoline derivant of 10-one-step method for synthesizing joins formula III in the concentrated hydrochloric acid solution of formula II and reacts, and next step syntheticly promptly gets in the condition of mixing dehydrating agent again, and said mixing dehydrating agent is concentrated hydrochloric acid and organic acid mixture,
R wherein
1, R
2, R
4Independent is alkyl, the hydrogen of C1-4, R
3Be alkyl, hydrogen, phenyl, halogeno-benzene, naphthyl, xenyl.
Said R
1, R
2, R
4Independent is methyl, hydrogen, R
3Be alkyl, hydrogen, phenyl.
Said organic acid is one or more in formic acid, acetate, propionic acid, butyric acid, the valeric acid.
Said concentrated hydrochloric acid and organic acid volume ratio are 1: 9～9: 1; The volume ratio that is more suitable for 3: 7～7: 3.
Said compound method comprises the steps: 1) under 50-90 ℃, in the concentrated hydrochloric acid solution of formula II, add formula III, reacted 2-10 hour; 2) add organic acid, at 90-110 ℃, back flow reaction was at 2-10 hour.
The reaction conditions of said step 1) is: under 70-85 ℃, reacted 2-8 hour.
Said step 2) reaction conditions is: 90-100 ℃, back flow reaction was at 2-8 hour.
The preparation method of the concentrated hydrochloric acid solution of said step 1) formula II is for to add reaction vessel with concentrated hydrochloric acid, and formula II adds reaction flask in batches, stirs 1-6 hour.
Said compound method also comprises post-processing step, and said post-processing step is that end reaction liquid is added ammoniacal liquor 0-5 ℃ the time, transfers pH=10-13, removes water layer, adds ketones solvent, separates out solid; Suction filtration, washing, drying.
Said ketones solvent is acetone, butanone, 2, one or more in the 5-hexanedione.
2,9-dimethyl--4,7-phenylbenzene-1,10-phenanthroline etc. 1,10-brown envelope morpholine verivate be synthetic through Skraup and Doebner-von Miller reaction, has the problem of the low and high pollution of productive rate; Improve productive rate and solve problem of environmental pollution, need consider from the synthetic reaction mechanism.It is synthetic 1 that the essence of one-step method for synthesizing is that O-Phenylene Diamine group verivate and ketenes formula structure react, and 10-brown envelope morpholine structure ring, so symmetrical expression 1,10-brown envelope morpholine verivate also can adopt single stage method synthetic.As starting raw material, be converted into hydrochloride with adjacent diphenylamine derivatives, easy like this reaction at sour environment; In sour environment, addition reaction can take place with III and generate IV in amido, and is converted into V very soon.
Compound V continues to repeat top reaction with III, obtains compound I.Compound V is synthetic easily, and the conversion of compound I then need be by oxygenant or suitable cyclization agent; Synthesis technique adopted the vitriol oil, SPA as dehydrating agent in the past, and five arsenic oxide arsenoxides or arsenic acid are as oxygenant, and cyclization and dehydrogenation condition are violent, so productive rate is low, side reaction is many.In building-up process, the vitriol oil, SPA use as dehydrating agent, and the reaction conditions productive rate that changes a little will have very big fluctuation, be not suitable for suitability for industrialized production.Control productive rate and need keep two step successive reactions to carry out smoothly, select suitable oxygenant and dewatering agent, reduce reaction conditions.Polymerization takes place because there are two keys in compound III easily under strong acid environment, therefore can adopt compound III to join reaction system, reduces the generation of by product.It is constant to add the compound III holding temperature, obtains compound IV, V, adds organic acid and has promoted condensation reaction, also plays the effect of phase transition simultaneously; Reduce reflux temperature with the mixing dehydrating agent, reduced the generation of side reaction.The product that reaction finishes to obtain is the form of hydrochloride, need it be discharged with alkali, and ammoniacal liquor is very economy and effective agents.The mixture that processing finishes is handled with ketones solvent, and by product is dissolved in ketones solvent, separates out high purity product.
The synthesis technique of this patent can carry out according to following:
(1) concentrated hydrochloric acid adds reaction vessel, and II adds reaction flask at a certain temperature in batches, stirs 1-6 hour, and II is converted into hydrochloride form.
(2) add III down at 70-85 ℃, reaction is 2-8 hour under this temperature, and the hydrochloride of II is converted into IV, V, and organic acid adds in batches.
(3) elevated temperature refluxes, and temperature is reflected at end in 2-8 hour at 90-100 ℃.
(4) reaction solution is 0-5 ℃ of dropping ammonia, and PH=8-10 removes water layer, adds ketones solvent, stirs, separates out solid; Suction filtration, washing, drying.
The technology that provides has above solved that present productive rate is low, by product is many, has reduced environmental pollution, has the following advantages:
(1) is stable hydrochloride form with active feedstock conversion, helps the carrying out that reacts.、
(2) the O-phenylene diamine derivatives hydrochloride is converted into IV, V under the hydrochloric acid condition, and organic acid plays phase-transfer catalyst and dehydrating agent effect; Organic acid reduces the polyreaction of III as buffer reagent; Non-oxidation agent system has reduced by-product answers, and promotes reaction to carry out.
(3) ketone solvent reduces separating step, reduces product losses, improves productive rate.
Description of drawings
The DSC spectrogram of Fig. 1, embodiment 1 compound, ordinary method heats up with 10 ℃/min under the nitrogen protection, 288.77 ℃ of product fusing points, the instrument model is: 2910MDSC V4.4E.
The DSC spectrogram of Fig. 2, comparative example 1 compound, ordinary method heats up with 10 ℃/min under the nitrogen protection, 287.96 ℃ of product fusing points, the instrument model is: 2910MDSC V4.4E.
The TGA spectrogram of Fig. 3, embodiment 1 compound, ordinary method heats up with 10 ℃/min under the nitrogen protection, and used instrument model is: TAG Q5000V3.5Build 252.
The TGA spectrogram of Fig. 4, comparative example 1 compound, ordinary method heats up with 10 ℃/min under the nitrogen protection, and used instrument model is: TAG Q5000V3.5Build 252.
The DSC spectrogram of Fig. 5, embodiment 3 compounds, ordinary method heats up with 10 ℃/min under the nitrogen protection, 221.36 ℃ of product fusing points, the instrument model is: 2910MDSC V4.4E.
The TGA spectrogram of Fig. 6, embodiment 3 compounds, ordinary method heats up with 10 ℃/min under the nitrogen protection, and used instrument model is: TAG Q5000V3.5Build 252.
The practical implementation method
2,9-dimethyl--4,7-phenylbenzene-1,10-phenanthroline
Comparative example 1: (five arsenic oxide arsenoxide methods)
Add the 10l concentrated hydrochloric acid earlier, stir, add O-Phenylene Diamine 885g then, 60 ℃ were stirred 2 hours; 70-85 ℃ of phenyl propenyl ketone 2630g adds, and stirs 3 hours, adds arsenic acid 1883g in the whipping process.Be warming up to 93 ℃, back flow reaction 8h, reaction solution is brown.Stop heating, reduce to room temperature, the ice bath cooling adds the 10kg ice cube in the stirring downhill reaction liquid in batches, adds ammonia soln again, regulates 8-10, divides and goes upper aqueous layer.
In the thick material of black, add 10l acetone and stir 1h, filter, get the about 1.7kg of yellow filter cake.Filter cake places the container 4l that adds methylene chloride, and stirs filtration in 1 hour, revolves to steam methylene dichloride filtrating, adds acetone behind the evaporate to dryness, filter, product 287.68g purity 96%, the product of purifying more than 98%, productive rate 8%.
HNMR(CDCl
3，400MHz)δ(ppm)：3.1(s，3H)，7.56(s，1H)，7.62(m，5H)，7.86(s，1H)。
MS(EI)360
Embodiment 1: (the inventive method)
Add the 6.5l concentrated hydrochloric acid earlier, add O-Phenylene Diamine 470g, 60 ℃ were stirred 2 hours, and 70-85 ℃ of phenyl propenyl ketone 1.3kg adds, and stirred 3 hours, added 5l acetate in the whipping process.Be warming up to 94 ℃, back flow reaction 8h, reaction solution is brown.Stop heating, reduce to room temperature, the ice bath cooling adds the 6kg ice cube in the stirring downhill reaction liquid in batches, adds ammonia soln again, regulates 8-10, divides and goes upper aqueous layer.
In the thick material of black, add 6l acetone and stir 1h, filter, get yellow filter cake 300g.Recrystallization gets product 230g purity 99%, productive rate 16%.
HNMR(CDCl
3，400MHz)δ(ppm)：3.1(s，3H)，7.56(s，1H)，7.62(m，5H)，7.86(s，1H)。
MS(EI)360
Embodiment 2: (amplifying according to embodiment 1)
According to embodiment 1 method, amplify 10 times, obtain productive rate at 16-28%, waste reaction solution is not because contain hazardous substance and can discharge.
Comparative Examples 2: (tetrachloro quinhydrones method)
Add the 500ml concentrated hydrochloric acid, add O-Phenylene Diamine 27g, 60 ℃ were stirred 2 hours, and 70-85 ℃ of phenyl propenyl ketone 80g adds, and stirs 3 hours, adds 135g tetrachloro quinhydrones in the whipping process in batches.Slowly be warming up to 94 ℃, back flow reaction 8h, reaction solution is brown.Stop heating, reduce to room temperature, adding 500g ice cube in the downhill reaction liquid is stirred in the ice bath cooling, adds ammonia soln again, regulates 8-10, divides and goes upper aqueous layer.
In the thick material of black, add 600ml acetone, stir 1h, filter, get yellow filter cake.Recrystallization gets product 13g purity 99%, productive rate 12%.
HNMR(CDCl
3，400MHz)δ(ppm)：3.1(s，3H)，7.56(s，1H)，7.62(m，5H)，7.86(s，1H)。
MS(EI)360
Comparative Examples 3: (amplifying) by Comparative Examples 2 tetrachloro quinhydrones methods
According to Comparative Examples 2 methods, amplify 10 times, caking phenomenon takes place in cooling, can't handle, and reheat also can't dissolved solids; Produce a large amount of insoluble solids,, polluted environment because the by product of tetrachloro quinhydrones contains a large amount of organic chlorides.4,7-phenylbenzene-1,10-phenanthroline
Comparative Examples 4: (tetrachloro quinhydrones method)
Concentrated hydrochloric acid 3l adds the 5l reaction flask, and 50 ℃ of branches add O-Phenylene Diamine 162g, stir 1 hour, add β-chloro-benzene acetone 556g then, and color becomes redness; Stir half a hour, add tetrachlorobenzoquinone, the very fast browning look of solution.Keep reflux temperature, react 4 hours stopped reaction.Be cooled to room temperature, add in the ice, in the ammoniacal liquor and PH=9-12, separate out solid and become tawny.Add methylene dichloride 20l extraction three times, concentrate methylene dichloride, obtain oily matter, add 15l acetone, separate out a large amount of solid 170g, recrystallization obtains 130 grams, purity 98%, productive rate 26%.Product produces the by product of a large amount of tetrachloro quinhydrones in process of production, is insoluble to organic solvent and hydrochloric acid, has brought environmental pollution.
HNMR(CDCl
3，400MHz)δ(ppm)：7.5(s，5H)，7.56(d，1H)，7.83(s，1H)，9.23(d，1H)。
Embodiment 3: (the inventive method)
Concentrated hydrochloric acid 3l adds the 5l reaction flask, and 50 ℃ of branches add O-Phenylene Diamine 162g, stir 1 hour, add β-chloro-benzene acetone 556g in batches, and color becomes redness; Stirred 1 hour, and dripped 3l acetate, the very fast browning look of solution.Keep reflux temperature, react 4 hours stopped reaction.Be cooled to room temperature, add in the ice, in the ammoniacal liquor and PH=9-12, separate out solid and become tawny.Add methylene dichloride 20l extraction three times, concentrate methylene dichloride, obtain oily matter, add 15l acetone, separate out a large amount of solid 400g, recrystallization obtains 260 grams, purity 98%, productive rate 52%.
HNMR(CDCl
3，400MHz)δ(ppm)：7.5(s，5H)，7.56(d，1H)，7.83(s，1H)，9.23(d，1H)。
5,6-dimethyl--1,10-phenanthroline
Embodiment 4: (the inventive method)
In four-hole boiling flask, add people's concentrated hydrochloric acid 100ml, add 60 ℃ 5,6-dimethyl-pentanoic 10g; Stirred 1 hour; Add glycerine and stir half a hour, add acetate 200ml, make reaction mixture temperature remain on 95 ℃ to 100 ℃ reactions 8 hours; Reaction finishes to be neutralized to PH=9-12 with in the mixture ice of falling people-water with ammonia soln.Divide and remove upper water, use 1l acetone, separate out a large amount of solids, recrystallization obtains product 40%.
HNMR(DMSO，400MHz)δ(ppm)：3.25(s，6H)，7.78(m，2H)，8.6(s，2H)，9.0(d，1H)。
2,9-dimethyl--1,10-phenanthroline
Embodiment 5: (the inventive method)
Phenyl propenyl ketone among the embodiment 1 is replaced with paraldehyde, repeat same operation, obtain 20% white solid 2,9-dimethyl--1,10-phenanthroline.
HNMR(DMSO，400MHz)δ(ppm)：3.0(s，6H)，7.5(d，2H)，8.4(d，2H)，9.1(d，2H)。
3,4,7,8-tetramethyl--1,10-phenanthroline
Embodiment 6: (the inventive method)
Phenyl propenyl ketone among the embodiment 1 is replaced with 3-methyl-3-methylene acetone, repeat same operation, obtain 30% white solid 3,4,7,8-tetramethyl--1,10-phenanthroline.
HNMR(DMSO，400MHz)δ(ppm)：3.1(s，12H)，8.6(d，2H)，9.0(s，2H)。
Mp(℃)：278-280
4,7-dimethyl--1,10-phenanthroline
Embodiment 7: (the inventive method)
Phenyl propenyl ketone among the embodiment 1 is replaced with the 3-methylene acetone, repeat same operation, obtain 40% white solid 4,7-dimethyl--1,10-phenanthroline.
HNMR(DMSO，400MHz)δ(ppm)：3.5(s，6H)，7.2(d，2H)，8.4(d，2H)，9.3(d，2H)。
Mp(℃)：194-196
Claims (9)
1. suc as formula symmetric 1 shown in the I; The luxuriant and rich with fragrance network quinoline derivant of 10-one-step method for synthesizing; Formula III is joined in the concentrated hydrochloric acid solution of formula II and react, next step syntheticly promptly gets in the condition of mixing dehydrating agent again, and said mixing dehydrating agent is concentrated hydrochloric acid and organic acid mixture; Said organic acid is one or more in formic acid, acetate, propionic acid, butyric acid, the valeric acid
R wherein
1, R
2, R
4Independent is alkyl, the hydrogen of C1-4, R
3Be alkyl, hydrogen, phenyl, halogeno-benzene, naphthyl, xenyl.
2. compound method according to claim 1, said R
1, R
2, R
4Independent is methyl, hydrogen, R
3Be alkyl, hydrogen, phenyl.
3. compound method according to claim 1 and 2, said concentrated hydrochloric acid and organic acid volume ratio are 1: 9～9: 1.
4. compound method according to claim 3, said concentrated hydrochloric acid and organic acid volume ratio are 3: 7～7: 3.
5. compound method according to claim 1 and 2 comprises the steps: 1) under 50-90 ℃, in the concentrated hydrochloric acid solution of formula II, add formula III, reacted 2-10 hour; 2) add organic acid, at 90-110 ℃, back flow reaction was at 2-10 hour.
6. compound method according to claim 5, the reaction conditions of said step 1) is: under 70-85 ℃, reacted said step 2 2-8 hour) reaction conditions be: 90-100 ℃, back flow reaction was at 2-8 hour.
7. compound method according to claim 5, the preparation method of the concentrated hydrochloric acid solution of said step 1) formula II is for to add reaction vessel with concentrated hydrochloric acid, and formula II adds reaction flask in batches, stirs 1-6 hour.
8. compound method according to claim 1 and 2, said compound method also comprises post-processing step, said post-processing step is that end reaction liquid is added ammoniacal liquor 0-5 ℃ the time, transfers pH=10-13, removes water layer, adds ketones solvent, separates out solid; Suction filtration, washing, drying.
9. compound method according to claim 8, said ketones solvent are acetone, butanone, 2, one or more in the 5-hexanedione.
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| CN2009100836296A CN101880279B (en) | 2009-05-06 | 2009-05-06 | One-step synthetic method of symmetrical 1,10-phenanthroline derivatives |
| PCT/CN2010/071408 WO2010127574A1 (en) | 2009-05-06 | 2010-03-30 | One-step synthesis method of symmetrical 1,10- phenanthroline derivative |
| HK11102715.7A HK1148735A1 (en) | 2009-05-06 | 2011-03-18 | One-step synthesis method of symmetric 1, 10-phenanthroline derivatives |
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Non-Patent Citations (5)
| Title |
|---|
| G. M. Badger et al.，.Studies on the Doebner-Miller, Skraup, and Related Reactions. IV. Intermediates and By-products in the Preparation of 1,10-Phenanthrolines.《Australian Journal of Chemistry》.1963,第16卷(第5期),840-844. * |
| Gary K. Lund et al.,.Long-chain alkyl-substituted 1,10-phenanthrolines as surfactant ligands for transition-metal ions. 1. Synthesis of 4- and 4,7-n-undecyl-substituted 1,10-phenanthrolines.《J. Chem. Eng. Data》.1981,第26卷(第2期),227-229. * |
| GaryK.Lundetal.，.Long-chainalkyl-substituted1 10-phenanthrolines as surfactant ligands for transition-metal ions. 1. Synthesis of 4- and 4 |
| Graeme Butt et al.,.A simple synthesis of some 1,10-phenanthrolines.《Journal of Heterocyclic Chemistry》.1981,第18卷(第3期),641. * |
| GraemeButtetal.，.Asimplesynthesisofsome1 10-phenanthrolines.《Journal of Heterocyclic Chemistry》.1981 |
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