CN103193813B - Preparation method of borphenyl pyridine - Google Patents
Preparation method of borphenyl pyridine Download PDFInfo
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- CN103193813B CN103193813B CN201310123558.4A CN201310123558A CN103193813B CN 103193813 B CN103193813 B CN 103193813B CN 201310123558 A CN201310123558 A CN 201310123558A CN 103193813 B CN103193813 B CN 103193813B
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Abstract
The invention discloses a preparation method of borphenyl pyridine. The method comprises the following steps: A, preparing phenylmagnesium chloride; B, synthesizing tetraphenyl boric magnesium chloride; C, synthesizing sodium tetraphenylborate; D, synthesizing pyridine hydrochloride; E, synthesizing tetrapheny boron pyridine; and F, synthesizing the borphenyl pyridine. The synthesizing diagram is shown in the specification. The method can be used for easily preparing a final product with high purity and good yield. The method has the characteristics of being simple in process, low in cost and high in product purity.
Description
Technical field
The present invention relates to novel organic boron sterilant---the simple synthesis of borphenyl pyridine, belongs to technical field of chemical synthesis.
Background technology
Although there have other method to carry out dock to be anticorrosion, the utilization of traditional biocide still dominates.The sterilant that past is used in marine finish is organic tin compound (tributyl tin, TBT), and such material has pollution to ocean.2004, the researchist of English Radar Audio Company (Invasta) is proposed commercially produced product Borocide brand, this be a kind of based on borphenyl pyridine containing boron biocide, its maximum feature is environmental friendliness, resolve into non-toxic substance very soon in the seawater, can be used for marine finish.In the prior art, the novel method (JP 2003238572,2003) that Hokko chemical industrial company adopts is a practicable industrial method, and the synthesis of their borphenyl pyridine needs to use sterling sodium tetraphenylborate, which adds synthesis cost.In building-up process, solvent for use is double solvents, so just makes the solvent be recovered use and is restricted.The tetraphenylboron pyridine de-benzene that is heated carries out under single solid, and due to heterogeneity of being heated, product purity is difficult to control.
Summary of the invention
The technical problem to be solved in the present invention overcomes prior art shortcoming, organic boron sterilant is provided---the brand-new synthetic method of one of borphenyl pyridine, the finished product of easy preparation high purity and better yield, has the advantages that technique is simple, with low cost, product purity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows.
A preparation method for borphenyl pyridine, its step comprises:
The preparation of A, phenyl-magnesium-chloride: pass into rare gas element in the reaction vessels that magnesium powder and iodine be housed, then add the mixing solutions of bromobenzene and tetrahydrofuran (THF) in reaction vessels, the color being stirred to iodine disappears; Be heated to 40 DEG C-70 DEG C, then drip the mixing solutions of chlorobenzene and tetrahydrofuran (THF), after dripping off, keep 2-5 hour at 30 DEG C-70 DEG C, and continue to stir; Chemical equation is:
The synthesis of B, tetraphenylphosphonichloride chloride boron magnesium: after question response liquid is cooled to 30 DEG C-50 DEG C, in reaction vessels, drip trimethyl borate and tetrahydrofuran (THF) mixed solution, after all dropwising, reaction solution becomes thick liquid; Reaction solution rotatory evaporator is steamed solvents tetrahydrofurane, and institute's residual solids is tetraphenylphosphonichloride chloride boron magnesium, wherein also containing a small amount of tetrahydrofuran (THF); Chemical equation is:
PhMgCl+B(OMe)
3——→Ph
4BMgCl；
The synthesis of C, sodium tetraphenylborate: the aqueous solution adding sodium carbonate in tetraphenylphosphonichloride chloride boron magnesium, is heated to 40 DEG C-70 DEG C, mechanical stirring 1-5 hour, suction filtration, wash, filtrate; Filtrate is removed remaining tetrahydrofuran (THF) with rotatory evaporator, and remaining solution is the aqueous solution of sodium tetraphenylborate; Chemical equation is:
Ph4BMgCl+Na
2CO
3——→Ph
4BNa；
The synthesis of D, pyridine hydrochloride: get pyridine soluble in water, drips a small amount of hydrochloric acid, prepares pyridine hydrochloride, for subsequent use; Chemical equation is:
The synthesis of E, tetraphenylboron pyridine: drip pyridine hydrochloride in the aqueous solution of sodium tetraphenylborate, and stir, obtain white precipitate, suction filtration gained solid is tetraphenylboron pyridine; Chemical equation is:
The synthesis of F, borphenyl pyridine: add organic solvent in tetraphenylboron pyridine, is heated to 50 DEG C-90 DEG C, stirs 7-9 hour; Place 5-15 hour, suction filtration obtains white solid, is borphenyl pyridine; Use ethanol, petroleum ether borphenyl pyridine crude product again, after washing, product is air-dry, obtain borphenyl pyridine sterling; Chemical equation is:
As a preferred technical solution of the present invention, in steps A, the amount ratio of each raw material is: magnesium powder/g ︰ iodine/g ︰ bromobenzene/mL ︰ tetrahydrofuran (THF)/mL=(14.4 ~ 17.6) ︰ (0.09 ~ 0.11) ︰ (2.3 ~ 2.8) ︰ (36 ~ 44); Chlorobenzene/mL ︰ tetrahydrofuran (THF)/mL=(59.4 ~ 72.6) ︰ (144 ~ 176).
As a preferred technical solution of the present invention, in step B, the amount ratio of each raw material is: trimethyl borate/mL ︰ tetrahydrofuran (THF)/mL=(15.8 ~ 19.3) ︰ (27 ~ 33).
As a preferred technical solution of the present invention, in step C, the amount ratio of each raw material is: sodium carbonate/g ︰ water/mL=(74.4 ~ 91.3) ︰ (517.5 ~ 632.5).
As a preferred technical solution of the present invention, in step D, the amount ratio of each raw material is: pyridine/g ︰ water/mL ︰ hydrochloric acid/mL=(12.51 ~ 15.29) ︰ (22.5 ~ 27.5) ︰ (13.2 ~ 16.2).
As a preferred technical solution of the present invention, in step F, the amount ratio of each raw material is: organic solvent/mL ︰ ethanol/mL ︰ sherwood oil/mL=(225 ~ 275) ︰ (50 ~ 150) ︰ (100 ~ 300).
As a preferred technical solution of the present invention, in steps A, described rare gas element is argon gas or nitrogen.
As a preferred technical solution of the present invention, in step F, described organic solvent is one or more combinations among benzene,toluene,xylene, hexanaphthene, hexane, pentane.
The beneficial effect that produces of technique scheme is adopted to be: to the invention provides novel organic boron sterilant---the simple synthesis of borphenyl pyridine, synthesizing raw materials usedly has chlorobenzene, bromobenzene, iodine, trimethyl borate, magnesium, pyridine, sodium carbonate, tetrahydrofuran (THF), hydrochloric acid, rare gas element and other organic solvent.Whole building-up reactions completes through one kettle way, and intermediate product is without the need to separating-purifying, and solvent can directly be reused after fractionation by distillation, is easy to the finished product preparing high purity and better yield.This synthetic method craft is simple, with low cost, product purity is high.
The testing data of technical solution of the present invention beneficial effect can referring to embodiment part.
Accompanying drawing explanation
Fig. 1 comprises the ir data (C) of product described in the ir data (b) of product prepared by the infrared spectrogram (a) of product prepared by embodiment 1, embodiment 1, document JP 2003238572; Comprehensive Correlation is known, the ir data of embodiment 1 gained the finished product and the ir data of Japanese Patent (JP 2003238572) basically identical, demonstrate the structure of synthesized compound, prove that the finished product are exactly borphenyl pyridine.
Fig. 2 is the liquid chromatogram of embodiment 1 products obtained therefrom.
Fig. 3 is the liquid chromatogram of tetraphenyl boron pyridine in embodiment 1.
Fig. 4 is the liquid chromatogram of pyridine in embodiment 1.
Contrasted from Fig. 2, Fig. 3, Fig. 4: containing unreacted tetraphenyl boron pyridine and pyridine in embodiment 1 the finished product; Under the preparation condition that embodiment 1 adopts, the purity of product is higher, reaches 98.48%, and yield is also higher, reaches 83.7%.
Fig. 5 is the liquid chromatogram of embodiment 2 products obtained therefrom, and as shown in Figure 5, under the preparation condition that embodiment 2 adopts, the purity of product is also higher, reaches 94.00%, and yield is also higher, reaches 82.4%.
Fig. 6 is the liquid chromatogram of embodiment 3 products obtained therefrom, and as shown in Figure 6, under the preparation condition that embodiment 3 adopts, the purity of product is 91.96%, still can reach more than 90.00%, and yield is 75.1%.
Embodiment
Following examples describe the present invention in detail.Various raw material used in the present invention and items of equipment are conventional commercial product, all can be bought by market and directly obtain.
Embodiment 1: a kind of preparation method of borphenyl pyridine, is realized by following steps:
Prepare the input amount of each material used all with trimethyl borate/mL=(15.8 ~ 19.3) be standard, solid is measured in mass, liquid cubing.
(1) being prepared in the 500mL three-necked flask that reflux condensing tube (above filling Y-tube), dropping funnel and magnetic agitation are housed of phenyl-magnesium-chloride (Grignard reagent) adds people 16.0g magnesium powder and 0.1g iodine, by argon replaces, first in reaction flask, add 2.5mL bromobenzene and 40mL tetrahydrofuran (THF) (THF), be stirred to reaction to cause (color of iodine disappears, and releases a large amount of heat).People 66.0mL chlorobenzene, 160.0mL tetrahydrofuran (THF) is added in dropping funnel.After oil bath is heated to 70 DEG C, slowly drip the mixing solutions of chlorobenzene and tetrahydrofuran (THF), 3h drips off.Drip off rear oil bath and keep 70 DEG C, continue stirring reaction 3h.
(2), after the synthesis question response liquid of tetraphenylphosphonichloride chloride boron magnesium is cooled to 50 DEG C, gets the trimethyl borate of 17.5mL and the tetrahydrofuran (THF) mixed solution of 30.0mL with transfer pipet, be added drop-wise in reaction solution, after all dropwising by dropping funnel.Gained thick liquid is transferred in 1000mL single port flask.Solvent (THF) is steamed, this solvent recoverable with rotary evaporation.Institute's residual solids is the mixture of tetraphenylphosphonichloride chloride boron magnesium and a small amount of THF.
PhMgCl+B(OMe)
3——→Ph
4BMgCl
(3) synthesis of sodium tetraphenylborate is by the sodium carbonate solution prepared (83.0g sodium carbonate is dissolved in the water of 575mL) in the tetraphenylphosphonichloride chloride boron magnesium entered except desolventizing, and oil bath is heated to 50 DEG C, mechanical stirring 1h.Suction filtration, washes with water 4X100mL.Gained filtrate removes remaining THF with rotary evaporation.Remaining solution had both been the aqueous solution of sodium tetraphenylborate.
Ph
4BMgCl+Na
2CO
3——→Ph
4BNa
(4) synthesis of pyridine hydrochloride is got pyridine 13.9g and is dissolved in 25mL water, drips the hydrochloric acid 14.7ml of 35.6%.
(5) aqueous solution of sodium tetraphenylborate is transferred in the beaker of 1000mL by the synthesis of tetraphenylboron pyridine, and electric stirring slowly drips the pyridine hydrochloride prepared.Obtain white precipitate, suction filtration gained solid is tetraphenylboron pyridine.
(6) obtained tetraphenylboron pyridine is transferred to and is equipped with in the 500mL three-necked flask of reflux condensing tube by the synthesis of borphenyl pyridine, then adds the toluene of 250mL, and oil bath is heated to 70 DEG C, electric stirring 8h.Place 12h.Suction filtration obtains white solid and is wanted product borphenyl pyridine, uses ethanol 2X(95%) 50mL, sherwood oil 2X100mL rinse.Place ventilation seasoning.
Product is white powder, and weight is 41.5g, and yield is that 83.7%(is in trimethyl borate), liquid chromatographic detection purity is 98.48%(normalization method).
The infrared spectrogram of the present embodiment products obtained therefrom and liquid chromatogram are referring to accompanying drawing 1,2.
Embodiment 2: a kind of preparation method of borphenyl pyridine, is realized by following steps:
Prepare the input amount of each material used all with trimethyl borate/mL=(15.8 ~ 19.3) be standard, solid is measured in mass, liquid cubing.
(1) being prepared in the 500mL three-necked flask that reflux condensing tube (above filling Y-tube), dropping funnel and magnetic agitation are housed of phenyl-magnesium-chloride (Grignard reagent) adds people 16.0g magnesium powder and 0.1g iodine, by argon replaces, first in reaction flask, add 2.5mL bromobenzene and 40mL tetrahydrofuran (THF) (THF), be stirred to reaction to cause (color of iodine disappears, and releases a large amount of heat).People 66.0mL chlorobenzene, 160.0mL tetrahydrofuran (THF) is added in dropping funnel.After oil bath is heated to 60 DEG C, slowly drip the mixing solutions of chlorobenzene and tetrahydrofuran (THF), 3h drips off.Drip off rear oil bath and keep 60 DEG C, continue stirring reaction 5h.
(2), after the synthesis question response liquid of tetraphenylphosphonichloride chloride boron magnesium is cooled to 40 DEG C, gets the trimethyl borate of 17.5mL and the tetrahydrofuran (THF) mixed solution of 30.0mL with transfer pipet, be added drop-wise in reaction solution, after all dropwising by dropping funnel.Gained thick liquid is transferred in 1000mL single port flask.Solvent (THF) is steamed, this solvent recoverable with rotary evaporation.Institute's residual solids is the mixture of tetraphenylphosphonichloride chloride boron magnesium and a small amount of THF.
PhMgCl+B(OMe)
3——→Ph
4BMgCl
(3) synthesis of sodium tetraphenylborate is by the sodium carbonate solution prepared (83.0g sodium carbonate is dissolved in the water of 575mL) in the tetraphenylphosphonichloride chloride boron magnesium entered except desolventizing, and oil bath is heated to 70 DEG C, mechanical stirring 5h.Suction filtration, washes with water 4X100mL.Gained filtrate removes remaining THF with rotary evaporation.Remaining solution had both been the aqueous solution of sodium tetraphenylborate.
Ph
4BMgCl+Na
2CO
3——→Ph
4BNa
(4) synthesis of pyridine hydrochloride is got pyridine 13.9g and is dissolved in 25mL water, drips the hydrochloric acid 14.7mL of 35.6%.
(5) aqueous solution of sodium tetraphenylborate is transferred in the beaker of 1000mL by the synthesis of tetraphenylboron pyridine, and electric stirring slowly drips the pyridine hydrochloride prepared.Obtain white precipitate, suction filtration, gained solid is tetraphenylboron pyridine.
(6) obtained tetraphenylboron pyridine is transferred to and is equipped with in the 500mL three-necked flask of reflux condensing tube by the synthesis of borphenyl pyridine, then adds the benzene of 250mL, and oil bath is heated to 90 DEG C, electric stirring 10h.Place 15h.Suction filtration obtains white solid and is wanted product borphenyl pyridine, uses ethanol 2X(95%) 50mL, sherwood oil 2X100mL rinse.Place ventilation seasoning.
Product is white powder, and weight is 40.8g, and yield is that 82.4%(is in trimethyl borate), liquid chromatographic detection purity is 94.00%(normalization method).
The liquid chromatogram of the present embodiment products obtained therefrom is referring to accompanying drawing 3.
Embodiment 3: a kind of preparation method of borphenyl pyridine, is realized by following steps:
Prepare the input amount of each material used all with trimethyl borate/mL=(15.8 ~ 19.3) be standard, solid is measured in mass, liquid cubing.
(1) being prepared in the 500mL three-necked flask that reflux condensing tube (above filling Y-tube), dropping funnel and magnetic agitation are housed of phenyl-magnesium-chloride (Grignard reagent) adds people 16.0g magnesium powder and 0.1g iodine, by argon replaces, first in reaction flask, add 2.5mL bromobenzene and 40mL tetrahydrofuran (THF) (THF), be stirred to reaction to cause (color of iodine disappears, and releases a large amount of heat).People 66.0mL chlorobenzene, 160.0mL tetrahydrofuran (THF) is added in dropping funnel.After oil bath is heated to 40 DEG C, slowly drip the mixing solutions of chlorobenzene and tetrahydrofuran (THF), 3h drips off.Drip off rear oil bath and keep 30 DEG C, continue stirring reaction 2h.
(2), after the synthesis question response liquid of tetraphenylphosphonichloride chloride boron magnesium is cooled to 30 DEG C, gets the trimethyl borate of 17.5mL and the tetrahydrofuran (THF) mixed solution of 30.0mL with transfer pipet, be added drop-wise in reaction solution, after all dropwising by dropping funnel.Gained thick liquid is transferred in 1000mL single port flask.Solvent (THF) is steamed, this solvent recoverable with rotary evaporation.Institute's residual solids is the mixture of tetraphenylphosphonichloride chloride boron magnesium and a small amount of THF.
PhMgCl+B(OMe)
3——→Ph
4BMgCl
(3) synthesis of sodium tetraphenylborate is by the sodium carbonate solution prepared (83.0g sodium carbonate is dissolved in the water of 575mL) in the tetraphenylphosphonichloride chloride boron magnesium entered except desolventizing, and oil bath is heated to 40 DEG C, mechanical stirring 2h.Suction filtration, washes with water 4X100mL.Gained filtrate removes remaining THF with rotary evaporation.Remaining solution had both been the aqueous solution of sodium tetraphenylborate.
Ph
4BMgCl+Na
2CO
3——→Ph
4BNa
(4) synthesis of pyridine hydrochloride is got pyridine 13.9g and is dissolved in 25mL water, drips the hydrochloric acid 14.7mL of 35.6%.
(5) aqueous solution of sodium tetraphenylborate is transferred in the beaker of 1000mL by the synthesis of tetraphenylboron pyridine, and electric stirring slowly drips the pyridine hydrochloride prepared.Obtain white precipitate, suction filtration gained solid is tetraphenylboron pyridine.
(6) obtained tetraphenylboron pyridine is transferred to and is equipped with in the 500mL three-necked flask of reflux condensing tube by the synthesis of borphenyl pyridine, then adds the hexanaphthene of 250mL, and oil bath is heated to 50 DEG C, electric stirring 5h.Place 10h.Suction filtration obtains white solid and is wanted product borphenyl pyridine, uses ethanol 2X(95%) 50mL, sherwood oil 2X 100mL rinses.Place ventilation seasoning.
Product is white powder, and weight is 37.4g, and yield is that 75.1%(is in trimethyl borate), liquid chromatographic detection purity is 91.96%(normalization method).
The liquid chromatogram of the present embodiment products obtained therefrom is referring to accompanying drawing 4.
Foregoing description only proposes, not as the single restricted condition to its technical scheme itself as the enforceable technical scheme of the present invention.
Claims (2)
1. a preparation method for borphenyl pyridine, its characterization step comprises:
The preparation of A, phenyl-magnesium-chloride: pass into rare gas element in the reaction vessels that magnesium powder and iodine be housed, then add the mixing solutions of bromobenzene and tetrahydrofuran (THF) in reaction vessels, the color being stirred to iodine disappears; Be heated to 40 DEG C-70 DEG C, then drip the mixing solutions of chlorobenzene and tetrahydrofuran (THF), after dripping off, keep 2-5 hour at 30 DEG C-70 DEG C, and continue to stir; Chemical equation is:
The synthesis of B, tetraphenylphosphonichloride chloride boron magnesium: after question response liquid is cooled to 30 DEG C-50 DEG C, in reaction vessels, drip trimethyl borate and tetrahydrofuran (THF) mixed solution, after all dropwising, reaction solution becomes thick liquid; Reaction solution rotatory evaporator is steamed solvents tetrahydrofurane, and institute's residual solids is tetraphenylphosphonichloride chloride boron magnesium, wherein also containing a small amount of tetrahydrofuran (THF); Chemical equation is:
PhMgCl+B(OMe)
3→Ph
4BMgCl；
The synthesis of C, sodium tetraphenylborate: the aqueous solution adding sodium carbonate in tetraphenylphosphonichloride chloride boron magnesium, is heated to 40 DEG C-70 DEG C, mechanical stirring 1-5 hour, suction filtration, wash, filtrate; Filtrate is removed remaining tetrahydrofuran (THF) with rotatory evaporator, and remaining solution is the aqueous solution of sodium tetraphenylborate; Chemical equation is:
Ph
4BMgCl+Na
2CO
3→Ph
4BNa；
The synthesis of D, pyridine hydrochloride: get pyridine soluble in water, drips a small amount of hydrochloric acid, prepares pyridine hydrochloride, for subsequent use; Chemical equation is:
The synthesis of E, tetraphenylboron pyridine: drip pyridine hydrochloride in the aqueous solution of sodium tetraphenylborate, and stir, obtain white precipitate, suction filtration gained solid is tetraphenylboron pyridine; Chemical equation is:
The synthesis of F, borphenyl pyridine: add organic solvent in tetraphenylboron pyridine, is heated to 50 DEG C-90 DEG C, stirs 7-9 hour; Place 5-15 hour, suction filtration obtains white solid, is borphenyl pyridine; Use ethanol, petroleum ether borphenyl pyridine crude product again, after washing, product is air-dry, obtain borphenyl pyridine sterling; Chemical equation is:
In steps A, the amount ratio of each raw material is: magnesium powder/g ︰ iodine/g ︰ bromobenzene/mL ︰ tetrahydrofuran (THF)/mL=(14.4 ~ 17.6) ︰ (0.09 ~ 0.11) ︰ (2.3 ~ 2.8) ︰ (36 ~ 44); Chlorobenzene/mL ︰ tetrahydrofuran (THF)/mL=(59.4 ~ 72.6) ︰ (144 ~ 176);
In step B, the amount ratio of each raw material is: trimethyl borate/mL ︰ tetrahydrofuran (THF)/mL=(15.8 ~ 19.3) ︰ (27 ~ 33);
In step C, the amount ratio of each raw material is: sodium carbonate/g ︰ water/mL=(74.4 ~ 91.3) ︰ (517.5 ~ 632.5);
In step D, the amount ratio of each raw material is: pyridine/g ︰ water/mL ︰ hydrochloric acid/mL=(12.51 ~ 15.29) ︰ (22.5 ~ 27.5) ︰ (13.2 ~ 16.2);
In step F, described organic solvent is one or more combinations among benzene,toluene,xylene, hexanaphthene, hexane, pentane; The amount ratio of each raw material is: organic solvent/mL ︰ ethanol/mL ︰ sherwood oil/mL=(225 ~ 275) ︰ (50 ~ 150) ︰ (100 ~ 300).
2. the preparation method of borphenyl pyridine according to claim 1, is characterized in that: in steps A, and described rare gas element is argon gas or nitrogen.
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