CN105153209A - Synthetic method for tetra(pentafluorophenyl)borate - Google Patents
Synthetic method for tetra(pentafluorophenyl)borate Download PDFInfo
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Abstract
The invention provides a synthetic method for tetra(pentafluorophenyl)borate. The synthetic method comprises the following steps: with pentafluorobromobenzene as a starting raw material, treating pentafluorobromobenzene with organic lithium or a Grignard reagent so as to obtain an intermediate A; reacting the intermediate A with trimethyl borate; and carrying out post-treatment so as to obtain the target product tetra(pentafluorophenyl)borate with a structural formula described in the specification. M+ in the product of the method is any one selected from the group consisting of organic carbocation, organic ammonium ion and alkali metal ion. Compared with the prior art, the invention has the following advantages: usage of tri(pentafluorophenyl)borane sensitive to water and oxygen is avoided; product yield is high; and the method has good process and operation practicality, simple steps and low requirements on equipment and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of boratory synthetic method, particularly relate to a kind of four (pentafluorophenyl group) boratory synthetic method.
Background technology
Four (pentafluorophenyl group) borate is for the important fine chemicals of catalyzer as the aspect such as metallocene polyolefin catalyst, hydrogen storage material, particularly as the important core promotor of metallocene catalyst system, there is very important purposes, by making metallocene compound ionization, represent the performance of unusual catalysis in olefine polymerization.
Than three, (pentafluorophenyl group) borine is easy operates for four (pentafluorophenyl group) borate, and the result of use in metallocene catalysis system is better.The synthesis of this compounds can be raw material with three (pentafluorophenyl group) borine, in containing the organic medium of ether, react to obtain (Organometallics, 2004,23:1459-1460 with the organometallic compound such as pentafluorophenyl group lithium; InorganicChemistry2007,46 (22): 9425-9437).Clearly, that must use three (pentafluorophenyl group) borine intermediate to the shortcoming that this synthetic method exists exactly.Another important synthetic method is that halogen borine and pentafluorophenyl group lithium react a step and obtain, but namely pentafluorophenyl group lithium decomposes more than-30 DEG C, and particularly, halogen borine is not easy to operation, therefore the abnormal harsh (US2003083526A1 of synthesis condition; WO98/22470A1; Chem.Eur.J.2007,13:7933-7947; JournalofOrganometallicChemistry, 2000,597:92-104).
As mentioned above, in prior art, synthesis four (pentafluorophenyl group) boratory synthetic method, severe reaction conditions, reaction scheme is longer, and cost is higher, is unfavorable for suitability for industrialized production.Therefore, research and develop a kind of reaction conditions gentle, step is simple, with low cost, and is beneficial to four (pentafluorophenyl group) boratory synthetic method of suitability for industrialized production, is one of study hotspot of current those skilled in the art.
Summary of the invention
For all deficiencies of the prior art, originally a kind of four (pentafluorophenyl group) boratory synthetic method is aimed to provide, described synthetic method with five bromofluorobenzenes for raw material, by simple operation and a series of compound of process synthesis four (pentafluorophenyl group) borate, this product structure formula is:
Described method comprises the following steps generally: with five bromofluorobenzenes for starting raw material, first through organolithium or Grignard reagent process, obtains intermediate A; Then with trimethyl borate reaction, then target product four (pentafluorophenyl group) borate is obtained through aftertreatment; Described method comprises reaction scheme as shown in Figure 7; Wherein, M
+for following any one: organic carbon positive ion, organoammonium ions, alkalimetal ion.
Particularly, M is worked as
+during for organic carbon positive ion or organoammonium ions, provide a kind of four (pentafluorophenyl group) boratory synthetic method, comprise the following steps: with five bromofluorobenzenes for starting raw material, first through isopropylmagnesium chloride process, then be obtained by reacting precursor four (pentafluorophenyl group) boric acid magnesium salts (I) with trimethyl borate, then carry out cationic exchange and obtain product compound (II); The reaction scheme of described method is:
Preferably, in described synthetic method, described M
+for triphenyl carbon cation or N, N-dimethyl benzene ammonium ion.
Further preferably, described synthetic method, comprises the following steps:
(1) Grignard reagent needed for preparation: under nitrogen protection, add in No. 1 reaction vessel that reflux condensing tube is housed 2-methyltetrahydrofuran (moisture <100ppm), magnesium chips, at least 1 droplet 1,2-ethylene dibromide, stir, first instill the 2 cbloropropane isopropyl chloride of 1/10-1/5, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reactions react completely to 2 cbloropropane isopropyl chloride, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride;
(2) under nitrogen protection, starting raw material five bromofluorobenzene, toluene is added in No. 2 reaction vessels, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, trimethyl borate (0 DEG C) can be dripped, drip off stirring ten minutes, slowly be warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts (I);
(3) under nitrogen protection, in No. 3 reaction vessels, add 1,2-ethylene dichloride, water, MX, stir and be cooled to 0 DEG C, the toluene solution of instillation (I), in keeping, temperature is less than 10 DEG C, drips off stirring and spends the night, and leaves standstill separatory, organic phases washed with water, organic phase is spin-dried for and obtains crude product (II), and crude product (II) 1,2-ethylene dichloride and normal heptane making beating obtain product compound (II);
Wherein, described MX is triphenylmethyl chloride or DMA hydrochloride.
Particularly, M is worked as
+during for alkalimetal ion, provide a kind of four (pentafluorophenyl group) boratory synthetic method, comprise the following steps: with five bromofluorobenzenes for starting raw material, first through isopropylmagnesium chloride process, then precursor four (pentafluorophenyl group) boric acid magnesium salts (I) is obtained by reacting with trimethyl borate, be converted into compound (III) again, finally carry out cationic exchange again and obtain product compound (II); The reaction scheme of described method is:
Preferably, in described synthetic method, described M
+for sodium ion or potassium ion.
Further preferably, described synthetic method, comprises the following steps:
(1) Grignard reagent needed for preparation: under nitrogen protection, add in No. 1 reaction vessel that reflux condensing tube is housed 2-methyltetrahydrofuran (moisture <100ppm), magnesium chips, at least 1 droplet 1,2-ethylene dibromide, stir, first instill the 2 cbloropropane isopropyl chloride of 1/10-1/5, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reactions react completely to 2 cbloropropane isopropyl chloride, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride;
(2) under nitrogen protection, starting raw material five bromofluorobenzene, toluene is added in No. 2 reaction vessels, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, trimethyl borate (0 DEG C) can be dripped, drip off stirring ten minutes, slowly be warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts (I);
(3) under nitrogen protection, in No. 3 reaction vessels, add (I), diethyl ether solution, water, 20 ~ 25 DEG C are stirred 0.5h, leave standstill separatory, gained organic phase is containing compound (III), be added dropwise in the MX aqueous solution, 20 ~ 25 DEG C are stirred fully, leave standstill separatory, organic phases washed with water, add toluene, steam ether and water, after purifying, namely vacuum-drying obtain product compound (II) again;
Wherein, described MX is Potassium monofluoride or Sodium Fluoride.
Still more preferably, in aforesaid method, starting raw material five bromofluorobenzene: isopropylmagnesium chloride: the mol ratio of trimethyl borate is 1:(0.8 ~ 1): (0.20-0.25).On this basis, more further preferably, starting raw material five bromofluorobenzene: isopropylmagnesium chloride: the mol ratio of trimethyl borate is 1:0.95:0.225.
In aforesaid method, when using 2 cbloropropane isopropyl chloride and magnesium chips prepares Grignard reagent, the mol ratio of 2 cbloropropane isopropyl chloride and magnesium chips is preferably 1:(1.0 ~ 1.1).
In aforesaid method, when using MX, the mol ratio of MX and starting raw material five bromofluorobenzene is preferably (0.5 ~ 0.72): 1.
Particularly, M is worked as
+during for lithium ion, provide another kind of four (pentafluorophenyl group) boratory synthetic method, comprise the following steps: with five bromofluorobenzenes for starting raw material, first pull out bromine through butyllithium, obtain pentafluorophenyl group lithium; Then with trimethyl borate reaction, then through aftertreatment, four (pentafluorophenyl group) lithium tetraborate is obtained; The reaction scheme of described method is:
Wherein, butyllithium can be n-Butyl Lithium or tert-butyl lithium.
Preferably, described synthetic method, comprises the following steps:
(1), under nitrogen protection, add starting raw material five bromofluorobenzene, Skellysolve A to reaction vessel, be cooled to-45 DEG C, drip butyllithium hexane solution, in keeping, temperature is less than-40 DEG C, dropwises, and stirs 4h in-45 DEG C, start again to drip trimethyl borate, dropwise ,-45 DEG C of insulated and stirred 4h, add water cancellation, by extracted with diethyl ether, organic phase is spin-dried for and obtains crude product;
(2), under nitrogen protection, namely the making beating of crude product normal heptane, aether backflow obtains product four (pentafluorophenyl group) lithium tetraborate.
Further preferably, in described synthetic method, five bromofluorobenzenes: butyllithium: the mol ratio of trimethyl borate is 1:(0.8 ~ 1): (0.20-0.25).
Still more preferably, in described synthetic method, five bromofluorobenzenes: butyllithium: the mol ratio of trimethyl borate is 1:0.95:0.235.
Compared with prior art, the present invention has the following advantages and feature: (1) avoids the use of three (pentafluorophenyl group) borine to water oxygen sensitivity; (2) product yield is higher; (3) technique and operate practical, step is simple, not high to equipment requirements, is applicable to factory and amplifies and produce.Visible, four (pentafluorophenyl group) provided by the invention boratory synthetic method, reaction conditions is gentle, and step is simple, with low cost, is conducive to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 solvent for use is the boratory HNMR collection of illustrative plates of triphenylcarbenium four (pentafluorophenyl group) of DMSO-d6
Fig. 2 solvent for use is the boratory FNMR collection of illustrative plates of triphenylcarbenium four (pentafluorophenyl group) of DMSO-d6
Fig. 3 solvent for use is the boratory HNMR collection of illustrative plates of the N of DMSO-d6, N-dimethyl puratized agricultural spray four (pentafluorophenyl group)
Fig. 4 solvent for use is the boratory FNMR collection of illustrative plates of the N of DMSO-d6, N-dimethyl puratized agricultural spray four (pentafluorophenyl group)
Fig. 5 solvent for use is the HNMR collection of illustrative plates of four (pentafluorophenyl group) lithium tetraborate of CDCl3
Fig. 6 solvent for use is the FNMR collection of illustrative plates of four (pentafluorophenyl group) lithium tetraborate of CDCl3
The boratory synthetic method general line of Fig. 7 tetra-(pentafluorophenyl group)
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiment.
Method one: particularly, works as M
+during for organic carbon positive ion or organoammonium ions, provide a kind of four (pentafluorophenyl group) boratory synthetic method, comprise the following steps: with five bromofluorobenzenes for starting raw material, first through isopropylmagnesium chloride process, then be obtained by reacting precursor four (pentafluorophenyl group) boric acid magnesium salts (I) with trimethyl borate, then carry out cationic exchange and obtain product compound (II); The reaction scheme of described method is:
In a preferred embodiment, in described synthetic method, described M
+for triphenyl carbon cation or N, N-dimethyl benzene ammonium ion.
In a further preferred embodiment, described synthetic method, comprises the following steps:
(1) Grignard reagent needed for preparation: under nitrogen protection, add in No. 1 reaction vessel that reflux condensing tube is housed 2-methyltetrahydrofuran (moisture <100ppm), magnesium chips, at least 1 droplet 1,2-ethylene dibromide, stir, first instill the 2 cbloropropane isopropyl chloride of 1/10-1/5, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reactions react completely to 2 cbloropropane isopropyl chloride, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride;
(2) under nitrogen protection, starting raw material five bromofluorobenzene, toluene is added in No. 2 reaction vessels, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, trimethyl borate (0 DEG C) can be dripped, drip off stirring ten minutes, slowly be warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts (I);
(3) under nitrogen protection, in No. 3 reaction vessels, add 1,2-ethylene dichloride, water, MX, stir and be cooled to 0 DEG C, the toluene solution of instillation (I), in keeping, temperature is less than 10 DEG C, drips off stirring and spends the night, and leaves standstill separatory, organic phases washed with water, organic phase is spin-dried for and obtains crude product (II), and crude product (II) 1,2-ethylene dichloride and normal heptane making beating obtain product compound (II);
Wherein, described MX is triphenylmethyl chloride or DMA hydrochloride.
Method two: particularly, works as M
+during for alkalimetal ion, provide a kind of four (pentafluorophenyl group) boratory synthetic method, comprise the following steps: with five bromofluorobenzenes for starting raw material, first through isopropylmagnesium chloride process, then precursor four (pentafluorophenyl group) boric acid magnesium salts (I) is obtained by reacting with trimethyl borate, be converted into compound (III) again, finally carry out cationic exchange again and obtain product compound (II); The reaction scheme of described method is:
In a preferred embodiment, in described synthetic method, described M
+for sodium ion or potassium ion.
In a further preferred embodiment, described synthetic method, comprises the following steps:
(1) Grignard reagent needed for preparation: under nitrogen protection, add in No. 1 reaction vessel that reflux condensing tube is housed 2-methyltetrahydrofuran (moisture <100ppm), magnesium chips, at least 1 droplet 1,2-ethylene dibromide, stir, first instill the 2 cbloropropane isopropyl chloride of 1/10-1/5, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reactions react completely to 2 cbloropropane isopropyl chloride, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride;
(2) under nitrogen protection, starting raw material five bromofluorobenzene, toluene is added in No. 2 reaction vessels, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, trimethyl borate (0 DEG C) can be dripped, drip off stirring ten minutes, slowly be warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts (I);
(3) under nitrogen protection, in No. 3 reaction vessels, add (I), diethyl ether solution, water, 20 ~ 25 DEG C are stirred 0.5h, leave standstill separatory, gained organic phase is containing compound (III), be added dropwise in the MX aqueous solution, 20 ~ 25 DEG C are stirred fully, leave standstill separatory, organic phases washed with water, add toluene, steam ether and water, after purifying, namely vacuum-drying obtain product compound (II) again;
Wherein, described MX is Potassium monofluoride or Sodium Fluoride.
In one further preferred embodiment, in aforesaid method, starting raw material five bromofluorobenzene: isopropylmagnesium chloride: the mol ratio of trimethyl borate is 1:(0.8-1): (0.20-0.25).On this basis, starting raw material five bromofluorobenzene: isopropylmagnesium chloride: the mol ratio of trimethyl borate is preferably 1:0.95:0.225 again.
In aforesaid method one or method two, when using 2 cbloropropane isopropyl chloride and magnesium chips prepares Grignard reagent, the mol ratio of 2 cbloropropane isopropyl chloride and magnesium chips is preferably 1:(1.0 ~ 1.1).
In aforesaid method one or method two, when using MX, the mol ratio of MX and starting raw material five bromofluorobenzene is preferably (0.5 ~ 0.72): 1.
Method three: particularly, works as M
+during for lithium ion, provide another kind of four (pentafluorophenyl group) boratory synthetic method, comprise the following steps: with five bromofluorobenzenes for starting raw material, first pull out bromine through butyllithium, obtain pentafluorophenyl group lithium; Then with trimethyl borate reaction, then through aftertreatment, four (pentafluorophenyl group) lithium tetraborate is obtained; The reaction scheme of described method is:
Wherein, butyllithium can be n-Butyl Lithium or tert-butyl lithium.
In a preferred embodiment, described synthetic method, comprises the following steps:
(1), under nitrogen protection, add starting raw material five bromofluorobenzene, Skellysolve A to reaction vessel, be cooled to-45 DEG C, drip butyllithium hexane solution, in keeping, temperature is less than-40 DEG C, dropwises, and stirs 4h in-45 DEG C, start again to drip trimethyl borate, dropwise ,-45 DEG C of insulated and stirred 4h, add water cancellation, by extracted with diethyl ether, organic phase is spin-dried for and obtains crude product;
(2), under nitrogen protection, namely the making beating of crude product normal heptane, aether backflow obtains product four (pentafluorophenyl group) lithium tetraborate.
In a further preferred embodiment, in described synthetic method, five bromofluorobenzenes: butyllithium: the mol ratio of trimethyl borate is 1:(0.8 ~ 1): (0.20-0.25).
In one further preferred embodiment, in described synthetic method, five bromofluorobenzenes: butyllithium: the mol ratio of trimethyl borate is 1:0.95:0.235.
Carry out exemplary illustration below by embodiment to the present invention, the reagent used in following embodiment is commercially available prod.
Embodiment 1
Triphenylcarbenium four (pentafluorophenyl group) boratory synthesis
(1) under nitrogen protection, 400ml2-methyltetrahydrofuran (moisture <100ppm) is added in the four-hole bottle that reflux condensing tube (logical cryogenic liquid) is housed, 39.28g magnesium chips, 11, 2-ethylene dibromide, stir, 125.6g2-chloropropane and 304ml2-methyltetrahydrofuran is added in constant pressure funnel, first instill the 2-methyltetrahydrofuran solution of the 2 cbloropropane isopropyl chloride of 1/10, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reaction to 2 cbloropropane isopropyl chlorides react completely, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, its concentration of titration measuring is about 1.89mol/L,
(2) under nitrogen protection, 160g five bromofluorobenzene, 1000ml toluene is added in four-hole bottle, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution (1.89M) of 321ml isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, 15.17g trimethyl borate can be dripped, in keeping, temperature about 0 DEG C, drips off stirring ten minutes, is slowly warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts;
(3) under nitrogen protection, 1000ml1 is added in four-hole bottle, 2-ethylene dichloride, 90.29g triphenylmethyl chloride, 1500ml water, stir and be cooled to 0 DEG C, instillation four (pentafluorophenyl group) boric acid magnesium salts toluene solution (dissolving with 1000ml toluene), in keeping, temperature is less than 10 DEG C, drip off stirring to spend the night, leave standstill separatory, organic phase is respectively with 500ml washing twice, organic phase is spin-dried for and obtains crude product triphenylcarbenium four (pentafluorophenyl group) borate, crude product triphenylcarbenium four (pentafluorophenyl group) borate 100ml1, 2-ethylene dichloride and the making beating of 3500ml normal heptane are filtered, filter cake 100ml normal heptane is washed and is once obtained product triphenylcarbenium four (pentafluorophenyl group) borate 119g, yield 80%.
As shown in Figure 1, its FNMR collection of illustrative plates as shown in Figure 2 for the boratory HNMR collection of illustrative plates of this product triphenylcarbenium four (pentafluorophenyl group).
Embodiment 2
N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) boratory synthesis
(1) under nitrogen protection, 400ml2-methyltetrahydrofuran (moisture <100ppm) is added in the four-hole bottle that reflux condensing tube (logical cryogenic liquid) is housed, 39.28g magnesium chips, 31, 2-ethylene dibromide, stir, 125.6g2-chloropropane and 304ml2-methyltetrahydrofuran is added in constant pressure funnel, first instill the 2-methyltetrahydrofuran solution of the 2 cbloropropane isopropyl chloride of 1/5, be heated to 40 DEG C, condensing reflux, the 2 cbloropropane isopropyl chloride instilled has reacted the remaining 2 cbloropropane isopropyl chloride of rear instillation, 40 DEG C of reaction to 2 cbloropropane isopropyl chlorides react completely, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, its concentration of titration measuring is about 1.89mol/L,
(2) under nitrogen protection, 160g five bromofluorobenzene, 1000ml toluene is added in four-hole bottle, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution (1.89M) of 321ml isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, 15.17g trimethyl borate can be dripped, in keeping, temperature about 0 DEG C, drips off stirring ten minutes, is slowly warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts;
(3) under nitrogen protection, 2000ml1 is added in four-hole bottle, 2-ethylene dichloride, 51gN, N-dimethyl benzene ammonium salt hydrochlorate, 1500ml water, stir and be cooled to 0 DEG C, instillation four (pentafluorophenyl group) boric acid magnesium salts toluene solution (dissolving with 1000ml toluene), in keeping, temperature is less than 10 DEG C, drip off stirring to spend the night, leave standstill separatory, organic phase is respectively with 500ml washing twice, organic phase is spin-dried for and obtains crude product N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate, crude product N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate 280ml1, 2-ethylene dichloride and the making beating of 1500ml normal heptane are filtered, filter cake 100ml normal heptane is washed and is once obtained product N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate 82g, yield 70%.
This product N, as shown in Figure 3, its FNMR collection of illustrative plates as shown in Figure 4 for the boratory HNMR collection of illustrative plates of N-dimethyl puratized agricultural spray four (pentafluorophenyl group).
Embodiment 3
The synthesis of four (pentafluorophenyl group) potassium borate
(1) under nitrogen protection, 400ml2-methyltetrahydrofuran (moisture <100ppm) is added in the four-hole bottle that reflux condensing tube (logical cryogenic liquid) is housed, 39.28g magnesium chips, 21, 2-ethylene dibromide, stir, 125.6g2-chloropropane and 304ml2-methyltetrahydrofuran is added in constant pressure funnel, first instill the 2-methyltetrahydrofuran solution of the 2 cbloropropane isopropyl chloride of 1/10, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reaction to 2 cbloropropane isopropyl chlorides react completely, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, its concentration of titration measuring is about 1.89mol/L,
(2) under nitrogen protection, 160g five bromofluorobenzene, 1000ml toluene is added in four-hole bottle, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution (1.89M) of 321ml isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, 15.17g trimethyl borate can be dripped, in keeping, temperature about 0 DEG C, drips off stirring ten minutes, is slowly warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts;
(3) under nitrogen protection, four (pentafluorophenyl group) boric acid magnesium salts 179g is added in four-hole bottle, 1000ml ether, 900ml water, 20 ~ 25 DEG C are stirred 0.5h, leave standstill separatory, aqueous phase discarded, organic phase is added dropwise to (27g Potassium monofluoride is dissolved in 400ml water) in potassium fluoride aqueous solution, 20 ~ 25 DEG C are stirred 0.5h, leave standstill separatory, organic phases washed with water once, organic phase adds 200ml toluene, revolve evaporate to dryness and obtain solid crude product, crude product 100ml toluene is washed once, wash once with 100ml normal heptane again, at 150-200 DEG C, vacuum-drying obtains four (pentafluorophenyl group) potassium borate 84g, yield 72%.
19FNMR(376MHz,acetone-d6):-133.2(m,8F,ο-C6F5),-164.6(t,4F,
3J
F-F＝18.8Hz,p-C6F5),-168.6(t,8F,
3J
F-F＝18.8Hz,m-C6F5)。
Embodiment 4
The synthesis of four (pentafluorophenyl group) Sodium Tetraborate
(1) under nitrogen protection, 400ml2-methyltetrahydrofuran (moisture <100ppm) is added in the four-hole bottle that reflux condensing tube (logical cryogenic liquid) is housed, 39.28g magnesium chips, 11, 2-ethylene dibromide, stir, 125.6g2-chloropropane and 304ml2-methyltetrahydrofuran is added in constant pressure funnel, first instill the 2-methyltetrahydrofuran solution of the 2 cbloropropane isopropyl chloride of 1/5, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reaction to 2 cbloropropane isopropyl chlorides react completely, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, its concentration of titration measuring is about 1.89mol/L,
(2) under nitrogen protection, 160g five bromofluorobenzene, 1000ml toluene is added in four-hole bottle, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution (1.89M) of 321ml isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, 15.17g trimethyl borate can be dripped, in keeping, temperature about 0 DEG C, drips off stirring ten minutes, is slowly warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts;
(3) under nitrogen protection, four (pentafluorophenyl group) boric acid magnesium salts 180g is added in four-hole bottle, 2000ml ether, 900ml water, 20 ~ 25 DEG C are stirred 0.5h, leave standstill separatory, aqueous phase discarded, organic phase is added dropwise to (13.6g Potassium monofluoride is dissolved in 350ml water) in sodium fluoride aqueous solution, 25 DEG C are stirred 2h, leave standstill separatory, organic phases washed with water once, organic phase adds 200ml toluene, revolve evaporate to dryness and obtain dope, 1500ml normal heptane is added in dope, obtain solid, filter, at 25 DEG C, vacuum-drying obtains four (pentafluorophenyl group) Sodium Tetraborate 86g, yield 76%.
19FNMR (DMSO-d6) :-130 (8F) ,-159 (4F), and-163.5 (8F) ppm.
Embodiment 5
The synthesis of four (pentafluorophenyl group) lithium tetraborate
(1), under nitrogen protection, add 50g five bromofluorobenzene, 250ml Skellysolve A to four-hole bottle, be cooled to-45 DEG C, drip 76ml n-Butyl Lithium (2.5M) hexane solution, in keeping, temperature is less than-40 DEG C, dropwises, stir 4h in-45 DEG C, then start to drip 4.94g trimethyl borate, dropwise,-45 DEG C of insulated and stirred 4h, add 200ml shrend to go out, use 200ml extracted with diethyl ether twice respectively, merge organic phase, add anhydrous magnesium sulfate drying, be spin-dried for and obtain crude product;
(2) under nitrogen protection, add 100g normal heptane, 60g ether, backflow making beating, filters, and namely vacuum-drying obtain 32g tetra-(pentafluorophenyl group) lithium tetraborate etherate (per molecule lithium salts is containing 2.5 molecule ether), yield 73%.
As shown in Figure 5, its FNMR collection of illustrative plates as shown in Figure 6 for the HNMR collection of illustrative plates of this product four (pentafluorophenyl group) lithium tetraborate.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (15)
1. four (pentafluorophenyl group) boratory synthetic method, is characterized in that, comprise the following steps: with five bromofluorobenzenes for starting raw material, first through organolithium or Grignard reagent process, obtains intermediate A; Then with trimethyl borate reaction, then target product four (pentafluorophenyl group) borate is obtained through aftertreatment; Described method comprises following reaction scheme:
Wherein, M
+for following any one: organic carbon positive ion, organoammonium ions, alkalimetal ion.
2. four (pentafluorophenyl group) according to claim 1 boratory synthetic method, it is characterized in that, comprise the following steps: with five bromofluorobenzenes for starting raw material, first through isopropylmagnesium chloride process, then be obtained by reacting precursor four (pentafluorophenyl group) boric acid magnesium salts (I) with trimethyl borate, then carry out cationic exchange and obtain product compound (II); The reaction scheme of described method is:
Wherein, M
+for organic carbon positive ion or organoammonium ions.
3. four (pentafluorophenyl group) according to claim 2 boratory synthetic method, is characterized in that, described M
+for triphenyl carbon cation or N, N-dimethyl benzene ammonium ion.
4. four (pentafluorophenyl group) according to claim 3 boratory synthetic method, is characterized in that, comprise the following steps:
(1) Grignard reagent needed for preparation: under nitrogen protection, add in No. 1 reaction vessel that reflux condensing tube is housed 2-methyltetrahydrofuran (moisture <100ppm), magnesium chips, at least 1 droplet 1,2-ethylene dibromide, stir, first instill the 2 cbloropropane isopropyl chloride of 1/10-1/5, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reactions react completely to 2 cbloropropane isopropyl chloride, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride;
(2) under nitrogen protection, starting raw material five bromofluorobenzene, toluene is added in No. 2 reaction vessels, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, trimethyl borate (0 DEG C) can be dripped, drip off stirring ten minutes, slowly be warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts (I);
(3) under nitrogen protection, in No. 3 reaction vessels, add 1,2-ethylene dichloride, water, MX, stir and be cooled to 0 DEG C, the toluene solution of instillation (I), in keeping, temperature is less than 10 DEG C, drips off stirring and spends the night, and leaves standstill separatory, organic phases washed with water, organic phase is spin-dried for and obtains crude product (II), and crude product (II) 1,2-ethylene dichloride and normal heptane making beating obtain product compound (II);
Wherein, described MX is triphenylmethyl chloride or DMA hydrochloride.
5. four (pentafluorophenyl group) according to claim 1 boratory synthetic method, it is characterized in that, comprise the following steps: with five bromofluorobenzenes for starting raw material, first through isopropylmagnesium chloride process, then precursor four (pentafluorophenyl group) boric acid magnesium salts (I) is obtained by reacting with trimethyl borate, be converted into compound (III) again, finally carry out cationic exchange again and obtain product compound (II); The reaction scheme of described method is:
Wherein, M
+for alkalimetal ion.
6. four (pentafluorophenyl group) according to claim 5 boratory synthetic method, is characterized in that, described M
+for sodium ion or potassium ion.
7. four (pentafluorophenyl group) according to claim 6 boratory synthetic method, is characterized in that, comprise the following steps:
(1) Grignard reagent needed for preparation: under nitrogen protection, add in No. 1 reaction vessel that reflux condensing tube is housed 2-methyltetrahydrofuran (moisture <100ppm), magnesium chips, at least 1 droplet 1,2-ethylene dibromide, stir, first instill the 2 cbloropropane isopropyl chloride of 1/10-1/5, be heated to 40 DEG C, condensing reflux, remaining 2 cbloropropane isopropyl chloride is instilled again after the 2 cbloropropane isopropyl chloride instilled has reacted, 40 DEG C of reactions react completely to 2 cbloropropane isopropyl chloride, make the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride;
(2) under nitrogen protection, starting raw material five bromofluorobenzene, toluene is added in No. 2 reaction vessels, stir and be cooled to 0 DEG C, drip the 2-methyltetrahydrofuran solution of isopropylmagnesium chloride, in keeping, temperature is less than 5 DEG C, drip off and sample detection at once, starting raw material five bromofluorobenzene residue 2% ~ 5%, trimethyl borate (0 DEG C) can be dripped, drip off stirring ten minutes, slowly be warming up to 80 DEG C of reaction 24h, filter, filtrate is revolved steaming and is obtained four (pentafluorophenyl group) boric acid magnesium salts (I);
(3) under nitrogen protection, in No. 3 reaction vessels, add (I), diethyl ether solution, water, 20 ~ 25 DEG C are stirred 0.5h, leave standstill separatory, gained organic phase is containing compound (III), be added dropwise in the MX aqueous solution, 20 ~ 25 DEG C are stirred fully, leave standstill separatory, organic phases washed with water, add toluene, steam ether and water, after purifying, namely vacuum-drying obtain product compound (II) again;
Wherein, described MX represents Potassium monofluoride or Sodium Fluoride.
8. four (pentafluorophenyl group) the boratory synthetic method according to any one of claim 2-7, it is characterized in that, wherein, starting raw material five bromofluorobenzene: isopropylmagnesium chloride: the mol ratio of trimethyl borate is 1:(0.8 ~ 1): (0.20-0.25).
9. four (pentafluorophenyl group) according to claim 8 boratory synthetic method, is characterized in that, wherein, and starting raw material five bromofluorobenzene: isopropylmagnesium chloride: the mol ratio of trimethyl borate is 1:0.95:0.225.
10. four (pentafluorophenyl group) the boratory synthetic method according to claim 4 or 7, is characterized in that, wherein, the mol ratio of 2 cbloropropane isopropyl chloride and magnesium chips is 1:(1.0 ~ 1.1).
11. four (pentafluorophenyl group) boratory synthetic methods according to claim 4 or 7, it is characterized in that, wherein, the mol ratio of MX and starting raw material five bromofluorobenzene is (0.5 ~ 0.72): 1.
12. four (pentafluorophenyl group) according to claim 1 boratory synthetic method, is characterized in that, comprise the following steps: with five bromofluorobenzenes for starting raw material, first pull out bromine through butyllithium, obtain pentafluorophenyl group lithium; Then with trimethyl borate reaction, then through aftertreatment, four (pentafluorophenyl group) lithium tetraborate is obtained; The reaction scheme of described method is:
wherein, butyllithium can be n-Butyl Lithium or tert-butyl lithium.
13. four (pentafluorophenyl group) according to claim 12 boratory synthetic method, is characterized in that, comprise the following steps:
(1), under nitrogen protection, add starting raw material five bromofluorobenzene, Skellysolve A to reaction vessel, be cooled to-45 DEG C, drip butyllithium hexane solution, in keeping, temperature is less than-40 DEG C, dropwises, and stirs 4h in-45 DEG C, start again to drip trimethyl borate, dropwise ,-45 DEG C of insulated and stirred 4h, add water cancellation, by extracted with diethyl ether, organic phase is spin-dried for and obtains crude product;
(2), under nitrogen protection, namely the making beating of crude product normal heptane, aether backflow obtains product four (pentafluorophenyl group) lithium tetraborate.
14. four (pentafluorophenyl group) boratory synthetic methods according to claim 12 or 13, it is characterized in that, wherein, five bromofluorobenzenes: butyllithium: the mol ratio of trimethyl borate is 1:(0.8 ~ 1): (0.20-0.25).
15. four (pentafluorophenyl group) according to claim 14 boratory synthetic method, is characterized in that, wherein, and five bromofluorobenzenes: butyllithium: the mol ratio of trimethyl borate is 1:0.95:0.235.
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| CN108610355A (en) * | 2016-12-09 | 2018-10-02 | 中国石油化工科技开发有限公司 | A method of sandwiching water and ether compound in removal perfluorophenyl borate |
| CN110041354A (en) * | 2019-04-15 | 2019-07-23 | 镇江巨杰新材料技术研发中心(有限合伙) | A kind of synthetic method of four penta phenyl fluoride borons acid potassium salt |
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| CN111943968A (en) * | 2020-09-02 | 2020-11-17 | 陆海峰 | Process for preparing tetrakis (pentafluorophenyl) borate |
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| CN108610355A (en) * | 2016-12-09 | 2018-10-02 | 中国石油化工科技开发有限公司 | A method of sandwiching water and ether compound in removal perfluorophenyl borate |
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| CN110078753A (en) * | 2019-04-18 | 2019-08-02 | 镇江巨杰新材料技术研发中心(有限合伙) | A kind of synthetic method of metallocene catalysis agent aid and its application in 1- decene polymerization process |
| CN110156606A (en) * | 2019-05-31 | 2019-08-23 | 镇江巨杰新材料技术研发中心(有限合伙) | The synthetic method and application of a kind of N, N- bis- (octadecyl) aniline |
| CN111943968A (en) * | 2020-09-02 | 2020-11-17 | 陆海峰 | Process for preparing tetrakis (pentafluorophenyl) borate |
| CN112599676A (en) * | 2020-09-29 | 2021-04-02 | 湖南大学 | Organic ammonium salt p-type dopant |
| CN112599676B (en) * | 2020-09-29 | 2022-11-01 | 湖南大学 | Organic ammonium salt p-type dopant |
| CN114621449A (en) * | 2022-04-19 | 2022-06-14 | 长春市兆兴新材料技术有限责任公司 | Fluorine-containing phenyl aluminum phosphonate polymer and preparation method thereof |
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