CN102617623B - A kind of method of synthesizing connection pinacol borate - Google Patents
A kind of method of synthesizing connection pinacol borate Download PDFInfo
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Abstract
Relate to a kind of method of synthesizing connection pinacol borate in the present invention, selected commercially business-like boron trichloride, dimethylamine and tetramethyl ethylene ketone to be starting raw material respectively, replaced by two steps, coupling, becomes Lipase absobed, and each step product all connects with solution throws into next step, simplify the operation, reduce the loss.The raw material that described synthetic method adopts is all cheap and easy to get, and chemical reaction condition is gentle, and transformation efficiency, yield and purity are all very high.Synthetic method of the present invention, to being amplified to nearly hundred feather weight, provides practicable synthetic method for scale operation joins pinacol borate.
Description
(1) technical field:
The present invention relates to organic synthesis preparative chemistry field, particularly a kind of synthetic method of pinacol borate.
(2) background technology:
The Suzuki that aryl boric acid and aryl halides are carried out under metal palladium complex effect reacts and has been widely used in aralkyl glycosylation reaction, but owing to there is boronate and boronate, hydrogen bond association between boronate and hydroxyl, product purity is very low.Come in there are some researches show, boric acid ester (as pinacol ester) also can be directly used in Suzuki reaction.Pinacol ester is in Suzuki reaction, and the selectivity that responds is high, mild condition, yield advantages of higher, unstable or need the compound improving reaction preference for some substrates, reacts be one and well select by pinacol ester and aryl halides.And to synthesize the most frequently used method of pinacol ester be exactly with halides and connection pinacol borate.So the effect of connection pinacol borate in organic synthesis is at present more and more important.Research in recent years about connection pinacol borate mainly concentrates in the application of Suzuki reaction.
The synthetic method of the connection pinacol borate that present stage is reported mainly contains two kinds:
Method one is for starting raw material with boron tribromide, dimethylamine and tetramethyl ethylene ketone, through replacing, coupling, esterification preparation (Journal of the American ChemicalSociety, vol.82.1960.6242-6245), wherein boron tribromide price is more expensive, causes raw materials cost higher, is not suitable for scale operation;
Method two be with boron trichloride, dimethylamine and tetramethyl ethylene ketone for raw material, be substituted, replace, coupling, esterification preparation (Gmelin Handbook, B:B-Verb.4), but its technique only can be amplified to tens grams, and operation is absolutely unsafe, and is not suitable for scale operation.
Therefore, be solve in prior art this difficult problem existed, suddenly wait to find a raw material to be easy to get, the with low cost and practicable synthetic route of applicable suitability for industrialized production.
(3) summary of the invention:
The object of the present invention is to provide a kind of method of synthesizing connection pinacol borate, overcome the deficiency that prior art exists.The method has selected commercially business-like boron trichloride, dimethylamine and tetramethyl ethylene ketone to be starting raw material respectively, is replaced, coupling by two steps, become Lipase absobed, raw materials used all cheap and easy to get, the first to three steps use same solvent, be convenient to recovery, economize in raw materials cost greatly; Route transformation in planta rate is high, and stable process conditions is simple to operate, is applicable to amplifying producing, for preparation connection pinacol borate provides a kind of new approaches being applicable to large-scale production.
Technical scheme of the present invention: a kind of synthetic method of pinacol borate, is characterized in that concrete steps are as follows:
(1) triamino replaces: the hydrocarbon solution adding main raw material dimethylamine in reactor, drips the hydrocarbon solution of boron trichloride in-20 ~ 0 DEG C, and drip and finish, system is warming up to 5 ~ 25 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, in system, add varsol, and stir, centrifugal, gained filtrate is the hydrocarbon solution of three (dimethylamino) borine, waits to throw next step; The consumption dissolving the varsol of main raw material dimethylamine is every gram of main raw material dimethylamine 2 ~ 14mL, the consumption dissolving the varsol of boron trichloride is every gram of main raw material dimethylamine 1 ~ 7mL, the mol ratio of main raw material dimethylamine and boron trichloride is 1.0: 0.17 ~ 0.3eq, and the consumption of the varsol added after reaction terminates is every gram of main raw material dimethylamine 1 ~ 5mL;
(2) diamino replaces: the hydrocarbon solution adding obtained three (dimethylamino) borine of step (1) in reactor, the hydrocarbon solution of boron trichloride is dripped in-20 ~ 0 DEG C, drip and finish, system is warming up to 5 ~ 25 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and system crosses diatomite, and gained filtrate is the hydrocarbon solution of two (dimethylamino) chloroborane, waits to throw next step; The consumption dissolving the varsol of boron trichloride is every gram of main raw material two (dimethylamino) chloroborane 1 ~ 9mL, and the mol ratio of main raw material two (dimethylamino) chloroborane and boron trichloride is 1.0: 0.5 ~ 1.0eq; Main raw material two (dimethylamino) chloroborane and diatomaceous weight ratio are 1: 0.1 ~ 1;
(3) coupling: add varsol, sodium Metal 99.5 in reactor, stirring and refluxing is melted completely to sodium Metal 99.5, the hydrocarbon solution of obtained two (dimethylamino) chloroborane of above-mentioned steps (2) is dripped in 85 ~ 105 DEG C, drip and finish, keep temperature-resistant and terminate to NMR detection reaction; Reaction is finished, and system is cooled to 20 ~ 40 DEG C, and filter, filtrate is concentrated into and obtains four (dimethylamino)-diboron hexahydrides without cut; The consumption of varsol is every gram of main raw material two (dimethylamino) chloroborane 1 ~ 10mL, and the mol ratio of main raw material two (dimethylamino) chloroborane and sodium Metal 99.5 is 1.0: 1.0 ~ 3.0eq;
(4) esterification: four (the dimethylamino)-diboron hexahydrides adding varsol, above-mentioned steps (3) gained in reactor successively, tetramethyl ethylene ketone is dripped in 10 ~ 30 DEG C, drip and finish, system is warming up to 85 ~ 105 DEG C, keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, and system is cooled to 15 ~ 25 DEG C, adds water and varsol extraction, separatory, and gained organic phase is through saturated common salt water washing, dry, is concentrated into and obtains pinacol borate without cut after filtration; The consumption of the varsol of reaction is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10mL, the mol ratio of main raw material four (dimethylamino)-diboron hexahydride and tetramethyl ethylene ketone is 1.0: 1.5 ~ 3.0eq, the consumption of water is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10ml, the consumption of the varsol of extraction is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10mL, and the consumption of saturated aqueous common salt is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10mL).
In above-mentioned said step (1), the consumption dissolving the varsol of main raw material dimethylamine is every gram of main raw material dimethylamine 3 ~ 6mL, the consumption dissolving the varsol of boron trichloride is every gram of main raw material dimethylamine 3 ~ 6mL, and the mol ratio of main raw material dimethylamine and boron trichloride is 1.0: 0.2 ~ 0.25eq.
In above-mentioned said step (2), the consumption dissolving the varsol of boron trichloride is every gram of main raw material two (dimethylamino) chloroborane 4 ~ 6mL, the mol ratio of main raw material two (dimethylamino) chloroborane and boron trichloride is 1.0: 0.6 ~ 0.8eq, and main raw material two (dimethylamino) chloroborane and diatomaceous weight ratio are 1: 0.4 ~ 0.6.
In above-mentioned said step (3), the consumption of varsol is every gram of main raw material two (dimethylamino) chloroborane 4 ~ 6mL, and the mol ratio of main raw material two (dimethylamino) chloroborane and sodium Metal 99.5 is 1.0: 2.0 ~ 2.2.
In above-mentioned said step (4), the consumption of the varsol of reaction is every gram of main raw material four (dimethylamino)-diboron hexahydride 3 ~ 6mL, the mol ratio of main raw material four (dimethylamino)-diboron hexahydride and tetramethyl ethylene ketone is 1: 2.0 ~ 2.5eq, the consumption of water is every gram of main raw material four (dimethylamino)-diboron hexahydride 3 ~ 6ml, the consumption of the varsol of extraction is every gram of main raw material four (dimethylamino)-diboron hexahydride 3 ~ 6mL, and the consumption of saturated aqueous common salt is every gram of main raw material four (dimethylamino)-diboron hexahydride 4 ~ 6mL.
In above-mentioned said step (1), varsol is normal heptane, normal hexane or hexanaphthene, and the hydrocarbon solution of dimethylamine is the normal heptane of dimethylamine, normal hexane or cyclohexane solution, and its concentration is 10% ~ 45%; The hydrocarbon solution of boron trichloride is the normal heptane of boron trichloride, normal hexane or cyclohexane solution, and its concentration is 10% ~ 45%.
In above-mentioned said step (2), varsol is normal heptane, normal hexane or hexanaphthene, and the hydrocarbon solution of boron trichloride is the normal heptane of boron trichloride, normal hexane or cyclohexane solution, and its concentration is 10% ~ 45%.
In above-mentioned steps (3), said varsol is normal heptane, normal hexane or hexanaphthene.
In above-mentioned steps (4), said varsol is toluene or dimethylbenzene.
In above-mentioned steps (1), said varsol is normal heptane, and the hydrocarbon solution of said dimethylamine is the n-heptane solution of the dimethylamine of concentration 25%, and the hydrocarbon solution of said boron trichloride is the n-heptane solution of the boron trichloride of concentration 25%; In step (2), said varsol is normal heptane, and the hydrocarbon solution of said boron trichloride is the n-heptane solution of the boron trichloride of concentration 25%; In step (3), said varsol is normal heptane; In step (4), said varsol is toluene.
Superiority of the present invention: 1, prior art mostly adopts boron tribromide (BBr
3) as raw material, the present invention adopts relatively inexpensive boron trichloride (BCl
3) as raw material, economize in raw materials cost greatly, for large-scale production lays the foundation; 2, boron trichloride (BCl is adopted in prior art
3) as raw material, industrial scale only can be amplified to tens grams, and operation is absolutely unsafe, after the present invention changes reaction conditions and optimizes, be applicable to amplifying and produce, current industrial scale is amplified to 3000L; 3, the present invention's reaction uses same solvent from the first step to the 3rd step, is convenient to solvent recuperation, cost-saving; 4, the present invention reacts each step product and connects all in the form of a solution and throw into next step, and simplify the operation, reduce the loss, transformation efficiency and the purity of each step reaction are all more stable, and four step total recoverys can reach 40 ~ 60%.
(4) accompanying drawing illustrates:
Fig. 1 is a kind of chemical reaction process figure synthesizing the method for connection pinacol borate involved by the present invention.
Composition graphs 1 can understand the technical scheme of foregoing invention more intuitively.
(5) embodiment:
For the interval range occurred in embodiment, be because in single test, temperature there will be certain floating with the carrying out of reaction process, its statement is the conventional representations in chemical industry synthesis field.
Embodiment 1: a kind of synthetic method of pinacol borate, is characterized in that concrete steps are as follows:
(1) triamino replaces: normal hexane (14mL/g) solution 200kg (444.4mol adding main raw material 10% dimethylamine in 500L reactor, 1.0eq), normal hexane (7mL/g) solution 104.2kg (88.9mol of 10% boron trichloride is dripped in-20 ± 2 DEG C, 0.2eq), drip and finish, system is warming up to 5 ± 2 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and adds normal hexane 26kg (2mL/g) in system, and stir, centrifugal, gained filtrate is the hexane solution 306kg (9.5kg, 66.6mol) of three (dimethylamino) borine, and yield 90%, waits to throw next step;
(2) diamino replaces: the hexane solution 306kg (9.5kg adding obtained three (dimethylamino) borine of step (1) in 500L reactor, 66.6mol), normal hexane (9mL/g) solution 62.5kg (53.3mol of 10% boron trichloride is dripped in-20 ± 2 DEG C, 0.8eq), drip and finish, system is warming up to 5 ± 2 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and system crosses diatomite 0.95kg (0.1g/g), and gained filtrate is the hexane solution 341.7kg (10.7kg, 79.9mol) of two (dimethylamino) chloroborane, and yield 80%, waits to throw next step;
(3) coupling: add normal hexane 7.1kg (1mL/g), sodium Metal 99.5 1.8kg (79.9mol in 500L reactor, 1.0eq), stirring and refluxing is melted completely to sodium Metal 99.5, in 85 ± 2 DEG C, drip the hexane solution 341.7kg (10.7kg of obtained two (dimethylamino) chloroborane of step (2), 79.9mol), drip and finish, system keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, and system is cooled to 20 ± 2 DEG C, press filtration, and filtrate merging is concentrated into and obtains four (dimethylamino)-diboron hexahydrides 5.1kg (5.1kg, 25.7mol) without cut, yield 65%;
(4) esterification: to 50L reactor in add four obtained (dimethylamino)-diboron hexahydride 5.1kg (5.1kg of dimethylbenzene 4.4kg (1mL/g), step (3) successively, 25.7mol), tetramethyl ethylene ketone 4.6kg (38.6mol is dripped in 10 ± 2 DEG C, 1.5eq), system is warming up to 85 ± 2 DEG C, keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, system is down to 15 ± 2 DEG C, add pure water 5.1kg (1mL/g) and dimethylbenzene 5.1kg (1mL/g) extraction, gained organic phase is washed through saturated aqueous common salt 5.8kg (1mL/g), dry, be concentrated into after filtration and obtain connection pinacol borate 5.7kg without cut, yield 87%.Four step total recoverys are 40.4%, product G C purity is 95.8%.
Embodiment 2:
(1) triamino replaces: normal heptane (4mL/g) solution 200kg (1111.1mol adding main raw material 25% dimethylamine in 500L reactor, 1.0eq), normal heptane (2mL/g) solution 88.6kg (188.9mol of 25% boron trichloride is dripped in-5 ± 2 DEG C, 0.17eq), drip and finish, system is warming up to 15 ± 2 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and adds normal heptane 34kg (1mL/g) in system, and stir, centrifugal, gained filtrate is the n-heptane solution 274kg (26.5kg, 185.2mol) of three (dimethylamino) borine, and yield 100%, waits to throw next step;
(2) diamino replaces: the n-heptane solution 274kg (26.5kg adding obtained three (dimethylamino) borine of step (1) in 500L reactor, 185.2mol), normal heptane (2mL/g) solution 43.4kg (92.6mol of 25% boron trichloride is dripped in-5 ± 2 DEG C, 0.5eq), drip and finish, system is warming up to 15 ± 2 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and system crosses diatomite 13.3kg (0.5g/g), and gained filtrate is the n-heptane solution 308.1kg (33.5kg, 250.0mol) of two (dimethylamino) chloroborane, and yield 90%, waits to throw next step;
(3) coupling: add normal heptane 68.3kg (3mL/g), sodium Metal 99.5 11.5kg (500.0mol in 500L reactor, 2.0eq), stirring and refluxing is melted completely to sodium Metal 99.5, in 105 ± 2 DEG C, drip the n-heptane solution 308.1kg (33.5kg of obtained two (dimethylamino) chloroborane of step (2), 250.0mol), drip and finish, system keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, and system is cooled to 25 ± 2 DEG C, press filtration, and filtrate merging is concentrated into and obtains four (dimethylamino)-diboron hexahydrides 17.3kg (17.3kg, 87.5mol) without cut, yield 70%;
(4) esterification: to 300L reactor in add four obtained (dimethylamino)-diboron hexahydride 17.3kg (17.3kg of toluene 60.2kg (4mL/g), step (3) successively, 87.5mol), tetramethyl ethylene ketone 23.8kg (201.3mol is dripped in 20 ± 2 DEG C, 2.3eq), system is warming up to 105 ± 2 DEG C, keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, system is down to room temperature, add pure water 51.9kg (3mL/g) and toluene 45.2kg (3mL/g) extraction, gained organic phase is washed through saturated aqueous common salt 78.2kg (4mL/g), dry, be concentrated into after filtration and obtain connection pinacol borate 20.0kg without cut, yield 90%.Four step total recoverys are 56.7%, product G C purity is 98.3%.
Embodiment 3:
(1) triamino replaces: hexanaphthene (2mL/g) solution 200kg (1666.7mol adding main raw material 45% dimethylamine in 1000L reactor, 1.0eq), hexanaphthene (1mL/g) solution 106.5kg (500.0mol of 45% boron trichloride is dripped in 0 ± 2 DEG C, 0.3eq), drip and finish, system is warming up to 25 ± 2 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and adds hexanaphthene 273kg (5mL/g) in system, stirs, centrifugal, gained filtrate is the cyclohexane solution 553.3kg (37.7kg, 263.9mol) of three (dimethylamino) borine, yield 95%, waits to throw next step;
(2) diamino replaces: the cyclohexane solution 553.3kg (37.7kg adding obtained three (dimethylamino) borine of step (1) in 1000L reactor, 263.9mol), hexanaphthene (1mL/g) solution 68.7kg (263.9mol of 45% boron trichloride is dripped in 0 ± 2 DEG C, 1.0eq), drip and finish, system is warming up to 25 ± 2 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and system crosses diatomite 37.7kg (1g/g), and gained filtrate is the cyclohexane solution 602.5kg (45.1kg, 336.5mol) of two (dimethylamino) chloroborane, and yield 85%, waits to throw next step;
(3) coupling: add hexanaphthene 351.8kg (10mL/g), sodium Metal 99.5 23.2kg (1009.5mol in 2000L reactor, 3.0eq), stirring and refluxing is melted completely to sodium Metal 99.5, in 95 ± 2 DEG C, drip the cyclohexane solution 602.5kg (45.1kg of obtained two (dimethylamino) chloroborane of step (2), 336.5mol), drip and finish, system keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, and system is cooled to 40 ± 2 DEG C, press filtration, and filtrate merging is concentrated into and obtains four (dimethylamino)-diboron hexahydrides 22.6kg (22.6kg, 114.4mol) without cut, yield 68%;
(4) esterification: to 500L reactor in add four obtained (dimethylamino)-diboron hexahydride 22.6kg (22.6kg of dimethylbenzene 194.4kg (10mL/g), step (3) successively, 114.4mol), tetramethyl ethylene ketone 40.6kg (343.2mol is dripped in 30 ± 2 DEG C, 3.0eq), system is warming up to 95 ± 2 DEG C, keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, system is down to room temperature, add pure water 226kg (10mL/g) and dimethylbenzene 196.6kg (10mL/g) extraction, gained organic phase is washed through saturated aqueous common salt 255.4kg (10mL/g), dry, be concentrated into after filtration and obtain connection pinacol borate 25.6kg without cut, yield 88%.Four step total recovery 48.4%, product G C purity are 97.2%.
As can be seen here, replaced, coupling disclosed in the present invention by two steps, the method for lactate synthesis connection pinacol borate, each step product all connects with solution throws into next step, simplifies the operation, reduces the loss.The raw material that described synthetic method adopts is all cheap and easy to get, and chemical reaction condition is gentle, and transformation efficiency, yield and purity are all very high.Synthetic method of the present invention, to being amplified to nearly hundred feather weight, provides practicable synthetic method for scale operation joins pinacol borate.
Claims (10)
1. synthesize a method for connection pinacol borate, it is characterized in that concrete steps are as follows:
(1) triamino replaces: the hydrocarbon solution adding main raw material dimethylamine in reactor, drips the hydrocarbon solution of boron trichloride in-20 ~ 0 DEG C, and drip and finish, system is warming up to 5 ~ 25 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, in system, add varsol, and stir, centrifugal, gained filtrate is the hydrocarbon solution of three (dimethylamino) borine, waits to throw next step; The consumption dissolving the varsol of main raw material dimethylamine is every gram of main raw material dimethylamine 2 ~ 14mL, the consumption dissolving the varsol of boron trichloride is every gram of main raw material dimethylamine 1 ~ 7mL, the mol ratio of main raw material dimethylamine and boron trichloride is 1.0:0.17 ~ 0.3eq, and the consumption of the varsol added after reaction terminates is every gram of main raw material dimethylamine 1 ~ 5mL;
(2) diamino replaces: the hydrocarbon solution adding obtained three (dimethylamino) borine of step (1) in reactor, the hydrocarbon solution of boron trichloride is dripped in-20 ~ 0 DEG C, drip and finish, system is warming up to 5 ~ 25 DEG C, is incubated to NMR detection reaction and terminates; Reaction is finished, and system crosses diatomite, and gained filtrate is the hydrocarbon solution of two (dimethylamino) chloroborane, waits to throw next step; The consumption dissolving the varsol of boron trichloride is every gram of main raw material three (dimethylamino) borine 1 ~ 9mL, and the mol ratio of main raw material three (dimethylamino) borine and boron trichloride is 1.0:0.5 ~ 1.0eq; Main raw material three (dimethylamino) borine and diatomaceous weight ratio are 1:0.1 ~ 1;
(3) coupling: add varsol, sodium Metal 99.5 in reactor, stirring and refluxing is melted completely to sodium Metal 99.5, the hydrocarbon solution of obtained two (dimethylamino) chloroborane of above-mentioned steps (2) is dripped in 85 ~ 105 DEG C, drip and finish, keep temperature-resistant and terminate to NMR detection reaction; Reaction is finished, and system is cooled to 20 ~ 40 DEG C, and filter, filtrate is concentrated into and obtains four (dimethylamino)-diboron hexahydrides without cut; The consumption of varsol is every gram of main raw material two (dimethylamino) chloroborane 1 ~ 10mL, and the mol ratio of main raw material two (dimethylamino) chloroborane and sodium Metal 99.5 is 1.0:1.0 ~ 3.0eq;
(4) esterification: four (the dimethylamino)-diboron hexahydrides adding varsol, above-mentioned steps (3) gained in reactor successively, tetramethyl ethylene ketone is dripped in 10 ~ 30 DEG C, drip and finish, system is warming up to 85 ~ 105 DEG C, keeps temperature-resistant and terminates to NMR detection reaction; Reaction is finished, and system is cooled to 15 ~ 25 DEG C, adds water and varsol extraction, separatory, and gained organic phase is through saturated common salt water washing, dry, is concentrated into and obtains joining pinacol borate without cut after filtration; The consumption of the varsol of reaction is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10mL, the mol ratio of main raw material four (dimethylamino)-diboron hexahydride and tetramethyl ethylene ketone is 1.0:1.5 ~ 3.0eq, the consumption of water is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10ml, the consumption of the varsol of extraction is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10mL, and the consumption of saturated aqueous common salt is every gram of main raw material four (dimethylamino)-diboron hexahydride 1 ~ 10mL.
2. according to a kind of said method of synthesizing connection pinacol borate of claim 1, it is characterized in that in said step (1), the consumption dissolving the varsol of main raw material dimethylamine is every gram of main raw material dimethylamine 3 ~ 6mL, the consumption dissolving the varsol of boron trichloride is every gram of main raw material dimethylamine 3 ~ 6mL, and the mol ratio of main raw material dimethylamine and boron trichloride is 1.0:0.2 ~ 0.25eq.
3. according to a kind of said method of synthesizing connection pinacol borate of claim 1, it is characterized in that in said step (2), the consumption dissolving the varsol of boron trichloride is every gram of main raw material three (dimethylamino) borine 4 ~ 6mL, the mol ratio of main raw material three (dimethylamino) borine and boron trichloride is 1.0:0.6 ~ 0.8eq, and main raw material three (dimethylamino) borine and diatomaceous weight ratio are 1:0.4 ~ 0.6.
4. according to a kind of said method of synthesizing connection pinacol borate of claim 1, it is characterized in that in said step (3), the consumption of varsol is every gram of main raw material two (dimethylamino) chloroborane 4 ~ 6mL, and the mol ratio of main raw material two (dimethylamino) chloroborane and sodium Metal 99.5 is 1.0:2.0 ~ 2.2.
5. according to a kind of said method of synthesizing connection pinacol borate of claim 1, it is characterized in that in said step (4), the consumption of the varsol of reaction is every gram of main raw material four (dimethylamino)-diboron hexahydride 3 ~ 6mL, the mol ratio of main raw material four (dimethylamino)-diboron hexahydride and tetramethyl ethylene ketone is 1:2.0 ~ 2.5eq, the consumption of water is every gram of main raw material four (dimethylamino)-diboron hexahydride 3 ~ 6ml, the consumption of the varsol of extraction is every gram of main raw material four (dimethylamino)-diboron hexahydride 3 ~ 6mL, the consumption of saturated aqueous common salt is every gram of main raw material four (dimethylamino)-diboron hexahydride 4 ~ 6mL.
6. according to a kind of said method of synthesizing connection pinacol borate of claim 1 or 2, it is characterized in that in said step (1), varsol is normal heptane, normal hexane or hexanaphthene, the hydrocarbon solution of dimethylamine is the normal heptane of dimethylamine, normal hexane or cyclohexane solution, and its concentration is 10% ~ 45%; The hydrocarbon solution of boron trichloride is the normal heptane of boron trichloride, normal hexane or cyclohexane solution, and its concentration is 10% ~ 45%.
7. according to a kind of said method of synthesizing connection pinacol borate of claim 1 or 3, it is characterized in that in said step (2), varsol is normal heptane, normal hexane or hexanaphthene, the hydrocarbon solution of boron trichloride is the normal heptane of boron trichloride, normal hexane or cyclohexane solution, and its concentration is 10% ~ 45%.
8., according to a kind of said method of synthesizing connection pinacol borate of claim 1 or 4, it is characterized in that in step (3), said varsol is normal heptane, normal hexane or hexanaphthene.
9., according to a kind of said method of synthesizing connection pinacol borate of claim 1 or 5, it is characterized in that in step (4), said varsol is toluene or dimethylbenzene.
10. according to a kind of said method of synthesizing connection pinacol borate of claim 1, it is characterized in that in step (1), said varsol is normal heptane, the hydrocarbon solution of said dimethylamine is the n-heptane solution of the dimethylamine of concentration 25%, and the hydrocarbon solution of said boron trichloride is the n-heptane solution of the boron trichloride of concentration 25%; In step (2), said varsol is normal heptane, and the hydrocarbon solution of said boron trichloride is the n-heptane solution of the boron trichloride of concentration 25%; In step (3), said varsol is normal heptane; In step (4), said varsol is toluene.
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| WO2004076467A1 (en) * | 2003-02-28 | 2004-09-10 | Boron Molecular Pty Ltd | Preparation of diboronic esters |
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| Title |
|---|
| "798. Trisaminoboranes";Aubrey D W et al.;《Journal of the Chemical Society (Resumed)》;19621231;第4088-4094页 * |
| "Bis-catecholate, bis-dithiocatecholate, and tetraalkoxy diborane (4) compounds: Aspects of synthesis and electronic structure";Lawlor F J,et al.;《Inorganic Chemistry》;19980918;第37卷(第20期);第5282-5288页 * |
| "Tetra-(amino)-diborons";Brotherton R J,et al.;《Journal of the American Chemical Society》;19601231;第82卷(第24期);第6242-6245页 * |
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