CN107556334B - The method for preparing borate based on three fragrant oxygen rare earth compoundings - Google Patents
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Abstract
The invention discloses the methods for preparing borate based on three fragrant oxygen rare earth compoundings, i.e., prepare borate using three fragrant oxygen catalyzed by rare-earth complex aldehyde compounds and borine hydroboration, and catalyst molecule formula is Nd (OAr)3(THF)2, Ar=[2,6- (tBu)2‑4‑MeC6H2], it reacts and generates as catalyst in borate with aldehyde compound in borine, it can under mild conditions (room temperature), with the extremely short time (10-30 minutes), addition reaction occurs for high yield (99%) catalysis borine and aldehyde, to be the first using such the metal complex catalyzed reaction of rare earth oxygen key.
Description
Technical field
The present invention relates to the applications of three fragrant oxygen rare earth compoundings, and in particular to utilizes three fragrant oxygen catalyzed by rare-earth complex hydroformylations
Close the method that the hydroboration of object generates borate.
Background technique
Organic boric acid ester can be used not only as plasticizer, the fluxing agent in welding process, flame retardant for textile, coupling agent, profit
A kind of important raw material in oil additive etc. and organic synthesis.For example, raw using carbonyls and borine equivalent reaction
At borate, it is a kind of method for efficiently synthesizing alcohol that then hydrolysis, which obtains alcohol,.Meanwhile boric acid or borate can be converted to it
His a variety of functional groups, it is a kind of important reagent in organic synthesis, the research as chiral drug also just gradually deeply in, it is existing
Chiral boric acid is being used to synthesize bortezomib as medicines structure unit, it is the multiple marrow for the treatment of of first approval
The Protease Inhibitor drugs of cancer and lymph cancer, so the application prospect of chiral boric acid or borate is very vast.Therefore, for
The synthesis of borate is still the hot spot of chemist research.But in the presence of no catalyst, borine be difficult with
Hydroboration occurs for carbonyls.
In existing document report, about catalysis hydroboration catalyst relate generally to main group metal catalyst and
Transition-metal catalyst.For rare-earth metal catalyst, different rare earth metal metal complexs shows different even phases
Anti- catalytic performance, for example, Hou Zhaomin seminar use rare earth metal alkyl complexes can with efficient catalytic secondary aliphatic amine with
Addition reaction (the Zhang W. X. of carbodiimides; Nishiura, M.; Hou Z. M. Synlett, 2006,
1213).And Wang Shaowu is catalyzed guanidineization reaction by rare-earth metal amide, to secondary aliphatic amine, needs extremely exacting terms
Guanidine (Zhou, S. L. could be obtained with the medium above yield; Wang, S. W.; Yang, G. S.; Li Q.;
Zhang, L. J.; Yao, Z. J.; Zhou, Z.; Song, H. B. Organometallics, 2007, 26,
3755).Rare earth ion belongs to hard Lewis acid, and relative to rare earth-carbon key, rare earth-nitrogen, rare earth ion is easy to and containing O atom
Hard base ligands show strong oxytropism, thus reactivity is relatively low；Therefore the prior art rarely has the cooperation of rare earth oxygen
The report of object catalysis, even if utilizing rare earth oxygen complex, it is also desirable to harsh reaction condition.
Summary of the invention
Goal of the invention of the invention is to provide the application of the fragrant oxygen rare earth compounding of one kind three, i.e., with three fragrant oxygen rare earth compoundings
Hydroboration occurs for catalyst efficient catalytic aldehyde compound and pinacol borine and obtains borate；The present invention is in addition to providing one
The catalyst that kind is efficiently easy to get, the mild condition of simultaneous reactions reduce post processing cost, and catalyst has wider substrate
The scope of application.
To achieve the above object of the invention, the technical solution adopted by the present invention is that:
A method of borate is prepared based on three fragrant oxygen rare earth compoundings, comprising the following steps:
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, catalyst is added in the reaction flask by dehydration and deoxidation processing
Nd(OAr)3(THF)2, aldehyde compound is then added, is uniformly mixed, adds borine, reacts at room temperature 10 ~ 30 min, obtains boric acid
Ester further uses CDCl3Reaction is terminated, solvent and extra borine is removed under reduced pressure in reaction solution, and raffinate adds hexane (3
× 5ml) washing, obtain corresponding different substituted boracic acid esters.
The invention also discloses three fragrant oxygen rare earth compoundings to close the application in object and borine hydroboration in catalytic hydroformylation.
In the present invention, the chemical structural formula of described three fragrant oxygen rare earth compoundings are as follows:
The molecular formula of above-mentioned three fragrant oxygen rare earth compoundings may be expressed as: Nd (OAr)3(THF)2, in formula: Ar=[2,6-
(tBu)2-4-MeC6H2]。
The invention also discloses the method that hydroboration occurs for three fragrant oxygen catalyzed by rare-earth complex aldehyde compounds and borine,
The following steps are included:
Under anhydrous and oxygen-free environment, under atmosphere of inert gases, catalyst is added in the reaction flask by dehydration and deoxidation processing
Nd(OAr)3(THF)2, aldehyde compound is then added, is uniformly mixed, adds borine, reacts at room temperature 10 ~ 30 min, completes hydroformylation
The hydroboration for closing object and borine further uses CDCl3Reaction is terminated, solvent is removed under reduced pressure in reaction solution, and raffinate adds again
Enter hexane (3 × 5 ml) washing, obtains product.
The present invention further discloses three fragrant oxygen rare earth compoundings and is preparing the application in borate；Especially with aldehyde
Compound and borine are that raw material prepares the application in borate.
In above-mentioned technical proposal, the catalyst amount be aldehyde compound mole 0.05-0.1 %, aldehyde compound with
The molar ratio of borine is 1:1.1, and reaction temperature is room temperature, reaction time 10-30min.
In the present invention, the general structure of the aldehyde compound are as follows:
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthalene or anthryl.
In the present invention, the borine is selected from pinacol borine.
Above-mentioned technical proposal can be expressed as follows:
Due to the application of above-mentioned technical proposal, the present invention has the following advantages compared with prior art:
1. using three fragrant oxygen catalyzed by rare-earth complex aldehyde compounds and borine hydroboration occurs for the present invention for the first time, it is
It prepares borate using aldehyde compound and borine generation hydroboration and provides new scheme, expanded three fragrant oxygen rare earths cooperations
The application of object.
2. the catalysis that hydroboration occurs for disclosed by the invention three fragrant oxygen catalyzed by rare-earth complex aldehyde compounds and borine
Active height (catalyst amount is only 0.05-0.1%), reaction condition is mild (room temperature), and the reaction time is short (10-30 min), and anti-
Product yield is high, and reaction is simple controllable, and post-processing is simple, reduces costs.
3. catalyst disclosed by the invention is for the aromatic aldehyde compound of different the position of substitution, different electronic effects, miscellaneous
Ring aldehyde compound, aliphatic aldehyde compound suffer from preferable universality, to obtain the acid esterification of different substituents structure
It closes object and more selections is provided.
Specific embodiment
The present invention is described further below with reference to embodiment:
Embodiment one: Nd (OAr)3(THF)2It is catalyzed benzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (81.3 then is added with syringe
μ L) benzaldehyde, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, and mixture is in room
The lower stirring of temperature, after reacting 10 min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With tetrahydro furan
It mutters, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product are as follows:1H
NMR (CDCl3, 400 MHz): δ7.33-7.20 (m, 5H), 4.91 (s, 2H), 1.23 (s, 12H)。
Embodiment two: Nd (OAr)3(THF)2It is catalyzed p-tolyl aldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (94.3 then is added with syringe
μ L) p-tolyl aldehyde, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine, mixing is added with syringe
Object is stirred at room temperature, and after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With
Tetrahydrofuran is added n-hexane (3 × 5 mL) washing, drains, obtain corresponding pinacol borate.The nuclear magnetic data of product
Are as follows:1H NMR (CDCl3, 400MHz): δ 7.23 (d, 2H), 7.13 (d, 2H), 4.88 (s, 2H), 2.32(s,
3H), 1.25(s, 12H)。
Embodiment three: Nd (OAr)3(THF)2It is catalyzed o-tolualdehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (94.3 then is added with syringe
μ L) o-tolualdehyde, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine, mixing is added with syringe
Object is stirred at room temperature, and after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With
Tetrahydrofuran is added n-hexane (3 × 5 mL) washing, drains, obtain corresponding pinacol borate.The nuclear magnetic data of product
Are as follows:1H NMR (CDCl3, 400MHz): δ7.41-7.38 (m, 1H), 7.19-7.13 (m, 3H), 4.93 (s,
2H), 2.31(s, 3H), 1.26(s, 12H)。
Example IV: Nd (OAr)3(THF)2It is catalyzed 2,4,6- trimethylbenzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (118 μ then are added with syringe
L) 2,4,6- trimethylbenzaldehydes, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe,
Mixture is stirred at room temperature, and after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, is removed under reduced pressure later
CDCl3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The core of product
Magnetic data are as follows:1H NMR (CDCl3, 400MHz): δ6.81 (s, 2H), 4.94 (s, 2H), 2.37(s, 6H),
2.23(s, 3H), 1.24(s, 12H)。
Embodiment five: Nd (OAr)3(THF)2It is catalyzed 4-Fluorobenzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (85.8 then is added with syringe
μ L) 4-Fluorobenzaldehyde, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine, mixture is added with syringe
It is stirred at room temperature, after reacting 20 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With four
Hydrogen furans is added n-hexane (3 × 5 mL) washing, drains, obtain corresponding pinacol borate.The nuclear magnetic data of product are as follows:1H NMR (CDCl3, 400MHz): δ7.33-7.29 (m, 2H), 7.03-6.97 (m, 2H), 4.87 (s, 2H),
1.25(s, 12H)。
Embodiment six: Nd (OAr)3(THF)2It is catalyzed p-chlorobenzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol then is added with syringe
(0.1125 g) p-chlorobenzaldehyde, dissolution are uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe,
Mixture is stirred at room temperature, and after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, is removed under reduced pressure later
CDCl3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The core of product
Magnetic data are as follows:1H NMR (400 MHz, CDCl3) δ 7.36 (s, 1H), 7.26 – 7.18 (m, 3H), 4.89
(s, 2H), 1.27 (s, 12H)。
Embodiment seven: Nd (OAr)3(THF)2It is catalyzed m chlorobenzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (90.6 then is added with syringe
μ L) m chlorobenzaldehyde, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine, mixture is added with syringe
It is stirred at room temperature, after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With four
Hydrogen furans is added n-hexane (3 × 5 mL) washing, drains, obtain corresponding pinacol borate.The nuclear magnetic data of product are as follows:1H NMR (400 MHz, CDCl3) δ 7.36 (s, 1H), 7.19-7.28 (m, 3H), 4.89 (s, 2H), 1.27
(s, 12H)。
Embodiment eight: Nd (OAr)3(THF)2It is catalyzed p-bromobenzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol then is added with syringe
(0.1480 g) p-bromobenzaldehyde adds 0.2 mL THF, and dissolution is uniformly mixed, then 0.88 mol is added with syringe
(127.7 μ L) pinacol borine, mixture are stirred at room temperature, and after reacting 10 min, 0.5 mLCDCl is added3, nuclear-magnetism yield
It is 99%, CDCl is removed under reduced pressure later3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, where obtains corresponding frequency
Alcohol borate.The nuclear magnetic data of product are as follows:1H NMR (400 MHz, CDCl3) δ 7.36 (s, 1H), 7.26 – 7.18
(m, 3H), 4.89 (s, 2H), 1.27 (s, 12H)。
Embodiment nine: Nd (OAr)3(THF)2It is catalyzed o-methoxybenzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol then is added with syringe
(0.1089 g) P-methoxybenzal-dehyde, dissolution are uniformly mixed, then 0.88 mol (127.7 μ L) pinacol is added with syringe
Borine, mixture are stirred at room temperature, and after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and decompression removes later
Remove CDCl3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.Product
Nuclear magnetic data are as follows:1H NMR (CDCl3, 400MHz): δ7.41 (d, 1H), 7.29-7.21 (m, 1H), 6.95 (t,
1H), 6.83 (d, 1H), 4.99 (s, 2H), 3.80 (s, 3H), 1.27(s, 12H)。
Embodiment ten: Nd (OAr)3(THF)2It is catalyzed 2- naphthaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol then is added with syringe
(0.1249 g) 2- naphthaldehyde, dissolution are uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, are mixed
It closes object to be stirred at room temperature, after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3
And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product
Are as follows:1H NMR (400 MHz, CDCl3) δ 7.80-7.82 (m, 4H), 7.43-7.48 (m, 3H), 5.09 (s,
2H), 1.28 (s, 12H)。
Embodiment 11: Nd (OAr)3(THF)2It is catalyzed 2 thiophene carboxaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (74.8 then is added with syringe
μ L) 2 thiophene carboxaldehyde, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine, mixture is added with syringe
It is stirred at room temperature, after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With four
Hydrogen furans is added n-hexane (3 × 5 mL) washing, drains, obtain corresponding pinacol borate.The nuclear magnetic data of product are as follows:1H NMR (400 MHz, CDCl3) δ 7.23-7.25 (m, 1H), 7.01 (m, 1H), 6.93-6.95 (m, 1H),
5.03 (s, 2H), 1.26 (s, 12H)。
Embodiment 12: Nd (OAr)3(THF)2It is catalyzed n-Heptaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol (111.4 then is added with syringe
μ L) n-Heptaldehyde, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, and mixture is in room
The lower stirring of temperature, after reacting 15 min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With tetrahydro furan
It mutters, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product are as follows:1H
NMR (400 MHz, CDCl3) δ 7.80-7.82 (m, 4H), 7.43-7.48 (m, 3H), 5.09 (s, 2H),
1.28 (s, 12H)。
Embodiment 13: Nd (OAr)3(THF)2Spirit catalytic of cinnamaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0008 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol cinnamic acid then is added with syringe
(100.6 μ L), dissolution are uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, and mixture is in room
The lower stirring of temperature, after reacting 15 min, is added 0.5 mLCDCl3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With tetrahydro furan
It mutters, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol borate.The nuclear magnetic data of product are as follows:1H
NMR (400 MHz, CDCl3) δ 7.38 (d, J = 7.4 Hz, 2H), 7.31 (t, J = 7.5 Hz, 2H),
7.23 (t, J = 7.2 Hz, 2H), 6.63 (d, J = 15.9 Hz, 1H), 6.29 (dt, J = 15.9, 5.3
Hz, 1H), 4.54 (dd, J = 5.3, 1.1 Hz, 2H), 1.28 (s, 12H)。
Embodiment 14: Nd (OAr)3(THF)2It is catalyzed paranitrobenzaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0004 mol (40 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol then is added with syringe
(0.1208 g) paranitrobenzaldehyde adds 0.2 mLTHF, and dissolution is uniformly mixed, then 0.88 mol is added with syringe
(127.7 μ L) pinacol borine, mixture are stirred at room temperature, and after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield
It is 99%, CDCl is removed under reduced pressure later3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, where obtains corresponding frequency
Alcohol borate.The nuclear magnetic data of product are as follows:1H NMR (CDCl3, 200 MHz), δ 1.19 (s, 12H), 4.93 (s,
2H), 7.43(d, J = 8.6 Hz, 2H), 8.12(d,3J = 8.9 Hz, 2H)。
Embodiment 15: Nd (OAr)3(THF)2It is catalyzed 2 thiophene carboxaldehyde and pinacol borine hydroboration
In the reaction flask by dehydration and deoxidation processing, argon gas protection is lower to be added 0.0008 mol (80 μ L) catalyst n d
(OAr)3(THF)2) (the catalyst stock solution of 0.01 M, solvent THF), 0.8 mol2- thiophene then is added with syringe
Formaldehyde (73.8 μ L), dissolution are uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine, mixture is added with syringe
It is stirred at room temperature, after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3With four
Hydrogen furans is added n-hexane (3 × 5 mL) washing, drains, obtain corresponding pinacol borate.The nuclear magnetic data of product are as follows:1H NMR (CDCl3, 200 MHz), δ 1.18(s, 12H), 4.74 (s, 2H), 6.22(s, 1H), 6.72 (s,
2H)。
Claims (2)
1. a kind of method for preparing borate based on three fragrant oxygen rare earth compoundings, comprising the following steps:
Under anhydrous and oxygen-free environment, in atmosphere of inert gases, three fragrant oxygen rare earths are added in the reaction flask by dehydration and deoxidation processing
Then aldehyde compound is added in complex, be uniformly mixed, and adds borine, reacts at room temperature 10 ~ 30 min, obtains borate；It is described
Borine is selected from pinacol borine；
The chemical structural formula of described three fragrant oxygen rare earth compoundings are as follows:
。
2. the method for preparing borate based on three fragrant oxygen rare earth compoundings according to claim 1, which is characterized in that described three
The dosage of fragrant oxygen rare earth compounding is the 0.05-0.1 % of aldehyde compound mole；The molar ratio of the aldehyde compound and borine is
1:1.1；The general structure of the aldehyde compound are as follows:
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthalene or anthryl.
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