CN107540700B - The method for preparing borate using three fragrant oxygen rare earth compoundings - Google Patents
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Abstract
The invention discloses the methods for preparing borate using three fragrant oxygen rare earth compoundings, i.e., prepare borate using three fragrant oxygen catalyzed by rare-earth complex ketone 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 ketone 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 ketone, 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 assimilations
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 ketone 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: it is a kind of to utilize three fragrant oxygen rare earth compounding systems
The method of standby borate, 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
Three fragrant oxygen rare earth compoundings, are then added ketone compound, are uniformly mixed, add borine, react at room temperature 10 ~ 30 min, obtain
Borate further uses CDCl3Reaction is terminated, solvent and extra borine is removed under reduced pressure in reaction solution, and raffinate adds oneself
Alkane (3 × 5ml) washing, obtains borate;
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 ketone 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, ketone compound is then added, is uniformly mixed, adds borine, reacts at room temperature 10 ~ 30 min, completes assimilation
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 ketone
Compound and borine are that raw material prepares the application in borate.
The present invention further discloses three fragrant oxygen rare earth compoundings in catalysis ketone compound and borine hydroboration
Application.
In above-mentioned technical proposal, the catalyst amount be ketone compound mole 0.05-0.1 %, ketone 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 borine is selected from pinacol borine.
In the present invention, the general structure of the ketone compound are as follows:
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthalene or anthryl, R2For alkyl.
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 ketone compounds and borine hydroboration occurs for the present invention for the first time, it is
It prepares borate using ketone 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 ketone 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 ketone compound of different the position of substitution, different electronic effects, miscellaneous
Cyclic ketone compound, aliphatic ketone 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 acetophenone 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 (93.3 then is added with syringe
μ L) acetophenone, it is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, mixture is at room temperature
After reacting 15 min, 0.5 mLCDCl is added in stirring3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And tetrahydrofuran, add
Enter 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 7.40 – 7.22 (m, 5H), 1.51 – 1.47 (d, J=6.5Hz, 3H), 1.24
(s, 6H), 1.21 (s, 6H)。 11B{1H} NMR (CDCl3, 128 MHz): 22.18 (s, B-O)。
Embodiment two: Nd (OAr)3(THF)2It is catalyzed melilotal 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 (106.8 then is added with syringe
μ L) melilotal, it is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, mixture exists
It stirs at room temperature, after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And tetrahydro
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 7.31 – 7.25 (m, 2H), 7.16 (t, J = 7.4 Hz, 2H), 5.24
(q, J = 6.4 Hz, 1H), 2.35 (s, 3H), 1.27 (s, 6H), 1.24 (s, 6H)。
Embodiment three: Nd (OAr)3(THF)2It is catalyzed o-methyl-benzene ethyl ketone 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 (104.6 then is added with syringe
μ L) o-methyl-benzene ethyl ketone, it is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, mixture exists
It stirs at room temperature, after reacting 30 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And tetrahydro
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 7.55 (m,1H), 7.33 – 7.08 (m, 3H), 5.45 (q, J = 6.4 Hz,
1H), 1.48 (d, J = 6.4 Hz, 3H), 1.26 (s, 6H), 1.22 (s, 6H)。
Example IV: Nd (OAr)3(THF)2It is catalyzed acetanisole 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
(0.1201 g) acetanisole 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 30 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 7.38 – 7.17 (m, 2H), 6.94
– 6.68 (m, 2H), 5.20 (q, J = 6.4 Hz, 1H), 3.79 (s, 3H), 1.47 (d, J = 6.4 Hz,
3H), 1.24 (s, 6H), 1.22 (s, 6H)。
Embodiment five: Nd (OAr)3(THF)2It is catalyzed parachloroacetophenone 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 (103.8 then is added with syringe
μ L) parachloroacetophenone, 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 7.31-7.26 (m, 4H,), 5.21(q, J=6.4 Hz, 1H ), 1.47
(d, J=6.4 Hz, 3H), 1.24 (s, 6H), 1.21 (s, 6H)。
Embodiment six: Nd (OAr)3(THF)2It is catalyzed parabromoacetophenone 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
(0.1592 g) parabromoacetophenone, 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 7.41 (m, 2H), 7.21 (m, 2H), 5.16 (q, J =
6.4 Hz, 1H), 1.42 (d, J = 6.5 Hz, 3H), 1.20 (s, 6H), 1.18 (s, 6H)。
Embodiment seven: Nd (OAr)3(THF)2It is catalyzed p-nitroacetophenone 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 then is added with syringe
(0.1321 g) p-nitroacetophenone, dissolution are uniformly mixed, then 0.88 mol (127.7 μ L) pinacol boron is added with syringe
Alkane, mixture are 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 8.16 – 8.08 (m, 2H), 7.47 (m, 2H), 5.26
(q, J = 6.5 Hz, 1H), 1.44 (d, J = 6.5 Hz, 3H), 1.19 (s, 6H), 1.16 (s, 6H)。
Embodiment eight: Nd (OAr)3(THF)2It is catalyzed benzophenone 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 then is added with syringe
(0.1458 g) benzophenone adds 0.2 mL THF, and dissolution is uniformly mixed, then 0.88 mol (127.7 is added with syringe
μ L) pinacol borine, mixture is stirred at room temperature, and after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%,
CDCl is removed under reduced pressure later3And tetrahydrofuran, n-hexane (3 × 5 mL) washing is added, drains, obtains corresponding pinacol boric acid
Ester.The nuclear magnetic data of product are as follows:1H NMR (400 MHz, CDCl3) δ 7.37-7.39 (m, 4H), 7.27-7.31 (m,
4H), 7.20-7.24 (m, 2H), 6.18 (s, 1H), 1.19 (s, 12H)。
Embodiment nine: Nd (OAr)3(THF)2It is catalyzed 1- (2- thienyl) ethyl ketone 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 (86.4 then is added with syringe
μ L) 1- (2- thienyl) ethyl ketone, 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 20 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 7.21 – 7.19 (m, 1H), 6.97 – 6.92 (m, 2H),
5.48 (q, J = 6.4 Hz, 1H), 1.60 (d, J = 6.4 Hz, 3H), 1.25 (d, J = 4.9 Hz,
12H)。
Embodiment ten: Nd (OAr)3(THF)2Catalyzing iso-butane acyl benzene 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 (123.5 then is added with syringe
μ L) isobutyrophenone, dissolution is uniformly mixed, then 0.88 mol (127.7 μ L) pinacol borine is added with syringe, and mixture exists
It stirs at room temperature, after reacting 15 min, 0.5 mLCDCl is added3, nuclear-magnetism yield is 99%, and CDCl is removed under reduced pressure later3And tetrahydro
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 7.34 –7.18 (m, 5H), 4.81 (d, J= 6.2 Hz, 1H), 1.96 (dq,
J= 13.4, 6.7 Hz, 1H), 1.19 (d, J= 16.3 Hz, 12H), 0.90 (d, J= 6.7 Hz, 3H),
0.83 (d, J= 6.8 Hz, 3H)。
Embodiment 11: Nd (OAr)3(THF)2It is catalyzed 1-tetralone 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 mol1- tetrahydro then is added with syringe
Naphthalenone (106.4 μ L), dissolution are 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 15 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 (400 MHz, CDCl3) δ 7.41 – 7.37(m, 1H), 7.19 – 7.14 (m, 2H), 7.11 –
7.04 (m, 1H), 5.20 (t, J= 4.9 Hz, 1H), 2.83 m, 1H), 2.70 (m, 1H), 2.12 – 1.99
(m, 1H), 2.00 –1.91 (m, 2H), 1.82 –1.69 (m, 1H), 1.30 (d, J= 5.8 Hz, 12H)。
Embodiment 12: Nd (OAr)3(THF)2It is catalyzed 3- methyl -2- butanone 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 mol3- methyl-then is added with syringe
2- butanone (86 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 0.79 (d, J=2.79,3H), 0.81 (d, J=2.8 Hz, 3H),
1.04 (d, J = 6.09Hz, 3H), 1.16 (s,12 H, Bpin-CH3), 1.56(m,1H), 3.87 (q, 1H)。
Claims (2)
1. a kind of method for preparing borate using 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 ketone 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 using 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 ketone compound mole;The ketone compound and the molar ratio of borine are
1:1.1;The general structure of the ketone compound are as follows:
Wherein R1For phenyl, substituted-phenyl, heterocyclic aryl, naphthalene or anthryl, R2For alkyl.
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