CN116082379A - Schiff base aluminum compound and preparation thereof and application thereof in hydroboration reaction of alkyne - Google Patents
Schiff base aluminum compound and preparation thereof and application thereof in hydroboration reaction of alkyne Download PDFInfo
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- CN116082379A CN116082379A CN202310200102.7A CN202310200102A CN116082379A CN 116082379 A CN116082379 A CN 116082379A CN 202310200102 A CN202310200102 A CN 202310200102A CN 116082379 A CN116082379 A CN 116082379A
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- -1 Schiff base aluminum compound Chemical class 0.000 title claims abstract description 63
- 239000002262 Schiff base Substances 0.000 title claims abstract description 45
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006197 hydroboration reaction Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 9
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 7
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims abstract description 6
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- LZPWAYBEOJRFAX-UHFFFAOYSA-N 4,4,5,5-tetramethyl-1,3,2$l^{2}-dioxaborolane Chemical group CC1(C)O[B]OC1(C)C LZPWAYBEOJRFAX-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910000085 borane Inorganic materials 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- DKFHWNGVMWFBJE-UHFFFAOYSA-N 1-ethynylcyclohexene Chemical group C#CC1=CCCCC1 DKFHWNGVMWFBJE-UHFFFAOYSA-N 0.000 claims description 3
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 2
- 230000036632 reaction speed Effects 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
- 239000000047 product Substances 0.000 description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- 239000012043 crude product Substances 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 238000010828 elution Methods 0.000 description 11
- 238000005070 sampling Methods 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- OOZKONVIIMFOKW-UHFFFAOYSA-N 1-ethynyl-2-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC=C1C#C OOZKONVIIMFOKW-UHFFFAOYSA-N 0.000 description 2
- PTRUTZFCVFUTMW-UHFFFAOYSA-N 1-ethynyl-3-fluorobenzene Chemical group FC1=CC=CC(C#C)=C1 PTRUTZFCVFUTMW-UHFFFAOYSA-N 0.000 description 2
- QXSWHQGIEKUBAS-UHFFFAOYSA-N 1-ethynyl-4-fluorobenzene Chemical group FC1=CC=C(C#C)C=C1 QXSWHQGIEKUBAS-UHFFFAOYSA-N 0.000 description 2
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- YFPQIXUNBPQKQR-UHFFFAOYSA-N 1-ethynyl-2-fluorobenzene Chemical group FC1=CC=CC=C1C#C YFPQIXUNBPQKQR-UHFFFAOYSA-N 0.000 description 1
- MYBSUWNEMXUTAX-UHFFFAOYSA-N 1-ethynyl-2-methylbenzene Chemical group CC1=CC=CC=C1C#C MYBSUWNEMXUTAX-UHFFFAOYSA-N 0.000 description 1
- PAHXLHWOHJTWRU-UHFFFAOYSA-N 1-ethynyl-3-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC=CC(C#C)=C1 PAHXLHWOHJTWRU-UHFFFAOYSA-N 0.000 description 1
- RENYIDZOAFFNHC-UHFFFAOYSA-N 1-ethynyl-3-methylbenzene Chemical group CC1=CC=CC(C#C)=C1 RENYIDZOAFFNHC-UHFFFAOYSA-N 0.000 description 1
- KAIIKEMMJNRWIV-UHFFFAOYSA-N 3-ethynylcyclohexene Chemical compound C#CC1CCCC=C1 KAIIKEMMJNRWIV-UHFFFAOYSA-N 0.000 description 1
- 238000006964 Chan-Lam coupling reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003934 aromatic aldehydes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LSCYTCMNCWMCQE-UHFFFAOYSA-N n-methylpyridin-4-amine Chemical compound CNC1=CC=NC=C1 LSCYTCMNCWMCQE-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/323—Hydrometalation, e.g. bor-, alumin-, silyl-, zirconation or analoguous reactions like carbometalation, hydrocarbation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/31—Aluminium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a Schiff base aluminum compound, a preparation method thereof and application thereof in the borohydride reaction of alkyne. The preparation method comprises the following steps: firstly condensing 2-aminopyridine and salicylaldehyde to prepare Schiff base ligand, and then reacting the Schiff base ligand with the same amount of diisobutyl aluminum hydride to generate the aluminum compound. The preparation method is simple, the synthesized Schiff base aluminum compound alkyne has obvious effect in the hydroboration reaction, the catalyst is only applicable to 5 percent, the reaction speed is high, the yield is high, and the method accords with the concept of green chemistry.
Description
Technical Field
The invention relates to the technical field of catalytic reaction of aluminum metal compounds, in particular to a Schiff base aluminum compound, a preparation method thereof and application thereof in alkyne hydroboration reaction.
Background
The organoborane compounds are multifunctional synthetic intermediates and can be subjected to various organic transformations. The direct addition of B-H bonds to various unsaturated bonds, namely the borohydride reaction, is a powerful tool for the preparation of organoborane derivatives. The organic boride generated by the borohydride reaction is an important organic intermediate in various chemical conversions and material synthesis, can be converted into various compounds through further reaction, and has important significance in modern industrial chemistry and academic research. Organoboron compounds are a key multifunctional reaction precursor in carbon-carbon and carbon-heteroatom bonding reactions, such as suzuki-Miyaura reactions and Chan-Lam cross-coupling reactions.
Many natural products contain a certain configuration of di-or tri-substituted olefin building blocks and efforts are being made to find more efficient ways to stereoselectively synthesize a certain configuration of multifunctional olefin compounds. An important class of these compounds is the alkene boranes, which possess unique reactive properties, an important intermediate in organic synthesis. The borohydride of alkynes is a very efficient process for the preparation of alkene boron compounds and polysubstituted alkenes. At present, the addition reaction of organic boric acid and unsaturated bond catalyzed by transition metal is a main method for preparing alkene boron compound. The catalyst used is mainly a transition metal complex such as Rh, ru, mo, ti. Whereas the main group metal as catalyst catalyzes less of the borohydride reaction of alkynes, especially aluminum compounds. Up to now, no schiff base aluminum compound has been reported to catalyze the borohydride reaction of alkynes.
The invention comprises the following steps:
the invention aims to: aiming at the defects existing in the prior art, the invention aims to provide a Schiff base aluminum compound which can be applied to alkyne hydroboration reaction. It is another object of the present invention to provide a process for preparing a Schiff base aluminum compound. It is a further object of the present invention to provide the use of the above Schiff base aluminum compound in an alkyne borohydride reaction.
The technical scheme is as follows: in order to achieve the aim of the invention, the invention adopts the following technical scheme:
a Schiff base aluminum compound: the concrete structure is as follows
The preparation method of the Schiff base aluminum compound comprises the following steps:
(1) Under the protection of nitrogen, refluxing 2, ethyl-cool-acetone, p-methylaminopyridine, salicylaldehyde and hydrochloric acid in a molar ratio of 1:1:0.001 in a methanol solvent for 4 hours, adding water after the reaction is finished to separate out yellow crystals, filtering, washing with a small amount of glacial methanol, and pumping to obtain a solid, namely the Schiff base ligand.
(2) Under the protection of nitrogen, slowly dropwise adding diisobutyl aluminum hydride into toluene solution of the ligand at a low temperature in a Schlenk reaction bottle under the condition of no water and no oxygen, stirring at room temperature overnight, standing for filtering, concentrating toluene, and putting into a low-temperature refrigerator for the next day to obtain a large number of crystals, namely the Schiff base aluminum compound.
The reaction formula of the method is as follows:
the application of the Schiff base aluminum compound in alkyne hydroboration reaction.
Use of a schiff base aluminum compound for alkyne in catalyzing a borohydride reaction of alkyne with borane, comprising the steps of:
under the condition of no water and no oxygen, the Schiff base aluminum compound is added into a Schlenk bottle with about 10ml under the protection of nitrogen in a glove box, then borane with corresponding proportion is added and mixed uniformly, alkyne is added, then the mixture is heated for 10 hours at 60 ℃, then the mixture is exposed to air to terminate the reaction, petroleum ether/ethyl acetate is taken as an elution system, and the crude product is purified by column chromatography to obtain the vinyl borane compound.
In the technical scheme, the alkyne is one of aromatic alkyne and aliphatic alkyne; the chemical structural general formula of the aromatic aldehyde is
Wherein R is hydrogen, halogen, methyl or trifluoromethyl.
The fatty alkyne is 1-ethynyl cyclohexene and 1-heptyne.
The borane is pinacol borane.
The dosage of the catalyst is 5% of the mole number of alkyne, the mole ratio of the borane to the alkyne is 1:1, the reaction temperature is 60 ℃, and the reaction time is 10 hours.
The above equation is as follows:
wherein R is 1 ,R 2 From the alkyne of choice.
Compared with the prior art, the invention has the following advantages
1) The invention uses the Schiff base compound to catalyze the reaction of alkyne and pinacol borane to synthesize the boric acid alkene for the first time, which is also the first time to apply the Schiff base compound to catalysis, has extremely high catalytic activity, simple structure and easy synthesis, not only enriches the new scheme for preparing the boric acid alkene by the hydroboration reaction of the base compound and the borane, but also expands the application of the Schiff base compound.
2) The Schiff base aluminum compound can catalyze the hydroboration reaction of alkyne and borane with high activity under mild conditions, the catalyst dosage only needs 5% of the molar quantity of the substrate, and compared with a few catalysts reported in literature, the reaction speed is very fast, and the conversion rate can almost reach 100%. The reaction condition is mild, the reaction is simple and controllable, and the method is in high accord with the concept of green chemistry.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1) Preparation of Schiff base ligands
Under the protection of nitrogen, 100mL of anhydrous methanol is added into a 250mL round-bottom flask, 40mmol of 2-aminopyridine, 40mmol of salicylaldehyde and 0.04mmol of hydrochloric acid are added, reflux is carried out at 70 ℃ for 4 hours, after the reaction is finished, water is added to separate out yellow crystals, the yellow crystals are filtered by a Buchner funnel, and the solid obtained is Schiff base ligand after washing by a small amount of glacial methanol and pumping. 1 H NMR(400MHz,CDCl 3 )δ13.8(s,1H),9.50(s,1H),8.24(d,J＝6.0Hz,1H),7.14(d,J＝6.0Hz,1H),7.10–7.00(m,3H),6.99–9.94(m,1H),6.74–6.51(m,2H). 13 C NMR(101MHz,CDCl 3 )δ165.0,162.5,157.5,148.7,137.7,133.7,133.5,122.0,120.4,118.9,117.4.
2) Preparation of Schiff base aluminum compounds
Under the anhydrous and anaerobic condition, 6.69mmol of diisobutyl aluminum hydride is slowly dripped into 6.67mmol of Schiff base ligand toluene solution at low temperature in a Schlenk reaction bottle under the protection of nitrogen, stirred at room temperature overnight, then the solution is kept stand for filtration, toluene is concentrated, and the solution is put into a low-temperature refrigerator for the next day to obtain a large number of crystals, namely the Schiff base aluminum compound. The yield was 67%. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ8.00(dd,J＝5.1,1.8Hz,1H),7.44(s,1H),7.22(dd,J＝7.5,1.7Hz,1H),7.12(td,J＝7.7,1.8Hz,1H),6.90–6.76(m,2H),6.65–6.48(m,2H),4.39(s,2H),3.37(s,1H),0.94(p,J＝10.8,9.0Hz,6H),-0.10(s,2H). 13 CNMR(101MHz,CDCl 3 )δ167.7,166.9,155.0,148.7,138.5,138.0,136.2,122.4,122.3,118.7,117.2,115.4,27.2,24.2,22.3,21.2.
example 2: schiff base aluminum compounds catalyze phenylacetylene and pinacol borane to synthesize alkenyl borate.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of phenylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. The calculated H-spectral yield was 99%. Nuclear magnetic data of the product: 1 H NMR(400MHz,Chloroform-d)δ7.57–7.45(m,2H),7.22–7.15(m,1H),7.04(td,J＝7.7,1.2Hz,1H),6.96(ddd,J＝10.6,8.2,1.2Hz,1H),6.17(d,J＝18.6Hz,1H),1.24(s,12H). 13 C NMR(101MHz,CDCl 3 )δ148.48,136.45,127.85,127.53,126.01,82.28,23.78.
example 3: schiff base aluminum compounds catalyze the synthesis of alkenyl borates from p-fluorophenylacetylene and pinacol borane.
Under the condition of no water and no oxygen, in a glove box under the protection of nitrogen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of p-fluorophenylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an eluting system, and purifying the crude product by adopting column chromatographyThe product was obtained, sampled, and treated with CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.50–7.42(m,2H),7.35(d,J＝18.4Hz,1H),7.02(t,J＝8.6Hz,2H),6.07(d,J＝18.4Hz,1H),1.31(s,12H). 13 C NMR(101MHz,CDCl 3 )δ163.36,160.89,147.14,132.70,127.73,127.64,114.64,114.43,82.37,23.78.
example 4: schiff base aluminum compounds catalyze the synthesis of alkenyl borates from tolane and pinacol borane.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of p-tolane, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.39–7.20(m,4H),7.05(d,J＝7.9Hz,3H),6.03(d,J＝18.5Hz,1H),2.25(s,3H),1.22(s,12H). 13 CNMR(101MHz,CDCl 3 )δ149.52,138.97,134.84,129.32,127.05,83.29,24.84,21.35.
example 5: schiff base aluminum compounds catalyze the synthesis of alkenyl borates from p-methyl oxy phenylacetylene and pinacol borane.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of p-methoxyphenylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.46–7.40(m,2H),7.35(d,J＝18.4Hz,1H),6.86(d,J＝8.8Hz,2H),6.01(d,J＝18.4Hz,1H),3.81(s,3H),1.31(s,12H). 13 C NMR(101MHz,CDCl 3 )δ160.31,149.08,130.43,128.48,113.99,83.22,55.28,24.82.
example 6: schiff base aluminum compounds catalyze m-fluorophenylacetylene and pinacol borane to synthesize alkenyl borate.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of m-fluorophenylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.26(d,J＝18.4Hz,1H),7.22–7.12(m,3H),7.09(d,J＝10.0Hz,1H),6.89(t,J＝7.6Hz,1H),6.08(d,J＝18.4Hz,1H),1.22(s,12H). 13 C NMR(101MHz,CDCl 3 )δ163.28,160.84,147.04,147.02,138.89,138.82,129.03,128.95,121.98,121.95,114.74,114.53,112.36,112.14,82.45,23.77.
example 7: schiff base aluminum compounds catalyze m-tolane and pinacol borane to synthesize alkenyl borate.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of m-tolylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.29(d,J＝18.4Hz,1H),7.23–7.18(m,2H),7.16–7.09(m,1H),7.01(d,J＝7.4Hz,1H),6.07(d,J＝18.4Hz,1H),2.25(s,3H),1.22(s,12H). 13 C NMR(101MHz,CDCl 3 )δ148.65,137.04,136.45,128.67,127.42,126.75,123.21,82.26,23.79,20.35.
example 8: schiff base aluminum compounds catalyze m-trifluoromethyl phenylacetylene and pinacol borane to synthesize alkenyl borate.
Under the condition of no water and no oxygen, under the protection of nitrogen, in a glove box, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle of about 10ml, then adding 1.0mmol of pinacol borane, uniformly mixing, and finally adding m-trifluoromethyl phenylacetylene1.0mmol, heating at 60deg.C for 10 hr, exposing to air to terminate the reaction, purifying the crude product by column chromatography with petroleum ether/ethyl acetate as eluting system to obtain product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.62(d,J＝2.1Hz,1H),7.55(d,J＝7.7Hz,1H),7.43(d,J＝7.7Hz,1H),7.38–7.27(m,2H),6.15(d,J＝18.4Hz,1H),1.22(s,12H). 13 C NMR(101MHz,CDCl 3 )δ146.63,137.26,130.53,130.21,129.89,129.57,128.98,128.96,128.05,124.39,124.27,122.71,121.69,118.98,82.53,23.75.
example 9: schiff base aluminum compounds catalyze m-o-fluorophenylacetylene and pinacol borane to synthesize alkenyl borate.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of o-fluorophenylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.56–7.41(m,2H),7.19(s,1H),7.04(td,J＝7.7,1.2Hz,1H),6.96(ddd,J＝10.6,8.2,1.2Hz,1H),6.17(d,J＝18.6Hz,1H),1.24(s,12H). 13 C NMR(101MHz,CDCl 3 )δ160.95,158.45,140.32,140.28,129.18,129.10,126.40,126.37,124.44,124.32,123.09,123.05,114.91,114.69,82.43,23.79.
example 10: schiff base aluminum compounds catalyze o-tolan and pinacol borane to synthesize alkenyl borate.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of o-tolylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.65(d,J＝18.3Hz,1H),7.56(dd,J＝6.6,2.5Hz,1H),7.22–7.11(m,3H),6.09(d,J＝18.2Hz,1H),2.43(s,3H),1.32(s,12H). 13 C NMR(101MHz,CDCl 3 )δ146.11,135.69,135.27,129.37,127.54,125.08,124.76,82.27,23.80,18.79.
example 11: schiff base aluminum compounds catalyze o-trifluoromethyl phenylacetylene and pinacol borane to synthesize alkenyl borate.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of o-trifluoromethyl phenylacetylene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.71–7.61(m,2H),7.56(d,J＝7.9Hz,1H),7.44(t,J＝7.6Hz,1H),7.30(t,J＝7.7Hz,1H),6.08(d,J＝18.0Hz,1H),1.24(s,12H). 13 C NMR(101MHz,CDCl 3 )δ143.72,135.94,130.84,127.16,126.48,124.74,124.68,124.56,121.84,82.53,23.78.
example 12: schiff base aluminum compounds catalyze the synthesis of alkenyl borates from m-1-ethynyl cyclohexene and pinacol borane.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of 1-ethynyl cyclohexene, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, using petroleum ether/ethyl acetate as an elution system, purifying the crude product by column chromatography to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ7.02(d,J＝18.2Hz,1H),5.96(d,J＝2.3Hz,1H),5.43(d,J＝18.3Hz,1H),2.15(d,J＝4.6Hz,4H),1.62(dd,J＝29.4,9.5Hz,4H),1.27(s,12H). 13 C NMR(101MHz,CDCl 3 )δ152.22,136.15,133.24,82.00,25.16,23.75,22.74,21.40,21.33.
example 12: schiff base aluminum compounds catalyze the synthesis of alkenyl borates from m-1-heptyne and pinacolborane.
Under the condition of no water and no oxygen, adding a catalyst of 0.05mmo1 into a Schlenk reaction bottle with about 10ml under the protection of nitrogen in a glove box, adding 1.0mmol of pinacol borane, uniformly mixing, finally adding 1.0mmol of 1-heptyne, heating at 60 ℃ for 10 hours, exposing to air to terminate the reaction, purifying the crude product by column chromatography with petroleum ether/ethyl acetate as an elution system to obtain a product, sampling, and using CDCl 3 And (3) dissolving the product. Nuclear magnetic data of the product: 1 H NMR(400MHz,CDCl 3 )δ6.73-6.66(m,1H),5.51-5.46(d,,J＝18.01Hz,1H),2.22-2.17(q,2H),1.48-1.43(br,4H),1.31(s,12H),1.28-1.23(m,4H),0.95-0.92(s,3H) 13 C NMR(101MHz,CDCl 3 )δ154.59,82.77,35.73,31.64,28.83,28.11,24.64,22.50,13.96.
Claims (7)
1. the structure of the Schiff base aluminum compound is as follows
2. A process for the preparation of a schiff base aluminum compound as claimed in claim 1, comprising the steps of:
(1) Under the protection of nitrogen, refluxing 2-aminopyridine, salicylaldehyde and p-hydrochloric acid in a molar ratio of 1:1:0.001 in an anhydrous methanol solvent for 4 hours, adding water after the reaction is finished to separate out yellow crystals, filtering, washing with a small amount of glacial methanol, and pumping to obtain a solid which is the Schiff base ligand.
(2) Under the condition of no water and no oxygen, slowly dripping diisobutyl aluminum hydride into toluene solution of the ligand at low temperature in a Schlenk reaction bottle under the protection of nitrogen, stirring at room temperature overnight, standing for filtration, concentrating toluene, and putting into a low-temperature refrigerator for the next day to obtain a large number of crystals, namely the Schiff base aluminum compound.
3. Use of a schiff base aluminium compound according to claim 1 in an alkyne borohydride reaction.
4. The method according to claim 3, wherein the terminal alkyne is one of aromatic alkyne and aliphatic alkyne; the borane is pinacol borane.
5. The method of claim 4, wherein the aromatic alkyne has the formula
Wherein R is hydrogen, halogen, methyl or trifluoromethyl.
6. The method according to claim 4, wherein the fatty alkyne is 1-ethynyl cyclohexene, 1-heptyne.
7. The method according to claim 3, wherein the Schiff base aluminum compound is: alkyne: borane 0.05:1:1, wherein the temperature of the hydroboration reaction is 60 ℃ and the time is 10 hours.
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