CN106188118B - Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis ketone and borine - Google Patents
Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis ketone and borine Download PDFInfo
- Publication number
- CN106188118B CN106188118B CN201610501608.1A CN201610501608A CN106188118B CN 106188118 B CN106188118 B CN 106188118B CN 201610501608 A CN201610501608 A CN 201610501608A CN 106188118 B CN106188118 B CN 106188118B
- Authority
- CN
- China
- Prior art keywords
- ketone
- borine
- rare earth
- reaction
- silicon amine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 System
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- 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
- B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
- B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
- B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
- B01J2231/344—Boronation, e.g. by adding R-B(OR)2
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- 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
- B01J2531/37—Lanthanum
-
- 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
- B01J2531/38—Lanthanides other than lanthanum
Abstract
The invention discloses a kind of application of three silicon amine rare earth compounding in the hydroboration of catalysis ketone and borine, ketone is 2 acetyl furans, 2 acetyl thiophenes, 2 acetonaphthones or (substitution) phenyl ketone.Three silicon amine rare earth compounding disclosed by the invention can be in a mild condition（Room temperature）The catalysis ketone of high activity and the hydroboration of borine, catalyst amount only need the 0.1~0.5% of ketone mole；Reaction speed quickly, reacts 10 minutes yields with regard to that can reach more than 90%, compared with existing catalyst system and catalyzing, both reduces catalyst amount, improve yield again, and required time is short, and reaction condition is gentle, highly meets atom economy synthesis.
Description
Technical field
The present invention relates to a kind of application technology of metal organic complex, and in particular to three silicon amine rare earth compoundings are being catalyzed
Application in the hydroboration of ketone and borine.
Background technology
Organo-borane is very important a kind of intermediate in organic conversion.The application of boric acid ester compound is very
Extensively, can not only polymeric additive, gasoline additive, bactericidal agent, fire retardant be used as to use, and may be used as lubricating oil
Additive and motor vehicle brake fluid.Meanwhile also just progressively going deep into as the research of special surfactant.Boric acid with boron oxygen key
Ester surfactant has good compatibility with polymer substance, therefore is commonly used for the antistatic additive of synthetic resin.
The most easy method of synthesis borate is the direct polycondensation reaction of boric acid and alcohol either phenol.Also some are other
Method, such as the direct reaction of boron oxide and alcohol or phenol, and the ester exchange reaction of borate and alcohol or phenol.But this
Some defects relatively all be present in a little methods, otherwise it is that raw material is not easy to obtain, otherwise it is that post-reaction treatment is more complicated, it is difficult to industrialize
Production.Early in nineteen thirty-nine, researcher is had found under conditions of without catalyst, and with diborane Borohydride reduction may occur for ketone
Reaction, opened up a new way to synthesize the borate of various different substituents.Most of all, utilize carbonyls
Addition reaction with borine be synthesis the borate containing different substituents most directly, the method for most atom economy.But study table
It is bright in the case of no catalyst, some borines（Such as pinacol borine）It is difficult to hydroboration occurs, it may be possible to this kind of boron
The lewis acidity of alkane is too low to be caused.Metallo-organic compound because its easily regulate and control, feature variation, catalytic activity compared with
By force, it is widely used in the reaction.It is currently reported mainly to be included with the hydroborated catalyst of catalysis of carbonyl compound：
Complex (Sarko, the C. R. of transition metal titanium, ruthenium and molybdenum; Guch, I. C.; DiMare, M. J. Org. Chem.1994, 59, 705-706)；Complex (Locatelli, the M. of second subgroup zinc; Cozzi, P. G. Angew. Chem., Int. Ed. 2003, 42, 4928-4930)；Main group metal magnesium, germanium and tin complex (Arrowsmith,
M.; Hadlington, T. J.; Hill, M. S.; Kociok-KÖhn, G. Chem. Commun.2012, 48,
4567-4569)。
In existing catalyst system and catalyzing, catalyst amount is larger, reaction time length, and generally inclined to the catalytic activity of ketone
It is low.So necessary explore new catalyst system and catalyzing come the deficiency before improving, up to the present, also find no on dilute
Report of the native complex as catalyst hydroboration.
The content of the invention
The goal of the invention of the present invention is to provide the application of three silicon amine rare earth compoundings, and it can be catalyzed ketone and pinacol borine
Borate is prepared, while there is high catalytic activity, low catalyst amount, the reaction time shortens, gentle excellent of reaction condition
Point, and have the good substrate scope of application.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：Three silicon amine rare earth compoundings are in catalysis ketone and borine
Application in synthetic reaction；The chemical structural formula of the three silicon amine rare earth compounding is as follows：
The one kind of wherein Ln in Lan, Nd, europium, ytterbium, samarium, yttrium.
Above-mentioned three silicon amine rare earth compounding can be catalyzed the hydroboration of ketone and pinacol borine, wherein, the ketone is
2- acetyl furans, 2- acetyl thiophenes or 2- acetonaphthones；Or the chemical structural formula of the ketone is, wherein
R is selected from hydrogen, halogen, nitro or methyl.
In above-mentioned technical proposal, the dosage of the three silicon amine rare earth compounding is the 0.1~0.5% of the mole of ketone；It is described
The dosage and ketone equivalent of borine.
In above-mentioned technical proposal, described synthesis reaction temperature is room temperature；Reaction time is 5~15 minutes, preferably 10 points
Clock.
The invention also discloses above-mentioned three silicon amine catalyzed by rare-earth complex ketone and the method for the hydroboration of borine, specifically
Step is：
Under the conditions of anhydrous and oxygen-free, under nitrogen protection, three silicon amine rare earth compoundings, borine are well mixed with ketone successively；
Reaction 5~15 minutes, uses CDCl3Terminating reaction, reaction solution removal of solvent under reduced pressure, obtain different substituted borates.
The present invention further discloses a kind of method for preparing borate, concretely comprise the following steps：
Under the conditions of anhydrous and oxygen-free, under nitrogen protection, three silicon amine rare earth compoundings, borine are well mixed with ketone successively；
Reaction 5~15 minutes, uses CDCl3Terminating reaction, reaction solution removal of solvent under reduced pressure, obtain different substituted borates.
In above-mentioned technical proposal, the ketone is 2- acetyl furans, 2- acetyl thiophenes or 2- acetonaphthones；It is or described
The chemical structural formula of ketone is, wherein R is selected from hydrogen, halogen, nitro or methyl；The borine is pinacol boron
Alkane.
In above-mentioned technical proposal, the dosage of the three silicon amine rare earth compounding is the 0.1~0.5% of the mole of ketone；It is described
The dosage and ketone equivalent of borine.
In above-mentioned technical proposal, described synthesis reaction temperature is room temperature.
The present invention further discloses application of the three silicon amine rare earth compoundings as catalyst in borate is prepared.
Above-mentioned technical proposal can represent as follows：
R1Come from reaction raw materials ketone.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. the present invention is first with the hydroboration of catalyzed by rare-earth complex ketone and pinacol borine, so as to develop one kind
The catalyst of new and effective catalysis hydroboration, its is simple in construction, and synthesis is easy, has not only expanded the cooperation of three silicon amine rare earths
The application of thing, more rich ketone and the method for pinacol borine synthetic reaction.
2. three silicon amine rare earth compounding disclosed by the invention can be in a mild condition（Room temperature）The catalysis ketone of high activity and
The hydroboration of borine, catalyst amount only need the 0.1 ~ 0.5% of ketone mole；Reaction speed quickly, is reacted 10 minutes
Reach more than 90% yield, compared with existing catalyst system and catalyzing, both reduce catalyst amount, and improve yield, it is required
Time is short, and reaction condition is gentle, highly meets atom economy synthesis.
3. three silicon amine rare earth compounding disclosed by the invention is wide to the scope of application of substrate, suitable for different substituents position
Put, the ketone of different electronic effects, be combined to provide more more options for the industry of borate；And course of reaction is simply controllable,
High income, product postprocessing is easy, is adapted to industrialized production.
Embodiment
With reference to embodiment, the invention will be further described：
Embodiment one:La[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL, 1
Mmol acetophenone (0.117 mL, 1 mmol)), then with liquid-transfering gun is added, after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 98%.The nuclear magnetic data of product:1H NMR
(CDCl3, 400 MHz) δ: 7.28~7.30(m, 2H), 7.21~7.25 (m, 2H), 7.13~7.17 (m, 1H),
5.18 (q, J = 6.4 Hz, 1H), 1.42 (d, J = 6.5 Hz, 3H), 1.16+1.13(two s, 6H each)
。
Embodiment two:Nd[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst n d [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL, 1
Mmol acetophenone (0.117 mL, 1 mmol)), then with liquid-transfering gun is added, after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 93%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment three:Sm[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Sm [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL, 1
Mmol acetophenone (0.117 mL, 1 mmol)), then with liquid-transfering gun is added, after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 93%.The nuclear magnetic data of product is the same as embodiment one.
Example IV:Eu[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Eu [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL, 1
Mmol acetophenone (0.117 mL, 1 mmol)), then with liquid-transfering gun is added, after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 96%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment five:Y[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Y [N (SiMe are added into the reaction bulb after dehydration and deoxidation is handled3)2]3
Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL, 1 mmol), then
Acetophenone (0.117 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature, one is drawn with dropper and drips in nuclear-magnetism
Guan Zhong, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 93%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment six:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL, 1
Mmol acetophenone (0.117 mL, 1 mmol)), then with liquid-transfering gun is added, after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 91%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment seven:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.25 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then acetophenone (0.117 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature, drawn with dropper
One drips in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 89%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment eight:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.5 mL, 0.01mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL, 1
Mmol acetophenone (0.117 mL, 1 mmol)), then with liquid-transfering gun is added, after 10min is reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 86%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment nine:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then acetophenone (0.117 mL, 1 mmol) is added with liquid-transfering gun, after 5 min are reacted at room temperature, drawn with dropper
One drips in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 90%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment ten:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then acetophenone (0.117 mL, 1 mmol) is added with liquid-transfering gun, after 20 min are reacted at room temperature, drawn with dropper
One drips in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 91%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment 11:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then acetophenone (0.117 mL, 1 mmol) is added with liquid-transfering gun, after 15min is reacted at room temperature, drawn with dropper
One drips in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 90%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment 12:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Toluene solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then acetophenone (0.117 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature, drawn with dropper
One drips in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 85%.The nuclear magnetic data of product is the same as embodiment one.
Embodiment 13:Yb[N(SiMe3)2]3It is catalyzed acetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst Yb [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Tetrahydrofuran solution (0.1 mL, 0.01 mol/L), then add pinacol borine (0.145 with liquid-transfering gun
ML, 1 mmol), then acetophenone (0.117 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature, use dropper
Draw one to drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 71%.The nuclear magnetic data of product is the same as implementation
Example one.
Embodiment 14:La[N(SiMe3)2]3It is catalyzed o-methyl-benzene ethyl ketone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then o-methyl-benzene ethyl ketone (0.131 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature, with drop
Pipe is drawn one and dripped in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 95%.The nuclear magnetic data of product:1H
NMR (CDCl3, 400 MHz) δ: 7.52~7.54(d, 1H), 7.08~7.21 (m, 3H), 7.13~7.17 (m,
1H), 5.43 (q, 1H), 2.43 (s, 3H) 1.45 (d, , 3H), 1.19+1.23(two s, 6H each) 。
Embodiment 15:La[N(SiMe3)2]3It is catalyzed melilotal and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then melilotal (0.134 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature, with drop
Pipe is drawn one and dripped in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 96%.The nuclear magnetic data of product:1H
NMR (CDCl3, 400 MHz) δ: 7.24~7.26(d, 2H), 7.11~7.13 (d, 2H), 5.21 (q, 1H),
2.32 (s, 3H), 1.47 (d, 3H), 1.21+1.23(two s, 6H each) 。
Embodiment 16:La[N(SiMe3)2]3It is catalyzed 1- (2- furyls) ethyl ketones and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then 1- (2- furyls) ethyl ketone (0.100 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature,
One is drawn with dropper to drip in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 96%.The nuclear magnetic data of product
:1H NMR (CDCl3, 400 MHz) δ: 7.38 (s, 1H), 6.33 (s, 1H), 6.28~6.27 (d, 1H),
5.28 (q, 1H), 1.60 (d, 3H), 1.58(s, 12H) 。
Embodiment 17:La[N(SiMe3)2]3It is catalyzed 1- (2- thienyls) ethyl ketones and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), then 1- (2- thienyls) ethyl ketone (0.108 mL, 1 mmol) is added with liquid-transfering gun, after 10 min are reacted at room temperature,
One is drawn with dropper to drip in nuclear magnetic tube, adds CDCl3Wiring solution-forming.It is computed1H spectrum yields are 93%.The nuclear magnetic data of product
:1H NMR (CDCl3, 400 MHz) δ: 7.25~7.24(d, 1H), 7.02~6.97 (m, 2H), 5.54 (q, 1H),
1.65 (d, 3H), 1.31+1.29(two s, 6H each) 。
Embodiment 18:La[N(SiMe3)2]3Catalysis synthesizes borate to fluoro acetophenone and pinacol borine
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), add to fluorine-based acetophenone (0.121 g, 1 mmol), after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 94%.The nuclear magnetic data of product:1H NMR
(CDCl3, 400 MHz) δ: 7.39~7.35(m, 2H), 7.05~7.01 (t, 2H), 5.26 (q, 1H), 1.51
(d, 3H), 1.28+1.25(two s, 6H each) 。
Embodiment 19:La[N(SiMe3)2]3It is catalyzed parachloroacetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), add to chloro acetophenone (0.130 g, 1 mmol), after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 93%.The nuclear magnetic data of product:1H NMR
(CDCl3, 400 MHz) δ: 7.33(s, 4H), 5.25 (q, 1H), 1.51 (d, 3H), 1.28+1.26(two s,
6H each) 。
Embodiment 20:La[N(SiMe3)2]3It is catalyzed parabromoacetophenone and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), add to bromo acetophenone (0.199 g, 1 mmol), after 10 min are reacted at room temperature, one is drawn with dropper
Drip in nuclear magnetic tube, add CDCl3Wiring solution-forming.It is computed1H spectrum yields are 94%.The nuclear magnetic data of product:1H NMR
(CDCl3, 400 MHz) δ: 7.49~7.47(d, 2H), 7.29~7.27 (d, 2H), 5.24 (q, 1H), 1.50
(d, 3H), 1.29+1.26(two s, 6H each) 。
Embodiment 21:La[N(SiMe3)2]3It is catalyzed 2- acetonaphthones and pinacol borine synthesis borate
Under atmosphere of inert gases, catalyst La [N are added into the reaction bulb after dehydration and deoxidation is handled
(SiMe3)2]3Hexane solution (0.1 mL, 0.01 mol/L), then with liquid-transfering gun add pinacol borine (0.145 mL,
1 mmol), add 2-acetonaphthone (0.170 g, 1 mmol), after 10 min are reacted at room temperature, with dropper draw one drip in
In nuclear magnetic tube, CDCl is added3Wiring solution-forming.It is computed1H spectrum yields are 85%.The nuclear magnetic data of product:1H NMR (CDCl3,
400 MHz) δ: 7.93~7.87(m, 4H), 7.59~7.51 (m, 3H), 5.51 (q, 1H), 1.67 (d, 3H),
1.34+1.30(two s, 6H each)。
Claims (7)
1. application of the three silicon amine rare earth compoundings in catalysis ketone and borine synthetic reaction；The change of the three silicon amine rare earth compounding
It is as follows to learn structural formula：
The one kind of wherein Ln in lanthanum, neodymium, europium, ytterbium, samarium, yttrium.
2. application according to claim 1, it is characterised in that：The ketone be 2- acetyl furans, 2- acetyl thiophenes or
Person's 2- acetonaphthones；Or the chemical structural formula of the ketone is, wherein R is selected from hydrogen, halogen, nitro or methyl；
The borine is pinacol borine.
3. application according to claim 1, it is characterised in that：The dosage of the three silicon amine rare earth compounding is mole of ketone
The 0.1~0.5% of amount；The dosage and ketone equivalent of the borine.
4. application according to claim 1, it is characterised in that：The synthesis reaction temperature is room temperature；Reaction time be 5~
15 minutes.
5. the method for the synthetic reaction of three silicon amine catalyzed by rare-earth complex ketone and borine, comprises the following steps：
Under the conditions of anhydrous and oxygen-free, under nitrogen protection, three silicon amine rare earth compoundings, borine are well mixed with ketone successively；Reaction 5
~15 minutes, use CDCl3Terminating reaction, reaction solution removal of solvent under reduced pressure, obtains product；The change of the three silicon amine rare earth compounding
It is as follows to learn structural formula：
The one kind of wherein Ln in lanthanum, neodymium, europium, ytterbium, samarium, yttrium.
6. according to the method for claim 5, it is characterised in that：The ketone be 2- acetyl furans, 2- acetyl thiophenes or
Person's 2- acetonaphthones；Or the chemical structural formula of the ketone is, wherein R is selected from hydrogen, halogen, nitro or methyl；
The borine is pinacol borine.
7. according to the method for claim 5, it is characterised in that：The dosage of the three silicon amine rare earth compounding is mole of ketone
The 0.1~0.5% of amount；The dosage and ketone equivalent of the borine；The reaction temperature is room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610501608.1A CN106188118B (en) | 2016-06-30 | 2016-06-30 | Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis ketone and borine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610501608.1A CN106188118B (en) | 2016-06-30 | 2016-06-30 | Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis ketone and borine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106188118A CN106188118A (en) | 2016-12-07 |
| CN106188118B true CN106188118B (en) | 2018-01-19 |
Family
ID=57462522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610501608.1A Active CN106188118B (en) | 2016-06-30 | 2016-06-30 | Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis ketone and borine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106188118B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948058B (en) * | 2017-03-17 | 2020-07-14 | 苏州大学 | Application of rare earth metal complexes of tricyclocene as catalyst in catalyzing aldehyde and pinacol borane synthesis reaction |
| CN106883256B (en) * | 2017-03-17 | 2018-12-21 | 苏州大学 | A method of borate is prepared using triscyclopentadienyl rare earth metal complex |
| CN110818733B (en) * | 2017-12-04 | 2022-04-26 | 苏州大学 | Method for preparing boric acid ester by using disilylamine rare earth complex to catalyze hydroboration reaction of imine and borane |
| WO2019136680A1 (en) * | 2018-01-11 | 2019-07-18 | 南通纺织丝绸产业技术研究院 | Application of tricyclopentadienyl rare-earth metal complex in catalyzing reaction of aldehyde and allylboronic acid |
| CN110256474B (en) * | 2019-07-17 | 2022-02-25 | 苏州大学 | Application of trisilamine rare earth complex in catalyzing reaction of carbonate and borane |
| CN110357914B (en) * | 2019-07-17 | 2022-02-25 | 苏州大学 | Application of trisilamine rare earth complex in preparation of boric acid ester by catalyzing reaction of ester and borane |
| CN110803995B (en) * | 2019-10-16 | 2022-07-08 | 温州医科大学 | Method for synthesizing tertiary amine derivative through hydroboration reaction of tertiary amide under catalysis of rare earth |
| CN110818608B (en) * | 2019-10-24 | 2021-03-02 | 温州医科大学 | Application of rare earth silicon amide as catalyst in preparation of indole or indole derivatives |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190674A (en) * | 2011-03-29 | 2011-09-21 | 苏州大学 | Amino aryloxy rare earth metal complex, preparation thereof and application thereof |
| CN103464207A (en) * | 2013-09-03 | 2013-12-25 | 安徽师范大学 | Rare-earth complex catalyst, and preparation method, application and application method thereof |
-
2016
- 2016-06-30 CN CN201610501608.1A patent/CN106188118B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102190674A (en) * | 2011-03-29 | 2011-09-21 | 苏州大学 | Amino aryloxy rare earth metal complex, preparation thereof and application thereof |
| CN103464207A (en) * | 2013-09-03 | 2013-12-25 | 安徽师范大学 | Rare-earth complex catalyst, and preparation method, application and application method thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Alkene-pinacolborane hydroborations catalyzed by lanthanum tris[bis(trimethylsilyl)amide]";Yoshikazu Horino et al.，;《Synlett》;20041011;第14卷;第2639-2641页 * |
| 二(β-二亚胺基)二价稀土配合物催化醛/酮与亚磷酸二乙酯的氢磷化反应;刘倩倩等;《有机化学》;20160506;第36卷;第2168-2174页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106188118A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106188118B (en) | Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis ketone and borine | |
| CN106040304B (en) | β-di-imidogen bivalent rare earth boron hydrogen complex is in catalysis aldehyde and the application in borine hydroboration | |
| CN106040303B (en) | β-di-imidogen bivalent rare earth boron hydrogen complex is in catalysis ketone and the application in borine hydroboration | |
| CN106883255B (en) | A method of borate is prepared based on triscyclopentadienyl rare earth metal complex | |
| CN106046036B (en) | Application of the three silicon amine rare earth compoundings in the hydroboration of catalysis aldehyde and borine | |
| CN106883256B (en) | A method of borate is prepared using triscyclopentadienyl rare earth metal complex | |
| CN107930696A (en) | Application of the front three cyclopentadienyl rare-earth complex in the hydroboration of catalysis imines and borine | |
| CN108409772A (en) | The method for preparing borate based on aldehyde | |
| CN107971036A (en) | Application of the two silicon amine rare earth compoundings in the hydroboration of catalysis imines and borine | |
| CN110357914B (en) | Application of trisilamine rare earth complex in preparation of boric acid ester by catalyzing reaction of ester and borane | |
| CN108083981A (en) | Triscyclopentadienyl rare earth metal complex is in catalysis aldehyde and the application in pi-allyl acid reaction | |
| CN108187746A (en) | Three silicon amine rare earth metal complexs are in catalysis aldehyde and the application in pi-allyl acid reaction | |
| CN106188119B (en) | Application of two (beta-diimine base) ytterbiums in catalysis ketone and borine hydroboration | |
| CN108440590A (en) | The method for preparing borate using fatty aldehyde | |
| CN108409770A (en) | The method for preparing borate based on anilino- lithium | |
| CN104327108A (en) | Preparation method of methyl aluminum complex of tetradentate nitrogen and oxygen ligand | |
| CN107827915B (en) | Amine bisphenol tetradentate ligand trivalent rare earth metal complex and application thereof | |
| CN107540700B (en) | The method for preparing borate using three fragrant oxygen rare earth compoundings | |
| CN107474063B (en) | A method of preparing borate | |
| CN108558923A (en) | Application of the anilino- lithium in catalysis ketone and borine hydroboration | |
| CN110256474A (en) | Application of the three silicon amine rare earth compoundings in catalysis carbonic ester and borine reaction | |
| CN107556334B (en) | The method for preparing borate based on three fragrant oxygen rare earth compoundings | |
| WO2018000401A1 (en) | Application of trisilicon amine rare earth complex for catalyzing hydroboration reaction between aldehyde and borane | |
| US11440924B2 (en) | Method for preparing borate ester on basis of tricyclopentadienyl rare earth metal complex | |
| CN109289914A (en) | Application of the o-methyl-benzene amido lithium in catalysis imines and borine hydroboration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |