CN107200756A - A kind of tertiary amine of shank type Ferrocene-Derived and its preparation method and application - Google Patents
A kind of tertiary amine of shank type Ferrocene-Derived and its preparation method and application Download PDFInfo
- Publication number
- CN107200756A CN107200756A CN201710329828.5A CN201710329828A CN107200756A CN 107200756 A CN107200756 A CN 107200756A CN 201710329828 A CN201710329828 A CN 201710329828A CN 107200756 A CN107200756 A CN 107200756A
- Authority
- CN
- China
- Prior art keywords
- ferrocene
- compound
- tertiary amine
- formula
- derived
- 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.)
- Granted
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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- 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
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/52—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of imines or imino-ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- 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
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of tertiary amine of shank type Ferrocene-Derived and its preparation method and application.Its application is 1 specially by the amount ratio of material:The tertiary amine and three of 1 shank type Ferrocene-Derived（Pentafluorophenyl group）Boron constitutes " being obstructed " Lewis Acids and Bases to catalyst, and the obtained catalyst is applied to catalysis hydrogenation of imines reduction reaction.The catalyst has stability good, and heavy metal catalyst can be substituted to a certain extent, can the heavy metal pollution from chemicals is avoided on source, with preferable application value and potential economic results in society.
Description
Technical field
The present invention relates to a kind of tertiary amine of shank type Ferrocene-Derived and its preparation method and application, shank type Ferrocene-Derived
Tertiary amine and three（Pentafluorophenyl group）" being obstructed " Lewis Acids and Bases of boron composition are to catalyst, and the catalyst is in catalysis hydrogenation of imines reduction
Application in reaction.
Background technology
In the past few decades, catalytic hydrogenation is often used with ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium
(Ir), platinum (Pt) etc. is the transition-metal catalyst of core, exist it is expensive, the problems such as heavy-metal residual.It is especially medical
Strict limitation of the industry to content of beary metal in food and medicine, limit to a certain extent noble metal catalyst in bulk drug and
Application in intermediate synthesis.
As the supplement of metal catalyzed hydrogenation, the catalytic hydrogenation of nonmetallic participation due to lacking suitable catalyst and
Report is relatively fewer.Until 2006, the report such as Stephen synthesized it is a kind of integrate lewis acid and base groups phosphine/
Borane compound " is obstructed " Lewis Acids and Bases to 1, in a mild condition can be with reversible absorption and release H2, process along with
Obvious color change.Then, Stephan etc. propose " being obstructed " Lewis Acids and Bases to (Frustrated Lewis Pairs,
FLPs concept), i.e., because the reasons such as steric hindrance can not form the big steric hindrance lewis acid and lewis base of classical adduct
Combination（Stephan, D. W.et al. Science 2006, 314, 1124.）.
2007, Stephen etc. was reported in toluene agent, certain temperature (80 ~ 140o) and H C2Under pressure (1 ~ 5 atm)
Utilize " being obstructed " Lewis Acids and Bases to realize the reduction of imines to 1, obtain 57% ~ 99% yield.This is first with " being obstructed " Louis
This acid-base pair 1 is catalyst, and the report of nonmetal catalyzed hydrogenation is directly carried out using hydrogen（Stephan, D. W.et al. Angew. Chem. Int. Ed. 2007, 46, 8050.）.
Then, Erker etc. reports the intramolecular of ethyl bridging and " is obstructed " Lewis Acids and Bases to 2, and pentane is molten at room temperature
Can prompt activation H in agent2, the catalytic hydrogenation of imines and enamine is realized, higher catalytic activity is shown（(a) Erker,
G.et al. Chem. Commun. 2007, 5072; (b) Erker, G. et al. Angew. Chem., Int. Ed. 2008, 47, 7543.）.
2011, N/B " was obstructed " Lewis Acids and Bases to 3 in the report synthetic molecules such as Erker, and they are by Phenylpiperidine base second
Alkene and Piers boron HB (C6F5)2Addition obtains 3, in a mild condition heterolytic fission H2Realize the reduction of itself substrate（Erker, G.et al. Chem. Sci. 2011, 2, 1842.）.
2014, Zhong Weihui etc. to 4, was reduced in a mild condition with luxuriant " being obstructed " Lewis Acids and Bases for frame design of ring
Imines obtains 93% yield；And the recovery problem of catalyst has been investigated, successfully realize three recoveries and do not influence
Reaction yield.（Zhong, W. -H.et al. CN 103613618. 2014.）
2016, Du Haifeng etc. was reported with B (C6F5)3For lewis acid, [Isosorbide-5-Nitrae] oxazines are lewis base, composition with substrate benzo
" being obstructed " Lewis Acids and Bases are to 5, and itself substrate is reduced into 3,4- dihydrobenzos [Isosorbide-5-Nitrae] Evil by the catalyst in atmosphere of hydrogen
Piperazine class compound, obtains higher reaction yield（Du, H.-F.et al. CN 105669586. 2016.）；
Be obstructed " Lewis Acids and Bases to 1, be obstructed " Lewis Acids and Bases to 2, be obstructed " Lewis Acids and Bases to 3, be obstructed " Lewis Acids and Bases
To 4, be obstructed " Lewis Acids and Bases to 5 and be obstructed " Lewis Acids and Bases are as follows to the structural formula of the Ar in 5：
。
" being obstructed " Lewis Acids and Bases are mainly characterized by environment-friendly, heavy metal free residual to catalytic reaction, meet green
The requirement of chemistry, with potential industrial applications prospect.By the development of 10 years, FLP fields had been achieved for many breakthroughs
Property progress, but compared to transition metal-catalyzed, still in the presence of, less stable more sensitive to aqueous vapor and air, prepare cost
Expensive the problems such as.Therefore, it is the technology that the present invention needs to solve to seek to prepare the FLP catalyst that easy, stability is good, activity is high
Problem.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of shank type Ferrocene-Derived
Tertiary amine and its preparation method and application, its application is specially by itself and three（Pentafluorophenyl group）Boron II constitutes " being obstructed " Lewis Acids and Bases
To catalyst, the catalytic hydrogen reduction that the catalyst is applied to imines reacts, and the catalyst has catalytic activity high, and stability is good
The advantages of.
A kind of tertiary amine of described shank type Ferrocene-Derived, it is characterised in that its structural formula such as formula（Ⅰ）It is shown：
,
Wherein R is N-2- methyl piperidines, N-2,6- lupetidines, N-1,2- dihydro-isoquinolines or N-1,2,3,4- Tetrahydroisoquinoli-s
Quinoline, the tertiary amine structure formula such as formula of four obtained shank type Ferrocene-Deriveds（Ⅰa）, formula（Ⅰb）, formula（Ⅰc）And formula（Ⅰd）It is shown：
。
The preparation method of the tertiary amine of described a kind of shank type Ferrocene-Derived, it is characterised in that including following process：
1）By formula（Ⅲ）Shown 1,1 '-diacetyl ferrocene is dissolved in organic solvent A, and diformazan is passed through at -80 ~ -75 DEG C
Amine gas, then add the sour stirring reactions of Lewis, are slowly increased to room temperature reaction 24 ~ 40 hours, are filtered to remove insoluble matter, filtrate
Through column chromatography for separation after concentration, it is made such as formula（Ⅳ）Shown compounds Ⅳ, its reaction equation is as follows：
；
2）By step 1）Obtained compounds Ⅳ is dissolved in dichloromethane, adds Pd/C, is reacted 4 ~ 10 hours at room temperature, reaction
Suction filtration after end, through column chromatography for separation after the concentration of gained dichloromethane layer, is obtained such as formula（Ⅴ）Shown compound V, it reacts
Equation is as follows：
；
3）By step 2）Obtained compound V is dissolved in absolute ethyl alcohol, adds sodium borohydride, is reacted at room temperature 2 ~ 6 hours, is steamed
Except solvent, aqueous sodium carbonate is added, is extracted with ethyl acetate, through column chromatography for separation after the concentration of gained organic layer, be made such as formula
（Ⅵ）Shown compound VI, its reaction equation is as follows：
；
4）By step 3）Obtained compound VI, DMAP and triethylamine is miscible in organic solvent B, at 0-2 DEG C
Acetic anhydride is added dropwise, drop finishes, and reacts at room temperature 2 ~ 6 hours, adds water and reaction is quenched, extracted with dichloromethane, organic layer is through drying, concentration
It is made afterwards such as formula（Ⅶ）Shown compound VII, its reaction equation is as follows：
；
5）By step 4）Obtained compound VII, secondary amine R-H are miscible in organic solvent C, and back flow reaction 2 ~ 4 hours is cooled to
Room temperature, it is 2 ~ 3 to add watery hydrochloric acid regulation system pH, adds aqueous sodium carbonate into the water layer separated, regulation water layer pH for 10 ~
After 11, extracted with dichloromethane, gained organic layer is separated through drying, concentration, silica gel column chromatography, is obtained such as formula（Ⅰ）Shown handle
Substituent R in the tertiary amine of type Ferrocene-Derived, secondary amine R-H is N-2- methyl piperidines, N-2,6- lupetidines, N-1,2- bis-
Hydrogen isoquinoline or N-1,2,3,4- tetrahydroisoquinolines, its reaction equation are as follows：
；
Involved 1,1 '-diacetyl ferrocene, compounds Ⅳ, compound V, compound VI, the structural formula point of compound VII
It is not as follows：
。
A kind of preparation method of the tertiary amine of described shank type Ferrocene-Derived, it is characterised in that step 1）Middle column chromatography for separation
Described eluant, eluent is that volume ratio is 50:1 petroleum ether and ethyl acetate mixture；The Lewis acid is FeCl3、AlCl3
Or TiCl4In any one, preferably AlCl3；The 1,1 '-diacetyl ferrocene, Lewis acid, the material of dimethylamine
The ratio between amount is 1: 1~4 :10 ~ 20, preferably 1: 2~3 : 16~20；Organic solvent A be dichloromethane or toluene, preferably
For dichloromethane；Organic solvent A quality consumption is 1,5 ~ 20 times of 1 '-diacetyl ferrocene III, preferably 10-15 times.
A kind of preparation method of the tertiary amine of described shank type Ferrocene-Derived, it is characterised in that step 2）Middle column chromatography for separation
Described eluant, eluent is that volume ratio is 30:1 petroleum ether and ethyl acetate mixture；The mass ratio of compounds Ⅳ, Pd/C
For 1:0.01 ~ 0.05, preferably 1: 0.02~0.04；The quality consumption of methylene chloride is 2 ~ 10 times of compounds Ⅳ,
Preferably 5 ~ 8 times.
A kind of preparation method of the tertiary amine of described shank type Ferrocene-Derived, it is characterised in that step 3）Middle column chromatography for separation
Described eluant, eluent is that volume ratio is 8:1 petroleum ether and ethyl acetate mixture；Compound V, NaBH4Material amount
The ratio between be 1:1 ~ 4, preferably 1: 1~2；The quality consumption of absolute ethyl alcohol is 3 ~ 6 times of compound V, preferably 4 ~ 6 times.
A kind of preparation method of the tertiary amine of described shank type Ferrocene-Derived, it is characterised in that step 4）Middle compound VI,
The ratio between acetic anhydride, triethylamine, amount of material of DMAP are 1: 1~4 : 1~4 :0.1 ~ 0.4, preferably 1:
2~3 : 2~3 : 0.2~0.3；Organic solvent B is any one in tetrahydrofuran, chloroform or dichloromethane, preferably tetrahydrochysene
Furans；The quality consumption of organic solvent B is 4 ~ 10 times of compound VI, preferably 6 ~ 8 times.
A kind of preparation method of the tertiary amine of described shank type Ferrocene-Derived, it is characterised in that step 5）Middle column chromatography for separation
Eluant, eluent used is that volume ratio is 8:1 petroleum ether and ethyl acetate mixture；Compound VII, secondary amine R-H material
The ratio between amount is 1:1 ~ 4, preferably 1: 1~2.0；Organic solvent C is any one in toluene, tetrahydrofuran or ethanol, excellent
Elect toluene as；Organic solvent C quality consumption is 3 ~ 10 times of compound VII, preferably 5 ~ 8 times.
A kind of application of the tertiary amine of described shank type Ferrocene-Derived in " being obstructed " Lewis Acids and Bases are constituted to catalyst,
The ratio between amount by material is 1:The tertiary amine and formula of 1 shank type Ferrocene-Derived（Ⅱ）Shown three（Pentafluorophenyl group）Boron composition is obtained
" being obstructed " Lewis Acids and Bases are to catalyst, three（Pentafluorophenyl group）The structure of boron and obtained " being obstructed " Lewis Acids and Bases to catalyst
Formula is as follows：
。
Application of described obtained " being obstructed " Lewis Acids and Bases to catalyst in catalysis hydrogenation of imines reduction reaction, its
Concrete application method is：
With such as formula（Ⅸ）Shown imine derivative is substrate, with such as formula（Ⅰ）The tertiary amine of shown shank type Ferrocene-Derived and
（Ⅱ）Shown three（Pentafluorophenyl group）" being obstructed " Lewis Acids and Bases of composition shown in boron are to for catalyst, at 50 ~ 120 DEG C and 1.0
Under the conditions of ~ 5.0 MPa Hydrogen Vapor Pressures, hydro-reduction reaction occurs in anhydrous organic solvent D, reacts 6 ~ 24 hours, reaction solution
Through column chromatography for separation after concentrated, the eluent containing compound Ⅹ is collected, organic solvent is evaporated off, be made such as formula（Ⅹ）Shown
Product Ⅹ；The eluant, eluent of column chromatography for separation is volume ratio 30:1 petroleum ether and the mixed liquor of ethyl acetate；Described imines
Derivative, the tertiary amine of shank type Ferrocene-Derived, three（Pentafluorophenyl group）The ratio between amount of material of boron is 1: 0.05~0.20 :
0.05 ~ 0.20, preferably 1: 0.1~0.2 : 0.1~0.2；Organic solvent D is one kind in pentane, n-hexane or toluene,
Preferably n-hexane；Organic solvent D quality consumption is 5 ~ 20 times of imine derivative；Its reaction equation is as follows：
。
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows：
The present invention designs and successfully synthesizes the tertiary amine of shank type Ferrocene-Derived, then by the tertiary amine of shank type Ferrocene-Derived and three
（Pentafluorophenyl group）Composition " being obstructed " Lewis Acids and Bases shown in boron to catalyst, N/B System Catalysts between novel molecular-be obstructed
Lewis Acids and Bases to catalyst, in the catalyst structure Lewis alkali using ferrocene as skeleton, with preferable chemical stability,
Catalytic activity is high, reaction condition is gentle, high income the advantages of, and heavy metal catalyst hydrogenating catalytic can be substituted to a certain extent
Agent, can the heavy metal pollution from chemicals is avoided on source, it is special with preferable application value and potential economic results in society
Hydrogenation of imines reduction reaction Shi Yu be catalyzed, the activation of hydrogen molecule and the hydrogenation of imines is realized.
Embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
Embodiment 1：The preparation of 1,1'- (1- methyl -3- oxygen -1,3- pi-allyls) ferrocene IV
In 250 mL three-necked flasks, by diacetyl ferrocene III（10.0 g, 37 mmol）It is dissolved in dichloromethane（150
g）In；Dry dimethylamine gas is passed through at -78 DEG C（24.2g, 0.55 mol）, AlCl is added portionwise3（9.8 g, 74
mmol）, it is slowly increased to room temperature reaction 30 hours；Insoluble matter is filtered, through silica gel after filtrate concentration（GF254, similarly hereinafter）Column chromatography point
From (eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is 50:1) 6.9 g compounds Ⅳs, m. p., are made：85 ~ 86 DEG C,
Yield 74%；1H NMR (400 MHz, CDCl3) δ 2.15 (s, 3H), 4.27-4.53 (m, 8H), 6.35 (s,
1H). 13C NMR (100 MHz, CDCl3) δ 26.0, 71.5 (2C), 72.3 (2C), 72.9 (2C), 73.0
(2C), 84.7, 86.0, 133.2, 152.5, 197.0。
Embodiment 2：The preparation of 1,1'- (1- methyl -3- oxygen -1,3- propyl group) ferrocene V
In 25 mL, two mouthfuls of flasks, by 1,1'- (1- methyl -3- oxygen -1,3- pi-allyl) ferrocene IV（5.04 g, 20 mmol）
It is dissolved in anhydrous methylene chloride（20 g）In, add under 5% Pd/C (0.1 g), normal temperature and pressure in H2Reacted 8 hours in atmosphere；
Reaction terminates rear suction filtration, through column chromatography for separation after the concentration of gained dichloromethane organic layer（Eluant, eluent be petroleum ether and ethyl acetate,
Volume ratio is 30: 1）, obtain 4.8 g compounds V, m.p.：102 ~ 104 DEG C, yield 96%;1H NMR (400 MHz,
CDCl3) δ 1.25 (d, J = 6.4 Hz, 3H), 2.60 (dd, J = 2.8, 6.8 Hz, 1H), 3.21-3.27
(m, 2H), 3.97 (s, 1H), 4.08 (s, 1H), 4.33 (d, J = 15.2 Hz, 2H), 4.49 (s, 1H),
4.67 (d, J = 14.8 Hz, 2H), 4.90 (s, 2H). 13C NMR (100 MHz, CDCl3) δ 22.70,
39.0, 52.2, 67.6, 68.4 (2C), 68.9 (2C), 69.9, 71.5, 72.3 (2C), 72.6 (2C)。
Embodiment 3：The preparation of 1,1'- (1- methyl -3- hydroxyl -1,3- propyl group) ferrocene VI
50 mL, two mouthfuls of flasks are taken, by 1,1'- (1- methyl -3- oxygen -1,3- propyl group) ferrocene V（5.08 g, 20 mmol）Dissolving
In absolute ethyl alcohol（20 g）In, add NaBH4（0.76 g, 20 mmol）, in N2Stir lucifuge under atmosphere to react 6 hours, reaction
Solvent is evaporated off after completely, adds 5% aqueous sodium carbonate, is extracted with ethyl acetate, through column chromatography for separation after the concentration of gained organic layer
（Eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is 8: 1）, 4.7 g compounds VI, m.p. are made：81 ~ 83 DEG C, yield
95%；1H NMR (400 MHz, CDCl3) δ 1.26 (d, J = 6.8 Hz, 3H), 1.98 (t, J = 11.2,
12.0 Hz, 1H), 2.36-2.41 (m, 4H), 2.55 (t, J = 6.8, 7.2 Hz, 1H), 4.01-4.15 (m,
8H), 4.43 (s, 1H), 4.54 (d, J = 6.8 Hz, 1H).13C NMR (100 MHz, CDCl3) δ 20.8,
24.6, 51.6, 65.1, 66.3, 67.1, 67.3, 68.4, 68.6, 68.9, 69.3, 70.2, 89.8, 91.0。
Embodiment 4：The preparation of 1,1'- [1- methyl -3- (acetoxyl group) -1,3- propyl group]-ferrocene VII
In 50 mL dropping funels, by 1,1'- (1- methyl -3- hydroxyls -1,3- propyl group) ferrocene VI（5.0 g, 20 mmol）、
DMAP（DMAP）（0.048 g, 4 mmol）And triethylamine（0.79 g, 40 mmol）It is miscible in chloroform（40 g）
In, acetic anhydride is added dropwise at 0 DEG C（4.08 g, 40 mmol）, drip and finish, react at room temperature 6 hours, add water and reaction is quenched, use dichloromethane
Alkane is extracted, and is obtained after organic layer drying, concentration through column chromatography for separation（Eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is 50:
1）, 6.0 g compounds VII, m. p. are made:89-91 DEG C, yield 91%；1H NMR (400 MHz, CDCl3) δ 1.27
(d, J = 5.6 Hz, 3H), 2.02-2.06 (m, 1H), 2.10 (s, 3H), 2.41-2.46 (m, 1H),
2.53-2.57 (m, 1H), 4.05-4.14 (m, 5H), 4.30-4.31 (m, 2H), 5.61-5.63 (dd, J =
1.6, 4.0 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 20.0, 21.3, 22.7, 25.7, 32.2,
48.6, 66.5, 67.4, 67.6, 67.8, 68.4, 68.5, 68.6, 69.0, 69.8, 85.0, 90.7,
170.3。
Embodiment 5：The a of 1,1'- [1- methyl -3- (pipecoline base) -1,3- propyl group]-ferrocene I preparation
In 100 mL, two mouthfuls of flasks, by compound VII（6.0 g）And pipecoline（3.97 g, 40 mmol）It is miscible in nothing
Water-toluene（48 g）In, back flow reaction 3 hours is cooled to room temperature, and it is 2 ~ 3 to add 10% HCl/water solution regulation system pH, past point
5% aqueous sodium carbonate is added in the water layer gone out, regulation water layer pH is 10 ~ 11, and gained organic layer is dried, and is concentrated to give 3.91 g 1,
The a of 1'- [1- methyl -3- (pipecoline base) -1,3- propyl group]-ferrocene I, yellow oily liquid, yield 58%；1H NMR
(400 MHz, CDCl3) δ 1.24 (d, J = 5.6 Hz, 3H), 1.35-1.37 (m, 2H), 1.49-1.63 (m,
4H), 2.05-2.09 (m, 1H), 2.43-2.49 (m, 5H), 2.73-2.79 (m, 1H), 3.17-3.19 (m,
1H), 3.95-4.19 (m, 8H). 13C NMR (100 MHz, CDCl3) δ 17.1, 22.9, 24.7, 26.4,
27.8, 34.0, 46.4, 49.1, 51.7, 67.1, 67.6, 68.0, 68.3, 68.4, 69.0, 69.2, 71.6,
80.9, 92.8。
Embodiment 6：The b of 1,1'- [1- methyl -3- (lupetidine base) -1,3- propyl group]-ferrocene I preparation
In 100 mL, two mouthfuls of flasks, by compound VII（6.0 g）And lupetidine（3.40 g, 30 mmol）It is miscible
In anhydrous tetrahydro furan（40 g）In, back flow reaction 4 hours is cooled to room temperature, adds 10% HCl/water solution regulation system pH and is
2 ~ 3,5% aqueous sodium carbonate is added into the water layer separated, regulation water layer pH is 10 ~ 11, and gained organic layer is dried, and is concentrated to give
The b of 3.72 g 1,1'- [1- methyl -3- (2,6- lupetidine base) -1,3- propyl group]-ferrocene I, yellow oily liquid, yield
53%；1H NMR (400 MHz, CDCl3) δ 1.09 (d, J = 5.2 Hz, 3H), 1.14 (d, J = 4.8 Hz,
3H), 1.24 (d, J = 6.0 Hz, 3H ), 1.35-1.42 (m, 2H), 1.54-1.58 (m, 2H), 2.17-
2.20 (m, 1H), 2.44-2.50 (m, 1H), 2.72-2.78 (m, 2H), 2.94-2.95 (d, J = 3.2 Hz,
1H), 3.77 (d, J = 8.8 Hz, 1H), 3.95-3.96 (m, 1H), 3.99-4.19 (m, 8H), 4.29-
4.32 (m, 1H),. 13C NMR (100 MHz, CDCl3) δ 17.0, 18.9, 20.1, 21.3, 28.4, 33.3,
33.4, 47.9, 50.6, 51.4, 51.7, 67.1, 67.6, 67.9, 68.3, 68.4, 69.0, 69.2, 71.7,
81.6, 92.7。
Embodiment 7：The c of 1,1'- [1- methyl -3- (1,2,3,4- tetrahydro isoquinolyls) -1,3- propyl group]-ferrocene I system
It is standby
In 100 mL, two mouthfuls of flasks, by compound VII（6.0 g）With 1,2,3,4- tetrahydroisoquinolines（2.68 g, 20 mmol）
It is miscible in absolute ethyl alcohol（30 g）In, back flow reaction 4 hours is cooled to room temperature, adds 10% HCl/water solution regulation system pH and is
2 ~ 3,5% aqueous sodium carbonate is added into the water layer separated, regulation water layer pH is 10 ~ 11, and gained organic layer is dried, and is concentrated to give
4.75 g 1,1'- [1- methyl -3- (1,2,3,4- tetrahydroisoquinoline) -1,3- propyl group]-ferrocene I c, m. p.: 67~68
DEG C, yield 64%；1H NMR (400 MHz, CDCl3) δ 1.31 (d, J = 6.8 Hz, 3H), 2.24-2.27 (m,
1H), 2.56-2.61 (m, 1H), 2.66-2.71 (m, 1H), 2.81-2.98 (m, 4H), 3.38-3.41 (m,
1H), 3.69-3.81 (m, 2H), 4.02-4.32 (m, 8H), 7.01-7.03 (m, 1H), 7.09-7.14 (m,
3H). 13C NMR (100 MHz, CDCl3) δ 18.0, 27.8, 29.7, 46.7, 48.4, 54.0, 57.6,
67.4, 67.7, 68.2, 68.3, 68.7, 69.1, 69.4, 71.4, 81.8, 92.3, 125.5, 126.0,
126.7, 128.6, 134.4, 135.2。
Embodiment 8：The d of 1,1'- [1- methyl -3- (1,2- dihydro-isoquinolines base) -1,3- propyl group]-ferrocene I preparation
In 100 mL, two mouthfuls of flasks, by compound VII（6.0 g）With 1,2- dihydro-isoquinolines（2.64 g, 20 mmol）It is miscible
In absolute ethyl alcohol（30 g）In, back flow reaction 4 hours is cooled to room temperature, and it is 2 ~ 3 to add 10% HCl/water solution regulation system pH,
5% aqueous sodium carbonate is added into the water layer separated, regulation water layer pH is 10 ~ 11, and gained organic layer is dried, and is concentrated to give 4.53
G 1,1'- [1- methyl -3- (1,2- dihydro-isoquinoline) -1,3- propyl group]-ferrocene I d, m. p.:62 ~ 64 DEG C, yield 61%
；1H NMR (400 MHz, CDCl3) δ 1.31 (d, J = 6.4 Hz, 3H), 2.27-2.30 (m, 1H), 2.58-
2.64 (m, 1H), 2.69-2.75 (m, 1H), 3.41-3.43 (m, 1H), 3.72-3.85 (m, 2H), 4.04-
4.35 (m, 8H), 5.68-6.14 (dd, J = 5.2, 6.4 Hz, 2H), 7.01-7.03 (m, 1H), 7.06-
7.08 (m, 1H), 7.14-7.16 (m, 2H). 13C NMR (100 MHz, CDCl3) δ 18.3, 28.7, 48.6,
57.1, 68.5, 68.8, 69.2, 69.6, 69.8, 70.3, 70.7, 72.2, 82.3, 93.5, 112.3,
126.4, 127.1, 127.7, 129.6, 134.2, 134.9, 136.3。
Embodiment 9 ~ 17 is application of the partial catalyst in the reaction of catalytic hydrogenation imine reduction
Embodiment 9：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I a（0.17 g, 0.5 mmol）With
Three（Pentafluorophenyl group）Boron II（0.25 g, 0.5 mmol）It is dissolved in 10 g anhydrous n-hexanes, in 80 DEG C and Hydrogen Vapor Pressure 2.0
Reacted 24 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.54 g, is yellow oily compound, yield 55%.1H
NMR (400 MHz, CDCl3) δ 1.49 (d, J = 6.8 Hz, 3H), 3.99 (s,1H), 4.43-4.48 (dd,J = 6.4 Hz, 6.8 Hz, 1H), 6.47-6.49 (t, 2H), 6.60-6.63 (m, 1H), 7.04-7.08 (m,
2H), 7.17-7.20 (m, 1H), 7.28-7.34 (m, 4H). MS (ESⅠ): m/e (%) = 197.2 (100)
[M]+。
Embodiment 10：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I a（0.25 g, 0.75 mmol）With
Three（Pentafluorophenyl group）Boron II（0.38 g, 0.75 mmol）It is dissolved in the anhydrous normal heptanes of 10 g, in 100 DEG C and Hydrogen Vapor Pressure 3.0
Reacted 20 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.57 g, is yellow oily compound, yield 58%.
Embodiment 11：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I a（0.34 g, 1.0 mmol）With
Three（Pentafluorophenyl group）Boron II（0.51 g, 1.0 mmol）It is dissolved in 10 g dry toluenes, in 120 DEG C and the MPa of Hydrogen Vapor Pressure 5.0
Under the conditions of react 18 hours, reaction solution concentration after through column chromatography for separation（Eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is
30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.60 g, is yellow oily compound, yield 61%.
Embodiment 12：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I b（0.18 g, 0.5 mmol）With
Three（Pentafluorophenyl group）Boron II（0.25 g, 0.5 mmol）It is dissolved in 10 g anhydrous n-hexanes, in 80 DEG C and Hydrogen Vapor Pressure 2.0
Reacted 24 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.62 g, is yellow oily compound, yield 63%.
Embodiment 13：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I b（0.26 g, 0.75 mmol）With
Three（Pentafluorophenyl group）Boron II（0.38 g, 0.75 mmol）It is dissolved in the anhydrous normal heptanes of 10 g, in 100 DEG C and Hydrogen Vapor Pressure 3.0
Reacted 20 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.70 g, is yellow oily compound, yield 71%.
Embodiment 14：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I b（0.38 g, 1.0 mmol）With
Three（Pentafluorophenyl group）Boron II（0.51 g, 1.0 mmol）It is dissolved in 10 g dry toluenes, in 120 DEG C and the MPa of Hydrogen Vapor Pressure 5.0
Under the conditions of react 16 hours, reaction solution concentration after through column chromatography for separation（Eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is
30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.71 g, is yellow oily compound, yield 72%.
Embodiment 15：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I c（0.19 g, 0.5 mmol）With
Three（Pentafluorophenyl group）Boron II（0.25 g, 0.5 mmol）It is dissolved in 10 g anhydrous n-hexanes, in 80 DEG C and Hydrogen Vapor Pressure 2.0
Reacted 24 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.50 g, is yellow oily compound, yield 51%.
Embodiment 16：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I c（0.28g, 0.75 mmol）With
Three（Pentafluorophenyl group）Boron II（0.38 g, 0.75 mmol）It is dissolved in the anhydrous normal heptanes of 10 g, in 100 DEG C and Hydrogen Vapor Pressure 3.0
Reacted 20 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.55 g, is yellow oily compound, yield 56%.
Embodiment 17：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I c（0.37 g, 1.0 mmol）With
Three（Pentafluorophenyl group）Boron II（0.51 g, 1.0 mmol）It is dissolved in 10 g dry toluenes, in 120 DEG C and the MPa of Hydrogen Vapor Pressure 5.0
Under the conditions of react 18 hours, reaction solution concentration after through column chromatography for separation（Eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is
30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.57 g, is yellow oily compound, yield 58%.
Embodiment 18：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I d（0.18 g, 0.5 mmol）With
Three（Pentafluorophenyl group）Boron II（0.25 g, 0.5 mmol）It is dissolved in 10 g anhydrous n-hexanes, in 80 DEG C and Hydrogen Vapor Pressure 2.0
Reacted 24 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.49 g, is yellow oily compound, yield 50%.
Embodiment 19：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I d（0.27 g, 0.75 mmol）With
Three（Pentafluorophenyl group）Boron II（0.38 g, 0.75 mmol）It is dissolved in the anhydrous normal heptanes of 10 g, in 100 DEG C and Hydrogen Vapor Pressure 3.0
Reacted 20 hours under the conditions of MPa, through column chromatography for separation after reaction solution concentration（Eluant, eluent is petroleum ether and ethyl acetate, volume ratio
For 30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.53 g, is yellow oily compound, yield 54%.
Embodiment 20：
, will in autoclaveN- phenyl acetophenone imines（0.98 g, 5 mmol）, chemical compounds I d（0.36 g, 1.0 mmol）With
Three（Pentafluorophenyl group）Boron II（0.51 g, 1.0 mmol）It is dissolved in 10 g dry toluenes, in 120 DEG C and the MPa of Hydrogen Vapor Pressure 5.0
Under the conditions of react 18 hours, reaction solution concentration after through column chromatography for separation（Eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is
30: 1）Target compound is madeN- (1- phenethyls) aniline is 0.56 g, is yellow oily compound, yield 57%.
Embodiment 18-29：
In autoclave, imine derivative is added（Formula Ⅸ）（1.0 g, 5.0 mmol）, formula（Ⅰ）Shown shank type Ferrocene-Derived
Tertiary amine（0.38 g, 1.0 mmol）, formula（Ⅱ）Shown three（Pentafluorophenyl group）Boron（0.51 g, 1.0 mmol）With it is anhydrous just oneself
The g of alkane 20, stirring reaction t hours under the conditions of 100 DEG C and the MPa of Hydrogen Vapor Pressure 3.0, through column chromatography for separation after reaction solution concentration
（Eluant, eluent is petroleum ether and ethyl acetate, and volume ratio is 30: 1）Target compound secondary amine derivative is made（Formula Ⅹ）, Mei Geshi
Apply target compound that the substituent in example in imine derivative and reaction obtain as shown in table 1, its reactional equation is as follows：
,
Described above is only the preferred embodiment of the present invention, it is noted that for those skilled in the art,
On the premise of not departing from present inventive concept, some improvement and polishing can also be made, these are improved and polishing also should be regarded as this hair
In bright protection domain.
Claims (10)
1. a kind of tertiary amine of shank type Ferrocene-Derived, it is characterised in that its structural formula such as formula（Ⅰ）It is shown：
,
Wherein R is N-2- methyl piperidines, N-2,6- lupetidines, N-1,2- dihydro-isoquinolines or N-1,2,3,4- Tetrahydroisoquinoli-s
Quinoline.
2. a kind of preparation method of the tertiary amine of shank type Ferrocene-Derived according to claim 1, it is characterised in that including such as
Lower process：
1）By formula（Ⅲ）Shown 1,1 '-diacetyl ferrocene is dissolved in organic solvent A, and diformazan is passed through at -80 ~ -75 DEG C
Amine gas, then add the sour stirring reactions of Lewis, are slowly increased to room temperature reaction 24 ~ 40 hours, are filtered to remove insoluble matter, filtrate
Through column chromatography for separation after concentration, it is made such as formula（Ⅳ）Shown compounds Ⅳ；
2）By step 1）Obtained compounds Ⅳ is dissolved in dichloromethane, adds Pd/C, is reacted 4 ~ 10 hours at room temperature, reaction
Suction filtration after end, through column chromatography for separation after the concentration of gained dichloromethane layer, is obtained such as formula（Ⅴ）Shown compound V；
3）By step 2）Obtained compound V is dissolved in absolute ethyl alcohol, adds sodium borohydride, is reacted at room temperature 2 ~ 6 hours, is steamed
Except solvent, aqueous sodium carbonate is added, is extracted with ethyl acetate, through column chromatography for separation after the concentration of gained organic layer, be made such as formula
（Ⅵ）Shown compound VI；
4）By step 3）Obtained compound VI, DMAP and triethylamine is miscible in organic solvent B, at 0-2 DEG C
Acetic anhydride is added dropwise, drop finishes, and reacts at room temperature 2 ~ 6 hours, adds water and reaction is quenched, extracted with dichloromethane, organic layer is through drying, concentration
It is made afterwards such as formula（Ⅶ）Shown compound VII；
5）By step 4）Obtained compound VII, secondary amine R-H are miscible in organic solvent C, and back flow reaction 2 ~ 4 hours is cooled to
Room temperature, it is 2 ~ 3 to add watery hydrochloric acid regulation system pH, adds aqueous sodium carbonate into the water layer separated, regulation water layer pH for 10 ~
After 11, extracted with dichloromethane, gained organic layer is separated through drying, concentration, silica gel column chromatography, is obtained such as formula（Ⅰ）Shown handle
Substituent R in the tertiary amine of type Ferrocene-Derived, secondary amine R-H is N-2- methyl piperidines, N-2,6- lupetidines, N-1,2- bis-
Hydrogen isoquinoline or N-1,2,3,4- tetrahydroisoquinolines；
Involved 1,1 '-diacetyl ferrocene III, compounds Ⅳ, compound V, compound VI, the structure of compound VII
Formula difference is as follows：
。
3. the preparation method of the tertiary amine of shank type Ferrocene-Derived according to claim 1, it is characterised in that step 1）Center pillar
Eluant, eluent described in chromatography is that volume ratio is 50:1 petroleum ether and ethyl acetate mixture；The Lewis acid is
FeCl3、AlCl3Or TiCl4In any one, preferably AlCl3；The 1,1 '-diacetyl ferrocene, Lewis acid, two
The ratio between amount of material of methylamine is 1: 1~4 :10 ~ 20, preferably 1: 2~3 : 16~20；Organic solvent A is dichloromethane
Or toluene, preferably dichloromethane；Organic solvent A quality consumption is 1,5 ~ 20 times of 1 '-diacetyl ferrocene III, is preferably
10-15 times.
4. the preparation method of the tertiary amine of shank type Ferrocene-Derived according to claim 1, it is characterised in that step 2）Center pillar
Eluant, eluent described in chromatography is that volume ratio is 30:1 petroleum ether and ethyl acetate mixture；Compounds Ⅳ, Pd/C
Mass ratio is 1:0.01 ~ 0.05, preferably 1:0.02~0.04；The quality consumption of methylene chloride is compounds Ⅳ
2 ~ 10 times, preferably 5 ~ 8 times.
5. the preparation method of the tertiary amine of shank type Ferrocene-Derived according to claim 1, it is characterised in that step 3）Center pillar
Eluant, eluent described in chromatography is that volume ratio is 8:1 petroleum ether and ethyl acetate mixture；Compound V, NaBH4's
The ratio between amount of material is 1:1 ~ 4, preferably 1: 1~2；The quality consumption of absolute ethyl alcohol is 3 ~ 6 times of compound V, preferably
For 4 ~ 6 times.
6. the preparation method of the tertiary amine of shank type Ferrocene-Derived according to claim 1, it is characterised in that step 4）Middleization
The ratio between compound VI, acetic anhydride, triethylamine, amount of material of DMAP are 1: 1~4 : 1~4 :0.1 ~ 0.4, it is excellent
Elect 1 as: 2~3 : 2~3 : 0.2~0.3；Organic solvent B is any one in tetrahydrofuran, chloroform or dichloromethane, excellent
Elect tetrahydrofuran as；The quality consumption of organic solvent B is 4 ~ 10 times of compound VI, preferably 6 ~ 8 times.
7. the preparation method of the tertiary amine of shank type Ferrocene-Derived according to claim 1, it is characterised in that step 5）Center pillar
Eluant, eluent used in chromatography is that volume ratio is 8:1 petroleum ether and ethyl acetate mixture；Compound VII, secondary amine R-H
The ratio between the amount of material be 1:1 ~ 4, preferably 1: 1~2.0；Organic solvent C is times in toluene, tetrahydrofuran or ethanol
Meaning is a kind of, preferably toluene；Organic solvent C quality consumption is 3 ~ 10 times of compound VII, preferably 5 ~ 8 times.
8. a kind of tertiary amine of shank type Ferrocene-Derived according to claim 1 is in " being obstructed " Lewis Acids and Bases to catalyst group
Application in, is 1 by the ratio between amount of material:The tertiary amine and formula of 1 shank type Ferrocene-Derived（Ⅱ）Shown three（Phenyl-pentafluoride
Base）Boron composition obtains " being obstructed " Lewis Acids and Bases to catalyst, three（Pentafluorophenyl group）Boron and obtained " being obstructed " Lewis Acids and Bases
It is as follows to the structural formula of catalyst：
。
9. a kind of obtained " being obstructed " Lewis Acids and Bases according to claim 8 are to catalyst in catalysis hydrogenation of imines reduction
Application in reaction.
10. application according to claim 9, it is characterised in that concrete application method is：
With such as formula（Ⅸ）Shown imine derivative is substrate, with such as formula（Ⅰ）The tertiary amine of shown shank type Ferrocene-Derived and
（Ⅱ）Shown three（Pentafluorophenyl group）" being obstructed " Lewis Acids and Bases of composition shown in boron are to for catalyst, at 50 ~ 120 DEG C and 1.0
Under the conditions of ~ 5.0 MPa Hydrogen Vapor Pressures, hydro-reduction reaction occurs in anhydrous organic solvent D, reacts 6 ~ 24 hours, reaction solution
Through column chromatography for separation after concentrated, the eluent containing compound Ⅹ is collected, organic solvent is evaporated off, be made such as formula（Ⅹ）Shown
Product Ⅹ；The eluant, eluent of column chromatography for separation is volume ratio 30:1 petroleum ether and the mixed liquor of ethyl acetate；Described imines
Derivative, the tertiary amine of shank type Ferrocene-Derived, three（Pentafluorophenyl group）The ratio between amount of material of boron is 1: 0.05~0.20 :
0.05~0.20；Organic solvent D is one kind in pentane, n-hexane or toluene, and its quality consumption is the 5 ~ 20 of imine derivative
Times；Imine derivative IX and product Ⅹ structural formula are as follows：
。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710329828.5A CN107200756B (en) | 2017-05-11 | 2017-05-11 | A kind of tertiary amine and its preparation method and application of shank type Ferrocene-Derived |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710329828.5A CN107200756B (en) | 2017-05-11 | 2017-05-11 | A kind of tertiary amine and its preparation method and application of shank type Ferrocene-Derived |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107200756A true CN107200756A (en) | 2017-09-26 |
| CN107200756B CN107200756B (en) | 2019-04-30 |
Family
ID=59905038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710329828.5A Active CN107200756B (en) | 2017-05-11 | 2017-05-11 | A kind of tertiary amine and its preparation method and application of shank type Ferrocene-Derived |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107200756B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613618A (en) * | 2013-11-06 | 2014-03-05 | 浙江工业大学 | [2.2] paracyclophane derivative as well as preparation method and application thereof |
-
2017
- 2017-05-11 CN CN201710329828.5A patent/CN107200756B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613618A (en) * | 2013-11-06 | 2014-03-05 | 浙江工业大学 | [2.2] paracyclophane derivative as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| DOMINIQUE P. HUBER等: "Heterolytic cleavage of dihydrogen by frustrated lewis pairs derived fromα-(dimesitylphosphino) ferrocenes and B(C6F5)3", 《ORGANOMETALLICS》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107200756B (en) | 2019-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5783715A (en) | Silylated ferrocenyldiphosphines, silylated ferrocenyldiphosphines bound to inorganic or polymeric organic supports and also metal complexes thereof, their preparation and uses | |
| Zhao et al. | Enamines: efficient nucleophiles for the palladium-catalyzed asymmetric allylic alkylation | |
| Li et al. | Highly enantioselective phenylacetylene addition to aldehydes catalyzed by a chiral N, O-ferrocene ligand | |
| AU2011360843A1 (en) | Catalyst for asymmetric hydrogenation of imine, synthesis method and application thereof | |
| Zhang et al. | Highly efficient enantioselective synthesis of bispiro [benzofuran-oxindole/benzofuran-chromanone] s through organocatalytic inter-/intramolecular Michael cycloaddition | |
| CN108440553A (en) | A kind of method of the glabridin of the asymmetric syntheses optical purity of ruthenium complex catalysts | |
| Wang et al. | Enantioselective synthesis of pyrano [2, 3-c] pyrrole via an organocatalytic [4+ 2] cyclization reaction of dioxopyrrolidines and azlactones | |
| CN110423190A (en) | A kind of method of iron complex catalysis ketone alpha-alkyl | |
| CN106905125A (en) | A kind of method that ketone α alkyl of cobalt catalysis is combined to ketones derivant | |
| Deng et al. | The synthesis of novel chiral N, O-ferrocenyl ligands and their application in the addition of diethylzinc to aldehydes | |
| CN111484459B (en) | Method for synthesizing chiral 3-trifluoromethyl-3, 4-dihydroquinoxalinone by palladium-catalyzed asymmetric hydrogenation | |
| CN107200756B (en) | A kind of tertiary amine and its preparation method and application of shank type Ferrocene-Derived | |
| Anderson et al. | The preparation of β-substituted amines from mixtures of epoxide opening products via a common aziridinium ion intermediate | |
| CN107417603B (en) | Preparation method of crizotinib intermediate | |
| CN115073251A (en) | Method for asymmetrically catalyzing and synthesizing nicotine | |
| US5481008A (en) | Process for the preparation of optically active compounds | |
| US7687630B2 (en) | Method for producing optically active quinuclidinols having one or more substituted groups at the 2-position | |
| CN113354599B (en) | Preparation method of nintedanib key intermediate | |
| EP0672649B1 (en) | Process for producing optically active diaminohexanone derivative | |
| Ma et al. | Divergent synthesis of chiral amines via Ni-catalyzed chemo-and enantioselective hydrogenation of alkynone imines | |
| CN109942474A (en) | A kind of neighbour's nitrine-hydrazine class compound and preparation method thereof | |
| CN109046458A (en) | A kind of preparation method of p-nitroacetophenone | |
| CN111574528B (en) | Method for preparing medical intermediate pyranoquinoline derivative | |
| Kressierer et al. | The first one-pot Alder-ene-reductive amination sequence | |
| CN108017572B (en) | Process for the preparation of (S) -3-hydroxypiperidines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |