CN109111393A - A kind of NNN ligand compound, cobalt-NNN complex compound, and preparation method and application - Google Patents
A kind of NNN ligand compound, cobalt-NNN complex compound, and preparation method and application Download PDFInfo
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- CN109111393A CN109111393A CN201810995806.7A CN201810995806A CN109111393A CN 109111393 A CN109111393 A CN 109111393A CN 201810995806 A CN201810995806 A CN 201810995806A CN 109111393 A CN109111393 A CN 109111393A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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- 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
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
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- 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
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- 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
- B01J2531/845—Cobalt
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Abstract
The present invention relates to a kind of NNN ligand compounds that coordinate bond is formed by three N atoms, and the cobalt-NNN complex compound formed by NNN ligand compound, and its preparation method and application, specifically, the NNN ligand compound contains pyridine and imine structure.The ligand compound and its can be with efficient catalytic alkynes silicon hydrogenation with the complex compound of cobalt, reaction condition is mild, selectivity is high, substrate spectrum is wide, yield and purity is high and target product have higher economic value, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of NNN ligand compounds that coordinate bond is formed by three N atoms, and by NNN ligand chemical combination
Object formed cobalt-NNN complex compound, and its preparation method and application, specifically, the NNN ligand compound contain pyridine and
Imine structure.The ligand compound and its α-vinyl silane compound is prepared in alkynes silicon hydrogenation selectivity with the complex compound of cobalt
In have well application.
Background technique
Vinyl silane compound is a kind of very important building block, be widely used in Tamao-Fleming oxidation,
In parental materials, coupling reaction.Its synthetic method is always an important field of research, is hydrogenated by acetylene hydrocarbon compound silicon anti-
Answering synthesis of vinyl silane compound is considered as convenient, the cheap, method with Atom economy.However the reaction usually needs
Want the noble metals such as Pt, Ru, Rh or Ir as catalyst, and the chemo-selective of product, stereoselectivity (tri- kinds of β-E, β-Z and α
Product) control it is challenging.β-E and β-Z is used as anti-Markovnikov addition (anti-Markovnikov) product, extensive
Research.However, more being lacked as alkynes silicon hydrogenation with the research of Markovnikov addition (Markovnikov) coordinates measurement α product
It is weary.In earlier 1900s, Trost and Yamamoto group independently reports Ru catalysis end-group alkyne silicon hydrogenation synthesis α-ethylene
Research (the J.Am.Chem.Soc.2001,123,12726 of base silane；J.Am.Chem.Soc.2005,127,17644；
Org.Lett.2002,4,2825).2011, the Markovnikov addition that Loh group reports base metal Cu catalysis alkynes silicon hydrogenation was anti-
It answers.But this method needs very expensive borosilicate reagent, seriously hinder its be widely applied (J.Am.Chem.Soc.2011,133,
1254).In recent years, tridentate ligand causes in the Markovnikov addition reaction that alkynes silicon hydrogenates and more and more pays close attention to and achieve
Certain progress.2016, Zheng Huang group reported the bis- oxazolines of pyridine-(Pybox) tridentate ligand and Co catalytic body
The Markovnikov addition that system can be hydrogenated with efficient catalytic alkynes silicon reacts (Angerw.Chem.Int.Ed.2016,55,10839).Almost
Meanwhile Zhan Lu group reports imines-pyridine-oxazoline tridentate ligand and Co catalyst system, can also efficiently complete alkynes
Hydrocarbon Markovnikov addition silicon hydrogenation (Angew.Chem.Int.Ed.2016,55,10835).Although the exploitation of tridentate ligand so that
Base metal catalysis alkynes silicon hydrogenation achieves certain progress, and still, used ligand synthesis is complicated at present, and type has
Limit；And used silane is also limited to diphenyl silane, type is relatively single.
Therefore there is still a need for exploitation new catalysts, it can be achieved that preparing Markovnikov addition product with high selectivity, while to the greatest extent may be used
Cheap metal active material can be used, to reduce cost.
Summary of the invention
The present invention expensive, selective low, substrate for catalyst in alkynes silicon hydrogenation in existing synthetic technology
The problem in science such as limitation is big, silane reagent is expensive, present inventors have developed a kind of novel NNN ligand compound and
Cobalt-NNN the complex compound prepared by the ligand, the cobalt-NNN complex compound can be applied to the silicon hydrogen of alkynes and level-one, two grade silanes
Change in reaction, it can be achieved that preparing Markovnikov addition product (α-vinyl silane compound) with high selectivity.
According to an aspect of the present invention, the present invention provides a kind of NNN ligand compound indicated by general formula 1, knots
Structure is as follows:
Wherein, R1And R2It is each independently H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Virtue
Base, the substituted C6~C30Aryl in substituent group be one or more C1~C30Alkyl and/or C6~C30Aryl；
R simultaneously1And R2It is not simultaneously H atom；
Preferably, R1And R2It is each independently H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15's
Aryl, the substituted C6~C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C10Alkyl or C substituted or unsubstituted6~C10Virtue
Base, the substituted C6~C10Aryl in substituent group be one or more methyl, ethyl, propyl, isopropyl, tert-butyl
And/or C6~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C6Alkyl or substituted or unsubstituted phenyl, it is described
Substituent group in substituted phenyl is one or more methyl, ethyl, propyl, isopropyl, tert-butyl and/or C6~C15Virtue
Base；
Preferably, R1And R2It is each independently H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, secondary
Butyl, tert-butyl, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethyl
Phenyl, triethyl group phenyl or triisopropyl phenyl；
Preferably, R1And R2Pass through linking group-(CH2)nIt is connected to each other to form ring, the integer that wherein n is 0~6 works as n
When being 0, R is indicated1And R2It is bonded directly with one another.
R3For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~C15
Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R3For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, it is described substituted
C6~C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R3For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, in the substituted phenyl
Substituent group is one or more C1~C4Alkyl；
Preferably, R3For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, benzene
Base, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl
Or triisopropyl phenyl.
R4For H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Aryl, the substituted C6~C30
Aryl in substituent group be one or more C1~C30Alkyl and/or C6~C30Aryl；
Preferably, R4For H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15Aryl, the substitution
C6~C15Aryl in substituent group be one or more C1~C15Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substitution
C6~C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, it is described substituted
C6~C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R4For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, in the substituted phenyl
Substituent group is one or more C1~C4Alkyl；
Preferably, R4For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, benzene
Base, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl
Or triisopropyl phenyl.
Wherein, work as R3For H, R1And R2When for isopropyl, R4It is not tert-butyl.
According to another aspect of the present invention, the present invention provides the preparation sides of the NNN ligand compound indicated by general formula 1
Method, the preparation method by following formulas indicate and the following steps are included:
Step 1) in organic solvent, compound SM3With N halosuccinimides (NBX, wherein X be
Cl, Br or I) reaction, obtain compound SM2。
Compound SM2Preparation method can be the conventional method of such halogenating reaction in this field, in the present invention especially
It is preferred that following carry out:
The preferred halogenated hydrocarbon solvent of organic solvent, further preferably carbon tetrachloride.
The compound SM3With the preferred 1mg/mL~200mg/mL of organic solvent mass ratio.
The reactant NBX and compound SM3The preferred 1:1~1.1:1 of molar ratio.
Preferably 0 DEG C~80 DEG C of the temperature of the halogenating reaction.
The process of the halogenating reaction can be using the common detection methods (such as TLC, GC, HPLC or NMR) in this field
It is detected, generally with compound SM3Disappearance be reaction end, reaction time preferred 2h~for 24 hours.
Step 2) in organic solvent, by compound SM2With organic amine R1R2NH carries out nucleophilic substitution, obtains chemical combination
Object SM1。
Compound SM1Preparation method can be the conventional method of such nucleophilic substitution in this field, in the present invention
It is particularly preferably following to carry out:
The preferred acetonitrile of the organic solvent, methylene chloride or tetrahydrofuran.
The compound SM2With the preferred 1mg/mL~200mg/mL of organic solvent mass ratio.
The R1R2NH and compound SM2The preferred 1:1~3:1 of molar ratio.
Preferably 0 DEG C~80 DEG C of the temperature of the condensation reaction.
The process of the condensation reaction can be using the common detection methods (such as TLC, GC, HPLC or NMR) in this field
It is detected, generally with compound SM2Disappearance be reaction end, reaction time preferred 1h~for 24 hours.
In step 3) organic solvent (or solvent-free), under the conditions of acid is existing, by compound SM1With amine R4NH2It is dehydrated
Condensation reaction obtains NNN ligand.
The preparation method of NNN ligand can be the conventional method of such condensation reaction in this field, especially excellent in the present invention
Choosing is following to be carried out:
The preferred benzene of the organic solvent and substituted benzene solvent, further preferably benzene or toluene.
The compound SM1With the preferred 1mg/mL~200mg/mL of mass volume ratio of the organic solvent.
The acid (Acid) can be organic acid or inorganic acid；It is further preferred that the organic acid can be to toluene
Sulfonic acid, formic acid, one or more in acetic acid, the inorganic acid can be sulfuric acid or hydrochloric acid.
The acid and the compound SM1The preferred 0.01:1~0.2:1 of molar ratio.
The R4NH2With the compound SM1The preferred 1:1~3:1 of molar ratio.
The temperature of the condensation reaction preferably 60 DEG C~reflux temperature.
The process of the condensation reaction can be using the common detection methods (such as TLC, GC, HPLC or NMR) in this field
It is detected, generally with compound SM1Disappearance be reaction end, reaction time preferred 1h~48h.
Wherein, R1、R2、R3、R4Definition with X is the same as described in general formula 1.
According to another aspect of the present invention, the present invention also provides Co-CNN complex compound, structural formulas as shown in general formula 2
It is as follows:
Wherein, R1And R2It is each independently H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Virtue
Base, the substituted C6~C30Aryl in substituent group be one or more C1~C30Alkyl and/or C6~C30Aryl；
R simultaneously1And R2It is not simultaneously H atom；
Preferably, R1And R2It is each independently H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15's
Aryl, the substituted C6~C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C10Alkyl or C substituted or unsubstituted6~C10Virtue
Base, the substituted C6~C10Aryl in substituent group be one or more methyl, ethyl, propyl, isopropyl, tert-butyl
And/or C6~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C6Alkyl or substituted or unsubstituted phenyl, it is described
Substituent group in substituted phenyl is one or more methyl, ethyl, propyl, isopropyl, tert-butyl and/or C6~C15Virtue
Base；
Preferably, R1And R2It is each independently H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, secondary
Butyl, tert-butyl, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethyl
Phenyl, triethyl group phenyl or triisopropyl phenyl；
Preferably, R1And R2Pass through linking group-(CH2)nIt is connected to each other to form ring, the integer that wherein n is 0~6 works as n
When being 0, R is indicated1And R2It is bonded directly with one another.
R3For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~C15
Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R3For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, it is described substituted
C6~C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R3For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, in the substituted phenyl
Substituent group is one or more C1~C4Alkyl；
Preferably, R3For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, benzene
Base, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl
Or triisopropyl phenyl.
R4For H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Aryl, the substituted C6~C30
Aryl in substituent group be one or more C1~C30Alkyl and/or C6~C30Aryl；
Preferably, R4For H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15Aryl, the substitution
C6~C15Aryl in substituent group be one or more C1~C15Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substitution
C6~C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, it is described substituted
C6~C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R4For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, in the substituted phenyl
Substituent group is one or more C1~C4Alkyl；
Preferably, R4For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, benzene
Base, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl
Or triisopropyl phenyl.
Wherein, work as R3For H, R1And R2When for isopropyl, R4It is not tert-butyl.
According to another aspect of the present invention, the present invention also provides the preparation sides of the Co-NNN complex compound as shown in general formula 2
Method, the preparation method by following formulas indicate and the following steps are included:
Under inert gas protection, in organic solvent by NNN ligand and CoX2It is reacted, is obtained as shown in general formula 2
NNN ligand-Co complex compound, wherein R1、R2、R3And R4Definition with upper described in general formula 1.
The preparation method of Co-NNN complex compound shown in the general formula 2 can be the routine side of such reaction in this field
Method is particularly preferably following in the present invention to carry out:
Gas in the gas shield can be one of nitrogen, argon gas, helium or a variety of.
The preferred ether solvent of organic solvent, further preferred tetrahydrofuran.
The NNN ligand and the preferred 1mg/mL~200mg/mL of organic solvent mass ratio.
The CoX2With the preferred 0.8:1~1.2:1 of NNN ligand molar ratio.
Preferably 0 DEG C~100 DEG C of the temperature of the reaction.
The process of the reaction can be examined using the common detection methods (such as TLC, HPLC or NMR) in this field
It surveys, generally using the disappearance of NNN ligand as reaction end, reaction time preferred 1h~48h.
According to another aspect of the present invention, the present invention also provides Co-NNN complex compounds shown in the general formula 2 to urge
Change the application in the silicon hydrogenation of alkynes.
According to another aspect of the present invention, the present invention also provides a kind of method of silicon hydrogenation for being catalyzed alkynes, institutes
State method by following formulas indicate and the following steps are included:
Under gas shield, in organic solvent, under the action of the Co-NNN complex compound shown in general formula 2 according to the present invention,
By alkynesWith silane R5R6R7SiH carries out addition reaction, obtains vinyl silane compound TM.
The organic solvent can be using the conventional organic solvent of the type addition reaction in this field, in the present invention especially
It is preferred that ether solvent, further preferred tetrahydrofuran or Isosorbide-5-Nitrae-dioxane.
Gas in the gas shield can be one of nitrogen, argon gas, helium.
The R5R6R7The SiH and preferred 1mg/mL~200mg/mL of organic solvent mass ratio.
NNN ligand-Co the complex compound and the alkynes indicated such as general formula 2Molar ratio preferably 0.001~
0.1。
The alkynesWith the R5R6R7Preferred 0.5:1~the 2:1 of SiH molar ratio.
Preferably -80 DEG C~80 DEG C of the temperature of the reaction.
The process of the reaction can be carried out using the common detection methods (such as TLC, GC, HPLC or NMR) in this field
Monitoring, generally with alkynesDisappearance be reaction end, reaction time preferred 1s~for 24 hours.
AlkynesWith silane R5R6R7It is carried out in the reaction that SiH is carried out, under the conditions of can be existing for the co-catalyst, institute
Stating co-catalyst can be sodium triethylborohydride (NaHBEt3), lithium methide (LiCH3), (trimethyl silane) methylate lithium
(TMSCH2Li), potassium tert-butoxide, sodium tert-butoxide, preferably sodium triethylborohydride；The alkynesWith the silane
R5R6R7When being carried out under the conditions of the reaction that SiH is carried out is existing for the co-catalyst, the co-catalyst and the alkynes
Molar ratio preferably 0.002~0.3.
Wherein, R8For H atom；C1~C30Alkyl；Substituted or unsubstituted C6~C30Aryl, the substituted C6~
C30Aryl in substituent group be one or more C1~C30Alkyl, C1~C30Alkoxy, halogen and/or C6~C30Virtue
Base；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C30Heteroaryl.
Preferably, R8For H atom；C1~C10Alkyl；Substituted or unsubstituted C6~C15Aryl, the substituted C6
~C15Aryl in substituent group be one or more C1~C10Alkyl, C1~C10Alkoxy, halogen and/or C6~C15's
Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C15Heteroaryl.
Preferably, R8For H atom；C1~C6Alkyl；Substituted or unsubstituted C6~C10Aryl, the substituted C6
~C10Aryl in substituent group be one or more C1~C6Alkyl, C1~C6Alkoxy, halogen and/or C6~C10's
Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C10Heteroaryl.
Preferably, R8For H atom；C1~C10Alkyl；Substituted or unsubstituted C6~C15Aryl, the substituted C6
~C15Aryl in substituent group be one or more C1~C10Alkyl, C1~C10Alkoxy, halogen and/or C6~C15's
Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C16Heteroaryl.
Preferably, R8For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, first
Oxygroup, ethyoxyl, propoxyl group, isopropoxy, butoxy, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethylbenzene
Base, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl, triisopropyl phenyl, 1- xenyl, 2- xenyl, 3- biphenyl
Base, 1- naphthalene, 2- naphthalene, 2- furyl, 3- furyl, 2- thienyl, 3- thienyl, 2- pyridyl group, 3- pyridyl group, 4- pyridine
Base, 4- quinolyl, 8- quinolyl.
R5、R6、R7It is each independently H atom；C1~C30Alkyl；C1~C30Alkyl siloxy；It is substituted or unsubstituted
C6~C30Aryl, the substituted C6~C30Aryl in substituent group be one or more C1~C30Alkyl, C1~
C30Alkoxy, halogen and/or C6~C30Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C30
Heteroaryl.
Preferably, R5、R6、R7It is each independently H atom；C1~C10Alkyl；C1~C10Alkyl siloxy；Replace
Or unsubstituted C6~C15Aryl, the substituted C6~C15Aryl in substituent group be one or more C1~C10Alkane
Base, C1~C10Alkoxy, halogen and/or C6~C15Aryl；Containing 1 to 3 selected from the heteroatomic of oxygen, sulphur or nitrogen-atoms
C5~C15Heteroaryl.
Preferably, R5、R6、R7It is each independently H atom；C1~C6Alkyl；C1~C6Alkyl siloxy；Replace or
Unsubstituted C6~C10Aryl, the substituted C6~C10Aryl in substituent group be one or more C1~C6Alkyl,
C1~C6Alkoxy, halogen and/or C6~C10Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~
C10Heteroaryl.
Preferably, R5、R6、R7It is each independently H atom；C1~C6Alkyl；C1~C6Alkyl siloxy；Replace or
Unsubstituted C6~C15Aryl, the substituted C6~C15Aryl in substituent group be one or more C1~C10Alkane
Base, C1~C10Alkoxy, halogen and/or C6~C15Aryl；Containing 1 to 3 selected from the heteroatomic of oxygen, sulphur or nitrogen-atoms
C5~C16Heteroaryl.
Preferably, R5、R6、R7Be each independently H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group,
Sec-butyl, tert-butyl, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, phenyl, aminomethyl phenyl, ethylphenyl, two
Aminomethyl phenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl, triisopropyl phenyl, three (front three silicon
Alkoxy) silane, three (trimethyl silicon substrate) silane, 2- furyl, 3- furyl, 2- thienyl, 3- thienyl, 2- pyridyl group,
3- pyridyl group, 4- pyridyl group, 4- quinolyl, 8- quinolyl.
According to another aspect of the present invention, the present invention also provides vinyl silane compound TM:
Wherein, R5、R6、R7And R8Definition it is same as above.
Beneficial effect
According to an aspect of the present invention, the present invention provides the preparations of a kind of NNN ligand compound, Co-NNN complex compound
Method and its application in alkynes hydrosilylation.NNN ligand of the invention contains imines, pyridine and amine coordination site, has
Electronics and spatial scalability can form Co-NNN complex compound with Co；Co-NNN complex compound of the invention can be with efficient catalytic
Alkynes silicon hydrogenation, reaction condition is mild, selectivity is high, substrate spectrum is wide, yield and purity is high and target product have compared with
High economic value is suitable for industrialized production.
Specific embodiment
Hereinafter, will be described in detail the present invention.Before doing so, it should be appreciated that in this specification and appended
Claims used in term should not be construed as being limited to general sense and dictionary meanings, and inventor should allowed
On the basis of the appropriate principle for defining term to carry out best interpretations, according to meaning corresponding with technical aspect of the invention and generally
Thought explains.Therefore, description presented herein is not intended to limitation originally merely for the sake of the preferred embodiment for illustrating purpose
The range of invention, it will thus be appreciated that without departing from the spirit and scope of the present invention, it can be obtained by it
His equivalents or improved procedure.
Following embodiment is enumerated only as the example of embodiment of the present invention, does not constitute any limit to the present invention
System, it will be appreciated by those skilled in the art that modification in the range of without departing from essence and design of the invention each falls within the present invention
Protection scope.The reagent and solvent of following discloses are purchased from Shanghai Aladdin biochemical technology limited liability company (aladdin),1H
NMR and13C NMR is measured by Brooker ASCEND400M nuclear-magnetism and Brooker AVANCW-III 600M nuclear-magnetism；GC-MS passes through
Agilent HP-7890 apparatus measures；High resolution mass spectrum uses Bruke Maxis UHR TOF apparatus measures.Except non-specifically saying
Bright, reagent and instrument used in the following embodiment are commercially available product.
Embodiment 1
2- acetyl group -6- bromo methyl cycloheptapyridine (SM2- 1) preparation:
Compound SM is added in 250mL round-bottomed bottle3(6.76g, 50.0mmol), N-bromosuccinimide (NBS,
8.90g, 50.0mmol), azodiisobutyronitrile (AIBN, 0.41g, 2.5mmol) and 150mL carbon tetrachloride, under magnetic agitation
70 DEG C of reaction 12h.When reaction solution is cooled to room temperature, washing twice, saturated common salt washing, then anhydrous sodium sulfate is dry, will be anti-
Liquid is answered to be concentrated, column chromatography for separation, with petroleum ether: the leacheate of methylene chloride volume ratio 3:1 elutes, and obtains compound SM2- 1 is light
Yellow oil (4.83g, yield 45.1%).
1δ=7.90 (d, J=7.7Hz, 1H) H NMR (600MHz, CDCl3), 7.79 (t, J=7.7Hz, 1H), 7.59
(d, J=7.7Hz, 1H), 4.56 (s, 2H), 2.68 (s, 3H)13C NMR(151MHz,CDCl3)δ199.82,156.36,
(153.17,137.86,126.83,120.69,33.30,25.66.HRMS ESI): theoretical value C8H9BrNO+[M+H]+:
213.9862 measured value: 213.9864.
1- (6- ((tert-butylamino) methyl) pyridine -2- base) second -1- ketone (SM1- 1) preparation:
In 25mL round-bottomed bottle, compound SM is added2- 1 (2.16g, 10.0mmol), is added tert-butylamine 5.0mL, and room temperature is anti-
10min is answered, reaction system 50mL methylene chloride is diluted, twice, saturated common salt is washed for washing, and anhydrous sodium sulfate is dry.Subtract
Pressure removes solvent to get compound as white solid SM1- 1 (2.06g, yield 99%).
1H NMR(400MHz,CDCl3) δ 7.87 (d, J=7.5Hz, 1H), 7.74 (t, J=7.7Hz, 1H), 7.49 (d, J
=7.6Hz, 1H), 3.94 (s, 2H), 2.71 (s, 3H), 1.20 (s, 9H)13C NMR(101MHz,CDCl3)δ200.30,
159.97,152.82,137.08,125.80,119.64,50.55,48.07,29.08,25. 68.HRMS (ESI): theoretical value
C12H19N2O+[M+H]+: 207.1492, measured value: 207.1496.
1- (6- ((diethylamino) methyl) pyridine -2- base) second -1- ketone (SM1- 2) preparation:
In 25mL round-bottomed bottle, compound SM is added2- 1 (2.16g, 10.0mmol), is added diethylamine 5.0mL, and room temperature is anti-
5min is answered, reaction system 50mL methylene chloride is diluted, twice, saturated common salt is washed for washing, and anhydrous sodium sulfate is dry.Decompression
Solvent is removed to get compound as white solid SM1- 2 (2.04g, yields 98%).
1H NMR(600MHz,CDCl3) δ 7.89 (d, J=7.6Hz, 1H), 7.78 (t, J=7.7Hz, 1H), 7.69 (d, J
=7.6Hz, 1H), 3.83 (s, 2H), 2.71 (s, 3H), 2.64 (dd, J=13.7,6.7Hz, 4H), 1.11 (t, J=7.1Hz,
6H).13C NMR(151MHz,CDCl3)δ200.54,152.84,137.03,126.50,119.78,58.76,47.40,
(25.71,11.84.HRMS ESI): theoretical value C12H19N2O+[M+H]+: 207.1492, measured value: 207.1495.
(E)-N- ((6- (1- (mesitylene base) ethyl) pyridine -2- base) methyl) -2- methyl propyl- 2- amine (NNN-1)
Preparation:
Under argon gas protection, compound SM is added in the 50mL there-necked flask of the drying equipped with water segregator1-1(450mg,
2.2mmol), 2,4,6- trimethylaniline (297mg, 2.2mmol), to benzene methanesulfonic acid (38mg, 10mol%), dry toluene
20mL.Reaction carries out 10-24h under conditions of reflux, and SM is worked as in TLC monitoring1- 1 consumption completely, stops reaction, neutral alumina
Column chromatography, using methylene chloride, methylene chloride (5% methanol) gradient elution, obtains compound N NN-1 (604mg, yield 85%)
Yellow oil.
1H NMR(400MHz,CDCl3) δ 8.22 (d, J=7.8Hz, 1H), 7.74 (t, J=7.8Hz, 1H), 7.40 (d, J
=7.6Hz, 1H), 6.88 (s, 2H), 4.01 (s, 2H), 3.22 (bs, 1H), 2.29 (s, 3H), 2.17 (s, 3H), 1.99 (s,
6H),1.26(s,9H).13C NMR(101MHz,CDCl3)δ167.30,155.69,146.21,136.92,132.10,
128.49,125.23,123.34,119.46,51.37,47.73,28.78,20.70,17.8 2,16.44.HRMS (ESI): reason
By value C21H30N3 +[M+H]+: 324.2434, measured value: 324.2438.
Embodiment 2
(E)-N- ((6- (1- ((2,6- diisopropyl phenyl) imino group) ethyl) pyridine -2- base) methyl) -2- methyl propyl-
The preparation of 2- amine (NNN-2):
Under argon gas protection, compound SM is added in the 50mL there-necked flask of the drying equipped with water segregator1-1(510mg,
2.5mmol), 2,6- diisopropyl aniline (443mg, 2.5mmol), to benzene methanesulfonic acid (44mg, 10mol%), dry toluene
20mL.Reaction carries out 10-24h under conditions of reflux, and SM is worked as in TLC monitoring1- 1 consumption completely, stops reaction, neutral alumina
Column chromatography, using methylene chloride, methylene chloride (5% methanol) gradient elution, obtains compound N NN-2 (714mg, yield 78%)
Yellow oil.
1H NMR(600MHz,CDCl3) δ 8.23 (d, J=7.8Hz, 1H), 7.75 (t, J=7.7Hz, 1H), 7.40 (d, J
=7.6Hz, 1H), 7.16 (d, J=7.6Hz, 2H), 7.11-7.06 (m, 1H), 4.01 (s, 2H), 2.77-2.70 (m, 2H),
2.20 (s, 3H), 1.26 (s, 9H), 1.14 (d, J=6.7Hz, 12H)13C NMR(151MHz,CDCl3)δ166.81,
155.55,146.47,136.93,135.77,123.47,123.34,122.93,119.44,47.76,28.86,28.21,
(23.16,22.87,17.17.HRMS ESI): theoretical value C24H36N3 +[M+H]+: 366.2904, measured value: 366.2905.
Embodiment 3
(E) preparation of-N- ethyl-N- ((6- (1- (trimethylphenyl) ethyl) pyridine -2- base) methyl) ethamine (NNN-3):
Under argon gas protection, compound SM is added in the 50mL there-necked flask of the drying equipped with water segregator1-2(450mg,
2.2mmol), 2,4,6- trimethylaniline (297mg, 2.2mmol), to benzene methanesulfonic acid (38mg, 1mol%), dry toluene
20mL.Reaction carries out 10-24h under conditions of reflux, and SM is worked as in TLC monitoring1- 1 consumption completely, stops reaction, neutral alumina
Column chromatography, using methylene chloride, methylene chloride (5% methanol) gradient elution, obtains compound N NN-3 (604mg, yield 85%)
Yellow oil.
1H NMR(400MHz,CDCl3) δ 8.19 (d, J=7.7Hz, 1H), 7.74 (t, J=7.7Hz, 1H), 7.55 (d, J
=7.6Hz, 1H), 6.88 (s, 2H), 3.81 (s, 2H), 2.63 (q, J=7.1Hz, 4H), 2.29 (s, 3H), 2.16 (s, 3H),
2.00 (s, 6H), 1.10 (t, J=7.1Hz, 6H)13C NMR(101MHz,CDCl3)δ167.86,155.66,146.35,
136.55,128.81,128.48,125.30,123.79,119.12,59.12,47.39,20.71,17.85,16.54,
12.03.HRMS (ESI) theoretical value C21H30N3 +[M+H]+: 324.2434, measured value: 324.2438.
Embodiment 4
The preparation of complex compound 1-a:
In nitrogen atmosphere glove box, compound N NN-1 (773mg, 2.4mmol) is added in schleck bottles of 100mL,
Be added anhydrous tetrahydro furan 20mL, react 15min at room temperature, by this reaction solution instill waterless cobaltous chloride (311mg,
In 20mL tetrahydrofuran suspension 2.4mmol), stir at room temperature for 24 hours.Green solid is collected by filtration, is washed with n-hexane, ether
Solid is washed, is dried in vacuo, obtains complex compound 1-a (1.1g, yield 85%).Analytical calculation value (C21H29Cl2CoN3.CH2Cl2):C,
49.09；H,5.81；N, 7.81. measured value: C, 49.08；H,5.75；N,7.82.
Embodiment 5
The preparation of complex compound 1-b:
In nitrogen atmosphere glove box, compound N NN-2 (183mg, 0.5mmol) is added in schleck bottles of 25mL,
Anhydrous tetrahydro furan 5mL is added, reacts 15min at room temperature, this reaction solution is instilled into waterless cobaltous chloride (59mg, 0.45mmol)
5mL tetrahydrofuran suspension in, stir at room temperature for 24 hours.Green solid is collected by filtration, washs solid with n-hexane, ether, very
Sky is dry, obtains complex compound 1-b (200mg, yield 81%).Analytical calculation value (C24H34Cl2CoN3):C,58.31；H,6.93；
N, 8.50. measured value: C, 58.04；H,6.99；N,8.46.
Effect example
Effect example 1
In nitrogen glove box, by complex compound 1-a (0.01mmol), phenylacetylene (0.5mmol), phenylsilane (0.5mmol)
It is added in 10mL Schleck pipe with 1mL dry tetrahydrofuran, NaHBEt is then added3(0.03mmol, 1M in THF), room
Temperature is lower to react 5min.Reaction solution is concentrated, using petroleum ether as eluant, eluent, column chromatographs to obtain target product (TM-1a, yield
91%).1H NMR(400MHz,CDCl3) δ 7.52-7.48 (m, 2H), 7.33-7.11 (m, 8H), 6.14 (d, J=2.3Hz,
1H), 5.74 (d, J=2.3Hz, 1H), 4.75 (s, 2H)13C NMR(101MHz,CDCl3)δ144.23,142.33,135.65,
131.36,131.23,129.95,128.56,128.18,127.34,126.53.GC-MS: theoretical value C14H14Si+[M]+:210,
Measured value: 210.
Effect example 2
In nitrogen glove box, by complex compound 1-a (0.01mmol), phenylacetylene (0.5mmol), diphenyl silane
(0.5mmol) and 1mL dry tetrahydrofuran are added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M in
THF), 5min is reacted at room temperature.Reaction solution is concentrated, using petroleum ether as eluant, eluent, column chromatographs to obtain target product (TM-1b, receipts
Rate 75%).1H NMR(400MHz,CDCl3)δ7.59–7.54(m,4H),7.41–7.31(m,8H),7.29–7.19(m,3H),
6.28 (dd, J=2.5,1.0Hz, 1H), 5.68 (d, J=2.5Hz, 1H), 5.39 (d, J=0.9Hz, 1H) .13C NMR
(101MHz,CDCl3)δ146.0,143.0,135.9,133.2,132.3,129.9,128.5,128.2,127.2,
126.8.GC-MS:Calc.for C20H18Si+[M]+: 286, measured value: 286.
Effect example 3
In nitrogen glove box, by complex compound 1-b (0.01mmol), phenylacetylene (0.5mmol), phenylsilane (0.5mmol)
It is added in 10mL Schleck pipe with 1mL dry tetrahydrofuran, NaHBEt is then added3(0.03mmol, 1M in THF), room
Temperature is lower to react 5min.Reaction solution is concentrated, using petroleum ether as eluant, eluent, column chromatographs to obtain target product (TM-1a, yield
85%).1H NMR(400MHz,CDCl3) δ 7.52-7.48 (m, 2H), 7.33-7.11 (m, 8H), 6.14 (d, J=2.3Hz,
1H), 5.74 (d, J=2.3Hz, 1H), 4.75 (s, 2H)13C NMR(101MHz,CDCl3)δ144.23,142.33,135.65,
131.36,131.23,129.95,128.56,128.18,127.34,126.53.GC-MS: theoretical value C14H14Si+[M]+:210,
Measured value: 210.
Effect example 4
In nitrogen glove box, by complex compound 1-a (0.01mmol), 4- Methoxy-phenylacetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Reaction solution is concentrated, using petroleum ether as eluant, eluent, column chromatographs to obtain target product (TM-
2a, yield 77%).1H NMR(600MHz,CDCl3)δ7.52–7.46(m,2H),7.30–7.20(m,5H),6.75–6.68(m,
2H), 6.08 (d, J=2.3Hz, 1H), 5.64 (d, J=2.3Hz, 1H), 4.73 (s, 2H), 3.65 (s, 3H)13C NMR
(151MHz,CDCl3)δ159.13,143.16,135.65,134.68,131.41,129.93,129.60,128.20,
127.66,113.99,55.29.GC-MS:Calc.for C15H16OSi+[M]+: 240, measured value: 240.
Effect example 5
The preparation of (1- (3- methoxyphenyl) vinyl) (phenyl) silane (TM-3a):
In nitrogen glove box, by complex compound 1-a (0.01mmol), 3- Methoxy-phenylacetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Silica gel column chromatography obtains colorless oil (yield 66%) using petroleum ether as eluant, eluent.1H
NMR(600MHz,CDCl3)δ7.52–7.48(m,1H),7.32–7.28(m,1H),7.27–7.23(m,1H),7.13–7.09
(m, 1H), 6.88-6.84 (m, 1H), 6.82-6.79 (m, 1H), 6.69 (dd, J=8.2,2.0Hz, 1H), 6.14 (d, J=
2.3Hz, 1H), 5.74 (d, J=2.4Hz, 1H), 4.73 (s, 1H), 3.65 (s, 2H)13C NMR(151MHz,CDCl3)δ
159.71,144.23,143.85,135.66,131.49,131.25,129.97,129.54,128.19,119.13,112.90,
112.08,55.17.Calc.for C15H16OSi+[M]+: 240, measured value: 240.
Effect example 6
The preparation of (1- (2- methoxyphenyl) vinyl) (phenyl) silane (TM-4a):
In nitrogen glove box, by complex compound 1-a (0.01mmol), 2- Methoxy-phenylacetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Silica gel column chromatography obtains colorless oil (yield 77%) using petroleum ether as eluant, eluent.1H
NMR(600MHz,CDCl3)δ7.52–7.48(m,1H),7.32–7.28(m,1H),7.27–7.23(m,1H),7.13–7.09
(m, 1H), 6.88-6.84 (m, 1H), 6.82-6.79 (m, 1H), 6.69 (dd, J=8.2,2.0Hz, 1H), 6.14 (d, J=
2.3Hz, 1H), 5.74 (d, J=2.4Hz, 1H), 4.73 (s, 1H), 3.65 (s, 2H)13C NMR(151MHz,CDCl3)δ
159.71,144.23,143.85,135.66,131.49,131.25,129.97,129.54,128.19,119.13,112.90,
112.08,55.17.Calc.for C15H16OSi+[M]+: 240, measured value: 240.
Effect example 7
The preparation of phenyl (1- (p-methylphenyl) vinyl) silane (TM-5a):
In nitrogen glove box, by complex compound 1-a (0.01mmol), 4- methyl phenylacetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Factually test reaction 5min.Silica gel column chromatography obtains colorless oil using petroleum ether as eluant, eluent
Object TM-5a (yield 88%).1H NMR(600MHz,CDCl3)δ7.52–7.48(m,1H),7.32–7.28(m,1H),7.27–
7.23 (m, 1H), 7.13-7.09 (m, 1H), 6.88-6.84 (m, 1H), 6.82-6.79 (m, 1H), 6.69 (dd, J=8.2,
2.0Hz, 1H), 6.14 (d, J=2.3Hz, 1H), 5.74 (d, J=2.4Hz, 1H), 4.73 (s, 1H), 3.65 (s, 2H)13C
NMR(151MHz,CDCl3)δ159.71,144.23,143.85,135.66,131.49,131.25,129.97,129.54,
128.19,119.13,112.90,112.08,55.17.Calc.forC15H16OSi+[M]+: 224, measured value: 224.
Effect example 8
The preparation of phenyl (1- (tolyl) vinyl) silane (TM-6a):
In nitrogen glove box, by complex compound 1-a (0.01mmol), 3- methyl phenylacetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Silica gel column chromatography obtains colorless oil compounds TM-6a and (produces using petroleum ether as eluant, eluent
Rate 83%).1H NMR(600MHz,CDCl3)δ7.52–7.48(m,1H),7.32–7.28(m,1H),7.27–7.23(m,1H),
7.13-7.09 (m, 1H), 6.88-6.84 (m, 1H), 6.82-6.79 (m, 1H), 6.69 (dd, J=8.2,2.0Hz, 1H), 6.14
(d, J=2.3Hz, 1H), 5.74 (d, J=2.4Hz, 1H), 4.73 (s, 1H), 3.65 (s, 2H)13C NMR(151MHz,
CDCl3)δ159.71,144.23,143.85,135.66,131.49,131.25,129.97,129.54,128.19,119.13,
112.90,112.08,55.17.Calc.forC15H16OSi+[M]+: 224, measured value: 224.
Effect example 9
The preparation of phenyl (1- (o-tolyl) vinyl) silane (TM-7a):
In nitrogen glove box, by complex compound 1-a (0.01mmol), 2- methyl phenylacetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Silica gel column chromatography obtains colorless oil compounds TM-7a and (produces using petroleum ether as eluant, eluent
Rate 84%).1H NMR(600MHz,CDCl3)δ7.52–7.48(m,1H),7.32–7.28(m,1H),7.27–7.23(m,1H),
7.13-7.09 (m, 1H), 6.88-6.84 (m, 1H), 6.82-6.79 (m, 1H), 6.69 (dd, J=8.2,2.0Hz, 1H), 6.14
(d, J=2.3Hz, 1H), 5.74 (d, J=2.4Hz, 1H), 4.73 (s, 1H), 3.65 (s, 2H)13C NMR(151MHz,
CDCl3)δ159.71,144.23,143.85,135.66,131.49,131.25,129.97,129.54,128.19,119.13,
112.90,112.08,55.17.Calc.forC15H16OSi+[M]+: 224, measured value: 224.
Effect example 10
3- (1- phenyl silicon substrate)-vinyl) pyridine (TM-8a) preparation:
In nitrogen glove box, by complex compound 1-a (0.01mmol), 3- pyridyl acetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Silica gel column chromatography obtains colorless oil with methylene chloride/petroleum ether (1:1) for eluant, eluent
Compound TM-8a (yield 57%).1H NMR(400MHz,CDCl3) δ 8.61 (s, 1H), 8.48 (d, J=2.8Hz, 1H), 7.64
(dt, J=7.9,1.7Hz, 1H), 7.59-7.54 (m, 2H), 7.44-7.33 (m, 3H), 7.23 (dd, J=7.8,4.8Hz,
1H), 6.26 (d, J=2.1Hz, 1H), 5.94 (d, J=2.1Hz, 1H), 4.83 (s, 2H)13C NMR(101MHz,CDCl3)δ
148.00,147.29,141.27,138.22,135.58,134.05,133.39,130.24,130.14,128.31,
123.46.GC-MS(EI):calcd.for C13H13NSi+[M]+: 211, measured value: 211.
Effect example 11:
Phenyl (1- (2- thienyl) vinyl) silane (TM-9a):
In nitrogen glove box, by complex compound 1-a (0.01mmol), 2- thiophene ethyl-acetylene (0.5mmol), phenylsilane
(0.5mmol) and 1mL dry tetrahydrofuran is added in 10mL Schleck pipe, and NaHBEt is then added3(0.03mmol,1M
In THF), 5min is reacted at room temperature.Silica gel column chromatography obtains colorless oil compounds TM-9a and (produces using petroleum ether as eluant, eluent
Rate 66%).1H NMR(400MHz,CDCl3) δ 7.69-7.66 (m, 2H), 7.49-7.38 (m, 3H), 7.20 (dd, J=5.1,
0.9Hz, 1H), 7.04 (dd, J=3.6,0.9Hz, 1H), 6.97 (dd, J=5.1,3.6Hz, 1H), 6.32 (d, J=1.5Hz,
1H), 5.70 (d, J=1.6Hz, 1H), 4.89 (s, 2H)13C NMR(101MHz,CDCl3)δ146.10,136.40,135.69,
130.60,130.15,128.87,128.26,127.60,125.93,124.54.GC-MS(EI):calcd.for C12H12SSi+
[M]+: 216, measured value: 216.
Claims (9)
1. a kind of NNN ligand compound indicated by general formula 1, structure are as follows:
Wherein, R1And R2It is each independently H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Aryl, institute
State substituted C6~C30Aryl in substituent group be one or more C1~C30Alkyl and/or C6~C30Aryl；
R simultaneously1And R2It is not simultaneously H atom；
Preferably, R1And R2It is each independently H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15Aryl,
The substituted C6~C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C10Alkyl or C substituted or unsubstituted6~C10Aryl, institute
State substituted C6~C10Aryl in substituent group be one or more methyl, ethyl, propyl, isopropyl, tert-butyl and/or C6
~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C6Alkyl or substituted or unsubstituted phenyl, the substitution
Phenyl in substituent group be one or more methyl, ethyl, propyl, isopropyl, tert-butyl and/or C6~C15Aryl；
Preferably, R1And R2Be each independently H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl,
Tert-butyl, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl,
Triethyl group phenyl or triisopropyl phenyl；
Preferably, R1And R2Pass through linking group-(CH2)nIt is connected to each other to form ring, the integer that wherein n is 0~6, when n is 0,
Indicate R1And R2It is bonded directly with one another；
R3For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~C15Virtue
Substituent group in base is one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R3For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, the substituted C6~
C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R3For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, the substitution in the substituted phenyl
Base is one or more C1~C4Alkyl；
Preferably, R3For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl, first
Base phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl or three
Isopropyl phenyl；
R4For H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Aryl, the substituted C6~C30Virtue
Substituent group in base is one or more C1~C30Alkyl and/or C6~C30Aryl；
Preferably, R4For H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~
C15Aryl in substituent group be one or more C1~C15Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~
C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, the substituted C6~
C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R4For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, the substitution in the substituted phenyl
Base is one or more C1~C4Alkyl；
Preferably, R4For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl, first
Base phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl or three
Isopropyl phenyl；
Wherein, work as R3For H, R1And R2When for isopropyl, R4It is not tert-butyl.
2. the preparation method of the NNN ligand compound according to claim 1 indicated by general formula 1, the preparation method by
Following formulas indicate and the following steps are included:
Step 1) in organic solvent, compound SM3It is reacted with N halosuccinimides, obtains compound SM2, the N is halogenated
Succinimide isStructure, wherein X is Cl, Br or I；
Step 2) in organic solvent, by compound SM2With organic amine R1R2NH carries out nucleophilic substitution, obtains compound SM1；
It is in step 3) organic solvent or solvent-free, under the conditions of acid is existing, by compound SM1With amine R4NH2It is anti-to carry out dehydrating condensation
It answers, obtains NNN ligand；
Wherein, R1、R2、R3、R4Definition with X is the same as described in general formula 1.
3. preparation method according to claim 2, which is characterized in that
In step 1),
The organic solvent is halogenated hydrocarbon solvent, further preferably carbon tetrachloride；
The compound SM3It is 1mg/mL~200mg/mL with the organic solvent mass ratio；
The reactant N halosuccinimides and the compound SM3Molar ratio be 1:1~1.1:1；
Preferably 0 DEG C~80 DEG C of the temperature of the halogenating reaction；
Reaction time preferred 2h~for 24 hours；
In step 2),
The preferred acetonitrile of the organic solvent, methylene chloride or tetrahydrofuran；
The compound SM2It is 1mg/mL~200mg/mL with the organic solvent mass ratio；
The R1R2NH and compound SM2Molar ratio be 1:1~3:1；
The temperature of the condensation reaction is 0 DEG C~80 DEG C；
Reaction time is 1h~for 24 hours；
In step 3),
The organic solvent is benzene and substituted benzene solvent, further preferably benzene or toluene；
The compound SM1Mass volume ratio with the organic solvent is 1mg/mL~200mg/mL；
The acid can be organic acid or inorganic acid；It is further preferred that the organic acid can be p-methyl benzenesulfonic acid, formic acid,
One or more in acetic acid, the inorganic acid can be sulfuric acid or hydrochloric acid；
The acid and the compound SM1Molar ratio be 0.01:1~0.2:1；
The R4NH2With the compound SM1Molar ratio be 1:1~3:1；
The temperature of the condensation reaction is 60 DEG C~reflux temperature；
Reaction time is 1h~48h.
4. a kind of Co-CNN complex compound, structural formula as shown in general formula 2 are as follows:
Wherein, R1And R2It is each independently H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Aryl, institute
State substituted C6~C30Aryl in substituent group be one or more C1~C30Alkyl and/or C6~C30Aryl；
R simultaneously1And R2It is not simultaneously H atom；
Preferably, R1And R2It is each independently H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15Aryl,
The substituted C6~C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C10Alkyl or C substituted or unsubstituted6~C10Aryl, institute
State substituted C6~C10Aryl in substituent group be one or more methyl, ethyl, propyl, isopropyl, tert-butyl and/or C6
~C15Aryl；
Preferably, R1And R2It is each independently H atom, C1~C6Alkyl or substituted or unsubstituted phenyl, the substitution
Phenyl in substituent group be one or more methyl, ethyl, propyl, isopropyl, tert-butyl and/or C6~C15Aryl；
Preferably, R1And R2Be each independently H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl,
Tert-butyl, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl,
Triethyl group phenyl or triisopropyl phenyl；
Preferably, R1And R2Pass through linking group-(CH2)nIt is connected to each other to form ring, the integer that wherein n is 0~6, when n is 0,
Indicate R1And R2It is bonded directly with one another；
R3For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~C15Virtue
Substituent group in base is one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R3For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, the substituted C6~
C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R3For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, the substitution in the substituted phenyl
Base is one or more C1~C4Alkyl；
Preferably, R3For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl, first
Base phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl or three
Isopropyl phenyl；
R4For H atom, C1~C30Alkyl or substituted or unsubstituted C6~C30Aryl, the substituted C6~C30Virtue
Substituent group in base is one or more C1~C30Alkyl and/or C6~C30Aryl；
Preferably, R4For H atom, C1~C15Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~
C15Aryl in substituent group be one or more C1~C15Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C10Alkyl or substituted or unsubstituted C6~C15Aryl, the substituted C6~
C15Aryl in substituent group be one or more C1~C6Alkyl and/or C6~C15Aryl；
Preferably, R4For H atom, C1~C6Alkyl or substituted or unsubstituted C6~C10Aryl, the substituted C6~
C10Aryl in substituent group be one or more C1~C4Alkyl；
Preferably, R4For H atom, C1~C4Alkyl or substituted or unsubstituted phenyl, the substitution in the substituted phenyl
Base is one or more C1~C4Alkyl；
Preferably, R4For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, phenyl, first
Base phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl or three
Isopropyl phenyl；
Wherein, work as R3For H, R1And R2When for isopropyl, R4It is not tert-butyl.
5. the preparation method of the Co-NNN complex compound according to claim 4 indicated by general formula 2, the preparation method by with
Lower reaction equation indicate and the following steps are included:
Under inert gas protection, in organic solvent by NNN ligand and CoX2It is reacted, obtains the NNN as shown in general formula 2
Ligand-Co complex compound, wherein R1、R2、R3And R4Definition with the definition in claim 1 formula of 1；
Preferably, in the preparation method:
Gas in the gas shield is one of nitrogen, argon gas, helium or a variety of；
The organic solvent is ether solvent, further preferred tetrahydrofuran；
The NNN ligand and the organic solvent mass ratio are 1mg/mL~200mg/mL；
The CoX2It is 0.8:1~1.2:1 with NNN ligand molar ratio；
The temperature of the reaction is 0 DEG C~100 DEG C；
Reaction time is 1h~48h.
6. application of the Co-NNN complex compound shown in general formula 2 in the silicon hydrogenation of catalysis alkynes according to claim 4.
7. it is a kind of be catalyzed alkynes silicon hydrogenation method, the method by following formulas indicate and the following steps are included:
Under gas shield, in organic solvent, under the action of the Co-NNN complex compound shown in general formula 2 according to the present invention, by alkynes
HydrocarbonWith silane R5R6R7SiH carries out addition reaction, obtains vinyl silane compound TM；
Wherein, R8For H atom；C1~C30Alkyl；Substituted or unsubstituted C6~C30Aryl, the substituted C6~C30's
Substituent group in aryl is one or more C1~C30Alkyl, C1~C30Alkoxy, halogen and/or C6~C30Aryl；
The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C30Heteroaryl；
Preferably, R8For H atom；C1~C10Alkyl；Substituted or unsubstituted C6~C15Aryl, the substituted C6~C15
Aryl in substituent group be one or more C1~C10Alkyl, C1~C10Alkoxy, halogen and/or C6~C15Virtue
Base；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C15Heteroaryl；
Preferably, R8For H atom；C1~C6Alkyl；Substituted or unsubstituted C6~C10Aryl, the substituted C6~C10
Aryl in substituent group be one or more C1~C6Alkyl, C1~C6Alkoxy, halogen and/or C6~C10Aryl；
The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C10Heteroaryl；
Preferably, R8For H atom；C1~C10Alkyl；Substituted or unsubstituted C6~C15Aryl, the substituted C6~C15
Aryl in substituent group be one or more C1~C10Alkyl, C1~C10Alkoxy, halogen and/or C6~C15Virtue
Base；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C16Heteroaryl；
Preferably, R8For H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, methoxyl group,
Ethyoxyl, propoxyl group, isopropoxy, butoxy, phenyl, aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, diethyl phenyl, two
Isopropyl phenyl, trimethylphenyl, triethyl group phenyl, triisopropyl phenyl, 1- xenyl, 2- xenyl, 3- xenyl, 1- naphthalene
Base, 2- naphthalene, 2- furyl, 3- furyl, 2- thienyl, 3- thienyl, 2- pyridyl group, 3- pyridyl group, 4- pyridyl group, 4- quinoline
Quinoline base, 8- quinolyl；
R5、R6、R7It is each independently H atom；C1~C30Alkyl；C1~C30Alkyl siloxy；Substituted or unsubstituted C6
~C30Aryl, the substituted C6~C30Aryl in substituent group be one or more C1~C30Alkyl, C1~C30's
Alkoxy, halogen and/or C6~C30Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C30It is miscellaneous
Aryl；
Preferably, R5、R6、R7It is each independently H atom；C1~C10Alkyl；C1~C10Alkyl siloxy；Replace or not
Substituted C6~C15Aryl, the substituted C6~C15Aryl in substituent group be one or more C1~C10Alkyl,
C1~C10Alkoxy, halogen and/or C6~C15Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35
~C15Heteroaryl；
Preferably, R5、R6、R7It is each independently H atom；C1~C6Alkyl；C1~C6Alkyl siloxy；Replace or does not take
The C in generation6~C10Aryl, the substituted C6~C10Aryl in substituent group be one or more C1~C6Alkyl, C1~
C6Alkoxy, halogen and/or C6~C10Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~C10
Heteroaryl；
Preferably, R5、R6、R7It is each independently H atom；C1~C6Alkyl；C1~C6Alkyl siloxy；Replace or does not take
The C in generation6~C15Aryl, the substituted C6~C15Aryl in substituent group be one or more C1~C10Alkyl, C1
~C10Alkoxy, halogen and/or C6~C15Aryl；The heteroatomic C of oxygen, sulphur or nitrogen-atoms is selected from containing 1 to 35~
C16Heteroaryl；
Preferably, R5、R6、R7It is each independently H atom, methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding
Base, tert-butyl, methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, phenyl, aminomethyl phenyl, ethylphenyl, dimethyl
Phenyl, diethyl phenyl, diisopropyl phenyl, trimethylphenyl, triethyl group phenyl, triisopropyl phenyl, three (trimethylsilane oxygen
Base) silane, three (trimethyl silicon substrate) silane, 2- furyl, 3- furyl, 2- thienyl, 3- thienyl, 2- pyridyl group, 3- pyrrole
Piperidinyl, 4- pyridyl group, 4- quinolyl, 8- quinolyl.
8. preparation method according to claim 7, which is characterized in that
The organic solvent is ether solvent, further preferred tetrahydrofuran or Isosorbide-5-Nitrae-dioxane；
Gas in the gas shield is one of nitrogen, argon gas, helium；
The R5R6R7SiH and the organic solvent mass ratio are 1mg/mL~200mg/mL；
NNN ligand-Co the complex compound and the alkynes indicated such as general formula 2Molar ratio be 0.001~0.1；
The alkynesWith the R5R6R7SiH molar ratio is 0.5:1~2:1；
The temperature of reaction is -80 DEG C~80 DEG C；Reaction time preferred 1s~for 24 hours.
9. preparation method according to claim 7, which is characterized in that selectively, the reaction exists in co-catalyst
Under conditions of carry out, the co-catalyst be sodium triethylborohydride (NaHBEt3), lithium methide (LiCH3), (trimethyl silane)
Methylate lithium (TMSCH2Li), potassium tert-butoxide, sodium tert-butoxide, preferably sodium triethylborohydride；The co-catalyst and the alkynes
HydrocarbonMolar ratio be 0.002~0.3.
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