CN106432001A - Synthesis method of dienyl sulfone compounds - Google Patents
Synthesis method of dienyl sulfone compounds Download PDFInfo
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- CN106432001A CN106432001A CN201610835232.8A CN201610835232A CN106432001A CN 106432001 A CN106432001 A CN 106432001A CN 201610835232 A CN201610835232 A CN 201610835232A CN 106432001 A CN106432001 A CN 106432001A
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- 0 CC(*)=CC=C(C=C)S(*)(=N)=N Chemical compound CC(*)=CC=C(C=C)S(*)(=N)=N 0.000 description 1
- MZQBHIMNXUATCF-KYPOTEAMSA-N CCC(C=C1)=CCC1S(C(C(CC1)=CC=C1Cl)=C=C(/C(/C)=C/C=C\C)/C(/C=C)=C/C=C)(=N)=O Chemical compound CCC(C=C1)=CCC1S(C(C(CC1)=CC=C1Cl)=C=C(/C(/C)=C/C=C\C)/C(/C=C)=C/C=C)(=N)=O MZQBHIMNXUATCF-KYPOTEAMSA-N 0.000 description 1
- INSUZSYHLALUCQ-UHFFFAOYSA-N CCc(cc1)ccc1S(N)(=C)=[U] Chemical compound CCc(cc1)ccc1S(N)(=C)=[U] INSUZSYHLALUCQ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
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Abstract
The invention relates to a synthesis method of dienyl sulfone compounds shown in a formula (IV) in the specification. The method comprises steps as follows: a compound shown in a formula (I), a compound shown in a formula (II) and a compound shown in a formula (III) react in an organic solvent in the presence of a compound catalyst, an oxidant, an aid and alkali, a compound shown in the formula (IV) is obtained through treatment after a reaction ends, wherein R1 and R2 are selected from H or halogen respectively and independently; R3 and R4 are selected from H, C1-C6 alkyl, C1-C6 alkoxy or halogen respectively and independently. According to the method, the purpose of promoting efficient conversion of materials is achieved through comprehensive coordination and promotion of specific reaction substrates and a catalytic reaction system, the good product, namely, the dienyl sulfone compound can be obtained, the process conditions are mild, and the method has broad market application prospect and industrial production potential.
Description
Technical field
The present invention relates to a kind of synthetic method of dialkylene sulfone compound, relate more particularly to dialkylene sulfone compound
Synthetic method, belong to organic chemical synthesis technical field.
Background technology
Diene class formation is the important synthesis precursor unit of many natural products and unnatural products, its unsaturation comprising
Double bond can carry out several functions modification, and purposes is quite varied, thus extensively should in conjugate addition and cycloaddition reaction
With this class formation not only shows efficient, single-minded reactivity, and sulfone class group also can be carried out by elimination reaction
Transformation.
Therefore, the high-efficiency synthesis method of exploitation dialkylene sulfone compound causes the strongly emerging of numerous research workers
Interest.
Up to the present, the multiple synthesis sides about being related to dialkylene sulfone compound have been occurred in that in prior art
Method, illustratively as follows：
(" the Cross-Coupling Reaction of Allenes with Aryl such as Fu Chunling
Halides.Synthesis of Polysubstituted 1,2-Allenyl Sulfones”,Or ganic Letters,
2005,7,1605-1607) report a kind of palladium chtalyst reacts, with aryl halide, the side that preparation replaces allene base sulfone compound
Method, its reaction equation is as follows：
Additionally, in recent years, about propiolic alcohol compound as synthon using also increasingly increasing, it is usually used in biology
Among the constructing of bioactive molecule, for example：
(" the Synthesis of Acrylonitriles through an FeCl3-Catalyz ed such as Hao Lu
Domino Propargylic Substitution/Aza-Meyer-Schuster Rearrangeme nt Sequence”,
Chem.Eur.J., 2012,18,6453-6456) report a kind of replacement of ferric trichloride catalytic, reset continuous reaction method,
Its reaction equation is as follows：
As above affiliated, disclose multiple synthetic methods of dialkylene sulfone compound in prior art.However, existing diene
The synthetic method of base sulfone compound still can not meet the demand of organic chemical synthesis technical field.
The invention provides a kind of synthetic method of allene base sulfone compound, the method is anti-using three unique components
Answer system, and coordinate the structure of the reaction system especially catalyst system and catalyzing of uniqueness, and reach the mesh promoting material high-efficiency conversion
, successfully allene base sulfone compound is obtained with high yield, and process conditions are gentle, shown the application of extensive market
Prospect.
Content of the invention
In order to seek the novel method for synthesizing of dialkylene sulfone compound, present inventor has performed in-depth study and spy
Rope, after having paid enough creative works, thus complete the present invention.
Specifically, technical scheme and content are related to dialkylene sulfone compound shown in a kind of lower formula (IV)
Synthetic method,
Methods described includes：In organic solvent and in the presence of composite catalyst, oxidant, auxiliary agent and alkali, lower formula (I)
Compound, formula (II) compound and formula (III) compound react, and react through post processing after terminating, thus obtaining described formula
(IV) compound,
Wherein, R1、R2It is each independently selected from H or halogen；
R3、R4It is each independently selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen.
In the described synthetic method of the present invention, described C1-C6The implication of alkyl refers to the straight chain with 1-6 carbon atom
Or branched alkyl, can be for example methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, uncle in non-limiting manner
Butyl, n-pentyl, isopentyl or n-hexyl etc..
In the described synthetic method of the present invention, described C1-C6Alkoxyl refers to there is C defined above1-C6Alkyl and O
The group that atom is directly connected to.
In the described synthetic method of the present invention, described halogen is fluorine, chlorine, bromine or iodine atom.
In the described synthetic method of the present invention, described composite catalyst is mol ratio 1:1 organo-nickel compounds and ten
The mixture of dicarbapentaborane three-iron.
Wherein, described organo-nickel compounds are two (triphenylphosphine) nickel chloride (NiCl2(PPh3)2), two (tricyclohexyl phosphines)
Nickel chloride (NiCl2(PCy3)2), double (1,5- cyclo-octadiene) nickel (Ni (COD)2) or nickel acetylacetonate (Ni (acac)2) in appoint
Meaning is a kind of, preferably two (tricyclohexyl phosphine) nickel chloride (NiCl2(PCy3)2) or double (1,5- cyclo-octadiene) nickel (Ni (COD)2),
Most preferably two (tricyclohexyl phosphine) nickel chloride (NiCl2(PCy3)2).
In the described synthetic method of the present invention, described oxidant is TBHP (TBHP), 2- iodoxy benzene
Formic acid (IBX), double (trifluoroacetic acid) iodobenzene (PhI (TFA)2) or iodobenzene diacetate (PhI (OAc)2) in any one, optimum
Elect double (trifluoroacetic acid) iodobenzene (PhI (TFA) as2).
In the described synthetic method of the present invention, described auxiliary agent is TFMS cuprous (CuOTf).
In the described synthetic method of the present invention, described alkali is NaOH, potassium tert-butoxide, diethanol amine, 1,8- diaza two
Ring 11 carbon -7- alkene (DBU) or N, any one in N- dimethylethanolamine (DMEA), most preferably N, N- dimethyl ethanol
Amine (DMEA).
In the described synthetic method of the present invention, described organic solvent is DMF (DMF), dimethyl is sub-
Any one in sulfone (DMSO), benzene, acetonitrile, polyethylene glycol 200 (PEG-200) or 1,4- dioxane or arbitrarily multiple mixing
Compound, most preferably volume ratio 1:2 N,N-dimethylformamide (DMF) and the mixture of polyethylene glycol 200 (PEG-200).
Wherein, the consumption of described organic solvent does not have strict restriction, and those skilled in the art can be according to actual conditions
Suitably selected and determined, to facilitate reaction to carry out and to post-process, here is no longer carried out in detail such as its consumption size
Thin description.
In the described synthetic method of the present invention, described formula (I) compound and formula (II) compound or formula (III) mole
Ratio is 1:1-2, for example, can be 1:1、1:1.5 or 1:2.
In the described synthetic method of the present invention, described formula (I) compound and composite catalyst (by organo-nickel compounds with
The total moles consumption sum meter of tri-iron dodecacarbonyl) mol ratio be 1:0.12-0.2, for example, can be 1:0.12、1:0.15、1:
0.18 or 1:0.2.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of oxidant:1.5-2.5,
Can be for example 1:1.5、1:2 or 1:2.5.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of auxiliary agent:0.08-0.14,
Can be for example 1:0.08、1:0.1、1:0.12 or 1:0.14.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of alkali:1.2-1.8, for example
Can be 1:1.2、1:1.4、1:1.6 or 1:1.8.
In the described synthetic method of the present invention, reaction temperature is 70-90 DEG C, for example, can be 70 DEG C, 80 DEG C or 90 DEG C.
In the described synthetic method of the present invention, the reaction time is 6-9 hour, for example, can be 6 hours, 7 hours, 8 hours
Or 9 hours.
In the described synthetic method of the present invention, the post processing after reaction terminates can be specific as follows：After reaction terminates, will be anti-
Answer liquid to filter while hot, the pH value adjusting filtrate, to neutral, is then fully washed with saturated aqueous common salt, add ethyl acetate extraction
2-3 time, merge organic phase, anhydrous sodium sulfate drying, reduced pressure concentration, gained residue crosses silica gel column chromatography, with equal-volume ratio
The mixed liquor of acetone and petroleum ether carries out drip washing, thus obtaining described formula (IV) compound.
In sum, the invention provides a kind of synthetic method of dialkylene sulfone compound, methods described is passed through specific
Reaction substrate and catalystic converter system synthesis work in coordination with and promote, thus reached promote material high-efficiency conversion purpose, can
Dialkylene sulfone compound is obtained with good product, and process conditions is gentle, show extensive market application foreground and
Industrial production potential.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, and not the real protection scope of the present invention is constituted with any type of any restriction, more non-general
Protection scope of the present invention is confined to this.
Wherein, in following all embodiments, the post processing after reaction terminates is all as follows：After reaction terminates, will react
Liquid filters while hot, and the pH value adjusting filtrate, to neutral, is then fully washed with saturated aqueous common salt, adds ethyl acetate extraction 2-
3 times, merge organic phase, anhydrous sodium sulfate drying, reduced pressure concentration, gained residue crosses silica gel column chromatography, with the third of equal-volume ratio
The mixed liquor of ketone and petroleum ether carries out drip washing, thus obtaining described formula (IV) compound.
Embodiment 1
Under room temperature, to appropriate organic solvent (for volume ratio 1:2 N,N-dimethylformamide is mixed with polyethylene glycol 200
Compound) in, add formula (I) compound, 100mmol upper formula (II) compound, 200mmol upper formula (III) chemical combination on 100mmol
Thing, 12mmol composite catalyst (for the mixture of 6mmol bis- (tricyclohexyl phosphine) nickel chloride and 6mmol tri-iron dodecacarbonyl),
Double (trifluoroacetic acid) iodobenzene (PhI (TFA) of 250mmol oxidant2), 8mmol auxiliary agent TFMS cuprous (CuOTf) and
180mmol alkali N, N- dimethylethanolamine (DMEA), then stirring is warming up to 70 DEG C, and stirring reaction 9 hours at such a temperature；
After reaction terminates, post-treated, obtain formula (IV) compound, yield is 95.5%.
1H NMR(CDCl3,400MHz):δ 7.68 (d, J=8.8Hz, 2H), 7.61-7.59 (m, 2H), 7.38-7.31 (m,
13H), 6.77 (d, J=8.8Hz, 2H), 3.81 (s, 3H).
Embodiment 2
Under room temperature, to appropriate organic solvent (for volume ratio 1:2 N,N-dimethylformamide is mixed with polyethylene glycol 200
Compound) in, add formula (I) compound, 200mmol upper formula (II) compound, 100mmol upper formula (III) chemical combination on 100mmol
The thing, (mixing for 10mmol bis- (tricyclohexyl phosphine) nickel chloride and 10mmol tri-iron dodecacarbonyl of 20mmol composite catalyst
Thing), double (trifluoroacetic acid) iodobenzene (PhI (TFA) of 150mmol oxidant2), 14mmol auxiliary agent TFMS cuprous (CuOTf)
With 120mmol alkali N, N- dimethylethanolamine (DMEA), then stirring is warming up to 90 DEG C, and stirring reaction 6 is little at such a temperature
When；
After reaction terminates, post-treated, obtain formula (IV) compound, yield is 95.8%.
1H NMR(CDCl3,400MHz):δ7.78-7.76(m,2H),7.58-7.57(m,2H),7.50-7.45(m,1H),
7.37-7.29(m,15H).
Embodiment 3
Under room temperature, to appropriate organic solvent (for volume ratio 1:2 N,N-dimethylformamide is mixed with polyethylene glycol 200
Compound) in, add formula (I) compound, 150mmol upper formula (II) compound, 150mmol upper formula (III) chemical combination on 100mmol
Thing, 16mmol composite catalyst (for the mixture of 8mmol bis- (tricyclohexyl phosphine) nickel chloride and 8mmol tri-iron dodecacarbonyl),
Double (trifluoroacetic acid) iodobenzene (PhI (TFA) of 200mmol oxidant2), 11mmol auxiliary agent TFMS cuprous (CuOTf) and
150mmol alkali N, N- dimethylethanolamine (DMEA), then stirring is warming up to 80 DEG C, and stirring reaction 7 hours at such a temperature；
After reaction terminates, post-treated, obtain formula (IV) compound, yield is 95.3%.
1H NMR(CDCl3,400MHz):δ7.85-7.83(m,4H),7.42-7.38(m,4H),7.37-7.34(m,8H),
7.09 (d, J=8.4Hz, 2H), 2.36 (s, 3H).
Embodiment 4
Under room temperature, to appropriate organic solvent (for volume ratio 1:2 N,N-dimethylformamide is mixed with polyethylene glycol 200
Compound) in, add formula (I) compound, 130mmol upper formula (II) compound, 180mmol upper formula (III) chemical combination on 100mmol
Thing, 18mmol composite catalyst (for the mixture of 9mmol bis- (tricyclohexyl phosphine) nickel chloride and 9mmol tri-iron dodecacarbonyl),
Double (trifluoroacetic acid) iodobenzene (PhI (TFA) of 220mmol oxidant2), 9mmol auxiliary agent TFMS cuprous (CuOTf) and
170mmol alkali N, N- dimethylethanolamine (DMEA), then stirring is warming up to 75 DEG C, and stirring reaction 8 hours at such a temperature；
After reaction terminates, post-treated, obtain formula (IV) compound, yield is 95.9%.
1H NMR(CDCl3,400MHz):δ 7.64 (d, J=8.4Hz, 2H), 7.41 (d, J=8.0Hz, 2H), 7.32-
7.28(m,6H),7.19-7.08(m,6H),2.41(s,3H).
Comparative example 1
Under room temperature, to appropriate organic solvent (for volume ratio 1:2 N,N-dimethylformamide is mixed with polyethylene glycol 200
Compound) in, add formula (I) compound, 150mmol upper formula (II) compound, 150mmol upper formula (III) chemical combination on 100mmol
Thing, 16mmol composite catalyst (for the mixture of 8mmol bis- (tricyclohexyl phosphine) nickel chloride and 8mmol tri-iron dodecacarbonyl),
Double (trifluoroacetic acid) iodobenzene (PhI (TFA) of 200mmol oxidant2), 11mmol auxiliary agent TFMS cuprous (CuOTf) and
150mmol alkali N, N- dimethylethanolamine (DMEA), then stirring is warming up to 80 DEG C, and stirring reaction 7 hours at such a temperature；
After reaction terminates, post-treated, obtain formula (IV) compound, yield is 74.6%.
1H NMR(CDCl3,400MHz):δ8.16-8.13(m,1H),7.66-7.64(m,2H),7.37-7.28(m,
15H),7.19-7.15(m,1H).
From above-mentioned comparative example 1, the substituent R in its Chinese style (III) compound4Ortho position positioned at sulfonamido
When, lead to products collection efficiency to be significantly reduced (compared with positioned at contraposition, such as embodiment 1,3-4).It is former that this is likely due to chlorine
When son is located at ortho position, due to the reason of strong sucting electronic effect, and the reactivity for sulfonamido has bigger impact, thus
Being passivated its reactivity, having led to react difficulty increasing, thus reducing yield.
The inventors discovered that, for this problem, significantly can be improved by adding activator, detailed content can
See in another patent application applied on the same day, be no longer described in detail here.
Below, in order to investigate the impact of each factor, embodiment 1-4 has been carried out repeat to test, thus having investigated synthesis
The impact of each technical characteristic in reaction system.
Embodiment 5-24：The impact of composite catalyst component
Embodiment 5-8：Using two (triphenylphosphine) nickel chloride (NiCl2(PPh3)2) replace two (tricyclohexyl phosphine) nickel chloride
(NiCl2(PCy3)2), other operation all sames, thus repeating to implement embodiment 1-4, sequentially obtain embodiment 5-8.
Embodiment 9-12：Using double (1,5- cyclo-octadiene) nickel (Ni (COD)2) replace two (tricyclohexyl phosphine) nickel chloride
(NiCl2(PCy3)2), other operation all sames, thus repeating to implement embodiment 1-4, sequentially obtain embodiment 9-12.
Embodiment 13-16：Using nickel acetylacetonate (Ni (acac)2) replace two (tricyclohexyl phosphine) nickel chloride (NiCl2
(PCy3)2), other operation all sames, thus repeating to implement embodiment 1-4, sequentially obtain embodiment 13-16.
Embodiment 17-20：The one-component two (tricyclohexyl phosphine) the use of consumption being the total consumption sum of original two kinds of components
Nickel chloride (NiCl2(PCy3)2), other operation all sames, thus repeating to implement embodiment 1-4, sequentially obtain embodiment 17-
20.
Embodiment 21-24：The one-component tri-iron dodecacarbonyl the use of consumption being the total consumption sum of original two kinds of components, its
It operates all same, thus repeating to implement embodiment 1-4, sequentially obtains embodiment 21-24.
Result see table 1.
Table 1
As can be seen here：1st, when using other organo-nickel compounds, products collection efficiency is all led to significantly reduce；2nd, when only
During using two (tricyclohexyl phosphine) nickel chloride, yield reduction becomes apparent from；3rd, when simply using tri-iron dodecacarbonyl, yield is anxious
Sharp fall as little as 10.4-11.6%, has had been out any potentiality of industrialized production.In conjunction with above-described embodiment 17-20,21-
24 result is visible, when simultaneously using two (tricyclohexyl phosphine) nickel chloride (NiCl2(PCy3)2) with the mixing of tri-iron dodecacarbonyl
When thing is as catalyst, create unexpected concerted catalysis effect between the two.
Embodiment 25-36：The impact of oxidant
Embodiment 25-28：Replace double (trifluoroacetic acid) iodobenzene (PhI (TFA) using TBHP (TBHP)2),
Other operation all sames, thus repeating to implement embodiment 1-4, sequentially obtain embodiment 25-28.
Embodiment 29-32：Replace double (trifluoroacetic acid) iodobenzene (PhI (TFA) using 2- iodosobenzoic acid (IBX)2), its
It operates all same, thus repeating to implement embodiment 1-4, sequentially obtains embodiment 29-32.
Embodiment 33-36：Using iodobenzene diacetate (PhI (OAc)2) replace double (trifluoroacetic acid) iodobenzene (PhI (TFA)2),
Other operation all sames, thus repeating to implement embodiment 1-4, sequentially obtain embodiment 33-36.
Experimental result is as shown in table 2 below.
Table 2
As can be seen here, for oxidant, even with double (trifluoroacetic acid) iodobenzene (PhI (TFA)2) very similar two
Acetic acid iodobenzene (PhI (OAc)2), products collection efficiency also has obvious reduction, and other oxidant then reduces and becomes apparent from.This proves
The selection of oxidant is non-obvious.
Embodiment 37-40：The impact of auxiliary agent
In addition to dispensing cuprous for auxiliary agent TFMS therein (CuOTf), other operation all sames, thus repeat to grasp
Make embodiment 1-4, obtain embodiment 37-40.It was found that the products collection efficiency of embodiment 37-40 is 88.5-89.3%, phase
Embodiment 1-4 is significantly reduced, this proves the use of TFMS cuprous (CuOTf), can significantly improve reaction
Effect, improves products collection efficiency further.
Embodiment 41-56：The impact of alkali
Embodiment 41-44：Replace N, N- dimethylethanolamine using NaOH, other operation all sames, thus repeat to implement
Embodiment 1-4, sequentially obtains embodiment 41-44.
Embodiment 45-48：Replace N, N- dimethylethanolamine using potassium tert-butoxide, other operation all sames, thus repeat
Implement embodiment 1-4, sequentially obtain embodiment 45-48.
Embodiment 49-52：Replace N, N- dimethylethanolamine using diethanol amine, other operation all sames, thus repeat
Implement embodiment 1-4, sequentially obtain embodiment 49-52.
Embodiment 53-56：Replace N, N- dimethylethanolamine using 1,8- diazabicylo 11 carbon -7- alkene (DBU)),
Other operation all sames, thus repeating to implement embodiment 1-4, sequentially obtain embodiment 53-56.
Result see table 3.
Table 3
As can be seen here：In all of alkali, DMEA can have the effect organized, other alkali, especially highly basic such as NaOH
Or DBU, result in and more significantly reduced.
Embodiment 57-80：The impact of organic solvent
Embodiment 57-60：Using single solvent DMF (DMF), other operation all sames, thus repeat
Implement embodiment 1-4, sequentially obtain embodiment 57-60.
Embodiment 61-64：Using single solvent dimethyl sulfoxide (DMSO) (DMSO), other operation all sames, thus repeat to implement
Embodiment 1-4, sequentially obtains embodiment 61-64.
Embodiment 65-68：Using single solvent benzene, other operation all sames, thus repeating to implement embodiment 1-4, suitable
Secondary obtain embodiment 65-68.
Embodiment 69-72：Using single solvent acetonitrile, other operation all sames, thus repeating to implement embodiment 1-4,
Sequentially obtain embodiment 69-72.
Embodiment 73-76：Using single solvent polyethylene glycol 200 (PEG-200), other operation all sames, thus repeat
Implement embodiment 1-4, sequentially obtain embodiment 73-76.
Embodiment 77-80：Using single solvent Isosorbide-5-Nitrae-dioxane, other operation all sames, thus repeat to implement reality
Apply a 1-4, sequentially obtain embodiment 77-80.
Result see table 4.
Table 4
As can be seen here：When using any single organic solvent, yield is all significantly reduced, especially acetonitrile and
PEG-200 reduces the most notable.But 1-4 is visible in conjunction with the embodiments, when the mixture using DMF and PEG-200, but achieve
Unexpected technique effect, this is unexpected.
In sum, the invention provides a kind of synthetic method of dialkylene sulfone compound, methods described is passed through specific
Reaction substrate and catalystic converter system synthesis work in coordination with and promote, thus reached promote material high-efficiency conversion purpose, can
Dialkylene sulfone compound is obtained with good product, and process conditions is gentle, show extensive market application foreground and
Industrial production potential.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents having read the present invention, those skilled in the art can make each to the present invention
Plant and change, change and/or modification, all these equivalent form of value equally falls within the guarantor that the application appended claims are limited
Within the scope of shield.
Claims (10)
1. the synthetic method of dialkylene sulfone compound shown in a kind of lower formula (IV),
Methods described includes：In organic solvent and in the presence of composite catalyst, oxidant, auxiliary agent and alkali, lower formula (I) chemical combination
Thing, formula (II) compound and formula (III) compound react, and react through post processing after terminating, thus obtaining described formula (IV)
Compound,
Wherein, R1、R2It is each independently selected from H or halogen；
R3、R4It is each independently selected from H, C1-C6Alkyl, C1-C6Alkoxy or halogen.
2. synthetic method as claimed in claim 1 it is characterised in that：Described composite catalyst is mol ratio 1:1 organic nickel
Compound and the mixture of tri-iron dodecacarbonyl；
Wherein, described organo-nickel compounds are two (triphenylphosphine) nickel chloride (NiCl2(PPh3)2), two (tricyclohexyl phosphine) chlorination
Nickel (NiCl2(PCy3)2), double (1,5- cyclo-octadiene) nickel (Ni (COD)2) or nickel acetylacetonate (Ni (acac)2) in any one
Kind, preferably two (tricyclohexyl phosphine) nickel chloride (NiCl2(PCy3)2) or double (1,5- cyclo-octadiene) nickel (Ni (COD)2), optimum
Elect two (tricyclohexyl phosphine) nickel chloride (NiCl as2(PCy3)2).
3. synthetic method as claimed in claim 1 or 2 it is characterised in that：Described oxidant is TBHP
(TBHP), 2- iodosobenzoic acid (IBX), double (trifluoroacetic acid) iodobenzene (PhI (TFA)2) or iodobenzene diacetate (PhI (OAc)2)
In any one, most preferably double (trifluoroacetic acid) iodobenzene (PhI (TFA)2).
4. the synthetic method as described in any one of claim 1-3 it is characterised in that：Described auxiliary agent is that TFMS is cuprous
(CuOTf).
5. the synthetic method as described in any one of claim 1-4 it is characterised in that：Described alkali is NaOH, potassium tert-butoxide, diethyl
Hydramine, 1,8- diazabicylo 11 carbon -7- alkene (DBU) or N, any one in N- dimethylethanolamine (DMEA), optimum
Elect N, N- dimethylethanolamine (DMEA) as.
6. the synthetic method as described in any one of claim 1-5 it is characterised in that：Described formula (I) compound is changed with formula (II)
The mol ratio of compound or formula (III) is 1:1-2.
7. the synthetic method as described in any one of claim 1-6 it is characterised in that：Described formula (I) compound and composite catalyzing
The mol ratio of agent is 1:0.12-0.2.
8. the synthetic method as described in any one of claim 1-7 it is characterised in that：Described formula (I) compound and oxidant
Mol ratio is 1:1.5-2.5.
9. the synthetic method as described in any one of claim 1-8 it is characterised in that：Described formula (I) compound is rubbed with auxiliary agent
That ratio is 1:0.08-0.14.
10. the synthetic method as described in any one of claim 1-9 it is characterised in that：Described formula (I) compound and alkali mole
Than for 1:1.2-1.8.
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Cited By (2)
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|---|---|---|---|---|
| CN113800998A (en) * | 2021-06-16 | 2021-12-17 | 浙江师范大学 | Preparation method of (2-bromoethynyl) benzene compound |
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