CN103570482B - A kind of 1,3-bis-replaces the preparation method of allenic compound - Google Patents
A kind of 1,3-bis-replaces the preparation method of allenic compound Download PDFInfo
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Abstract
The present invention provides a kind of 1,3-bis-replaces the preparation method of allenic compound, under the effect of alkali, under the catalysis of copper, the end alkynes of the hydrazone of alkyl aldehydes or aromatic base aldehyde and alkyl or aromatic base replacement reacts in organic solvent, it reaction vessel is inert atmosphere, being heated by oil bath or other modes, reacted within 1 hour, product uses sand core funnel to filter at reduced pressure, adopt the method for normal pressure or underpressure distillation to concentrate, obtained the product of purifying by column chromatography. The coupling that the present invention achieves the end alkynes that the derivative hydrazone of alkyl aldehydes or aromatic base aldehyde and alkyl or aromatic base replace the first preparation 1,3-bis-that is converted replaces connection alkene, and functional group has good tolerance, reaction efficiency height, preparation cost is low, extensively can replace connection alkene for the preparation of 1,3-bis-.
Description
Technical field
The invention belongs to organic synthesis field, particularly relate to the preparation method that a kind of 1,3-bis-replaces allenic compound.
Background technology
1,3-bis-replaces allenic compound important status in organic synthesis, is widely used in the middle of scientific research. In scientific research, 1,3-bis-replaces allenic compound and is mainly used in organic synthesis, and they as molecular building block, can participate in organic chemical reactions of a great variety and build comparatively complicated target compound; The axial chirality that 1,3-bis-replaces connection alkene its central carbon atom all right participates in catalysis induction asymmetric synthesis. All the time, the synthetic method of 1,3-bis-substitution compound is carried out constantly Improvement and perfection by people. In synthetic method known at present, major part all prepares aromatic boronic acid ester composite by following two kinds of methods: one, by aldehyde, and end alkynes and amine obtain 1,3-bis-under the promotion or catalysis of zinc, copper and replaces connection alkene1; Two, under the catalysis of Grubbs catalyzer, obtain 1,3-bis-by the method for olefin metathesis and replace connection alkene2; Three, enamine and end alkynes obtain 1,3-bis-replacement connection alkene under gold catalysis3. The shortcoming of these methods is: (1) system is comparatively complicated, and in required catalyst system, additive is many. (2) latter two method is with precious metal as catalyzer, increases cost, and easily brings pollution in last handling process. (3) the third method complicated operation, can only carry out micro-reaction in nuclear magnetic tube, cannot amplify application.
Summary of the invention
It is an object of the invention to provide the preparation method that a kind of efficiently easy 1,3-bis-replaces allenic compound, the method has and compares substrate adaptability widely, can synthesize numerous 1,3-bis-with different substituents by the method and replace allenic compound.
The technical scheme of the inventive method is as follows:
1,3-bis-replaces a preparation method for allenic compound, and the end alkynes of the hydrazone that alkyl aldehydes or aromatic base aldehyde derive and alkyl or aromatic base is obtained by reacting 1,3-bis-under the catalysis of copper under the effect of alkali in organic solvent and replaces allenic compound.
Functional group is had good tolerance by the method for the present invention, and the hydrazone of aromatic base aldehyde can with one or more substituting group, and the hydrazone of alkyl aldehydes can be straight chain, side chain or band aromatic base; The end alkynes participating in reaction can be replaced by aromatic base or alkyl. Described substituting group limits never in any form, and common substituting group is alkyl, aromatic base, alkoxyl group, amido, ester group, nitro and halogen etc. such as. Can with one or more in these substituting groups on described aromatic base, when having multiple substituting group, this multiple substituting group can be identical or different.
The preferred Tosylhydrazone of hydrazone that abovementioned alkyl aldehyde or aromatic base aldehyde derive.
Abovementioned alkyl preferably refers to have the alkyl of 1��10 carbon atom, such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, sec-butyl, amyl group, neo-pentyl, styroyl, hydrocinnamyl etc., it is more preferable to methyl, the tertiary butyl.
Above-mentioned alkoxyl group preferably refers to have the alkoxyl group of 1��10 carbon atom, such as methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, sec-butoxy, allyloxy etc.; More preferably there is the alkoxyl group of 1��4 carbon atom, it is particularly preferred to methoxyl group and allyloxy.
Above-mentioned ester group is formic acid ester group, acetate groups, propionic acid ester group and butyric acid ester group etc. such as.
Above-mentioned amido is amido, N, N-dimethyl amido etc.
Above-mentioned halogen refers to fluorine, chlorine, bromine atoms.
In the method for the present invention, described 1,3-bis-replaces the allenic compound connection alkene that preferably two aromatic bases or alkyl replace.
In the method for the present invention, described alkali is that 1,3-bis-replaces allenic compound sodium hydroxide, sodium hydride or metal alkoxide, it is preferable that metal alkoxide is sodium methylate such as, trimethyl carbinol lithium, it is particularly preferred to trimethyl carbinol lithium.
In the method for the present invention, described solvent is toluene, acetonitrile, 1,2-ethylene dichloride and ether solvent, it is preferable that ether solvent is 1,4-dioxane such as. Its consumption is preferably 10��12.5mL/mmol end alkynes.
When described 1,3-bis-replaces the connection alkene that allenic compound is two aromatic bases or alkyl replacement, the reaction formula of the inventive method can be expressed as follows:
Wherein, formula I represents Tosylhydrazone, and formula II compound is end alkynes, and formula III compounds represented 1,3-bis-replaces connection alkene.
The inventive method copper catalyst can adopt monovalence mantoquita, it is preferable that CuI. Useful commercial reagent, it is not necessary to special processing. Its consumption is preferably based on the 20% of described end alkynes.
The inventive method two kinds of preferred molar ratios of reactant are hydrazone: end alkynes=1.5:1��2.5: 1.
The temperature of reaction of above-mentioned reaction and reaction times are within one hour. Temperature of reaction is generally in the scope of 70 DEG C to 110 DEG C. Heat-processed can adopt oil bath (such as silicone oil, paraffin oil etc.) or other type of heating.
Reaction product is preferably carried out aftertreatment by the present invention after completion of the reaction, comprises and takes out filter, concentrated and purifying.
Described filtration journey of taking out can use sand core funnel to filter at reduced pressure.
Described concentration process can adopt the method such as air distillation, underpressure distillation, such as, concentrate with rotavapor under vacuum.
Described purge process obtains pure product by column chromatography.
The method of the present invention achieves the end alkynes coupling that the derivative hydrazone of alkyl aldehydes or aromatic base aldehyde and alkyl or aromatic base replace first and transforms and obtain 1,3-bis-and replace connection alkene, and reaction efficiency height, preparation cost is low, extensively can replace allenic compound for the preparation of 1,3-bis-. Compared to the prior art, the present invention has following advantage:
1, main raw material involved in the present invention is the hydrazone that alkyl aldehydes or aromatic base aldehyde derive, and this raw material can be prepared easily via aldehyde and the hydrazine of alkyl or aromatic base, and cheap, it is not necessary to complex operations;
2, the copper salt that the catalyzer that reaction involved by the inventive method uses is cheapness, uses Grubbs catalyzer or gold complex etc. to be important supplementing as catalyzer compared to coupling before or rearrangement reaction;
3, functional group is had good tolerance and universality by reaction involved by the inventive method, substituting group on aromatic base can be alkyl, alkoxyl group, ester group, nitro, cyano group and halogen atom (F, Cl, Br) etc., and the alkyl of various straight or branched can also complete reaction.
Embodiment
The present invention is further described below in conjunction with embodiment, but the protection domain not limited the present invention in any way.
Embodiment 1
1,3-phenylbenzene connects the synthesis of diene
275mg (i.e. 1.0mmol) phenyl aldehyde Tosylhydrazone is added, 120mg (i.e. 1.5mmol) trimethyl carbinol lithium, 11.46mg (i.e. 0.06mmol) cuprous iodide, 5mL1,2-ethylene dichloride in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into inert gas environment after sealing in system, such as nitrogen environment, add 41mg (i.e. 0.4mmol) phenylacetylene, react at 90 DEG C 1 hour (being heated by oil bath (such as such as silicone oil, paraffin oil etc.) or alternate manner), take out the solid insoluble in the system of filtering after reaction, it may also be useful to Rotary Evaporators concentrating under reduced pressure, do eluent column chromatography purification with sherwood oil and can obtain 1,3-phenylbenzene connects diene, and its structure is shown below:
This compound is colourless liquid, and product rate is 78%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.50 (s, 2H), 7.11-7.14 (m, 2H), 7.20-7.27 (m, 8H);13CNMR(100MHz,CDCl3)��98.4,127.0,127.3,128.7,133.6,207.8��
Embodiment 2
1-(3-methyl) phenyl-3-phenyl connects the synthesis of diene
254mg (i.e. 0.88mmol) 3-tolyl aldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-(3-methyl) phenyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 67%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 2.23 (s, 3H), 6.45-6.50 (m, 2H), 6.94-6.98 (m, 1H), 7.05-7.14 (m, 4H), 7.20-7.28 (m, 4H);13CNMR(100MHz,CDCl3) �� 21.3,98.3,98.4,124.2,127.0,127.2,127.6,128.2,128.6,128.7,133.4,133.7,138.4,207.7; IR (film, cm-1)3027,1937,1603,1410,1261,798,695,667��
Embodiment 3
1-phenmethyl-3-phenyl connects the synthesis of diene
218mg (i.e. 0.72mmol) phenylacetic aldehyde Tosylhydrazone is added, 96mg (i.e. 1.2mmol) trimethyl carbinol lithium, 19.1mg (i.e. 0.10mmol) cuprous iodide, 4.5mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 0.75 hour at 110 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-phenmethyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 48%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 3.40 (dd, J=2.4Hz, J=7.2Hz, 2H), 5.65 (dd, J=7.2, J=13.9Hz, 1H), 6.09-6.12 (m, 1H), 7.10-7.16 (m, 2H), 7.19-7.26 (m, 8H);13CNMR(100MHz,CDCl3)��35.6,94.4,94.9,126.3,126.7,126.8,128.5,128.6,134.6,140.0,205.7��
Embodiment 4
1-(4-cyano group) phenyl-3-phenyl connects the synthesis of diene
275mg (i.e. 0.92mmol) 4-cyanobenzaldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5.5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, taking sherwood oil: ethyl acetate is done eluent column chromatography purification as 30:1 (volume ratio) and can be obtained 1-(4-cyano group) phenyl-3-phenyl and connect diene, and its structure is shown below:
This compound is slightly yellow liquid, product rate 65%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.56 (d, J=6.4Hz, 1H), 6.60 (d, J=6.4Hz, 1H), 7.17-7.20 (m, 1H), 7.25 (d, J=4.4Hz, 4H), 7.34 (d, J=8.4Hz, 2H), 7.50 (d, J=8.4Hz, 2H);13CNMR(100MHz,CDCl3)��97.6,99.3,110.5,118.9,127.1,127.4,127.8,128.9,132.3,132.5,138.8,209.2��
Embodiment 5
1-(2-allyloxy) phenyl-3-phenyl connects the synthesis of diene
290mg (i.e. 0.88mmol) 2-alkene third oxygen phenyl aldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, taking sherwood oil: ethyl acetate is done eluent column chromatography purification as 30:1 (volume ratio) and can be obtained 1-(2-allyloxy) phenyl-3-phenyl and connect diene, and its structure is shown below:
This compound is colourless liquid, product rate 63%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 4.48 (d, J=5.2Hz, 2H), 5.18 (dd, J=1.2Hz, J=10.8Hz, 1H), 5.34 (dd, J=1.6Hz, J=17.2Hz, 1H), 5.92-6.02 (m, 1H), 6.47 (d, J=6.8Hz, 1H), 6.77-6.82 (m, 2H), 6.96 (d, J=6.8Hz, 1H), 7.06-7.13 (m, 2H), 7.19-7.33 (m, 5H);13CNMR(100MHz,CDCl3)��69.3,92.5,97.8,112.5,117.4,121.0,122.3,126.9,127.0,128.0,128.3,128.6,133.3,134.0,155.2,208.3��
Embodiment 6
1-(4-phenyl) phenyl-3-phenyl connects the synthesis of diene
308mg (i.e. 0.88mmol) 4-phenyl phenyl aldehyde aldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-(4-phenyl) phenyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 55%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.52 (s, 2H), 7.19-7.34 (m, 10H), 7.44-7.49 (m, 4H);13CNMR(100MHz,CDCl3)��98.1,98.5,126.9,127.0,127.2,127.3,127.4,127.45,128.7,132.6,133.5,140.2,140.7,208.1��
Embodiment 7
1-(3-nitro) phenyl-3-phenyl connects the synthesis of diene
281mg (i.e. 0.88mmol) 3-nitrobenzaldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, taking sherwood oil: ethyl acetate is done eluent column chromatography purification as 30:1 (volume ratio) and can be obtained 1-(3-nitro) phenyl-3-phenyl and connect diene, and its structure is shown below:
This compound is weak yellow liquid, product rate 40%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.57 (d, J=6.4Hz, 1H), 6.62 (d, J=6.4Hz, 1H), 7.17-7.20 (m, 1H), 7.24-7.27 (m, 4H), 7.39 (t, J=8.0Hz, 1H), 7.58 (d, J=7.6Hz, 1H), 7.98 (d, J=8.0Hz, 1H), 8.09 (s, 1H);13CNMR(100MHz,CDCl3)��97.0,99.5,121.5,122.0,127.2,127.8,128.9,129.5,132.5,132.6,135.9,148.7,208.4��
Embodiment 8
1-(3,5-dimethoxy) phenyl-3-phenyl connects the synthesis of diene
294mg (i.e. 0.88mmol) 3 is added in the long pipe type reaction tubes of 25mL, 5-dimethoxy benzaldehyde Tosylhydrazone, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, taking sherwood oil: ethyl acetate is done eluent column chromatography purification as 30:1 (volume ratio) and can be obtained 1-(3,5-dimethoxy) phenyl-3-phenyl and connect diene, and its structure is shown below:
This compound is slightly weak yellow liquid, product rate 56%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 3.69 (s, 6H), 6.28 (t, J=2.0Hz, 1H), 6.44-6.46 (m, 3H), 6.52 (d, J=6.4Hz, 1H), 7.13-7.17 (m, 1H), 7.22-7.28 (m, 4H);13CNMR(100MHz,CDCl3)��1.0,55.3,98.6,99.7,105.0,127.0,127.3,128.7,133.5,135.7,161.0,207.9��
Embodiment 9
2-second oxygen acyl p-methoxy-phenyl-3-phenyl connects the synthesis of diene
334mg (i.e. 0.88mmol) 2-second oxygen acyl methoxybenzaldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, taking sherwood oil: ethyl acetate is done eluent column chromatography purification as 20:1 (volume ratio) and can be obtained 2-second oxygen acyl p-methoxy-phenyl-3-phenyl and connect diene, and its structure is shown below:
This compound is slightly weak yellow liquid, product rate 55%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 1.22 (t, J=7.2Hz, 3H), 4.18 (q, J=7.2Hz, 2H), 4.58 (s, 2H), 6.49 (d, J=6.8Hz, 1H), 6.70 (d, J=8.4Hz, 1H), 6.85 (t, J=7.2Hz, 1H), 7.02 (d, J=6.8Hz, 1H), 7.06-7.15 (m, 2H), 7.20-7.28 (m, 4H), 7.35 (dd, J=1.2andJ=7.6Hz, 1H);13CNMR(100MHz,CDCl3)��14.1,61.3,66.1,92.4,97.9,112.5,122.0,122.8,126.9,127.1,128.2,128.3,128.6,133.8,154.5,168.8,208.3��
Embodiment 10
1-styroyl-3-phenyl connects the synthesis of diene
278mg (i.e. 0.88mmol) phenylpropyl aldehyde Tosylhydrazone is added, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 4mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 0.5 hour at 110 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-styroyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 77%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 2.30-2.40 (m, 2H), 2.64-2.75 (m, 2H), 5.48 (q, J=6.4Hz, 1H), 6.01 (t, J=2.8Hz, 1H), 7.05-7.20 (m, 10H);13CNMR(100MHz,CDCl3)��30.5,35.3,94.3,94.9,125.9,126.5,126.6,128.3,128.4,128.5,134.8,141.5,205.2.
Embodiment 11
1-(3,4-bis-chlorine) phenyl-3-phenyl connects the synthesis of diene
390mg (i.e. 0.88mmol) 3 is added in the long pipe type reaction tubes of 25mL, 4-dichlorobenzaldehyde Tosylhydrazone, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-(3,4-bis-chlorine) phenyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 70%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.41 (d, J=6.4Hz, 1H), 6.54 (d, J=6.4Hz, 1H), (dd, J=1.6Hz, J=8.4Hz, 1H), 7.15-7.18 (m, 1H), 7.24-7.28 (m, 5H), 7.32 (d, J=1.6Hz, 1H);13CNMR(100MHz,CDCl3)��96.8,99.2,126.1,127.1,127.7,128.5,128.8,130.6,130.9,132.7,132.8,133.9,208.1��
Embodiment 12
1-(4-bromine) phenyl-3-phenyl connects the synthesis of diene
312mg (i.e. 0.88mmol) 4-bromobenzaldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-(4-bromine) phenyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 67%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.46 (d, J=6.4Hz, 1H), 6.51 (d, J=6.4Hz, 1H), 7.12-7.17 (m, 3H), 7.22-7.29 (m, 4H), 7.35 (d, J=8.4Hz, 2H);13CNMR(100MHz,CDCl3)��97.6,98.8,121.0,127.0,127.5,128.5,128.8,131.8,132.6,133.1,207.9��
Embodiment 13
1-(4-fluorine) phenyl-3-phenyl connects the synthesis of diene
242mg (i.e. 0.88mmol) phenyl aldehyde Tosylhydrazone is added, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 48mg (i.e. 0.4mmol) 4-fluorobenzene acetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-(4-fluorine) phenyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 66%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.50 (q, J=6.5Hz, 2H), 6.92 (t, J=8.0Hz, 2H), 7.13-7.16 (m, 1H), 7.21-7.27 (m, 6H);13CNMR(100MHz,CDCl3)��94.4,98.6,115.6,115.8,127.0,127.4,128.4,128.5,128.8,133.4,207.5��
Embodiment 14
1-phenyl-3-the tertiary butyl connects the synthesis of diene
The special valeral Tosylhydrazone of 204mg (i.e. 0.8mmol) is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 4.5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 0.6 hour at 110 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain the 1-phenyl-3-tertiary butyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 80%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 1.05 (s, 9H), 5.49 (d, J=6.4, Hz, 1H), 6.10 (d, J=6.4Hz, 1H), 7.08-7.11 (m, 1H), 7.21 (d, J=4.4Hz, 4H);13CNMR(100MHz,CDCl3)��30.3,32.7,96.2,106.9,126.4,126.6,128.5,135.3,202.4��
Embodiment 15
1-naphthalene-3-phenyl connects the synthesis of diene
285mg (i.e. 0.88mmol) naphthaldehyde Tosylhydrazone is added, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 70 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-naphthalene-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 68%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.58 (d, J=6.4Hz, 1H), 6.68 (d, J=6.4Hz, 1H), 7.15-7.44 (m, 8H), 7.65-7.71 (m, 4H);13CNMR(100MHz,CDCl3)��98.6,98.8,124.8,125.8,125.9,126.3,127.0,127.4,127.7,128.4,128.8,131.1,132.8,133.6,133.7,208.4��
Embodiment 16
1-phenyl-3-cyclohexyl connects the synthesis of diene
246mg (i.e. 0.88mmol) hexahydrobenzaldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 30.56mg (i.e. 0.16mmol) cuprous iodide, 5mL1,4-tetrahydrofuran (THF). Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 0.75 hour at 110 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-phenyl-3-cyclohexyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 45%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 1.11-1.27 (m, 5H), 1.55-1.78 (m, 5H), 2.05 (s, 1H), 5.49 (t, J=6.0Hz, 1H), 6.06-6.08 (m, 1H), 7.09-7.22 (m, 5H);13CNMR(100MHz,CDCl3)��26.0,26.1,33.1,33.2,37.6,95.4,101.0,126.4,126.6,128.5,135.2,204.1.
Embodiment 17
The own base of 1-phenyl-3-connects the synthesis of diene
242mg (i.e. 0.88mmol) phenyl aldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 75.6mg (i.e. 1.4mmol) sodium methylate, 15.28mg (i.e. 0.08mmol) cuprous iodide, 4.5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 45mg (i.e. 0.4mmol) 1-octyne, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain the 1-own base of phenyl-3-and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 63%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 0.80 (t, J=6.8Hz, 3H), 1.18-1.32 (m, 6H), 1.35-1.44 (m, 2H), 2.04 (dq, J=3.0Hz, J=7.1Hz, 2H), 5.48 (q, J=6.8Hz, 1H), 6.04 (td, J=2.9Hz, J=6.1Hz, 1H), 7.07-7.12 (m, 1H), 7.21 (d, J=4.4Hz, 4H);13CNMR(100MHz,CDCl3)��14.0,22.6,28.8,28.9,29.1,31.6,64.5,95.1,126.6,128.5,135.2,205.1��
Embodiment 18
1-phenyl-3-(2 naphthalene) ethyl connects the synthesis of diene
310mg (i.e. 0.88mmol) 2-naphthalene acetaldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 41mg (i.e. 0.4mmol) phenylacetylene, react 1 hour at 110 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-phenyl-3-(2 naphthalene) ethyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 68%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 2.44-2.51 (m, 2H), 3.15 (t, J=7.7Hz, 2H), 5.55 (dd, J=6.6Hz, J=13.1Hz, 1H), 6.05 (td, J=2.8Hz, J=6.0Hz, 1H), 7.04-7.38 (m, 9H), 7.61 (d, J=7.6Hz, 1H), 7.73 (d, J=7.6Hz, 1H), 7.92 (d, J=8.1Hz, 1H);13CNMR(100MHz,CDCl3)��29.8,32.5,94.5,95.2,123.7,125.4,125.5,125.8,126.2,126.6,126.7,126.8,128.5,128.7,131.8,133.9,134.8,137.6,205.2��
Embodiment 19
1-(the 4-tertiary butyl) phenyl-3-phenyl connects the synthesis of diene
242mg (i.e. 0.88mmol) phenyl aldehyde Tosylhydrazone is added, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 63mg (i.e. 0.4mmol) 4-tert.-butylbenzene acetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-(the 4-tertiary butyl) phenyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 61%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 1.23 (s, 9H), 6.50 (s, 2H), 7.16-7.26 (m, 9H);13CNMR(100MHz,CDCl3)��31.3,34.6,98.1,98.3,125.7,126.7,127.0,127.2,128.7,130.6,133.8,150.5,207.8.
Embodiment 20
1-(3-methyl) phenyl-3-tertiary butyl connects the synthesis of diene
254mg (i.e. 0.88mmol) 3-tolyl aldehyde Tosylhydrazone is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 33mg (i.e. 0.4mmol) 3,3-dimethyl-ethyl acetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, using Rotary Evaporators concentrating under reduced pressure, do eluent column chromatography purification with sherwood oil and can obtain 1-(3-methyl) phenyl-3-tertiary butyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 42%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 1.05 (s, 9H), 2.25 (s, 3H), 5.48 (d, J=6.4Hz, 1H), 6.08 (d, J=6.4Hz, 1H), 6.92 (d, J=7.6Hz, 1H), 7.02 (d, J=6.0Hz, 2H), 7.09-7.16 (m, 1H);13CNMR(100MHz,CDCl3)��21.4,30.3,32.7,96.2,106.8,123.5,127.1,127.4,128.4,135.2,138.1,202.4.
Embodiment 21
1-(4-trifluoromethyl) phenyl-3-phenyl connects the synthesis of diene
242mg (i.e. 0.88mmol) phenyl aldehyde Tosylhydrazone is added, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 68mg (i.e. 0.4mmol) 4-trifluoromethyl phenylacetylene, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-(4-trifluoromethyl) phenyl-3-phenyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 60%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.54 (dd, J=7.4Hz, J=17.5Hz, 2H), 7.09-7.18 (m, 4H), 7.23-7.25 (m, 3H), 7.34 (d, J=8.0Hz, 1H), 7.46 (d, J=8.0Hz, 1H);13CNMR(100MHz,CDCl3)��97.6,99.0,125.6,125.7,127.1,127.7,128.2,128.9,130.3,132.9,137.3,208.7��
Embodiment 22
1-styroyl-3-butyl connects the synthesis of diene
186mg (i.e. 0.6mmol) phenylpropyl aldehyde Tosylhydrazone is added, 88mg (i.e. 1.1mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 4mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add the own alkynes of 34mg (i.e. 0.4mmol) 1-, react 0.6 hour at 110 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-styroyl-2-normal-butyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 82%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 0.81 (t, J=6.8Hz, 3H), 1.23-1.28 (m, 4H), 1.84-1.90 (m, 2H), 2.19-2.25 (m, 2H), (2.64 t, J=7.8Hz, 2H), 4.97-5.07 (m, 2H), 7.07-7.21 (m, 5H);13CNMR(100MHz,CDCl3)��13.9,22.1,28.6,30.7,31.3,35.5,90.2,91.5,125.7,128.2,128.5,141.9,204.0��
Embodiment 23
1-styroyl-3-the tertiary butyl connects the synthesis of diene
The special valeral Tosylhydrazone of 224mg (i.e. 0.88mmol) is added in the long pipe type reaction tubes of 25mL, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 30mg (i.e. 0.08mmol) four acetonitrile six fluorine phosphine copper, 5mL1,4-dioxane. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 52mg (i.e. 0.4mmol) 4-phenyl-ethyl acetylene, react 1 hour at 110 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain the 1-styroyl-3-tertiary butyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 89%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 0.93 (s, 9H), 2.20-2.26 (m, 2H), 2.63 (t, J=8.0Hz, 2H), 5.03 (td, J=3.0Hz, J=6.2Hz, 1H), 5.12 (q, J=6.4Hz, 1H), 7.07-7.21 (m, 5H);13CNMR(100MHz,CDCl3)��30.2,30.9,31.7,35.5,92.1,103.5,125.8,128.3,128.5,142.0,201.1.
Embodiment 24
1-phenyl-3-butyl connects the synthesis of diene
242mg (i.e. 0.88mmol) phenyl aldehyde Tosylhydrazone is added, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 34 (i.e. 0.4mmol) own alkynes of mg1-, react 1 hour at 90 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil to obtain 1-phenyl-3-butyl and connect diene, its structure is shown below:
This compound is colourless liquid, product rate 66%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 0.84 (t, J=7.2Hz, 3H), 1.29-1.46 (m, 4H), 2.06 (dq, J=3.0Hz, J=7.1Hz, 2H), 5.49 (q, J=6.8Hz, 1H), 6.04 (td, J=3.0Hz, J=6.2Hz, 1H), 7.09-7.12 (m, 1H), 7.21 (d, J=4.4, Hz, 4H);13CNMR(100MHz,CDCl3)��13.9,22.2,28.4,31.3,94.5,95.1,126.5,126.6,128.5,135.1,205.1��
Embodiment 25
1-(3-thiophene) base-3-(2-naphthalene) connects the synthesis of diene
285mg (i.e. 0.88mmol) naphthaldehyde Tosylhydrazone is added, 112mg (i.e. 1.4mmol) trimethyl carbinol lithium, 15.28mg (i.e. 0.08mmol) cuprous iodide, 5mL1,4-dioxane in the long pipe type reaction tubes of 25mL. Reaction tubes will be replaced into nitrogen environment after sealing in system, add 43mg (i.e. 0.4mmol) 3-ethynyl thiophene, react 1 hour at 70 DEG C, the solid insoluble in the system of filtering is taken out after reaction, use Rotary Evaporators concentrating under reduced pressure, doing eluent column chromatography purification with sherwood oil and can obtain 1-(3-thiophene) base-3-(2-naphthalene) even diene, its structure is shown below:
This compound is weak yellow liquid, product rate 58%, and its nuclear magnetic data is as follows:
1HNMR(400MHz,CDCl3) �� 6.61 (dd, J=6.4Hz, J=14.4Hz, 1H), 6.74 (s, 1H), 7.02-7.16 (m, 1H), 2.26-7.24 (m, 3H), 7.52 (d, J=8.4Hz, 1H), 7.60-7.68 (m, 4H);13CNMR(100MHz,CDCl3)��93.15,98.0,121.5,124.8,125.8,125.9,126.0,126.4,127.0,127.5,127.6,127.7,128.0,128.1,128.4,130.5,208.6��
Reference
1) (a) Kuang, J.; Ma, S.J.Org.Chem.2009,74,1763. (b) Kuang, J.; Ma, S.J.Am.Chem.Soc.2010,132,1786. (c) Kuang, J.; Luo, H.; Ma, S.Adv.Synth.Catal.2012,354,933.
2) Ahmed, M.; Arnuald, T.; Barrett, A.G.M.; Braddock, D.C.; Flack, K.; Procopiou, P.A.Org.Lett.2000,2,551.
3) Lavallo, V.; Frey, G.D.; Kouser, S.; Donnadieu, B.; Bertrand, G.Proc.Natl.Acad.Sci.USA2007,104,13569.
Claims (9)
1. one kind 1, 3-bis-replaces the preparation method of allenic compound, under the effect of alkali, adopt copper catalyst, Tosylhydrazone shown in formula I and the end alkynes shown in formula II are reacted in organic solvent, described alkali is sodium methylate or trimethyl carbinol lithium, the mol ratio of described Tosylhydrazone and end alkynes is 1.5:1��2.5:1, described copper catalyst is cuprous iodide or four acetonitrile six fluorine phosphine copper, its consumption is 15%��40% equivalent of described end alkynes, the reaction times of described reaction is within 1 hour, obtain 1 shown in formula III, 3-bis-replaces allenic compound, reaction formula is as follows:
Wherein, R1Represent the aromatic base comprising heterocycle, or there is the alkyl of 1��10 carbon atom; Described end alkynesComprise phenylacetylene, 4-fluorobenzene acetylene, 1-octyne, 4-tert.-butylbenzene acetylene, 3,3-dimethyl-ethyl acetylene, 4-trifluoromethyl phenylacetylene, the own alkynes of 1-, 4-phenyl-ethyl acetylene or 3-ethynyl thiophene.
2. preparation method as claimed in claim 1, it is characterised in that, in reaction vessel, first add described hydrazone, alkali, copper catalyst and organic solvent, after sealing, reaction vessel interior is replaced into inert gas environment, then add described end alkynes and react.
3. preparation method as claimed in claim 1 or 2, it is characterised in that, described organic solvent is selected from toluene, acetonitrile, 1,2-ethylene dichloride and ether solvent.
4. preparation method as claimed in claim 3, it is characterised in that, described ether solvent is 1,4-dioxane.
5. preparation method as claimed in claim 1 or 2, it is characterised in that, described copper catalyst is cuprous iodide.
6. preparation method as claimed in claim 1 or 2, it is characterised in that, the mol ratio of described hydrazone and end alkynes is 2.2:1.
7. preparation method as claimed in claim 1 or 2, it is characterised in that, the consumption of described copper catalyst is 20% equivalent of described end alkynes.
8. preparation method as claimed in claim 1 or 2, it is characterised in that, the temperature of reaction is 70 DEG C to 110 DEG C, is heated by oil bath or alternate manner.
9. preparation method as claimed in claim 1 or 2, it is characterised in that, use sand core funnel to filter at reduced pressure reaction product after described reaction completes; Adopt air distillation or vacuum distillation method to concentrate, obtained the product of purifying by column chromatography.
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| CN104844410B (en) * | 2015-04-28 | 2017-10-10 | 北京大学 | A kind of synthetic method of the yne compounds of 1,1 difluoro 1,3 |
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| CN114149300A (en) * | 2021-11-01 | 2022-03-08 | 南京林业大学 | Synthesis method of copper-catalyzed trifluoromethyl allene compound |
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