CN105622536A - Trifluoromethyl alkenyl isoxazole compound and preparation method and application thereof - Google Patents
Trifluoromethyl alkenyl isoxazole compound and preparation method and application thereof Download PDFInfo
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- CN105622536A CN105622536A CN201511021687.8A CN201511021687A CN105622536A CN 105622536 A CN105622536 A CN 105622536A CN 201511021687 A CN201511021687 A CN 201511021687A CN 105622536 A CN105622536 A CN 105622536A
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- CRAWTEWGUZTCGH-YRNVUSSQSA-N Cc1n[o]c(/C=C(/C(F)(F)F)\c2ccc(C)cc2)c1[N+]([O-])=O Chemical compound Cc1n[o]c(/C=C(/C(F)(F)F)\c2ccc(C)cc2)c1[N+]([O-])=O CRAWTEWGUZTCGH-YRNVUSSQSA-N 0.000 description 1
- XMWYZNJUJGQZQQ-LCYFTJDESA-N Cc1n[o]c(/C=C(/CF)\c2c(cccc3)c3ccc2)c1[N+]([O-])=O Chemical compound Cc1n[o]c(/C=C(/CF)\c2c(cccc3)c3ccc2)c1[N+]([O-])=O XMWYZNJUJGQZQQ-LCYFTJDESA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
The invention relates to a trifluoromethyl alkenyl isoxazole compound and a preparation method thereof and application in organic synthesis, and belongs to the technical field of organic fluorine compound synthesis. The compound has a structure shown in a general formula I in the description. The preparation method of the general formula I comprises the steps of mixing 3-substitute group-4-nitryl-5-methylisoxazole, trifluoromethyl aryl ketones, and a catalyst with a solvent, reacting under the conditions of room temperature by stirring, and performing washing, extracting, separating, and purifying after a reaction is completed to obtain an intermediate; then, dissolving the intermediate, an acid-binding agent, and thionyl chloride in the solvent, reacting under heating and stirring, and performing washing, extracting, separating, and purifying after a reaction is completed to obtain the target product, namely the trifluoromethyl alkenyl isoxazole compound. The compound is a very useful trifluoromethyl synthesized building block, can be used as a trifluoromethyl synthon to act with a nitromethane compound, a malononitrile compound or an indole compound and the like, and can be used for structuring a series of organic fluorine compounds of complex structures containing trifluoromethyl groups.
Description
Technical field
The present invention relates to organofluorine compound synthesis technical field, relate to a class trifluoromethylation different azole compounds of alkene base and its preparation method and the application in organic synthesis specifically.
Background technology
Organic fluorine chemistry is as an important branch of organic chemistry, the focus having become chemical research field instantly and one of topic attracted people's attention. It is subject in fields such as medicine, agricultural chemicals and materials chemistries paying close attention to widely and application at present. If Efavirenz (efavirenz) is hiv reverse transcriptase inhibitor (AntimicrobAgentsChemother.1995,39,2602.); Celecoxib (happiness is happy preserves) is the medicine (ExpertOpin.Investig.Drugs2008,17,197.) of a kind for the treatment of of arthritis; Trifluranlin (trifluralin) is the weedicide (Bioorg.Med.Chem.Lett.2010,20,5179.) of broad-spectrum high efficacy. Therefore, develop high-efficient simple, safe green, Atom economy, controllability synthetic method to construct and be converted into fluorinated organic compound very important.
The compound being contained trifluoromethyl by trifluoromethyl building block synthesis is the very effective method (Chem.Rev.2011,111,455.) of one. In recent years, through the unremitting effort of organic chemists, develop the trifluoromethyl building block that some are novel, such as ��-trifluoromethyl nitroolefin derivative (J.Am.Chem.Soc.2013,135,2983.), ��-trifluoromethyl ketenes derivative (Angew.Chem.Int.Ed.2010,49,576.) and 2,2,2-tri-fluorine ethylidene malonic ester derivative (OrgLett.2010,12,4655.) etc. Although the kind of trifluoromethyl building block a lot, have also been obtained and applies widely, but what the trifluoromethyl building block of development structure novelty urgently needed.
Summary of the invention
The object of the present invention is intended to develop the trifluoromethylation different azole compounds of alkene base of a class formation novelty, simultaneously, it is provided that the preparation method of the above-mentioned trifluoromethylation different azole compounds of alkene base and its application in organic synthesis.
The trifluoromethylation different azole compounds of alkene base of the present invention has general formula I:
In general formula I, R is hydrogen, methyl, benzyl or aromatic group; R ' is methyl or phenyl.
Preferred:
R is aromatic group; R ' is methyl or phenyl.
Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
It is as follows that the preparation method of the trifluoromethylation different azole compounds of alkene base of the present invention comprises step:
(1)
3-substituting group-4-nitro different the azoles of-5-methyl, trifluoromethyl aryl ketones are added in a reactor, in a solvent, continues to add catalyzer, react under stirring at room temperature, after completion of the reaction, through washing, extraction, separation, purifying, obtain intermediate A; Described catalyzer is triethylamine, DABCO (1,4-diazabicylo [2,2,2] octane), N, N-lutidine or DBU (1,8-diazabicylo 11 carbon-7-alkene). Described solvent is water, methyl alcohol, ethanol, ��, ��-dimethyl formamide, acetonitrile, tetrahydrofuran (THF) or toluene etc.
(2)
Above-mentioned intermediate A is added in another reactor, in a solvent, continue to add acid binding agent, thionyl chloride, react under heated and stirred, after completion of the reaction, through washing, extraction, separation, purifying, obtain the target product trifluoromethylation different azole compounds of alkene base.
Described acid binding agent is triethylamine or pyridine. Described solvent is water, methyl alcohol, ethanol, ��, ��-dimethyl formamide, acetonitrile, tetrahydrofuran (THF) or toluene.
The described 3-substituting group-4-nitro different azole compounds of-5-methyl, trifluoromethyl aromatic ketone compound, catalyzer, acid binding agent, thionyl chloride mol ratio be: the 3-substituting group-4-nitro different azole compounds of-5-methyl: trifluoromethyl aromatic ketone compound: catalyzer: acid binding agent: thionyl chloride=1:1.5-2:0.1��1:3��6:2��4.
R, R in synthetic method ' consistent with above-mentioned general formula I sign scope.
The application 1 of the trifluoromethylation different azole compounds of alkene base of the present invention in organic synthesis: it can be used as reaction substrate, preparing the organofluorine compound of general formula II containing trifluoromethyl group with the reaction of Nitromethane 99Min. compounds under catalyzer Tetrabutyl amonium bromide, mineral alkali and toluene effect, its reaction is as follows:
In general formula II, R is hydrogen, methyl, benzyl or aromatic group, it is preferable that R is aromatic group; R ' is methyl or phenyl; R " it is hydrogen, methyl, ethyl, sec.-propyl, benzyl or aromatic group; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
The application 2 of the trifluoromethylation different azole compounds of alkene base of the present invention in organic synthesis: it can be used as reaction substrate, containing the organofluorine compound of trifluoromethyl group with malononitrile derivative reaction preparation general formula III under catalyzer Tetrabutyl amonium bromide, mineral alkali and toluene effect, its reaction is as follows:
In general formula III, R is hydrogen, methyl, benzyl or aromatic group, it is preferable that R is aromatic group; R ' is methyl or phenyl; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
The application 3 of the trifluoromethylation different azole compounds of alkene base of the present invention in organic synthesis: it can be used as reaction substrate, under catalyzer dinaphthol phosphoric acid ester and methylene dichloride exist, containing the organofluorine compound of trifluoromethyl group with Benzazole compounds reaction preparation general formulae IV, its reaction is as follows:
In general formulae IV, R is hydrogen, methyl, benzyl or aromatic group, it is preferable that R is aromatic group; R ' is methyl or phenyl; R " ' it is hydrogen, methyl, methoxyl group, fluorine, chlorine or bromine; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
The present invention provides a kind of from simple substrate, synthesize the method for the trifluoromethylation different azole compounds of alkene base simply, efficiently, and the method has the advantages such as simple to operate, reaction conditions is gentle, receipts rate height, substrate universality are good, atom utilization height, environment compatibility are good. In addition, this compounds is brand-new, the very useful trifluoromethyl building block of a kind of structure, trifluoromethyl synthon and Nitromethane 99Min. compounds, malonic ester compounds or malononitrile derivative etc. can be it can be used as to act on, for building the organofluorine compound containing trifluoromethyl group of a series of complex structure, be conducive to the research and development of the organofluorine compound containing trifluoromethyl group.
Embodiment
Further describe the present invention below in conjunction with example, contribute to understanding further the present invention by following example, but do not limit the scope of the invention.
The preparation of example 1:3-methyl-4-nitro-5-(3,3,3-tri-fluoro-2-phenyl third-1-alkene-1-base) different azoles
A 25mLSchlenk bottle is weighed into 3, different azoles (the 0.14g of 5-dimethyl-4-nitro, 1.0mmol), the fluoro-1-Phenyl ethyl ketone (0.26g of 2,2,2-tri-, 1.5mmol), in system, add 5.0mL water and triethylamine (0.05g, 0.5mmol), it is placed in stirring at room temperature 24h. TLC detection reaction is complete, adds 10mL ethyl acetate and 5mL water to system, separatory, and aqueous phase is extracted with ethyl acetate (10mLx2), merges organic phase, anhydrous MgSO4Drying, column chromatography (leacheate: petrol ether/ethyl acetate=10/1to5/1), obtains corresponding intermediate.
This intermediate is joined in a 50mL round-bottomed bottle, add 10.0mL dry toluene again, ice-water bath cools, add anhydrous pyridine (0.32g successively, the thionyl chloride (0.36g, 3.0mmol) 4.0mmol), heavily steamed, finishes, load onto reflux condensing tube and the drying tube containing Calcium Chloride Powder Anhydrous, it is placed in 80 DEG C and stirs 24h. React complete, add 20mL diluted ethyl acetate to system, successively with water, saturated common salt water washing, separatory, anhydrous MgSO4Drying, column chromatography (leacheate: petrol ether/ethyl acetate=30/1to20/1), can obtain target product 3-methyl-4-nitro-5-(3,3,3-tri-fluoro-2-phenyl third-1-alkene-1-base) different azoles 0.25g, light yellow solid, receipts rate 86%. Z:E=3:97;1HNMR(400MHz,CDCl3) �� 2.52 (s, 3H), 7.30 (d, J=6.8Hz, 2H), 7.41-7.48 (m, 3H), 7.72 (s, 1H);13CNMR(100MHz,CDCl3)��163.7,155.5,142.5(q,JC-F=31.5Hz), 130.5,130.0,128.7,128.6,127.9,122.3 (q, JC-F=273.4Hz), 116.0 (q, JC-F=6.4Hz), 11.4;19FNMR(376MHz,CDCl3)��-67.14(s,3F),-59.66��
The preparation of example 2:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-fluorophenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, the 3,5-dimethyl different azoles of-4-nitro, 2,2, the fluoro-1-of 2-tri-(4-fluorophenyl) second ketone, 1,4-diazabicylo [2,2,2] the throwing material mol ratio of octane, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtain target product 3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-fluorophenyl) third-1-alkene-1-base) different azoles 0.29g, light yellow solid, receipts rate 93%. Z:E=3:97;1HNMR(400MHz,CDCl3) �� 2.53 (s, 3H), 7.13 (dd, J=8.8Hz, 2H), 7.30 (dd, J=5.2Hz, 2H), 7.74 (d, J=1.2Hz, 1H);13CNMR(100MHz,CDCl3)��163.7(d,JC-F=249.2Hz), 163.5,155.6,141.3 (q, JC-F=31.5Hz), 130.8,130.7,126.4 (d, JC-F=4.4Hz), 122.2 (q, JC-F=273.3Hz), 116.4 (q, JC-F=6.2Hz), 115.9 (d, JC-F=21.9Hz), 11.4;19FNMR(376MHz,CDCl3)��-67.30(s,3F),-59.90,-109.97(s,1F)��
The preparation of example 3:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-chloro-phenyl-) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, the fluoro-1-of 2,2,2-tri-(4-chloro-phenyl-) second ketone, N, the throwing material mol ratio of N-lutidine, thionyl chloride and triethylamine is 1:1.5:0.5:3:4, obtain target product 3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-chloro-phenyl-) third-1-alkene-1-base) different azoles 0.30g, light yellow solid, receipts rate 89%. Z:E=4:96;1HNMR(400MHz,CDCl3) �� 2.53 (s, 3H), 7.25 (d, J=8.0Hz, 2H), 7.42 (d, J=8.4Hz, 2H), 7.75 (s, 1H);13CNMR(100MHz,CDCl3)��163.3,155.6,141.2(q,JC-F=31.5Hz), 136.5,130.0,129.0,128.9,122.1 (q, JC-F=273.4Hz), 116.4 (q, JC-F=6.1Hz), 11.4;19FNMR(376MHz,CDCl3)��-67.14(s,3F),-59.77��
The preparation of example 4:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-fluorophenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, the fluoro-1-of 2,2,2-tri-(4-bromophenyl) second ketone, 1, the throwing material mol ratio of 8-diazabicylo 11 carbon-7-alkene, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtain target product 3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-fluorophenyl) third-1-alkene-1-base) different azoles 0.33g, light yellow solid, receipts rate 87%. Z:E=3:97;1HNMR(400MHz,CDCl3) �� 2.53 (s, 3H), 7.18 (d, J=8.0Hz, 2H), 7.58 (d, J=8.4Hz, 2H), 7.75 (s, 1H);13CNMR(100MHz,CDCl3)��163.3,155.6,141.1(q,JC-F=31.3Hz), 131.9,130.2,129.3,124.7,122.0 (q, JC-F=273.5Hz), 116.4 (q, JC-F=6.4Hz), 11.4;19FNMR(376MHz,CDCl3)��-67.12(s,3F),-59.75��
The preparation of example 5:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-aminomethyl phenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(4-aminomethyl phenyl) second ketone, triethylamine, thionyl chloride and pyridine is 1:2:0.5:4:3, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(4-aminomethyl phenyl) third-1-alkene-1-base) different azoles 0.26g, light yellow solid, receipts rate 83%. Z:E=5:95;1HNMR(400MHz,CDCl3) �� 2.36 (s, 3H), 2.49 (s, 3H), 7.18 (dd, J=17.6Hz, 7.6Hz, 4H), 7.65 (d, J=1.2Hz, 1H);13CNMR(100MHz,CDCl3)��163.9,155.5,142.6(q,JC-F=30.9Hz), 140.3,129.3,128.5,127.6,122.4 (q, JC-F=273.4Hz), 115.6 (q, JC-F=6.4Hz), 21.3,11.4;19FNMR(376MHz,CDCl3)��-67.07(s,3F),-59.65��
The preparation of example 6:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-p-methoxy-phenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(4-p-methoxy-phenyl) second ketone, triethylamine, thionyl chloride and pyridine is 1:1.5:0.3:3:2, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(4-p-methoxy-phenyl) third-1-alkene-1-base) different azoles 0.27g, light yellow solid, receipts rate 80%. Z:E=7:93;1HNMR(400MHz,CDCl3) �� 2.61 (s, 3H), 3.92 (s, 3H), 7.01 (d, J=8.8Hz, 2H), 7.32 (d, J=8.4Hz, 2H), 7.73 (s, 1H);13CNMR(100MHz,CDCl3)��164.1,161.0,155.5,142.4(q,JC-F=30.8Hz), 130.2,122.6,122.4 (q, JC-F=273.5Hz), 115.3 (q, JC-F=6.3Hz), 114.1,55.2,11.5;19FNMR(376MHz,CDCl3)��-66.94(s,3F),-59.61��
The preparation of example 7:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(3-p-methoxy-phenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(3-p-methoxy-phenyl) second ketone, triethylamine, thionyl chloride and pyridine is 1:1.5:0.5:3:5, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(3-p-methoxy-phenyl) third-1-alkene-1-base) different azoles 0.25g, light yellow solid, receipts rate 77%. Z:E=3:97;1HNMR(400MHz,CDCl3) �� 2.52 (s, 3H), 3.80 (s, 3H), 6.83 (s, 1H), 6.85 (d, J=8.0Hz, 1H), 7.00 (dd, J=8.0Hz, 2.4Hz, 1H), 7.33 (t, J=8.0Hz, 1H), 7.71 (s, 1H);13CNMR(100MHz,CDCl3)��163.7,159.5,155.5,142.2(q,JC-F=31.1Hz), 131.6,129.8,128.6,127.9,122.2 (q, JC-F=273.4Hz), 120.9,116.0 (q, JC-F=6.4Hz), 115.4,114.3,55.2,11.4;19FNMR(376MHz,CDCl3)��-67.11(s,3F),-59.74��
The preparation of example 8:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(2-p-methoxy-phenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(2-p-methoxy-phenyl) second ketone, triethylamine, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(2-p-methoxy-phenyl) third-1-alkene-1-base) different azoles 0.28g, light yellow solid, receipts rate 85%. Z:E=3:97;1HNMR(400MHz,CDCl3) �� 2.51 (s, 3H), 3.71 (s, 3H), 6.96 (d, J=8.0Hz, 1H), 7.01 (t, J=7.2Hz, 1H), 7.21 (d, J=6.8Hz, 1H), 7.44 (t, J=7.2Hz, 1H), 7.82 (s, 1H);13CNMR(100MHz,CDCl3)��164.1,157.2,155.3,138.8(q,JC-F=31.9Hz), 131.5,129.5,122.4 (q, JC-F=273.5Hz), 120.5,119.6,117.2 (q, JC-F=6.0Hz), 111.2,55.5,11.5;19FNMR(376MHz,CDCl3)��-67.12(s,3F),-60.65��
The preparation of example 9:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-tert-butyl-phenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(4-tert-butyl-phenyl) second ketone, triethylamine, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(4-tert-butyl-phenyl) third-1-alkene-1-base) different azoles 0.30g, light yellow solid, receipts rate 84%. Z:E=4:96;1HNMR(400MHz,CDCl3) �� 1.26 (s, 9H), 2.45 (s, 3H), 7.15 (d, J=8.0Hz, 2H), 7.35 (d, J=8.0Hz, 2H), 7.61 (s, 1H);13CNMR(100MHz,CDCl3)��164.0,155.5,153.3,142.7(q,JC-F=30.8Hz), 128.4,127.5,125.5,122.4 (q, JC-F=273.6Hz), 115.5 (q, JC-F=6.3Hz), 34.7,31.1,11.4;19FNMR(376MHz,CDCl3)��-66.89(s,3F),-59.60��
The preparation of example 10:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(4-phenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(4-phenyl) second ketone, triethylamine, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(4-phenyl) third-1-alkene-1-base) different azoles 0.30g, light yellow solid, receipts rate 81%. Z:E=9:91;1HNMR(400MHz,CDCl3) �� 2.50 (s, 3H), 7.34-7.36 (m, 3H), 7.43 (t, J=7.2Hz, 2H), 7.58-7.63 (m, 4H), 7.72 (s, 1H);13CNMR(100MHz,CDCl3)��163.8,155.5,142.9,142.3(q,JC-F=30.9Hz), 139.9,129.3,129.1,128.8,127.9,127.4,127.2,127.1,122.3 (q, JC-F=273.5Hz), 115.9 (q, JC-F=6.4Hz), 11.4;19FNMR(376MHz,CDCl3)��-66.81(s,3F),-59.48��
The preparation of example 11:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(3,5-3,5-dimethylphenyl) third-1-alkene-1-base) different azoles
With experiment 1 similar method, the 3,5-dimethyl different azoles of-4-nitro, 2,2, the fluoro-1-(3 of 2-tri-, 5-3,5-dimethylphenyl) second ketone, triethylamine, thionyl chloride and pyridine throwing material mol ratio be 1:1.5:0.5:3:4, obtain target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-(3 of 3-tri-, 5-3,5-dimethylphenyl) the third-1-alkene-1-base) different azoles 0.23g, light yellow solid, receipts rate 72%. Z:E=2:98;1HNMR(400MHz,CDCl3) �� 2.32 (s, 6H), 2.53 (s, 3H), 6.89 (s, 2H), 7.09 (s, 1H), 7.68 (s, 1H);13CNMR(100MHz,CDCl3)��164.0,155.4,143.0(q,JC-F=30.7Hz), 138.2,131.7,130.4,126.1,122.3 (q, JC-F=273.6Hz), 115.5 (q, JC-F=6.4Hz), 21.2,11.5;19FNMR(376MHz,CDCl3)��-67.11(s,3F),-59.64��
The preparation of example 12:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(naphthalene-2-base) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(naphthalene-2-base) second ketone, triethylamine, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(naphthalene-2-base) third-1-alkene-1-base) different azoles 0.29g, light yellow solid, receipts rate 82%. Z:E=8:92;1HNMR(400MHz,CDCl3) �� 2.49 (s, 3H), 7.35 (d, J=7.2Hz, 1H), 7.52-7.58 (m, 2H), 7.82-7.91 (m, 5H);13CNMR(100MHz,CDCl3)��163.7,155.5,142.5(q,JC-F=31.1Hz), 133.6,132.7,128.6,128.5,128.4,127.9,127.8,127.3,126.7,12 5.5,122.4 (q, JC-F=273.5Hz), 116.1 (q, JC-F=6.4Hz), 11.4;19FNMR(376MHz,CDCl3)��-66.75(s,3F),-59.30��
The preparation of example 13:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(thiophene-2-base) third-1-alkene-1-base) different azoles
With experiment 1 similar method, 3, the 5-dimethyl different azoles of-4-nitro, 2, the throwing material mol ratio of the fluoro-1-of 2,2-tri-(thiophene-2-base) second ketone, triethylamine, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtains target product 3-methyl-4-nitro-5-(3,3, the fluoro-2-of 3-tri-(thiophene-2-base) third-1-alkene-1-base) different azoles 0.26g, light yellow solid, receipts rate 86%. Z:E=35:65;1HNMR(400MHz,CDCl3) �� 2.57 (s, 3H), 7.10 (dd, J=3.6Hz, 1.2Hz, 1H), 7.26 (d, J=2.0Hz, 1H), 7.53 (d, J=4.0Hz, 1H), 7.61 (s, 1H);13CNMR(100MHz,CDCl3)��163.6,155.7,135.5(q,JC-F=31.9Hz), 131.2,129.9,129.7,128.6,127.6,121.8 (q, JC-F=274.0Hz), 115.8 (q, JC-F=6.2Hz), 11.5;19FNMR(376MHz,CDCl3)��-67.05(s,3F),-60.47��
The preparation of example 14:3-phenyl-4-nitro-5-(3,3,3-tri-fluoro-2-phenyl third-1-alkene-1-base) different azoles
With experiment 1 similar method, 5-methyl-3-phenyl different the azoles of-4-nitro, 2,2, the throwing material mol ratio of the fluoro-1-Phenyl ethyl ketone of 2-tri-, triethylamine, thionyl chloride and pyridine is 1:1.5:0.5:3:4, obtain target product 3-phenyl-4-nitro-5-(3,3,3-tri-fluoro-2-phenyl third-1-alkene-1-base) different azoles 0.31g, light yellow solid, receipts rate 86%. Z:E=2:98;1HNMR(400MHz,CDCl3) �� 7.38 (d, J=8.0Hz, 2H), 7.47-7.55 (m, 8H), 7.75 (s, 1H);13CNMR(100MHz,CDCl3)��164.4,157.5,142.6(q,JC-F=31.2Hz), 130.9,130.7,130.5,130.1,129.1,128.7,128.6,128.5,124.9,12 2.3 (q, JC-F=273.5Hz), 115.8 (q, JC-F=6.4Hz);19FNMR(376MHz,CDCl3)��-67.10(s,3F),-59.52��
The preparation of example 15:3-methyl-4-nitro-5-(3,3,3-tri-fluoro-2-(nitromethyla)-2-hydrocinnamyl) isoxzzole
3-methyl-4-nitro-5-(3 is added in a 10mLSchlenk bottle, 3,3-tri-fluoro-2-phenyl third-1-alkene-1-base) isoxzzole (0.06g, 0.2mmol), Tetrabutyl amonium bromide (0.013g, 0.04mmol), Anhydrous potassium carbonate (0.083g, 0.6mmol) and 1.0mL dry toluene, Nitromethane 99Min. (0.061g is added again in system, 1.0mmol), finish, it is placed in stirring at room temperature reaction 24h. TLC detection reaction is complete, direct column chromatography (leacheate: petrol ether/ethyl acetate=10/1), target product 3-methyl-4-nitro-5-(3 can be obtained, 3,3-tri-fluoro-2-(nitromethyla)-2-hydrocinnamyl) isoxzzole 0.069g, white solid, receipts rate 96%.1HNMR(400MHz,CDCl3) �� 2.55 (s, 3H), 4.49 (dd, J=34.0Hz, 16.8Hz, 2H), 5.38 (s, 2H), 7.42 (s, 5H);13CNMR(100MHz,CDCl3)��168.7,155.7,131.6,131.3,129.7,129.3,126.5,125.2(q,JC-F=283.7Hz), 74.8,51.1 (q, JC-F=25.3Hz), 28.1,11.5;19FNMR(376MHz,CDCl3)��-72.06(s,3F)��
The preparation of example 16:2-(the fluoro-3-of 1,1,1-tri-(3-methyl-4-isoxzzole-5-base)-2-phenyl third-2-base) propane dinitrile
3-methyl-4-nitro-5-(3 is added in a 10mLSchlenk bottle, 3,3-tri-fluoro-2-phenyl third-1-alkene-1-base) isoxzzole (0.06g, 0.2mmol), Tetrabutyl amonium bromide (0.013g, 0.04mmol), Anhydrous potassium carbonate (0.083g, 0.6mmol) and 1.0mL dry toluene, propane dinitrile (0.066g is added again in system, 1.0mmol), finish, it is placed in stirring at room temperature reaction 24h. TLC detection reaction is complete, direct column chromatography (leacheate: petrol ether/ethyl acetate=10/1), target product 2-(1 can be obtained, 1, the fluoro-3-of 1-tri-(3-methyl-4-isoxzzole-5-base)-2-phenyl third-2-base) propane dinitrile 0.069g, light yellow solid, receipts rate 95%.1HNMR(400MHz,CDCl3) �� 2.52 (s, 3H), 4.37 (dd, J=34.4Hz, 16.4Hz, 2H), 4.98 (s, 1H), 7.50-7.56 (m, 5H);13CNMR(100MHz,CDCl3)��165.9,155.9,132.0,130.5,129.7,129.6,126.5,124.7(q,JC-F=285.3Hz), 109.5,54.7 (q, JC-F=25.2Hz), 30.2,28.5,11.4;19FNMR(376MHz,CDCl3)��-67.78(s,3F)��
The preparation of example 17:3-methyl-4-nitro-5-(the fluoro-2-of 3,3,3-tri-(1 ��-indol-3-yl)-2-hydrocinnamyl) isoxzzole
3-methyl-4-nitro-5-(3 is added in a 10mLSchlenk bottle, 3,3-tri-fluoro-2-phenyl third-1-alkene-1-base) isoxzzole (0.060g, 0.2mmol), indoles (0.036g, 0.3mmol), dinaphthol phosphoric acid ester (0.014g, 0.04mmol) with 1.0mL methylene dichloride, finish, it is placed in stirring at room temperature reaction 24h. TLC detection reaction is complete, direct column chromatography (leacheate: petrol ether/ethyl acetate=10/1), target product 3-methyl-4-nitro-5-(3 can be obtained, 3, the fluoro-2-of 3-tri-(1 ��-indol-3-yl)-2-hydrocinnamyl) isoxzzole 0.077g, light yellow solid, receipts rate 92%.1HNMR(400MHz,CDCl3) �� 2.53 (s, 3H), 4.32 (dd, J=32.0Hz, 14.4Hz, 2H), 6.65 (d, J=8.5Hz, 1H), 6.91 (t, J=8.0Hz, 1H), 7.18 (t, J=8.0Hz, 1H), 7.35-7.43 (m, 6H), 7.45 (d, J=1.5Hz, 1H), 8.34 (s, 1H);13CNMR(100MHz,CDCl3)��168.6,155.5,136.3,134.5,129.6,128.9,128.7,128.5,127.1,125.4,124.9(q,JC-F=283.5Hz), 122.6,120.6,120.1,111.6,109.3,54.5 (q, JC-F=25.8Hz), 28.3,11.5;19FNMR(376MHz,CDCl3)��-67.76(s,3F)��
Utilizing the compounds of this invention can realize single stage method and prepare the above-mentioned organofluorine compound containing trifluoromethyl group biology, receipts rate height, by product is few.
Claims (8)
1. the trifluoromethylation different azole compounds of alkene base, it is characterised in that, it is the compound with following chemical structure of general formula I:
General formula I
In general formula I, R is hydrogen, methyl, benzyl or aromatic group; R ' is methyl or phenyl; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
2. the trifluoromethylation different azole compounds of alkene base as claimed in claim 1, it is characterised in that, R is aromatic group; R ' is methyl or phenyl; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
3. prepare the method for the different azole compounds of trifluoromethylation alkene base as claimed in claim 1, it is characterised in that, comprise the following steps:
(1)
3-substituting group-4-nitro different the azoles of-5-methyl, trifluoromethyl aryl ketones are added in a reactor, in a solvent, adds catalyzer, react under stirring at room temperature, after completion of the reaction, through washing, extraction, separation, purifying, obtain intermediate A;
Described catalyzer is triethylamine, DABCO(1,4-diazabicylo [2,2,2] octane), N, N-lutidine or DBU(1,8-diazabicylo 11 carbon-7-alkene); Described solvent is water, methyl alcohol, ethanol, N, dinethylformamide, acetonitrile, tetrahydrofuran (THF) or toluene;
(2)
Above-mentioned intermediate A is added in another reactor, in a solvent, add acid binding agent, thionyl chloride, react under heated and stirred, after completion of the reaction, through washing, extraction, separation, purifying, obtain the target product trifluoromethylation different azole compounds of alkene base;
Described acid binding agent is triethylamine or pyridine; Described solvent is water, methyl alcohol, ethanol, N, dinethylformamide, acetonitrile, tetrahydrofuran (THF) or toluene;
R, R ' consistent with claim 1 general formula I sign scope.
4. the preparation method of the trifluoromethylation different azole compounds of alkene base as claimed in claim 3, it is characterized in that, reactant molar ratio is: the 3-substituting group-4-nitro different azole compounds of-5-methyl: trifluoromethyl aromatic ketone compound: catalyzer: acid binding agent: thionyl chloride=1:1.5-2:0.1 ~ 1:3 ~ 6:2 ~ 4.
5. the application of the different azole compounds of trifluoromethylation alkene base in organic synthesis as claimed in claim 1, it is characterized in that: it can be used as reaction substrate, with the reaction of Nitromethane 99Min. compounds under catalyzer Tetrabutyl amonium bromide, mineral alkali and toluene effect, prepare the organofluorine compound of general formula II containing trifluoromethyl group:
In general formula II, R is hydrogen, methyl, benzyl or aromatic group; R ' is methyl or phenyl; R ' ' is hydrogen, methyl, ethyl, sec.-propyl, benzyl or aromatic group; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
6. the application of the different azole compounds of trifluoromethylation alkene base in organic synthesis as claimed in claim 1, it is characterized in that: it can be used as reaction substrate, with malononitrile derivative reaction under catalyzer Tetrabutyl amonium bromide, mineral alkali and toluene effect, preparation general formula III is containing the organofluorine compound of trifluoromethyl group:
In general formula III, R is hydrogen, methyl, benzyl or aromatic group; R ' is methyl or phenyl; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
7. the application of the different azole compounds of trifluoromethylation alkene base in organic synthesis as claimed in claim 1, it is characterized in that: it can be used as reaction substrate, under catalyzer dinaphthol phosphoric acid ester and methylene dichloride exist, with Benzazole compounds reaction, preparation general formulae IV is containing the organofluorine compound of trifluoromethyl group:
In general formulae IV, R is hydrogen, methyl, benzyl or aromatic group; R ' is methyl or aromatic group; R ' ' ' is hydrogen, is methyl, methoxyl group, fluorine, chlorine or bromine; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
8. such as the application of claim 5-7 trifluoromethylation different azole compounds of alkene base as described in one of them in organic synthesis, it is characterised in that: R selects aromatic group, and R ' is methyl or phenyl; Described aromatic group is phenyl, 4-aminomethyl phenyl, 4-p-methoxy-phenyl, 3-p-methoxy-phenyl, 2-p-methoxy-phenyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-tert-butyl-phenyl, 4-phenyl, 3,5-3,5-dimethylphenyl, 2-naphthyl or 2-thienyl.
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| CN113200933A (en) * | 2021-05-19 | 2021-08-03 | 河南师范大学 | Method for synthesizing optically active benzocarboxylate compound by asymmetric addition reaction |
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