CN104030983A - Fluorine-containing triphenylpyrazole derivative and preparation method thereof - Google Patents

Fluorine-containing triphenylpyrazole derivative and preparation method thereof Download PDF

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Publication number
CN104030983A
CN104030983A CN201410107346.1A CN201410107346A CN104030983A CN 104030983 A CN104030983 A CN 104030983A CN 201410107346 A CN201410107346 A CN 201410107346A CN 104030983 A CN104030983 A CN 104030983A
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Prior art keywords
fluorine
derivative
triphenylpyrazole
phenyl
crude product
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Inventor
成浩楠
章建民
沈苏波
方芳
郭玉威
姚霞萍
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member

Abstract

The invention relates to a fluorine-containing triphenylpyrazole derivative and a preparation method thereof. The structural formula of the derivative is described in the specification; in the structural formula, Fn is a difluoro or trifluoro substituted phenyl group. The novel fluorine-containing triphenylpyrazole derivative has special physical and chemical properties. Phenylpyrazole pesticides destroy the central nervous system of an insect by retarding the chloride ion channel of a GABA acceptor; through simultaneous combination of three phenyl groups, the fluorine-containing triphenylpyrazole derivative has immense potential and a great research value in many subjects and application research fields like organic chemistry, material science, medicinal chemistry, superconductors and ferromagnets.

Description

Fluorine-containing triphenyl pyrazole derivatives and preparation method thereof
Technical field
The present invention relates to a kind of fluorine-containing triphenyl pyrazole derivatives and preparation method thereof.
Technical background
Pyrazoles is very important nitrogenous five member ring heterocyclic compound, the compound that contains pyrazole ring structural unit has biological activity widely, such as thering is antibacterium, antiviral, antimycotic, tuberculosis, desinsection isoreactivity, thereby cause the further investigation of people to this compounds.All the time, patent and bibliographical information pyrazole compound have good pesticide activity, and because pyrazole compound shows efficiently, low toxicity and structure diversity, so its research and development is that agricultural chemicals and medicine have increased a new approach.
Wherein substituted-phenyl heterogeneous ring compound is because of the structural similitude of itself and proporphyrinogen oxidase effect substrate protoporphyrin, and is considered to potential proporphyrinogen oxidase inhibitor.Consider that pyrazole ring is a good active group, many pyrazole derivatives have higher biological activity.
According to a lot of pertinent literatures, phenylpyrazole insecticides is that a class is destroyed insect central nervous system by retardance GABA acceptor chloride channel, causes being overexcited of insect N&M, causes the novel pesticide of insect convulsions, death.Due to its special insecticidal mechanism and efficient biological activity, in agriculture production, play the important and pivotal role.
Summary of the invention
One of object of the present invention is to provide a kind of fluorine-containing triphenyl pyrazole compound.
Two of object of the present invention is to provide the preparation method of this compounds.
For achieving the above object, reaction equation of the present invention is:
According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:
A fluorine-containing triphenyl pyrazole compound compounds, is characterized in that the structure of this compound is:
Fn wherein: be difluoro～trifluoro substituted-phenyl.
A method of preparing above-mentioned fluorine-containing triphenyl pyrazole compound compounds, is characterized in that the method has following steps:
A. will by the mol ratio of 1:1 to 1:1.2, be dissolved in deionized water containing fluorobenzaldehyde and methyl phenyl ketone, 100 ℃ of backflows, stirring reaction 16 hours, through cooling, recrystallization, obtains fluorine-containing diphenylprop ketenes;
B. the fluorine-containing diphenylprop ketenes of step a gained, reactant phenylhydrazine are dissolved in organic solvent dehydrated alcohol by the mol ratio of 1:1.5 to 1:2,50-60 ℃ is stirred 2.5-3 hour, reaction finishes, obtain crude product, this crude product, through recrystallization separation and purification, obtains target product triphenyl pyrazole compound.
Pyrazole compound of the present invention is the compound that a class has good fungicidal activity, very promising as sterilant research and development.In conjunction with three phenyl, at numerous subjects such as organic chemistry, Materials science, pharmaceutical chemistry, superconductor and ferro-magnetic and Applied research fields, all there is huge potentiality and researching value simultaneously.
Embodiment
Embodiment mono-: in round-bottomed flask, add 2,3-F phenyl aldehyde 0.43g, methyl phenyl ketone 0.38g and sodium carbonate 0.12g, water is solvent, and 100 ℃ are reacted 16 hours, cooling, cross leaching filter cake, and recrystallization obtains 3-(2,3-fluorophenyl)-1-phenyl acrylketone.In round-bottomed flask, add 3-(2,3-difluorophenyl)-1-phenyl acrylketone 0.24g and phenylhydrazine 0.16g, take dehydrated alcohol as solvent, under 50 ℃ of conditions, react 3 hours, be spin-dried for and obtain crude product.Crude product is through recrystallization, suction filtration, and separation and purification, obtains target product 1,3-phenylbenzene-5-(2,3-difluorophenyl)-pyrazoles.Faint yellow solid, productive rate: 56 %.
IR?(KBr,?cm -1):?v?3084,?3027,?1593,?1488,?1391,?1272,?1132,?1067,?757,?734,?685
1H?NMR?(500?MHz,?CDCl 3):?δ?7.75-7.73?(m,?2H),?7.42-7.39?(m,?2H),?7.37-7.33?(m,?1H),?7.25-7.21?(m,?2H),?7.?09-7.05?(m,?3H),?6.99-6.96?(m,?2H),?6.85-6.82?(m,?1H),?5.62-5.58?(m,?1H),?3.95-3.89?(m,?1H),?3.17-3.12?(m,?1H)。
19F?NMR?(470?MHz,?CDCl 3):?δ?-137.81?to?-137.88?(m,?1F),?-143.94?to?-144.01?(m?1F)。
13C?NMR?(125?MHz,?CDCl 3):?δ?151.72,?149.73,?147.28,144.48,?132.48,?131.70,?129.15,?128.94(t,?J?=?17.3?Hz),?128.67,?125.87,?124.85(dd,?J?=?4.4,?6.54?Hz),?122.21(t,?J?=?2.95?Hz),?119.56,?116.52,?113.28,?57.39(t,?J?=?2.67?Hz),?42.20。
Embodiment bis-: in round-bottomed flask, add 2,4-F phenyl aldehyde 0.43g, methyl phenyl ketone 0.38g and sodium carbonate 0.12g, water is solvent, and 100 ℃ are reacted 16 hours, cooling, cross leaching filter cake, and recrystallization obtains 3-(2,4-fluorophenyl)-1-phenyl acrylketone.In round-bottomed flask, add 3-(2,4 difluorobenzene base)-1-phenyl acrylketone 0.24g and phenylhydrazine 0.16g, take dehydrated alcohol as solvent, under 50 ℃ of conditions, react 3 hours, be spin-dried for and obtain crude product.Crude product is through recrystallization, suction filtration, and separation and purification, obtains target product 1,3-phenylbenzene-5-(2,4 difluorobenzene base)-pyrazoles.Light green solid, productive rate: 60 %.
IR?(KBr,?cm -1):?v?3065,?2923,?1595,?1499,?1392,?1262,?1127,?961,?743,?686
1H?NMR?(500?MHz,?CDCl 3):?δ?7.70-7.67?(m,?2H),?7.52-7.49?(m,?3H),?7.33-7.28?(m,?1H),?7.23-7.20?(m,?2H),?7.?09-7.06?(m,?1H),?6.97-6.95?(m,?1H),?6.83-6.81?(m,?1H),?6.81-6.77?(m,?1H),?6.69-6.65?(m,?1H),?5.27-5.23?(m,?1H),?3.92-3.90?(m,?1H),?3.68-3.63?(m,?1H)。
19F?NMR?(470?MHz,?CDCl 3):?δ?-127.55?to?-128.28?(m,?1F),?-139.04?to?-139.71?(m?1F)。
13C?NMR?(125?MHz,?CDCl 3):?δ?151.52,?148.53,?147.33,?144.57,?141.73,?137.18,?136.07,?129.75,?128.34(t,?J?=?17.3?Hz),?127.77,?124.55(dd,?J?=?4.4,?6.54?Hz),?119.21(t,?J?=?2.95?Hz),?116.57,?116.08,?114.18,?60.24(t,?J?=?2.67?Hz),?41.55。
Embodiment tri-: in round-bottomed flask, add 2,5-F phenyl aldehyde 0.43g, methyl phenyl ketone 0.38g and sodium carbonate 0.12g, water is solvent, and 100 ℃ are reacted 16 hours, cooling, cross leaching filter cake, and recrystallization obtains 3-(2,5-fluorophenyl)-1-phenyl acrylketone.In round-bottomed flask, add 3-(2,5-difluorophenyl)-1-phenyl acrylketone 0.24g and phenylhydrazine 0.16g, take dehydrated alcohol as solvent, under 50 ℃ of conditions, react 3 hours, be spin-dried for and obtain crude product.Crude product is through recrystallization, suction filtration, and separation and purification, obtains target product 1,3-phenylbenzene-5-(2,5-difluorophenyl)-pyrazoles.Faint yellow solid, productive rate: 56 %.
IR?(KBr,?cm -1):?v?3068,?2917,?1596,?1488,?1380,?1240,?1117,?875,?750,?688
1H?NMR?(500?MHz,?CDCl 3):?δ?7.74-7.72?(m,?2H),?7.41-7.38?(m,?2H),?7.36-7.33?(m,?1H),?7.25-7.21?(m,?2H),?7.?11-7.08?(m,?1H),?7.07-7.04?(m,?2H),?6.94-6.90?(m,?2H),?6.85-6.82?(m,?1H),?5.56-5.52?(m,?1H),?3.94-3.88?(m,?1H),?3.15-3.10?(m,?1H)。
19F?NMR?(470?MHz,?CDCl 3):?δ?-117.16?to?-117.24?(m,?1F),?-124.77?to?-124.85?(m,?1F)。
13C?NMR?(125?MHz,?CS 2–CDCl 3):?δ?158.23,?156.60(d,?J?=?2.71?Hz),?152.17,?147.34,?144.50,?131.08(dd,?J?=?7.27,?16.66?Hz),?129.18,?129.18,?128.67,?125.90,?119.66,?117.04(d,?J?=?8.99?Hz),?116.85(d,?J?=?8.26?Hz),?115.80(d,?J?=?8.35?Hz),?114.31(t,?J?=?2.30?Hz),?113.30,?57.56,?42.20。
Embodiment tetra-: in round-bottomed flask, add 3,4-F phenyl aldehyde 0.43g, methyl phenyl ketone 0.38g and sodium carbonate 0.12g, water is solvent, and 100 ℃ are reacted 16 hours, cooling, cross leaching filter cake, and recrystallization obtains 3-(3,4-difluorophenyl)-1-phenyl acrylketone.In round-bottomed flask, add 3-(3,4-difluorophenyl)-1-phenyl acrylketone 0.24g and phenylhydrazine 0.16g, take dehydrated alcohol as solvent, under 50 ℃ of conditions, react 3 hours, be spin-dried for and obtain crude product.Crude product is through recrystallization, suction filtration, and separation and purification, obtains target product 1,3-phenylbenzene-5-(3,4-difluorophenyl)-pyrazoles.Light green solid, productive rate: 56 %.
IR?(KBr,?cm -1):?v?3061,?2923,?1594,?1520,?1498,?1390,?1292,?1110,?863,?819,?742,?687。
1H?NMR?(500?MHz,?CDCl 3):?δ?7.70-7.67?(m,?2H),?7.52-7.49?(m,?3H),?7.28-7.23?(m,?2H),?7.20-7.17?(m,?1H),?7.?06-7.04?(m,?1H),?6.87-6.85?(m,?2H),?6.83-6.81?(m,?1H),?6.71-6.67?(m,?1H),?5.23-5.19?(m,?1H),?3.92-3.90?(m,?1H),?3.65-3.63(m,?1H)。
19F?NMR?(470?MHz,?CDCl 3):?δ?-119.36?to?-119.79?(m,?1F),?-127.27?to?-127.85?(m,?1F)。
13C?NMR?(125?MHz,?CDCl 3):?δ?151.72,?149.53,?147.58,?144.08,?140.73,?136.48,?135.70,?129.15,?128.84(t,?J?=?17.3?Hz),?128.27,?124.15(dd,?J?=?4.4,?6.54?Hz),?120.21(t,?J?=?2.95?Hz),?116.92,?116.77,?114.78,?60.99(t,?J?=?2.67?Hz),?41.20。
Embodiment five: in round-bottomed flask, add 3,4,5-F phenyl aldehyde 0.43g, methyl phenyl ketone 0.38g and sodium carbonate 0.12g, water is solvent, and 100 ℃ are reacted 16 hours, cooling, cross leaching filter cake, and recrystallization obtains 3-(3,4,5-fluorophenyl)-1-phenyl acrylketone.In round-bottomed flask, add 3-(3,4,5-trifluorophenyl)-1-phenyl acrylketone 0.27g and phenylhydrazine 0.16g, take dehydrated alcohol as solvent, under 50 ℃ of conditions, react 3 hours, be spin-dried for and obtain crude product.Crude product is through recrystallization, suction filtration, and separation and purification, obtains target product 1,3-phenylbenzene-5-(3,4,5-trifluorophenyl)-pyrazoles.Light green solid, productive rate: 56 %.
IR?(KBr,?cm -1):?v?3062,?1595,?1532,?1499,?1450,?1392,?1359,?1134,?1041,?751,?691。
1H?NMR?(500?MHz,?CDCl 3):?δ?7.70-7.67?(m,?2H),?7.52-7.49?(m,?3H),?7.33-7.28?(m,?2H),?6.83-6.81?(m,?2H),?6.77-6.74?(m,?1H),?6.59-6.55?(m,?2H),?5.29-5.27?(m,?1H),?3.93-3.90?(m,?1H),?3.66-3.63?(m,?1H)。
19F?NMR?(470?MHz,?CDCl 3):?δ?-136.51?to?-136.60?(m,?2F),?-141.47?to?-141.60?(m,?1F)。
13C?NMR?(125?MHz,?CDCl 3):?δ?151.72,?149.93,?143.58,?142.08,?139.73,?136.48,?131.70,?129.15,?128.84(t,?J?=?17.3?Hz),?128.27,?120.15(dd,?J?=?4.4,?6.54?Hz),?116.92,?116.77,?111.78,?60.44?(t,?J?=?2.67?Hz),?40.20。
test result shows:when the quantity of F increases, fluorescence intensity also increases thereupon, and the difference of F position on phenyl ring, on fluorescence intensity also impact to some extent.Generally speaking, in the fluorine-containing triphenyl pyrazoles of compound, the more fluorescence intensities of contain fluorine atoms are stronger.We think because be fluorine atom because of its sucting electronic effect and conjugation slightly thereof, can increase fluorescence intensity to a certain extent.This compounds is having potential using value aspect fluorescent probe, fluorescent material and superconductor and ferro-magnetic.

Claims (2)

1. a fluorine-containing triphenyl pyrazole compound, is characterized in that the structure of this compound is:
Wherein: Fn is for being difluoro～trifluoro substituted-phenyl.
2. a method of preparing fluorine-containing triphenyl pyrazole compound according to claim 1, is characterized in that the method has following steps:
A. will by the mol ratio of 1:1 to 1:1.2, be dissolved in deionized water containing fluorobenzaldehyde and methyl phenyl ketone, 100 ℃ of backflows, stirring reaction 16 hours, through cooling, recrystallization, obtains fluorine-containing diphenylprop ketenes;
B. the fluorine-containing diphenylprop ketenes of step a gained, reactant phenylhydrazine are dissolved in organic solvent dehydrated alcohol by the mol ratio of 1:1.5 to 1:2,50-60 ℃ is stirred 2.5-3 hour, reaction finishes, obtain crude product, this crude product, through recrystallization separation and purification, obtains the fluorine-containing triphenyl pyrazole compound of target product.
CN201410107346.1A 2014-03-21 2014-03-21 Fluorine-containing triphenylpyrazole derivative and preparation method thereof Pending CN104030983A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88103735A (en) * 1987-06-17 1988-12-28 三井东压化学株式会社 It is the medicine of active ingredient treatment cerebrovascular disease that new pyrazoline derivative reaches with this compound
JPS6479157A (en) * 1987-06-17 1989-03-24 Mitsui Toatsu Chemicals Novel 2-pyrazolines and remedy for cerebrovascular disorder containing said compound as active component
CN102796045A (en) * 2012-09-11 2012-11-28 山东大学 Pyrazoline derivatives, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN88103735A (en) * 1987-06-17 1988-12-28 三井东压化学株式会社 It is the medicine of active ingredient treatment cerebrovascular disease that new pyrazoline derivative reaches with this compound
JPS6479157A (en) * 1987-06-17 1989-03-24 Mitsui Toatsu Chemicals Novel 2-pyrazolines and remedy for cerebrovascular disorder containing said compound as active component
CN102796045A (en) * 2012-09-11 2012-11-28 山东大学 Pyrazoline derivatives, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陆蓓琼，等: "Synthesis and Fluorescent Property of Pyrazoline Derivatives", 《CHIN. J. CHEM.》 *

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Application publication date: 20140910