CN103073393A - Method for preparing hydroxy-substituted polycyclic aromatic compound - Google Patents

Method for preparing hydroxy-substituted polycyclic aromatic compound Download PDF

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CN103073393A
CN103073393A CN2013100094150A CN201310009415A CN103073393A CN 103073393 A CN103073393 A CN 103073393A CN 2013100094150 A CN2013100094150 A CN 2013100094150A CN 201310009415 A CN201310009415 A CN 201310009415A CN 103073393 A CN103073393 A CN 103073393A
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CN103073393B (en
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夏莹
曲培源
刘振兴
葛睿
肖卿
张艳
王剑波
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Peking University
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Abstract

The invention discloses a method for preparing hydroxyl-substituted polycyclic aromatic compound. Dicarbonyl compounds such as intramolecular aldehyde ketone react with sulfohydrazide to obtain single N-sulfonyl-hydrazone, and the single N-sulfonyl-hydrazone reacts in an organic solvent under the alkaline condition, as a result, the hydroxy-substituted polycyclic aromatic compound is obtained. The method utilizes the activity difference between aldehyde and ketone, comprises a procedure of intramolecular carbon-carbon bond insertion-aromatization of the intermediate of the single N-sulfonyl-hydrazone, is short in reaction time and high in reaction yield, can well forbear and universally adapt to functional groups, and can be widely used for preparing various hydroxyl-substituted polycyclic armomatic compounds.

Description

The preparation method of the condensed ring aromatic compound that a kind of hydroxyl replaces
Technical field
The invention belongs to the organic synthesis field, relate in particular to a kind of preparation method of poly-ring aromatic compounds.
Background technology
The condensed ring aromatic compound that hydroxyl replaces is the very important organic compound of a class, and wherein, polysubstituted compound more has great significance to human lives and scientific research on the aromatic rings such as naphthols, phenanthrol.The phenanthrol derivative is the natural product that a class is distributed widely in the Nature, also is the important intermediate of organic synthesis, also is the important molecule type of a class in the pharmacology simultaneously, such as antimalarial drug class, anticarcinogen, anti-HIV etc.Simultaneously, the character such as the special photochemistry of phenanthrol analog derivative, light conduction is widely used in the materials chemistry it.The derivative of naphthols is widely used in laboratory, factory industry, is the basic framework of various bioactive natural products, pharmaceuticals, such as antibiotic, the antiviral agent of rosanomycin, Rifampin and other etc.In addition, the phenolic hydroxyl group on these phenolic compounds can be converted into corresponding triflate, then via various transition metal-catalyzed linked reactions, can further synthesize the poly-ring aromatic compounds of various polysubstituted functionalizations.
All the time, people constantly carry out Improvement and perfection to the synthetic method of the fused ring compound that hydroxyl replaces, but also without comparison general method construct the condensed ring aromatic compound that all kinds of hydroxyls replace.Synthetic for phenanthrol, comparatively ripe method is Friedel-Crafts acylations aromizing strategy in the ortho-metalated strategy of people's development such as Snieckus and the molecule, but these method conditions are harsh, and the former uses highly basic, and the latter uses strong Lewis; The regioselectivity of reaction and the universality of functional group also have problems etc.For naphthols, what present general synthetic method without comparison also, present method can only be for some particular type naphthols is synthetic.Therefore, the common method of the fused ring compound of development synthesis of hydroxy replacement just has a very big significance.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method of condensed ring aromatic compound of efficient hydroxyl replacement of easily going, the method has very widely substrate adaptability, can synthesize the derivative of numerous naphthols, phenanthrol by the method.
The technical scheme of the inventive method is as follows:
The preparation method of the condensed ring aromatic compound that a kind of hydroxyl replaces, then the double carbonyl compounds such as the interior aldehyde ketone of molecule under the effect of alkali, react in organic solvent by obtaining single N-sulphonyl hydrazone with the sulfonyl hydrazide reaction, obtain the condensed ring aromatic compound that hydroxyl replaces.
Above-mentioned double carbonyl compound is selected from 2, one or more in 2 '-dibenzyl aldehyde ketone, 2-ketone group aryl-thiazolinyl aldehyde and the 2-aldehyde radical aryl-alkenyl ketone; Wherein, described ketone is selected from one or more in aryl aryl ketones, aryl alkyl ketone, aryl alkenyl ketone, aromatic yl polysulfide yl ketone and the thiazolinyl alkyl ketone.On the described aryl with one or more substituting groups; On described thiazolinyl and the alkynyl with one or more substituting groups.Reaction formula can be expressed as follows:
Wherein: formula I, I ', I " represent double carbonyl compound, the various aromatic nucleus that have or not replacement of Ar and Ar ' expression comprise the full carbon aromatic ring such as phenyl ring, naphthalene nucleus or contain the assorted aromatic nucleus that the heteroatomss such as aerobic, sulphur, nitrogen replace, R 1, R 7And R 10The full carbon aromatic ring of expression alkyl, thiazolinyl, alkynyl, replacement or contain assorted aromatic nucleus that the heteroatomss such as aerobic, sulphur, nitrogen replace etc., R 2, R 3, R 6, and R 11Expression hydrogen, alkyl, alkoxyl group, halogen atom, trifluoromethyl, nitro, phenyl etc., R 4, R 5, R 8And R 9Expression alkyl, phenyl etc., R 4And R 5Mutually independence or Cheng Huan, R 8And R 9Mutually independence or Cheng Huan.
Method of the present invention has good tolerance to functional group, and 2, the aromatic base Ar of 2 '-dibenzyl double carbonyl compound and Ar ' are upper also can be with one or more substituting groups except carbonyl, and with respect to carbonyl, substituent position can be ortho position, contraposition and a position.Described substituting group limits never in any form, and common substituting group is alkyl, alkoxyl group, trifluoromethyl, thiazolinyl, alkynyl, aromatic base, ester group, nitro, hydroxyl for example, halogen etc.When having a plurality of substituting group, these a plurality of substituting groups can be identical or different, and two adjacent substituting groups can separate or Cheng Huan.
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 etc.; The alkyl that more preferably has 1～4 carbon atom, particularly preferably methyl, ethyl and propyl group.
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 etc.; The alkoxyl group that more preferably has 1～4 carbon atom, particularly preferably methoxyl group, oxyethyl group and isopropoxy.
Above-mentioned ester group such as formic acid ester group, acetate groups, propionic acid ester group and acrylate-based etc.
Above-mentioned halogen refers to fluorine, chlorine, bromine or iodine atom.
Aromatic base substituting group on above-mentioned aromatic base Ar and the Ar ' also can be to replace or unsubstituted heterocyclic aromatic base (such as furans, thiophene and indoles etc.) and non-heterocyclic aromatic base (such as phenyl ring and naphthalene nucleus etc.), can be with one or more substituting groups that are selected from following radicals: alkyl, alkoxyl group, trifluoromethyl, perfluoroalkyl, thiazolinyl, ester group, nitro, hydroxyl and halogen.Each substituent preferable range as mentioned above.
In the method for the present invention, described sulfonyl hydrazide is preferably arylsulfonyl hydrazine, particularly preferably p-toluene sulfonyl hydrazide.
In the method for the present invention, described alkali refers generally to metal alkoxides alkoxide and carbonate, such as sodium methylate, trimethyl carbinol lithium, cesium carbonate etc., particularly preferably sodium methylate and trimethyl carbinol lithium.
When described sulfonyl hydrazide is p-toluene sulfonyl hydrazide, when alkali was sodium methylate, the reaction formula of the inventive method can be expressed as follows:
When described sulfonyl hydrazide is p-toluene sulfonyl hydrazide, when alkali was trimethyl carbinol lithium, the reaction formula of the inventive method can be expressed as follows:
Wherein, " represent double carbonyl compound, formula II compound is p-toluene sulfonyl hydrazide, the condensed ring aromatic compound that formula III compounds represented hydroxyl replaces for formula I, I ', I.
The employed organic solvent of the inventive method is selected from a kind of in the following collection: Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF), toluene etc.Its consumption is preferably the 20mL/mmol-100mL/mmol double carbonyl compound.
The molar ratio of the inventive method agents useful for same and raw material is double carbonyl compound: p-toluene sulfonyl hydrazide: alkali=1: (1-1.03): (1.2-2.5).The effect of p-toluene sulfonyl hydrazide is that aldehyde ketone is converted into the sulphonyl hydrazone, transforms fully for making aldehyde, and the consumption mol ratio of hydrazine is a bit larger tham 1.
The temperature of reaction of above-mentioned reaction and reaction times: the temperature of reaction that the first step generates hydrazone is 60～90 ℃, and the reaction times is 10～30min, and preferred 70 ℃ of reaction 30min are as the criterion fully with double carbonyl compound and p-toluene sulfonyl hydrazide consumption; Second step temperature of reaction under the effect of alkali is 25～90 ℃, and the reaction times is 30min～3h, preferred 70 ℃ of reaction 30min.Heat-processed can adopt oil bath (for example silicone oil, paraffin wet goods) or other type of heating.
The present invention preferably carries out aftertreatment to reaction product after reaction is finished, comprise concentrated and purifying.
Described concentration process can adopt the methods such as air distillation, underpressure distillation, for example uses the Rotary Evaporators vacuum concentration.
Described purge process is to obtain pure product by column chromatography, or the rear dry concentrated pure product that to get of separatory extraction.
Embodiment
Further describe the present invention below in conjunction with embodiment, but the scope that does not limit the present invention in any way.
Synthesizing of embodiment 1a 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1b 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 10ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100052
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1c 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 15ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100061
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1d 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 30ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100062
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1e 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 56mg (0.30mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is pink solid, and productive rate is 92%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1f 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 60 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100072
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1g 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 10min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100081
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1h 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 90 ℃ of reaction 10min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100082
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1i 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (20mg, 0.36mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is pink solid, and productive rate is 85%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1j 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (33mg, 0.60mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100092
The gained compound is pink solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1k 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 1h that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100101
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1l 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml THF.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 90 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100102
The gained compound is pink solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
1HNMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)；13C?NMR(100MHz，CDCl3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1m 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6mldioxane.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 90 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100111
The gained compound is pink solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
1HNMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1n 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (60mg, 0.75mmol), 90 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100112
The gained compound is pink solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1o 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add Cs 2CO 3(243mg, 0.75mmol), 90 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100121
The gained compound is pink solid, and productive rate is 64%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1p 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 90 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100122
The gained compound is pink solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1q 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, recover room temperature, add NaOMe (41mg, 0.75mmol), in 60 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100131
The gained compound is pink solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1r 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, recover room temperature, add NaOMe (41mg, 0.75mmol), in 50 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is pink solid, and productive rate is 80%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，?126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 1s 10-phenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-2-formaldehyde 85.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, recover room temperature, add NaOMe (41mg, 0.75mmol), 25 ℃ of lower reaction 3h that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100141
The gained compound is pink solid, and productive rate is 62%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.67(d，J＝7.9Hz，1H)，8.63(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.69-7.36(m，10H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.03，134.46，132.43，131.42，131.00，129.74，128.56，127.19，126.78，126.59，126.38，125.32，124.95，123.97，123.05，122.55，122.48，117.22.
Synthesizing of embodiment 2 10-p-methylphenyl-9 phenanthrol
Under argon shield, add successively with 1,1-biphenyl-2 '-to methyl benzoyl-2-formaldehyde 90mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene in the 25ml Schlenk bottle after the oven dry.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100142
Gained compound white solid, productive rate are 94%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.70(d，J＝8.1Hz，1H)，8.66(d，J＝8.2Hz，1H)，8.38(d，J＝7.8Hz，1H)，7.72-7.63(m，2H)，7.50-7.34(m，7H)，5.49(s，1H)，2.48(s，3H)；? 13C?NMR(100MHz，CDCl 3)δ146.09，138.42，132.60，131.27，131.18，130.93，130.49，127.11，126.74，126.57，126.36，125.40，124.94，123.90，123.01，122.53，122.48，117.16，21.36.
Synthesizing of embodiment 3 10-p-methoxyphenyl-9 phenanthrol
Under argon shield, add successively with 1,1-biphenyl-2 '-to anisoyl-2-formaldehyde 94.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene in the 25ml Schlenk bottle after the oven dry.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=10: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100151
The gained compound is pink solid, and productive rate is 88%, and its nuclear magnetic data is as follows:
1HNMR(400MHz，CDCl 3)δ8.71(d，J＝8.1Hz，1H)，8.66(d，J＝8.1Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.72-7.64(m，2H)，7.50-7.37(m，5H)，7.14(d，J＝8.1Hz，1H)，5.50(s，1H)，3.91(s，3H)； 13C?NMR(100MHz，CDCl 3)δ159.81，146.32，132.82，132.63，130.92，127.11，126.76，126.58，126.36，126.05，125.37，124.92，123.89，123.02，122.54，122.48，116.83，115.24，55.38.
Synthesizing of embodiment 4 10-rubigan-9 phenanthrol
Under argon shield, add successively with 1,1-biphenyl-2 '-to chlorobenzene formacyl-2-formaldehyde 96mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene in the 25ml Schlenk bottle after the oven dry.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=50: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100161
The gained compound is pink solid, and productive rate is 76%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.68(d，J＝8.1Hz，1H)，8.65(d，J＝8.2Hz，1H)，8.37(d，J＝8.0Hz，1H)，7.72-7.63(m，2H)，7.57(d，J＝8.0Hz，2H)，7.50-7.38(m，4H)，7.32(d，J＝8.1Hz，1H)，5.33(s，1H)； 13C?NMR(100MHz，CDCl 3)δ146.13，134.78，132.89，132.16，131.08，130.06，127.43，126.93，126.72，126.42，125.06，124.83，124.16，123.05，122.65，122.52，115.98.
Synthesizing of embodiment 5 10-p-nitrophenyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-p-nitrophenyl formyl radical-2-formaldehyde 99mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=20: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is yellow solid, and productive rate is 41%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.74-8.69(m，2H)，8.48(d，J＝8.2Hz，2H)，8.39(d，J＝8.0Hz，1H)，7.78-7.69(m，4H)，7.54(t，J＝7.5Hz，1H)，7.46(t，J＝7.4Hz，1H)，7.27(d，J＝9.5Hz，1H)，5.25(s，1H)； 13C?NMR(100MHz，CDCl 3)δ148.02，146.07，142.23，132.72，131.44，131.35，127.90，127.21，126.96，126.55，124.84，124.72，124.56，123.03，122.85，122.64，115.35
Synthesizing of embodiment 6 10-(2,4-3,5-dimethylphenyl)-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1 biphenyl-2 '-(2,4 dimethylbenzoyl)-2-formaldehyde 94mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=60: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100171
The gained compound is pink solid, and productive rate is 98%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.69(d，J＝8.0Hz，1H)，8.64(d，J＝8.2Hz，1H)，8.38(d，J＝7.8Hz，1H)，7.69-7.62(m，2H)，7.46(t，J＝7.5Hz，1H)，7.39(t，J＝7.4Hz，1H)，7.25-7.17(m，4H)，5.28(s，1H)，2.42(s，3H)，2.00(s，3H)； 13C?NMR(100MHz，CDCl 3)δ146.00，138.96，138.79，132.27，131.85，131.56，130.99，130.04，127.78，127.02，126.88，126.48，126.40，125.08，124.98，123.89，122.98，122.61，122.49，116.37，21.26，19.49。
Synthesizing of embodiment 7 10-(thiophene-2)-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively 1,1-biphenyl-2 '-(thiophene 2-formyl radical)-2-formaldehyde 87.6mg (0.30mmol), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=20: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100181
The gained compound is white solid, and productive rate is 92%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.69-8.62(m，2H)，8.39(d，J＝7.8Hz，1H)，7.73-7.48(m，6H)，7.30-7.21(m，2H)，5.85(s，1H)； 13C?NMR(100MHz，CDCl 3)δ148.25，134.52，132.99，131.44，130.18，128.64，128.19，127.78，127.04，126.69，126.20，125.18，124.54，124.17，123.33，122.52，122.46，109.15.
(1-methyl isophthalic acid-hydrogen-indoles-3-)-9 phenanthrol is synthetic for embodiment 8 10-
Under argon shield; to the oven dry after 25ml Schlenk bottle in add successively 1; 1-biphenyl-2 ' (1-methyl isophthalic acid hydrogen indoles 3-formyl radical)-2-formaldehyde 102mg (0.30mmol), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=20: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100182
Gained compound productive rate is 73%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ9.97(s，1H)，8.13(d，J＝7.6Hz，1H)，7.89(d，J＝7.4Hz，1H)，7.63(d，J＝6.8Hz，1H)，7.53(t，J＝7.4Hz，2H)，7.45-7.42(m，1H)，7.35-7.29(m，6H)，7.24(d，J＝1.4Hz，1H)，3，76(s，3H)； 13C?NMR(100MHz，CDCl 3)δ191.86，190.78，143.85，141.44，138.14，137.50，136.78，133.98，133.05，131.69，131.03，129.13，128.23，127.84，127.80，127.59，126.48，123.60，122.70，122.51，117.08，109.59，33.50.
Synthesizing of embodiment 9 10-styryl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-(styryl-formyl radical)-2-formaldehyde 93.6mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100191
The gained compound is yellow solid, and productive rate is 62%, and its nuclear magnetic data is as follows:
1H?NMR(500MHz，CDCl 3)δ8.66-8.62(m，2H)，8.40(d，J＝7.8Hz，1H)，7.86(d，J＝7.7Hz，1H)，7.69-7.60(m，4H)，7.56-7.50(m，2H)，7.47-7.34(m，4H)，7.06(d，J＝16.8Hz，1H)，6.34(s，1H)； 13C?NMR(125MHz，CDCl 3)δ146.58，136.38，131.79，130.89，128.90，128.49，127.31，126.98，126.61，126.59，126.24，125.03，124.32，124.22，123.37，122.85，122.79，122.44，112.87
Synthesizing of embodiment 10 10-phenylacetylene base-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-(phenylacetylene base-formyl radical)-2-formaldehyde 93mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (60mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100192
The gained compound is brown solid, and productive rate is 32%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.64(d，J＝8.2Hz，1H)，8.60(d，J＝8.2Hz，1H)，8.38(d，J＝7.9Hz，1H)，8.28(d，J＝7.9Hz，1H)，7.73-7.53(m，6H)，7.43-7.42(m，3H)，6.62(s，1H)； 13C?NMR(100MHz，CDCl 3)δ153.11，131.61，131.25，131.12，128.81，128.59，128.26，127.46，126.76，126.19，125.52，124.76，124.06，123.16，122.71，122.65，101.25，99.32，82.06.
Synthesizing of embodiment 11 10-methyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-ethanoyl-2-formaldehyde 67.2mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (60mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=50: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100201
The gained compound is yellow solid, and productive rate is 76%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CD 3COCD 3)δ8.77-8.72(m，2H)，8.41-8.39(m，1H)，8.12(s，1H)，8.00(d，J＝8.2Hz，1H)，7.66-7.58(m，3H)，7.51(t，J＝7.5Hz，1H)，2.65(s，3H)；? 13C?NMR(100MHz，CD 3COCD 3)δ148.04，134.19，131.19，127.75，127.70，127.44，127.16，127.08，124.63，124.46，123.65，123.41，123.25，112.76，11.78.
Synthesizing of embodiment 12 10-ethyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-propionyl-2-formaldehyde 71.4mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 90 ℃ of reaction 30min, add LiO tBu (60mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=50: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100211
The gained compound is white solid, and productive rate is 84%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CD 3COCD 3)δ8.78-8.74(m，2H)，8.42-8.40(m，1H)，8.11(s，1H)，8.05(d，J＝8.2Hz，1H)，7.65-7.59(m，3H)，7.52-7.48(m，1H)，3.25(q，J＝7.5Hz，2H)，1.30(t，J＝7.5Hz，3H)，2.65(s，3H)； 13C?NMR(100MHz，CD 3COCD 3)δ147.51，133.09，131.24，127.81，127.73，127.56，127.14，124.53，124.23，123.89，123.42，123.28，119.08，19.15，14.52.
Synthesizing of embodiment 13 10-cyclopropyl-9 phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1 biphenyl-2 '-cyclopropyl formyl radical-2-formaldehyde 75mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (60mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100212
The gained compound is pink solid, and productive rate is 87%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CD 3COCD 3)δ8.72(d，J＝7.8Hz，1H)，8.69(d，J＝8.2Hz，1H)，8.43(d，J＝7.7Hz，1H)，8.38(d，J＝7.5Hz，1H)，8.02(s，1H)，7.67-7.57(m，3H)，7.50-7.46(m，1H)，2.03-1.96(m，1H)，1.37-1.32(m，2H)，0.72-0.68(m，2H)； 13CNMR(100MHz，CD 3COCD 3)δ150.31，134.68，131.72，127.60，127.45，127.24，127.11，126.99，125.44，124.42，123.59，123.26，115.24，8.70，7.93
Synthesizing of embodiment 14 10-tertiary butyl 9-oxo-10-hydrogen phenanthrene
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-pivaloyl group-2-formaldehyde 79.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (60mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100221
The gained compound is white solid, and productive rate is 91%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CD 3COCD 3)δ8.09(d，J＝8.0Hz，1H)，8.03(d，J＝7.8Hz，1H)，7.80(dd，J＝7.7，0.9Hz，1H)，7.71(dt，J＝8.0，1.3Hz，1H)，7.48-7.40(m，2H)，7.34-7.33(m，2H)，3.46(s，1H)，0.82(s，9H)； 13C?NMR(100MHz，CD 3COCD 3)δ202.14，139.56，136.59，135.04，133.63，133.21，132.41，129.21，128.71，128.32，126.73，125.07，123.95，64.39，37.02，28.44
Synthesizing of embodiment 15 7-Trifluoromethyl-1 0-phenyl-9-phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-4 ' trifluoromethyl-2-formaldehyde 106.2mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 90 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100222
The gained compound is pink solid, and productive rate is 87%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.77(d，J＝8.6Hz，1H)，8.69(s，1H)，8.65(d，J＝7.9Hz，1H)，7.88(d，J＝8.7Hz，1H)，7.64-7.40(m，8H)，5.51(s，1H)； 13C?NMR(100MHz，CDCl 3)δ145.83，133.78，133.21，132.95，131.24，129.95，128.93，28.38(q，J＝?32Hz)，127.90，125.65，125.59，124.52，124.50(q，J＝271Hz)，124.47，123.37，123.02，120.92(q，J＝4.2Hz)，118.52
Synthesizing of embodiment 16 6-chloro-10-phenyl-9-phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-5 ' chloro-2-formaldehyde 96.0mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100231
The gained compound is yellow solid, and productive rate is 80%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.63(s，1H)，8.52(d，J＝7.9Hz，1H)，8.29(d，J＝8.7Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.60-7.35(m，9H)，5.44(s，1H)； 13C?NMR(100MHz，CDCl 3)δ145.71，134.04，133.44，132.87，132.16，131.32，129.82，128.73，127.40，127.02，125.43，125.39，124.79，124.24，123.25，122.62，122.18，117.51
Synthesizing of embodiment 17 10-phenyl-[5,6] benzo 9-phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively the 2-benzoyl naphthalene 100.8mg (0.30mmol) with 1-(1-formyl radical phenyl 2-), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=15: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is pink solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.63(s，1H)，8.52(d，J＝7.9Hz，1H)，8.29(d，J＝8.7Hz，1H)，8.38(d，J＝7.9Hz，1H)，7.60-7.35(m，9H)，5.44(s，1H)； 13C?NMR(100MHz，CDCl 3)δ145.71，134.04，133.44，132.87，132.16，131.32，129.82，128.73，127.40，127.02，125.43，125.39，124.79，124.24，123.25，122.62，122.18，117.51
Synthesizing of embodiment 18 2-methoxyl group-10-phenyl-9-phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-4-methoxyl group-2-formaldehyde 94.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=15: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100241
The gained compound is red solid, and productive rate is 97%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.53(t，J＝10Hz，2H)，8.34(d，J＝8.0Hz，1H)，7.65-7.43(m，7H)，7.08(d，J＝8.8Hz，1H)，6.76(s，1H)，5.45(s，1H)，3.68(s，3H)；? 13C?NMR(100MHz，CDCl 3)δ158.46，146.60，134.44，133.95，131.32，131.08，129.81，128.60，127.26，125.56，124.18，123.83，123.04，121.97，120.71，116.92，113.29，106.93，55.08.
Embodiment 19 2,3-methylene-dioxy-10-phenyl-9 phenanthrol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-3 4-methylene-dioxy-2-formaldehyde 99mg (0.30mmol), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=15: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100251
The gained compound is pink solid, and productive rate is 95%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl3)δ8.47(d，J＝8.2Hz，1H)，8.34(d，J＝8.0Hz，1H)，8.01(s，1H)，7.66-7.42(m，7H)，6.74(s，1H)，5.99(s，2H)，5.30(s，1H)；13C?NMR(100MHz，CDCl3)δ147.74，146.01，145.10，134.66，131.32，130.54，129.84，128.79，128.65，126.90，125.68，123.89，123.04，122.23，121.86，117.60，103.38，101.13，100.91
Synthesizing of embodiment 20 3-fluoro-10-phenyl-9-phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-5-fluoro-2-formaldehyde 91.2mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=50: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100252
The gained compound is red solid, and productive rate is 87%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.54(d，J＝8.0Hz，1H)，8.38(d，J＝6.8Hz，1H)，8.26(d，J＝11Hz，1H)，7.69-7.42(m，7H)，7.36-7.32(m，1H)，7.18-7.14(m，1H)，5.40(s，1H)； 13C?NMR(100MHz，CDCl 3)δ160.10(d，J＝243Hz)，145.43(d，J＝2.2Hz)，134.23，131.35，130.23(d，J＝4.2Hz)，129.84，129.03，128.74，127.67(d，J＝7.9Hz)，127.30(d，J＝8.6Hz)，127.23，127.21，125.34，123.20，122.67，116.93，115.49(d，J＝23.3Hz)，107.68(d，J＝22.4Hz).
Synthesizing of embodiment 21 2-nitro-10-phenyl-9-phenanthrol
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 1,1-biphenyl-2 '-benzoyl-4 nitros-2-formaldehyde 99.3mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=20: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100261
The gained compound is yellow solid, and productive rate is 75%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.75-8.70(m，2H)，8.44-8.43(m，1H)，8.28(s，1H)，8.24(d，J＝9.0Hz，1H)，7.79-7.45(m，7H)，5.08(s，1H)； 13C?NMR(100MHz，CDCl 3)δ147.88，146.30，132.82，132.36，131.24，130.26，129.90，129.40，128.55，128.11，126.20，123.94，123.53，123.40，121.00，117.67，117.38
Synthesizing of embodiment 22 2-methoxyl group-5-methyl isophthalic acid 0-(4-hexyloxy phenyl)-9-phenanthrol
Under argon shield; to the oven dry after 25ml Schlenk bottle in add successively 1; 1-biphenyl-2 '-(4-hexyloxy benzoyl)-4-methoxyl group-6 '-methyl-2-formaldehyde 129.2mg (0.30mmol), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (60mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100262
The gained compound is pink solid, and productive rate is 93%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.74(d，J＝9.3Hz，1H)，8.30(d，J＝7.5Hz，1H)，7.49-7.43(m，2H)，7.32-7.30(m，2H)，7.07-7.03(m，3H)，6.84(s，1H)，5.49(s，1H)，?3.97(t，J＝6.5Hz，2H)，3.69(s，3H)，3.08(s，3H)，1.80(quint，J＝6.8Hz，2H)，1.47(quint，J＝6.8Hz，2H)，1.37-1.35(m，4H)，0.93-0.90(m，3H)； 13C?NMR(100MHz，CDCl 3)δ159.32，157.41，147.05，135.74，134.19，132.48，131.89，130.88，128.90，126.04，125.42，124.92，122.10，121.34，116.57，115.80，111.52，107.29，68.08，54.99，31.59，29.23，27.43，25.74，22.59，14.02
Embodiment 23 4-Phenylnaphtho[1,2-b] furan-5-ol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 2-(2-benzoylphenyl)-3-formylfuran 82.8mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100271
The gained compound is yellow solid, and productive rate is 87%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.34(d，J＝8.3Hz，1H)，8.26(d，J＝8.1Hz，1H)，7.66(s，1H)，7.62-7.44(m，7H)，6.64(s，1H)，5.64(s，1H)； 13C?NMR(100MHz，CDCl 3)δ145.27，144.17，143.74，134.89，129.86，129.66，128.17，126.83，124.80，123.42，122.81，121.41，119.76，114.06，106.96
Embodiment 24 5-Phenylnaphtho[2,1-b] furan-4-ol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively the benzoyl 82.8mg (0.30mmol) with 2-(2-benzoyl furans-3), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is yellow solid, and productive rate is 90%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.09(d，J＝8.0Hz，1H)，7.78(s，1H)，7.58-7.41(m，7H)，7.36-7.32(m，1H)，7.28(s，1H)，5.45(s，1H)； 13C?NMR(100MHz，CDCl 3)δ144.66，142.96，138.36，133.99，131.44，130.73，129.40，128.35，125.74，125.01，124.23，123.81，123.36，123.25，118.52，106.04
Embodiment 25 4-Phenylnaphtho[2,1-b] thiophen-5-ol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 3-(2-benzoylphenyl)-2-formyl radical thiophene 87.6mg (0.30mmol) 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=20: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is green solid, and productive rate is 93%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.36(d，J＝8.2Hz，1H)，8.28(d，J＝8.1Hz，1H)，7.91(d，J＝5.4Hz，1H)，7.64-7.48(m，7H)，7.33(d，J＝5.4Hz，1H)，5.60(s，1H)； 13CNMR(100MHz，CDCl 3)δ145.23，139.25，134.86，129.99，129.96，129.88，129.30，129.00，126.99，125.06，123.43，123.35，123.32，123.15，122.09，115.99
Embodiment 26 5-Phenylnaphtho[2,1-b] thiophen-4-ol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively the benzoyl 87.6mg (0.30mmol) with 2-(2-benzoyl thiophene-3), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100291
The gained compound is light yellow solid, and productive rate is 99%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.30(d，J＝8.0Hz，1H)，7.99(d，J＝5.0Hz，1H)，7.61-7.56(m，3H)，7.52-7.37(m，6H)，5.52(s，1H)； 13C?NMR(100MHz，CDCl 3)δ145.20，137.70，133.90，132.10，131.46，129.67，128.57，128.30，126.55，125.67，125.51，125.28，123.75，123.66，122.35，116.76
Embodiment 27 5-Phenylbenzo[1,2-b:4,3-b '] dithiophen-4-ol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with 33 '-bithiophene-2 '-benzoyl 2-formyl radical 89.4mg (0.30mmol), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100292
The gained compound is yellow solid, and productive rate is 99%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.67-7.54(m，7H)，7.48-7.45(m，1H)，7.31(d，J＝5.3Hz，1H)，5.59(s，1H)； 13C?NMR(100MHz，CDCl 3)δ144.27，139.04，135.29，134.49，129.89，129.78，128.91，128.78，127.23，126.50，123.99，122.23，121.96，115.74
Embodiment 28 5-Phenylthieno[3,2-e] benzofuran-4-ol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively the 2 formyl radical thiophene 84.6mg (0.30mmol) with 3-(2-benzoyl furans 3-), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100301
The gained compound is green solid, and productive rate is 40%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.75(s，1H)，7.64-7.46(m，6H)，7.36(d，J＝5.4Hz，1H)，7.07(s，1H)，5.35(br，1H)； 13C?NMR(100MHz，CDCl 3)δ145.01，142.82，136.94，136.30，134.85，129.88，129.53，128.65，125.88，124.69，122.44，121.67，117.10，106.11
Embodiment 29 4-Phenylphenanthro[3,4-b] thiophen-5-ol synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively 3-(2-benzoyl 1-naphthyl)-2-formyl radical thiophene 102.6mg (0.30mmol), 58mg (0.309mmol) p-toluene sulfonyl hydrazide, 6ml toluene.Behind 70 ℃ of reaction 30min, add NaOMe (41mg, 0.75mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (45mg, 0.75mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=30: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100302
The gained compound is green solid, and productive rate is 77%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ9.12(d，J＝8.3Hz，1H)，8.55(d，J＝5.3Hz，1H)，8.37(d，J＝8.9Hz，1H)，7.98(d，J＝7.7Hz，1H)，7.84(d，J＝8.9Hz，1H)，7.71-7.51(m，7H)，7.46(d，J＝5.2Hz，1H)，5.60(s，1H)； 13C?NMR(100MHz，CDCl 3)δ145.51，?141.86，134.81，133.17，130.25，130.04，130.01，129.19，129.03，128.69，126.89，126.56，126.26，126.09，125.81，123.66，121.80，121.20，117.72
Embodiment 30 3-methyl-2,4-phenylbenzene 1-naphthols synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with Z-3-(2-benzoylphenyl)-2-methyl-3 cinnamic aldehyde 65.2mg (0.20mmol) 38mg (0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100311
The gained compound is white solid, and productive rate is 87%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.27(d，J＝8.3Hz，1H)，7.56-7.28(m，11H)，7.29(d，J＝7.5Hz，2H)，5.26(s，1H)，1.89(s，3H)； 13C?NMR(100MHz，CDCl 3)δ147.44，140.32，135.88，133.27，132.02，131.07，130.78，130.71，129.62，128.35，128.31，126.80，126.31，126.01，124.41，122.53，122.29，122.15，19.26
Embodiment 31 4-methyl-2,3-phenylbenzene 1-naphthols synthetic
Under argon shield, to the oven dry after 25ml Schlenk bottle in add successively with Z-3-(2-benzoylphenyl)-2-phenyl-crotonic aldehyde 65.2mg (0.20mmol) 38mg (0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100321
The gained compound is white solid, and productive rate is 80%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.34(d，J＝8.1Hz，1H)，8.06(d，J＝8.4Hz，1H)，7.61-7.52(m，2H)，7.26-7.22(m，2H)，7.19-7.10(m，6H)，7.01(d，J＝7.7Hz，2H)，5.35(s，1H)，2.40(s，3H)； 13C?NMR(100MHz，CDCl 3)δ146.32，140.85，138.79，135.72，132.97，131.13，130.39，128.72，127.42，127.38，126.71，126.13，125.10，124.35，123.45，123.36，122.84，121.87，16.24
Embodiment 32 2,4-phenylbenzene-3-methyl-7,8-methylene-dioxy-1-naphthols synthetic
Under argon shield; add successively in the 25ml Schlenk bottle after the oven dry with (Z)-3-(6-Benzoylbenzo[d] [1; 3] dioxol-5-yl)-2-methyl-3-phenylacrylaldehyde74.2mg (0.20mmol); 38mg (0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100322
The gained compound is yellow solid, and productive rate is 76%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)7.55-7.51(m，3H)，7.48-7.37(m，6H)，7.27-7.23(m，2H)，6.65(s，1H)，5.95(s，2H)，5.15(s，1H)，1.84(s，3H)； 13C?NMR(100MHz，CDCl 3)δ147.93，147.01，146.41，140.61，136.02，130.78，130.66，130.63，130.46，129.56，128.46，128.20，126.81，121.74，118.47，115.25，102.81，100.87，98.88，19.09
Embodiment 33 2; 3-phenylbenzene-4-methyl 6; synthesizing under argon shield of 7-methylene-dioxy-1-naphthols; add successively in the 25ml Schlenk bottle after the oven dry with (Z)-3-(6-Benzoylbenzo[d] [1; 3] dioxol-5-yl)-and 2-phenylbut-2-enal (74.2mg, 0.20mmol), p-toluene sulfonyl hydrazide (38mg; 0.204mmol), 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100331
The gained compound is white solid, and productive rate is 74%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)7.62(s，1H)，7.36(s，1H)，7.24-7.21(m，2H)，7.19-7.09(m，6H)，7.01-6.09(m，2H)，6.07(s，2H)，5.24(s，1H)，2.30(s，3H)； 13C?NMR(100MHz，CDCl 3)δ148.44，146.92，145.89，140.96，137.56，135.85，131.19，130.50，130.24，129.10，128.68，127.34，126.05，122.55，121.11，119.75，101.25，101.08，99.56，16.72
Embodiment 34 2,4-phenylbenzene-3-methyl-7 Trifluoromethyl-1s-naphthols synthetic
Under argon shield; add successively (Z)-3-(2-Benzoyl-4-(trifluoromethyl) phenyl)-2-methyl-3-phenylacrylaldehyde (78.8mg in the 25ml Schlenk bottle after the oven dry; 0.20mmol); p-toluene sulfonyl hydrazide (38mg; 0.204mmol), 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100332
The gained compound is white solid, and productive rate is 78%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)8.60(s，1H)，7.59-7.56(m，2H)，7.51-7.38(m，8H)，7.29-7.27(m，2H)，5.37(s，1H)，1.92(s，3H)； 13C?NMR(100MHz，CDCl 3)δ148.15，?139.56，135.18，134.92，134.37，131.20，130.63，130.52，129.83，128.67，128.57，127.19，127.06，126.19(q，J＝35.0Hz)，124.63(q，J＝271.9Hz)，123.79，121.80(q，J＝3.1Hz)，121.26，120.46(q，J＝4.5Hz)，19.47
Embodiment 35 2,3-phenylbenzene-4-methyl-7 Trifluoromethyl-1s-naphthols synthetic
Under argon shield; add successively (Z)-3-(2-Benzoyl-4-(trifluoromethyl) phenyl)-2-phenylbut-2-enal (78.8mg in the 25ml Schlenk bottle after the oven dry; 0.20mmol); p-toluene sulfonyl hydrazide (38mg; 0.204mmol), 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100341
The gained compound is white solid, and productive rate is 64%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDC l3)8.66(s，1H)，8.16(d，J＝8.9Hz，1H)，7.75(dd，J＝8.9，1.7Hz，1H)，7.29-7.09(m，8H)，7.01-6.99(m，2H)，5.45(s，1H)，2.42(s，3H)； 13CNMR(100MHz，CDCl 3)δ147.03，141.20，140.28，135.03，134.18，130.95，130.12，128.91，127.78，127.54，126.82(q，J＝32.3Hz)，126.47，125.46，124.61(q，J＝271.7Hz)，123.59，123.17，122.51，122.18(q，J＝3.0Hz)，121.0(q，J＝4.6Hz)，16.28.
Embodiment 36 4-Phenyl-2; 3-dihydro-1H-cyclopenta[a] the synthesizing under argon shield of naphthalen-5-ol; to the oven dry after 25ml Schlenk bottle in add successively 2-(2-Benzoylphenyl)-cyclopent-1-enecarbaldehyde (55.2mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100351
The gained compound is yellow oil, and productive rate is 93%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)8.25(d，J＝8.3Hz，1H)，7.75(d，J＝8.1Hz，1H)，7.53-7.40(m，7H)，5.42(s，1H)，3.26-3.22(m，2H)，2.86-2.82(m，2H)，2.16(pent，J＝7.4Hz，2H)； 13C?NMR(100MHz，CDCl 3)δ146.94，140.07，135.70，130.88，130.40，130.00，129.42，128.03，126.38，124.26，124.11，123.31，123.10，119.41，33.60，31.03，24.44.
Embodiment 37 10-phenyl-1,2,3,4-4 hydrogen-9-phenanthrol synthetic
Under argon shield; to the oven dry after 25ml Schlenk bottle in add successively 2-(2-Benzoylphenyl)-cyclohex-1-enecarbaldehyde (58mg, 0.20mmol), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100352
The gained compound is yellow solid thing, and productive rate is 99%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)8.25(d，J＝8.1Hz，1H)，7.96(d，J＝8.4Hz，1H)，7.53-7.42(m，5H)，7.32(d，J＝7.4Hz，2H)，5.04(s，1H)，3.09(t，J＝6.1Hz，2H)，2.43(t，J＝5.6Hz，2H)，1.91-1.88(m，2H)，1.74-1.72(m，2H)，； 13C?NMR(100MHz，CDCl 3)δ146.10，135.60，133.03，132.78，130.75，129.52，128.19，126.36，124.37，123.79，122.74，122.67，122.57，122.14，29.47，25.78，23.16，23.01.
Embodiment 38 6-Phenyl-8; 9; 10; 11-tetrahydro-7H-cyclohepta[a] the synthesizing under argon shield of naphthalen-5-ol; to the oven dry after 25ml Schlenk bottle in add successively 2-(2-Benzoylphenyl)-cyclohept-1-enecarbaldehyde (60mg, 0.20mmol), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100361
The gained compound is yellow solid thing, and productive rate is 86%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)8.26(d，J＝8.3Hz，1H)，8.10(d，J＝8.6Hz，1H)，7.54-7.41(m，5H)，7.32(d，J＝6.9Hz，2H)，5.08(s，1H)，3.25(t，J＝5.3Hz，2H)，2.68(t，J＝5.4Hz，2H)，1.86-1.80(m，2H)，1.73-1.67(m，2H)，1.54-1.49(m，2H)； 13CNMR(100MHz，CDCl 3)δ146.13，139.44，136.32，131.77，130.77，130.75，129.46，128.12，126.27，124.02，123.17，122.83，122.45，122.35，31.86，31.62，27.59，27.20，26.98.
Embodiment 39 6-Phenyl-7; 8; 9,10,11; 12-hexahydrocycloocta[a] the synthesizing under argon shield of naphthalen-5-ol; to the oven dry after 25ml Schlenk bottle in add successively 2-(2-Benzoylphenyl)-cyclooct-1-enecarbaldehyde (63.6mg, 0.20mmol), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is yellow solid thing, and productive rate is 85%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)8.25(d，J＝8.1Hz，1H)，8.05(d，J＝8.5Hz，1H)，7.54-7.42(m，5H)，7.34(d，J＝7.7Hz，2H)，4.96(s，1H)，3.25(t，J＝5.7Hz，2H)，2.70(t，J＝5.1Hz，2H)，1.82(s，2H)，1.43-1.37(m，6H)； 13C?NMR(100MHz，CDCl 3)δ146.60，136.84，136.15，131.94，130.96，129.34，128.21，127.80，126.23，124.14，123.77，122.96，122.76，122.42，31.48，30.41，29.66，26.58，26.50，26.38.
Embodiment 40
4-Phenyl-2; 3-dihydro-1H-cyclopenta[5; 6] naphtho[2,3-d] the synthesizing under argon shield of [1,3] dioxol-5-ol; to the oven dry after 25ml Schlenk bottle in add successively with 2-(6-Benzoylbenzo[d] [1; 3] dioxol-5-yl) cyclopent-1-enecarbaldehyde (64mg, 0.20mmol), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100372
The gained compound is yellow solid thing, and productive rate is 77%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)7.55(s，1H)，7.52-7.48(m，2H)，7.42-7.38(m，3H)，7.03(s，1H)，6.01(s，2H)，5.32(s，1H)，3.13(t，J＝7.4Hz，2H)，2.81(t，J＝7.3Hz，2H)，2.13(p，J＝7.4Hz，2H)； 13C?NMR(100MHz，CDCl 3)δ147.97，146.55，146.37，138.55，135.83，130.29，130.03，129.37，127.90，127.54，119.33，118.48，100.87，100.80，100.03，33.43，31.31，24.40
Embodiment 41
4-Phenyl-7-(trifluoromethyl)-2; 3-dihydro-1H-cyclopenta[a] the synthesizing under argon shield of naphthalen-5-ol; to the oven dry after 25ml Schlenk bottle in add successively the cyclopent-1-enecarbaldehyde (68.8mg with 2-(2-Benzoyl-4-(trifluoromethyl) phenyl); 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100381
The gained compound is yellow solid thing, and productive rate is 79%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)8.58(s，1H)，7.82(d，J＝8.6Hz，1H)，7.65(dd，J＝8.6，1.4Hz，1H)，7.56-7.39(m，5H)，5.52(s，1H)，3.24(t，J＝7.4Hz，2H)，2.86(t，J＝7.3Hz，2H)，2.18(pent，J＝7.4Hz，2H)； 13C?NMR(100MHz，CDCl 3)δ147.69，142.98，134.96，131.42，131.05，129.83，129.63，128.42，125.96(q，J＝32.0Hz)，125.10，124.73(q，J＝271.9Hz)，122.25，121.93(q，J＝3.0Hz)，121.38(q，J＝4.5Hz)，120.64，33.74，30.96，24.40.
Embodiment 42
(1S, 4S)-4,11,11-trimethyl-10-phenyl-1,2,3,4-tetrahydro-1,4-methanophenanthren-9-ol's is synthetic
Under argon shield; to the oven dry after 25ml Schlenk bottle in add successively the ((1S with 2-; 4S)-3-Benzoyl-1; 7; 7-trimethylbicyclo[2.2.1] hept-2-en-2-yl) benzaldehyde (68.8mg, 0.20mmol), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Product is colorless oil, and productive rate is 89%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.30(d，J＝8.3Hz，1H)，8.22(d，J＝8.4Hz，1H)，7.55-7.34(m，7H)，5.41(s，1H)，2.70(d，J＝2.9Hz，1H)，2.01-1.85(m，2H)，1.72(s，3H)，1.33-1.28(m，1H)，1.08-1.02(m，1H)，0.91(s，3H)，0.68(s，3H)； 13C?NMR(100MHz，CDCl 3)δ145.95，144.88，135.40，134.90，132.38，130.04，129.79，129.38，128.25，127.92，125.63，123.47，123.07，122.97，122.64，118.16，58.37，55.66，52.11，33.41，26.69，20.18，19.28，15.47.
Embodiment 43 3-methyl isophthalic acids, 4-phenylbenzene beta naphthal synthetic
Under argon shield; add successively (Z)-2-(2-methyl-3-oxo-1 in the 25ml Schlenk bottle after the oven dry; 3-diphenylprop-1-en-1-yl) benzaldehyde (65.2mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, O.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100392
The gained compound is yellow solid, and productive rate is 92%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.62-7.58(m，2H)，7.53-7.42(m，6H)，7.38-7.30(m，4H)，7.29-7.22(m，1H)，7.18-7.14(m，1H)，5.29(s，1H)，2.18(s，3H)； 13C?NMR(100MHz，CDCl 3)δ149.03，139.94，139.66，134.63，131.69，131.34，130.19，129.70，128.49，128.36，127.10，126.51，125.35，124.55，124.43，123.08，119.94，14.46.
Embodiment 44 4-methyl isophthalic acids, 3-phenylbenzene beta naphthal synthetic
Under argon shield, add successively (Z)-2-(4-Oxo-3,4-diphenylbut-2-en-2-yl) benzaldehyde (65.2mg in the 25ml Schlenk bottle after the oven dry; 0.20mmol); (38mg, 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100401
The gained compound is yellow solid, and productive rate is 75%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.34(d，J＝8.1Hz，1H)，8.06(d，J＝8.4Hz，1H)，7.61-7.52(m，2H)，7.26-7.22(m，2H)，7.19-7.10(m，6H)，7.01(d，J＝7.7Hz，2H)，5.35(s，1H)，2.40(s，3H)； 13C?NMR(100MHz，CDCl 3)δ146.32，140.85，138.79，135.72，132.97，131.13，130.39，128.72，127.42，127.38，126.71，126.13，125.10，124.35，123.45，123.36，122.84，121.87，16.24.
Embodiment 45 7-methoxyl group-4-methyl isophthalic acid, 3-phenylbenzene-beta naphthal synthetic
Under argon shield; add successively (Z)-5-Methoxy-2-(4-oxo-3 in the 25ml Schlenk bottle after the oven dry; 4-diphenylbut-2-en-2-yl) benzaldehyde (71.2mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100402
The gained compound is yellow solid, and productive rate is 68%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.95(d，J＝9.2Hz，1H)，7.55-7.35(m，10H)，7.05(dd，?J＝9.2，2.6Hz，1H)，6.81(d，J＝2.6Hz，1H)，4.96(s，1H)，3.67(s，3H)，2.44(s，3H)；? 13C?NMR(100MHz，CDCl3 )δ157.88，148.21，136.98，135.44，134.30，133.09，131.17，130.54，129.12，128.67，127.85，127.76，127.62，126.27，123.37，118.78，115.22，104.43，55.06，16.65.
Embodiment 46 1,3-phenylbenzene-4,6-dimethyl-beta naphthal synthetic
Under argon shield; add successively (Z)-4-Methyl-2-(4-oxo-3 in the 25ml Schlenk bottle after the oven dry; 4-diphenylbut-2-en-2-yl) benzaldehyde (68.2mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100411
The gained compound is yellow solid, and productive rate is 74%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.81(s，1H)，7.54-7.35(m，11H)，7.20(d，J＝8.4Hz，1H)，4.91(s，1H)，2.51(s，3H)，2.46(s，3H)； 13C?NMR(100MHz，CDCl 3)δ146.93，137.14，135.42，132.89，132.43，131.25，131.01，130.37，130.04，129.00，128.67，128.27，128.16，127.79，127.65，125.21，123.75，119.40，21.73，16.61.
Embodiment 47 6-fluoro-3-methyl isophthalic acids, 4-phenylbenzene-beta naphthal synthetic
Under argon shield; add successively (Z)-4-Fluoro-2-(2-methyl-3-oxo-1 in the 25ml Schlenk bottle after the oven dry; 3-diphenylprop-1-en-1-yl) benzaldehyde (68.8mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100421
The gained compound is yellow solid, and productive rate is 96%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.62-7.58(m，2H)，7.54-7.43(m，6H)，7.36-7.28(m，3H)，7.04-6.96(m，2H)，5.23(s，1H)，2.18(s，3H)； 13C?NMR(100MHz，CDCl 3)δ159.15(d，J＝241.9Hz)，148.47，139.26(d，J＝5.2Hz)，139.15，134.41，131.22，130.06，129.79，129.06(d，J＝8.3Hz)，128.66，128.56，127.36，126.76，126.67，125.87，120.08，115.26(d，J＝24.9Hz)，109.94(d，J＝21.9Hz)，14.60.
Embodiment 48 5-Phenyl-2; 3-dihydro-1H-cyclopenta[a] the synthesizing under argon shield of naphthalen-4-ol; to the oven dry after 25ml Schlenk bottle in add successively (the 55.2mg with 2-(2-Benzoylcyclopent-1-en-1-yl) benzaldehyde; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100422
The gained compound is yellow solid thing, and productive rate is 89%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.75(d，J＝8.0Hz，1H)，7.59-7.53(m，2H)，7.49-7.45(m，1H)，7.41-7.37(m，3H)，7.34-7.25(m，2H)，5.14(s，1H)，3.33-3.29(m，2H)，3.14-3.11(m，2H)，2.33-2.66(m，2H)； 13C?NMR(100MHz，CDCl 3)δ147.63，141.88，134.68，133.05，131.43，131.05，129.51，128.22，125.92，125.33，125.21，124.42，123.12，119.45，31.69，30.62，24.30
Embodiment 49 5-Ethyl-2; 3-dihydro-1H-cyclopenta[a] the synthesizing under argon shield of naphthalen-4-ol; to the oven dry after 25ml Schlenk bottle in add successively (the 45.2mg with 2-(2-Propionylcyclopent-1-en-1-yl) benzaldehyde; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=50: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100431
The gained compound is the solid thing of white, and productive rate is 74%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.92(d，J＝8.5Hz，1H)，7.72(d，J＝8.1Hz，1H)，7.45-7.41(m，1H)，7.35-7.31(m，1H)，4.78(s，1H)，3.25(t，J＝7.5Hz，2H)，3.08-3.00(m，4H)，2.30-2.22(m，2H)，1.26(t，J＝7.5Hz，3H)； 13C?NMR(100MHz，CDCl 3)δ147.69，139.58，132.56，130.45，126.41，125.24，125.03，123.46，122.88，119.79，31.65，30.15，24.21，18.10，14.42.
Embodiment 50
8-Methyl-5-phenyl-2; 3-dihydro-1H-cyclopenta[a] the synthesizing under argon shield of naphthalen-4-ol; to the oven dry after 25ml Schlenk bottle in add successively 2-(2-Benzoylcyclopent-1-en-1-yl)-4-methylbenzaldehyde (58.0mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100432
The gained compound is orange solid thing, and productive rate is 72%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.57-7.39(m，6H)，7.28(d，J＝8.6Hz，1H)，7.12(dd，J＝8.6，1.4Hz，1H)，5.07(s，1H)，3.29(t，J＝7.5Hz，2H)，3.12(t，J＝7.4Hz，2H)，2.47(s，3H)，2.29(pent，J＝7.5Hz，2H)； 13C?NMR(100MHz，CDCl 3)δ146.95，14115，134.87，132.57，131.40，131.14，131.01，129.47，128.14，127.51，126.07，125.11，123.60，119.37，31.65，30.62，24.32，21.46.
Embodiment 51
7-Methoxy-5-phenyl-2; 3-dihydro-1H-cyclopenta[a] the synthesizing under argon shield of naphthalen-4-ol; to the oven dry after 25ml Schlenk bottle in add successively 2-(2-Benzoylcyclopent-1-en-1-yl)-5-methoxybenzaldehyde (60.0mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=50: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is orange solid thing, and productive rate is 81%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.68(d，J＝8.9Hz，1H)，7.59-7.55(m，2H)，7.50-7.41(m，3H)，7.00(dd，J＝8.9，2.1Hz，1H)，6.72(s，1H)，5.10(s，1H)，3.68(s，3H)，3.28(t，J＝7.4Hz，2H)，3.10(t，J＝7.4Hz，2H)，2.29(pent，J＝7.4Hz，2H)； 13C?NMR(100MHz，CDCl 3)δ157.40，148.21，141.93，134.86，134.27，131.35，129.63，128.48，128.23，125.98，121.38，118.78，114.81，104.73，55.05，31.77，30.41，24.37.
Embodiment 52 10-phenyl-5,6,7,8-tetrahydrochysene-9-phenanthrol synthetic
Under argon shield; add successively 6 in the 25ml Schlenk bottle after the oven dry '-Benzoyl-2 '; 3 '; 4 '; 5 '-tetrahydro-[1,1 '-biphenyl]-2-carbaldehyde (58.0mg, 0.20mmol); 38mg (0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100451
The gained compound is the solid thing of white, and productive rate is 85%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.68(d，J＝8.9Hz，1H)，7.59-7.55(m，2H)，7.50-7.41(m，3H)，7.00(dd，J＝8.9，2.1Hz，1H)，6.72(s，1H)，5.10(s，1H)，3.68(s，3H)，3.28(t，J＝7.4Hz，2H)，3.10(t，J＝7.4Hz，2H)，2.29(pent，J＝7.4Hz，2H)； 13C?NMR(100MHz，CDCl 3)δ157.40，148.21，141.93，134.86，134.27，131.35，129.63，128.48，128.23，125.98，121.38，118.78，114.81，104.73，55.05，31.77，30.41，24.37.
Embodiment 53 5-Phenyl-8; 9; 10; 11-tetrahydro-7H-cyclohepta[a] the synthesizing under argon shield of naphthalen-6-ol; to the oven dry after 25ml Schlenk bottle in add successively 2-(2-Bbenzoylcyclohept-1-en-1-yl) benzaldehyde (60.8mg, 0.20mmol), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100452
The gained compound is yellow oil, and productive rate is 88%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.09(d，J＝9.1Hz，1H)，7.59-7.55(m，2H)，7.51-7.47(m，1H)，7.42-7.40(m，2H)，7.34-7.25(m，3H)，5.14(s，1H)，3.33-3.30(m，2H)，3.17-3.14(m，2H)，1.97-1.91(m，2H)，1.78-1.66(m，4H)； 13C?NMR(100MHz，CDCl 3)?δ147.93，141.06，135.09，132.09，131.50，131.27，129.65，128.35，126.85，125.17，125.12，123.45，123.05，119.00，32.32，28.22，26.78，26.64，26.09.
Embodiment 54
5-Cyclopropyl-7; 8; 9,10,11; 12-hexahydrocycloocta[a] the synthesizing under argon shield of naphthalen-6-ol; to the oven dry after 25ml Schlenk bottle in add successively the benzaldehyde (56.2mg, 0.20mmol) with 2-(2-(Cyclopropanecar-bonyl) cyclooct-1-en-1-yl), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100461
The gained compound is white solid, and productive rate is 82%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.31(d，J＝8.3Hz，1H)，8.00(d，J＝8.4Hz，1H)，7.44-7.40(m，1H)，7.34-7.30(m，1H)，6.39(s，1H)，3.25(t，J＝6.1Hz，2H)，3.04(t，J＝5.8Hz，2H)，1.91-1.71(m，5H)，1.45-1.39(m，2H)，1.35-1.24(m，4H)，0.75-0.71(m，2H)； 13C?NMR(100MHz，CDCl 3)δ151.54，137.05，133.28，128.97，126.99，124.79，124.35，124.13，122.68，114.69，30.45，30.41，27.10，26.45，26.27，25.62，7.08，6.60.
Embodiment 55
(1S, 4S)-4,11,11-Trimethyl-9-phenyl-1,2,3,4-tetrahydro-1,4-methanophenanthren-10-ol's is synthetic
Under argon shield; to the oven dry after 25ml Schlenk bottle in add successively the ((1S with 2-; 4S)-3-acetyl-1; 7; 7-trimethylbicyclo[2.2.1] hept-2-en-2-yl) benzaldehyde (68.8mg; 0.20mmol), 38mg (0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5 mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100471
Product is colorless oil, and productive rate is 85%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ8.25(d，J＝8.4Hz，1H)，7.58-7.40(m，6H)，7.28-7.19(m，2H)，5.00(s，1H)，3.23(d，J＝3.5Hz，1H)，2.19-2.12(m，1H)，1.97-1.90(m，1H)，1.76(s，3H)，1.37-1.31(m，1H)，1.20-1.14(m，1H)，1.02(s，3H)，0.72(s，3H)； 13CNMR(100MHz，CDCl 3)δ145.77，145.61，135.12，134.81，132.76，131.59，131.52，129.48，129.42，128.13，125.92，125.20，124.22，123.34，122.42，119.45，58.88，56.33，49.30，33.20，26.01，20.23，19.44，15.41.
Embodiment 56 4-Methyl-5,7-diphenylbenzo[b] thiophen-6-ol synthetic
Under argon shield; add successively (Z)-3-(4-Oxo-3 in the 25ml Schlenk bottle after the oven dry; 4-diphenylbut-2-en-2-yl) thiophene-2-carbaldehyde (66.2mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100472
The gained compound is yellow solid, and productive rate is 86%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.64-7.62(m，2H)，7.53-7.49(m，4H)，7.45-7.35(m，5H)，7.26(d，J＝5.5Hz，1H)，4.93(s，1H)，2.37(s，3H)； 13C?NMR(100MHz，CDCl 3)δ146.97，140.74，136.22，136.15，133.23，130.84，130.58，129.68，129.04，129.00，128.13，127.94，127.22，123.77，122.66，118.85，17.56.
Embodiment 57 5-Methyl-4,7-diphenylbenzo[b] thiophen-6-ol synthetic
Under argon shield; add successively (Z)-3-(2-Methyl-3-oxo-1 in the 25ml Schlenk bottle after the oven dry; 3-diphenylprop-1-en-1-yl) thiophene-2-carbaldehyde (66.2mg; 0.20mmol); (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
The gained compound is gray solid, and productive rate is 72%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.62-7.57(m，4H)，7.51-7.35(m，6H)，7.07(d，J＝5.5Hz，1H)，6.88(d，J＝5.5Hz，1H)，5.31(s，1H)，2.19(s，3H)； 13C?NMR(100MHz，CDCl 3)δ148.30，139.80，138.43，137.30，135.32，133.22，129.88，129.76，129.65，128.84，128.23，127.15，124.05，123.05，121.10，119.48，13.73.
Embodiment 58 4-Ethyl-7; 8-dihydro-6H-indeno[5; 4-b] the synthesizing under argon shield of thiophen-5-ol; to the oven dry after 25ml Schlenk bottle in add successively (the 56.8mg with 3-(2-Propionylcyclopent-1-en-1-yl) thiophene-2-carbaldehyde; 0.20mmol); (38mg, 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100482
The gained compound is gray solid, and productive rate is 53%, and its nuclear magnetic data is as follows:
1HNMR(400MHz，CDCl 3)δ7.26-7.24(m，1H)，7.19(d，J＝5.5Hz，1H)，4.60(s，1H)，?3.15(t，J＝7.4Hz，2H)，2.96-2.86(m，4H)，2.28-2.20(m，2H)，1.29(t，J＝7.6Hz，3H)；? 13C?NMR(100MHz，CDCl 3)δ146.85，139.88，137.09，130.13，127.83，123.44，122.21，120.21，32.22，29.29，25.08，22.37，13.10.
Embodiment 59
4-Phenyl-7; 8; 9,10-tetrahydro-6H-cyclohepta[3,4] benzo[1; 2-b] the synthesizing under argon shield of thiophen-5-ol; to the oven dry after 25ml Schlenk bottle in add successively 3-(2-Benzoylcyclohept-1-en-1-yl) thiophene-2-carbaldehyde (62mg, 0.20mmol), (38mg; 0.204mmol) p-toluene sulfonyl hydrazide, 4ml toluene.Behind 70 ℃ of reaction 30min, add LiO tBu (40mg, 0.5mmol), 70 ℃ of lower reaction 30min that continue.In system, add AcOH (30mg, 0.5mmol, 2.5eq) cancellation reaction and recover room temperature.After reaction system was concentrated, use PE/EA=100: 1 column chromatography purification can obtain product.Reaction formula is shown below:
Figure BDA00002723433100491
The gained compound is orange solids, and productive rate is 68%, and its nuclear magnetic data is as follows:
1H?NMR(400MHz，CDCl 3)δ7.56-7.55(m，4H)，7.50-7.44(m，1H)，7.40-7.39(m，1H)，7.17-7.15(m，1H)，5.17(s，1H)，3.18-3.04(m，4H)，1.93-1.91(m，2H)，1.76-1.67(m，4H)； 13C?NMR(100MHz，CDCl 3)δ147.13，139.39，138.61，135.71，132.31，129.85，129.79，128.71，128.14，122.76，122.39，118.40，32.71，31.87，27.33，26.13。

Claims (12)

1. the preparation method of the condensed ring aromatic compound that replaces of a hydroxyl, then double carbonyl compound under the effect of alkali, reacts in organic solvent by obtaining single N-sulphonyl hydrazone with the sulfonyl hydrazide reaction, obtains the condensed ring aromatic compound that hydroxyl replaces.
2. preparation method as claimed in claim 1 is characterized in that, described double carbonyl compound is selected from 2, one or more in 2 '-dibenzyl aldehyde ketone, 2-ketone group aryl-thiazolinyl aldehyde and the 2-aldehyde radical aryl-alkenyl ketone; Wherein, described ketone is selected from one or more in aryl aryl ketones, aryl alkyl ketone, aryl alkenyl ketone, aromatic yl polysulfide yl ketone and the thiazolinyl alkyl ketone.
3. preparation method as claimed in claim 2 is characterized in that, on the described aryl with one or more substituting groups; On described thiazolinyl and the alkynyl with one or more substituting groups.
4. preparation method as claimed in claim 2 or claim 3 is characterized in that, described aryl comprises heterocyclic aromatic base and non-heterocyclic aromatic base; Described heterocyclic aromatic base comprises furans, thiophene and indoles; Described non-heterocyclic aromatic base comprises phenyl ring and naphthalene nucleus.
5. preparation method as claimed in claim 3, it is characterized in that, described substituting group is selected from one or more in alkyl, cycloalkyl, alkoxyl group, trifluoromethyl, thiazolinyl, aromatic base, ester group, nitro, hydroxyl and the halogen, when with a plurality of substituting group, these a plurality of substituting groups are identical or different, the separate or Cheng Huan of two adjacent substituting groups.
6. preparation method as claimed in claim 5 is characterized in that, described alkyl preferably has the alkyl of 1～10 carbon atom, comprises methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, sec-butyl, amyl group, neo-pentyl; Described alkoxyl group preferably has the alkoxyl group of 1～10 carbon atom, comprises methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, sec-butoxy; Described ester group comprises formic acid ester group, acetate groups, propionic acid ester group and acrylate-based; Described halogen is selected from fluorine, chlorine, bromine or iodine atom.
7. preparation method as claimed in claim 1 is characterized in that, described sulfonyl hydrazide is p-toluene sulfonyl hydrazide; The mol ratio of described p-toluene sulfonyl hydrazide and double carbonyl compound is (1-1.03): 1.
8. preparation method as claimed in claim 1 is characterized in that, described alkali is selected from metal alkoxides alkoxide and carbonate, comprises sodium methylate, trimethyl carbinol lithium and cesium carbonate; The mol ratio of described alkali and double carbonyl compound is (1.2-2.5): 1.
9. preparation method as claimed in claim 8 is characterized in that, when described alkali was sodium methylate, the reaction formula of the method can be expressed as follows:
Figure FDA00002723433000021
When described alkali was trimethyl carbinol lithium, the reaction formula of the method can be expressed as follows:
Figure FDA00002723433000022
Wherein, " represent double carbonyl compound, formula II compound is p-toluene sulfonyl hydrazide, the condensed ring aromatic compound that formula III compounds represented hydroxyl replaces for formula I, I ', I.
10. preparation method as claimed in claim 1 is characterized in that, described organic solvent is selected from a kind of in Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) and the toluene; The consumption of described organic solvent is 20～100ml/mmol double carbonyl compound.
11. preparation method as claimed in claim 1 is characterized in that, the temperature of reaction that double carbonyl compound and sulfonyl hydrazide reaction generate hydrazone is 60～90 ℃, and the reaction times is 10～30min; Under the effect of alkali, the temperature of reaction of reacting in organic solvent is 25～90 ℃, and the reaction times is 30min～3h.
12. preparation method as claimed in claim 1 is characterized in that, adopts air distillation, vacuum distillation method to concentrate to reaction product after described reaction is finished, by the dry concentrated product that obtains purifying after column chromatography or the separatory extraction.
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