CN108017613A - Ruthenium is catalyzed the method that heterocycle arone prepares more virtue substitution naphthalene derivativeses with tolans reaction - Google Patents

Ruthenium is catalyzed the method that heterocycle arone prepares more virtue substitution naphthalene derivativeses with tolans reaction Download PDF

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CN108017613A
CN108017613A CN201711358060.0A CN201711358060A CN108017613A CN 108017613 A CN108017613 A CN 108017613A CN 201711358060 A CN201711358060 A CN 201711358060A CN 108017613 A CN108017613 A CN 108017613A
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张殊佳
高杰
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Dalian University
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Abstract

This divisional application is related to the method that ruthenium catalysis heterocycle arone prepares more virtue substitution naphthalene derivativeses with tolans reaction.The present invention uses more cheap ruthenium that aromatic ketone β H are activated synthesis hexatomic ring and generate more virtue substitution naphthalene derivativeses as catalyst；Without additive and oxidant in reaction process, using only simple alkali, carry out under mild reaction conditions.Synthetic method provided by the invention is simple and practicable, scientific and reasonable, environmentally protective, economical and practical, is adapted to large-scale production.

Description

Ruthenium is catalyzed heterocycle arone and prepares more virtue substitution naphthalene derivativeses with tolans reaction Method
The application is Application No. 2017113298008, the applying date is on December 13rd, 2017, entitled " a kind of The divisional application of the ruthenium catalysis aromatic ketone fragrant methods for substituting naphthalene derivativeses more with the preparation of tolans cyclization and application ".
Technical field
The present invention relates to medical science and field of photovoltaic materials, relate generally to more virtue substitution naphthalene derivativeses preparation method and Using.
Background technology
More virtue substitution naphthalene derivativeses are due to its unique electrochemistry, photochemical properties and the function material that they are conjugated in n Application on material, makes it more and more extensive in the application of organic fluorescence materials, semi-conducting material etc., and more virtue substitution naphthalenes Derivative also has important application in terms of pharmaceutical synthesis.The preparation method used in the prior art compares pervious ring metal Change, aryl halide, aryl acid etc. have very big breakthrough than relatively severe condition.At present, use passed through more in a mild condition Cross c h bond (or even the double c h bonds) activation of metal catalytic fragrance phenyl ring and the naphthalene that cyclization prepares more virtue substitutions occurs for alkynes Derivative.But this method existing defects, these reactions need the metal salt of a certain amount of ligand or equivalent to do oxidant ability Catalytic cycle is completed, not only increases production cost, and metal salt is mostly heavy metal (copper, silver etc.) salt of environmental pollution Class.Based on this, this area needs more environmentally-friendly, green, economic method to synthesize more virtue substitution naphthalene derivativeses.
The content of the invention
To make up the deficiencies in the prior art, the present invention provides one kind without additive and oxidant in a mild condition with More cheap ruthenium ([RuCl2(p-cymene)]2) as catalyst synthesized it is more virtue substitution naphthalene derivatives methods.
The present invention adopts the following technical scheme that：More virtue substitution naphthalene derivatives, have the structure as shown in general formula I：
Wherein, R1ForOne kind in-H or-F, R2For-CH3、-CH2CH3、-CH3、Or-CF3In one kind.
Preferably, more virtue substitution naphthalene derivatives are：
Another object of the present invention is that the preparation method of above-mentioned more virtue substitution naphthalene derivatives is claimed, i.e.,：By hexichol Acetylene, as raw material, adds [RuCl with aromatic ketone2(p-cymene)]2, alkali and non-polar organic solvent, in a nitrogen environment plus Heat obtains more virtue substitution naphthalene derivatives to 80-100 DEG C of reaction 12-24h through column chromatography for separation；The tolans and virtue Ketone musk molar ratio is 1:2, [RuCl2(p-cymene)]2Account for the 15mol% of tolans, the molar ratio of alkali and aromatic ketone is 1:1.
Preferably, the aromatic ketone is：Wherein R1ForIn-H or-F One kind, R2For-CH3、-CH2CH3、-CH3、Or-CF3In one kind.
Preferably, aromatic ketone is In one kind.
Further, the non-polar organic solvent for benzene, toluene, dichloroethanes, chloroform, styrene, cyclohexane or oneself It is any in alkane.It is preferred that toluene.
Further, the alkali is KOAc, Na2CO3、Cs2CO3、K2CO3、Li2CO3, one kind in NaOAc, LiOAc or More than one.It is preferred that KOAc and Na2CO3。
As the preferred embodiment of the invention, the preparation method of more virtue substitution naphthalene derivativeses is：By aromatic ketone and two Phenylacetylene is placed in tube sealing, adds [RuCl2(p-cymene)]2And toluene, while dry sodium carbonate and potassium acetate are added in nitrogen Be heated under compression ring border 100 DEG C of reactions 24 it is small when, obtain more virtue substitution naphthalene derivatives through column chromatography for separation.
3rd purpose of the invention is that above-mentioned more virtue substitution naphthalene derivatives are claimed in medicine preparation and photoelectric material Application on field.
For example it is used for Novel tyrosine protein kinase inhibitorOr blue light material Preparation.
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention uses more cheap ruthenium ([RuCl2(p-cymene)]2) catalyst is used as, aromatic ketone β-H are activated and are synthesized Hexatomic ring generates more virtue substitution naphthalene derivativeses；Without additive and oxidant in reaction process, using only simple alkali, in temperature Carried out with reaction condition.Synthetic method provided by the invention is simple and practicable, scientific and reasonable, environmentally protective, economical and practical, is adapted to Large-scale production.
Embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally Experimental method is conventional method used by invention, and experiment equipment used, material, reagent etc. can chemically company be bought.
Embodiment 1
Tolans (18mg, 0.1mmol), corresponding aromatic ketone are added into the 25mL tube sealings with magneton (0.2mmol), catalyst [RuCl2(p-cymene)]2(9mg, 15%mol), 0.5mL toluene, adds dry sodium carbonate afterwards (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), substitutes nitrogen three times, when reaction 24 is small at 100 DEG C, then through column (eluant, eluent is chromatographic isolation：Petroleum ether) so as to obtain target compound.It is characterized as below.
4,5- diphenyl -6- (thiophene -2- methylene) benzo [b] thiophene：Yield：40%.1H NMR(CDCl3,400MHz) δ 7.81 (s, 1H), 7.33 (d, J=5.2Hz, 1H), 7.10-7.18 (m, 9H), 7.00-7.02 (m, 3H), 6.87 (dd, J1= 3.6Hz；J2=5.2Hz, 1H), 6.59-6.60 (m, 1H), 4.07 (s, 2H)13C NMR(CDCl3,100MHz)δ144.1, 139.7,139.4,135.7,130.8,130.4,127.5,126.7,126.5,126.4,125.9,124.2,123.8, 122.1,34.5.HRMS(EI-TOF)calcdfor C25H18S2(M+):382.0850,found:382.0847.
Embodiment 2
Tolans (18mg, 0.1mmol), corresponding aromatic ketone are added into the 25mL tube sealings with magneton (0.2mmol), catalyst [RuCl2(p-cymene)]2(9mg, 15%mol), 0.5mL toluene, adds dry sodium carbonate afterwards (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), substitutes nitrogen three times, when reaction 24 is small at 100 DEG C, then through column (eluant, eluent is chromatographic isolation：Petroleum ether) so as to obtain target compound.It is characterized as below.
3- methyl isophthalic acids, 2,7- triphenyl naphthalenes：Yield：65%.Fusing point：163-165℃.1H NMR(CDCl3,400MHz)δ 7.91 (d, J=8.4Hz, 1H), 7.79 (s, 1H), 7.69-7.73 (m, 2H), 7.52 (d, J=7.2Hz, 2H), 7.37 (t, J= 8.0Hz, 2H), 7.29 (d, J=7.2Hz, 1H), 7.10-7.23 (m, 8H), 7.02-7.05 (m, 2H), 2.26 (s, 3H)13C NMR(CDCl3,100MHz)δ141.5,140.6,140.4,139.2,139.0,137.9,134.7,132.1,131.5, 131.1,130.1,128.8,127.7,127.6,127.5,127.4,127.2,127.1,126.4,126.2,125.5, 124.9,22.0.HRMS(EI-TOF)calcdfor C29H22(M+):370.1722,found:370.1723.
Embodiment 3
Tolans (18mg, 0.1mmol), corresponding aromatic ketone are added into the 25mL tube sealings with magneton (0.2mmol), catalyst [RuCl2(p-cymene)]2(9mg, 15%mol), 0.5mL toluene, adds dry sodium carbonate afterwards (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), substitutes nitrogen three times, when reaction 24 is small at 100 DEG C, then through column (eluant, eluent is chromatographic isolation：Petroleum ether) so as to obtain target compound.It is characterized as below.
3- ethyl -1,2- diphenyl naphthalenes：Yield：25%.Fusing point：124-125℃.1H NMR(CDCl3,400MHz)δ 7.79-7.81(m,1H),7.72(s,1H),7.37-7.40(m,2H),7.22-7.26(m,1H),7.01-7.14(m,8H), 6.96-6.98(m,2H),2.51(dd,J1=7.6Hz；J2=14.8Hz, 2H), 1.08 (t, J=7.6Hz, 3H)13C NMR (CDCl3,100MHz)δ140.4,140.3,139.6,139.5,138.8,133.0,131.2,131.0,130.4,127.4, 127.4,126.8,126.3,126.1,125.8,125.7,125.3,27.4,15.1.HRMS(EI-TOF)calcd for C24H20(M+):308.1565,found:308.1567.
Embodiment 4
Tolans (18mg, 0.1mmol), corresponding aromatic ketone are added into the 25mL tube sealings with magneton (0.2mmol), catalyst [RuCl2(p-cymene)]2(9mg, 15%mol), 0.5mL toluene, adds dry sodium carbonate afterwards (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), substitutes nitrogen three times, when reaction 24 is small at 100 DEG C, then through column (eluant, eluent is chromatographic isolation：Petroleum ether) so as to obtain target compound.It is characterized as below.
The fluoro- 3- methyl isophthalic acids of 7-, 2- diphenyl naphthalenes：Yield：30%.Fusing point：139-140℃.1H NMR(CDCl3,400MHz) δ7.81(dd,J1=6.0Hz；J2=8.8Hz, 1H), 7.75 (s, 1H), 7.06-7.23 (m, 10H), 7.01-7.03 (m, 2H), 2.24(s,3H).13C NMR(CDCl3,100MHz)δ161.6,159.2,140.8,140.3,138.9,138.2(d,JC-F= 5.6Hz),133.7(d,JC-F=2.3Hz), 132.3,132.2,130.9,129.9 (d, JC-F=5.6Hz), 129.4 (d, JC-F =8.6Hz), 127.6 (d, JC-F=4.9Hz), 127.3,126.6,126.3,116.2,115.9,110.3,110.1, 21.8.HRMS(EI-TOF)calcdfor C23H17F(M+):312.1314,found:312.1312.
Embodiment 5
Tolans (18mg, 0.1mmol), corresponding aromatic ketone are added into the 25mL tube sealings with magneton (0.2mmol), catalyst [RuCl2(p-cymene)]2(9mg, 15%mol), 0.5mL toluene, adds dry sodium carbonate afterwards (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), substitutes nitrogen three times, when reaction 24 is small at 100 DEG C, then through column (eluant, eluent is chromatographic isolation：Petroleum ether) so as to obtain target compound.It is characterized as below.
3- isobutyl group -1,2- diphenyl naphthalenes：Yield：35%.Fusing point：107-108℃.1H NMR(CDCl3,400MHz)δ 7.85-7.87(m,1H),7.73(s,1H),7.43-7.47(m,2H),7.29-7.33(m,1H),7.07-7.21(m,8H), 7.01-7.03 (m, 2H), 2.48 (d, J=7.2Hz, 2H), 1.66-1.73 (m, 1H), 0.76-0.78 (d, J=6.4Hz, 6H) .13C NMR(CDCl3,100MHz)δ140.3,140.0,139.6,138.9,137.9,132.7,131.3,131.1,130.7, 127.7,127.4,127.4,127.2,126.8,126.3,126.1,125.6,125.3,43.5,29.8,29.1, 22.6.HRMS(EI-TOF)calcdfor C26H24(M+):336.1878,found:336.1882.
Embodiment 6
Tolans (18mg, 0.1mmol), corresponding aromatic ketone are added into the 25mL tube sealings with magneton (0.2mmol), catalyst [RuCl2(p-cymene)]2(9mg, 15%mol), 0.5mL toluene, adds dry sodium carbonate afterwards (21mg, 0.2mmol) and potassium acetate (19mg, 0.2mmol), substitutes nitrogen three times, when reaction 24 is small at 100 DEG C, then through column (eluant, eluent is chromatographic isolation：Petroleum ether) so as to obtain target compound.It is characterized as below.
1,2- diphenyl -3- (trifluoromethyl) naphthalene：Yield：45%.Fusing point：118-119℃.1H NMR(CDCl3, 400MHz) δ 8.34 (s, 1H), 8.02 (d, J=8.0Hz, 1H), 7.57-7.60 (m, 1H), 7.94-7.50 (m, 2H), 7.18- 7.24(m,3H),7.13-7.16(m,3H),7.05-7.11(m,4H).13C NMR(CDCl3,100MHz)δ141.6,138.1, 137.7,135.9,134.0,131.4,130.8(d,JC-F=5.8Hz), 129.4,128.9,128.4,128.3,128.2, 127.6,127.1,126.9,126.9,126.8,126.2,126.2.HRMS(EI-TOF)calcd for C23H15F3(M+): 348.1126,found:348.1124.
Comparative example：
Tolans 0.1mmol, aromatic ketone are added into the 25mL tube sealings with magneton(0.2mmol), is urged Agent [RuCl2(p-cymene)]20.01mol, adds 0.5mL organic solvents and the alkali with the equimolar drying of aromatic ketone afterwards, Substitute nitrogen three times, reacted at 100 DEG C 24 it is small when, then through pillar layer separation, (eluant, eluent is：Petroleum ether) so as to obtain target CompoundYield is calculated, the results are shown in Table 1.
Table 1
* yield when catalyst is 0.015mmol
Contrasted from 1 data of table and to embodiment 1-6 yields, when organic solvent selects toluene, alkali is sodium carbonate and vinegar During sour potassium, when catalyst amount is 15mol%, yield highest.So in experimentation using this optimum reaction condition into OK.
The above, is only the preferable embodiment of the invention, but the protection domain of the invention is not This is confined to, any one skilled in the art is in the technical scope that the invention discloses, according to the present invention The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it It is interior.

Claims (6)

1. a kind of method that ruthenium catalysis heterocycle arone prepares more virtue substitution naphthalene derivativeses with tolans reaction, it is characterised in that By tolans and aromatic ketoneAs raw material, [RuCl is added2(p-cymene)]2, alkali and nonpolar have Solvent, is heated to 80-100 DEG C of reaction 12-24h in a nitrogen environment, and the derivative of more virtue substitution naphthalenes is obtained through column chromatography for separation Thing；The tolans is 1 with aromatic ketone molar ratio:2, [RuCl2(p-cymene)]2Account for the 15mol% of tolans, alkali Molar ratio with aromatic ketone is 1:1.
2. according to the method described in claim 1, it is characterized in that, the non-polar organic solvent is benzene, toluene, two chloroethenes It is any in alkane, chloroform, styrene, cyclohexane or hexane.
3. according to the method described in claim 2, it is characterized in that, organic solvent is toluene.
4. according to the method described in claim 1, it is characterized in that, the alkali is KOAc, Na2CO3、Cs2CO3、K2CO3、 Li2CO3, one or more in NaOAc, LiOAc.
5. according to the method described in claim 4, it is characterized in that the alkali is KOAc and Na2CO3。
A kind of 6. application of virtue substitution naphthalene derivatives more as claimed in claim 1 in medicine preparation and field of photovoltaic materials.
CN201711358060.0A 2017-12-13 2017-12-13 Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzed reaction of heterocyclic aromatic ketone and tolane Active CN108017613B (en)

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CN201711329800.8A CN107973778B (en) 2017-12-13 2017-12-13 A kind of ruthenium catalysis aromatic ketone replaces the methods and application of naphthalene derivatives with the more virtues of tolans cyclization preparation
CN201711358060.0A CN108017613B (en) 2017-12-13 2017-12-13 Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzed reaction of heterocyclic aromatic ketone and tolane

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CN201711358067.2A Active CN108047198B (en) 2017-12-13 2017-12-13 Method for preparing polyaryl substituted naphthalene derivative by reaction of aryl ketone and tolane under catalysis of ruthenium
CN201711358009.XA Active CN107935812B (en) 2017-12-13 2017-12-13 Method for preparing polyaryl substituted naphthalene derivative by reaction of alkyl aryl ketone and tolane under catalysis of ruthenium
CN201711358060.0A Active CN108017613B (en) 2017-12-13 2017-12-13 Method for preparing polyaryl substituted naphthalene derivative by ruthenium-catalyzed reaction of heterocyclic aromatic ketone and tolane
CN201711358055.XA Pending CN108101734A (en) 2017-12-13 2017-12-13 A kind of method that ruthenium catalysis fluorine-containing aromatic ketone prepares more virtue substitution naphthalene derivativeses with tolans reaction
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