CN105016988B - Polyalkyloxy substituted 1,2-benzochrysene derivative and preparation method therefor - Google Patents
Polyalkyloxy substituted 1,2-benzochrysene derivative and preparation method therefor Download PDFInfo
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Abstract
The present invention relates to a 1,2-benzochrysene derivative comprising a plurality of alkoxy substituents and a synthesis method therefor. Diphenylacetylene, phenylacetaldehyde or a derivative thereof is used as a substrate. A 1,2-diaryl naphthalene derivative or a 1,2-benzochrysene compound can be selectively synthesized by controlling the proportion of the oxidant ferric chloride to the diphenylacetylene derivative. The 1,2-diaryl naphthalene derivative may be further oxidized by ferric chloride to produce a 1,2-benzochrysene compound or a chloro-1,2-benzochrysene compound, wherein the carbon atoms at 10 position are substituted by chlorine atoms. The 1,2-benzochrysene compound may also react with a bromide source NBS to produce a bromo-1,2-benzochrysene compound, wherein the carbon atoms at 10 position are substituted by bromine atoms. The 1,2-benzochrysene compound, comprising a plurality of long chain alkoxy substituents, is capable of self-assemble into an ordered spherulite or liquid crystal phase. The chloro-1,2-benzochrysene compound or the bromo-1,2-benzochrysene compound may be further used as a primitive for construction of liquid crystal, OLED and other photoelectric materials.
Description
Technical field
The present invention relates to 1, the 2- benzos that a kind of many alkoxyls replace bend derivative and preparation method thereof.
Background technology
п is conjugated polyaromatic compounds（polycyclic aromatic hydrocarbons PAHs）Due to compared with
The functions such as big п electron delocalization areas, the HOMO-LUMO energy gaps of controllable adjustment, and self assembly, selfreparing, by people's
Extensive concern.This kind of compound can be widely used in the photoelectricity such as liquid crystal display, solar cell, Organic Light Emitting Diode and turn
Change, in electromagnetic device.For example, benzophenanthrene molecule is used to improve the visual angle of liquid crystal display as phase compensation film
（Jpn. Org. Synth. Soc. 2002, 60, 1190）.
At present, comprising hexatomic ring class polyaromatic compound within four and four in molecule synthesis and performance study are
Achieve significant progress, such as naphthalene, phenanthrene, pyrene, benzophenanthrene.By contrast, it is how fragrant containing more than four hexatomic ring classes in molecule
Hydrocarbon compound is long due to synthesis step, and the low reason of yield, correlative study is also fewer.Meanwhile, п conjugation polyaromatic compounds
With the expansion of conjugate area, it is also beneficial to improve the charge transport rate of material, improves the luminescent properties of material.
It is that a class is made up of five hexatomic rings that 1,2- benzo is bent, comprising the п conjugation polyaromatics that a fyord and two ports are curved
Class compound.It is the important organic semiconducting materials with biologically active of a class.At present, 1,2- benzos are bent as organic half
It is 1,2- benzene that conductor material is used for the reason for liquid crystal, OLED show and the relevant report such as illuminating material is also fewer, and this is possible
And it is relatively difficult to bend synthesis.1,2- benzo is bent and is initially extracted from oil.1938, Hewett, C. L.
With phenanthrene as initiation material, reacted using Pschorr and build naphthalene ring again at luxuriant and rich with fragrance 9,10,1,2- benzos have been synthesized at first
Bend（JACS, 1938, 193- 196）.Hereafter, Lehr, R. E. and Harvey, R. G. et al. respectively at 1989 and
1996 bend skeleton structure by Hewett, the improvement of C. L. synthetic methods, equally also having synthesized 1,2- benzos（J. Org.
Chem. 1989, 54, 3533-3544；J. Org. Chem. 1996, 60, 6123-6128）.Harvey, R. in 1981
G. bent as raw material with 5,6- dicarbapentaborane, first react and generate diacetyl diol, derivatives with acetenyl lithium reagent, then through aluminum hydride
Lithium is reduced, and finally by cyclization, dehydration 1,2- of synthesis benzos bend skeleton structure.1987, Lehr, R. E. was first passed through
Five steps synthesize 1,2-Dihydrobenzo [g] chrysen- 4 (3H)-on, then again by reducing elimination, dehydroaromatizationof
1,2- of synthesis benzos bend skeleton structure（J. Org. Chem. 1987, 52, 5574-5582）.Above synthetic method exists anti-
The shortcomings of answering harsh step length, condition, low yield, if method described above is in the wrong to build 1, the 2- benzos containing multiple substituents
Structure relative difficulty is bigger.
The content of the invention
First goal of the invention of the present invention is just to provide 1, the 2- benzos molecule in the wrong that a kind of many alkoxyls replace.Research table
Bright, such compound has very high order, by the number for adjusting alkoxyl, can make it have certain liquid crystal property,
Can as good liquid crystal material, while such compound has good luminescent properties, can as OLED blue emitting materials,
Charge transport materials are used.
The present invention realizes its first goal of the invention, and the technical scheme for being adopted is：The 1,2- that many alkoxyls of one class replace
Benzo bends derivative, with following formulas（I）Structure, wherein R1It is-CmH2m+1, m represent carbon number be 1 to 20 it is whole
Number；R2, R3It is H or-OCnH2n+1, n represents the integer that carbon number is 1 to 20；X can be that H atom, Cl atoms or Br are former
Son..
Formula（I）In, R1、R2、R3There are following six kinds of combinations with X：1）Four replacement 1,2- benzos are bent：R1It is former for carbon containing
The alkyl of subnumber 1 ~ 20, R2、R3It is H atom with X；2）Five replacement 1,2- benzos are bent：R1For the alkyl of carbon atom quantity 1 ~ 20, R2
For the alkoxyl of carbon number 1 ~ 20, R3It is H atom with X；3）Six replacement 1,2- benzos are bent：R1For the alkane of carbon atom quantity 1 ~ 20
Base, R2And R3For the alkoxyl of carbon number 1 ~ 20, X is H；4）Four replacement 1,2- benzos of pre- sense dough are bent：R1For carbon containing
The alkyl of atomicity 1 ~ 20, R2And R3For H atom, X is Cl or Br atoms；5）Five replacement 1,2- benzos of pre- sense dough are bent：
R1For the alkyl of carbon atom quantity 1 ~ 20, R2For the alkoxyl of carbon number 1 ~ 20, R3For H atom, X is Cl or Br atoms；6）In advance
Six replacement 1,2- benzos of sense dough are bent：R1For the alkyl of carbon atom quantity 1 ~ 20, R2And R3For the alkane of carbon number 1 ~ 20
Epoxide, X is Cl or Br atoms.
Compared with prior art, formula of the invention（I）Many alkoxyls replace 1,2- benzos bend molecule beneficial effect
It is really：
1st, such compound is difficult by the method reported such as with luxuriant and rich with fragrance or bend as initiation material, is synthesized by multistep ring expansion.
2nd, by such compound of pre- sense dough can based on construction module further build other liquid crystal,
The photoelectric materials such as OLED.
3rd, such compound can be self-assembled into the spherocrystal or columnar phase liquid crystal phase to form very well ordered.
4th, maximum emission wavelength of such compound in dichloromethane solution is 405 nm, can be used as the organic blueness of structure
The primitive of luminescent material.
Second object of the present invention is just to provide above-mentioned formula（I）Many alkoxyls replace benzo bend molecule system
Preparation Method.
The present invention realizes its second goal of the invention, the technical scheme for being adopted i.e. formula for（I）Many alkoxyls replace
Benzo bends the synthetic method of molecule：
Method one, tolans, phenylacetaldehyde or derivatives thereof are dissolved in dichloroethane solution, add ferric trichloride
FeCl3, step generation X is that 1, the 2- benzos of H bend derivative.In this method, ferric trichloride and diphenyl acetylene derivatire rub
You are than being 3：1 ~ 8 ：1.
Method two, tolans, phenylacetaldehyde or derivatives thereof are dissolved in dichloroethane solution, add ferric trichloride
FeCl3, room temperature reaction generation intermediate 1,2- diphenyl naphthalene derivatives；After the completion of the step reaction, removed by a short column
Iron ion, then crude product is continued to put in dichloroethane solution, add FeCl3, room temperature reaction is to thin-layer chromatography detection nothing
Intermediate is present；Then the methyl alcohol that a small amount of frost is added in reaction system extracts reaction of going out, and is removed using Rotary Evaporators organic
Solvent, residual solids pass through the isolated product of silica column chromatography.Wherein the first step generates the derivative of 1,2- diphenyl naphthalenes
Ferric trichloride is used to be 0.6 with the mol ratio of diphenyl acetylene derivatire during this intermediate of thing：1 ~ 2 ：1.Second step is given birth to
It is that 1,2- benzos that H or Cl atoms replace bend deriving for ferric trichloride used and 1,2- diphenyl naphthalene during derivative into X
The mol ratio of thing is 3：1 ~ 12 ：1.
No matter method one or the X of the synthesis of method two for 1, the 2- benzos of H bend derivative can also again with 1 ~ 2 equivalent
The benzo of the higher pre- sense dough of bromine of the bromine such as NBS or bromine source reaction reaction of formation activity bends derivative.
The substituent of the diphenyl acetylene derivatire used by said method is the alkoxyl of C1 ~ C20；Phenylacetaldehyde used, its
Substituent R2, R3Can be H or the alkoxy chain for C1 ~ C20.
Said method solvent for use can be dichloroethanes（DME）, dichloromethane（DCM）Or it is arbitrary in nitromethane
Kind, wherein it is preferred that dichloroethanes（DME）.
The preferred ferric trichloride of oxidant used used by said method.
Method made above this have the advantage that：
（1）From unlike the method reported：The method does original using diaryl acetylene and phenylacetaldehyde simple and easy to get
Material, by single step reaction or two step cascade reactions can rapid build 1,2- benzos bend skeleton；
（2）By the control of tri-chlorination iron in reaction, can selectively synthesize side chain number from 4 to 6 different replacement numbers
1,2- benzos bend 1, the 2- benzos of molecule or the pre- sense dough of C10 positions chlorine and bend molecule, can as further build liquid crystal or
The reactive functionality of the organic film semiconductor material such as luminous organic material；
（3）X for the benzo of H atom bend molecule can further with the reaction of the bromine source such as NBS or bromine, in C10 positions by replacing
Reaction generates bromo benzo and bends molecule
Description of the drawings
The proton nmr spectra of compound is obtained in Fig. 1 embodiments 3.
The carbon-13 nmr spectra of compound is obtained in Fig. 2 embodiments 3.
The proton nmr spectra of compound is obtained in Fig. 3 embodiments 4.
The carbon-13 nmr spectra of compound is obtained in Fig. 4 embodiments 4.
The proton nmr spectra of compound is obtained in Fig. 5 embodiments 6.
The carbon-13 nmr spectra of compound is obtained in Fig. 6 embodiments 6.
The single crystal diffraction figure of compound is obtained in Fig. 7 embodiments 4.
The Polarized Texture figure of compound is obtained in Fig. 8 embodiments 5.
The DSC curve figure of compound is obtained in Fig. 9 embodiments 5.
X-ray diffraction pattern of the compound at 30 and 90 degrees Celsius is obtained in Figure 10 embodiments 5.
UV absorption and fluorescence emission spectrum of the compound in dichloromethane solution is obtained in Figure 11 embodiments 3,4,5.
Specific embodiment
Embodiment is given below to be specifically described the present invention, it is necessary to it is pointed out here that be that following examples are only used
In being further described to the present invention, it is impossible to be interpreted as limiting the scope of the invention, the people that is skilled in technique of this area
Member still belongs to the protection model of the present invention according to some nonessential modifications and adaptations that the content of the invention described above is made to the present invention
Enclose.
What deserves to be explained is, the intermediate diaryl acetylene, phenylacetaldehyde and 1,2- diphenyl naphthalene used by following embodiment
The synthesis of derivative is prior art, referring to document：Eur. J. Org. Chem. 2005, 2689-2693；Print during chemical industry
2006, 20, 21-22; Tetrahedron Lett. 2013, 54, 179-182。
Embodiment 1
The compound that the present embodiment is provided is formula（I）In compound, wherein R1It is alkyl that carbon atom quantity is 1,
R2、R3It is H atom with X.By method one, it is as follows that it prepares reaction：
By 1 mole per part of compound 1-（3,4- dimethoxys）-2-（3,4- dimethoxys）- tolans, 1.2
Mole per part of phenylacetaldehyde is dissolved in dry DCE, then adds 5 moles of every part of ferric trichlorides, room temperature reaction, TLC detections
It is complete to tolans reaction.Revolving removes after solvent directly column chromatography for separation, recrystallize light yellow solid is product, produce
Rate 47%.
Nucleus magnetic hydrogen spectrum1HNMR (CDCl3, 400MHz): 8.98 (d, J = 8.4 Hz, 1H), 8.47 (d, J =
8.8 Hz, 1H), 8.41 (s, 1H), 8.00-8.02 (m, 2H), 7.94 (d, J = 8.8 Hz, 1H), 7.88
(s, 1H), 7.86 (s, 1H), 7.56-7.63 (m, 2H), 4.17 (s, 3H), 4.16 (s, 3H), 4.15
(s, 3H), 4.06 (s, 3H).
Nuclear-magnetism carbon is composed13C NMR (CDCl3, 100MHz): 149.53, 149.09, 148.84, 147.89,
133.07, 130.24, 128.28, 127.61, 126.89, 126.59, 126.04, 125.66, 125.47,
125.24, 124.14, 123.63, 123.49, 120.84, 110.88, 104.86, 104.15, 103.84,
56.14, 56.10, 56.07, 56.04.
Mass spectrum Mass (APCI, m/z), calcd for C26H22O4, [M]+ 398.15, found [M+H]+
399.16.
Embodiment 2
The compound that the present embodiment is provided is formula（I）In compound, wherein R1It is alkyl that carbon atom quantity is 6,
R2、R3It is alkoxyl that carbon atom quantity is 6, X is H atom.By method one, it is as follows that it prepares reaction：
By 1 mole per part of compound 1-（3,4- bis- hexyloxies）-2-（3,4- bis- hexyloxies）- tolans, 1.2 rub
The hexyloxy phenylacetaldehydes of 3,4- bis- of per part of that are dissolved in dry DCE, then add 3 moles of every part of ferric trichlorides, and room temperature is anti-
Should, TLC detects complete to tolans reaction.Direct column chromatography for separation, ethyl acetate and methyl alcohol is mixed after revolving removing solvent
Close liquid recrystallize yellow powder shape solid is product, yield 27%.
Nucleus magnetic hydrogen spectrum1HNMR (CDCl3, 400MHz): δ (ppm): 8.40 (s, 1H, ArH), 8.37 (s,
1H, ArH), 8.31 (d, J = 9.2Hz, 1H, ArH), 7.99 (s, 1H, ArH),7.91 (s, 1H, ArH),
7.77 (d, J = 8.8Hz, 1H, ArH), 7.30 (s, 1H, ArH), 4.23-4.30 (m, 6H), 4.20 (t,J = 6.8Hz, 2H, ArOCH2), 4.14 (td, J = 6.8Hz, J = 2.4Hz, 4H, ArOCH2), 1.91-1.97
(m, 12H, CH2), 1.52-1.61 (m, 12H, CH2), 1.35-1.42 (m, 24H, CH2), 0.92-0.96 (m,
18H, CH3).
Nuclear-magnetism carbon is composed13C NMR (CDCl3, 100MHz): 149.21, 149.18, 148.86, 148.49,
147.81, 128.85, 126.04, 125.39, 125.30, 124.14, 123.84, 123.75, 119.10,
112.00, 109.92, 108.73, 107.07, 106.93, 106.75, 69.70, 69.56, 69.35, 69.27,
69.21, 68.83, 31.70, 31.67, 31.65, 31.63, 29.43, 29.41, 29.34, 29.17, 25.87,
25.85, 25.83, 25.81, 22.67, 22.65, 22.63, 14.06, 14.00.
Mass spectrum Mass (APCI, m/z), calcd for C58H86O6, [M]+ 878.64, found [M+H]+
879.58.
Embodiment 3
The compound that the present embodiment is provided is formula（I）In compound, wherein R1It is alkyl that carbon atom quantity is 1, R2
It is alkoxyl that carbon atom quantity is 1, R3It is H atom with X.By method two, it is as follows that it prepares reaction：
By 1 mole of every part of compound 1-（3,4- dimethoxys）-2-（3,4- dimethoxys）- tolans, 1.2 moles
Every part of p-methoxy phenylacetaldehyde is dissolved in dichloroethane solution, adds 1.2 moles per part of ferric trichloride FeCl3Room temperature reaction
Generate intermediate naphthalene derivatives.After the completion of the step reaction, iron ion is removed by a short column；Crude product is continued again put into
To in dichloroethane solution, 5 moles per part of FeCl is added3, room temperature reaction to thin-layer chromatography detection is without intermediate presence；Then
The methyl alcohol that a small amount of frost is added in reaction system extracts reaction of going out, and using Rotary Evaporators filtrate solvent is removed, and residual solids are led to
Cross the isolated light yellow powder solid of silica column chromatography and be product.Gross production rate：53%.
Nucleus magnetic hydrogen spectrum1H NMR (CDCl3, 400MHz): 8.48 (s, 1H), 8.40 (sd, J = 2 Hz, 1H),
8.35 (d, J = 9.2 Hz, 1H), 8.00 (s, 1H), 7.87-7.94(m, 4H), 7.25 (dd, J = 8.0
Hz, J = 2.4 Hz, 1H), 4.14 (m, 9H), 4.07 (s, 3H), 3.98 (s, 3H).
Nuclear-magnetism carbon is composed13C NMR (CDCl3, 100MHz): 157.96, 149.54, 149.07, 148.65,
147.74, 131.40, 129.77, 128.22, 127.57, 126.41, 125.27, 125.15, 124.15,
123.75, 123.69, 118.64, 116.86, 110.04, 108.08, 104.98, 104.34, 103.81,
56.14, 56.11, 56.07, 56.03, 55.49.
Mass spectrum Mass (APCI, m/z), calcd for C27H24O5, [M]+ 428.16, found [M+H]+
429.19.
Embodiment 4
The compound that the present embodiment is provided is formula（I）In compound, wherein R1It is alkyl that carbon atom quantity is 1, R2
It is alkoxyl that carbon atom quantity is 1, R3It is Cl atoms for H atom and X.By method two, it is as follows that it prepares reaction：
By 1 mole of every part of compound 1-（3,4- dimethoxys）-2-（3,4- dimethoxys）- tolans, 1.2 moles
Every part of p-methoxy phenylacetaldehyde is dissolved in dichloroethane solution, adds 1.2 moles per part of ferric trichloride FeCl3Room temperature reaction
Generate intermediate naphthalene derivatives.After the completion of the step reaction, iron ion is removed by a short column；Crude product is continued again put into
To in dichloroethane solution, 10 moles per part of FeCl is added3, room temperature reaction to thin-layer chromatography detection is without intermediate presence；So
The methyl alcohol for adding a small amount of frost in reaction system afterwards extracts reaction of going out, and using Rotary Evaporators filtrate solvent, residual solids are removed
Product is by the isolated light yellow powder solid of silica column chromatography.Gross production rate：44%.
Nucleus magnetic hydrogen spectrum1H NMR (CDCl3, 400MHz): 8.35-8.38 (m, 2H), 8.34 (s, 1H), 8.33
(s, 1H), 7.83 (s, 1H), 7.81 (s, 1H), 7.80 (s, 1H), 7.32 (dd, J = 9.0 Hz, J =
2.6 Hz, 1H), 4.16 (s, 3H), 4.15 (s, 3H), 4.14 (s, 3H), 4.04 (s, 3H), 3.97 (s,
3H).
Nuclear-magnetism carbon is composed13C NMR (CDCl3, 100MHz): 158.41, 149.82, 149.19, 148.80,
147.87, 132.72, 130.21, 127.58, 126.49, 125.22, 125.13, 124.46, 124.30,
123.16, 122.71, 118.89, 117.29, 109.98, 108.66, 104.70, 104.31, 103.74,
56.12, 56.09, 56.06, 55.56.
Mass spectrum Mass (APCI, m/z), calcd for C27H23ClO5, [M]+ 462.12, found [M+H]+
463.20.
Embodiment 5
The compound that the present embodiment is provided is formula（I）In compound, wherein R1It is alkyl that carbon atom quantity is 6,
R2、R3It is alkoxyl that carbon atom quantity is 6 and X is Cl atoms.By method two, it is as follows that it prepares reaction：
By 1 mole of every part of compound 1-（The hexyloxies of 3,4- bis-）-2-（The hexyloxies of 3,4- bis-）- tolans, 1.2 moles
Per part 3, the hexyloxy phenylacetaldehydes of 4- bis- are dissolved in dichloroethane solution, add 1.2 moles per part of ferric trichloride FeCl3Room temperature
Reaction generates intermediate naphthalene derivatives.After the completion of the step reaction, iron ion is removed by a short column；Crude product is continued again
In putting into dichloroethane solution, 9 moles per part of FeCl is added3, room temperature reaction to thin-layer chromatography detection is without intermediate presence；
Then the methyl alcohol that a small amount of frost is added in reaction system extracts reaction of going out, and using Rotary Evaporators filtrate solvent is removed, and residual is solid
Body is product by the isolated light yellow powder solid of silica column chromatography.Gross production rate：43%.
Nucleus magnetic hydrogen spectrum1H NMR (CDCl3, 400MHz): 8.39 (s, 1H), 8.35 (s, 1H), 8.30 (s,
1H), 7.88 (s, 1H), 7.87 (s, 1H), 7.85 (s, 1H), 7.73 (s, 1H), 4.24-4.30 (m,
8H), 4.10-4.16 (m, 4H), 1.88-1.99 (m, 12H), 1.50-1.60 (m, 12H), 1.35-1.42 (m,
24H), 0.93-0.96 (m, 18H).
Nuclear-magnetism carbon is composed13C NMR (CDCl3, 100MHz): 149.53, 149.40, 149.30, 149.18,
148.74, 147.97, 128.92, 126.52, 126.14, 125.84, 125.42, 124.65, 123.99,
123.25, 123.16, 119.26, 112.04, 112.03, 110.11, 106.86, 106.71, 106.66,
105.41, 69.70, 69.54, 69.40, 69.33, 69.26, 68.90, 31.70, 31.67, 31.64, 31.62,
31.60, 29.42, 29.39, 29.34, 29.29, 29.10, 25.86, 25.85, 25.83, 22.67, 22.65,
22.62, 14.06, 14.00.
Mass spectrum Mass (APCI, m/z), calcd for C58H87ClO6, [M]+ 912.60, found [M+H]+
913.55.
Embodiment 6
The compound that the present embodiment is provided is formula（I）In compound, wherein R1It is alkyl that carbon atom quantity is 1, R2
It is alkoxyl that carbon atom quantity is 1, R3It is Br atoms for H atom and X.It is as follows that it prepares reaction：
The X that 1 mole per part is synthesized by method one or method two is bent for the 1,2- pentamethoxyls benzo of H atom and is dissolved in N,
Dinethylformamide（DMF）In solution, 1.2 moles of every part of NBS are added, 80oC reacts overnight.Then reactant liquor is arrived
In entering frozen water, filter gained filter cake and light yellow solid is obtained by column chromatography for separation be product.Yield 83%.
Nucleus magnetic hydrogen spectrum1H NMR (CDCl3, 400MHz): 8.58 (s, 1H), 8.34-8.37 (m, 3H), 7.87
(s, 1H), 7.85 (s, 1H), 7.83 (s, 1H), 7.32 (dd, J = 9.0 Hz, J = 2.4 Hz, 1H),
4.16-4.17 (m, 9H), 4.05 (s, 3H), 3.98 (s, 1H).
Nuclear-magnetism carbon is composed13C NMR (CDCl3, 100MHz): 158.40, 149.86, 149.24, 148.89,
147.89, 132.58, 129.21, 127.95, 126.23, 125.31, 125.04, 124.33, 123.18,
122.69, 122.58, 121.21, 117.52, 110.03, 108.58, 104.70, 104.32, 103.76,
56.16, 56.13, 56.10, 56.06, 55.58.
Mass spectrum Mass (APCI, m/z), calcd for C58H87BrO6, [M]+ 506.07, found [M+H]+
507.21.
Claims (4)
1. 1, the 2- benzos that many alkoxyls of a class replace bend the preparation method of derivative, and such compound has following formulas（I）
Structure, wherein R1It is-CmH2m+1, m represents the integer that carbon number is 1 to 20；R2, R3It is H or-OCnH2n+1, n represents carbon
Atomicity is 1 to 20 integer；X can be H atom, Cl atoms or Br atoms；
Its synthesis step is：
Method one, diphenyl acetylene derivatire, phenylacetaldehyde or derivatives thereof are dissolved in organic solvent, add ferric trichloride
FeCl3, step generation X is that 1, the 2- benzos of H bend derivative；In this method, ferric trichloride and diphenyl acetylene derivatire rub
You are than being 3：1 ~ 8 ：1；
Method two, diphenyl acetylene derivatire, phenylacetaldehyde or derivatives thereof are dissolved in organic solvent, add ferric trichloride
FeCl3, room temperature reaction generation intermediate 1,2- diphenyl naphthalene derivatives；After the completion of the step reaction, removed by a short column
Iron ion, then crude product is continued to put in organic solvent, add FeCl3, room temperature reaction to thin-layer chromatography detection is without centre
Body is present；Then the methyl alcohol that a small amount of frost is added in reaction system is quenched reaction, and using Rotary Evaporators organic solvent is removed,
Residual solids pass through the isolated product of silica column chromatography；Wherein the first step generate 1,2- diphenyl naphthalene derivatives this
Ferric trichloride is used to be 0.6 with the mol ratio of diphenyl acetylene derivatire during intermediate：1 ~ 2 ：1；It is H that second step generates X
The mol ratio of ferric trichloride used and 1,2- diphenyl naphthalene derivatives is 3 during 1,2- benzo derivative in the wrong：1 ~ 7 ：
1；Second step generates 1, the 2- benzos that X is that Cl atoms replace and bends ferric trichloride used and 1,2- diphenyl naphthalene during derivative
Derivative mol ratio be 7：1 ~ 12 ：1；
No matter method one or the X of the synthesis of method two for 1, the 2- benzos of H bend derivative can also again with the NBS of 1 ~ 2 equivalent or
The benzo of the higher pre- sense dough of bromine of bromine reaction reaction of formation activity bends derivative.
2. according to claim 1 formula is（I）Many alkoxyls replace 1,2- benzos bend derivative preparation method, should
Diphenyl acetylene derivatire used by method, described substituent R1For the alkyl of C1 ~ C20.
3. according to claim 1 formula is（I）Many alkoxyls replace 1,2- benzos bend derivative preparation method, should
Phenylacetaldehyde used by method or derivatives thereof, its substituent R2, R3It is the alkoxyl of H or C1 ~ C20.
4. according to claim 1 formula is（I）Many alkoxyls replace 1,2- benzos bend derivative preparation method, should
Organic solvent used by method is dichloroethanes（DME）.
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