CN1730452A - Dphenylacetylene derivative and its preparation method and uses - Google Patents
Dphenylacetylene derivative and its preparation method and uses Download PDFInfo
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- CN1730452A CN1730452A CN 200510088782 CN200510088782A CN1730452A CN 1730452 A CN1730452 A CN 1730452A CN 200510088782 CN200510088782 CN 200510088782 CN 200510088782 A CN200510088782 A CN 200510088782A CN 1730452 A CN1730452 A CN 1730452A
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- difluoro
- methoxydiphenylacetylene
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- triphenylphosphine
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- 238000002360 preparation method Methods 0.000 title claims description 15
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- -1 3, 4-difluoro-2-methoxy phenylacetylene Chemical group 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 4
- DNXSLLIDTGLIHX-UHFFFAOYSA-N 1-bromo-3,4-difluoro-2-methoxybenzene Chemical compound COC1=C(F)C(F)=CC=C1Br DNXSLLIDTGLIHX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001555 benzenes Chemical class 0.000 claims description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical group Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000012769 display material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 8
- 238000004090 dissolution Methods 0.000 abstract 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000010992 reflux Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000012047 saturated solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XILRUONFYBUYIE-UHFFFAOYSA-N 1-butyl-4-iodobenzene Chemical compound CCCCC1=CC=C(I)C=C1 XILRUONFYBUYIE-UHFFFAOYSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- QBYHVVBZXPJPKK-JOCQHMNTSA-N C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(I)C=C1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(I)C=C1 QBYHVVBZXPJPKK-JOCQHMNTSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000008424 iodobenzenes Chemical class 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a diphenylacetylene derivative, its preparing process and use, wherein the derivative has structural formula I, wherein R is alkyl, m is 0 or 1. By introducing a methoxyl onto the lateral direction of the molecule, the diphenylacetylene derivative can increase the width of the liquid crystal molecules, improve dissolution property, and keep the large optical birefringent of the liquid crystal molecules.
Description
Technical Field
The invention relates to a tolane derivative, a preparation method thereof and application of the tolane derivative in the field of liquid crystal display.
Background
Polar nematic Liquid Crystal materials having large optical anisotropy (Δ n), low viscosity, and good photochemical stability are finding increasingly widespread use in the fields of displays, optical communications, and laser beam control applications (s.t.wu, d.k.yang, Reflective Liquid Crystal Display, Wiley, 2001). To obtain a large Δ n, molecules having a linear conjugated structure are generally selected, of which diphenylacetylene-based liquid crystals are one. To further increase Δ n, various structural molecular designs have been used, such as the introduction of two carbon-carbon triple bonds to a benzene ring (Xushoyi et al, Chinese patent CN1450040A) or the introduction of groups with large conjugation degree such as cyano or isothiocyanates at the ends of the molecule (A. Spadlo, R. Dabrowski, et a1, 2003, liq. Cryst., 30(2), 191-198). These structures do increase the Δ n of the liquid crystal molecules, but also bring about higher melting points and clearing points, resulting in reduced solubility of the molecules.
Disclosure of Invention
The invention aims to provide a tolane derivative and a preparation method thereof.
The structure of the tolane derivative provided by the invention is shown as formula I,
(formula I)
Wherein,
r is alkyl; m is 0 or 1.
More specifically, R is an alkyl group having 1 to 15 carbon atoms, and in this case, the tolane derivative of the present invention is one of the following compounds:
4' -methyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -ethyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -propyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -butyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -pentyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -hexyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -heptyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -octyl-3, 4-difluoro-2-methoxydiphenylacetylene
4' -nonyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -decyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -undecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -dodecyl-3, 4-difluoro-2-methoxy-diphenylacetylene,
4' -tridecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -tetradecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -pentadecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -methylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -ethylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (trans-4 "-propylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -butylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -pentylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (trans-4 "-hexylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -heptylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -octylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -nonylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -decylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -undecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -dodecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -tridecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -tetradecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -pentadecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -methylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -ethylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-propylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -butylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-pentylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-hexylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-heptylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -octylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -nonylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-decylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-undecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -dodecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-tridecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -tetradecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-pentadecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene.
The preparation method of the tolane derivative is obtained by coupling reaction of 3, 4-difluoro-2-methoxy phenylacetylene and halogenated benzene derivative with a structure shown in a formula II under the action of a catalyst; the catalyst is tetrakis (triphenylphosphine) palladium, triphenylphosphine and cuprous iodide;
Wherein,
r is alkyl; m is 0 or 1; x is I or Br.
Among them, the halogenated benzene derivative is preferably an iodobenzene derivative, and the reaction yield is high. The reaction temperature of the coupling reaction is 70-100 ℃, and the reaction time is 16-24 hours.
In the preparation process, the 3, 4-difluoro-2-methoxy phenylacetylene is synthesized according to the following method: reacting 3, 4-difluoro-2-methoxy bromobenzene with 2-methyl 3-butine-2-alcohol under the action of a catalyst to generate 4- (3 ', 4 ' -difluoro-2 ' -methoxy) phenyl-2-methyl 3-butine-2-alcohol, and then reacting with strong base to remove acetone to obtain the compound; the catalyst is bis (triphenylphosphine) palladium chloride, triphenylphosphine and cuprous iodide.
Wherein the temperature of the catalytic reaction is 60-100 ℃, and the reaction time is 10-12 hours; the temperature of the acetone removal reaction is 100-120 ℃, and the reaction time is 3-6 hours. As the strong base, NaOH, KOH or the like is usually used.
It is another object of the present invention to provide uses of the tolane derivatives of the present invention.
The tolane derivative has the advantages of low melting point, large optical anisotropy (delta n) and the like, is a liquid crystal display material with excellent performance, and has wide application prospect in the fields of liquid crystal display and liquid crystal light modulators.
The tolane derivative introduces a methoxyl group in the lateral direction of the molecule, and because the space volume of the group is smaller and the galvanic distance is not large, the width of the liquid crystal molecule can be increased, the melting point is reduced while the nematic phase performance of the liquid crystal molecule is maintained, and the solubility is increased; meanwhile, the large optical birefringence performance of the liquid crystal molecules can be kept, and the melting point and clearing point of the molecules are reduced. The compound of the invention has simple preparation method, excellent performance and wide application prospect.
Detailed Description
Example 1 preparation of 4' -butyl-3, 4-difluoro-2-methoxydiphenylacetylene
1. Preparation of 3, 4-difluoro-2-methoxyphenylacetylene
In a 500ml three-necked flask equipped with a reflux condenser and a vacuum stirrer, 44.6g (0.20mol) of 3, 4-difluoro-2-methoxybromobenzene, 42.0g (0.50mol) of 2-methyl-3-butyn-2-ol, 0.54g (0.0008mol) of bis (triphenylphosphine) palladium chloride, 0.54g (0.03mol) of cuprous iodide, 1.08g (0.004mol) of triphenylphosphine and 250ml of triethylamine were charged. Introducing argon gas for protection, heating to 80 ℃ in an oil bath under stirring, refluxing for 12h, cooling to room temperature, adding 200ml of ammonium chloride saturated solution under stirring, stopping stirring after about half an hour, and standing for layering. The separated aqueous phase is extracted three times with 200ml dichloromethane, the organic phase is mixed with the extract after the solvent is removed by rotary evaporation, and is washed to acidity by using dilute hydrochloric acid with the concentration of 3 percent and then washed to neutrality by using water. The solution was rotary evaporated to dryness to obtain 35g of a bright yellow oily liquid.
The bright yellow oily liquid obtained in the previous step was added to a 500ml three-necked flask equipped with a stirrer and a reflux condenser, 250ml of toluene was used as a solvent, and ground 6.0g of sodium hydroxide was added under stirring, the mixture was heated in an oil bath to 110 ℃ and the solution gradually changed from yellow to brownish black, refluxed at this temperature for 5 hours, cooled to room temperature, filtered with suction, and the solid was removed. And (3) carrying out rotary evaporation on the filtrate, removing toluene and acetone by evaporation, then carrying out reduced pressure distillation on the residual liquid, and collecting 50-52 ℃ fractions under the pressure of 100pa to obtain 27g of colorless oily liquid, namely 3, 4-difluoro-2-methoxyphenylacetylene, wherein the purity of the gas chromatography is 99%, and the yield is 80%.
The mass spectrum data of the 3, 4-difluoro-2-methoxy phenylacetylene are as follows:
MS(m/z)：168(M+)，167，143，137，112，93，74，31。
2. preparation of 4' -butyl-3, 4-difluoro-2-methoxydiphenylacetylene
In a 500ml three-necked flask equipped with a reflux condenser and a vacuum stirrer, 8.4g (0.05mol) of 3, 4-difluoro-2-methoxyphenylacetylene, 13.0g (0.05mol) of 4-butyliodobenzene, 7.5ml of triethylamine, 0.8g (0.004mol) of CuI, 1.0g (0.004mol) of triphenylphosphine, 2.4g (0.002mol) of tetrakis (triphenylphosphine) palladium, and 100ml of benzene were charged. Introducing argon gas for protection, heating with oil bath under uniform stirring, controlling the temperature of the oil bath at about 85 ℃, and refluxing for 16 h. After the reaction, the mixture was cooled to room temperature, and 100ml of NH was added thereto under stirring4And (3) continuously stirring the Cl saturated solution for half an hour, standing and separating the solution, extracting the water phase with 100ml of benzene for three times, combining the organic phase and the extract, washing the mixture to be neutral, performing rotary evaporation, and evaporating the solvent to obtain a black brown solid. And (3) putting the solid in a silica gel column, eluting the silica gel column by using petroleum ether, and evaporating the petroleum ether after eluting to obtain a crude product. The crude product was recrystallized from 200ml of absolute ethanol to give 10.5g of white crystalline 4' -butyl-3, 4-difluoro-2-methoxydiphenylacetylene in a yield of 70%.
DSC：Cr29.9℃ I
IR: wave number/cm-1＝3020，3018，2953，2933，2872，2839，2210，1915，1880，1612，1497，1475，1423，1331，1284，1205，1080，1061，984，930，812，690，642，552
MS(m/z)：300，269，258，257，243，241，225，214，201，193，188，175，167，151，149，128，115，107，91，81，75，63 51，43，41
The identification result shows that the obtained compound is the target compound.
The 4' -butyl-3, 4-difluoro-2-methoxydiphenylacetylene has a large optical anisotropy Δ n (Δ n thereof is 0.26).
The following compounds can be prepared in the same way:
4' -methyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -ethyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -propyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -pentyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -hexyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -heptyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -octyl-3, 4-difluoro-2-methoxydiphenylacetylene
4' -nonyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -decyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -undecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -dodecyl-3, 4-difluoro-2-methoxy-diphenylacetylene,
4' -tridecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -tetradecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -pentadecyl-3, 4-difluoro-2-methoxydiphenylacetylene.
Example 2 preparation of 4' - (trans-4 "-propylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene
1. 3, 4-difluoro-2-methoxyphenylacetylene was prepared in the same manner as in example 1.
2. Preparation of 4' - (trans-4 "-propylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene
In a 500ml three-necked flask equipped with a reflux condenser and a vacuum stirrer, 8.4g (0.05mol) of 3, 4-difluoro-2-methoxyphenylacetylene, l6.4g (0.05mol) of 4- (trans-4' -propylcyclohexyl) iodobenzene, 7.5ml of triethylamine, 0.8g (0.004mol) of CuI, 1.0g (0.004mol) of triphenylphosphine, 2.4g (0.002mol) of tetrakis (triphenylphosphine) palladium, and 100ml of benzene were charged. Introducing argon gas for protection, stirring at uniform speed, heating with oil bath, controlling the temperature of the oil bath at about 85 deg.C, and refluxing for 20 hr. After the reaction, the mixture was cooled to room temperature, and 100ml of NH was added thereto under stirring4And (3) continuously stirring the Cl saturated solution for half an hour, standing and separating the solution, extracting the water phase with 150ml of benzene for three times, combining the organic phase and the extract, washing the mixture to be neutral, performing rotary evaporation, and evaporating the solvent to obtain a black brown solid. And (3) putting the solid in a silica gel column, eluting the silica gel column by using petroleum ether, and evaporating the petroleum ether after eluting to obtain a crude product. The crude product was recrystallized from 300ml of absolute ethanol to give 23.9g of white crystal 4' - (trans-4 "-propylcyclohexyl) -3, 4-difluoro-2-methoxytolane in a yield of 65%.
DSC：Cr 72.09℃ N 130.26℃ I
IR: wave number/cm-1＝3010，2960，2920，2850，2212，1913，1876，1608，1493，1477，1425，1323，1261，1236，1203，1095，1061，1022，980，937，810，694，660，619，553MS(m/z)：368，353，325，294，283，270，268，257，243，238，225，214，207，201，199，188，167167，155，141，129，125，115，107，91，81，69，55
The identification result shows that the obtained compound is the target compound.
The 4' - (trans-4 "-propylcyclohexyl) -3, 4-difluoro-2-methoxytolane had a large optical anisotropy Δ n (Δ n thereof was 0.22).
The following compounds can be prepared in the same way:
4 '- (trans-4' -methylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -ethylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -butylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -pentylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (trans-4 "-hexylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -heptylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -octylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -nonylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -decylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -undecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -dodecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -tridecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -tetradecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (trans-4 "-pentadecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene.
Example 3 preparation of 4' - (4 "-pentylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene
1. 3, 4-difluoro-2-methoxyphenylacetylene was prepared in the same manner as in example 1.
2. Preparation of 4' - (4 "-pentylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene
In a 500ml three-necked flask equipped with a reflux condenser and a vacuum stirrer, 8.4g (0.05mol) of 3, 4-difluoro-2-methoxyphenylacetylene, 17.5g (0.05mol) of 4' -alkyl-4-iodobiphenyl, 7.5ml of triethylamine, 0.8g (0.004mol) of CuI, 1.0g (0.004mol) of triphenylphosphine, 2.4g (0.002mol) of tetrakis (triphenylphosphine) palladium, and 100ml of benzene were charged. Introducing argon gas for protection, heating with oil bath under uniform stirring, controlling the temperature of the oil bath at about 85 ℃, and refluxing for 24 h. After the reaction, the mixture was cooled to room temperature, and 100ml of NH was added thereto under stirring4And (3) continuously stirring the Cl saturated solution for half an hour, standing and separating the solution, extracting the water phase with 250ml of benzene for three times, combining the organic phase and the extract, washing the mixture to be neutral, performing rotary evaporation, and evaporating the solvent to obtain a yellow solid. And (3) putting the solid in a silica gel column, leaching with a mixed solvent of petroleum ether and ethyl acetate, eluting, and evaporating to remove the organic solvent to obtain a crude product. The crude product was recrystallized from 500ml of anhydrous ethanol to give 13.3g of 4' - (4 "-pentylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene as a white crystal in a yield of 68%.
DSC：Cr99.93℃ N 133.29℃ I
IR: wave number/cm-1＝3008，2958，2927，2854，2208，1919，1873，1608，1504，1475，1425，1329，1279，1234，1203，1115，1061，980，933，812，721，675，636，536MS(m/z)：390，375，359，347，333，319，304，300，288，270，267，255，247，235，195，189，167，143，119，115，91，75，55
The identification result shows that the obtained compound is the target compound.
The 4' - (4 "-pentylphenyl) -3, 4-difluoro-2-methoxytolane had a large optical anisotropy Δ n (Δ n thereof was 0.30).
The following compounds can be prepared using the same procedure:
4 '- (4' -methylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -ethylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-propylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -butylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-hexylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-heptylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -octylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -nonylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-decylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-undecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -dodecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-tridecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -tetradecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-pentadecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene.
Claims (10)
1. The structure of the tolane derivative is shown as formula I,
wherein,r is alkyl; m is 0 or 1.
2. A tolane derivative according to claim 1, wherein: and R is alkyl with 1-15 carbon atoms.
3. A tolane derivative according to claim 1, wherein: the tolane derivative is one of the following compounds:
4' -methyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -ethyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -propyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -butyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -pentyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -hexyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -heptyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -octyl-3, 4-difluoro-2-methoxydiphenylacetylene
4' -nonyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -decyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -undecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -dodecyl-3, 4-difluoro-2-methoxy-diphenylacetylene,
4' -tridecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -tetradecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4' -pentadecyl-3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -methylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -ethylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (trans-4 "-propylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -butylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -pentylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (trans-4 "-hexylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -heptylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -octylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -nonylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -decylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -undecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -dodecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -tridecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -tetradecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (trans-4' -pentadecylcyclohexyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -methylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -ethylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-propylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -butylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-pentylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-hexylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-heptylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -octylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -nonylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-decylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-undecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -dodecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-tridecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4 '- (4' -tetradecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene,
4' - (4 "-pentadecylphenyl) -3, 4-difluoro-2-methoxydiphenylacetylene.
4. The preparation method of the tolane derivative of claim 1, which is obtained by coupling reaction of 3, 4-difluoro-2-methoxy phenylacetylene and halogenated benzene derivative with the structure of formula II under the action of a catalyst; the catalyst is tetrakis (triphenylphosphine) palladium, triphenylphosphine and cuprous iodide;
Wherein,r is alkyl; m is 0 or 1; x is I or Br.
5. The method of claim 4, wherein: and X is I.
6. The method of claim 4, wherein: the reaction temperature of the coupling reaction is 70-100 ℃, and the reaction time is 16-24 hours.
7. The production method according to any one of claims 4 to 6, characterized in that: the 3, 4-difluoro-2-methoxy phenylacetylene is synthesized by the following method: reacting 3, 4-difluoro-2-methoxy bromobenzene with 2-methyl 3-butine-2-alcohol under the action of a catalyst to generate 4- (3 ', 4 ' -difluoro-2 ' -methoxy) phenyl-2-methyl 3-butine-2-alcohol, and then reacting with strong base to remove acetone to obtain the compound; the catalyst is bis (triphenylphosphine) palladium chloride, triphenylphosphine and cuprous iodide.
8. The method of claim 7, wherein: the temperature of the catalytic reaction is 60-100 ℃, and the reaction time is 10-12 hours; the temperature of the acetone removal reaction is 100-120 ℃, and the reaction time is 3-6 hours.
9. The method of claim 7, wherein: the strong base is NaOH or KOH.
10. A liquid crystal display material containing as a main component a tolane derivative as claimed in claim 1.
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| CN103492530A (en) * | 2011-04-27 | 2014-01-01 | 默克专利股份有限公司 | Compounds of liquid crystalline medium and use thereof for high-frequency components |
| CN107868665A (en) * | 2016-09-27 | 2018-04-03 | 捷恩智株式会社 | Liquid crystal compounds, liquid-crystal composition and liquid crystal display cells |
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| US5498367A (en) * | 1994-03-30 | 1996-03-12 | Hoffmann-La Roche Inc. | Optically active tolanes |
| EP1479748B1 (en) * | 2003-05-21 | 2010-03-17 | MERCK PATENT GmbH | Tolane derivatives and liquid crystalline medium |
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| CN103492530A (en) * | 2011-04-27 | 2014-01-01 | 默克专利股份有限公司 | Compounds of liquid crystalline medium and use thereof for high-frequency components |
| KR20140028006A (en) * | 2011-04-27 | 2014-03-07 | 메르크 파텐트 게엠베하 | Compounds of liquid crystalline medium and use thereof for high-frequency components |
| JP2014514325A (en) * | 2011-04-27 | 2014-06-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Compounds for liquid crystal media and their use for high frequency components |
| CN103492530B (en) * | 2011-04-27 | 2015-09-09 | 默克专利股份有限公司 | The compound of liquid crystal media and its purposes for high frequency assembly |
| US9169438B2 (en) | 2011-04-27 | 2015-10-27 | Merck Patent Gmbh | Compounds of liquid crystalline medium and use thereof for high-frequency components |
| TWI577784B (en) * | 2011-04-27 | 2017-04-11 | 馬克專利公司 | Compounds for a liquid-crystalline medium, and the use thereof for high-frequency components |
| CN107868665A (en) * | 2016-09-27 | 2018-04-03 | 捷恩智株式会社 | Liquid crystal compounds, liquid-crystal composition and liquid crystal display cells |
| CN107868665B (en) * | 2016-09-27 | 2022-07-26 | 捷恩智株式会社 | Liquid crystal compound, liquid crystal composition, and liquid crystal display element |
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