CN110818537B - One-pot synthesis method of phenoxyeneyne ether compound - Google Patents
One-pot synthesis method of phenoxyeneyne ether compound Download PDFInfo
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Abstract
The invention discloses a one-pot synthesis method of a phenoxyalkine ether compound, which takes estrone, indole or a compound I-1 as a reactant I, 2-acetylenethinylthiophene, 3-acetylenepyridine or a compound II-1 as a reactant II, and can react in a reaction system formed by tetrabutylammonium iodide, iodobenzene acetate, cuprous iodide, cesium carbonate and a dimethyl sulfoxide solvent in a one-pot way to obtain a target product of the phenoxyalkine ether compound. The synthesis method has the advantages of simple reaction conditions and cheap and easily-obtained reaction raw materials; meanwhile, the reaction can be directly carried out in the air atmosphere without additional gas protection in the reaction process; and the 'one-pot method' does not need to separate an intermediate, and has step and atom economy; in addition, the method also has good functional group tolerance and stereoselectivity, and can selectively synthesize the phenol-oxygen-ene alkyne ether compounds.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a one-pot synthesis method of a phenol-oxy-eneyne ether compound.
Background
The enyne ether derivatives represented by the phenoxyenyne ether compounds are not only important reaction intermediates in organic and pharmaceutical chemistry, but also have wide application in the synthesis of functional materials, natural product analogs and pharmaceutically active compounds. Therefore, starting from the simplest substrates, the construction of efficient synthetic schemes is of great importance in the fields of organic and pharmaceutical chemistry. The synthesis methods of the eneyne ether compounds reported in the literature are not many, and among them, the representative methods are:
(1) From phenol and 1, 4-diphenylbutadiyne in Pd (PPh) 3 ) 4 The phenol oxyalkyne ether compound can be obtained after the reaction for 1 to 2 days in a toluene solvent under the catalysis of (see Tetrahedron Lett.2002,43, 1085-1088); or from (E) -1, 2-dichlorovinylphenyl ether and phenylacetylene likewise in Pd (PPh) 3 ) 4 The reaction gave the target compound in 56-95% yield (see j. Org. Chem.2010,19, 6354-6371) as follows:
(2) With acetic anhydride, NBS and phenylacetylene in AgBF 4 The halogenated enol acetate in the Z formula can be synthesized by the reaction under the catalysis, and then the halogenated enol acetate reacts with phenylacetylene in another molecule in Pd (PPh) 3 ) 2 Cl 2 The eneyne ether compound is obtained by the reaction under the catalysis of (1), and the yield is 85-87% (see org. Lett.2010,14, 3262-3265); or phenol and bromophenylacetylene are firstly catalyzed by alkali to obtain a Z-type 2-bromovinyl phenyl ether intermediate, and then Pd (CH) is added 3 CN) 2 Cl 2 Catalytic Sonogashira coupling gives phenoxyenyne ether compounds in 96% yield (see org. Lett.2010,22, 5968-5971); or by benzoic acid and phenylacetylene iodine reagent firstly in AuCl (PPh) 3 ) Obtaining a Z-type beta-iodoenol ester intermediate under the catalysis of the (A), and then passing through Pd (PPh) 3 ) 4 Catalytic Sonogashira coupling gave the desired product in 80-97% yield (see j. Org. Chem.2017,82, 1507-1516) along the following reaction scheme:
(3) From propargylThe ester and the vinyl hydrazide react in a 1, 2-dichloroethane solvent at 80 ℃ by using a gold compound as a catalyst to obtain the phenol oxyalkyne ether compound, wherein the yield is 74% (see chem. Commun.2015,51, 15462-15464), and the reaction route is as follows:
however, the above synthetic methods have many defects and shortcomings:
1) Most of alkyne or phenol in the reaction needs to be functionalized in advance, then the alkyne or phenol reacts under the catalysis of alkali or metal reagent to obtain an intermediate, and then a target product is obtained from the intermediate through a Sonogashira coupling reaction catalyzed by Pd, so that the reaction process is complicated, and the separation of the intermediate also causes the methods to be inefficient, the economy is low, and the source range of the substrate is greatly limited;
2) Most of the above reactions use expensive metal reagents as catalysts, and the reaction time is long, so that the reaction is further limited in the application process.
Therefore, it is necessary to improve the existing methods for synthesizing the enyne ether compounds, and to obtain a synthetic method of the phenoxyenyne ether compounds, which has the advantages of low synthesis cost, simple reaction conditions, wide substrate application range and high stereoselectivity.
Disclosure of Invention
In view of the above, the present invention aims to provide a one-pot synthesis method of phenoxyalkenylene ether compounds.
In order to achieve the purpose, the invention provides the following technical scheme:
1. a one-pot synthesis method of a phenol oxyalkynene ether compound comprises the following specific steps:
adding tetrabutylammonium iodide, iodobenzene acetate, cuprous iodide, cesium carbonate, a reactant I, a reactant II and an organic solvent into a closed reaction vessel according to the molar volume ratio of 1;
the reactant I is estrone, indole or a compound I-1, and the structural formula of the compound I-1 is as follows:
the reactant II is 2-acetylene thiophene, 3-acetylene pyridine or a compound II-1, and the structural formula of the compound II-1 is as follows:
wherein R is 1 Hydrogen, fluorine, chlorine, bromine, iodine, aldehyde group, trifluoromethyl, methyl, isopropyl, tert-butyl, methoxy or phenyl; r is 2 Is hydrogen, fluorine, chlorine, bromine, methyl, propyl, methoxy or phenyl.
Preferably, the organic solvent is dimethyl sulfoxide.
Preferably, the specific operations of the purification are as follows: and (3) extracting the mixture in the reaction vessel after the reaction is finished by using a mixed solvent of water and ethyl acetate in a volume ratio of 1.
Preferably, the reaction is carried out in the closed reaction vessel under the condition of 110 ℃ in an air atmosphere for 22h.
Preferably, the compound I-1 is any one of phenol, 2-fluorophenol, 2-chlorophenol, 2-bromophenol, 2-iodophenol, 2-methylphenol, 2-isopropylphenol, 3-fluorophenol, 3-chlorophenol, 3-bromophenol, 3-iodophenol, 3-trifluoromethylphenol, 3-methylphenol, 3-methoxyphenol, 3-tert-butylphenol, 4-chlorophenol, 4-bromophenol, 4-iodophenol, 4-methylphenol, 4-phenylphenol, 4-hydroxybenzaldehyde or 2-naphthol.
Preferably, the compound II-1 is any one of phenylacetylene, 2-chlorophenylacetylene, 2-bromophenylacetylene, 3-fluorophenylacetylene, 3-chlorophenylacetylene, 3-bromophenylacetylene, 3-methylphenylacetylene, 3-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4-methylphenylacetylene or 4-propylphenylacetylene.
The invention has the beneficial effects that: the invention discloses a one-pot synthesis method of a phenoxyeneyne ether compound, on one hand, raw materials adopted in the one-pot synthesis method are cheap and easy to obtain, and the synthesis cost of the phenoxyeneyne ether compound can be reduced; on the other hand, the one-pot synthesis method has atom and step economy, follows the principles of green chemistry and economy, and can prepare the phenol oxyalkyne ether compound by one-step reaction in series from the simplest and most easily obtained compound; meanwhile, the tolerance and stereoselectivity of the functional group of the reaction in the synthetic method are higher, the yield of the phenol-oxygen-eneyne ether compound is higher, and the highest yield can reach 88%.
Detailed Description
The preferred embodiments of the present invention will be described in detail below.
Example 1 preparation of (Z) - (1-phenoxy-1-en-3-yne-1, 4-di) diphenyl (Compound III-1)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1, drying an extracted organic phase for 0.5 hour by using anhydrous sodium sulfate, filtering, adding a little silica gel into a filtrate, removing the solvent by a rotary evaporator, and separating and purifying by using a silica gel column, wherein the eluant is petroleum ether, so that the compound III-1 49mg can be obtained; e = 86; the yield is 83%; a yellow solid; m.p.108-109 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.65(dd,J＝6.9,1.7,2H),7.41–7.36(m,3H),7.32(t,J＝8.0,2H),7.28–7.25(m,3H),7.22(dd,J＝6.9,2.5,2H),7.14–7.10(m,2H),7.05(t,J＝7.4,1H),6.13(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.4,157.2,134.5,131.4,129.5,128.7,128.1,128.0,125.6,123.4,122.2,116.6,97.4,95.5,85.0；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 16 O[M+H] + ,297.1279；found,297.1277。
Example 2 preparation of (Z) - (1- (2-fluorophenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-2)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 45mg (0.40 mmol) of 2-fluorophenol, 44 mu L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 84; the yield was 62%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.69–7.66(m,2H),7.40(dd,J＝5.3,1.8,3H),7.29–7.27(m,3H),7.24(dd,J＝6.6,3.2,2H),7.18(ddd,J＝10.8,5.4,2.0,1H),7.09(td,J＝8.1,2.2,1H),7.04–7.00(m,2H),6.09(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.5,153.7,152.1,144.9,144.8,134.2,131.4,129.6,128.7,128.1,128.1,125.5,124.3,124.3,123.4,123.3,123.2,118.7,116.6,116.4,97.5,94.4,84.3；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 FO[M+H] + ,315.1185；found,315.1178。
Example 3 preparation of (Z) - (1- (2-chlorophenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-3)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 51mg (0.40 mmol) of 2-chlorophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL sealed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield was 61%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.64–7.61(m,2H),7.42(dd,J＝7.9,1.4,1H),7.37–7.35(m,3H),7.23(ddd,J＝11.5,6.3,4.0,5H),7.12–7.09(m,1H),6.95(ddd,J＝13.5,7.6,1.2,2H),6.09(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.2,152.8,134.1,131.4,130.3,129.6,128.8,128.1,128.1,127.6,125.5,123.5,123.3,123.3,117.2,97.5,95.2,84.4；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 ClO[M+H] + ,331.0890；found,331.0884。
Example 4 preparation of (Z) - (1- (2-bromophenoxy) but-1-en-3-yn-1, 4-di) diphenyl (Compound III-4)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 69mg (0.40 mmol) of 2-bromophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 84; the yield is 58%; a yellow solid; m.p.95-96 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.63–7.59(m,3H),7.37–7.35(m,3H),7.23(dd,J＝7.0,3.7,5H),7.16–7.12(m,1H),6.93(d,J＝8.2,1H),6.88(t,J＝7.6,1H),6.11(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.2,153.8,134.0,133.4,131.5,129.7,128.8,128.4,128.1,128.1,125.5,123.6,123.3,116.9,112.5,97.6,95.4,84.4；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 BrO[M+H] + ,375.0385；found,375.0381。
Example 5 preparation of (Z) - (1- (2-iodophenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-5)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 88mg (0.40 mmol) of 2-iodophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 80; the yield is 52%; a yellow solid; m.p.96-97 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.87(dd,J＝7.9,1.2,1H),7.65(dd,J＝7.5,1.8,2H),7.41–7.39(m,3H),7.27(d,J＝2.4,5H),7.23–7.19(m,1H),6.89(d,J＝8.3,1H),6.79(dd,J＝10.9,4.2,1H),6.15(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.4,156.3,139.5,134.0,131.5,129.7,129.4,128.8,128.1,125.6,125.5,124.1,123.4,116.6,115.7,97.7,95.5,84.6；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 IO[M+H] + ,423.0246；found,423.0247。
Example 6 preparation of (Z) - (1- (2-methylphenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-6)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 43mg (0.40 mmol) of 2-methylphenol, 44 muL (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 85; the yield is 41%; a yellow solid; m.p.109-110 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.65(dd,J＝7.4,2.1,2H),7.42–7.37(m,3H),7.26–7.25(m,4H),7.17(dd,J＝6.6,3.0,2H),7.08(d,J＝7.4,1H),6.97(t,J＝7.3,1H),6.87(d,J＝8.1,1H),6.07(s,1H),2.50(s,3H)；
13 C NMR(151MHz,CDCl 3 )δ＝160.0,155.5,134.9,131.3,130.9,129.4,128.7,128.1,127.9,127.4,126.8,125.5,123.6,122.4,115.4,96.8,93.9,84.9,16.4；
HRMS(ESI/TOF-Q):m/z calcd.for C 23 H 18 O[M+H] + ,311.1436；found,311.1433。
Example 7 preparation of (Z) - (1- (2-isopropylphenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-7)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 54mg (0.40 mmol) of 2-isopropylphenol, 44 microliter (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 84; the yield is 35%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.61(dd,J＝7.4,2.2,2H),7.37–7.33(m,3H),7.31(dd,J＝7.5,1.5,1H),7.20(dd,J＝5.1,1.8,3H),7.08(dd,J＝6.5,3.0,2H),7.05–6.98(m,2H),6.81(dd,J＝7.9,0.9,1H),6.05(s,1H),3.56(dt,J＝13.8,6.9,1H),1.35(d,J＝6.9,6H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.5,154.3,137.2,134.8,131.4,129.4,128.7,128.0,127.9,126.5,126.4,125.4,123.5,122.4,115.2,97.2,94.0,85.1,27.5,22.8；
HRMS(ESI/TOF-Q):m/z calcd.for C 25 H 22 O[M+H] + ,339.1749；found,339.1743。
Example 8 preparation of (Z) - (1- (3-fluorophenoxy) but-1-en-3-yn-1, 4-di) diphenyl (Compound III-8)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 45mg (0.40 mmol) of 3-fluorophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with a volume ratio of 1; z, E = 83; the yield is 83%; a yellow solid; m.p.87-88 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.63(dd,J＝6.4,3.0,2H),7.42–7.38(m,3H),7.31–7.24(m,6H),6.92(dd,J＝8.3,1.9,1H),6.86(dt,J＝10.3,2.3,1H),6.76(td,J＝8.3,2.0,1H),6.18(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝164.4,162.8,158.9,158.5,158.4,134.0,131.4,130.3,130.2,129.7,128.8,128.3,128.2,125.4,123.3,112.2,112.2,109.2,109.1,104.4,104.3,97.8,96.3,84.6；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 FO[M+H] + ,315.1185；found,315.1179。
Example 9 preparation of (Z) - (1- (3-chlorophenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-9)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 51mg (0.40 mmol) of 3-chlorophenol, 44 mu L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield was 77%; a yellow solid; m.p.83-84 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.62(dd,J＝6.4,3.0,2H),7.40(dd,J＝4.9,1.8,3H),7.30–7.27(m,3H),7.24(dd,J＝8.9,5.1,3H),7.14(s,1H),7.04–6.97(m,2H),6.16(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.9,157.9,134.9,134.0,131.4,130.3,129.7,128.8,128.2,128.2,125.4,123.2,122.5,117.1,114.8,97.9,96.1,84.6；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 ClO[M+H] + ,331.0890；found,331.0886。
Example 10 preparation of (Z) - (1- (3-bromophenoxy) but-1-en-3-yn-1, 4-di) diphenyl (Compound III-10)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 69mg (0.40 mmol) of 3-bromophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 75%; a yellow solid; m.p.79-80 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.65–7.59(m,2H),7.40(dd,J＝4.8,1.7,3H),7.32–7.28(m,4H),7.25(d,J＝1.8,2H),7.17(d,J＝6.9,2H),7.05–7.01(m,1H),6.16(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.9,157.9,134.0,131.4,130.6,129.7,128.8,128.2,128.2,125.4,123.2,122.8,120.0,115.2,98.0,96.1,84.6；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 BrO[M+H] + ,375.0385；found,375.0382。
Example 11 preparation of (Z) - (1- (3-iodophenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-11)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 88mg (0.40 mmol) of 3-iodophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 68%; and (4) yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.62(dd,J＝6.5,3.1,2H),7.54–7.50(m,1H),7.41–7.37(m,4H),7.29(dd,J＝6.3,2.8,3H),7.24(dd,J＝6.6,3.0,2H),7.05(ddd,J＝29.2,11.8,4.8,2H),6.15(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.9,157.7,134.0,131.4,131.4,130.8,129.7,128.8,128.2,125.9,125.4,123.2,115.9,98.1,95.9,94.1,84.7；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 IO[M+H] + ,423.0246；found,423.0245。
Example 12 preparation of (Z) - (1- (3-trifluoromethylphenoxy) but-1-en-3-yn-1, 4-di) biphenyl (Compound III-12)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 65mg (0.40 mmol) of 3-trifluoromethylphenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL sealed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1, drying the organic phase after the extraction by using anhydrous sodium sulfate for 0.5 hour, filtering, adding a little silica gel into the filtrate, performing rotary evaporation on the solvent by using a rotary evaporator, and performing separation and purification by using a silica gel column, wherein the eluent is petroleum ether, thus obtaining 37mg-12 mg of the compound III; e = 87; the yield is 51%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.66–7.61(m,2H),7.41(dd,J＝9.7,5.3,5H),7.32–7.23(m,5H),7.16(d,J＝7.2,2H),6.19(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.8,157.3,133.9,131.3,130.1,129.8,128.8,128.3,128.2,125.4,123.1,119.5,119.0,118.9,118.9,118.9,113.8,113.8,98.3,96.0,84.5；
HRMS(ESI/TOF-Q):m/z calcd.for C 23 H 15 F 3 O[M+H] + ,365.1153；found,365.1147。
Example 13 preparation of (Z) - (1- (3-methylphenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-13)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 43mg (0.40 mmol) of 3-methylphenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL sealed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 53%; a yellow solid; m.p.113-114 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.69–7.61(m,2H),7.39(dd,J＝10.0,5.0,3H),7.30–7.14(m,6H),6.95(s,1H),6.88(dd,J＝29.0,7.8,2H),6.11(s,1H),2.34(s,3H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.6,157.3,139.5,134.7,131.4,129.4,129.2,128.7,128.1,128.0,125.6,123.5,123.1,117.4,113.6,97.3,95.4,85.1,21.4；
HRMS(ESI/TOF-Q):m/z calcd.for C 23 H 18 O[M+H] + ,311.1436；found,311.1431。
Example 14 preparation of (Z) - (1- (3-methoxyphenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-14)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 50mg (0.40 mmol) of 3-methoxyphenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with a volume ratio of 1; z, E = 83; the yield is 45%; a yellow solid; m.p.99-100 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.69–7.60(m,2H),7.41–7.35(m,3H),7.31–7.25(m,5H),7.21(t,J＝8.1,1H),6.71(dd,J＝9.9,1.9,2H),6.63–6.56(m,1H),6.13(s,1H),3.79(d,J＝1.1,3H)；
13 C NMR(151MHz,CDCl 3 )δ＝160.9,159.3,158.4,134.5,131.5,129.9,129.5,128.7,128.2,128.1,125.6,123.5,109.0,107.9,103.0,97.3,95.8,85.0,55.3；
HRMS(ESI/TOF-Q):m/z calcd.for C 23 H 18 O 2 [M+H] + ,327.1385；found,327.1384。
Example 15 preparation of (Z) - (1- (3-tert-butylphenoxy) but-1-en-3-yn-1, 4-di) biphenyl (Compound III-15)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 60mg (0.40 mmol) of 3-tert-butylphenol, 44 mu L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 86; the yield was 43%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.68–7.65(m,2H),7.39(d,J＝6.3,3H),7.29–7.26(m,1H),7.24(dd,J＝10.6,7.5,4H),7.17–7.14(m,2H),7.09(d,J＝7.6,1H),6.89(d,J＝8.2,1H),6.09(s,1H),1.32(s,9H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.6,157.0,153.0,134.9,131.4,129.4,128.9,128.7,128.6,128.0,127.9,125.6,119.3,114.4,113.3,97.7,94.6,85.2,34.8,31.3；
HRMS(ESI/TOF-Q):m/z calcd.for C 26 H 24 O[M+H] + ,353.1905；found,353.1904。
Example 16 preparation of (Z) - (1- (4-chlorophenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-16)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 51mg (0.40 mmol) of 4-chlorophenol, 44 mu L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 75%; a yellow solid; m.p.86-87 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.57(dd,J＝6.7,2.9,2H),7.36–7.33(m,3H),7.24(dt,J＝12.2,2.8,5H),7.19(dd,J＝6.5,2.8,2H),7.00(t,J＝6.1,2H),6.09(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.1,155.8,134.1,131.4,129.6,129.4,128.8,128.2,127.3,125.5,123.3,117.9,97.8,95.7,84.7；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 ClO[M+H] + ,331.0890；found,331.0888。
Example 17 preparation of (Z) - (1- (4-bromophenoxy) but-1-en-3-yn-1, 4-di) diphenyl (Compound III-17)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 69mg (0.40 mmol) of 4-bromophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 80; the yield is 72%; a yellow solid; m.p.95-96 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.58–7.55(m,2H),7.37(d,J＝8.7,2H),7.36–7.33(m,3H),7.26–7.23(m,3H),7.19(dd,J＝5.9,2.5,2H),6.98–6.94(m,2H),6.09(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.0,156.4,134.1,132.4,131.4,129.7,128.8,128.2,125.5,123.2,118.4,114.7,97.8,95.7,84.7；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 BrO[M+H] + ,375.0385；found,375.0379。
Example 18 preparation of (Z) - (1- (4-iodophenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-18)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 88mg (0.40 mmol) of 4-iodophenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 65%; a yellow solid; m.p.106-107 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.62–7.60(m,3H),7.38(dd,J＝6.4,3.8,3H),7.34–7.25(m,4H),7.22(dd,J＝6.6,3.0,2H),6.89(d,J＝8.9,2H),6.13(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.9,157.2,138.4,134.1,131.4,129.7,128.8,128.2,125.5,123.2,119.0,97.9,95.7,84.7；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 15 IO[M+H] + ,423.0246；found,423.0239。
Example 19 preparation of (Z) - (1- (4-methylphenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-19)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 43mg (0.40 mmol) of 4-methylphenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 80; the yield is 26%; a yellow liquid;
1 H NMR(600MHz,CDCl 3 )δ＝7.63(dd,J＝7.4,2.0,2H),7.39–7.35(m,3H),7.27–7.25(m,3H),7.23(dt,J＝7.5,3.6,2H),7.10(d,J＝8.4,2H),7.00(d,J＝8.5,2H),6.07(s,1H),2.31(s,3H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.7,155.1,134.7,131.6,131.4,129.9,129.4,128.6,128.1,128.0,125.7,123.6,116.6,97.1,95.0,85.1,20.5；
HRMS(ESI/TOF-Q):m/z calcd.for C 23 H 18 O[M+H] + ,311.1436；found,311.1430。
example 20 preparation of (Z) - (1- (4-Phenylphenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-20)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 68mg (0.40 mmol) of 4-phenylphenol, 44 μ L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 85; the yield is 88%; a yellow solid; m.p.97-98 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.68–7.66(m,2H),7.55(t,J＝7.6,4H),7.44–7.39(m,5H),7.33(t,J＝7.4,1H),7.23(dd,J＝14.6,7.0,3H),7.20–7.17(m,4H),6.13(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.4,156.8,140.8,135.5,134.6,131.4,129.5,128.7,128.2,128.1,128.0,126.7,125.6,123.4,117.0,97.8,95.2,85.0；
HRMS(ESI/TOF-Q):m/z calcd.for C 28 H 20 O[M+H] + ,373.1592；found,373.1593。
Example 21 preparation of (Z) - (1- (4-Methylphenoxy) but-1-en-3-yne-1, 4-di) biphenyl (Compound III-21)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 49mg (0.40 mmol) of 4-hydroxybenzaldehyde, 44 muL (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 51%; a yellow solid; m.p.88-89 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝9.92(s,1H),7.87(dd,J＝9.1,2.1,2H),7.64–7.56(m,2H),7.44–7.37(m,3H),7.30–7.20(m,5H),7.17(dd,J＝8.0,1.4,2H),6.24(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝190.6,162.1,158.3,133.6,131.9,131.3,131.2,129.9,128.9,128.4,128.2,125.3,123.0,116.6,98.4,96.8,84.3；
HRMS(ESI/TOF-Q):m/z calcd.for C 23 H 16 O 2 [M+H] + ,325.1229；found,325.1222。
Example 22 preparation of (Z) - (1-Naphthyloxy-1-en-3-yne-1, 4-di) biphenyl (Compound III-22)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 58mg (0.40 mmol) of 2-naphthol, 44 mu L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 84; the yield is 32%; a yellow solid; m.p.123-124 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.82(dd,J＝13.8,8.5,2H),7.73–7.68(m,3H),7.46–7.41(m,2H),7.40–7.36(m,5H),7.22–7.19(m,1H),7.16(t,J＝7.4,2H),7.10–7.07(m,2H),6.20(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.4,155.1,134.4,134.3,131.3,129.8,129.6,129.5,128.7,128.0,128.0,127.7,127.1,126.4,125.6,124.2,123.3,118.4,111.6,97.3,95.8,84.9；
HRMS(ESI/TOF-Q):m/z calcd.for C 26 H 18 O[M+H] + ,347.1436；found,347.1434。
Example 23 preparation of (Z) -2,2' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (chlorobenzene) (Compound III-23)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 55mg (0.40 mmol) of 2-chlorophenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 83; the yield is 58%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.56–7.52(m,1H),7.42–7.35(m,2H),7.32–7.27(m,2H),7.26–7.24(m,3H),7.23–7.20(m,1H),7.17(td,J＝7.5,1.2,1H),7.10(dd,J＝8.6,0.9,2H),7.00(t,J＝7.4,1H),6.03(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.6,156.8,136.6,134.2,132.5,131.2,130.2,129.8,129.6,129.5,128.5,125.2,124.2,122.9,122.8,121.9,116.8,96.8,95.5,85.9；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 Cl 2 O[M+H] + ,365.0500；found,365.0493。
Example 24 preparation of (Z) -2,2' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (bromobenzene) (Compound III-24)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 72mg (0.40 mmol) of 2-bromophenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 85; the yield is 51%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.60(d,J＝8.0,1H),7.56–7.51(m,2H),7.31(dd,J＝6.8,5.5,1H),7.29(s,1H),7.25(d,J＝7.6,2H),7.21(d,J＝7.5,1H),7.18–7.15(m,1H),7.13(dd,J＝13.4,5.0,3H),7.00(t,J＝7.3,1H),5.96(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.6,156.1,135.5,133.9,133.4,132.3,131.0,130.4,129.3,129.2,127.3,126.8,125.7,125.3,122.8,122.2,117.8,99.6,95.1,88.7；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 Br 2 O[M+H] + ,452.9490；found,452.9483。
Example 25 preparation of (Z) -3,3' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (fluorobenzene) (Compound III-25)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 48mg (0.40 mmol) of 3-fluoroacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 87; the yield is 72%; a yellow solid; m.p.81-82 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.43(d,J＝8.0,1H),7.38–7.31(m,4H),7.21(td,J＝8.0,6.1,1H),7.12–7.05(m,4H),6.97(ddd,J＝8.9,6.0,1.7,2H),6.87–6.82(m,1H),6.10(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝163.8,163.1,162.2,161.4,158.8,158.7,156.9,136.8,136.8,130.3,130.3,129.7,129.6,129.6,127.3,127.2,125.1,125.0,122.6,121.3,121.3,118.2,118.1,116.6,116.6,116.4,115.6,115.4,112.7,112.5,96.9,96.9,95.8,85.5；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 F 2 O[M+H] + ,333.1091；found,333.1082。
Example 26 preparation of (Z) -3,3' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (chlorobenzene) (Compound III-26)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 55mg (0.40 mmol) of 3-chlorophenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 67%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.63(s,1H),7.52(d,J＝7.7,1H),7.37–7.29(m,4H),7.24(d,J＝8.0,1H),7.18(t,J＝7.8,1H),7.11–7.07(m,4H),7.05(d,J＝7.7,1H),6.08(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.7,156.8,136.4,134.9,134.0,131.3,129.9,129.6,129.4,129.3,128.4,125.7,124.9,123.7,122.7,116.7,96.8,95.6,85.8；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 Cl 2 O[M+H] + ,365.0500；found,365.0494。
Example 27 preparation of (Z) -3,3' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (bromobenzene) (Compound III-27)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 72mg (0.40 mmol) of 3-bromophenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 84; the yield was 61%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.80(s,1H),7.54(dd,J＝33.6,7.9,2H),7.41–7.32(m,3H),7.25(dd,J＝10.3,4.8,2H),7.13–7.07(m,5H),6.07(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.6,156.8,136.6,134.2,132.5,131.2,130.2,129.8,129.6,129.5,128.5,125.2,124.2,122.9,122.8,121.9,116.8,96.8,95.5,85.9；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 Br 2 O[M+H] + ,452.9490；found,452.9483。
Example 28 preparation of (Z) -3,3' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (methylbenzene) (Compound III-28)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 46mg (0.40 mmol) of 3-methylphenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with a volume ratio of 1; e = 83; the yield is 56%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.46–7.43(m,2H),7.34–7.30(m,2H),7.27(t,J＝7.6,1H),7.17(dd,J＝21.3,7.6,2H),7.13–7.11(m,2H),7.09–7.02(m,2H),7.02–6.98(m,2H),6.10(s,1H),2.38(s,3H),2.30(s,3H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.5,157.3,138.3,137.7,134.6,132.0,130.3,129.4,128.9,128.6,128.4,128.0,126.1,123.3,122.8,122.1,116.6,97.7,95.3,84.8,21.5,21.1；
HRMS(ESI/TOF-Q):m/z calcd.for C 24 H 20 O[M+H] + ,325.1592；found,325.1590。
Example 29 preparation of (Z) -3,3' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (methoxybenzene) (Compound III-29)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 53mg (0.40 mmol) of 3-methoxyphenylacetylene and 1mL of dimethyl sulfoxide into a 10mL sealed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with a volume ratio of 1; e = 81; the yield is 45%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 )δ＝7.35–7.28(m,3H),7.24(d,J＝7.8,1H),7.16(t,J＝7.9,2H),7.13–7.09(m,2H),7.04(t,J＝7.4,1H),6.92(dd,J＝8.0,2.1,1H),6.84–6.81(m,2H),6.70(d,J＝1.0,1H),6.11(s,1H),3.82(s,3H),3.77(s,3H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.9,159.4,159.2,157.3,136.0,129.7,129.5,129.2,124.4,124.0,122.2,118.2,116.6,116.1,115.1,115.0,111.2,97.5,95.6,84.8,55.3,55.3；
HRMS(ESI/TOF-Q):m/z calcd.for C 24 H 20 O 3 [M+H] + ,357.1491；found,357.1487。
Example 30 preparation of (Z) -4,4' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (fluorobenzene) (Compound III-30)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 48mg (0.40 mmol) of 4-fluoroacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 77%; a yellow solid; m.p.98-99 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.61(dd,J＝8.3,5.6,2H),7.32(t,J＝7.8,2H),7.15(dd,J＝8.2,5.7,2H),7.11–7.03(m,5H),6.95(t,J＝8.5,2H),6.01(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝164.3,163.2,162.7,161.6,158.5,157.0,138.4,133.2,133.2,130.7,130.7,129.5,127.6,127.5,122.4,119.5,119.4,119.0,116.6,115.9,115.7,115.5,115.3,96.3,94.8,84.5；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 F 2 O[M+H] + ,333.1091；found,333.1083。
Example 31 preparation of (Z) -4,4' - (1-phenoxy-1-en-3-yne-1, 4-diyl) bis (chlorobenzene) (Compound III-31)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 55mg (0.40 mmol) of 4-chlorophenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with a volume ratio of 1; e = 83; the yield is 72%; a yellow solid; m.p.108-109 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.56(d,J＝8.5,2H),7.37–7.30(m,4H),7.23(d,J＝8.3,2H),7.11–7.04(m,5H),6.06(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.7,156.9,135.6,134.2,132.9,132.6,129.5,129.0,128.5,126.8,122.5,121.8,116.6,96.7,95.3,85.7；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 Cl 2 O[M+H] + ,365.0500；found,365.0493。
Example 32 preparation of (Z) -4,4' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (bromobenzene) (Compound III-32)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 72mg (0.40 mmol) of 4-bromophenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 71%; a yellow solid; m.p.128-129 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.50(s,4H),7.38(d,J＝8.2,2H),7.31(t,J＝7.8,2H),7.08–7.00(m,5H),6.06(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝158.8,156.9,133.4,132.8,131.9,131.4,129.5,127.1,123.9,122.5,122.4,122.2,116.6,96.9,95.4,85.9；
HRMS(ESI/TOF-Q):m/z calcd.for C 22 H 14 Br 2 O[M+H] + ,452.9490；found,452.9483。
Example 33 preparation of (Z) -4,4' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (methylbenzene) (Compound III-33)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 46mg (0.40 mmol) of 4-methylphenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 84; the yield is 52%; a yellow solid; m.p.123-124 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.52(d,J＝8.2,2H),7.30(dd,J＝8.4,7.4,2H),7.17(d,J＝8.1,2H),7.11–7.08(m,4H),7.07–7.00(m,3H),6.07(s,1H),2.35(d,J＝24.9,6H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.2,157.3,139.5,138.1,131.8,131.2,129.4,129.4,128.9,125.5,122.0,120.5,116.5,97.3,94.8,84.5,21.4,21.3；
HRMS(ESI/TOF-Q):m/z calcd.for C 24 H 20 O[M+H] + ,325.1592；found,325.1588。
Example 34 preparation of (Z) -4,4' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bis (propylbenzene) (Compound III-34)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 58mg (0.40 mmol) of 4-propylphenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 82; the yield is 50%; a yellow solid; m.p.86-87 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.55(d,J＝8.2,2H),7.31(dd,J＝8.4,7.6,2H),7.19(d,J＝8.2,2H),7.12(d,J＝8.0,4H),7.07(d,J＝8.1,2H),7.03(t,J＝7.3,1H),6.09(s,1H),2.63–2.60(m,2H),2.58–2.55(m,2H),1.65(ddd,J＝21.1,15.0,7.5,4H),0.96(dt,J＝17.9,7.3,6H)；
13 C NMR(151MHz,CDCl 3 )δ＝159.2,157.4,144.3,142.8,132.0,131.3,129.4,128.8,128.3,125.4,122.0,120.7,116.5,97.4,94.9,84.6,37.9,37.8,24.3,24.3,13.8,13.7；
HRMS(ESI/TOF-Q):m/z calcd.for C 28 H 28 O[M+H] + ,381.2218；found,381.2216。
Example 35 preparation of (Z) -2,2' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bithiophene (Compound III-35)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 43mg (0.40 mmol) of 2-acetylenethiophene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; z, E = 66; the yield is 57%; a yellow solid; m.p.90-91 ℃.
1 H NMR(600MHz,CDCl 3 )δ＝7.34(dd,J＝8.4,7.6,2H),7.30(ddd,J＝5.6,3.5,0.8,2H),7.21(dd,J＝5.1,1.0,1H),7.14(d,J＝8.0,2H),7.09(t,J＝7.4,1H),7.03(dd,J＝4.9,3.8,1H),6.93(dt,J＝5.0,3.2,2H),6.00(s,1H)；
13 C NMR(151MHz,CDCl 3 )δ＝157.0,154.6,138.8,131.7,129.5,128.0,127.2,126.9,126.8,126.0,123.5,122.7,116.9,93.3,90.9,88.6；
HRMS(ESI/TOF-Q):m/z calcd.for C 18 H 12 OS 2 [M+H] + ,309.0408；found,309.0401。
Example 36 preparation of (Z) -3,3' - (1-phenoxy-1-en-3-yn-1, 4-diyl) bipyridine (Compound III-36)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 38mg (0.40 mmol) of phenol, 41mg (0.40 mmol) of 3-ethynylpyridine and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 75; the yield was 54%; a yellow liquid.
1 H NMR(600MHz,CDCl 3 ,75:25mixture of Z/E isomers)δ＝9.15(dd,J＝265.6,1.8,1H),8.67–8.45(m,2H),8.41–8.30(m,1H),7.93–7.59(m,1H),7.47–7.26(m,4H),7.25–7.05(m,4H),5.76(d,J＝429.9,1H)；
13 C NMR(151MHz,CDCl 3 ,75:25mixture of Z/E isomers)δ＝161.5,157.7,156.6,154.9,152.1,151.7,150.4,149.3,148.4,148.3,147.1,138.2,137.9,135.1,132.9,130.4,130.1,129.7,125.0,123.4,123.1,123.0,123.0,122.9,120.3,120.3,116.9,95.5,94.8,91.2,90.9,89.1,87.5；
HRMS(ESI/TOF-Q):m/z calcd.for C 20 H 14 N 2 O[M+H] + ,299.1184；found,299.1182。
EXAMPLE 37 preparation of (8S,9R, 13R, 14R) -3- ((Z) -1, 4-diphenyl-1-en-3-yn-1-yl) oxy) -13-methyl-6, 7,8,9,11,12,13,14,15, 16-decahydro-17H-cyclopenta-lene [ a ] (Compound IV)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 108mg (0.40 mmol) of estrone, 44 mu L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ under an air atmosphere for 22 hours, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 80; the yield is 65%; a yellow solid; m.p.72-73 ℃.
1 H NMR(600MHz,CDCl 3 ,80:20mixture of Z/E isomers)δ＝8.16–7.62(m,2H),7.48–7.20(m,9H),6.94–6.81(m,2H),5.72(d,J＝403.0,1H),2.96–2.85(m,2H),2.58–1.91(m,7H),1.74–1.39(m,6H),0.94(d,J＝21.1,3H)；
13 C NMR(151MHz,CDCl 3 ,80:20mixture of Z/E isomers)δ＝163.0,159.7,155.2,153.7,138.4,137.7,135.8,134.8,134.1,133.7,131.4,131.0,129.6,129.4,128.6,128.3,128.0,128.0,128.0,127.9,127.8,126.7,126.2,125.6,124.0,123.6,120.0,117.3,116.9,114.3,97.3,94.6,90.4,85.3,50.5,48.0,44.2,44.1,38.3,38.2,35.9,31.6,29.6,29.5,26.5,26.4,25.9,21.6,13.9；
HRMS(ESI/TOF-Q):m/z calcd.for C 34 H 32 O 2 [M+H] + ,473.2481；found,473.2479。
Example 38 preparation of (Z) -1 (1, 4-diphenylbutyl-1-en-3-yn-1-yl) -1H indole (Compound V)
The reaction steps are as follows: adding 8mg (0.02 mmol) of tetrabutylammonium iodide, 64mg (0.20 mmol) of iodobenzene acetate, 4mg (0.02 mmol) of cuprous iodide, 130mg (0.40 mmol) of cesium carbonate, 47mg (0.40 mmol) of indole, 44 mu L (0.4 mmol) of phenylacetylene and 1mL of dimethyl sulfoxide into a 10mL closed reaction tube, stirring and reacting at 110 ℃ for 22 hours under an air atmosphere, cooling to room temperature after the reaction is finished, performing series extraction on the mixture after the reaction by using a mixed solvent of water and ethyl acetate with the volume ratio of 1; e = 75; the yield is 70%; a yellow solid; m.p.94-95 ℃.
1 H NMR(600MHz,CDCl 3 ,75:25mixture of Z/E isomers)δ＝7.74–7.11(m,15H),6.86(ddd,J＝45.7,34.4,5.8,1H),6.22(dd,J＝74.2,4.3,1H)；
13 C NMR(151MHz,CDCl 3 ,75:25mixture of Z/E isomers)δ＝147.1,146.7,146.1,145.9,136.7,136.6,136.6,136.2,136.1,136.1,135.2,134.8,133.0,132.4,131.5,131.4,131.4,130.9,130.0,129.9,129.8,129.7,129.7,129.4,129.2,129.2,129.1,128.9,128.8,128.6,128.5,128.4,128.4,128.3,128.3,128.3,128.2,128.2,126.9,126.8,123.6,123.5,123.1,123.1,122.8,122.4,121.9,121.6,121.6,121.2,121.2,121.1,120.8,120.8,120.3,112.9,112.8,112.1,104.2,103.5,103.3,102.8,102.6,101.9,97.9,97.0,95.1,94.5,87.1,86.6,86.2；
HRMS(ESI/TOF-Q):m/z calcd.for C 24 H 17 N[M+H] + ,320.1439；found,320.1431。
The above examples show that the one-pot synthesis method of the phenoxyalkine ether compound has the advantages of cheap and easily available raw materials and simple reaction steps, and the phenoxyalkine ether compound can be prepared through a series one-step reaction; meanwhile, the tolerance and stereoselectivity of the functional group of the reaction in the synthetic method are higher, the yield of the phenol-oxygen-eneyne ether compound is higher, and the highest yield can reach 88%.
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, although the invention has been described in detail with reference to the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (6)
1. A one-pot synthesis method of a phenol oxyalkynene ether compound is characterized by comprising the following specific steps:
adding tetrabutylammonium iodide, iodobenzene acetate, cuprous iodide, cesium carbonate, a reactant I, a reactant II and an organic solvent into a closed reaction vessel according to the molar volume ratio of 1;
the reactant I is estrone, indole or a compound I-1, and the structural formula of the compound I-1 is as follows:
the reactant II is 2-acetylene thiophene, 3-acetylene pyridine or a compound II-1, and the structural formula of the compound II-1 is as follows:
wherein R is 1 Hydrogen, fluorine, chlorine, bromine, iodine, aldehyde group, trifluoromethyl, methyl, isopropyl, tert-butyl, methoxy or phenyl; r 2 Is hydrogen, fluorine, chlorine, bromine, methyl, propyl, methoxy or phenyl.
2. The one-pot synthesis method of the phenoxyeneyne ether compounds according to claim 1, wherein the organic solvent is dimethylsulfoxide.
3. The one-pot synthesis method of the phenoxyalkine ether compounds according to claim 1, characterized in that the purification comprises the following specific operations: and (3) extracting the mixture in the reaction vessel after the reaction is finished by using a mixed solvent of water and ethyl acetate in a volume ratio of 1.
4. The one-pot synthesis method of the phenoxyalkine ether compounds according to claim 1, wherein the reaction is carried out in the sealed reaction vessel under an air atmosphere at 110 ℃ for 22 hours.
5. The one-pot synthesis method of the phenoxyalkine ether compound according to claim 1, wherein the compound I-1 is any one of phenol, 2-fluorophenol, 2-chlorophenol, 2-bromophenol, 2-iodophenol, 2-methylphenol, 2-isopropylphenol, 3-fluorophenol, 3-chlorophenol, 3-bromophenol, 3-iodophenol, 3-trifluoromethylphenol, 3-methylphenol, 3-methoxyphenol, 3-tert-butylphenol, 4-chlorophenol, 4-bromophenol, 4-iodophenol, 4-methylphenol, 4-phenylphenol, 4-hydroxybenzaldehyde, or 2-naphthol.
6. The one-pot synthesis method of the phenoxyalkine ether compound according to claim 1, wherein the compound II-1 is any one of phenylacetylene, 2-chlorophenylacetylene, 2-bromophenylacetylene, 3-fluorophenylacetylene, 3-chlorophenylacetylene, 3-bromophenylacetylene, 3-methylphenylacetylene, 3-methoxyphenylacetylene, 4-fluorophenylacetylene, 4-chlorophenylacetylene, 4-bromophenylacetylene, 4-methylphenylacetylene or 4-propylphenylacetylene.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061125A (en) * | 2015-08-17 | 2015-11-18 | 西南大学 | Synthesis method for 1,5-ketonic ester compound under catalyzing of inorganic base |
| CN108101786A (en) * | 2017-12-26 | 2018-06-01 | 西南大学 | Palladium salt is catalyzed the synthetic method of phenol oxy alkylene ether compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105061125A (en) * | 2015-08-17 | 2015-11-18 | 西南大学 | Synthesis method for 1,5-ketonic ester compound under catalyzing of inorganic base |
| CN108101786A (en) * | 2017-12-26 | 2018-06-01 | 西南大学 | Palladium salt is catalyzed the synthetic method of phenol oxy alkylene ether compound |
Non-Patent Citations (2)
| Title |
|---|
| Light-Driven Intermolecular Charge Transfer Induced Reactivity of Ethynylbenziodoxol(on)e and Phenols;Liu,Bin等;《Journal of the American Chemical Society (2018)》;20181010;第140卷(第40期);全文 * |
| Sequential and one-pot reactions of phenols with bromoalkynes for the synthesis of (Z)-2-bromovinyl phenyl ethers and benzo[b]furans;Wang,Shi-Hua等;《Organic Letters (2011)》;20111018;第13卷(第22期);摘要部分、table 3、supporting information实施例4.1部分以及Scheme S2 * |
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