CN102746076B - Preparation method of substituted alkene - Google Patents
Preparation method of substituted alkene Download PDFInfo
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- CN102746076B CN102746076B CN201210257357.9A CN201210257357A CN102746076B CN 102746076 B CN102746076 B CN 102746076B CN 201210257357 A CN201210257357 A CN 201210257357A CN 102746076 B CN102746076 B CN 102746076B
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Abstract
The invention discloses a preparation method of substituted alkene. The preparation method is characterized in that Heck coupling reaction and decarboxylation coupling reaction occur in turn under the action of a catalyst with an acrylic compound and halogenated aromatic hydrocarbon as a reaction substrate to obtain the substituted alkene, wherein the halogenated hydrocarbon is a halogenated aromatic hydrocarbon or a halogenated aliphatic hydrocarbon, the halogen atom is selected from chlorine, bromine or iodine; the acrylic compound refers to a compound containing both double bond and carboxyl group, the catalyst is a catalyst composed of palladium catalyst/ligand. The method provided by the invention has the advantages of simple operation, mild condition, convenient post-processing and wide range of suitable substrates.
Description
Technical field
The present invention relates to a kind of preparation of substituted olefine, be specifically related to the method for a kind of catalytic coupling synthesis substituted olefine, especially a kind of cascade reaction that Heck coupling and decarboxylation coupling occur successively obtains the method for substituted olefine.
Background technology
Double bond is extensively present in the intermediate of medicine and material, effectively synthesizes the extensive concern receiving people nearly ten years about it.Therefore find a kind of novel synthetic method particularly important to its development in application aspect.
In prior art, the method for synthesis substituted olefine has following several:
the most direct synthetic method is then the reaction that the phosphorus ylide that obtained through microcosmic salt by halohydrocarbon and aldehyde, reactive ketone synthesize alkene, i.e. and Wittig reaction (see: G. Wittig; Chem. Ber. 1954,87,1318).
in 2006, Gang Zou seminar reported and makes catalyzer with palladium complex, alkali made by sodium-acetate, TBAB is that solvent reacts at 120oC, obtained polysubstituted alkene (see G. Zou, W. Huang; New J. Chem., 2006,30,803-809).
in calendar year 2001; the Yoshida seminar of Jingdone district university of Japan finds to use 2-pyridine; first there is Heck reaction and then Hiyama coupling occur in dimethylvinylsiloxy base silane, also can obtain polysubstituted alkene (see Kenichiro Itami, Jun-ichi Yoshida; J. Am. Chem. Soc., 2001,123,11577-11585).
In order to expand the scope of suitable substrates, need the preparation method studying new substituted olefine.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of preparation method of substituted olefine, to expand the scope of suitable substrates.
To achieve the above object of the invention, the technical solution used in the present invention is: a kind of preparation method of substituted olefine, with acrylic compounds and halohydrocarbon for reaction substrate, under the catalysis of catalyzer, there is Heck coupling and decarboxylation linked reaction successively, prepare substituted olefine, described halohydrocarbon refers to halogenated aromatic or halogenated aliphatic hydrocarbon, and described halogen atom is selected from: chlorine, bromine or iodine; Described acrylic compounds refers to the compound simultaneously containing double bond and carboxyl, and described catalyzer is the catalyzer of palladium catalyst/part composition.
In technique scheme, described substituted olefine refers to that at least two substituent olefin(e) compounds are contained at double bond two ends.
Preferred technical scheme, described Palladous chloride, palladium, tetra-triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, triphenylphosphine palladium chloride or 1,1'-bis-(diphenyl phosphine) ferrocene palladium chloride (II), described part is for containing Phosphine ligands, as triphenylphosphine, tri-butyl phosphine, tricyclohexyl phosphine etc., the mol ratio of palladium/part is 0.05 ~ 0.10: 0.10 ~ 0.20.
In technique scheme, reaction system comprises: acrylic compounds, the first halogenated aryl hydrocarbon, the second halogenated aryl hydrocarbon, palladium catalyst, part, basic salt and solvent, and described basic salt is selected from the one in potassiumphosphate, salt of wormwood, cesium carbonate or silver carbonate; Described solvent is selected from one or both the mixture in methyl-sulphoxide, DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone; Preparation method specifically comprises the following steps:
(1) add palladium catalyst, part, alkali, solvent, the first halohydrocarbon and acrylic compounds, heat 8 ~ 20 hours the oil bath of 120 DEG C ~ 150 DEG C after sealing;
(2) add the second halohydrocarbon and the second alkali again, heat at least 20 hours the oil bath of 120 DEG C ~ 150 DEG C after sealing;
(3) cool to room temperature, the cancellation that adds water is reacted, and finally extracts and obtains substituted olefine.
In technique scheme, the mol ratio of acrylic compounds, the first halohydrocarbon, the second halohydrocarbon, catalyzer, part, alkali is 1: 1: 1:0.05 ~ 0.10: 0.10 ~ 0.20: 2 ~ 4, the quality of solvent be acrylic compounds, the first halohydrocarbon, 20 ~ 150 times of the second halohydrocarbon quality sum.
When halohydrocarbon is selected from hydrobromic ether or hydrochloric ether, described reaction system also comprises sodium iodide, and the consumption of sodium iodide is 1 ~ 2 times of halohydrocarbon amount of substance, and the reaction times in step (2) is more than 48 hours.
In step (3), extracting the method obtaining substituted olefine is be extracted with ethyl acetate at least 2 times, merges organic phase and uses anhydrous sodium sulfate drying, obtain product by column chromatography after concentrated, the eluent used during column chromatography is sherwood oil: ethyl acetate=24:1(volume ratio).
In technique scheme, the difference of the substituted olefine prepared as required, described first halohydrocarbon and the second halohydrocarbon are identical compound, or described first halohydrocarbon and the second halohydrocarbon are different compounds.
Described acrylic compounds is selected from vinylformic acid, methacrylic acid, 2-butylene acid or 2-pentenoic acid.
Because technique scheme is used, the present invention compared with prior art has following advantages:
1, synthetic method of the present invention is compared with the method for synthesizing substituted olefine in the past, simple to operate, mild condition, convenient post-treatment.
2, catalyst system of the present invention is when catalyzed reaction, and applicable substrate spectrum is wider, comprises all kinds of aryl halides.
3, because catalyst system of the present invention has very high selectivity, there is (reaction product detects through GC-MS) without side reaction.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment one:
PdCl is loaded successively in a Schlenk test tube
2(0.025 mmol), triphenylphosphine (0.05 mmol), salt of wormwood (1.0 mmol), and DMAc(2 mL), add iodobenzene (0.5 mmol) and vinylformic acid (0.5 mmol) respectively with microsyringe.Then the oil bath at 150 DEG C after the sealing of this system is heated about 5 hours, then adds methoxyl group iodobenzene (0.5 mmol), silver carbonate (1.0 mmol), and the oil bath then at 150 DEG C after the sealing of this system is heated about 24 hours.Then system cool to room temperature is allowed, add 2mL shrend to go out reaction, then be extracted with ethyl acetate (4 mL × 3), merge organic phase and use anhydrous sodium sulfate drying, can obtain coupled product 1-base benzene 2-p-methoxyphenyl ethene (85.2 mg) by simple column chromatography (eluent uses sherwood oil: ethyl acetate=24:1) after concentrated, yield is 81%.Its nuclear magnetic data is:
1h NMR (400 MHz, CDCl
3) (δ, ppm) 3.81 (s, 3H), 6.89 (d; J=8.4 Hz, 2H), 6.96 (d, J=16.0 Hz; 1H), 7.05 (d, J=16.0 Hz, 1H); 7.22 (t, J=7.6 Hz, 1H), 7.33 (d; J=7.6 Hz, 2H), 7.44 (d, J=8.4 Hz; 2H), 7.48 (d, J=7.6 Hz, 2H);
13c NMR (75 MHz, CDCl
3) (δ, ppm) 55.2,114.1,126.2,126.5,127.1,127.7,128.1,128.6,130.1,137.6,159.2; High resolution mass spectrum data are: HRMS (ESI
+) calcd. for [C
15h
14o]
+requires m/z 210.1045, found 210.1044.
Embodiment two
PdCl is loaded successively in a Schlenk test tube
2(0.025 mmol), triphenylphosphine (0.05 mmol), salt of wormwood (1.0 mmol), and DMAc(2 mL), add iodobenzene (0.5 mmol) and vinylformic acid (0.5 mmol) respectively with microsyringe.Then the oil bath at 150 DEG C after the sealing of this system is heated about 5 hours, then adds iodobenzene (0.5 mmol), silver carbonate (1.0 mmol), and the oil bath then at 150 DEG C after the sealing of this system is heated about 24 hours.Then system cool to room temperature is allowed, add 2mL shrend to go out reaction, then be extracted with ethyl acetate (4 mL × 3), merge organic phase and use anhydrous sodium sulfate drying, can obtain coupled product 1-base benzene 2-phenylethylene (68.4 mg) by simple column chromatography (eluent use sherwood oil) after concentrated, yield is 76%.Its nuclear magnetic data is: 7.14 (d, J=16.0 Hz, 1H); 7.30 (t, J=7.2 Hz, 1H); 7.40 (t, J=7.6 Hz, 2H); 7.47-7.58 (m, 3H), 7.60 (d; J=7.6 Hz, 2H), 7.74 (d; J=7.2 Hz, 1H), 7.80 (d; J=8.0 Hz, 1H), 7.87 (d; J=7.6 Hz, 1H), 7.88 (d; J=16.0 Hz, 1H), 8.22 (d; J=8.4 Hz, 1H);
13c NMR (300 MHz, CDCl
3) (δ, ppm) 110.99,114.82,120.83,125.26,131.46,132.03,158.34,160.33; High resolution mass spectrum data are: HRMS (ESI
+) calcd. for [C
14h
12]
+requires m/z 180.0936, found 180.0939.
Embodiment three
Pd (OAc) is loaded successively in a Schlenk test tube
2(0.025 mmol), triphenylphosphine (0.05 mmol), salt of wormwood (1.0 mmol), and DMAc(2 mL), add iodobenzene (0.5 mmol) and vinylformic acid (0.5 mmol) respectively with microsyringe.Then the oil bath at 150 DEG C after the sealing of this system is heated about 5 hours, then adds methyl iodobenzene (0.5 mmol), silver carbonate (1.0 mmol), and the oil bath then at 150 DEG C after the sealing of this system is heated about 24 hours.Then system cool to room temperature is allowed, add 2mL shrend to go out reaction, then be extracted with ethyl acetate (4 mL × 3), merge organic phase and use anhydrous sodium sulfate drying, can obtain coupled product 1-base benzene 2-p-methoxyphenyl ethene (77.7 mg) by simple column chromatography (eluent use sherwood oil) after concentrated, yield is 80%.Its nuclear magnetic data is: 2.35 (s, 3H), 7.05 (d, J=16.4 Hz; 1H), 7.09 (d, J=16.4 Hz, 1H); 7.16 (d, J=8.0 Hz, 2H), 7.23 (t; J=7.6 Hz, 1H), 7.34 (t, J=7.6 Hz; 2H), 7.41 (d, J=8.0 Hz, 2H); 7.49 (d, J=7.6 Hz, 2H);
13c NMR (75 MHz, CDCl
3) (δ, ppm) 21.5,126.6,127.6,127.9,128.8,128.9,129.6,134.7,137.7; High resolution mass spectrum data are: HRMS (ESI
+) calcd. for [C
15h
14]
+requires m/z 194.1096, found 194.1097.
Embodiment four
PdCl is loaded successively in a Schlenk test tube
2(0.025 mmol), tricyclohexyl phosphine (0.05 mmol), salt of wormwood (1.0 mmol), and DMAc(2 mL), add respectively chloroiodobenzone (0.5 mmol) and vinylformic acid (0.5 mmol) with microsyringe.Then the oil bath at 150 DEG C after the sealing of this system is heated about 5 hours, then adds iodobenzene (0.5 mmol), silver carbonate (1.0 mmol), and the oil bath then at 150 DEG C after the sealing of this system is heated about 24 hours.Then system cool to room temperature is allowed, add 2mL shrend to go out reaction, then be extracted with ethyl acetate (4 mL × 3), merge organic phase and use anhydrous sodium sulfate drying, can obtain coupled product 1-base benzene 2-p-methoxyphenyl ethene (82.5 mg) by simple column chromatography (eluent uses sherwood oil: ethyl acetate=24:1) after concentrated, yield is 77%.Its nuclear magnetic data is:
1h NMR (400 MHz, CDCl
3) (δ, ppm) 7.07 (s, 2H); 7.28 (d, J=7.2 Hz, 1H); 7.32 (d, J=8.0 Hz, 2H); 7.37 (t, J=7.6 Hz, 2H); 7.44 (d, J=8.0 Hz, 2H); 7.51 (d, J=7.6 Hz, 2H);
13c NMR (300 MHz, CDCl
3) (δ, ppm) 126.8,127.7,127.9,128.1,128.9,129.1,129.5,133.3,136.1,137.2; High resolution mass spectrum data are: HRMS (ESI
+) calcd. for [C
14h
11cl]
+requires m/z 214.0549, found 214.0551.
Embodiment five
In a Schlenk test tube, PdCl is loaded successively one
2(0.025 mmol), triphenylphosphine (0.05 mmol), salt of wormwood (1.0 mmol), and DMAc(2 mL), add respectively methyl iodobenzene (0.5 mmol) and vinylformic acid (0.5 mmol) with microsyringe.Then the oil bath at 150 DEG C after the sealing of this system is heated about 5 hours, then adds methoxyl group iodobenzene (0.5 mmol), silver carbonate (1.0 mmol), and the oil bath then at 150 DEG C after the sealing of this system is heated about 24 hours.Then system cool to room temperature is allowed, add 2mL shrend to go out reaction, then be extracted with ethyl acetate (4 mL × 3), merge organic phase and use anhydrous sodium sulfate drying, can obtain coupled product 1-base benzene 2-p-methoxyphenyl ethene (89.7 mg) by simple column chromatography (eluent uses sherwood oil: ethyl acetate=24:1) after concentrated, yield is 80%.Its nuclear magnetic data is:
1h NMR (400 MHz, CDCl
3) (δ, ppm) 2.34 (s, 3H); 3.80 (s, 3H), 6.82 (d; J=8.0 Hz, 2H), 6.91 (d; J=4.4 Hz, 2H), 7.08 (d; J=8.0 Hz; 2H), 7.30-7.39 (m, 4H);
13c NMR (75 MHz, CDCl
3) (δ, ppm) 21.1,55.2,114.1,126.1,126.5,127.2,127.5,129.3,130.3,137.0,159.1; High resolution mass spectrum data are: HRMS (ESI
+) calcd. for [C
16h
16o]
+requires m/z 224.1201, found 224.1203.
Embodiment six
Pd (OAc) is loaded successively in a Schlenk test tube
2(0.025 mmol), triphenylphosphine (0.05 mmol), salt of wormwood (1.0 mmol), and DMAc(2 mL), add iodobenzene (0.5 mmol) and vinylformic acid (0.5 mmol) respectively with microsyringe.Then the oil bath at 150 DEG C after the sealing of this system is heated about 5 hours, then adds phenyl iodobenzene (0.5 mmol), silver carbonate (1.0 mmol), and the oil bath then at 150 DEG C after the sealing of this system is heated about 24 hours.Then system cool to room temperature is allowed, add 2mL shrend to go out reaction, then be extracted with ethyl acetate (4 mL × 3), merge organic phase and use anhydrous sodium sulfate drying, can obtain coupled product 1-base benzene 2-p-methoxyphenyl ethene (96.0 mg) by simple column chromatography (eluent use sherwood oil) after concentrated, yield is 75%.Its nuclear magnetic data is:
1h NMR (400 MHz, CDCl
3) (δ, ppm) 7.16 (s, 2H); 7.28 (t, J=8.0 Hz, 1H); 7.35 (t, J=7.2 Hz, 1H); 7.38 (t, J=7.2 Hz, 2H); 7.45 (t, J=7.6 Hz, 2H); 7.54 (d, J=7.2 Hz, 2H); 7.60 (d, J=8.8 Hz, 2H); 7.62 (d; J=8.8 Hz, 2H), 7.63 (d; J=7.2 Hz, 2H); High resolution mass spectrum data are: HRMS (ESI
+) calcd. for [C
20h
16]
+requires m/z 256.1252, found 256.1254.
Claims (6)
1. the preparation method of a substituted olefine, it is characterized in that: with vinylformic acid, the first halohydrocarbon and the second halohydrocarbon for reaction substrate, under the catalysis of catalyzer, there is Heck coupling and decarboxylation linked reaction successively, prepare substituted olefine, described first halohydrocarbon and the second halohydrocarbon are selected from iodobenzene, respectively to methyl iodobenzene, to methoxyl group iodobenzene, to chloroiodobenzone or to phenyl iodobenzene; Described catalyzer is the catalyzer of palladium catalyst/part composition;
Reaction system comprises: vinylformic acid, the first halohydrocarbon, the second halohydrocarbon, palladium catalyst, part, alkali and solvent, and described alkali is selected from the one in potassiumphosphate, salt of wormwood, cesium carbonate or silver carbonate; Described solvent is selected from one or both the mixture in methyl-sulphoxide, DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone; Preparation method specifically comprises the following steps:
(1) add palladium catalyst, part, alkali, solvent, the first halohydrocarbon and vinylformic acid, heat 8 ~ 20 hours the oil bath of 120 DEG C ~ 150 DEG C after sealing;
(2) add the second halohydrocarbon and the second alkali again, heat at least 20 hours the oil bath of 120 DEG C ~ 150 DEG C after sealing;
(3) cool to room temperature, the cancellation that adds water is reacted, and finally extracts and obtains substituted olefine.
2. the preparation method of substituted olefine according to claim 1, it is characterized in that, described substituted olefine refers to that at least two substituent olefin(e) compounds are contained at double bond two ends.
3. the preparation method of substituted olefine according to claim 1, it is characterized in that, described palladium catalyst is Palladous chloride, palladium, tetra-triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, triphenylphosphine palladium chloride or 1,1'-bis-(diphenyl phosphine) ferrocene palladium chloride (II), described part is for containing Phosphine ligands, and the mol ratio of palladium/part is 0.05 ~ 0.10: 0.10 ~ 0.20.
4. the preparation method of substituted olefine according to claim 1, it is characterized in that: the mol ratio of vinylformic acid, the first halohydrocarbon, the second halohydrocarbon, catalyzer, part, alkali is 1: 1: 1:0.05 ~ 0.10: 0.10 ~ 0.20: 2 ~ 4, the quality of solvent be vinylformic acid, the first halohydrocarbon, 20 ~ 150 times of the second halohydrocarbon quality sum.
5. the preparation method of substituted olefine according to claim 1, it is characterized in that: in step (3), extracting the method obtaining substituted olefine is, be extracted with ethyl acetate at least 2 times, merge organic phase and use anhydrous sodium sulfate drying, obtain product by column chromatography after concentrated, the eluent used during column chromatography is sherwood oil: ethyl acetate=24:1(volume ratio).
6. the preparation method of substituted olefine according to claim 1, is characterized in that: described first halohydrocarbon and the second halohydrocarbon are different compounds.
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| CN102010279A (en) * | 2010-12-01 | 2011-04-13 | 西北师范大学 | Method for preparing vinylaromatic derivatives |
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Non-Patent Citations (3)
| Title |
|---|
| Microwave-Promoted Heck Coupling Using Ultralow Metal Catalyst Concentrations;Riina K. Arvela等;《J. Org. Chem.》;20050129;第70卷;第1786-1790页 * |
| Palladium-catalyzed decarboxylative cross-coupling reaction of cinnamic acid with aryl iodide;zhiyong wang等;《Org. Biomol. Chem.》;20090114;第7卷;第863-865页 * |
| 张壮予等.芳基碘化物在(聚(苯乙烯)联吡啶)钯(0)催化下的乙烯基化反应.《分子催化》.1987,第1卷(第2期), * |
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