CN100564333C - A kind of synthetic method of 1-aryl (group)-1-ethylenialkene compounds - Google Patents

A kind of synthetic method of 1-aryl (group)-1-ethylenialkene compounds Download PDF

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CN100564333C
CN100564333C CNB2007101570924A CN200710157092A CN100564333C CN 100564333 C CN100564333 C CN 100564333C CN B2007101570924 A CNB2007101570924 A CN B2007101570924A CN 200710157092 A CN200710157092 A CN 200710157092A CN 100564333 C CN100564333 C CN 100564333C
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ethylenialkene
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裴文
王艳峰
黄君伟
吴香梅
孙莉
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Zhejiang University of Technology ZJUT
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Abstract

The present invention relates to a kind of with the macroreticular weakly base styrene series anion exchange resin as solid alkali, palladium is a catalyzer, do not use under organophosphorus ligand and small molecules organic amine or the mineral alkali condition, utilize the synthetic method of Heck prepared in reaction 1-aryl (group)-1-ethylenialkene compounds, technical solution of the present invention is: halohydrocarbon and tetrahydrobenzene are in aprotic polar solvent, in the presence of palladium and macroreticular weakly base styrene series anion exchange resin, in 50 ℃～150 ℃ following stirring reactions 1～30 hour, reaction finishes, the reaction solution separation and purification gets product 1-aryl (group)-1-ethylenialkene compounds; Technical solution of the present invention is presented as technology novelty, low, easy to operate, the recyclable regeneration use in anionite-exchange resin reaction end back of cost with respect to its beneficial effect of prior art, and environmental pollution is little.

Description

A kind of synthetic method of 1-aryl (group)-1-ethylenialkene compounds
(1) technical field
The present invention relates to a kind of is catalyzer with the macroreticular weakly base styrene series anion exchange resin as solid alkali, palladium, do not use under organophosphorus ligand and small molecules organic amine or the mineral alkali condition, utilize the synthetic method of Heck prepared in reaction 1-aryl (group)-1-ethylenialkene compounds.
(2) background technology
Being connected with the carbonyl of unsaturated link(age), long-chain carbon and the oxy-compound of long-chain carbon on the aromatic ring is the important intermediate of natural goods and many medicines, be one and have polyfunctional compound, carry out the synthetic and exploitation of new drug of natural goods or relative medicine is carried out the transformation of traditional technology by this compound, important academic significance and wide application prospect are arranged.
The Heck linked reaction forms in the reaction at the C-C key has critical role, is normally synthesized the important method of functionalized aromatic hydroxy compound under catalyzing by metal palladium by halogenated aryl hydrocarbon, is that of Friedel-Crafts reaction replenishes.In the Heck linked reaction, we find the stereoselectivity that polar solvent helps reacting in experimental result, have obtained the terminal olefin compound of highly selective.Reclaim difficulty because polar solvent finishes the back in reaction, be difficult to reach the purpose of reduction of discharging.Emerging Green Chemistry lyate ion liquid is compared with organic solvent to have non-volatilely, nonflammable explosive, and organism and inorganics are had good solubility, and reaction can be carried out at homogeneous phase, stable to water and air, is convenient to operation and processing, easily reclaims.Therefore, we have invented and have utilized ionic liquid as reaction medium, carry out the synthetic of 1-aryl (group)-1-ethylenialkene compound, and a kind of synthetic technology of Green Chemistry is provided.But in this reaction, the organophosphorus ligand of use and small molecules organic amine or mineral alkali are difficult to reclaim, and are difficult to carry out large-scale industrial production, also environment are had certain pollution.
The D301 resin is a globular macroreticular weakly base styrene series anion exchange resin, and this resin has tertiary amine groups on the vinylbenzene skeleton, can regenerate with alkali.Compare with the gel-type weakly basic styrene type anion exchange resin with strong-basicity styrene series anion exchange resin, organic molecule is had good adsorption and desorption ability, stain resistance is good, and regeneration cost is low.In recent years, this technology has been widely used in each technical field of Chemical Manufacture.Therefore, utilize macroreticular weakly base styrene series anion exchange resin solid alkali to substitute organic amine in the present invention, and avoided the use organic phosphine compound, improved reactive activity as the reaction part.Can solve the pollution problem that chemical reaction process occurs.Be convenient to operation and processing, ion exchange resin easily reclaims, be a kind of have application prospect the Green Chemistry synthetic technology.
(3) summary of the invention
The object of the invention is to provide a kind of environment-friendly preparation method thereof of the 1-aryl (group)-1-ethylenialkene compound suc as formula (I) or (II).
For reaching goal of the invention the present invention by the following technical solutions:
Suc as formula (III) or the halohydrocarbon (IV) and tetrahydrobenzene in aprotic polar solvent, in the presence of palladium and the macroreticular weakly base styrene series anion exchange resin shown in formula V, in 50 ℃～150 ℃ following stirring reactions 1～30 hour, reaction finishes, the reaction solution separation and purification gets product 1-aryl (group)-1-ethylenialkene compounds; The ratio of described halohydrocarbon, tetrahydrobenzene, palladium, macroreticular weakly base styrene series anion exchange resin amount of substance is 1: 1～5: 0.005～0.01: 1～2;
Figure C20071015709200061
In its Chinese style (I), the formula (III), R 1For-H ,-CHO ,-CN ,-F ,-COCH 3,-CF 3,-CH 3,-OCH 3,-OC 2H 5,-OC 3H 7,-OCOCH 3,-Ph ,-OH or-NH 2, X 1Be chlorine, bromine or iodine; R in formula (II), the formula (IV) 2For-H ,-CHO ,-CN ,-F ,-COCH 3,-CF 3,-CH 3,-OCH 3,-OC 2H 5,-OC 3H 7,-OCOCH3 ,-Ph ,-OH or-NH 2, X 2Be chlorine, bromine or iodine; In the formula V, R 3, R 4Independent separately is methyl or hydrogen, and n represents contained number of repeat unit purpose mean value on the polymer macromolecule chain, for weighing the index of polymer molecule size.
Aprotic polar solvent of the present invention is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, tetramethylene sulfone or 1-methyl-2-pyrrolidone.
The volumetric usage of aprotic polar solvent of the present invention is counted 10～100mL/mmol by halohydrocarbon.
R described in formula of the present invention (I), the formula (III) 1Be preferably-H ,-CHO ,-CN ,-COCH 3,-CH 3,-OCH 3,-Ph.
R described in formula of the present invention (II), the formula (IV) 2Be preferably-H ,-CHO ,-CN ,-COCH 3,-CH 3,-OCH 3,-Ph.
Macroreticular weakly base styrene series anion exchange resin of the present invention is a Styrene-DVB D301 type resin, can adopt the resin of commercially available Styrene-DVB (D301 R), Styrene-DVB (D301 T), Styrene-DVB (D301 G), Styrene-DVB (D392) or Styrene-DVB (D380) model.
Temperature of reaction of the present invention is preferably 140 ℃, and the reaction times is preferably 10 hours.
The ratio of halohydrocarbon of the present invention, tetrahydrobenzene, palladium, macroreticular weakly base styrene series anion exchange resin amount of substance is 1: 2: 0.005: 1.5.
Reaction solution separation and purification of the present invention is: after the reaction solution cooling, with the toluene extraction, extraction liquid gets described 1-aryl (group)-1-ethylenialkene compounds with anhydrous magnesium sulfate drying, concentrated, enriched material through column chromatography for separation.
Concrete method of the present invention comprise the steps: suc as formula (III) or the halohydrocarbon (IV) and tetrahydrobenzene in aprotic polar solvent, in the presence of palladium and the macroreticular weakly base styrene series anion exchange resin shown in formula V, in 50 ℃～150 ℃ following stirring reactions 1～30 hour, reaction finishes, after the reaction solution cooling, extract with toluene, extraction liquid anhydrous magnesium sulfate drying, concentrated, enriched material gets described 1-aryl (group)-1-ethylenialkene compounds through column chromatography for separation; The ratio of described halohydrocarbon, tetrahydrobenzene, palladium, macroreticular weakly base styrene series anion exchange resin amount of substance is 1: 1～5: 0.005～0.01: 1～2; Described aprotic polar solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, tetramethylene sulfone or 1-methyl-2-pyrrolidone, and described aprotic polar solvent volumetric usage is counted 50mL/mmol by halohydrocarbon.
After macroreticular weakly base styrene series anion exchange resin reaction of the present invention finished, recyclable regeneration was used.
Technical solution of the present invention is presented as technology novelty, low, easy to operate, the recyclable regeneration use in anionite-exchange resin reaction end back of cost with respect to its beneficial effect of prior art, and environmental pollution is little.
(4) embodiment
Below in conjunction with specific embodiment preparation method of the present invention is described further, but protection scope of the present invention is not limited to this.
Embodiment 1
Prepare 1-phenyl-1-tetrahydrobenzene by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 410 milligrams of tetrahydrobenzene (5 mmole), 2.24 milligrams of palladium (0.01 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 50 milliliters of-1 methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 10 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 142 milligrams of product 1-phenyl-1-tetrahydrobenzene, yield 90%.Boiling point: 251～253 ℃;
MS(m/z)：158(M +)。
Embodiment 2
Prepare 1-phenyl-1-tetrahydrobenzene by chlorobenzene
With 113 milligrams of chlorobenzenes (1 mmole), 410 milligrams of tetrahydrobenzene (5 mmole), 2.24 milligrams of palladium (0.01 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 10 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 128 milligrams of product 1-phenyl-1-tetrahydrobenzene, yield 81%.
Embodiment 3
Prepare 1-(4 '-acetylphenyl)-1-tetrahydrobenzene by the 4-bromoacetophenone
With 198 milligrams of 4-bromoacetophenones (1 mmole), 82 milligrams of tetrahydrobenzene (1 mmole), 2.24 milligrams of palladium (0.01 mmole), Styrene-DVB (D301 T) resin 0.4 gram (2 mmole), 50 milliliters of dimethyl sulfoxide (DMSO), place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 30 hours.After reaction finishes, cooling, with 50 milliliters of extractions of methylene dichloride three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 164 milligrams of product 1-(4 '-acetylphenyl)-1-tetrahydrobenzene, yield 82%.
1H?NMR(CDCl 3)δppm：1.65～1.67(m，4H)，1.95～1.97(m，4H)，2.60(s，3H)，5.98(dd，J＝6.5Hz，1H)，7.43～7.47(m，2H)，7.83～7.86(m，2H)；
13C?NMR(CDCl 3)δppm：23.44，26.35，26.93，29.36，31.22，118.19，123.35，126.38，128.78，128.81，135.48，136.15，143.92，199.95；
MS(m/z)：200(M +)。
Embodiment 4
Utilize and reclaim Styrene-DVB (D301R) resin 0.3 gram (1.5 mmole), prepare 1-phenyl-1-tetrahydrobenzene by bromobenzene
Styrene-DVB (D301 R) resin is reclaimed and get by embodiment 1, and other reactant and consumption thereof and step be with embodiment 1, must product 1-phenyl-136 milligrams of 1-tetrahydrobenzene, yield 86%.
Embodiment 5
Prepare 1-phenyl-1-tetrahydrobenzene by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 164 milligrams of tetrahydrobenzene (2 mmole), 1.2 milligrams of palladium (0.005 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 50 milliliters of dimethyl formamides, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 10 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 126 milligrams of product 1-phenyl-1-tetrahydrobenzene, yield 80%.
Embodiment 6
Prepare 1-(3 '-cyano-phenyl)-1-tetrahydrobenzene by the 3-bromobenzylcyanide
With 182 milligrams of 3-bromobenzylcyanides (1 mmole), 164 milligrams of tetrahydrobenzene (2 mmole), 1.2 milligrams of palladium (0.005 mmole), Styrene-DVB (D301 T) resin 0.3 gram (1.5 mmole), 100 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 150 ℃ of reactions 30 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 148 milligrams of product 1-(3 '-cyano-phenyl)-1-tetrahydrobenzene, yield 81%.
1H?NMR(CDCl 3)δppm：1.66～1.67(m，4H)，1.96～1.97(m，4H)，5.98(dd，J＝6.5Hz，1H)，7.40～7.42(m，2H)，7.80～7.826(m，2H)；
13C?NMR(CDCl 3)δppm：23.36，26.35，26.95，31.20，112.61，115.91，118.19，129.35，129.68，130.78，131.81，135.48，140.22；
MS(m/z)：183(M +)。
Embodiment 7
Prepare 1-(4 '-aminomethyl phenyl)-1-tetrahydrobenzene by the 4-toluene bromide
With 171 milligrams of 4-toluene bromides (1 mmole), 164 milligrams of tetrahydrobenzene (2 mmole), 1.2 milligrams of palladium (0.005 mmole), Styrene-DVB (D301 T) resin 0.24 gram (1 mmole), 50 milliliters of dimethyl sulfone, place 200 milliliters of there-necked flasks, stirring heating was 150 ℃ of reactions 30 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 153 milligrams of product 1-(4 '-aminomethyl phenyl)-1-tetrahydrobenzene, yield 89%.
1H?NMR(CDCl 3)δppm：1.65～1.66(m，4H)，1.96～1.97(m，4H)，2.36(s，3H)，5.98(dd，J＝6.5Hz，1H)，7.03～7.05(m，2H)，7.18～7.20(m，2H)；
13C?NMR(CDCl 3)δppm：23.44，24.31，26.25，26.93，31.02，118.19，126.38，126.39，129.01，129.10，135.15，136.42，137.95；
MS(m/z)：172(M +)。
Embodiment 8
Prepare 1-(2 '-naphthyl)-1-tetrahydrobenzene by the 2-bromonaphthalene
With 207 milligrams of 2-bromonaphthalenes (1 mmole), 164 milligrams of tetrahydrobenzene (2 mmole), 1.2 milligrams of palladium (0.005 mmole), Styrene-DVB (D 392) resin 0.3 gram (1.5 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 140 ℃ of reactions 1 hour.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 198 milligrams of product 1-(2 '-naphthyl)-1-tetrahydrobenzene, yield 95%.
1H?NMR(CDCl 3)δppm：1.65～1.66(m，4H)，1.96～1.97(m，4H)，5.98(dd，J＝6.5Hz，1H)，7.33～7.45(m，3H)，7.68～7.76(m，4H)；
13C?NMR(CDCl 3)δppm：23.45，26.35，26.93，31.12，118.19，123.58，125.20，126.10，126.49，127.81，128.11，128.21，133.35，133.65，141.75；
MS(m/z)：208(M +)。
Embodiment 9
Prepare 1-(2 '-naphthyl)-1-tetrahydrobenzene by the 2-bromonaphthalene
With 207 milligrams of 2-bromonaphthalenes (1 mmole), 164 milligrams of tetrahydrobenzene (2 mmole), 1.2 milligrams of palladium (0.005 mmole), Styrene-DVB (D 301G) resin 0.4 gram (2 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 100 ℃ of reactions 10 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 187 milligrams of product 1-(2 '-naphthyl)-1-tetrahydrobenzene, yield 90%.
Embodiment 10
Prepare 1-phenyl-1-tetrahydrobenzene by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 410 milligrams of tetrahydrobenzene (5 mmole), 2.24 milligrams of palladium (0.01 mmole), Styrene-DVB (D301 R) resin 0.3 gram (1.5 mmole), 50 milliliters of 1-methyl-2-pyrrolidones, place 200 milliliters of there-necked flasks, stirring heating was 50 ℃ of reactions 30 hours.After reaction finishes, cooling, with 50 milliliters of extractions of toluene three times, the extraction liquid anhydrous magnesium sulfate drying filters, and is concentrated, and column chromatography for separation gets 126 milligrams of product 1-phenyl-1-tetrahydrobenzene, yield 80%.

Claims (9)

  1. A formula (I) or (II) shown in the synthetic method of 1-aryl (group)-1-ethylenialkene compounds, it is characterized in that described method comprise the steps: suc as formula (III) or the halohydrocarbon (IV) and tetrahydrobenzene in aprotic polar solvent, in the presence of palladium and the macroreticular weakly base styrene series anion exchange resin shown in formula V, in 50 ℃～150 ℃ following stirring reactions 1～30 hour, reaction finishes, the reaction solution separation and purification gets product 1-aryl (group)-1-ethylenialkene compounds; The ratio of described halohydrocarbon, tetrahydrobenzene, palladium, macroreticular weakly base styrene series anion exchange resin amount of substance is 1: 1～5: 0.005～0.01: 1～2;
    Figure C2007101570920002C1
    In its Chinese style (I), the formula (III), R 1For-H ,-CHO ,-CN ,-F ,-COCH 3,-CF 3,-CH 3,-OCH 3,-OC 2H 5,-OC 3H 7,-OCOCH 3,-Ph ,-OH or-NH 2, X 1Be chlorine, bromine or iodine; R in formula (II), the formula (IV) 2For-H ,-CHO ,-CN ,-F ,-COCH 3,-CF 3,-CH 3,-OCH 3,-OC 2H 5,-OC 3H 7,-OCOCH 3,-Ph ,-OH or-NH 2, X 2Be chlorine, bromine or iodine; In the formula V, R 3, R 4Independent separately is methyl or hydrogen, and n represents contained number of repeat unit purpose mean value on the polymer macromolecule chain, for weighing the index of polymer molecule size.
  2. 2. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1 is characterized in that described aprotic polar solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, tetramethylene sulfone or 1-methyl-2-pyrrolidone.
  3. 3. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1 is characterized in that the volumetric usage of described aprotic polar solvent is counted 10～100mL/mmol by halohydrocarbon.
  4. 4. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1 is characterized in that R described in described formula (I), the formula (III) 1For-H ,-CHO ,-CN ,-COCH 3,-CH 3,-OCH 3Or-Ph.
  5. 5. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1 is characterized in that being R described in described formula (II), the formula (IV) 2For-H ,-CHO ,-CN ,-COCH 3,-CH 3,-OCH 3Or-Ph.
  6. 6. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1 is characterized in that described macroreticular weakly base styrene series anion exchange resin is a Styrene-DVB D301 type resin.
  7. 7. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1 is characterized in that described macroreticular weakly base styrene series anion exchange resin is the resin of Styrene-DVB D301 R, Styrene-DVB D301 T, Styrene-DVB D301 G, Styrene-DVB D392 or Styrene-DVB D380 model.
  8. 8. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1 is characterized in that described temperature of reaction is 140 ℃, and the reaction times is 10 hours.
  9. 9. the synthetic method of 1-aryl (group)-1-ethylenialkene compounds as claimed in claim 1, it is characterized in that described method comprise the steps: suc as formula (III) or the halohydrocarbon (IV) and tetrahydrobenzene in aprotic polar solvent, in the presence of palladium and the macroreticular weakly base styrene series anion exchange resin shown in formula V, in 50 ℃～150 ℃ following stirring reactions 1～30 hour, reaction finishes, after the reaction solution cooling, extract with toluene, the extraction liquid anhydrous magnesium sulfate drying, concentrate, enriched material gets described 1-aryl (group)-1-ethylenialkene compounds through column chromatography for separation; The ratio of described halohydrocarbon, tetrahydrobenzene, palladium, macroreticular weakly base styrene series anion exchange resin amount of substance is 1: 1～5: 0.005～0.01: 1～2; Described aprotic polar solvent is dimethyl formamide, dimethyl sulfoxide (DMSO), dimethyl sulfone, tetramethylene sulfone or 1-methyl-2-pyrrolidone, and described aprotic polar solvent volumetric usage is counted 50mL/mmol by halohydrocarbon.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000169400A (en) * 1998-12-09 2000-06-20 Sumika Chemical Analysis Service Ltd Production of styrene trimer
CN1778779A (en) * 2004-11-18 2006-05-31 浙江工业大学 1-aryl (group) - 1 - ethylenialkene and production thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000169400A (en) * 1998-12-09 2000-06-20 Sumika Chemical Analysis Service Ltd Production of styrene trimer
CN1778779A (en) * 2004-11-18 2006-05-31 浙江工业大学 1-aryl (group) - 1 - ethylenialkene and production thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Steric Hindrance in Ketone—NaphtholCondensations.TheCondensations of the Naphthols withCyclohexanone. Joseph B. Niederl,et al.J. Am. Chem. Soc,Vol.62 No.2. 1940 *

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