CN1778779A - 1-aryl (group) - 1 - ethylenialkene and production thereof - Google Patents
1-aryl (group) - 1 - ethylenialkene and production thereof Download PDFInfo
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- CN1778779A CN1778779A CN 200410084469 CN200410084469A CN1778779A CN 1778779 A CN1778779 A CN 1778779A CN 200410084469 CN200410084469 CN 200410084469 CN 200410084469 A CN200410084469 A CN 200410084469A CN 1778779 A CN1778779 A CN 1778779A
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Abstract
1-aryl-1-cyclohexene and its production are disclosed. The process is carried out by adding arene halide and cyclohexene into ionic liquid, agitating and reacting at 20-150 DEG C fro 1-50hrs under the existing of catalyst, phosphate ligand and organic ammonium, after-treating to obtain product 1-aryl-1-cyclohexene and synthesizing 5-phenacyl amyl aldehyde or 1-aryl-1,6-hexandiol. It is simple and has high efficiency and no environmental pollution.
Description
(1) technical field
The present invention relates to 1-aryl (group)-1-ethylenialkene compound and preparation method thereof.
(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, normally synthesizes functionalized aromatic hydroxy compound by halogenated aryl hydrocarbon under catalyzing by metal palladium, is that of Friedel-Crafts reaction replenishes.
Ionic liquid is the fluid cpds of being made up of ion fully as emerging Green Chemistry solvent, normally is made up of with Tetrafluoroboric acid and acid radical anions such as phosphofluoric acid and chlorine aluminic acid alkyl imidazole or alkyl pyridine quaternary ammonium cation.Ionic 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.But ionic liquid also catalysis quickens the process of chemical reaction and improves the selectivity of reaction.Use ionic liquid to be reaction medium simultaneously, synthetic have functionalized aromatic hydroxy compound, also be a kind of have application prospect green synthesis techniques.
(3) summary of the invention
The object of the invention is to provide a kind of 1-aryl (group)-1-ethylenialkene compound and preparation method thereof, and being set out by this compound to make the oxy-compound of long carbochain, and then is used to prepare medicine or natural goods.
Described 1-aryl (group)-1-ethylenialkene is suc as formula (I) or (II),
In its Chinese style (I) and the formula (II), R, R ' are independent separately for electrophilic or push away electron substituent group, as one of following :-H ,-CHO ,-CN ,-F ,-COCH
3,-CF
3,-CH
3,-OCH
3,-OC
2H
5,-OC
3H
7,-OCOCH
3,-Ph ,-OH ,-NH
2, it is one of following that R, R ' are preferably separately :-H ,-COOCH
3,-CN ,-CH
3R ' most preferably is hydrogen.
The method for preparing above-mentioned 1-aryl (group)-1-ethylenialkene, comprise the steps: that halogenated aryl hydrocarbon and tetrahydrobenzene are in ionic liquid, in the presence of catalyzer, phosphorus part, organic amine, in 20 ℃～150 ℃ following stirring reactions 1～50 hour, aftertreatment got product 1-aryl (group)-1-ethylenialkene;
Described halogenated aryl hydrocarbon is suc as formula (III) or (IV), and R, R ' definition are with claim 1;
Described ionic liquid is suc as formula the 3-Methylimidazole inorganic acid salt shown in (III) or 1-alkyl-3-Methylimidazole inorganic acid salt [Bmim]
+L
-, k represents that H or carbon atom quantity are the alkyl of n=1～18 in the formula (III), L is one of following: BF
4, PF
6, OAc, CF
3SO
3, N (SO
2CF
3)
2Ionic liquid is preferably 3-methyl imidazolium tetrafluoroborate or 1-alkyl-3-methyl imidazolium tetrafluoroborate, and alkyl is the alkyl of carbon atom quantity n=1～18.More preferably 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methyl imidazolium tetrafluoroborate.
Described catalyzer is divalence or non-valent nickel or palladium compound, as Ni (OAc)
2, NiCl
2, Pd (OAc)
2, PdCl
2, Pd (dba)
2Deng, be preferably to one of following: nickel acetate, nickelous chloride, palladium, Palladous chloride;
Described phosphorus part is 1, two (phenylbenzene is seen) ethane or 1 of 2-, two (phenylbenzene is seen) propane of 3-or (Dppp) 1, two (phenylbenzene is seen) butane of 4-.
Described organic amine is preferably triethylamine.
In the preparation process reaction finish, described aftertreatment can be: with reaction solution layering deionizing liquid, toluene extract the 1-aryl (group)-1-ethylenialkene.
Described temperature of reaction is preferably 50 ℃～140 ℃, preferred 5～40 hours of reaction times.
Each material of the present invention is recommended to react by following proportioning:
The mol ratio of halogenated aryl hydrocarbon, vinyl carbinol, palladium or nickel catalyzator, part, organic amine is 1: 2～5: 0.04～0.1: 0.08～0.2: 0.16～0.4.
1-aryl (group)-1-ethylenialkene described in the present invention is preparation according to the following steps preferably:
With halogenated aryl hydrocarbon 1 mmole, palladium 0.04 mmole or nickel acetate 0.1 mmole, 1, two (phenylbenzene is seen) propane 0.08 mmoles of 3-or 0.2 mmole, tetrahydrobenzene 3 mmoles, triethylamine 0.16 mmole or 0.2 mmole, 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 10 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 12 hours.After reaction finishes, cooling, aftertreatment is identified product with nuclear magnetic resonance spectrum and mass spectrum.
The reaction formula of above-mentioned reaction is:
Above-mentioned product postprocessing can be with reaction solution layering deionizing liquid, toluene extract product aryl substituted cyclohexene.
After described palladium or nickel catalyzator and ionic liquid reaction finish, recyclable recycling.
Described 1-aryl (group)-1-ethylenialkene carries out oxidation with common oxygenant to the two keys of tetrahydrobenzene, gets compound 5-benzoyl valeral (VI); Again compound (VI) is reduced to the carbonyl on the carbochain with common reductive agent, make 1-aryl-1,6-hexylene glycol (VII).
Preparation method's technology of the present invention is simple, yield is high, and is easy to operate, 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 prepares 1-phenyl-1-tetrahydrobenzene by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 9 milligrams of palladium (0.04 mmole), 1, two 33 milligrams in (phenylbenzene is seen) propane (0.08 mmole) of 3-, 410 milligrams of tetrahydrobenzene (5 mmole), 17 milligrams of triethylamines (0.16 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, toluene extract 142 milligrams of product 1-phenyl-1-tetrahydrobenzene, yield 90%.Boiling point: 251～253 ℃;
MS(m/z)：158(M
+)。
Embodiment 2 prepares 1-phenyl-1-tetrahydrobenzene by chlorobenzene
With 113 milligrams of chlorobenzenes (1 mmole), 9 milligrams of palladium (0.04 mmole), 1, two 33 milligrams in (phenylbenzene is seen) propane (0.08 mmole) of 3-, 410 milligrams of tetrahydrobenzene (5 mmole), 17 milligrams of triethylamines (0.16 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 115 ℃ of reactions 20 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, toluene extract 128 milligrams of product 1-phenyl-1-tetrahydrobenzene, yield 81%.
Embodiment 3 prepares 1-(4 '-acetylphenyl)-1-tetrahydrobenzene by the 4-bromoacetophenone
With 198 milligrams of 4-bromoacetophenones (1 mmole), 9 milligrams of palladium (0.04 mmole), 1, two 33 milligrams in (phenylbenzene is seen) propane (0.08 mmole) of 3-, 410 milligrams of tetrahydrobenzene (5 mmole), 17 milligrams of triethylamines (0.16 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 120 ℃ of reactions 10 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, toluene extract 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 utilizes and reclaims ionic liquid, prepares 1-phenyl-1-tetrahydrobenzene by bromobenzene
Ionic liquid is reclaimed and get by embodiment 1, the catalyzer Palladous chloride, 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 prepares 1-phenyl-1-tetrahydrobenzene by bromobenzene
With 157 milligrams of bromobenzenes (1 mmole), 26 milligrams of nickel acetates (0.1 mmole), 1, two 49 milligrams in (phenylbenzene is seen) propane (0.12 mmole) of 3-, 410 milligrams of tetrahydrobenzene (5 mmole), 20 milligrams of triethylamines (0.2 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 126 milligrams of product 2-phenyl vinyl carbinols, yield 80%.
Embodiment 6 prepares 1-(3 '-cyano-phenyl)-1-tetrahydrobenzene by the 3-bromobenzylcyanide
With 182 milligrams of 3-bromobenzylcyanides (1 mmole), 26 milligrams of nickel acetates (0.1 mmole), 1, two 49 milligrams in (phenylbenzene is seen) propane (0.12 mmole) of 3-, 410 milligrams of tetrahydrobenzene (5 mmole), 20 milligrams of triethylamines (0.2 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 115 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, toluene extract 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 prepares 1-(4 '-aminomethyl phenyl)-1-tetrahydrobenzene by the 4-toluene bromide
With 171 milligrams of 4-toluene bromides (1 mmole), 26 milligrams of nickel acetates (0.1 mmole), 1, two 49 milligrams in (phenylbenzene is seen) propane (0.12 mmole) of 3-, 410 milligrams of tetrahydrobenzene (5 mmole), 20 milligrams of triethylamines (0.2 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, dichloromethane extraction get 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 prepares 1-(2 '-naphthyl)-1-tetrahydrobenzene by the 2-bromonaphthalene
With 207 milligrams of 2-bromonaphthalenes (1 mmole), 13 milligrams of nickelous chlorides (0.1 mmole), 1, two 49 milligrams in (phenylbenzene is seen) propane (0.12 mmole) of 3-, 410 milligrams of tetrahydrobenzene (5 mmole), 20 milligrams of triethylamines (0.2 mmole), 2 milliliters of 1-butyl-3-methyl imidazolium tetrafluoroborate, place 50 milliliters of there-necked flasks, stirring heating was 110 ℃ of reactions 15 hours.After reaction finishes, cooling, reaction solution layering deionizing liquid, toluene extract 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 prepares 5-benzoyl valeral by 1-phenyl-1-tetrahydrobenzene
1-phenyl-1-tetrahydrobenzene 158 milligrams (1 mmoles) is placed 50 milliliters of there-necked flasks; add 10 milliliters of sherwood oils; under agitation feed ozone after 1 hour; add water decomposition, dichloromethane extraction, anhydrous magnesium sulfate drying; filter; concentrate, column chromatography for separation gets 168 milligrams of product 5-benzoyl valerals, yield 88%.
1H?NMR(CDCl
3)δppm：1.45～1.46(m，2H)，1.66～1.67(m，2H)，2.46～2.47(m，2H)，2.56～2.57(m，2H)，7.33～7.40(m，3H)，7.88～7.91(m，2H)；
13C?NMR(CDCl
3)δppm：22.1，23.9，39.0，43.3，128.6，128.7，128.8，133.4，136.7，199.8，202.3；MS(m/z)：190(M
+)。
Embodiment 10 prepares 1-phenyl-1 by 5-benzoyl valeral, the 6-hexylene glycol
With 190 milligrams of 5-benzoyl valerals (1 mmole); sodium borohydride places 50 milliliters of there-necked flasks for 100 milligrams, adds 15 milliliters of tetrahydrofuran (THF)s, stirs under the room temperature and spends the night; adding dilute acid solution decomposes; dichloromethane extraction, anhydrous magnesium sulfate drying filters; concentrate; column chromatography for separation gets product 1-phenyl-1,150 milligrams of 6-hexylene glycols, yield 76%.
1H?NMR(CDCl
3)δppm：1.28～1.30(m，4H)，1.46～1.50(m，2H)，1.76～1.78(m，2H)，2.06～2.11(w，2H)，3.56～3.58(m，2H)，4.51～4.53(m，1H)，7.23～7.30(m，5H)；
13C?NMR(CDCl
3)δppm：22.9，24.9，39.0，62.3，75.8，126.6，128.6，128.7，128.8，133.4，136.7；MS(m/z)：194(M
+)。
Claims (10)
1, a kind of 1-aryl (group)-1-ethylenialkene compound suc as formula (I) or (II),
In its Chinese style (I) and the formula (II), R, R ' independently are electrophilic separately or push away electron substituent group.
2,1-aryl (group)-1-ethylenialkene compound as claimed in claim 1 is characterized in that described R or R ' are respectively for one of following :-CHO ,-CN ,-F ,-COCH
3,-CF
3,-CH
3,-OCH
3,-OC
2H
5,-OC
3H
7,-OCOCH
3,-Ph ,-OH ,-NH
2
3,1-aryl (group)-1-ethylenialkene compound as claimed in claim 2 is characterized in that described R or R ' are for one of following :-COOCH
3,-CN ,-CH
3
4,1-aryl (group)-1-ethylenialkene compound as claimed in claim 1 is characterized in that described R ' is a hydrogen.
5, a kind of preparation method of the aryl (group)-1-ethylenialkene of 1-according to claim 1 compound, it is characterized in that comprising the steps: that halogenated aryl hydrocarbon and tetrahydrobenzene are in ionic liquid, in the presence of catalyzer, phosphorus part, organic amine, in 20 ℃～150 ℃ following stirring reactions 1～50 hour, aftertreatment got product 1-aryl (group)-1-ethylenialkene;
Described halogenated aryl hydrocarbon is suc as formula (III) or (IV), and R, R ' definition are with claim 1;
Described ionic liquid is 3-Methylimidazole inorganic acid salt or the 1-alkyl-3-Methylimidazole inorganic acid salt [Bmim] shown in formula V
+L
-, k represents that H or carbon atom quantity are the alkyl of n=1～18 in the formula V, L is one of following: BF
4, PF
6, OA
c, CF
3SO
3, N (SO
2CF
3)
2
Described catalyzer is divalence or non-valent nickel or palladium compound;
Described phosphorus part is 1, two (phenylbenzene is seen) ethane or 1 of 2-, two (phenylbenzene is seen) propane or 1 of 3-, two (phenylbenzene is seen) butane of 4-.
6, preparation method as claimed in claim 5 is characterized in that described ionic liquid is 1-butyl-3-methyl imidazolium tetrafluoroborate or 1-ethyl-3-methyl imidazolium tetrafluoroborate.
7, preparation method as claimed in claim 5 is characterized in that described catalyzer is one of following: nickel acetate, nickelous chloride, palladium, Palladous chloride; Described organic amine is a triethylamine.
8,, it is characterized in that described aftertreatment is as the described preparation method of one of claim 5～7: with reaction solution layering deionizing liquid, toluene extract the 1-aryl (group)-1-ethylenialkene.
9, preparation method as claimed in claim 8 is characterized in that: described temperature of reaction is 50～140 ℃, and the reaction times is 5～40 hours; The mol ratio of described halogenated aryl hydrocarbon, tetrahydrobenzene, catalyzer, phosphorus part, organic amine is 1: 2～5: 0.04～0.1: 0.08～0.2: 0.16～0.4.
10, the described 1-aryl (group)-1-ethylenialkene of claim 1 compound is used for synthetic 5-benzoyl valeral or 1-aryl-1,6-hexylene glycol.
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|---|---|---|---|
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100564333C (en) * | 2007-11-23 | 2009-12-02 | 浙江工业大学 | A kind of synthetic method of 1-aryl (group)-1-ethylenialkene compounds |
| CN106542950A (en) * | 2016-10-26 | 2017-03-29 | 梧州学院 | A kind of method for preparing limonene by 3 carenes |
-
2004
- 2004-11-18 CN CNB2004100844694A patent/CN100360481C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100564333C (en) * | 2007-11-23 | 2009-12-02 | 浙江工业大学 | A kind of synthetic method of 1-aryl (group)-1-ethylenialkene compounds |
| CN106542950A (en) * | 2016-10-26 | 2017-03-29 | 梧州学院 | A kind of method for preparing limonene by 3 carenes |
| CN106542950B (en) * | 2016-10-26 | 2019-03-26 | 梧州学院 | A method of limonene is prepared by 3- carene |
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| Publication number | Publication date |
|---|---|
| CN100360481C (en) | 2008-01-09 |
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