CN104045541B - The synthetic method of aromatic ketone compounds - Google Patents

The synthetic method of aromatic ketone compounds Download PDF

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CN104045541B
CN104045541B CN201410276567.1A CN201410276567A CN104045541B CN 104045541 B CN104045541 B CN 104045541B CN 201410276567 A CN201410276567 A CN 201410276567A CN 104045541 B CN104045541 B CN 104045541B
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zncl
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ketone compounds
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CN104045541A (en
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王爱玲
邢鹏飞
郑学良
李长平
郑学仿
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Dalian Haihua Pharmaceutical Technology Co.,Ltd.
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Dalian University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom

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  • Organic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to the synthetic method of aromatic ketone compounds, particularly a kind of dark melt and dissolved dose of (Deep altogether? Eutectic? Solvents, DES) method of Fu Ke (F-C) acylation reaction of catalysis. Use compound fragrant hydrocarbon and acylting agent by F-C acylation reaction synthesizing fragrant ketone compounds, in course of reaction, use DES (ZnCl2/ ChCl=2:1) as catalyst. DES (ZnCl in the present invention2/ ChCl=2:1) not only make reaction dissolvent simultaneously but also make catalysts; Technique is simple, and stability is strong, non-volatile, and catalytic activity is high; When post-reaction treatment, do not need acid adding, simple and convenient, environmental protection.

Description

The synthetic method of aromatic ketone compounds
Technical field
The present invention relates to a kind of method of catalytic manufacture of aromatic ketone compounds, in particular, relate to a kind of dark melt and dissolved dose of method that catalyzes and synthesizes aromatic ketone compounds by friedel-crafts acylation that be total to of utilizing.
Background technology
Fu Ke (F-C) acylation reaction is a kind of reaction of important preparation aromatic ketone compounds; the product aromatic ketone compounds that it obtains is the important intermediate of a class; this compounds can be used for synthetic drug (as naproxen, dextromethorphan); dyestuff and agrochemicals medicine etc.; because it is with a wide range of applications, people conduct in-depth research for its synthetic method.
F-C acylation reaction is the electrophilic substitution reaction between a kind of aromatic compound and acylating reagent; acylating reagent is generally acyl chlorides, acid anhydrides, carboxylic acid; and the selection of catalyst is the key problem of such reaction, be generally with Bronsted acid or lewis acid (the anhydrous AlCl of industrial general employing3) make catalyst. But these catalyst self have higher toxicity and volatility, and instrument and equipment is had to severe corrosive; Catalyst is to water sensitive, and consumption is large, mostly is expensive heavy metal, recycles rate low, may produce corrosive gas and a large amount of waste liquid in post-reaction treatment process, causes serious environmental pollution, does not meet the requirement of Green Chemistry theory.
In order to solve the deficiency of traditional catalyst, recent domestic has carried out more research to catalyst, attempts using different types of catalyst, to improve reaction condition, the productive rate that improves F-C acylation reaction, service life and the recuperability of catalyst. There is bibliographical information to use transition metal (In, Hf, Ag; Ga) catalysis F-C acylation reaction is (referring to (a) PhuongHoangTran; FritzDuus, ThachNgocLe, Friedel – Craftsacylationusingbismuthtriflatein[BMI] [PF6]，TetrahedronLetters,2012,53,222–224.(b)RamaraoParella,Naveen,AmitKumar,SrinivasaraoArulanandaBabu，CatalyticFriedel–Craftsacylation:magneticnanopowderCuFe2O4Asanefficientandmagneticallyseparablecatalyst, TetrahedronLetters, 2013,54,1738 – 1742.), although productive rate is relatively better, transition metal is expensive, reaction transformation time is longer. also there is bibliographical information to use metallic-OTf class catalyst (referring to (a) KobayashiS, IwamotoS, CatalyticFriedel-Craftsacylationofbenzene, chlorobenzene, andfluorobenzeneusinganovelcatalystsystem, hafniumtriflateandtrifluoromethanesulfonicacid, TetrahedronLetters, 1998, 39, 4697-4700. (b) HwangJP, SuryaPrakashGK, GeorgeAO, TrifluoromethanesulfonicacidcatalyzednovelFriedel-Crafts acylationofaromaticswithmethylbenzoate, Tetrahedron, 2000, 56, 7199-7203.), but such catalyst activity is not high, expensive, be difficult to preparation, be unsuitable for industrial production.
In addition; most F-C acylation reactions need to carry out in organic solvent; and that organic solvent exists is volatile, inflammable, price is higher, most poisonous, to shortcomings such as environment are unfriendly, be therefore also the main bugbear that people face for the processing of a large amount of waste liquids that produce in chemical industry. Along with social development, people more thirst for pursuing the quality of the life of environmental protection, and Green Chemistry has been subject to increasing attention, find a kind of green solvent, and green catalyst is vital, are doubly subject to World Science man's extensive attention always.
In this patent, develop a kind of new environmentally friendly reaction system, reaction medium in this reaction system had both made catalyst and had also done reaction dissolvent, and this reaction medium low price, can reuse, and had realized a kind of cheap, safety of synthesizing fragrant ketone compounds, the method for environmental protection.
Summary of the invention
The object of the invention is large for the catalyst toxicity existing in current techniques, corrosivity is high, environmental pollution is serious, poor catalyst stability and the deficiency such as be difficult to reuse; a kind of dark melt and dissolved dose of (DeepEutecticSolvents altogether for preparing aromatic ketone compounds for F-C acyl group is provided; DES) catalyst, and utilize DES to catalyze and synthesize the method for aromatic ketone compounds by F-C acylation reaction.
F-C acylation reaction general formula under DES catalytic condition is:
1 for replacing aromatic ring, fragrant heterocycle compound, and 2 is carboxylic acid halides, anhydrides compound, and 3 is aromatic ketone compounds, and DES is zinc chloride (ZnCl2What)/Choline Chloride (ChCl) mol ratio was 2/1 is total to melt and dissolved dose deeply.
The synthetic method of a kind of aromatic ketone compounds of the present invention, is used compound fragrant hydrocarbon and acylting agent by F-C acylation reaction synthesizing fragrant ketone compounds, it is characterized in that, uses DES (ZnCl in course of reaction2/ ChCl=2:1) as catalyst.
According in above-described method, preferably, described compound fragrant hydrocarbon is for replacing aromatic ring compounds, and described acylting agent is acyl halides compound.
According in above-described method, preferably, replacing aromatic ring compounds based on 1 equivalent is standard, described DES (ZnCl2/ ChCl=2:1) amount be 0.25-2 equivalent, the amount of described carboxylic acid halides is 1.1 equivalents, reaction temperature is 55-100 DEG C, the reaction time is 10-40min.
According in above-described method, preferably, described compound fragrant hydrocarbon is fragrant heterocycle compound, and described acylting agent is acyl halides compound.
According in above-described method, preferably, be standard based on 1 equivalent virtue heterocycle compound, described DES (ZnCl2/ ChCl=2:1) amount be 0.5-1.5 equivalent, the amount of described carboxylic acid halides is 1.1 equivalents, reaction temperature is 55 DEG C, the reaction time is 15-40min.
According in above-described method, preferably, described compound fragrant hydrocarbon is for replacing aromatic ring compounds, and described acylting agent is anhydrides compound.
According in above-described method, preferably, replacing aromatic ring compounds based on 1 equivalent is standard, described DES (ZnCl2/ ChCl=2:1) amount be 0.5-1.5 equivalent, the amount of described acid anhydrides is 1.1 equivalents, reaction temperature is 55 DEG C, the reaction time is 15-40min.
According in above-described method, preferably, described reaction system does not need to add other solvent, described DES (ZnCl2/ ChCl=2:1) not only make reaction dissolvent simultaneously but also make catalysts.
According in above-described method, preferably, described DES (ZnCl2/ ChCl=2:1) reusable, environmental protection, remains unchanged substantially reclaiming catalytic effect after 4 times.
According in above-described method, preferably, when described post-reaction treatment, do not need to be acidified with acid, directly extraction, alkali cleaning, dry, decompression distillation, post separates can obtain ketone compounds.
Technical scheme of the present invention is: a kind of synthetic method of aromatic ketone compounds, and use compound fragrant hydrocarbon and acylting agent by F-C acylation reaction synthesizing fragrant ketone compounds, in course of reaction, use DES (ZnCl2/ ChCl=2:1) as catalyst. Comprise the following steps:
By 25mmol (3.49g) Choline Chloride (ChCl) and 50mmol (6.82g) zinc chloride (ZnCl2) join in the round-bottomed flask of 250ml, mixture is stirred under 150 DEG C of conditions 8h both a kind of transparency liquid, i.e. DES (ZnCl2/ChCl＝2:1)。
By the DES (ZnCl of 0.25-2 equivalent2/ ChCl=2:1) join in reaction vessel, then add the compound 1 of 1 equivalent, be warming up to 55 DEG C, slowly add the compound 2 of 1.1 equivalents, after stirring reaction 10-40min, stop reaction. Add water and ethyl acetate extraction, ethyl acetate layer carries out alkali cleaning, drying, and decompression distillation, post separates and obtains target product.
DES (ZnCl described in described step2/ ChCl=2:1) not only made reaction dissolvent simultaneously but also
Make catalysts.
Described DES (ZnCl2/ ChCl=2:1) be zinc chloride (ZnCl2What)/Choline Chloride (ChCl) mol ratio was 2/1 is total to melt and dissolved dose deeply, and its representation is as follows:
DES is emerging in recent years a kind of green solvent, and the appearance of DES has caused people's extensive concern. The eutectic mixture that DES is normally combined by hydrogen bond acceptor (as quaternary ammonium salt, quaternary alkylphosphonium salt etc.) and the hydrogen-bond donor (as acid amides, compounds such as carboxylic acid and polyalcohols) of certain stoichiometric proportion. DES has that price is low, stable in water, preparation simply, not volatile, nonflammable, catalytic activity is high, easy storage, the recyclable plurality of advantages such as recycle.
The present invention has the following advantages: DES (ZnCl compared with preparing arone compound technique with tradition2/ ChCl=2:1) have the effect of catalysts and solvents concurrently, in course of reaction, do not need to add other solvent; Technique is simple, and stability is strong, non-volatile, and catalytic activity is high; When post-reaction treatment, do not need acid adding, simple and convenient, environmental protection.
Detailed description of the invention
The present invention illustrates by following examples, but the present invention is not limited to following embodiment, and before and after not departing from, under the scope of described aim, change is included in technical scope of the present invention.
Embodiment 1
Experimental technique: by 1,2 of 2mmol, 4-trimethoxy-benzene joins in the round-bottomed flask of 15mL, is warming up to 55 DEG C, slowly adds the chlorobenzoyl chloride of 2.2mmol, by the progress of thin-layered chromatography monitoring reaction. Discovery does not have product to generate, and there is no DES (ZnCl2/ ChCl=2:1) react under existence condition and do not carry out.
Reaction equation:
Embodiment 2
Experimental technique: by the DES (ZnCl of 1 equivalent (2mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add 1,2 of 1 equivalent (2mmol), 4-trimethoxy-benzene, be warming up to 55 DEG C, slowly add the chlorobenzoyl chloride of 1.1 equivalents (2.2mmol), after stirring reaction 10min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the material benzinum obtaining: the solvent of ethyl acetate=6:1 carries out post separation. Both obtained 2,4,5-trimethoxyphenyl Benzophenone, yield is 89.7%.
Reaction equation:
Embodiment 3
Experimental technique: by the water layer decompression distillation in example 2, the recyclable DES (ZnCl that obtains2/ ChCl=2:1). Utilize and reclaim the DES (ZnCl obtaining2/ ChCl=2:1) repeat the step of embodiment 2. So repeat 4 times, find DES (ZnCl2/ ChCl=2:1) catalytic effect substantially remain unchanged. 89.4%, 89.2%, 88.5%, 87.7%. the productive rate of products therefrom is respectively:
Reaction equation:
Embodiment 4
Experimental technique: by the DES (ZnCl of 0.25 equivalent (0.5mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add 1,2 of 1 equivalent (2mmol), 4-trimethoxy-benzene, be warming up to 55 DEG C, slowly add the chlorobenzoyl chloride of 1.1 equivalents (2.2mmol), after stirring reaction 40min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the material benzinum obtaining: the solvent of ethyl acetate=6:1 carries out post separation. Both obtained 2,4,5-trimethoxyphenyl Benzophenone, yield is 34.4%.
Reaction equation:
Embodiment 5
Experimental technique: by the DES (ZnCl of 2 equivalents (4mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add 1,2 of 1 equivalent (2mmol), 4-trimethoxy-benzene, be warming up to 55 DEG C, slowly add the chlorobenzoyl chloride of 1.1 equivalents (2.2mmol), after stirring reaction 15min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the material benzinum obtaining: the solvent of ethyl acetate=6:1 carries out post separation. Both obtained 2,4,5-trimethoxyphenyl Benzophenone, yield is 82.9%.
Reaction equation:
Embodiment 6
Experimental technique: by the DES (ZnCl of 1 equivalent (2mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add 1,2 of 1 equivalent (2mmol), 4-trimethoxy-benzene, be warming up to 100 DEG C, slowly add the chlorobenzoyl chloride of 1.1 equivalents (2.2mmol), after stirring reaction 10min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the material benzinum obtaining: the solvent of ethyl acetate=6:1 carries out post separation. Can obtain 2,4,5-trimethoxyphenyl Benzophenone, yield is 62.5%, has also occurred accessory substance simultaneously.
Reaction equation:
Embodiment 7
Experimental technique: by the DES (ZnCl of 0.5 equivalent (1mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add the thiophene of 1 equivalent (2mmol), be warming up to 55 DEG C, slowly add the chlorobenzoyl chloride of 1.1 equivalents (2.2mmol), after stirring reaction 40min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the solid matter benzinum obtaining: the solvent of ethyl acetate=5:1 carries out post separation. Both obtained 2-thiophene Benzophenone, yield is 35%.
Reaction equation:
Embodiment 8
Experimental technique: by the DES (ZnCl of 1 equivalent (2mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add the thiophene of 1 equivalent (2mmol), be warming up to 55 DEG C, slowly add the chlorobenzoyl chloride of 1.1 equivalents (2.2mmol), after stirring reaction 30min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the solid matter benzinum obtaining: the solvent of ethyl acetate=5:1 carries out post separation. Both obtained 2-thiophene Benzophenone, yield is 62%.
Reaction equation:
Embodiment 9
Experimental technique: by the DES (ZnCl of 1.5 equivalents (3mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add the thiophene of 1 equivalent (2mmol), be warming up to 55 DEG C, slowly add the chlorobenzoyl chloride of 1.1 equivalents (2.2mmol), after stirring reaction 15min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the solid matter benzinum obtaining: the solvent of ethyl acetate=5:1 carries out post separation. Both obtained 2-thiophene Benzophenone, yield is 51%.
Reaction equation:
Embodiment 10
Experimental technique: by the DES (ZnCl of 0.5 equivalent (1mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add 1,2 of 1 equivalent (2mmol), 4-trimethoxy-benzene, be warming up to 55 DEG C, slowly add the acetic anhydride of 1.1 equivalents (2.2mmol), after stirring reaction 40min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the material benzinum obtaining: the solvent of ethyl acetate=3:1 carries out post separation. Both obtained 2,4,5-trimethoxy acetophenone, yield is 70%.
Reaction equation:
Embodiment 11
Experimental technique: by the DES (ZnCl of 1 equivalent (2mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add 1,2 of 1 equivalent (2mmol), 4-trimethoxy-benzene, be warming up to 55 DEG C, slowly add the acetic anhydride of 1.1 equivalents (2.2mmol), after stirring reaction 20min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the material benzinum obtaining: the solvent of ethyl acetate=3:1 carries out post separation. Both obtained 2,4,5-trimethoxy acetophenone, yield is 90.5%.
Reaction equation:
Embodiment 12
Experimental technique: by the DES (ZnCl of 1.5 equivalents (3mmol)2/ ChCl=2:1) join in the round-bottomed flask of 15mL, then add 1,2 of 1 equivalent (2mmol), 4-trimethoxy-benzene, be warming up to 55 DEG C, slowly add the acetic anhydride of 1.1 equivalents (2.2mmol), after stirring reaction 15min, stop reaction. Add respectively after 5mL water and 5mL ethyl acetate extracting twice the saturated NaHCO of ethyl acetate layer3Clean once, then use anhydrous MgSO4Dry, decompression distillation afterwards, the material benzinum obtaining: the solvent of ethyl acetate=3:1 carries out post separation. Both obtained 2,4,5-trimethoxy acetophenone, yield is 75.5%.
Reaction equation:
。

Claims (6)

1. a synthetic method for aromatic ketone compounds, is used compound fragrant hydrocarbon and acylBase reagent, by F-C acylation reaction synthesizing fragrant ketone compounds, is characterized in that, anti-Answer and in process, use DES (ZnCl2/ ChCl=2:1) as catalyst; Described areneCompound is for replacing aromatic ring compounds, and described acylting agent is acyl halides compound; BaseReplacing aromatic ring compounds in 1 equivalent is standard, described DES (ZnCl2/ChCl＝2:1)Amount be 0.25-2 equivalent, the amount of described carboxylic acid halides is 1.1 equivalents, reaction temperature is55-100 DEG C, the reaction time is 10-40min;
Described reaction system does not need to add other solvent, described DES(ZnCl2/ ChCl=2:1) not only make reaction dissolvent simultaneously but also make catalysts;
Described DES (ZnCl2/ ChCl=2:1) be zinc chloride (ZnCl2)/Choline Chloride (ChCl)Mol ratio is 2/1 dark melt and dissolved dose altogether, and its representation is as follows:
2. a synthetic method for aromatic ketone compounds, is used compound fragrant hydrocarbonBy F-C acylation reaction synthesizing fragrant ketone compounds, its feature exists with acylting agentIn, in course of reaction, use DES (ZnCl2/ ChCl=2:1) as catalyst; Described virtueFragrant hydrocarbon compound is fragrant heterocycle compound, and described acylting agent is carboxylic acid halides class chemical combinationThing; Be standard based on 1 equivalent virtue heterocycle compound, described DES (ZnCl2/ChCl＝2:1)Amount be 0.5-1.5 equivalent, the amount of described carboxylic acid halides is 1.1 equivalents, reaction temperature is 55 DEG C,Reaction time is 15-40min;
Described reaction system does not need to add other solvent, described DES(ZnCl2/ ChCl=2:1) not only make reaction dissolvent simultaneously but also make catalysts;
Described DES (ZnCl2/ ChCl=2:1) be zinc chloride (ZnCl2)/Choline Chloride (ChCl)
3. a synthetic method for aromatic ketone compounds, is used compound fragrant hydrocarbon and acylBase reagent, by F-C acylation reaction synthesizing fragrant ketone compounds, is characterized in that, anti-Answer and in process, use DES (ZnCl2/ ChCl=2:1) as catalyst; Described areneCompound is for replacing aromatic ring compounds, and described acylting agent is anhydrides compound; BaseReplacing aromatic ring compounds in 1 equivalent is standard, described DES (ZnCl2/ChCl＝2:1)Amount be 0.5-1.5 equivalent, the amount of described acid anhydrides is 1.1 equivalents, reaction temperature is 55 DEG C,Reaction time is 15-40min;
Described reaction system does not need to add other solvent, described DES(ZnCl2/ ChCl=2:1) not only make reaction dissolvent simultaneously but also make catalysts;
Described DES (ZnCl2/ ChCl=2:1) be zinc chloride (ZnCl2)/Choline Chloride (ChCl)
4. according in the method described in claim 1-3, it is characterized in that described reactionSystem does not need to add other solvent, described DES (ZnCl2/ ChCl=2:1) both reactedSolvent is made again catalysts simultaneously.
5. according in the method described in claim 1-3, it is characterized in that described DES(ZnCl2/ ChCl=2:1) reusable, environmental protection, is reclaiming catalytic effect after 4 timesSubstantially remain unchanged.
6. according in the method described in claim 1-3, it is characterized in that, after described reactionWhen processing, do not need to be acidified with acid, directly extraction, alkali cleaning, dry, decompression distillation, post dividesFrom obtaining ketone compounds.
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