CN107721950A - A kind of synthesis technique of new polysubstituted dihydrofuran - Google Patents
A kind of synthesis technique of new polysubstituted dihydrofuran Download PDFInfo
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- CN107721950A CN107721950A CN201710964187.0A CN201710964187A CN107721950A CN 107721950 A CN107721950 A CN 107721950A CN 201710964187 A CN201710964187 A CN 201710964187A CN 107721950 A CN107721950 A CN 107721950A
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- polysubstituted
- dihydrofuran
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a kind of synthesis technique of new polysubstituted dihydrofuran.It will be seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O is dissolved in acetonitrile solvent；Add beta unsaturated ketone and
Description
Technical field
The present invention relates to visible light catalytic field, and in particular to a kind of synthesis technique of new polysubstituted dihydrofuran.
Background technology
A Typical Representative of the furan nucleus as five-ring heterocycles, universally present in natural products, because of its intrinsic life
Thing activity and in the lasting attention that attract organic synthesis circle.In recent years research shows that polysubstituted bark mutters compound anti-
Virus, antibacterial, antitumor, anti-inflammatory desinsection etc. all have good effect.Furan derivatives are as a kind of important heterocycle
Intermediate, in fully synthetic, it can be utilized to synthesize many biological natural products, while it is also that synthesis is chemical, producing high-molecular
Learn, the important matrix of materials chemistry.Therefore, the synthesis of furan derivatives causes the attention of numerous scientists.
In recent years, the method using metal catalytic combining polysubstituted furan ring is more and more, and it is big to can be generally divided into two
Class.First, by the method for coupling, structure of modification is carried out to furan nucleus；Second, carry out furan nucleus by precursor of open chain compound
Construct.
The first kind：Pass through furan nucleus coupling reaction combining polysubstituted furan derivative.Stille is coupled：Utilize 3- (three fourths
Ji Xi) furans or 2- (tributyl tin) furans and alkenyl halide, halogenated aryl hydrocarbon, allylic compound, phthalein chlorine, alcoxyl phthalein chlorine etc.
Reaction, various substituted 3- substitutions or 2- substituted furan derivatives are synthesized；Suzuki is coupled：Huang is that positive wait also utilizes 3,4- bis-
(trimethyl silicane) furans and BCl3After reaction forms borane reagent, occur under palladium chtalyst with aryl, alkenyl or allyl halide
Suzuki reacts to obtain 3- substitutions -4- (trimethyl silicane) furans.It again with BCl3The above-mentioned reaction of generation, finally obtain 3,4- bis- and take
For furans product；Kumada is coupled：Pridgen etc. is using furans bromide and grignard reagent reacting, in Ni (dppe) Cl2Or Ni
(Pph3)Cl2Furans coupled product has been obtained under catalysis fine yield.Negishi is coupled：Using BuLi and furan nucleus 2- positions or
After H reaction generation lithium reagents on 5- positions, metal exchange reaction occurs with zinc chloride or zinc bromide and obtains organic zinc reagent, it is organic
Under tetrakis triphenylphosphine palladium catalysis Negishi coupling reactions occur for zincon, obtain polysubstituted furan derivatives.
Second class：Using open chain compound as precursor combining polysubstituted furan derivative.Alkenyl ketone is joined as precursor using 1,2-：
The discoveries such as Marshall join ketenes under the catalysis of silver or rhodium, and 1,2- connection alkenyl ketone can reset generation furans cycle compound.Separately
Outside, connection ketenes is almost completely converted into furan nucleus product in 0.2mol 10% silver nitrate silica gel system, resulting in one
The good method of series synthesis furan nucleus of the 2- positions containing functional group, and be widely used in the natural products containing furan nucleus；With β-iodine
Generation and beta, gamma-beta-unsaturated ketone are precursor combining polysubstituted furan derivative：β-iodo and beta, gamma-beta-unsaturated ketone are complexed in ring-type palladium
Direct cyclization product is obtained under thing catalysis, dimer 3, the furans products of 3- bis- are mainly obtained under tetrakis triphenylphosphine palladium catalysis；
Using metal carbene as precursor combining polysubstituted furan derivative：Diazo-ketones is at Rh (OAc)2Metal carbene is formed under catalysis, with alkynes
Hydrocarbon reaction first generates metal carbene intermediate, and the reaction that Cabbeen and carbonyl in metallic molecule occur for the intermediate can obtain take more
For furans product.
Above-mentioned synthetic method finds in an experiment, raw material complex and expensive, and step is various, and yield is relatively low.The first kind synthesizes
Method is furans to be transformed, it is necessary to first synthesize corresponding furan nucleus precursor；And the second a large amount of oxidations of class synthetic method
Agent, catalyst, and need to heat, cause energy waste.
2011, Wu Chuan morals group was with [WZn (VO)2(ZnW9O34)2]12-For catalyst, 30% hydrogen peroxide is oxidant,
Acetonitrile is solvent, and 12 hours are reacted in the case where being heated to 60 DEG C, and the acetylacetone,2,4-pentanedione for obtaining 65% yield is the polysubstituted furan of substrate
Mutter ring derivatives.This is [the WZn (VO) first using acetylacetone,2,4-pentanedione as raw material2(ZnW9O34)2]12-Polysubstituted furan is synthesized for catalyst
To mutter ring derivatives, acetylacetone,2,4-pentanedione raw material is easy to get and cheap, but the reaction used catalyst is complex, is not easily-synthesized,
And still need to be heated to 60 DEG C using hydrogen peroxide as oxidant just react, it is roughly the same with the article above method.
The content of the invention
The present invention is intended to provide the synthetic method that a kind of low energy consumption of new polysubstituted dihydrofuran is green, the synthesis
Method is simple, reactions steps are short, easy to operate, and organic solvent consumption is small, catalyst recoverable, and post processing is simple, product
High income, purity is high, and environmental protection pressure is small.
It is as follows using technical scheme to reach above-mentioned purpose：
A kind of synthesis technique of new polysubstituted dihydrofuran, comprises the following steps：
It will be seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O is dissolved in acetonitrile solvent；Add alpha, beta-unsaturated ketone andPoint
Son sieve, oxygen reaction is passed through under the irradiation of sunshine；Filtering, dry, by column chromatography eluting, obtain polysubstituted dihydro
Furans.
By such scheme, the alpha, beta-unsaturated ketone includes acetylacetone,2,4-pentanedione, methyl acetoacetate, propionyl methyl acetate.
It is described by such schemeMolecular sieve is that aperture isAlkali metal aluminosilicate, wherein SiO2/Al2O3=2.
By such scheme, alpha, beta-unsaturated ketone in molar ratio:[Ru(bpy)3]Cl2·6H2O=1：(0.01-0.2), by quality
Compare alpha, beta-unsaturated ketone：Molecular sieve=1:(0.5-4).
By such scheme, the concentration of the alpha, beta-unsaturated ketone is 0.1g/mL-0.15g/mL, it is seen that photochemical catalyst [Ru
(bpy)3]Cl2·6H2O concentration is 0.0032g/mL-0.0035g/mL.
By such scheme, reaction temperature is 20-30 DEG C, reaction time 1-24h.
By such scheme, the petroleum ether by volume of eluant, eluent used in the column chromatography：Ethyl acetate=3:1.
Relative to prior art, the present invention has the beneficial effect that：
This method simplicity is easily operated, and reactions steps are short, and raw material is cheap and easy to get, overall production rate and the more original side of product purity
Method increases, and uses visible light catalytic, without heating, low energy consumption, and using oxygen as oxidant, low stain.Side in document
Method one side expensive raw material price, the oxidant used is complex to be not easy to obtain；On the other hand, course of reaction is required for heating,
Energy consumption is more.
This method feature of environmental protection is good, using new visible light catalyst [Ru (bpy)3]Cl2·6H2O is catalyzed, and reacts knot
The recyclable recycling of beam rear catalyst, reacts in the sun, without heating, is never had been reported that in document before being.Entirely
Course of reaction does not discharge any gas for having pollution using oxygen as oxidant.
Brief description of the drawings
Fig. 1：The products therefrom single crystal diffraction collection of illustrative plates of embodiment 1；
Fig. 2：The products therefrom hydrogen nuclear magnetic resonance spectrogram of embodiment 1；
Fig. 3：The products therefrom carbon-13 nmr spectra figure of embodiment 1；
Fig. 4：The products therefrom hydrogen nuclear magnetic resonance spectrogram of embodiment 3；
Fig. 5：The products therefrom carbon-13 nmr spectra figure of embodiment 3；
Fig. 6：The products therefrom hydrogen nuclear magnetic resonance spectrogram of embodiment 4；
Fig. 7：The products therefrom carbon-13 nmr spectra figure of embodiment 4.
Embodiment
Following examples further explain technical scheme, but not as limiting the scope of the invention.
Embodiment 1
It will be seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O (6.4mg, 0.01mmol) is dissolved in 2ml acetonitrile solutions, is added
Enter acetylacetone,2,4-pentanedione (100mg, 1mmol),Molecular sieve (200mg), by oxygen ball intercalation reaction bottle, under sunshine irradiation,
Strong stirring 16h is complete until raw material reaction.After reaction terminates, by reacting liquid filtering, filtrate is taken, by column chromatography, with stone
Oily ether：Ethyl acetate=3:1 is eluent, isolated 2,5- dimethyl -2,3- dihydroxy -3,4- diacetyl -2,3- bis-
Hydrogen furans (103mg).
As shown in figure 1, the shape that the structure is presented under single crystal diffraction；
(NMR VARIANMercury Plus400 type test conditions as shown in Figure 2：500MHz), the structure has six classes
The different hydrogen of environment is learned, respectively positioned at 7.45 (1H), 5.62 (1H), 2.23 (3H), 2.12 (3H), 2.20 (3H), 1.48 (3H)
Ppm, it is consistent with the spectrogram of document report, it is seen that the compound is correct；
(NMR VARIANMercury Plus400 type test conditions as shown in Figure 3：125MHz), the structure has ten classes
The different carbon of environment is learned, respectively positioned at 206.3,193.8,170.3,116.5,111.8,88.8,29.3,27.1,22.7,
15.9ppm, it is consistent with the spectrogram of document report, it is seen that the compound is correct.
Embodiment 2
It will be seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O (320mg, 0.5mmol) is dissolved in 100ml acetonitrile solutions, is added
Enter acetylacetone,2,4-pentanedione (5g, 50mmol),Molecular sieve (10g), by oxygen ball intercalation reaction bottle, under sunshine irradiation, strength
16h is stirred until raw material reaction is complete.After reaction terminates, by reacting liquid filtering, filtrate is taken, by column chromatography, with petroleum ether：
Ethyl acetate=3:1 is eluent, isolated 2,5- dimethyl -2,3- dihydroxy -3,4- diacetyl-DHF
(5.15g)。
Embodiment 3
It will be seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O (6.4mg, 0.01mmol) is dissolved in 2ml acetonitrile solutions, is added
Enter methyl acetoacetate (116mg, 1mmol),Molecular sieve (232mg), by oxygen ball intercalation reaction bottle, in solar irradiation
Penetrate down, strong stirring 16h is complete until raw material reaction.After reaction terminates, by reacting liquid filtering, filtrate is taken, by column chromatography,
With petroleum ether：Ethyl acetate=3:1 is eluent, isolated 2,5- dimethyl -2,3- dihydroxy -3,4- dimethyl dicarboxylate
Base -2,3 dihydro furan (114mg).
As shown in figure 4, the structure has the different hydrogen of five class chemical environments, respectively positioned at 7.31 (1H), 5.57 (1H), 3.58
(6H), 2.16 (3H), 1.45 (3H) ppm are consistent with the spectrogram of document report, it is seen that the compound is correct；
As shown in figure 5, the structure has the different carbon of ten class chemical environments, respectively positioned at 171.4,170.4,165.0,
111.8,106.7,85.8,52.1,51.0,22.2,19.4ppm, it is consistent with the spectrogram of document report, it is seen that the compound is just
True.
Embodiment 4
It will be seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O (6.4mg, 0.01mmol) is dissolved in 2ml acetonitrile solutions, is added
Enter propionyl methyl acetate (130mg, 1mmol),Molecular sieve (260mg), by oxygen ball intercalation reaction bottle, in solar irradiation
Penetrate down, strong stirring 16h is complete until raw material reaction.After reaction terminates, by reacting liquid filtering, filtrate is taken, by column chromatography,
With petroleum ether：Ethyl acetate=3:1 is eluent, isolated 2,5- diethyl -2,3- dihydroxy -3,4- dimethyl dicarboxylate
Base -2,3 dihydro furan (109mg).
As shown in fig. 6, the structure has the different hydrogen of eight class chemical environments, respectively positioned at 6.99 (1H), 5.47 (1H), 3.59
(3H), 3.57 (3H) 2.67 (2H), 2.59 (2H) 1.07 (3H) 0.94 (3H) ppm are consistent with the spectrogram of document report, it is seen that should
Compound is correct；
As shown in fig. 7, the structure has the different carbon of 12 class chemical environments, respectively positioned at 174.4,171.8,164.9,
112.6,106.0,85.9,52.1,50.9,28.1,21.6,11.0,8.2ppm, it is consistent with the spectrogram of document report, it is seen that should
Compound is correct.
Claims (7)
1. a kind of synthesis technique of new polysubstituted dihydrofuran, it is characterised in that comprise the following steps：
It will be seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O is dissolved in acetonitrile solvent；Add alpha, beta-unsaturated ketone andMolecule
Sieve, oxygen reaction is passed through under the irradiation of sunshine；Filtering, dry, by column chromatography eluting, obtain polysubstituted dihydro furan
Mutter.
2. the synthesis technique of polysubstituted dihydrofuran as claimed in claim 1, it is characterised in that the alpha, beta-unsaturated ketone includes second
Acyl acetone, methyl acetoacetate, propionyl methyl acetate.
3. the synthesis technique of polysubstituted dihydrofuran as claimed in claim 1, it is characterised in that describedMolecular sieve is that aperture isAlkali metal aluminosilicate, wherein SiO2/Al2O3=2.
4. the synthesis technique of polysubstituted dihydrofuran as claimed in claim 1, it is characterised in that alpha, beta-unsaturated ketone in molar ratio:
[Ru(bpy)3]Cl2·6H2O=1：(0.01-0.2), in mass ratio alpha, beta-unsaturated ketone：Molecular sieve=1:(0.5-4).
5. the synthesis technique of polysubstituted dihydrofuran as claimed in claim 1, it is characterised in that the concentration of the alpha, beta-unsaturated ketone
For 0.1g/mL-0.15g/mL, it is seen that photochemical catalyst [Ru (bpy)3]Cl2·6H2O concentration is 0.0032g/mL-0.0035g/
mL。
6. the synthesis technique of polysubstituted dihydrofuran as claimed in claim 1, it is characterised in that reaction temperature is 20-30 DEG C, instead
It is 1-24h between seasonable.
7. the synthesis technique of polysubstituted dihydrofuran as claimed in claim 1, it is characterised in that the column chromatography is used to be eluted
Agent petroleum ether by volume：Ethyl acetate=3:1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910104A (en) * | 2015-06-26 | 2015-09-16 | 武汉大学 | Method for synthesizing dihydrofuran derivatives under catalytic action of copper |
| CN105461668A (en) * | 2013-07-03 | 2016-04-06 | 郑州裕昌有机硅化工有限公司 | New chiral dihydrobenzofuran compound |
-
2017
- 2017-10-17 CN CN201710964187.0A patent/CN107721950A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461668A (en) * | 2013-07-03 | 2016-04-06 | 郑州裕昌有机硅化工有限公司 | New chiral dihydrobenzofuran compound |
| CN104910104A (en) * | 2015-06-26 | 2015-09-16 | 武汉大学 | Method for synthesizing dihydrofuran derivatives under catalytic action of copper |
Non-Patent Citations (2)
| Title |
|---|
| XIAO-YAN WANG ET AL.: "[Ru(bpy)3]Cl2-catalyzed aerobic oxidative cleavage β-diketones to carboxylic acids under visible light irradiation", 《TETRAHEDRON LETTERS》 * |
| ZHEN-PENG SHANG ET AL.: "Visible-light-mediated aerobic oxidative dimerizative annulation of b-carbonylketones: a facile strategy to construct highly functionalized furans", 《TETRAHEDRON LETTERS》 * |
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Application publication date: 20180223 |