CN110028409A - A kind of polysubstituted naphthalene derivatives and preparation method thereof - Google Patents
A kind of polysubstituted naphthalene derivatives and preparation method thereof Download PDFInfo
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- CN110028409A CN110028409A CN201910295100.4A CN201910295100A CN110028409A CN 110028409 A CN110028409 A CN 110028409A CN 201910295100 A CN201910295100 A CN 201910295100A CN 110028409 A CN110028409 A CN 110028409A
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
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- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/753—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of polycyclic acids
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- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
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Abstract
The invention discloses a kind of polysubstituted naphthalene derivatives and preparation method thereof, and using four acetylene compounds and phenylacetylene as raw material, in toluene solvant, 100~110 DEG C of 12~14h of reaction separate after reaction, purify, polysubstituted naphthalene derivatives can be obtained.Compared with prior art, the present invention provides a kind of preparation methods of completely new polysubstituted naphthalene, generate a series of new polysubstituted naphthalene derivatives.The polysubstituted naphthalene derivatives of synthesis have compared with high atom economy, the more complicated multiplicity of structure, have certain utilization prospect.
Description
Technical field
The present invention relates to organic compound synthesis technical fields, and in particular to a kind of polysubstituted naphthalene derivatives and its preparation side
Method.
Background technique
Naphthalene is industrial most important hydrocarbon with condensed rings, is production synthesis mainly for the production of phthalic anhydride, various naphthols, naphthylamines etc.
It resin, plasticizer, the intermediate of dyestuff, surfactant, synthetic fibers, coating, pesticide, medicine, fragrance, rubber chemicals and kills
The raw material of worm agent.Naphthalene is also used for manufacture dyestuff intermediate, camphor ball, leather and Wood protecting agent etc. simultaneously.Using naphthalene as raw material, warp
The operation of the units such as sulfonation, nitrification, reduction, amination, hydrolysis is crossed, a variety of intermediates can be made.The application of naphthalene is also being widened, new product
" super plastic material " i.e. naphthalenesulfonate formaldehyde condensation compound, can be used as cement additive, increase the plastic deformation of concrete without
Reduce its intensity.Demand of the naphthalene in a few years from now on will be increased with the speed of 5-10%.
Summary of the invention
The purpose of the present invention is to provide a kind of polysubstituted naphthalene derivatives, the more complicated multiplicity of structure, have wide fortune
Use prospect.
Another object of the present invention is to provide a kind of preparation methods of polysubstituted naphthalene derivatives, and preparation method is mild, letter
It is single, efficient.
Specific technical solution of the present invention is as follows:
A kind of polysubstituted naphthalene derivatives, structural formula are as follows:
Wherein, E CO2R；R is straight chained alkyl, branched alkyl or the unsaturated hydrocarbons within six carbon；
R1For straight chained alkyl, branched alkyl, ester group or the alkoxy or halogen within six carbon；
R2For the straight chained alkyl or branched alkyl or halogen within six carbon.
Further, the R is preferably isopropyl；R1Preferably methyl or chlorine；R2Preferably methyl or chlorine.
Further, the structural formula of the polysubstituted naphthalene derivatives are as follows:
The present invention also provides the preparation methods of the polysubstituted naphthalene derivatives, and the preparation method comprises the following steps:
Four acetylene compounds are reacted with the phenylacetylene replaced in toluene with contraposition, separates, purify after reaction, take can be obtained more
For naphthalene derivatives.
Further, the four acetylene compounds structural formulaR is six carbon
Within straight chained alkyl, branched alkyl or unsaturated hydrocarbons, preferably isopropyl；R1For straight chained alkyl, the branch within six carbon
Alkyl, ester group or alkoxy or halogen, preferably methyl or chlorine.
The structural formula of phenylacetylene that the contraposition replaces isWherein R2For the straight chain within six carbon
Alkyl or branched alkyl or halogen, preferably methyl or chlorine.
The reaction refers to 12~14h of reaction under conditions of 100-110 DEG C.
The ratio between the amount of substance of phenylacetylene that four acetylene compound, contraposition replace is 1:2.0-2.2；Four acetylenic
Compound is 0.2~0.3mol/L relative to the concentration of toluene.
The method of the separation, purifying are as follows: by reaction solution extraction and separation, collect organic phase and be concentrated, acetic acid is then added
Ethyl ester is just dissolved to concentrate, and petroleum ether is then added and is crystallized, filters, white can be obtained with petroleum ether filter residue
Powdered product.
The ratio between volume of the ethyl acetate and petroleum ether is 1:20~25；The time of the crystallization is 10~14h.
The extraction and separation are to be extracted using water and ethyl acetate to reaction solution.
The present invention is using four acetylene compounds and phenylacetylene as raw material, in toluene solvant, 100~110 DEG C of reactions 12~
14h, under heating conditions, four alkynes itself occur HDDA and react to form benzyne intermediate, and then benzyne intermediate takes with contraposition
The phenylacetylene in generation occurs nucleophilic addition and forms polysubstituted naphthalene derivatives, and mechanism figure is as shown in Figure 10.
Compared with prior art, the present invention provides a kind of preparation methods of completely new polysubstituted naphthalene, generate a series of new
Polysubstituted naphthalene derivatives.The polysubstituted naphthalene derivatives of synthesis have compared with high atom economy, and the more complicated multiplicity of structure has
Certain utilization prospect.
Detailed description of the invention
Fig. 1 is the general structure of polysubstituted naphthalene derivatives；
Fig. 2 is the structural formula of polysubstituted naphthalene derivatives prepared by embodiment 1；
Fig. 3 is the structural formula of polysubstituted naphthalene derivatives prepared by embodiment 2；
Fig. 4 is the nuclear magnetic resonance spectroscopy of polysubstituted naphthalene derivatives prepared by embodiment 1；
Fig. 5 is the carbon-13 nmr spectra of polysubstituted naphthalene derivatives prepared by embodiment 1；
Fig. 6 is the nuclear magnetic resonance spectroscopy of polysubstituted naphthalene derivatives prepared by embodiment 2；
Fig. 7 is the carbon-13 nmr spectra of polysubstituted naphthalene derivatives prepared by embodiment 2；
Fig. 8 is 1 preparation process equation of embodiment；
Fig. 9 is 2 preparation process equation of embodiment；
Figure 10 is the reaction mechanism figure of polysubstituted naphthalene derivatives；
Specific embodiment
Below with reference to embodiment and Figure of description, the present invention is described in detail.
Embodiment 1
A kind of polysubstituted naphthalene derivatives, structural formula are as follows:
The preparation methods of the polysubstituted naphthalene derivatives the following steps are included:
1) using 830mmol sodium hydride as alkali, 200mmol Diisopropyl malonate and 440mmol propargyl bromide are added to
It in 210mL anhydrous acetonitrile, is stirred to react under ice-water bath 8.5 hours, product adds water washing, is extracted with ethyl acetate, decompression rotation
Dry, using volume ratio as ethyl acetate: petroleum ether=1:80 is that eluant, eluent carries out column chromatography, after drying is concentrated under reduced pressure, obtains white
Solid product, i.e. compound 1；
2) by 80mmol compound 1 with 200mmol to methylbenzene acetylenebromide mixing Pd (PPh3)2Cl2/CuI
In the anhydrous and oxygen-free catalyst system of (2.56mmol/0.85mmol), molar ratio Pd (PPh3)2Cl2: CuI=3:1, with 336mmol
Triethylamine makees alkali, using 150mL anhydrous acetonitrile as solvent, is stirred to react at room temperature 11 hours, product is washed with water, and uses ethyl acetate
Extraction, decompression is spin-dried for, using volume ratio as ethyl acetate: petroleum ether=1:80 is that eluant, eluent carries out column chromatography, and drying is concentrated under reduced pressure
Afterwards, faint yellow solid product, i.e. compound 2 are obtained.
3) under conditions of 110 DEG C, 2mmol compound 2 prepared by step 2) is in 10mL toluene with 4.2mmol to chlorine
Phenylacetylene reacts 12 hours, and reaction solution water and ethyl acetate extraction collect organic phase, and removing organic solvent is concentrated under reduced pressure,
Then ethyl acetate is added just to dissolve to concentrate, the petroleum ether that two decaploids product is added later carries out standing still for crystals 12h, takes out
Filter, the product Compound 3 of white powder, as polysubstituted naphthalene derivatives, yield can be obtained with petroleum ether filter residue
It is 81.1%.
Products therefrom white powder product structure passes through1H NMR、13C NMR is measured, as a result as follows:
1H NMR (500MHz, CDCl3) δ 7.44 (d, J=8.3Hz, 2H), 7.37 (d, J=8.4Hz, 2H), 7.29 (d, J
=7.3Hz, 1H), 7.16 (d, J=7.2Hz, 1H), 7.04 (s, 4H), 6.91-6.78 (m, 8H), 5.03-4.96 (m, 2H),
3.79 (s, 2H), 3.06 (s, 2H), 2.30 (s, 3H), 2.27 (s, 3H), 1.19 (dd, J=11.8,6.2Hz, 12H).
13C NMR (126MHz, CDCl3) δ 171.53,143.25,142.80,142.25,141.02,140.28,
138.69,138.61,138.16,136.47,134.91,133.93,131.95,131.74,131.69,131.57,130.37,
129.54,129.30,128.59,128.27,127.99,127.37,120.88,120.72,97.80,87.72,59.37,
44.40,40.99,21.87,21.50,1.42ppm.
Embodiment 2
A kind of polysubstituted naphthalene derivatives, structural formula are as follows:
The preparation method of the polysubstituted naphthalene, comprising the following steps:
1) using 830mmol sodium hydride as alkali, 200mmol Diisopropyl malonate and 440mmol propargyl bromide are added to
It in 210mL anhydrous acetonitrile, is stirred to react under ice-water bath 8.5 hours, product adds water washing, is extracted with ethyl acetate, decompression rotation
Dry, using volume ratio as ethyl acetate: petroleum ether=1:80 is that eluant, eluent carries out column chromatography, after drying is concentrated under reduced pressure, obtains white
Solid product, i.e. compound 1；
2) by 80mmol compound 1 with 200mmol to chlorobenzene acetylenebromide mixing Pd (PPh3)2Cl2/CuI(2.56mmol/
In anhydrous and oxygen-free catalyst system 0.85mmol), molar ratio Pd (PPh3)2Cl2: CuI=3:1 makees alkali with 336mmol triethylamine,
It using 150mL anhydrous acetonitrile as solvent, is stirred to react at room temperature 11 hours, product is washed with water, and is extracted with ethyl acetate, decompression rotation
Dry, using volume ratio as ethyl acetate: petroleum ether=1:80 is that eluant, eluent carries out column chromatography, after drying is concentrated under reduced pressure, is obtained yellowish
Color solid product, i.e. compound 4.
3) under conditions of 110 DEG C, 2mmol compound 4 prepared by step 2) is in 10mL toluene with 4.2mmol to first
Base phenylacetylene reacts 12 hours, and reaction solution water and ethyl acetate extraction collect organic phase, and it is organic molten that removing is concentrated under reduced pressure
Then agent is added ethyl acetate and just dissolves to concentrate, the petroleum ether that two decaploids product is added later is stood still for crystals
12h is filtered, can be obtained the product Compound 5 of white powder with petroleum ether filter residue, as polysubstituted naphthalene derivatives,
Yield is 82.3%.
White powder product structure passes through1H NMR、13C NMR is measured.As a result as follows:
1H NMR (400MHz, CDCl3) δ 7.34 (dd, J=13.6,7.7Hz, 3H), 7.28 (d, J=4.9Hz, 2H),
7.26-7.23 (m, 3H), 7.05 (d, J=8.6Hz, 2H), 6.93 (q, J=8.7Hz, 4H), 6.80 (q, J=8.0Hz, 4H),
5.02 (m, 2H), 3.78 (s, 2H), 3.11 (s, 2H), 2.48 (s, 3H), 2.30 (s, 3H), 1.20 (dd, J=13.7,6.2Hz,
12H)。
13C NMR (126MHz, CDCl3) δ 171.56,142.42,141.59,141.29,140.79,140.45,
139.48,139.25,137.40,136.06,135.99,134.55,133.31,132.87,132.32,131.88,130.83,
130.36,130.30,129.88,129.16,128.97,128.76,128.26,127.13,122.13,119.89,117.50,
96.32,89.22,69.26,59.34,44.20,40.90,21.87,21.85,21.65,21.38,1.41ppm.
The above-mentioned detailed description carried out referring to embodiment to a kind of polysubstituted naphthalene derivatives and preparation method thereof, is illustrative
Without being restrictive, several embodiments can be enumerated according to limited range, therefore do not departing from overall structure of the invention
Change and modification under thinking, should belong within protection scope of the present invention.
Claims (10)
1. a kind of polysubstituted naphthalene derivatives, which is characterized in that the structural formula of the polysubstituted naphthalene derivatives are as follows:
Wherein, E CO2R；R is straight chained alkyl, branched alkyl or the unsaturated hydrocarbons within six carbon；R1It is straight within six carbon
Alkyl group, branched alkyl, ester group or alkoxy or halogen；R2For the straight chained alkyl or branched alkyl or halogen within six carbon
Element.
2. polysubstituted naphthalene derivatives according to claim 1, which is characterized in that the R is isopropyl；R1For methyl or chlorine；
R2For methyl or chlorine.
3. polysubstituted naphthalene derivatives according to claim 1, which is characterized in that the structural formula of the polysubstituted naphthalene derivatives
Are as follows:
4. the preparation method of polysubstituted naphthalene derivatives as claimed in any one of claims 1-3, which is characterized in that the preparation
Method the following steps are included: by four acetylene compounds in toluene with contraposition replace phenylacetylene react, after reaction separate,
Purifying, can be obtained polysubstituted naphthalene derivatives.
5. the preparation method according to claim 4, which is characterized in that the four acetylene compounds structural formulaR is straight chained alkyl, branched alkyl or the unsaturated hydrocarbons within six carbon；R1For
Straight chained alkyl, branched alkyl, ester group or alkoxy or halogen within six carbon.
6. the preparation method according to claim 4, which is characterized in that the structural formula of phenylacetylene that the contraposition replaces isWherein R2For the straight chained alkyl or branched alkyl or halogen within six carbon.
7. the preparation method according to claim 4, which is characterized in that the reaction refers under conditions of 100~110 DEG C
React 12~14h.
8. the preparation method according to claim 4, which is characterized in that the benzene second that four acetylene compound, contraposition replace
The ratio between amount of substance of alkynes is 1:2.0~2.2；Four acetylene compound is 0.2~0.3mol/L relative to the concentration of toluene.
9. the preparation method according to claim 4, which is characterized in that the separation, the method purified are as follows: extract reaction solution
Separation is taken, organic phase is collected and is concentrated, ethyl acetate is then added and is just dissolved to concentrate, petroleum ether is then added and is tied
Crystalline substance is filtered, the product of white powder can be obtained with petroleum ether filter residue.
10. preparation method according to claim 9, which is characterized in that the ratio between the ethyl acetate and the volume of petroleum ether
For 1:20~25；The time of the crystallization is 10~14h.
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| CN114874252A (en) * | 2022-06-06 | 2022-08-09 | 安徽师范大学 | Silomethylnaphthalene derivative and preparation method and application thereof |
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| XIAO XIAO等: "Benzocyclobutadienes: An unusual mode of access reveals unusual modes of reactivity", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
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| CN114874252A (en) * | 2022-06-06 | 2022-08-09 | 安徽师范大学 | Silomethylnaphthalene derivative and preparation method and application thereof |
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