CN110028409B - Polysubstituted naphthalene derivative and preparation method thereof - Google Patents
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- 150000002790 naphthalenes Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims abstract description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 239000003208 petroleum Substances 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- MWLDFOCAVDOKBW-UHFFFAOYSA-N 1-(2-bromoethynyl)-4-chlorobenzene Chemical compound ClC1=CC=C(C#CBr)C=C1 MWLDFOCAVDOKBW-UHFFFAOYSA-N 0.000 description 1
- XINBRILTVYGCQV-UHFFFAOYSA-N 1-(2-bromoethynyl)-4-methylbenzene Chemical compound CC1=CC=C(C#CBr)C=C1 XINBRILTVYGCQV-UHFFFAOYSA-N 0.000 description 1
- LFZJRTMTKGYJRS-UHFFFAOYSA-N 1-chloro-4-ethynylbenzene Chemical group ClC1=CC=C(C#C)C=C1 LFZJRTMTKGYJRS-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical group CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
- C07C2603/14—Benz[f]indenes; Hydrogenated benz[f]indenes
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a polysubstituted naphthalene derivative and a preparation method thereof, wherein a tetraalkyne compound and phenylacetylene are used as raw materials, the raw materials are reacted in a toluene solvent at 100-110 ℃ for 12-14 h, and after the reaction is finished, the reaction product is separated and purified to obtain the polysubstituted naphthalene derivative. Compared with the prior art, the invention provides a brand-new preparation method of the polysubstituted naphthalene, and a series of novel polysubstituted naphthalene derivatives are generated. The synthesized polysubstituted naphthalene derivative has higher atom economy, more complex and diversified structure and certain application prospect.
Description
Technical Field
The invention relates to the technical field of organic compound synthesis, in particular to a polysubstituted naphthalene derivative and a preparation method thereof.
Background
Naphthalene is the most important fused cyclic hydrocarbon in industry, is mainly used for producing phthalic anhydride, various naphthols, naphthylamine and the like, and is a raw material for producing synthetic resin, plasticizers, intermediates of dyes, surfactants, synthetic fibers, coatings, pesticides, medicines, perfumes, rubber auxiliaries and insecticides. Meanwhile, naphthalene is also used for manufacturing dye intermediates, camphor balls, leather, wood protective agents and the like. Naphthalene is used as a raw material, and various intermediates can be prepared by unit operations such as sulfonation, nitration, reduction, amination and hydrolysis. The application of naphthalene is also widened, and a novel product, namely a superplastic material, namely a naphthalene sulfonate formaldehyde condensate can be used as a cement additive to increase the plastic deformation of concrete without reducing the strength of the concrete. The demand for naphthalene will grow at a rate of 5-10% over the next few years.
Disclosure of Invention
The invention aims to provide a polysubstituted naphthalene derivative which has a more complex and diversified structure and a wide application prospect.
The invention also aims to provide a preparation method of the polysubstituted naphthalene derivative, which is mild, simple and efficient.
The specific technical scheme of the invention is as follows:
a polysubstituted naphthalene derivative has a structural formula as follows:
wherein E isCO2R; r is linear alkyl, branched alkyl or unsaturated hydrocarbon within six carbons;
R1is a straight chain alkyl, branched alkyl, ester group or alkoxy within six carbons, or halogen;
R2is straight-chain alkyl or branched-chain alkyl within six carbons, or halogen.
Further, R is preferably isopropyl; r1Preferably methyl or chlorine; r2Preferably methyl or chlorine.
Further, the structural formula of the polysubstituted naphthalene derivative is as follows:
the invention also provides a preparation method of the polysubstituted naphthalene derivative, which comprises the following steps: the tetrayne compounds and toluene react with para-substituted phenylacetylene, and the polysubstituted naphthalene derivatives can be obtained after the reaction is finished and separation and purification are carried out.
Further, the tetrayne compound has a structural formula
R is a linear alkyl, branched alkyl or unsaturated hydrocarbon within six carbons, preferably isopropyl; r1Is a straight chain alkyl, branched alkyl, ester or alkoxy within six carbons or a halogen, preferably methyl or chlorine.
The structural formula of the para-substituted phenylacetylene is shown in the specification
Wherein R is2Is a straight chain or branched alkyl group within six carbons, or a halogen, preferably methyl or chlorine.
The reaction is carried out for 12-14 h under the condition of 100-110 ℃.
The mass ratio of the tetrayne compound to the para-substituted phenylacetylene is 1: 2.0-2.2; the concentration of the tetrayne compounds relative to toluene is 0.2-0.3 mol/L.
The separation and purification method comprises the following steps: and (3) extracting and separating the reaction liquid, collecting an organic phase, concentrating, adding ethyl acetate until the concentrate is just dissolved, adding petroleum ether for crystallization, performing suction filtration, and washing filter residues with the petroleum ether to obtain a white powdery product.
The volume ratio of the ethyl acetate to the petroleum ether is 1: 20-25; the crystallization time is 10-14 h.
The extraction separation is to extract the reaction liquid by using water and ethyl acetate.
The method comprises the steps of taking a tetraalkyne compound and phenylacetylene as raw materials, reacting for 12-14 h at 100-110 ℃ in a toluene solvent, carrying out HDDA reaction on the tetraalkyne in a heating condition to form a phenylacetylene intermediate, and carrying out nucleophilic addition reaction on the phenylacetylene intermediate and para-substituted phenylacetylene to form the polysubstituted naphthalene derivative, wherein a mechanism diagram of the polysubstituted naphthalene derivative is shown in figure 10.
Compared with the prior art, the invention provides a brand-new preparation method of the polysubstituted naphthalene, and a series of novel polysubstituted naphthalene derivatives are generated. The synthesized polysubstituted naphthalene derivative has higher atom economy, more complex and diversified structure and certain application prospect.
Drawings
FIG. 1 is a general structural formula of a polysubstituted naphthalene derivative;
FIG. 2 is a structural formula of a polysubstituted naphthalene derivative prepared in example 1;
FIG. 3 is a structural formula of a polysubstituted naphthalene derivative prepared in example 2;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of a polysubstituted naphthalene derivative prepared in example 1;
FIG. 5 is a nuclear magnetic resonance carbon spectrum of a polysubstituted naphthalene derivative prepared in example 1;
FIG. 6 is a nuclear magnetic resonance hydrogen spectrum of a polysubstituted naphthalene derivative prepared in example 2;
FIG. 7 is a nuclear magnetic resonance carbon spectrum of a polysubstituted naphthalene derivative prepared in example 2;
FIG. 8 is the equation for the preparation of example 1;
FIG. 9 is the equation for the preparation process of example 2;
FIG. 10 is a reaction mechanism diagram of a polysubstituted naphthalene derivative;
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
A polysubstituted naphthalene derivative has a structural formula as follows:
the preparation method of the polysubstituted naphthalene derivative comprises the following steps:
1) adding 200mmol of diisopropyl malonate and 440mmol of propargyl bromide into 210mL of anhydrous acetonitrile by using 830mmol of sodium hydride as a base, stirring and reacting for 8.5 hours in an ice-water bath, adding water to wash a product, extracting with ethyl acetate, and performing rotary drying under reduced pressure to obtain the product, wherein the volume ratio of the product to the ethyl acetate: performing column chromatography by using petroleum ether as an eluent at a ratio of 1:80, and concentrating and drying under reduced pressure to obtain a white solid product, namely the compound 1;
2) 80mmol of Compound 1 was mixed with 200mmol of p-methylphenylethynyl bromide in Pd (PPh)3)2Cl2In the anhydrous oxygen-free catalytic system of CuI (2.56mmol/0.85mmol), the mole ratio of Pd (PPh)3)2Cl2CuI 3:1, using 336mmol triethylamine as base, using 150mL anhydrous acetonitrile as solvent, stirring reaction at room temperature for 11 hours, washing product with water, extracting with ethyl acetate, decompressing and spin-drying, using ethyl acetate: and (3) performing column chromatography by using petroleum ether as an eluent, and concentrating and drying under reduced pressure to obtain a light yellow solid product, namely the compound 2.
3) Reacting 2mmol of the compound 2 prepared in the step 2) with 4.2mmol of p-chlorophenyl acetylene in 10mL of toluene at 110 ℃ for 12 hours, extracting the reaction liquid by using water and ethyl acetate, collecting an organic phase, decompressing and concentrating to remove an organic solvent, then adding ethyl acetate until the concentrate is just dissolved, then adding twenty times of petroleum ether in volume, standing and crystallizing for 12 hours, performing suction filtration, and washing filter residues by using the petroleum ether to obtain a white powdery product compound 3, namely the polysubstituted naphthalene derivative, wherein the yield is 81.1%.
The obtained product is white powder and has a product structure1H NMR、13C NMR, as follows:
1H NMR(500MHz，CDCl3)δ7.44(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)δ171.53，143.25，142.80，142.25，141.02，140.28，138.69，138.61，138.16，136.47，134.91，133.93，131.95，131.74，131.69，131.57，130.37，129.54，129.30，128.59，128.27，127.99，127.37，120.88，120.72，97.80，87.72，59.37，44.40，40.99，21.87，21.50，1.42ppm。
example 2
A polysubstituted naphthalene derivative has a structural formula as follows:
the preparation method of the polysubstituted naphthalene comprises the following steps:
1) adding 200mmol of diisopropyl malonate and 440mmol of propargyl bromide into 210mL of anhydrous acetonitrile by using 830mmol of sodium hydride as a base, stirring and reacting for 8.5 hours in an ice-water bath, adding water to wash a product, extracting with ethyl acetate, and performing rotary drying under reduced pressure to obtain the product, wherein the volume ratio of the product to the ethyl acetate: performing column chromatography by using petroleum ether as an eluent at a ratio of 1:80, and concentrating and drying under reduced pressure to obtain a white solid product, namely the compound 1;
2) 80mmol of the compound 1 is mixed with 200mmol of p-chlorophenyl ethynyl bromide in Pd (PPh)3)2Cl2In the anhydrous oxygen-free catalytic system of CuI (2.56mmol/0.85mmol), the mole ratio of Pd (PPh)3)2Cl2:CAnd uI ═ 3:1, 336mmol of triethylamine as a base, 150mL of anhydrous acetonitrile as a solvent, stirring and reacting at room temperature for 11 hours, washing the product with water, extracting with ethyl acetate, and spin-drying under reduced pressure to obtain a reaction product, wherein the volume ratio of ethyl acetate: and (3) performing column chromatography by using petroleum ether as an eluent, and concentrating and drying under reduced pressure to obtain a light yellow solid product, namely the compound 4.
3) Under the condition of 110 ℃, 2mmol of the compound 4 prepared in the step 2) reacts with 4.2mmol of p-methylphenylacetylene in 10mL of toluene for 12 hours, the reaction liquid is extracted by water and ethyl acetate, an organic phase is collected and decompressed and concentrated to remove an organic solvent, then ethyl acetate is added until a concentrate is just dissolved, then twenty times of petroleum ether in volume is added for standing and crystallization for 12 hours, suction filtration is carried out, and filter residue is washed by the petroleum ether to obtain a white powdery product compound 5, namely the polysubstituted naphthalene derivative, wherein the yield is 82.3%.
White powder product structure by1H NMR、13C NMR. The results are as follows:
1H NMR(400MHz，CDCl3)δ7.34(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)δ171.56，142.42，141.59，141.29，140.79，140.45，139.48，139.25，137.40，136.06，135.99，134.55，133.31，132.87，132.32，131.88，130.83，130.36，130.30，129.88，129.16，128.97，128.76，128.26，127.13，122.13，119.89，117.50，96.32，89.22，69.26，59.34，44.20，40.90，21.87，21.85，21.65，21.38，1.41ppm。
the above detailed description of a polysubstituted naphthalene derivative and its preparation process with reference to the examples is illustrative and not restrictive, and several examples are to be construed as limiting the scope thereof, and therefore all changes and modifications that come within the spirit of the invention are desired to be protected.
Claims (6)
1. A preparation method of polysubstituted naphthalene derivative is characterized in that the structural formula of the polysubstituted naphthalene derivative is as follows:
wherein E is CO2R; r is linear alkyl, branched alkyl or unsaturated hydrocarbon within six carbons; r1Is a straight chain alkyl, branched alkyl, ester group or alkoxy within six carbons, or halogen; r2Is a straight chain alkyl or branched alkyl within six carbons, or halogen;
the preparation method of the polysubstituted naphthalene derivative comprises the following steps: reacting a tetraalkynes compound with para-substituted phenylacetylene in toluene at 100-110 ℃ for 12-14 h, and separating and purifying after the reaction is finished to obtain a polysubstituted naphthalene derivative;
the mass ratio of the tetrayne compound to the para-substituted phenylacetylene is 1: 2.0 to 2.2;
the structural formula of the tetrayne compound is shown as
The structural formula of the para-substituted phenylacetylene is shown in the specification
2. The method for producing a polysubstituted naphthalene derivative according to claim 1, wherein said R is isopropyl; r1Is methyl or chlorine; r2Is methyl or chlorine.
3. The method for preparing a polysubstituted naphthalene derivative according to claim 1, wherein the polysubstituted naphthalene derivative has the structural formula:
4. the method according to claim 1, wherein the concentration of the tetraalkynes compound relative to toluene is 0.2 to 0.3 mol/L.
5. The preparation method according to claim 1, wherein the separation and purification method comprises: and (3) extracting and separating the reaction liquid, collecting an organic phase, concentrating, adding ethyl acetate until the concentrate is just dissolved, adding petroleum ether for crystallization, performing suction filtration, and washing filter residues with the petroleum ether to obtain a white powdery product.
6. The method according to claim 5, wherein the volume ratio of ethyl acetate to petroleum ether is 1: 20-25; the crystallization time is 10-14 h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910295100.4A CN110028409B (en) | 2019-04-12 | 2019-04-12 | Polysubstituted naphthalene derivative and preparation method thereof |
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