CN110028409A - A kind of polysubstituted naphthalene derivatives and preparation method thereof - Google Patents

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

A kind of polysubstituted naphthalene derivative and preparation method thereof

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 technique

Naphthalene is the most important fused-ring hydrocarbon in industry. It is mainly used in the production of phthalic anhydride, various naphthols, naphthylamines, etc. It is an intermediate in the production of synthetic resins, plasticizers, dyes, surfactants, synthetic fibers, coatings, pesticides, etc. , raw materials for medicine, fragrance, rubber auxiliaries and pesticides. At the same time, naphthalene is also used in the manufacture of dye intermediates, mothballs, leather and wood protection agents. Using naphthalene as raw material, through sulfonation, nitration, reduction, amination, hydrolysis and other unit operations, a variety of intermediates can be prepared. The application of naphthalene is still expanding. The new product "super plastic material", naphthalene sulfonate formaldehyde condensate, can be used as a cement additive to increase the plastic deformation of concrete without reducing its strength. The demand for naphthalene will grow at a rate of 5-10% in the next few years.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a kind of polysubstituted naphthalene derivatives, the structure is more complex and diverse, and has broad application prospects.

Another object of the present invention is to provide a preparation method of polysubstituted naphthalene derivatives, which is mild, simple and efficient.

The specific technical scheme of the present invention is as follows:

A kind of polysubstituted naphthalene derivative, its structural formula is:

Wherein, E is CO ₂ R; R is a straight-chain alkyl group, branched-chain alkyl group or unsaturated hydrocarbon within six carbons;

R ₁ is a straight-chain alkyl group, branched-chain alkyl group, ester group or alkoxy group, or halogen within six carbons;

R ₂ is a straight-chain or branched-chain alkyl group within six carbons, or a halogen.

Further, the R is preferably isopropyl; R ₁ is preferably methyl or chlorine; R ₂ is preferably methyl or chlorine.

Further, the structural formula of the polysubstituted naphthalene derivative is:

The present invention also provides a preparation method of the polysubstituted naphthalene derivatives, the preparation method includes the following steps: reacting tetrayne compounds with toluene with para-substituted phenylacetylene, and separating and purifying after the reaction is completed, and then A polysubstituted naphthalene derivative is obtained.

Further, the tetrayne compound structural formula R is a straight-chain alkyl, branched-chain alkyl or unsaturated hydrocarbon within six carbons, preferably isopropyl; R ₁ is a straight-chain alkyl, branched alkyl, ester or alkoxy within six carbons group or halogen, preferably methyl or chlorine.

The structural formula of the para-substituted phenylacetylene is wherein R ₂ is a straight-chain or branched-chain alkyl group within six carbons, or halogen, preferably methyl or chlorine.

The reaction refers to the reaction at 100-110° C. for 12-14 hours.

The ratio of the amount of the tetrayne compound to the para-substituted phenylacetylene is 1:2.0-2.2; the concentration of the tetrayne compound relative to toluene is 0.2-0.3 mol/L.

The method of separation and purification is as follows: extracting and separating the reaction solution, collecting the organic phase and concentrating, then adding ethyl acetate until the concentrate is just dissolved, then adding petroleum ether for crystallization, suction filtration, and washing the filter residue with petroleum ether to obtain White powdery product.

The volume ratio of the ethyl acetate to the petroleum ether is 1:20-25; the crystallization time is 10-14 hours.

The extraction separation is to use water and ethyl acetate to extract the reaction solution.

The present invention uses tetrayne compounds and phenylacetylene as raw materials, reacts in toluene solvent at 100-110 DEG C for 12-14 hours, and under heating conditions, tetrayne itself undergoes HDDA reaction to form benzyne intermediate, and then benzyne intermediate Nucleophilic addition reaction with para-substituted phenylacetylene to form polysubstituted naphthalene derivatives, the mechanism diagram of which is shown in Figure 10.

Compared with the prior art, the present invention provides a brand-new preparation method of multi-substituted naphthalene, and generates a series of new multi-substituted naphthalene derivatives. The synthesized polysubstituted naphthalene derivatives have higher atom economy, more complex and diverse structures, and have certain application prospects.

Description of drawings

Fig. 1 is the general structural formula of polysubstituted naphthalene derivatives;

Fig. 2 is the structural formula of the polysubstituted naphthalene derivative prepared by embodiment 1;

Fig. 3 is the structural formula of the polysubstituted naphthalene derivative prepared by embodiment 2;

Fig. 4 is the hydrogen nuclear magnetic resonance spectrum of the polysubstituted naphthalene derivative prepared in Example 1;

Fig. 5 is the carbon nuclear magnetic resonance spectrum of the polysubstituted naphthalene derivatives prepared in Example 1;

Fig. 6 is the hydrogen nuclear magnetic resonance spectrum of the polysubstituted naphthalene derivative prepared in Example 2;

Fig. 7 is the carbon nuclear magnetic resonance spectrum of the polysubstituted naphthalene derivative prepared in Example 2;

Fig. 8 is the preparation process equation of embodiment 1;

Fig. 9 is the preparation process equation of embodiment 2;

Fig. 10 is the reaction mechanism diagram of polysubstituted naphthalene derivatives;

Detailed ways

The present invention will be described in detail below with reference to the embodiments and accompanying drawings.

Example 1

A kind of polysubstituted naphthalene derivative, its structural formula is:

The preparation method of the polysubstituted naphthalene derivatives comprises the following steps:

1) Using 830 mmol of sodium hydride as a base, 200 mmol of diisopropyl malonate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile, and the reaction was stirred under an ice-water bath for 8.5 hours. The product was washed with water and extracted with ethyl acetate. , spin-dried under reduced pressure, carry out column chromatography with the volume ratio of ethyl acetate: petroleum ether=1:80 as the eluent, and concentrated and dried under reduced pressure to obtain a white solid product, namely compound 1;

2) In an anhydrous and oxygen-free catalytic system in which 80 mmol of compound 1 and 200 mmol of p-methylphenylethynyl bromide were mixed with Pd(PPh ₃ ) ₂ Cl ₂ /CuI (2.56 mmol/0.85 mmol), the molar ratio was Pd(PPh ₃ ) ₂ Cl ₂ :CuI=3:1, using 336 mmol triethylamine as a base, using 150 mL anhydrous acetonitrile as a solvent, the reaction was stirred at room temperature for 11 hours, the product was washed with water, extracted with ethyl acetate, and spin-dried under reduced pressure. ethyl acetate:petroleum ether=1:80 as eluent for column chromatography, after concentration and drying under reduced pressure, a pale yellow solid product, namely compound 2, was obtained.

3) Under the condition of 110 ° C, 2 mmol of compound 2 prepared in step 2) was reacted with 4.2 mmol of p-chlorophenylacetylene in 10 mL of toluene for 12 hours, the reaction solution was extracted with water and ethyl acetate, the organic phase was collected, and concentrated under reduced pressure Remove the organic solvent, then add ethyl acetate until the concentrate just dissolves, then add 20 times the volume of petroleum ether for standing crystallization for 12 hours, suction filtration, and wash the filter residue with petroleum ether to obtain a white powdery product compound 3, namely It is a polysubstituted naphthalene derivative with a yield of 81.1%.

The product structure of the obtained product white powder was determined by ¹ H NMR and ¹³ C NMR, and the results were as follows:

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.44 (d, J=8.3 Hz, 2H), 7.37 (d, J=8.4 Hz, 2H), 7.29 (d, J=7.3 Hz, 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, 6.2 Hz, 12H).

¹³ C NMR(126MHz，CDCl ₃ )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 kind of polysubstituted naphthalene derivative, its structural formula is:

The preparation method of described polysubstituted naphthalene, comprises the following steps:

1) Using 830 mmol of sodium hydride as a base, 200 mmol of diisopropyl malonate and 440 mmol of propargyl bromide were added to 210 mL of anhydrous acetonitrile, and the reaction was stirred under an ice-water bath for 8.5 hours. The product was washed with water and extracted with ethyl acetate. , spin-dried under reduced pressure, carry out column chromatography with the volume ratio of ethyl acetate: petroleum ether=1:80 as the eluent, and concentrated and dried under reduced pressure to obtain a white solid product, namely compound 1;

2) 80mmol of compound 1 and 200mmol of p-chlorophenylethynyl bromide were mixed in an anhydrous and oxygen-free catalytic system of Pd(PPh ₃ ) ₂ Cl ₂ /CuI (2.56 mmol/0.85 mmol), the molar ratio Pd(PPh ₃ ) ₂ Cl ₂ : CuI=3:1, with 336 mmol triethylamine as the base, with 150 mL of anhydrous acetonitrile as the solvent, the reaction was stirred at room temperature for 11 hours, the product was washed with water, extracted with ethyl acetate, and spin-dried under reduced pressure. Ethyl acetate:petroleum ether=1:80 was used as the eluent to carry out column chromatography, and after concentration and drying under reduced pressure, a pale yellow solid product, namely compound 4, was obtained.

3) Under the condition of 110 ° C, 2 mmol of compound 4 prepared in step 2) was reacted with 4.2 mmol of p-methylphenylacetylene in 10 mL of toluene for 12 hours, the reaction solution was extracted with water and ethyl acetate, the organic phase was collected, and reduced pressure Concentrate to remove the organic solvent, then add ethyl acetate until the concentrate just dissolves, then add 20 times the volume of petroleum ether for standing crystallization for 12 hours, suction filtration, and wash the filter residue with petroleum ether to obtain a white powdery product compound 5, That is, it is a polysubstituted naphthalene derivative, and the yield is 82.3%.

The white powder product structure was determined by ¹ H NMR, ¹³ C NMR. The result is as follows:

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.34 (dd, J=13.6, 7.7 Hz, 3H), 7.28 (d, J=4.9 Hz, 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, 6.2 Hz, 12H).

¹³ C NMR(126MHz，CDCl ₃ )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-mentioned detailed description of a polysubstituted naphthalene derivative and its preparation method with reference to the examples is illustrative rather than restrictive, and several examples can be listed according to the limited scope, so it is not departing from the generality of the present invention. Changes and modifications under the concept should fall within the protection scope of the present invention.

Claims (10)

1. a multi-substituted naphthalene derivative, is characterized in that, the structural formula of described multi-substituted naphthalene derivative is: Wherein, E is CO ₂ R; R is a straight-chain alkyl, branched-chain alkyl or unsaturated hydrocarbon within six carbons; R ₁ is a straight-chain alkyl, branched alkyl, ester group or within six carbons Alkoxy, or halogen; R ₂ is a straight-chain or branched-chain alkyl group within six carbons, or halogen. 2 . The polysubstituted naphthalene derivative according to claim 1 , wherein the R is isopropyl; R ₁ is methyl or chlorine; R ₂ is methyl or chlorine. 3 . 3. The multi-substituted naphthalene derivative according to claim 1, wherein the structural formula of the multi-substituted naphthalene derivative is: 4. the preparation method of the polysubstituted naphthalene derivative as described in any one of claim 1-3, it is characterised in that the preparation method comprises the following steps: the tetrayne compound is in toluene with para-substituted phenylacetylene After the reaction is completed, separation and purification can be performed to obtain the polysubstituted naphthalene derivative. 5. preparation method according to claim 4, is characterized in that, described tetrayne compound structural formula R is a straight-chain alkyl group within six carbons, a branched-chain alkyl group or an unsaturated hydrocarbon; R ₁ is a straight-chain alkyl group within six carbons, a branched-chain alkyl group, an ester group or an alkoxy group, or a halogen. 6. preparation method according to claim 4 is characterized in that, the structural formula of the phenylacetylene of described para-position replacement is wherein R ₂ is a straight-chain or branched-chain alkyl group within six carbons, or a halogen. 7 . The preparation method according to claim 4 , wherein the reaction refers to a reaction at 100-110° C. for 12-14 hours. 8 . 8 . The preparation method according to claim 4 , wherein the ratio of the amount of the tetrayne compound to the para-substituted phenylacetylene is 1:2.0-2.2; the tetrayne compound is relative to the The concentration of toluene is 0.2 to 0.3 mol/L. 9. preparation method according to claim 4, is characterized in that, the method for described separation, purification is: reaction liquid is extracted and separated, collect organic phase and concentrate, then add ethyl acetate to concentrate just to dissolve, then add The petroleum ether is crystallized, filtered with suction, and the filter residue is washed with petroleum ether to obtain a white powdery product. 10 . The preparation method according to claim 9 , wherein the volume ratio of the ethyl acetate to the petroleum ether is 1:20-25; the crystallization time is 10-14 h. 11 .