Method for synthesizing beta-functionalized alpha-naphthol compound from beta-substituted alpha-tetralone

Abstract

The invention discloses a method for synthesizing a beta-functionalized alpha-naphthol compound from beta-substituted alpha-tetralone. The method comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; 2, performing alkali-oxygen reaction to prepare a mixture B; 3, extracting and separating to obtain a product; in the first step, the reaction solvent is one or more of methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butanol, isobutanol, tertiary butanol, acetonitrile, N, N-dimethylformamide, methylbenzene, tetrahydrofuran and 1, 4-dioxane; according to the method, beta-substituted alpha-tetralone is used as a reaction substrate, air or oxygen is used as an oxidizing agent, and the beta-functionalized alpha-naphthol compound is directly synthesized under the action of a solvent and alkali. The method has the advantages of simple synthesis route, simple operation, green and environment-friendly reaction process, mild reaction conditions, cheap and easily available reaction reagents, short synthesis period, easy product separation and high product yield.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemical synthesis, in particular to a method for synthesizing a beta-functionalized alpha-naphthol compound from beta-substituted alpha-tetralone. Background Art

[0002] α-Naphthol compounds are common structural units in natural products, bioactive molecules, and organic dyes. For example, the VATPase inhibitor Diphyllin, α-hydroxy-β-naphthoic acid methyl ester that inhibits macrophage inflammatory response, the anticoccidial drug butyquinate, and the dyes Acid Yellow 1 and Mordant Black 11 are all β-substituted α-naphthol derivatives. β-substituted α-naphthol derivatives have a wide range of applications in the fields of biomedicine and materials, so the synthesis of β-substituted α-naphthol derivatives is of great significance.

[0003] In the prior art, the methods for synthesizing β-substituted α-naphthol compounds are mainly the Friedel-Crafts reaction of α-naphthol and the Fries rearrangement reaction of α-naphthol derivatives, as well as CH activation / cyclization reaction involving alkynes, etc. However, these methods have the disadvantages of using strong Lewis acids, metal catalysts, strong oxidants, etc., resulting in high costs and environmental pollution. In addition, most of the methods proposed by some technologies are only applicable to the synthesis of a single type of α-naphthol derivatives at the β position. For example, using AIBX, a derivative of 2-iodoxybenzoic acid, as an oxidant, the dehydrogenation aromatization of β-ester-α-tetralone is achieved to obtain β-ester-α-naphthol. In this reaction, although β-ester-α-naphthol is synthesized, 1.5 times the amount of AIBX is required, and AIBX is currently unavailable for purchase and can only be prepared through a five-step reaction, resulting in a low efficiency of the method. Therefore, it is of great application value to study a green synthesis route that has a simple preparation process, does not require the use of catalysts and chemical oxidants, and can achieve many types of β-substituted α-naphthol derivatives. Summary of the invention

[0004] The object of the present invention is to provide a method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone, so as to solve the problems mentioned in the above background technology.

[0005] To achieve the above object, the present invention provides the following technical solution: a method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone, wherein the method for synthesizing a β-functionalized α-naphthol from a β-substituted α-tetralone is as follows:

[0006]

[0007] Specifically, the following steps are included: step 1, dissolving the substrate to prepare mixture A; step 2, alkaline oxygen reaction to prepare mixture B; step 3, extracting and separating to obtain the product;

[0008] Wherein in the above step 1, the β-substituted α-tetralone compound is dissolved in a reaction solvent to obtain a mixture A;

[0009] In the above step 2, the following steps are specifically included:

[0010] 2.1 Add a base to the mixture A obtained in step 1;

[0011] 2.2 adding an oxidant to the mixture A in step 2.1;

[0012] 2.3 The mixture A in step 2.2 is placed in a temperature range of -10°C to 80°C to react to obtain a mixture B;

[0013] In the above step 3, the following steps are specifically included:

[0014] 3.1 Add water to the mixture B obtained in step 2.3 to quench the reaction;

[0015] 3.2 Add ethyl acetate to the mixture B in step 3.1, and wash to obtain a mixture C;

[0016] 3.3 The mixture C obtained in step 3.2 is dried, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0017] 3.4 The mixture D obtained in step 3.3 is separated by column chromatography to obtain a β-functionalized α-naphthol compound.

[0018] Preferably, the R group in the α-tetralone and α-naphthol is selected from one of an ester group, an aldehyde group, a nitroso group, a nitro group, an acetyl group, a benzoyl group, a cinnamoyl group, a sulfonyl group, a phosphoryl group or a carboxylic acid and its derivatives.

[0019] Preferably, R 1 It is selected from one of alkoxy, alkyl, ester, cyano, aldehyde, acyl, halogen, substituted phenyl or aromatic heterocyclic group.

[0020] Preferably, the R 1 When selected from alkoxy, alkoxy includes methoxy, 1-20 carbon substituted straight chain alkoxy and 1-20 carbon substituted branched chain alkoxy; R 1 When selected from alkyl, the alkyl group includes a straight-chain aliphatic hydrocarbon group substituted with 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group substituted with 1 to 20 carbon atoms, a monohalogenated aliphatic hydrocarbon group and a polyhalogenated aliphatic hydrocarbon group; R 1 When selected from ester groups, the ester groups include methyl ester groups, multi-carbon substituted straight-chain ester groups and multi-carbon substituted branched-chain ester groups; R 1 When selected from halogen, including fluorine, chlorine and bromine: R1 When selected from substituted phenyl groups, the substituted phenyl groups are phenyl groups.

[0021] Preferably, in step 1, the reaction solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, acetonitrile, N,N-dimethylformamide, toluene, tetrahydrofuran, and 1,4-dioxane.

[0022] Preferably, in step 2.1, the base is one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride, potassium tert-butoxide, sodium methoxide, potassium methoxide, and lithium diisopropylamide.

[0023] Preferably, in step 2.1, the amount of the base used is 0.5 to 5 times the amount of the β-substituted α-tetralone compound.

[0024] Preferably, in step 2.2, the oxidant is one of air, pure oxygen, and a gas mixed with oxygen and air in any proportion.

[0025] Preferably, in step 3.2, the washing method is specifically: washing the organic phase three times with water and washing the organic phase once with a saturated sodium chloride aqueous solution.

[0026] Preferably, in step 3.3, anhydrous sodium sulfate is used for drying.

[0027] Compared with the prior art, the invention has the following beneficial effects: the invention uses β-substituted α-tetralone as a reaction substrate, uses air or oxygen as an oxidant, and directly synthesizes β-functionalized α-naphthol compounds under the action of a solvent and a base. Compared with the prior art, the invention has the advantages of a simple synthesis route, simple operation, a green and environmentally friendly reaction process, mild reaction conditions, cheap and readily available reaction reagents, a short synthesis cycle, easy product separation, and a high product yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The figure is a flow chart of the method of the present invention. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Please refer to the attached Figure 1 , a technical solution provided by the present invention:

[0031] Example:

[0032] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone is as follows:

[0033]

[0034] Wherein, the R group in α-tetralone and α-naphthol is selected from one of ester group, aldehyde group, nitroso group, nitro group, acetyl group, benzoyl group, cinnamoyl group, sulfonyl group, phosphoryl group or carboxylic acid and its derivatives, and R in α-tetralone and α-naphthol is selected from one of ester group, aldehyde group, nitroso group, nitro group, acetyl group, benzoyl group, cinnamoyl group, sulfonyl group, phosphoryl group or carboxylic acid and its derivatives. 1 is selected from one of alkoxy, alkyl, ester, cyano, aldehyde, acyl, halogen, substituted phenyl or aromatic heterocyclic groups, R 1 When selected from alkoxy, alkoxy includes methoxy, 1-20 carbon substituted straight chain alkoxy and 1-20 carbon substituted branched chain alkoxy; R 1 When selected from alkyl, the alkyl group includes a straight-chain aliphatic hydrocarbon group substituted with 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group substituted with 1 to 20 carbon atoms, a monohalogenated aliphatic hydrocarbon group and a polyhalogenated aliphatic hydrocarbon group; R 1 When selected from ester groups, the ester groups include methyl ester groups, multi-carbon substituted straight-chain ester groups and multi-carbon substituted branched-chain ester groups; R 1 When selected from halogen, including fluorine, chlorine and bromine: R 1 When selected from substituted phenyl, the substituted phenyl is phenyl;

[0035] Specifically, the following steps are included: step 1, dissolving the substrate to prepare mixture A; step 2, alkaline oxygen reaction to prepare mixture B; step 3, extracting and separating to obtain the product;

[0036] In the above step 1, the β-substituted α-tetralone compound is dissolved in a reaction solvent to obtain a mixture A; wherein the reaction solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, acetonitrile, N,N-dimethylformamide, toluene, tetrahydrofuran, and 1,4-dioxane;

[0037] In the above step 2, the following steps are specifically included:

[0038] 2.1 Add a base to the mixture A obtained in step 1; wherein the base is one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride, potassium tert-butoxide, sodium methoxide, potassium methoxide, and lithium diisopropylamide; the amount of the base is 0.5 to 5 times the amount of the β-substituted α-tetralone compound;

[0039] 2.2 Adding an oxidant to the mixture A in step 2.1; wherein the oxidant is one of air, pure oxygen, and a gas mixed with oxygen and air in any proportion;

[0040] 2.3 The mixture A in step 2.2 is placed in a temperature range of -10°C to 80°C to react to obtain a mixture B;

[0041] In the above step 3, the following steps are specifically included:

[0042] 3.1 Add water to the mixture B obtained in step 2.3 to quench the reaction;

[0043] 3.2 Add ethyl acetate to the mixture B in step 3.1, and wash to obtain a mixture C; wherein the washing method is specifically: washing the organic phase three times with water and washing the organic phase once with a saturated sodium chloride aqueous solution;

[0044] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0045] 3.4 The mixture D obtained in step 3.3 is separated by column chromatography to obtain a β-functionalized α-naphthol compound.

[0046] Experimental Example 1:

[0047] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0048] In the above step 1, 1 mmol of β-methyl ester-α-tetralone is dissolved in 2 mL of methanol to obtain a mixture A;

[0049] In the above step 2, the following steps are specifically included:

[0050] 2.1 Add 1 mmol of potassium carbonate to the mixture A obtained in step 1;

[0051] 2.2 introducing air into the mixture A in step 2.1;

[0052] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0053] In the above step 3, the following steps are specifically included:

[0054] 3.1 Add water to the mixture B obtained in step 2.3 to quench the reaction;

[0055] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0056] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0057] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 192 mg of a white solid, which was denoted as a. The yield was 95%. The structural formula of compound a is as follows:

[0058]

[0059] After NMR detection, the nuclear magnetic data of compound a are as follows:

[0060] 1 H NMR (500MHz, CDCl3) δ12.01 (s, 1H), 8.47–8.45 (m, 1H), 7.76 (dd, J = 8.9, 1.7Hz, 2H), 7.61 (ddd, J=8.2,6.9,1.3Hz,1H),7.53(ddd,J=8.2,6.9,1.3Hz,1H),7.28(d,J=8.7Hz,1H),3.99(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ171.49,160.99,137.26,129.44,127.51,125.80,124.82,124.29,123.94,118.65,105.64,52.33.

[0061] Experimental Example 2:

[0062] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0063] In the above step 1, 1 mmol of 7-fluoro-β-methyl-α-tetralone is dissolved in 2 mL of ethanol to obtain a mixture A;

[0064] In the above step 2, the following steps are specifically included:

[0065] 2.1 Add 1 mmol of sodium carbonate to the mixture A obtained in step 1;

[0066] 2.2 introducing oxygen into the mixture A in step 2.1;

[0067] 2.3 The mixture A in step 2.2 was reacted at 60°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0068] In the above step 3, the following steps are specifically included:

[0069] 3.1 Add water to the mixture B obtained in step 2.3 to quench the reaction;

[0070] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0071] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0072] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 202 mg of a light yellow or white solid, which was denoted as b. The yield was 92%. The structural formula of compound b is as follows:

[0073]

[0074] After NMR detection, the NMR data of compound b are as follows:

[0075] 1 H NMR(500MHz, CDCl3)δ11.94(s,1H),8.03(dd,J=10.1,2.7Hz,1H),7.80–7.71( m,2H),7.39(ddd,J=8.9,8.2,2.7Hz,1H),7.29(d,J=8.8Hz,1H),4.03(s,3H); 13 C{ 1 H}NMR(125MHz, CDCl3)δ171.29,161.62,160.09(d,J=5.0Hz),159.66,134.04,129.83(d,J=8.6Hz),125.6 7(d,J=8.9Hz), 123.53(d,J=2.6Hz), 119.37(d,J=25.0Hz), 118.38, 107.90(d,J=22.4Hz), 106.28, 52.42.

[0076] Experimental Example 3:

[0077] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0078] In the above step 1, 1 mmol of 7-methoxy-β-methylester-α-tetralone is dissolved in 2 mL of tetrahydrofuran to obtain a mixture A;

[0079] In the above step 2, the following steps are specifically included:

[0080] 2.1 Add 1 mmol of sodium hydride to the mixture A obtained in step 1;

[0081] 2.2 introducing air into the mixture A in step 2.1;

[0082] 2.3 The mixture A in step 2.2 was reacted at 40°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0083] In the above step 3, the following steps are specifically included:

[0084] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0085] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0086] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0087] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 190 mg of a light yellow or white solid, which was denoted as compound c. The yield was 62%. The structural formula of compound c is as follows:

[0088]

[0089] After NMR detection, the NMR data of compound c are as follows:

[0090] 1 H NMR (500MHz, CDCl3) δ11.97(s,1H),7.72–7.66(m,3H),7.29(dd,J=8.9,2.6Hz,1H),7.28–7.19(m,1H),4.02(s,3H),3.99(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ171.65,159.75,157.80,132.54,129.04,125.71,121.97,121.93,118.43,106.02,101.98,55.50,52.32.

[0091] Experimental Example 4:

[0092] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0093] In the above step 1, 1 mmol of 4-methyl-β-carbomethoxy-α-tetralone is dissolved in 2 mL of 1,4-dioxane to obtain a mixture A;

[0094] In the above step 2, the following steps are specifically included:

[0095] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0096] 2.2 introducing oxygen into the mixture A in step 2.1;

[0097] 2.3 The mixture A in step 2.2 was reacted at 75°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0098] In the above step 3, the following steps are specifically included:

[0099] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0100] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0101] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0102] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 155 mg of a light yellow or white solid, which was denoted as d. The yield was 52%. The structural formula of compound d is as follows:

[0103]

[0104] After NMR detection, the NMR data of compound d are as follows:

[0105] 1H NMR(500MHz, CDCl3)δ11.81(s,1H),8.46(dd,J=8.4,1.3Hz,1H),7.91–7.86(m,1H),7.65(ddd,J=8.3,6.8 ,1.4Hz,1H),7.58(d,J=1.2Hz,1H),7.54(ddd,J=8.1,6.8,1.2Hz,1H),3.99(s,3H),2.56(d,J=1.1Hz,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ171.45,159.68,136.45,129.31,125.46,124.94,124.50,124.40,124.06,123.86,105.01,52.23,18.82.

[0106] Experimental Example 5:

[0107] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0108] In the above step 1, 1 mmol of β-toluenesulfonyl-α-tetralone is dissolved in 2 mL of methanol to obtain a mixture A;

[0109] In the above step 2, the following steps are specifically included:

[0110] 2.1 Add 1 mmol of potassium carbonate to the mixture A obtained in step 1;

[0111] 2.2 introducing air into the mixture A in step 2.1;

[0112] 2.3 The mixture A in step 2.2 was reacted at 65°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0113] In the above step 3, the following steps are specifically included:

[0114] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0115] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0116] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0117] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 229 mg of a white solid, which was denoted as e. The yield was 77%. The structural formula of compound e is as follows:

[0118]

[0119] After NMR detection, the NMR data of compound e are as follows:

[0120] 1 H NMR (500MHz, CDCl3) δ10.38(s,1H),8.40(d,J=8.4Hz,1H),7.86(d,J=8.2Hz,2H),7.74(d,J=8.1Hz,1H),7.65–7 .59(m,1H),7.59–7.53(m,1H),7.50(d,J=8.9Hz,1H),7.34(d,J=8.8Hz,1H),7.31(d,J=8.0Hz,2H),2.39(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ154.43,144.78,139.02,136.93,130.09,129.88, 127.63,126.93,126.63,125.14,123.96,122.92,120.48,116.04,21.64.

[0121] Experimental Example 6:

[0122] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0123] In the above step 1, 1 mmol of 7-fluoro-2-toluenesulfonyl-1-tetralone is dissolved in 2 mL of acetonitrile to obtain a mixture A;

[0124] In the above step 2, the following steps are specifically included:

[0125] 2.1 Add 1 mmol of sodium hydroxide to the mixture A obtained in step 1;

[0126] 2.2 introducing oxygen into the mixture A in step 2.1;

[0127] 2.3 The mixture A in step 2.2 was reacted at 40°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0128] In the above step 3, the following steps are specifically included:

[0129] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0130] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0131] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0132] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 208 mg of a white solid, which was denoted as compound f. The yield was 66%. The structural formula of compound f is as follows:

[0133]

[0134] After NMR detection, the NMR data of compound f are as follows:

[0135] 1 H NMR (500MHz, CDCl3) δ10.35(s,1H),8.00(dd,J=9.9,2.6Hz,1H),7.86(d,J=8.3Hz,2H),7.73(dd,J=9 .0,5.3Hz,1H),7.47(d,J=8.9Hz,1H),7.42–7.37(m,1H),7.33(dd,J=12.1,8.5Hz,3H),2.40(s,3H); 13 C{ 1 H}NMR(125MHz, CDCl3)δ162.11,160.14,153.59(d,J=5.1Hz),145.00,138.76,133.79,130.16,130.08(d,J=8.6Hz),1 26.99, 126.19 (d, J = 9.1Hz), 122.27 (d, J = 2.6Hz), 120.27, 119.98 (d, J = 25.1Hz), 117.07, 108.11 (d, J = 22.9Hz), 21.65.

[0136] Experimental Example 7:

[0137] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0138] In the above step 1, 1 mmol of 7-methoxy-2-toluenesulfonyl-1-tetralone is dissolved in 2 mL of tetrahydrofuran to obtain a mixture A;

[0139] In the above step 2, the following steps are specifically included:

[0140] 2.1 Add 1 mmol of potassium methoxide to the mixture A obtained in step 1;

[0141] 2.2 introducing air into the mixture A in step 2.1;

[0142] 2.3 The mixture A in step 2.2 was reacted at 75°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0143] In the above step 3, the following steps are specifically included:

[0144] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0145] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0146] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0147] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 216 mg of a light brown solid, which was denoted as compound g. The yield was 54%. The structural formula of compound g is as follows:

[0148]

[0149] After NMR detection, the nuclear magnetic data of compound g are as follows:

[0150] 1 H NMR (500MHz, CDCl3) δ10.35(s,1H),7.89(d,J=8.1Hz,2H),7.77–7.59(m,2H),7.42(d,J=8.8Hz,1H),7.37–7.24(m,4H),3.99(s,3H),2.43(s,3H); 13 C{1 H}NMR(125MHz,CDCl3)δ158.43,153.09,144.73,139.09,132.25,130.07,129 .17,126.91,126.21,122.51,120.59,120.24,116.60,101.99,55.57,21.63.

[0151] Experimental Example 8:

[0152] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0153] In the above step 1, 1 mmol of 2-nitroso-1-tetralone is dissolved in 2 mL of methanol to obtain a mixture A;

[0154] In the above step 2, the following steps are specifically included:

[0155] 2.1 Add 1 mmol of potassium carbonate to the mixture A obtained in step 1;

[0156] 2.2 introducing air into the mixture A in step 2.1;

[0157] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0158] In the above step 3, the following steps are specifically included:

[0159] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0160] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0161] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0162] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 119 mg of orange-yellow solid, which was denoted as compound h. The yield was 69%. The structural formula of compound h is as follows:

[0163]

[0164] After NMR detection, the NMR data of compound h are as follows:

[0165] 1 H NMR (500MHz, CDCl3) δ12.16(s,1H),7.88(d,J=9.2Hz,1H),7.77(d,J=2.6Hz,1H),7 .71(d,J=8.9Hz,1H),7.35(dd,J=8.9,2.6Hz,1H),7.31–7.27(m,1H),3.99(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ158.72,154.43,132.69,129.39,128.88,126.31,123.75,119.95,117.06,103.30,55.69.

[0166] Experimental Example 9:

[0167] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0168] In the above step 1, 1 mmol of 7-methoxy-2-nitroso-1-tetralone is dissolved in 2 mL of propanol to obtain a mixture A;

[0169] In the above step 2, the following steps are specifically included:

[0170] 2.1 Add 1 mmol of sodium carbonate to the mixture A obtained in step 1;

[0171] 2.2 introducing air into the mixture A in step 2.1;

[0172] 2.3 The mixture A in step 2.2 was reacted at 70°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0173] In the above step 3, the following steps are specifically included:

[0174] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0175] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0176] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0177] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 130 mg of orange-yellow solid, which was denoted as i. The yield was 64%. The structural formula of compound i is as follows:

[0178]

[0179] After NMR detection, the NMR data of compound i are as follows:

[0180] 1 H NMR (500MHz, CDCl3) δ12.16(s,1H),7.88(d,J=9.2Hz,1H),7.77(d,J=2.6Hz,1H),7 .71(d,J=8.9Hz,1H),7.35(dd,J=8.9,2.6Hz,1H),7.31–7.27(m,1H),3.99(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ158.72,154.43,132.69,129.39,128.88,126.31,123.75,119.95,117.06,103.30,55.69.

[0181] Experimental Example 10:

[0182] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0183] In the above step 1, 1 mmol of 4-methyl-2-nitroso-1-tetralone is dissolved in 2 mL of methanol to obtain a mixture A;

[0184] In the above step 2, the following steps are specifically included:

[0185] 2.1 Add 1 mmol of potassium carbonate to the mixture A obtained in step 1;

[0186] 2.2 introducing oxygen into the mixture A in step 2.1;

[0187] 2.3 The mixture A in step 2.2 was reacted at 75°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0188] In the above step 3, the following steps are specifically included:

[0189] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0190] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0191] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0192] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 112 mg of orange-yellow solid, which was denoted as j. The yield was 60%. The structural formula of compound j is as follows:

[0193]

[0194] After NMR detection, the nuclear magnetic data of compound j are as follows:

[0195] 1 H NMR (500MHz, CDCl3) δ12.19(s,1H),8.59(ddd,J=8.3,1.4,0.7Hz,1H),7.97(dt,J=8.4,0.9Hz,1H),7. 88(q,J=1.1Hz,1H),7.81(ddd,J=8.4,6.9,1.4Hz,1H),7.68(ddd,J=8.2,6.9,1.2Hz,1H),2.64(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ154.60,137.03,131.38,127.70,126.90,126.80,125.66,125.26,124.52,118.67,18.84.

[0196] Experimental Example 11:

[0197] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0198] In the above step 1, 1 mmol of 7-methoxy-2-phosphoryl-1-tetralone is dissolved in 2 mL of methanol to obtain a mixture A;

[0199] In the above step 2, the following steps are specifically included:

[0200] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0201] 2.2 introducing air into the mixture A in step 2.1;

[0202] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0203] In the above step 3, the following steps are specifically included:

[0204] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0205] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0206] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0207] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 127 mg of a reddish brown solid, which was denoted as compound k. The yield was 45%. The structural formula of compound k is as follows:

[0208]

[0209] After NMR detection, the nuclear magnetic data of compound k are as follows:

[0210] 1 H NMR(500MHz, CDCl3)δ11.09(d,J=1.1Hz,1H),7.71–7.65(m,2H),7.32–7.27( m,2H),7.14(dd,J=12.5,8.4Hz,1H),4.00(s,3H),3.82(s,3H),3.79(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ160.33,158.04,132.45,129.11,125.89,122.95,121.91,119.38,101.75,100.01,55.57,53.03,52.99.

[0211] Experimental Example 12:

[0212] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0213] In the above step 1, 1 mmol of 2-formyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0214] In the above step 2, the following steps are specifically included:

[0215] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0216] 2.2 introducing oxygen into the mixture A in step 2.1;

[0217] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0218] In the above step 3, the following steps are specifically included:

[0219] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0220] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0221] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0222] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 146 mg of a white solid, which was denoted as 1. The yield was 85%. The structural formula of compound 1 is as follows:

[0223]

[0224] After NMR detection, the nuclear magnetic data of compound 1 are as follows:

[0225] 1H NMR (500MHz, CDCl3) δ12.67(s,1H),9.98(s,1H),8.45(d,J=8.4Hz,1H),7.79(d,J=8.2Hz,1H),7.67(ddd ,J=8.3,6.9,1.4Hz,1H),7.56(ddd,J=8.3,6.9,1.3Hz,1H),7.49(d,J=8.5Hz,1H),7.38(d,J=8.6Hz,1H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ196.39,161.98,137.60,130.67,127.68,126.53,126.22,124.59,124.39,119.52,114.32.

[0226] Experimental Example 13:

[0227] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0228] In the above step 1, 1 mmol of 2-acetyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0229] In the above step 2, the following steps are specifically included:

[0230] 2.1 Add 1 mmol of potassium methoxide to the mixture A obtained in step 1;

[0231] 2.2 introducing air into the mixture A in step 2.1;

[0232] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0233] In the above step 3, the following steps are specifically included:

[0234] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0235] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0236] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0237] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 164 mg of a white solid, which was denoted as m. The yield was 88%. The structural formula of compound m is as follows:

[0238]

[0239] After NMR detection, the NMR data of compound m are as follows:

[0240] 1 H NMR (500MHz, CDCl3) δ14.06(s,1H),8.50(dd,J=8.3,1.4Hz,1H),7.80(d,J=8.1Hz,1H),7.67(td ,J=8.6,8.2,2.2Hz,2H),7.57(ddd,J=8.2,6.9,1.2Hz,1H),7.31(d,J=8.8Hz,1H),2.74(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ204.35,162.57,137.45,130.11,127.46,126.00,125.30,124.98,124.51,118.38,113.29,26.96.

[0241] Experimental Example 14:

[0242] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0243] In the above step 1, 1 mmol of 7-fluoro-2-acetyl-1-tetralone is dissolved in 2 mL of anhydrous 1,4-dioxane to obtain a mixture A;

[0244] In the above step 2, the following steps are specifically included:

[0245] 2.1 Add 1 mmol of potassium carbonate to the mixture A obtained in step 1;

[0246] 2.2 introducing air into the mixture A in step 2.1;

[0247] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0248] In the above step 3, the following steps are specifically included:

[0249] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0250] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0251] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0252] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 175 mg of a white solid, which was denoted as n. The yield was 46%. The structural formula of compound n is as follows:

[0253]

[0254] After NMR detection, the NMR data of compound n are as follows:

[0255] 1 H NMR (500MHz, CDCl3) δ13.87(s,1H),8.04(dd,J=10.0,2.7Hz,1H),7.75(dd,J=8.9,5.3Hz,1 H),7.61(d,J=8.8Hz,1H),7.38(td,J=8.4,2.7Hz,1H),7.27(d,J=8.5Hz,1H),2.70(s,3H); 13 C{ 1 H}NMR(125MHz, CDCl3)δ204.49,161.77,161.57(d,J=4.9Hz),159.80,134.23,129.81(d,J=8.5Hz),126.3 0 (d, J = 8.7Hz), 124.21 (d, J = 2.6Hz), 120.06 (d, J = 25.2Hz), 118.15, 113.66, 108.46 (d, J = 22.3Hz), 27.01.

[0256] Experimental Example 15:

[0257] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0258] In the above step 1, 1 mmol of 7-methoxy-2-acetyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0259] In the above step 2, the following steps are specifically included:

[0260] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0261] 2.2 introducing air into the mixture A in step 2.1;

[0262] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0263] In the above step 3, the following steps are specifically included:

[0264] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0265] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0266] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0267] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 175 mg of a yellow solid, which was denoted as o. The yield was 81%. The structural formula of compound o is as follows:

[0268]

[0269] After NMR detection, the NMR data of compound o are as follows:

[0270] 1 H NMR (500MHz, CDCl3) δ16.92 (s, 1H), 7.61–7.57 (m, 1H), 7.55 (d, J = 2.8Hz, 1H), 7.49 ( s,1H),7.13(d,J=8.3Hz,1H),7.02(dd,J=8.3,2.8Hz,1H),3.87(s,3H),2.75(s,3H); 13 C{ 1H}NMR (125MHz, CDCl3) δ204.6,161.22,157.94,132.70,128.98,126.23,122.65,122.61,118.16,113.58,102.43,55.53,26.99.

[0271] Experimental Example 16:

[0272] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0273] In the above step 1, 1 mmol of 4-methyl-2-acetyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0274] In the above step 2, the following steps are specifically included:

[0275] 2.1 Add 1 mmol of potassium carbonate to the mixture A obtained in step 1;

[0276] 2.2 introducing oxygen into the mixture A in step 2.1;

[0277] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0278] In the above step 3, the following steps are specifically included:

[0279] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0280] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0281] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0282] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 166 mg of a yellow solid, which was denoted as p. The yield was 83%. The structural formula of compound p is as follows:

[0283]

[0284] After NMR detection, the NMR data of compound p are as follows:

[0285] 1 H NMR (500MHz, CDCl3) δ13.91(s,1H),8.54(d,J=8.3Hz,1H),7.92(d,J=8.4Hz,1H ),7.75–7.68(m,1H),7.62–7.55(m,1H),7.48(s,1H),2.72(s,3H),2.62(s,3H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ204.23,161.28,136.74,130.04,125.70,125.40,124.98,124.62,124.18,124.09,112.84,26.97,19.05.

[0286] Experimental Example 17:

[0287] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0288] In the above step 1, 1 mmol of 2-benzoyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0289] In the above step 2, the following steps are specifically included:

[0290] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0291] 2.2 introducing air into the mixture A in step 2.1;

[0292] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0293] In the above step 3, the following steps are specifically included:

[0294] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0295] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0296] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0297] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 218 mg of a yellow solid, which was denoted as q. The yield was 88%. The structural formula of compound q is as follows:

[0298]

[0299] After NMR detection, the NMR data of compound q are as follows:

[0300] 1 H NMR (500MHz, CDCl3) δ13.96 (s, 1H), 8.56–8.51 (m, 1H), 7.77 (d, J = 8.1Hz, 1H), 7.75–7. 70(m,2H),7.66(ddd,J=8.2,6.9,1.4Hz,1H),7.63–7.51(m,5H),7.23(d,J=8.8Hz,1H); 13 C{ 1 H}NMR(125MHz,CDCl3)δ201.47,163.99,138.28,137.38,131.69,130.40, 129.14,128.40,127.49,127.39,126.02,125.37,124.55,117.93,112.64.

[0301] Experimental Example 18:

[0302] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0303] In the above step 1, 1 mmol of 7-fluoro-2-benzoyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0304] In the above step 2, the following steps are specifically included:

[0305] 2.1 Add 1 mmol of potassium methoxide to the mixture A obtained in step 1;

[0306] 2.2 introducing air into the mixture A in step 2.1;

[0307] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0308] In the above step 3, the following steps are specifically included:

[0309] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0310] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0311] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0312] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 210 mg of a yellow solid, which was denoted as r. The yield was 79%. The structural formula of compound r is as follows:

[0313]

[0314] After NMR detection, the NMR data of compound r are as follows:

[0315] 1 H NMR (500MHz, CDCl3) δ16.77(s,1H),7.70(dd,J=9.2,2.7Hz,1H),7.62–7.56(m,2H),7.51–7.45(m,5H),7.20–7.17(m,1H),7.13(td,J=8.3,2.7Hz,1H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ186.37,182.25,162.88,160.93,137.48,136.31,130.79,129.97,129.22.

[0316] Experimental Example 19:

[0317] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0318] In the above step 1, 1 mmol of 7-methoxy-2-benzoyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0319] In the above step 2, the following steps are specifically included:

[0320] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0321] 2.2 introducing oxygen into the mixture A in step 2.1;

[0322] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0323] In the above step 3, the following steps are specifically included:

[0324] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0325] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0326] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0327] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 197 mg of a yellow solid, which was denoted as s. The yield was 71%. The structural formula of compound s is as follows:

[0328]

[0329] After NMR detection, the NMR data of compound s are as follows:

[0330] 1 H NMR(500MHz, CDCl3)δ13.84(s,1H),7.80(d,J=2.5Hz,1H),7.76–7.70(m,2H),7.67(dd,J=8.9,2.1Hz,1H),7.63–7.56(m,1H),7 .56–7.49(m,2H),7.41(dd,J=8.8,2.1Hz,1H),7.30(dt,J=8.9,2.4Hz,1H),7.17(dd,J=9.0,2.1Hz,1H),3.98(d,J=2.1Hz,3H); 13 C{ 1 H}NMR(125MHz,CDCl3)δ201.64,162.60,158.04,138.43,132.68,131.60,129 .13,128.98,128.32,126.35,125.15,122.88,117.70,112.99,102.63,55.55.

[0331] Experimental Example 20:

[0332] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0333] In the above step 1, 1 mmol of 4-methyl-2-benzoyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0334] In the above step 2, the following steps are specifically included:

[0335] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0336] 2.2 introducing air into the mixture A in step 2.1;

[0337] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0338] In the above step 3, the following steps are specifically included:

[0339] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0340] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0341] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0342] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 202 mg of a yellow solid, which was denoted as t. The yield was 77%. The structural formula of compound t is as follows:

[0343]

[0344] After NMR detection, the NMR data of compound t are as follows:

[0345] 1H NMR (500MHz, CDCl3) δ13.83 (s, 1H), 8.57 (dt, J = 8.4, 1.0Hz, 1H), 7.93–7.88 (m, 1H),7.75–7.67(m,3H),7.63–7.52(m,4H),7.36(d,J=1.2Hz,1H),2.53(s,3H); 13 C{ 1 H}NMR(125MHz,CDCl3)δ201.36,162.77,138.39,136.71,131.60,130.36,129 .10,128.40,126.83,125.73,125.46,125.02,124.14,123.78,112.20,19.01.

[0346] Experimental Example 21:

[0347] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, performing an alkali-oxygen reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0348] In the above step 1, 1 mmol of 2-cinnamoyl-1-tetralone is dissolved in 2 mL of anhydrous tetrahydrofuran to obtain a mixture A;

[0349] In the above step 2, the following steps are specifically included:

[0350] 2.1 Add 1 mmol of potassium tert-butoxide to the mixture A obtained in step 1;

[0351] 2.2 introducing air into the mixture A in step 2.1;

[0352] 2.3 The mixture A in step 2.2 was reacted at 25°C for 6 hours. When the raw material spot disappeared during thin layer chromatography, the reaction was stopped to obtain a mixture B;

[0353] In the above step 3, the following steps are specifically included:

[0354] 3.1 Add 5 mL of water to the mixture B obtained in step 2.3 to quench the reaction;

[0355] 3.2 Add 20 mL of ethyl acetate to the mixture B in step 3.1, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0356] 3.3 The mixture C obtained in step 3.2 is dried over anhydrous sodium sulfate, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D;

[0357] 3.4 The mixture D obtained in step 3.3 was separated by column chromatography to obtain 192 mg of a yellow solid, which was denoted as u. The yield was 70%. The structural formula of compound u is as follows:

[0358]

[0359] After NMR detection, the NMR data of compound u are as follows:

[0360] 1 H NMR (500MHz, CDCl3) δ14.84(s,1H),8.51(d,J=8.4Hz,1H),8.00(d,J=15.5Hz,1H),7.86(d,J=8.9Hz,1H),7.80–7.73(m,2H),7.71(dd,J= 6.7,2.9Hz,2H),7.65(ddd,J=8.1,6.8,1.3Hz,1H),7.55(ddd,J=8.2,6.8,1.2Hz,1H),7.46(dd,J=5.1,2.0Hz,3H),7.32(d,J=8.9Hz,1H); 13 C{ 1 H}NMR (125MHz, CDCl3) δ193.32,164.49,145.15,137.46,134.85,130.89,130.28, 129.10,128.73,127.46,126.01,125.56,124.58,123.97,120.57,118.30,113.53.

[0361] Comparative Example 1:

[0362] The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone specifically comprises the following steps: step 1, dissolving a substrate to prepare a mixture A; step 2, catalyzing a reaction to prepare a mixture B; step 3, extracting and separating to obtain a product;

[0363] In the above step 1, 1 mmol of 2-carbomethoxy-1-tetralone is dissolved in a mixed solution of diethylene glycol dimethyl ether and water to obtain a mixture A;

[0364] In the above step 2, a catalytic amount of AIBX is added to the mixture A obtained in step 1 to carry out a reaction, and the raw material point disappears when detected by thin layer chromatography, and the reaction is stopped to obtain a mixture B;

[0365] In the above step 3, the following steps are specifically included:

[0366] 3.1 Add 20 mL of ethyl acetate to the mixture B obtained in step 2, wash the organic phase three times with water, and wash the organic phase once with a saturated sodium chloride aqueous solution to obtain a mixture C;

[0367] 3.2 The mixture C obtained in step 3.1 was dried over anhydrous sodium sulfate, and ethyl acetate was recovered by vacuum distillation to obtain a mixture D, which was denoted as v. The yield was 74%. The structure of compound v was the same as that of compound a obtained in Experimental Example 1.

[0368] Based on the above, the advantages of the present invention are that when the present invention is used, the α-tetralone compound substituted at the β position is used as a reaction substrate, and air, oxygen or a gas mixed in any proportion of air and oxygen is used as an oxidant, and the β-functionalized α-naphthol compound is directly synthesized under the action of a solvent and a base, and has the advantages of a simple synthesis route, simple operation, and a green and environmentally friendly reaction process. The reaction conditions of the reaction are mild, the reaction reagents are cheap and easily available, and no catalyst and chemical oxidant are required in the preparation process. In addition, the synthesis cycle is short, the product is easy to separate, and the product yield is high. The present invention can be used to synthesize α-naphthol compounds substituted with multiple functional groups at the β position, such as β-ester α-naphthol, β-acyl α-naphthol, β-sulfonyl α-naphthol, β-nitro α-naphthol, and β-phosphoryl α-naphthol.

[0369] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone, characterized in that: The method for synthesizing β-functionalized α-naphthol from the β-substituted α-tetralone is as follows: Specifically, the following steps are included: step 1, dissolving the substrate to prepare mixture A; step 2, alkaline oxygen reaction to prepare mixture B; step 3, extracting and separating to obtain the product; Wherein in the above step 1, the β-substituted α-tetralone compound is dissolved in a reaction solvent to obtain a mixture A; In the above step 2, the following steps are specifically included: 2.1 Add a base to the mixture A obtained in step 1; 2.2 adding an oxidant to the mixture A in step 2.1; 2.3 The mixture A in step 2.2 is placed in a temperature range of -10°C to 80°C to react to obtain a mixture B; In the above step 3, the following steps are specifically included: 3.1 Add water to the mixture B obtained in step 2.3 to quench the reaction; 3.2 Add ethyl acetate to the mixture B in step 3.1, and wash to obtain a mixture C; 3.3 The mixture C obtained in step 3.2 is dried, and ethyl acetate is recovered by vacuum distillation to obtain a mixture D; 3.4 The mixture D obtained in step 3.3 is separated by column chromatography to obtain a β-functionalized α-naphthol compound.

2. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: The R group in the α-tetralone and α-naphthol is selected from one of an ester group, an aldehyde group, a nitroso group, a nitro group, an acetyl group, a benzoyl group, a cinnamoyl group, a sulfonyl group, a phosphoryl group or a carboxylic acid and its derivatives.

3. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: The α-tetralone and α-naphthol R 1 It is selected from one of alkoxy, alkyl, ester, cyano, aldehyde, acyl, halogen, substituted phenyl or aromatic heterocyclic group.

4. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 3, characterized in that: The R 1 When selected from alkoxy, alkoxy includes methoxy, 1-20 carbon substituted straight chain alkoxy and 1-20 carbon substituted branched chain alkoxy; R 1 When selected from alkyl, the alkyl group includes a straight-chain aliphatic hydrocarbon group substituted with 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group substituted with 1 to 20 carbon atoms, a monohalogenated aliphatic hydrocarbon group and a polyhalogenated aliphatic hydrocarbon group; R 1 When selected from ester groups, the ester groups include methyl ester groups, multi-carbon substituted straight-chain ester groups and multi-carbon substituted branched-chain ester groups; R 1 When selected from halogen, including fluorine, chlorine and bromine: R 1 When selected from substituted phenyl groups, the substituted phenyl groups are phenyl groups.

5. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: In the step 1, the reaction solvent is one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, acetonitrile, N,N-dimethylformamide, toluene, tetrahydrofuran, and 1,4-dioxane.

6. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: In the step 2.1, the base is one or more of potassium carbonate, sodium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride, potassium tert-butoxide, sodium methoxide, potassium methoxide, and lithium diisopropylamide.

7. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: In the step 2.1, the amount of the base used is 0.5 to 5 times the amount of the β-substituted α-tetralone compound.

8. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: In step 2.2, the oxidant is one of air, pure oxygen, and a gas mixed with oxygen and air in any proportion.

9. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: In the step 3.2, the washing method is specifically as follows: washing the organic phase three times with water and once with a saturated sodium chloride aqueous solution.

10. The method for synthesizing a β-functionalized α-naphthol compound from a β-substituted α-tetralone according to claim 1, characterized in that: In step 3.3, anhydrous sodium sulfate is used for drying.

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