A class of aminonaphthoquinone derivatives and their preparation and fungicidal, weed-killing and algaecidal uses

Abstract

The present invention (named: a class of aminonaphthoquinone derivatives and their preparation and sterilization, weeding and algae killing uses) relates to 33 2-chloro-3-aminonaphthoquinone formate, urea, amide and sulfonamide derivatives and their preparation methods, as well as their uses in sterilization, weeding and algae killing. The 33 2-chloro-3-aminonaphthoquinone formate, urea, amide and sulfonamide derivatives are generated by reacting 2,3-dichloronaphthoquinone with potassium cyanate, substituted alcohol or amine, or with sulfonamide; or by reacting 2-chloro-3-aminonaphthoquinone with different amides. These compounds can be used as fungicides to control tomato gray mold, or as herbicides to control weeds such as Amaranthus retroflexus and Crabgrass, or as algaecides to control algae.

Description

Technical Field

[0001] The invention relates to a class of naphthoquinone carbamate, urea, benzamide, sulfonamide compounds and preparation and use thereof, and specifically to the field of agricultural herbicides, fungicides and algaecides. Background Art

[0002] 2,3-Dichloro-1,4-naphthoquinone is an important intermediate for the synthesis of medicines, dyes, and pesticides. The compound can be used to prevent and treat a variety of plant diseases such as apple brown rot, pear black spot, and tomato gray mold. The compound is also used to treat wheat, peanuts, corn, and a variety of vegetable seeds to prevent and treat seed and seedling diseases. 2-Amino-3-chloro-1,4-naphthoquinone is also known as algaecide and aminochloronaphthoquinone, and has been used as an algaecide and paddy field herbicide. Carbamate herbicides, urea herbicides, amide herbicides, and sulfonamide herbicides are all important herbicide categories that are currently widely used. This patent uses 2,3-dichloro-1,4-naphthoquinone and 2-amino-3-chloro-1,4-naphthoquinone as the lead, and based on the idea of ​​splicing active substructures, designs and synthesizes a series of naphthoquinone carbamates, ureas, benzamides, and sulfonamide compounds. Screening found that some compounds have significant herbicidal, antibacterial, or algaecidal activities. Summary of the invention

[0003] The purpose of the present invention is to provide a preparation method of naphthoquinone carbamate, urea, benzamide and sulfonamide, which can be applied in agriculture to prevent and control field weeds, crop diseases or water algae.

[0004] The technical solution of the present invention is as follows:

[0005] (1) The naphthoquinone carbamate compound provided by the present invention has the following general structural formula:

[0006] R 1 Selected from: alkyl, cyclohexyl, cycloalkylmethyl, substituted benzyl, substituted phenethyl;

[0007] Naphthoquinone carbamate compound synthesis reaction formula:

[0008] Preparation method of the general formula compound: Add dimethyl sulfoxide, potassium cyanate, 2,3-dichloro-1,4-naphthoquinone and substituted alcohol into a reaction bottle at room temperature, react for 12 to 24 hours, and obtain the target product Ⅰ.

[0009] (2) The naphthoquinone urea compound provided by the present invention has the following general structural formula:

[0010] Where R 2 : hydrogen atom, alkyl group; R 3: alkyl, substituted alkyl, cyclohexyl, substituted phenyl;

[0011] Naphthoquinone urea compound synthesis reaction formula:

[0012] Preparation method of the general formula compound: Add dimethyl sulfoxide, potassium cyanate, 2,3-dichloro-1,4-naphthoquinone and substituted amine into a reaction bottle at room temperature, react for 12 to 24 hours, and then treat to obtain the target product II.

[0013] (3) The naphthoquinone benzamide compounds provided by the present invention have the following general structural formula:

[0014] Where R 4 : methyl, bromine atom;

[0015] Naphthoquinone benzamide compound synthesis reaction formula:

[0016] Preparation method of the compound of the general formula: under nitrogen protection, add anhydrous tetrahydrofuran and sodium hydride to the reaction bottle, stir at room temperature for 30 minutes, add substituted benzoyl chloride, react for 1-2 hours, and then treat to obtain the target product III.

[0017] (4) The naphthoquinone sulfonamide compound provided by the present invention has the following general structural formula:

[0018] Where R 5 : substituted phenyl, thiophene, substituted pyridine;

[0019] Naphthoquinone sulfonamide compound synthesis reaction formula:

[0020] Preparation method of the compound of the general formula: Add cesium carbonate, 2,3-dichloro-1,4-naphthoquinone and substituted sulfonamide to DMF at room temperature, react for 6 to 12 hours, and then treat to obtain the target product IV. DETAILED DESCRIPTION

[0021] Example 1 Preparation of Compound I-1

[0022] 0.63 g (7.5 mmol) of potassium cyanate was suspended in a mixture of 20 mL of anhydrous DMSO and 10 mL of methanol, and then 1.1 g (5.0 mmol) of 2,3-dichloro-1,4-naphthoquinone was added. The mixture was stirred at room temperature for 24 h. After the reaction was completed, 50 mL of distilled water was added, and the mixture was cooled at 0 °C for 30 min. The mixture was filtered, and the precipitate was washed with a large amount of distilled water and dried. The mixture was separated and purified by silica gel column chromatography [the mobile phase was V (petroleum ether): V (dichloromethane) = 8:1–1:1], and recrystallized by methanol / water V (methanol): V (water) = 4:1. Compounds I-2 to I-19 were synthesized in a similar manner to I-1. 1 H NMR (500 MHz), 13 C NMR (126 MHz) and MS (ESI) spectra and data are as follows.

[0023] I-1 1 H NMR (CDCl3) δ 8.05 (s, 1H), 7.99 (s, 1H), 7.73 –7.60 (m, 2H), 4.24 (s, 3H); 13 C NMR δ 179.98, 178.87, 157.09, 134.68,134.26, 131.33, 131.10, 128.57, 127.27, 127.18, 62.20; MS: C 12 H8ClNO4([M+H] + ), 266.65.

[0024] I-2 1 H NMR (CDCl3) δ 8.13 (s, 1H), 8.07 (s,1H), 7.77 –7.70 (m, 2H), 4.62 (q, J = 7.0 Hz, 2H), 1.46 (t, J = 7.0 Hz, 3H); MS:C 13 H 10 ClNO4([M+H] + ), 280.68.

[0025] I-3 1 H NMR (CDCl3) δ 8.14 (d, J = 7.9 Hz, 1H),8.08 (d, J= 7.3 Hz, 1H), 7.79–7.70 (m, 2H), 4.16 (t, J = 6.7 Hz, 2H), 1.70 (h, J =7.3 Hz, 2H), 0.96 (t, J = 7.4 Hz, 3H); 13 C NMR δ 179.33, 177.67, 151.21, 139.58,134.76,134.13, 131.48, 131.38, 130.33, 127.47, 127.13, 68.48, 22.10, 10.27;MS: C 14 H 12 ClNO4([M+H] + ) , 294.70。

[0026] I-4 1 H NMR (CDCl3) δ 8.16 (d, J = 7.6 Hz, 1H),8.10 (d, J = 7.1 Hz, 1H), 7.79–7.72 (m, 2H),7.19 (s, 1H), 5.02 (p, J = 6.2 Hz,1H), 1.32 (d, J = 6.3 Hz, 6H); 13 C NMR δ 179.39, 177.72, 150.63, 139.67, 134.75,134.10, 131.51, 131.13, 130.35, 127.46, 127.11, 71.01,21.90; MS: C 14 H 12 ClNO4([M+H] + ) , 294.70。

[0027] I-5 1 H NMR (CDCl3) δ 8.18 (d, J = 8.9 Hz, 1H),8.12 (d, J = 8.9 Hz, 1H), 7.81–7.75 (m, 2H), 7.26 (s, 1H), 4.23 (t, J = 6.7 Hz,2H), 1.69 (s, 2H), 1.44 (dt,J = 15.0, 7.4 Hz, 2H), 0.97 (t, J = 7.4 Hz, 3H); 13 CNMR δ 179.33, 177.68, 151.22, 139.58, 134.77, 134.13, 131.48, 130.33, 127.48,127.13,66.81, 30.73, 19.00, 13.71; MS: C 15 H 14 ClNO4([M+H] + ) , 308.73。

[0028] I-6 1 H NMR (CDCl3) δ 8.11 (d, J = 7.2 Hz, 1H),8.05 (d, J = 8.5 Hz, 1H), 7.74–7.67 (m, 2H), 7.17 (s, 1H), 3.94 (d, J = 6.7 Hz,2H), 1.94 (dt, J = 13.4, 6.7 Hz, 1H), 0.91 (d, J = 6.7 Hz, 6H); 13 C NMR δ 179.34,177.68, 151.23, 139.58, 134.77, 134.14, 131.49, 131.40, 130.34, 127.48,127.14, 72.92, 27.88, 19.00; MS: C 15 H 14 ClNO4([M+H] + ), 308.73。

[0029] I-7 1 H NMR (CDCl3) δ 8.16 (d, J = 6.9 Hz,1H), 8.10 (d, J = 8.7 Hz, 1H), 7.76 (p, J = 7.5 Hz, 2H), 4.20 (t, J= 6.8 Hz, 2H),1.72–1.67 (m, 2H), 1.39–1.30 (m, 4H), 0.92 (s, 3H); 13 C NMR (CDCl3) δ 179.32,177.67, 151.23, 139.60, 134.76, 134.13, 131.47, 131.37, 130.33, 127.47,127.13, 67.09, 28.40, 27.89, 22.31, 13.96; MS: C 16 H 16 ClNO4([M+H] + ), 322.76。

[0030] I-8 1 H NMR (CDCl3) δ 8.17 (d, J = 7.0 Hz, 1H),8.10 (d, J = 7.2 Hz, 1H), 7.75 (q, J = 7.3 Hz, 2H), 7.24–7.22 (m, 1H), 4.24 (t, J =6.9 Hz, 2H), 1.71 (dd, J = 13.4, 6.7 Hz, 1H), 1.58 (q, J = 6.9 Hz, 2H), 0.94 (dd, J = 6.6, 1.4 Hz, 6H); 13 C NMR (CDCl3) δ 179.32, 177.67, 151.21, 139.58, 134.76,134.13, 131.47, 131.38, 130.32, 127.47, 127.13, 65.63,37.36, 24.95, 22.46;MS: C 16 H 16 ClNO4([M+H] + ), 322.76。

[0031] I-9 1 H NMR (CDCl3) δ 8.10 (d, J = 6.9Hz, 1H), 8.04 (d, J = 7.3 Hz, 1H), 7.70 (p,J = 7.4 Hz, 2H), 4.14 (t, J = 6.8 Hz,2H), 1.64–1.60 (m, 2H), 1.30 (d, J = 8.1 Hz, 2H), 1.25–1.15 (m, 8H), 0.81 (t, J =6.8 Hz, 3H); 13 C NMR δ 179.33, 177.67, 151.21, 139.59, 134.76,134.12, 131.49,131.35, 130.33, 127.47, 127.13, 67.12, 31.77, 29.17, 28.71, 25.77, 22.65,14.10; MS: C 19 H 22 ClNO4([M+H] + ), 364.84。

[0032] I-10 1 H NMR (CDCl3) δ 8.17 (d, J = 8.3Hz, 1H), 8.11 (d, J = 8.5 Hz, 1H), 7.80–7.73 (m, 2H), 7.22 (s, 1H), 4.14 (dd, J =5.8, 3.4 Hz, 2H), 1.64–1.61 (m, 1H),1.42–1.36 (m, 2H), 1.31 (d, J = 12.2 Hz,6H), 0.92–0.86 (m, 6H); 13 C NMR δ 179.34, 177.68, 151.34, 139.61, 134.76,134.13, 131.48, 131.39, 130.34, 127.47, 127.13, 69.36, 38.91, 30.25, 28.92,23.63, 22.97,14.06, 10.97; MS: C 19 H 22 ClNO4([M+H] + ), 364.84。

[0033] I-11 1H NMR (CDCl3) δ 8.16 (d, J = 7.0 Hz, 1H),8.10 (d, J = 7.3 Hz, 1H), 7.76 (p, J = 7.4 Hz, 2H), 7.22 (s, 1H), 4.76 (tt, J =9.1, 3.8 Hz, 1H), 1.95 (dd, J = 12.4, 3.7 Hz, 2H), 1.75 (dt, J = 12.8, 3.9 Hz,2H), 1.55 (dt, J = 8.0, 4.1 Hz, 1H), 1.53–1.43 (m, 2H), 1.37 (td, J = 14.1, 8.8,3.3 Hz, 2H), 1.31–1.20 (m,1H); MS: C 17 H 16 ClNO4([M+H] + ), 334.74。

[0034] I-12 1 H NMR (CDCl3) δ 8.21 (d, J = 9.4Hz, 1H), 8.13 (d, J = 7.4 Hz, 1H), 7.80 (t, J = 8.4 Hz, 1H), 7.40–7.30 (m, 2H),7.29 –7.24 (m, 4H), 4.48–4.45 (m, 2H), 3.09–3.02(m, 2H); 13 C NMR δ 179.25,177.64, 150.98, 139.44, 137.23, 134.78, 134.16, 131.63, 131.47, 130.31,128.94, 128.63,127.49, 127.16, 126.77, 67.18, 35.21; MS: C 19 H 13 ClFNO4([M+H] + ),374.76。

[0035] I-13 1H NMR (CDCl3) δ 8.11 (d, J = 20.3Hz, 2H), 7.76 (d, J = 9.0 Hz, 2H), 7.48 (d, J = 14.0 Hz, 2H), 7.08 (t, J = 8.7 Hz,2H), 5.61 (s, 2H); 13 C NMR δ 179.91, 178.50, 163.88, 161.91, 156.03, 134.42,134.04, 131.06, 130.74, 130.24,130.17, 127.08, 126.91, 115.72, 115.55, 74.90;MS: C 18 H 11 ClFNO4([M+H] + ), 360.74。

[0036] I-14 1 H NMR (CDCl3) δ 8.26 (d, J = 7.0Hz, 1H), 8.18 (d, J = 7.3 Hz, 1H), 7.85 (p, J = 7.4, 6.7 Hz, 2H), 7.43 (d, J = 7.9Hz, 2H), 7.34 (d, J = 8.0 Hz, 2H), 5.30 (s, 2H), 3.05–2.97 (m, 1H), 1.34 (d, J =6.9 Hz, 6H); 13 C NMR δ 179.25, 177.64, 150.99, 149.61, 139.49,134.76, 134.14,132.41, 131.52, 131.46, 130.32, 128.82, 127.48, 127.14, 126.81, 68.61, 33.94,23.94.; MS: C 21 H 18 ClNO4([M+H] + ), 384.83。

[0037] I-15 1H NMR (CDCl3) δ 8.05 (s, 1H),7.96 (d, J = 9.0 Hz, 1H), 7.68–7.64 (m, 2H), 7.17 (s, 4H), 4.70 (t, J = 6.7 Hz,2H), 3.02 (t, J = 6.7 Hz, 2H); 13 C NMR (126 MHz, CDCl3) δ179.73, 178.51, 156.37,135.84, 134.37,133.93, 130.57, 128.65, 126.98, 126.85, 74.59, 36.41; MS:C 19 H 13 C l2 NO4([M+H] + ), 384.83。

[0038] I-16 1 H NMR (CDCl3) δ 8.05 (s, 1H), 7.99(s, 1H), 7.65 (d, J = 9.0 Hz, 2H), 7.19 (t, J = 7.9 Hz, 1H), 6.98–6.92 (m, 2H),6.78 (d, J = 10.6 Hz, 1H), 5.55 (s, 2H), 3.73 (s, 3H); 13 C NMR δ 179.90, 178.55,159.78, 156.17, 137.55,134.35, 133.99, 131.07, 130.80, 129.69, 127.03,126.91, 114.45, 113.24, 75.48, 55.28; MS: C 19 H 14 ClNO5([M+H] + ), 372.77。

[0039] I-17 1 H NMR (CDCl3) δ 8.12 (dd, J = 31.9, 8.5Hz, 2H), 7.75 (p, J= 6.3 Hz, 2H), 7.26 (s, 1H), 4.03 (d, J = 7.4 Hz, 2H), 1.17(tt, J = 7.8, 4.7 Hz, 1H), 0.60 (q, J = 5.4 Hz, 2H), 0.32 (q, J = 5.1 Hz, 2H); 13 CNMR δ 179.34, 177.69, 151.21, 139.58, 134.76, 134.13, 131.49, 131.34, 130.33,127.47,127.13, 71.79, 9.82, 3.38; MS: C 15 H 12 ClNO4([M+H] + ), 306.71。

[0040] I-18 1 H NMR (CDCl3) δ 8.10 (d, J = 8.8 Hz,1H), 8.03 (d, J = 8.8 Hz, 1H), 7.73–7.66 (m, 2H), 4.12 (d, J = 6.8 Hz, 2H), 2.60(p, J = 7.5 Hz, 1H), 2.06–1.98 (m, 2H), 1.90–1.81 (m, 2H), 1.74 (p, J = 9.8, 8.6Hz, 2H); 13 C NMR δ 179.31, 177.67, 151.31, 139.59, 134.75, 134.13, 131.47,131.37, 130.33, 127.46,127.12, 70.64, 34.05, 24.67, 18.41; MS: C 16 H 14 ClNO4([M+H] + ), 306.71。

[0041] I-19 1 H NMR (DMSO- d 6) δ 9.83 (s, 1H), 8.07(d, J= 9.0 Hz, 1H), 8.03 (d, J = 9.0 Hz, 1H), 7.90 (d, J = 9.0 Hz, 2H), 3.98 (d, J =7.0 Hz, 2H), 2.17 (p, J = 7.4 Hz, 1H), 1.68 (t, J = 9.8 Hz, 2H), 1.53 (ddd, J =23.2, 13.3, 6.3 Hz, 4H), 1.25 (dd, J = 12.5, 6.8 Hz, 2H); 13 MS: C 17 H 16 ClNO4([M+H] + ), 334.77.

[0042] Example 2 Preparation of Compound II-1:

[0043] 0.63 g (7.5 mmol) of potassium cyanate was suspended in a mixture of 20 mL of anhydrous DMSO and 10 mL of diethylamine, and then 1.1 g (5.0 mmol) of 2,3-dichloro-1,4-naphthoquinone was added. The mixture was stirred at room temperature for 24 h. After the reaction was completed, 50 mL of distilled water was added, and the mixture was cooled at 0 °C for 30 min. The mixture was filtered, and the precipitate was washed with a large amount of distilled water and dried. The mixture was separated and purified by silica gel column chromatography [the mobile phase was V (petroleum ether): V (dichloromethane) = 8:1 – 1:1], and recrystallized from methanol / water V (methanol): V (water) = 4:1. Compounds II-2 to II-8 were synthesized in a similar manner to II-1. 1 H NMR (500 MHz), 13 C NMR (126 MHz) and MS (ESI) spectra and data are as follows.

[0044] II-1 1 H NMR (CDCl3) δ 8.05 (d, J = 7.5 Hz, 1H),7.94 (d, J = 7.4 Hz, 1H), 7.63 (dt,J = 19.6, 7.4 Hz, 2H), 3.55 (q, J = 7.1 Hz,4H), 1.18 (t, J = 7.1 Hz, 6H); 13 C NMR δ 182.50, 177.97, 150.88, 134.91, 133.87,132.96, 132.37, 131.79, 131.68, 126.79, 126.46, 123.83, 59.25, 46.80, 14.03;MS: C 15 H 15 ClN2O3([M+H] + ), 307.75。

[0045] II-2 1 H NMR (DMSO- d 6) δ 7.95 (dd, J = 11.8, 7.7, 1.5Hz, 2H), 7.79 (dt, J = 18.5, 7.4, 1.5 Hz, 2H), 3.46 (d, J = 24.4 Hz, 2H), 3.19(s, 6H); 13 C NMR δ 181.89, 177.32, 151.90, 134.61, 133.57, 131.78, 131.53,127.07, 126.02, 118.10, 44.61; MS: C 13 H 11 ClN2O3([M+H] + ), 279.69。

[0046] II-3 1 H NMR ( DMSO- d 6) δ 7.86 (t, J = 6.5 Hz,2H), 7.73 (t, J = 7.5 Hz, 1H), 7.64 (t, J = 7.6 Hz, 1H), 6.62 (d, J = 8.8 Hz, 1H),4.61 (ddt, J = 12.8, 8.8, 6.4 Hz, 1H), 1.19 (d,J = 6.4 Hz, 6H); 13 C NMR δ 180.54,176.01, 144.77, 135.43, 133.16,132.46, 130.21, 127.00, 126.32, 46.15, 23.89;MS: C 14 H 13 ClN2O3([M+H] + ), 293.72。

[0047] II-4 1 H NMR (DMSO- d 6) δ 8.01 (d, J = 7.6 Hz,1H), 7.89 (d, J = 7.6 Hz, 1H), 7.59 (d, J = 7.5 Hz, 1H), 7.49 (t, J = 7.5 Hz, 1H),6.06 (s, 1H), 3.56 (d, J = 6.7 Hz, 2H), 1.82 (dd, J = 13.5, 6.7 Hz,1H), 0.89 (d, J = 6.7 Hz, 6H); 13 C NMR δ 180.51, 176.75, 144.26, 134.92, 132.78, 132.36,129.72, 126.80, 126.77, 52.14, 29.90, 19.90; MS: C 15 H 15 ClN2O3([M+H] + ), 307.75。

[0048] II-5 1 H NMR (DMSO- d 6) δ 7.96 (dd, J = 11.2, 8.1Hz, 2H), 7.82 (t, J = 8.2 Hz, 1H), 7.73 (t, J = 8.2 Hz, 1H), 7.32 (s, 1H), 3.26–3.17 (m, 1H), 0.91–0.71 (m, 4H); 13C NMR δ 180.19, 176.38, 146.89, 135.34,133.19, 132.49, 130.25, 126.84, 126.36, 109.84,28.01, 9.99; MS: C 14 H 11 ClN2O3([M+H] + ), 291.70。

[0049] II-6 1 H NMR (DMSO- d 6) δ 7.94 (d, J = 7.7 Hz,2H), 7.78 (dt, J = 34.3, 7.3 Hz, 2H), 7.48 (s, 1H), 6.23 (tt, J = 56.0, 3.8 Hz,1H), 4.13 (t, J = 14.2 Hz, 2H); 13 C NMR δ 180.55, 176.07, 146.05, 135.26, 133.43,131.79, 130.60, 127.00, 126.21, 117.68, 115.77, 113.85, 111.95, 56.54, 46.36,46.14, 45.92. MS:C 13 H9ClF2N2O3([M+H] + ), 315.67。

[0050] II-7 1 H NMR (DMSO- d 6) δ 7.96 (d, J = 9.0 Hz,2H), 7.83 (t, J = 8.2 Hz, 1H), 7.76–7.71 (m, 1H), 6.67 (s, 1H), 4.36–4.27 (m,1H), 1.94 (d, J = 12.3 Hz, 2H), 1.73 (d, J = 13.4 Hz, 2H), 1.59 (d, J = 12.8 Hz,1H), 1.45 (q, J = 12.4 Hz, 2H), 1.31 (q,J = 12.5 Hz, 2H), 1.16 (t, J = 12.5 Hz,1H); 13 C NMR δ 180.55, 176.03, 135.48, 135.48, 133.19,132.49, 130.21, 127.04,126.35, 56.52, 53.05, 33.86, 25.30, 24.89, 18.98; MS: C 17 H 17 ClN2O3([M+H] + ),315.67.

[0051] II-8 1 H NMR (DMSO- d 6) δ 8.05 (d, J = 7.7 Hz,1H), 7.76 (d, J = 8.0 Hz, 1H), 7.60 (t, J = 7.5 Hz, 1H), 7.46 (t, J = 7.5 Hz, 3H),7.33 (t, J = 7.5 Hz, 1H), 7.14 (t, J = 7.7 Hz, 1H), 7.01 (t, J = 7.5 Hz, 2H); 13 MS: C 17 H 10 BrClN2O3([M+H] + ), 315.67.

[0052] Example 3 Preparation of Compound III-1

[0053] Under nitrogen protection, 0.5 g (2.5 mmol) 2-amino-3-chloro-1,4-naphthoquinone, 0.32 g NaH and 5 mL anhydrous tetrahydrofuran were added to the reaction bottle and stirred at room temperature for 30 min; 365 μL (3.0 mmol) substituted benzoyl chloride was added, reacted for 1 h, and 10 mL ethanol was added; then 15 mL saturated ammonium chloride solution and 15 mL ethyl acetate were added in sequence, the liquid was extracted, the organic phase was collected, washed three times with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and purified by column chromatography [the mobile phase was V (petroleum ether): V (acetone) = 95:5]; the compound was synthesized. 1 H NMR (500 MHz), 13 C NMR (126 MHz) and MS (ESI) spectra and data are as follows.

[0054] III-1 1 H NMR (DMSO- d 6) δ 10.38 (s, 1H), 8.16–8.09 (m, 1H), 8.09 –8.04 (m, 1H), 7.93 (t, J = 7.4 Hz, 4H), 7.37 (d, J = 7.8 Hz,2H), 2.41 (s, 3H); 13 C NMR δ 179.06, 178.05, 165.61, 143.32, 142.47, 136.80,135.17, 131.47, 131.30, 130.40, 129.58, 128.87, 127.32, 127.25, 21.59;MS:C 18 H 12 ClNO3([M+H] + ), 315.67.

[0055] III-2 1 H NMR (DMSO- d 6) δ 10.67 (s, 1H), 8.22 (t, J = 1.7 Hz, 1H), 8.15–8.10 (m, 1H), 8.09–8.06(m, 1H), 8.00 (d, J = 7.9 Hz,1H), 7.95–7.92 (m, 2H), 7.88 (d, J = 7.2 Hz, 1H), 7.55 (t, J= 7.9 Hz, 1H); 13 C NMRδ 178.87, 177.98, 164.36, 141.97, 137.42,135.80, 135.25, 135.23, 135.20,131.50, 131.38, 131.27, 127.93, 127.35, 127.26, 122.25; MS: C 17 H9BrClNO3([M+H] + ),315.67.

[0056] Example 4 Preparation of Compound IV-1

[0057] 0.22 g (1.0 mmol) 2,3-dichloro-1,4-naphthoquinone, 1.0 mmol substituted sulfonamide, 0.47 g (1.4 mmol) cesium carbonate were added to 4 mL N,N-dimethylformamide and stirred at room temperature for 12 h. After the reaction, distilled water was added to precipitate. The solid product was filtered and recrystallized from methanol. Synthesis of compound 1 H NMR (500 MHz), 13 C NMR (126 MHz) and MS (ESI) spectra and data are as follows.

[0058] IV-1 1 H NMR (\DMSO- d 6) δ 7.94 (d, J = 7.4Hz, 1H), 7.88 (d, J = 7.3 Hz, 1H), 7.82 (d, J = 8.0 Hz, 2H), 7.75 (t, J = 7.2 Hz,1H), 7.68 (t, J = 7.2 Hz, 1H), 7.47 (d, J = 8.0 Hz, 2H), 1.31 (s, 9H); 13 C NMR δ180.60, 176.09, 152.98, 152.72, 146.01,134.26, 133.06, 132.38, 131.62,126.66, 125.78, 125.69, 125.20, 34.99, 31.51; MS: C 20 H 18 ClNO4S ([M+H] + ),404.88.

[0059] IV-2 1 H NMR (DMSO- d 6) δ 8.07 (d, J = 5.8 Hz,1H), 8.04–7.98 (m, 2H), 7.90 (dd, J = 6.2, 2.8 Hz, 2H), 7.78 (d, J = 3.7 Hz, 1H),7.24–7.18 (m, 1H); 13 C NMR δ 179.19, 177.99, 142.40, 140.53, 137.37,135.10,135.08, 131.44, 130.98, 128.00, 127.21, 127.19; MS: C 14 H8ClNO4S2([M+H] + ),354.79。

[0060] IV-3 1 H NMR ( DMSO- d 6) δ 8.31 (d, J = 7.9 Hz,1H), 7.94 (d, J = 7.5 Hz, 1H), 7.81 (dd, J = 11.4, 7.8 Hz, 2H), 7.75 (q, J = 7.8Hz, 2H), 7.68 (t, J = 7.5 Hz, 1H), 7.63 (t, J = 7.6 Hz, 1H); 13 C NMR δ 180.60,176.67, 152.66, 147.45, 134.33,132.75, 132.65, 132.57, 131.48, 130.38,129.40, 127.59, 127.54, 126.69, 125.78, 125.24, 125.06, 124.98, 122.87; MS:C 17 H9ClF3NO4S ([M+H] + ), 416.77。

[0061] IV-4 1H NMR (DMSO- d 6) δ 9.03 (s, 1H), 8.44 (s, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.71 (d, J = 7.4 Hz, 1H), 7.63 (t, J = 7.0 Hz, 1H),7.57 (t, J = 7.5 Hz, 1H), 7.47 (d, J = 5.3 Hz, 1H); 13 MS: C 15 H8Cl2N2O4S ([M+H] + ), 384.20.

[0062] Example 5: Initial screening of herbicidal activity

[0063] Weigh 20 mg of the compound, add 1 mL of DMSO, and prepare a 20,000 mg / L concentration of the drug solution; dilute the obtained drug solution twice to prepare a 10,000 mg / L concentration; in a sterile operating table, take 0.15 mL of each of the two concentrations of the target compound solution, add it to 30 mL of 0.5% agar solution, shake to mix, and quickly pour it into a small beaker, each small beaker is about 10 mL, cool and solidify, and the final compound concentration in the culture medium is 200 μg / mL and 50 μg / mL; each concentration is repeated 3 times, and an equal amount of DMSO culture medium is added as a blank control (CK), and the control agents are algae quinone (ACNQ) and diuron (Diuron); the seeds of Digitaria retroflexa and Amaranthus retroflexus that have been germinated and whitened are respectively inoculated on the culture medium, 10 seeds are inoculated in each small cup, and placed in an incubator (25 ℃, relative humidity 70%, L / D = 12 h: 12 h) and cultured in the blank control. When the blank control roots grew to an appropriate length, the length of the seed roots and stems was measured. The root and stem growth inhibition rate was calculated according to the following formula:

[0064] Inhibition rate / % = [control root (stem) length - treatment root (stem) length] / control root (stem) length × 100

[0065] The herbicidal activity data of compounds Ⅰ-1 to Ⅳ-3 are listed in Table 1.

[0066] Table 1 Preliminary screening of herbicidal activity of target compounds (cup method) (inhibition rate / %)

[0067]

[0068] Example 6 Evaluation of antibacterial activity

[0069] Weigh 20 mg of the target compound and dissolve it in 1 mL of DMSO to obtain a solution with a concentration of 20000 μg / mL; dilute the obtained solution twice to prepare a series of target concentrations; weigh 43 g of PDA culture medium and dissolve it in 1000 mL of distilled water, and sterilize it at 120 ℃ for 30 min. In the sterile operating table, pipette 150 ul of the test solution, add it to 30 mL of sterile PDA culture medium, mix well, pour it into sterile culture dishes, 10 mL per culture dish, and cool it to solidify; add an equal amount of DMSO as the control culture medium; pick the test bacterial cake, put the hyphae down in the center of the treated culture medium, and repeat three times for each treatment; place it in a constant temperature culture room at 25 ± 1 ℃, and culture it until the hyphae grows to about 1 cm from the edge of the culture dish. The colony diameter is measured by the cross method, and the inhibition rate is calculated according to the following formula:

[0070] Mycelium growth inhibition rate / % = (control colony diameter - treated colony diameter) / control colony diameter × 100%

[0071] Toxicity equations and EC of some compounds 50 See Table 2.

[0072] Table 2 Inhibitory effects of target compounds on Botrytis cinerea

[0073]

[0074] Example 7 Algicidal Activity Determination

[0075] There is a correlation between algae density and absorbance value. Algae density can be obtained by measuring the absorbance value of algae. In the early stage of the experiment, a blood cell counting plate was used to observe the changes in the number of algae under a microscope at the same time every day, and the absorbance at 688 nm was measured. The linear equation between algae density and absorbance was established after 8 consecutive days. Then, only the absorbance at 688 nm needs to be measured and the corresponding algae density can be obtained by substituting it into the equation.

[0076] The algae were cultured to the logarithmic growth phase, and the initial algae density was 2.6×10 6 / mL, poured into 50 ml conical flasks, 40 mL per bottle; weighed 20 mg of the compound, dissolved with 1 mL DMSO, the solution concentration was 20000 mg / L, doubled to get 10000 mg / L solution, aspirated 20 ul and added to the algae solution, the final algae solution culture medium compound concentration was 5 and 10 μg / mL; each treatment was repeated three times, with an equal amount of DMSO as the blank control, and the control agents were dimethoate and diuron; 26 ± 2 ℃, 12 h light and 12 h dark, light intensity 4000 lux; after 72 h of culture, the absorbance at 688 nm was measured, and the inhibition rate was calculated according to the following formula;

[0077] IR (%) = ( N0-N / N0 )× 100%

[0078] Among them, IR is the inhibition rate, N is the algae density of the drug-dosing group, N 0 is the algae density of the blank control group;

[0079] The inhibition rate data was greater than 100%, indicating that some algal cells were decomposed by the compounds.

[0080] Table 3 Inhibition results of target compounds on Selaginella fasciata (inhibition rate / %)

[0081]

Claims

1. The structure of a class of aminonaphthoquinone derivatives is shown in the general formula: The structure described by the general formula is any one of the following compounds:

2. The compound according to claim 1, characterized in that: Selected from the following compounds:

3. The compound according to claim 1, characterized in that: Selected from the following compounds:

4. The compound according to claim 1, characterized in that: Selected from the following compounds:

5. Use of the compound as claimed in claim 2 for controlling weeds, wherein the weeds are Amaranthus retroflexus and Digitaria sanguinalis.

6. Use of the compound according to claim 3 in preventing and controlling plant diseases, wherein the plant disease is tomato gray mold.

7. Use of the compound as claimed in claim 4 as an algae killer, wherein the algae is Capricornus sphenanthera.

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