A method for preparing isatoic anhydride synthesized from carbon dioxide

Abstract

The invention provides a preparation method of synthesizing isatoic anhydride from carbon dioxide, belonging to the field of organic chemical synthesis. In a reaction container, carbon dioxide, 2-haloaniline and derivatives thereof are used as raw materials, and in the presence of a palladium metal catalyst, a ligand, a reducing agent, an alkali and an organic solvent, stirring and heating reaction are carried out, and isatoic anhydride is synthesized by mixing and reacting at 25-200 DEG C. The reaction mechanism is as follows: carbon dioxide forms reaction intermediates such as methyl silicate and methyl borate under the action of an alkali and a reducing agent, 2-haloaniline and derivatives thereof react with reaction intermediates such as methyl silicate and methyl borate under the action of a metal catalyst to form a carbonyl metal compound, then carbon dioxide reacts with 2-haloaniline and derivatives thereof under the action of an alkali and a reducing agent to obtain an intermediate, and finally an isatoic anhydride compound is obtained by reaction. The catalyst system has universality for various types of 2-haloaniline and derivatives thereof, and the raw materials are widely available, cheap and easily available, and the reaction process is simple and controllable.

Description

Technical Field

[0001] The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for preparing isatoic anhydride by synthesizing isocyanate from carbon dioxide. Background Art

[0002] Isatoic anhydride, also known as isocyanate, is an important chemical. Isatoic anhydride homologues and derivatives are widely used in the chemical and fine chemical production industries, and have important applications in medicine, pesticides, dyes, foaming agents, flame retardants, preservatives, bleaching agents, fungicides, etc.

[0003] There are many traditional synthetic methods for preparing isatoic anhydride homologues and derivatives, and the simplest and most commonly used production method is to react phthalimide with liquid alkali, sodium hypochlorite, and hydrochloric acid in a water system to obtain isatoic anhydride. For example: 1) Synthesis of isatoic anhydride using anthranilic acid as a raw material with phosgene or ethyl chloroformate, and isatoic anhydride can also be obtained by reacting methyl anthranilate with phosgene, but this method requires the use of highly toxic phosgene; 2) Synthesis of isatoic anhydride from phthalimide, such as dissolving phthalimide in an aqueous solution of sodium hydroxide and adding sodium hypochlorite for oxidation to obtain isatoic anhydride. Such as Chinese invention patents CN101973955B; CN101928257B, etc., but these methods are complicated, the source of reaction raw materials is limited, or there are many side reactions, the product yield is low and the reaction selectivity is poor, and a large amount of waste, such as wastewater, is generated at the same time, which cannot meet the requirements of today's green production. Therefore, the development of new and efficient methods for synthesizing isatoic anhydride has important practical significance.

[0004] Carbonylation is a type of reaction with good atom economy and can efficiently synthesize high-value-added carbonyl compounds; the transition metal-catalyzed amine carbonyl reaction of carbon monoxide and aniline compounds to synthesize isatoic anhydride has the advantages of simple steps, atom economy, and readily available raw materials (Journal of the American Chemical Society 2012, 134, 17490-17493), but this method requires the use of highly toxic carbon monoxide gas and an equivalent amount of copper salt as an oxidant, resulting in a large amount of metal waste. Subsequently, Zhang et al. (ACS Catalysis 2017, 7, 8072-8076) used Pd(PPh) 4 As a catalyst, high-pressure carbon monoxide and carbon dioxide are used as carbonyl sources under alkaline conditions to synthesize isocyanic anhydride. The reaction conditions are relatively mild and the yield is high. However, this type of reaction uses toxic carbon monoxide gas as the carbonyl source, requires special detection equipment, and mixes multiple high-pressure gases. The operation is complicated, which limits its application scenarios and is not conducive to industrial production. Summary of the invention

[0005] In order to solve the above technical problems, the present invention provides a preparation method of isatoic anhydride synthesized from carbon dioxide. Carbon dioxide is an ideal C1 synthon that is cheap, readily available, non-toxic and renewable. The synthesis of isatoic anhydride by carbonyl reaction using carbon dioxide as a carbonyl source has important economic and environmental value. Specifically, 2-haloaniline and its derivatives and carbon dioxide are used as raw materials, and a palladium metal catalyst and a commercial ligand are used as a combined catalyst to prepare isatoic anhydride homologues and derivatives through a one-step carbonylation reaction. The preparation method has cheap and readily available raw materials, high reaction selectivity and efficiency, and a simple route.

[0006] To achieve the above object, the present invention first provides a method for preparing isatoic anhydride by synthesizing isatoic anhydride from carbon dioxide, comprising the following steps:

[0007] In a nitrogen atmosphere, 2-haloaniline and its derivatives shown in Formula 1, a metal catalyst, a ligand, a reducing agent, a base and a solvent are added to a reaction container, the gas in the reaction container is removed, and CO is introduced. 2 , mixed and reacted at 25-200°C for 1-36 h to synthesize the isatoic anhydride shown in Formula 2, the general reaction formula is as follows:

[0008] ;

[0009] Wherein, x in Formula 1 is selected from any one of F, Br, and I, and R 1 Selected from hydrogen, C 1 -C 10 Any one of alkyl, phenol, cyano, trifluoromethyl, nitro, methoxy, ester, carboxyl, and aryl; R 2 Selected from hydrogen, C 1 -C 10 Any one of alkyl, aryl, and naphthyl;

[0010] The metal catalyst is a palladium compound.

[0011] Preferably, the palladium compound is selected from divalent or zerovalent palladium compounds.

[0012] Preferably, the divalent palladium compound is selected from one or more combinations of palladium acetate, palladium dichloride, bis(triphenylphosphine)palladium dichloride, (1,5-cyclooctadiene)palladium dichloride, allylpalladium chloride, bis(acetonitrile)palladium dichloride, palladium trifluoroacetate, tetrakistriphenylphosphine palladium, bis(acetylacetone)palladium, bis(dibenzylideneacetone)palladium, and tris(dibenzylideneacetone)dipalladium.

[0013] Preferably, the ligand is selected from one or more monodentate or polydentate phosphine ligands.

[0014] Preferably, the ligand is selected from triphenylphosphine, triphenylphosphine oxide, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,1'-bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 4,6-bis(diphenylphosphino)-10H-phenoxazine, 1,2-bis(di-tert-butylphosphinomethyl)benzene, 1,1'-bis(di-tert-butylphosphinomethyl)ferrocene, 1,1,1-tris(diphenylphosphinomethyl)ethane, bis(2-diphenylphosphinoethyl)phenylphosphine.

[0015] Preferably, the CO 2 Selected from 11 CO 2 , 12 CO 2 , 13 CO 2 , 14 CO 2 Any one of the CO 2 The pressure is 1 to 40 bar.

[0016] Preferably, the reducing agent is selected from any one of hydrogen, silane or borane.

[0017] Preferably, the silane is selected from phenylsilane, trimethoxysilane, polymethylhydrogensiloxane, triethylsilane, phenylsilane, diphenylsilane, and triisopropylsilane.

[0018] Preferably, the borane is selected from 9-borabicyclo[3.3.1]nonane and pinacol borane.

[0019] Preferably, the base is selected from any one of triethylamine, N-ethyldiisopropylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, ethylenediamine, isopropylamine, sodium carbonate, cesium carbonate, potassium hydroxide, potassium carbonate, potassium phosphate, and piperazine.

[0020] Preferably, the solvent is selected from any one of dichloromethane, dichloroethane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, acetonitrile, methanol, ethanol, 1,4-dioxane, N-methylpyrrolidone, toluene, xylene, mesitylene, and chlorobenzene.

[0021] Preferably, the molar ratio of the 2-haloaniline and its derivatives to the metal catalyst is 1 to 1000:1; the molar ratio of the ligand to the metal catalyst is 0.1 to 100:1; the molar ratio of the 2-haloaniline and its derivatives to the base is 0.1 to 10:1; the molar ratio of the 2-haloaniline and its derivatives to the reducing agent is 0.1 to 10:1.

[0022] The mechanism of the synthesis catalysis in this scheme is as follows:

[0023] The reaction uses 2-haloaniline and its derivatives as the reaction raw materials, carbon dioxide as the carbonyl source, and in the presence of a reducing agent and a base, a heating carbonylation reaction can produce an isatonic anhydride compound; the specific reaction principle is as follows:

[0024] ;

[0025] Carbon dioxide forms reaction intermediates A such as methyl silicate and methyl borate under the action of alkali and reducing agent, 2-haloaniline and its derivatives react with reaction intermediates A such as methyl silicate and methyl borate under the action of metal catalyst to form carbonyl metal compound B, then carbon dioxide reacts with 2-haloaniline and its derivatives under the action of alkali and reducing agent to obtain intermediate C, and finally the isatonic anhydride compound is obtained in the reaction.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] This scheme uses palladium metal catalysts and commercial ligands as the catalyst system to catalyze the carbonylation reaction of 2-haloaniline and its derivatives with carbon dioxide to prepare isocyanic anhydride. The reaction conditions are mild, the reaction selectivity and efficiency are high, and the route is simple.

[0028] Compared with the prior art, the method disclosed in this scheme uses only carbon dioxide gas as the carbonyl source, avoids the use of multiple high-pressure gases, is simple to operate, shortens multi-step reactions to a one-step reaction, and is simple to handle.

[0029] The catalyst system disclosed in the present invention is universal for various types of 2-haloaniline and its derivatives, the raw materials are widely available, cheap and easy to obtain, the reaction process is simple and controllable, and it is suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1This is the H NMR spectrum of the product in Example 1;

[0032] Figure 2 This is the NMR carbon spectrum of the product in Example 1;

[0033] Figure 3 This is the H NMR spectrum of the product in Example 2;

[0034] Figure 4 This is the NMR carbon spectrum of the product in Example 2;

[0035] Figure 5 This is the H NMR spectrum of the product in Example 3;

[0036] Figure 6 This is the NMR carbon spectrum of the product in Example 3;

[0037] Figure 7 This is the H NMR spectrum of the product in Example 4;

[0038] Figure 8 This is the NMR carbon spectrum of the product in Example 4;

[0039] Fig. 9 This is the H NMR spectrum of the product in Example 5;

[0040] Fig.10 This is the NMR carbon spectrum of the product in Example 5;

[0041] Fig.11 This is the H NMR spectrum of the product in Example 6;

[0042] Fig.12 This is the NMR carbon spectrum of the product in Example 6;

[0043] Fig.13 This is the H NMR spectrum of the product in Example 7;

[0044] Fig.14 This is the NMR carbon spectrum of the product in Example 7;

[0045] Fig.15 This is the H NMR spectrum of the product of Example 8;

[0046] Fig.16 This is the NMR carbon spectrum of the product in Example 8;

[0047] Fig.17 This is the H NMR spectrum of the product of Example 9;

[0048] Fig.18 This is the NMR carbon spectrum of the product in Example 9;

[0049] Fig.19 This is the H NMR spectrum of the product in Example 10;

[0050] Fig. 20This is the NMR carbon spectrum of the product in Example 10;

[0051] Fig.21 This is the H NMR spectrum of the product in Example 11;

[0052] Fig. 22 This is the NMR carbon spectrum of the product in Example 11;

[0053] Fig.23 This is the H NMR spectrum of the product of Example 12;

[0054] Fig.24 This is the NMR carbon spectrum of the product in Example 12;

[0055] Fig.25 This is the H NMR spectrum of the product of Example 13;

[0056] Fig.26 This is the H NMR spectrum of the product of Example 14;

[0057] Fig. 27 This is the H NMR spectrum of the product of Example 15. DETAILED DESCRIPTION

[0058] In order to make the technical problems, technical solutions and advantages to be solved by the present invention more clear, a detailed description will be given below with reference to the accompanying drawings and specific embodiments.

[0059] The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention. Without departing from the spirit and substance of the present invention, modifications or substitutions made to the methods, steps or conditions of the present invention are within the scope of the present invention.

[0060] Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art; unless otherwise specified, the reagents used in the examples are commercially available.

[0061] Example 1 Preparation of isatoic anhydride compound 1.

[0062] Under nitrogen atmosphere, tetrakistriphenylphosphine palladium (0.01 mmol), 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene (0.01 mmol, Xantphos) and a magnet were added to a 5 mL reaction bottle. Then, raw material 1 (1 mmol), 9-boranebicyclo[3.3.1]nonane (9-BBN, 1.5 mmol) and cesium carbonate (2.0 mmol), toluene (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 10 bar. After the addition was completed, the reactor was placed in a metal module preheated to 120 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Separation by silica gel chromatography column gave compound 1 with a yield of 92%, and the reaction formula is as follows:

[0063] .

[0064] The H NMR spectrum of compound 1 is shown in Figure 1 As shown, the carbon spectrum is Figure 2 As shown, the NMR data of compound 1:

[0065] 1 H NMR (400 MHz, Chloroform- d ) δ 8.10 (d, J = 7.8, 1H), 7.75 – 7.69(m, 1H), 7.23 (d, J = 8.4 Hz, 1H), 7.13 (d, J = 8.4 Hz, 1H), 4.04 – 3.88 (m,2H), 1.75 (h, J = 7.4 Hz, 2H), 1.00 (t, J = 7.4 Hz, 3H).

[0066] 13 C NMR (100 MHz, Chloroform- d ) δ 158.7, 147.9, 141.4, 137.7, 131.0, 124.0, 114.0, 111.8, 46.5, 20.3, 11.1.

[0067] Example 2 Preparation of isatoic anhydride compound 2.

[0068] Under nitrogen atmosphere, bis(dibenzylideneacetone)palladium (0.01 mmol), 1,1'-bis(diphenylphosphino)ferrocene (0.01 mmol, DPPF) and magnetron were added to a 5 mL reaction bottle. Then, raw material 2 (1 mmol), phenylsilane (1.5 mmol), and tetrahydrofuran (THF) (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 20 bar. After the addition was completed, the reactor was placed in a metal module preheated to 100 degrees Celsius and stirred for 14 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Separated by silica gel chromatography, compound 2 was obtained with a yield of 90%, and the reaction formula is as follows:

[0069] .

[0070] The H NMR spectrum of compound 2 is shown in Figure 3 As shown, the carbon spectrum is Figure 4 As shown, the NMR data of compound 2: 1 H NMR (400 MHz, Chloroform- d ) δ 8.07 – 8.05 (m, 1H), 7.67 – 7.63 (m, 1H), 7.43 –7.41 (m, 1H), 7.30 (t, J = 1.7 Hz, 1H), 7.23 – 7.18 (m, 2H), 6.36 – 6.35 (m,1H), 5.03 (s, 2H).

[0071] 13 C NMR (100 MHz, Chloroform- d ) δ 158.4, 148.0, 144.0, 141.0, 137.3, 134.4, 131.1, 124.2, 119.2, 114.2, 111.9, 110.1, 40.2.

[0072] Example 3 Preparation of isatoic anhydride compound 3.

[0073] Under nitrogen atmosphere, palladium chloride (0.01 mmol), triphenylphosphine (0.02 mmol) and magnetron were added to a 5 mL reaction bottle. Then, raw material 3 (1 mmol), trimethoxysilane (3 mmol), triethylenediamine (2 mmol), and acetonitrile (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 20 bar. After the addition was completed, the reactor was placed in a metal module preheated to 200 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Separated by silica gel chromatography, compound 3 was obtained with a yield of 90%, and the reaction formula is as follows:

[0074] .

[0075] The H NMR spectrum of compound 3 is shown in Figure 5 As shown, the carbon spectrum is Figure 6 As shown, the NMR data of compound 3: 1 H NMR (400 MHz, Chloroform-d) δ 8.20 – 8.12 (m, 1H), 7.67 – 7.59 (m, 1H), 7.35 (d,J = 6.7 Hz, 2H), 7.32 – 7.24 (m, 5H), 5.30 (s, 2H).

[0076] 13 C NMR (100 MHz, Chloroform- d ) δ 158.5, 148.6, 141.5, 137.3, 134.5, 129.3, 128.3, 127.9, 126.7, 124.3, 114.9, 111.9, 48.6.

[0077] Example 4 Preparation of isatoic anhydride compound 4.

[0078] Under nitrogen atmosphere, palladium trifluoroacetate (0.01 mmol), 1,2-bis(diphenylphosphine)methane (0.01 mmol, DPPB) and a magnet were added to a 5 mL reaction bottle. Then, raw material 4 (1 mmol) and 1,4-dioxane (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 20 bar and the hydrogen was pressurized to 50 bar. After the addition was completed, the reactor was placed in a metal module preheated to 130 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 4 was obtained with a yield of 81% using a silica gel chromatography column. The reaction formula is as follows:

[0079] .

[0080] The H NMR spectrum of compound 4 is shown in Figure 7 As shown, the carbon spectrum is Figure 8 As shown, the NMR data of compound 4: 1 H NMR(400 MHz, Chloroform-d) δ 8.15 – 8.12 (m, 1H), 7.64 – 7.62 (m, 1H), 7.24 (d,J = 2.1 Hz, 1H), 7.21 – 7.19 (s, 1H), 7.19 – 7.17 (m, 1H), 7.16 – 7.10 (m,3H), 5.25 (s, 2H), 2.31 (s, 3H).

[0081] 13 C NMR (101 MHz, Chloroform- d ) δ 158.5, 148.6, 141.5, 138.1, 137.3, 131.4, 130.9, 129.9, 126.7, 124.2, 114.9, 111.9, 48.4, 21.2.

[0082] Example 5 Preparation of isatoic anhydride compound 5.

[0083] Under nitrogen atmosphere, palladium acetate (0.01 mmol), 1,2-bis(diphenylphosphine)butane (0.01 mmol, DPPB) and a magnet were added to a 5 mL reaction bottle. Then, raw material 5 (1 mmol), pinacol borane (3 mmol), and toluene (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 20 bar. After the addition was completed, the reactor was placed in a metal module preheated to 100 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 5 was obtained with a yield of 88% using a silica gel chromatography column. The reaction formula is as follows:

[0084] .

[0085] The H NMR spectrum of compound 5 is shown in Fig. 9 As shown, the carbon spectrum is Fig.10 As shown, the NMR data of compound 5: 1 HNMR (400 MHz, Chloroform-d) δ 8.07 (d, J = 7.8 Hz, 1H), 7.58 – 7.54 (m, 1H), 7.21 (d, J = 3.9 Hz, 2H), 7.01 (d, J = 8.5 Hz, 1H), 6.95 (t, J = 8.6 Hz, 2H),5.17 (s, 2H).

[0086] 13 C NMR (100 MHz, Chloroform- d ) δ 162.5 (d, J = 247.1 Hz), 158.3,148.6, 141.3, 137.9, 131.1, 128.65 (d, J = 8.1 Hz), 124.4, 116.2 (d, J = 21.8Hz), 114.6, 111.9, 48.0.

[0087] Example 6 Preparation of isatoic anhydride compound 6.

[0088] Under nitrogen atmosphere, bis(triphenylphosphine)palladium dichloride (0.01 mmol), 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene (0.01 mmol, Xantphos) and a magnet were added to a 5 mL reaction bottle. Then, raw material 6 (1 mmol), polymethylhydrogensiloxane (3 mmol), triethylamine (2 mmol), and dichloroethane (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 20 bar. After the addition was completed, the reactor was placed in a metal module preheated to 80 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 6 was obtained with a yield of 92% using a silica gel chromatography column. The reaction formula is as follows:

[0089] .

[0090] The H NMR spectrum of compound 6 is shown in Fig.11 As shown, the carbon spectrum is Fig.12 As shown, the NMR data of compound 6: 1 HNMR (400 MHz, Chloroform-d) δ 8.18 – 8.13 (m, 1H), 7.67 – 7.64 (m, 1H), 7.29 – 7.25 (m, 4H), 6.89 – 6.86 (m, 2H), 5.24 (s, 2H), 3.78 (s, 3H).

[0091] 13 C NMR (101 MHz, Chloroform- d ) δ 159.4, 158.5, 148.6, 141.4, 137.3, 130.8, 128.2, 127.7, 124.2, 114.8, 114.5, 111.8, 55.3, 48.0.

[0092] Example 7 Preparation of isatoic anhydride compound 7.

[0093] Under nitrogen atmosphere, di(acetylacetonate)palladium (0.01 mmol), 1,2-bis(diphenylphosphine)propane (0.01 mmol, DPPP) and a magnet were added to a 5 mL reaction bottle. Then, raw material 7 (1 mmol), triethylsilane (3 mmol), and THF (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 20 bar. After the addition was completed, the reactor was placed in a metal module preheated to 100 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 7 was obtained with a yield of 82% using a silica gel chromatography column. The reaction formula is as follows:

[0094] .

[0095] The H NMR spectrum of compound 7 is shown in Fig.13 As shown, the carbon spectrum is Fig.14 As shown, the NMR data of compound 7: 1 HNMR (400 MHz, Chloroform- d ) δ 8.19 – 8.16 (m, 1H), 7.65 – 7.64 (m, 1H), 7.49(d, J = 8.4 Hz, 2H), 7.31 (d, J = 6.6 Hz, 2H), 7.19 (d, J = 8.2 Hz, 2H), 5.25(s, 2H).

[0096] 13 C NMR (101 MHz, Chloroform- d ) δ 158.2, 148.5, 141.1, 137.4, 134.4, 131.0, 130.1, 127.8, 124.4, 122.2, 114.5, 111.8, 48.0.

[0097] Example 8 Preparation of isatoic anhydride compound 8.

[0098] Under nitrogen atmosphere, tetrakistriphenylphosphine palladium (0.01 mmol), 1,1'-bis(di-tert-butylphosphinomethyl)ferrocene (0.01 mmol, DPPF) and a magnet were added to a 5 mL reaction bottle. Then, raw material 8 (1 mmol), phenylsilane (3 mmol), and dimethylformamide (DMF) (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 20 bar. After the addition was completed, the reactor was placed in a metal module preheated to 60 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Separation by silica gel chromatography column gave compound 8 with a yield of 83%, and the reaction formula is as follows:

[0099] .

[0100] The H NMR spectrum of compound 8 is shown in Fig.15 As shown, the carbon spectrum is Fig.16 As shown, the NMR data of compound 9: 1 HNMR (400 MHz, DMSO- d 6 ) δ 11.72 (s, 1H), 7.86 – 7.83 (m, 1H), 7.72 – 7.61 (m, 1H), 7.27 – 7.05 (m, 2H).

[0101] 13 C NMR (100 MHz, DMSO- d 6 ) δ 159.9, 147.2, 141.4, 137.0, 129.0, 123.6,115.4, 110.2.

[0102] Example 9 Preparation of isatoic anhydride compound 9.

[0103] Under nitrogen atmosphere, palladium acetate (0.01 mmol), 1,2-bis(diphenylphosphine)butane (0.01 mmol, DPPB) and a magnet were added to a 5 mL reaction bottle. Then, raw material 9 (1 mmol), polymethylhydrogensiloxane (3 mmol), and DMF (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 5 bar. After the addition was completed, the reactor was placed in a metal module preheated to 80 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 9 was obtained with a yield of 82% using a silica gel chromatography column. The reaction formula is as follows:

[0104] .

[0105] The H NMR spectrum of compound 9 is shown in Fig.17 As shown, the carbon spectrum is Fig.18 As shown, the NMR data of compound 9: 1 HNMR (400 MHz, DMSO- d 6 ) δ 7.22 (s, 1H), 6.64 (s, 1H), 3.85 (s, 3H), 3.79 (s, 3H).

[0106] 13 C NMR (100 MHz, DMSO- d 6 ) δ 159.5, 156.6, 147.5, 145.7, 137.7, 108.5,101.2, 97.8, 56.2, 55.9.

[0107] Example 10 Preparation of isatoic anhydride compound 10.

[0108] Under nitrogen atmosphere, tris(dibenzylideneacetone)dipalladium (0.005mmol), 1,1,1-tris(diphenylphosphinomethyl)ethane (0.01mmol, Triphos) and a magnet were added to a 10 mL reaction bottle. Then, raw material 10 (1mmol), polymethylhydrogensiloxane (3mmol), and dimethyl sulfoxide (DMSO) (2mL) were added. The reaction tube was sealed, the air in the reaction bottle was removed and purged with carbon dioxide three times, and finally 20mL of carbon dioxide was added. After the addition was completed, the reactor was placed in a metal module preheated to 120 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 10 was obtained with a yield of 86% by separation using a silica gel chromatography column. The reaction formula is as follows:

[0109] .

[0110] The H NMR spectrum of compound 10 is shown in Fig.19 As shown, the carbon spectrum is Fig. 20 As shown, the NMR data of compound 10: 1 HNMR (400 MHz, DMSO- d 6 ) δ 11.65 (s, 1H), 7.65 (d, J = 2.0 Hz, 1H), 7.52 (dd, J= 8.4, 2.1 Hz, 1H), 7.03 (d, J = 8.3 Hz, 1H), 2.30 (s, 3H).

[0111] 13 C NMR (100 MHz, DMSO- d 6 ) δ 159.9, 147.2, 139.3, 138.0, 133.0, 128.3, 115.3, 110.0, 20.1.

[0112] Example 11 Preparation of isatoic anhydride compound 11.

[0113] Under nitrogen atmosphere, bis(acetonitrile)palladium dichloride (0.01 mmol), 4,6-bis(diphenylphosphine)-10H-phenoxazine (0.01 mmol) and a magnet were added to a 5 mL reaction bottle. Then, raw material 11 (1 mmol), diphenylsilane (3 mmol), and DMF (2 mL) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 10 bar. After the addition was completed, the reactor was placed in a metal module preheated to 100 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 11 was obtained with a yield of 88% using a silica gel chromatography column. The reaction formula is as follows:

[0114] .

[0115] The H NMR spectrum of compound 11 is shown in Fig.21 As shown, the carbon spectrum is Fig. 22 As shown, the NMR data of compound 11: 1 HNMR (400 MHz, DMSO- d 6 ) δ 11.79 (s, 1H), 7.62 – 7.56 (m, 2H), 7.16 – 7.13 (m, 1H).

[0116] 13 C NMR (100 MHz, DMSO- d 6 ) δ 159.3, 157.7 (d, J = 241.8 Hz), 146.9,138.2, 124.9 (d, J = 24.3 Hz), 117.7 (d, J= 7.9 Hz), 114.0 (d, J = 24.1 Hz),111.4 (d, J = 8.5 Hz).

[0117] Example 12 Preparation of isatoic anhydride compound 12.

[0118] Under nitrogen atmosphere, palladium acetate (0.01 mmol), 1,2-bis(diphenylphosphine)butane (0.01 mmol, DPPB) and a magnet were added to a 5 mL reaction bottle. Then, raw material 12 (1 mmol), triisopropylsilane (2 mmol), and N-methylpyrrolidone (2 mL, NMP) were added. The reaction tube was placed in a reactor, the reactor was sealed, the air in the reactor was removed and purged with carbon dioxide three times, and finally the carbon dioxide was pressurized to 30 bar. After the addition was completed, the reactor was placed in a metal module preheated to 600 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. Compound 12 was obtained with a yield of 92% using a silica gel chromatography column. The reaction formula is as follows:

[0119] .

[0120] The H NMR spectrum of compound 12 is shown in Fig.23 As shown, the carbon spectrum is Fig.24 As shown, the NMR data of compound 12: 1 HNMR (400 MHz, DMSO- d 6 ) δ 11.87 (s, 1H), 7.76 (d, J = 1.9 Hz, 1H), 7.74 – 7.65(m, 1H), 7.11 (d, J = 8.7 Hz, 1H).

[0121] 13 C NMR (100 MHz, DMSO-d6) δ 159.0, 146.8, 140.3, 136.7, 127.7, 127.3, 117.5, 111.9.

[0122] Example 13 Preparation of isatoic anhydride compound 13.

[0123] Under nitrogen atmosphere, palladium chloride (0.01 mmol), 1,5-bis(diphenylphosphino)pentane (0.01 mmol) and a magnet were added to a 10 mL reaction bottle. Then, raw material 13 (1 mmol), polymethylhydrogensiloxane (3 mmol) and DMSO (2 mL) were added. The reaction tube was sealed, the air in the reaction tube was removed and the reaction tube was heated to 40 ℃ for 2 h. 14 CO 2 Wash three times, the final 20 mL 14 CO 2 After the addition was completed, the reaction tube was placed in a metal module preheated to 100 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. The compound 13 was obtained with a yield of 95% by separation using a silica gel chromatography column. The reaction formula is as follows:

[0124] .

[0125] The H NMR spectrum of compound 13 is shown in Fig.25 As shown, the NMR data of compound 13: 1 H NMR (400 MHz, DMSO- d 6 ) δ 11.87 (s, 1H), 7.93 (d, J = 2.3 Hz, 1H), 7.85 (dd, J = 8.7, 2.3Hz, 1H), 7.09 (s, 1H).

[0126] Example 14 Preparation of isatoic anhydride compound 14.

[0127] Under nitrogen atmosphere, palladium acetate (0.01 mmol), Xantphos (0.01 mmol) and a magnet were added to a 10 mL reaction bottle. Then, raw material 14 (1 mmol), diphenylsilane (3 mmol) and DMF (2 mL) were added. The reaction tube was sealed, the air in the reaction tube was removed and the reaction tube was heated to 40 ℃ for 2 h. 13 CO 2 Wash three times and finally add 20 mL 13 CO 2 After the addition was completed, the reaction tube was placed in a metal module preheated to 100 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. The compound 14 was obtained with a yield of 85% by separation using a silica gel chromatography column. The reaction formula is as follows:

[0128] .

[0129] The H NMR spectrum of compound 14 is shown in Fig.26As shown, the NMR data of compound 14:

[0130] 1 H NMR (400 MHz, DMSO-d6) δ 11.66 (s, 1H), 7.80 (d, J = 8.8 Hz, 1H), 6.80 (dd, J = 8.8, 2.4 Hz, 1H), 6.57 (d, J = 2.4 Hz, 1H), 3.82 (s, 3H).

[0131] Example 15 Preparation of isatoic anhydride compound 15.

[0132] Under nitrogen atmosphere, palladium acetate (0.01 mmol), 1,2-bis(diphenylphosphino)butane (0.01 mmol, DPPB) and a magnet were added to a 10 mL reaction bottle. Then, raw material 15 (1 mmol), polymethylhydrogensiloxane (3 mmol), and DMF (2 mL) were added. The reaction tube was sealed, the air in the reaction tube was removed, and the reaction tube was heated to 40 ℃ for 2 hours. 11 CO 2 Wash three times and finally add 20 mL 13 CO 2 After the addition was completed, the reaction tube was placed in a metal module preheated to 100 degrees Celsius and stirred for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and the pressure was slowly released. The compound 15 was obtained with a yield of 90% by separation using a silica gel chromatography column. The reaction formula is as follows:

[0133] .

[0134] The H NMR spectrum of compound 15 is shown in Fig. 27 As shown, the NMR data of compound 15: 1 H NMR (400 MHz, DMSO- d 6 ) δ 11.65 (s, 1H), 7.65 (d, J = 2.0 Hz, 1H), 7.52 (dd, J = 8.4, 2.1Hz, 1H), 7.03 (d, J = 8.3 Hz, 1H), 2.30 (s, 3H).

[0135] The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. For those skilled in the art, improvements and changes obtained without departing from the technical concept of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing isatoic anhydride synthesized from carbon dioxide, characterized in that: The following steps are involved: In a nitrogen atmosphere, 2-haloaniline and its derivatives, a metal catalyst, a ligand, a reducing agent, a base and a solvent as shown in Formula 1 are added to a reaction container, the gas in the reaction container is removed, CO2 is introduced, and the mixture is reacted at 25 to 200° C. for 1 to 36 h to synthesize the isatoic anhydride as shown in Formula 2. The general reaction formula is as follows: ， Wherein, x in Formula 1 is selected from any one of F, Br, and I, and R 1 Selected from hydrogen, C1-C 10 Any one of alkyl, phenol, cyano, trifluoromethyl, nitro, methoxy, and carboxyl; R 2 Selected from hydrogen, C1-C 10 Any one of alkyl and naphthyl; The metal catalyst is selected from one or more combinations of palladium acetate, palladium dichloride, bis(triphenylphosphine)palladium dichloride, (1,5-cyclooctadiene)palladium dichloride, allylpalladium chloride, bis(acetonitrile)palladium dichloride, palladium trifluoroacetate, tetrakistriphenylphosphine palladium, di(acetylacetone)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium; The ligand is selected from triphenylphosphine, triphenylphosphine oxide, bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,5-bis(diphenylphosphino)pentane, 1,1'-bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 4,6-bis(diphenylphosphino)-10H-phenoxazine, 1,2-bis(di-tert-butylphosphinomethyl)benzene, 1,1'-bis(di-tert-butylphosphinomethyl)ferrocene, 1,1,1-tris(diphenylphosphinomethyl)ethane, bis(2-diphenylphosphinoethyl)phenylphosphine; The reducing agent is selected from any one of hydrogen, phenylsilane, trimethoxysilane, polymethylhydrogensiloxane, triethylsilane, diphenylsilane, triisopropylsilane, 9-borabicyclo[3.3.1]nonane and pinacol borane.

2. The preparation method according to claim 1, characterized in that: The CO2 is selected from 11 CO2, 12 CO2, 13 CO2, 14 Any one of CO2, wherein the pressure of the CO2 is 1 to 40 bar.

3. The preparation method according to claim 1, characterized in that: The base is selected from any one of triethylamine, N-ethyldiisopropylamine, triethylenediamine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,5, 7-triazidobicyclo(4.4.0)dec-5-ene, ethylenediamine, isopropylamine, sodium carbonate, cesium carbonate, potassium hydroxide, potassium carbonate, potassium phosphate, and piperazine.

4. The preparation method according to claim 1, characterized in that: The solvent is selected from any one of dichloromethane, dichloroethane, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, acetonitrile, methanol, ethanol, 1,4-dioxane, N-methylpyrrolidone, toluene, xylene, mesitylene, and chlorobenzene.

5. The preparation method according to claim 1, characterized in that: The molar ratio of the 2-haloaniline and its derivatives to the metal catalyst is 1 to 1000:1; the molar ratio of the ligand to the metal catalyst is 0.1 to 100:1; the molar ratio of the 2-haloaniline and its derivatives to the base is 0.1 to 10:1; the molar ratio of the 2-haloaniline and its derivatives to the reducing agent is 0.1 to 10:1.

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