1-allyl hydrazine carboxylic acid tert-butyl ester as well as preparation method and application thereof

Abstract

The invention specifically discloses 1-allyl hydrazine carboxylic acid tert-butyl ester as well as a preparation method and application thereof. According to the preparation method, tert-butoxyformylhydrazine is taken as a raw material, an intermediate is obtained after imino protection and N-allylation, and then a target product is obtained after deimino protection. The synthesis method is simple to operate, mild in condition, high in yield and good in repeatability, does not need to use a highly toxic hydrazine reagent, and does not need column separation operation. The preparation method provided by the invention is simple in process, relatively low in cost, mild and easy to control in reaction condition, safe and reliable in production process and suitable for industrialization.

Description

Technical Field

[0001] The invention belongs to the field of medical technology, and in particular relates to tert-butyl 1-allylhydrazinecarboxylate, a preparation method and application thereof. Background Art

[0002] Adavosertib (AZD1775) is a pyrazolo[5,4-d]pyrimidin-3-one small molecule Wee1 kinase inhibitor with IC 50 The value is 5.1nM. Adavosertib is the most studied Weel kinase inhibitor and has entered the clinical phase II research stage. In theory, Adavosertib can act on p53 gene deletion / mutation tumors as a single drug, and can be combined with traditional chemotherapy drugs and radiotherapy to enhance its therapeutic effect. It can also act on the DNA repair process with emerging PARP inhibitors to kill tumor cells.

[0003] 1-allylhydrazinecarboxylic acid tert-butyl ester is a key intermediate for the synthesis of Adavosertib and its analogs. The reported literature and patents (ACS Chem.Biol.2016, 11:921-930, ChemMedChem, 2018, 13(16):1681-1694, Wo201775629, CN113402520) all use tert-butyl carbazate as the starting material, obtain an amino-protected intermediate under the action of phthalic anhydride, and then react with an allylation agent under the action of a base and a phase transfer catalyst (such as triethylbenzylammonium chloride) to obtain an N-allylated intermediate, and remove the phthalic acid protecting group under the action of hydrazine hydrate or methylhydrazine to obtain tert-butyl 1-allylhydrazinecarboxylate.

[0004] The synthesis method of 1-allylhydrazinecarboxylic acid tert-butyl ester reported in the above-mentioned documents and patents uses a large amount of highly toxic hydrazine hydrate / methylhydrazine reagents, which has great potential hazards to the synthesis operators. Phase transfer catalysts are used in the synthesis process, which are easy to cause residues and are not conducive to quality control. In addition, individual steps also require silica gel column chromatography purification, which greatly reduces the possibility of industrial production of the synthesis process. Based on the above-mentioned defects, we adopted a more reasonable synthesis strategy, selectively protecting the primary amine group by the imino group, which integrates the reaction and recrystallization purification, and then introduces the allyl group, and finally uses a mild and low-toxic deprotection method to obtain the target product 1-allylhydrazinecarboxylic acid tert-butyl ester, and the whole process does not require column separation and purification. Compared with the synthesis method reported in the above-mentioned document patent, the preparation method provided by this method is simple in process, the reaction conditions are mild and easy to control, the production process is safe and reliable, and it is suitable for industrialization. Summary of the invention

[0005] The present invention aims to provide a method for preparing tert-butyl 1-allylhydrazinecarboxylate. The structural formula A of tert-butyl 1-allylhydrazinecarboxylate is as follows:

[0006]

[0007] After in-depth and meticulous research, the inventors proposed the following new process route: using tert-butoxyformyl hydrazide as a raw material, first using an aldehyde or ketone to react with its exposed amino group to generate an imine intermediate, then using an allylation reagent to introduce an allyl group to its amide nitrogen atom, and finally removing the imine protecting group by a water-soluble hydrazide reagent, hydrazine monohydrochloride or hydroxylamine hydrochloride to obtain the target product. The method is simple in process, the reaction conditions are mild and easy to control, the production process is safe and reliable, and it is suitable for industrial production.

[0008] A method for preparing tert-butyl 1-allylhydrazinecarboxylate, the reaction formula is as follows:

[0009]

[0010] The method comprises heating compound B in the presence of a benzaldehyde derivative in an alcohol solvent to react, so that compound B is converted into an imine intermediate C-1:

[0011]

[0012] The substituent R1 is a hydrogen atom, a straight chain or branched chain alkyl group having 1 to 5 carbon atoms, a straight chain or branched chain alkoxy group having 1 to 5 carbon atoms, a halogen atom, a cyano group, a nitro group, or an amide group;

[0013] The method comprises heating compound B in the presence of a diketone compound in an alcohol solvent to react, so that compound B is converted into an imine intermediate C-2:

[0014]

[0015] The substituents R2 and R3 are phenyl or straight or branched chain alkyl groups having 1 to 5 carbon atoms in length.

[0016] The molar ratio of the benzaldehyde derivative to compound B is 0.85-1.1:1; the molar ratio of the diketone compound to compound B is 0.45-0.55:1. The molar ratio of the catalyst to compound B is 0.01-1:1. The ratio of the alcohol solvent (volume, unit: ml) to the mass of compound B (unit: g) is 5-15:1. The reaction temperature is 50-150°C. The reaction time is 1-24 hours.

[0017] Further preferably, the benzaldehyde derivative is benzaldehyde, and the molar ratio of the amount relative to compound B is 1.05:1; the diketone compounds are benzoyl, 2,3-butanedione and 3,4-hexanedione, and the molar ratio of the amount relative to compound B is 0.47:1. The catalysts are pyridinium p-toluenesulfonate and pyridinium benzenesulfonate, and the molar ratio of the amount relative to compound B is 0.05-0.25:1. The alcohol solvents are methanol, ethanol and isopropanol, and the amount (volume, unit: ml) relative to the mass (unit: g) of compound B is 10:1. The reaction temperature is 70-100°C. The reaction time is 5-16 hours.

[0018] The method comprises converting compound C-1 into D-1 in the presence of an allylation agent and a base in an aprotic solvent at room temperature or in an ice bath:

[0019]

[0020] The method comprises converting compound C-2 into D-2 in the presence of an allylation agent and a base in an aprotic solvent at room temperature or in an ice bath:

[0021]

[0022] The molar ratio of the allylation agent used relative to compound C-1 is 1 to 5:1, and the molar ratio relative to compound C-2 is 2 to 10:1. The molar ratio of the base used relative to compound C-1 is 1 to 5:1, and the molar ratio relative to compound C-2 is 2 to 10:1. The amount of the aprotic solvent used (volume, unit: ml) relative to the mass (unit: g) of compounds C-1 and C-2 is 10 to 50:1. The reaction temperature is -20 to 50°C. The reaction time is 5 to 48 hours.

[0023] Further preferably, the allylation agent is allyl chloride and allyl bromide, and the molar ratio of the amount thereof relative to compound C-1 is 2.2:1, and the molar ratio relative to compound C-2 is 4.2:1; the base is potassium tert-butoxide, sodium tert-butoxide and sodium hydride, and the molar ratio of the amount thereof relative to compound C-1 is 2.5:1, and the molar ratio relative to compound C-2 is 4.5:1; the aprotic solvent is tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and isopropyl ether, and the amount thereof (volume, unit: ml) relative to the mass (unit: g) of compound C-1 and C-2 is 30:1. The reaction temperature is 0-25°C. The reaction time is 12-24 hours.

[0024] The method comprises using a water-soluble hydrazide reagent, hydrazine monohydrochloride or hydroxylamine hydrochloride to heat in a polar solvent to remove D-1 or the imine structure in D-1 to obtain the target product A.

[0025]

[0026] The molar ratio of the water-soluble hydrazide reagent, hydrazine monohydrochloride or hydroxylamine hydrochloride to compound D-1 is 1 to 6:1, and the molar ratio to compound D-2 is 2 to 10:1; the amount of the polar solvent (volume, unit: ml) to the mass of compound D-1 and D-2 (unit: g) is 5 to 15:1. The reaction temperature is 50 to 150° C. The reaction time is 5 to 48 hours.

[0027] Further preferably, the water-soluble hydrazide reagent is 2-hydrazine-N,N,N-trimethyl-2-oxoethylammonium chloride (also known as Girard reagent T) and 1-(2-hydrazine-2-oxoethyl)pyridinium chloride (also known as Girard reagent P), and the molar ratio of hydrazine monohydrochloride or hydroxylamine hydrochloride to compound D-1 is 3:1, and the molar ratio to compound D-2 is 5:1. The polar solvent is methanol, ethanol, isopropanol, pyridine, and the amount (volume, unit: ml) relative to the mass (unit: g) of compound D-1 and D-2 is 10:1. The reaction temperature is 70-100°C. The reaction time is 12-24 hours. DETAILED DESCRIPTION

[0028] The present invention is further described in the following examples. All examples are actual examples. These examples are for illustrative purposes only and should not be construed as limiting the appended claims.

[0029] Example 1 (E) -2-Benzylidene tert-butyloxycarboxylic acid hydrazide (C-1)

[0030]

[0031] 20.00 g of tert-butoxyformyl hydrazide (151.33 mmol, 1.00 eq) was dissolved in 150 mL of anhydrous ethanol, and 16.38 g of benzaldehyde (154.36 mmol, 1.02 eq) was added, heated to reflux, reacted for about 5 hours, cooled to room temperature, filtered, and the filter cake was washed twice with anhydrous ether. After drying, 32.43 g of a white solid was obtained, with a yield of 95.4%. 1 H NMR (300MHz, DMSO-d6) δ10.89 (s, 1H), 8.00 (s, 1H), 7.69-7.51 (m, 2H), 7.49-7.27 (m, 3H), 1.48 (s, 9H).

[0032] Example 2 2,2′-(1,2-diphenylethane-1,2-diylidene)(2E,2′E)-bis(hydrazine-1-carboxylic acid) di-tert-butyl ester (C-2-a)

[0033]

[0034] 13.33 g of tert-butoxyformyl hydrazide (99.89 mmol, 2.1 eq) was dissolved in 50 mL of anhydrous ethanol, 10.00 g of benzoyl (47.57 mmol, 1 eq) and 1.20 g of pyridinium p-toluenesulfonate (4.76 mmol, 0.1 eq) were added, heated to reflux, reacted for about 12 hours, cooled to room temperature, filtered, and the filter cake was washed with anhydrous ethanol and anhydrous ether in turn, and dried to obtain 17.44 g of a white solid with a yield of 83.6%. 1 H NMR (400MHz, DMSO-d6) δ8.52 (s, 2H), 7.60-7.40 (m, 6H), 7.38-7.26 (m, 4H), 1.31 (s, 18H).

[0035] Example 32, 2′-(Butane-2,3-diylidene)(2E,2′E)-bis(hydrazine-1-carboxylic acid) di-tert-butyl ester (C-2-b)

[0036]

[0037] Dissolve 16.12 g of tert-butoxyformyl hydrazide (119.50 mmol, 2.1 eq) in 50 mL of anhydrous ethanol, add 5.0 g of 2,3-butanedione (56.90 mmol, 1 eq) and 1.44 g of pyridinium p-toluenesulfonate (5.69 mmol, 0.1 eq), heat to reflux, react for about 16 hours, cool to room temperature, filter, wash the filter cake with anhydrous ethanol and anhydrous ether in turn, and dry to obtain 17.18 g of a white solid, with a yield of 96.0%. 1 H NMR (400MHz, DMSO-d6) δ9.87 (s, 2H), 2.00 (s, 6H), 1.47 (s, 9H).

[0038] Example 42, 2′-(Hexane-3,4-diylidene)(2E,2′E)-bis(hydrazine-1-carboxylic acid) di-tert-butyl ester (C-2-c)

[0039]

[0040] Dissolve 12.03 g of tert-butoxyformyl hydrazide (90.15 mmol, 2.1 eq) in 100 mL of anhydrous ethanol, add 5.0 g of 3,4-hexanedione (42.93 mmol, 1 eq) and 1.09 g of pyridinium p-toluenesulfonate (4.29 mmol, 0.1 eq), heat to reflux, react for about 16 hours, cool to room temperature, filter, wash the filter cake with anhydrous ethanol and anhydrous ether in turn, and obtain 13.43 g of a white solid after drying. Yield: 91.4%. 1 H NMR (400MHz, DMSO-d6) δ10.00 (s, 2H), 2.60 (q, J=7.4Hz, 4H), 1.47 (s, 18H), 0.87 (t, J=7.4Hz, 6H).

[0041] Example 5 (E) 1-allyl-2-benzylidene tert-butyloxycarboxylic acid hydrazide (D-1)

[0042]

[0043] 20.00g C-1 (90.80mmol, 1eq) was added to 800mL anhydrous tetrahydrofuran, placed in an ice bath for mechanical stirring, 26.49g potassium tert-butoxide (236.08mmol, 2.6eq) was weighed, and added to the system in batches several times, keeping the system temperature not higher than 5°C. 24.16g allyl bromide (199.76mmol, 2.2eq) was weighed and added dropwise to the system, and the ice bath was removed after the dropwise addition, and the reaction was transferred to room temperature overnight. Filter, evaporate the filtrate under reduced pressure, extract the residue with 800mL ethyl acetate and 500mL saturated brine, wash the organic layer with water again, dry the organic layer with anhydrous sodium sulfate, and evaporate the solvent under reduced pressure to obtain 23.00g of light yellow oil, with a yield of 97.3%. 1 H NMR (400MHz, Chloroform-d) δ7.80-7.61 (m, 3H), 7.44-7.32 (m, 3H), 5.84 (ddt, J=1 7.2, 10.5, 4.5Hz, 1H), 5.28-5.09 (m, 2H), 4.55 (dd, J=4.4, 2.2Hz, 2H), 1.60 (s, 9H).

[0044] Example 6 1,1′-diallyl-2,2′-(1,2-diphenylethane-1,2-diylidene)(2E,2′E)-bis(hydrazine-1-carboxylic acid) di-tert-butyl ester (D-2-a)

[0045]

[0046] 10.00g C-2-a (22.8mmol, 1eq) was added to 300mL anhydrous tetrahydrofuran, placed in an ice bath for mechanical stirring, 10.00g sodium tert-butoxide (102.60mmol, 4.5eq) was weighed, and added to the system in batches several times, keeping the system temperature not higher than 5°C. 11.80g allyl bromide (95.80mmol, 4.2eq) was weighed and added dropwise to the system, and the ice bath was removed after the dropwise addition, and the reaction was transferred to room temperature overnight. Filter, evaporate the filtrate under reduced pressure, extract the residue with 300mL ethyl acetate and 200mL saturated brine, wash the organic layer with water again, dry the organic layer with anhydrous sodium sulfate, evaporate the solvent under reduced pressure to obtain a yellow oil, which solidified after cooling to obtain 11.56g, with a yield of 97.8%. 1 H NMR (400MHz, DMSO-d6) δ7.49-7.28 (m, 10H), 5.76 (ddt, J=16.5, 10.3, 6.1Hz, 2H), 5.23-5.03 (m, 4H), 4.01 (d, J=6.1Hz, 4H), 115 (s, 18H).

[0047] Example 7 1,1′-diallyl-2,2′-(butane-2,3-diylidene)(2E,2′E)-bis(hydrazine-1-carboxylic acid) di-tert-butyl ester (D-2-b)

[0048]

[0049] 5.00g C-2-b (15.90mmol, 1 eq) was added to 200mL anhydrous tetrahydrofuran, placed in an ice bath for mechanical stirring, 7.02g sodium tert-butoxide (71.60mmol, 4.5eq) was weighed, and added to the system in batches several times, keeping the system temperature not higher than 5°C. 8.25g allyl bromide (66.80mmol, 4.2eq) was weighed and added dropwise to the system, and the ice bath was removed after the dropwise addition, and the reaction was transferred to room temperature overnight. Filter, evaporate the filtrate under reduced pressure, extract the residue with 200mL ethyl acetate and 100mL saturated brine, wash the organic layer with water again, dry the organic layer with anhydrous sodium sulfate, and evaporate the solvent under reduced pressure to obtain 5.36g of yellow oil, with a yield of 85.4%. 1 H NMR (400MHz, Chloroform-d) δ5.88 (ddt, J=16.6, 10.2, 6.3Hz, 2H), 5.26-5.11 (m, 4H), 4.20 (dt, J=6.3, 1.4Hz, 4H), 2.08 (s, 6H), 1.47 (s, 18H).

[0050] Example 8 1,1′-diallyl-2,2′-(hexane-3,4-diylidene)(2E,2′E)-bis(hydrazine-1-carboxylic acid) di-tert-butyl ester (D-2-c)

[0051]

[0052] 5.00g C-2-c (14.60mmol, 1eq) was added to 200mL anhydrous tetrahydrofuran, placed in an ice bath for mechanical stirring, 6.44g sodium tert-butoxide (65.70mmol, 4.5eq) was weighed, and added to the system in batches several times, keeping the system temperature not higher than 5°C. 7.57g allyl bromide (61.32mmol, 4.2eq) was weighed and added dropwise to the system, and the ice bath was removed after the dropwise addition, and the mixture was transferred to room temperature for overnight reaction. The mixture was filtered, and the filtrate was evaporated under reduced pressure. The residue was extracted with 200mL ethyl acetate and 100mL saturated brine, and the organic layer was washed with water again, and the organic layer was dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure to obtain 3.49g of a yellow oil, with a yield of 56.6%. 1 H NMR (400MHz, Chloroform-d) δ5.85 (ddt, J=16.6, 10.2, 6.3Hz, 2H), 5.24-5.09 (m, 4H), 4 .18 (dt, J=6.3, 1.4Hz, 4H), 2.62 (q, J=7.6Hz, 4H), 1.47 (s, 18H), 1.03 (t, J=7.5Hz, 6H).

[0053] Example 9 tert-Butyl 1-allylhydrazinecarboxylate (A)

[0054]

[0055] 12.6g D-1 (48.40mmol, 1eq) and 48.46g (289.07mmol, 6eq) Girard reagent T were dissolved in 250mL anhydrous methanol and heated to reflux overnight. After the reaction was complete, the solvent was evaporated under reduced pressure, and the residue was extracted with 200mL ethyl acetate and 100mL water. The aqueous layer was extracted twice with ethyl acetate, and the organic layers were combined. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 6.92g of a yellow oily substance with a yield of 83.04%. 1 H NMR (400MHz, DMSO-d6) δ5.80 (ddt, J=17.2, 9.4, 5.4Hz, 1H), 5.10 (d, J=1.6Hz, 1H), 5.07 (dq, J=6.6, 1.7Hz, 1H), 4.48 (s, 2H), 3.85 (dt, J=5.6, 1.6Hz, 2H), 1.40 (s, 9H).

[0056] Example 10 tert-Butyl 1-allylhydrazinecarboxylate (A)

[0057]

[0058] 1.93g D-2-a (3.72mmol, 1eq) and 1.04g hydrazine monohydrochloride (149mmol, 4eq) were added to 50mL anhydrous methanol and heated to reflux for 10 hours. Filter, evaporate the filtrate under reduced pressure, extract the residue with 50mL ethyl acetate and 30mL water, extract the water layer with ethyl acetate twice, and combine the organic layers. Dry the organic layer with anhydrous sodium sulfate, evaporate the solvent under reduced pressure, and obtain 0.62g of yellow oil, yield: 49%. 1 H NMR (400MHz, DMSO-d6) δ5.80 (ddt, J=17.2, 9.4, 5.4Hz, 1H), 5.10 (d, J=1.6Hz, 1H), 5.07 (dq, J=6.6, 1.7Hz, 1H), 4.48 (s, 2H), 3.85 (dt, J=5.6, 1.6Hz, 2H), 1.40 (s, 9H).

[0059] Example 11 tert-Butyl 1-allylhydrazinecarboxylate (A)

[0060]

[0061] 0.5 g of D-1 (1.92 mmol, 1 eq) and 0.27 g of hydroxylamine hydrochloride (3.84 mmol, 2 eq) were added to 5 mL of anhydrous pyridine and reacted at 60°C overnight. The solution was evaporated under reduced pressure, and the residue was extracted with 50 mL of ethyl acetate and 30 mL of water. The aqueous layer was extracted twice with ethyl acetate, and the organic layers were combined. The organic layer was dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 0.27 g of a yellow oil, with a yield of 82.5%. 1 H NMR (400MHz, DMSO-d6) δ5.80 (ddt, J=17.2, 9.4, 5.4Hz, 1H), 5.10 (d, J=1.6Hz, 1H), 5.07 (dq, J=6.6, 1.7Hz, 1H), 4.48 (s, 2H), 3.85 (dt, J=5.6, 1.6Hz, 2H), 1.40 (s, 9H).

Claims

1. The following compounds and their pharmaceutically acceptable salts:

2. A method for preparing compound A and its salts, the method using tert-butoxyformyl hydrazide as a raw material, first using an aldehyde or a ketone to react with its exposed amino group to generate an imine intermediate, then using an allylation reagent to introduce an allyl group into its amide nitrogen atom, and then removing the imine protecting group by a water-soluble hydrazide reagent or a hydroxylamine reagent to obtain compound A.

3. The method according to claim 2, wherein the generation of the imine intermediate is: in the presence of a benzaldehyde derivative or a diketone compound, in the presence of a catalyst, compound B is converted into C-1, C-2 by heating in an alcohol solvent: It is small, the substituent R1 is a hydrogen atom, a straight chain or branched alkyl group with a length of 1-5 carbon atoms, a straight chain or branched alkoxy group with a length of 1-5 carbon atoms, a halogen atom, a cyano group, a nitro group, or an amide group; R2 and R3 are phenyl groups or straight chain or branched alkyl groups with a length of 1-5 carbon atoms.

4. The method according to claim 2, wherein the introduction of an allyl group into the amide nitrogen atom is carried out by converting compound C-1 into D-1, or converting compound C-2 into D-2, in the presence of an allylation agent and a base in an aprotic solvent at room temperature or in an ice bath:

5. The method according to claim 2, wherein the removal of the imine protecting group is: using any one of a water-soluble hydrazide reagent, hydrazine monohydrochloride, and hydroxylamine hydrochloride to heat in a polar solvent to remove the imine structure of D-1 or D-1 smaller, to obtain the target product A 6. According to the method of claim 3, the molar ratio of the amount of the benzaldehyde derivative to compound B is (0.85-1.1):1; the molar ratio of the amount of the diketone compound to compound B is (0.45-0.55):1; the molar ratio of the amount of the catalyst to compound B is (0.01-, 1):1; the volume amount (ml) of the alcohol solvent to the mass (g) of compound B is (5-15):1; the reaction temperature is 50-150°C; and the reaction time is 1-24 hours.

7. The method according to claim 6, wherein the benzaldehyde derivative is benzaldehyde, and its molar ratio relative to compound B is 1.05:1; the diketone compounds are benzoyl, 2,3-butanedione and 3,4-hexanedione, and their molar ratio relative to compound B is 0.47:1; the catalysts are pyridinium p-toluenesulfonate and pyridinium benzenesulfonate, and their molar ratio relative to compound B is (0.05-0.25):1; the alcohol solvent is selected from methanol, ethanol and isopropanol; the volume amount of alcohol (ml) relative to the mass (g) of compound B is 10:1; the reaction temperature is 70-100°C; and the reaction time is 5-16 hours.

8. The method according to claim 4, wherein the molar ratio of the allylation agent to compound C-1 is (1-5):1, and the molar ratio to compound C-2 is 2-10:1; the molar ratio of the base to compound C-1 is (1-5):1, and the molar ratio to compound C-2 is (2-10):1; the volume (ml) of the aprotic solvent to the mass (g) of compound C-1 and / or C-2 is (10-50):1; the reaction temperature is -20-50°C. The reaction time is 5-48 hours.

9. The method according to claim 8, wherein the allylation reagents are allyl chloride and allyl bromide, and the molar ratio of the allylation reagents to compound C-1 is 2.2:1, and the molar ratio of the allylation reagents to compound C-2 is 4.2:1; the bases are potassium tert-butoxide, sodium tert-butoxide and sodium hydride, and the molar ratio of the allylation reagents to compound C-1 is 2.5:1, and the molar ratio of the allylation reagents to compound C-2 is 4.5:1; the aprotic solvents are tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and isopropyl ether, and the volume ratio (ml) of the allylation reagents to compound C-1 and / or C-2 is 30:1; the reaction temperature is 0 to 25°C; and the reaction time is 12 to 24 hours.

10. The method according to claim 5, wherein the molar ratio of the water-soluble hydrazide reagent, hydrazine monohydrochloride or hydroxylamine hydrochloride to compound D-1 is (1-6):1, and the molar ratio to compound D-2 is (2-10):1; the volume amount (ml) of the polar solvent to the mass (g) of compound D-1 and / or D-2 is (5-15):1; the reaction temperature is 50-150°C; and the reaction time is 5-48 hours.

11. The method according to claim 10, wherein the water-soluble hydrazide reagent is 2-hydrazino-N,N,N-trimethyl-2-oxoethylammonium chloride and 1-(2-hydrazino-2-oxoethyl)pyridinium chloride, the molar ratio of hydrazine monohydrochloride or hydroxylamine hydrochloride to compound D-1 is 3:1, and the molar ratio to compound D-2 is 5:1; the polar solvent is methanol, ethanol, isopropanol, pyridine, and the volume (ml) thereof is 10:1 to the mass (g) of compound D-1 and / or D-2; the reaction temperature is 70-100°C; and the reaction time is 12-24 hours.

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