A tert-butyl 1-allylhydrazinecarboxylate, a method for preparing the same and use thereof

Abstract

The application discloses a kind of 1-allyl hydrazine carboxylic acid tert-butyl ester, its preparation method and purposes.The application uses tert-butoxy formyl hydrazine as raw material, after imino protection, N-allylation intermediate is obtained, and after deimino protection, the target product is obtained.The synthesis method is simple in operation, mild in condition, high in yield and good in repeatability, without using toxic hydrazine reagent, without column separation operation.The preparation method provided by the application is simple in process, low in cost, mild in reaction condition and easy to control, safe and reliable in production process, and suitable for industrialization.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of medicine, and particularly relates to tert-butyl 1-allylhydrazinecarboxylate, a preparation method and use thereof. BACKGROUND

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

[0003] Tert-butyl 1-allylhydrazinecarboxylate is a key intermediate for synthesizing 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 hydrazinecarboxylate as a starting material to obtain an amino-protected intermediate under the action of phthalic anhydride, then the intermediate is subjected to N-allylation under the action of an allylation reagent, a base and a phase transfer catalyst (such as triethylbenzylammonium chloride) to obtain an N-allylated intermediate, and then the phthaloyl protecting group is removed under the action of hydrazine hydrate or methylhydrazine to obtain tert-butyl 1-allylhydrazinecarboxylate.

[0004] The synthesis method of tert-butyl 1-allylhydrazinecarboxylate reported in the above-mentioned literature and patents uses a large amount of hydrazine hydrate / methylhydrazine reagent which is highly toxic, and has great potential harm to the synthesis operator. The phase transfer catalyst used in the synthesis process is easy to cause residue, which is not conducive to quality control. In addition, individual steps also need silica gel column chromatography purification, which greatly reduces the possibility of industrial production of the synthesis process. Based on the above defects, we adopted a more reasonable synthesis strategy, selectively protected the primary amine group through an imine group, which integrated reaction and recrystallization purification into one step, then introduced an allyl group, and finally used a mild and low-toxicity deprotection method to obtain the target product tert-butyl 1-allylhydrazinecarboxylate, without column separation and purification in the whole process. Compared with the synthesis method reported in the above-mentioned literature and patents, the preparation method provided by the present application has the advantages of simple process, mild and easy-to-control reaction conditions, safe and reliable production process, and suitability for industrialization. SUMMARY

[0005] The application aims to provide a preparation method of 1-allylhydrazine tert-butyl carboxylate.

[0006]

[0007] The inventors propose the following new process route through deep and careful research: using tert-butoxy formyl hydrazine as raw material, first reacting with aldehyde or ketone to generate imine intermediate, then introducing allyl to the amide nitrogen atom by using allylating agent, and finally removing the imine protecting group by using water-soluble hydrazine reagent, monohydric acid hydrazine or hydroxylamine hydrochloride to obtain the target product. The method is simple in process, mild and easy to control in reaction condition, safe and reliable in production process, and suitable for industrial production.

[0008] A preparation method of 1-allylhydrazine tert-butyl carboxylate, the reaction formula is as follows:

[0009]

[0010] The method comprises heating and reacting compound B in the presence of benzaldehyde derivative in an alcohol solvent to convert compound B into imine intermediate C-1:

[0011]

[0012] The substituent R1 is hydrogen atom, straight-chain or branched-chain alkyl with a length of 1-5 carbon atoms, straight-chain or branched-chain alkoxy with a length of 1-5 carbon atoms, halogen atom, cyano group, nitro group, amide group;

[0013] The method comprises heating and reacting compound B in the presence of diketone compound in an alcohol solvent to convert compound B into imine intermediate C-2:

[0014]

[0015] The substituents R2 and R3 are phenyl or straight-chain or branched-chain alkyl with a length of 1-5 carbon atoms.

[0016] The amount of the benzaldehyde derivative is 0.85-1.1:1 in terms of molar ratio of compound B; the amount of the diketone compound is 0.45-0.55:1 in terms of molar ratio of compound B; the amount of the catalyst is 0.01-1:1 in terms of molar ratio of compound B; the amount of the alcohol solvent (volume, unit: milliliter) is 5-15:1 in terms of mass ratio of compound B (unit: gram); the reaction temperature is 50-150 DEG C; and the reaction time is 1-24 hours.

[0017] Further preferably, the benzaldehyde derivative is benzaldehyde, the molar ratio of the amount used to compound B is 1.05:1; the diketone compound is benzil, 2,3-butanedione and 3,4-hexanedione, the molar ratio of the amount used to compound B is 0.47:1. The catalyst is pyridinium p-toluenesulfonate and pyridinium benzenesulfonate, the molar ratio of the amount used to compound B is 0.05-0.25:1. The alcohol solvent is methanol, ethanol and isopropanol, the ratio of the amount used (volume, unit: milliliter) to the mass of compound B (unit: gram) 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 allylating agent and a base in an aprotic solvent at room temperature or under ice bath:

[0019]

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

[0021]

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

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

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

[0025]

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

[0027] Further preferably, the water-soluble hydrazine reagent is 2-hydrazino-N,N,N-trimethyl-2-oxoethylammonium chloride (also known as Girard's reagent T) and 1-(2-hydrazino-2-oxoethyl)pyridinium chloride (also known as Girard's reagent P), the amount of hydrazine monohydrochloride or hydroxylamine hydrochloride is 3:1 in mole ratio with respect to compound D-1, and 5:1 in mole ratio with respect to compound D-2; the polar solvent is methanol, ethanol, isopropanol or pyridine, and the amount thereof is 10:1 in volume (unit: mL) with respect to the mass (unit: g) of compounds D-1 and D-2. The reaction temperature is 70-100°C. The reaction time is 12-24 hours. DETAILED DESCRIPTION

[0028] The present application is further described in the following examples. All examples are true 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-butyloxycarbonyl hydrazine (C-1)

[0030]

[0031] 20.00 g of tert-butyloxycarbonyl hydrazine (151.33 mmol, 1.00 eq) was dissolved in 150 mL of anhydrous ethanol, 16.38 g of benzaldehyde (154.36 mmol, 1.02 eq) was added, heated to reflux, the reaction was about 5 hours, cooled to room temperature, filtered, the filter cake was washed with anhydrous diethyl ether twice, and dried to obtain 32.43 g of white solid, the yield was 95.4%. 1 H NMR (300 MHz, DMSO-d6) δ 10.89 (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'-(l,2-diphenylethane-l,2-diyl)(2E,2'E)-bis(hydrazine-l-carboxylate) di-tert-butyl ester (C-2-a)

[0033]

[0034] To 13.33 g of tert-butoxyformhydrazide (99.89 mmol, 2.1 eq) dissolved in 50 mL of absolute ethanol, 10.00 g of benzil (47.57 mmol, 1 eq) and 1.20 g of pyridinium p-toluenesulfonate (4.76 mmol, 0.1 eq) were added, heated to reflux, the reaction was left for about 12 hours, cooled to room temperature, filtered, the filter cake was washed with absolute ethanol and then with absolute diethyl ether, dried to obtain 17.44 g of a white solid, yield 83.6%. 1 H NMR (400 MHz, DMSO-d6) δ 8.52 (s, 2H), 7.60-7.40 (m, 6H), 7.38-7.26 (m, 4H), 1.31 (s, 18H).

[0035] Example 3 2,2'-(l,2-diphenylethane-l,2-diyl)(2E,2'E)-bis(hydrazine-l-carboxylate) di-tert-butyl ester (C-2-a)

[0036]

[0037] To 16.12 g of tert-butoxyformhydrazide (119.50 mmol, 2.1 eq) dissolved in 50 mL of absolute ethanol, 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) were added, heated to reflux, the reaction was left for about 16 hours, cooled to room temperature, filtered, the filter cake was washed with absolute ethanol and then with absolute diethyl ether, dried to obtain 17.18 g of a white solid, yield 96.0%. 1 H NMR (400 MHz, DMSO-d6) δ 9.87 (s, 2H), 2.00 (s, 6H), 1.47 (s, 9H).

[0038] Example 4 2,2'-(l,2-diphenylethane-l,2-diyl)(2E,2'E)-bis(hydrazine-l-carboxylate) di-tert-butyl ester (C-2-a)

[0039]

[0040] To a solution of 12.03 g of tert-butyloxycarbonylhydrazine (90.15 mmol, 2.1 eq) in 100 mL of absolute ethanol, 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) were added, heated to reflux, the reaction was left for about 16 hours, cooled to room temperature, filtered, the filter cake was washed with absolute ethanol and then with absolute diethyl ether, dried and 13.43 g of white solid was obtained, yield: 91.4%. 1 H NMR (400 MHz, DMSO-d6) δ 10.00 (s, 2H), 2.60 (q, J = 7.4 Hz, 4H), 1.47 (s, 18H), 0.87 (t, J = 7.4 Hz, 6H).

[0041] Example 5 (E) 1-allyl-2-benzylidene tert-butyloxycarbonylhydrazine (D-1)

[0042]

[0043] To a solution of 20.00 g of C-1 (90.80 mmol, 1 eq) in 800 mL of absolute tetrahydrofuran, mechanical stirring was performed in an ice bath, 26.49 g of potassium tert-butoxide (236.08 mmol, 2.6 eq) was weighed and added in several portions, keeping the temperature of the system below 5°C. 24.16 g of allyl bromide (199.76 mmol, 2.2 eq) was weighed and added dropwise to the system, after the dropwise addition was completed, the ice bath was removed and the system was transferred to room temperature and left to react overnight. It was filtered, the filtrate was evaporated under reduced pressure and the residue was extracted with 800 mL of ethyl acetate and 500 mL of saturated aqueous brine, the organic layer was washed again with water, the organic layer was dried with anhydrous sodium sulfate and the solvent was evaporated under reduced pressure, obtaining 23.00 g of a yellowish oil, yield: 97.3%. 1 H NMR (400 MHz, Chloroform-d) δ 7.80 - 7.61 (m, 3H), 7.44 - 7.32 (m, 3H), 5.84 (ddt, J = 17.2, 10.5, 4.5 Hz, 1H), 5.28 - 5.09 (m, 2H), 4.55 (dd, J = 4.4, 2.2 Hz, 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] To 10.00 g of C-2-a (22.8 mmol, 1 eq) in 300 mL of anhydrous tetrahydrofuran, mechanical stirring was performed under ice bath, 10.00 g of sodium tert-butoxide (102.60 mmol, 4.5 eq) was weighed and added into the system in batches, the temperature of the system was kept below 5 °C. 11.80 g of allyl bromide (95.80 mmol, 4.2 eq) was added dropwise into the system, after the dropwise addition was completed, the ice bath was removed and the system was transferred to room temperature for overnight reaction. Filtration was performed, the filtrate was evaporated under reduced pressure, the residue was extracted with 300 mL of ethyl acetate and 200 mL of saturated brine, the organic layer was washed with water again, the organic layer was dried with anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, a yellow oil was obtained, which solidified after cooling, and 11.56 g was obtained, yield: 97.8%. 1 H NMR (400 MHz, Chloroform-d) δ 5.88 (ddt, J = 16.6, 10.2, 6.3 Hz, 2H), 5.26 - 5.11 (m, 4H), 4.20 (dt, J = 6.3, 1.4 Hz, 4H), 2.08 (s, 6H), 1.47 (s, 18H).

[0047] Example 7 1,1'-Diallyl-2,2'-(butane-2,3-diylidene)(2E,2'E)-bis(hydrazine-1-carboxylate) di-tert-butyl ester (D-2-b)

[0048]

[0049] To 5.00 g of C-2-b (15.90 mmol, 1 eq) in 200 mL of anhydrous tetrahydrofuran, mechanical stirring was performed under ice bath, 7.02 g of sodium tert-butoxide (71.60 mmol, 4.5 eq) was weighed and added into the system in batches, the temperature of the system was kept below 5 °C. 8.25 g of allyl bromide (66.80 mmol, 4.2 eq) was added dropwise into the system, after the dropwise addition was completed, the ice bath was removed and the system was transferred to room temperature for overnight reaction. Filtration was performed, the filtrate was evaporated under reduced pressure, the residue was extracted with 200 mL of ethyl acetate and 100 mL of saturated brine, the organic layer was washed with water again, the organic layer was dried with anhydrous sodium sulfate, the solvent was evaporated under reduced pressure, a yellow oil 5.36 g was obtained, yield: 85.4%. 1 H NMR (400 MHz, Chloroform-d) δ 5.88 (ddt, J = 16.6, 10.2, 6.3 Hz, 2H), 5.26 - 5.11 (m, 4H), 4.20 (dt, J = 6.3, 1.4 Hz, 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- carboxylate) di-tert-butyl ester (D-2-c)

[0051]

[0052] To 5.00 g of C-2-c (14.60 mmol, 1 eq) in 200 mL of anhydrous tetrahydrofuran was added 6.44 g of sodium tert-butoxide (65.70 mmol, 4.5 eq) in portions, keeping the temperature of the system below 5 °C. 7.57 g of allyl bromide (61.32 mmol, 4.2 eq) was added dropwise to the system, which was removed from the ice bath and transferred to room temperature overnight. It was filtered and the filtrate was evaporated under reduced pressure. The residue was extracted with 200 mL of ethyl acetate and 100 mL of saturated brine. The organic layer was washed once more with water, dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure, obtaining 3.49 g of a yellow oil, yield: 56.6%. 1 H NMR (400 MHz, Chloroform-d) δ 5.85 (ddt, J = 16.6, 10.2, 6.3 Hz, 2H), 5.24 - 5.09 (m, 4H), 4.18 (dt, J = 6.3, 1.4 Hz, 4H), 2.62 (q, J = 7.6 Hz, 4H), 1.47 (s, 18H), 1.03 (t, J = 7.5 Hz, 6H).

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

[0054]

[0055] To 12.6 g of D-1 (48.40 mmol, 1 eq) and 48.46 g (289.07 mmol, 6 eq) of Girard's reagent T in 250 mL of anhydrous methanol was heated to reflux overnight. After the reaction was complete, the solvent was evaporated under reduced pressure and the residue was extracted with 200 mL of ethyl acetate and 100 mL of water. The aqueous layer was extracted twice more 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, obtaining 6.92 g of a yellow oil, yield: 83.04%. 1 H NMR (400 MHz, DMSO-d6) δ 5.80 (ddt, J = 17.2, 9.4, 5.4 Hz, 1H), 5.10 (d, J = 1.6 Hz, 1H), 5.07 (dq, J = 6.6, 1.7 Hz, 1H), 4.48 (s, 2H), 3.85 (dt, J = 5.6, 1.6 Hz, 2H), 1.40 (s, 9H).

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

[0057]

[0058] To a solution of 0.5 g of D-1 (1.92 mmol, 1 eq) and 0.27 g of hydroxylamine hydrochloride (3.84 mmol, 2 eq) in 5 mL of anhydrous pyridine was heated 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 more 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 a yellow oil 0.27 g, yield: 82.5%. 1 H NMR (400 MHz, DMSO-d6) δ 5.80 (ddt, J = 17.2, 9.4, 5.4 Hz, 1H), 5.10 (d, J = 1.6 Hz, 1H), 5.07 (dq, J = 6.6, 1.7 Hz, 1H), 4.48 (s, 2H), 3.85 (dt, J = 5.6, 1.6 Hz, 2H), 1.40 (s, 9H).

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

[0060]

[0061] To a solution of 0.5 g of D-1 (1.92 mmol, 1 eq) and 0.27 g of hydroxylamine hydrochloride (3.84 mmol, 2 eq) in 5 mL of anhydrous pyridine was heated 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 more 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 a yellow oil 0.27 g, yield: 82.5%. 1 H NMR (400 MHz, DMSO-d6) δ 5.80 (ddt, J = 17.2, 9.4, 5.4 Hz, 1H), 5.10 (d, J = 1.6 Hz, 1H), 5.07 (dq, J = 6.6, 1.7 Hz, 1H), 4.48 (s, 2H), 3.85 (dt, J = 5.6, 1.6 Hz, 2H), 1.40 (s, 9H).

Claims

1. A method for preparing compound A and its salts, using tert-butyloxycarbonyl hydrazine as raw material, first reacting with any one of aldehyde and ketone to generate imine intermediate, then introducing allyl to the amide nitrogen atom of the imine intermediate using allylating agent, and finally removing the imine protecting group by using water-soluble hydrazine reagent or hydroxylamine reagent to obtain compound A; wherein: the generation of imine intermediate is: compound B is converted into C-1 and C-2 in the presence of benzaldehyde derivative or diketone compound and catalyst, and in an alcoholic solvent under heating; wherein the substituent R1 is hydrogen atom, straight-chain or branched alkyl group with length of 1-5 carbon atoms, straight-chain or branched alkoxy group with length of 1-5 carbon atoms, halogen atom, cyano group, nitro group, amide group; R2 and R3 are phenyl group or straight-chain or branched alkyl group with length of 1-5 carbon atoms; the catalyst is pyridinium p-toluenesulfonate and pyridinium benzenesulfonate; the introduction of allyl to the amide nitrogen atom is: compound C-1 is converted into D-1, or compound C-2 is converted into D-2 in the presence of allylating agent and base in aprotic solvent at room temperature or under ice bath; the removal of imine protecting group is: the imine structure in D-1 or D-2 is removed by using any one of water-soluble hydrazine reagent, monohydrochloride hydrazine and hydroxylamine hydrochloride in polar solvent under heating to obtain target product A; the amount of benzaldehyde derivative is (0.85-1.1) : 1 in terms of molar ratio relative to compound B; the amount of diketone compound is (0.45-0.55) : 1 in terms of molar ratio relative to compound B; the amount of catalyst is (0.01-1) : 1 in terms of molar ratio relative to compound B; the volume amount of alcoholic solvent is (5-15) milliliter : 1 gram in terms of mass ratio relative to compound B; the reaction temperature is 50-150℃; and the reaction time is 1-24 hours; the benzaldehyde derivative is benzaldehyde, and the amount thereof is 1.05 : 1 in terms of molar ratio relative to compound B; the diketone compound is biphenyl-3,3'-dicarboxaldehyde, 2,3-butanedione and 3,4-hexanedione, and the amount thereof is 0.47 : 1 in terms of molar ratio relative to compound B; the catalyst is pyridinium p-toluenesulfonate and pyridinium benzenesulfonate, and the amount thereof is (0.05-0.25) : 1 in terms of molar ratio relative to compound B; the alcoholic solvent is selected from methanol, ethanol and isopropanol; the volume amount of alcohol is 10 milliliter : 1 gram in terms of mass ratio relative to compound B; the reaction temperature is 70-100℃; and the reaction time is 5-16 hours; the amount of allylating agent is (1-5) : 1 in terms of molar ratio relative to compound C-1, and 2-10 : 1 in terms of molar ratio relative to compound C-2; the amount of base is (1-5) : 1 in terms of molar ratio relative to compound C-1, and (2-10) : 1 in terms of molar ratio relative to compound C-2; the volume amount of aprotic solvent is (10-50) milliliter : 1 gram in terms of mass ratio relative to compound C-1 and / or C-2; the reaction temperature is -20-50℃; and the reaction time is 5-48 hours. ​ ​ ​ 。 2. The method of claim 1, wherein, ​ 3. The method of claim 2, wherein, ​ 4. The method of claim 1, wherein, ​ 5. The method of claim 4, wherein, The allylating agent is allyl chloride and allyl bromide, the amount of which is 2.2:1 in terms of the molar ratio of compound C-1 and 4.2:1 in terms of the molar ratio of compound C-2; the base is potassium tert-butoxide, sodium tert-butoxide and sodium hydride, the amount of which is 2.5:1 in terms of the molar ratio of compound C-1 and 4.5:1 in terms of the molar ratio of compound C-2; the aprotic solvent is tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and isopropyl ether, the amount of which is 30 mL:1 g in terms of the volume ratio of compound C-1 and / or C-2; the reaction temperature is 0-25℃; and the reaction time is 12-24 hours.

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

7. The method of claim 6, wherein, The water-soluble hydrazide reagent is 2-hydrazino-N,N,N-trimethyl-2-oxoethylammonium chloride and 1-(2-hydrazino-2-oxoethyl)pyridinium chloride, and the amount of hydrazine monohydrochloride or hydroxylamine hydrochloride is 3:1 in terms of the molar ratio of compound D-1 and 5:1 in terms of the molar ratio of compound D-2; the polar solvent is methanol, ethanol, isopropanol and pyridine, the amount of which is 10 mL:1 g in terms of the volume ratio of compound D-1 and / or D-2; the reaction temperature is 70-100℃; and the reaction time is 12-24 hours.

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