A tetrahalogenphenol tetrahalosulfonphthalein alkali metal salt and preparation method thereof

Abstract

The invention provides a tetrahalophenol tetrahalosulfonphthalein alkali metal salt and a preparation method thereof, and belongs to the technical field of tetrahalophenol tetrahalosulfonphthalein salt formation. The tetrahalophenol tetrahalosulfonphthalein alkali metal salt described in the invention is tetrahalophenol tetrahalosulfonphthalein lithium salt, tetrahalophenol tetrahalosulfonphthalein sodium salt and tetrahalophenol tetrahalosulfonphthalein potassium salt; the preparation method of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt is: tetrahalophenol tetrahalosulfonphthalein and alkali metal salt are subjected to salt formation reaction in a non-protonic solvent, crystallized to obtain a crude product, and then recrystallized in a non-protonic solvent to obtain a pure tetrahalophenol tetrahalosulfonphthalein alkali metal salt. The preparation method of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt provided by the invention overcomes the problem that the existing tetrahalophenol tetrahalosulfonphthalein is difficult to dissolve in water, and the preparation process is simple, the conditions are mild, the product purity is high, the yield is high, the cost is low, and it can be mass-produced, which is beneficial to further research and application.

Description

Technical Field

[0001] The invention relates to the technical field of tetrahalophenol tetrahalosulfonphthalein salt formation, in particular to a tetrahalophenol tetrahalosulfonphthalein alkali metal salt and a preparation method thereof. Background Art

[0002] Tetrahalogenated phenol tetrahalogenatedsuofonephthalein (THPTHSP) belongs to the sulfonphthalein class of compounds. Due to its high stability and good color fixation effect, it is widely used in dyes and detection reagents. Its structural formula is as follows:

[0003]

[0004] In formula (1), X is Cl, Br or I; Y is Cl, Br or I;

[0005] When X and Y are both Br, the compound is tetrabromophenol tetrabromosulfonphthalein, ie, tetrabromophenol blue (TBPB), which is an important protein error indicator in clinical diagnosis.

[0006] Tetrahalophenol and tetrahalosulfonphthalein are poorly soluble in water. In clinical diagnostic reagents, large amounts of organic solvents are often used to dissolve them, wasting reagents and increasing costs. These problems affect their further research and application.

[0007] Therefore, how to overcome the deficiencies of the prior art and increase the water solubility of tetrahalophenol tetrahalosulfonphthalein to achieve the purpose of convenient use is a technical problem that needs to be solved at present. Summary of the invention

[0008] The purpose of the present invention is to provide a tetrahalophenol tetrahalosulfonphthalein alkali metal salt and a preparation method thereof, so as to solve the technical problems that the existing tetrahalophenol tetrahalosulfonphthalein has poor water solubility and is inconvenient to use.

[0009] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0010] The present invention provides a tetrahalophenol tetrahalosulfonphthalein alkali metal salt, and the structural formula of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt is as follows:

[0011]

[0012] Wherein, X is independently Cl, Br or I; Y is independently Cl, Br or I; and M is Li, Na or K.

[0013] The present invention also provides a method for preparing a tetrahalophenol tetrahalosulfonphthalein alkali metal salt, comprising the following steps:

[0014] 1) Salt formation: tetrahalophenol tetrahalosulfonphthalein and alkali metal salt are mixed in a solvent to carry out salt formation reaction, and crystallize to obtain a crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt;

[0015] 2) Recrystallization: The crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt is mixed with a solvent for recrystallization to obtain tetrabromophenol tetrabromosulfonphthalein alkali metal salt.

[0016] Furthermore, the alkali metal salt is one of alkali metal carbonate, alkali metal acetate and alkali metal bicarbonate.

[0017] Furthermore, in step 1) and step 2), the solvent is independently one or more of tetrahydrofuran, acetone, acetonitrile, dioxane, dimethyl sulfoxide, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, ether, petroleum ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, ethylene glycol dimethyl ether, benzene, toluene and xylene.

[0018] Furthermore, the molar ratio of the tetrahalophenol tetrahalosulfonphthalein to the alkali metal salt is 1:0.8-2.0, and the mass volume ratio of the tetrahalophenol tetrahalosulfonphthalein to the solvent is 1g:1-20mL.

[0019] Furthermore, the temperature of the salt-forming reaction is 25 to 85° C., and the time of the salt-forming reaction is 0.5 to 24 h.

[0020] Furthermore, the mass volume ratio of the crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt to the solvent is 1 g: 1-20 mL.

[0021] Furthermore, the recrystallization temperature is 25 to 85° C., and the recrystallization time is 0.5 to 24 hours.

[0022] Beneficial effects of the present invention:

[0023] The invention obtains tetrahalophenol tetrahalosulfonphthalein alkali metal salt by salting and recrystallizing tetrahalophenol tetrahalosulfonphthalein, thereby overcoming the problem that the prior tetrahalophenol tetrahalosulfonphthalein is difficult to dissolve in water. The purity of the finally obtained tetrahalophenol tetrahalosulfonphthalein alkali metal salt product reaches 98.0%, and the total yield reaches 80%. The preparation method of the invention is simple, the conditions are mild, the product purity is high, the yield is high, the cost is low, and it can be mass-produced, which is beneficial to further promotion and application. DETAILED DESCRIPTION

[0024] The present invention provides a tetrahalophenol tetrahalosulfonphthalein alkali metal salt, and the structural formula of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt is as follows:

[0025]

[0026] Wherein, X is independently Cl, Br or I; Y is independently Cl, Br or I; and M is Li, Na or K.

[0027] In the present invention, the tetrahalophenol tetrahalosulfonphthalein alkali metal salt is preferably tetrahalophenol tetrahalosulfonphthalein lithium salt, tetrahalophenol tetrahalosulfonphthalein sodium salt or tetrahalophenol tetrahalosulfonphthalein potassium salt, and more preferably tetrahalophenol tetrahalosulfonphthalein sodium salt or tetrahalophenol tetrahalosulfonphthalein potassium salt.

[0028] The present invention also provides a method for preparing a tetrahalophenol tetrahalosulfonphthalein alkali metal salt, comprising the following steps:

[0029] 1) Salt formation: tetrahalophenol tetrahalosulfonphthalein and alkali metal salt are mixed in a solvent to carry out salt formation reaction, and crystallize to obtain a crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt;

[0030] 2) Recrystallization: The crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt is mixed with a solvent for recrystallization to obtain tetrabromophenol tetrabromosulfonphthalein alkali metal salt.

[0031] In the present invention, the reaction formula for the synthesis of tetrahalophenol tetrahalosulfonphthalein alkali metal salt is as follows:

[0032]

[0033] Wherein, X is independently Cl, Br or I; Y is independently Cl, Br or I; and M is Li, Na or K.

[0034] In the present invention, the alkali metal salt is one of alkali metal carbonate, alkali metal acetate and alkali metal bicarbonate, preferably alkali metal bicarbonate, more preferably lithium bicarbonate, sodium bicarbonate or potassium bicarbonate.

[0035] In the present invention, in step 1) and step 2), the solvent is independently one or more of tetrahydrofuran, acetone, acetonitrile, dioxane, dimethyl sulfoxide, ethyl acetate, dichloromethane, chloroform, carbon tetrachloride, ether, petroleum ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, ethylene glycol dimethyl ether, benzene, toluene and xylene.

[0036] In the present invention, when the solvent used is a protic solvent, the color of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt will deepen, so it is not suitable to be used; when the solvent selected is an aprotic solvent, the color of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt will not change, so it can be used.

[0037] In the present invention, in step 1), the solvent is preferably one or more of tetrahydrofuran, acetone, acetonitrile and dioxane.

[0038] In the present invention, the molar ratio of the tetrahalophenol tetrahalosulfonphthalein to the alkali metal salt is 1:0.8-2.0, 1:0.9-1.8, and more preferably 1:1-1.6.

[0039] In the present invention, the mass volume ratio of the tetrahalophenol tetrahalosulfonphthalein to the solvent is 1 g: 1 to 20 mL, preferably 1 g: 2 to 18 mL, and more preferably 1 g: 3 to 15 mL.

[0040] In the present invention, the temperature of the salt-forming reaction is 25 to 85° C., and the time of the salt-forming reaction is 0.5 to 24 h; preferably, the temperature of the salt-forming reaction is 30 to 80° C., and the time of the salt-forming reaction is 0.5 to 13 h; further preferably, the temperature of the salt-forming reaction is 35 to 75° C., and the time of the salt-forming reaction is 1 to 12 h.

[0041] In the present invention, in step 2), the recrystallization is divided into a first recrystallization and a second recrystallization, and the solvent used in the first recrystallization is preferably ethyl acetate, dichloromethane or chloroform; the solvent used in the second recrystallization is preferably diethyl ether, petroleum ether, n-propyl ether or isopropyl ether.

[0042] In the present invention, in step 2), in the first recrystallization, the tetrahalophenol tetrahalosulfonphthalein alkali metal salt is insoluble in the solvent, while the tetrahalophenol tetrahalosulfonphthalein is easily soluble, so that the free tetrahalophenol tetrahalosulfonphthalein remaining in the reaction can be removed; in the second recrystallization, the polar small molecular impurities contained in the tetrahalophenol tetrahalosulfonphthalein alkali metal salt are easily soluble in the solvent, while the tetrahalophenol tetrahalosulfonphthalein alkali metal salt is insoluble, thereby achieving the removal of impurities; therefore, the recrystallization uses two different aprotic solvents for each recrystallization, and the effect is better.

[0043] In the present invention, after two recrystallizations using aprotic solvents of different properties, the purity of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt product is as high as 98.0%, and the total yield of the two recrystallizations is as high as 88%.

[0044] In the present invention, the mass volume ratio of the crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt to the solvent is 1 g: 1 to 20 mL, preferably 1 g: 2 to 18 mL, and more preferably 1 g: 3 to 15 mL.

[0045] In the present invention, in step 2), when the mass volume ratio of the crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt to the solvent is too large, the recrystallization is not sufficient and the purification effect is poor; when the mass volume ratio of the crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt to the solvent is too small, the reagent is wasted and the yield is reduced.

[0046] In the present invention, the recrystallization temperature is 25-85°C, and the recrystallization time is 0.5-24h; preferably, the recrystallization temperature is 30-80°C, and the recrystallization time is 0.5-13h, and more preferably, the recrystallization temperature is 35-75°C, and the recrystallization time is 1-12h.

[0047] In the present invention, in step 2), when the recrystallization temperature is lower than 35°C, dissolution and dispersion are not sufficient; when the recrystallization temperature is higher than 75°C, the product color is too dark; when the recrystallization temperature is 35-75°C, the recrystallization is relatively sufficient and the effect is better. When the recrystallization time is less than 1 hour, dissolution and dispersion are not sufficient; when the recrystallization time is greater than 12 hours, the product color is darker.

[0048] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0049] The tetrahalophenol tetrahalosulfonphthalein used in the following experimental examples and embodiments was purchased from commercially available raw materials, and the purity was above 90.0%.

[0050] Experimental Example 1

[0051] Comparison of salt-forming reaction effects

[0052] (1) Alkali metal salts

[0053] Take tetrabromophenol tetrabromosulfonphthalein, weigh 4 portions, each 98.5 g (0.1 mol), add them to the reactor, weigh 1.2 eq of sodium hydroxide, sodium carbonate, sodium bicarbonate, and sodium acetate, add them to the reactor, add 300 mL of acetonitrile, stir and react at 55°C for 5 hours, stop the reaction, cool to room temperature, filter, dry the filter cake, weigh it, and obtain a crude product. Relevant experimental data are shown in Table 1.

[0054] Table 1 Selection of alkali metal salts

[0055]

[0056] The data in Table 1 show that: sodium hydroxide is used as a reaction base, the alkalinity is too strong, the crude product color is too dark, the yield is low, the purity is low, and it does not meet the requirements; sodium carbonate is used as a reaction base, the alkalinity is strong, the crude product color is darker, the yield is low, and the purity is low; sodium acetate is used as a reaction base, the alkalinity is weak, the reaction is slow, the crude product appearance color is lighter, and the purity is lower; alkali metal salts use sodium bicarbonate as a reactant, the crude product yield is higher, the purity is higher, and the color is lighter. It can be seen that specific alkali metal salts are required to achieve the technical purpose of this application.

[0057] (2) Alkali metal salt equivalent

[0058] Take tetrabromophenol tetrabromosulfonphthalein raw material, weigh 5 portions, each portion 98.5 grams (0.1 moL), add them to the reactor respectively, add 0.8 eq, 0.9 eq, 1.0 eq, 1.8 eq and 2.0 eq of sodium bicarbonate respectively, add 300 mL of tetrahydrofuran respectively, stir and react at 65 ° C for 4 hours, stop the reaction, cool to room temperature, filter, dry the filter cake, weigh it, and obtain a crude product. Relevant experimental data are shown in Table 2.

[0059] Table 2 Selection of alkali metal salt feed equivalent

[0060]

[0061] The data in Table 2 show that when the feed ratio of sodium bicarbonate to tetrabromophenol tetrabromosulfonphthalein is 0.8eq, the reaction is incomplete, the yield is low, and the purity is low; when the feed ratio is 2.0eq, the alkali is excessive, the color of the crude product is darker, and the purity is low; when the feed ratio is 0.9eq~1.8eq, the yield is higher, the purity is higher, and the color is lighter.

[0062] (3) Salt-forming solvent

[0063] Take tetrabromophenol tetrabromosulfonphthalein raw material, weigh 5 portions, each portion 98.5 grams (0.1 moL), add them to the reactor respectively, then weigh 1.15eq of sodium bicarbonate respectively, add them to the reactor in sequence, add 500mL of tetrahydrofuran, acetone, acetonitrile, dioxane, and methanol respectively, react at 60°C for 4 hours, filter after the reaction is completed, dry the filter cake, weigh it, and obtain a crude product. Relevant experimental data are shown in Table 3.

[0064] Table 3 Selection of salt-forming solvents

[0065]

[0066] The data in Table 3 show that when the reaction solvent is tetrahydrofuran, acetone, acetonitrile or dioxane, the yield can reach more than 94% and the purity is more than 94%; when the reaction solvent is methanol (protic solvent), the yield and purity are lower.

[0067] (4) Amount of salt-forming solvent used

[0068] Take tetrabromophenol tetrabromosulfonphthalein raw material, weigh 5 portions, each portion 98.5 grams (0.1 moL), add them to the reactor, then add 1.2 eq of sodium bicarbonate, add acetonitrile according to the mass volume ratio (g: mL) of 1:1, 1:2, 1:3, 1:18, 1:20, stir at 70°C for 3 hours, stop the reaction, cool to room temperature, filter, dry the filter cake, weigh, and obtain a crude product. Relevant experimental data are shown in Table 4.

[0069] Table 4 Selection of the amount of salt-forming solvent used

[0070]

[0071] The data in Table 4 show that when the mass volume ratio of tetrabromophenol tetrabromosulfonphthalein to acetonitrile is 1g:1mL, the reaction is incomplete and the purity is low; when the mass volume ratio is 1g:20mL, the yield is too low; when the mass volume ratio is 1g:2-18mL, the crude product yield is higher and the purity is higher.

[0072] (5) Salt formation temperature

[0073] Take tetrabromophenol tetrabromosulfonphthalein raw material, weigh 5 portions, each portion 98.5 grams (0.1 moL), add them to the reactor respectively, weigh 1.2 eq of sodium bicarbonate respectively, add them to the reactor respectively, add 550 mL of dioxane respectively, stir and react at 30°C, 35°C, 50°C, 75°C, 80°C for 5 hours, stop the reaction, cool to room temperature, filter, dry the filter cake, weigh it, and obtain a crude product. Relevant experimental data are shown in Table 5.

[0074] Table 5 Selection of salt formation temperature

[0075]

[0076]

[0077] The data in Table 5 show that when the reaction temperature is 30°C, the reaction is incomplete, the yield is low, and the purity is low; when the reaction temperature is 80°C, the side reactions increase, the yield is low, and the purity is low; when the reaction temperature is 35°C to 75°C, the yield is high and the purity is high.

[0078] (6) Salt-forming reaction time

[0079] Take tetrabromophenol tetrabromosulfonphthalein raw material, weigh 5 portions, each portion 98.5 grams (0.1 moL), add them to the reactor, add 1.1 eq of sodium bicarbonate, add them to 300 mL of acetone, stir and react at 50°C for 0.5 hours, 1 hour, 2 hours, 12 hours, and 13 hours, stop the reaction, cool to room temperature, filter, dry the filter cake, weigh it, and obtain a crude product. Relevant experimental data are shown in Table 6.

[0080] Table 6 Selection of salt-forming reaction time

[0081]

[0082] The data in Table 6 show that when the reaction time is 0.5 hours, the reaction is not complete, the yield is low, and the purity is low; when the reaction time is 13 hours, the side reactions increase, the yield is low, and the purity is low; when the reaction time is 1 to 12 hours, the yield is high and the purity is high.

[0083] Experimental Example 2

[0084] Comparison of recrystallization effects

[0085] Salt-forming reaction: Take tetrabromophenol tetrabromosulfonphthalein, weigh 3942.2 g (4.0 mol), add to the reactor, add 1.3 eq of sodium bicarbonate 358.8 g, add 15.0 L of acetonitrile, stir and react at 65 ° C for 3 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 3802.5 g of crude tetrabromophenol tetrabromosulfonphthalein sodium salt, with a yield of 94.4% and a purity of 95.41%, which is reserved;

[0086] (1) First recrystallization solvent

[0087] Take the crude tetrabromophenol tetrabromosulfonphthalein sodium salt obtained in the previous step, weigh 5 portions, each 100 g, add them to the reactor, add 450 mL of ethyl acetate, dichloromethane, chloroform, dimethyl sulfoxide, and ethanol, stir at 55°C for 4 hours, stop stirring, cool to room temperature, filter, dry the filter cake, weigh it, and obtain a pure product. Relevant experimental data are shown in Table 7.

[0088] Table 7 Selection of the first recrystallization solvent

[0089]

[0090] The data in Table 7 show that when the first recrystallization solvent is ethyl acetate, dichloromethane, or chloroform, the yield and purity are higher; when the recrystallization solvent is dimethyl sulfoxide, the yield and purity are lower; when the recrystallization solvent is ethanol, the product yield and purity are both lower than those of dimethyl sulfoxide.

[0091] (2) Second recrystallization solvent

[0092] First recrystallization: Take the crude product of tetrabromophenol tetrabromosulfonphthalein sodium salt obtained in the previous step, weigh 500.0 g, add it to the reactor, add 3000 mL of ethyl acetate, stir at 55° C. for 4 hours, stop stirring, cool to room temperature, filter, dry the filter cake, weigh it, and obtain 471.5 g of pure product, with a yield of 94.3% and a purity of 97.23%;

[0093] Second recrystallization: Take the first recrystallization product obtained in the previous step, weigh 5 portions, 100 grams each, and add them into the reactor respectively, then add 600 mL of ether, petroleum ether, n-propyl ether, isopropyl ether, and ethylene glycol dimethyl ether respectively, stir at 35°C for 12 hours, stop stirring, cool to room temperature, filter, dry the filter cake, weigh it, and obtain a pure product. Relevant experimental data are shown in Table 8.

[0094] Table 8 Selection of solvent for the second recrystallization

[0095]

[0096] The data in Table 8 show that when the recrystallization solvent is ether, petroleum ether, n-propyl ether, and isopropyl ether, the purity of the obtained product after the second recrystallization is more than 98%, and the yield of the second recrystallization is more than 94%; when the recrystallization solvent is ethylene glycol dimethyl ether, the purity and yield of the obtained product are lower.

[0097] (3) Amount of recrystallization solvent used

[0098] Take the crude product of tetrabromophenol tetrabromosulfonphthalein sodium salt prepared in the previous step, weigh 5 portions, 100 grams each, and add them into the reactor respectively, and then add ethyl acetate according to the mass volume ratio g:mL of 1:1, 1:2, 1:3, 1:18, and 1:20 respectively, stir at 65°C for 3 hours, stop stirring, cool to room temperature, filter, dry the filter cake, weigh it, and obtain the product. The relevant experimental data are shown in Table 9.

[0099] Table 9 Selection of the amount of recrystallization solvent used

[0100]

[0101] The data in Table 9 show that when the mass volume ratio of crude tetrabromophenol tetrabromosulfonphthalein to ethyl acetate is 1g:1mL, the stirring and dispersion are not sufficient, the recrystallization is incomplete, and the product purity is low; when the mass volume ratio is 1g:20mL, the product yield is too low; when the mass volume ratio is 1g:2-18mL, the yield is higher and the purity is higher.

[0102] (4) Recrystallization temperature

[0103] Take the crude product of tetrabromophenol tetrabromosulfonphthalein sodium salt obtained in the previous step, weigh 5 portions, 100 g each, and add them into the reactor respectively, add 300 mL of chloroform respectively, stir at 30°C, 35°C, 55°C, 75°C, and 80°C for 6 hours, stop stirring, cool to room temperature, filter, dry the filter cake, weigh it, and obtain the product. The relevant experimental data are shown in Table 10.

[0104] Table 10 Selection of recrystallization temperature

[0105]

[0106] The data in Table 10 show that: when the recrystallization temperature is 30°C, the recrystallization is not sufficient and the purity is low; when the reaction temperature is 80°C, the side reactions increase and the purity decreases; when the reaction temperature is 35-75°C, the yield is high and the purity is high.

[0107] (5) Recrystallization time

[0108] Take the crude product of tetrabromophenol tetrabromosulfonphthalein sodium salt obtained in the previous step, weigh 5 portions, 100 grams each, and add them into the reactor in sequence, then add 500 mL of ethyl acetate respectively, stir for 0.5 hour, 1 hour, 2 hours, 12 hours, and 13 hours respectively, stop stirring, cool to room temperature, filter, dry the filter cake, weigh it, and obtain the product. The relevant experimental data are shown in Table 11.

[0109] Table 11 Selection of recrystallization time

[0110]

[0111] The data in Table 11 show that: when the recrystallization time is 0.5 hours, the recrystallization is not sufficient and the purity is not improved; when the recrystallization time is 13 hours, the color of the obtained crude product deepens, the side reactions increase, and the purity decreases; when the recrystallization time is 1 to 12 hours, the yield is high and the purity is high.

[0112] Example 1

[0113] Preparation of Tetrachlorophenol Tetrachlorosulfonphthalein Lithium Salt

[0114] 1) Salt formation: weigh 63.0 g (0.1 mol) of tetrachlorophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 420 mL of tetrahydrofuran, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 59.5 g of tetrachlorophenol tetrachlorosulfonphthalein lithium salt crude product, with a yield of 93.5% and a purity of 95.15%;

[0115] 2) Recrystallization: Recrystallization for the first time: 59.5 grams of tetrachlorophenol tetrachlorosulfonphthalein lithium salt crude products are joined in the reactor, 450mL of ethyl acetate are added, stirred 2 hours at 60 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and 56.3 grams are weighed, and yield is 94.6%, and purity is 97.23%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, 580mL of ether is added, stirred 2 hours at 35 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and make the pure product of tetrachlorophenol tetrachlorosulfonphthalein lithium salt, 53.2 grams are weighed, and yield is 94.5%, and total recovery is 83.7%, and purity is 98.58%.

[0116] Example 2

[0117] Preparation of Tetrabromophenol Tetrachlorosulfonphthalein Lithium Salt

[0118] 1) Salt formation: weigh 80.8 g (0.1 mol) of tetrabromophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of tetrahydrofuran, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 76.2 g of tetrabromophenol tetrachlorosulfonphthalein crude product, with a yield of 93.7% and a purity of 95.43%;

[0119] 2) Recrystallization: First recrystallization: 76.2 grams of tetrabromophenol tetrachlorosulfonphthalein lithium salt crude product were added to the reactor, 450 mL of ethyl acetate were added, stirred at 60 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filter cakes dried, collected, weighed 72.2 grams, yield 94.8%, purity 97.32%; Second recrystallization: the first recrystallization product was added to the reactor, 650 mL of ether were added, stirred at 35 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filter cakes dried, collected, and pure tetrabromophenol tetrachlorosulfonphthalein lithium salt was obtained, weighed 67.7 grams, yield 93.8%, total recovery 83.2%, purity 98.79%.

[0120] Example 3

[0121] Preparation of Tetraiodophenol Tetrachlorosulfonphthalein Lithium Salt

[0122] 1) Salt formation: Weigh 99.6 g (0.1 mol) of tetraiodophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of acetonitrile, stir and react at 65° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 92.7 g of tetraiodophenol tetrachlorosulfonphthalein lithium salt crude product, with a yield of 92.5% and a purity of 95.68%;

[0123] 2) Recrystallization: First recrystallization: 92.7 grams of tetraiodophenol tetrachlorosulfonphthalein lithium salt crude product were added to the reactor, 450 mL of ethyl acetate were added, stirred at 60 ° C for 2 hours, the mixture was cooled to room temperature, filtered, filtered, dried over filtration, and collected, and weighed 87.2 grams, with a yield of 94.1% and a purity of 97.66%. Second recrystallization: the recrystallized product was added to the reactor, 650 mL of petroleum ether were added, stirred at 55 ° C for 2 hours, the mixture was cooled to room temperature, filtered, dried over filtration, and collected, and the pure tetraiodophenol tetrachlorosulfonphthalein lithium salt was obtained, with a weight of 81.4 grams, a yield of 93.4%, a total recovery of 81.3%, and a purity of 98.24%.

[0124] Example 4

[0125] Preparation of Tetrachlorophenol Tetrabromosulfonphthalein Lithium Salt

[0126] 1) Salt formation: weigh 80.8 g (0.1 mol) of tetrachlorophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of acetonitrile, stir and react at 65° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 75.5 g of tetrachlorophenol tetrabromosulfonphthalein lithium salt crude product, with a yield of 92.8% and a purity of 95.14%;

[0127] 2) Recrystallization: Recrystallization for the first time: tetrachlorophenol tetrabromosulfonphthalein lithium salt crude product 75.5 grams, join in the reactor, add methylene chloride 450mL, stir 5 hours in 40 ℃, stop stirring, cool to room temperature, filter, filtration cakes torrefaction, collect, weigh 70.8 grams, yield 93.8%, purity 97.03%; Recrystallization for the second time: the recrystallization product for the first time joins in the reactor, adds sherwood oil 650mL, stir 3 hours in 50 ℃, stop stirring, cool to room temperature, filter, filtration cakes torrefaction, collect, make the pure product of tetrachlorophenol tetrabromosulfonphthalein lithium salt, weigh 66.3 grams, yield 93.7%, total recovery 81.5%, purity 98.55%.

[0128] Example 5

[0129] Preparation of Tetrabromophenol Tetrabromosulfonphthalein Lithium Salt

[0130] 1) Salt formation: weigh 98.6 g (0.1 mol) of tetrabromophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 550 mL of acetonitrile, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 92.6 g of tetrabromophenol tetrabromosulfonphthalein crude product, with a yield of 93.4% and a purity of 94.73%;

[0131] 2) Recrystallization: First recrystallization: 92.6 grams of tetrabromophenol tetrabromosulfonphthalein lithium salt crude product were added to the reactor, 350 mL of dichloromethane were added, stirred at 40 ℃ for 5 hours, stirring was stopped, cooled to room temperature, filtered, filtration cakes dried, collected, weighed 86.8 grams, yield 93.7%, purity 96.89%; Second recrystallization: the first recrystallization product was added to the reactor, 650 mL of petroleum ether were added, stirred at 60 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filtration cakes dried, collected, and pure tetrabromophenol tetrabromosulfonphthalein lithium salt was obtained, weighed 80.5 grams, yield 92.7%, total recovery 81.2%, purity 98.54%.

[0132] Example 6

[0133] Preparation of Tetraiodophenol Tetrabromosulfonphthalein Lithium Salt

[0134] 1) Salt formation: Weigh 117.4 g (0.1 mol) of tetraiodophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 400 mL of acetone, stir and react at 40° C. for 8 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 109.3 g of tetraiodophenol tetrabromosulfonphthalein lithium salt crude product, with a yield of 92.7% and a purity of 94.58%;

[0135] 2) Recrystallization: Recrystallization for the first time: 109.3 grams of tetraiodophenol tetrabromosulfonphthalein lithium salt crude product are joined in the reactor, 450mL of methylene chloride are added, stirred 8 hours at 40 ℃, stop stirring, cool to room temperature, filter, filter cakes torrefaction, collect, weigh 102.5 grams, yield 93.8%, purity 96.45%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, 650mL of n-propyl ether are added, stirred 2 hours at 55 ℃, stop stirring, cool to room temperature, filter, filter cakes torrefaction, collect, make the pure product of tetraiodophenol tetrabromosulfonphthalein lithium salt, weigh 95.9 grams, yield 93.6%, total recovery 81.3%, purity 98.86%.

[0136] Example 7

[0137] Preparation of Tetrachlorophenol Tetraiodosulfonphthalein Lithium Salt

[0138] 1) Salt formation: weigh 99.6 g (0.1 mol) of tetrachlorophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of acetone, stir and react at 40° C. for 10 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 94.0 g of tetrachlorophenol tetraiodosulfonphthalein lithium salt crude product, with a yield of 93.8% and a purity of 94.56%;

[0139] 2) Recrystallization: First time recrystallization: 94.0 grams of tetrachlorophenol tetraiodosulfonphthalein lithium salt crude product are joined in the reactor, 450mL of chloroform are added, stirred 2 hours at 75 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction, collected, weighed 87.8 grams, yield 93.4%, purity 97.48%; Second time recrystallization: the recrystallized product is joined in the reactor for the first time, 750mL of n-propyl ether are added, stirred 6 hours at 50 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction, collected, made the pure tetrachlorophenol tetraiodosulfonphthalein lithium salt, weighed 82.2 grams, yield 93.6%, total recovery 82.1%, purity 99.02%.

[0140] Example 8

[0141] Preparation of Tetrabromophenol Tetraiodosulfonphthalein Lithium Salt

[0142] 1) Salt formation: Weigh 117.4 g (0.1 mol) of tetrabromophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of dioxane, stir and react at 60° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 108.7 g of tetrabromophenol tetraiodosulfonphthalein lithium salt crude product, with a yield of 92.2% and a purity of 94.73%;

[0143] 2) Recrystallization: First recrystallization: 108.7 grams of tetrabromophenol tetraiodosulfonphthalein lithium salt crude product were added to the reactor, 450 mL of chloroform were added, stirred at 70 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filter cakes dried, collected, weighed 102.4 grams, yield 94.2%, purity 96.95%; Second recrystallization: the first recrystallization product was added to the reactor, 650 mL of isopropyl ether were added, stirred at 60 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filter cakes dried, collected, and pure tetrabromophenol tetraiodosulfonphthalein lithium salt was obtained, weighed 95.9 grams, yield 93.7%, total recovery 81.3%, purity 98.67%.

[0144] Example 9

[0145] Preparation of Tetraiodophenol Tetraiodosulfonphthalein Lithium Salt

[0146] 1) Salt formation: Weigh 136.2 g (0.1 mol) of tetraiodophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of dioxane, stir and react at 60° C. for 3 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 126.7 g of tetraiodophenol tetraiodosulfonphthalein lithium salt crude product, with a yield of 92.7% and a purity of 94.21%;

[0147] 2) Recrystallization: First time recrystallization: 126.7 grams of tetraiodophenol tetraiodosulfonphthalein lithium salt crude product are joined in the reactor, 350mL of chloroform are added, stirred 3 hours at 60 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction are collected, and 119.5 grams are weighed, and yield is 94.3%, and purity is 96.42%; Second time recrystallization: the recrystallized product is joined in the reactor for the first time, 550mL of isopropyl ether are added, stirred 4 hours at 55 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction are collected, and the pure product of tetraiodophenol tetraiodosulfonphthalein lithium salt is obtained, and 112.1 grams are weighed, and yield is 93.8%, and total recovery is 82.0%, and purity is 98.33%.

[0148] Example 10

[0149] Preparation of Tetrachlorophenol Tetrachlorosulfonphthalein Sodium Salt

[0150] 1) Salt formation: weigh 63.0 g (0.1 mol) of tetrachlorophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of tetrahydrofuran, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 61.2 g of crude tetrachlorophenol tetrachlorosulfonphthalein sodium salt, with a yield of 93.9% and a purity of 94.23%;

[0151] 2) Recrystallization: Recrystallization for the first time: 61.2 grams of tetrachlorophenol tetrachlorosulfonphthalein sodium salt crude products are joined in the reactor, 450mL of ethyl acetate is added, stirred 2 hours at 60 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and 58.1 grams are weighed, and yield is 94.9%, and purity is 97.36%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, 550mL of ether is added, stirred 2 hours at 35 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and make the pure product of tetrachlorophenol tetrachlorosulfonphthalein sodium salt, 54.5 grams are weighed, and yield is 93.8%, and total recovery is 83.6%, and purity is 98.41%.

[0152] Embodiment 11

[0153] Preparation of Tetrabromophenol Tetrachlorosulfonphthalein Sodium Salt

[0154] 1) Salt formation: weigh 80.8 g (0.1 mol) of tetrabromophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of tetrahydrofuran, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 77.0 g of crude tetrabromophenol tetrachlorosulfonphthalein sodium salt, with a yield of 92.8% and a purity of 95.17%;

[0155] 2) Recrystallization: First recrystallization: 77.0 grams of tetrabromophenol tetrachlorosulfonphthalein sodium salt crude product were added to the reactor, 350 mL of ethyl acetate were added, stirred at 60 ° C for 2 hours, the mixture was cooled to room temperature, filtered, filtered, dried, and collected, and weighed 71.9 grams, with a yield of 93.4% and a purity of 97.15%. Second recrystallization: the recrystallized product was added to the reactor, 750 mL of ether were added, stirred at 35 ° C for 2 hours, the mixture was cooled to room temperature, filtered, dried, and collected, and the pure tetrabromophenol tetrachlorosulfonphthalein sodium salt was obtained, with a weight of 67.7 grams, a yield of 94.1%, a total recovery of 81.6%, and a purity of 98.82%.

[0156] Example 12

[0157] Preparation of Tetraiodophenol Tetrachlorosulfonphthalein Sodium Salt

[0158] 1) Salt formation: Weigh 99.6 g (0.1 mol) of tetraiodophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of acetonitrile, stir and react at 65° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 94.7 g of a crude product of tetraiodophenol tetrachlorosulfonphthalein sodium salt, with a yield of 93.1% and a purity of 94.77%;

[0159] 2) Recrystallization: First recrystallization: 94.7 grams of tetraiodophenol tetrachlorosulfonphthalein sodium salt crude product are joined in the reactor, 550mL of ethyl acetate are added, stirred at 60 ℃ for 2 hours, stirring is stopped, cooled to room temperature, filtered, filter cakes drying is collected, and weighs 88.8 grams, yield 93.8%, purity 96.52%; Second recrystallization: the recrystallization product is joined in the reactor for the first time, 650mL of petroleum ether are added, stirred at 55 ℃ for 2 hours, stirring is stopped, cooled to room temperature, filtered, filter cakes drying is collected, and pure tetraiodophenol tetrachlorosulfonphthalein sodium salt is obtained, weighing 83.7 grams, yield 94.3%, total recovery 82.2%, purity 98.15%.

[0160] Embodiment 13

[0161] Preparation of Tetrachlorophenol Tetrabromosulfonphthalein Sodium Salt

[0162] 1) Salt formation: weigh 80.8 g (0.1 mol) of tetrachlorophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 550 mL of acetonitrile, stir and react at 65° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 76.7 g of crude tetrachlorophenol tetrabromosulfonphthalein sodium salt, with a yield of 92.5% and a purity of 94.87%;

[0163] 2) Recrystallization: Recrystallization for the first time: 76.7 grams of tetrachlorophenol tetrabromosulfonphthalein sodium salt crude product are joined in the reactor, add methylene chloride 450mL, stirred 5 hours at 40 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction, collected, weighed 71.7 grams, yield 93.5%, purity 96.74%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, adds sherwood oil 550mL, stirred 3 hours at 50 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction, collected, made the pure product of tetrachlorophenol tetrabromosulfonphthalein sodium salt, weighed 67.0 grams, yield 93.4%, total recovery 80.7%, purity 98.19%.

[0164] Embodiment 14

[0165] Preparation of Tetrabromophenol Tetrabromosulfonphthalein Sodium Salt

[0166] 1) Salt formation: weigh 98.6 g (0.1 mol) of tetrabromophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 550 mL of acetonitrile, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 93.1 g of crude tetrabromophenol tetrabromosulfonphthalein sodium salt, with a yield of 92.4% and a purity of 94.88%;

[0167] 2) Recrystallization: First recrystallization: 93.1 grams of tetrabromophenol tetrabromosulfonphthalein sodium salt crude product were added to the reactor, 450 mL of dichloromethane were added, stirred for 5 hours at 40 ℃, the mixture was cooled to room temperature, filtered, filtered, dried over filtration, and collected, and weighed 86.7 grams, with a yield of 93.1% and a purity of 96.54%. Second recrystallization: the recrystallized product was added to the reactor, 650 mL of petroleum ether were added, stirred for 2 hours at 60 ℃, the mixture was cooled to room temperature, filtered, dried over filtration, and collected, and the pure tetrabromophenol tetrabromosulfonphthalein sodium salt was obtained, with a weight of 81.6 grams, a yield of 94.1%, a total recovery of 81.0%, and a purity of 98.33%.

[0168] Embodiment 15

[0169] Preparation of Tetraiodophenol Tetrabromosulfonphthalein Sodium Salt

[0170] 1) Salt formation: Weigh 117.4 g (0.1 mol) of tetraiodophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of acetone, stir and react at 40° C. for 8 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 112.0 g of crude tetraiodophenol tetrabromosulfonphthalein sodium salt, with a yield of 93.7% and a purity of 94.12%;

[0171] 2) Recrystallization: Recrystallization for the first time: 112.0 grams of tetraiodophenol tetrabromosulfonphthalein sodium salt crude products are joined in the reactor, 350mL of methylene chloride are added, stirred for 8 hours at 40 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and 103.6 grams are weighed, with a yield of 92.5% and a purity of 96.87%; Recrystallization for the second time: the recrystallized product is joined in the reactor for the first time, 650mL of n-propyl ether is added, stirred for 2 hours at 55 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and the pure product of tetraiodophenol tetrabromosulfonphthalein sodium salt is obtained, with a weight of 96.0 grams, a yield of 92.7%, a total recovery of 80.3%, and a purity of 98.32%.

[0172] Example 16

[0173] Preparation of Tetrachlorophenol Tetraiodosulfonphthalein Sodium Salt

[0174] 1) Salt formation: weigh 99.6 g (0.1 mol) of tetrachlorophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of acetone, stir and react at 40° C. for 10 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 94.7 g of crude tetrachlorophenol tetraiodosulfonphthalein sodium salt, with a yield of 93.1% and a purity of 94.93%;

[0175] 2) Recrystallization: Recrystallization for the first time: 94.7 grams of tetrachlorophenol tetraiodosulfonphthalein sodium salt crude product are joined in the reactor, 350mL of chloroform are added, stirred 2 hours at 75 ℃, stop stirring, cool to room temperature, filter, filter cakes torrefaction, collect, weigh 87.9 grams, yield 92.8%, purity 97.10%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, 550mL of n-propyl ether are added, stirred 6 hours at 50 ℃, stop stirring, cool to room temperature, filter, filter cakes torrefaction, collect, make the pure product of tetrachlorophenol tetraiodosulfonphthalein sodium salt, weigh 82.9 grams, yield 94.3%, total recovery 81.5%, purity 99.16%.

[0176] Embodiment 17

[0177] Preparation of Tetrabromophenol Tetraiodosulfonphthalein Sodium Salt

[0178] 1) Salt formation: Weigh 117.4 g (0.1 mol) of tetrabromophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of dioxane, stir and react at 60° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 111.5 g of crude tetrabromophenol tetraiodosulfonphthalein sodium salt, with a yield of 93.3% and a purity of 94.85%;

[0179] 2) Recrystallization: First recrystallization: 111.5 grams of tetrabromophenol tetraiodosulfonphthalein sodium salt crude product are joined in the reactor, 450mL of chloroform are added, stirred at 70 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filter cakes drying was collected, and 103.4 grams were weighed, with a yield of 92.7% and a purity of 96.97%; Second recrystallization: the recrystallized product was joined in the reactor for the first time, 550mL of isopropyl ether was added, stirred at 60 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filter cakes drying was collected, and pure tetrabromophenol tetraiodosulfonphthalein sodium salt was obtained, with a weight of 97.6 grams, a yield of 94.4%, a total recovery of 81.6%, and a purity of 98.76%.

[0180] Embodiment 18

[0181] Preparation of Tetraiodophenol Tetraiodosulfonphthalein Sodium Salt

[0182] 1) Salt formation: Weigh 136.2 g (0.1 mol) of tetraiodophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of dioxane, stir and react at 60° C. for 3 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 128.5 g of crude tetraiodophenol tetraiodosulfonphthalein sodium salt, with a yield of 92.9% and a purity of 95.11%;

[0183] 2) Recrystallization: Recrystallization for the first time: 128.5 grams of tetraiodophenol tetraiodosulfonphthalein sodium salt crude products are joined in the reactor, 350mL of chloroform is added, stirred 3 hours at 60 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and 118.6 grams are weighed, with a yield of 92.3% and a purity of 97.03%; Recrystallization for the second time: the recrystallized product is joined in the reactor for the first time, 600mL of isopropyl ether is added, stirred 4 hours at 55 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and the pure product of tetraiodophenol tetraiodosulfonphthalein sodium salt is obtained, with a weight of 110.8 grams, a yield of 93.4%, a total recovery of 80.1%, and a purity of 99.23%.

[0184] Embodiment 19

[0185] Preparation of Tetrachlorophenol Tetrachlorosulfonphthalein Potassium Salt

[0186] 1) Salt formation: weigh 63.0 g (0.1 mol) of tetrachlorophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of tetrahydrofuran, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 62.6 g of crude tetrachlorophenol tetrachlorosulfonphthalein potassium salt, with a yield of 93.7% and a purity of 94.86%;

[0187] 2) Recrystallization: Recrystallization for the first time: 62.6 grams of tetrachlorophenol tetrachlorosulfonphthalein potassium salt crude products are joined in the reactor, 350mL of ethyl acetate are added, stirred 2 hours at 60 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and 58.8 grams are weighed, and yield is 94.0%, and purity is 97.58%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, 650mL of ether are added, stirred 2 hours at 35 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and pure tetrachlorophenol tetrachlorosulfonphthalein potassium salt is obtained, and 55.3 grams are weighed, and yield is 94.0%, and total recovery is 82.8%, and purity is 99.07%.

[0188] Embodiment 20

[0189] Preparation of Tetrabromophenol Tetrachlorosulfonphthalein Potassium Salt

[0190] 1) Salt formation: Weigh 80.8 g (0.1 mol) of tetrabromophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of tetrahydrofuran, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 78.5 g of crude tetrabromophenol tetrachlorosulfonphthalein potassium salt, with a yield of 92.8% and a purity of 95.34%;

[0191] 2) Recrystallization: First time recrystallization: 78.5 grams of tetrabromophenol tetrachlorosulfonphthalein potassium salt crude product were added to the reactor, 450 mL of ethyl acetate were added, stirred at 60 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filtration cakes dried, collected, weighed 72.9 grams, yield 92.9%, purity 97.66%; Second time recrystallization: the recrystallized product was added to the reactor, 650 mL of ether were added, stirred at 35 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filtration cakes dried, collected, and pure tetrabromophenol tetrachlorosulfonphthalein potassium salt was obtained, weighed 67.8 grams, yield 93.0%, total recovery 80.2%, purity 98.91%.

[0192] Embodiment 21

[0193] Preparation of Tetraiodophenol Tetrachlorosulfonphthalein Potassium Salt

[0194] 1) Salt formation: Weigh 99.6 g (0.1 mol) of tetraiodophenol tetrachlorosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 500 mL of acetonitrile, stir and react at 65° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 96.2 g of a crude product of tetraiodophenol tetrachlorosulfonphthalein potassium salt, with a yield of 93.1% and a purity of 95.18%;

[0195] 2) Recrystallization: First time recrystallization: 96.2 grams of tetraiodophenol tetrachlorosulfonphthalein potassium salt crude product are joined in the reactor, 450mL of ethyl acetate are added, stirred at 60 ℃ for 2 hours, stirring is stopped, cooled to room temperature, filtered, filter cakes drying is collected, and weighs 90.0 grams, yield 93.6%, purity 97.12%; Second time recrystallization: the recrystallization product is joined in the reactor for the first time, 550mL of petroleum ether are added, stirred at 55 ℃ for 2 hours, stirring is stopped, cooled to room temperature, filtered, filter cakes drying is collected, and pure tetraiodophenol tetrachlorosulfonphthalein potassium salt is obtained, weighing 83.4 grams, yield 92.7%, total recovery 80.7%, purity 98.97%.

[0196] Embodiment 22

[0197] Preparation of Tetrachlorophenol Tetrabromosulfonphthalein Potassium Salt

[0198] 1) Salt formation: weigh 80.8 g (0.1 mol) of tetrachlorophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of acetonitrile, stir and react at 65° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, collect, and obtain 79.4 g of crude tetrachlorophenol tetrabromosulfonphthalein potassium salt, with a yield of 93.9% and a purity of 94.95%;

[0199] 2) Recrystallization: Recrystallization for the first time: 79.4 grams of tetrachlorophenol tetrabromosulfonphthalein potassium salt crude product are joined in the reactor, add methylene chloride 350mL, stirred 5 hours at 40 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction, collected, weighed 74.2 grams, yield 93.4%, purity 97.22%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, adds sherwood oil 650mL, stirred 3 hours at 50 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction, collected, made the pure product of tetrachlorophenol tetrabromosulfonphthalein potassium salt, weighed 70.0 grams, yield 94.4%, total recovery 82.8%, purity 98.63%.

[0200] Embodiment 23

[0201] Preparation of Tetrabromophenol Tetrabromosulfonphthalein Potassium Salt

[0202] 1) Salt formation: Weigh 98.6 g (0.1 mol) of tetrabromophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 450 mL of acetonitrile, stir and react at 70° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 94.7 g of crude tetrabromophenol tetrabromosulfonphthalein potassium salt, with a yield of 92.5% and a purity of 94.52%;

[0203] 2) Recrystallization: First time recrystallization: 94.7 grams of tetrabromophenol tetrabromosulfonphthalein crude product were added to the reactor, 450 mL of dichloromethane were added, stirred at 40 ℃ for 5 hours, stirring was stopped, cooled to room temperature, filtered, filtration cakes dried, collected, weighed 89.1 grams, yield 94.1%, purity 97.05%; Second time recrystallization: the recrystallized product was added to the reactor, 650 mL of petroleum ether were added, stirred at 60 ℃ for 2 hours, stirring was stopped, cooled to room temperature, filtered, filtration cakes dried, collected, and pure tetrabromophenol tetrabromosulfonphthalein was obtained, weighed 82.7 grams, yield 92.8%, total recovery 80.8%, purity 98.68%.

[0204] Embodiment 24

[0205] Preparation of Tetraiodophenol Tetrabromosulfonphthalein Potassium Salt

[0206] 1) Salt formation: Weigh 117.4 g (0.1 mol) of tetraiodophenol tetrabromosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 400 mL of acetone, stir and react at 40° C. for 8 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 113.3 g of crude tetraiodophenol tetrabromosulfonphthalein potassium salt, with a yield of 93.5% and a purity of 94.37%;

[0207] 2) Recrystallization: Recrystallization for the first time: 113.3 grams of tetraiodophenol tetrabromosulfonphthalein potassium salt crude products are joined in the reactor, 350mL of methylene dichloride are added, stirred 8 hours at 40 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and 105.6 grams are weighed, and yield is 93.2%, and purity is 96.69%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, 750mL of n-propyl ether is added, stirred 2 hours at 55 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction is collected, and the pure product of tetraiodophenol tetrabromosulfonphthalein potassium salt is obtained, and 99.4 grams are weighed, and yield is 94.1%, and total recovery is 82.0%, and purity is 98.76%.

[0208] Embodiment 25

[0209] Preparation of Tetrachlorophenol Tetraiodosulfonphthalein Potassium Salt

[0210] 1) Salt formation: weigh 99.6 g (0.1 mol) of tetrachlorophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of acetone, stir and react at 40° C. for 10 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 96.4 g of crude tetrachlorophenol tetraiodosulfonphthalein potassium salt, with a yield of 93.2% and a purity of 94.36%;

[0211] 2) Recrystallization: Recrystallization for the first time: 96.4 grams of tetrachlorophenol tetraiodosulfonphthalein potassium salt crude product are joined in the reactor, 450mL of chloroform are added, stirred 2 hours at 75 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction are collected, and 90.3 grams are weighed, and yield is 93.7%, and purity is 97.35%; Recrystallization for the second time: the recrystallization product is joined in the reactor for the first time, 650mL of n-propyl ether are added, stirred 6 hours at 50 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction are collected, and pure tetrachlorophenol tetraiodosulfonphthalein potassium salt is obtained, and 85.2 grams are weighed, and yield is 94.4%, and total recovery is 82.4%, and purity is 99.41%.

[0212] Embodiment 26

[0213] Preparation of Tetrabromophenol Tetraiodosulfonphthalein Potassium Salt

[0214] 1) Salt formation: Weigh 117.4 g (0.1 mol) of tetrabromophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of dioxane, stir and react at 60° C. for 2 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 112.0 g of crude tetrabromophenol tetraiodosulfonphthalein potassium salt, with a yield of 92.4% and a purity of 94.87%;

[0215] 2) Recrystallization: First recrystallization: 112.0 grams of tetrabromophenol tetraiodosulfonphthalein crude product were added to the reactor, 450 mL of chloroform were added, stirred at 70 ° C for 2 hours, the mixture was cooled to room temperature, filtered, filtered, dried, and collected. The product weighed 104.3 grams, with a yield of 93.1% and a purity of 96.82%. Second recrystallization: The product was added to the reactor, 450 mL of isopropyl ether were added, stirred at 60 ° C for 2 hours, the mixture was cooled to room temperature, filtered, dried, and collected. The product weighed 98.6 grams, with a yield of 94.5%, a total recovery of 81.4%, and a purity of 98.79%.

[0216] Embodiment 27

[0217] Preparation of Tetraiodophenol Tetraiodosulfonphthalein Potassium Salt

[0218] 1) Salt formation: Weigh 136.2 g (0.1 mol) of tetraiodophenol tetraiodosulfonphthalein and add it to a reactor, add 1.2 eq of lithium bicarbonate, add 350 mL of dioxane, stir and react at 60° C. for 3 hours, stop stirring, cool to room temperature, filter, dry the filter cake, and collect to obtain 129.0 g of a crude product of tetraiodophenol tetraiodosulfonphthalein potassium salt, with a yield of 92.2% and a purity of 94.62%;

[0219] 2) Recrystallization: Recrystallization for the first time: 129.0 grams of tetraiodophenol tetraiodosulfonphthalein potassium salt crude product are joined in the reactor, 500mL of chloroform are added, stirred 3 hours at 60 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction are collected, and 119.8 grams are weighed, and yield is 92.9%, and purity is 96.48%; Recrystallization for the second time: the recrystallized product is joined in the reactor for the first time, 550mL of isopropyl ether are added, stirred 4 hours at 55 ℃, stopped stirring, cooled to room temperature, filtered, filtration cakes torrefaction are collected, and the pure product of tetraiodophenol tetraiodosulfonphthalein potassium salt is obtained, and 113.3 grams are weighed, and yield is 94.6%, and total recovery is 81.0%, and purity is 98.71%.

[0220] The solubility of tetrahalophenol tetrahalosulfonphthalein lithium salt, tetrahalophenol tetrahalosulfonphthalein sodium salt, tetrahalophenol tetrahalosulfonphthalein potassium salt and tetrahalophenol tetrahalosulfonphthalein obtained in Examples 1 to 27 was tested, and the relevant data comparison results are shown in Table 12.

[0221] Table 12 Solubility of tetrabromophenol tetrabromosulfonphthalein alkali metal salt obtained in Examples 1 to 3

[0222]

[0223]

[0224] Definitions of terms used to describe solubility:

[0225] Very soluble: refers to the fact that 1g (mL) of solute can be dissolved in less than 1mL of solvent;

[0226] Soluble: refers to the solute 1g (mL) can be dissolved in 1 to less than 10mL of solvent;

[0227] Solubility: refers to the solute 1g (mL) can be dissolved in 10 to less than 30mL of solvent;

[0228] Slightly soluble: refers to the solute 1g (mL) can be dissolved in 30 to less than 100mL of solvent;

[0229] Slightly soluble: refers to the solute 1g (mL) can be dissolved in 100 to less than 1000mL of solvent;

[0230] Very slightly soluble: Soluble means that 1g (mL) of solute can be dissolved in 1000 to less than 10000mL of solvent;

[0231] Almost insoluble or insoluble: Soluble means that 1g (mL) of the solute cannot be completely dissolved in 10000mL of the solvent;

[0232] As can be seen from Table 12, tetrahalophenol tetrahalosulfonphthalein is almost insoluble in water, but tetrahalophenol tetrahalosulfonphthalein lithium salt, tetrahalophenol tetrahalosulfonphthalein sodium salt and tetrahalophenol tetrahalosulfonphthalein potassium salt have significantly increased solubility in water.

[0233] As can be seen from the above embodiments, the present invention provides a tetrahalophenol tetrahalosulfonphthalein alkali metal salt and a preparation method thereof. The present invention obtains a tetrahalophenol tetrahalosulfonphthalein alkali metal salt by salting, crystallizing and recrystallizing tetrahalophenol tetrahalosulfonphthalein, thereby overcoming the problem of poor water solubility of the existing tetrahalophenol tetrahalosulfonphthalein. The purity of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt product finally obtained reaches 98.0%, and the total yield reaches 80%. The preparation process is simple, the conditions are mild, the product purity is high, the yield is high, the cost is low, and it can be mass-produced, which is beneficial to further application.

[0234] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a tetrahalophenol tetrahalosulfonphthalein alkali metal salt, characterized in that: The following steps are involved: 1) Salt formation: tetrahalophenol tetrahalosulfonphthalein and alkali metal salt are mixed in a solvent to carry out salt formation reaction, and crystallize to obtain a crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt; 2) Recrystallization: The crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt is mixed with a solvent for recrystallization to obtain tetrabromophenol tetrabromosulfonphthalein alkali metal salt; In the step 1), the solvent is tetrahydrofuran, acetone, acetonitrile or dioxane; In the step 2), the recrystallization is divided into a first recrystallization and a second recrystallization, the solvent used in the first recrystallization is ethyl acetate, dichloromethane or chloroform; the solvent used in the second recrystallization is diethyl ether, petroleum ether, n-propyl ether or isopropyl ether; The structural formula of the tetrahalophenol tetrahalosulfonphthalein alkali metal salt is as follows: ； wherein X is independently Cl, Br or I; Y is independently Cl, Br or I; M is Li, Na or K; In the step 1), the molar ratio of the tetrahalophenol tetrahalosulfonphthalein to the alkali metal salt is 1:0.9-1.8, and the mass volume ratio of the tetrahalophenol tetrahalosulfonphthalein to the solvent is 1 g:2-18 mL; The temperature of the salt-forming reaction is 35-75°C, and the time of the salt-forming reaction is 1-12h; In the step 2), the mass volume ratio of the crude tetrahalophenol tetrahalosulfonphthalein alkali metal salt to the solvent is 1 g: 2-18 mL; The recrystallization temperature is 35-75°C, and the recrystallization time is 1-12h; The alkali metal salt is one of alkali metal carbonate, alkali metal acetate and alkali metal bicarbonate.

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