CN115700243A - Method for synthesizing di-tert-butyl dicarbonate based on oxalic acid bis (trichloromethyl) ester - Google Patents
Method for synthesizing di-tert-butyl dicarbonate based on oxalic acid bis (trichloromethyl) ester Download PDFInfo
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Abstract
The invention provides a method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate, which takes tert-butyl alcohol alkali metal salt, carbon dioxide and trichloromethyl oxalate as reaction raw materials; mixing tertiary butanol alkali metal salt with a solvent, and introducing anhydrous carbon dioxide gas to the end of the reaction to obtain a mixed solution; and step two, after the reaction in the step one is finished, adding a catalyst into the mixed solution generated in the step one, dissolving the oxalic acid trichloromethyl ester in the same solvent as the solvent in the step one, adding the solution into the mixed solution generated in the step one, and then carrying out heat preservation, pressure maintaining and stirring. The catalyst is tertiary amine organic matter or mixture of tertiary amine organic matter. Compared with the existing method, the method has the advantages of fast reaction, high yield, high purity, easy separation and the like, the theoretical atomic utilization rate is 56.14 percent, and the theoretical atomic utilization rate is about 13 percent higher than that of other non-phosgene methods and is close to that of the phosgene method.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, relates to di-tert-butyl dicarbonate, and particularly relates to a method for synthesizing di-tert-butyl dicarbonate based on oxalic acid trichloromethyl ester.
Background
Di-tert-butyl dicarbonate (also known as di-tert-butyl dicarbonate) is an amino protective agent in the organic synthesis process, is widely used in the synthesis field of chemicals such as special proteins, polypeptide drugs, amino-containing organic intermediates and the like, and has the advantages of high protective activity, easy deprotection, low cost and the like. Two main categories of synthetic methods for di-tert-butyl dicarbonate are reported in the literature. One is prepared by taking carbonic acid mono-tert-butyl ester alkali metal salt and carbonyl chloride compounds as raw materials; the other one is prepared by taking carbonic acid mono-tert-butyl ester alkali metal salt and aromatic or aliphatic sulfonyl chloride compounds as raw materials.
U.S. Pat. Nos. 5206407 and 5162565 disclose methods for preparing phosgene compounds as raw materials. Phosgene is also taken as a representative raw material of phosgene, and is firstly used for industrial production due to the high yield and byproduct benefit, but phosgene has high danger and high activity, so the adopted reaction solvent can only be an organic solvent without active hydrogen, the dissolving capacity of the solvent to the mono-tert-butyl carbonate alkali metal salt is very small, and the reaction temperature is low, and the system is viscous, so the reaction is incomplete, the yield is low, and the separation is difficult.
Chinese patents with application numbers CN201810780760.7, CN201611267410.8, CN201611267401.9, CN201210013100.9, CN201110260454.9, CN200610086299.2 and the like respectively disclose methods of replacing gas phosgene with diphosgene (trichloromethyl chloroformate, also known as liquid phosgene) and triphosgene (trichloromethyl carbonate, also known as solid phosgene), which avoid the danger of gas phosgene, and have the advantage of higher reaction yield than other acyl chloride raw materials, the theoretical utilization rate of chlorine in molecules is 100% as with gas phosgene, the atomic economy is also the same as with gas phosgene, and the theoretical atomic utilization rate is 57.52% [ atomic utilization rate = (molecular weight of expected product/total molecular weight of all products) × 100% ], which is a mainstream process currently applied to industrial production. Actually, diphosgene and triphosgene are still converted into phosgene to participate in the reaction process, so the solvent for the reaction cannot use alcohols such as tertiary butanol and the like with high solubility to raw materials and intermediates, and the diphosgene and the triphosgene have uncertainty of producing a large amount of gas phosgene by sudden explosive decomposition during catalytic decomposition, so a low-temperature reaction must be adopted, and the problems of incomplete reaction, low yield, difficult separation and the like caused by the low reaction temperature and the viscous system of a gas phosgene method system also exist. The inventor of the above patents has improved the solubility of the alkali metal salts of t-butanol and mono-t-butyl carbonate by selecting different solvents or even mixing a plurality of solvents, so as to make the reaction involving phosgene (liquid phosgene, solid phosgene) easier and more complete, but not ideal at present, so that one has added a phase transfer catalyst to the system to improve the reaction activity, which increases the difficulty of the subsequent product separation and wastewater treatment. Chinese patent nos. CN202011405302.9 and cn202022897240.X, which are based on the defects of the phosgene process, better solve the defects by using a supercritical carbon dioxide system, but still belong to the phosgene process, and have a large reaction system pressure and large equipment investment. Because of the special dangerousness of phosgene, the safety supervision department of China sets the process related to phosgene as a dangerous process, so that the new project is not approved in principle as long as phosgene including diphosgene and triphosgene is related to phosgene, so that the process for synthesizing di-tert-butyl dicarbonate by using phosgene method as a representative raw material cannot meet the industrial production practice, and a new synthesis path needs to be developed.
US5162565 discloses a method of using chloroacetyl chloride as raw material instead of phosgene, wherein monochloroacetyl chloride and dichloroacetyl chloride have low activity, only 5% yield, and trichloroacetyl chloride has high activity up to about 80%, but due to high cost of trichloroacetyl chloride, sodium trichloroacetate as a by-product is not well treated, the theoretical utilization rate of chlorine in trichloroacetyl chloride is only 25%, and the theoretical atomic utilization rate is 43.08%, so that the method has no report of industrial application.
Czechs slovac patent No.247846 and chinese patent CN98122657.4 disclose a method using aromatic or aliphatic sulfonyl chloride as a raw material, which avoids the danger of phosgene method, and can use tert-butyl alcohol as a solvent, where tert-butyl alcohol is a solvent which has relatively high solubility and does not cause side reactions with currently known raw materials and intermediates such as sodium tert-butoxide, potassium tert-butoxide, mono-tert-butyl-mono-sodium carbonate, mono-tert-butyl-mono-potassium carbonate, but the largest problem of the process is the separation problem of by-product aromatic or aliphatic sulfonate, aromatic or aliphatic sodium sulfonate and final products, and in addition, the raw material cost is relatively high, the generated by-product sodium sulfonate is not easy to treat, the treatment cost of the generated waste water is high, and the theoretical atomic utilization rate is low (for example, the theoretical atomic utilization rate of p-toluenesulfonyl chloride is 42.37%), so the process has not been industrially applied so far.
From the existing literature, the synthesis of di-tert-butyl dicarbonate is mainly a two-step reaction, the raw materials of the second step reaction determine the solvents of the first and second step reaction systems, the solubility of the solvents to the reaction raw materials and intermediates directly influences the total yield of the reaction, phosgene as the representative phosgene has high reaction activity and the highest theoretical atom utilization rate, but the requirements on the solvents of the reaction systems are also high, so that the selection of the reaction solvents is limited, and it can be said that no ideal organic solvent is found so far. Sulfonyl chlorides have low reaction activity, can adopt a solvent with high solubility of sodium tert-butoxide and potassium tert-butoxide which are a pair of raw materials, but have the problems of low yield, difficult disposal of byproducts and the like, so that a new synthetic route, particularly a non-phosgene method, is developed and is the direction of the technical workers in the field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate, and solve the technical problems that the yield of a non-phosgene synthesis method in the prior art needs to be further improved and byproducts are difficult to separate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for synthesizing di-tert-butyl dicarbonate based on dicloromethyl oxalate uses tert-butyl alcohol alkali metal salt, carbon dioxide and dicloromethyl oxalate as reaction raw materials;
the method comprises the following steps:
mixing alkali metal salt of tert-butyl alcohol with a solvent, and introducing anhydrous carbon dioxide gas to a reaction end point to obtain a mixed solution;
step two, after the reaction in the step one is finished, adding a catalyst into the mixed solution generated in the step one, dissolving the oxalic acid trichloromethyl ester in the same solvent as the solvent in the step one, adding the solution into the mixed solution generated in the step one, and then carrying out heat preservation, pressure maintaining and stirring;
the catalyst is tertiary amine organic matter or mixture of tertiary amine organic matter.
The invention also has the following technical characteristics:
preferably, the alkali metal salt of tert-butanol is sodium tert-butoxide or potassium tert-butoxide.
Preferably, the tertiary amine organic compound is trimethylamine, triethylamine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetraethylethylenediamine or N, N, N ', N' -tetramethylpropanediamine, N, N, N ', N' -tetraethylpropanediamine, N, N, N ', N' -tetramethylbutanediamine, N, N, N ', N' -tetraethylbutanediamine, N, N, N ', N' -tetramethylpentanediamine, N, N, N ', N' -tetraethylpentanediamine, N, N, N ', N' -tetramethylhexanediamine, N, N, N ', N' -tetraethylhexanediamine, N-methylmorpholine, N-ethylmorpholine, pyridine, N, N-dimethylaminopyridine or N, N-diethylaminopyridine.
Preferably, the solvent is one or more of alkane solvents, olefin solvents, aromatic solvents, ether solvents, halogenated alkane solvents, halogenated olefin solvents, amide solvents and tertiary amine solvents.
Preferably, the alkane solvent is cyclohexane, n-hexane or petroleum ether;
the olefin solvent is cyclohexene or cyclopentene;
the aromatic hydrocarbon solvent is benzene, toluene, xylene or ethylbenzene;
the halogenated alkane solvent is dichloromethane, dichloroethane or chloro-tert-butane;
the halogenated olefin solvent is trichloroethylene or trichloropropene;
the ether solvent is tetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxane or ethylene glycol dimethyl ether;
the amide solvent is N, N-dimethylformamide or N, N-dimethylacetamide;
the tertiary amine solvent is triethylamine, N-methylmorpholine or N-ethylmorpholine.
Preferably, the molar ratio of the tert-butanol alkali metal salt to the trichloromethyl oxalate is 1: (0.1583-0.175).
Preferably, the molar ratio of the catalyst to the oxalic acid trichloromethyl ester is (0.001-0.1): 1.0.
preferably, in the step one, the reaction temperature is between room temperature and 80 ℃, the pressure is between normal pressure and 1.0Mpa, and the reaction time is between 30 and 120min.
Preferably, in the second step, the temperature is controlled within the range of room temperature to 80 ℃, the pressure is normal pressure to 1.0Mpa, and the reaction time is 30-120 min.
Preferably, in the second step, after the heat preservation is finished, the temperature is reduced to normal pressure for filtration, a filter cake is washed by a solvent for three times, the filter cake is alkali metal chloride salt, the filtrate and the washing liquid are combined, the residual catalyst and the byproduct are washed by water, the washing water is exchanged with water for treatment, the washed reaction solution is dehydrated and dried, then is subjected to reduced pressure concentration at low temperature, the distilled solvent is returned to the system for use, and the concentrated solution is frozen and crystallized to obtain the product.
Compared with the prior art, the invention has the following technical effects:
compared with the prior art, the method has the advantages of fast reaction, high yield, high purity, easy separation and the like, the theoretical atomic utilization rate is 56.14 percent, which is higher than that of other non-phosgene methods by about 13 percent and is close to that of the phosgene method.
The invention (II) adopts a new method, the byproducts of the reaction are inorganic substances of sodium chloride or potassium chloride, carbon dioxide and carbon monoxide which are insoluble in the selected solvent, the inorganic substances are well separated from the system, and the generated waste salt is better disposed, safe and environment-friendly.
The invention (III) does not use phosgene, adopts non-phosgene non-hazardous reaction raw materials to replace hazardous materials and hazardous processes such as phosgene carbonyl chloride and the like in the prior art, and compared with a phosgene method, the reaction is shortened from three steps to two steps.
The Invention (IV) adopts new reaction raw materials, has relatively wide and mild requirements on reaction solvents and reaction systems, and is beneficial to industrialization.
(VI) the solvent and raw materials adopted by the invention are cheap and easy to obtain.
The present invention will be explained in further detail with reference to examples.
Detailed Description
It is to be noted that all the raw materials in the present invention, unless otherwise specified, may be those known in the art.
The yield in the present invention is based on the starting material tert-butanol alkali metal salt.
Through a large number of repeated tests and argumentations, the invention considers that the key problem of efficiently and safely realizing the synthesis of the di-tert-butyl dicarbonate is to find a new process, in particular a new non-phosgene process. The method has the advantages of fast reaction speed, high yield, good separation of by-products and capability of overcoming the dangers of a phosgene method and other non-phosgene methods. In theory, all organic matters and inorganic matters with active chlorine in molecules can be used as raw materials for synthesizing the di-tert-butyl dicarbonate, but the actual situation is not ideal, and the invention discovers a method for replacing the existing carbonyl chloride and sulfonyl chloride with the dicloromethyl oxalate through years of research.
The invention also finds that the temperature of the reaction is increased to be higher than the room temperature by adopting the oxalic acid trichloromethyl ester as the reaction raw material, so that the selection of the solvent is much wider, the system is not sticky any more, the reaction is very favorable, and a plurality of common solvents or the mixture of the common solvents can be used for the method.
The invention also discloses a catalyst which can catalyze the reaction of the oxalic acid trichloromethyl ester and the mono-tert-butyl ester mono-sodium (potassium) carbonate under a mild condition.
The invention provides a method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate, which takes tert-butyl alcohol alkali metal salt, carbon dioxide and trichloromethyl oxalate as reaction raw materials and synthesizes the di-tert-butyl dicarbonate in two steps in a special solvent system through a catalyst.
Specifically, the reaction principle of the process is as follows:
C(CH 3 ) 3 -OM+CO 2 →C(CH 3 ) 3 -O-CO-OM
3C(CH 3 ) 3 -O-CO-O-OC-O-C(CH 3 ) 3 +6MCl+2CO 2 +2CO
(M＝Na、K)
the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
Example 1:
this embodiment provides a method for synthesizing di-tert-butyl dicarbonate based on dicloromethyl oxalate, which comprises the following specific steps: 19.2g of sodium tert-butoxide (0.2 mol), 400g of n-hexane and 0.15g of triethylamine are weighed and added into a 1000ml tetrafluoro lined high-pressure reaction kettle with a stirrer, a thermometer, a pressure gauge, a gas inlet pipe and a heating and cooling coil, a feeding port is closed, stirring is started, cooling water is started, carbon dioxide is introduced, and the reaction is carried out for 120min at the pressure of 0.6Mpa and the temperature of 40 ℃. Dissolving 10.29g (0.03166 mol) of oxalic acid trichloromethyl ester with 100g of n-hexane, injecting into the reaction system through a plunger pump, and reacting at 40 ℃ under 0.6Mpa for 120min. After the reaction is finished, the temperature is reduced to room temperature and the pressure is released by emptying, the filtrate is filtered, a small amount of normal hexane is used for washing a filter cake to obtain a byproduct sodium chloride, the filtrate and a washing solution are combined and washed to be neutral by 300ml of water, an organic phase is dried by anhydrous magnesium sulfate and then concentrated to obtain 20.0g of di-tert-butyl dicarbonate, the purity is 99.1 percent, and the yield is 91.8 percent.
Example 2:
this embodiment provides a method for synthesizing di-tert-butyl dicarbonate based on dicloromethyl oxalate, which comprises the following specific steps: 22.4g of potassium tert-butoxide (0.2 mol), 400g of cyclohexane and 0.12g of triethylamine are weighed and added into a tetrafluoro-lined 1000ml high-pressure reaction kettle with a stirrer, a thermometer, a pressure gauge, a gas inlet pipe and a heating and cooling coil, a feeding port is closed, stirring is started, cooling water is started, carbon dioxide is introduced, and the reaction is carried out at room temperature under the pressure of 0.6MPa for 120min. 11.37g (0.03499 mol) of bistrichloromethyl oxalate was dissolved in 100g of cyclohexane and injected into the reaction system by a plunger pump, and the reaction was carried out at room temperature under a pressure of 0.6MPa for a further 120min. After the reaction, the pressure was released, the reaction mixture was filtered, and the cake was washed with a small amount of cyclohexane to give potassium chloride as a by-product, the filtrate and the washing solution were combined and washed with 300ml of water to neutrality, and the organic phase was dried over anhydrous magnesium sulfate and concentrated to give 20.3g of di-tert-butyl dicarbonate. The purity was 99.2% and the yield was 93.1%.
Examples 3 to 10:
this embodiment provides a method for synthesizing di-tert-butyl dicarbonate based on oxalic acid bis (trichloromethyl) ester, which comprises the following steps: referring to example 1, the kind of solvent, the kind of catalyst, the reaction temperature, the pressure and the time were changed. The results of the experiment are shown in table 1 below.
TABLE 1 specific Synthesis conditions for examples 3 to 10
Comparative example 1: (other non-phosgene processes)
This comparative example shows a non-phosgene process for preparing di-tert-butyl dicarbonate, which is the same as the procedure of example 1 except that the starting material is changed to trichloroacetyl chloride. The by-product is the mixture of sodium chloride and sodium trichloroacetate, and the main product di-tert-butyl dicarbonate (16.92 g) is obtained, the purity is 98.7%, and the yield is 77.6%.
Comparative example 2: (other non-phosgene processes)
This comparative example shows a non-phosgene process for preparing di-tert-butyl dicarbonate, which is identical to the procedure of example 1, except that the starting material is changed to dichloroacetyl chloride. The by-products are sodium chloride and sodium dichloroacetate, a solid main product of di-tert-butyl dicarbonate is not obtained, a liquid product is a mixture of the di-tert-butyl dicarbonate and tert-butyl alcohol, the gas chromatographic analysis shows that the liquid product contains about 0.88g of the product, and the yield is 4%.
Comparative example 3: (other non-phosgene processes)
This comparative example shows a non-phosgene process for the preparation of di-tert-butyl dicarbonate, which is identical to the procedure of example 1, except that the starting material is changed to oxalyl chloride. The by-product is sodium chloride, the main solid product of di-tert-butyl dicarbonate is not obtained, the liquid product is a mixture of di-tert-butyl dicarbonate and tert-butyl alcohol, and the gas chromatographic analysis shows that the product contains about 11.77g, and the yield is 54%.
Comparative example 4: (other non-phosgene processes)
This comparative example shows a process for preparing di-tert-butyl dicarbonate by a non-phosgene method, which is the same as the procedure of example 1 except that the starting material is changed to p-toluenesulfonyl chloride. The by-product is a mixture of sodium chloride and sodium p-toluenesulfonate, and 17.83g of main product di-tert-butyl dicarbonate with the purity of 99.1 percent and the yield of 81.8 percent is obtained.
Comparative example 5: (other non-phosgene processes)
This comparative example shows a non-phosgene process for the preparation of di-tert-butyl dicarbonate, which is identical to the procedure of example 1, except that the starting material is changed to benzenesulfonyl chloride. The by-product is the mixture of sodium chloride and sodium benzenesulfonate, and the main product di-tert-butyl dicarbonate (16.24 g), purity (98.5%) and yield (74.5%) are obtained.
Comparative example 6: (other non-phosgene methods)
This comparative example shows a non-phosgene process for the preparation of di-tert-butyl dicarbonate, which is identical to the procedure of example 1, except that the starting material was changed to p-nitrobenzenesulfonyl chloride. The by-product is the mixture of sodium chloride and sodium p-nitrobenzenesulfonate, and 18.1g of the main product, namely di-tert-butyl dicarbonate, is obtained, the purity is 98.8 percent, and the yield is 83.0 percent.
Comparative examples 7 to 11: (other non-phosgene processes)
This comparative example shows a non-phosgene process for the preparation of di-tert-butyl dicarbonate, which is identical to the procedure of example 1, except that the starting materials were changed to sulfone dichloride, sulfoxide chloride, silicon tetrachloride, titanium tetrachloride, tin tetrachloride. No di-tert-butyl dicarbonate product is obtained.
Comparative example 12: (other non-phosgene processes)
This comparative example shows a non-phosgene process for preparing di-tert-butyl dicarbonate, which is the same as the procedure of example 2 except that the starting material is changed to trichloroacetyl chloride. The by-product is the mixture of potassium chloride and potassium trichloroacetate, and 17.44g of the main product di-tert-butyl dicarbonate is obtained, the purity is 98.5 percent, and the yield is 80 percent.
Comparative example 13: (other non-phosgene processes)
This comparative example shows a non-phosgene process for the preparation of di-tert-butyl dicarbonate, which is identical to the procedure of example 2, except that the starting material is changed to oxalyl chloride. The by-product is potassium chloride, the solid main product of di-tert-butyl dicarbonate is not obtained, the liquid product is a mixture of di-tert-butyl dicarbonate and tert-butyl alcohol, the gas chromatographic analysis shows that the product contains about 13.5g, and the yield is 62%.
Comparative example 14: (other non-phosgene methods)
This comparative example shows a non-phosgene process for preparing di-tert-butyl dicarbonate, which is the same as the procedure of example 2 except that the starting material is changed to p-toluenesulfonyl chloride. The by-product is a mixture of potassium chloride and potassium p-toluenesulfonate, 18.2g of the main product di-tert-butyl dicarbonate is obtained, the purity is 99.3 percent, and the yield is 83.5 percent.
It is obvious from the above comparative example that the method of the present invention has high yield compared with the existing non-phosgene method, the reaction by-product is only single sodium chloride or potassium chloride, and the waste water treatment is simple. The atom economy of the reaction is high, and the theoretical atom utilization rate is higher than that of other methods. The data of the present process compared to other non-phosgene processes are summarized in Table 2 below:
TABLE 2 summary of data comparing this process with other non-phosgene processes
Claims (10)
1. A method for synthesizing di-tert-butyl dicarbonate based on dicloromethyl oxalate is characterized in that alkali metal salt of tert-butyl alcohol, carbon dioxide and dicloromethyl oxalate are used as reaction raw materials;
the method comprises the following steps:
mixing tertiary butanol alkali metal salt with a solvent, and introducing anhydrous carbon dioxide gas to the end of the reaction to obtain a mixed solution;
step two, after the reaction in the step one is finished, adding a catalyst into the mixed solution generated in the step one, dissolving the dimethyl dithiooxalate in the solvent which is the same as the solvent in the step one, adding the dimethyl dithiooxalate into the mixed solution generated in the step one, and then carrying out heat preservation, pressure maintaining and stirring;
the catalyst is tertiary amine organic matter or mixture of tertiary amine organic matter.
2. The method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as in claim 1, wherein the alkali metal salt of tert-butanol is sodium tert-butoxide or potassium tert-butoxide.
3. The method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as in claim 1, wherein the tertiary amine organic substance is trimethylamine, triethylamine, N, N, N ', N' -tetramethylethylenediamine, N, N, N ', N' -tetraethylethylenediamine, N, N, N ', N' -tetramethylpropylenediamine, N, N, N ', N' -tetraethylpropylenediamine, N, N, N ', N' -tetramethylbutanediamine, N, N, N ', N' -tetraethylbutanediamine, N, N, N ', N' -tetramethylpentanediamine, N, N, N ', N' -tetraethylpentanediamine, N, N, N ', N' -tetramethylhexanediamine, N, N, N ', N' -tetraethylhexanediamine, N-methylmorpholine, N-ethylmorpholine, pyridine, N, N-dimethylaminopyridine or N, N-diethylaminopyridine.
4. The method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as claimed in claim 1, wherein the solvent is one or more of alkane solvents, olefin solvents, aromatic solvents, ether solvents, halogenated alkane solvents, halogenated olefin solvents, amide solvents and tertiary amine solvents.
5. The method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as claimed in claim 4, wherein the alkane solvent is cyclohexane, n-hexane or petroleum ether;
the olefin solvent is cyclohexene or cyclopentene;
the aromatic hydrocarbon solvent is benzene, toluene, xylene or ethylbenzene;
the halogenated alkane solvent is dichloromethane, dichloroethane or chloro-tert-butane;
the halogenated olefin solvent is trichloroethylene or trichloropropene;
the ether solvent is tetrahydrofuran, 1, 3-dioxolane, 1, 4-dioxane or ethylene glycol dimethyl ether;
the amide solvent is N, N-dimethylformamide or N, N-dimethylacetamide;
the tertiary amine solvent is triethylamine, N-methylmorpholine or N-ethylmorpholine.
6. The method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as claimed in claim 1, wherein the molar ratio of the alkali metal tert-butoxide to the trichloromethyl oxalate is 1: (0.1583-0.175).
7. The method for synthesizing di-tert-butyl dicarbonate based on dichloromethyl oxalate according to claim 1, wherein the molar ratio of the catalyst to the dichloromethyl oxalate is (0.001-0.1): 1.0.
8. the method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as in claim 1, wherein the reaction temperature is room temperature to 80 ℃, the pressure is normal pressure to 1.0Mpa, and the reaction time is 30 to 120min.
9. The method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as in claim 1, wherein in step two, the temperature is controlled within the range of room temperature to 80 ℃, the pressure is normal pressure to 1.0Mpa, and the reaction time is 30 to 120min.
10. The method for synthesizing di-tert-butyl dicarbonate based on trichloromethyl oxalate as in claim 1, wherein in step two, after the heat preservation is completed, the temperature is reduced to normal pressure for filtration, a filter cake is washed with a solvent for three times, the filter cake is an alkali metal chloride salt, the filtrate and a washing solution are combined, the residual catalyst and byproducts are washed with water, the washing water is subjected to water exchange treatment, the washed reaction solution is dehydrated and dried, then reduced pressure concentration is performed at low temperature, the distilled solvent is returned to a system for application, and the concentrated solution is frozen and crystallized to obtain the product.
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