CN115322096A - Method for synthesizing di-tert-butyl dicarbonate by adopting phase transfer catalysis method - Google Patents
Method for synthesizing di-tert-butyl dicarbonate by adopting phase transfer catalysis method Download PDFInfo
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- CN115322096A CN115322096A CN202211125429.4A CN202211125429A CN115322096A CN 115322096 A CN115322096 A CN 115322096A CN 202211125429 A CN202211125429 A CN 202211125429A CN 115322096 A CN115322096 A CN 115322096A
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- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 38
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 238000003408 phase transfer catalysis Methods 0.000 title claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims abstract description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims abstract description 23
- YZVKCRIFBGZDNI-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxycarbonyl] carbonate Chemical compound CC(C)(C)OC(=O)OC(=O)OC(=O)OC(C)(C)C YZVKCRIFBGZDNI-UHFFFAOYSA-N 0.000 claims abstract description 23
- QNOFBICLSSWXDX-UHFFFAOYSA-N OC(O)=O.CC(C)(C)[Na] Chemical compound OC(O)=O.CC(C)(C)[Na] QNOFBICLSSWXDX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- 239000003517 fume Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- -1 di-tert-butylphenol dicarbonate Chemical compound 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- MFPWEWYKQYMWRO-UHFFFAOYSA-N tert-butyl carboxy carbonate Chemical compound CC(C)(C)OC(=O)OC(O)=O MFPWEWYKQYMWRO-UHFFFAOYSA-N 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 210000003739 neck Anatomy 0.000 claims description 3
- 239000012044 organic layer Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 239000013557 residual solvent Substances 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GEXJFIOPGAASTP-UHFFFAOYSA-N $l^{1}-azanylethane Chemical compound CC[N] GEXJFIOPGAASTP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims 1
- 239000002912 waste gas Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XRMMWCIXXAENCM-UHFFFAOYSA-N 2h-pyran-2,3,4,5-tetrol Chemical compound OC1OC=C(O)C(O)=C1O XRMMWCIXXAENCM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/68—Preparation of metal alcoholates
- C07C29/70—Preparation of metal alcoholates by converting hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of chemical products, and discloses a method for synthesizing di-tert-butyl dicarbonate by adopting a phase transfer catalysis method, which comprises the following steps: s1: reacting sodium tert-butoxide with carbon dioxide to generate mono-tert-butyl sodium carbonate; s2: reacting the generated mono-tert-butyl sodium carbonate with phosgene, solid light and aliphatic/aromatic sulfonyl chloride to generate di-tert-butyl tricarbonate; s3: the generated di-tert-butyl tricarbonate reacts with catalyst triethylamine or N, N-tetramethyl ethylenediamine to release a molecule of carbon dioxide to generate the di-tert-butyl dicarbonate.
Description
Technical Field
The invention relates to the technical field of chemical products, in particular to a method for synthesizing di-tert-butyl dicarbonate by adopting a phase transfer catalysis method.
Background
Di-tert-butyl dicarbonate having the formula C 10 H 18 O 5 CAS,24424-99-5, molecular weight 218.24, melting point 22-23 ℃, noneThe color crystal or colorless liquid with boiling point of 240 deg.c (760 mmHg) is easy to decompose and the decomposition is faster with higher temperature. Dissolving in organic solvent such as tetrahydrofuran, n-hexane, benzene, chloroform, petroleum ether, and ethyl acetate, and slightly dissolving in water. Di-tert-butyl dicarbonate (Diboc) is an amino protective agent, is used for introducing a tert-Butyloxycarbonyl (BOC) protective agent in organic synthesis, and is particularly suitable for amino protection of amino acid. Is widely applied to the synthesis of various products such as medicines, protein and polypeptide synthesis, biochemistry, foods, cosmetics and the like; the traditional method for synthesizing the di-tert-butyl dicarbonate is to prepare tert-butyl alcohol through tert-butyl chloride, but the tert-butyl chloride is extremely unstable and has low yield, so that a method for synthesizing the di-tert-butyl dicarbonate by adopting a phase transfer catalysis method is provided.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a method for synthesizing di-tert-butyl dicarbonate by adopting a phase transfer catalysis method, and solves the problems.
(II) technical scheme
In order to achieve the above purpose, the invention provides the following technical scheme: a method for synthesizing di-tert-butyl dicarbonate by adopting a phase transfer catalysis method comprises the following steps:
s1: reacting sodium tert-butoxide with carbon dioxide to generate mono-tert-butyl sodium carbonate;
s2: reacting the generated mono-tert-butyl sodium carbonate with phosgene, solid light and aliphatic/aromatic sulfonyl chloride to generate di-tert-butyl tricarbonate;
s3: reacting the generated di-tert-butyl tricarbonate with catalyst triethylamine or N, N-tetramethyl ethylenediamine to release a molecule of carbon dioxide to generate the di-tert-butyl dicarbonate.
Preferably, the preparation of sodium tert-butoxide in S1 comprises the following steps:
s21: feeding: 600 g of tert-butyl alcohol, 400 g of n-hexane and 60 g of metallic sodium are successively put into a 2L high-pressure kettle and steel balls are put into the high-pressure kettle;
s22: the autoclave is operated and heated for about 1 hour, the temperature rises to 100 ℃, and the pressure of the autoclave rises along with the rise of the temperature;
s23: the temperature rises to 100 ℃, the reaction pressure rises to 0.15MPa, then, a vent valve of the reaction kettle is opened, the pressure is controlled between 0.15MPa and 0.20MPa, the reaction is carried out for 6 hours, the pressure does not rise any more, and the reaction is finished;
s24: carrying out desolventizing: stopping heating, opening an air release valve, slowly reducing the pressure to 0.1MPa, evaporating the solvent, reducing the pressure to zero within about 1.5 hours, reducing the temperature to about 100 ℃, heating to evaporate residual solvent until the temperature reaches 90 ℃, and starting vacuumizing when the solution slowly flows out;
s25: slowly increasing the vacuum degree, adjusting the vacuum gauge pressure to 0.1MPa, pumping for 1 hour until no solvent flows out, finishing desolventizing, cooling and discharging to obtain sodium tert-butoxide solid.
Preferably, the reaction of sodium tert-butoxide in S1 with carbon dioxide to produce mono-tert-butyl sodium carbonate comprises the following steps:
s31: introducing dry nitrogen into the flask, adding 44.8 g (0.40 mol) of sodium tert-butoxide free of alcohol and 550 ml of anhydrous tetrahydroxypyran into the flask, and stirring for 5-10 min to obtain a solution;
s32: immersing the reaction flask in a salt-ice bath to maintain the temperature at 5-10 ℃, and introducing dry carbon dioxide for about 30 minutes under vigorous stirring to generate dense slurry;
s33: at the same time, 86 ml of dry benzene were added to the dropping funnel and bubbled with light until the volume of the phosgene solution in benzene reached 105 ml, corresponding to 24 g (0.24 mol) of phosgene;
s34: after the addition reaction of the carbon dioxide is finished, dropwise adding a phosgene solution into the cooled reactant under vigorous stirring for about 1 hour, keeping the temperature of a cold bath at 5-10 ℃, reducing the viscosity of the reaction mixture to be still white emulsion, and obtaining the mono-tertiary butyl sodium carbonate;
s35: when the addition reaction of phosgene was completed, stirring was continued for 45 minutes while introducing anhydrous nitrogen ethyl hair to blow out most of the excess phosgene.
Preferably, the generation of di-tert-butyl tricarbonate in S2 comprises the following steps:
s41: removing the instrument from the flask, plugging the two necks, concentrating about 650 ml of solvent to 100 ml under reduced pressure using a rotary evaporator, the flask still being cooled with an ice-salt bath to maintain 5-10 ℃;
s42: the reaction mixture, with a small amount of phosgene remaining, is discharged into a fume hood by means of a suction pump or vacuum pump, the material collected in the cold trap is also evacuated in the fume hood, the residue containing finely divided sodium chloride is suction filtered using a large-bore sand core funnel, which is precooled with 50 ml of ice-cold pentane before use;
s43: during filtration, the filter funnel is covered with a large-caliber funnel, nitrogen is introduced to isolate the materials from humid air, the residue in the flask is washed into the filter funnel by using ice-cold pentane, and then the filter residue is washed by using 200 ml of ice-cold pentane;
s44: mixing the filtrate with pentane washing liquid, concentrating at 0 deg.c and reduced pressure in a rotary evaporator to obtain white solid, dissolving the coarse product in 1250 ml pentane, cooling to-15 deg.c to separate white crystal, and concentrating the mother liquid in a rotary evaporator to obtain pure ditert-butyl tricarbonate product.
Preferably, the reaction of di-tert-butyl tricarbonate in S3 to tert-butyl dicarbonate comprises the following steps:
s51: adding 20.0 g (0.076 mol) of solution of di-tert-butyl tricarbonate in carbon tetrachloride and triethylamine as a catalyst into a beaker provided with an electromagnetic stirring rod, and immediately and rapidly releasing carbon dioxide;
s52: stirring at 25 deg.C for 45 min to completely release carbon dioxide, and adding 35 ml of water solution containing citric acid to make the water layer weakly acidic;
s53: the organic layer was separated, dried over anhydrous magnesium sulfate, concentrated at 25 ℃ by a rotary evaporator, and the residue was distilled under reduced pressure to give di-tert-butylphenol dicarbonate as a colorless liquid.
Preferably, the preparation equipment required in the preparation process of the di-tert-butyl dicarbonate comprises a flask, a mechanical stirrer, a 200 ml constant pressure dropping funnel, a calcium chloride drying tube, a 1L three-neck flask with the inner diameter not less than 6 mm extending to the bottom of the flask, a drying device and a dropping funnel calibrated in advance.
(III) advantageous effects
Compared with the prior art, the invention provides a method for synthesizing di-tert-butyl dicarbonate by adopting a phase transfer catalysis method, which has the following beneficial effects:
1. the method for synthesizing the di-tert-butyl dicarbonate by adopting the phase transfer catalysis method comprises the steps of generating mono-tert-butyl sodium carbonate by reacting sodium tert-butoxide with carbon dioxide, then generating di-tert-butyl tricarbonate by reacting the generated mono-tert-butyl sodium carbonate with phosgene, solid light and aliphatic/aromatic sulfonyl chloride, and finally generating the di-tert-butyl tricarbonate by reacting the generated di-tert-butyl tricarbonate with a catalyst triethylamine or N, N-tetramethylethylenediamine, and discharging one molecule of carbon dioxide to generate the di-tert-butyl dicarbonate.
Drawings
FIG. 1 is a schematic view of the process flow structure of the present invention;
FIG. 2 is a schematic view of a process flow of the present invention;
FIG. 3 is a schematic view of a chemical reaction scheme according to the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Referring to FIGS. 1-3, a method for synthesizing di-tert-butyl dicarbonate by phase transfer catalysis comprises the following steps:
s1: reacting sodium tert-butoxide with carbon dioxide to generate mono-tert-butyl sodium carbonate;
s2: reacting the generated mono-tert-butyl sodium carbonate with phosgene, solid light and aliphatic/aromatic sulfonyl chloride to generate di-tert-butyl tricarbonate;
s3: reacting the generated di-tert-butyl tricarbonate with catalyst triethylamine or N, N-tetramethylethylenediamine to release a molecule of carbon dioxide to generate the di-tert-butyl dicarbonate, wherein the reaction flow chart is shown in figure 3, and the reaction formula is shown in the following figure:
and the preparation equipment required in the preparation process of the di-tert-butyl dicarbonate comprises a flask, a mechanical stirrer, a 200 ml constant pressure dropping funnel, a calcium chloride drying tube, a 1L three-neck flask which extends to the bottom of the flask and has the inner diameter not less than 6 mm, and a dropping funnel which is dried and calibrated in advance.
The preparation of sodium tert-butoxide in S1 comprises the following steps:
s21: feeding: putting 600 g of tert-butyl alcohol, 400 g of n-hexane and 60 g of metallic sodium into a 2L high-pressure kettle in sequence, and putting steel balls into the high-pressure kettle;
s22: the autoclave is operated and heated for about 1 hour, the temperature rises to 100 ℃, and the pressure of the autoclave rises along with the rise of the temperature;
s23: the temperature rises to 100 ℃, the reaction pressure rises to 0.15MPa, then, a vent valve of the reaction kettle is opened, the pressure is controlled between 0.15MPa and 0.20MPa, the reaction is carried out for 6 hours, the pressure does not rise any more, and the reaction is finished;
s24: carrying out desolventizing: stopping heating, opening an air release valve, slowly reducing the pressure to 0.1MPa, evaporating the solvent, reducing the pressure to zero within about 1.5 hours, reducing the temperature to about 100 ℃, heating to evaporate residual solvent until the temperature reaches 90 ℃, and starting vacuumizing when the solution slowly flows out;
s25: slowly increasing the vacuum degree, adjusting the pressure of a vacuum gauge to 0.1MPa, pumping for 1 hour until no solvent flows out, ending desolventizing, cooling and discharging to obtain sodium tert-butoxide solid.
In the S1, sodium tert-butoxide reacts with carbon dioxide to generate mono-tert-butyl sodium carbonate, and the method comprises the following steps:
s31: introducing dry nitrogen into the flask, adding 44.8 g (0.40 mol) of sodium tert-butoxide free of alcohol and 550 ml of anhydrous tetrahydroxypyran into the flask, and stirring for 5-10 min to obtain a solution;
s32: immersing the reaction flask in a salt-ice bath to maintain the temperature at 5-10 ℃, and introducing dry carbon dioxide for about 30 minutes under vigorous stirring to generate dense slurry;
s33: at the same time, 86 ml of dry benzene were added to the dropping funnel and bubbled with light until the volume of the phosgene solution in benzene reached 105 ml, corresponding to 24 g (0.24 mol) of phosgene;
s34: after the addition reaction of the carbon dioxide is finished, dropwise adding a phosgene solution into the cooled reactant under vigorous stirring for about 1 hour, keeping the temperature of a cold bath at 5-10 ℃, reducing the viscosity of the reaction mixture to be still white emulsion, and obtaining the mono-tertiary butyl sodium carbonate;
s35: when the addition reaction of phosgene was completed, stirring was continued for 45 minutes while introducing anhydrous ethyl-nitrogen to blow out most of the excess phosgene.
In the preparation process, sulfuryl chloride introduced into sulfur is removed, and the difference between solid light and phosgene is remained, namely gas light is used for replacing solid light.
The generation of the di-tert-butyl tricarbonate in the S2 comprises the following steps:
s41: removing the instrument from the flask, plugging the two necks, concentrating about 650 ml of solvent to 100 ml under reduced pressure using a rotary evaporator, the flask still being cooled with an ice-salt bath to maintain 5-10 ℃;
s42: the reaction mixture, with a small amount of phosgene remaining, is discharged into a fume hood by means of a suction pump or vacuum pump, the material collected in the cold trap is also evacuated in the fume hood, the residue containing finely divided sodium chloride is suction filtered using a large-bore sand core funnel, which is precooled with 50 ml of ice-cold pentane before use;
s43: during filtration, the filter funnel is covered with a large-caliber funnel, nitrogen is introduced to isolate the materials from humid air, the residue in the flask is washed into the filter funnel by using ice-cold pentane, and then the filter residue is washed by using 200 ml of ice-cold pentane;
s44: mixing the filtrate with pentane washing liquid, concentrating at 0 deg.c and reduced pressure in a rotary evaporator to obtain white solid, dissolving the coarse product in 1250 ml pentane, cooling to-15 deg.c to separate white crystal, and concentrating the mother liquid in a rotary evaporator to obtain pure ditert-butyl tricarbonate product.
The reaction of di-tert-butyl tricarbonate in S3 to produce tert-butyl dicarbonate comprises the following steps:
s51: adding 20.0 g (0.076 mol) of solution of di-tert-butyl tricarbonate in carbon tetrachloride and triethylamine as a catalyst into a beaker provided with an electromagnetic stirring rod, and immediately and rapidly releasing carbon dioxide;
s52: stirring at 25 deg.C for 45 min to completely release carbon dioxide, and adding 35 ml of water solution containing citric acid to make the water layer weakly acidic;
s53: the organic layer was separated, dried over anhydrous magnesium sulfate, concentrated at 25 ℃ by a rotary evaporator, and the residue was distilled under reduced pressure to give di-tert-butylphenol dicarbonate as a colorless liquid.
The process flow chart of the method for synthesizing the di-tert-butyl dicarbonate by adopting the phase transfer catalysis method is shown in figure 2, and the yield of the di-tert-butyl dicarbonate is as high as 80-91%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for synthesizing di-tert-butyl dicarbonate by adopting a phase transfer catalysis method is characterized by comprising the following steps:
s1: reacting sodium tert-butoxide with carbon dioxide to generate mono-tert-butyl sodium carbonate;
s2: reacting the generated mono-tert-butyl sodium carbonate with phosgene, solid light and aliphatic/aromatic sulfonyl chloride to generate di-tert-butyl tricarbonate;
s3: reacting the generated di-tert-butyl tricarbonate with a catalyst triethylamine or N, N-tetramethyl ethylene diamine,evolution of one molecule of CO 2 Tert-butyl dicarbonate is formed.
2. The method for synthesizing di-tert-butyl dicarbonate by using the phase transfer catalysis method according to claim 1, characterized in that: the preparation of the sodium tert-butoxide in S1 comprises the following steps:
s21: putting 600 g of tert-butyl alcohol, 400 g of n-hexane and 60 g of metallic sodium into a 2L high-pressure kettle in sequence, and putting steel balls into the high-pressure kettle;
s22: the autoclave was operated to heat for about 1 hour, the temperature rising to 100 ℃;
s23: the temperature is increased to 100 ℃, the reaction pressure is increased to 0.15MPa, a vent valve of the reaction kettle is opened, the pressure is controlled between 0.15MPa and 0.20MPa, the reaction is carried out for 6 hours, the pressure is not increased any more, and the reaction is finished;
s24: carrying out desolventizing: stopping heating, opening an air release valve, slowly reducing the pressure to 0.1MPa, evaporating the solvent, reducing the pressure to zero within about 1.5 hours, reducing the temperature to about 100 ℃, heating to evaporate residual solvent until the temperature reaches 90 ℃, and starting vacuumizing when the solution slowly flows out;
s25: slowly increasing the vacuum degree, adjusting the pressure of a vacuum gauge to 0.1MPa, pumping for 1 hour until no solvent flows out, ending desolventizing, cooling and discharging to obtain sodium tert-butoxide solid.
3. The method for synthesizing di-tert-butyl dicarbonate by using phase transfer catalysis as claimed in claim 1, characterized in that: the method for preparing the mono-tert-butyl sodium carbonate by reacting sodium tert-butoxide in the S1 with carbon dioxide comprises the following steps:
s31: introducing dry nitrogen into the flask, adding 44.8 g (0.40 mol) of sodium tert-butoxide free of alcohol and 550 ml of anhydrous tetrahydrofuran into the flask, and stirring for 5-10 min to obtain a solution;
s32: immersing the reaction flask in a salt-ice bath to maintain the temperature at 5-10 ℃, and introducing dry carbon dioxide for about 30 minutes under vigorous stirring to generate dense slurry;
s33: at the same time, 86 ml of dry benzene were added to the dropping funnel and bubbled with light until the volume of the phosgene solution in benzene reached 105 ml, corresponding to 24 g (0.24 mol) of phosgene;
s34: after the addition reaction of the carbon dioxide is finished, dropwise adding a phosgene solution into the cooled reactant under vigorous stirring, wherein the time is about 1 hour, the cold bath temperature is kept at 5-10 ℃, the viscosity of the reaction mixture is reduced and the reaction mixture still is white emulsion, and mono-tert-butyl sodium carbonate is obtained;
s35: when the addition reaction of phosgene was completed, stirring was continued for 45 minutes while introducing anhydrous ethyl-nitrogen to blow out most of the excess phosgene.
4. The method for synthesizing di-tert-butyl dicarbonate by using the phase transfer catalysis method according to claim 3, characterized by comprising the following steps: the method for generating the di-tert-butyl tricarbonate in the S2 comprises the following steps:
s41: removing the apparatus from the flask, plugging the two necks, concentrating about 650 ml of solvent to 100 ml under reduced pressure using a rotary evaporator, the flask still being cooled with an ice-salt bath to maintain 5-10 ℃;
s42: exhausting waste gas from the air pump or vacuum pump into a fume hood, evacuating the material collected in the cold trap in the fume hood, suction filtering the residue containing sodium chloride with a large-caliber sand core funnel, and pre-cooling the funnel with 50 ml of ice-cold pentane before use;
s43: during filtration, the filter funnel is covered with a large-caliber funnel, nitrogen is introduced to isolate the materials from humid air, the residue in the flask is washed into the filter funnel by using ice-cold pentane, and then the filter residue is washed by using 200 ml of ice-cold pentane;
s44: mixing the filtrate with pentane washing liquid, concentrating at 0 deg.c and reduced pressure in a rotary evaporator to obtain white solid, dissolving the coarse product in 1250 ml pentane, cooling to-15 deg.c to separate white crystal, and concentrating the mother liquid in a rotary evaporator to obtain pure ditert-butyl tricarbonate.
5. The method for synthesizing di-tert-butyl dicarbonate by using phase transfer catalysis as claimed in claim 4, characterized in that: the reaction of the di-tert-butyl tricarbonate in the S3 to generate the tert-butyl dicarbonate comprises the following steps:
s51: adding 20.0 g (0.076 mol) of solution of di-tert-butyl tricarbonate in carbon tetrachloride and triethylamine as a catalyst into a beaker provided with an electromagnetic stirring rod, and immediately and rapidly releasing carbon dioxide;
s52: stirring at 25 deg.C for 45 min to completely release carbon dioxide, and adding 35 ml of water solution containing appropriate amount of citric acid to make the water layer weakly acidic;
s53: the organic layer was separated, dried over anhydrous magnesium sulfate, concentrated at 25 ℃ by a rotary evaporator, and the residue was distilled under reduced pressure to give di-tert-butylphenol dicarbonate as a colorless liquid.
6. The method for synthesizing di-tert-butyl dicarbonate by using the phase transfer catalysis method according to claim 1, characterized in that: the preparation equipment needed in the preparation process of the di-tert-butyl dicarbonate comprises a flask, a mechanical stirrer, a 200 ml constant pressure dropping funnel, a calcium chloride drying tube, a 1L three-neck flask which extends to the bottom of the flask and has the inner diameter not less than 6 mm, a drying device and a dropping funnel calibrated in advance.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222504A (en) * | 1997-11-10 | 1999-07-14 | 德山株式会社 | Process for producing di-tert-butyl dicarbonate |
| CN1915963A (en) * | 2006-08-30 | 2007-02-21 | 荆和祥 | Method for preparing di-tert-butyl dicarbonate |
| CN101172950A (en) * | 2006-10-31 | 2008-05-07 | 上海中远化工有限公司 | Method for synthesizing di-tert-butyl dicarbonic acid ester |
| CN106748793A (en) * | 2016-12-31 | 2017-05-31 | 山东金城柯瑞化学有限公司 | The synthetic method of di-tert-butyl dicarbonate |
| CN108794335A (en) * | 2018-07-17 | 2018-11-13 | 常州大学 | A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1222504A (en) * | 1997-11-10 | 1999-07-14 | 德山株式会社 | Process for producing di-tert-butyl dicarbonate |
| CN1915963A (en) * | 2006-08-30 | 2007-02-21 | 荆和祥 | Method for preparing di-tert-butyl dicarbonate |
| CN101172950A (en) * | 2006-10-31 | 2008-05-07 | 上海中远化工有限公司 | Method for synthesizing di-tert-butyl dicarbonic acid ester |
| CN106748793A (en) * | 2016-12-31 | 2017-05-31 | 山东金城柯瑞化学有限公司 | The synthetic method of di-tert-butyl dicarbonate |
| CN108794335A (en) * | 2018-07-17 | 2018-11-13 | 常州大学 | A method of di-tert-butyl dicarbonate is synthesized using phase transfer catalysis process |
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