CN114425329B - Catalyst for synthesis of pregnenolone acetate, and preparation method and application thereof - Google Patents
Catalyst for synthesis of pregnenolone acetate, and preparation method and application thereof Download PDFInfo
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- CN114425329B CN114425329B CN202210240137.9A CN202210240137A CN114425329B CN 114425329 B CN114425329 B CN 114425329B CN 202210240137 A CN202210240137 A CN 202210240137A CN 114425329 B CN114425329 B CN 114425329B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- CRRKVZVYZQXICQ-RJJCNJEVSA-N Pregnenolone acetate Chemical compound C([C@@H]12)C[C@]3(C)[C@@H](C(C)=O)CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 CRRKVZVYZQXICQ-RJJCNJEVSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000003786 synthesis reaction Methods 0.000 title description 6
- 230000015572 biosynthetic process Effects 0.000 title description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 128
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 72
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 47
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 36
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- MZWRIOUCMXPLKV-RFOVXIPZSA-N 16-Dehydropregnenolone acetate Chemical compound C([C@@H]12)C[C@]3(C)C(C(C)=O)=CC[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 MZWRIOUCMXPLKV-RFOVXIPZSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 94
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 70
- 238000005406 washing Methods 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 26
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 23
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 20
- 230000009467 reduction Effects 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 15
- 239000012018 catalyst precursor Substances 0.000 claims description 14
- 238000010411 cooking Methods 0.000 claims description 14
- 238000010306 acid treatment Methods 0.000 claims description 12
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 230000009257 reactivity Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- -1 palladium ions Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000583 progesterone congener Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 150000003431 steroids Chemical class 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003163 gonadal steroid hormone Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 210000001672 ovary Anatomy 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000186 progesterone Substances 0.000 description 1
- 229960003387 progesterone Drugs 0.000 description 1
- 229940095055 progestogen systemic hormonal contraceptives Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000003270 steroid hormone Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/617—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
- C07J7/0005—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21
- C07J7/001—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group
- C07J7/0015—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group not substituted in position 17 alfa
- C07J7/002—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms not substituted in position 21 substituted in position 20 by a keto group not substituted in position 17 alfa not substituted in position 16
Abstract
The invention discloses a catalyst for synthesizing pregnenolone acetate, a preparation method and application thereof. In addition, the invention also provides a catalyst prepared by the preparation method and a method for synthesizing pregnenolone acetate by using the catalyst. According to the invention, the modified activated carbon is obtained by modifying the activated carbon treated by ammonium persulfate through magnesium salt, pd is loaded on the modified activated carbon as a carrier, and the catalyst for synthesizing pregnenolone acetate is obtained, so that the yield exceeds 75.0% in the reaction of synthesizing pregnenolone acetate from dehydropregnenolone acetate under the action of the catalyst, and the catalyst has high reactivity and activity.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a catalyst for synthesis of pregnenolone acetate, a preparation method and application thereof.
Background
Pregnenolone acetate is also called 3 beta-hydroxy pregn-5-ene-20-one-3-acetate, is the most critical intermediate for synthesizing steroid progesterone, is an endogenous steroid and a progestogen sex hormone, is secreted by ovaries of females, and contains 21 carbon atoms, is an intermediate for synthesizing all steroid hormones, and belongs to one of progestogens.
The pregnenolone acetate is generally prepared by synthesizing an intermediate pregnenolone acetate (also called 3 beta-hydroxy pregna-5, 16-diene-20-ketone-3-acetate), and the pregnenolone acetate (also called 3 beta-hydroxy pregna-5-ene-20-ketone-3-acetate) is prepared by hydrogenation reaction of an olefinic bond (C=C) at the 16-position in the pregnenolone acetate structure under a certain condition so as to be converted into the pregnenolone acetate, and belongs to steroid double bond hydrogenation reaction, however, the present preparation of the pregnenolone acetate has the defect of low yield and selectivity due to higher hydrogenation difficulty of the pregnenolone acetate.
In addition, in organic hydrogenation reactions, where one or more side reactions are present, it is often desirable to balance the relationship between selectivity, activity and catalyst stability, and it is particularly important to select a suitable high efficiency catalyst. The palladium-carbon catalyst is a catalytic material prepared by loading noble metal palladium on carrier active carbon, has the characteristics of small feeding amount, high activity, stable performance, environmental protection, easy recovery and the like, and is widely applied to the reaction processes of medicine industry, petrochemical industry, dye-perfume industry, electronic industry and other fine chemical industry. As the supported catalyst, the palladium-carbon catalyst is prepared by the following methods: impregnation, hydrolysis impregnation, ion exchange, and precipitation. Organic hydrogenation raw materials and reaction processes are complex, palladium-carbon catalysts are various, the universality of one or more catalysts is difficult to realize, and most of catalysts with specificity are difficult to meet the requirements of the reaction on stable reaction activity, high selectivity and stability. Therefore, the design and preparation of the catalyst with high activity, selectivity and stability are particularly important for synthesizing pregnenolone acetate.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst for synthesizing pregnenolone acetate, a preparation method and application thereof, aiming at the defects of the prior art. According to the invention, the modified activated carbon is obtained by modifying the activated carbon treated by ammonium persulfate through magnesium salt, pd is loaded on the modified activated carbon as a carrier, and the catalyst for synthesizing pregnenolone acetate is obtained, so that the yield exceeds 75.0% in the reaction of synthesizing pregnenolone acetate from dehydropregnenolone acetate under the action of the catalyst, and the catalyst has high reactivity and activity.
In order to solve the technical problems, the invention adopts the following technical scheme: a method for preparing a catalyst for synthesizing pregnenolone acetate, which is characterized by comprising the following steps: and modifying the ammonium persulfate treated active carbon by magnesium salt to obtain modified active carbon, and taking the modified active carbon as a carrier to load Pd to obtain the catalyst for synthesizing pregnenolone acetate.
The preparation method of the catalyst for synthesizing pregnenolone acetate is characterized by comprising the following steps of:
step one, boiling active carbon in a nitric acid solution, filtering, and washing with water to obtain acid-treated active carbon;
Stirring the activated carbon subjected to the acid treatment in the step one in ammonium persulfate solution for 2-4 hours at the temperature of 60-80 ℃, filtering, and washing with water to obtain the activated carbon subjected to the ammonium persulfate treatment;
step three, under the normal temperature condition, placing the activated carbon treated by the ammonium persulfate in the step two into a magnesium salt solution, stirring for 1-2 h, and filtering to obtain modified activated carbon;
step four, placing the modified active carbon in the step three in palladium nitrate solution, stirring for 30-60 min, controlling the pH of the system to 7-9 in the stirring process, filtering, and washing to obtain a catalyst precursor;
and fifthly, reducing the catalyst precursor in the fourth step to obtain the catalyst for synthesizing pregnenolone acetate.
The preparation method of the catalyst for synthesizing pregnenolone acetate is characterized in that the mass of the nitric acid solution in the first step is 8-10 times of that of active carbon, and the mass percentage concentration of the nitric acid solution is 3-5%; the specific surface area of the activated carbon is 700m 2/g～1000m2/g; the cooking temperature is 80-100 ℃ and the cooking time is 1-2 h; and step one, washing with water until the pH is 6-8.
The preparation method of the catalyst for synthesizing pregnenolone acetate is characterized in that the mass of the ammonium persulfate solution in the second step is 8-10 times of the mass of the active carbon in the first step, and the mass percentage concentration of the ammonium persulfate solution is 2-5%; and step two, washing with water until the pH is 6.
The preparation method of the catalyst for synthesizing pregnenolone acetate is characterized in that the mass of the magnesium salt solution in the step three is 5-8 times of that of the active carbon in the step one, the mass percentage concentration of the magnesium salt in the magnesium salt solution is 1-2%, and the magnesium salt is magnesium nitrate or magnesium chloride.
The preparation method of the catalyst for synthesizing pregnenolone acetate is characterized in that the palladium ion concentration in the palladium nitrate solution in the fourth step is 0.1 g/mL-0.5 g/mL.
The preparation method of the catalyst for synthesizing pregnenolone acetate is characterized in that the reduction is carried out by using a reducing agent solution, the reduction temperature is 90-100 ℃, the reduction time is 1-2 h, the mass percentage of the reducing agent solution is 10-20%, and the reducing agent solution is sodium borohydride solution or hydrazine hydrate solution.
In addition, the invention also provides a catalyst for synthesizing pregnenolone acetate, which is prepared by the preparation method of the catalyst for synthesizing pregnenolone acetate.
Furthermore, the invention also provides a method for synthesizing pregnenolone acetate by using the catalyst for synthesizing pregnenolone acetate, which is characterized by comprising the following steps: mixing and reacting raw materials, a solvent and the catalyst at the temperature of 40+/-5 ℃ to obtain pregnenolone acetate; the raw material is dehydropregnenolone acetate.
The method is characterized in that the hydrogenation pressure in the mixing reaction is 0.2Mpa, the mass of the catalyst is 0.04 times of that of dehydropregnenolone acetate, the mass percentage of Pd in the catalyst is 5%, and the solvent is absolute ethyl alcohol.
The pregnenolone acetate synthesis reaction equation of the invention is shown as follows:
Compared with the prior art, the invention has the following advantages:
1. According to the invention, the modified activated carbon is obtained by modifying the activated carbon treated by ammonium persulfate through magnesium salt, pd is loaded on the modified activated carbon as a carrier, and the catalyst for synthesizing pregnenolone acetate is obtained, so that the yield exceeds 75.0% in the reaction of synthesizing pregnenolone acetate from dehydropregnenolone acetate under the action of the catalyst, and the catalyst has high reactivity and activity.
2. Preferably, the method for preparing the catalyst for synthesizing pregnenolone acetate comprises the steps of sequentially treating active carbon with nitric acid solution, ammonium persulfate and magnesium salt solution to obtain modified active carbon, wherein the modified active carbon carrier has the characteristic of richer surface active sites, is favorable for anchoring alkaline groups in catalytic reaction, and has high carrier stability.
3. Preferably, the method for preparing the catalyst for synthesizing the pregnenolone acetate comprises the steps of modifying the activated carbon by using a magnesium salt solution, wherein the modified activated carbon surface contains oxygen carboxyl and magnesium positive ions, so that the subsequent combination with Pd can be effectively promoted, the electron transfer speed in the catalytic reaction process is improved, the adsorption and desorption of reactants and product molecules are promoted, and in addition, the adsorption of Pd ions on the outer surface of a carrier can be effectively promoted by using the alloy effect of magnesium ions and Pd ions, and the reactivity of the catalyst in the catalytic reaction is improved.
4. The preparation method of the catalyst for synthesizing pregnenolone acetate is simple, easy to operate and low in cost.
The technical scheme of the invention is further described in detail below with reference to the examples.
Detailed Description
Example 1
The embodiment provides a preparation method of a catalyst for synthesizing pregnenolone acetate, which comprises the following steps:
Step one, 100g of activated carbon is steamed in 1000g of nitric acid solution, filtered and washed to obtain the activated carbon after acid treatment; the mass percentage concentration of the nitric acid solution is 3%; the cooking temperature is 80 ℃, and the cooking time is 1h; the water washing is water washing until the pH value is 6; the specific surface area of the activated carbon is 700m 2/g～800m2/g;
Stirring the activated carbon subjected to the acid treatment in the step one in 1000g of ammonium persulfate solution for 2 hours at the temperature of 60 ℃, filtering, and washing to obtain the activated carbon subjected to the ammonium persulfate treatment; the mass percentage concentration of the ammonium persulfate solution is 2%; the water washing is water washing until the pH value is 6;
step three, under the normal temperature condition, placing the activated carbon treated by the ammonium persulfate in the step two into 500g of magnesium salt solution, stirring for 1h, and filtering to obtain modified activated carbon; the magnesium salt solution is magnesium chloride solution, and the mass percentage concentration of magnesium chloride in the magnesium salt solution is 1%; the normal temperature is 20-25 ℃;
Step four, according to the preset palladium content in the Pd/C catalyst, placing the modified active carbon in the step three into a palladium nitrate solution, stirring for 30min, controlling the pH of a system to be 7 in the stirring process, filtering and washing to obtain a catalyst precursor; the concentration of palladium ions in the palladium nitrate solution is 0.1g/mL; controlling the pH of the system by using an ammonia water solution; the catalyst with the preset palladium content can be 5% Pd/C;
step five, reducing the catalyst precursor in the step four to obtain a catalyst for synthesizing pregnenolone acetate; the reduction is carried out by using a reducing agent solution, wherein the reducing agent solution is sodium borohydride solution, the reduction temperature is 90 ℃, and the reduction time is 1h; the volume of the reducing agent solution is 50 times of the mass of Pd, and the mass percentage of the reducing agent solution is 20%.
Comparative example 1
According to the preset palladium content in the Pd/C catalyst, stirring and mixing the palladium nitrate solution and the active carbon, stabilizing for 1h, aging for 12h, introducing hydrogen for reduction for 1h, washing, and filtering to obtain the Pd/C catalyst, wherein the catalyst with the preset palladium content can be 5% Pd/C.
Example 2
The embodiment provides a preparation method of a catalyst for synthesizing pregnenolone acetate, which comprises the following steps:
Step one, 100g of activated carbon is steamed in 1000g of nitric acid solution, filtered and washed to obtain the activated carbon after acid treatment; the mass percentage concentration of the nitric acid solution is 5%; the cooking temperature is 100 ℃, and the cooking time is 2 hours; the water washing is water washing until the pH value is 6; the specific surface area of the activated carbon is 800m 2/g～900m2/g;
stirring the activated carbon subjected to the acid treatment in the step one in 1000g of ammonium persulfate solution for 4 hours at the temperature of 80 ℃, filtering, and washing to obtain the activated carbon subjected to the ammonium persulfate treatment; the mass percentage concentration of the ammonium persulfate solution is 5%; the water washing is water washing until the pH value is 6;
step three, under the normal temperature condition, placing the activated carbon treated by the ammonium persulfate in the step two into 500g of magnesium salt solution, stirring for 2 hours, and filtering to obtain modified activated carbon; the magnesium salt solution is magnesium chloride solution, and the mass percentage concentration of magnesium chloride in the magnesium salt solution is 2%; the normal temperature is 20-25 ℃;
Step four, according to the preset palladium content in the Pd/C catalyst, placing the modified active carbon in the step three into a palladium nitrate solution, stirring for 60min, controlling the pH of a system to be 8 in the stirring process, filtering and washing to obtain a catalyst precursor; the concentration of palladium ions in the palladium nitrate solution is 0.5g/mL; controlling the pH of the system by using an ammonia water solution; the catalyst with the preset palladium content can be 5% Pd/C;
step five, reducing the catalyst precursor in the step four to obtain a catalyst for synthesizing pregnenolone acetate; the reduction is carried out by using a reducing agent solution, wherein the reducing agent solution is sodium borohydride solution, the reduction temperature is 100 ℃, and the reduction time is 2 hours; the volume of the reducing agent solution is 50 times of the mass of Pd, and the mass percentage of the reducing agent solution is 10%.
Example 3
The embodiment provides a preparation method of a catalyst for synthesizing pregnenolone acetate, which comprises the following steps:
Step one, 100g of activated carbon is steamed in 1000g of nitric acid solution, filtered and washed to obtain the activated carbon after acid treatment; the mass percentage concentration of the nitric acid solution is 4%; the cooking temperature is 100 ℃, and the cooking time is 1.5h; the water washing is water washing until the pH value is 6; the specific surface area of the activated carbon is 800m 2/g～900m2/g;
Stirring the activated carbon subjected to the acid treatment in the step one in 1000g of ammonium persulfate solution for 4 hours at the temperature of 80 ℃, filtering, and washing to obtain the activated carbon subjected to the ammonium persulfate treatment; the mass percentage concentration of the ammonium persulfate solution is 4%; the water washing is water washing until the pH value is 6;
Step three, under the normal temperature condition, placing the activated carbon treated by the ammonium persulfate in the step two into 800g of magnesium salt solution, stirring for 2 hours, and filtering to obtain modified activated carbon; the magnesium salt solution is magnesium chloride solution, and the mass percentage concentration of magnesium chloride in the magnesium salt solution is 2%; the normal temperature is 20-25 ℃;
Step four, according to the preset palladium content in the Pd/C catalyst, placing the modified active carbon in the step three into a palladium nitrate solution, stirring for 60min, controlling the pH of a system to be 9 in the stirring process, filtering and washing to obtain a catalyst precursor; the concentration of palladium ions in the palladium nitrate solution is 0.2g/mL; controlling the pH of the system by using an ammonia water solution; the catalyst with the preset palladium content can be 5% Pd/C;
Step five, reducing the catalyst precursor in the step four to obtain a catalyst for synthesizing pregnenolone acetate; the reduction is carried out by using a reducing agent solution, wherein the reducing agent solution is sodium borohydride solution, the reduction temperature is 100 ℃, and the reduction time is 2 hours; the volume of the reducing agent solution is 50 times of the mass of Pd, and the mass percentage of the reducing agent solution is 15%.
Example 4
The embodiment provides a preparation method of a catalyst for synthesizing pregnenolone acetate, which comprises the following steps:
Step one, 100g of activated carbon is steamed in 800g of nitric acid solution, filtered and washed to obtain the activated carbon after acid treatment; the mass percentage concentration of the nitric acid solution is 5%; the cooking temperature is 90 ℃, and the cooking time is 2 hours; the water washing is water washing until the pH value is 7; the specific surface area of the activated carbon is 900m 2/g～1000m2/g;
Stirring the activated carbon subjected to the acid treatment in the step one in 800g of ammonium persulfate solution for 3 hours at the temperature of 70 ℃, filtering, and washing to obtain the activated carbon subjected to the ammonium persulfate treatment; the mass percentage concentration of the ammonium persulfate solution is 4%; the water washing is water washing until the pH value is 6;
Step three, under the normal temperature condition, placing the activated carbon treated by the ammonium persulfate in the step two into 600g of magnesium salt solution, stirring for 1.5 hours, and filtering to obtain modified activated carbon; the magnesium salt solution is magnesium nitrate solution, and the mass percentage concentration of magnesium chloride in the magnesium salt solution is 1.5%; the normal temperature is 20-25 ℃;
Step four, according to the preset palladium content in the Pd/C catalyst, placing the modified active carbon in the step three into a palladium nitrate solution, stirring for 40min, controlling the pH of a system to be 7 in the stirring process, filtering and washing to obtain a catalyst precursor; the concentration of palladium ions in the palladium nitrate solution is 0.1g/mL; controlling the pH of the system by using an ammonia water solution; the catalyst with the preset palladium content can be 5% Pd/C;
step five, reducing the catalyst precursor in the step four to obtain a catalyst for synthesizing pregnenolone acetate; the reduction is carried out by using a reducing agent solution, wherein the reducing agent solution is hydrazine hydrate solution, the reduction temperature is 95 ℃, and the reduction time is 1.5h; the volume of the reducing agent solution is 50 times of the mass of Pd, and the mass percentage of the reducing agent solution is 20%.
Example 5
The embodiment provides a preparation method of a catalyst for synthesizing pregnenolone acetate, which comprises the following steps:
Step one, 100g of activated carbon is steamed in 900g of nitric acid solution, filtered and washed to obtain the activated carbon after acid treatment; the mass percentage concentration of the nitric acid solution is 3%; the cooking temperature is 100 ℃, and the cooking time is 1h; the water washing is water washing until the pH value is 8; the specific surface area of the activated carbon is 800m 2/g～900m2/g;
Stirring the activated carbon subjected to the acid treatment in the step one in 900g of ammonium persulfate solution for 3 hours at the temperature of 75 ℃, filtering, and washing to obtain the activated carbon subjected to the ammonium persulfate treatment; the mass percentage concentration of the ammonium persulfate solution is 2%; the water washing is water washing until the pH value is 6;
Step three, under the normal temperature condition, placing the activated carbon treated by the ammonium persulfate in the step two into 500g of magnesium salt solution, stirring for 2 hours, and filtering to obtain modified activated carbon; the magnesium salt solution is magnesium nitrate solution, and the mass percentage concentration of magnesium chloride in the magnesium salt solution is 1.5%; the normal temperature is 20-25 ℃;
Step four, according to the preset palladium content in the Pd/C catalyst, placing the modified active carbon in the step three into a palladium nitrate solution, stirring for 40min, controlling the pH of a system to be 7 in the stirring process, filtering and washing to obtain a catalyst precursor; the concentration of palladium ions in the palladium nitrate solution is 0.5g/mL; controlling the pH of the system by using an ammonia water solution; the catalyst with the preset palladium content can be 5% Pd/C;
Step five, reducing the catalyst precursor in the step four to obtain a catalyst for synthesizing pregnenolone acetate; the reduction is carried out by using a reducing agent solution, wherein the reducing agent solution is hydrazine hydrate solution, the reduction temperature is 90 ℃, and the reduction time is 2 hours; the volume of the reducing agent solution is 50 times of the mass of Pd, and the mass percentage of the reducing agent solution is 10%.
Application example 1
The present application provides a method for synthesizing pregnenolone acetate using the catalysts of examples 1 to 5 and comparative example 1, comprising:
Mixing 10g of dehydropregnenolone acetate, 100g of absolute ethyl alcohol and 0.4g of the catalyst for reaction for 2 hours at the temperature of 40+/-5 ℃ and the hydrogen pressure of 0.2Mpa to obtain pregnenolone acetate; the mass percentage of Pd in the catalyst is 5%. Sampling and chromatographic analysis of purity of the product in the reacted system, separating the material in the reactor, calculating crude product yield, and the result is shown in Table 1.
TABLE 1 pregnenolone acetate catalyst reaction results
According to Table 1, in the process of synthesizing pregnenolone acetate by using the pregnenolone acetate synthesis catalyst prepared by the method of the invention, the purity of the product and the yield of the crude product are obviously higher than those of the traditional catalyst (comparative example 1), the purity of the product can reach 99.9% at the highest, and the yield of the crude product is higher than 75.8%.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any simple modification, variation and equivalent structural changes of the above embodiment according to the technical matter of the present invention still fall within the scope of the technical solution of the present invention.
Claims (7)
1. A method for synthesizing pregnenolone acetate by using a catalyst for synthesizing pregnenolone acetate, which is characterized by comprising the following steps: mixing and reacting the raw materials, a solvent and a catalyst for synthesizing pregnenolone acetate at 40+/-5 ℃ to obtain pregnenolone acetate; the raw material is dehydropregnenolone acetate;
The preparation method of the catalyst for synthesizing pregnenolone acetate comprises the following steps: modifying the ammonium persulfate treated active carbon by magnesium salt to obtain modified active carbon, and taking the modified active carbon as a carrier to load Pd to obtain a catalyst for synthesizing pregnenolone acetate; the method specifically comprises the following steps:
step one, boiling active carbon in a nitric acid solution, filtering, and washing with water to obtain acid-treated active carbon;
Stirring the activated carbon subjected to the acid treatment in the step one in ammonium persulfate solution for 2-4 hours at the temperature of 60-80 ℃, filtering, and washing with water to obtain the activated carbon subjected to the ammonium persulfate treatment; the mass of the ammonium persulfate solution is 8-10 times that of the active carbon in the first step, and the mass percentage concentration of the ammonium persulfate solution is 2-5%;
thirdly, under the normal temperature condition, placing the activated carbon treated by the ammonium persulfate in the second step in a magnesium salt solution, stirring for 1-2 h, and filtering to obtain modified activated carbon;
Step four, placing the modified activated carbon in the step three in a palladium nitrate solution, stirring for 30-60 min, controlling the pH of the system to 7-9 in the stirring process, filtering, and washing to obtain a catalyst precursor;
and fifthly, reducing the catalyst precursor in the fourth step to obtain the catalyst for synthesizing pregnenolone acetate.
2. The method according to claim 1, wherein in the step one, the mass of the nitric acid solution is 8-10 times that of the activated carbon, and the mass percentage concentration of the nitric acid solution is 3-5%; the specific surface area of the activated carbon is 700 m/g-1000 m/g; the cooking temperature is 80-100 ℃, and the cooking time is 1-2 hours; and step one, washing with water until the pH is 6-8.
3. The method of claim 1, wherein the washing in step two is a washing with water to a pH of 6.
4. The method according to claim 1, wherein in the third step, the mass of the magnesium salt solution is 5-8 times that of the activated carbon in the first step, the mass percentage concentration of the magnesium salt in the magnesium salt solution is 1-2%, and the magnesium salt is magnesium nitrate or magnesium chloride.
5. The method of claim 1, wherein the palladium ion concentration in the palladium nitrate solution in step four is 0.1g/mL to 0.5g/mL.
6. The method according to claim 1, wherein the reduction in the fifth step is performed by using a reducing agent solution, the reducing temperature is 90 ℃ to 100 ℃, the reducing time is 1h to 2h, the mass percentage of the reducing agent solution is 10% -20%, and the reducing agent solution is sodium borohydride solution or hydrazine hydrate solution.
7. The method according to claim 1, wherein the hydrogenation pressure in the mixed reaction is 0.2Mpa, the mass of the catalyst is 0.04 times that of dehydropregnenolone acetate, the mass percentage of Pd in the catalyst is 5%, and the solvent is absolute ethanol.
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| GB933105A (en) * | 1959-01-12 | 1963-08-08 | Merck & Co Inc | Steroid compounds |
| TW200626556A (en) * | 2004-11-23 | 2006-08-01 | Warner Lambert Co | Novel pyrazole-based HMG CoA reductase inhibitors |
| CN103450306A (en) * | 2013-08-27 | 2013-12-18 | 西安高远生化有限责任公司 | Synthetic method of pregnenolone acetate |
| CN110743590A (en) * | 2019-10-21 | 2020-02-04 | 西安凯立新材料股份有限公司 | High-selectivity catalyst for synthesizing vitamin A intermediate and preparation method thereof |
| CN113976113A (en) * | 2021-11-30 | 2022-01-28 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing megestrol acetate, preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB933105A (en) * | 1959-01-12 | 1963-08-08 | Merck & Co Inc | Steroid compounds |
| TW200626556A (en) * | 2004-11-23 | 2006-08-01 | Warner Lambert Co | Novel pyrazole-based HMG CoA reductase inhibitors |
| CN103450306A (en) * | 2013-08-27 | 2013-12-18 | 西安高远生化有限责任公司 | Synthetic method of pregnenolone acetate |
| CN110743590A (en) * | 2019-10-21 | 2020-02-04 | 西安凯立新材料股份有限公司 | High-selectivity catalyst for synthesizing vitamin A intermediate and preparation method thereof |
| CN113976113A (en) * | 2021-11-30 | 2022-01-28 | 西安凯立新材料股份有限公司 | Catalyst for synthesizing megestrol acetate, preparation method and application thereof |
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