CN114768716A - Is used for preparing 10αPhotochemical reaction device for methyl-steroid compound and application thereof - Google Patents
Is used for preparing 10αPhotochemical reaction device for methyl-steroid compound and application thereof Download PDFInfo
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- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/123—Ultraviolet light
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a photochemical reaction device for preparing 10 alpha-methyl-steroid compounds, which comprises: the photochemical conversion reactor is used for accommodating reaction liquid to perform photochemical conversion reaction; a light source for emitting broad-spectrum ultraviolet light; a filter having Cu therein2+The filtering liquid is arranged between the photochemical conversion reactor and the light source in the photochemical conversion reaction process, and the broad-spectrum ultraviolet light emitted by the light source penetrates through the filtering liquid and irradiates into the photochemical conversion reactor for filtering. The invention also provides application of the photochemical reaction device in synthesizing the 10 alpha-methyl-steroid compound. The photochemical reaction device utilizes the optical filters of the filtering liquid containing copper ions with different concentrations to filter the light source at different reaction stages, is beneficial to obtaining ultraviolet light with specific requirements, is beneficial to carrying out photochemical conversion reaction, and has few byproducts and yieldIs high.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a photochemical reaction device and application thereof.
Background
Dydrogesterone (Dydrogesterone), also known as Dydrogesterone, has the chemical name 9 β,10 α -pregna-4, 6-diene-3, 20-dione, CAS number: 152-62-5, of the formula:
dydrogesterone has pregnane as mother nucleus, which has the following skeleton structure, including four ABCD rings (from left to right, the four rings are defined as A, B, C and D), and the carbon numbers (1-21) are as follows, and are marked as C-1 position, C-2 position, etc.
Dydrogesterone is widely used for preventing miscarriage and preventing abortion, and also widely used for treating various diseases caused by insufficient endogenous progesterone, such as: dysmenorrhea, endometriosis, secondary amenorrhea, irregular menstrual cycle, dysfunctional uterine bleeding, premenstrual syndrome, threatened abortion or habitual abortion caused by progestational hormone deficiency, infertility caused by corpus luteum deficiency, etc.
Some current synthetic routes of dydrogesterone are to start from ergosterol, synthesize 10 alpha configuration intermediate by photochemistry, and then obtain dydrogesterone by chemical synthesis through several steps. The ultraviolet lamp source adopted in the light conversion process of the dydrogesterone intermediate is an LED ultraviolet lamp. The LED ultraviolet lamp has single wavelength, low power (the power of a single lamp bead is about 3-5 mW), limited wavelength selection range (ultraviolet light sources sold in the market are only available at 254nm, 265nm, 275nm and 310 nm), large-scale photochemical reaction needs to integrate a large number of LED lamp beads, the light source is complex to manufacture, and the cost is very high.
The ultraviolet high-pressure mercury lamp can reach higher power (the power is 20kw commonly used in industry), so the cost can be reduced by adopting the ultraviolet high-pressure mercury lamp, and the requirement of a light source required by the large-scale photochemical reaction of the dydrogesterone intermediate is met. However, the ultraviolet high-pressure mercury lamp has a wide spectral range (the ultraviolet region has a broad spectral distribution from 250nm to 370 nm). The two photochemical reactions of the dydrogesterone intermediate are respectively an open-loop reaction and a closed-loop reaction, and respectively need specific wavelength ranges, which is contrary to the wide spectral range emitted by an ultraviolet high-pressure mercury lamp and is not beneficial to the large-scale photochemical reaction of the dydrogesterone intermediate applied by the ultraviolet high-pressure mercury lamp. Therefore, the photochemical reaction device with the controllable ultraviolet light source waveband is provided and has great significance for large-scale photochemical reaction of the dydrogesterone intermediate.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings in the background technology, and provide a photochemical reaction device with controllable ultraviolet light source band and used for preparing 10 alpha-methyl-steroid compounds and application thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a photochemical reaction apparatus for producing 10 α -methyl-steroids, comprising:
the photochemical conversion reactor is used for accommodating reaction liquid to perform photochemical conversion reaction;
a light source for emitting broad-spectrum ultraviolet light;
a filter having Cu therein2+The filter liquid is arranged between the photochemical conversion reactor and a light source in the photochemical conversion reaction process, and the broad-spectrum ultraviolet light emitted by the light source penetrates through the filter liquid to irradiate the photochemical conversion reactor for filtering;
the filter is set to have a first state and a second state for a first stage and a second stage of the photochemical conversion reaction, respectively, and Cu in the filter liquid in the first state2+Is less than Cu in the filter liquid in the second state2+The concentration of (c);
or the optical filter comprises a first optical filter and a second optical filter which are respectively used for a first stage and a second stage of photochemical conversion reaction, and Cu in the optical filter liquid of the first optical filter2+Is less than Cu in the filter liquid of the second filter2+The concentration of (2).
In the photochemical reaction device, it is preferable that the conversion from the first state to the second state is performed by adjusting or replacing a concentration of the filter liquid in the filter.
In the above photochemical reaction apparatus, preferably, the photochemical conversion reactor includes a first reactor and a second reactor, the first filter and the second filter are respectively disposed correspondingly, and are used for a first stage and a second stage of photochemical conversion, and the reaction solution can be introduced from the first reactor to the second reactor through a connecting pipeline. That is, the present invention adopts two sets of reaction equipment corresponding to the first stage and the second stage of photochemical conversion, respectively.
In the above photochemical reaction apparatus, preferably, the optical filter is detachably disposed in the photochemical conversion reactor; the light filter (meaning first light filter and second light filter) includes interior casing and shell body, constitute first closed region between interior casing and the shell body and be used for installing filtering liquid, interior casing inside encloses into second semi-closed region and is used for the holding the light source. In the invention, after the optical filter is arranged in the photochemical conversion reactor, a sealing cover is arranged in a matching way and used for sealing the top of the photochemical conversion reactor. After the light source is arranged in the second semi-closed area, a sealing cover is also arranged in a matching way and used for sealing the top of the second semi-closed area.
In the photochemical reaction device, preferably, a filter cooling system is disposed on the first closed region; the filter liquid cooling system comprises a filter liquid inlet pipe, a filter liquid storage tank, a filter liquid outlet pipe, a filter liquid pump and a first cooling source, wherein two ends of the filter liquid inlet pipe and two ends of the filter liquid outlet pipe are respectively communicated with the first closed area and the filter liquid storage tank to form a circulation loop, and the first cooling source and the filter liquid pump are arranged in the filter liquid inlet pipe and/or on the filter liquid outlet pipe. Since the light source generates a large amount of heat, the temperature of the filter is too high after the light source directly irradiates the filter, and a large amount of by-products are generated. By arranging the filter liquid cooling system, the temperature of the reaction system can be maintained conveniently. The filter liquid pump is preferably a peristaltic pump, and the specific type of the first cooling source is not limited, for example, a cooling mode of heat exchange of a cooling jacket can be adopted.
In the above photochemical reaction apparatus, preferably, the photochemical conversion reactor is provided with a reaction solution level stabilizing system; the reaction liquid level stabilizing system comprises a reaction liquid inlet pipe, a reaction liquid storage tank, a reaction liquid outlet pipe and a reaction liquid pump, wherein two ends of the reaction liquid inlet pipe and two ends of the reaction liquid outlet pipe are respectively communicated with the photochemical conversion reactor and the reaction liquid storage tank to form a circulation loop, and the reaction liquid pump is arranged on the reaction liquid inlet pipe. In the invention, the reaction liquid outlet pipe is positioned above the photochemical conversion reactor, the reaction liquid pump is arranged on the reaction liquid inlet pipe, the reaction liquid overflows from the reaction liquid outlet pipe, and the reaction liquid pump pumps the reaction liquid back to the photochemical conversion reactor. In the reaction process, the solvent can be volatilized and lost, the liquid level of the reaction liquid storage tank is observed to be reduced, the reaction solvent can be conveniently replenished by utilizing the reaction liquid level stabilizing system, the concentration of the reaction liquid is maintained, and the reaction is favorably carried out.
In the above photochemical reaction apparatus, preferably, a second cooling system is provided on an outer wall of the photochemical conversion reactor; the second cooling system comprises a cooling jacket, a cooling liquid inlet, a cooling liquid outlet and a second cooling source which are arranged on the outer wall of the photochemical conversion reactor, and two ends of the cooling liquid inlet and two ends of the cooling liquid outlet are respectively connected with the cooling jacket and the second cooling source. In order to further ensure the reaction temperature of the reaction liquid, the invention is also provided with a second cooling system, and a second cooling source in the second cooling system can adopt a refrigerator with good refrigeration efficiency through the second cooling system. The cooling liquid inlet and the cooling liquid outlet are respectively arranged at the upper end and the lower end of the cooling jacket.
In the photochemical reaction device, Cu in the filtering liquid used in the first stage is preferable2+Is 0.1-0.5 wt%, is used for Cu in the filter liquid in the second stage2+The concentration of (B) is 0.5-1.2 wt%. More preferably, Cu is used in the filter liquid in the first stage2+Is 0.3-0.5 wt%, is used for Cu in the filter liquid in the second stage2+The concentration of (B) is 0.7-1.0 wt%.
In the photochemical reaction device, it is preferable that Cu is provided in the filter liquid2+The copper source of (a) is copper chloride.
The filter liquid of the present invention contains Cu2+The filter liquid can be an aqueous solution or other solution which does not affect Cu2+Other of the filter effect being able to dissolve Cu2+Is a colorless solvent. Our studies show that different concentrations of Cu2+The light absorption characteristics are different, the filter liquid with low concentration is used for the ring opening of the first stage of the invention, the ring opening is facilitated, the conversion to the required configuration is facilitated (if the ultraviolet high-pressure mercury lamp is directly used for irradiation during the ring opening of the first stage, the configuration proportion of the side products is high due to containing unnecessary wavelength (such as light with the wavelength of about 254 nm), and the damage to the raw materials is reduced. And the closed loop needs a filter solution with higher concentration, so that the filtration of low wavelength is enhanced, the reaction balance is shifted to the closed loop, and higher yield can be obtained. The copper ion filter liquid with specific concentration adopted by the invention can filter part or all of light with wavelength less than 270nm (basically filter light with wavelength of about 254 nm) by the filter liquid in the first stage, and can filter part or all of light with wavelength less than 300nm by the filter liquid in the second stage. Further studies have shown that Cu is provided2+The copper source also has an influence on the filtering effect, different kinds of anions influence the filtering, and more preferably, copper chloride is used as the copper providing source2+The copper source is matched with the specific concentration, and is more favorable for meeting the light filtering effect required by the invention compared with copper sulfate, copper acetate and the like.
In the above photochemical reaction apparatus, preferably, the light source is an ultraviolet high-pressure mercury lamp, and generates light including part or all of wavelengths in the range of 200-400 nm. After the light source generated by the ultraviolet high-pressure mercury lamp passes through the filter liquid, the filter liquid at the first stage filters part or all of the light with the wavelength less than 270nm, and the filter liquid at the second stage filters part or all of the light with the wavelength less than 300nm, so that the requirements of different stages on the light source wave band during reaction of the reaction liquid are facilitated.
In the above photochemical reaction apparatus, preferably, a magnetic stirrer is disposed at the bottom of the photochemical conversion reactor.
The term "broad spectrum ultraviolet light" as used herein refers to ultraviolet light comprising a broad range of wavelengths, relative to a single wavelength or a single spectral peak of an LED uv lamp. For example, light comprising part or all of the wavelengths in the range of 200-400nm, and for example, ultraviolet light having a plurality of spectral peaks in the range of 253-367 nm. Under the above definition, an ultraviolet high-pressure mercury lamp is a light source that emits a broad spectrum of ultraviolet light. In view of the problems to be solved by the present invention, the broad-spectrum ultraviolet light at least comprises part or all of the light with the wavelength less than 270nm (for example, the light with about 254 nm), part or all of the light with the range of 270-300nm, and part or all of the light with the range of 300-350 nm. Light sources that emit broad-spectrum ultraviolet light may also emit some other wavelength band of light, such as visible light.
In order to better understand the photochemical reaction device, the invention also provides an application of the photochemical reaction device in synthesizing 10 alpha-methyl-steroid compounds, and the C-10 methyl of the 5, 7-diene steroid compounds with the C-10 position being beta-methyl is turned over to alpha configuration. The method comprises the following specific steps: a process for the preparation of 10 α -methyl-steroids (intermediates or starting materials for the synthesis of dydrogesterone) comprising the steps of: carrying out photochemical conversion on a 5, 7-diene steroid compound with a beta-methyl at a C-10 position in a photochemical conversion reactor under the irradiation of a light source and the filtering of a filter to ensure that the methyl at the C-10 position is inverted from a beta configuration to an alpha configuration; the need for different filtering at the two stages of the reaction can be achieved by replacing the filter or replacing the filter's filter fluid.
The "two stages of photochemical transformation" in the above application generally includes the following two stages from a mechanistic point of view (the general reaction process of the steroid ring skeleton is as follows): the first stage is open-loop under the irradiation of ultraviolet light with a certain wavelength range (generally 270-300nm), and the second stage is closed-loop under the irradiation of ultraviolet light with another certain wavelength range (generally 300-350 nm). In terms of macroscopic operation, the first stage is to irradiate ultraviolet light with a certain wavelength range for a period of time, the second stage is to irradiate ultraviolet light with another certain wavelength range for another period of time, and the irradiation time is adjusted according to the specific reaction degree.
The above-mentioned "5, 7-diene steroid compound having a beta-methyl group at the C-10 position" means a compound having a steroid skeleton in which the C-3 position and the C-17 position or other positions may be substituted with a substituent.
The methyl at the C-10 position has the following steroid skeleton after being inverted from beta configuration to alpha configuration.
There are various intermediates or starting materials for the synthesis of dydrogesterone, exemplified by ergosterol and the like. They all need to undergo a photochemical conversion, the mechanism of which is about the same, so that the process of the invention can be applied to such compounds.
Compared with the prior art, the invention has the advantages that:
1. the photochemical reaction device utilizes the optical filters of the filtering liquid containing copper ions with different concentrations to filter the light source at different reaction stages, is beneficial to obtaining ultraviolet light with specific requirements, is beneficial to carrying out photochemical conversion reaction, and has few byproducts and high yield.
2. The photochemical reaction device allows a light source emitting broad-spectrum ultraviolet light to be used by arranging the optical filter, has low cost of the light source, and is beneficial to the industrial production of the dydrogesterone intermediate.
3. The photochemical reaction device disclosed by the invention is simple in structure, convenient to use and wide in market application prospect.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions in the prior art are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of a photochemical reaction apparatus for preparing 10 α -methyl-steroid compound in example 1.
Fig. 2 is a schematic structural diagram of the photochemical reaction apparatus for preparing 10 α -methyl-steroid compound in example 2 (the liquid level stabilizing system and the second cooling system of the reaction solution are not shown in the figure).
Illustration of the drawings:
1. a photochemical conversion reactor; 2. a light source; 3. a filter; 4. a filter inlet tube; 5. a filtering liquid storage tank; 6. a filter liquid outlet pipe; 7. a filter liquid pump; 8. a first cooling source; 9. a reaction solution inlet pipe; 10. a reaction liquid storage tank; 11. a reaction liquid outlet pipe; 12. a reaction liquid pump; 13. a cooling jacket; 14. a coolant inlet; 15. a coolant outlet; 16. a second cooling source; 17. a magnetic stirrer; 18. connecting a pipeline; 31. an inner housing; 32. an outer housing; 33. a first enclosed area; 34. a second semi-enclosed area; 101. a first reactor; 102. a second reactor; 301. a first filter; 302. a second filter.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
as shown in fig. 1, the photochemical reaction apparatus for preparing 10 α -methyl-steroid compound of the present embodiment includes:
a photochemical conversion reactor 1 for accommodating a reaction liquid to perform a photochemical conversion reaction;
a light source 2 for emitting broad-spectrum ultraviolet light;
a filter 3 having Cu therein2+The filtering liquid is arranged between the photochemical conversion reactor 1 and the light source 2 in the photochemical conversion reaction process, and the broad-spectrum ultraviolet light emitted by the light source 2 irradiates the photochemical conversion reactor 1 through the filtering liquid for filtering;
the filter 3 is set to have a first state and a second state for a first stage and a second stage of the photochemical conversion reaction, respectively, the first state being the state in which Cu is contained in the filter liquid2+Is less than Cu in the filter liquid in the second state2+The concentration of (c).
In this embodiment, the transition from the first state to the second state is achieved by adjusting or replacing the concentration of the filter liquid in the filter 3.
In this embodiment, the optical filter 3 is detachably disposed in the photochemical conversion reactor 1; the filter 3 includes an inner casing 31 and an outer casing 32, a first closed region 33 is formed between the inner casing 31 and the outer casing 32 for accommodating the filtering liquid, and a second semi-closed region 34 is defined by the inner casing 31 for accommodating the light source 2.
In this embodiment, the first closed region 33 is provided with a filter cooling system; the filter liquid cooling system comprises a filter liquid inlet pipe 4, a filter liquid storage tank 5, a filter liquid outlet pipe 6, a filter liquid pump 7 (such as a peristaltic pump) and a first cooling source 8, wherein two ends of the filter liquid inlet pipe 4 and two ends of the filter liquid outlet pipe 6 are respectively communicated with the first closed area 33 and the filter liquid storage tank 5 to form a circulation loop, and the first cooling source 8 and the filter liquid pump 7 are arranged on the filter liquid inlet pipe 4 and/or the filter liquid outlet pipe 6.
After the first-stage reaction is finished, copper salt or concentrated copper salt solution is added into the filtering liquid storage tank 5 to enable the filtering liquid in the optical filter 3 to reach the Cu required by the second stage2+And (4) concentration.
In this embodiment, the photochemical conversion reactor 1 is provided with a reaction liquid level stabilizing system; the reaction liquid level stabilizing system comprises a reaction liquid inlet pipe 9, a reaction liquid storage tank 10, a reaction liquid outlet pipe 11 and a reaction liquid pump 12 (such as a peristaltic pump), wherein two ends of the reaction liquid inlet pipe 9 and two ends of the reaction liquid outlet pipe 11 are respectively communicated with the photochemical conversion reactor 1 and the reaction liquid storage tank 10 to form a circulation loop, and the reaction liquid pump 12 is arranged on the reaction liquid inlet pipe 9.
In this embodiment, a second cooling system is disposed on the outer wall of the photochemical conversion reactor 1; the second cooling system comprises a cooling jacket 13, a cooling liquid inlet 14, a cooling liquid outlet 15 and a second cooling source 16 which are arranged on the outer wall of the photochemical conversion reactor 1, and two ends of the cooling liquid inlet 14 and two ends of the cooling liquid outlet 15 are respectively connected with the cooling jacket 13 and the second cooling source 16.
In this embodiment, Cu in the filter liquid used in the first stage2+Is 0.1-0.5 wt% (any of the above ranges), and is used in the second stage of the filter solution2+The concentration of (B) is 0.5 to 1.2 wt% (both ranges above).
In this example, Cu was provided in the filter liquid2+The copper source of (a) is copper chloride.
In this embodiment, the light source 2 is an ultraviolet high-pressure mercury lamp and generates light including a part or all of wavelengths in the range of 200-400 nm.
In this embodiment, the bottom of the photochemical conversion reactor 1 is provided with a magnetic stirrer 17.
In this embodiment, the distance between the outer wall of the outer housing 32 and the inner wall of the photochemical conversion reactor 1 (i.e., the width of the reaction solution) has a large influence on the reaction process. For a certain light source 2, the concentration of the reaction substrate (i.e. 5, 7-diene steroid compound with beta-methyl at the C-10 position) is certain, and if the distance is too small, the specific wavelength emitted by the light source 2 cannot be completely absorbed by the reaction solution, and the illumination efficiency is very low. Therefore, the distance should be larger than a certain value, so that the illumination efficiency can be improved and the cost can be reduced.
In this example, the power of the ultraviolet high-pressure mercury lamp was controlled to 20kW, the concentration of the substrate was controlled to 1g/10mL, the distance was controlled to more than 5cm, the concentration of the substrate was controlled to 1g/50mL, and the distance was controlled to more than 10 cm. If the power of the ultraviolet high-pressure mercury lamp is 500W, the concentration of the reaction substrate is 1g/30mL, the distance is controlled to be larger than 2cm, the concentration of the reaction substrate is 1g/50mL, and the distance is controlled to be larger than 3 cm.
For industrial suitability, the distance should be at least 2cm overall, the lamp power being increased, the corresponding distance being increased, the reaction substrate concentration being increased, and the corresponding distance being increased.
The embodiment also provides an application of the photochemical reaction device in synthesizing a 10 alpha-methyl-steroid compound, and the specific application is as follows: the method is characterized in that the methyl at the C-10 position of the 5, 7-diene steroid compound with the C-10 position being beta-methyl is inverted into alpha configuration (the method can be used for preparing dydrogesterone), and the method comprises the following specific steps:
adding 40g of compound A and 500mL of tetrahydrofuran into a photochemical reaction bottle, opening a ring at 5-10 ℃ under the irradiation of an ultraviolet high-pressure mercury lamp (500W), filtering by using a filter solution (1 wt% copper chloride aqueous solution) during ring opening, illuminating for 8 hours, and monitoring raw materials by HPLC: product 70: about 20, filtering by using a filter solution (the concentration of copper chloride is 2 wt%), continuing to illuminate for 8 hours, and monitoring by HPLC, wherein the raw materials: product 55: stopping about 35; concentrating the organic phase, replacing methanol to a small volume, cooling to-20 deg.C, freezing for 4 hr, filtering, and oven drying to obtain white solid 16g, which is mainly used as raw material; and (3) concentrating the mother liquor, replacing acetonitrile to a small volume, discharging, cooling to-20 ℃, freezing for 4 hours, filtering, and drying to obtain 9.8g of a white solid, namely the compound B, wherein the primary yield is about 24.5%.
Comparative tests were carried out under the reaction conditions shown in Table 1 in accordance with the above-mentioned reaction procedures, and the other conditions were the same as in this example, and the results are shown in Table 1 below.
Table 1: conditions and results of the experiment
| Open loop filtering | Closed loop filtering | First yield | |
| Comparative example 1 | Without filtering light | Without filtering light | 9% (product does not separate out) |
| Comparative example 2 | 1% copper chloride filtering | 1% copper chloride filtering | 20％ |
| Comparative example 3 | 1% |
2% copper acetate light filtration | 22.5％ |
| This example | 1% |
2% copper chloride Filter | 24.5％ |
In this example, the following nuclear magnetic data were examined for compound B:1HNMR(400MHz,CDCl3)δ7.78(d,J＝8.3Hz,2H),7.34(d,J＝8.1Hz,2H),5.66-5.64(m,1H),5.43–5.41(m,1H),4.09(s,1H),3.96(dd,J＝9.3,3.1Hz,1H),3.83(dd,J＝9.3,6.0Hz,1H),2.49-2.45(m,5H),2.29-2.24(m,2H),1.67–1.47(m,15H),0.97(d,J＝6.7Hz,3H),0.72(s,3H),0.57(s,3H)。
the photochemical procedure in the specific application described above is as follows:
the 5, 7-diene steroid compound with the beta-methyl group at the C-10 position of the present example is
Wherein OTs group has absorption in deep ultraviolet region, and absorbs ultraviolet ray in deep ultraviolet region of high-pressure mercury lamp, so that the reaction has higher yield; meanwhile, the existence of OTs groups enables the product to be separated more easily, and the complexity of post-treatment is reduced.
Wherein the compound A is a new compound, and a synthetic route for preparing the dydrogesterone by using the compound A is shown as the following formula. The synthesis route is short and the total yield is high.
Example 2:
as shown in fig. 2, the photochemical reaction apparatus for preparing 10 α -methyl-steroid compound of this embodiment includes:
a photochemical conversion reactor 1 for accommodating a reaction liquid to perform a photochemical conversion reaction;
a light source 2 for emitting broad-spectrum ultraviolet light;
a filter 3 having Cu therein2+The filter liquid is arranged between the photochemical conversion reactor 1 and the light source 2 in the photochemical conversion reaction process, and the broad-spectrum ultraviolet light emitted by the light source 2 is irradiated into the photochemical conversion reactor 1 through the filter liquid for filtering;
the optical filter 3 comprises a first optical filter 301 and a second optical filter 302 for the first stage and the second stage of the photochemical conversion reaction, respectively, the Cu in the filter liquid of the first optical filter 3012+Is less than Cu in the filter liquid of the second filter 3022 +The concentration of (c).
In this embodiment, the photochemical conversion reactor 1 includes a first reactor 101 and a second reactor 102, a first filter 301 and a second filter 302 are respectively disposed correspondingly for the first stage and the second stage of photochemical conversion, and the reaction solution can be introduced from the first reactor 101 to the second reactor 102 through a connecting pipe 18.
After the first stage reaction is completed, the reaction solution is introduced into the second reactor 102 to perform the second stage reaction without adjusting the concentration of the filtering solution.
Other components and applications of the present embodiment are the same as those of embodiment 1.
Claims (10)
1. A photochemical reaction apparatus for producing 10 α -methyl-steroid compounds, comprising:
the photochemical conversion reactor (1) is used for accommodating reaction liquid to carry out photochemical conversion reaction;
a light source (2) for emitting broad-spectrum ultraviolet light;
a filter (3) containing Cu therein2+The light filtering liquid is arranged between the photochemical conversion reactor (1) and the light source (2) in the photochemical conversion reaction process, and the broad-spectrum ultraviolet light emitted by the light source (2) penetrates through the light filtering liquid to irradiate the photochemical conversion reactor (1) for filtering;
the filter (3) is set to have a first state and a second state for a first stage and a second stage of the photochemical conversion reaction, respectively, and Cu in the filter liquid in the first state2+Is less than Cu in the filter liquid in the second state2+The concentration of (d);
or the optical filter (3) comprises a first optical filter (301) and a second optical filter (302) respectively used for the first stage and the second stage of photochemical conversion reaction, and Cu in the optical filter liquid of the first optical filter (301)2+Is less than Cu in the filter liquid of the second filter (302)2+The concentration of (c).
2. Photochemical reaction device according to claim 1, characterized in that the transition of the first state to the second state is achieved by adjusting or changing the filter concentration in the filter (3).
3. The photochemical reaction apparatus according to claim 1, characterized in that the photochemical conversion reactor (1) comprises a first reactor (101) and a second reactor (102), a first filter (301) and a second filter (302) are respectively disposed correspondingly for the first stage and the second stage of photochemical conversion, and the reaction liquid is introduced from the first reactor (101) into the second reactor (102) through a connecting pipe (18).
4. Photochemical reaction device in accordance with any one of claims 1-3 characterized in that the filter (3) is detachably arranged in the photochemical conversion reactor (1); filter (3) are including interior casing (31) and shell body (32), constitute first closed region (33) between interior casing (31) and shell body (32) and be used for installing filter liquid, interior casing (31) inside encloses into second semi-closed region (34) and is used for the holding light source (2).
5. The photochemical reaction device according to claim 4, characterized in that the first closed region (33) is provided with a filter liquid cooling system; filter cooling system includes that filter import pipe (4), filter storage tank (5), filter outlet pipe (6), filter liquid pump (7) and first cooling source (8), the both ends of filter import pipe (4) the both ends of filter outlet pipe (6) respectively with first closed region (33) and filter storage tank (5) intercommunication are in order to constitute a circulation circuit, first cooling source (8) and filter liquid pump (7) are located filter import pipe (4) and/or on filter outlet pipe (6).
6. Photochemical reaction device according to any one of claims 1-3, characterized in that the photochemical conversion reactor (1) is provided with a reaction liquid level stabilization system; the reaction liquid level stabilizing system comprises a reaction liquid inlet pipe (9), a reaction liquid storage tank (10), a reaction liquid outlet pipe (11) and a reaction liquid pump (12), wherein two ends of the reaction liquid inlet pipe (9) and two ends of the reaction liquid outlet pipe (11) are respectively communicated with the photochemical conversion reactor (1) and the reaction liquid storage tank (10) to form a circulation loop, and the reaction liquid pump (12) is arranged on the reaction liquid inlet pipe (9) and/or the reaction liquid outlet pipe (11).
7. The photochemical reaction apparatus as claimed in any one of claims 1-3, characterized in that Cu in the filter used in the first stage2+Is 0.1-0.5 wt%, is used for Cu in the filter liquid in the second stage2+The concentration of (B) is 0.5-1.2 wt%.
8. The photochemical reaction device as claimed in any one of claims 1-3, wherein Cu is provided in the filter liquid2+The copper source of (a) is copper chloride.
9. The photochemical reaction apparatus as claimed in any one of claims 1-3, characterized in that the light source (2) is an ultraviolet high-pressure mercury lamp, generating light comprising part or all of the wavelengths in the range of 200-400 nm.
10. Use of a photochemical reaction apparatus according to any one of claims 1-9 for the synthesis of 10 α -methyl-steroids to invert the C-10 methyl group of 5, 7-diene steroids having the C-10 position being a β -methyl group to the α configuration.
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