CN114805815B - Terminal purinyl organic silicon compound and preparation method thereof - Google Patents
Terminal purinyl organic silicon compound and preparation method thereof Download PDFInfo
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- CN114805815B CN114805815B CN202210485651.9A CN202210485651A CN114805815B CN 114805815 B CN114805815 B CN 114805815B CN 202210485651 A CN202210485651 A CN 202210485651A CN 114805815 B CN114805815 B CN 114805815B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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Abstract
The invention discloses a purine-terminated organosilicon compound, a preparation method and application thereof, wherein the structural formula of the purine-terminated organosilicon compound is shown in the specification
Wherein n is an integer and has a value range of 1-100; r 1 、R 2 、R 3 、R 4 Is H or a B group, R 1 、R 2 、R 3 、R 4 The same or different; the B group being
Description
Technical Field
The invention belongs to the technical field of organic silicon compounds, and particularly relates to a purine-terminated organic silicon compound and a preparation method thereof.
Background
The purine derivative compound is widely applied to production regulators, antiviral drugs and the like of various animals and plants, and has remarkable biological drug property. How to detect purine derivative compounds does not leave the effective identification and response of the original fixed relative purine compounds. The existing kit mainly depends on an electrochemical response signal of a standard substance aiming at the detection response of purine, carries out quantitative analysis according to the correlation degree of the electrochemical signal of a detection sample and the electrochemical signal of the standard substance, and has limited actual qualitative accuracy.
Improved recognition of the structure of the immobilized relative purines will aid in the qualitative analysis of purine derivatives. The organosilicon material is widely applied to the field of biological pharmacy due to biological inertia. Designing a compound based on an organosilicon structure that responds strongly to purine recognition would provide benefits such as electrode modification.
Disclosure of Invention
The purpose of the present invention is to provide a terminal purinyl organosilicon compound having excellent adsorption ability to a purinyl compound, and a method for producing the same.
The terminal purine group organic silicon compound has the structural formula
Wherein n is an integer and has a value range of 1-100; r is 1 、R 2 、R 3 、R 4 Is H or a B group, R 1 、R 2 、R 3 、R 4 The same or different; group B is->
R is C1-C3 alkyl.
When R is 1 、R 2 、R 3 Is H, R 4 When the group B is selected, the structural formula of the organic silicon compound is as follows:
when R is 1 、R 2 Is H, R 3 、R 4 When the group B is selected, the structural formula of the organic silicon compound is as follows:
when R is 1 、R 3 Is H, R 2 、R 4 When the group B is selected, the structural formula of the organic silicon compound is as follows:
the preparation method of the terminal purinyl organosilicon compound provided by the invention comprises the following steps:
(1) Dissolving triphosgene in dehydrated organic solvent to obtain triphosgene solution;
(2) Dissolving purine in the other part of dehydrated organic solvent to obtain purine solution;
(3) At normal temperature, the triphosgene solution is dropped into the purine solution in the ice water bath, and the addition reaction is carried out for 1 to 2 hours at the temperature of between 0 and 5 ℃ to generate purine acyl chloride;
(4) Dropwise adding the solution after the reaction into the hydroxyl-terminated polysiloxane subjected to high-temperature vacuum dehydration, adding alkaline alumina, and stirring and reacting for 2-4 h at normal temperature; in the step, the alkaline alumina is mainly used as an acid-binding agent to adsorb hydrogen chloride generated by reaction;
(5) And sequentially filtering, cleaning, extracting, drying and dehydrating the reaction product to obtain the end purine base organic silicon compound.
The reaction principle of the method of the invention is shown as the following reaction formula:
an addition reaction formula of triphosgene and purine is shown in formula (1):
a compound (I) of a mono-purine, which has the reaction formula shown in formula (2):
a compound (II) of a bispurine represented by the following reaction formula (3):
a compound (III) of a bispurine represented by the formula (4):
in some embodiments, the organic solvent in steps (1) and (2) is the same, and is an ester solvent such as ethyl acetate, butyl acetate, sec-butyl acetate, and the like.
In some embodiments, the hydroxyl-terminated polysiloxane is a single-ended monohydroxy polysiloxane, a single-ended bishydroxy polysiloxane, or a double-ended monohydroxy polysiloxane.
In some embodiments, the hydroxyl-terminated polysiloxane has a hydroxyl to purinyl chloride molar ratio of 1:1.
the terminal purine group structure of the compound enables the compound to have good adsorption on purine compounds; the organosilicon chain segment is a compatible part, so that the organosilicon chain segment can meet the requirement of biological inertia and good high-low temperature non-crystalline performance.
Compared with the prior art, the invention has the following characteristics and beneficial effects:
the terminal purine organic silicon compound has better adsorption and recognition responsiveness to purine compounds, is superior to the traditional inert polydimethylsiloxane compound, and can be widely used for analysis and detection, adsorption enrichment treatment and the like of purine compounds with similar structures.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following embodiments. It should be understood that the embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
The sources of raw materials referred to in the examples are as follows: ethyl acetate is a commercially available analytical reagent;
molecular sieves, technical grade, qingdao Henxin added new materials science and technology, inc.; triphosgene, industrial grade, wuhan Hua Xiangke jie biotechnology limited; purine, technical grade, lake south china pharmaceuticals, ltd; 70-80 micron alkaline alumina, reagent grade, national pharmaceutical group chemical reagents ltd; single-ended monohydroxypolysiloxane, technical grade, tech-2170, shanghai teger polymer technologies, inc; single-ended bishydroxypolysiloxane, technical grade, tech-2176, shanghai teger polymer technologies, inc; bis-terminal monohydroxypolysiloxanes, technical grade, tech-2120, shanghai teger polymers technology ltd.
Example 1
Weighing ethyl acetate, adding activated at high temperature
Molecular sieve is kept overnight, and dehydration is carried out for standby; taking 100 g of dehydrated ethyl acetate purification solvent, adding 14.84 g (0.05 mol) of triphosgene, and stirring until the solvent is dissolved; taking another 100 g of dehydrated ethyl acetate purification solvent, adding 18.02 g (0.15 mol) of purine, and stirring until the purine is dissolved; slowly dripping the ethyl acetate solution of triphosgene into the ethyl acetate solution of purine in the ice water bath, wherein the dripping time is controlled to be 120 minutesControlling the temperature in an ice water bath at 0 ℃ to react to generate purine acyl chloride; adding a purine acyl chloride solution into 300 g of single-end monohydroxy polysiloxane (the number average molecular weight is 2000) dehydrated at high temperature in vacuum, adding 5 g of basic alumina, and stirring and reacting at normal temperature for 4 hours; and adding a sodium bicarbonate aqueous solution into the container after the reaction is finished, cleaning, separating, finally cleaning with clear water, and drying for later use.
Example 2
Weighing ethyl acetate, adding activated at high temperature
Molecular sieve is kept overnight, and dehydration is carried out for standby; taking 100 g of dehydrated ethyl acetate purification solvent, adding 14.84 g (0.05 mol) of triphosgene, and stirring until the solvent is dissolved; taking 100 g of dehydrated ethyl acetate purification solvent, adding 18.02 g (0.15 mol) of purine, and stirring until the purine is dissolved; slowly dripping the ethyl acetate solution of triphosgene into the ethyl acetate solution of purine in an ice water bath, wherein the dripping time is controlled to be 120 minutes, the temperature of the ice water bath is controlled to be 0 ℃, and purine acyl chloride is generated through reaction; adding 150 g of vacuum high-temperature dehydrated single-end dihydroxy polysiloxane (the number average molecular weight is 2000) into a purine acyl chloride solution, adding 5 g of alkaline alumina, and stirring at normal temperature for reaction for 4 hours; and adding a sodium bicarbonate aqueous solution into the container after the reaction is finished, cleaning, separating, finally cleaning with clear water, and drying for later use.
Example 3
Weighing ethyl acetate, adding activated at high temperature
Molecular sieve is kept overnight, and dehydration is carried out for standby; taking 100 g of dehydrated ethyl acetate purification solvent, adding 14.84 g (0.05 mol) of triphosgene, and stirring until the solvent is dissolved; taking 100 g of dehydrated ethyl acetate purification solvent, adding 18.02 g (0.15 mol) of purine, and stirring until the purine is dissolved; slowly dripping the ethyl acetate solution of triphosgene into the ethyl acetate solution of purine in an ice water bath, wherein the dripping time is controlled to be 120 minutes, the temperature of the ice water bath is controlled to be 0 ℃, and purine acyl chloride is generated through reaction; the purine acyl chloride solution is added into 150 g which is dehydrated at high temperature in vacuumAdding 5 g of alkaline alumina into the double-end monohydroxy polysiloxane (the number average molecular weight is 2000), and stirring and reacting for 4 hours at normal temperature; and adding a sodium bicarbonate aqueous solution into the container after the reaction is finished, cleaning, separating, finally cleaning with clear water, and drying for later use.
In examples 1 to 3, the vacuum high-temperature dehydration was performed in a vacuum 120 degree environment.
Example 4
Dissolving polyvinylidene fluoride (PVDF) with the molecular weight of 20 ten thousand in a tetrahydrofuran solvent to prepare a solution with the mass concentration of 15%; the terminal purinyl organosilicon compounds prepared in examples 1 to 3 were added to the PVDF solution at a concentration of 1% by mass. After being dispersed to be uniform at high speed, the mixture is smeared on a glass plate and baked to form a film at 90 ℃ for standby. Respectively soaking PVDF (polyvinylidene fluoride) membranes containing purine-terminated organic silicon compounds with different sizes in aqueous solution of cytosine fluorescently labeled by dansyl chloride, taking out the PVDF membranes after 1 hour, and measuring the fluorescence intensity of the solution. Experiments show that the terminal purinyl organosilicon compounds prepared in examples 1-3 are all characterized by: as the area of the soaked PVDF membrane increases, the fluorescence intensity of the solution tends to decrease gradually. The result shows that the PVDF film containing the terminal purine organic silicon compound has stronger adsorption effect on cytosine and reduces the concentration of cytosine in the solution. And the fluorescence intensity of the membrane with different sizes is not obviously changed after the membrane is soaked without the added PVDF membrane.
Although the present invention has been described in detail with reference to specific embodiments thereof, it will be understood by those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A terminal purinyl organosilicon compound characterized by:
the structural formula is
Wherein n is an integer and has a value range of 1-100; r 1 、R 2 、R 3 、R 4 Is H or a B group, R 1 、R 2 、R 3 、R 4 The same or different; b group is->
R is C1-C3 alkyl.
2. The terminal purinyl organosilicon compound according to claim 1, wherein:
when R is 1 、R 2 、R 3 Is H, R 4 When the group B is used, the structural formula of the organic silicon compound is as follows:
3. the terminal purinyl organosilicon compound according to claim 1, wherein:
when R is 1 、R 3 Is H, R 2 、R 4 When the group B is selected, the structural formula of the organic silicon compound is as follows:
4. the process for producing a terminal purinyl organosilicon compound according to claim 1, which comprises:
(1) Dissolving triphosgene in dehydrated organic solvent to obtain triphosgene solution;
(2) Dissolving purine in another dehydrated organic solvent to obtain a purine solution;
(3) At normal temperature, the triphosgene solution is dripped into the purine solution in the ice water bath, and the addition reaction is carried out for 1-2 h at the temperature of 0-5 ℃ to generate purine acyl chloride;
(4) Dropwise adding the solution after the reaction into the hydroxyl-terminated polysiloxane subjected to high-temperature vacuum dehydration, adding alkaline alumina, and stirring and reacting for 2-4 h at normal temperature;
(5) Sequentially filtering, cleaning, extracting, drying and dehydrating the reaction product to obtain a terminal purinyl organic silicon compound;
the organic solvent in the steps (1) and (2) is the same and is one of ester solvents such as ethyl acetate, butyl acetate, sec-butyl acetate and the like.
5. The method of claim 4, wherein:
the hydroxyl-terminated polysiloxane is single-ended monohydroxy polysiloxane, single-ended dihydroxy polysiloxane or double-ended monohydroxy polysiloxane.
6. The method of claim 4, wherein:
the mol ratio of the hydroxyl-terminated polysiloxane to the purine acyl chloride is 1:1.
7. the terminal purinyl organosilicon compound of any of claims 1-3 for use as a purine structural compound assay.
8. Use of the terminal purinyl organosilicon compound according to any of claims 1 to 3 as an adsorbent for purine structural compounds.
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| US5270426A (en) * | 1990-01-22 | 1993-12-14 | Shin-Etsu Chemical Co., Ltd. | Organosilicon compound |
| AU2004293463A1 (en) * | 2003-11-20 | 2005-06-09 | Angiotech International Ag | Implantable sensors and implantable pumps and anti-scarring agents |
| JP5563147B2 (en) * | 2010-04-01 | 2014-07-30 | ザ プロクター アンド ギャンブル カンパニー | Organosilicone |
| JP6206373B2 (en) * | 2014-10-17 | 2017-10-04 | 信越化学工業株式会社 | Method for producing organosilicon compound and metal surface treatment agent |
| JP6533387B2 (en) * | 2014-12-26 | 2019-06-19 | 株式会社ダイセル | Curable resin composition, cured product thereof, and semiconductor device |
| JP6866802B2 (en) * | 2017-08-09 | 2021-04-28 | 信越化学工業株式会社 | Silicone skeleton-containing polymer compound, photosensitive resin composition, photosensitive resin film, photosensitive dry film, laminate, and pattern forming method |
| CN110924174A (en) * | 2019-12-09 | 2020-03-27 | 张礼国 | Fabric softener and preparation method thereof |
| CN111265720A (en) * | 2020-04-13 | 2020-06-12 | 成都吱吖科技有限公司 | Adipose tissue material rich in stem cells and preparation method thereof |
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