CN112898350A - Preparation method of guaiacol-derived bisiminomanganese complex - Google Patents
Preparation method of guaiacol-derived bisiminomanganese complex Download PDFInfo
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- CN112898350A CN112898350A CN202110084954.5A CN202110084954A CN112898350A CN 112898350 A CN112898350 A CN 112898350A CN 202110084954 A CN202110084954 A CN 202110084954A CN 112898350 A CN112898350 A CN 112898350A
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- guaiacol
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- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229960001867 guaiacol Drugs 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 23
- 150000002696 manganese Chemical class 0.000 claims abstract description 21
- -1 formaldehyde, diamine Chemical class 0.000 claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 150000004985 diamines Chemical class 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 8
- 229910000071 diazene Inorganic materials 0.000 claims description 8
- 230000002194 synthesizing effect Effects 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000004427 diamine group Chemical group 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000007040 multi-step synthesis reaction Methods 0.000 abstract description 2
- 102000019197 Superoxide Dismutase Human genes 0.000 description 9
- 108010012715 Superoxide dismutase Proteins 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 8
- YUZJJFWCXJDFOQ-UHFFFAOYSA-K manganese(3+);2-methoxy-6-[2-[(3-methoxy-2-oxidophenyl)methylideneamino]ethyliminomethyl]phenolate;chloride Chemical group [Cl-].[Mn+3].COC1=CC=CC(C=NCCN=CC=2C(=C(OC)C=CC=2)[O-])=C1[O-] YUZJJFWCXJDFOQ-UHFFFAOYSA-K 0.000 description 7
- 239000003642 reactive oxygen metabolite Substances 0.000 description 6
- 210000003491 skin Anatomy 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 102000016938 Catalase Human genes 0.000 description 4
- 108010053835 Catalase Proteins 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004060 metabolic process Effects 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000006907 apoptotic process Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002354 daily effect Effects 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 210000000434 stratum corneum Anatomy 0.000 description 1
- 210000000106 sweat gland Anatomy 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic System
- C07F13/005—Compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention belongs to the field of organic synthesis, fine chemicals and daily chemicals, and particularly relates to a preparation method of a guaiacol-derived bisimine manganese complex. The method takes guaiacol, formaldehyde, diamine and manganese salt as raw materials to synthesize the bisimine manganese complex derived from the guaiacol by one step. Compared with the multi-step synthesis method in the prior art, the method is simple and convenient to operate, cheap and easily available in reagents, green, safe, efficient and environment-friendly, and suitable for industrial production.
Description
Technical Field
The invention belongs to the field of organic synthesis, fine chemicals and daily chemicals, and particularly relates to a preparation method of a guaiacol-derived bisimine manganese complex.
Background
The guaiacol-derived manganese diimine complex of the present invention can be represented by the following general formula:
wherein R is1，R2All are hydrogen atoms, and when X is chlorine, the structure is ethyl bis iminoThe methyl guaiacol manganese chloride is EUK-134 for short. EUK-134 is a very potent antioxidant active ingredient of skin in the cosmetic industry. The human body takes food and water every day, and the food and water are transported to various body tissues through the digestive system and the circulatory system, metabolized in cells, and energy is released. During the entire metabolic process, large amounts of ROS (reactive oxygen species) are produced. These ROS can destroy normal cells of the human body, leading to apoptosis and even necrosis. However, the human body has evolved over the billions of years to form a precise antioxidant system to deal with ROS and maintain normal metabolism, wherein two important components are: superoxide dismutase (SOD), Catalase (CAT). The two components are closely matched, so that ROS generated in the metabolic process can be eliminated, but the effect of SOD in skin care products is not ideal. The reason for this is that SOD has a large molecular weight, hardly penetrates the stratum corneum, and most of it stays on the skin surface and cannot enter the skin to function. In addition, SOD has poor stability, and after production, the activity is seriously reduced after long storage and shelf life. In addition, even if a small amount of the protein enters the skin through pores and sweat glands, the protein is easily hydrolyzed by protein and has poor stability, and the protein is quickly metabolized in the human body. These properties of SOD prevent its use in cosmetics. EUK-134 was developed to avoid the disadvantages of SOD, and it has stable properties and low molecular weight, and can penetrate directly into skin to exert its effect. Even superoxide dismutase (SOD) and Catalase (CAT) synergistically complete the work of eliminating ROS, EUK-134 can be independently completed, the properties are more stable, and the antioxidant effect is better. In the last 10 years, the application of the composition in medical treatment and anti-aging is increasing. A great deal of third-party literature data has proved EUK-134 to have excellent oxidation resistance. Belongs to one of the excellent antioxidant components.
EUK-134, some documents report that guaiacol-derived manganese diimine complexes are synthesized by steps of synthesizing guaiacol aldehyde from salicylaldehyde or guaiacol, then reacting with diamine to form imine, and finally reacting the imine with manganese salt to obtain the guaiacol-derived manganese diimine complexes. The main steps of such a process are shown in the following formula:
the method has more steps and lower synthesis efficiency.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for synthesizing a guaiacol-derived manganese diimine complex in one step by using guaiacol, formaldehyde, diamine and manganese salt as raw materials.
The guaiacol-derived manganese diimine complex can be represented by the following general formula (1):
wherein R is1And R2Selected from hydrogen atoms or any same or different alkyl, aryl or heterocyclic groups, and X is selected from common anions such as chlorine, bromine, iodine, acetate and the like. For example, formula (1) may be of the following structure:
further, the air conditioner is provided with a fan,
the specific reaction formula is as follows: r in the formula (1)1And R2May be chemically bonded, thus forming a cyclic structure, such as:
further, the formula (1) may also be a compound containing a chiral center, and a representative structure is as follows:
the synthesis method can be represented by the following formula:
wherein R in the diamine structure of the raw material of the reaction1And R2R in structure of diimine manganese complex derived from guaiacol serving as target product1And R2Consistently, selected from a hydrogen atom or any of the same or different alkyl, aryl or heterocyclyl groups; in addition, R1And R2May be chemically bonded, thus forming a cyclic diamine.
In the reaction, when the diamine is chiral diamine, the method can synthesize chiral guaiacol derivative bisiminomanganese complexes, and representative examples are the following three compounds:
the manganese salt MnX2Wherein X is consistent with X in the structure of the target product guaiacol derived manganese diimine complex and is selected from common anions such as chlorine, bromine, iodine, acetate and the like.
The mass ratio of the guaiacol to the manganese salt is 2-2.4: 1.
the amount ratio of the diamine to the manganese salt is 1-1.2: 1.
the mass ratio of the formaldehyde to the manganese salt is 2-3: 1.
the solvent for the reaction is selected from benzene, toluene, nitrobenzene, chlorobenzene, xylene, and the like.
The general steps of the reaction are: adding the raw materials and the solvent into a reaction container according to a certain proportion, installing a water separator, heating up for reflux reaction, stopping the reaction when the water layer in the water separator is not increased any more, cooling to room temperature, and filtering to obtain a solid product.
The invention has the beneficial effects that:
the invention provides a method for synthesizing a guaiacol-derived bisimine manganese complex by one step by using guaiacol, formaldehyde, diamine and manganese salt as raw materials. Compared with the multi-step synthesis method in the prior art, the method is simple and convenient to operate, cheap and easily available in reagents, green, safe, efficient and environment-friendly, and suitable for industrial production.
Detailed Description
Example one (synthesis of EUK-134):
150 ml of toluene, 25 g of guaiacol, 7 g of formaldehyde, 6.5 g of diamine and 12.5 g of manganese salt are sequentially added into a 500ml reaction bottle, a water separator is arranged, the temperature is raised, reflux reaction is carried out, the reaction is stopped when a water layer in the water separator is not increased any more, the reaction is cooled to room temperature, filtering is carried out, and a filter cake is washed by a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 85%.
Example two:
150 ml of benzene, 25 g of guaiacol, 7 g of formaldehyde, 9 g of diamine and 12.5 g of manganese salt are sequentially added into a 500ml reaction bottle, a water separator is arranged, the temperature is raised for reflux reaction, the reaction is stopped when a water layer in the water separator is not increased any more, the reaction is cooled to room temperature, the filtration is carried out, and a filter cake is washed by a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 84%.
Example three:
adding 150 ml of dimethylbenzene, 25 g of guaiacol, 7 g of formaldehyde, 17 g of diamine and 12.5 g of manganese salt into a 500ml reaction bottle in sequence, installing a water separator, heating up for reflux reaction, stopping the reaction until a water layer in the water separator is not increased any more, cooling to room temperature, filtering, and washing a filter cake with a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 82%.
Example four:
150 ml of chlorobenzene, 25 g of guaiacol, 7 g of formaldehyde, 12 g of diamine and 22 g of manganese salt are sequentially added into a 500ml reaction bottle, a water separator is arranged, the temperature is raised for reflux reaction, the reaction is stopped when a water layer in the water separator is not increased any more, the reaction is cooled to room temperature, the filtration is carried out, and a filter cake is washed by a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 88%.
Example five:
150 ml of chlorobenzene, 25 g of guaiacol, 7 g of formaldehyde, 25 g of diamine and 17 g of manganese salt are sequentially added into a 500ml reaction bottle, a water separator is arranged, the temperature is raised for reflux reaction, the reaction is stopped when a water layer in the water separator is not increased any more, the reaction is cooled to room temperature, the filtration is carried out, and a filter cake is washed by a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 80%.
Example six (synthesis of chiral compound):
150 ml of chlorobenzene, 25 g of guaiacol, 7 g of formaldehyde, (R, R) -cyclohexanediamine and 12.5 g of manganese salt are sequentially added into a 500ml reaction bottle, a water separator is arranged, the temperature is raised for reflux reaction, the reaction is stopped when a water layer in the water separator is not increased any more, the reaction is cooled to room temperature, the filtration is carried out, and a filter cake is washed by a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 85 percent.
Example seven (synthesis of chiral compound):
150 ml of chlorobenzene, 25 g of guaiacol, 7 g of formaldehyde, (S, S) -cyclohexanediamine and 12.5 g of manganese salt are sequentially added into a 500ml reaction bottle, a water separator is arranged, the temperature is raised for reflux reaction, the reaction is stopped when a water layer in the water separator is not increased any more, the reaction is cooled to room temperature, the filtration is carried out, and a filter cake is washed by a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 84%.
Example eight (synthesis of chiral compound):
150 ml of chlorobenzene, 25 g of guaiacol, 7 g of formaldehyde, (S, R) -cyclohexanediamine and 12.5 g of manganese salt are sequentially added into a 500ml reaction bottle, a water separator is arranged, the temperature is raised for reflux reaction, the reaction is stopped when a water layer in the water separator is not increased any more, the reaction is cooled to room temperature, the filtration is carried out, and a filter cake is washed by a proper amount of absolute ethyl alcohol to obtain a target product with the yield of 85 percent.
Claims (10)
1. A method for synthesizing a guaiacol-derived bisimine manganese complex represented by a formula (1) in one step by using guaiacol, formaldehyde, diamine and manganese salt as raw materials.
Wherein R is1And R2Selected from hydrogen atoms or any of the same or different alkyl, aryl or heterocyclic groups, R1And R2Can also be connected by chemical bonds to form a ring structure; x is selected from common anions such as chlorine, bromine, iodine, acetate and the like.
2. The method of claim 1, wherein the method of synthesis of the guaiacol-derived manganese diimine complex is represented by the following formula:
wherein R in the diamine structure of the raw material of the reaction1And R2R in structure of diimine manganese complex derived from guaiacol serving as target product1And R2Consistently, selected from a hydrogen atom or any of the same or different alkyl, aryl or heterocyclyl groups; in addition, R1And R2May be chemically bonded, thus forming a cyclic diamine.
3. A process for the synthesis of guaiacol-derived manganese diimine complexes as claimed in claims 1 and 2 wherein the manganese salt MnX2Wherein X is consistent with X in the structure of the target product guaiacol derived manganese diimine complex and is selected from common anions such as chlorine, bromine, iodine, acetate and the like.
4. The method for synthesizing guaiacol-derived manganese diimine complexes according to claims 1 and 2, wherein the ratio of the amounts of guaiacol and manganese salt is 2-2.4: 1.
5. the method for synthesizing guaiacol-derived manganese diimine complexes according to claims 1 and 2, wherein the ratio of the amount of diamine to manganese salt is 1-1.2: 1.
6. the method for synthesizing guaiacol-derived manganese diimine complexes according to claims 1 and 2, wherein the mass ratio of formaldehyde to manganese salt is 2-3: 1.
7. the process for the synthesis of guaiacol-derived manganese diimine complexes according to claims 1 and 2, wherein the solvent of the reaction is selected from benzene, toluene, nitrobenzene, chlorobenzene, xylene, etc.
8. A method for the synthesis of guaiacol-derived manganese diimine complexes according to claims 1 and 2, wherein the general steps of the reaction are: adding the raw materials and the solvent into a reaction container according to a certain proportion, installing a water separator, heating up for reflux reaction, stopping the reaction when the water layer in the water separator is not increased any more, cooling to room temperature, and filtering to obtain a solid product.
9. The method for synthesizing guaiacol-derived manganese diimine complexes according to claims 1 and 2, wherein the method is used for the synthesis of chiral guaiacol-derived manganese diimine complexes.
10. A method for the synthesis of guaiacol-derived manganese diimine complexes according to claims 1 and 2, wherein the method is used for the synthesis of chiral guaiacol-derived manganese diimine complexes as follows:
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117683068A (en) * | 2024-02-02 | 2024-03-12 | 山东天晟生物科技有限公司 | Preparation method and application of ethyl bis (iminomethyl) guaiacol manganese chloride |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117683068A (en) * | 2024-02-02 | 2024-03-12 | 山东天晟生物科技有限公司 | Preparation method and application of ethyl bis (iminomethyl) guaiacol manganese chloride |
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