CN114920629B - Gemini pyrogallic acid compound and preparation method and application thereof - Google Patents
Gemini pyrogallic acid compound and preparation method and application thereof Download PDFInfo
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- CN114920629B CN114920629B CN202210511892.6A CN202210511892A CN114920629B CN 114920629 B CN114920629 B CN 114920629B CN 202210511892 A CN202210511892 A CN 202210511892A CN 114920629 B CN114920629 B CN 114920629B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 pyrogallic acid compound Chemical class 0.000 title claims abstract description 21
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 9
- XFSAZBKSWGOXRH-UHFFFAOYSA-N 2-(2-carbonochloridoyloxyethoxy)ethyl carbonochloridate Chemical compound ClC(=O)OCCOCCOC(Cl)=O XFSAZBKSWGOXRH-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002274 desiccant Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical group [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 5
- 239000003899 bactericide agent Substances 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 2
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 17
- JZXPEQZMRNCVJW-UHFFFAOYSA-N carboxy hydrogen carbonate 2-(2-hydroxyethoxy)ethanol Chemical compound C(=O)(O)OC(=O)O.C(COCCO)O JZXPEQZMRNCVJW-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229940126062 Compound A Drugs 0.000 description 8
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 229920001817 Agar Polymers 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 229940074391 gallic acid Drugs 0.000 description 2
- 235000004515 gallic acid Nutrition 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 240000006766 Cornus mas Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000103090 Eucalyptus robusta Species 0.000 description 1
- 240000001745 Rheum palmatum Species 0.000 description 1
- 235000008090 Rheum palmatum Nutrition 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JXASPPWQHFOWPL-UHFFFAOYSA-N Tamarixin Natural products C1=C(O)C(OC)=CC=C1C1=C(OC2C(C(O)C(O)C(CO)O2)O)C(=O)C2=C(O)C=C(O)C=C2O1 JXASPPWQHFOWPL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940095672 calcium sulfate Drugs 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000005221 swamp mahogany Nutrition 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000012137 tryptone Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
- C07C43/135—Saturated ethers containing hydroxy or O-metal groups having more than one ether bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
- A01N31/14—Ethers
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
- A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a gemini pyrogallic acid compound, a preparation method and application thereof, wherein the compound is diethylene glycol diglycidyl ether di-pyrogallic acid ether or di-pyrogallic acid diethylene glycol dicarbonate. The two pyrogallic acid gemini structures are formed by connecting the pyrogallic acid with the two connecting agents, and the pyrogallic acid compound with the gemini structure has good bactericidal performance and good application prospect.
Description
Technical Field
The invention relates to a pyrogallic acid substance, in particular to a gemini pyrogallic acid compound and a preparation method and application thereof.
Background
Gallic acid is a polyphenol organic compound widely existing in plants such as rheum palmatum, eucalyptus robusta, dogwood and the like, and can also be prepared by fermentation. The gallic acid and water are subjected to decarboxylation reaction at a certain temperature, and the pyrogallic acid can be prepared by purification. Pyrogallic acid is a chemical intermediate widely applied to the fields of medicine, life, chemical industry and the like, and is mainly applied to the production of antioxidants, flame retardants, printing and dyeing assistants, coatings, photosensitive materials, surfactants and the like. With the general acceptance of the green development concept, the development of new functional chemicals using more natural compounds has received much attention from the industry.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention provides a novel compound with a gemini pyrogallic acid structure, a preparation method thereof and application thereof as a bactericide.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a gemini pyrogallic acid compound having the following structural formula:
wherein R is
Or alternatively
When R is
In the process, the structural formula of the compound is as follows:
when R is
In the process, the structural formula of the compound is as follows: />
Further, the invention also provides a preparation method of the gemini pyrogallic acid compound, which comprises the steps of dissolving pyrogallic acid in an organic solvent, adding diethylene glycol diglycidyl ether and a catalyst, reacting for 3-12 hours at 70-130 ℃, cooling to room temperature after the reaction is finished, adjusting pH to be neutral, separating by silica gel column chromatography, wherein an eluent is ethyl acetate: methanol=8:2 (volume ratio), concentrating and crystallizing to obtain the final product;
the reaction equation is as follows:
the structural formula of the obtained compound is as follows:
Further, the invention also provides a preparation method of the other gemini pyrogallic acid compound, which comprises the steps of dissolving pyrogallic acid in an organic solvent, adding diethylene glycol bischloroformate, a neutralizer and a drying agent, reacting for 3-12 hours at the temperature of-5-25 ℃, filtering to remove solids after the reaction is finished, separating filtrate by silica gel column chromatography, wherein the eluting agent is ethyl acetate: methanol=7:3 (volume ratio), concentrating and crystallizing to obtain the final product;
the reaction equation is as follows:
the structural formula of the obtained compound is as follows:
Specifically, in the preparation process of the compound A, the organic solvent is isopropanol, dioxane or cyclohexanone; the catalyst is KOH, boron trifluoride diethyl etherate or NaOH, and the mass ratio of the diethylene glycol diglycidyl ether to the catalyst is 1: (0.01-0.1).
Specifically, in the preparation process of the compound A, the molar ratio of the pyrogallic acid to the diethylene glycol diglycidyl ether is 1.0: (0.1 to 0.4).
Specifically, in the preparation process of the compound B, the organic solvent is isopropanol, dioxane or cyclohexanone.
Specifically, in the preparation process of the compound B, the neutralizing agent is sodium carbonate, sodium bicarbonate or potassium carbonate, and the molar ratio of the neutralizing agent to diethylene glycol bischloroformate is 1: (1-2).
Specifically, in the preparation process of the compound B, the drying agent is magnesium sulfate, calcium sulfate or calcium chloride, and the mass ratio of the drying agent to diethylene glycol bischloroformate is 1: (0.1-1).
Specifically, in the preparation process of the compound B, the molar ratio of the pyrogallic acid to the diethylene glycol bischloroformate is 1: (0.1 to 0.4).
Furthermore, the invention also provides application of the gemini pyrogallic acid compound in serving as a sterilization functional component.
The beneficial effects are that:
the two pyrogallic acid gemini structures are formed by connecting the pyrogallic acid with the two connecting agents, and the pyrogallic acid compound with the gemini structure has good bactericidal performance and good application prospect.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is an infrared spectrum of diethylene glycol diglycidyl ether prepared in example 1 (compound A), and diethylene glycol dicarbonate of diethylene glycol diglycidyl ether (compound B).
Detailed Description
The invention will be better understood from the following examples.
Example 1
Preparation of compound A diethylene glycol diglycidyl ether di-pyrogallic acid ether:
12.50g (0.1 mol) of pyrogallic acid (molecular weight 125.01) and 8.73g (0.04 mol) of diethylene glycol diglycidyl ether (molecular weight 218.25) were dissolved in 250g of isopropanol, and 0.15g of boron trifluoride diethyl ether as a catalyst was added thereto, heated to 90℃and reacted for 8 hours. After cooling, pH was adjusted to neutrality with 5% hydrochloric acid solution, the impurities were removed by filtration, and the product was obtained by column chromatography separation, concentration and crystallization in a yield of 12.0 g and 68% (based on diethylene glycol diglycidyl ether). The infrared spectrum of the product is shown in figure 1.
Preparation of compound B, di-pyrogallic acid diethylene glycol dicarbonate:
after 12.50g (0.1 mol) of pyrogallic acid and 9.24g (0.04 mol) of diethylene glycol bischloroformate (molecular weight 231.03) were dissolved in 250g of isopropanol, 2.12g of sodium carbonate as a neutralizing agent was added, 1.2g of anhydrous magnesium sulfate as a drying agent was added, and the reaction time at-5℃was 6 hours. The solids were removed by filtration and separated by column chromatography to give 12.2 g of the product in 69% yield (based on diethylene glycol bischloroformate). The infrared spectrum of the product is shown in figure 1.
The column chromatography adopts a silica gel column, and the eluent is ethyl acetate: methanol=7:3 (volume ratio).
The infrared spectra of diethylene glycol diglycidyl ether pyrogallic acid ether and diethylene glycol dicarbonate of this example are shown in FIG. 1, which shows that the diethylene glycol diglycidyl ether pyrogallic acid ether is present at 1080cm -1 An absorption peak of ether bond appears at 1280-1240cm -1 The synthesis of diethylene glycol diglycidyl ether pyrogallic acid ether is shown by the absence of an epoxy bond stretching vibration peak. For the di-pyrogallic acid diethylene glycol dicarbonate, it is at 1774cm -1 The expansion vibration peak of the carbonic ester appears, which proves the synthesis of the di-pyrogallic acid diglycol dicarbonate.
Example 2
Preparation of compound A diethylene glycol diglycidyl ether di-pyrogallic acid ether:
12.50g (0.1 mol) of pyrogallic acid and 2.18g (0.01 mol) of diethylene glycol diglycidyl ether were dissolved in 250g of dioxane, and 0.20g of KOH was added as a catalyst. Heated to 110 ℃ and reacted for 6 hours. After cooling, pH was adjusted to neutrality with 5% hydrochloric acid solution, the filtrate was collected by filtration, and the resultant was separated by column chromatography, concentrated and crystallized to give 3.8 g of a product in 86% yield (based on diethylene glycol diglycidyl ether). Product analysis data: 1H NMR (300 MHz, CDCl 3) delta ppm 6.71-6.82 (m, 2H), 6.53-6.64 (m, 2H), 6.39-6.48 (m, 2H), 5.71-5.83 (br, 4H), 4.74-4.83 (m, 2H), 4.08 (d, J=5.4 Hz, 4H), 3.63-3.75 (m, 4H), 3.52-3.61 (m, 4H), 2.66 (br, 2H). LCMS [ M+1] +:443
Preparation of compound B, di-pyrogallic acid diethylene glycol dicarbonate:
after 12.50g (0.1 mol) of pyrogallic acid and 2.31g (0.01 mol) of diethylene glycol bischloroformate were dissolved in 250g of dioxane, 1.68g of anhydrous sodium bicarbonate as a neutralizing agent was added, 1.2g of anhydrous calcium sulfate as a drying agent was added, and the reaction time at 5℃was 5 hours. The impurities are removed by filtration, the filtrate is collected and separated by column chromatography, and the product is obtained by concentration and crystallization, 3.4 g, and the yield is 83% (calculated by diethylene glycol bischloroformate). Product analysis data: 1H NMR (300 MHz, CDCl 3) delta ppm 6.73-6.81 (m, 2H), 6.47-6.62 (m, 2H), 6.36-6.45 (m, 2H), 5.84-6.01 (br, 4H), 3.71-3.82 (m, 4H), 3.58-3.69 (m, 4H). LCMS [ M+1] +:411
Example 3
Preparation of compound A diethylene glycol diglycidyl ether di-pyrogallic acid ether:
12.50g (0.1 mol) of pyrogallic acid and 6.55g (0.03 mol) of diethylene glycol diglycidyl ether were dissolved in 250g of dioxane, and 0.25g of KOH was added as a catalyst. Heated to 100℃and reacted for 9h. After cooling, pH was adjusted to neutrality with 5% hydrochloric acid solution, the filtrate was collected by filtration, and the resultant was separated by column chromatography, concentrated and crystallized to give 9.5 g of a product with a yield of 72% (based on diethylene glycol diglycidyl ether). Product elemental analysis: c54.91%; h:5.62%; o:39.47%.
Preparation of compound B, di-pyrogallic acid diethylene glycol dicarbonate:
12.6g (0.1 mol) of pyrogallic acid and 6.55g (0.03 mol) of diethylene glycol bischloroformate were dissolved in 250g of cyclohexanone, and 2.07g of anhydrous potassium carbonate as a neutralizing agent was added thereto, and the reaction time at 20℃was 8 hours. The impurities are removed by filtration, the filtrate is collected and separated by column chromatography, and the concentrated crystallization gives 9.1 g of product with a yield of 74% (based on diethylene glycol bischloroformate). Product elemental analysis: c:52.32%; h,4.72%; o,42.96%.
Example 4
The sterilization performance is evaluated according to the standard QB/T2738-2005 daily chemical product antibacterial effect and ISO9252:1989 (E) microorganism detection Specification-plate counting method, adding quantitative bacterial culture solution into the sample, and detecting microorganism after a certain time. A proper amount of sample is sucked by a sterile straw and uniformly mixed in a tryptone agar medium, then the peptone agar medium is cultured for 48 hours at 35 ℃, and the peptone agar medium is taken out to observe the growth condition of microorganisms on an agar plate for reading. The results are shown in Table 1.
From Table 1, it can be seen that both the compound A and the compound B have good bactericidal effects; the two compounds are respectively added into the formula of the liquid laundry detergent without the bactericide and the preservative, so that the liquid laundry detergent also has good bactericidal effect.
TABLE 1
Note that: the liquid laundry detergent in table 1 is a liquid laundry detergent without bactericide and preservative, and the formula is as follows (in mass percent): 83.40% of deionized water and 0.10% of EDTA tetrasodium; sodium hydroxide 0.75%; sulfonic acid 6.00%; AES (endorsement) 5.50%; 0.05% of fluorescent whitening agent; 6501 (1:1.5) 3.00%; DMDMH0.20%; essence (CP 92863C) 0.10%; deionized water 0.10%; blue paste 0.0003%; rose essence 0.00005%; sodium chloride 0.80%.
The invention provides a gemini pyrogallic acid compound, a preparation method and an application thought and a method thereof, and particularly the method and the way for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by those skilled in the art without departing from the principle of the invention, and the improvements and modifications are also regarded as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (7)
1. A gemini pyrogallic acid compound characterized by having the following structural formula:
2. the method for preparing the gemini pyrogallic acid compound according to claim 1, which is characterized in that pyrogallic acid is dissolved in an organic solvent, diethylene glycol bischloroformate, a neutralizer and a drying agent are added, the mixture is reacted for 3 to 12 hours at the temperature of-5 to 25 ℃, after the reaction is finished, solids are removed by filtration, and the filtrate is subjected to column chromatography and concentrated crystallization to obtain the gemini pyrogallic acid compound;
the reaction equation is as follows:
the structural formula of the obtained compound is as follows:
3. the method for preparing a gemini pyrogallic acid compound according to claim 2, wherein the organic solvent is isopropanol, dioxane or cyclohexanone.
4. The method for preparing the gemini pyrogallic acid compound according to claim 2, wherein the neutralizing agent is sodium carbonate, sodium bicarbonate or potassium carbonate, and the molar ratio of the neutralizing agent to diethylene glycol bischloroformate is 1: (1-2).
5. The method for preparing the gemini pyrogallic acid compound according to claim 2, wherein the drying agent is magnesium sulfate, calcium sulfate or calcium chloride, and the mass ratio of the drying agent to diethylene glycol bischloroformate is 1: (0.1-1).
6. The method for producing a gemini pyrogallic acid compound according to claim 2, wherein the molar ratio of pyrogallic acid to diethylene glycol bischloroformate is 1: (0.1 to 0.4).
7. Use of the gemini pyrogallic acid compound according to claim 1 for the preparation of bactericides.
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