CN114920629A - Gemini pyrogallic acid compound and preparation method and application thereof - Google Patents

Gemini pyrogallic acid compound and preparation method and application thereof Download PDF

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CN114920629A
CN114920629A CN202210511892.6A CN202210511892A CN114920629A CN 114920629 A CN114920629 A CN 114920629A CN 202210511892 A CN202210511892 A CN 202210511892A CN 114920629 A CN114920629 A CN 114920629A
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gemini
pyrogallic acid
compound
diethylene glycol
acid compound
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CN114920629B (en
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陈洪龄
赵雨萌
林勇强
梁齐波
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Guangdong Micro Control Biotechnology Co ltd
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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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  • 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)
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  • 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 an application thereof, wherein the compound is diethylene glycol diglycidyl ether dipyrogallic acid ether or diethylene glycol dicarbonate of the dipyrogallic acid. The pyrogallic acid gemini structures of the two pyrogallic acids are formed by connecting the pyrogallic acid by two connecting agents to form a novel gemini structure, and the pyrogallic acid compound with the gemini structure shows better sterilization performance and has good application prospect.

Description

Gemini pyrogallic acid compound and preparation method and application thereof
Technical Field
The invention relates to pyrogallic acid substances, in particular to a gemini pyrogallic acid compound and a preparation method and application thereof.
Background
Gallic acid is a polyphenol organic compound, widely exists in Rheum palmatum, Eucalyptus robusta, Corni fructus, etc., and can also be prepared by fermentation method. The gallic acid and water are subjected to decarboxylation reaction at a certain temperature, and the pyrogallic acid can be prepared after purification. The 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 auxiliaries, coatings, photosensitive materials, surfactants and the like. With the general acceptance of the green development concept, more natural compounds are utilized to develop new functional chemicals, which are receiving wide attention from the industry.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of the prior art and provides a novel gemini pyrogallic acid structure compound, a preparation method thereof and application thereof as a bactericide.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a gemini pyrogallic acid compound has the following structural general formula:
Figure BDA0003638310510000011
wherein R is
Figure BDA0003638310510000012
Or alternatively
Figure BDA0003638310510000013
When R is
Figure BDA0003638310510000014
When the compound has the structural formula:
Figure BDA0003638310510000015
when R is
Figure BDA0003638310510000021
When the compound is represented by the structural formula:
Figure BDA0003638310510000022
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 at 70-130 ℃ for 3-12h, cooling to room temperature after the reaction is finished, adjusting the pH value to be neutral, and separating by silica gel column chromatography, wherein an eluent is ethyl acetate: concentrating and crystallizing the methanol with the volume ratio of 8:2 to obtain the compound;
the reaction equation is as follows:
Figure BDA0003638310510000023
the structural formula of the obtained compound is as follows:
Figure BDA0003638310510000024
denoted compound a, diethylene glycol diglycidyl ether pyrogallol ether.
Further, the invention also provides another preparation method of the gemini pyrogallic acid compound, which comprises the steps of dissolving pyrogallic acid in an organic solvent, adding diethylene glycol bischloroformate, a neutralizing agent and a drying agent, reacting at-5-25 ℃ for 3-12h, filtering to remove solids after the reaction is finished, and separating the filtrate through silica gel column chromatography, wherein an eluent is ethyl acetate: concentrating and crystallizing the methanol which is 7:3 (volume ratio) to obtain the compound;
the reaction equation is as follows:
Figure BDA0003638310510000025
the structural formula of the obtained compound is as follows:
Figure BDA0003638310510000031
the compound B is referred to as diethylene glycol dicarbonate, pyrogallic acid.
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 pyrogallic acid to diethylene glycol diglycidyl ether is 1.0: (0.1-0.4).
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 pyrogallic acid to diethylene glycol bischloroformate is 1: (0.1-0.4).
Furthermore, the invention also provides the application of the gemini pyrogallic acid compound as a sterilization functional component.
Has the advantages that:
the pyrogallic acid with two gemini structures is formed by connecting the pyrogallic acid with two linking agents, and the gemini structure pyrogallic acid compound shows good bactericidal performance and has good application prospect.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is an infrared spectrum of diethylene glycol diglycidyl ether dipyrogallol ether (Compound A) prepared in example 1 and diethylene glycol diglycol dicarbonate (Compound B) as a pyrogallol.
Detailed Description
The invention will be better understood from the following examples.
Example 1
Preparation of compound a diethylene glycol diglycidyl ether pyrogallol ether:
12.50g (0.1mol) of pyrogallic acid (molecular weight 125.01) and 8.73g (0.04mol) of diethylene glycol diglycidyl ether (molecular weight 218.25) were dissolved in 250g of isopropanol, 0.15g of boron trifluoride diethyl etherate as a catalyst was added, and the mixture was heated to 90 ℃ and reacted for 8 hours. After cooling, the pH was adjusted to neutrality with 5% hydrochloric acid solution, filtered to remove impurities, separated by column chromatography, concentrated and crystallized to give the product 12.0 g, in 68% yield (based on diethylene glycol diglycidyl ether). The infrared spectrum of the product is shown in FIG. 1.
Preparation of compound B diglycol digallate:
after 12.50g (0.1mol) of pyrogallic acid and 9.24g (0.04mol) of diethylene glycol bischloroformate (molecular weight 231.03) were dissolved in 250g of isopropanol, 2.12g of sodium carbonate as a neutralizing agent and 1.2g of anhydrous magnesium sulfate as a drying agent were added, and the reaction time was 6 hours at-5 ℃. The solid was removed by filtration, separated by column chromatography, and concentrated to give the product 12.2 g with a yield of 69% (based on diethylene glycol bischloroformate). The IR spectrum of the product is shown in FIG. 1.
The column chromatography adopts a silica gel column, and the eluent is ethyl acetate: methanol was 7:3 (volume ratio).
The infrared spectra of diethylene glycol diglycidyl ether pyrogallic acid ether and diethylene glycol dicarbonate of the present example are shown in FIG. 1, and the spectrum is 1080cm for diethylene glycol diglycidyl ether pyrogallic acid ether -1 The absorption peak of ether bond appears at 1280-1240cm -1 Shows the synthesis of diglycol diglycidyl ether pyrogallic acid ether. For the diglycol dicarbonate of the pyrogallic acid, it is at 1774cm -1 The stretching vibration peak of the carbonic ester appears, and the synthesis of the diglycol dicarbonate of the pyrogallic acid is proved.
Example 2
Preparation of compound a diethylene glycol diglycidyl ether pyrogallic acid ether:
12.50g (0.1mol) of pyrogallic acid and 2.18g (0.01mol) of diethylene glycol diglycidyl ether were dissolved in 250g of dioxane, and 0.20g of KOH, a catalyst, was added. Heated to 110 ℃ and reacted for 6 h. After cooling, the pH was adjusted to neutrality with 5% hydrochloric acid solution, the filtrate was collected by filtration, separated by column chromatography, and concentrated by crystallization to give the product 3.8 g in 86% yield (based on diethylene glycol diglycidyl ether). Product analysis data: 1H NMR (300MHz, CDCl3) δ 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 ═ 5.4Hz,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 diglycol digallate:
after 12.50g (0.1mol) of pyrogallic acid and 2.31g (0.01mol) of diethylene glycol bischloroformate were dissolved in 250g of dioxane, 1.68g of anhydrous sodium bicarbonate and 1.2g of anhydrous calcium sulfate as a drying agent were added, and the reaction time was 5 hours at 5 ℃. The filtrate was collected by filtration to remove impurities, and subjected to column chromatography, concentration and crystallization to give 3.4 g of a product in a yield of 83% (based on diethylene glycol bischloroformate). Product analysis data: 1H NMR (300MHz, CDCl3) 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 pyrogallol ether:
12.50g (0.1mol) of pyrogallic acid and 6.55g (0.03mol) of diethylene glycol diglycidyl ether were dissolved in 250g of dioxane, and 0.25g of KOH, a catalyst, was added. Heated to 100 ℃ and reacted for 9 h. After cooling, the pH was adjusted to neutrality with 5% hydrochloric acid solution, the filtrate was collected by filtration to remove impurities, and the product was isolated by column chromatography, concentrated and crystallized to give 9.5 g in 72% yield (based on diethylene glycol diglycidyl ether). Elemental analysis of the product: c54.91%; h: 5.62 percent; o: 39.47 percent.
Preparation of compound B diglycol digallate:
12.6g (0.1mol) of pyrogallic acid and 6.55g (0.03mol) of diethylene glycol bischloroformate were dissolved in 250g of cyclohexanone, and 2.07g of anhydrous potassium carbonate as a neutralizing agent was added to the solution to react at 20 ℃ for 8 hours. The filtrate was collected by filtration to remove impurities, and subjected to column chromatography, concentration and crystallization to give 9.1 g of a product in a yield of 74% (based on diethylene glycol bischloroformate). Elemental analysis of the product: c: 52.32 percent; h, 4.72%; o,42.96 percent.
Example 4
The bactericidal performance is evaluated according to the antibacterial and bacteriostatic effects of standard QB/T2738-: 1989(E) Standard for microbial detection-plate count assay, a defined amount of bacterial culture was added to the sample and tested for microbial detection after a defined period of time. Sucking a proper amount of sample by using a sterile pipette, uniformly mixing the sample in a tryptone agar culture medium, then culturing the tryptone agar culture medium for 48 hours at 35 ℃, taking out the culture medium, observing the growth condition of the microorganism on an agar plate, and reading. The results are shown in Table 1.
As can be seen from Table 1, compound A and compound B have good bactericidal effects; the two compounds are respectively added into the formula of the laundry detergent without the bactericide and the preservative, so that a good sterilizing effect is also embodied.
TABLE 1
Figure BDA0003638310510000061
Note: the laundry detergent in table 1 is a laundry detergent without adding a bactericide and a preservative, and the formula is as follows (in mass percent): 83.40% of deionized water and 0.10% of EDTA tetrasodium; 0.75 percent of sodium hydroxide; 6.00 percent of sulfonic acid; AES (praise) 5.50%; 0.05% of fluorescent whitening agent; 6501 (1: 1.5) 3.00%; 0.20 percent of DMDMH; essence (CP92863C) 0.10%; 0.10 percent of deionized water; 0.0003 percent of blue paste; 0.00005% of rose essence; 0.80 percent of sodium chloride.
The present invention provides a gemini pyrogallic acid compound, a preparation method and application thereof, and a plurality of methods and ways for implementing the technical scheme, and the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, a plurality of improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.

Claims (10)

1. A gemini pyrogallic acid compound is characterized by having the following structural general formula:
Figure FDA0003638310500000011
wherein R is
Figure FDA0003638310500000012
Or alternatively
Figure FDA0003638310500000013
When R is
Figure FDA0003638310500000014
When the compound has the structural formula:
Figure FDA0003638310500000015
when R is
Figure FDA0003638310500000016
When the compound has the structural formula:
Figure FDA0003638310500000017
2. the method for preparing the gemini pyrogallic acid compound as claimed in claim 1, is characterized in that the pyrogallic acid is dissolved in an organic solvent, diethylene glycol diglycidyl ether and a catalyst are added, the reaction is carried out for 3-12h at 70-130 ℃, the reaction is cooled to room temperature after the reaction is finished, the pH is adjusted to be neutral, and the gemini pyrogallic acid compound is obtained by column chromatography, concentration and crystallization;
the reaction equation is as follows:
Figure FDA0003638310500000018
the structural formula of the obtained compound is as follows:
Figure FDA0003638310500000019
3. the method for preparing the gemini pyrogallic acid compound as claimed in claim 1, wherein the pyrogallic acid is dissolved in an organic solvent, diethylene glycol bischloroformate, a neutralizing agent and a drying agent are added, the mixture is reacted at-5 to 25 ℃ for 3 to 12 hours, after the reaction is finished, the solid is removed by filtration, and the filtrate is subjected to column chromatography, concentration and crystallization to obtain the gemini pyrogallic acid compound;
the reaction equation is as follows:
Figure FDA0003638310500000021
the structural formula of the obtained compound is as follows:
Figure FDA0003638310500000022
4. the method for producing a gemini pyrogallic acid compound as defined in claim 2, wherein the organic solvent is isopropyl alcohol, 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).
5. The method for producing a gemini pyrogallic acid compound as claimed in claim 2, wherein the molar ratio of pyrogallic acid to diethylene glycol diglycidyl ether is 1.0: (0.1-0.4).
6. The method for producing the gemini pyrogallic acid compound as claimed in claim 3, wherein the organic solvent is isopropyl alcohol, dioxane or cyclohexanone.
7. The method for preparing gemini pyrogallic acid compound as claimed in claim 3, wherein the neutralizing agent is sodium carbonate, sodium bicarbonate or potassium carbonate, and the molar ratio of the neutralizing agent to the diethylene glycol bischloroformate is 1: (1-2).
8. The method for preparing gemini pyrogallic acid compound according to claim 3, wherein the drying agent is magnesium sulfate, calcium sulfate or calcium chloride, and the mass ratio of the drying agent to the diethylene glycol bischloroformate is 1: (0.1 to 1).
9. The method for producing a gemini pyrogallic acid compound according to claim 3, wherein the molar ratio of pyrogallic acid to diethylene glycol bischloroformate is 1: (0.1-0.4).
10. Use of the gemini pyrogallol compound according to claim 1 as a bactericidal functional ingredient.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008001878A1 (en) * 2006-06-29 2008-01-03 Shiseido Company Ltd. Hydroxy ether compound, process for production of the compound, and use of the compound
CN103080058A (en) * 2010-08-30 2013-05-01 味之素株式会社 Aromatic compound containing specific branch
CN109824491A (en) * 2019-03-28 2019-05-31 三峡大学 A kind of production method of 2,3,4,4 '-tetrahydroxybenzophenones

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008001878A1 (en) * 2006-06-29 2008-01-03 Shiseido Company Ltd. Hydroxy ether compound, process for production of the compound, and use of the compound
CN103080058A (en) * 2010-08-30 2013-05-01 味之素株式会社 Aromatic compound containing specific branch
US20170008922A1 (en) * 2010-08-30 2017-01-12 Ajinomoto Co., Inc. Branched chain-containing aromatic compound
CN109824491A (en) * 2019-03-28 2019-05-31 三峡大学 A kind of production method of 2,3,4,4 '-tetrahydroxybenzophenones

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