CN111662208B - Trimeric quaternary ammonium salt surfactant constructed by dynamic imine bonds, and preparation method and application thereof - Google Patents

Trimeric quaternary ammonium salt surfactant constructed by dynamic imine bonds, and preparation method and application thereof Download PDF

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CN111662208B
CN111662208B CN201910169502.XA CN201910169502A CN111662208B CN 111662208 B CN111662208 B CN 111662208B CN 201910169502 A CN201910169502 A CN 201910169502A CN 111662208 B CN111662208 B CN 111662208B
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quaternary ammonium
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CN111662208A (en
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王毅琳
刘斌
范雅珣
李浩飞
赵微微
罗思琪
王�华
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
    • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C223/00—Compounds containing amino and —CHO groups bound to the same carbon skeleton
    • C07C223/06—Compounds containing amino and —CHO groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0001—Post-treatment of organic pigments or dyes
    • C09B67/0004—Coated particulate pigments or dyes
    • C09B67/0008—Coated particulate pigments or dyes with organic coatings
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Abstract

A trimeric cation quaternary ammonium salt surfactant constructed by dynamic imine bonds, a preparation method and application thereof; the preparation process provided by the invention is simple, the reaction condition is mild, the reaction period is short, the post-treatment is simple, and the industrial production is easy to realize. The trimeric cationic quaternary ammonium salt compound of the invention can be used in acid or CO2Dissociating under the action of the enzyme. The quaternary ammonium salt compound can be used as a surfactant, has good surface activity and aggregation behavior, can be applied to washing, emulsification, a phase transfer catalyst, micelle catalysis, substance extraction and substance separation, and can promote water drops to spread on a super-hydrophobic surface.

Description

Trimeric quaternary ammonium salt surfactant constructed by dynamic imine bonds, and preparation method and application thereof
Technical Field
The invention relates to the technical field of novel compounds containing quaternary ammonium salts, in particular to a trimeric cationic quaternary ammonium salt surfactant constructed by dynamic imine bonds, and a preparation method and application thereof.
Background
The trimeric surfactant has lower critical aggregation concentration, higher surface activity, higher aggregate charge density and richer aggregation behavior than the traditional single-chain surfactant and Gemini surfactant, so that the trimeric surfactant has richer application potential. However, conventional covalently bonded trimeric surfactants are generally difficult and expensive to synthesize, thereby limiting the use of trimeric surfactants. The existing idea is to optimize the synthetic route of the trimeric surfactant on one hand, but still faces a plurality of obstacles; on the other hand, the trimeric surfactant is obtained through non-covalent bond construction, and some reports are provided at present, but the non-covalent bond type trimeric surfactant generally has the defects of poor stability, limited types of available surfactants and the like.
Dynamic covalent bonds are a class of covalent bonds that have reversible formation and dissociation, have the strength of a covalent bond, and are capable of breaking down, and reforming, under certain conditions. The surfactant is constructed through dynamic covalent bonds, can be stable under certain conditions and has stability, aggregation behavior and phase behavior similar to those of common covalent bond type surfactants under the conditions; when the conditions are changed, the surfactant dissociates, losing its aggregation and phase properties, and when the conditions are restored, the surfactant can reform again, thereby imparting dynamic properties to the surfactant. And a series of different surfactants can be obtained at high yield under mild conditions through dynamic covalent bond construction, so that the synthesis of the surfactants is simplified, and the types of the surfactants are greatly enriched. Some reports have been made on single-chain and Gemini surfactants built by dynamic covalent bonds, but no report has been made on trimeric dynamic covalent bond-based surfactants.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a trimeric cationic quaternary ammonium salt surfactant constructed by dynamic imine bonds, and a preparation method and application thereof. The surfactant has good surface activity and aggregation behavior, and is wide in application field.
The purpose of the invention is realized by the following technical scheme:
a compound having the structure of formula (1):
Figure BDA0001987453540000021
in the formula (1), X is any one of Cl, Br and I;
each R1Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one, two or more RaSubstituted C1-C20An alkylene group of (a);
each R2And R3Same or different, independently from each other selected from H, C1-C10Alkyl of (C)1-C10Alkoxy, halogen, -OH, -NO2At least one of-CN, -SCN;
R4,R5and R6Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one, two or more RbSubstituted of the following groups: c1-12Alkyl radical, C2-12Alkenyl radical, C2-12Alkynyl, C1-12Alkoxy radical, C3-20Cycloalkyl, 3-20 membered heterocyclyl, C6-20Aryl, 5-20 membered heteroaryl;
each RaIdentical or different, independently from each other selected from O, S, N;
each RbIdentical or different, independently of one another, from O, S, N, halogen, -NO2、-CN、-SCN、C1-12Alkyl radical, C2-12Alkenyl radical, C1-12Alkoxy radical, C3-20Cycloalkyl radical, C6-20Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl.
According to the invention, each R1Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one, two or more RaSubstituted C1-C16Each R is a linear alkylene group ofaIdentical or different, independently from each other selected from O, S, N; as an example, each R1Identical or different, independently of one another, from one of the following structures:
Figure BDA0001987453540000022
also preferably, each of said R1Are identical or different and are each independently selected from the group consisting of-CH2-、-CH2CH2-、-CH2CH2CH2-one of the above.
According to the invention, each R2And R3Identical or different, independently of one another, from the group consisting of-H, -CH3、-CH2CH3、-OH、-OCH3、-F、-Cl、-Br、-I、-NO2At least one of, -CN, -SCN, preferably, each R2And R3Identical or different, independently of one another, from the group-H, -CH3、-OCH3、-F、-Cl、-Br、-NO2Preferably, R2And R3Is selected from-H.
According to the invention, R4,R5And R6Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one, two or more RbSubstituted of the following groups: c1-12Straight chain alkyl group of (1), C2-12Linear alkenyl of (A), C1-12Linear alkoxy of (C)3-20Cycloalkyl radical, C6-20Aryl, 5-20 membered heteroaryl;
each RbAre identical or different and are independently selected from O,S, N, halogen, -NO2、C1-12Alkyl radical, C2-12Alkenyl radical, C1-12Alkoxy radical, C3-20Cycloalkyl radical, C6-20Aryl, 5-20 membered heteroaryl;
as an example, R4,R5And R6Identical or different, independently of one another, from the group consisting of unsubstituted or optionally substituted by one, two or more RbSubstituted of the following groups:
Figure BDA0001987453540000031
each RbIdentical or different, independently of one another, from O, S, N, halogen, -NO2、C1-12Alkyl radical, C2-12Alkenyl radical, C1-12Alkoxy radical, C3-20Cycloalkyl radical, C6-20Aryl, 5-20 membered heteroaryl.
Preferably, R4,R5And R6Identical or different, independently of one another, from the group consisting of unsubstituted or substituted by C1-12Alkyl substituted
Figure BDA0001987453540000032
According to the present invention, the compound is represented by the following formula (1-1):
Figure BDA0001987453540000041
wherein n is an integer of 3 to 25, and n-2 represents-CH in parentheses2-a number, illustratively, n is 3,4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25.
According to the invention, the compound represented by the formula (1) has the following structure:
Figure BDA0001987453540000042
Figure BDA0001987453540000051
the present invention also provides a method for producing the compound represented by the above formula (1), comprising the steps of:
1) carbonylating the compound represented by the formula (2) to obtain a compound represented by the formula (3);
2) carrying out nucleophilic substitution reaction on the compound shown in the formula (3) and the compound shown in the formula (4) to generate a quaternary ammonium salt compound shown in the formula (5);
3) reacting a compound of formula (5) with a primary amine compound NH2R4、NH2R5And NH2R6Reacting to generate a compound shown in a formula (1);
Figure BDA0001987453540000052
Figure BDA0001987453540000061
wherein R is1、R2、R3、R4、R5And R6Is as defined above.
According to the preparation method of the present invention, in step 1), the carbonylation of the compound of formula (2) can be achieved by a method conventional in the art, wherein the compound of formula (2) can be commercially available or obtained by chemical synthesis. The reaction conditions for the carbonylation are as follows:
dissolving the compound shown in the formula (2) in an organic solvent (for example, one or more of dichloromethane, chloroform, 1, 2-dichloroethane and toluene can be used, the amount of the organic solvent can be used for example, the concentration of the compound shown in the formula (2) is 0.3-2mol/L), cooling to 0-5 ℃ by an ice bath, and adding ZnCl2Or TiCl4As a catalyst (the amount of the catalyst is 1.2 to 2 times the molar amount of the compound represented by the formula (2)), maintaining the temperature at 0 to 2 ℃, and then adding the carbonylation reagent 1, 1-dichloromethyl etherPreferably, the molar ratio of the compound shown as the formula (2) to the compound is 0.80-0.95:1), slowly adding into the mixed system, continuously stirring for reaction for 5-10min after the dropwise addition is finished, slowly heating to 35 ℃, continuously stirring for 15-30min, slowly pouring the reaction mixture into a flask filled with ice water after the reaction is finished, transferring into a separating funnel, extracting twice with an extracting agent (such as one or more of dichloromethane, chloroform, 1, 2-dichloroethane and toluene) to obtain an organic phase, and then using saturated NaHCO to obtain an organic phase3Washing the organic phase with water solution, evaporating to remove solvent to obtain crude product, and performing column chromatography (using ethyl acetate/petroleum ether at a volume ratio of 1:7 as eluent) to obtain purified compound shown in formula (3) as deep yellow oil phase.
According to the preparation method of the invention, in the step 2), the compound shown in the formula (3) and the compound shown in the formula (4) are subjected to nucleophilic substitution reaction, namely quaternization reaction of tertiary amine. The reaction conditions for the nucleophilic substitution reaction are as follows:
dissolving the compound shown in the formula (4) in a polar organic solvent (such as one or more of ethanol, methanol, acetonitrile, DMF, acetone and nitromethane, wherein the amount of the organic solvent is such that the concentration of the compound shown in the formula (4) is 0.05-0.2mol/L), protecting a reaction mixture with an inert gas (such as carbon dioxide, nitrogen or argon), stirring and heating to a reflux temperature, dropwise adding the compound shown in the formula (3) (the molar ratio of the compound shown in the formula (4) to the compound shown in the formula (3) is 3.1-6) into the mixture, and continuing the reaction for 48-72 hours after the dropwise adding is finished until the reactant reaches a higher conversion rate (the conversion rate of the reaction can be monitored by chromatography or mass spectrometry). After the reaction, the reaction mixture is cooled to room temperature, and the mixture after the reaction is washed by adding a poor solvent for the compound represented by formula (5) and a good solvent for the compound represented by formula (3) (e.g., chloroform, acetone, ethyl acetate, diethyl ether, isopropanol, 1, 2-dichloroethane, preferably acetone or ethyl acetate). And filtering the mixture after washing to obtain filter residue, washing the filter residue for 2-3 times by using the washing reagent, and evaporating the organic solvent after filtering to obtain a yellowish-brown solid crude product. Recrystallizing the crude product with dichloromethane and isopropanol, evaporating the solvent to dryness, and recrystallizing the obtained yellow solid with ethanol and ethyl acetate or ethanol and acetone to obtain light yellow pure product, which is the compound shown in formula (5).
According to the preparation method of the invention, in the step 3), the primary amine compound NH2R4、NH2R5And NH2R6Any compound containing primary amine functional groups that may be commercially available or obtained by chemical synthesis, preferred primary amine compounds may be of the following structure:
Figure BDA0001987453540000071
according to the preparation method of the invention, in the step 3), the reaction is a reaction common in the field, and the reaction has the advantages of mild reaction, high reaction rate, high reaction conversion rate, no side reaction, reversibility under certain conditions and the like. The specific reaction conditions are preferably those which can be carried out in an organic solvent (preferably, such as DMF, DMA, ethanol, methanol and DMSO) or an aqueous phase (preferably, an aqueous alkaline solution), and the temperature of the reaction can be any temperature from subzero to less than 70 ℃. The molar ratio of the reactants is 1:1 (the molar ratio of the compound of formula (5) to the primary amine compound is 1:1), the concentration of the reactants is arbitrary, and the reaction product can be precipitated by evaporating the solvent or adding a poor solvent to obtain a pure product. Specifically, the reaction product of the compound represented by the formula (1) can be obtained by the in situ preparation of the compound represented by the formula (5) and various primary amine compounds.
The invention also provides the application of the compound shown in the formula (1) as a trimeric quaternary ammonium salt surfactant.
Preferably, the trimeric quaternary ammonium salt surfactant is used for washing, emulsification, phase transfer catalyst, micelle catalysis, substance extraction, substance separation, promotion of water drop on a super-hydrophobic surface, and realization of wrapping, slow release, preservation and enrichment of substances.
Preferably, the trimeric quaternary ammonium salt surfactant is used in the fields of medicines, pesticides, perfumes, pigment dyes or foods and the like.
Preferably, the trimeric quaternary ammonium surfactant can be used as a carrier of medicines and active organic substances (such as pesticides, dyes and perfumes) or used for the formulation of medicines and active substances. In particular, the drug and active substance may be hydrophobic, hydrophilic, acid-labile and combinations of various active substances; in particular, the support is nanoized; in particular, the formulations may release the active substance under specific conditions and may be used as sustained release formulations of the active substance.
Preferably, the trimeric quaternary ammonium surfactant acts as a highly efficient spreading agent to control the impact spreading of aqueous droplets on superhydrophobic surfaces.
Preferably, the trimeric quaternary ammonium salt surfactant can be used for a nano pesticide formulation to increase the absorption efficiency of a pesticide, and particularly, the nano pesticide can be naturally degraded under an environmental condition, thereby gradually releasing an active substance and being used for slow release of the nano pesticide.
Preferably, the trimeric quaternary ammonium salt surfactant can be used for improving the deposition of the pesticide in the spraying process and prolonging the retention time of the pesticide on the surface of the plant leaf, so that the utilization rate of the pesticide is increased, the loss of the pesticide is reduced, and the pollution of pesticide application to the environment is reduced.
The invention also provides a preparation which comprises the compound shown in the formula (1).
According to the present invention, the preparation may be a drug, a pesticide (nano pesticide), a perfume, a pigment dye, a food additive, a detergent, an emulsifier, a phase transfer catalyst, a micelle catalyst, a substance extractant, etc.
The invention also provides an intermediate, which has a structure shown in a formula (5):
Figure BDA0001987453540000081
wherein R is1、R2And R3Is as defined above.
The present invention also provides a method for producing an intermediate represented by the above formula (5), the method comprising the steps of:
1) carbonylating the compound represented by the formula (2) to obtain a compound represented by the formula (3);
2) carrying out nucleophilic substitution reaction on the compound shown in the formula (3) and the compound shown in the formula (4) to generate a quaternary ammonium salt compound shown in the formula (5);
Figure BDA0001987453540000082
Figure BDA0001987453540000091
wherein R is1、R2And R3Is as defined above.
The invention also provides application of the intermediate shown in the formula (5) to preparation of the compound shown in the formula (1).
Terms and explanations:
liquid-liquid phase separation: refers to the phenomenon that a homogeneous phase colloidal solution spontaneously separates phases to form incompatible two phases; one phase contains less colloidal substances called dilute phase, the other phase contains more colloidal substances called condensed phase, and the condensed phase contains hydrophilic and hydrophobic micro-regions with different polarities, so that substances with different polarities can be adsorbed and coated.
As used herein, the following terms and phrases are intended to have the following meanings, unless otherwise indicated. A particular term or phrase, unless specifically defined, should not be considered as indefinite or unclear, but rather construed according to ordinary meaning. When a trade name appears herein, it is intended to refer to its corresponding commodity or its active ingredient.
Unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.
Wherein "more" means three or more.
The term "halogen" refers to F, Cl, Br and I. In other words, F, Cl, Br, and I may be described as "halogen" in the present specification.
The term "C1-20Alkyl is understood to preferably mean a straight-chain saturated monovalent hydrocarbon radical having from 1 to 20 carbon atoms, preferably C1-18An alkyl group. "C1-18Alkyl "is understood to preferably denote a straight-chain saturated monovalent hydrocarbon radical having 1,2, 3,4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl and the like.
The term "C2-12Alkenyl "is understood to preferably mean a straight-chain monovalent hydrocarbon radical comprising one or more double bonds and having from 2 to 12 carbon atoms, preferably" C2-10Alkenyl ". "C2-10Alkenyl "is understood to preferably mean a straight-chain monovalent hydrocarbon radical which contains one or more double bonds and has 2, 3,4, 5,6, 7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms (" C)2-3Alkenyl "), it being understood that in the case where the alkenyl group comprises more than one double bond, the double bonds may be separated from each other or conjugated. The alkenyl group is, for example, vinyl, allyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (Z) -pent-2-enyl, (E) -pent-1-enyl, (Z) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, (E) -hex-3-enyl, m-E-1-enyl, m-E-n-4-enyl, m-E-n-2-enyl, m-E-n-1-enyl, m-n-yl, m-n-1-enyl, m-E-4-enyl, m-pent-3-enyl, m-yl, m-2-enyl, m-pent-3-2-enyl, m-yl, m-pent-2-enyl, m-1-enyl, m-pent-2-enyl, m-pent-2-enyl, m-pent-enyl, m-2-enyl, m-pent-2-enyl, m-pent-2-enyl, m-2-enyl, m-pent-2-enyl, m-2-enyl, m-pent-2-enyl, m-2, m-enyl, m-2, m-enyl, m-2, m, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E) -hex-1-enyl, (Z) -hex-1-enyl.
The term "C2-12Alkynyl "is understood to mean a straight-chain monovalent hydrocarbon radical comprising one or more triple bonds and having from 2 to 12 carbon atoms, preferably" C2-C10Alkynyl ". The term "C2-C10Alkynyl "is understood as preferably meaning a straight-chain monovalent hydrocarbon radical which contains one or more triple bonds and has a structure of 2, 3,4. 5,6, 7, 8, 9 or 10 carbon atoms, in particular 2 or 3 carbon atoms ("C)2-C3-alkynyl "). The alkynyl group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl.
The term "C3-20Cycloalkyl is understood to mean a saturated or unsaturated, monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C3-10Cycloalkyl groups ". The term "C3-10Cycloalkyl "is understood to mean a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3,4, 5,6, 7, 8, 9 or 10 carbon atoms. Said C is3-10Cycloalkyl groups may be monocyclic hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic hydrocarbon groups such as decalin rings.
The term "3-20 membered heterocyclyl" means a saturated or unsaturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5 heteroatoms independently selected from N, O and S, preferably "3-10 membered heterocyclyl". The term "3-10 membered heterocyclyl" means a saturated monovalent monocyclic or bicyclic hydrocarbon ring comprising 1-5, preferably 1-3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the rest of the molecule through any of the carbon atoms or nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclyl group may be bicyclic, for example but not limited to a 5,5 membered ring, such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring, such as a hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydrooxazolyl, or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic radical is non-aromatic.
The term "C6-20Aryl "is understood to preferably mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6 to 20 carbon atoms, preferably" C6-14Aryl ". The term "C6-14Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C6-14Aryl group "), in particular a ring having 6 carbon atoms (" C6Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C9Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C10Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C13Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C)14Aryl), such as anthracenyl.
The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and comprising 1 to 5 heteroatoms independently selected from N, O and S, such as "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5,6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which comprises 1 to 5, preferably 1 to 3, heteroatoms each independently selected from N, O and S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl, and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g., positional isomers thereof. Thus, for some illustrative, non-limiting examples, pyridyl or pyridinylene includes pyridin-2-yl, pyridinylene-2-yl, pyridin-3-yl, pyridinylene-3-yl, pyridin-4-yl, and pyridinylene-4-yl; thienyl or thienylene includes thien-2-yl, thien-3-yl and thien-3-yl.
"hetero" denotes a heteroatom or group of heteroatoms, each independently selected from-O-, -S-, - (O), (S), -O-N-, -C (O) O-, -C (O) -, -C (S) -, -S (O)2-,-S(＝O)-,-C(＝O)NH-,-NH-,-C(＝NH)-,-S(＝O)2NH-, -S (═ O) NH-and-NHC (═ O) NH-, -P-, -P (═ O) Me2In any of the above cases, the number of heteroatoms or groups of heteroatoms is independently selected from 1,2 or 3.
The invention has the beneficial effects that:
1. the trimeric cationic quaternary ammonium salt compound is obtained by simple quaternization reaction of alkyl halide containing benzaldehyde and tertiary amine, and the trimeric quaternary ammonium salt head group and various amino-containing substances can be obtained at room temperature to obtain trimeric quaternary ammonium salt compounds with various structures and properties.
2. The trimeric cationic quaternary ammonium salt compound of the invention can be used in acid or CO2Dissociating under the action of the enzyme. The quaternary ammonium salt compound can be used as a surfactant, has good surface activity and aggregation behavior, and can be applied to washing, emulsification, phase transfer catalysts and glueThe method comprises the following steps of beam catalysis, substance extraction and substance separation, and promotes water drops to spread on a super-hydrophobic surface.
3. The trimeric cationic quaternary ammonium salt compound can be prepared into different preparations, and the preparations can be medicines, pesticides, spices, pigment dyes, food additives, detergents, emulsifiers, phase transfer catalysts, micelle catalysts, substance extractants and the like; taking pesticides, particularly nano pesticides as an example, the nano pesticides can impact on a super-hydrophobic surface without sputtering and rebound. The nano pesticide can also have good rain erosion resistance on the surface of the super-hydrophobic cabbage leaf, and gradually dissociates on the surface of the leaf to release active substances, so that a slow release effect is achieved. The nano pesticide prepared by the trimeric quaternary ammonium salt compound can greatly improve the use efficiency of the pesticide in four aspects of spraying, rain wash, absorption efficiency, action period and the like.
Drawings
FIG. 1 is NMR of 4- (3-bromopropyl) -benzaldehyde of preparation example 11H NMR spectrum.
FIG. 2 is NMR of 4- (3-bromopropyl) -benzaldehyde of preparation example 113C NMR spectrum.
FIG. 3 is an EI mass spectrum of 4- (3-bromopropyl) -benzaldehyde of preparation example 1.
FIG. 4 shows TDA- (PhC ═ O) of preparation 23Nuclear magnetic resonance of1H NMR spectrum.
FIG. 5 shows TDA- (PhC ═ O) of preparation 23Nuclear magnetic resonance of13C NMR spectrum.
FIG. 6 shows TDA- (PhC ═ O) of preparation 23The spectrum of the high-resolution ESI mass spectrum.
FIG. 7 shows TDA- (Imine C7) of example 13Nuclear magnetic resonance1H NMR spectrum.
FIG. 8 shows TDA- (Imine C7) in example 13Nuclear magnetic resonance after dissociation at pH 6.61H NMR spectrum.
FIG. 9 shows the results of example 2TDA-(Imine C8)3Nuclear magnetic resonance1H NMR spectrum.
FIG. 10 shows TDA- (Imine C8) in example 23Nuclear magnetic resonance after dissociation at pH 6.61H NMR spectrum.
FIG. 11 shows TDA- (Imine C10) of example 33Nuclear magnetic resonance1H NMR spectrum.
FIG. 12 shows TDA- (Imine C10) of example 33Nuclear magnetic resonance after dissociation at pH 6.61H NMR spectrum.
FIG. 13 shows TDA- (Imine C7) of example 13And its surface tension curve after dissociation at pH 4.0.
FIG. 14 shows TDA- (Imine C8) of example 23And its surface tension curve after dissociation at pH 4.0.
FIG. 15 shows TDA- (Imine C10) of example 33And its surface tension profile after dissociation at pH 6.6 and pH 4.0.
FIG. 16 shows TDA- (Imine C10) in example 43Liquid-liquid phase separation microscope picture at 5 mmol/L.
FIG. 17 shows TDA- (Imine C10) in example 43And (3) carrying out liquid-liquid phase separation on the microscope picture of the hydrophobic pesticide buprofezin.
FIG. 18 shows TDA- (Imine C10) of example 63Liquid-liquid phase separation entrapping water-soluble fluorescein in CO2Release profile at acceleration.
FIG. 19 shows TDA- (Imine C10) of example 73The process of impact spreading of the liquid-liquid phase separation aqueous solution on the super-hydrophobic substrate.
FIG. 20 shows TDA- (Imine C10) of example 83And (3) carrying out liquid-liquid phase separation on the impact spreading process of the aqueous solution of the fluorescein with different concentrations on the super-hydrophobic substrate.
FIG. 21 is a photograph of the contact angle of the surface of the superhydrophobic substrate prepared using the superhydrophobic coating in examples 7 and 8.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Preparation example 1 preparation of 4- (3-bromopropyl) -benzaldehyde raw material
Figure BDA0001987453540000131
20g (100mmol) of 1-bromo-3-phenylpropane are dissolved in 120mL of dichloromethane, cooled to 0-5 ℃ in an ice bath and 28.45g (150mmol) of TiCl are added4Keeping the temperature at 0-2 ℃ as a catalyst, slowly dropwise adding a carbonylation reagent of 1, 1-dichloromethyl ether 10.44(90mmol) into a mixed system, continuously stirring for reaction for 5min after dropwise adding, slowly heating to 35 ℃, continuously stirring for 15min, slowly pouring a reaction mixture into a flask filled with ice water after reaction, transferring the flask into a separating funnel, extracting twice with dichloromethane to obtain an organic phase, and then using saturated NaHCO3The organic phase is washed with an aqueous solution, the solvent is evaporated to obtain a crude product, and the crude product is subjected to column chromatography (the volume ratio of ethyl acetate to petroleum ether is 1:7 as an eluent) to obtain 12.26g of purified 4- (3-bromopropyl) -benzaldehyde, which is a dark yellow oil phase. The yield thereof was found to be 60%.
The detection results are as follows:
1H-NMR(CDCl3):δ9.98(s,1H),7.83(d,2H,J＝8.3Hz),7.38(d,2H,J＝8.1Hz),3.39(t,2H,J＝6.3Hz),2.87(t,2H,J＝7.4Hz),2.19(m,2H)；
13C-NMR(CDCl3):δ191.5(CHO),147.7(Ar-C),134.4(Ar-C),129.7(Ar-CH),128.9(ArCH),33.8(CH2),33.3(CH2),32.5(CH2)；
MS(EI+)m/z[M+H]+C10H12calculated BrO molecular ion peaks: 227.0066, respectively; measured value: 226,228.1H NMR，13The results of C-NMR and MS-EI showed that the product was identical to the target product.
Preparation 2. Quaternary ammonium salt Compound TDA- (PhC ═ O)3Preparation of
Figure BDA0001987453540000141
After dissolving 2.76g (12mmol) of tris- (2-dimethylaminoethyl) amine in 120ml of a mixed solvent of ethanol and acetone 1:5, protecting the reaction mixture with nitrogen, stirring and heating to reflux temperature, 10.896g (48mmol) of the starting 4- (3-bromopropyl) -benzaldehyde is added dropwise to the mixture and the reaction is continued for 48h after the dropwise addition is completed until the reaction mass reaches a higher conversion (the conversion of the reaction is monitored by mass spectrometry). After completion of the reaction, the reaction mixture was cooled to room temperature, and acetone was added to wash the reacted mixture. And filtering the mixture after washing to obtain filter residue, washing the filter residue for 3 times by using the washing reagent, and evaporating the organic solvent after filtering to obtain a yellowish-brown solid crude product. The crude product was recrystallized from dichloromethane and isopropanol, and the solvent was evaporated to dryness, and the obtained yellow solid was further recrystallized from ethanol and acetone to obtain a pale yellow pure product 4.38g (4.8mmol) which was the compound of formula (5), TDA- (PhC ═ O)3The yield thereof was found to be 40%.
The detection results are as follows:
1H NMR(D2O,400MHz,ppm):δ9.84(s,3H,CHO),7.87(d,6H,CH),7.46(d,6H,CH),3.38(m,12H,N+-CH2-N,N+-CH2-Ar),3.09(s,18H,N+-CH3),3.00
13C NMR(400MHz,D2O):δ195.84,148.27,134.16,130.52,129.26,64.23,60.48,51.09,46.62,31.60,23.44.
HRMS-ESI(m/z):C42H63N4O3Br3[M]calculated molecular ion peaks: 911.7, respectively; found 223.8[ M-3Br-]3+/3)；376.2[M-2Br-]2+/2)；831.7[M-Br-]+)。
1H NMR，13The results of C-NMR and HRMS-ESI show that the product is consistent with the target product.
EXAMPLE 1 trimeric quaternary surfactant TDA- (Imine C7)3Preparation of the aqueous solution
The compound prepared in preparation example 2 and heptamine are directly mixed in a 1:3 molar ratio in an alkaline aqueous solution to prepare a uniform solution, and the mixed solution can be directly used as a surfactant solution for testing and use.
Surface tension test: the surface tension was measured by increasing the concentration by the hanging strip method, and the pH of all solutions was fixed at 12.5 and the temperature was maintained at 25 ℃ in order to completely convert the imine bond of the surfactant. TDA- (Imine C7) is obtained by performing surface tension-concentration logarithm (gamma-logc) curve and defining the turning point of the curve as critical aggregation concentration (CMC) of the surfactant3The critical aggregation concentration is 0.1mmol/L, which is one twentieth of the critical aggregation concentration (2.0mmol/L) of the Gemini surfactant with the corresponding structure, and the surface tension after CMC is 31.5 +/-0.2 mN/m.
And (3) dissociative behavior test: in the water phase, imine bonds are mostly stable under alkaline conditions, and exchange and dissociation can occur under neutral and acidic conditions, so that the surfactant in the invention can be dissociated under a specific pH value through the structural design. The dissociation behavior can be determined by nuclear magnetic and/or surface tension testing. The dissociation operation is carried out by introducing carbon dioxide into a deuterated aqueous solution of the surfactant to lower the pH of the solution. Controlling the introduction of CO2The duration is long, solutions with different pH values can be obtained, and the dissociation degree of the surfactant can be obtained by testing the nuclear magnetic hydrogen spectrum under the pH value; the surface tension test can obtain the CMC at the pH, thereby indirectly obtaining the dissociation degree of the surfactant. And tests show that the surface tension method has higher sensitivity compared with the nuclear magnetic method for the surfactant. The surfactant was tested to completely dissociate at pH 4.0 and to essentially complete dissociation at pH 6.6.
EXAMPLE 2 trimeric quaternary surfactant TDA- (Imine C8)3Preparation of an aqueous solution:
preparation of Triquaternized ammonium salt surfactant TDA- (Imine C8) according to the preparation method of example 13Aqueous solution, except that the heptylamine in example 1 was replaced with octylamine.
Surface tension test: the testing and characterization method is the same as that in example 1, the critical aggregation concentration CMC of the obtained surfactant is 5.5 mu mol/L, which is lower than the CMC (1.5mmol/L) of the corresponding Gemini surfactant by more than 2 orders of magnitude, and the surface tension value after CMC is 30.0 +/-0.5 mN/m.
And (3) dissociative behavior test: the test characterization method is the same as example 1, the complete dissociation pH is 4.0, and the surfactant is basically dissociated at pH 6.6.
EXAMPLE 3 trimeric quaternary surfactant TDA- (Imine C10)3Preparation of an aqueous solution:
preparation of Triquaternized ammonium salt surfactant TDA- (Imine C8) according to the preparation method of example 13Aqueous solution, except that the heptylamine in example 1 was replaced with decylamine.
Surface tension test: the testing and characterizing method is the same as that of the example 1, the critical aggregation concentration CMC of the obtained surfactant is 1.5 mu mmol/L, and the surface tension of the CMC is 30.0 +/-0.5 mN/m.
And (3) dissociative behavior test: the test characterization method is the same as example 1, the complete dissociation pH is 4.0, and the surfactant is basically dissociated at pH 6.6.
EXAMPLE 4 trimeric quaternary surfactant TDA- (Imine C10)3Liquid-liquid phase separation for carrying performance test of hydrophobic organic matters:
when the loading capacity is lower than the maximum loading capacity, the loading efficiency of the hydrophobic organic matter in the liquid-liquid phase aqueous solution can reach more than 99 percent, so the maximum loading capacity of the hydrophobic active substance is tested for the loading behavior of the hydrophobic active substance.
Preferably, the liquid-liquid phase separation solution when the concentration of the surfactant solution is 5.0mmol/L is used as an occlusion carrier of the active substance, and the pesticide buprofezin is used as the occlusion carrier of the hydrophobic active substance. The occlusion capacity was determined as follows: adding a certain mass of excess (not less than 0.5 wt%) buprofezin solid into a certain volume (not less than 5mL) of liquid-liquid phase separation solution, and stirring at room temperature for 36h until the solution is balanced. And (3) taking medium-speed precision filter paper, filtering the solution after the dissolution balance, washing with water, combining the solutions, fixing the volume to a certain volume, and testing the content of sulfur in the sample by ICP-MS (inductively coupled plasma-mass spectrometry) so as to determine the content of the buprofezin. As a result, the maximum amount of the buprofezin encapsulated in the surfactant liquid-liquid phase separation solution was found to be 11.5 wt% (the amount of the encapsulated buprofezin was defined as the mass of the encapsulated buprofezin relative to the mass of the surfactant as the carrier).
EXAMPLE 5 trimeric quaternary surfactant TDA- (Imine C10)3Liquid-liquid phase separation entrapment Performance test for hydrophilic substances:
for the entrapment of water-soluble substances in liquid-liquid phase separation, entrapment efficiency is an important index, and different aqueous solutions for liquid-liquid phase separation generally have larger difference in entrapment efficiency for water-soluble organic substances because the water-soluble organic substances can be distributed in both the aqueous phase and the surfactant coacervate phase. Therefore, the encapsulating capacity and the encapsulating efficiency of the water-soluble organic matter are tested simultaneously for the encapsulating behavior of the water-soluble organic matter.
Preferably, the liquid-liquid phase separation solution at a concentration of 5.0mmol/L of the surfactant solution is used as a carrier for the active material to be occluded, and the water-soluble dye fluorescein is selected as an object to be occluded for the water-soluble active material.
The entrapment efficiency and the entrapment amount of the water-soluble organic matter can be simultaneously measured, and the operation is as follows: adding a certain amount of fluorescein into a liquid-liquid phase separation solution with a certain volume (not less than 3mL), stirring at room temperature for 36h until the solution is balanced, centrifuging and separating out a supernatant, testing the absorbance of the fluorescein in the supernatant by an ultraviolet-visible spectrophotometry, and comparing with a standard curve under the same pH value to obtain the concentration of the fluorescein in the supernatant.
The packing efficiency is calculated as: 100-concentration of fluorescein in supernatant/concentration of added fluorescein 100%.
The amount of entrapment was calculated as: mass of added fluorescein x entrapment efficiency.
According to the characterization method, the encapsulation efficiency of the surfactant to fluorescein with any concentration below the maximum encapsulation amount is over 93%, and the encapsulation efficiency to fluorescein with the concentration of 1mmol/L reaches 98%. The maximum loading was measured to be 7.52%.
EXAMPLE 6 trimeric quaternary surfactant TDA- (Imine C10)3And (3) testing the release performance of the liquid-liquid phase separation encapsulated water-soluble fluorescein:
the test method and the operation are as follows: adding trimeric quaternary ammonium salt surfactant TDA- (Imine C10)3Mixing the liquid-liquid phase separation water solution and fluorescein, stirring until the fluorescein is basically wrapped in the liquid-liquid phase, filling the solution into a dialysis bag, taking pure water as a slow release medium, and introducing CO2Sampling at certain time intervals as a dissociation reagent, and testing the concentration of fluorescein in the sample by adopting an ultraviolet-visible spectrophotometry so as to obtain the release rate. The experiment was stopped when the release rates before and after the release were substantially unchanged.
Testing specific parameters: regulating the pH value to 12.5 by using surfactant with the concentration of 5.0mmol/L and fluorescein with the concentration of 0.3 mmol/L; the volume ratio of the solution to the slow-release medium in the dialysis bag is 1:20, 3mL of the solution is sampled every time, and 3mL of pure water is newly added.
The calibration curve was obtained by measuring the absorbance of a series of standard concentrations of fluorescein in pH 9.2 sodium phosphate buffer solution, adjusting the pH of the sample to 9.2 after each sample (by mixing the sample solution with 0.2mol/L Na)2HPO41:1) and then performing an absorbance test, and comparing with a standard curve to obtain the concentration of the fluorescein in the release medium.
The impact of the liquid drops on the super-hydrophobic substrate is implemented according to the following method: the substrate was placed horizontally (cabbage leaves were fixed by tape and laid flat on a glass plate), a syringe (needle inner diameter 0.17mm) containing the solution (stirred well) was placed directly above the substrate (needle height 30cm from substrate) and placed vertically, the droplets were controlled in extrusion speed and volume by an injection pump so that the extruded droplets had a volume of 40 μ L and a diameter of 1.8mm, and the impact of the droplets was recorded and analyzed by a high-speed camera.
EXAMPLE 7 trimeric quaternary surfactant TDA- (Imine C10)3Impact behavior of liquid-liquid phase separated aqueous solution on superhydrophobic substrate test:
the surfactant was used at a concentration of 5.0mmol/L (0.66 wt% based on the aqueous solution) and a pH of 12.5, and as a result, the surfactant had a good effect of suppressing impact sputtering and rebound of water droplets on the superhydrophobic surface.
EXAMPLE 8 trimeric quaternary surfactant TDA- (Imine C10)3And (3) performing impact behavior test on the super-hydrophobic substrate by using the aqueous solution of the liquid-liquid phase separation entrapping fluorescein.
The surfactant was used at a concentration of 5.0mmol/L (0.66% by mass of the aqueous solution), a pH of 12.5, and an entrapped fluorescein concentration of 0.5mmol/L or 1.0mmol/L (2.5% and 5.0% by mass of the surfactant, respectively), which resulted in good impact spreading on the superhydrophobic substrate.
Fig. 21 is a contact angle photograph of 157 ° for the surface of the superhydrophobic substrate prepared using the superhydrophobic coating in examples 7 and 8.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (15)

1. A compound represented by the following formula (1-1):
Figure FDA0003172682480000011
wherein n is an integer of 7 to 10, and n-2 represents-CH in parentheses2-the number of the cells.
2. The compound of claim 1, wherein the compound of formula (1-1) has the following structure:
Figure FDA0003172682480000012
Figure FDA0003172682480000021
3. a process for producing a compound represented by the formula (1-1) as claimed in any one of claims 1 to 2, comprising the steps of:
1) subjecting the compound represented by the formula (2-1) to carbonylation treatment to obtain a compound represented by the formula (3-1);
2) carrying out nucleophilic substitution reaction on the compound shown in the formula (3-1) and the compound shown in the formula (4) to generate a quaternary ammonium salt compound shown in the formula (5-1);
3) reacting a compound of the formula (5-1) with a primary amine compound NH2CH2(CH2)n-2CH3Reacting to generate a compound shown as a formula (1-1), wherein n is defined as the claim 1;
Figure FDA0003172682480000031
4. the process of claim 3, wherein in step 1), the reaction conditions for the carbonylation are as follows:
dissolving the compound shown in the formula (2-1) in an organic solvent, cooling to 0-5 ℃ in an ice bath, and adding ZnCl2Or TiCl4Slowly adding catalyst dropwise into the mixed system, continuously stirring for 5-10min after dropwise adding, slowly heating to 35 deg.C, continuously stirring for 15-30min, slowly pouring the reaction mixture into a flask containing ice water, transferring into a separating funnel, extracting twice with extractant to obtain organic phase, and adding saturated NaHCO3Washing the organic phase with water solution, evaporating to remove solvent to obtain crude product, and performing column chromatography to obtain purified compound shown in formula (3-1).
5. The method according to claim 3, wherein in step 2), the reaction conditions of the nucleophilic substitution reaction are as follows:
dissolving the compound shown in the formula (4) in a polar organic solvent, protecting a reaction mixture with inert gas, stirring and heating to a reflux temperature, dropwise adding the compound shown in the formula (3-1) into the mixture, and continuing to react for 48-72 hours after dropwise adding until the reactant reaches a higher conversion rate; after the reaction is completed, cooling the reaction mixture to room temperature, adding a poor solvent for the compound represented by the formula (5-1) and a good solvent for the compound represented by the formula (3-1) to wash the reacted mixture; filtering the mixture after washing to obtain filter residue, washing the filter residue for 2-3 times by using the washing reagent, and evaporating the organic solvent after filtering to obtain a yellowish-brown solid crude product; recrystallizing the crude product with dichloromethane and isopropanol, evaporating the solvent to dryness, and recrystallizing the obtained yellow solid with ethanol and ethyl acetate or ethanol and acetone to obtain light yellow pure product, which is the compound shown in formula (5-1).
6. Use of a compound of formula (1-1) according to any one of claims 1-2 as a trimeric quaternary surfactant.
7. The use according to claim 6, wherein the trimeric quaternary ammonium surfactant is used for washing, emulsification, phase transfer catalysts, micelle catalysis, substance extraction, substance separation, promoting water droplets on superhydrophobic surfaces, and for achieving encapsulation, slow release, preservation and enrichment of substances.
8. Use according to claim 6, wherein the trimeric quaternary ammonium surfactant is used in the pharmaceutical, agrochemical, fragrance, pigment dye or food field.
9. Use according to claim 6, wherein the trimeric quaternary ammonium surfactant is used as a carrier for drugs and active organic substances, or in formulations for drugs and active substances, wherein the drugs and active substances are hydrophobic, hydrophilic, acid-labile and combinations of various active substances.
10. Use according to claim 6, wherein the trimeric quaternary ammonium surfactant acts as a high efficiency spreading agent controlling the impact spreading of aqueous droplets on superhydrophobic surfaces.
11. A formulation comprising a compound of formula (1-1) according to any one of claims 1-2.
12. The formulation of claim 11, wherein the formulation is at least one of a drug, a pesticide, a fragrance, a pigment dye, a food additive, a detergent, an emulsifier, a phase transfer catalyst, a micelle catalyst, or a material extractant.
13. An intermediate having the structure of formula (5-1):
Figure FDA0003172682480000041
14. a process for the preparation of the intermediate of claim 13, comprising the steps of:
1) subjecting the compound represented by the formula (2-1) to carbonylation treatment to obtain a compound represented by the formula (3-1);
2) carrying out nucleophilic substitution reaction on the compound shown in the formula (3-1) and the compound shown in the formula (4) to generate a quaternary ammonium salt compound shown in the formula (5-1);
Figure FDA0003172682480000042
Figure FDA0003172682480000051
15. use of the intermediate of claim 13 for the preparation of a compound represented by formula (1-1) of claim 1.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003335780A (en) * 2002-05-16 2003-11-28 Mitsubishi Chemicals Corp Quaternary ammonium salt having spirochirality and its utilization
CN103193673A (en) * 2013-03-19 2013-07-10 淮海工学院 Quaternary ammonium salt (salicylidene amino acid) supported functional ligand and preparation method thereof
CN103435623A (en) * 2013-09-05 2013-12-11 中国科学院长春应用化学研究所 Metalloporphyrin complex and preparation method thereof, and preparation method of polycarbonate
CN104927053A (en) * 2014-03-18 2015-09-23 富士施乐株式会社 Polyimide precursor composition, method for manufacturing polyimide molded body, and polyimide molded body
CN108314763A (en) * 2017-01-17 2018-07-24 中国科学院化学研究所 A kind of dynamic based on oxime can repair polyurethane and preparation method thereof
CN109160885A (en) * 2018-08-08 2019-01-08 百合花集团股份有限公司 Fatty acid type quaternary cationics and the preparation method and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1170356A1 (en) * 2000-07-06 2002-01-09 The Procter & Gamble Company Laundry additive sachet
US7875318B2 (en) * 2007-04-24 2011-01-25 Momentive Performance Materials Inc. Method of applying an anti-corrosion and/or adhesion promoting coating to a metal and resulting coated metal
CN103125510A (en) * 2013-03-22 2013-06-05 广州市医德生物科技有限责任公司 Compound phthalic dicarboxaldehyde polyquaternium cationic surface active agent disinfectant and preparation and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003335780A (en) * 2002-05-16 2003-11-28 Mitsubishi Chemicals Corp Quaternary ammonium salt having spirochirality and its utilization
CN103193673A (en) * 2013-03-19 2013-07-10 淮海工学院 Quaternary ammonium salt (salicylidene amino acid) supported functional ligand and preparation method thereof
CN103435623A (en) * 2013-09-05 2013-12-11 中国科学院长春应用化学研究所 Metalloporphyrin complex and preparation method thereof, and preparation method of polycarbonate
CN104927053A (en) * 2014-03-18 2015-09-23 富士施乐株式会社 Polyimide precursor composition, method for manufacturing polyimide molded body, and polyimide molded body
CN108314763A (en) * 2017-01-17 2018-07-24 中国科学院化学研究所 A kind of dynamic based on oxime can repair polyurethane and preparation method thereof
CN109160885A (en) * 2018-08-08 2019-01-08 百合花集团股份有限公司 Fatty acid type quaternary cationics and the preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Responsive Wormlike Micelles from Dynamic Covalent Surfactants;Christophe B. Minkenberg，等;《Langmuir》;20120808;第28卷(第38期);第13571页右栏反应式1，摘要，第13571页右栏反应式1，第13570页右栏倒数第1段-第13571页左栏第3段，第13575页右栏第1段 *
Star-Shaped Trimeric Quaternary Ammonium Bromide Surfactants: Adsorption and Aggregation Properties;Tomokazu Yoshimura，等;《Langmuir》;20120529;第28卷(第25期);第9323页左栏图1 *

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