CN110105284A - Cashew nut phenol quaternary ammonium salt and application thereof - Google Patents
Cashew nut phenol quaternary ammonium salt and application thereof Download PDFInfo
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- CN110105284A CN110105284A CN201910460348.1A CN201910460348A CN110105284A CN 110105284 A CN110105284 A CN 110105284A CN 201910460348 A CN201910460348 A CN 201910460348A CN 110105284 A CN110105284 A CN 110105284A
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract
The present invention relates to a kind of cashew nut phenol quaternary ammonium salt and application thereof, the cashew nut phenol quaternary ammonium salt its be compound shown in Formulas I.Cashew nut phenol quaternary ammonium salt provided by the invention can be used as the application of the antibacterial agent of cationic surfactant and/or anti-Staphylococcus aureus, bacillus subtilis or Escherichia coli.In Formulas I, R is the C replaced3~C6Chain alkyl；X is halogen (F, Cl, Br or I) anion；M (even if entire molecule is electroneutral) identical as the positively charged number of institute in R；The substituted C3~C6The substituent group of chain alkyl is selected from: hydroxyl, it is one or more kinds of in 5~6 member heterocyclic ring containing nitrogen quaternary ammonium salt bases or 5~6 substituted member heterocyclic ring containing nitrogen quaternary ammonium salt bases, and the substituent group at least contains 5~6 member heterocyclic ring containing nitrogen quaternary ammonium salt bases or 5~6 substituted member heterocyclic ring containing nitrogen quaternary ammonium salt bases；Wherein, the substituent group of 5~6 substituted member heterocyclic ring containing nitrogen quaternary ammonium salt bases is C1~C6Linear chain or branched chain alkyl.
Description
Technical field
The present invention relates to a kind of cashew nut phenol quaternary ammonium salts and application thereof, specifically, being related to a kind of cashew nut phenols nitrogen-containing hetero
Ring-like quaternary ammonium salt and its application as cationic surfactant and/or antibacterial agent.
Background technique
Anacardol (Cardanol) is obtained by refining in natural cashew nut shell oil, is that a kind of renewable and biodegradability is good
Good natural resources.Since the monomer molecule of anacardol has a variety of functional groups that can be used for chemical derivatization, such as phenolic hydroxyl group, benzene
Carbon-carbon double bond on ring and carbon long-chain, therefore anacardol is a molecular structure very with derivative potentiality.
So far, the surfactant synthesized using anacardol as starting material is mostly nonionic surfactant and anion
Surfactant (rarely seen cationic surfactant).Therefore, it is necessary to which developing a kind of novel can improve surfactant
The derivative obtained cationic surfactant of anacardol of surface property and anti-microbial property (this also becomes the present invention and needs to solve
The technical issues of).
Summary of the invention
The present inventor designs through extensive and in-depth study and prepares a kind of cashew nut phenols quarternary ammonium salt compound.
It finds after tested, cashew nut phenols quarternary ammonium salt compound disclosed by the invention has good surface property, can be used as cation form
Face activating agent.In addition, finding through antibacterial test, cashew nut phenol quaternary ammonium salt of the present invention has sterilization (especially gram-positive bacteria)
Activity can be used as fungicide (or antibacterial agent).
It is an advantage of the invention to provide a kind of cashew nut phenol quaternary ammonium salts of structure novel.
Cashew nut phenol quaternary ammonium salt of the present invention is compound shown in Formulas I:
In Formulas I, R is the C replaced3~C6Chain alkyl；X is halogen (F, Cl, Br or I) anion；Institute is positively charged in m and R
Number is identical (even if entire molecule is electroneutral)；
The substituted C3~C6The substituent group of chain alkyl is selected from: hydroxyl (OH), 5~6 yuan of nitrogenous (N) heterocyclic quaternary ammonium salt
(containing two kinds) one or more kinds of in base or substituted 5~6 yuan of nitrogenous (N) heterocyclic quaternary ammonium alkali, and the substituent group (replaces
C3~C6The substituent group of chain alkyl) it is at least nitrogenous containing one 5~6 yuan nitrogenous (N) heterocyclic quaternary ammonium alkali or substituted 5~6 yuan
(N) heterocyclic quaternary ammonium alkali；
Wherein, the substituent group of nitrogenous (N) the heterocyclic quaternary ammonium alkali in substituted 5~6 yuan is C1~C6Linear chain or branched chain
Alkyl.
It is another object of the present invention to disclose a kind of use of above-mentioned cashew nut phenol quaternary ammonium salt (compound shown in Formulas I)
On the way, i.e., application of the above-mentioned cashew nut phenol quaternary ammonium salt (compound shown in Formulas I) as cationic surfactant and/or antibacterial agent.
In addition, a further object of the invention is, provides and a kind of prepare above-mentioned cashew nut phenol quaternary ammonium salt (Formulas I shownization
Close object) method, described method includes following steps:
(1) as anacardol (compound shown in Formula II) and corresponding halogenated hydrocarbons (YAY) or halogenated epoxideReaction, the step of obtaining intermediate (formula III or IV shown in compound)；
(2) as intermediate (formula III or IV shown in compound) and corresponding quaternary ammonium salt or nitrogen-containing heterocycle reactant salt, mesh is made
The step of marking object (compound shown in Formulas I).
Wherein, A is the C of divalent3~C6Chain alkyl, Y are halogen (F, Cl, Br or I), the integer that n is 1~4.Used
Starting material (anacardol, compound shown in Formula II), halogenated hydrocarbons (YAY) and halogenated epoxideIt is knownization
Object is closed, it can directly commercially available acquisition or obtained by the method for existing literature report.
Detailed description of the invention
Fig. 1 is the signal of the water contact angle of cashew nut phenol quaternary ammonium salt disclosed by the invention (compound shown in Formulas I a~Ie)
Figure；
Fig. 2 is the surface tension concentration curve for being cashew nut phenol quaternary ammonium salt of the invention (compound shown in Formulas I a~Ie).
Specific embodiment
In a preferred technical solution of the invention, R is the C replaced3~C6Chain alkyl；The integer that m is 1~4；
The substituted C3~C6The substituent group of chain alkyl is selected from: (containing two kinds) one or more kinds of in following groups:
And the substituent group at least contains group shown in formula A, B, C or a D:
Hydroxyl (OH),
Wherein, R1,R2And R3It is respectively and independently selected from C1~C6Linear chain or branched chain alkyl in it is a kind of, curve mark is to take
Subrogate (similarly hereinafter).
In preferred technical solution, R is the C replaced3~C6Alkenyl or substituted C3~C6Alkyl, the substitution
C3~C6Alkenyl or substituted C3~C6The substituent group of alkyl is selected from: (containing two kinds) one or more kinds of in following groups,
And the substituent group at least contains group shown in formula A, B, C or a D:
Hydroxyl (OH),
Wherein, R1,R2And R3It is respectively and independently selected from C1~C3Linear chain or branched chain alkyl in it is a kind of.
In presently preferred technical solution, compound shown in Formulas I as cationic surfactant and/or
Antibacterial agent (gram-positive bacteria (such as staphylococcus aureus and bacillus subtilis) and part Gram-negative bacteria (large intestine
Bacillus etc.)) application.
In addition, the method for compound shown in preparation formula I provided by the invention, specifically comprises the following steps:
(1) in the case where there is inert gas existence condition, as anacardol (compound shown in Formula II) and corresponding halogenated hydrocarbons (YAY)
It is reacted in 40 DEG C~80 DEG C, obtains compound shown in formula III；Or,
In the case where there is inert gas existence condition, compound and halogenated epoxide as shown in Formula IIIn 70 DEG C
~100 DEG C of reactions, obtain compound shown in formula IV；
(2) in anhydrous and oxygen-free or under having inert gas existence condition, the compound as shown in formula III and corresponding nitrogen-containing heterocycle
Salt or quaternary ammonium salt are reacted in 60 DEG C~120 DEG C, obtain partial target object；Or,
It in pH value is 7-8 and under having inert gas existence condition, the compound as shown in formula IV and corresponding nitrogen-containing hetero first
Ring salt reacts 0.1 hour to 24 hours in 0 DEG C~5 DEG C, then reacts 1 hour to 24 hours, is remained then at 30 DEG C~50 DEG C
Remaining object.
In order to illustrate more clearly of the present invention, below with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection scope of invention.
Embodiment 1
The preparation of compound shown in Formulas I a:
(1) in the case where there is argon gas existence condition, it is resistance to that the bromo- 2- butylene (30mmol, 3equiv) of trans- Isosorbide-5-Nitrae-two is placed in 100mL
In pressure pipe, 30mL acetone is added, waits and is completely dissolved in acetone, adds potassium carbonate (60mmol, 6equiv) stirring, slowly add
Enter to use anacardol (10mmol, 1equiv) mixed liquor of acetone solution, be reacted 12 hours at 56 DEG C, reaction solution is poured into Bush's leakage
In bucket, potash solid is filtered out, obtains organic solution, then dry sample processed, silicagel column column chromatographs (eluant, eluent is petroleum ether), obtains
To intermediate (compound shown in formula III a)；
(2) 1- methylpyrazole (6mmol, 1.2equiv) is added in schlenk reaction tube, is added under the conditions of anhydrous and oxygen-free
The compound as shown in formula III a (5mmol, 1equiv) and acetonitrile (CH3CN) the mixture formed, in the case where there is argon gas existence condition,
It reacts at least 24 hours in 80 DEG C~100 DEG C, is ground with n-hexane, be centrifuged away liquid phase (so operating at least in triplicate),
Gained white solid after drying be object (compound shown in Formulas I a), melting point compound shown in Formulas I a be 40.9 DEG C~
41.3℃。
1H NMR (400MHz, DMSO) δ 8.54 (d, J=2.5Hz, 1H), 8.51 (d, J=2.9Hz, 1H), 7.22-7.12
(m, 1H), 6.90 (t, J=2.9Hz, 1H), 6.84-6.68 (m, 3H), 6.11-5.86 (m, 2H), 5.23 (d, J=5.3Hz,
2H), 4.59 (d, J=3.8Hz, 2H), 4.11 (s, 3H), 2.51 (t, 2H), 1.54 (dd, J=13.4,6.6Hz, 2H), 1.23
(m, 24H), 0.85 (t, J=6.8Hz, 3H)
13C NMR(101MHz,DMSO)δ157.97,149.53,144.11,138.52,137.23,132.37,129.31,
123.93,120.97,114.73,111.74,107.34,66.48,50.50,36.87,35.22,31.34,30.93,29.05,
28.89,28.75,22.14,14.01.
HRMS(ESI-TOF)m/z:[M+H]+Theoretical value (Calcd for) C29H48N2OBr 519.2950；Experiment value
(Found)519.2958。
Embodiment 2
The preparation of compound shown in Formulas I b:
(1) triethylene diamine (10mmol, 5equiv) is added in schlenk reaction tube, under the conditions of anhydrous and oxygen-free, is added
Enter the mixture being made of bromobutane (2mmol, 1equiv) and acetonitrile (solvent), is reacted at least 24 hours at 82 DEG C.By acetonitrile
It is spin-dried for.Methanol, which is added, makes remaining solid dissolution completely, adds ether and solid, filtering is precipitated, obtained solid is chemical combination shown in formula i
Object；
(2) outside divided by 1- methylpyrazole in 1 step of compound alternative embodiment shown in formula i (2), other Step By Conditions with
1 step of embodiment (2) is identical, obtains white solid (compound shown in Formulas I b), and the fusing point of compound shown in Formulas I b is 65.2 DEG C
~66.3 DEG C.
1H NMR (400MHz, DMSO) δ 7.20 (t, J=8.2Hz, 1H), 6.78 (m, J=6.4Hz, 3H), 6.39 (dt, J
=15.1,4.4Hz, 1H), 6.08-5.99 (m, 1H), 4.66 (d, J=3.6Hz, 2H), 4.33 (d, J=7.3Hz, 2H), 3.91
(s, 12H), 3.55 (t, J=8.1Hz, 2H), 2.54 (t, J=7.9Hz, 2H), 1.70-1.64 (m, 2H), 1.53 (d, J=
6.1Hz, 2H), 1.25 (m, J=14.0Hz, 26H), 0.94 (t, J=7.3Hz, 3H), 0.85 (t, J=6.7Hz, 3H)
13C NMR(101MHz,DMSO)δ157.93,144.17,140.33,129.39,121.08,117.52,114.75,
111.61,66.59,64.19,50.47,35.22,31.33,30.95,29.07,28.74,23.34,22.14,19.06,
14.01,13.52.
HRMS(ESI-TOF)m/z:[M+H]+Calcd for C35H63N2OBr2685.3307；Found 685.3331.
Embodiment 3
The preparation of compound shown in Formulas I c:
Outside divided by bromobutane in 2 step of bromohexane alternative embodiment (1), other steps and agents useful for same and 2 step of embodiment
Suddenly (1) is identical, obtains compound shown in formula ii；
Outside divided by 1- methylpyrazole in 1 step of compound alternative embodiment shown in formula ii (2), other Step By Conditions and reality
It is identical to apply 1 step of example (2), obtains white solid (compound shown in Formulas I c), the fusing point of compound shown in Formulas I c is 190 DEG C~
193.4℃。
1H NMR (400MHz, DMSO) δ 7.20 (t, J=8.2Hz, 1H), 6.79 (d, J=6.5Hz, 3H), 6.39 (dd, J
=14.6,3.8Hz, 1H), 6.04 (dd, J=15.1,7.5Hz, 1H), 4.66 (d, J=3.7Hz, 2H), 4.33 (d, J=
7.3Hz, 2H), 3.90 (s, 12H), 3.57-3.49 (t, 2H), 2.54 (t, J=7.5Hz, 2H), 1.70 (dd, J=9.2,
5.6Hz, 2H), 1.59-1.51 (m, 2H), 1.25 (d, J=14.6Hz, 28H), 0.91 (t, J=7.1Hz, 3H), 0.85 (t, J
=6.8Hz, 3H)
13C NMR(101MHz,DMSO)δ157.98,144.23,140.45,129.45,121.14,117.52,114.80,
111.66,66.64,64.28,63.58,56.13,50.52,50.35,35.27,31.38,31.00,30.69,29.11,
28.97,28.79,25.25,22.19,21.91,21.36,18.62,14.06,13.92.
HRMS(ESI-TOF)m/z:[M+H]+Calcd for C37H67N2OBr2713.3620；Found 713.3624.
Embodiment 4
The preparation of compound shown in Formulas I d:
(1) anacardol (10mmol, 1equiv), potassium carbonate (60mmol, 6equiv) and 30mL acetonitrile are placed in pressure resistance instead
Answer in device, stir 30 minutes, add epoxychloropropane (30mmol, 3equiv), and keep under 80 DEG C~90 DEG C states to
It is 12 hours few, it filters (filtering out solid), concentration gained filtrate obtains concentrate, by gained concentrate through the chromatography (elution of silicagel column column
Liquid are as follows: petrol ether/ethyl acetate=15:1, v/v), obtain compound shown in formula IV a；
(2) thiazole (11mmol, 1.1equiv) is placed in another reactor, in the case where there is argon gas existence condition, bromine is added
Change hydrogen (10mmol, 1equiv), is stirred to react at least 6 hours at 35 DEG C, unreacted is evaporated off and obtains hydrogen bromide and thiazole, obtains
Intermediate (compound shown in formula iii)；
Compound shown in formula iii (5mmol, 5equiv) and methanol are placed in another reactor, in 0 DEG C~5 DEG C items
Under part, the mixture of the compound as shown in formula IV a (5mmol, 5equiv) and methanol composition is added, adjusts reactant with thiazole
PH value is 7-8, and is kept at least 1 hour in 0 DEG C~5 DEG C states, is warming up to 30 DEG C~50 DEG C, and kept for 1 hour in this state
To 3 hours, revolving removed methanol and excessive thiazole, and gained yellow paste product is dissolved in a small amount of methanol, n-hexane is added
To there is white precipitate precipitation, filter, filter cake washed with n-hexane after be object (white solid, compound shown in Formulas I d),
The fusing point of compound shown in Formulas I d is 37.5 DEG C~38.6 DEG C.
1H NMR (400MHz, DMSO) δ 10.19 (s, 1H), 8.58 (d, J=4.5Hz, 1H), 8.36 (d, J=3.5Hz,
1H), 7.24-7.14 (m, 1H), 6.83-6.70 (m, 3H), 5.22 (s, 1H), 4.84 (d, J=10.3Hz, 1H), 4.67 (dd, J
=13.3,8.5Hz, 1H), 4.28 (dd, J=8.3,3.3Hz, 1H), 3.99 (dq, J=10.1,5.1Hz, 2H), 2.52-2.50
(t, 2H), 1.56 (dd, J=17.3,11.0Hz, 2H), 1.25 (m, J=14.8Hz, 24H), 0.85 (t, J=6.7Hz, 3H)
13C NMR(101MHz,CDCl3)δ144.16,137.82,133.22,129.34,126.38,121.09,
114.60,111.65,94.82,69.33,67.41,57.43,35.22,31.33,29.07,22.14,14.00.
HRMS(ESI-TOF)m/z:[M+H]+Calcd for C27H45NO2SBr 526.2354；Found 526.2344.
Embodiment 5
The preparation of compound shown in Formulas I e:
Outside divided by thiazole in N- methylmorpholine alternative embodiment 4, other Step By Conditions are same as Example 4, obtain
White solid (compound shown in Formulas I e), the fusing point of compound shown in Formulas I e are 43.2 DEG C~43.6 DEG C.
1H NMR (400MHz, DMSO) δ 7.20 (t, J=7.9Hz, 1H), 6.78 (t, J=5.0Hz, 3H), 5.81 (s,
1H), 4.50 (d, J=5.8Hz, 1H), 3.96 (dt, J=14.3,7.3Hz, 6H), 3.76-3.53 (m, 6H), 3.30 (s, 3H),
2.50 (t, J=1.7Hz, 2H), 1.56 (dd, J=17.0,10.3Hz, 2H), 1.25 (d, J=14.3Hz, 24H), 0.85 (t, J
=6.8Hz, 3H)
13C NMR(101MHz,DMSO)δ158.16,144.08,129.29,121.08,114.63,111.67,69.97,
63.38,60.35,59.87,52.52,35.19,31.30,30.95,29.05,28.90,28.72,22.11,13.97.
HRMS(ESI-TOF)m/z:[M+H]+Calcd for C29H53NO3Br 542.3209；Found 542.3191.
Embodiment 6
The test of the critical solution temperature (Krafft Point) of compound shown in Formulas I a~Ie:
Compound shown in above-mentioned Formulas I a~Ie is each configured to the suspension that solid content is 1.0wt%.Institute is heated respectively
Suspension is stated to shape is clarified, then chilling (cooling using cold water or ice water) is to having Precipitation and record the temperature of Precipitation
Degree.Each test sample is tested three times, takes its average value, concrete outcome be shown in Table 1 (compound shown in Formulas I a~Ie it is critical
Solution temperature (Krafft Point)).
Table 1
As shown in Table 3, in compound shown in Formulas I a~Ie, in addition to the compound shown in the Formulas I c, remaining compound it is critical molten
It is lower (i.e. low-temperature water-soluble is good) to solve temperature.
Embodiment 7
The test of the water contact angle of compound shown in Formulas I a~Ie:
Compound shown in above-mentioned Formulas I a~Ie is made into 0.1wt% solution respectively, then uniformly spreads over sheet glass respectively
On, be placed in 100 DEG C of baking ovens 3 hours, with hundred Ou Lin optical contact angle measuring instruments test respectively deionized water with a containing Formulas I~
Compound solution shown in Ie (on the glass sheet) forms film drop angle (i.e. water contact angle) and deionized water and glass (blank
Control) water contact angle, concrete outcome is shown in Fig. 1 and table 2 (water contact angle of compound shown in Formulas I a~Ie)
Table 2
As shown in Table 2, the contact angle of compound shown in Formulas I a~Ie (formed film) and water is respectively less than connecing for water and glass
Feeler.Therefore, compound shown in Formulas I a~Ie has good wetability (spreading property between hydrone is good).
Embodiment 8
The measurement of compound surface tension shown in Formulas I a~Ie:
Under conditions of temperature is 18 DEG C~22 DEG C, in 20mL deionized water solution, it is added dropwise concentration 1mmol/L's respectively
Compound shown in Formulas I a~Ie, by using the JK99B type Full-automatic tension instrument of Shanghai Zhongchen digital technology equipment Co., Ltd
The surface tension for measuring various concentration solution (before every measurement, platinum piece is thoroughly cleaned and drying, each experiment repeat
For several times until obtaining good reproducibility).As a result see Fig. 2 (surface tension concentration curve of compound shown in Formulas I a~Ie) and
Table 3 (compound surface tension data shown in Formulas I a~Ie).
Table 3
In table 3: pC20=-log C20；Amin=1024/(NAΓmax)；CMC is critical
Micellar concentration；γCMCBe solution concentration be CMC when surface tension value；C20It is surface when solution surface tension reduces 20mN/m
Surfactant concentration；pC20It is C20Negative logarithmic function；ΓmaxFor maximum surface mole fraction, i.e., in the superficial layer of per surface area, institute
The difference of amount and equivalent the solvent amount of the substance of contained solute in solution bulk of substance containing solute；AminIt is reached for liquid-vapor interface
When to saturation, minimum area shared by binding molecule；Comparison is cetyl trimethylammonium bromide (commercialization cationic surface
Activating agent).
As shown in Figure 2, the surface tension of compound water solution shown in Formulas I a~Ie is with the variation tendency of concentration: first dropping
It is low, it tends to balance after critical micelle concentration (CMC) to be achieved, the property with Typical surfactants.
As shown in Table 3, in compound shown in Formulas I a~Ie (totally five compounds), minimum critical micelle concentration CMC value
0.002mM (compound shown in Formulas I e), minimum surface tension γ can be reachedCMCValue can reach 11.32mN/m, surface-active
It is to be much better than comparison (commercialization cationic surfactant-cetyl trimethylammonium bromide).
Embodiment 9
The minimum inhibitory concentration (MIC) of compound shown in Formulas I a~Ie and the measurement of minimum bactericidal concentration (MBC):
(1) test uses bacterial strain: staphylococcus aureus (ATCC 25923), bacillus subtilis (ATCC 6633), big
Enterobacteria (ATCC 25922) and pseudomonas aeruginosa (ATCC 27853).Commercially available acquisition can be passed through.
Fluid nutrient medium: 1000mL deionized water, 10gNaCl, 10g peptone and 5g yeast extract；
Agar medium: 1000mL deionized water, 10gNaCl, 10g peptone, 5g yeast extract and 18g agar powder.
(2) measurement of the MIC of compound shown in Formulas I a~Ie:
(i) measuring method of MIC
Compound shown in Formulas I a~Ie is prepared to the test stoste of 1280 μ g/mL respectively using sterile water, then is used twice
It is 640 μ g/mL, 320 μ g/mL, 160 μ g/mL, 80 μ g/mL, 40 μ g/mL, 20 μ g/mL, 10 μ g/ that dilution method, which respectively obtains concentration,
ML, 5 μ g/mL, 2.5 μ g/mL and 1.25 μ g/mL test dilution.
The test stoste of above-mentioned various concentration and test dilution are added separately in 96 hole polystyrene plates of sterilizing, the
1 to the 11st hole is separately added into test stoste and test dilution, and every 10 μ L of hole, the 10 sterilized deionized waters of μ L are added in the 12nd hole
As growth control.Then 90 μ L 10 are added in each hole5Bacterium (ATCC 25923, ATCC 6633, ATCC of cfu/mL
25922 and ATCC 27853) suspension.96 orifice plates are placed on after being cultivated 24 hours in 37 DEG C of incubators, whether observation bacterium grows,
The minimum concentration that Kong Zhongwei grows bacterium is MIC.
(ii) concrete outcome is shown in Table 4 (MIC and MBC of compound shown in Formulas I a~Ie).
(3) measurement of the MBC of compound shown in Formulas I a~Ie:
(i) measuring method of MBC
Compound shown in Formulas I a~Ie is prepared to the test stoste of 2048 μ g/mL respectively using sterile water, then is used twice
Dilution method respectively obtains the test dilution that concentration is 1024 μ g/mL, 512 μ g/mL, 256 μ g/mL, 128 μ g/mL and 64 μ g/mL
Liquid.
The preparation of antibacterial culture medium: take sterilizing after liquid state agar medium 15mL be added while hot 1mL by Formulas I a~
The preparation test of compound shown in Ie stoste, (stoste and the concentration of twice of dilution of testing is respectively 2048 μ to twice of dilution
G/mL, 1024 μ g/mL, 512 μ g/mL, 256 μ g/mL, 128 μ g/mL and 64 μ g/mL) and sterilized deionized water (blank pair
According to) mix, pouring into culture dish makes its solidification, respectively obtain in culture medium concentration be 128 μ g/mL, 64 μ g/mL, 32 μ g/mL,
16,8 μ g/mL and 4 μ g/mL test groups and blank control (sterilized deionized water).
10 are added in above-mentioned culture medium5Bacterium (ATCC 25923, ATCC 6633, ATCC 25922 and the ATCC of cfu/mL
27853) 100 μ L of suspension, is smoothened with spreader, and culture dish is placed in 37 DEG C of incubators and is cultivated 24 hours, observes bacterium
Whether grow and count the bacterial strain number of all samples and control group.
MBC minimum bactericidal concentration is the Cmin that viable bacteria growth reduces 99.9% or more, is accounted for by bacterial strain number in sample
The ratio of control group bacterial strain number is observed, and concrete outcome is shown in Table 4 (MIC and MBC of compound shown in Formulas I a~Ie).
Table 4
In table 4, positive control is existing commercially available antibacterial agent, trade name " Kathon CG "；The unit of MIC and MBC is μ g/
mL。
As known from Table 4, compound shown in Formulas I a~Ie for gram-positive bacteria and part Gram-negative bacteria have compared with
Good antibiotic property, and part of compounds is to gram-positive bacteria staphylococcus aureus, bacillus subtilis and Gram-negative
Bacterium Escherichia coli antibacterial and " Kathon CG " are suitable.
Claims (4)
1. a kind of cashew nut phenol quaternary ammonium salt is compound shown in Formulas I:
In Formulas I, m be 1~4 integer；X is halogen anion；R is the C replaced3~C6Chain alkyl；
The substituted C3~C6The substituent group of chain alkyl is selected from: it is one or more kinds of in following groups, and the substituent group
At least containing group shown in formula A, B, C or a D:
Hydroxyl
Wherein, R1,R2And R3It is respectively and independently selected from C1~C6Linear chain or branched chain alkyl in it is a kind of.
2. cashew nut phenol quaternary ammonium salt as described in claim 1, which is characterized in that wherein R is the C replaced3~C6Alkenyl takes
The C in generation3~C6Alkyl；
The substituted C3~C6Alkenyl or substituted C3~C6The substituent group of alkyl is selected from: in following groups one or two with
On, and the substituent group at least contains group shown in formula A, B, C or a D:
Hydroxyl,
Wherein, R1,R2And R3It is respectively and independently selected from C1~C3Linear chain or branched chain alkyl in it is a kind of.
3. cashew nut phenol quaternary ammonium salt as claimed in claim 2, which is characterized in that the cashew nut phenol quaternary ammonium salt is Formulas I a institute
Show compound shown in compound and Formulas I e:
4. the cashew nut phenol quaternary ammonium salt as described in any one of claims 1 to 3 as cationic surfactant and/or resists
The application of the antibacterial agent of staphylococcus aureus, bacillus subtilis or Escherichia coli.
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| CN111690476A (en) * | 2020-06-22 | 2020-09-22 | 王智勇 | Special cleaning agent for garbage can and preparation method thereof |
| CN114249881A (en) * | 2021-12-06 | 2022-03-29 | 浙江万盛股份有限公司 | Non-solvent cardanol aldehyde amine epoxy resin curing agent containing thiazole structure and preparation method thereof |
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| CN111690476A (en) * | 2020-06-22 | 2020-09-22 | 王智勇 | Special cleaning agent for garbage can and preparation method thereof |
| CN114249881A (en) * | 2021-12-06 | 2022-03-29 | 浙江万盛股份有限公司 | Non-solvent cardanol aldehyde amine epoxy resin curing agent containing thiazole structure and preparation method thereof |
| CN114249881B (en) * | 2021-12-06 | 2023-09-26 | 浙江万盛股份有限公司 | Solvent-free cashew phenol aldehyde amine epoxy resin curing agent containing thiazole structure and preparation method thereof |
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