CN101870663B - Acrylpimaric amide derivative as well as preparation method and application thereof - Google Patents
Acrylpimaric amide derivative as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN101870663B CN101870663B CN2010102287239A CN201010228723A CN101870663B CN 101870663 B CN101870663 B CN 101870663B CN 2010102287239 A CN2010102287239 A CN 2010102287239A CN 201010228723 A CN201010228723 A CN 201010228723A CN 101870663 B CN101870663 B CN 101870663B
- Authority
- CN
- China
- Prior art keywords
- korean pine
- propylene korean
- amide derivatives
- acyl chlorides
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CCC(CC1C(C)(CCC2)C(CC3)C2(C)C(NCc2ccccc2)=O)C(*)=CC13C(N)=O Chemical compound CCC(CC1C(C)(CCC2)C(CC3)C2(C)C(NCc2ccccc2)=O)C(*)=CC13C(N)=O 0.000 description 3
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an acrylpimaric amide compound as well as a preparation method and application thereof, which belong to the field of acrylpimaric amide compound derivatives. The invention discloses the structural general formula of the acrylpimaric amide compound. The invention also discloses the preparation method of the compound. In the invention, a biomass resource of rosin is used asa raw material, the characteristic of the tricyclic diterpene structure of the rosin is combined, an amine class compound is introduced into the structure of rosin-based binary acid, and the amide class derivative of acrylpimaric acid is prepared. The derivative not only has better lipid solubility but also has a certain biological activity, especially a bacteriostatic action. The acrylpimaric acid used by the invention is from the modified product of a natural product of the rosin, the cost is low, and the preparation method is simple.
Description
Technical field
The invention belongs to the natural product chemistry field, relate to the method for preparing propylene Korean pine amide derivatives take rosin acrylic acid as raw material, also relate to the application of this analog derivative.
Background technology
Rosin is a kind of natural reproducible resource, is described as " lignicolous oil ", is to be obtained through fractionation by distillation by the resin that the pine tree resin canal is secreted.At present, rosin and deep processed product thereof have been widely used among the industry such as paint, soap, paper, printing ink, tackiness agent, electrical equipment, agricultural chemicals, spices, food medicine and makeup, it is the indispensable industrial chemicals of national economy, China is again rosin production big country, and annual production ranks first in the world.Rosin acrylic acid is that rosin reacts the diprotic acid of the luxuriant and rich with fragrance skeleton of tricyclic diterpene that obtains by the Diels-Alder Diene-addition, and existing its is applied to research report of coating, tackiness agent, tensio-active agent etc.Rosin acrylic acid used herein is called preparation method, the patent publication No. of rosin acrylic acid according to the contriver in name: the method preparation in CN101591238A.
Amide substance has been used to sterilant, insecticidal/acaricidal agent, weedicide, repellent, plant-growth regulator etc. at present owing to having extensive biological activity.Amides is made the history that sterilant uses existing decades, since the discovery systemic fungicide carboxin such as Von Schmeling in 1966, has developed altogether the sterilant kind of more than 20 structural similitude.Simultaneously, a lot of amide substances also have good insecticidal activity, the phthalic diamides sterilant that particularly has novel chemical structure, its be represented as that Japanese pharmaceuticals found in 1998 Flubendiamide (common name: flubendiamide, trade name: Belt, Fenos), it is mainly used in vegetables, fruit, paddy rice and cotton control lepidoptera pest, not only adult and larva is had good activity.And speed of action is fast, the lasting period is long, there is no cross resistance with conventional pesticides, to segmental appendage class beneficial insect safety.
Summary of the invention
The purpose of this invention is to provide a kind of propylene Korean pine amide derivatives and its preparation method and application, the products therefrom activity is high, and cost is low, and the preparation method is simple.
The present invention adopts following technical scheme: a kind of propylene Korean pine amide derivatives, and general structure is as follows:
Wherein the substituting group that represents of R is benzyl, phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,4-xylyl, 3,5-xylyl, guaiacyl, m-methoxyphenyl, p-methoxyphenyl, to fluorophenyl, rubigan, to any one in bromophenyl, p-trifluoromethyl phenyl.
A kind of method for preparing described propylene Korean pine amide derivatives is pressed the following formula reaction,
Wherein the substituting group that represents of R is benzyl, phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,4-xylyl, 3,5-xylyl, guaiacyl, m-methoxyphenyl, p-methoxyphenyl, to fluorophenyl, rubigan, to any one in bromophenyl, p-trifluoromethyl phenyl.
Described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, triphosgene.
The temperature of reaction of chloride is the reflux temperature of chloride reagent.
Described aminated compounds with phenyl ring is aniline, benzylamine, Ortho Toluidine, meta-aminotoluene, para-totuidine, 2,4-xylidene(s), 3,5-xylidene(s), adjacent methyl oxyaniline, a methyl oxyaniline, to any one in methyl oxyaniline, para-fluoroaniline, p-Chlorobenzoic acid amide, para-bromoaniline, p-trifluoromethylaniline.
Propylene Korean pine acyl chlorides with the reaction of the aminated compounds of phenyl ring the time, is that 1: 2.0～4.0 ratio feeds intake according to propylene Korean pine acyl chlorides and ratio with the amount of substance of the aminated compounds of phenyl ring.
The temperature of propylene Korean pine acyl chlorides with the reaction of the aminated compounds of phenyl ring the time is 5～50 ℃.
The acyl chloride reaction time is 0.5～24h.
Take described propylene Korean pine amide derivatives as activeconstituents, the application in fungistat.
Beneficial effect:
1. preparation method of the present invention is simple, and raw material is from natural product, and low price has improved the added value of rosin greatly.
2. the present invention take biomass resource as raw material, is incorporated into rosin tricyclic diterpene structure in aminated compounds, has prepared the amide derivatives of rosin acrylic acid.This analog derivative not only has fat-soluble preferably, and has certain biological activity, particularly bacteriostatic action, and part of compounds has restraining effect preferably to streptococcus aureus and intestinal bacteria.
3. the filter paper method is adopted in bacteriostatic activity test of the present invention, and precision takes sample respectively, is placed in sterile test tube, adds appropriate dissolve with ethanol, adds sterilized water and gets 256 μ g/mL solution.Take streptococcus aureus (gram-positive microorganism) and intestinal bacteria (Gram-negative bacteria) as tested bacterial classification, adopt beef extract-peptone to cultivate tested bacteria, with transfering loop from above-mentioned substratum (scrape 1～2 ring) the fresh bacterium that takes a morsel, add in nutrient solution, and take turns doing 10 times and increase progressively diluent, selecting bacterial concentration is (5.0-10.0) * 10
6The diluent of cfu/mL is as test bacterium liquid.Get on the beef extract-peptone plate culture medium that the 1mL bacteria suspension is uniformly coated on 90mm.The cut-off footpath is that 6mm aseptic filter paper absorption liquid to be measured is placed on the flat board that is coated with bacteria suspension, 3 repetitions of each sample.Cultivate after 24 hours and observe, measure filter paper inhibition zone diameter on every side.The bacteriostatic action of compound a and f is stronger, and the inhibition zone diameter of streptococcus aureus is respectively 1.5mm and 0.93mm; Colibacillary inhibition zone diameter is respectively 2mm and 3.5mm.
Embodiment
Rosin acrylic acid used herein is called preparation method, the patent publication No. of rosin acrylic acid according to the contriver in name: the method preparation in CN101591238A, be usually to be dissolved in organic solvent such as methylene dichloride in order to be easier to reaction during general the use, then react.All the other reagent are all commercially available conventional reagent.
Embodiment 1
A kind of propylene Korean pine amide derivatives, its general structure is as follows:
Wherein the substituting group that represents of R is benzyl, phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,4-xylyl, 3,5-xylyl, guaiacyl, m-methoxyphenyl, p-methoxyphenyl, to fluorophenyl, rubigan, to any one in bromophenyl, p-trifluoromethyl phenyl.
A kind of method for preparing described propylene Korean pine amide derivatives is pressed the following formula reaction,
Wherein the substituting group that represents of R is benzyl, phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,4-xylyl, 3,5-xylyl, guaiacyl, m-methoxyphenyl, p-methoxyphenyl, to fluorophenyl, rubigan, to any one in bromophenyl, p-trifluoromethyl phenyl.
Described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, triphosgene.
The temperature of reaction of chloride is the reflux temperature of chloride reagent, can select 45～65 ℃.
Described aminated compounds with phenyl ring is aniline, benzylamine, Ortho Toluidine, meta-aminotoluene, para-totuidine, 2,4-xylidene(s), 3,5-xylidene(s), adjacent methyl oxyaniline, a methyl oxyaniline, to any one in methyl oxyaniline, para-fluoroaniline, p-Chlorobenzoic acid amide, para-bromoaniline, p-trifluoromethylaniline.
Propylene Korean pine acyl chlorides with the reaction of the aminated compounds of phenyl ring the time, is that 1: 2.0～4.0 ratio feeds intake according to propylene Korean pine acyl chlorides and ratio with the amount of substance of the aminated compounds of phenyl ring.
The temperature of propylene Korean pine acyl chlorides with the reaction of the aminated compounds of phenyl ring the time is 5～50 ℃.
The acyl chloride reaction time is 0.5～24h.
Take described propylene Korean pine amide derivatives as activeconstituents, the application in fungistat.
Embodiment 2
Compound a
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.06mol benzylamine in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 12h.React complete, separating-purifying gets compound a.Yield 70.4%, m.p.140.8～141.6.
IR(cm
-1)：3363，3259(N-H)；3060，2926(-CH
3，-CH
2)；1659(N-C＝O)；738，697(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.33(m，2H，CONH-)；5.61-7.29(m，10H，Ar-H)；5.39(S，H，C＝CH-)；4.3-4.7(m，4H，Ar-CH
2-)；2.57(S，H，-CH
2CH-CO)；1.24-1.82(m，10H，-CH
2-)；1.53(m，H，-CH-(Me)
2)；0.58-1.14(m，12H，CH
3).MS：(ESI(+))m/s553(M+H
+).
Embodiment 3
Compound b
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add 0.06mol aniline in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets compound b.Yield 72%, m.p.135.6～137.4.
IR(cm
-1)：3354(N-H)；2961，2861(-CH
3，-CH
2)；1663(N-C＝O)；754，691(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.44(m，2H，CONH-)；7.01-7.38(m，10H，Ar-H)；5.59(S，H，C＝CH-)；2.68(S，H，-CH
2CH-CO)；1.28-2.50(m，10H，-CH
2-)；1.57(m，H，-CH-(Me)
2)；0.66-1.17(m，12H，CH
3).MS：(ESI(+))m/s525(M+H
+).
Embodiment 4
Compound c
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.06mol Ortho Toluidine in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets compound c.Yield 60%, m.p.125.7～126.9.
IR(cm
-1)：3301(N-H)；2924，2864(-CH
3，-CH
2)；1663(N-C＝O)；748(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.78(m，2H，CONH-)；6.99-7.34(m，8H，Ar-H)；5.62(S，H，C＝CH-)；2.69(S，H，-CH
2CH-CO)；2.20(S，6H，Ar-CH
3)；2.04-2.19(m，10H，-CH
2-)；1.55(m，H，-CH-(Me)
2)；0.67-1.81(m，12H，CH
3).
MS：(ESI(+))m/s553(M+H
+).
Embodiment 5
Compound d
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.06mol meta-aminotoluene in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets compound d.Yield 45%, m.p.126.9～127.8.
IR(cm
-1)：3338(N-H)；2922，2864(-CH
3，-CH
2)；1663(N-C＝O)；778，689(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.38(m，2H，CONH-)；6.86-7.31(m，8H，Ar-H)；5.58(S，H，C＝CH-)；2.67(S，H，-CH
2CH-CO)；2.31(S，6H，Ar-CH
3)；1.27-2.17(m，10H，-CH
2-)；1.58(m，H，-CH-(Me)
2)；0.65-1.17(m，12H，CH
3).MS：(ESI(+))m/s553(M+H
+).
Embodiment 6
Verbindung
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.06mol para-totuidine in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets Verbindung.Yield 53%, m.p.142～142.9.
IR(cm
-1)：3334(N-H)；2922，2864(-CH
3，-CH
2)；1662(N-C＝O)；812(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.37(m，H，CONH-)；7.35(m，H，CONH-)；7.04-7.29(m，8H，Ar-H)；5.57(S，H，C＝CH-)；2.66(S，H，-CH
2CH-CO)；2.28(S，6H，Ar-CH
3)；1.26-2.17(m，10H，-CH
2-)；1.54(m，H，-CH-(Me)
2)；0.81-1.16(m，12H，CH
3).
MS：(ESI(+))m/s553(M+H
+).
Embodiment 7
Compound f
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add 0.06mol 2 in the 250mL there-necked flask, 4-xylidine, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets compound f.Yield 47%, m.p.207.7～208.5.
IR(cm
-1)：3265(N-H)；2920，2861(-CH
3，-CH
2)；1670(N-C＝O)；804，685(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.59(m，2H，CONH-)；7.26(m，3H，Ar-H)；6.95(m，3H，Ar-H)；5.62(S，H，C＝CH-)；2.69(S，H，-CH
2CH-CO)；2.10-2.35(S，12H，Ar-CH
3)，1.58-2.49(m，10H，-CH
2-)；1.57(m，H，-CH-(Me)
2)；0.66-1.47(m，12H，CH
3).
MS：(ESI(+))m/s581(M+H
+).
Embodiment 8
Compound g
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add 0.06mol 3 in the 250mL there-necked flask, 5-xylidine, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, react complete, separating-purifying gets compound g.Yield 68%, m.p.140.8～142.9.
IR(cm
-1)：3348(N-H)；2921，2864(-CH
3，-CH
2)；1664(N-C＝O)；836，686(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.30(m，2H，CONH-)；6.68(m，2H，Ar-H)；7.03-7.14(m，4H，Ar-H)；5.57(S，H，C＝CH-)；2.68(S，H，-CH
2CH-CO)；1.42-2.28(S，12H，Ar-CH
3)；1.26-2.54(m，10H，-CH
2-)；1.52(m，H，-CH-(Me)
2)；0.65-1.16(m，12H，CH
3).
MS：(ESI(+))m/s553(M+H
+).
Embodiment 9
Compound h
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.08mol ORTHO ANISIDINE in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets compound h.Yield 73%, m.p.129.8～130.5.
IR(cm
-1)：3343，3357(N-H)；2929，2866(-CH
3，-CH
2)；1672(N-C＝O)；745(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：8.34(m，2H，CONH-)；6.83-7.80(m，8H，Ar-H)；5.59(S，H，C＝CH-)；3.87(m，6H，-OCH
3)；2.68(S，H，-CH
2CH-CO)；1.02-2.55(m，10H，-CH
2-)；1.54(m，H，-CH-(Me)
2)；0.67-1.16(m，12H，CH
3).MS：(ESI(+))m/s585(M+H
+).
Embodiment 10
Compound i
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.08mol m-anisidine in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets compound i.Yield 75%, m.p.120～120.5.
IR(cm
-1)：3349(N-H)；2927，2864(-CH
3，-CH
2)；1664(N-C＝O)；770，686(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.39(m，2H，CONH-)；6.55-7.38(m，8H，Ar-H)；5.59(S，H，C＝CH-)；3.79(m，6H，-OCH
3)；2.68(S，H，-CH
2CH-CO)；1.28-2.53(m，10H，-CH
2-)；1.54(m，H，-CH-(Me)
2)；0.65-1.17(m，12H，CH
3).MS：(ESI(+))m/s585(M+H
+).
Embodiment 11
Compound j
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.08mol P-nethoxyaniline in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 24h.React complete, separating-purifying gets compound j.Yield 77%, m.p.130.8～131.5.
IR(cm
-1)：3324(N-H)；2925，2864(-CH
3，-CH
2)；1661(N-C＝O)；825(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.38(m，2H，CONH-)；6.78-7.31(m，8H，Ar-H)；5.57(S，H，C＝CH-)；3.17(m，6H，-OCH
3)；2.67(S，H，-CH
2CH-CO)；1.26-2.51(m，10H，-CH
2-)；1.55(m，H，-CH-(Me)
2)；0.65-1.16(m，12H，CH
3).MS：(ESI(+))m/s585(M+H
+).
Embodiment 12
Compound k
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.07mol para-fluoroaniline in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 12h.React complete, separating-purifying gets compound k.Yield 68%, m.p.129.3～130.4.
IR(cm
-1)：3298(N-H)；2927，2865(-CH
3，-CH
2)；1647(N-C＝O)；827(Ar-H).
1HNMR(CDCl
3.8/ppm.300MHz)：7.42(m，2H，CONH-)；7.19-7.37(m，4H，Ar-H)；6.97(m，4H，Ar-H)；5.57(S，H，C＝CH-)；2.68(S，H，-CH
2CH-CO)；1.27-2.52(m，10H，-CH
2-)；1.55(m，H，-CH-(Me)
2)；0.65-1.16(m，12H，CH
3).MS：(ESI(+))m/s561(M+H
+).
Embodiment 13
Compound l
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.07mol p-Chlorobenzoic acid amide in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 12h.React complete, separating-purifying gets compound l.Yield 65%, m.p.156.4～157.4.
IR(cm
-1)：3338(N-H)；2925，2865(-CH
3，-CH
2)；1665(N-C＝O)；824(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.45(m，2H，CONH-)；7.19-7.40(m，8H，Ar-H)；5.56(S，H，C＝CH-)；2.68(S，H，-CH
2CH-CO)；1.27-2.51(m，10H，-CH
2-)；1.56(m，H，-CH-(Me)
2)；0.79-1.18(m，12H，CH
3).MS：(ESI(+))m/s594(M+H
+).
Embodiment 14
Compound m
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.07mol para-bromoaniline in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 12h.React complete, separating-purifying gets compound m.Yield 70%, m.p.140.7～141.4.
IR(cm
-1)：3344(N-H)；2924，2864(-CH
3，-CH
2)；1665(N-C＝O)；822(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.41(m，2H，CONH-)；7.23-7.38(m，8H，Ar-H)；5.55(S，H，C＝CH-)；2.67(S，H，-CH
2CH-CO)；1.18-2.54(m，10H，-CH
2-)；1.54(m，H，-CH-(Me)
2)；0.64-1.16(m，12H，CH
3).MS：(ESI(+))m/s683(M+H
+).
Embodiment 15
Compound n
Add 0.02mol rosin acrylic acid and 80mL methylene dichloride in the there-necked flask of the 250mL that condensing reflux pipe, thermometer and drying tube are housed, be stirred to dissolution of solid, add the 0.05mol sulfur oxychloride, after reflux 4h, decompression steams solvent and excess chlorination sulfoxide, makes propylene Korean pine acyl chlorides.
Add the 0.07mol p-trifluoromethylaniline in the 250mL there-necked flask, 40mL methylene dichloride and 10mL triethylamine.Drip aforesaid propylene Korean pine acyl chlorides, dropwise under rear normal temperature and react 12h.React complete, separating-purifying gets compound n.Yield 40%, m.p.158.9～160.2.
IR(cm
-1)：3343(N-H)；2928，2868(-CH
3，-CH
2)；1671(N-C＝O)；838(Ar-H).
1HNMR(CDCl
3.δ/ppm.300MHz)：7.64(m，2H，CONH-)；7.26-7.58(m，8H，Ar-H)；5.58(S，H，C＝CH-)；2.69(S，H，-CH
2CH-CO)；1.21-2.54(m，10H，-CH
2-)；1.56(m，H，-CH-(Me)
2)；0.66-1.17(m，12H，CH
3).MS：(ESI(+))m/s661(M+H
+).
Embodiment 16
Adopt the filter paper method, precision takes sample respectively, is placed in sterile test tube, adds appropriate dissolve with ethanol, adds sterilized water and gets 256 μ g/mL solution.Take streptococcus aureus (gram-positive microorganism) and intestinal bacteria (Gram-negative bacteria) as tested bacterial classification, adopt beef extract-peptone to cultivate tested bacteria, with transfering loop from above-mentioned substratum (scrape 1～2 ring) the fresh bacterium that takes a morsel, add in nutrient solution, and take turns doing 10 times and increase progressively diluent, selecting bacterial concentration is (5.0～10.0) * 10
6The diluent of cfu/ml is as test bacterium liquid.Get on the beef extract-peptone plate culture medium that the 1ml bacteria suspension is uniformly coated on 90mm.The cut-off footpath is that 6mm aseptic filter paper absorption liquid to be measured is placed on the flat board that is coated with bacteria suspension, 3 repetitions of each sample.Cultivate after 24 hours and observe, measure filter paper inhibition zone diameter on every side.
Inhibition zone diameter (mm)
Sterilization effect to 2 kinds of bacteriums is entirely not identical, because intestinal bacteria are Gram-negative bacteria, streptococcus aureus is gram-positive microorganism, if the sterilant action site at cell walls, the resistance of gram-positive microorganism is slightly strong.If act on cytolemma sterilization effect is identical.
Claims (9)
1. a propylene Korean pine amide derivatives, is characterized in that, general structure is as follows:
Wherein the substituting group that represents of R is benzyl, o-tolyl, a tolyl, p-methylphenyl, 2,4-xylyl, guaiacyl, m-methoxyphenyl, rubigan, to any one in bromophenyl.
2. method for preparing propylene Korean pine amide derivatives claimed in claim 1 is characterized in that: press the following formula reaction,
Wherein the substituting group that represents of R is benzyl, o-tolyl, a tolyl, p-methylphenyl, 2,4-xylyl, guaiacyl, m-methoxyphenyl, rubigan, to any one in bromophenyl.
3. the method for preparing propylene Korean pine amide derivatives as claimed in claim 2, it is characterized in that: described chloride reagent is any one in sulfur oxychloride, phosphorus trichloride, phosphorus pentachloride, oxalyl chloride, triphosgene.
4. the method for preparing propylene Korean pine amide derivatives as claimed in claim 2, it is characterized in that: the temperature of reaction of chloride is the reflux temperature of chloride reagent.
5. the method for preparing propylene Korean pine amide derivatives as claimed in claim 2, it is characterized in that: described aminated compounds with phenyl ring is any one in benzylamine, Ortho Toluidine, meta-aminotoluene, para-totuidine, toluene 24 diamine, adjacent methyl oxyaniline, a methyl oxyaniline, p-Chlorobenzoic acid amide, para-bromoaniline.
6. the method for preparing propylene Korean pine amide derivatives as claimed in claim 2, it is characterized in that: propylene Korean pine acyl chlorides is with the reaction of the aminated compounds of phenyl ring the time, and the ratio that is 1:2.0～4.0 according to propylene Korean pine acyl chlorides and ratio with the amount of substance of the aminated compounds of phenyl ring feeds intake.
7. the method for preparing propylene Korean pine amide derivatives as claimed in claim 2 is characterized in that: the temperature of propylene Korean pine acyl chlorides with the aminated compounds reaction of phenyl ring the time is 5～50 ℃.
8. the method for preparing propylene Korean pine amide derivatives as claimed in claim 2, it is characterized in that: the acyl chloride reaction time is 0.5～24h.
9. propylene Korean pine amide derivatives claimed in claim 1 is activeconstituents, is preparing for the application in the fungistat of intestinal bacteria and/or streptococcus aureus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102287239A CN101870663B (en) | 2010-07-15 | 2010-07-15 | Acrylpimaric amide derivative as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102287239A CN101870663B (en) | 2010-07-15 | 2010-07-15 | Acrylpimaric amide derivative as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101870663A CN101870663A (en) | 2010-10-27 |
| CN101870663B true CN101870663B (en) | 2013-06-19 |
Family
ID=42995766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102287239A Active CN101870663B (en) | 2010-07-15 | 2010-07-15 | Acrylpimaric amide derivative as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101870663B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219707B (en) * | 2011-04-22 | 2014-12-24 | 中国林业科学研究院林产化学工业研究所 | Acrylpimaric dioxime derivative as well as preparation method and application thereof |
| CN102875487A (en) * | 2012-10-17 | 2013-01-16 | 广西大学 | Synthesis method for acrylpimaric acid base dithiadiazole derivative |
| JP6996077B2 (en) * | 2015-12-28 | 2022-01-17 | 荒川化学工業株式会社 | Adhesive-imparting resin, adhesive / adhesive, hot melt adhesive |
| CN110294986B (en) * | 2019-07-12 | 2021-04-27 | 广西民族大学 | Preparation method of rosin-based and acrylamide thermal polymerization anticorrosive film with high pitting potential |
| CN116730932A (en) * | 2023-06-12 | 2023-09-12 | 西北农林科技大学 | Preparation and application of propylene pimara (1, 5-o-nitrobenzyl) -1,2, 4-triazole |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5939885A (en) * | 1982-08-28 | 1984-03-05 | Arakawa Chem Ind Co Ltd | Acrylopimaric acid diglycidyl ester |
-
2010
- 2010-07-15 CN CN2010102287239A patent/CN101870663B/en active Active
Non-Patent Citations (5)
| Title |
|---|
| IOAN BICU et al..Polymers from a Levopimaric Acid-Acrylic Acid Diels-Alder Adduct:Synthesis and Characterization.《Journal of Polymer Science:Part A:Polymer Chemistry》.2007,第45卷5979-5990. |
| JP昭59-39885A 1984.03.05 |
| Polymers from a Levopimaric Acid-Acrylic Acid Diels-Alder Adduct:Synthesis and Characterization;IOAN BICU et al.;《Journal of Polymer Science:Part A:Polymer Chemistry》;20071231;第45卷;5979-5990 * |
| UV固化丙烯海松酸聚氨酯丙烯酸酯的合成及应用;竺青等;《热固性树脂》;20081130;第23卷(第6期);24-26,31 * |
| 竺青等.UV固化丙烯海松酸聚氨酯丙烯酸酯的合成及应用.《热固性树脂》.2008,第23卷(第6期),24-26,31. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101870663A (en) | 2010-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101870663B (en) | Acrylpimaric amide derivative as well as preparation method and application thereof | |
| DK170732B1 (en) | Insecticide 2,2-dimethyl-3R- (2,2-dichlorovinyl) -cyclopropane-1R-carboxylic acid S-alpha-3-phenoxybenzyl ester and insecticide preparation | |
| CN109503562B (en) | 2- [4- (2-thienyl) ] pyrimidyl urea derivative and preparation method and application thereof | |
| CN109942561B (en) | 4- (2-thienyl) pyrimidine derivative and preparation method and application thereof | |
| CN108456108A (en) | The preparation method of micro- bio-feritlizer in a kind of supplement type | |
| CN109730067B (en) | Gemini quaternary ammonium salt bactericide containing naphthalene ring rigid connecting group and preparation method and application thereof | |
| CN102219707B (en) | Acrylpimaric dioxime derivative as well as preparation method and application thereof | |
| CN109535136B (en) | 2- [4- (2-furyl) ] pyrimidylurea compound and preparation method and application thereof | |
| US4023956A (en) | Amide phosphorothiolate herbicides | |
| CN104131061B (en) | A kind of preparation method of oxytetracycline quaternary ammonium salt | |
| CN102747007A (en) | Stenotrophomonas sp.XP and application of Stenotrophomonas sp.XP in acetamiprid degradation | |
| CN102898354A (en) | Oxime ether derivatives of spirocyclic tetronic acid, the preparation thereof, and insecticidal, acaricidal, bactericidal and herbicidal usages thereof | |
| Malik et al. | Biological Evaluation of Chiral Amides Synthesized from Diacetyl-L-tartaric Acid and Aromatic Amines | |
| SU426362A3 (en) | METHOD FOR OBTAINING DICHLORBENZYLTHYOETHYLAMINES | |
| US3210420A (en) | Haloaromatic amides of propiolic acid | |
| CN108409594B (en) | Water-soluble rosin derivative, preparation method thereof and application thereof as antifeedant | |
| US3859441A (en) | Anti-arthropodal cyclic dithioketals of glyoxyloyl halide 1-phenylhydrazones | |
| CN102657204A (en) | Synergetic insecticide composition | |
| CN109400591B (en) | 4- (2-furyl) pyrimidine compound and preparation method and application thereof | |
| CN109535135B (en) | 2-methylpyrimidine compound and preparation method and application thereof | |
| RU2030413C1 (en) | Derivatives of dihydropyran showing herbicidal activity | |
| US3370084A (en) | Esters of 2-methyl-4-chlorophenoxy alkanoic acids | |
| US3644637A (en) | Fungicidal mucononitriles | |
| CN104610142A (en) | 3-bishydrazide diphenylurea derivative, and preparation method and application of 3-bishydrazide diphenylurea derivative | |
| CN105418448B (en) | A kind of biamide structure compound and preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |