CN1365971A - Antibacterial activity, induction, separation and synthesis of N-acyltryptamine derivative as plant protecting chemical - Google Patents
Antibacterial activity, induction, separation and synthesis of N-acyltryptamine derivative as plant protecting chemical Download PDFInfo
- Publication number
- CN1365971A CN1365971A CN 02103940 CN02103940A CN1365971A CN 1365971 A CN1365971 A CN 1365971A CN 02103940 CN02103940 CN 02103940 CN 02103940 A CN02103940 A CN 02103940A CN 1365971 A CN1365971 A CN 1365971A
- Authority
- CN
- China
- Prior art keywords
- chloroform
- tryptamines
- water
- see table
- compound
- 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.)
- Granted
Links
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The present invention relates to two kinds of N-acyl tryptamine pisatinum derivatives and their antibacterial activity, induction, separation and synthesis. These two kinds of acyl tryptamine pisatinums can be used as the pilot compound to synthesize 25 derivatives. The said compounds have high supression action to different plant's pathogenic bacteria and candida albicans, so it can be used as antibacteria medicines to prevent and treat plant diseases.
Description
Technical field
The present invention relates to inducing and separating of tool anti-microbial activity plant protecting chemical, the synthetic method of plant protecting chemical derivative, and, belong to the technical field of agricultural chemicals and medicine as the application of efficient germicide.
Background technology
The plant-source antibacterial material is one of main mechanism of infecting of opposing pathogen that plant obtains in the long-term coevolution process with cause of disease, and plant protecting chemical (phytoalexin) is the induction type antimicrobial compounds.So far, have at least 400 kinds of plant protecting chemicals to obtain separating and evaluation, they mainly are distributed in the plant of 35 sections, and wherein Gramineae, pulse family and solanaceous crops are the plants of finding that so far plant protecting chemical is maximum.On chemical structure, plant protecting chemical roughly is divided into phenols, flavonoid, terpene, alkaloid etc.Plant protecting chemical is degraded easily in plant materials, and it is carried out synthetic its derivative of chemical research, might develop efficient, safe new type bactericide.Though there is the chemical structure of many plant protecting chemicals to obtain illustrating, but the successful example of developing sterilant based on this is also few, major cause has: (1) government and enterprise pay attention to not enough to the plant-source antibacterial compound, lack going deep into and extensive studies plant protecting chemical; (2) antibacterial activity in vitro of most plant protecting chemicals is not high, lacks synthetic, the germ resistance of its derivative and the evaluation of protection effect.
Paddy rice is main food crop, and for a long time, rice blast is one of serious hindrance of Rice Production.In order to control the harm of rice blast, people have carried out deep research to the mechanism of rice anti-rice blast.Kind of plant protecting chemical surplus having separated 10 from paddy rice so far is divided into diterpene, flavones and oxidation of fat acids on the structure.From paddy rice, extract and separate N-acyl-trypamine class plant protecting chemical (N-acyltryptamine) and do not appear in the newspapers as yet.
Have now found that N-acyl-trypamine compounds has multiple physiologically active, can be used as antianxiety agent, tranquilizer and the medicament of sleeping peacefully be used for clinical (Chemical Abstract, 1997,123:350261); Also can be used as (United StatesPatent, 1995,5403851) such as internal secretion medicine, immunity system medicine, ophthalmic diseases medicine and animal-feed additives.But have not yet to see N-acyl-trypamine compounds as the agricultural and report medical antibacterial agent.
Goal of the invention
In order to protect environment, the protection mankind and sustainable development of agriculture are badly in need of carrying out the development of the environmental protection type agricultural chemical of efficient, low toxicity, low residue.One of purpose of the present invention provides the method for inducing and extracting of N-acyl-trypamine class plant protecting chemical; Another purpose provides the synthetic method of plant protecting chemical derivative; The 3rd purpose provides N-acyl-trypamine compounds as the high-efficient antibacterial agent examples of applications.
Summary of the invention
To achieve these goals, the invention provides following technological method:
The present invention relates to paddy rice (Oryza sativa cv.Aichiasahi) N-acyl-trypamine plant protecting chemical and derivative thereof; comprise anti-microbial activity, induce, separation method, synthetic method; find high-activity compound, be used for control of plant disease and clinical as antibacterials.
Separation and purification obtains two kinds of N-acyl-trypamine plant protecting chemicals from the rice leaf: N-benzoyl tryptamines (N-benzoyltryptamine) and N-cinnamoyl tryptamines (N-cinnamoyltryptamine).With N-benzoyl tryptamines and N-cinnamoyl tryptamines is lead compound, adopts chemical synthesis process to synthesize other 25 kinds of N-acyl-trypamine compounds (embodiment 3～embodiment 27).Paddy rice plant protecting chemical N-benzoyl tryptamines and N-cinnamoyl tryptamines and derivative thereof have significant anti-microbial activity.
The present invention relates to by the N-acyl-trypamine derivative shown in the general formula [I], [I] is as follows for general formula:
Wherein:
R
1Represent hydrogen and at random substituted group (as hydroxyl, halogen, alkoxyl group, nitro, aryl, cyano group, alkylthio, amino, heterocyclic radical) on indole ring;
R
2Represent hydrogen and at random substituted group (as hydroxyl, halogen, alkoxyl group, nitro, aryl, cyano group, alkylthio, amino, heterocyclic radical) on aromatic ring;
R
3Represent at random substituted group as-(CH=CH) n-,-(CH
2) n-,-(C ≡ C) n-};
R
4Represent at random substituted group as-(CH=CH) n-,-(CH
2) n-,-(C ≡ C) n-}.
The invention provides induction method, extraction and separation method, analytical procedure, synthetic method and authentication method that paddy rice N-benzoyl tryptamines and N-cinnamoyl tryptamines plant protecting chemical form.
The induction method of the paddy rice N-acyl-trypamine plant protecting chemical that the present invention relates to is; with Pyricularia oryzae (Magnaporthe grisea) conidial suspension spray inoculation paddy rice seedling; then at 100% relative humidity, lucifuge clip inoculation blade after for some time; standby, so that extract and separate plant protecting chemical.
The extraction and the separation method of paddy rice N-acyl group-tryptamines plant protecting chemical that patent of the present invention relates to are: rice leaf lipid-soluble substance by vegetable chemistry separation method (as silica gel column chromatography, preparation of lamina chromatography and high performance liquid chromatography), is obtained N-benzoyl tryptamines and two kinds of plant protecting chemicals of N-cinnamoyl tryptamines.
The high performance liquid chromatography (HPLC) of 48 hours the full-cream extract of rice leaf of inoculation Pyricularia oryzae is seen accompanying drawing 1.In identical retention time, two strong absorption peak P1 and P2 appear in Pyricularia oryzae inoculation leaf extract.P1 is a N-benzoyl tryptamines, and P2 is a N-cinnamoyl tryptamines.
The invention provides the synthetic method of N-benzoyl tryptamines and two kinds of plant protecting chemicals of N-cinnamoyl tryptamines.Get in the pyridine that a certain amount of tryptamines is dissolved in proper volume; under the ice-water bath cooling, drip Benzoyl chloride (in order to preparation N-benzoyl tryptamines) or drip cinnamyl chloride (in order to preparation N-cinnamoyl tryptamines); under the ice-water bath cooling, stir for some time (as 1 hour); at room temperature stir for some time (as 3 hours) then; reaction mixture is poured in the frozen water; chloroform with proper volume divides three extractions; chloroform part water and dilute hydrochloric acid washing; be removed until pyridine; chloroform is partly used siccative (as anhydrous sodium sulphate) drying; vacuum concentration promptly gets reaction product, and structural formula is as follows.The hydrogen spectrum of reaction product (
1H-NMR) and carbon spectrum (
13C-NMR) data are shown in table 2 and table 3, and embodiment-1 is a N-benzoyl tryptamines, and embodiment-2 is a N-cinnamoyl tryptamines.
N-benzoyl tryptamines (embodiment-1)
N-cinnamoyl tryptamines (embodiment-2)
The present invention is based on synthesizing series N-acyl-trypamine compound; by anti-phytopathogen (comprising rice blast fungus, watermelon Fusarium oxysporum, cucumber Fusarium oxysporum, cotton wilt fusarium, gibberella saubinetii, cotton dry thread Pyrenomycetes, the withered bacterium of rice line) and human body pathogenic bacteria (comprising Candida albicans) structure activity relationship study research; find the high reactivity material, as novel antibacterials.The thinking of its compound structure design is, introduces at the aromatic ring of indole ring, benzoyl or cinnamoyl to contain oxygen, halogen, hydroxyl etc. and have with aromatic ring and form the pi-conjugated substituting group of p-, to improve the anti-microbial activity of compound.To achieve these goals, the present invention further provides following technological method.
Method A: in reaction vessel that tryptamines and excess of triethylamine is mixed; add an amount of chloroform; in ice-water bath cooling and stir under; the solution of acid chloride of mole numbers such as dropping and triethylamine; under lucifuge, react; allow reaction mixture rise to room temperature naturally; stirring is spent the night; the water that adds proper volume, with after chloroform layer separates, water layer is again with the equal amounts of chloroform washing once with water layer; the combined chloroform layer; use acid solution (as 10% hydrochloric acid) successively; alkali lye (as the 2M sodium hydroxide solution) and water washing, and with after siccative (as the anhydrous sodium sulphate) drying, reclaim solvent and promptly obtain acylate.
Method B: in reaction vessel that serotonin hydrochloride and water and excessive alkali aqueous solution (as 2M sodium hydroxide) is mixed; add an amount of chloroform; under the ice-water bath cooling and stirring; the solution of acid chloride of mole numbers such as dropping and alkali aqueous solution; under lucifuge, react; allow reaction mixture rise to room temperature naturally; stirring is spent the night; white precipitate occurs, filter, divide three washing precipitations with the chloroform of proper volume; then precipitation is dissolved in ethyl acetate; use acid solution (as 10% hydrochloric acid) successively; alkali lye (as the 2M sodium hydroxide solution) and water washing, and with after siccative (as the anhydrous sodium sulphate) drying, reclaim solvent and promptly obtain acylate.
Compound by the synthetic general formula [I] of technological method of the present invention has anti-microbial activity.Is 0.15 (μ g/ml) as N-benzoyl-serotonine to Pyricularia oryzae bacterial strain P131 germ tube growth 503nhibiting concentration; to Pyricularia oryzae bacterial strain R1528 germ tube growth 503nhibiting concentration is 0.44 (μ g/ml), and its action intensity is respectively 110 times (16.6 μ g/ml) and 46 times (20.2 μ g/ml) of guide's thing N-benzoyl tryptamines.
Embodiment with method A and the synthetic N-acyl group-tryptamines of B and N-acyl group-serotonin derivative is as follows.(Yield %) sees Table 1 for reaction product, fusing point (M.P., ℃) and yield.The hydrogen spectrum of reaction product (
1H-NMR) and carbon spectrum (
13C-NMR) data see Table 2 and table 3 respectively.
The yield and the fusing point compound R of table 1 reaction product N-acyl-trypamine
1R
2R
3R
4Synthetic method yield (%) M.P. (℃) embodiment-1----CH
2-CH
2-A--embodiment-2---CH
20=CH
21--CH
2-CH
2-A 96.7 135-136 embodiment-3 5-HO----CH
2-CH
2-B 72.4 195-197 embodiment-4 5-HO-o-Cl---CH
2-CH
2-B 91.2 62-64 embodiment-5 5-HO-p-Cl---CH
2-CH
2-B 91.2 142-144 embodiment-6 5-HO-2,4-2Cl---CH
2-CH
2-B 79.3-embodiment-7 5-HO-3,4-2Cl---CH
2-CH
2-B 80.0 179-181 embodiment-8 5-HO-p-OCH
3 20The CH of---
2-CH
2-B 89.1 209-210 embodiment-9 5-HO---CH
20=CH
21--CH
2-CH
2-B 100.0 80-82 embodiment-10 5-HO---CH
2 20--CH
2-CH
2-B 91.8-embodiment-ll---CH
2 20--CH
2-CH
2-A 94.2 139-140 embodiment-12-o-Cl--CH
2-CH
2-A 90.2-embodiment-13-p-C1--CH
2-CH
2-A 92.2-embodiment-14-2,4-2Cl---CH
2-CH
2-A 91.5-embodiment-15-3,4-2Cl---CH
2-CH
2-A 91.5-embodiment-16-p-F---CH
2-CH
2-A 77.8 138-140 embodiment-17-o-F---CH
2-CH
2-A 78.9-embodiment-18 5-HO-p-F---CH
2-CH
2-B 58.6 172-173 embodiment-19 5-HO-o-F---CH
2-CH
2-B 58.0-embodiment-20-2,4-2F---CH
2-CH
2-A 85.0-embodiment-21-3,4-2F---CH
2-CH
2-A 94.1 79-81 embodiment-22-2,4,5-3F---CH
2-CH
2-A 58.3-embodiment-23 5-HO-2,4-2F---CH
2-CH
2-B 93.9-embodiment-24 5-HO-3,4-2F---CH
2-CH
2-B 61.8-embodiment-25 5-HO-2,4,5-3F---CH
2-CH
2-B 68.6 177-179 embodiment-26 5-HO-o-NH
2The CH of---
2-CH
2-B 63.7-embodiment-27 5-MeO-o-NH
2The CH of---
2-CH
2-B 84.4 86-89
The hydrogen spectrum data of table 2 reaction product N-acyl-trypamine
*Compound 1-H 5-O-H Arom-H 10-H 11-H 12-H 20-H 21-H NH
2CH
3Embodiment-1 8.2s-7.07-3.10t 3.80d 6.20s----
7.64m 6.5Hz 6.5Hz embodiment-2 11.64s-7.24-3.39t, 4.11q, 9.08s 7.06s 7.10s--
8.16m 7.2Hz 6.8Hz embodiment-3 11.55s 9.41t, 7.19-3.31t, 4.04q, 8.71s----
5.3Hz 8.44m 7.4Hz 6.8Hz embodiment-4 11.54s 9.19t, 7.21-3.399t, 4.09m 8.71s---
5.6Hz 8.14m 7.2Hz embodiment-5 11.56s 9.30s 7.20-3.30t, 4.01q, 8.71s----
8.29m 7.2Hz 6.7Hz embodiment-6 11.56s 9.32t, 7.20-3.31t, 4.01q, 8.71s----
5.5Hz 8.71m 7.0Hz 7.0Hz embodiment-7 11.52s 9.42t, 7.22-3.33t, 4.03q, 8.71s----
5.4Hz 8.41m 7.2Hz 6.9Hz embodiment-8 11.54s 9.06t, 6.99-3.32t, 4.06q, 8.71s----
5.8Hz 8.30m 7.4Hz 6.8Hz embodiment-9 11.53s 8.89t, 7.20-3.28t, 4.03q, 8.71s 6.93d, 6.97d ,--
5.6Hz 8.08m 7.2Hz 6.8Hz 10.8Hz 10.4Hz embodiment-10 11.40s 8.71s 7.17-3.16t, 4.10m 8.58s 3.78m---
7.66m 7.2Hz embodiment-11 11.81s-7.19-3.19t, 4.07q, 8.71s 3.77m---
8.67m 7.2Hz 7.1Hz embodiment-12 7.91s-6.92-2.95t, 3.66q, 6.06s----
7.48m 7.0Hz 7.0Hz embodiment-13 8.13s-7.10-3.13t, 3.82q, 6.19s----
7.67m 7.0Hz 7.0Hz embodiment-14 8.13s-7.10-3.04t, 3.85q, 6.29s----
7.67m 6.3Hz 6.3Hz embodiment-15 8.13s-7.10-3.13t, 3.81q, 6.18s----
7.77m 6.3Hz 6.3Hz embodiment-16 11.85s-7.15-8.30m 3.37t, 4.05q, 8.73s----
7.2Hz 6.4Hz embodiment-17 11.85s-7.21-8.82m 3.36t, 4.07q, 8.71s----
7.2Hz 6.4Hz embodiment-18 11.56s 9.23d, 7.11-8.25m 3.30t, 4.01q, 8.69s----
5.2Hz 7.2Hz 6.8Hz embodiment-19 11.60s 8.82d 7.08 3.33t, 4.07q, 8.71s----
5.2Hz 8.13m 7.2Hz 6.8Hz embodiment-20-----8.71s----embodiment-21 11.86s-7.19-8 54m 3.34t, 4.10q, 8.71s----
7.2Hz 6.4Hz embodiment-22 11.88s-7.18-8.83m 3.35t, 4.04q, 8.71s----
5.8Hz 5.2Hz embodiment-23 12.09s 8.86d 6.95-8.25m 33.3t, 4.02q, 8.71s----
5.2Hz 7.2Hz 6.7Hz embodiment-24 11.58s 9.39d 7.00-8.54m 3.31t, 4.00q, 8.71s----
6.0Hz 7.2Hz 6.8Hz embodiment-25 11.64s 8.87d 7.17-8.01m 3.31t, 4.00m 8.71s----
5.2Hz 7.2Hz embodiment-26 11.59s 9.00t 6.82-8.39m 3.38m 4.00m 8.70s--6.61m-
5.4Hz embodiment-27 11.69s-7.01-8.11m 3.33t, 4.02q, 8.71s--6.62q, 3.78s
7.2Hz 6.4Hz 7.2Hz
*Chemical displacement value (δ) unit is ppm
3N-*C--1 -2 -3 -4 -5 -6 -7 -8 -92 122.07d 123.2d 124.0d 124.0d 124.1d 124.1d 124.0d 124.1d 124.2d3 113.05s 113.4s 112.6s 113.0s 112.7s 112.7s 112.5s 112.7s 112.5s4 118.75d 119.5d 112.9d 113.1d 113.0d 113.0d 113.0d 112.7d 113.0d5 119.37d 119.4d 152.3s 152.4s 152.4s 152.3s 152.4s 152.3s 152.3s6 122.29d 122.1d 104.1d 104.2d 104.1d 104.0d 104.1d 104.7d 104.7d7 111.27d 112.3d 112.6d 112.4d 112.5d 112.7d 112.8d 112.7d 112.7d8 136.44s 137.9s 132.5s 132.6s 132.6s 132.4s 132.6s 132.6s 132.6s9 127.32s 128.7s 129.6s 129.7s 129.7s 129.6s 129.7s 129.6s 129.6s10 25.29t 26.5t 26.6t 26.6t 26.5t 26.3t 26.4t 26.7t 26.6t11 40.22t 41.3t 41.5t 41.5t 41.6t 41.7t 41.7t 41.5t 41.0t13 167.44s 166.8s 167.8s 168.0s 166.8s 165.5s 165.8s 167.4s 166.4s14 134.69s 140.2s 136.4s 136.4s 132.6s 135.8s 135.6s 128.6s 139.9s15 126.81d 128.7d 130.3d 138.4s 134.7s 136.9s 131.0s 132.6s 128.6d16 128.48d 124.0d 128.7d 129.7d 129.0d 130.8d 129.7s 114.1d 124.2d17 131.30d 129.8d 132.8d 133.5d 137.0s 136.9s 135.1s 162.4s 129.7d18 128.48d 123.8d 127.9d 124.5d 128.9d 134.3d 136.3d 112.9d 124.2d19 126.81d 128.3d 131.2d 132.6d 132.6d 135.4d 132.6d 132.6d 128.1d20-112.3d-----55.4q** 113.0d21-136.1d-----136.0d*Chemical displacement value (δ) unit is ppm; ^-CH
2-be assigned.**-O-CH
3Be assigned
Carbon spectrum data * C-embodiment-10 EXAMPLE Example-12 embodiment-13 embodiment-14 embodiment-15 embodiment-16 embodiment-17 embodiment-18 of continuous table 3 reaction product N-acyl-trypamine
-11 2 124.1d 123.3d 122.2d 122.1d 122.2d 122.1d 123.8d 123.8d 123.9d3 112.4s 113.2s 112.8s 113.0s 112.7s 112.9s 113.3s 113.1s 113.0s4 113.0d 119.2d 118.7d 118.7d 118.7d 118.6d 119.2d 119.3d 104.1d5 152.4s 119.2d 119.5d 119.6d 119.6d 119.7d 121.9d 121.9d 152.4d6 104.1d 121.8d 122.3d 122.4d 122.3d 122.4d 119.2d 119.3d 104.1d7 112.8d 112.0d 112.2d 111.3d 111.3d 111.4d 112.0d 112.1d 112.6d8 132.6s 137.7s 130.6s 133.0s 133.5s 133.0s 137.7d 137.8d 132.6d9 129.6s 128.5s 127.2s 127.3s 127.2s 127.3s 132.6s 134.3s 130.5s10 26.5t 26.2t 25.2t 25.2t 25.1t 25.1t 26.3t 26.2t 26.6t11 41.6t 41.4t 40.2t 40.4t 40.3t 40.6t 41.6t 41.4t 41.7t13 171.4s 171.0s 166.5s 166.3s 165.4s 165.2s 166.7s 164.3s 166.9s14 135.3s 135.3s 135.2s 136.4s 136.4s 136.4s 128.6s 128.5s 129.7s15 129.6d 129.8d 136.4s 128.7d 131.4s 126.0d 130.3d 161.8s 130.5d16 129.0d 128.9d 127.0d 128.3d 127.4d 134.5s 115.4d 116.2d 115.5d17 127.1d 127.3d 131.1d 137.5s 136.6s 135.7s 166.0s 132.9d 166.1s18 129.0d 128.8d 130.2d 128.3d 130.0d 129.1d 115.6d 124.8d 115.7d19 129.1d 128.9d 130.0d 128.7d 131.2d 130.5d 130.4d 131.5d 130.5d20 61.0t ^60.8d ^- - - - - - -21-- - - - - - - -
*Chemical displacement value (δ) unit is ppm; ^-CH
2-be assigned.
Carbon spectrum data * C-embodiment-19 embodiment-20 embodiment-21 embodiment-22 embodiment-23 embodiment-24 embodiment-25 embodiment-26 embodiment of continuous table 3 reaction product N-acyl-trypamine
-27 2 124.1d 123.5d 123.6d 123.8d 123.8d 124.0d 124.1d 124.1d 124.1d3 112.2s 112.8s 113.0s 112.9s 113.6s 112.4s 112.1s 112.4s 113.3s4 104.1d 119.0d 120.0d 119.3d 106.1d 104.0d 104.0d 104.4d 101.3d5 152.3s 121.7d 121.7d 122.0d 150.2s 152.3s 152.4s 152.4s 154.5s6 104.1d 119.0d 120.1d 119.2d 105.9d 104.0d 104.0d 104.1d 101.3d7 112.6d 111.7d 111.8d 112.2d 112.5d 112.6d 112.6d 112.7d 112.4d8 132.7s 137.5s 137.5s 137.8s 133.2s 133.5s 132.5s 132.6s 132.9s9 131.5s 134.5s 133.3s 128.5s 128.8s 129.6s 129.5s 129.6s 129.0s10 26.4t 25.9t 26.0t 26.1t 26.0t 26.3t 26.1t 26.7t 26.5t11 41.3t 41.2t 41.5t 41.6t 41.5t 41.7t 41.5t 41.1t 41.2t13 164.3s 165.4s 165.3s 165.5s 167.5s 166.6s 162.2s 163.7s 170.4s14 129.5s 120.6s 133.3s 120.6s 121.0s 133.4s 119.4s 117.3s 116.9s15 161.8s 163.1s 125.6s 162.3s 163.5s 124.7d 162.2s 128.8d 128.7d16 116.4d 104.5d 118.5d 106.6d 104.6d 117.5d 106.6d 116.8d 117.2d17 132.6d 165.3s 153.2s 150.1s 165.6s 152.3s 150.1s 132.2d 132.2d18 124 8d 111.8d 148.8d 137.8d 111.9d 149.1s 135.8s 115.8d 115.6d19 131.5d 132.9d 118.3d 119.3d 133.1d 117.4d 119.2d 152.4s 150.8s20- - - - - - - - -21- - - - - - - - -CH
3O--------55.8q* chemical displacement value (δ) unit is ppm; ^-CH
2-be assigned.
Description of drawings
Fig. 1 is high performance liquid chromatography (HPLC) figure of 48 hours full-cream extract of rice leaf of inoculation Pyricularia oryzae and the full-cream extract of simulation inoculation rice leaf, Figure 1A is the HPLC figure of the full-cream extract of simulation inoculation rice leaf, and Figure 1B is the HPLC figure of the full-cream extract of Pyricularia oryzae inoculation rice leaf.The chromatography column that adopts is a C18 reversed-phase liquid chromatography post; Moving phase is methyl alcohol: water=52: 48 (v/v); Flow velocity: 1ml/min; Absorbing wavelength 220nm.Under identical extraction conditions and chromatography condition, two strong absorption peak P1 and P2 appear in Pyricularia oryzae inoculation leaf (Figure 1B) extract, and retention time (Retention time) respectively is 21.31min and 28.42min; And simulation inoculation rice leaf (Figure 1A) extract very little absorption peak P1 and P2 only occur in identical retention time.P1 is a N-benzoyl tryptamines, and P2 is a N-cinnamoyl tryptamines.
Embodiment
In order to understand the present invention better, further specify essentiality content of the present invention below in conjunction with embodiment, but content of the present invention is not limited thereto.
Embodiment-1: get in the pyridine that the 0.6g tryptamines is dissolved in 15ml, under the ice-water bath cooling, drip the 0.58g Benzoyl chloride, under the ice-water bath cooling, stirred 1 hour, at room temperature stirred then 3 hours, reaction mixture is poured in the frozen water, chloroform with 15ml divides three extractions, and chloroform part water and dilute hydrochloric acid washing are removed until pyridine, chloroform is partly used anhydrous sodium sulfate drying, the vacuum concentration solvent promptly gets product embodiment-2, and structural formula is as follows, and molecular formula is C
17H
16N
2O, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-1 structural formula
Embodiment-2: get in the pyridine that the 0.6g tryptamines is dissolved in 15ml, under the ice-water bath cooling, drip the 0.62g cinnamyl chloride, under the ice-water bath cooling, stirred 1 hour, at room temperature stirred then 3 hours, reaction mixture is poured in the frozen water, chloroform with 15ml divides three extractions, and chloroform part water and dilute hydrochloric acid washing are removed until pyridine, chloroform is partly used anhydrous sodium sulfate drying, the vacuum concentration solvent promptly gets product embodiment-2, and structural formula is as follows, and molecular formula is C
19H
18N
2O, EIMS 290 (M
+, 13), 159 (C
10H
9NO
+, 8), 143 (C
9H
8NO
+, 77), 131 (C
9H
7O
+, 29), 130 (C
9H
8N
+, 65), 117 (C
8H
7N
+, 3), 115 (C
9H
7 +, 4), 103 (C
9H
6 +, 22), 91 (C
6H
5CH
2 +, 8), 77 (C
6H
5 +, 17) and .IR (KBr), cm
-13311 (NH), 263,2840 (C-H), 1653 (C=O), 1607,1558 (C=C), 1457,1348,1379 (C-H), 1219,1076,1060,1006 (C-O), 978,819,744,686 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-2 structural formula
Embodiment-3: in reaction vessel with serotonin hydrochloride (100mg, 0.4702mM) mixed with the 2M sodium hydroxide solution of water (5ml) and excessive 150-200%, add the 5ml chloroform, under the ice-water bath cooling and stirring, Benzoyl chloride (the being dissolved in the 1ml chloroform) solution of mole numbers such as dropping and sodium hydroxide, under lucifuge, react, allow reaction mixture rise to room temperature naturally, stirring is spent the night, white precipitate appears, filter, divide three washing precipitations, then precipitation is dissolved in ethyl acetate with the 30ml chloroform, use 10% hydrochloric acid successively, 2M sodium hydroxide solution and water washing and with behind the anhydrous sodium sulfate drying, the vacuum concentration solvent promptly gets product embodiment-3, and structural formula is as follows, and molecular formula is C
17H
16N
2O
2, EIMS 280 (M
+, 12), 263 (M
+-OH, 2), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 62), 130 (C
9H
8N
+, 2), 117 (C
8H
7N
+, 7), 105 (C
6H
5CO
+, 28), 91 (C
6H
5CH
2 +, 7), 77 (C
6H
5 +, 29) and .IR (KBr), cm
-13426,3294 (OH, NH), 1701 (C=O), 1578,1538 (C=C), 1454,1376 (C-H), 1186,1290,1066 (C-O), 939,850,708,624 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-3 structural formula
Embodiment-4: by the synthetic embodiment-4 of the synthetic described method of embodiment-3, but acyl chlorides is the 2-chloro-benzoyl chloride.Embodiment-4 structural formula is as follows, and molecular formula is C
17H
15ClN
2O
2, EIMS 314 (M
+, 11), 297 (M
+-OH, 0.2), 263 (M
+-Cl-OH, 0.2), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 70), 130 (C
9H
8N
+, 2), 117 (C
8H
7N
+, 7), 105 (C
6H
5CO
+, 4), 91 (C
6H
5CH
2 +, 7), 77 (C
6H
5 +, 5) and .IR (KBr), cm
-13310 (OH, NH), 1692 (C=O), 1593,1538 (C=C), 1471,1315 (C-H), 1276,1187,1050 (C-O), 933,746 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-4 structural formula
Embodiment-5: by the synthetic embodiment-5 of the synthetic described method of embodiment-3, but acyl chlorides is the 4-chloro-benzoyl chloride.Embodiment-5 structural formula is as follows, and molecular formula is C
17H
15ClN
2O
2, EIMS 314 (M
+, 11), 297 (M
+-OH, 0.2), 263 (M+-Cl-OH, 0.2), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 70), 130 (C
9H
8N
+, 2), 117 (C
8H
7N
+, 7), 105 (C
6H
5CO
+, 4), 91 (C
6H
5CH
2 +, 7), 77 (C
6H
5 +, 5) and .IR (KBr), cm
-13412,3344 (OH, NH), 1624 (C=O), 1567,1546 (C=C), 1486,1443 (C-H), 1285,1184,1094 (C-O), 937,844,754 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-5 structural formula
Embodiment-6: by the synthetic embodiment-6 of the synthetic described method of embodiment-3, but acyl chlorides is a 2,4 dichlorobenzyl chloride.Embodiment-6 structural formula is as follows, and molecular formula is C
17H
14Cl
2N
2O
2, EIMS 349 (M
+, 2), 348 (M
+-1,12), 331 (M
+-OH, 1), 314 (M
+-Cl, 0.5), 278 (0.2), 190 (M+-C
10H
9NO, 2), 173 (C
6H
2Cl
2CO
+, 20), 174 (C
6H
3Cl
2CO
+, 12), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 91), 130 (C
9H
8N
+, 3), 117 (C
8H
7N
+, 10), 109 (C
5H
5NO
+, 6), 105 (C
6H
5CO
+, 5), 91 (C
6H
5CH
2 +, 11), 77 (C
6H
5 +, 6) and .IR (KBr), cm
-13375 (OH, NH), 1642 (C=O), 1588,1542 (C=C), 1460,1378 (C-H), 1217,1190,1063 (C-O), 938,801,762,624 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-6 structural formula
Embodiment-7: by the synthetic embodiment-7 of the synthetic described method of embodiment-3, but acyl chlorides is 3, the 4-dichlorobenzoyl chloride.Embodiment-7 structural formula is as follows, and molecular formula is C
17H
14Cl
2N
2O
2, EIMS 349 (M
+, 5), 348 (M
+-1,29), 331 (M
+-OH, 1), 314 (M
+-Cl, 3), 190 (M+-C
10H
9NO, 2), 173 (C
6H
2Cl
2CO
+, 42), 174 (C
6H
3Cl
2CO
+, 28), 159 (C
10H
9NO
+, 99), 146 (C
9H
8NO
+, 100), 130 (C
9H
8N
+, 8), 117 (C
8H
7N
+, 24), 109 (C
5H
5NO
+, 6), 105 (C
6H
5CO
+, 5), 91 (C
6H
5CH
2 +, 11), 77 (C
6H
5 +, 6) and .IR (KBr), cm
-13333 (OH, NH), 1640 (C=O), 1589,1542 (C=C), 1466,1375,1313 (C-H), 1221,1183,1030 (C-O), 936,839,754 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-7 structural formula
Embodiment-8: by the synthetic embodiment-8 of the synthetic described method of embodiment-3, but acyl chlorides is the 4-methoxy benzoyl chloride.Embodiment-8 structural formula is as follows, and molecular formula is C
18H
18N
2O
3, EIMS 310 (M
+, 19), 293 (M
+-OH, 0.2), 175 (C
10H
11N
2O
+, 2), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 77), 135 (C
8H
7O
2 +, 61), 130 (C
9H
8N
+, 4), 117 (C
8H
7N
+, 10), 109 (C
5H
5NO+, 2), 105 (C
6H
5CO
+, 3), 91 (C
6H
5CH
2 +, 11), 77 (C
6H
5 +, 25) and .IR (KBr), cm
-13411,3313 (OH, NH), 2932,2849 (CH
3), 1615,1603 (C=O), 1543,1504 (C=C), 1485,1320 (C-H), 1259,1180,1063,1024 (C-O), 936,847,803,664 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-8 structural formula
Embodiment-9: by the synthetic embodiment-9 of the synthetic described method of embodiment-3, but acyl chlorides is a cinnamyl chloride.Embodiment-9 structural formula is as follows, and molecular formula is C
19H
18N
2O
2, EIMS 306 (M
+, 19), 175 (C
10H
11N
2O
+, 2), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 90), 131 (C
9H
7O
+, 48), 117 (C
8H
7N
+, 15), 109 (C
5H
5NO
+, 2), 105 (C
6H
5CO
+, 2), 103 (C
8H
7 +, 46), 91 (C
6H
5CH
2 +, 16), 77 (C
6H
5 +, 40) and .IR (KBr), cm
-13383 (OH, NH), 1662 (C=O), 1611,1540 (C=C), 1454,1372 (C-H), 1215,1187,1069 (C-O), 965,937,833,766 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-9 structural formula
Embodiment-10: by the synthetic embodiment-10 of the synthetic described method of embodiment-3, but acyl chlorides is a phenyllacetyl chloride.Embodiment-10 structural formula is as follows, and molecular formula is C
18H
18N
2O
2, EIMS 294 (M
+, 24), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 77), 130 (C
9H
8N
+, 6), 117 (C
8H
7N
+, 11), 105 (C
6H
5CO
+, 2), 91 (C
6H
5CH
2 +, 56), 77 (C
6H
5 +, 5) and .IR (KBr), cm
-13335 (OH, NH), 2727 (C-H), 1703 (C=O), 1539,1496,1456 (C=C), 1342,1190,1031 (C-H), 1285,1184,1094 (C-O), 932,798,700,678 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-10 structural formula
Embodiment-11: in reaction vessel with tryptamines (100mg, 0.4702mM) mixed with excessive 150～200% triethylamines, add the 10ml chloroform, in ice-water bath cooling and stir under, phenyllacetyl chloride (the being dissolved in the 1ml chloroform) solution of mole numbers such as dropping and triethylamine, react under lucifuge, allow reaction mixture rise to room temperature naturally, stirring is spent the night, add 10ml water, with water layer with after chloroform layer separates, water layer more once with the equal amounts of chloroform washing, the combined chloroform layer, use 10% hydrochloric acid successively, 2M sodium hydroxide solution and water washing and with behind the anhydrous sodium sulfate drying, the vacuum concentration solvent promptly gets product embodiment-11, and structural formula is as follows, and molecular formula is C
18H
18N
2O, EIMS 278 (M
+, 42), 159 (C
10H
9NO
+, 12), 143 (C
9H
8NO
+, 100), 131 (C
9H
7O
+, 36), 130 (C
9H
8N
+, 95), 117 (C
8H
7N
+, 15), 115 (C
9H
7 +, 25), 103 (C
9H
6 +, 32), 91 (C
6H
5CH
2 +, 80), 77 (C
6H
5 +, 42) and .IR (KBr), cm
-13395 (NH), 3252 (C-H), 3077 (CH), 1655 (C=O), 1635,1566 (C=C), 1457,1355,1379 (C-H), 1275,1095,1071 (C-O), 930,800,744,695 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-11 structural formula
Embodiment-12: by the synthetic embodiment-12 of the synthetic described method of embodiment-11, but acyl chlorides is the 2-chloro-benzoyl chloride.Embodiment-12 structural formula is as follows, and molecular formula is C
17H
15ClN
2O, EIMS 298 (M
+, 15), 143 (C
9H
8NO
+, 78), 130 (C
9H
8N
+, 100), 117 (C
8H
7N
+, 7), 105 (C
6H
5CO
+, 5), 77 (C
6H
5 +, 28) and .IR (KBr), cm
-13261 (NH), 1624 (C=O), 1594,1567 (C=C), 1455,1433 (C-H), 1221,1172,1106 (C-O), 733,727 (=CH).
1H-NMR (table 2),
13C-NMR (table 3).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-12 structural formula
Embodiment-13: by the synthetic embodiment-13 of the synthetic described method of embodiment-11, but acyl chlorides is the 4-chloro-benzoyl chloride.Embodiment-13 structural formula is as follows, and molecular formula is C
17H
15ClN
2O, EIMS 298 (M
+, 16), 143 (C
9H
8NO
+, 100), 130 (C
9H
8N
+, 92), 117 (C
8H
7N
+, 3), 105 (C
6H
5CO
+, 2), 77 (C
6H
5 +, 15).IR(KBr)，cm
-1?3390，3230(NH)，1632(C＝O)，1596，1550(C＝C)，1487，1454(C-H)，1227，1201，1180(C-O)，849，740，683(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-13 structural formula
Embodiment-14: by the synthetic embodiment-14 of the synthetic described method of embodiment-11, but acyl chlorides is a 2,4 dichlorobenzyl chloride.Embodiment-14 structural formula is as follows, and molecular formula is C
17H
14Cl
2N
2O, EIMS 332 (M
+, 12), 173 (C
6H
2Cl
2CO
+, 20), 143 (C
9H
8NO
+, 100), 130 (C
9H
8N
+, 88), 117 (C
8H
7N
+, 3), 105 (C
6H
5CO
+, 1), 77 (C
6H
5 +, 11) and .IR (KBr), cm
-13362,3294 (NH), 1628 (C=O), 1587,1540 (C=C), 1466 (C-H), 1222,1106 (C-O), 877,866,826,723, (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-14 structural formula
Embodiment-15: by the synthetic embodiment-15 of the synthetic described method of embodiment-11, but acyl chlorides is 3, the 4-dichlorobenzoyl chloride.Embodiment-15 structural formula is as follows, and molecular formula is C
17H
14Cl
2N
2O, EIMS 332 (M
+, 20), 173 (C
6H
2Cl
2CO
+, 19), 143 (C
9H
8NO
+, 98), 130 (C
9H
8N
+, 100), 117 (C
8H
7N
+, 2), 105 (C
6H
5CO
+, 0.5), 77 (C
6H
5 +, 8) and .IR (KBr), cm
-13392,3285 (NH), 1630 (C=O), 1589,1545 (C=C), 1462 (C-H), 1348,1229,1132 (C-O), 886,845,757,738 (=CH).Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-15 structural formula
Embodiment-16: by the synthetic embodiment-16 of the synthetic described method of embodiment-11, but acyl chlorides is the 4-fluorobenzoyl chloride.Embodiment-16 structural formula is as follows, and molecular formula is C
17H
15FN
2O, EIMS m/z:283 (M
++ 1,12), 282 (M
+, 41), 264 (M
++ 1-F, 0.5), 155 (C
8H
10FNO
+, 1), 143 (C
10H
9N
+, 100), 130 (C
9H
8N
+, 93), 123 (C
7H
7FO
+, 55), 115 (C
8H
5N
+, 13), 103 (C
6H
3CO
+, 22), 95 (C
6H
4F
+, 33), 77 (C
6H
5 +, 26).IR(KBr)cm
-1：3391，3283(NH)，1628(C＝O)，2933，1564，1506(C＝C)，1454，1328(C-H)，1242，1162，1096(C-O)，855，741，669(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-16 structural formula
Embodiment-17: by the synthetic embodiment-17 of the synthetic described method of embodiment-11, but acyl chlorides is the 2-fluorobenzoyl chloride.Embodiment-17 structural formula is as follows, and molecular formula is C
17H
15FN
2O, EIMS m/z:283 (M
++ 1,10), 282 (M
+, 34), 264 (M
++ 1-F, 0.5), 155 (C
8H
10FNO
+, 2), 143 (C
10H
9N
+, 100), 130 (C
9H
8N
+, 89), 123 (C
7H
7FO
+, 50), 115 (C
8H
5N
+, 13), 103 (C
6H
3CO
+, 22), 95 (C
6H
4F
+, 42), 77 (C
6H
5 +, 26).IR(KBr)，cm
-1?3276(NH)，1621(C＝O)，1565(C＝C)，1454，1333(C-H)，1221，1166，1105(C-O)，845，763，746(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-17 structural formula
Embodiment-18: by the synthetic embodiment-18 of the synthetic described method of embodiment-3, but acyl chlorides is the 4-fluorobenzoyl chloride.Embodiment-18 structural formula is as follows, and molecular formula is C
17H
15FN
2O
2, EIMS m/z:299 (M
++ 1,8), 298 (M
+, 34), 281 (M
+-OH, 2), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 90), 130 (C
9H
8N
+, 2), 117 (C
8H
7N
+, 20), 105 (C
6H
5CO
+, 2), 91 (C
6H
5CH
2 +, 22), 77 (C
6H
5 +, 7).IR(KBr)，cm
-1?3408，3324(OH，NH)，2929，1629(C＝O)，1584，1548(C＝C)，1500，1443，1370(C-H)，1287，1185，1160(C-O)，937，851，759(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-18 structural formula
Embodiment-19: by the synthetic embodiment-19 of the synthetic described method of embodiment-3, but acyl chlorides is the 2-fluorobenzoyl chloride.Embodiment-19 structural formula is as follows, and molecular formula is C
17H
15FN
2O
2, EIMS m/z:299 (M
++ 1,6), 298 (M
+, 28), 281 (M
+-OH, 2), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 91), 130 (C
9H
8N
+, 7), 117 (C
8H
7N
+, 22), 105 (C
6H
5CO
+, 2), 91 (C
6H
5CH
2 +, 21), 77 (C
6H
5 +, 7).IR(KBr)，cm
-1?3419，3311(OH，NH)，2927，2862，1641(C＝O)，1530(C＝C)，1479，1433(C-H)，1294，1218，1099(C-O)，937，839，755(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-19 structural formula
Embodiment-20: by the synthetic embodiment-20 of the synthetic described method of embodiment-11, but acyl chlorides is the 2,4 difluorobenzene formyl chloride.Embodiment-20 structural formula is as follows, and molecular formula is C
17H
14F
2N
2O, EIMS m/z:301 (M
++ 1,8), 300 (M
+, 31), 155 (C
8H
10FNO
+, 2), 143 (C
10H
9N
+, 97), 130 (C
9H
8N
+, 100), 115 (C
8H
5N
+, 16), 113 (C
6H
3F
2 +, 36), 103 (C
6H
3CO
+, 30), 91 (C
6H
5CH
2 +, 2), 77 (C
6H
5 +, 26).IR(KBr)，cm
-1?3248(NH)，1654(C＝O)，1530(C＝C)，1488，1338(C-H)，1296，1262，1229，1091(C-O)，968，843，746(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-20 structural formula
Embodiment-21: by the synthetic embodiment-21 of the synthetic described method of embodiment-11, but acyl chlorides is 3, the 4-difluoro benzoyl chloride.Embodiment-21 structural formula is as follows, and molecular formula is C
17H
14F
2N
2O, EIMS m/z:301 (M
++ 1,3), 300 (M
+, 15), 155 (C
8H
10FNO
+, 2), 143 (C
10H
9N
+, 100), 130 (C
9H
8N
+, 95), 115 (C
8H
5N
+, 5), 113 (C
6H
3F
2 +, 29), 103 (C
6H
3CO
+, 10), 91 (C
6H
5CH
2 +, 2), 77 (C
6H
5 +, 14).IR(KBr)cm
-1?3347(NH)，3067，1636(C＝O)，1547，1513(C＝C)，1447，1322(C-H)，1284，1204，1109(C-O)，934，736(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-21 structural formula
Embodiment-22: by the synthetic embodiment-22 of the synthetic described method of embodiment-11, but acyl chlorides is 2,4, the 5-trifluorobenzoyl chloride.Embodiment-22 structural formula is as follows, and molecular formula is C
17H
13F
3N
2O, EIMS m/z:319 (M
++ 1,5), 318 (M
+, 23), 190 (C
8H
5F
3NO
+, 5), 176 (C
7H
5F
3NO
+, 28), 159 (C
7H
2F
3O
+, 100), 143 (C
10H
9N
+, 61), 131 (C
6H
2F
3 +, 47), 130 (C
9H
8N
+, 68), 115 (C
8H
5N
+, 4), 113 (C
6H
2F
2 +, 5), 103 (C
6H
3CO
+, 6), 91 (C
6H
5CH
2 +, 2), 77 (C
6H
5 +, 11).IR(KBr)cm
-13267(NH)，3064，1662(C＝O)，1611，1540(C＝C)，1425，1342(C-H)，1196，1141，1069(C-O)，901，862，839，791，751(＝CH)，607。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-22 structural formula
Embodiment-23: by the synthetic embodiment-23 of the synthetic described method of embodiment-3, but acyl chlorides is the 2,4 difluorobenzene formyl chloride.Embodiment-23 structural formula is as follows, and molecular formula is C
17H
14F
2N
2O
2, EIMS m/z:316 (M
+, 2), 299 (C
17H
13F
2N
2O, 70), 286 (45), 159 (C
10H
9NO
+, 8), 146 (C
9H
8NO
+, 13), 141 (C
7H
3F
2O
+, 100), 130 (C
9H
8N
+, 6), 113 (C
6H
3F
2 +, 24), 105 (C
6H
5CO
+, 2), 91 (C
6H
5CH
2 +, 3), 77 (C
6H
5 +, 2).IR(KBr)cm
-1?3396，3293(OH，NH)，3065(C-H)，1654(C＝O)，1540，1493，1432(C＝C)，1266(C-H)，1184，1113(C-O)，970，855，762(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-23 structural formula
Embodiment-24: by the synthetic embodiment-24 of the synthetic described method of embodiment-3, but acyl chlorides is 3, the 4-difluoro benzoyl chloride.Embodiment-24 structural formula is as follows, and molecular formula is C
17H
14F
2N
2O
2, EIMS m/z:316 (M
+, 60), 299 (C
17H
13F
2N
2O, 17), 286 (10), 160 (C
10H
10NO
+, 35), 159 (C
10H
9NO
+, 100), 146 (C
9H
8NO
+, 100), 141 (C
7H
3F
2O
+, 65), 130 (C
9H
8N
+, 6), 117 (C
8H
7N
+, 17), 113 (C
6H
3F
2 +, 50), 105 (C
6H
5CO
+, 2), 91 (C
6H
5CH
2 +, 16), 77 (C
6H
5 +, 5).IR(KBr)，cm
-1IR(KBr)cm
-1?3405，3162(OH，NH)，2952，2882(C-H)，1643(C＝O)，1550，1503，1468(C＝C)，1294(C-H)，1202，1105，1070(C-O)，932，852，776(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-24 structural formula
Embodiment-25: by the synthetic embodiment-25 of the synthetic described method of embodiment-3, but acyl chlorides is 2,4, the 5-trifluorobenzoyl chloride.Embodiment-25 structural formula is as follows, and molecular formula is C
17H
13F
3N
2O
2, EIMS m/z:334 (M
+, 8), 298 (C
17H
12F
2N
2O, 1), 176 (C
7H
5F
3NO
+, 5), 160 (C
10H
10NO
+, 8), 159 (C
10H
9NO
+, 75), 146 (C
9H
8NO
+, 48), 141 (C
7H
3F
2O
+, 4), 13 (C
9H
9N
+, 15), 117 (C
8H
7N
+, 5), 113 (C
6H
3F
2 +, 2), 105 (C
6H
5CO
+, 5), 91 (C
6H
5CH
2 +, 16), 77 (C
6H
5 +, 5).IR(KBr)cm
-13316(OH，NH)，1651(C＝O)，1542，1426(C＝C)，1327，1276，1192(C-H)，1141，1103，1044(C-O)，931，845，798(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-25 structural formula
Embodiment-26: by the synthetic embodiment-26 of the synthetic described method of embodiment-3, but acyl chlorides is the 2-amino benzoyl chloride.Embodiment-26 structural formula is as follows, and molecular formula is C
17H
17N
3O
2, EIMS m/z:296 (M
++ 1,10), 295 (M
+, 40), 163 (C
9H
11N
2O
+, 9), 159 (C
10H
9NO
+, 8), 146 (C
9H
8NO
+, 100), 130 (C
9H
8N
+, 11), 105 (C
6H
5CO
+, 5), 92 (C
6H
6N, 65), 77 (C
6H
5 +, 14).IR(KBr)cm
-13369(OH，NH)，2918，1625(C＝O)，1579，1542(C＝C)，1485，1366(C-H)，1283，1159，1095(C-O)，935，755(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-26 structural formula
Embodiment-27: in reaction vessel with 5-methoxytryptamine hydrochloride (100mg, 0.4702mM) mixed with the 2M sodium hydroxide solution of water (5ml) and excessive 150～200%, add the 5ml chloroform, under the ice-water bath cooling and stirring, 2-amino benzoyl chloride (the being dissolved in the 1ml chloroform) solution of mole numbers such as dropping and sodium hydroxide, under lucifuge, react, allow reaction mixture rise to room temperature naturally, stirring is spent the night, white precipitate appears, filter, divide three washing precipitations, then precipitation is dissolved in ethyl acetate with the 30ml chloroform, use 10% hydrochloric acid successively, 2M sodium hydroxide solution and water washing and with behind the anhydrous sodium sulfate drying, the vacuum concentration solvent promptly gets product embodiment-27, and structural formula is as follows, and molecular formula is C
18H
19N
3O
2, EIMS m/z:309 (M
+, 5), 163 (C
9H
11N
2O
+, 55), 146 (C
9H
8NO
+, 7), 137 (C
7H
7N
2 +O, 15), 105 (C
6H
5CO
+, 1), 92 (C
6H
6N, 92), 77 (C
6H
5 +, 5).IR(KBr)cm
-1?3358(NH)，2990，2930，1629(C＝O)，1582，1536，1485(C＝C)，1325，1260，1214(C-H)，1157，1034，1016(C-O)，922，825，807，755(＝CH)。Yield and fusing point data see Table 1, the hydrogen spectrum (
1H-NMR) data see Table 2, the carbon spectrum (
13C-NMR) data see Table 3.
Embodiment-27 structural formula
Embodiment-28: synthetic compound of the present invention is to the inhibiting case study of plant pathogenic fungi mycelial growth
1, bacterial classification: cotton wilt fusarium (Fusarium oxysporum f.sp.vasinfectum), the cotton Huang bacterium (Verticillium dahliae) that withers, watermelon Fusarium oxysporum (Fusarium oxysporum f.sp.niveum), cucumber Fusarium oxysporum (Fuusarium oxysporum f.sp.cucumerimum), the withered bacterium of rice line (Rhizoctonia solani fromrice), cotton standing dead rhizoctonia (Rhizoctonia solani from cotton), gibberella saubinetii (Fusariumgraminearum).
2, substratum:
1. PDA (Potato Dextrose Agar) substratum: the succeeding transfer culture and the bacterial classification that are used for the fungi of trying are preserved.Every liter of substratum contains the 200g potato and boils filtrate (concrete operations are the beans 200g that fetches earth, and peeling is cut into small pieces or small pieces, boils 30min in the boiling water, four layers of filtered through gauze), glucose 20g, agar 20g, adjust pH to 5.5,121 ℃ of moist heat sterilization 15min.
2. Cha Shi (Czapek-Dox) substratum: the succeeding transfer culture and the bacterial classification that are used for verticillium dahliae, cotton standing dead rhizoctonia, the withered bacterium of rice line are preserved.Every liter of substratum contains KCl 0.5g, KH
2PO
41g, MgSO
47H
2O 0.5g (separating sterilization), NaNO with other composition
32g, FeSO
47H
2O 10mg, sucrose 30g, agar 20g (liquid nutrient medium does not then add agar), adjust pH to 6.0,121 ℃ of moist heat sterilization 15min.
3. Armstrong sickle-like bacteria substratum: the liquid culture (comprise shaking table suspension culture and microwell plate cultivate) that is used for Fusarium (Fusarium) fungi.Every liter of substratum contains KCl 1.6g, KH
2PO
41.1g, MgSO
47H
2O 0.4g (separating sterilization), Ca (NO with other composition
3)
24H
2O 8.49g, MnSO
4H
2O0.2 μ g, FeCl
36H
2O 0.2 μ g, ZnSO
47H
2O 0.2 μ g, glucose 20g, adjust pH to 4.5,121 ℃ of moist heat sterilization 15min.
3, compound concentration preparation: get the 1mg sample, dissolve fully, and be settled to 1ml, make the mother liquor of 1000 μ g/ml ,-20 ℃ of preservations with dehydrated alcohol.The compound mother liquor is diluted to different concns before the experiment temporarily, and makes the alcohol concn of solution be fixed as 10%.
4, fungi liquid suspension culture: at volume is to add sterilized liquid nutrient medium 20ml in the aseptic triangular flask of 50ml.Picking grows in a little mycelia at fungal colony edge on the solid medium in the 20ml nutrient solution, suspension culture (175 ± 5rpm) on shaking table, 25 ℃, secretly, every cultivation 48-72 hour (different strain incubation time difference), change nutrient solution 1 time (promptly get and contain bacteria culture fluid 200 μ l in the 20ml fresh medium, the continuation cultivation).
5, be used for the preparation that anti-microbial activity is measured bacterium liquid: get the bacteria suspension of cultivating 48-72 hour, hypha body is smashed to pieces with tweezers, the individual layer filtered through gauze, the fresh medium of 2 times of concentration of adding will be lacked mycelia and will be diluted to finite concentration, be used for anti-microbial activity and measure.
6, concrete operations: get the microwell plate that contains 96 holes, every hole adds the compound solution 50 μ l of different concns, each concentration repeats 5 holes, every hole adds the bacterium liquid 50 μ l that prepared, after being mixed on the shaking table, measure the absorbance value in each hole in 655nm wavelength place, lucifuge is cultivated then, the absorbance value in each hole of replication after 48 hours or longer for some time.
7, inhibiting rate and growth half inhibiting rate (IC
50) calculating: adopt 3 times of standard deviation method of inspection rejecting abnormalities data.The difference of the mean value (Δ T) that the mean value (Δ C) that the contrast absorbance value changes and compound change at a certain concentration absorbance value multiply by 100% again divided by the mean value (Δ C) that the contrast absorbance value changes, and is the inhibiting rate of compound when a certain concentration.
8, to the inhibiting mensuration of plant pathogenic fungi mycelial growth (table 4)
Table 4 compound is to the restraining effect of plant pathogenic fungi mycelial growth
Mycelial growth 503nhibiting concentration (IC
50, μ g/ml) and compound
The withered bacterium embodiment-1 0.26 1.00 1.05 of the cotton Rhizoctonia solani Kuhn rice line of watermelon Fusarium oxysporum cucumber Fusarium oxysporum cotton wilt fusarium gibberella saubinetii---embodiment-2 2.21 0.11 1.10---embodiment-12 0.46 8.20 0.44---embodiment-13 0.30-0.83 3.5 19.20-embodiment-14 0.76 15.30 0.22 0.60--embodiment-15 0.70 8.50 0.90 0.49-0.86
Embodiment-29: synthetic compound of the present invention is to the case study of magnaporthe grisea spore germination inhibitor
1, bacterial classification: Pyricularia oryzae P131 and S1528 (Magnaporthe grisea P131 and S1528).
2, substratum: oat tomato substratum (Oat tomato Agar) is used for the cultivation of Pyricularia oryzae.Contain tomato juice 150ml (get tomato 250g, squeeze the juice, filter with double gauze then) in every liter of substratum with juice extractor, (30g rolled oats adds water 1000ml to oat juice 750ml, boils 15min, filter with double gauze then), agar 20g, 121 ℃ of moist heat sterilization 15min.
3, compound concentration preparation: get the 1mg sample, dissolve fully, and be settled to 1ml, make the mother liquor of 1000 μ g/ml ,-20 ℃ of preservations with dehydrated alcohol.Before the experiment compound mother liquor is diluted to different concentration, and makes the alcohol concn of solution be fixed as 20%.
4, the preparation of the cultivation of Pyricularia oryzae and spore suspension: 1) be coated with bacterium: wash with the mycelia of 700 μ l sterilized waters with Pyricularia oryzae, move on the substratum, coating is even, natural airing (about 30 minutes), 25 ℃ of following illumination cultivation; 2) the living mycelia of gas washing: wait to grow (general 2 days) behind the aerial hyphae, add the 1ml sterilized water, interrupt aerial hyphae gently, be inverted airing, covering sterile gauze, 25 ℃ of illumination cultivation with the cotton balls of sterilization; 3) preparation of spore suspension: grow (general 1 day) behind the grey spore, wash spore with sterilized water, with four layers of filtered through gauze, centrifugal 15 minutes of 2640g (rotating speed 5000rpm), remove supernatant liquor, spore is made spore suspension with sterilized water, uses four layers of filtered through gauze then, with Neubauer blood counting chamber counting, then spore suspension is diluted to 1 * 10
6Individual ml.
5, concrete operations: get compound solution 30 μ l, spore suspension 30 μ l are mixed in the eppendorf pipe, get 10 μ l on wave carrier piece, form water droplet, cultivated 16 hours in relative humidity 100%, 25 ℃ of lucifuges, then in microscopically observation spore germination and germ tube upgrowth situation.Under low power lens, 100～200 spores of casual inspection, spore have all calculations of germ tube to germinate, do not have for not germinateing.
Obtain the spore germination inhibiting rate and the germ tube growth inhibition ratio of each concentration earlier, adopt interpolation formula to obtain compound 503nhibiting concentration (IC then
50).Spore germination inhibiting rate and germ tube growth inhibition ratio calculation formula are as follows:
6, to the mensuration (table 5) of magnaporthe grisea spore germination inhibitor.
Table 5 compound is to the restraining effect of Pyricularia oryzae bacterial strain P131 and S1528
/: expression is not carried out anti-microbial activity as yet and is measured.
| Compound | Pyricularia oryzae bacterial strain P131 | Pyricularia oryzae bacterial strain S1528 | ||
| Germ tube growth 503nhibiting concentration (μ g/ml) | Spore germination 503nhibiting concentration (μ g/ml) | Germ tube growth 503nhibiting concentration (μ g/ml) | Spore germination 503nhibiting concentration (μ g/ml) | |
| Embodiment-1 | ????16.60 | ????- | ????20.02 | ????- |
| Embodiment-2 | ????13.55 | ????- | ????17.38 | ????- |
| Embodiment-3 | ????0.15 | ????5.83 | ????0.44 | ????6.25 |
| Embodiment-4 | ????0.45 | ????5.31 | ????2.49 | ????15.63 |
| Embodiment-5 | ????0.44 | ????2.32 | ????0.55 | ????15.63 |
| Embodiment-6 | ????1.32 | ????11.36 | ????1.55 | ????7.50 |
| Embodiment-7 | ????0.27 | ????5.00 | ????1.99 | ????9.06 |
| Embodiment-8 | ????1.98 | ????7.32 | ????2.05 | ????5.00 |
| Embodiment-9 | ????0.12 | ????4.57 | ????1.01 | ????3.59 |
| Embodiment-10 | ????0.63 | ????6.50 | ????0.99 | ????5.83 |
| Embodiment-11 | ????0.36 | ????7.75 | ????0.40 | ????1.83 |
| Embodiment-12 | ????4.94 | ????- | ????28.54 | ????- |
| Embodiment-13 | ????12.44 | ????- | ????1.91 | ????- |
| Embodiment-14 | ????1.98 | ????7.88 | ????2.04 | ????14.63 |
| Embodiment-15 | ????1.64 | ????7.72 | ????1.77 | ????8.22 |
| Embodiment-16 | ????41.30 | ????- | ????/ | ????/ |
| Embodiment-17 | ????23.54 | ????42.75 | ????/ | ????/ |
| Embodiment-18 | ????- | ????- | ????/ | ????/ |
| Embodiment-19 | ????- | ????- | ????/ | ????/ |
| Embodiment-20 | ????27.84 | ????35.74 | ????/ | ????/ |
| Embodiment-21 | ????38.50 | ????41.79 | ????/ | ????/ |
| Embodiment-22 | ????65.17 | ????63.94 | ????/ | ????/ |
| Embodiment-23 | ????50.77 | ????- | ????/ | ????/ |
| Embodiment-24 | ????- | ????- | ????/ | ????/ |
| Embodiment-25 | ????- | ????- | ????/ | ????/ |
| Embodiment-26 | ????- | ????- | ????/ | ????/ |
| Embodiment-27 | ????73.52 | ????98.16 | ????/ | ????/ |
Embodiment-30: the active case study of synthetic compound anti-candida albicans of the present invention
1, bacterial classification: Candida albicans (Candida albicans Berkh ATCC10231).
2, Candida albicans substratum: the flat board that is used for Candida albicans is cultivated and liquid culture.Every liter of substratum contains KH
2PO
40.5g, MgSO
47H
2O 0.5g (separating sterilization), CaCl with other composition
22H
2O 0.3g, (NH
4)
2SO
42g, KI0.1g, asparagine (L-asparagine) 2g, glucose 20g, trace element (B, Mn, Zn, Cu, Mo, it is Fe) a small amount of that (specifically joining method is: from containing MnCl
24H
2O 450.7mg, (NH
4)
6Mo
7O
244H
2O 23mg, H
3BO
3282.2mg, ZnSO
47H
2O 11mg, CuSO
45H
2O 9.8mg, FeC
6H
5O
75H
2Get 1ml in the 500ml mother liquor of O 2.998g), D-vitamin H (vitamin H) 2mg, agar 20g (liquid nutrient medium does not then add), adjust pH to 5.5,121 ℃ of moist heat sterilization 15min.
3, Candida albicans fluid suspension culture: at volume is to add sterilized liquid nutrient medium 20ml in the aseptic triangular flask of 50ml.Picking grows in a little mycelia at fungal colony edge on the solid medium in the 20ml nutrient solution, (175 ± 5rpm), 25 ℃ of suspension culture on shaking table, secretly, nutrient solution 1 time (promptly get and contain bacteria culture fluid 200 μ l in the 20ml fresh medium, the continuation cultivation) is changed in every cultivation 48-72 hour.
4, compound concentration preparation: get the 1mg sample, dissolve fully, and be settled to 1ml, make the mother liquor of 1000 μ g/ml ,-20 ℃ of preservations with dehydrated alcohol.The compound mother liquor is diluted to different concns before the experiment temporarily, and makes the alcohol concn of solution be fixed as 10%.
5, concrete operations: get the microwell plate that contains 96 holes, every hole adds the compound solution 50 μ l of different concns, each concentration repeats 5 holes, every hole adds the bacterium liquid 50 μ l that prepared, after being mixed on the shaking table, measure the absorbance value in each hole in 655nm wavelength place, lucifuge is cultivated then, the absorbance value in each hole of replication after 48 hours or longer for some time.
6, inhibiting rate and growth half inhibiting rate (IC
50) calculating: adopt 3 times of standard deviation method of inspection rejecting abnormalities data.The difference of the mean value (Δ T) that the mean value (Δ C) that the contrast absorbance value changes and compound change at a certain concentration absorbance value multiply by 100% again divided by the mean value (Δ C) that the contrast absorbance value changes, and is the inhibiting rate of compound when a certain concentration.
7, to the inhibiting mensuration of albicans growth
In the compound of being tested, 6 compounds are arranged, and oidiomycetic growth shows restraining effect (result is as shown in table 6) to white under examination concentration.
Table 6 compound is to the oidiomycetic restraining effect of white
Compound I C
50(μ g/ml) Compound I C
50(μ g/ml)
Embodiment-1 6.15 embodiment-17 14.56
Embodiment-2 8.31 embodiment-21 10.59
Embodiment-5 16.46 embodiment-22 19.89
Embodiment-6 14.38 embodiment-23 12.45
Embodiment-10 63.15 embodiment-25 10.14
Embodiment-14 8.74 embodiment-24 12.69
Embodiment-15 11.98 embodiment-26 5.08
Embodiment-16 12.95 embodiment-27 3.80
Embodiment-31: synthetic part of compounds of the present invention is to the prevention effect case study of cotton wilt
1, bacterial classification: cotton wilt fusarium (Fusarium oxysporum f.sp.vasinfectum)
2, substratum: 1) PDA (Potato Dextrose Agar) substratum: the succeeding transfer culture and the bacterial classification that are used for the fungi of trying are preserved.Every liter of substratum contains the 200g potato and boils filtrate (concrete operations are the beans 200g that fetches earth, and peeling is cut into small pieces or small pieces, boils 30min in the boiling water, four layers of filtered through gauze), glucose 20g, agar 20g, adjust pH to 5.5,121 ℃ of moist heat sterilization 15min.2) the husky substratum of wheat: get wheat in beaker, add water boil 30min, then with the volume ratio mixing of the fine sand that sieves and clean with 1: 2,121 ℃ of moist heat sterilization 60min.
3, the preparation of inoculum: the colony edge of the cotton wilt fusarium of the cultivation of making a fresh start cuts the agar block that contains mycelia, is inoculated in the triangular flask that wheat sand substratum is housed, and fully mixing was cultivated about 10 days down for 25 ℃, noted every day shaking up, and was used for the preparation of sick soil.
4, pre-treatment before the planting seed: cotton seeds is lint (500 seeds need the 10ml vitriol oil approximately) in 100 ± 5 ℃ of vitriol oils, and is extremely neutral with the tap water flushing then, removes blighted grain, dries.Before the vernalization, seed in 58 ℃ of warm water soaking 30min, is placed on the wet gauze then vernalization (being generally 24h) in 37 ℃ of thermostat containers.
5, the preparation of compound: compound concentration is 20 μ g/g.Adorn native 500g by every kind of processing and calculate (be that every alms bowl is adorned native 125g, totally 4 little alms bowls), take by weighing compound 10mg, use earlier the 3ml dissolve with ethanol, add 5g quartz sand, mix thoroughly, treat after the ethanol volatilization standby.
6, the preparation of sick soil: take by weighing sterilized cultivating soil in basin, add the wheat sand (cultivating soil: wheat sand=10: 1, w/w that contains cotton wilt fusarium by a certain percentage; Or cultivating soil: the wheat sand of oven dry=15: 1, w/w), mixing.Take by weighing the 500g sick soil, add the quartz sand that contains compound, making compound concentrations is 20ug/g.Other gets and contains bacterium but do not contain compound, contain compound but do not contain soil that bacterium and bacterium and compound do not contain in contrast.
7, sowing: will urge the seed of bud to broadcast in the cup, broadcast 5 seeds for every glass, soak from the cup bottom with sterilized water, be put in the growth room then and cultivate, 22 ℃, treat that cotton seedling is unearthed the 3rd week and the 7th week of back observations, the cotton wilt symptom of this research mainly shows as blue or green withered type, and diseased plant shows as short and small simultaneously.If blue or green dried-up dead, promptly be considered to withered.The method for expressing of prevention effect is:
8, the prevention effect of cotton wilt is measured (table 7)
Select compound embodiment-7, embodiment-14 and embodiment-15 for use, adopt the pot experiment method to measure the prevention effect of compound cotton wilt.The concentration of compound in soil is 20mg/kg, the results are shown in Table 7.Embodiment-7, embodiment-14 and embodiment-15 pair cotton wilt all have certain prevention effect, and wherein the protection effect of embodiment-14 and embodiment-15 is better than embodiment-7.
Table 7 compound is to the prevention effect of cotton wilt
-: represent this hurdle vacancy.
| Handle | Cultivate the observations in 3 weeks | Cultivate the observations in 7 weeks | ||
| The rate (%) of here withering | Prevention effect (%) | The rate (%) of here withering | Prevention effect (%) | |
| Contrast 1 (not adding fungi) contrast 2 (adding fungi) embodiment, 7 (adding fungi) embodiment, 14 (adding fungi) embodiment, 15 (adding fungi) embodiment, 7 (not adding fungi) embodiment 14 (not adding fungi) embodiment 15 (not adding fungi) | ????0 ????60 ????50 ????11 ????20 ????0 ????0 ????0 | ????- ????- ????16.67 ????81.67 ????66.67 ????- ????- ????- | ????0 ????90 ????75 ????44 ????50 ????0 ????0 ????0 | ????- ????- ????16.67 ????51.11 ????44.44 ????- ????- ????- |
Claims (8)
1, the N-acyl-trypamine compound (N-acyltryptamines) shown in the general formula [I], general formula [I] is:
Wherein:
R
1Represent hydrogen and at random substituted group (as hydroxyl, halogen, alkoxyl group, nitro, aryl, cyano group, alkylthio, amino, heterocyclic radical) on indole ring;
R
2Represent hydrogen and at random substituted group (as hydroxyl, halogen, alkoxyl group, nitro, aryl, cyano group, alkylthio, amino, heterocyclic radical) on aromatic ring;
R
3Represent at random substituted group as-(CH=CH) n-,-(CH
2) n-,-(C ≡ C) n-};
R
4Represent at random substituted group as-(CH=CH) n-,-(CH
2) n-,-(C ≡ C) n-}.
2; with Pyricularia oryzae (Magnaporthe grisea) conidial suspension spray inoculation paddy rice seedling; then in 100% relative humidity; lucifuge is clip inoculation blade after for some time; rice leaf lipid-soluble substance is passed through the vegetable chemistry separation method (as silica gel column chromatography; preparation of lamina chromatography and high performance liquid chromatography); the described N-acyl-trypamine of claim 1 compound is arrived in separation and purification: N-benzoyl tryptamines (N-benzoyltryptamine) and two kinds of plant protecting chemicals of N-cinnamoyl tryptamines (N-cinnamoyltryptamine); pass through wave spectrum analysis; carried out structure determination, its structural formula is as follows:
N-benzoyl tryptamines
N-cinnamoyl tryptamines
3, get in the pyridine that a certain amount of tryptamines is dissolved in proper volume; under the ice-water bath cooling, drip Benzoyl chloride; under the ice-water bath cooling, stir for some time (as 1 hour); at room temperature stir for some time (as 3 hours) then, reaction mixture is poured in the frozen water, divides three extractions with the chloroform of proper volume; chloroform part water and dilute hydrochloric acid washing; be removed until pyridine, chloroform is partly used siccative (as anhydrous sodium sulphate) drying, and vacuum concentration promptly gets N-benzoyl tryptamines.
4, get in the pyridine that a certain amount of tryptamines is dissolved in proper volume; under the ice-water bath cooling, drip cinnamyl chloride; under the ice-water bath cooling, stir for some time (as 1 hour); at room temperature stir for some time (as 3 hours) then, reaction mixture is poured in the frozen water, divides three extractions with the chloroform of proper volume; chloroform part water and dilute hydrochloric acid washing; be removed until pyridine, chloroform is partly used siccative (as anhydrous sodium sulphate) drying, and vacuum concentration promptly gets N-cinnamoyl tryptamines.
5; in reaction vessel that tryptamines and excess of triethylamine is mixed; add an amount of chloroform; in ice-water bath cooling and stir under; the solution of acid chloride of mole numbers such as dropping and triethylamine; under lucifuge, react; allow reaction mixture rise to room temperature naturally; stirring is spent the night; the water that adds proper volume, with after chloroform layer separates, water layer is again with the equal amounts of chloroform washing once with water layer; the combined chloroform layer; use acid solution (as 10% hydrochloric acid) successively; alkali lye (as the 2M sodium hydroxide solution) and water washing, and with after siccative (as the anhydrous sodium sulphate) drying are reclaimed solvent and are promptly obtained the 5-position acylate of hydroxyl not in the claim 1.
6; in reaction vessel that serotonin hydrochloride and water and excessive alkali aqueous solution (as 2M sodium hydroxide) is mixed; add an amount of chloroform; under the ice-water bath cooling and stirring; the solution of acid chloride of mole numbers such as dropping and alkali aqueous solution; under lucifuge, react; allow reaction mixture rise to room temperature naturally; stirring is spent the night; white precipitate occurs, filter, divide three washing precipitations with the chloroform of proper volume; then precipitation is dissolved in ethyl acetate; use acid solution (as 10% hydrochloric acid) successively; alkali lye (as the 2M sodium hydroxide solution) and water washing, and, reclaim the acylate that solvent promptly obtains the 5-position hydroxyl in the claim 1 with after siccative (as the anhydrous sodium sulphate) drying.
7, the N-acyl-trypamine compound in the claim 1 is by anti-phytopathogen (comprising rice blast fungus, watermelon Fusarium oxysporum, cucumber Fusarium oxysporum, cotton wilt fusarium, gibberella saubinetii, cotton dry thread Pyrenomycetes, the withered bacterium of rice line) structure activity relationship study research; find the high reactivity material; antibacterials as novel are used for controlling plant diseases.
8, the N-acyl-trypamine compound in the claim 1 is found the high reactivity material by the research of anti-human body pathogenic bacteria (as Candida albicans) structure activity relationship study, as novel antibacterials, is used for clinical.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021039402A CN1166637C (en) | 2002-02-19 | 2002-02-19 | Antibacterial activity, induction, separation and synthesis of N-acyltryptamine derivative as plant protecting chemical |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021039402A CN1166637C (en) | 2002-02-19 | 2002-02-19 | Antibacterial activity, induction, separation and synthesis of N-acyltryptamine derivative as plant protecting chemical |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1365971A true CN1365971A (en) | 2002-08-28 |
| CN1166637C CN1166637C (en) | 2004-09-15 |
Family
ID=4739940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021039402A Expired - Fee Related CN1166637C (en) | 2002-02-19 | 2002-02-19 | Antibacterial activity, induction, separation and synthesis of N-acyltryptamine derivative as plant protecting chemical |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1166637C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007006734A1 (en) * | 2005-07-12 | 2007-01-18 | Bayer Cropscience Sa | New benzoheterocyclylethylbenzamide derivatives |
| WO2012080220A1 (en) * | 2010-12-13 | 2012-06-21 | Katholieke Universiteit Leuven, K.U. Leuven R&D | Novel compounds for the treatment of neurodegenerative diseases |
| CN109042662A (en) * | 2018-10-10 | 2018-12-21 | 福建农林大学 | A kind of application of rice leaf extract in prevention and treatment rice blast |
| CN110012908A (en) * | 2019-05-22 | 2019-07-16 | 浙江养生堂天然药物研究所有限公司 | The method that prevention and treatment pathogen infects plant |
| CN110177581A (en) * | 2016-11-16 | 2019-08-27 | 通用医疗公司 | Myeloperoxidase imaging agent |
| CN112806376A (en) * | 2021-01-15 | 2021-05-18 | 南京农业大学 | Application of 5-methoxyindole or molecular structure analogue thereof in inhibiting phytopathogen |
| EP4142714A4 (en) * | 2020-04-29 | 2024-05-15 | Emory University | N-acetylserotonin derivatives as trkb activators and uses thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2008000449A (en) * | 2005-07-12 | 2008-03-10 | Bayer Cropscience Sa | Benzoheterocyclylethylcarboxamide derivatives. |
| KR101698646B1 (en) * | 2014-10-28 | 2017-01-23 | 경희대학교 산학협력단 | Composition comprising extract of UV-induced rice for controlling plant disease and use thereof |
-
2002
- 2002-02-19 CN CNB021039402A patent/CN1166637C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007006734A1 (en) * | 2005-07-12 | 2007-01-18 | Bayer Cropscience Sa | New benzoheterocyclylethylbenzamide derivatives |
| WO2012080220A1 (en) * | 2010-12-13 | 2012-06-21 | Katholieke Universiteit Leuven, K.U. Leuven R&D | Novel compounds for the treatment of neurodegenerative diseases |
| US9284271B2 (en) | 2010-12-13 | 2016-03-15 | Katholieke Universiteit Leuven, K.U. Leuven R&D | Compounds for the treatment of neurodegenerative diseases |
| CN110177581A (en) * | 2016-11-16 | 2019-08-27 | 通用医疗公司 | Myeloperoxidase imaging agent |
| US20190315689A1 (en) * | 2016-11-16 | 2019-10-17 | The General Hospital Corporation | Myeloperoxidase Imaging Agents |
| US11352326B2 (en) * | 2016-11-16 | 2022-06-07 | The General Hospital Corporation | Myeloperoxidase imaging agents |
| CN109042662A (en) * | 2018-10-10 | 2018-12-21 | 福建农林大学 | A kind of application of rice leaf extract in prevention and treatment rice blast |
| CN109042662B (en) * | 2018-10-10 | 2020-12-29 | 福建农林大学 | Application of rice leaf extract in preventing and treating rice blast |
| CN110012908A (en) * | 2019-05-22 | 2019-07-16 | 浙江养生堂天然药物研究所有限公司 | The method that prevention and treatment pathogen infects plant |
| EP4142714A4 (en) * | 2020-04-29 | 2024-05-15 | Emory University | N-acetylserotonin derivatives as trkb activators and uses thereof |
| CN112806376A (en) * | 2021-01-15 | 2021-05-18 | 南京农业大学 | Application of 5-methoxyindole or molecular structure analogue thereof in inhibiting phytopathogen |
| CN112806376B (en) * | 2021-01-15 | 2022-02-15 | 南京农业大学 | Application of 5-methoxyindole or molecular structure analogue thereof in inhibiting phytopathogen |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1166637C (en) | 2004-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1189086C (en) | Pest control agent comprising multiple micro-organism | |
| CN1293058C (en) | O-cyclopropyl-carboxanilides and their use as fungicides | |
| CN1537108A (en) | Iodobenzopyrran-4-one derivatives having fungicidal activity | |
| CN1847200A (en) | Pollution-less pesticide fertilizer for preventing and controlling blight and its production process | |
| CN1990484A (en) | Silybin esters derivatives and preparation and use thereof | |
| CN1437583A (en) | Trifluoromethylpyrrole carboxamides and trifluoromethylpyrrolethionamides as fungicides | |
| CN101812034A (en) | 2-substituent-5-(2,4-dichlorophenyl)-1,3,4-oxadiazole derivative, synthetic method and application thereof | |
| CN108477170A (en) | A kind of quinolines and preparation method thereof and the purposes in controlling plant diseases | |
| CN1365971A (en) | Antibacterial activity, induction, separation and synthesis of N-acyltryptamine derivative as plant protecting chemical | |
| CN112806364A (en) | Application of magnolol and derivatives thereof in preparation of medicines for preventing and treating or resisting plant diseases | |
| CN1282324A (en) | Thiazole-, isothiazole-and thiadiazole-derivatives having microbicidal and plant immunizing activities | |
| CN1281136C (en) | Pesticidal disease-preventing plant growth promoter and its prepn | |
| CN112741115B (en) | Composite plant extract for inhibiting Edwardsiella tarda in water environment and preparation method and application thereof | |
| CN101050209A (en) | Eudesmane type sesquiterpene lactone compound extracted from Carpesium macrocephalum and having antibacterial activity, and its application | |
| CN117158440A (en) | Application of turmeric carbon nanodots in prevention and treatment of wheat scab | |
| CN1200608C (en) | Medicine for resisting rice blast, its preparation method and application | |
| CN1596658A (en) | Antidisease induction agent containing yeast cell extract for plant | |
| CN109206395A (en) | The synthetic method and its agricultural biological activity of benzo oxa- class compound | |
| CN107624767A (en) | A kind of application of dipeptide compounds | |
| CN110437099B (en) | Aromatic hydrazide compound and preparation method and application thereof | |
| CN1216885C (en) | Heterocycle substd. condensed heterocyclic derivs. with bioactivity | |
| CN1166670C (en) | ANtioxidizing pseudo-enzyme compound and its preparing process and application | |
| KR20080098204A (en) | Method fro preparation of hongkuk tempeh | |
| CN112062691B (en) | Citral phenylbutyric acid oxime ester compound and synthetic method and application thereof | |
| CN116444522B (en) | Curcumin adenine derivative compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040915 |