CN102010417A - Sanguinarine derivatives and synthesis method and use thereof - Google Patents
Sanguinarine derivatives and synthesis method and use thereof Download PDFInfo
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- CN102010417A CN102010417A CN 201010537251 CN201010537251A CN102010417A CN 102010417 A CN102010417 A CN 102010417A CN 201010537251 CN201010537251 CN 201010537251 CN 201010537251 A CN201010537251 A CN 201010537251A CN 102010417 A CN102010417 A CN 102010417A
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- sanguinarine
- derivative
- dihydrosanguinarine
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- room
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- WZKXZGYBAVGAKA-UHFFFAOYSA-N Cc(cc1)ccc1NC1N(C)c2c(cc3OCOc3c3)c3ccc2-c2ccc3OCOc3c12 Chemical compound Cc(cc1)ccc1NC1N(C)c2c(cc3OCOc3c3)c3ccc2-c2ccc3OCOc3c12 WZKXZGYBAVGAKA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to sanguinarine derivatives and a synthesis method and use thereof. In the invention, 5-isopropoxy-5,6-dihydrosanguinarine, 5-p-methylphenylamino-5,6-dihydrosanguinarine and 5-benzylamino-5,6-dihydrosanguinarine are synthesized by using sanguinarine as a raw material under different conditions. The bactericidal activities of the three compounds are measured at different concentrations, and corresponding EC50 values are calculated. Compared with the conventional bactericide, the sanguinarine derivatives have the characteristics of high degradability, low residue and the like and can be synthesized by a simple and economic method. Thus, the sanguinarine derivatives are valuable bactericide pilot compounds and can be used for preventing and controlling rhizoctonia solani.
Description
Technical field
The present invention relates to the application of sanguinarine(e) derivative and synthetic method and fungicidal activity thereof.
Background technology
As everyone knows, alkaloid is a class natural product of studying the earliest, and human body, animal or Agricultural pests are had extensively and the intensive physiological activity.The monomeric substance that activity is good carries out systematically structure of modification or modification as template compound to it, and to carry out structure activity relationship (QSAR) research be one of popular domain of natural product research and deep development application.Sanguinarine(e) (C
20H
14NO
4, be naturally occurring benzo coffee pyridine Alkaloid Sanguinarine), have anticancer, desinsection, sterilization, anti-inflammatory isoreactivity.Because there is C=N in sanguinarine(e)
+The two keys of ionic, nucleophilic reagent add to easily and form a pseudobase on the C atom.In addition, 5-methoxyl group-5,6-dihydrosanguinarine and 5-oxyethyl group-5,6-dihydrosanguinarine report that also the by product as separation and Extraction benzo coffee pyridine Alkaloid obtains.Therefore, at C=N
+Structure of modification is carried out at the position, synthetic a series of derivative, and the activity of discussion sanguinarine(e) and structure activity relationship are highly significant.
Still being difficult sanguinarine(e) at present both at home and abroad is synthetic its derivative of raw material, and is applied to the report of rice banded sclerotial blight extremely.
Summary of the invention
The purpose of this invention is to provide a kind of sanguinarine(e) derivative and synthetic method and application thereof.The present invention has the obvious sterilization activity, is applied to the control of rice sheath blight disease especially.
Sanguinarine(e) derivant structure provided by the present invention is as follows:
Fungicidal activity provided by the present invention is at rice banded sclerotial blight, and the Plating that utilize to exsomatize has been measured under the compound 1-3 different concns inhibiting rate and the EC to rice banded sclerotial blight respectively
50Value.
The synthetic method that the invention provides the sanguinarine(e) derivative is respectively:
Compound 1: sanguinarine(e) is dissolved in Virahol, adds NaOH solution, and stirring at room obtains product.
Compound 2: the acetonitrile solution of sanguinarine(e), add monomethylaniline and triethylamine, stirring at room obtains product.
Compound 3: the acetonitrile solution of sanguinarine(e), add benzylamine, stirring at room obtains product.
The invention provides the sanguinarine(e) derivative and have good inhibition rice banded sclerotial blight activity, compare with traditional sterilant, have the characteristics of aspects such as easy degraded, low residue, and synthetic method is simple, economical, be the of great value sterilant lead compound of a class, can be used for the control of rice banded sclerotial blight bacterium.
Embodiment:
Compound 1: sanguinarine(e) 110mg is dissolved in the 5ml Virahol, adds 0.1N NaOH solution 5ml, stirring at room 24 hours.Phenomenon: white solid appears in orange-yellow fading away.Suction filtration, washing obtains product, productive rate 65%.Mp：247～250℃。
1H?NMR(CDCl
3，400MHz)(δ，ppm)：7.76(d，J＝8.4Hz，1H)，7.65(s，1H)，7.47(d，J＝8.4Hz，1H)，7.39(d，J＝8Hz，1H)，7.12(s，1H)，6.91(d，J＝8.4Hz，1H)，6.11(s，1H)，6.06(s，3H)，5.53(s，1H)，4.33(quint，J
1＝6.4Hz，J
2＝6Hz)，2.73(s，3H)，1.28(d，J＝6Hz，1H)，0.90(d，J＝6.4Hz，1H).
13C?NMR(CDCl
3，100MHz)(δ，ppm)：148.0，147.3，145.1，138.7，130.9，126.9，125.9，123.6，123.0，120.3，116.4，113.6，108.6，104.6，101.7，101.0，100.6，82.3，66.9，40.8，23.4，21.2.HRMS(ESI)：m/z(％)calcd?for[C
23H
21NO
5+Na]
+：414.1312；found：414.1316。
The acetonitrile solution 10ml of compound 2:110mg sanguinarine(e), to monomethylaniline 0.1g, stirring at room adds triethylamine 1-2 then and drips.Stirring at room 24h.Phenomenon: white solid appears in orange-yellow fading away.Suction filtration, washing obtains product, productive rate 75%.Mp：221～224℃。
1H?NMR(CDCl
3，400MHz)(δ，ppm)：7.74(d，J＝8.4Hz，1H)，7.48(s，1H)，7.47(d，J＝8.4Hz，1H)，7.39(d，J＝8.4Hz，1H)，7.06(s，1H)，6.99(d，J＝7.6Hz，2H)，6.94(d，J＝8Hz，1H)，6.73(d，J＝7.6Hz，2H)，6.07(s，1H)，6.03(s，1H)，6.00(s，1H)，5.96(s，1H)，5.65(s，1H)，2.71(s，3H)，2.24(s，3H).
13C?NMR(CDCl
3，100MHz)(δ，ppm)：148.0，147.6，147.4，144.9，144.0，131.1，129.5，127.9，127.4，123.8，123.2，119.9，116.5，114.5，113.8，108.5，104.2，101.7，101.1，100.9，20.5。HRMS(ESI)：m/z(％)calcd?for[C
23H
21NO
5+Na]
+：461.1482；found：461.1485。
The acetonitrile solution 10ml of compound 3:110mg sanguinarine(e) adds benzylamine 0.1ml, stirring at room 24 hours.Phenomenon: white solid appears in orange-yellow fading away.Suction filtration, washing obtains product, productive rate 75%.Mp：180～181℃。
1H?NMR(CDCl
3，400MHz)(δ，ppm)：7.78(s，1H)，7.74(d，J＝8.8Hz，1H)，7.50(d，J＝8.4Hz，1H)，7.36(m，1H)，7.34(s，2H)，7.31～7.27(m，1H)，7.23～7.20(m，1H)，7.14(s，1H)，6.88(s，1H)，6.12(s，1H)，6.08(s，2H)，6.00(s，1H)，4.99(s，1H)，4.00(dd，J
1＝13.2Hz，J
2＝12.8Hz，2H)，2.64(s，3H).
13CNMR(CDCl
3，100MHz)(δ，ppm)：148.2，147.5，147.3，144.9，140.2，131.1，128.4，128.3，127.7，126.7，125.5，123.9，123.4，120.2，116.4，115.5，108.1，104.6，101.6，101.1，100.7，68.5，48.3，41.0.Mp：180～181℃。HRMS(ESI)：m/z(％)calcd?for[C
23H
21NO
5+Na]
+：4611482；found：461.1486。
As follows under the compound 1-3 different concns provided by the invention to the rice banded sclerotial blight inhibiting rate:
Adopt the Plating that exsomatizes, measured the inhibiting rate of target compound rice banded sclerotial blight.
Plating exsomatizes: a certain amount of medicament is dissolved in the proper amount of acetone, then with containing 200 μ gmL
-1Emulsifier aqueous solution is diluted to desired concn, respectively draws the 1mL soup then and injects in the culture dish, adds the 9mL substratum more respectively, makes 50 μ gmL after shaking up
-1The pastille flat board, do blank with the flat board that adds the 1mL aqua sterilisa.Punch tool with diameter 4mm cuts the bacterium dish along the mycelia outer rim, moves on the pastille flat board.Every processing triplicate.Culture dish is placed on cultivation in 24 ± 1 ℃ of constant incubators." Invest, Then Investigate " was respectively handled bacterium dish expansion diameter in 48 hours, averaged, and relatively calculated relative bacteriostasis rate with blank.
The EC of compound 1-3 provided by the invention
50Value is as follows respectively:
Claims (5)
1. sanguinarine(e) derivative is characterized in that its structure is:
2. the synthetic method of the described sanguinarine(e) derivative 1 of claim 1 is characterized in that the step that comprises:
Under the stirring at room, the aqueous isopropanol of sanguinarine(e) adds NaOH solution, and stirring reaction 24 hours at room temperature obtains 5-isopropoxy-5, the 6-dihydrosanguinarine then.
3. the synthetic method of the described sanguinarine(e) derivative 2 of claim 1, it is characterized in that the step that comprises: under the stirring at room, the acetonitrile solution of sanguinarine(e) adds monomethylaniline, add the catalytic amount triethylamine then, stirring at room is 24 hours then, obtain 5-to toluidine-5, the 6-dihydrosanguinarine.
4. the synthetic method of the described sanguinarine(e) derivative 3 of claim 1 is characterized in that the step that comprises: under the stirring at room, the acetonitrile solution of sanguinarine(e) adds benzylamine, and stirring reaction 24 hours at room temperature obtains 5-benzyl amino-5, the 6-dihydrosanguinarine then.。
5. the application of the described sanguinarine(e) derivative of claim 1 is characterized in that it is used for the control of rice banded sclerotial blight bacterium.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010537251 CN102010417A (en) | 2010-11-10 | 2010-11-10 | Sanguinarine derivatives and synthesis method and use thereof |
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| CN 201010537251 CN102010417A (en) | 2010-11-10 | 2010-11-10 | Sanguinarine derivatives and synthesis method and use thereof |
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ID=43840765
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775417A (en) * | 2012-04-06 | 2012-11-14 | 西北农林科技大学 | Sanguinarine alcoholate, preparation method and application thereof in plant bactericide drug |
| CN112079846A (en) * | 2020-08-17 | 2020-12-15 | 贵州梵净山生态农业股份有限公司 | Sanguinarine derivative and chelerythrine derivative and application thereof |
| CN112457322A (en) * | 2020-12-02 | 2021-03-09 | 铜仁职业技术学院 | Insecticidal and antibacterial 5-imino substituted derivative and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11310530A (en) * | 1998-04-30 | 1999-11-09 | Maruho Co Ltd | Nitrogen monoxide production inhibitor |
| WO2008016596A2 (en) * | 2006-07-31 | 2008-02-07 | Marinus Pharmaceuticals, Inc. | Pseudobase benzo [c] phenanthridines with improved efficacy, stability, and safety |
-
2010
- 2010-11-10 CN CN 201010537251 patent/CN102010417A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11310530A (en) * | 1998-04-30 | 1999-11-09 | Maruho Co Ltd | Nitrogen monoxide production inhibitor |
| WO2008016596A2 (en) * | 2006-07-31 | 2008-02-07 | Marinus Pharmaceuticals, Inc. | Pseudobase benzo [c] phenanthridines with improved efficacy, stability, and safety |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102775417A (en) * | 2012-04-06 | 2012-11-14 | 西北农林科技大学 | Sanguinarine alcoholate, preparation method and application thereof in plant bactericide drug |
| CN102775417B (en) * | 2012-04-06 | 2014-03-19 | 西北农林科技大学 | Sanguinarine alcoholate, preparation method and application thereof in plant bactericide drug |
| CN112079846A (en) * | 2020-08-17 | 2020-12-15 | 贵州梵净山生态农业股份有限公司 | Sanguinarine derivative and chelerythrine derivative and application thereof |
| CN112457322A (en) * | 2020-12-02 | 2021-03-09 | 铜仁职业技术学院 | Insecticidal and antibacterial 5-imino substituted derivative and preparation method and application thereof |
| CN112457322B (en) * | 2020-12-02 | 2022-06-17 | 铜仁职业技术学院 | Insecticidal and antibacterial 5-imino substituted derivative, and preparation method and application thereof |
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Application publication date: 20110413 |