Preparation of 2-N-ACIL-9-Hydroxylovanic compounds and their re-grouped derivatives for the treatmen

专利摘要:
2-N-acyl-9-hydroxy-lobanic compounds, and their regrouped derivatives, processing methods and uses for the treatment of infections caused by phytopathogenic fungi, as fungistatic agents with low ecological impact. The present invention comprises compounds with the general formula 1 (Figure 1) and general formula 2 (Figure 2) and its preparation, wherein R1 , R2and R <sub > 3are hydrogen atoms or chains or cycles that may contain carbon, hydrogen or other hetero atoms atoms. These compounds can be used as plant protection agents to control diseases caused by fungi of the genus Botrytis. (Machine-translation by Google Translate, not legally binding)
公开号:ES2675585A1
申请号:ES201700028
申请日:2017-01-11
公开日:2018-07-11
发明作者:Isidro Gonzalez Collado；Antonio José MACÍAS SÁNCHEZ；Antonio RUANO GONZALEZ；Dhionne CORREIRA GOMEZ；Jacqueline Aparecida TAKAHASHI
申请人:Universidade Federal de Minas Gerais；Universidad de Cadiz；
IPC主号:

专利说明:

2-N-ACIL-9-HIDROXICLOV ANIC COMPOUNDS AND THEIR RE-GROUPED DERIVATIVES, PREPARATION PROCEDURES AND USES FORTHE TREATMENT OF INFECTIONS PRODUCED BY PHYTOPATOGENIC FUNGI, AS FUNGISTATIC AGENTS OF LOW
5 ECOLOGICAL IMPACT. MASTERY OF THE TECHNIQUE
The invention belongs to the field of agricultural fungicides. 10 PRIOR STATE OF THE ART
Numerous species of fungi are capable of acting as pathogens on economically important plants. In order to prevent and reducediseases caused by pathogenic fungi has developed a widerange of compounds with fungistatic or fungicidal activity.
15 Plant pathogens of considerable commercial importance are fungi of the genus Bolrytis. The genus BOlrylis includes several species such as: B. cinerea, B. a / li, B. squamosa. Among them, B. cinerea is of special interest due to the large economic losses it produces. This pathogen attacks fruits such as grapes and strawberries, vegetables such as beans,
20 carrots and cucumbers and ornamental plants such as begonias, chrysanthemums, geraniums, roses and tulips.
The development of tolerance by species of the genus Botry tis to various commercial fungicides has led to their loss of efficacy or to the need for the use of larger amounts of them. This fact united
25 to the increasing concern of public opinion about the proper use of chemical control agents and their impact on the environment, results in the need to develop new fungal chemical control agents with reduced persistence in the ecosphere and that, therefore, do not enter the food chain.
Therefore, it is interesting to obtain new fungicides and fungistatic agents with low ecological impact and methods to treat or prevent fungal infections. Previous examples of compounds to treat fungal infections are the 2-0.9 substituted c1ovanic derivatives (ES2154185 Al), the 2-N, 9-substituted c1ovanic derivatives (ES 2241482 Al), the derivatives with a phenylethanol skeleton (ES 2221805 Al ) And derivatives of (phenylhydroxyethylamino) benzoic (ES 2325513 Al).
EXPLANATION OF THE INVENTION
The invention comprises compounds with the general formula 1 (Figure 1) where R "R2 and R3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
The invention comprises compounds with the general formula 2 (Figure 2) where R "R2 and R3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
To prepare compounds of general formula 1, with R "R2 YR3 as previously defined, the following procedure can be used:
Starting from the sesquiterpene carium oxide filene (3) (Figure 3), it is possible to obtain c1ovan derivatives of the general formula 1, by acid-catalyzed regrouping, using a nitrile of the general formula (R,) (R2) (R3) CCN, where R "R2 YR3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
To prepare compounds of general formula 2, with R "R2 YR3 as previously defined, the following procedure can be used:
Starting from compounds of general formula 1, it is possible to obtain,
by means of acid-catalyzed regrouping and use of a microwave reactor, clovan derivatives of general formula 2, where R "R2 and R3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
On the other hand, starting from the caryophyllene oxide sesquiterpene (3) (Figure 3) it is possible to obtain regrouped clovan derivatives of general formula 2, by acid-catalyzed regrouping, using a nitrile of general formula (R,) (R2) (R3 ) CCN as solvent and a microwave reactor, where R "R2 and R3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
These compounds, of general formula 1 and general formula 2, are capable of reducing the growth of a fungus by applying a sufficient amount of them.
These compounds can be used to prophylactically reduce the growth of the fungus, or to reduce the growth of a fungus already present in the area to be treated. Preferably, the disclosed compounds are used to reduce or prevent the growth of plant pathogenic fungi; however, these compounds can be used to inhibit fungal growth in various non-agricultural applications (eg, to reduce moisture damage to wood, paints, etc.). BRIEF DESCRIPTION OF THE FIGURES
For the better understanding of what is described in this specification, a series of figures are attached that describe the compounds to which reference is made throughout the text.
Figure 1.- Compounds of general formula 1, where R1, R2 and R3 are chains or rings that can contain carbon, hydrogen or other heteroatoms.
Figure 2.- Compounds of general formula 2, where R1, R2 and R3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
Figure 3.-caryophyllene oxide (3).
Figure 4.- Compounds 4, 5 and 6 of general formula 1.
Figure 5.- Compounds 7, 8 and 9 of general formula 2.
Figure 6.- Table that describes the 13C_RMN data for compounds 4, 5 and 6.
Figure 7.- Table that describes the 13C_RMN data for compounds 7, 8 and 9.
Figure 8.- Percentages of inhibition of the growth of the mycelium of the fungus B. cinerea by compound 4, as a function of the concentration. Control: irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol).
Figure 9.- Percentages of inhibition of the growth of the mycelium of the fungus B. cinerea by compound 5, as a function of the concentration. Control: irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol).
Figure 10.- Percentages of inhibition of the growth of the mycelium of the fungus B. cinerea by compound 6, as a function of the concentration. Control: irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol).
Figure 11.- Percentages of inhibition of the growth of the mycelium of the fungus B. cinerea by compound 7, as a function of the concentration. Control: irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol).
Figure 12.- Percentages of inhibition of the growth of the mycelium of the fungus B. cinerea by compound 8, as a function of the concentration. Control: irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol).
Figure 13.- Percentages of inhibition of the growth of the mycelium of the fungus B. cinerea by compound 9, as a function of the concentration. Control: irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol).
Figure 14.- Table that describes the minimum inhibitory concentration of compounds 4 to 9 and irgasan, to reduce by 50% (MICso), the growth of the treated colony of the fungus B. cinerea. MODE OF EMBODIMENT OF THE INVENTION. EXAMPLES OF PREPARATION AND ACTIVITY.
Example l. Preparation of N- (9-hydroxylovan-2-yl) acetamide (4) (Figure 4).
0.150 g (0.68 mmol) of carbon dioxide (3) are added to a Schlenck flask with a margetic stirring bar, leaving the medium in an inert atmosphere. Then 1 mL of dry acetonitrile (CH3CN) and 0.067 g of Sn (OTf) 2 (0.17 mmole) are added. After 24 hours of magnetic stirring at room temperature, the reaction mixture is purified by column chromatography with increasing gradients of ethyl acetate (AcOEt) in hexane, obtaining 121 mg of compound 4.
Physical and spectroscopic data for compound 4.
Amorphous solid. [a] 25 D = -32 (c = 0.454, methane .
IRvmax (film) 3407, 2946, 1642, 1565, 1464, 1383, 1218, 757cm-1
IH-NMR (400 MHz, CD30D) 8 (ppm) 0.90 (s, 3H, H3-15), 0.91 (s, 3H, s, H3-14 ~), 0.99 (d, J = 12.8 Hz, lH, H-12-b), 0.99 (m, lH, H-llb), 1.04 (s, 3H, H3-13a), 1.10 (m, lH, H-7b) , 1.38 (m, lH, H-7a), 1.40 (m, 1H, H-3b), 1.43 (m, 1H, H-5 ~), 1.46 (m, 2H, H2-6), 1.50 (m, 1H, H-11a), 1.53 (m, 1H, H-3a), 1.55 (m, lH, H-12a), 1.56 (m, IH, H-10b), 1.95 (s, 3H, H3-18), 1.98 (m, 1H, Hl Oa), 4.09 (dd, J = 12.8, 6.0 Hz, 1 H, H-2a).
13C_NMR (100 MHz, CD30D) (see Figure 6)
Example 2. Preparation of N- (9-hydroxylovan-2-yl) pivalamide (5) (Figure 4).
O, ISO g (0.68 mmol) of caryophyllene oxide (3) are added to a flask
5 Schlenck with a margetic stirring bar, leaving the medium in an inert atmosphere. Then 3 mL of dry 2,2-dimethylpropionitrile "CH3) 3CCN) and 0.067 g of Sn (OTf) 2 (0.17 mmol) are added. After 24 hours of magnetic stirring at room temperature, the reaction mixture is purified by column chromatography with increasing gradients of ethyl acetate (AcOEt) in hexane,
10 obtaining 144mg of compound 5.
Physical and spectroscopic data for compound 5
Amorphous solid. [a] 25 D = -27 (c = 0.37, methanol)
IR vmax (film) 3428, 29S1, 2866, 1643, IS36, 1464, 7SS cm-)
IH-NMR (400 MHz, CDCI3) or (ppm) 0.88 (s, 3H, H3-13a), 0.92 (s, 3H,
15 H3-IS), 0.94 (m, lH, H-llb) 1.00 (s, 3H, H3-14P), 1.02 (m, IH, H-12-b), 1, OS ( m, lH, H-7b), 1.17 (s, 9H, H3-19, H3-20, H3-21), 1.33 (m, lH, H3b), 1.34 (m, 1H, H -SP), 1.37 (m, 2H, H2-6), 1.37 (m, IH, H-7a), 1.41 (m, IH, H-Ila), I, S3 (d, J = 13.2 Hz, lH, H-12a), 1.60 (m, IH, H-3a), 1.60 (m, 1H, Hl Ob), 1.93 (m, 1H, H- I0a), 3.24 (m, 1H, H-9P), 4.10 (ddd, J =
12.7; 8.9; 6.0 Hz, IH, H-2a), S, SI (d, J = 8.9Hz, IH, H-16).
13C_NMR (100 MHz, CDCI)) (see Figure 6) Example 3. Preparation of 2-phenyl-N- (9-hydroxyclovan-2-yl) acetamide (6) (Figure
4).
0.150 g (0.68 mmol) of caryophyllene oxide (3) are added to a Schlenck flask with a margetic stirring bar, leaving the medium in an inert atmosphere. TO
Then 3 mL of dry phenylacetonitrile (PhCH2CN) and 0.067 g of Sn (OTf) 2 (0.17 mmol) are added. After 24 hours of magnetic stirring at room temperature, the reaction mixture is purified by column chromatography with increasing gradients of ethyl acetate (AcOEt) in hexane, obtaining 198mg of compound 6.
10 Physical and spectroscopic data for compound 6
Amorphous solid. [afsD = -7 (c = 0.22, methanol).
lRvm ~ (film) 3675,3419,3311, 2928,2946,2864, 1649, 1551, 1364, 1384.757 cm-I
IH-NMR (400 MHz, CDCI)) or (ppm) 0.69 (ddt, J = 10.0, 4.8, 2.4 Hz, IH,
H-Ilb) 0.87 (s, 3H, H) -13a), 0.93 (s, 3H, H) -15), 0.95 (s, 3H, H) -14P), 1.03 (m, IH, H-7b), 1.04 (m, IH, H-12-b), 1.19 (m, 2H, H-3b, H-Ila), 1.27 (m, IH, H-5P), 1.26-1.40 (m, 2H, H2-6), 1.36 (m, IH, H-7a), 1.51 (m, IH, H-12a), 1, 53 (m, IH, H-I0b), 1.54 (m, IH, H-3a), 1.88 (m, IH, H10a), 3.24 (m, IH, H-9P), 3, 58 (m, 2H, H2-18), 4.11 (ddd, J = 12.4, 9.3;
5.9 Hz, 1H, H-2a), 5.22 (d, J = 9.3 Hz, 1H, H-16), 7.25-7.31 (3H, H-20, H -22, H-24), 7.33-7.37 (2H, H-21, H-23).
13C_NMR (100 MHz, CDCI)) (see Figure 6).
Example 4. Preparation of N- «IS, 2S, 5S, 8S) -4,4,9
trimethyl tricyclo [6.2.2.01,5] dodec-9-en-2-yl) acetamide (7) (Figure 5).
Procedure A.
0.037 g (0.17 mmol) of carbon dioxide (3) are added to a flask of
5 high pressure, leaving the medium in an inert atmosphere. Next, 14 mL of dry acetonitrile (CH) CN) and 0.020 g of Sn (OTf) 2 (0.05 mmol) are added and after sealing the reactor, it is subjected to a microwave radiation of 1000 W, until reaching a temperature of 240 ° C. After reaching said temperature, the reactor is allowed to cool to room temperature, the mixture is opened and purified.
10 reaction by column chromatography with increasing gradients of ethyl acetate (AcOEt) in hexane, obtaining 22mg of compound 7.
Procedure B.
0.037 g (0.13 mmol) of N- (9-hydroxylovan-2-yl) acetamide (4) are added to a high pressure flask, leaving the medium under an inert atmosphere. Then 14 mL of dry acetonitrile (CH) CN) and 0.017 g of Sn (OTf) 2 (0.04 mmol) are added and after sealing the reactor, it is subjected to microwave radiation of 1000 W, until reach a temperature of 240 ° C. After reaching said temperature, the reactor is allowed to cool to room temperature, the reaction mixture is opened and purified by column chromatography with increasing gradients of
20 ethyl acetate (AcOEt) in hexane, obtaining 20mg of compound 7.
Physical and spectroscopic data for compound 7.
Amorphous solid. [a] 25 D = -40 (c = 0.15, methanol)
IR V max (film) 3000, 2800, 1650, 1550, 1400, 1250 cm-I
I H NMR (500 MHz, CDCi) 8 0.75 (s, 3H, H) -14P), 0.90 (m, lH, H-1 2a),
0.92 (s, 3H, H) -13a), 1.06 (m, IH, H-7a), 1.11 (dd, J = 12.7, 3.1 Hz, IH, H-5), 1.19 (m, 1H, H -II a), 1.25 (m, 2H, H-3a, H-12b), 1.34 (m, 1H, Hllb), 1.44 (m, H-6a), 1.69 (d, J = 1.5 Hz, 3H, H-15), 1.76 (m, H-3b, H-6b, H-7b), 1.96 (s, 3H, H3-18), 2.29 (t, J = 7.1 Hz, IH, H-8), 4.36 (ddd, J = 12.4, 9.2, 6.7 Hz, 1H, H-2), 5.36 (d, J = 8.6 Hz, 1H, H-16), 5.63 (s, 1H, H10).
13C_NMR (125 MHz, CD30D) (see Figure 7)
Example 5. Preparation of N - ((IS, 2S, 5S, 8S) -4,4,9-trimethyltricyclo [6.2.2.0I, 5] dodec9-en-2-yl) pivalamide (8) (Figure 5)
Procedure A.
0.037 g (0.17 mmol) of caryophyllene oxide (3) are added to a high pressure flask, leaving the medium under an inert atmosphere. Then 14 mL of dry 2,2-dimethylpropionitrile ((CH3) 3CCN) and 0.020 g of Sn (OTf) 2 (0.05 mmol) are added and after sealing the reactor, it is subjected to microwave radiation of 1000 W, until reaching a temperature of 240 ° C. After reaching said temperature, the reactor is allowed to cool to room temperature, the reaction mixture is opened and purified by column chromatography with increasing gradients of ethyl acetate (AcOEt) in hexane, obtaining 24mg of compound 8.
Procedure B.
0.037 g (0.13 mmol) of N- (9-hydroxylovan-2-yl) pivalamide (S) are added to a high pressure flask, leaving the medium under an inert atmosphere. Then 14 mL of dry 2,2-dimethylpropionitrile ((CH3) 3CCN) and 0.017 g of Sn (OTf) 2 (0.04 mmol) are added and after sealing the reactor, it is subjected to microwave radiation of 1000 W, until reaching a temperature of 240 ° C. After reaching said temperature, the reactor is allowed to cool to room temperature, the reaction mixture is opened and purified by column chromatography with increasing gradients of ethyl acetate (AcOEt) in hexane, obtaining 23mg of compound 8.
Physical and spectroscopic data for compound 8.
Amorphous solid. [a] D = -59 (c = 0.56, methanol).
IR vmax (film) 3000, 2800, 1650, 1550, 1400, 1250 cm, l
5 IH NMR (400 MHz, CD30D) 8 0.76 (s, 3H, H3-14 ~), 0.88 (m, lH, H12a), 0.93 (s, 3H, H3-13a), 1.04 (m, lH, H-7a), 1.13 (m, 2H, H-5, H-lla),
1.18 (s, 9H, H3-19, H3-20, H3-21), 1.27 (m, 2H, H-3a, H-12b), 1.34 (m, IH, H-IIb), 1.43 (m, IH, H-6a), 1.69 (d, J = 1.5 Hz, 3H, H3-15), 1.73 (m, IH, H-7b), 1.79 (m, 2H, H-3b, H-6b), 2.28 (t, J = 7.1 Hz, lH, H-8), 4.32
10 (ddd, J = 12.3, 8.7, 6.7 Hz, IH, H-2), 5.48 (d, J = 8.5 Hz, IH, H-16), 5.64 (s, IH, H-IO).
13C_NMR (1 OOMHz, CD30D) (see Figure 7).
15 Example 6. Preparation of 2-phenyl-N - «(lS, 2S'sS, 8S) -4,4,9-trimethyltricyclo [6.2.2.01,5] dodec-9-en-2-yl) acetamide (9) ( Figure 5)
0.022 g (0.06 mmol) of 2-phenyl-N- (9-hydroxylovan-2-yl) acetamide (6) are added to a high pressure flask, leaving the medium under an inert atmosphere. Then 14 mL of dry acetonitrile (CH3CN) and 0.008 g of
20 Sn (OTt) 2 (0.02 mmol) and after sealing the reactor, it is subjected to a microwave radiation of 1000 W, until reaching a temperature of 240 ° C. After reaching said temperature, the reactor is allowed to cool to room temperature, the reaction mixture is opened and purified by column chromatography with increasing gradients of ethyl acetate (AcOEt) in hexane, obtaining
25 13mg of compound 9.
Spectroscopic data for compound 9.
Amorphous solid. [a] D = -51 (c = 0.25, methanol).
IR vmax (film) 3650, 3600, 3000, 2800, 1650, 1550, 1100, 1050, 1020 cm-1
10 NMR (400 MHz, CDCh) o0.75 (s, 3H, H3-14P), 0.88 (m, IH, H-12a),
0.94 (s, 3H, H3-13a), 1.07 (m, 2H, H-7a, H-IIa), 1.17 (m, 1H, H-5), 1.27 (m, 2H, H-3a, H-12b), 1041 (m, 2H, H-6a, H-II b), 1.50 (m, lH, H-3a) 1.63 (m, lH, H-3b), 1.66 (d, J = 1.5 Hz , 3H, H-15), 1.69 (m, IH, H-6b), 1.76 (m, IH "H-7b), 2.26 (t, J = 7.1 Hz, IH, H-8), 3048 (s, 2H, H-18), 4.27 (dd, J = 12.5, 6.7 Hz, lH, H-2), 5.59 (s, 1H, H-IO), 7.21 (m, IH, H-22), 7.27
10 (s, 4H, H-20, H-21, H-22, H-23).
13C_NMR (IOOMHz, CD30D) (see Figure 7).
Example 7. Test of inhibition of the growth of the mycelium of B. cinerea by
part of compounds 4-9. Microdilution method.
The lowest concentration that inhibits mycelial growth by 50%, with respect to the positive control (MICso) was evaluated in triplicate, by the microdilution method, using 96-well microplates. Solutions of compounds 4-9 were prepared in DMSO (12.5 mg / mL). From those
20 stock solutions, solutions of the compounds were prepared in the range 1250'06 flg / mL (compounds 4-6) or 62'5-0'06 flg / mL (compounds 7-9) using Sabourad-glucose medium, so that the final DMSO concentration does not exceed 2%. Both solutions inoculated with the fungus (Medium + Compound + Fungus, MCH) and non-inoculated solutions (Medium +
25 Composite, MC). On the other hand, control solutions were prepared containing the microorganism inoculated in the culture medium (positive control, Medium + Fungus, MH) and the sterile culture medium without inoculation (Medium, M). The
final spore concentration in the inoculated solutions is 5 x
spores / mL.
The plates were incubated for 72 hours at a temperature of 2SoC to 30 ° C together with a fungus control plate (MH) and a 5 medium control plate (M). Irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol) was used as a negative control (inhibition of the fungus in a wide range of concentrations). The tests were carried out in triplicate. After the aforementioned time, the absorbance reading was carried out at 492nm in an absorbance reader equipment in ELISA-type 96-well plates and the percentages of inhibition (1%) were calculated.
10 using the means +/- standard deviation to construct the curves that represent the percentage of inhibition (%) versus the concentration (Percentage of inhibition (1%) = 100-100 * (Abs492MCH-Abs492MC) / (Abs492MH-Abs492M Estimates of MICso values for each compound were obtained from these curves, by fitting a dose-response curve.

权利要求:
Claims (9)
[1]
1.-2-N-acyl-9-hydroxylovanic compounds, with the general formula 1 (Figure 1),
where R "R2 and R3 are hydrogen atoms or chains or rings that can
contain carbon, hydrogen or other heteroatoms.
[2]
2.-2-N-acyl substituted regrouped clovanic compounds, with the general formula 2 (Figure 2), where R "R2YR3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
[2]
2.-Use of the compounds referred to in claims 1 and 2 for the treatment of infections caused by phytopathogenic fungi, as fungistatic agents with low ecological impact.
[3]
3.-Use of the compounds referred to in claims 1 and 2 to control infections caused by phytopathogenic fungi of the genus Botrytis.
[4]
4. Use of the compounds referred to in claims 1 and 2 to inhibit fungal growth in various non-agricultural applications.
[5]
5.-Use of the compounds referred to in claims 1 and 2 to reduce the damage that fungal growth produces on wood and paints.
[6]
6.-A process to prepare compounds of formula 1 (Figure 1), according to claim 1, characterized by the reaction of caryophyllene oxide (compound
5 of formula 3) with nitriles of formula (R1) (R2) (R3) CCN and catalyzed by acid, where R1, R2 and R3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
[7]
7.-A process to prepare compounds of formula 2 (Figure 2), according to claim 2, characterized by the reaction of compounds of fomlu] to 1
10 (Figure 1), according to claim 1, in acetonitrile, catalyzed by acid and carried out in a microwave reactor, where R1, R2 and R3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
[8]
8.-A procedure to prepare compounds of formula 2 (Figure 2), according to
15 claim 2, characterized by the reaction of caryophylene oxide (compound of formula 3) in nitriles of general formula (R1) (R2) (R3) CCN, catalyzed by acid and carried out in a microwave reactor, where R1, R2YR3 are hydrogen atoms or chains or rings that can contain carbon, hydrogen or other heteroatoms.
Figure 1
Figure 2
Figure 3
14 14
Figure 4
13 14 13 14 13 14
H H 2 H
go ~ H
18 17 16
15 15
7 19 8 9
20 21
Figure 5
13C_RMN data for compounds 4, 5, and 6
4' Sb6b
Position oc (100 MHz)oc (125 MHz)oc (125 MHz)
1 45.3743.6943.80
2 58.9957.3757.64
3 46.1845.8745.65
4 38.5337.6037.65
5 51, 9450.6150.50
6 21.6820.5220.52
7 34.3533.0432.99
8 35, 9034.7434.75
9 75, 6474.8274.87
10 26.6225.5325.49
II 28.8327.3627.13
12 36.9435.6235.57
13a 31.1830.8230.77
14 ~ 24.9724.5224.55
fifteen 29.0728.1328. 14
16 ---
17 172.88178.17170.60
18 22.7338.7244.04
19 -27.61135.14
twenty -27.61129.41
twenty-one -27.61128.96
22 --127.28
2. 3 --128.96
24 --129.41
to CDJOD. b CDC1J.
Figure 6.
13C_RMN data for compounds 7, 8, and 9
7 ' 8 '98
Position ocClOO MHz)ocC 100 MHz)ocC 100 MHz)
1 47.847.9449.55
2 57.7657.6159.42
3 47.7648 .0248.00
4 38.0638.0439.13
5 56.1056.2557.51
6 26.6 126.7327.90
7 29.9629.9831.16
8 37.9836.9838.53
9 135.31134.94136. 16
10 131.70131.92133.44
eleven 32.6432.3233.73
12 2 1.2521 .2922.53
13a 28. 1228.1328.52
14p 22.4722.5222.95
fifteen 21.9422.0322. 18
16 ---
17 169.54177.92173.76
18 23.4438.6643 .94
19 27 .70137.31
twenty 27.70130.20
twenty-one 27 .70129.58
22 127.90
2. 3 129.58
24 130.20
8 CD3OD.
Figure 7.
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Inhibition of mycelial growth of B. cinerea by compound 8
90
70
SO 30 - + - Irgasan -a-Compound 8
it
-10
- S 15 35
H.H
Figure 12.
Inhibition of mycelial growth of B. cinerea by compound 9
-S
15 35 ss
Concentration (¡g / mL)
- + -Irgasan
-a-Compound 9
; j !.
c:
'or
'or
: c
: c
.5
Qj
"C
Qj
.¡¡;
...
c:
Qj
v
"
or
~
90 70 SO 30 10 -10
Figure 13.
Minimum inhibitory concentration of compounds 4 to 9 and irgasan, to reduce by 50% (MICso), the growth of the treated colony of the fungus B. cinerea (MICso, ¡.¡glmL (¡.¡ M)).
Compound 4: 23 '8 ¡.¡glmL (85'3 ¡.¡M)Compound S: 13'6 ¡.¡glmL (42'4 ¡.¡M)Compound 6: 25'0 ¡.¡glmL (70'4 ¡.¡M).Compound 7: 3'2 ¡.¡glmL (12'2 ¡.¡M).Compound 8: 3'2 ¡.¡glmL (10'6 ¡.¡M).Composite 9: 11'6 ¡.¡glmL (34'4 ¡.¡M).Irgasan (5-chloro-2- (2,4-dichlorophenoxy) phenol): 0.2 ¡.¡glmL (0.8¡. ¡M).
Figure 14

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同族专利:

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公开号 | 公开日

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ES2675585B2|2018-10-24|

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BR102017028211A2|2018-08-14|

引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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ES2241482A1|2004-03-12|2005-10-16|Universidad De Cadiz|Set of e.g. botrytis and fusarium infection medicines comprises environmentally friendly chains containing carbon, hydrogen and other hetero atoms|

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ES201700028A|ES2675585B2|2017-01-11|2017-01-11|Preparation of 2-N-ACIL-9-Hydroxyclovanic compounds and their regrouped derivatives for the treatment of infections caused by phytopathogenic fungi, as fungistatic agents with low ecological impact|ES201700028A| ES2675585B2|2017-01-11|2017-01-11|Preparation of 2-N-ACIL-9-Hydroxyclovanic compounds and their regrouped derivatives for the treatment of infections caused by phytopathogenic fungi, as fungistatic agents with low ecological impact|

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BR102017028211-2A| BR102017028211A2|2017-01-11|2017-12-27|2-n-acyl-9-hydroxyclovanic compounds and their grouped derivatives, preparation and use processes|