CN105153260B - A kind of C21Pregnane analog derivative and its preparation method and application - Google Patents
A kind of C21Pregnane analog derivative and its preparation method and application Download PDFInfo
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- CN105153260B CN105153260B CN201510643334.5A CN201510643334A CN105153260B CN 105153260 B CN105153260 B CN 105153260B CN 201510643334 A CN201510643334 A CN 201510643334A CN 105153260 B CN105153260 B CN 105153260B
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Abstract
The invention discloses a kind of C21Pregnane analog derivative and preparation method thereof, it is a kind of novel agrochemical.Its general structure isFormula（I）Middle R1For：−I、
Description
Technical field
The present invention relates to a series of C21The synthetic method of pregnane class medicine, further relate to the series compound activity into
Divide the inhibitory action to plant pathogenic fungi, belong to New pesticides discovery field.
Background technology
Plant disease brings about great losses to crop yield every year, although the method for control plant disease and measure are a variety of
It is various, but bactericide still occupies an important position in plant disease integrated control.Currently used many chemical bactericide tools
There is the characteristics of wide spectrum, efficient, less toxic, considerably improve the effect of bactericide control plant disease.But some chemical sterilizations
Agent has the resistance to the action of a drug, to environment, food accumulative pollution the problems such as, so to biogenic pesticide, particularly from natural plants, dynamic
The developmental research that new type bactericide is found and developed in thing and microorganism is current study hotspot.
The wettable powder formulation preparation WP20 of the ethyl acetate extract of cynanchum wilfordii root is preventing barley powdery mildew sprawling side
Face is more more effective than commercially available bactericide polyoxin B-WP10.Wherein cynanchum wilfordii glycosides C1N, cynanchum wilfordii glycosides C1G and cynanchum wilfordii glycosides C1GG
It is demonstrated by the antifungal activity stronger than polyoxin B.In addition, in greenhouse, the ethyl acetate extract of cynanchum wilfordii root can
Moist powder dosage formulation WP20 can be controlled effectively by the microbial powdery mildew of strawberry of powdery mildew of cucumber.Show, contain in cynanchum wilfordii
In terms of the crude extract of the steroidal of carbon 21 can be used in control powdery mildew as environmentally friendly botanical fungicide.(Mi-
Young Yoon,et al.Potent in Vivo Antifungal Activity against Powdery Mildews
of Pregnane Glycosides from the Roots of Cynanchum wilfordii.[J].J.Agric.Food
Chem.2011,59,12210–12216.)
Cynanchum wilfordii is safe and non-toxic, environmentally friendly to people and animals clinically as traditional Chinese medicine extensive utilization, but right
Phytopathogen tobacco black shank, capsicum wilt bacterium, rice blast fungus, Sclerotinia sclerotiorum, wheat scab and pears are black
The sick inhibitory action of star and the preventive and therapeutic effect to plant disease have no research report.
The content of the invention
The purpose of the present invention is with C contained in cynanchum wilfordii21Pregnane class extract, it is former to separate the announcement identified up to booth
Material, synthesizes a series of C21Pregnane analog derivative, therefrom filter out the compound of more excellent farm crop fungus resistant activity.Announcement reaches
Booth structural formula：
The present invention reaches booth as raw material to accuse, through a series of chemical synthesis, synthesis of derivatives such as table 1：
Following table 1 lists the structure of each derivative of logical formula (I) (for convenience of follow-up explanation, spy is represented with different code names):
Table 1：
The present invention screens to above-mentioned synthesis compound, finds wherein compound 1i, 1k, 1y have more excellent anti-agriculture
Crop fungi activity.
A kind of C of the present invention21Pregnane analog derivative, represented by having structure formula：
R in (I) formula (I) in formula1For：Base, signified derivative reach booth than accusing,
Hymexazol or carbendazim have more excellent anti-crop fungi activity, especially more preferable to Sclerotinia sclerotiorum effect.
The chemical name and structural formula of each derivative be：Compound 1k chemical names are that 3- sulfonyls announcement reaches booth (3-O-
Methanesulfonylcaudatin), structural formula is：
Compound 1i chemical names are that 3- iodos announcement reaches booth (3-Iodocaudatin), and structural formula is：
Compound 1y chemical names are that 3-O- nicotinoyl base announcement reaches booth (3-O-nicotinicylcaudatin), and structural formula is：
A kind of C of the present invention21The preparation method of pregnane analog derivative, be using accuse up to booth as raw material, dichloromethane be solvent,
Substitute based raw material with corresponding under nitrogen protection：Mesyl chloride, N- N-iodosuccinimides, nicotinic acid reaction produce novel substance,
Examined by TLC until reacting complete, extracted with organic solvent, merge extraction organic phase concentration through silica gel column chromatography, use oil
Ether and acetone mixture elute to obtain product.
Wherein compound 1k preparation method is：Weigh announcement and reach booth sample 1mol, in round-bottomed bottle, add DCC
(Dicyclohexylcarbodiimide) dicyclohexylcarbodiimide 1-2mol, DMAP (4-
Dimethylaminopyridine) DMAP 0.4mol, adds dichloromethane, and dichloromethane dosage presses 0.5mL bis-
Chloromethanes/1mmol, which is accused, reaches booth, and dissolving is complete, then adds mesyl chloride (methanesulfonyl chloride) 1-2mol,
Nitrogen is protected, and normal-temperature reaction 24 hours, is detected by TLC, is generated new material, until reaction raw materials reaction is complete, adds two
Chloromethanes, dichloromethane dosage is accused by 5-6mL dichloromethane/1mmol reaches booth, then, respectively with saturation aqueous tartaric acid solution,
Saturated sodium bicarbonate aqueous solution extracts, and combined dichloromethane extract is concentrated to give crude product, by silica gel column chromatography, uses petroleum ether：
Acetone=9：1 liquid elute white amorphous powder sample 3-O- mesyls accuse reach booth (3-O-
methanesulfonylcaudatin)。
Wherein compound 1i preparation method is：Weigh announcement and reach booth sample 1mol, in round-bottomed bottle, triphenylphosphine
(triphenylphosphine, Ph3P) 1-2mol, N- N-iodosuccinimide (N-iodosuccinimide, NIS) 1-
3mol, dichloromethane is added, dichloromethane dosage is accused, nitrogen protection complete up to booth dissolving by 0.5mL dichloromethane/1mmol, often
Temperature reaction 24 hours, is detected by TLC, adds dichloromethane, and dichloromethane dosage is accused by 5-6mL dichloromethane/1mmol to be reached
Booth, then, extracted respectively with saturation aqueous tartaric acid solution, saturated sodium bicarbonate aqueous solution, the concentration of combined dichloromethane extract
Crude product is obtained, passes through silica gel column chromatography (petroleum ether：Acetone=9：1) elute white amorphous powder sample 3- iodos accuse reach booth
(3-Iodocaudatin)。
A kind of C of the present invention21The application of pregnane analog derivative, it is agriculture of the compound in preventing and treating crop disease fungal pathogenses
Application in medicine or pesticides additive agent, refer to preparing preventing and treating Sclerotinia sclerotiorum, tobacco black shank, capsicum wilt bacterium, water
Application in the agricultural chemicals or pesticides additive agent of rice Pyricularia oryzae, wheat scab and pear scab, wherein especially with sclerotinia sclerotiorum
Bacterium effect is best.
The advantage of the invention is that：To natural products C21The precursor structure of pregnane class carries out functional group's transformation, synthesis system
Standby series derivates, that is, serial 3 hydroxyls have been synthesized by the derivative compound that Cl, Br, I substitute and 3 hydroxyls are acylated, because
The present invention precursor structure be natural products derivative, activity very well, so being designed using this precursor structure as lead compound
The series derivates of synthesis all have certain bioactivity, the wherein IC to Sclerotinia sclerotiorum such as compound 1i, 1k, 1y50
Respectively 0.12,0.0035,0.0068 μM；There is more excellent anti-crop fungi activity than accusing up to booth, hymexazol or carbendazim,
Because the precursor structure of the present invention is the derivative of natural products, have it is nontoxic to person poultry safety, it is friendly to bad border, so this hair
The product of bright exploitation is a kind of efficient, low toxicity, the excellent Pesticidal products of low-residual.
Embodiment
Technical scheme is described further with reference to specific experiment and embodiment.
Embodiment 1.3- mesyls accuse the preparation up to booth (3-O-methanesulfonylcaudatin, 1k)
Announcement is weighed up to booth sample 100mg (0.2mmol) in 25ml round-bottomed bottles, addition DCC
(Dicyclohexylcarbodiimide) dicyclohexylcarbodiimide 83mg (0.4mmol), DMAP (4-
Dimethylaminopyridine) DMAP 10mg (0.08mmol), dichloromethane 10ml dissolvings are added, then
Mesyl chloride (methanesulfonyl chloride) 47mg (0.4mmol) is added, nitrogen is protected, normal-temperature reaction 24 hours,
Detected by TLC, generate new material, until reaction raw materials are reacted completely, with saturation aqueous tartaric acid solution and unsaturated carbonate hydrogen
Sodium water solution and the extraction of saline solution and dichloromethane, concentrate the crude product of dichloromethane, pass through silica gel column chromatography (petroleum ether：Acetone
=9：1) white amorphous powder sample 3-O-methanesulfonylcaudatin, yield 86.2% are eluted to obtain.
1H NMR(500MHz,CDCl3)δ5.55(s,1H,H-6),5.46(s,1H,H-2′),4.58-4.56(m,2H,H-
3,12),4.24(s,2H,2×-OH),3.02(s,3H,-O-SO2-CH3),2.83(m,H,H-16),2.62-2.58(m,2H,H-
4),2.39-2.36(m,H,H-4′),2.29(s,H,-OH),2.23(brs,2H,H-7),2.16(s,3H,21-CH3),2.13
(s,3H,7′-CH3),2.03-1.82(overlap,9H,H-1,2,11,15,16),1.56-1.52(m,1H,H-9),1.38
(s,3H,18-CH3),1.17(s,3H,19-CH3), 1.08-1.06 (d, 6H, J=6.9Hz, 5 ', 6 '-CH3)；13C NMR
(125MHz,CDCl3)δ208.82(C-20),167.23(C-3′),166.06(C-1′),138.24(C-5),120.06(C-
6),112.90(C-2′),91.33(C-17),87.76(C-14),81.32(C-3),74.02(C-8),71.63(C-12),
58.04(C-13),43.50(C-9),38.80(C-4′),38.31(C-1),38.19(S-CH3),39.02(C-4),36.72
(C-10),34.33(C-15),33.47(C-7),31.62(C-16),28.11(C-2),27.18(C-21),24.11(C-11),
20.91(C-5′),20.82(C-6′),18.29(C-19),16.50(C-7′),9.33(C-18)；ESI-MS:m/z 591.2[M
+Na]+,1159.6[2M+Na]+.
The 3- iodos of embodiment 2. accuse the preparation up to booth (3-Iodocaudatin, 1i)
Announcement is weighed up to booth sample 100mg (0.204mmol) in 25mL round-bottomed bottles, triphenylphosphine
(triphenylphosphine, Ph3P) 113mg (0.427mmol), N- N-iodosuccinimide (N-iodosuccinimide,
NIS) 138mg (0.612mmol), dichloromethane 10mL dissolvings is added, nitrogen protection, normal-temperature reaction 24 hours, are examined by TLC
Survey, generate new material, until reaction raw materials reaction is complete, with saturation aqueous tartaric acid solution and saturated sodium bicarbonate aqueous solution and
Saline solution and dichloromethane extraction, concentrate the crude product of dichloromethane, pass through silica gel column chromatography (petroleum ether：Acetone=9:1) elute
Obtain white amorphous powder sample 3- iodos and accuse and reach booth (3-Iodocaudatin, 1i), yield 57.4%.
1H NMR(500MHz,CDCl3) δ 5.53 (s, 1H, H-2 '), 5.37 (d, J=4.85Hz, 1H, H-6), 4.57-
4.54 (dd, J=11.15,4.70Hz, 1H, H-12), 4.27 (s, 1H ,-OH), 4.18 (s, 1H ,-OH), 4.05-3.99 (m,
1H, H- 3), 3.01-2.96 (t, J=13.05,12.7,1.55Hz, 1H, H-4), 2.87-2.81 (m, H, H-16), 2.74-
2.71 (dd, J=13.60,4.35Hz, 1H, H-4), 2.39-2.34 (m, H, H-4 '), 2.25 (s, 2H, H-7), 2.20 (s, H ,-
OH),2.16(s,3H,21-CH3),2.13(s,3H,7′-CH3),2.00-1.78(overlap,7H,H-1,2,15,16),1.60
(s,2H,H-11),1.54-1.51(m,1H,H-9),1.39(s,3H,18-CH3),1.18(s,3H,19-CH3),1.07-1.06
(d, J=6.80Hz, 6H, 5 ', 6 '-CH3)；13C NMR(125MHz,CDCl3)δ208.81(C-20),167.09(C-1′),
166.00(C-3′),142.58(C-5),117.78(C-6),112.89(C-2′),91.37(C-17),87.85(C-14),
73.88(C-8),71.54(C-12),57.95(C-13),43.99(C-9),38.17(C-4′),36.84(C-10),45.99
(C-1),43.46(C-4),35.60(C-7),34.12(C-15),33.26(C-16),31.70(C-2),28.89(C-3),
27.16(C-21),23.94(C-11),20.91(C-6′),20.82(C-5′),18.43(C-19),16.50(C-7′),9.34
(C-18)；ESI-MS:m/z 623.2[M+Na]+,1223.3[2M+Na]+.
The 3-O- nicotinoyl base of embodiment 3. accuses the preparation up to booth (3-O- (nicotinyl) caudatin, 1y)
Announcement is weighed up to booth sample 100mg (0.204mmol) in 25mL round-bottomed bottles, addition DCC
(Dicyclohexylcarbodiimide) dicyclohexylcarbodiimide 83mg (0.4mmol), DMAP (4-
Dimethylaminopyridine) DMAP 10mg (0.08mmol), nicotinic acid (Nicotinic acid) is added
50mg (0.408mmol), nitrogen protections, dichloromethane 10ml dissolvings are then added, normal-temperature reaction 24 hours, are detected by TLC,
New material is generated, until reaction raw materials are reacted completely, with saturation aqueous tartaric acid solution and saturated sodium bicarbonate aqueous solution and food
Salt solution and dichloromethane extraction, concentrate the crude product of dichloromethane, pass through silica gel column chromatography (petroleum ether：Acetone=8:2) elute
White amorphous powder sample 3-O- nicotinoyl base, which is accused, reaches booth (3-O- (nicotinyl) caudatin, 1y), yield 93.7%.
1H NMR(500MHz,CDCl3) δ 9.21 (d, J=1.45Hz, 1H, H-3 "), 8.77-8.76 (dd, J=6.55,
4.95,1.65Hz, 1H, H-5 "), 8.32-8.29 (tt, J=7.95,2.05,1.85Hz, 1H, H-7 "), 7.42-7.39 (m,
1H,H-6″),5.54(s,1H,H-2′),5.46(brs,1H,H-6),4.96-4.89(m,1H,H-3),4.61-4.58(1H,t,
J=5.55,5.10Hz, H-12), 4.39 (s, H ,-OH), 4.29 (s, H ,-OH), 2.90-2.84 (m, H, H-16), 2.56-
2.55(m,2H,H-4),2.48(s,H,-OH),2.39-2.36(m,H,H-4′),2.25(s,2H,H-7),2.18(s,3H,21-
CH3),2.14(s,3H,7′-CH3),2.05-1.78(overlap,9H,H-1,2,11,15,16),1.61-1.58(m,1H,H-
9),1.42(s,3H,19-CH3),1.23(s,3H,18-CH3), 1.07-1.08 (d, J=6.75Hz, 6H, 5 ', 6 '-CH3)；13C
NMR(100MHz,CDCl3)δ208.9(C-20),167.0(C-1′),166.0(C-3′),164.5(C-1″),153.1(C-
5″),150.7(C-3″),138.8(C-5),137.1(C-7″),126.3(C-2″),123.3(C-6″),119.3(C-6),
112.8 (C-2 '), 91.4 (C-17), 87.9 (C-14), 74.9 (C-3), 74.1 (C-8), 71.5 (C-12), 57.9 (C-13),
43.5 (C-9), 38.3 (C-4), 38.1 (C-4 '), 37.9 (C-1), 36.9 (C-10), 34.2 (C-15), 33.2 (C-7), 31.7
(C-16), 27.2 (C-21), 26.9 (C-2), 24.1 (C-11), 20.9 (C-6 '), 20.8 (C-5 '), 18.4 (C-19), 16.5
(C-7 '), 9.4 (C-18)；ESI-MS, m/z：618.2[M+Na]+, 1213.6 [2M+Na]+.
Determination of activity of the series derivates of embodiment 4. by taking anti-Sclerotinia sclerotiorum as an example
The Sclerotinia sclerotiorum used in following examples is by the natural product chemistry emphasis experiment of the Chinese Academy of Sciences of Guizhou Province
Room provides.The activation of strain is：Using oese, 3 ring strains of scraping are accessed on potato dextrose agar (PDA),
Cultivated 72 hours at 28 DEG C.
Bacteriostasis is detected using virulence flat band method.With a diameter of 4mm card punch respectively in the Sclerotina Sclerotiorum in Winter Rape activated
The bacteria cake for taking a diameter of 4mm is beaten on the PDA plate of core germ, is then respectively adding in the band poison and control flat board of active material
Centre, each handle 3 repetitions.28 DEG C are cultivated lucifuge 7 days, observe antibacterial situation.Bacteria cake diameter is surveyed with crossing method, is calculated
Specific inhibiting rate.
Inhibition rate (I, %)=(C-T)/(C-4mm) × 100%
I active material inhibiting rates, C blank control bacteria cake growth diameters, bacteria cake growth diameter on T virulence flat boards.
According to the different inhibiting rates under gradient concentration, IC is calculated50Value, the results are shown in Table 2.
IC50 measurement result of the series derivates of table 2. to Sclerotinia sclerotiorum
| Compd | IC50(μM) | Compd | IC50(μM) | Compd | IC50(μM) |
| 1 | 9.18 | 1m | 164.91 | 1z | 190.36 |
| 1a | 35.80 | 1n | 206.81 | 2 | 2.44 |
| 1b | 17.67 | 1o | 35.95 | 3 | 0.44 |
| 1c | 69.16 | 1p | 45.97 | 4 | 0.83 |
| 1d | 4.62 | 1q | 125.09 | 5 | 11.82 |
| 1e | 1.16 | 1r | 51.02 | 6 | 0.95 |
| 1f | 1.91 | 1s | 1349.21 | 7 | 6.39 |
| 1g | 1.08 | 1t | 170.05 | 8 | 2.14 |
| 1h | 0.81 | 1u | 67.41 | 9 | 30.72 |
| 1i | 0.12 | 1v | 1.08 | 10 | 0.94 |
| 1j | 2.56 | 1w | 1.57 | 11 | 57.21 |
| 1k | 0.0035 | 1x | 56.10 | Carbendazim | 1.73 |
| 1l | 0.37 | 1y | 0.0068 | Hymexazo | 96.87 |
aEach sample average is repeated 5 times,bPositive control Wei hymexazos and carbendazim.
From table 2., compound 1i, 1k and 1y IC50Value is respectively 0.12,0.0035,0.0068 μM；Than accuse up to booth,
Hymexazol or carbendazim have more excellent anti-crop fungi activity.
Claims (7)
- A kind of 1. C21Pregnane analog derivative, it is characterized in that the chemical name and structural formula of each derivative are：Compound 1i chemical names are that 3- iodos announcement reaches booth (3-Iodocaudatin), and structural formula is：Compound 1k chemical names are that 3-O- mesyls announcement reaches booth (3-O-methanesulfonylcaudatin), structural formula For：
- A kind of 2. C as defined in claim 121The preparation method of pregnane analog derivative, it is characterized in that using accuse up to booth as Raw material, dichloromethane are solvent, substitute based raw material with corresponding under nitrogen protection：Mesyl chloride, N- N-iodosuccinimides Reaction produces novel substance, is examined by TLC until reacting complete, is extracted with organic solvent, merge extraction organic phase concentration through silicon Plastic column chromatography, product is eluted to obtain with petroleum ether and acetone mixture.
- A kind of 3. C according to claim 221The preparation method of pregnane analog derivative, it is characterized in that compound 1i system Preparation Method is：Weigh announcement and reach booth sample 1mol, in round-bottomed bottle, triphenylphosphine 1-2mol, N- N-iodosuccinimide 1-3mol, Dichloromethane is added, dichloromethane dosage is accused, nitrogen protection complete up to booth dissolving by 0.5mL dichloromethane/1mmol, and normal temperature is anti- Answer 24 hours, detected by TLC, add dichloromethane, dichloromethane dosage is accused by 5-6mL dichloromethane/1mmol reaches booth, so Afterwards, extracted respectively with saturation aqueous tartaric acid solution, saturated sodium bicarbonate aqueous solution, combined dichloromethane extract is concentrated to give slightly Product, by silica gel column chromatography, petroleum ether and acetone mixture elute white amorphous powder sample 3- iodos are accused and reach booth (3- Iodocaudatin)。
- A kind of 4. C according to claim 221The preparation method of pregnane analog derivative, it is characterized in that compound 1k system Preparation Method is：Weigh announcement and reach booth sample 1mol, in round-bottomed bottle, add dicyclohexylcarbodiimide 1-2mol, 4- dimethylamino Pyridine 0.4mol, dichloromethane is added, dichloromethane dosage is accused by 0.5mL dichloromethane/1mmol reaches booth, and dissolving is complete, then Mesyl chloride 1-2mol is added, nitrogen protection, normal-temperature reaction 24 hours, is detected by TLC, generates new material, until reaction Raw material reaction is complete, adds dichloromethane, and dichloromethane dosage is accused by 5-6mL dichloromethane/1mmol reaches booth, then, uses respectively Saturation aqueous tartaric acid solution, saturated sodium bicarbonate aqueous solution extraction, combined dichloromethane extract are concentrated to give crude product, pass through silica gel Column chromatography, petroleum ether and acetone mixture elute white amorphous powder sample 3-O- mesyls accuse reach booth (3-O- methanesulfonylcaudatin)。
- A kind of 5. C according to claim 121The application of pregnane analog derivative, it is characterized in that prepared by the derivative Prevent and treat the application in the agricultural chemicals or pesticides additive agent of crop disease fungal pathogenses.
- A kind of 6. C according to claim 521The application of pregnane analog derivative, it is characterized in that prepared by the derivative Prevent and treat Sclerotinia sclerotiorum, tobacco black shank, capsicum wilt bacterium, rice blast fungus, wheat scab and pear scab Application in agricultural chemicals or pesticides additive agent.
- A kind of 7. C according to claim 521The application of pregnane analog derivative, it is characterized in that prepared by the derivative Prevent and treat the application in the agricultural chemicals or pesticides additive agent of Sclerotinia sclerotiorum.
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