CN106866419A - One terpenoid ester compounds and its production and use - Google Patents
One terpenoid ester compounds and its production and use Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
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- C07C229/56—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton with amino and carboxyl groups bound to carbon atoms of the same non-condensed six-membered aromatic ring with amino and carboxyl groups bound in ortho-position
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- C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton
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Abstract
The invention belongs to chemosynthesis technical field, the terpene ester compounds with formula (I) structure are disclosed, wherein X is hetero atom O, S, N；N is 0 or 1；Substituent R is monosubstituted or polysubstituted hydrogen, halogen, cyano group, hydroxyl, nitro, C1~C5 saturations or unsaturated aliphatic hydrocarbyl moiety, C1~C5 alkoxies, phenyl, substituted-phenyl, benzyl, substituted benzyl, pyridine radicals, substituted pyridinyl.Its synthetic route with (+) fenchol, substituted aroma acid and its derivative be initiation material for initial reactant, synthetic route is reasonable, has the advantages that yield is high, easily separated.Terpene ester compounds of the present invention can be used to prevent and treat the pest and disease damage aspect of agricultural.
Description
Technical field
The invention belongs to chemosynthesis technical field, it is related to the terpene ester compounds that a class formation is new, and in particular to
The preparation method and application of Tschimganin analogs.
Background technology
Terpene ester type compound is developed to very early and more and more medicine, because its special structure and activity are special
Levy so that increasing researcher constantly pursues the transformation of its structure, change in the hope of its activity or new beneficial
The appearance of activity.The increase or change of some functional groups can be greatly improved the medicine of compound in terpene ester compounds
Effect, reduce to the toxic and side effect of human body, and compound effects property can be changed.
With the enhancing that people's environmental protection, social sustainable development are realized, the side effect of agricultural chemicals is minimized, exploitation is biological
Reasonable agricultural chemicals has turned into global common recognition.Botanical pesticide has low toxicity, low-residual, substantially harmless to non-target organism, right
The advantages of environmental nonpollution, development and appliable plant source pesticide have been increasingly becoming a kind of trend.And as the public eats to green
Product, pollution-free food demand it is increasing, market is also growing day by day to the demand of botanical pesticide.Development plant source agriculture
Medicine turns into the inexorable trend of society and scientific development.
It is one of important channel of novel pesticide research and development that lead compound is found from natural products.
Tschimganin is isolated terpene ester compounds from traditional pesticide plant asafoetide, with preferable desinsection, it is antitumor and
The bacteriostatic activity of wide spectrum.
Fungal diseases of plants is a class disease of maximum in plant disease, and it includes sunflower sclerotium (Sunflower
Sclerotinia rot), rape sclerotium (Rape sclerotinia rot), cotton silk core pathogen
(Rhizoctoniasolani), watermelon anthrax opportunistic pathogen [Colleetotrichumlagenarium (Pass.) Ell.et
Halst], Pear black spot opportunistic pathogen (Alternariakikuchiana Tanaka), rice blast pathogen
[Phyriculariagrisea (Cooke) Sacc.] and leaf muld of tomato opportunistic pathogen [Fulviafulva (Cooke) Cif.] etc., pole
The big yield and quality that have impact on crops.Insect pest is one of threat of maximum in agricultural production, and all kinds of insect pests are all made every year
Into huge loss.In recent years, the appearance of novel pesticide, especially with various unique insecticidal mechanisms and efficient safety
The novel pesticide of property, is increasingly pursued by people.
Therefore, the novel Tschimganin analogs of structure are sought, for extending its application, by with important reality
Meaning, and with very big market potential.
The content of the invention
The present invention show that a class has the Tschimganin analogs of general character structure by numerous studies.Based on this, this
Invention provides the Tschimganin analogs synthetic method, and bioactivity to various Tschimganin analogs is carried out
Research.
Terpene ester compounds of the present invention, i.e. Tschimganin analogs, the chemical constitution with formula (I)：
In formula (I), X is hetero atom O, S, N；N is 0 or 1；Substituent R is monosubstituted or polysubstituted hydrogen, halogen, cyano group, hydroxyl
Base, nitro, C1~C5 saturations or unsaturated aliphatic hydrocarbyl moiety, C1~C5 alkoxies, phenyl, substituted-phenyl, benzyl, substituted benzyl,
Pyridine radicals, substituted pyridinyl.
For the structure of full and accurate description formula (I) the terpene ester compounds, the present invention is explained to the term in context
Illustrate, but this is explained not represent and the scope of the present invention is particularly limited to.
Term " halogen " should represent fluorine, chlorine, bromine or iodine.
Term " cyano group " should represent the group of-CN.
Term " hydroxyl " should represent the group of-OH.
Term " nitro " should represent-NO2Group.
Term " aliphatic group " refers to the chain alkyl without phenyl ring.And there is the carbon of aliphatic compound base attribute
Hydrogen compound is called aliphatic hydrocarbon." C1~C5 saturated fats alkyl " is " alkyl " of C1~C5.Term " alkyl " should refer to from alkane
Hydrogen atom and derivative univalent perssad are removed on any carbon atom of hydrocarbon, the carbon atom of " alkyl " forms the bone of straight or branched
Frame, therefore, " alkyl " can be divided into " straight chained alkyl " and " branched alkyl ".The term include primary, secondary, tertiary alkyl subclass, such as methyl,
Ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl, isohesyl.It is special
Not, term " alkane " refers to the only saturated hydrocarbon compound containing carbon, hydrogen." C1~C5 unsaturated aliphatic hydrocarbyl moieties " refers to have
The chain alkyl of the C1~C5 of unsaturated bond.
Term " alkoxy " refers to the group that a hydrogen on alkane is substituted with an oxygen." C1~C5 alkoxies " refers to C1~C5
The group that a hydrogen on alkane is substituted with an oxygen.
Term " phenyl " should represent hydrogen on phenyl ring (C6) it is substituted after group." substituted-phenyl " refers to the carbon on phenyl
The hydrogen of atom is by other substituent groups." substituted-phenyl " can be divided into monosubstituted phenyl and polysubstituted phenyl.Term is " monosubstituted
Phenyl " is interpreted as the hydrogen of the one of carbon atom of phenyl by other substituent groups.For example, this hydrogen can by halogen (fluorine,
Chlorine, bromine or iodine) substitution, formed it is o-, m-, to halogenophenyl；Or replaced by methyl, form an o-methyl-phenyl, aminomethyl phenyl, right
Aminomethyl phenyl；Or by methoxy substitution, form o-methoxyphenyl, m-methoxyphenyl, p-methoxyphenyl.
Term " polysubstituted phenyl " should refer to the hydrogen of phenyl two of which or two or more carbon atom by other substituent groups.
For example, two chlorine atoms, or two fluorine atoms, or one fluorine atom of a chlorine atom can replace the hydrogen on different carbon atoms；
Benzene ring hydrogen is replaced by methyl and fluorine atom, can form 2- fluorine p-methylphenyls；Or benzene ring hydrogen is taken by methyl and chlorine
In generation, 3- chloro-2-methyl phenyl can be formed；Or benzene ring hydrogen is replaced by two trifluoromethyls, can form 3,5- fluoroforms
Base phenyl.
Term " benzyl " is also called benzyl, structure be phenyi-methylene-.Term " substituted benzyl " is interpreted as benzyl
On hydrogen by other substituent groups, this substituted radical can be on phenyl, it is also possible on methylene.
Term " pyridine radicals " is interpreted as the group after the hydrogen on pyridine is substituted.And " substituted pyridinyl " is interpreted as pyrrole
The hydrogen of the carbon atom in piperidinyl is by other substituent groups.
Additionally, the present invention gives two kinds of preparation methods of the terpene ester compounds.The first preparation method：With formula
(II) compound of structure is raw material, according to the esterification in organic synthesis, with DMAP (DMAP) and two rings
Hexyl carbodiimide (DCC) catalytic esterification obtains the terpene ester compounds of formula (I).
In formula (II), X is hetero atom O, S, N；N is 0 or 1；R is monosubstituted or polysubstituted hydrogen, halogen, cyano group, hydroxyl, nitre
Base, C1~C5 saturations or unsaturated aliphatic hydrocarbyl moiety, C1~C5 alkoxies, phenyl, substituted-phenyl, benzyl, substituted benzyl, pyridine
Base, substituted pyridinyl.The explanation of each term referring to formula (I) description, therefore not to repeat here.
To substituted aroma acid, (+)-fenchol, DMAP is added in reaction vessel, dichloromethane dissolving is added simultaneously
Stirring, ice bath is cooled to 0 DEG C；By the dichloromethane solution of dicyclohexylcarbodiimide, it is slowly dropped under ice bath above-mentioned molten
In liquid, after completion of dropping, ice bath is removed, recover to room temperature and stir, obtain the terpene ester compounds of formula (I).Specific synthesis road
Line is：
Second preparation method：Compound with formula (II) structure as raw material, i.e., first with thionyl chloride to formula (II) structure
Compound carry out chloride, obtain the terpene ester compounds of formula (I) according to the esterification synthesis in organic synthesis.
To substituted benzoic acid is added in reaction vessel, dissolved with toluene, add thionyl chloride and N, N- dimethyl formyl
Amine, heating stirring is back to reaction and terminates, and after the completion of reaction, carries out air-distillation, sloughs toluene and unnecessary thionyl chloride etc.,
Substituted benzoyl chloride is obtained, adds dichloromethane dissolving standby；It is another to take a reaction bulb, (+)-fenchol and triethylamine are added, with two
Chloromethanes dissolves, and the dichloromethane solution of substituted benzoyl chloride is added dropwise under ice bath, after completion of dropping, removes ice bath, recovers to room
Temperature is simultaneously stirred, and obtains the terpene ester compounds of formula (I).Specifically synthetic route is：
On the other hand, the present invention gives use of the terpene ester compounds of formula (I) structure in terms of agricultural pest is prevented and treated
On the way.
On the other hand, the present invention gives a kind of pharmaceutical composition, and its active component contains the terpene esterification of formula (I) structure
Compound.
Compared with prior art, terpene ester compounds of the present invention and its synthetic method have following beneficial effects or excellent
Point：
(1) synthetic route of the terpene ester compounds of formula (I) structure is novel, yield is high and product is easily isolated, it may be said that
It is the optimal route for preparing such compound.Using synthetic route of the invention, the compound from formula (II) structure is raw material,
Different Tschimganin analogs can be obtained.
(2) Tschimganin analogs of the present invention, compound structure is novel, modification transformation leeway is big.Through biometric
Examination show that this compound has excellent mite killing, desinsection and bactericidal activity, can carry out depth as pesticide activity lead compound
Enter research, and applied possibly as disinfectant use in agriculture, with potential production application value.
The present invention is further described in the examples below, without being intended to limit as indicated in claim in any form
Protection scope of the present invention.
Specific embodiment
Embodiment 1, the synthesis of Tschimganin analogs
The present embodiment with commercial reagents (+)-fenchol and substituted benzoic acid as initiation material, in DMAP
And dicyclohexylcarbodiimide (DCC) catalytic esterification obtains target product (DMAP).The synthetic route of target product is as follows.
Specific operation process：Accurately weigh substituted benzoic acid 0.01mol, (+)-fenchol 0.011mol, 4- dimethylamino pyrrole
Pyridine (DMAP) 0.002mol adds 25mL dichloromethane (DCM) dissolving stirrings in 50mL single necked round bottom flask, and ice bath is cooled to
0℃；0.008mol dicyclohexylcarbodiimides (DCC) accurately are weighed, is dissolved in 5mL dichloromethane, be slowly dropped under ice bath
In above-mentioned solution, after completion of dropping, ice bath is removed, recovered to after 10h is stirred at room temperature, original is treated in thin-layer chromatography (TLC) detection reaction
After material is wholly absent, stop reaction.Now system is the suspension with solid, using decompression suction funnel removal solids
Matter, collects liquid portion, and solvent is sloughed by Rotary Evaporators, obtains crude product.Crude product uses column chromatography, is washed through solvent
It is de-, eluent is collected successively with test tube, pure target product is obtained after merging.
Embodiment 2, the synthesis of Tschimganin analogs
The present embodiment is with commercial reagents (+)-fenchol and substituted benzoic acid as initiation material.
Specific operation process：It is accurate to weigh substituted benzoic acid 0.01mol, add 10mL toluene, 5mL thionyl chlorides and 5 drops
DMF, heating stirring flows back 2 hours；After the completion of reaction, air-distillation is carried out, slough toluene and unnecessary two
Chlorine sulfoxide etc., obtains substituted benzoyl chloride, adds dichloromethane dissolving standby；A reaction bulb separately is taken, (+)-fenchol is accurately weighed
0.011mol, 10mL dichloromethane and triethylamine 0.03mol, are added dropwise the dichloromethane solution of substituted benzoyl chloride, drop under ice bath
Recession is added except ice bath, is recovered to room temperature and is stirred, obtain the terpene ester crude product of formula (I).Crude product uses column chromatography, through launching
Agent is eluted, and eluent is collected successively with test tube, and pure target product is obtained after merging.
Embodiment 3, the structural characterization of several Tschimganin analogs
The present embodiment works out each compound reference title in the present invention to Tschimganin analog derivatives with SDH.
SDH-2：Chemical name is bicyclic [2.2.1] the hept- 2- bases -2- hydroxyls -3,5- of (1S, 2S, 4R) -1,7,7- trimethyls
Dinitrobenzoic acid ester, yellow powder.
1H NMR(400MHz,CDCl3) δ 12.90 (s, 1H), 9.06 (d, J=2.8Hz, 1H), 8.98 (d, J=2.9Hz,
1H), 4.75 (d, J=1.9Hz, 1H), 1.87 (dd, J=3.7,2.2Hz, 2H), 1.65-1.55 (m, 2H), 1.39-1.33 (m,
2H),1.23(s,3H),1.17(s,3H),0.89(s,3H).
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C17H19N2O7 -(M-H)-363.11977, measured value is 363.11548.
SDH-4：Chemical name be (1S, 2S, 4R) -1, bicyclic [2.2.1] heptane -2- yl benzoic acid esters of 7,7- trimethyls,
Colorless oil.
1H NMR(400MHz,CDCl3)δ8.14–8.04(m,2H),7.64–7.54(m,1H),7.51–7.43(m,2H),
4.65 (d, J=1.9Hz, 1H), 2.02-1.92 (m, 1H), 1.85-1.77 (m, 2H), 1.72-1.67 (m, 1H), 1.59-1.49
(m, 1H), 1.28 (dd, J=10.3,1.5Hz, 1H), 1.21 (s, 3H), 1.14 (s, 3H), 0.87 (s, 3H)
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C17H23O2 +(M+H)+259.16926, measured value is 259.16925.
SDH-7：Chemical name is bicyclic [2.2.1] the hept- 2- base -4- fluobenzoic acids of (1S, 2S, 4R) -1,7,7- trimethyls
Ester, colorless oil.
1H NMR(400MHz,CDCl3) δ 8.14-8.05 (m, 2H), 7.18-7.11 (m, 2H), 4.63 (d, J=1.9Hz,
1H), 1.98-1.88 (m, 1H), 1.80 (tt, J=9.1,3.0Hz, 2H), 1.71-1.66 (m, 1H), 1.54 (ddt, J=
12.6,5.7,4.0Hz, 1H), 1.28 (dd, J=10.4,1.5Hz, 1H), 1.20 (s, 3H), 1.13 (s, 3H), 0.86 (s,
3H).
13C NMR(101MHz,CDCl3)δ166.93,165.90,164.41,132.04,131.95,126.95,
126.92,115.59,115.37,86.84,48.61,48.40,41.45,39.83,29.74,26.89,25.91,20.29,
19.49.
HRMS, calculated value is C17H22FO2 +(M+H)+277.15983, measured value is 277.15979.
SDH-14：Chemical name is bicyclic [2.2.1] heptane -2- bases -2- chlorobenzene first of (1S, 2S, 4R) -1,7,7- trimethyls
Acid esters, white solid.
1H NMR(400MHz,CDCl3)δ7.90–7.85(m,1H),7.50–7.40(m,2H),7.37–7.31(m,1H),
4.65 (d, J=2.0Hz, 1H), 1.97-1.87 (m, 1H), 1.82-1.72 (m, 2H), 1.71-1.65 (m, 1H), 1.52 (tdd,
J=12.5,5.8,4.1Hz, 1H), 1.27 (dd, J=10.3,1.5Hz, 1H), 1.23 (s, 3H), 1.16 (s, 3H), 0.90 (s,
3H).
13C NMR(101MHz,CDCl3)δ166.16,133.59,132.33,131.41,131.10,130.65,
126.56,88.01,48.49,48.44,41.46,39.77,29.71,26.91,25.85,20.38,19.56.
HRMS, calculated value is C17H22ClO2 +(M+H)+293.13028, measured value is 293.13025.
SDH-18：Chemical name is bicyclic [2.2.1] the hept- 2- base -2- iodo-benzoic acids of (1S, 2S, 4R) -1,7,7- trimethyls
Ester, white solid.
1H NMR(400MHz,CDCl3) δ 8.02 (dd, J=7.9,1.1Hz, 1H), 7.83 (dd, J=7.8,1.7Hz,
1H), 7.43 (td, J=7.6,1.2Hz, 1H), 7.21-7.13 (m, 1H), 4.66 (d, J=1.9Hz, 1H), 1.95-1.86 (m,
1H), 1.82-1.73 (m, 2H), 1.72-1.66 (m, 1H), 1.52 (tdd, J=12.5,5.8,4.1Hz, 1H), 1.27 (dd, J
=10.3,1.5Hz, 1H), 1.24 (s, 3H), 1.18 (s, 3H), 0.91 (s, 3H)
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C17H22IO2 +(M+H)+385.06590, measured value is 385.06583.
SDH-20：Chemical name is bicyclic [2.2.1] the hept- 2- bases -4- cyano group benzene first of (1S, 2S, 4R) -1,7,7- trimethyls
Acid esters, white solid.
1H NMR(400MHz,CDCl3) δ 8.19-8.15 (m, 2H), 7.80-7.75 (m, 2H), 4.66 (d, J=1.9Hz,
1H), 1.95-1.86 (m, 1H), 1.84-1.75 (m, 2H), 1.72-1.66 (m, 1H), 1.55 (tdd, J=12.6,5.7,
4.1Hz, 1H), 1.29 (dd, J=10.5,1.6Hz, 1H), 1.20 (s, 3H), 1.13 (s, 3H), 0.85 (s, 3H)
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C18H22NO2 +(M+H)+284.16451, measured value is 284.16534.
SDH-22：Chemical name is bicyclic [2.2.1] the hept- 2- base -2- nitrobenzoyls of (1S, 2S, 4R) -1,7,7- trimethyls
Acid esters, white solid.
1H NMR(400MHz,CDCl3) δ 7.89-7.84 (m, 1H), 7.82-7.78 (m, 1H), 7.66 (dqd, J=15.0,
7.5,1.6Hz, 2H), 4.64 (d, J=2.0Hz, 1H), 1.80-1.76 (m, 1H), 1.73-1.63 (m, 3H), 1.53-1.43
(m, 1H), 1.25 (dd, J=10.3,1.5Hz, 1H), 1.21 (s, 3H), 1.15 (s, 3H), 0.87 (s, 3H)
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C17H22NO4 +(M+H)+304.15433, measured value is 304.15475.
SDH-23：Chemical name is bicyclic [2.2.1] heptane -2- base -3- nitrobenzene of (1S, 2S, 4R) -1,7,7- trimethyls
Formic acid esters, white solid.
1H NMR(400MHz,CDCl3) δ 8.88 (dd, J=2.8,1.1Hz, 1H), 8.48-8.37 (m, 2H), 7.73-
7.66 (m, 1H), 4.68 (d, J=1.9Hz, 1H), 1.99-1.88 (m, 1H), 1.82 (tq, J=9.0,2.9Hz, 2H), 1.70
(ddd, J=10.4,4.0,2.3Hz, 1H), 1.64-1.51 (m, 1H), 1.33-1.28 (m, 1H), 1.21 (s, 3H), 1.14 (s,
3H),0.87(s,3H).
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C17H22NO4 +(M+H)+304.15433, measured value is 304.15439.
SDH-24：Chemical name is bicyclic [2.2.1] the hept- 2- base -4- nitrobenzoyls of (1S, 2S, 4R) -1,7,7- trimethyls
Acid esters, light yellow solid.
1H NMR(400MHz,CDCl3) δ 8.35-8.29 (m, 2H), 8.27-8.21 (m, 2H), 4.67 (d, J=1.9Hz,
1H), 1.97-1.86 (m, 1H), 1.86-1.76 (m, 2H), 1.70 (ddd, J=10.4,4.0,2.3Hz, 1H), 1.63-1.51
(m, 1H), 1.30 (dd, J=10.5,1.5Hz, 1H), 1.21 (s, 3H), 1.14 (s, 3H), 0.86 (s, 3H)
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C17H22NO4 +(M+H)+304.15433, measured value is 304.15427.
SDH-28：Chemical name is bicyclic [2.2.1] heptane -2- bases 4- tert-butyl groups-benzene of (1S, 2S, 4R) -1,7- trimethyls
Formic acid esters, white solid.
1H NMR(400MHz,CDCl3) δ 8.06-8.02 (m, 2H), 7.52-7.48 (m, 2H), 4.64 (d, J=1.9Hz,
1H), 2.02-1.93 (m, 1H), 1.85-1.77 (m, 2H), 1.69 (dd, J=10.3,1.7Hz, 1H), 1.59-1.51 (m,
1H), (s, the 3H) of 1.37 (s, 9H), 1.27 (dd, J=10.4,1.5Hz, 1H), 1.21 (s, 3H), 1.13 (s, 3H), 0.87
13C NMR(101MHz,CDCl3)δ168.35,159.92,129.55,126.55,90.53,48.70,48.23,
41.40,40.09,29.59,26.81,25.78,20.32,19.45.
HRMS, calculated value is C21H31O2 +(M+H)+315.23186, measured value is 315.23184.
Embodiment 4, the acaricidal activity of Tschimganin analog derivatives
The present embodiment determines acaricidal activity of the Tschimganin analogs to Mite using agar blade method.Tool
The operating procedure of body is as follows：
(1) agar is configured：It is accurate to weigh 0.45g agar, 100mL distilled water is added, heating makes agar be dissolved completely in steaming
In distilled water, in each hole for being poured into 12 orifice plates before agar solution does not solidify, the 2/ of hole cumulative volume is accounted for per hole pouring volume
3, it is standby after agar solidifies completely.
(2) blade is prepared：The consistent fresh kidney beans blade of leaf age is chosen, the circular blade consistent with 12 orifice plate diameters is cut into；Will
In the test liquid medicine of the blade immersion 5mL for shearing, taken out after 30s in drying and being put into 12 orifice plates, blade back faces up.
(3) mite is connect：The female into mite (Mite, Tetranychus of the age in days of bouncing 3~4 is provoked with No. zero writing brush
Truncatus) 30, mechanical damage should not be caused when with writing brush type brush to tetranychid, immigration was soaked on the blade of medicament, was covered
Handy sealed membrane winds with one circuit.Examined using binocular anatomical lens after 24h, 48h, mite foot is gently touched with writing brush tip, with
Motionless person is death.The death rate and corrected mortality are calculated by formula (1) and (2).
In this experiment, if the control group death rate is between 5~20%, corrected mortality must be obtained；If control group is dead
Rate is represented below 5% with the death rate；If the control group death rate is more than 20%, this failure of an experiment.
In formula：P1Represent the death rate；K represents dead borer population；N represents the total borer population for the treatment of.
In formula：P2Represent corrected mortality；PtRepresent the treatment death rate；P0Represent the blank death rate.
The acaricidal activity of each Tschimganin analogs is referring to table 1.
Table 1, the acaricidal activity test result of Tschimganin analogs
As can be seen from Table 1, there is various Tschimganin analogs more obvious mite killing worm to live to Mite
Property.Compound SDH-23 in 50 μ g/mL, 24h to the acaricidal activity of Mite up to 84.44%, with comparison medicament biphenyl
Hydrazine ester, pyridaben and Hexythiazox are suitable.
Embodiment 5, the insecticidal activity of Tschimganin analogs
The present embodiment determines cytotoxicity of the Tschimganin analogs to bollworm using dip method.Specific behaviour
Make step as follows.
With reference to《Farm-chemical indoor determination test rule insecticide》NY/T1154.6-2006, determine tschimganin
Virulence of the analog to the instar larvae of bollworm 3.After 3 instar larvaes are impregnated into 5s in each concentration liquid, unnecessary medicine is blotted with filter paper
Liquid, accesses chow diet.Often treatment is repeated 3 times, often repeatedly 10 test worms.Dead worm is checked after chemicals treatment 24h, 48h, 72h
Number.Larva corrected mortality is calculated according to formula (3).The acaricidal activity of each Tschimganin analogs is referring to table 2.
Corrected mortality=(the treatment death rate-control death rate)/(100- compares the death rate) ×
100% (3)
Table 2, cytotoxicity test result of the Tschimganin analogs to bollworm
As can be seen from Table 2, compound SDH-25, SDH-26, SDH-27, SDH-28 shows certain desinsection and lives
Property.Preferably, the desinsection death rate of 48h can reach 60% to the activity of wherein SDH-28.But, majority of compounds is to bollworm
Grow and have large effect, after pharmacy effect, test worm shows slow-growing, hypogenetic symptom.Show this
Although class medicament insecticidal activity is relatively low, may have certain insect growth regulator activity, it is necessary to in-depth study be subject to it is bright
Really.
Embodiment 6, the bacteriostatic activity of Tschimganin analogs
The present embodiment determines suppression of the Tschimganin analogs to frequently seen plants pathogen using using growth rate method
System activity.Specific operating procedure is as follows.
Experiment is all operated in superclean bench, and material therefor is sterilized using high-pressure sterilizing pot.Aseptically,
Picking test strain is placed in the PDA culture medium flat board center containing different agents concentration, is control with blank PDA culture medium, is placed in
Cultivated in 25 DEG C of constant incubators, each gradient parallel testing 3 times.Growing state according to bacterium colony in blank culture dish is adjusted
Pathogen mycelial growth situation is looked into, after bacterium colony fully grows in blank, the bacterium colony of each treatment is measured with crossing method
Diameter.Mycelial growth inhibition rate is calculated by formula (4).The bacteriostatic activity of each Tschimganin analogs is referring to table 3.
Table 3, bacteriostatic activity test result (inhibiting rate %) of Tschimganin analogs
As can be seen from Table 3, most Tschimganin analogs are to day certain herbaceous plants with big flowers sclerotium, rape sclerotium, cotton silk core cause of disease
Bacterium, watermelon anthrax opportunistic pathogen show different degrees of bacteriostatic activity, and wherein SDH-2, SDH-7, SDH-11, SDH-18's is antibacterial
Activity shows stronger inhibitory action more than 50%, SDH-2 to 4 kinds of pathogens, the bacteriostatic activity with wide spectrum, and with
Comparison medicament Fluoxastrobin, trifloxystrobin have substantially suitable inhibitory activity.
Further narration has been done to the present invention above in conjunction with embodiment, but the present invention is not limited to above-mentioned implementation method,
In the ken that one skilled in the relevant art possesses, can also be made on the premise of present inventive concept is not departed from
Various change.
Claims (8)
1. there are the terpene ester compounds of formula (I) structure：
Wherein, X is hetero atom O, S, N；N is 0 or 1；
R is monosubstituted or polysubstituted hydrogen, halogen, cyano group, hydroxyl, nitro, C1~C5 saturations or unsaturated aliphatic hydrocarbyl moiety, C1~C5
Alkoxy, phenyl, substituted-phenyl, benzyl, substituted benzyl, pyridine radicals, substituted pyridinyl.
2. prepare claim 1 described in terpene ester compounds method, its with the compound of formula (II) structure as raw material, by be esterified
It is synthesized：
Wherein, X is hetero atom O, S, N；N is 0 or 1；
R is monosubstituted or polysubstituted hydrogen, halogen, cyano group, hydroxyl, nitro, C1~C5 saturations or unsaturated aliphatic hydrocarbyl moiety, C1~C5
Alkoxy, phenyl, substituted-phenyl, benzyl, substituted benzyl, pyridine radicals, substituted pyridinyl.
3. preparation method according to claim 2, its synthetic route is：
4. preparation method according to claim 2, its synthetic route is：
5. preparation method according to claim 3, it include to added in reaction vessel substituted aroma acid, (+)-fenchol,
DMAP, adds dichloromethane to dissolve and stir, and ice bath is cooled to 0 DEG C；By the dichloro of dicyclohexylcarbodiimide
Dichloromethane, is slowly dropped in above-mentioned solution under ice bath, after completion of dropping, removes ice bath, recovers to room temperature and stirs.
6. preparation method according to claim 3, it is included to substituted benzoic acid is added in reaction vessel, molten with toluene
Solution, adds thionyl chloride and DMF, and heating stirring is back to reaction and terminates；Air-distillation, sloughs toluene
With unnecessary thionyl chloride etc., substituted benzoyl chloride is obtained, add dichloromethane dissolving standby；A reaction vessel separately is taken, is added
(+)-fenchol and triethylamine, are dissolved with dichloromethane, and the dichloromethane solution of substituted benzoyl chloride, completion of dropping are added dropwise under ice bath
Afterwards, ice bath is removed, is recovered to room temperature and is stirred.
7. terpene ester compounds according to claim 1 prevent and treat agricultural pest in terms of purposes.
8. pharmaceutical composition, its active component contains the terpene ester compounds described in claim 1.
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