CN109503368A - A kind of gibberellin analog and its preparation method and application - Google Patents
A kind of gibberellin analog and its preparation method and application Download PDFInfo
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- CN109503368A CN109503368A CN201811347048.4A CN201811347048A CN109503368A CN 109503368 A CN109503368 A CN 109503368A CN 201811347048 A CN201811347048 A CN 201811347048A CN 109503368 A CN109503368 A CN 109503368A
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- gibberellin
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N45/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds having three or more carbocyclic rings condensed among themselves, at least one ring not being a six-membered ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/86—Ring systems containing bridged rings containing four rings
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
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Abstract
The invention belongs to biochemical field, a kind of gibberellin analog and its preparation method and application is particularly related to.The gibberellin analog is named as GA12-X, molecular formula C20H30O5, molecular weight 350.21, chemical structure are as follows:.The preparation method of the gibberellin analog, using phosphoric acid as catalyst, reacts 6-8h under 70-75 DEG C of water bath condition using gibberellin as parent to get GA12-X.The structure is had no in 136 kinds of gibberellin class plant hormones having been found that, inventor also passes through Scifinder data base querying, does not also find the structure, it can be seen that, which is a kind of new compound.
Description
Technical field
The invention belongs to biochemical field, a kind of gibberellin analog and its preparation method and application is particularly related to.
Background technique
Gibberellin (Gibberellins, GAs) can be acted on as a kind of plant hormone being widely present in plant
In the whole life cycle of higher plant, such as promote the sprouting of seed, the elongation of stem, the induction of flower and the maturation of seed etc.,
And the response that plant can also mediate its own to environmental factor by adjusting the synthesis of endogenous gibberellin biological.Therefore, red
The regulation of mycin biosynthesis to plant development and its play the role of to the adaptation of environment particularly important.So far,
It was found that gibberellin be up to as many as 136 kinds.More importantly in the past ten years, people are not found new red mould
Element or new gibberellin route of synthesis and preparation method.It is current studies have shown that only wherein minority GA is with bioactivity, example
Such as GA1, GA3, GA4, GA7, they have some common ground in structure, for example, possess β hydroxyls of C-3, C-6 carboxyls with
And the lactone (Yamaguchi, 2008) between C-4 and C-10.If 3 β hydroxyl is by C-2 and C-3 other function
It just will form biologically active mesostate GA5 or GA6 replaced group.The GA of other biological form only exists
Play a part of intermediate product in the synthesis process of gibberellin, there is no biological functions for itself.It is all at present known red
Mycin belongs to diterpenoids compound, has similar chemical structure, all contains gibberellane skeleton (containing 4 rings), by
In double bond, hydroxy number and position difference, and various gibberellin are formed, the common gibberellin structure in part is as shown in formula.
。
Summary of the invention
The research of the invention finds that a kind of gibberellin analog and its preparation method and application, to find new gibberellin class
Plant hormone and activity research provide basis.
The technical scheme of the present invention is realized as follows:
A kind of gibberellin analog, the gibberellin analog are named as GA12-X, molecular formula C20H30O5, molecular weight is
350.21 chemical structure are as follows:
。
The preparation method of the gibberellin analog, using gibberellin as parent, using phosphoric acid as catalyst, at 70-75 DEG C
6-8h is reacted under water bath condition to get GA12-X；
Chemical reaction are as follows:。
The preparation method of the gibberellin analog, steps are as follows:
(1) GA12 is dissolved in methanol solution, prepares certain density GA12 standard solution；
(2) 3.5mL deionized water and 0.5 mL phosphoric acid solution are added into GA12 standard solution, obtains mixed solution；
(3) mixed solution in step (2) is placed in 70-75 DEG C of water-bath, magnetic agitation is reacted 6-8 hours, and GA12-X is completed
Preparation.
The concentration of GA12 standard solution is 1-3 mg/mL in the step (1).
The concentration of phosphoric acid solution is 0.5-1 mol/L in the step (2).
The revolving speed of magnetic agitation is 500-800rpm in the step (3).
Application of the gibberellin analog as plant hormone and research phytohormone activity.
It is that the technical program can generate the utility model has the advantages that
The molecular formula of compound prepared by the present invention is C20H30O5, the molecular formula of raw material (i.e. parent) is C20H28O4, the two
Differ H2O, this can also be confirmed from the molecular weight of its mass spectrogram, its m/z divides in the negative ion mode by GA12 and GA12-X
Not Wei 331.3 and 349.3, the two difference 18, with H2The molecular weight of O matches.There is ultraviolet suction at 204 nm in conjunction with GA12
Receive, and GA12-X at the wavelength without UV absorption, it may be possible to caused by being disappeared due to the double bond that contains in GA12 molecule.It is comprehensive
The above analysis, we conclude that the molecular structure of GA12-X is, in 136 kinds of gibberellin class plant hormones having been found that
In have no the structure, inventor also passes through Scifinder data base querying, does not also find the structure, it can be seen that, the compound
For a kind of new compound.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is the reaction mechanism figure for preparing GA12-X.
Fig. 2 is the LC-ESI-MS spectrogram of 1 reaction product of embodiment.
Fig. 3 is the LC-ESI-MS spectrogram of No. 6 samples in embodiment 1.
Fig. 4 is the high resolution mass spectrum analysis chart of GA12-X sample prepared by embodiment 1.
Fig. 5 is the high resolution mass spectrum fragment ion figure of GA12-X sample prepared by embodiment 1.
The nuclear magnetic data figure of Fig. 6, the 7 GA12-X samples prepared for embodiment 1.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
A certain amount of GA12 standard items are dissolved into methanol (chromatographically pure) solution, the GA12 that concentration is 1 mg/mL is configured to and marks
Quasi- solution is placed in 4 DEG C of refrigerators stand-by.It is stand-by that the phosphoric acid of chromatographically pure is configured to the phosphoric acid solution that concentration is 1 mol/L.
The phosphoric acid solution that 2.0 mL deionized waters and 0.5mL concentration are 0.5 mol/L is added to 1 mL GA12 standard solution respectively
In, the solution finally made is placed in 70 DEG C of water-baths, reacts 6 hours and can obtain in the case where revolving speed is 500 rpm magnetic agitations
To noval chemical compound GA12-X.
Embodiment 2
A certain amount of GA12 standard items are dissolved into methanol (chromatographically pure) solution, the GA12 that concentration is 3 mg/mL is configured to and marks
Quasi- solution is placed in 6 DEG C of refrigerators stand-by.It is stand-by that the phosphoric acid of chromatographically pure is configured to the phosphoric acid solution that concentration is 1 mol/L.
The phosphoric acid solution that 3.5 mL deionized waters and 1 mL concentration are 1 mol/L is added in 3mL GA12 standard solution respectively, it will
The solution finally made is placed in 75 DEG C of water-baths, and reacting 8 hours in the case where revolving speed is 800 rpm magnetic agitations can be obtained newization
Close object GA12-X.
Embodiment 3
A certain amount of GA12 standard items are dissolved into methanol (chromatographically pure) solution, the GA12 that concentration is 2 mg/mL is configured to and marks
Quasi- solution is placed in 5 DEG C of refrigerators stand-by.The phosphoric acid of chromatographically pure is configured to the phosphoric acid solution that concentration is 0.8 mol/L to wait for
With.It is molten that the phosphoric acid solution that 2.8 mL deionized waters and 0.8 mL concentration are 1 mol/L is added to 2 mL GA12 standards respectively
In liquid, the solution finally made is placed in 73 DEG C of water-baths, is reacted 7 hours in the case where revolving speed is 750 rpm magnetic agitations
Obtain noval chemical compound GA12-X.
Embodiment 4
A certain amount of GA12 standard items are dissolved into methanol (chromatographically pure) solution, the GA12 that concentration is 1 mg/mL is configured to and marks
Quasi- solution is placed in 6 DEG C of refrigerators stand-by.The phosphoric acid of chromatographically pure is configured to the phosphoric acid solution that concentration is 0.9 mol/L to wait for
With.The phosphoric acid solution that 3 mL deionized waters and 0.9 mL concentration are 0.7 mol/L is added to 2.5 mL GA12 standards respectively
In solution, the solution finally made is placed in 70 DEG C of water-baths, reacts 6 hours i.e. in the case where revolving speed is 700 rpm magnetic agitations
Noval chemical compound GA12-X can be obtained.
Application examples
One, embodiment 1 prepares the LC-ESI-MS analysis of product
The product of preparation is analyzed by High performance liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method, is used
Analysis chromatography and mass spectrum major parameter it is as follows:
1. chromatographic column: ZORBAX Eclipse XDB-C18,2.1 × 150 mm, 3.5 μm
2. mobile phase: 80% methanol/20% water
3. flow velocity: 0.2 mL/min
4. sample volume: 10 μ L
Electrospray ionisation source 5. (ESI) negative ion mode
6. capillary voltage: 3.5 kV
7. atomization gas temperature: 500 DEG C
Under these experimental conditions, obtained chromatography-mass spectroscopy figure is as shown in Fig. 2, retention time 4.85 min and 15.18 min
The mass-to-charge ratio at corresponding peak is respectively 349.3 and 331.3, by being compared with the map of GA12 standard sample, when reservation
Between be GA12 for 15.18 min sample peak, the mass-to-charge ratio of primary product is 349.3 because be in the negative ion mode into
Capable measurement, so the molecular weight of the primary product of the reaction is 350, the molecular weight relative to GA12 parent increases 18.
Two, it is purified by preparing the GA12-X that chromatography prepares embodiment 1
Using GA12 as raw material, using phosphoric acid as catalyst, new compound GA12-X is prepared by way of addition, GA12 is difficult
100% fully reacting.Therefore, in the reaction product other than product, it is also possible to have raw material (GA12) and by-product, need into
One step purifies it, this research purifies above-mentioned reaction solution by preparing chromatography, and chromatographic condition is as follows:
1. chromatographic column: ZORBAX Eclipse XDB-C18,9.4 × 250 mm, 5 μm
2. mobile phase: 80% methanol/20% water
3. flow velocity: 3 mL/min
4. sample volume: 0.5 mL
Fractional Collections are carried out to preparative liquid chromatography effluent, collection procedure is as follows: without collecting before preceding 2.0 min,
With this to 2.0-3.0 min, 3.0-4.0 min, 4.0-5.0 min, 5.0-6.0 min, 6.0-7.0 min, 7.0-8.0
Min, 8.0-9.0 min, 9.0-10.0 min, 10-11 min, 11-12 min are collected, and number is 1,2,3,4 respectively,
5,6,7,8,9, No. 10 samples.And sample collected by institute's different time sections is carried out by the LC-ESI-MS that front is established
Detection, test result show the product that mass-to-charge ratio is 349.3 in No. 6 samples, and LC-ESI-MS spectrogram is as shown in Figure 3.From
We are not difficult to find out in figure, the sample that collected sample is only 349.3 containing mass-to-charge ratio.
Three, HPLC-DAD and the LC-ESI-MS analysis of GA12 and GA12-X
Under same experimental conditions, using high performance liquid chromatography ultraviolet (HPLC-DAD) and liquid chromatography mass (LC-ESI-MS)
Joint technology respectively analyzes GA12 and GA12-X, the experimental results showed that, in both the above analysis method, can it observe
To the sample peak (m/z, 331.3) of GA12.GA12-X is only capable of observing the peak (m/z, 349.3) of response in LC-ESI-MS,
GA-12X does not observe corresponding chromatographic peak in HPLC-DAD (result is as shown in Figure 4).
Four, the high resolution mass spectrum analysis of GA12-X and structure prediction
High resolution mass spectrum fragment ion analysis (as shown in Figure 5) has been carried out to the sample of prepared GA12-X.It is raw by profession
Object informatics software, we show that the molecular formula of compound is C20H30O5, the molecular formula of raw material (i.e. parent) is C20H28O4,
The two differs H2O, this can also be confirmed from the molecular weight of its mass spectrogram (see figure 2), GA12 and GA12-X are in anion mould
Its m/z is respectively 331.3 and 349.3, the two difference 18, with H under formula2The molecular weight of O matches.In combination GA12 in 204 nm
There is a UV absorption at place, and GA12-X at the wavelength without UV absorption, it may be possible to since the double bond contained in GA12 molecule disappears
It is caused.
Five, the structure elucidation of GA12-X
Nmr analysis (experimental result is as shown in Figure 6,7) has been carried out to the sample of prepared GA12-X.It is guided by mass spectrum
Analysis partly prepares mass spectrum and GA12-X is separated and has been enriched with, and has carried out data point to GA12-X using 850 MHz nuclear-magnetisms
Analysis.By one-dimensional nuclear-magnetism and two-dimentional nmr analysis, we confirm the result of GA12-X, and structure is.The structure is had no in 136 kinds of gibberellin class plant hormones having been found that, I
Also by Scifinder data base querying, do not find the structure yet, it can be seen that, which is a kind of new compound.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. a kind of gibberellin analog, it is characterised in that: the gibberellin analog is named as GA12-X, and molecular formula is
C20H30O5, molecular weight 350.21, chemical structure are as follows:
。
2. the preparation method of gibberellin analog described in claim 1, it is characterised in that: using gibberellin as parent, with phosphoric acid
For catalyst, 6-8h is reacted under 70-75 DEG C of water bath condition to get GA12-X.
3. the preparation method of gibberellin analog as claimed in claim 2, which is characterized in that steps are as follows:
(1) GA12 is dissolved in methanol solution, prepares certain density GA12 standard solution；
(2) 3.5mL deionized water and 0.5 mL phosphoric acid solution are added into GA12 standard solution, obtains mixed solution；
(3) mixed solution in step (2) is placed in 70-75 DEG C of water-bath, magnetic agitation is reacted 6-8 hours, and GA12-X is completed
Preparation.
4. the preparation method of gibberellin analog as claimed in claim 3, it is characterised in that: GA12 is marked in the step (1)
The concentration of quasi- solution is 1-3 mg/mL.
5. the preparation method of gibberellin analog as claimed in claim 3, it is characterised in that: phosphoric acid is molten in the step (2)
The concentration of liquid is 0.5-1 mol/L.
6. the preparation method of gibberellin analog as claimed in claim 3, it is characterised in that: magnetic force stirs in the step (3)
The revolving speed mixed is 500-800 rpm.
7. application of the gibberellin analog described in claim 1 as plant hormone and research phytohormone activity.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060098676A (en) * | 2005-03-03 | 2006-09-19 | 경상북도농업기술원생물자원연구소 | Novel microbacterium aurum ma-8 and method for producing seed tuber in yam using the same |
| CN101786953A (en) * | 2010-03-17 | 2010-07-28 | 北华大学 | Kaurane-type diterpenoid compound as well as preparation method and medical application thereof |
| CN105837434A (en) * | 2016-04-22 | 2016-08-10 | 武汉大学 | Diterpenoids extracted from herba siegesbeckiae, and preparation method and application thereof |
| CN107105642A (en) * | 2015-01-14 | 2017-08-29 | 斯托尔勒企业公司 | Plant growth regulator and the non-aqueous solution of polarity and/or semi-polarity organic solvent |
-
2018
- 2018-11-13 CN CN201811347048.4A patent/CN109503368A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060098676A (en) * | 2005-03-03 | 2006-09-19 | 경상북도농업기술원생물자원연구소 | Novel microbacterium aurum ma-8 and method for producing seed tuber in yam using the same |
| CN101786953A (en) * | 2010-03-17 | 2010-07-28 | 北华大学 | Kaurane-type diterpenoid compound as well as preparation method and medical application thereof |
| CN107105642A (en) * | 2015-01-14 | 2017-08-29 | 斯托尔勒企业公司 | Plant growth regulator and the non-aqueous solution of polarity and/or semi-polarity organic solvent |
| CN105837434A (en) * | 2016-04-22 | 2016-08-10 | 武汉大学 | Diterpenoids extracted from herba siegesbeckiae, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ALEJANDRO F. BARRERO ET AL.: "Metabolism of gibberellins and ent-kaurenoids in mutants of Gibberella fujikuroi", 《PHYTOCHEMISTRY》 * |
| KARIMA M. ABOUAMER ET AL.: "The Stereochemistry of Some Reactions at C-16 in Gibberellins; An X-Ray Crystallographic Study of the Methyl Esters of Gibberellin A2 and Gibberellin A9 Hydrochloride", 《J. CHEM. SOC. PERKIN TRANS. I》 * |
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