CN105837549B - A kind of ocean terpene natural products ent chromazonarol synthetic method - Google Patents
A kind of ocean terpene natural products ent chromazonarol synthetic method Download PDFInfo
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- CN105837549B CN105837549B CN201610238607.2A CN201610238607A CN105837549B CN 105837549 B CN105837549 B CN 105837549B CN 201610238607 A CN201610238607 A CN 201610238607A CN 105837549 B CN105837549 B CN 105837549B
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- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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Abstract
The present invention relates to a kind of ocean terpene natural productsentChromazonarol synthetic method, belongs to the field of chemical synthesis.The present invention is using fragrant perillaldehyde and the dimethoxy benzene of 2 iodine 1,4 as initiation material.Fragrant perillaldehyde and unifor generate fragrant purple perilla sulphonyl hydrazone by condensation reaction, fragrant purple perilla sulphonyl hydrazone and 2 iodine 1,4 dimethoxy benzenes obtain enolization compound by coupling reaction, enolization compound obtains alkene terpene compound by intramolecular reduction reaction and double bond isomerization reaction, alkene terpene compound undergoes oxidation reaction and reduction reaction obtains alkene phenolic compounds, and alkene phenolic compounds obtains target ocean terpene natural products by cyclizationent‑chromazonarol.The present invention has the characteristics that few reactions steps, easy to operate, good product selectivity, is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of ocean terpene natural productsent- chromazonarol synthetic method.
Background technology
Ocean terpene natural productsent-chromazonarol（See accompanying drawing 1）In 1975 first from marine spongedysidea pallescensMiddle separation and Extraction (Experientia, 1975, 31(10): 1117-1118).This kind of chemical combination
The skeleton of thing is made up of sequiterpene part and quinones or hydroquinones part.This kind of compound show including it is antiviral,
The multiple biological activities such as anticancer, antimycotic, anti-malarial, treating tuberculosis and immunological regulation (Science China Chemistry,
2013, 56(3): 349-353; Tetrahedron, 2000, 56(7): 949-953; The Journal of Organic Chemistry, 1995, 60(22): 7290-7292; Journal of natural products,
1998, 61(12): 1502-1508)。
At present to Yu Haiyang terpene natural productsent- chromazonarol synthetic method there is synthetic route compared with
The drawback such as long, initiation material or reaction reagent costliness.Barrero et al. reported in the research of 1999, reacts and completes through 12 steps
Ocean terpene natural productsent- chromazonarol study on the synthesis (Bioorganic & medicinal chemistry letters, 1999, 9(16): 2325-2328)；Research reports of the Villamizar et al. in 2006,
The inflammable sex pill such as isobutyl group lithium has been used in course of reaction, the study on the synthesis of the natural products is completed through the reaction of 10 steps
(Synthetic communications, 2006, 36(3): 311-320)；Research reports of the Baran et al. in 2012,
Used in course of reaction the valuable reaction reagent such as silver fluoride (Journal of the American Chemical Society, 2012, 134(20): 8432-8435)。
In view of the studies above present situation, exploitation it is a kind of it is easy to operate, cost is cheap, is adapted to the ocean terpene day of industrialized production
Right productent- chromazonarol chemical synthesis process just seems particularly necessary.The natural products that the present invention reports
Synthetic method possesses few reactions steps, easy to operate, good product selectivity, is adapted to the advantages that industrialized production.
The content of the invention
1. present invention aims at provide a kind of ocean terpene natural productsent- chromazonarol synthetic method.
Reactions steps are few, good product selectivity, suitable industrialized production.
To achieve the above object, the present invention comprises the following steps：
A) fragrant perillaldehyde 1 and unifor generate fragrant purple perilla sulphonyl hydrazone 2 by condensation reaction；
B) in the basic conditions, the iodo- Isosorbide-5-Nitrae-dimethoxy benzenes 3 of 2- and the via palladium-catalyzed coupling reaction of fragrant purple perilla sulphonyl hydrazone 2,
Synthesize enolization compound 4；
C) in the presence of hydrogen donor and acid reduction reaction and double bond isomerization reaction occur for enolization compound 4, synthesize alkene
Terpene compound 5；
D) alkene terpene compound 5 is through peroxidization and reduction reaction, synthesis alkene phenolic compounds 6；
E) alkene phenolic compounds 6 obtains target natural products through acid catalysis cyclizationent-chromazonarol。
2. the step a prioritization schemes：Fragrant perillaldehyde 1 generates the reaction of fragrant purple perilla sulphonyl hydrazone 2 with unifor, excellent
It is solvent first to select the fatty alcohols such as methanol, ethanol, and reaction temperature is 0 °C and arrives backflow, and the reaction time is 1 ~ 12 hour condition.
3. the step b prioritization schemes：In the basic conditions, the iodo- Isosorbide-5-Nitrae-dimethoxy benzenes 3 of 2- and fragrant purple perilla sulphonyl hydrazone 2
Via palladium-catalyzed coupling reaction synthesizes enolization compound 4, prioritizing selection potassium hydroxide, sodium carbonate, cesium carbonate, potassium carbonate etc.
Alkali, bi triphenyl phosphorus palladium chloride, double acetonitrile palladium chlorides, three（Dibenzalacetone）Two palladiums, [double (diphenylphosphines) two of 1,1'-
Luxuriant iron] palladium chloride, tetra-triphenylphosphine palladium etc. be catalyst, prioritizing selection tetrahydrofuran, toluene, acetonitrile, 1,2- dichloroethanes,
Isosorbide-5-Nitrae-dioxane, DMF etc. are solvent, and reaction temperature is 0 °C and arrives backflow, and the reaction time is 6 ~ 24 hours
Condition.
4. the step c prioritization schemes：In the presence of hydrogen donor and acid reduction reaction and double occurs for enolization compound 4
Key isomerization reaction, the reaction of structure alkene terpene compound 5, prioritizing selection trimethyl silane, triethyl silicane, tri-phenyl-silane are
Hydrogen donor, prioritizing selection trifluoroacetic acid are acid, and dichloromethane is solvent, and reaction temperature is -20 °C to 40 °C, and the reaction time is
3 ~ 12 hours conditions.
5. the step d prioritization schemes：Alkene terpene compound 5 synthesizes alkene phenolic compounds 6 through peroxidization and reduction reaction
Reaction, prioritizing selection DDQ, ammonium ceric nitrate, iodobenzene diacetate etc. be oxidant, acetone-water, acetonitrile-water,
Water etc. is reaction dissolvent, and prioritizing selection sodium dithionite, palladium carbon catalytic hydrogen reduction, tetrahydrofuran-water, methanol etc. are reaction
Solvent, reaction temperature be room temperature to 0 °C to 40 °C, 1 ~ 6 hour reaction time condition.
6. the step e prioritization schemes：Alkene phenolic compounds 6 obtains target natural products through acid catalysis cyclizationent- chromazonarol reaction, the prioritizing selection concentrated sulfuric acid, p-methyl benzenesulfonic acid, BFEE etc. is sour, nitro third
Alkane, toluene, dichloromethane etc. are solvent, and reaction temperature is -78 °C and arrives room temperature, 1 ~ 6 hour reaction time condition.
Compared with related synthesis report before, the invention has the characteristics that：
1. for the present invention using known fragrant perillaldehyde and the iodo- Isosorbide-5-Nitrae-dimethoxy benzenes of 2- as initiation material, reactions steps are few, fit
Close industrialized production.
2. total recovery is high, good product selectivity.
Brief description of the drawings
Accompanying drawing 1 is:Ocean terpene natural productsent- chromazonarol structural formula figure.
Accompanying drawing 2 is:The specific synthetic route chart of the present invention.
Embodiment
Embodiment 1：Fragrant purple perilla sulphonyl hydrazone（2, see accompanying drawing 2）Synthesis
Take fragrant 2.38 grams of perillaldehyde（1,10.0 mmol）It is dissolved in 30 milliliters of absolute methanols, adds unifor
1.86 gram（10.0 mmol）, stirring reaction 3 hours at room temperature, TLC detection reactions terminate.Concentration, produces white solid perfume (or spice) purple perilla
Sulphonyl hydrazone.
Embodiment 2：Enolization compound（4, see accompanying drawing 2）Synthesis
Take fragrant 407 milligrams of purple perilla sulphonyl hydrazone（2,1.0 mmol）It is dissolved in 4 milliliters of anhydrous tetrahydro furans, adds four triphenyls
23 milligrams of phosphine palladium（0.02 mmol）, 622 milligrams of potassium carbonate（4.5 mmol）Row's argon gas is filled repeatedly three times, drains air.Separately take 2-
Iodo- 264 milligrams of 1,4- dimethoxy benzenes（3,1.0 mmol）It is dissolved in 2 milliliters of anhydrous tetrahydro furans, is slowly added dropwise to above-mentioned anti-
Answer in system, be warming up to 110 °C, stirring reaction 10 hours, TLC detection reactions terminate.The milli of water 30 is added into reaction system
Rise, ethyl acetate extraction（10 mL x 3）, merge organic phase, saturated common salt water washing, anhydrous sodium sulfate drying, filter, it is dense
Contracting, column chromatography purification, obtains 315 milligrams of pale yellow oil, yield 81%.
Embodiment 3：Alkene terpene compound（5, see accompanying drawing 2）Synthesis
Take 179 milligrams of enolization compound（4,0.5 mmol）It is dissolved in 2 milliliters of dry methylene chlorides, adds triethyl silicane
174 milligrams（1.5 mmol）0 °C of stirring reaction 5 minutes, 114 milligrams of trifluoroacetic acid is added dropwise（1.0 mmol）It is small to continue reaction 5
When, TLC detection reactions terminate.Add 10 milliliters of water, ethyl acetate extraction（10 mL x 3）, merge organic phase, saturated aqueous common salt
Washing, anhydrous sodium sulfate drying, filter, concentration, column chromatography purification, obtain 146 milligrams of weak yellow liquid, yield 85%.Nuclear-magnetism is total to
The hydrogen that shakes is composed1H NMR (400 MHz, CDCl3) d 6.78(d, 1H, J = 8.4 Hz), 6.69(d, 2H, J = 10.8
Hz), 3.85(s, 3H), 3.79(s, 3H), 3.42(d, 1H, J = 17.8 Hz), 3.26(d, 1H, J = 17.8
Hz), 1.52(s, 3H), 1.05(s, 3H), 0.94(s, 3H), 0.88(s, 3H) ;Carbon-13 nmr spectra13C NMR
(100 MHz, CDCl3) 153.4, 151.5, 137.2, 131.3, 129.0, 116.1, 110.2, 109.1,
55.8, 55.6, 51.9, 41.7, 38.9, 36.0, 33.5, 33.4, 33.3, 26.9, 21.8, 20.3, 20.2,
19.2, 18.9。
Embodiment 4：Alkene phenolic compounds（6, see accompanying drawing 2）Synthesis
Take 171 milligrams of alkene terpene compound（5,0.5 mmol）It is dissolved in 2 milliliters of acetonitrile-waters（1:1）In, add ammonium ceric nitrate
548 milligrams（1.0 mmol）Reaction 2 hours is stirred at room temperature, TLC detection reactions terminate.Add 10 milliliters of water, ethyl acetate extraction
（10 mL x 3）, merge organic phase, saturated common salt water washing, anhydrous sodium sulfate drying, filter, concentration, column chromatography purification, obtain
141 milligrams of yellow solid, yield 90%.By 156 milligrams of yellow liquid（0.5 mmol）It is dissolved in 2 milliliters of tetrahydrofuran-water（1：
1）In, add 237 milligrams of sodium dithionite（1.5 mmol）, 32.2 milligrams of TBAB（0.1 mmol）It is stirred at room temperature
Reaction 2 hours, TLC detection reactions terminate.Add 10 milliliters of water, ethyl acetate extraction（10 mL x 3）, merge organic phase, satisfy
And brine It, anhydrous sodium sulfate drying, filtering, concentrate and produce.
Embodiment 5：ent- chromazonarol synthesis
By 157 milligrams of alkene phenolic compounds（6,0.5 mmol）It is dissolved in 2 milliliters of dry methylene chlorides, fills row's argon gas three repeatedly
It is secondary, drain air, -20 °C of 355 milligrams of BFEEs of addition（2.5 mmol）, reaction 2 hours, TLC detections is stirred at room temperature
Reaction terminates.Add water quenching to go out reaction, ethyl acetate extracts（10 mL x 3）, merge organic phase, saturated common salt water washing, nothing
Aqueous sodium persulfate is dried, and is filtered, concentration, column chromatography purification, obtains 140 milligrams of pale yellow oil, yield 89%.Hydrogen nuclear magnetic resonance
Spectrum1H NMR (400 MHz, CDCl3) d6.62 (d, 1H, J = 7.9 Hz), 6.56 (d, 2H, J = 8.2 Hz),
2.57 (d, 2H, J = 8.8 Hz), 1.17 (s, 3H), 0.90 (s, 3H), 0.88 (s, 3H), 0.84 (s,
3H) ;Carbon-13 nmr spectra13C NMR (100 MHz, acetone-d6) 152.3, 148.1, 124.7, 118.9,
117.4, 115.9, 77.7, 57.9, 54.3, 43.6, 43.1, 40.9, 38.5, 34.8, 34.8, 24.1,
22.9, 22.1, 21.4, 20.2, 16.2。
The present invention relates to fragrant perillaldehyde generate the reaction of fragrant purple perilla sulphonyl hydrazone, palladium chtalyst coupling reaction, it is acid catalyzed also
The 5 steps reactions such as the cyclization that original reaction and double bond isomerization reaction, oxidation reaction and reduction reaction, acid act on, synthesize ocean
Terpene natural productsent-chromazonarol.Above-mentioned specific implementation citing is only the preferred embodiments of the present invention, is not to this
The limitation of other forms is made in invention.
Claims (6)
1. a kind of marine natural products ent-chromazonarol synthetic method, it is characterised in that including following synthesis step
Suddenly：
A) fragrant perillaldehyde 1Fragrant purple perilla sulphonyl hydrazone 2 is generated by condensation reaction with unifor
B) in the case where reaction temperature is 110 DEG C of alkalescence condition, the iodo- Isosorbide-5-Nitrae-dimethoxy benzenes 3 of 2-With fragrant purple perilla sulphur
Acylhydrazone 2Via palladium-catalyzed coupling reaction, synthesize enolization compound 4
C) enolization compound 4In the presence of triethyl group silicon hydrogen and trifluoroacetic acid, it is anti-that reduction occurs
Should and double bond isomerization reaction, synthesis alkene terpene compound 5
D) alkene terpene compound 5By anti-as the oxidation of oxidant using ammonium ceric nitrate or iodobenzene diacetate
Alkene phenolic compounds 6 should be synthesized with the reduction reaction using tetrahydrofuran-water as reaction dissolvent
E) alkene phenolic compounds 6React, obtain through the acid catalysed cyclisation using the concentrated sulfuric acid or BFEE as acid
To target marine natural products ent-chromazonarol
2. synthetic method according to claim 1, in step a, prioritizing selection methanol or ethanol are solvent, and reaction temperature is
0 DEG C is arrived backflow, and the reaction time is 1~12 hour.
3. synthetic method according to claim 1, in step b, prioritizing selection potassium hydroxide, sodium carbonate, cesium carbonate or carbon
Sour potassium is alkali, bi triphenyl phosphorus palladium chloride, double acetonitrile palladium chlorides, three (dibenzalacetone) two palladium, [1,1'- double (diphenyl
Phosphorus) ferrocene] palladium chloride or tetra-triphenylphosphine palladium be catalyst, prioritizing selection tetrahydrofuran, toluene, acetonitrile, Isosorbide-5-Nitrae-dioxy
Six rings or DMF are solvent, and the preferential reaction time is 6~24 hours.
4. synthetic method according to claim 1, in step c, prioritizing selection dichloromethane is solvent, reaction temperature for-
20 DEG C to 40 DEG C, the reaction time is 3~12 hours.
5. synthetic method according to claim 1, in step d, the oxidation reaction prioritizing selection acetonitrile-water or water that are related to are
Reaction dissolvent；The reduction reaction prioritizing selection sodium dithionite being related to is reducing agent, 0 DEG C to 40 DEG C of reaction temperature, during reaction
Between be 1~6 hour.
6. synthetic method according to claim 1, in step e, prioritizing selection nitropropane or dichloromethane are solvent, instead
Temperature is answered to arrive room temperature, 1~6 hour reaction time for -78 DEG C.
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| CN106588854A (en) * | 2016-12-02 | 2017-04-26 | 哈尔滨工业大学（威海） | Synthetic method of marine natural product Puupehenol |
| CN107266410B (en) * | 2017-07-29 | 2020-01-03 | 威海创惠环保科技有限公司 | Synthesis method of 8-epi-puupehedione |
| CN107915699B (en) * | 2017-12-18 | 2019-12-10 | 威海创惠环保科技有限公司 | Synthetic method of Corallidictyalal D |
| CN115368336B (en) * | 2022-08-15 | 2023-11-14 | 威海海洋生物医药产业技术研究院有限公司 | Synthesis method of natural product elegansin D |
| CN115677583A (en) * | 2022-10-31 | 2023-02-03 | 南京科络思生物科技有限公司 | Phenylhydrazine-based natural product photoaffinity probe reactant, and preparation method and application thereof |
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| CN105131071A (en) * | 2015-07-14 | 2015-12-09 | 浙江花园生物高科股份有限公司 | Synthesis method of 25-hydroxycholesteryl acetate-7-p-toluenesulfonylhydrazone |
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| CN105131071A (en) * | 2015-07-14 | 2015-12-09 | 浙江花园生物高科股份有限公司 | Synthesis method of 25-hydroxycholesteryl acetate-7-p-toluenesulfonylhydrazone |
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| Title |
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| An Efficient Method for the Synthesis of (+)-Cyclozonarone, Isozonarol Δ8,9 and Isozonarone Δ8,9;José Villamizaret al;《Synthetic Communications》;20060821;第33卷(第7期);第1121-1129页· * |
| Palladium-Catalyzed Coupling of Sulfonylhydrazones with Heteroaromatic 2‑Amino-Halides (Barluenga Reaction): Exploring the Electronics of the Sulfonylhydrazone;Hongyu Tan et al;《Organic Process Research & Development》;20150807;第19卷;第1044-1048页 * |
| 海洋天然产物ent-chromazonarol的合成研究;张振国;《中国优秀硕士学位论文全文数据库 医药卫生科技辑》;20170215(第2期);第E079-106页，尤其是正文第19-23页 * |
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Application publication date: 20160810 Assignee: Weihai marine biological medicine industry technology Research Institute Co.,Ltd. Assignor: Weihai Chuang Hui environmental protection & Technology Co.,Ltd. Contract record no.: X2022980023986 Denomination of invention: A synthetic method of ent chromazonarol, a marine terpenoid natural product Granted publication date: 20180323 License type: Common License Record date: 20221129 |