CN109369532A - A kind of Pseudolarix acid B photoaffinity probe halogen intermediate and preparation method thereof - Google Patents

A kind of Pseudolarix acid B photoaffinity probe halogen intermediate and preparation method thereof Download PDF

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CN109369532A
CN109369532A CN201811299224.1A CN201811299224A CN109369532A CN 109369532 A CN109369532 A CN 109369532A CN 201811299224 A CN201811299224 A CN 201811299224A CN 109369532 A CN109369532 A CN 109369532A
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stirred
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倪润炎
王伟
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Suzhou Light Point Biotechnology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
    • C07D229/02—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms containing three-membered rings
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of Pseudolarix acid B photoaffinity probe halogen intermediate and preparation method thereof, its general formula of the chemical structures are as follows:By designing new synthetic route, the compound 6 of high yield, high-purity can be obtained, and can be used for continuing being reacted with other raw materials to be used to prepare Pseudolarix acid B photoaffinity probe.

Description

A kind of Pseudolarix acid B photoaffinity probe halogen intermediate and preparation method thereof
Technical field
The invention belongs to fluorescence probe fields, are related to a kind of fluorescence probe halogen intermediate, and in particular to a kind of corter pseudolaricis Acetic acid photoaffinity probe halogen intermediate and preparation method thereof.
Background technique
Pseudolarix acid B is one of the bark of pinaceae plant golden larch diterpene sour component, it is applied to resist in medicine Fungi, hemostasis and neurodermatitis etc..Some researches show that Pseudolarix acid B can inhibit revascularization, can be used in the recent period Prevention or treating cancer, diabetes, psoriasis, hemangioma etc..
Fluorescence probe, which refers to, has characteristic fluorescence, and its photoluminescent property (excitation and transmitting in ultraviolet-visible-near infrared region Wavelength, intensity, service life, polarization etc.) it can change and delicately change with the property of local environment, such as polarity, refractive index, viscosity A kind of fluorescence molecule.Currently used fluorescence probe has fluoresceins probe, inorganic ions fluorescence probe, fluorescent quantum Point, molecular beacon etc.；It is in addition to being applied to the quantitative analysis of nucleic acid and protein, in nucleic acid staining, DNA electrophoresis, nucleic acid molecules It suffers from and is widely applied on hybridization, quantitative PCR technique and DNA sequencing.Fluorescence probe is most commonly used to fluorescent immune method acceptance of the bid Remember antigen or antibody, also can be used for microenvironment, as surfactant micellar, bimolecular film, protein active sites etc. are microcosmic The detection of characteristic；Usually require that the molar absorption coefficient of probe is big, fluorescence quantum yield is high；Fluorescence emission wavelengths be in long wave and There is biggish Stokes shift；When for immunoassay, and the combination of antigen or antibody should not influence their activity；Obviously Need fluorescence probe that there is special chemical structure；This just needs to be related to the intermediate of synthetic route and compounding design.
Summary of the invention
A kind of Pseudolarix acid B photoaffinity probe halogen is provided the invention aims to overcome the deficiencies in the prior art Intermediate.
In order to achieve the above objectives, the technical solution adopted by the present invention is that: in a kind of Pseudolarix acid B photoaffinity probe halogen Mesosome, its general formula of the chemical structure are as follows:
Another object of the present invention is to provide a kind of preparation of above-mentioned Pseudolarix acid B photoaffinity probe halogen intermediate Method, it the following steps are included:
(a) diisopropylamine, THF are added into reaction vessel, is cooled to 0 DEG C or less under nitrogen protection；It is added dropwise just Butyl lithium continues that ethyl acetoacetate is added dropwise after stirring, allyl bromide, bromoallylene is added dropwise after stirring again；It is warmed to room temperature and is stirred after dripping off Reaction；It is then poured into saturated ammonium chloride solution, extraction, washing, concentrated column obtain compound 1；
(b) back flow reaction is carried out after mixing the compound 1, p-methyl benzenesulfonic acid, benzene and ethylene glycol；Saturated carbon is used respectively Sour hydrogen sodium, saturated sodium-chloride washing, concentrated column obtain compound 2；
(c) it is cooled to 0 DEG C after mixing the compound 2 with tetrahydrofuran or hereinafter, LiAlH is added portionwise4, after adding It is warmed to room temperature and is stirred to react；Water quenching is added to go out, extracts, wash, concentrated column obtains compound 3；
(d) it is stirred to react after mixing the compound 3, acetone, water and p-methyl benzenesulfonic acid, concentrated column obtains chemical combination Object 4；
(e) under conditions of the dry ice bath, the compound 4 is added in liquefied ammonia and is reacted；Azanol-O- sulphur is then added The methanol solution of acid, is warming up to room temperature and is stirred to react；It is filtered to remove insoluble matter, methanol and three second are added after filtrate is spin-dried for The methanol solution of iodine is added dropwise under conditions of ice bath, continues to be stirred to react for amine；Extraction, washing, concentrated column obtain compound 5；
(f) will imidazoles, triphenylphosphine and methylene chloride be added reaction flask in, be cooled to 0 DEG C or hereinafter, be added elemental iodine into Row reaction；The dichloromethane solution of the compound 5 is then added, is protected from light；Add saturated sodium bisulfite solution to be quenched, extracts It takes, concentrated column obtains compound 6.
Due to the above technical solutions, the present invention has the following advantages over the prior art: corter pseudolaricis second of the present invention Sour photoaffinity probe halogen intermediate can obtain the compound 6 of high yield, high-purity by the new synthetic route of design, and It can be used for continuing being reacted with other raw materials to be used to prepare Pseudolarix acid B photoaffinity probe.
Detailed description of the invention
Fig. 1 is the synthesis of Pseudolarix acid B photoaffinity probe halogen intermediate of the present invention and Pseudolarix acid B photoaffinity probe Route map；
Fig. 2 is nuclear magnetic spectrogram-hydrogen spectrum of compound 4；
Fig. 3 is nuclear magnetic spectrogram-hydrogen spectrum of compound 5；
Fig. 4 is nuclear magnetic spectrogram-hydrogen spectrum of compound 6；
Fig. 5 is nuclear magnetic spectrogram-hydrogen spectrum of compound 8；
Fig. 6 is nuclear magnetic spectrogram-carbon spectrum of compound 8.
Specific embodiment
Below in conjunction with figure embodiment, invention is further explained.
Embodiment 1
The present embodiment provides a kind of Pseudolarix acid B photoaffinity probe halogen intermediate, Pseudolarix acid B photoaffinity probe and Preparation method, as shown in Figure 1, it the following steps are included:
(a) add diisopropylamine (187.1g, 1.8494mol), 900mL THF in 2L there-necked flask, drop under nitrogen protection Temperature is to 0 DEG C (or 0 DEG C or less)；It is added dropwise n-BuLi (740mL, 1.8494mol), stirs 30min after dripping off；Continue that second is added dropwise Ethyl acetoacetic acid ethyl ester (109.4g, 0.8406mol), stirs 15min after dripping off；Continue be added dropwise allyl bromide, bromoallylene (100g, 0.8406mol), 0 DEG C of temperature control is warmed to room temperature stirring 3h, raw material fully reacting hereinafter, dripping off.It is molten that system is poured into saturated ammonium chloride It in liquid, is extracted twice with EA, merges organic phase；Saturated sodium-chloride washing, concentrated column obtain yellow oil 80g compound 1, Yield: 57%；
(b) 1 (77g, 0.458mol), TsOHH are added into 1L there-necked flask2O (17.6g), benzene (300mL) and ethylene glycol (284g, 4.578mol), reflux water-dividing；It is stirred to react 6h；TLC detection display raw material fully reacting.It is separately added into unsaturated carbonate The washing of hydrogen sodium, saturated sodium-chloride washing；Dry concentration, column excessively obtains yellow oily liquid 80g compound 2, yield: 83%；
(c) compound 2 (78g, 0.367mol), THF (780mL) are added into 2L single port bottle, is cooled to 0 DEG C；In batches plus Enter LiAlH4(20.9g, 0.551mol are divided into 3~4 batches), 0 DEG C of temperature control or so；It adds, is warmed to room temperature stirring, TLC prison naturally It controls to raw material fully reacting.Water quenching is added to go out, pad diatomite filtering, EA is washed three times；Liquid separation, water phase EA extract primary, conjunction And organic phase, saturated sodium-chloride washing；Concentrated column obtains yellow oily liquid 55g compound 3, yield 89%.
(d) compound 3 (55g, 0.323mol), acetone (550mL), water (55mL) and TsOH are added into 1L single port bottle H2O (6.15g, 0.032mol), TLC are monitored to raw material fully reacting；It crosses column and obtains 4 (its core of pale yellow oily liquid 34g compound Magnetic spectrum figure as shown in Fig. 2, specifically:1H NMR(400MHz,CDCl3)δ(ppm):3.84(t,2H),5.71-2.67(m,5H), 2.46-2.42(m,2H),1.95(t,1H))；
(e) ammonia is cooled to liquefied ammonia with the dry ice bath (- 40 DEG C), liquefied ammonia is added in compound 4 (5g, 39.7mmol, 1eq) In, it is reacted 5 hours under conditions of -40 DEG C；The methanol (50mL) of hydroxylamine-o-sulfonic acid (5.83g, 51.6mmol, 1.3eq) is added Solution warms naturally to room temperature reaction overnight after adding；After contact plate is without raw material, it is filtered to remove insoluble matter, filtrate is added after being spin-dried for Methanol (50ml) and triethylamine (40ml, 293.6mmol, 7.4eq), ice bath be cooled to 0 DEG C of dropwise addition iodine (13g, 51.6mmol, Methanol (50ml) solution 1.3eq), natural temperature reaction 4 hours.Add saturated salt solution, isopropyl ether extraction, washes, dry, rotation It is dry, cross column purification and obtain product 1.0g compound 5, yield: 18.2% (its nuclear magnetic spectrogram as shown in figure 3, specifically:1H NMR (400MHz,CDCl3)δ(ppm):3.51(t,2H),2.08-2.01(m,3H),1.74-1.69(m,4H))；
(f) by imidazoles (740mg, 10.87mmol, 3.0eq), triphenylphosphine (1.05g, 3.99mmol, 1.1eq) and dichloro Methane (5ml) is added in reaction flask, is cooled to 0 DEG C, is added elemental iodine (1.1g, 4.35mmol, 1.2eq), adds insulation reaction 30 minutes, methylene chloride (1ml) solution of compound 5 (500mg, 3.62mmol, 1eq) is added under low temperature, adds heat preservation and is protected from light Reaction 4 hours.Saturated sodium bisulfite solution is added to be quenched, ethyl acetate extraction is dry, is spin-dried for, and crosses column purification and obtains product 400mgization Close object 6, yield: 46% (its nuclear magnetic spectrogram as shown in figure 4, specifically:1H NMR(400MHz,CDCl3)δ(ppm):2.91(t, 2H),2.16-2.03(m,5H),1.71(t,2H))。
(g) by compound 6 (400mg, 1.6mmol, 1.0eq), sodium azide (125mg, 1.92mmol, 1.2eq) and DMF (4ml) is added in reaction flask, is warming up to 70 DEG C, is protected from light 5 hours；Water quenching is added to go out, ethyl acetate extraction is dry, is spin-dried for, obtains Crude product 200mg compound 7, yield: 76%.
(h) by compound 7 (150mg, 0.92mmol, 1.0eq), triphenylphosphine (278mg, 1.06mmol, 1.15eq), four Hydrogen furans (3ml) and water (0.3ml) are added in reaction flask, and reacting at normal temperature without light 15 hours, contact plate discovery must contain change without raw material The reaction solution for closing object 8 remains in next step；
(i) by Pseudolarix acid B (200mg, 0.46mmol, 1.0eq), HOBT (162mg, 1.2mmol, 2.6eq), EDCI Reaction flask is added in (142mg, 0.74mmol, 1.6eq), DIPEA (143mg, 1.11mmol, 2.4eq) and methylene chloride (10ml) In, normal-temperature reaction 1 hour, the reaction solution of compound 8 is added, adds reacting at normal temperature without light 4 hours；Water quenching is added to go out, methylene chloride Extraction, it is dry, it is spin-dried for, crosses column purification and obtain product 220mg PAB- probe compound (i.e. Pseudolarix acid B photoaffinity probe chemical combination Object), two step yields: 44% (step h and step i), nuclear magnetic spectrogram is as shown in Figure 5 and Figure 6, specifically:1H NMR (400MHz, CDCl3) δ 7.26-7.20 (m, 1H), 6.96 (d, J=11.4Hz, 1H), 6.51 (dd, J=15.0,11.3Hz, 1H), 5.83 (d, J=15.0Hz, 1H), 3.72 (s, 3H), 3.29 (d, J=5.4Hz, 1H), 3.20 (q, J=6.4Hz, 2H), 3.08 (dd, J=14.3,6.4Hz, 1H), 2.89 (dd, J=15.6,6.3Hz, 1H), 2.75 (dd, J=15.1,8.8Hz, 1H), 2.64-2.58 (m, 1H), 2.19-2.10 (m, 4H), 2.04 (dd, J=7.2,2.6Hz, 2H), 1.99 (s, 3H), 1.85- 1.71 (m, 7H), 1.66 (t, J=7.1Hz, 3H) .ESI calcd.for C30H38N3O7[M+H]+:552.2；Found: 552.2704
Embodiment 2
The present embodiment provides a kind of Pseudolarix acid B photoaffinity probe halogen intermediate and preparation method thereof, it and embodiment It is almost the same in 1, unlike: in step (f), elemental iodine 1.5eq is added, crosses column purification and obtains product 450mg compound 6.
Embodiment 3
The present embodiment provides a kind of Pseudolarix acid B photoaffinity probe halogen intermediate and preparation method thereof, it and embodiment It is almost the same in 1, unlike: in step (f), elemental iodine 1.0eq is added, crosses column purification and obtains product 350mg compound 6.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, it is all according to the present invention Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.

Claims (2)

1. a kind of Pseudolarix acid B photoaffinity probe halogen intermediate, which is characterized in that its general formula of the chemical structure are as follows:
2. the preparation method of Pseudolarix acid B photoaffinity probe halogen intermediate described in claim 1, which is characterized in that it includes Following steps:
(a) diisopropylamine, THF are added into reaction vessel, is cooled to 0 DEG C or less under nitrogen protection；Normal-butyl is added dropwise Lithium continues that ethyl acetoacetate is added dropwise after stirring, allyl bromide, bromoallylene is added dropwise after stirring again；It is warmed to room temperature and is stirred instead after dripping off It answers；It is then poured into saturated ammonium chloride solution, extraction, washing, concentrated column obtain compound 1；
(b) back flow reaction is carried out after mixing the compound 1, p-methyl benzenesulfonic acid, benzene and ethylene glycol；Unsaturated carbonate hydrogen is used respectively Sodium, saturated sodium-chloride washing, concentrated column obtain compound 2；
(c) it is cooled to 0 DEG C after mixing the compound 2 with tetrahydrofuran or hereinafter, LiAlH is added portionwise4, risen to after adding Room temperature is stirred to react；Water quenching is added to go out, extracts, wash, concentrated column obtains compound 3；
(d) it is stirred to react after mixing the compound 3, acetone, water and p-methyl benzenesulfonic acid, concentrated column obtains compound 4；
(e) under conditions of the dry ice bath, the compound 4 is added in liquefied ammonia and is reacted；Hydroxylamine-o-sulfonic acid is then added Methanol solution is warming up to room temperature and is stirred to react；It is filtered to remove insoluble matter, methanol and triethylamine are added after filtrate is spin-dried for, The methanol solution of iodine is added dropwise under conditions of ice bath, continues to be stirred to react；Extraction, washing, concentrated column obtain compound 5；
(f) imidazoles, triphenylphosphine and methylene chloride are added in reaction flask, are cooled to 0 DEG C or are carried out instead hereinafter, elemental iodine is added It answers；The dichloromethane solution of the compound 5 is then added, is protected from light；Add saturated sodium bisulfite solution to be quenched, extracts, is dense The column that contracted obtains compound 6.
CN201811299224.1A 2018-11-02 2018-11-02 A kind of Pseudolarix acid B photoaffinity probe halogen intermediate and preparation method thereof Pending CN109369532A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018591A1 (en) * 2001-08-14 2003-03-06 Shanghai Institute Of Materia Medica, Chinese Academy Of Sciences Novel pseudolaric acid-b derivatives, their preparation and pharmaceutical compositions
CN102219772A (en) * 2011-06-20 2011-10-19 东莞广州中医药大学中医药数理工程研究院 Cortex pseudolaricis acid complex with bioactivity and preparation method thereof
CN102408403A (en) * 2011-09-26 2012-04-11 宋云龙 Pseudolaric acid derivatives, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018591A1 (en) * 2001-08-14 2003-03-06 Shanghai Institute Of Materia Medica, Chinese Academy Of Sciences Novel pseudolaric acid-b derivatives, their preparation and pharmaceutical compositions
CN102219772A (en) * 2011-06-20 2011-10-19 东莞广州中医药大学中医药数理工程研究院 Cortex pseudolaricis acid complex with bioactivity and preparation method thereof
CN102408403A (en) * 2011-09-26 2012-04-11 宋云龙 Pseudolaric acid derivatives, and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KENJI HAYAKAWA ET AL.: "Novel Bicycloannulation via Tandem Vinylation and Intramolecular Diels-Alder Reaction of Five-Membered Heterocycles: A New Approach to Construction of Psoralen and Azapsoralen", 《J. AM. CHEM. SOC.》 *
YIQING ZHOU ET AL.: "Chemical proteomics reveal CD147 as a functional target of pseudolaric acid B in human cancer cells", 《CHEMCOMM》 *
YUSHENG XIE ET AL.: "Fluorescent Probes for Single-Step Detection and Proteomic Profiling of Histone Deacetylases", 《J. AM. CHEM. SOC.》 *

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Application publication date: 20190222