CN105153000B - The benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting and its application - Google Patents
The benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting and its application Download PDFInfo
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Abstract
The invention discloses a kind of benzophenanthrene Anion Recognition acceptor of the thiocarbamide of sulfo-amino containing contracting schiff bases side chain and its application, the structural formula of the benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting is：；The benzophenanthrene Anion Recognition acceptor of the thiocarbamide of sulfo-amino containing the contracting schiff bases side chain is applied to F‑、CH3COO‑And H2PO4 ‑Selective recognition.It is an advantage of the invention that in N benzamidothiourea, introduce the triphenylene with larger conjugated system and be used as signal reports unit, thiocarbamide, which be ensure that, as hydrogen bond donor can provide 2 NH protons, and it between anion in the way of dual hydrogen bond with that can be combined with larger binding constant Kass.
Description
Technical field
The invention belongs to Anion Recognition technical field, the more particularly to a kind of thiocarbamide of sulfo-amino containing contracting schiff bases side chain
Benzophenanthrene Anion Recognition acceptor and its application.
Background technology
Anion is prevalent in nature, for example, most of category such as DNA, enzyme, polypeptide, amino acid in organism
In anion, the mankind can also produce substantial amounts of anion during life, agricultural production, industrial production etc..Inorganic anion
Have carboxylic acid ion, phosphate anion in organism, there is substantial amounts of chlorion in ocean, have in acid rain nitrate anion from
Son, sulfate ion, anion are equal in the fields such as chemical science, bioscience, catalytic science, environmental science, medical science
There is highly important effect.For example, anion can deliver the gene information of organism, DNA belongs to polyanion species, enzyme
Also it is anionic species to have most of.PO4 3—Processing and the highly important life mistake such as storage, transmission of energy in information
Important function is served in journey.Fluorine is the ultimate constituent of animal skeleton, tooth, and human body fluorinated volume is not enough or excessive all pole
Change physiologically or on pathology easily is being produced, so as to have influence on the health of human body.ATP2—It is in the energetic supersession of organism
It is indispensable.Lacking dihydrogen phosphate ions in blood will likely cause renal function to occur obstacle.Chlorion is in human body
Serve effect of adjustment body fluid osmotic pressure etc..In addition to important function in vivo, anion is in environmental area
Importance also should not be underestimated, and such as because substantial amounts of agrochemical is used, cause NO in the eutrophication of water body, drinking water3 -Content
Too high to trigger human carcinogen etc., anion contamination has seriously threatened the living environment of the mankind.Therefore, design simultaneously
Living environment monitoring and the prevention of disease of Anion Recognition acceptor of the synthesis with high selectivity to us, the survey of anion
Fixed, improvement, has very important significance.The fast development studied with Anion Recognition, urea or ghiourea group, multiamide base,
Containing groups such as five-ring heterocycles by extensive with the recognition group for being anion receptor, wherein the anion receptor containing urea, thiocarbamide is ground
Studying carefully becomes Anion Recognition study hotspot, and 2 NH protons can be provided by being primarily due to urea, thiocarbamide as hydrogen bond donor, its
With that can be combined between anion in the way of dual hydrogen bond with larger binding constant Kass.Detection between Subjective and Objective
The method also signal reports unit of factor receptor it is different and different, conventional detection method has：Electrochemical process, ultraviolet-visible are inhaled
Receive spectroscopic methodology, fluorescent spectrometry, nuclear magnetic resonance spectroscopy and X-ray crystallography, optical colorimetry etc..The above method has
Respective advantage and disadvantage, with optical colorimetry, UV-Vis Spectrophotometry, electrochemical process using more.Anion Recognition chemistry
Just it was suggested early in 1967, but in acceptor design aspect, in the N benzamidothiourea that forefathers study, introduces and increase conjugated system
The anion receptor of triphenylene yet there are no document report.In terms of environment-identification.This patent proposes one kind and contained
The benzophenanthrene Anion Recognition acceptor of contracting sulfo-amino thiocarbamide schiff bases side chain and application, by hydrogen nuclear magnetic resonance spectrometer, infrared
Spectrometer, uv-visible absorption spectra instrument, thermogravimetric analyzer and XRF finish to benzophenanthrene anion receptor
Structure is characterized, and studies synthesized anion receptor and anion such as nitrate anion, acetic acid using UV-Vis Spectrophotometry
The interaction of root, dihydrogen phosphate, fluorine ion etc., determines the anion of best identified.
The content of the invention
It is an object of the invention to provide a kind of benzophenanthrene Anion Recognition of the thiocarbamide of sulfo-amino containing contracting schiff bases side chain by
Body and its application.
The structural formula of benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting of the present invention is：
。
The benzophenanthrene Anion Recognition acceptor for preparing the above-mentioned thiocarbamide of sulfo-amino containing contracting schiff bases side chain is concretely comprised the following steps：
The synthesis of (1) two hexyloxy-phenol：30mL absolute ethyl alcohols are measured in 50mL three-necked flasks, and are put into clean magnetic
Son, weighs KI (0.249g, 0.0015mol), 1- bromos n-hexane (5.9g, 0.036mol), catechol successively
(3.3g, 0.030mol) is added in three-necked flask, opens magnetic stirrer dissolving.After after catechol all dissolving, claim
Take Anhydrous potassium carbonate（4.55g, 0.033mol）It is slowly added under agitation in above-mentioned three-necked flask, Anhydrous potassium carbonate adds
Enter after finishing, nitrogen protection is carried out to device, then stir 1 hour at ambient temperature.It is by oil bath pan temperature control is constant
80 DEG C, it is heated to reflux.After reaction 12 hours, stop heating and being cooled to room temperature, by reacted mixture suction filtration, filter cake is used
Acetone is washed, suction filtration, repeats suction filtration twice.By filtrate concentrated by rotary evaporation, then through vacuum distillation, 140 ~ 143 DEG C are collected
（0.5mmHg）Cut, obtains colourless oil liquid, as two hexyloxy-phenols.
(2) synthesis of adjacent two hexyloxies benzene：50mL absolute ethyl alcohols are measured in 100mL three-necked flasks, and are put into clean
Magneton.Then KI is weighed successively（0.7304g, 0.0044mol）, 1- bromo n-hexanes（7.04g, 0.044mol）, adjacent benzene
Diphenol（2.2g, 0.02mol）Add in three-necked flask, open magnetic stirrer.After after catechol all dissolving, weigh
Anhydrous potassium carbonate（6.9g, 0.05mol）Slowly add in above-mentioned three-necked flask under agitation, Anhydrous potassium carbonate has been added
Bi Hou, nitrogen protection is carried out to device, is then stirred 1 hour at ambient temperature.By oil bath pan temperature control it is constant be 80
DEG C, heating reflux reaction.After reaction 48 hours, stop heating and be cooled to room temperature, then by reacted mixture suction filtration, filter
Cake is washed with acetone, suction filtration, repeats suction filtration twice.By filtrate concentrated by rotary evaporation, then through vacuum distillation, 149 ~ 157 DEG C are collected
（0.7mmHg）Cut, obtains colourless oil liquid, as adjacent two hexyloxies benzene.
(3) synthesis of the hexyloxy benzophenanthrenes of hydroxyl -3,6,7,10,11- five：Dichloromethane is measured successively（80mL）And nitro
Methane（9.6mL）250mL single-necked flasks are added, and add anhydrous ferric trichloride（15.55g, 0.0969mol）With clean magneton,
Flask is placed in ice water bath environment, 0 ~ 4 DEG C of temperature is controlled, then measure two hexyloxy-phenols successively（1.39g, 0.0072mol）
With adjacent two hexyloxies benzene（4.0g, 0.0144mol）It is dissolved in dichloromethane（40mL）In, and be transferred in normal pressure funnel, slow drop
It is added in liquor ferri trichloridi, with about 0.5 hour completion of dropping, continuing temperature control made it be reacted under 0-4 DEG C of environment.
After reaction 2 hours, 30mL methanol terminating reactions are added, reactant mixture is subjected to suction filtration, filter cake dichloromethane with Buchner funnel
Alkane is washed, suction filtration.With saturated aqueous common salt and watery hydrochloric acid, respectively extraction once, takes organic layer to filtrate respectively, adds anhydrous sodium sulfate and does
It is dry, after filtered again, silica gel is added in filtrate（11g）, solvent is evaporated off with Rotary Evaporators, obtains containing target product
Dry silica gel substrate.Crude product is through silica gel column chromatography separating-purifying, and leacheate is petrol ether/ethyl acetate mixed solution.
(4) synthesis of the side chain of carbamoyl benzoate containing 4- benzophenanthrene：Weigh the hexyloxy benzos of 2- hydroxyls -3,6,7,10,11- five
It is luxuriant and rich with fragrance（0.744g, 0.001mol）, 4- carbamoyl benzoates (0.18g, 0.0012mol), dicyclohexylcarbodiimide (0.2575g),
DMAP (0.0153g) sequentially adds 100 mL single-necked flasks, and adds clean magneton, vacuumizes, vacuumizes
0.5 hour.Then measure through dry dichloromethane（30mL）Add in single-necked flask, magnetic agitation dissolving is carried out to device
Nitrogen is protected, normal-temperature reaction 12 hours, after reactant mixture, dichloromethane are freezed, with sand core funnel suction filtration reactant mixture,
Filter cake is washed with the dichloromethane after freezing, suction filtration.Silica gel is added in filtrate（2g）, solvent is evaporated off with Rotary Evaporators, obtains
To the dry silica gel substrate containing target product.Crude product is through silica gel column chromatography separating-purifying, and leacheate is petroleum ether/dichloromethane
Alkane mixed solution.
(5) synthesis of the benzophenanthrene anion receptor of the thiocarbamide of sulfo-amino containing contracting schiff bases side chain：Measure the anhydrous second of 30mL
Alcohol adds clean magneton in 100mL single-necked flasks.Weigh thiosemicarbazide（0.0474g, 0.52mmol）It is added to single port
In flask, stirring and dissolving.4- carbamoyl benzoate side chain benzophenanthrenes will be contained（0.38g, 0.43mmol）Dissolved with 10mL dichloromethane,
Under agitation, it is added drop-wise to dropwise in above-mentioned single-necked flask, then adds appropriate glacial acetic acid and adjust pH about to 3-4, normal temperature is stirred
Mix 1 hour.Heating, temperature is set as 60 DEG C, boils off the dichloromethane in reactant mixture.Then it is 83 by temperature setting
DEG C, back flow reaction 4 hours.It is cooled to after room temperature, taking-up magneton and adds silica gel into reactant mixture（1.5g）, use rotary evaporation
Solvent is evaporated off in instrument, obtains the dry silica gel substrate containing anion receptor R1.Crude product is through silica gel column chromatography separating-purifying, elution
Liquid is absolute dichloromethane, obtains the benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting, yield
82.3%, fusing point is：198.2~201.4 ℃.
The benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting of the present invention is applied to F-、
CH3COO- And H2PO4 -Selective recognition.
The present invention determines the Change of absorption of the receptor solution containing anion using UV-Vis Spectrophotometry.With N,
Dinethylformamide is medium, and it is 2.5 × 10 to determine in concentration-5 Mol/L acceptor（3mL）It is middle addition concentration be 1.5 ×
10-2Mol/L Cl-, Br-, I-, NO3 -, HSO4 -、F-、CH3COO- And H2PO4 -Anion solutions 0-250 μ L it is ultraviolet-can
See absorption spectrum.Test result indicates that, add Cl-, Br-, I-, NO3 -, HSO4 - Deng anion, its ultraviolet-ray visible absorbing light
Spectrum shows acceptor with above-mentioned anion without obvious effect without significant change；And adding F-、CH3COO- And H2PO4 - It is ultraviolet-
Visible absorption spectra there occurs obvious change, show acceptor and F-、CH3COO- And H2PO4 -Acted on, it is achieved thereby that
The benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting is to F-、CH3COO- And H2PO4 -Selectivity know
Not.
It is an advantage of the invention that in N benzamidothiourea, introducing the triphenylene with larger conjugated system and being used as letter
Number reporting unit, it is ensured that thiocarbamide can provide 2 NH protons as hydrogen bond donor, and it can be with dual hydrogen between anion
The mode of key is combined and has larger binding constant Kass.
Brief description of the drawings
Fig. 1 is the structure of the benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting in the present invention
Formula.
Fig. 2 is the benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting in the embodiment of the present invention
Infrared spectrogram.
Fig. 3 is 0 ~ 50 equivalent F of addition in the embodiment of the present invention-Acceptor UV-visible absorption spectrum.
Fig. 4 is 0 ~ 50 equivalent CH of addition in the embodiment of the present invention3COO-Acceptor UV-visible absorption spectrum.
Fig. 5 is 0 ~ 50 equivalent H of addition in the embodiment of the present invention2PO4 -Acceptor UV-visible absorption spectrum.
Embodiment
With reference to specific embodiment, the present invention is furture elucidated, but embodiment is not intended to limit protection scope of the present invention.
Embodiment：
The benzophenanthrene Anion Recognition acceptor for preparing sulfo-amino containing contracting thiocarbamide schiff bases side chain is concretely comprised the following steps：
The synthesis of (1) two hexyloxy-phenol：30mL absolute ethyl alcohols are measured in 50mL three-necked flasks, and are put into clean magnetic
Son, weighs KI (0.249g, 0.0015mol), 1- bromos n-hexane (5.9g, 0.036mol), catechol successively
(3.3g, 0.030mol) is added in three-necked flask, opens magnetic stirrer dissolving.After after catechol all dissolving, claim
Take Anhydrous potassium carbonate（4.55g, 0.033mol）It is slowly added under agitation in above-mentioned three-necked flask, Anhydrous potassium carbonate adds
Enter after finishing, nitrogen protection is carried out to device, then stir 1 hour at ambient temperature.It is by oil bath pan temperature control is constant
80 DEG C, it is heated to reflux.After reaction 12 hours, stop heating and being cooled to room temperature, by reacted mixture suction filtration, filter cake is used
Acetone is washed, suction filtration, repeats suction filtration twice.By filtrate concentrated by rotary evaporation, then through vacuum distillation, 140 ~ 143 DEG C are collected
（0.5mmHg）Cut, obtains colourless oil liquid, as two hexyloxy-phenols.
(2) synthesis of adjacent two hexyloxies benzene：50mL absolute ethyl alcohols are measured in 100mL three-necked flasks, and are put into clean
Magneton.Then KI is weighed successively（0.7304g, 0.0044mol）, 1- bromo n-hexanes（7.04g, 0.044mol）, adjacent benzene
Diphenol（2.2g, 0.02mol）Add in three-necked flask, open magnetic stirrer.After after catechol all dissolving, weigh
Anhydrous potassium carbonate（6.9g, 0.05mol）Slowly add in above-mentioned three-necked flask under agitation, Anhydrous potassium carbonate has been added
Bi Hou, nitrogen protection is carried out to device, is then stirred 1 hour at ambient temperature.By oil bath pan temperature control it is constant be 80
DEG C, heating reflux reaction.After reaction 48 hours, stop heating and be cooled to room temperature, then by reacted mixture suction filtration, filter
Cake is washed with acetone, suction filtration, repeats suction filtration twice.By filtrate concentrated by rotary evaporation, then through vacuum distillation, 149 ~ 157 DEG C are collected
（0.7mmHg）Cut, obtains colourless oil liquid, as adjacent two hexyloxies benzene.
(3) synthesis of the hexyloxy benzophenanthrenes of hydroxyl -3,6,7,10,11- five：Dichloromethane is measured successively（80mL）And nitro
Methane（9.6mL）250mL single-necked flasks are added, and add anhydrous ferric trichloride（15.55g, 0.0969mol）With clean magneton,
Flask is placed in ice water bath environment, 0 ~ 4 DEG C of temperature is controlled, then measure two hexyloxy-phenols successively（1.39g, 0.0072mol）
With adjacent two hexyloxies benzene（4.0g, 0.0144mol）It is dissolved in dichloromethane（40mL）In, and be transferred in normal pressure funnel, slow drop
It is added in liquor ferri trichloridi, with about 0.5 hour completion of dropping, continuing temperature control made it be reacted under 0-4 DEG C of environment.
After reaction 2 hours, 30mL methanol terminating reactions are added, reactant mixture is subjected to suction filtration, filter cake dichloromethane with Buchner funnel
Alkane is washed, suction filtration.With saturated aqueous common salt and watery hydrochloric acid, respectively extraction once, takes organic layer to filtrate respectively, adds anhydrous sodium sulfate and does
It is dry, after filtered again, silica gel is added in filtrate（11g）, solvent is evaporated off with Rotary Evaporators, obtains containing target product
Dry silica gel substrate.Crude product is through silica gel column chromatography separating-purifying, and leacheate is petrol ether/ethyl acetate mixed solution.
(4) synthesis of the side chain of carbamoyl benzoate containing 4- benzophenanthrene：Weigh the hexyloxy benzos of 2- hydroxyls -3,6,7,10,11- five
It is luxuriant and rich with fragrance（0.744g, 0.001mol）, 4- carbamoyl benzoates (0.18g, 0.0012mol), dicyclohexylcarbodiimide (0.2575g),
DMAP (0.0153g) sequentially adds 100 mL single-necked flasks, and adds clean magneton, vacuumizes, vacuumizes
0.5 hour.Then measure through dry dichloromethane（30mL）Add in single-necked flask, magnetic agitation dissolving is carried out to device
Nitrogen is protected, normal-temperature reaction 12 hours, after reactant mixture, dichloromethane are freezed, with sand core funnel suction filtration reactant mixture,
Filter cake is washed with the dichloromethane after freezing, suction filtration.Silica gel is added in filtrate（2g）, solvent is evaporated off with Rotary Evaporators, obtains
To the dry silica gel substrate containing target product.Crude product is through silica gel column chromatography separating-purifying, and leacheate is petroleum ether/dichloromethane
Alkane mixed solution.
(5) synthesis of the benzophenanthrene anion receptor of the thiocarbamide of sulfo-amino containing contracting schiff bases side chain：Measure the anhydrous second of 30mL
Alcohol adds clean magneton in 100mL single-necked flasks.Weigh thiosemicarbazide（0.0474g, 0.52mmol）It is added to single port
In flask, stirring and dissolving.4- carbamoyl benzoate side chain benzophenanthrenes will be contained（0.38g, 0.43mmol）Dissolved with 10mL dichloromethane,
Under agitation, it is added drop-wise to dropwise in above-mentioned single-necked flask, then adds appropriate glacial acetic acid and adjust pH about to 3-4, normal temperature is stirred
Mix 1 hour.Heating, temperature is set as 60 DEG C, boils off the dichloromethane in reactant mixture.Then it is 83 by temperature setting
DEG C, back flow reaction 4 hours.It is cooled to after room temperature, taking-up magneton and adds silica gel into reactant mixture（1.5g）, use rotary evaporation
Solvent is evaporated off in instrument, obtains the dry silica gel substrate containing anion receptor R1.Crude product is through silica gel column chromatography separating-purifying, elution
Liquid is absolute dichloromethane, obtains the benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting, yield
82.3%, fusing point is：198.2 ~ 201.4 DEG C, confirm that its structural formula is through infrared spectrum, proton nmr spectra：
。
The benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting is applied to made from the present embodiment
Anion selectivity is recognized：
The Change of absorption of the receptor solution containing anion is determined using UV-Vis Spectrophotometry.Concretely comprise the following steps
Using DMF as medium, it is 2.5 × 10 to determine in concentration-5 Mol/L acceptor（3mL）Middle addition concentration is 1.5
×10-2Mol/L anion solutions, determine uv-visible absorption spectra, are compareed with blank group, investigate ultraviolet-ray visible absorbing light
The change of spectrum, as a result shows F-、CH3COO- And H2PO4 -Absworption peak at 347nm gradually weakens, and one is occurred in that at 455nm
The new absworption peak of group, suggests the formation of new complex（See Fig. 3,4 and 5）, illustrate acceptor and F-、CH3COO- And H2PO4 -Hair
The effect of having given birth to, it is achieved thereby that the benzophenanthrene Anion Recognition acceptor of the thiocarbamide schiff bases side chain of sulfo-amino containing contracting is to F-、
CH3COO- And H2PO4 -Selective recognition.
Claims (2)
1. a kind of benzophenanthrene Anion Recognition acceptor of the thiocarbamide of sulfo-amino containing contracting schiff bases side chain, it is characterised in that this contains contracting sulphur
It is for the structural formula of the benzophenanthrene Anion Recognition acceptor of thiosemicarbazides schiff bases side chain：
；
The benzophenanthrene Anion Recognition acceptor for preparing the above-mentioned thiocarbamide of sulfo-amino containing contracting schiff bases side chain is concretely comprised the following steps：
The synthesis of (1) two hexyloxy-phenol：30mL absolute ethyl alcohols are measured in 50mL three-necked flasks, and are put into clean magneton,
KI 0.249g, 1- bromo n-hexane 5.9g, catechol 3.3g are weighed successively to add in three-necked flask, open magnetic agitation
Device stirring and dissolving；After catechol all dissolving after, weigh Anhydrous potassium carbonate 4.55g be slowly added under agitation it is above-mentioned
In three-necked flask, after Anhydrous potassium carbonate addition is finished, nitrogen protection is carried out to device, then stirred 1 hour at ambient temperature；
By oil bath pan temperature control it is constant be 80 DEG C, be heated to reflux；After reaction 12 hours, stop heating and be cooled to room temperature, will react
Mixture suction filtration afterwards, filter cake is washed with acetone, suction filtration, repeats suction filtration twice；By filtrate concentrated by rotary evaporation, then through vacuum distillation,
140 ~ 143 DEG C of cuts are collected, colourless oil liquid, as two hexyloxy-phenols is obtained；
(2) synthesis of adjacent two hexyloxies benzene：50mL absolute ethyl alcohols are measured in 100mL three-necked flasks, and are put into clean magneton；
Then KI 0.7304g, 1- bromo n-hexane 7.04g, Catechol 2 .2g are weighed successively to add in three-necked flask, open magnetic
Power agitator is stirred；On after catechol all dissolving, weighing Anhydrous potassium carbonate 6.9g and slowly adding under agitation
State in three-necked flask, after Anhydrous potassium carbonate addition is finished, nitrogen protection is carried out to device, then stirring 1 is small at ambient temperature
When；By oil bath pan temperature control it is constant be 80 DEG C, heating reflux reaction；After reaction 48 hours, stop heating and being cooled to room
Temperature, then by reacted mixture suction filtration, filter cake is washed with acetone, suction filtration, repeats suction filtration twice；By filtrate concentrated by rotary evaporation,
Again through vacuum distillation, 149 ~ 157 DEG C of cuts are collected, colourless oil liquid are obtained, as adjacent two hexyloxies benzene；
(3) synthesis of the hexyloxy benzophenanthrenes of hydroxyl -3,6,7,10,11- five：Dichloromethane 80mL and nitromethane are measured successively
9.6mL adds 250mL single-necked flasks, and adds anhydrous ferric trichloride 15.55g and clean magneton, and flask is placed in into ice-water bath ring
In border, 0 ~ 4 DEG C of temperature is controlled, then measure two hexyloxy-phenol 1.39g successively and adjacent two hexyloxies benzene 4.0g is dissolved in dichloromethane
In 40mL, and it is transferred in normal pressure funnel, is slowly dropped in liquor ferri trichloridi, with about 0.5 hour completion of dropping, continues
Temperature control makes it be reacted under 0 ~ 4 DEG C of environment；After reaction 2 hours, 30mL methanol terminating reactions are added, by reactant mixture
Suction filtration is carried out with Buchner funnel, filter cake is washed with dichloromethane, suction filtration；Filtrate is respectively extracted with saturated aqueous common salt and watery hydrochloric acid respectively
Once, take organic layer, add anhydrous sodium sulfate drying, after filtered again, silica gel 11g is added in filtrate, rotary evaporation is used
Solvent is evaporated off in instrument, obtains the dry silica gel substrate containing target product；Crude product is through silica gel column chromatography separating-purifying, leacheate
Petrol ether/ethyl acetate mixed solution；
(4) synthesis of the side chain of carbamoyl benzoate containing 4- benzophenanthrene：Weigh the hexyloxy benzophenanthrenes of 2- hydroxyls -3,6,7,10,11- five
0.744g, 4- carbamoyl benzoate 0.18g, dicyclohexylcarbodiimide 0.2575g, DMAP 0.0153g add successively
Enter 100 mL single-necked flasks, and add clean magneton, vacuumize, vacuumize 0.5 hour；Then measure through dry dichloromethane
Alkane 30mL add single-necked flask in, magnetic agitation dissolving, to device carry out nitrogen protection, normal-temperature reaction 12 hours, after will reaction
Mixture, dichloromethane freezing, with sand core funnel suction filtration reactant mixture, filter cake is washed with the dichloromethane after freezing, suction filtration；
Silica gel 2g is added in filtrate, solvent is evaporated off with Rotary Evaporators, the dry silica gel substrate containing target product is obtained；Crude product
Through silica gel column chromatography separating-purifying, leacheate is petroleum ether/dichloromethane mixed solution；
(5) synthesis of the benzophenanthrene anion receptor of the thiocarbamide of sulfo-amino containing contracting schiff bases side chain：Measure 30mL absolute ethyl alcohols in
In 100mL single-necked flasks, and add clean magneton；Weigh thiosemicarbazide 0.0474g to be added in single-necked flask, stir molten
Solution；4- carbamoyl benzoates side chain benzophenanthrene 0.38g 10mL dichloromethane will be contained to dissolve, under agitation, be added drop-wise to dropwise
In above-mentioned single-necked flask, appropriate glacial acetic acid regulation pH to 3 ~ 4, stirring at normal temperature 1 hour are then added；Heating, temperature is set as 60
DEG C, boil off the dichloromethane in reactant mixture；Then it is 83 DEG C, back flow reaction 4 hours by temperature setting；It is cooled to room temperature,
Take out after magneton toward addition silica gel 1.5g in reactant mixture, solvent is evaporated off with Rotary Evaporators, obtains containing anion receptor
Dry silica gel substrate；Crude product is through silica gel column chromatography separating-purifying, and leacheate is absolute dichloromethane, that is, obtains containing the thio ammonia that contracts
The benzophenanthrene Anion Recognition acceptor of base thiocarbamide schiff bases side chain.
2. according to claim 1 the benzophenanthrene Anion Recognition acceptor of the thiocarbamide of sulfo-amino containing contracting schiff bases side chain should
With, it is characterised in that the benzophenanthrene Anion Recognition acceptor for containing contracting sulfo-amino thiocarbamide schiff bases side chain is applied to anion
F-、CH3COO-And H2PO4 -Selective recognition.
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