CN108822144A - Fluorine boron ring expansion porphyrin compound, armaticity or anti-aromaticity ring expansion porphyrin compound and synthetic method - Google Patents
Fluorine boron ring expansion porphyrin compound, armaticity or anti-aromaticity ring expansion porphyrin compound and synthetic method Download PDFInfo
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- 238000006049 ring expansion reaction Methods 0.000 title claims abstract description 119
- -1 porphyrin compound Chemical class 0.000 title claims abstract description 115
- LIQLLTGUOSHGKY-UHFFFAOYSA-N [B].[F] Chemical group [B].[F] LIQLLTGUOSHGKY-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 28
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 17
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims abstract description 15
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 49
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 20
- 230000001681 protective effect Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 229910052796 boron Inorganic materials 0.000 claims description 11
- 150000004032 porphyrins Chemical class 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 10
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 6
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical group CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 17
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 229960001866 silicon dioxide Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 125000000168 pyrrolyl group Chemical group 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- PBTPREHATAFBEN-UHFFFAOYSA-N dipyrromethane Chemical compound C=1C=CNC=1CC1=CC=CN1 PBTPREHATAFBEN-UHFFFAOYSA-N 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002240 furans Chemical class 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000010415 tropism Effects 0.000 description 2
- GGSGPPFRVNQBCV-UHFFFAOYSA-N 2,5-bis(1h-pyrrol-2-ylmethyl)-1h-pyrrole Chemical compound C=1C=C(CC=2NC=CC=2)NC=1CC1=CC=CN1 GGSGPPFRVNQBCV-UHFFFAOYSA-N 0.000 description 1
- 244000186140 Asperula odorata Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 235000008526 Galium odoratum Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000001425 electrospray ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- WHLUQAYNVOGZST-UHFFFAOYSA-N tifenamil Chemical group C=1C=CC=CC=1C(C(=O)SCCN(CC)CC)C1=CC=CC=C1 WHLUQAYNVOGZST-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
This application involves a kind of fluorine boron ring expansion porphyrin compound and its synthetic methods, shown in structural formula such as formula (I)：Ar is aryl.The synthetic method of the fluorine boron ring expansion porphyrin compound, before fluorine boron ring expansion porphyrin compound cyclization, first two pyrroles are locked by boronation, then using alpha-brominated two pyrroles's alkene of fluorine boron and tripyrrole alkane as raw material, nucleophilic substitution is carried out, stable fluorine boron ring expansion porphyrin compound is obtained.The stable fluorine boron ring expansion porphyrin compound can be used for synthesizing stable anti-aromaticity ring expansion porphyrin compound and stable armaticity ring expansion porphyrin compound.
Description
Technical field
The present invention relates to chemosynthesis technical field, more particularly to a kind of fluorine boron ring expansion porphyrin compound, armaticity or
Anti-aromaticity ring expansion porphyrin compound and synthetic method.
Background technique
Ring expansion porphyrin is a kind of containing the porphyrin analog for having more than 18 pi-electron conjugated systems.Although Woodward and
Johnson has found the presence of ring expansion porphyrin in nineteen sixties, but until phase later 1980s and nine
It is related to expand after the synthetic method of two pyrrolidines of important as precursors needed for synthesizing ring expansion porphyrin and tripyrrole alkane is mature at the beginning of the ten's
The research of ring porphyrin just has significant progress.Compared with porphyrin, ring expansion porphyrin has bigger cavity and more coordinations former
Son, therefore the unique performance not having with some porphyrins.Since ring expansion porphyrin is known in metal coordination, ion and molecule
Not, photodynamic therapy (PDT) sensitizer, the fields such as Magnetic resonance imaging (MRI) contrast agent and nonlinear optical material have latent
Application and widely paid close attention to by people, chemists design the ring expansion porphyrins for having synthesized different cavity sizes
And their performance is conducted extensive research.
Smaragdyrin is contained made of being connected as five pyrroles by three methines and two pyrroles-pyrroles's key
The Conjugate macrocycle compound of 22 pi-electrons, structural formula are as follows：
1966, Woodward et al. proposed being named as there may be and according to color for this kind of compound
Smaragdyrin, however up to now, the structure of samragdyrin remains a mystery.
Chemists have carried out a large amount of explorations to the synthesis of Smaragdyrin class compound and performance.1972,
Broadhurst, Grigg and Johnson et al. report the synthesis of oxa- Smaragdyrin for the first time and name it to be
Norsapphyrin, they have synthesized the Dioxasmaragdyrin class compound containing two furan nucleus, by mass spectrum and ultraviolet
Visible spectrum characterizes it.The seminar attempts the Smaragdyrin class compound of five pyrrole rings of synthesis, although absorbing
Spectrum shows its characteristic absorption, but since its is unstable, without its isolated sterling.Chandrashekar seminar adopts
With [3+2] synthetic strategy, with 16-oxatripyrrane or 16-thiatripyrrane and dipyrromethane in trifluoro second
Condensation reaction occurs under the catalytic action of acid, last oxidative dehydrogenation successfully synthesizes the 25- containing furan nucleus respectively
Oxasmaragdyrin and the 25-thismaragdyrin class compound containing thiphene ring.Wu et al. is then synthesized with identical method
25-oxasmaragdyrin that middle position fluorenyl replaces simultaneously synthesizes stable free radical with it.Chandrashekar seminar adopts
With similar method, is reacted under the same conditions with tripyrrane with dipyrromethane and attempt to synthesize containing five pyrrole rings
Smaragdyrin compound, but do not obtain the similar compound regrettably.
In conclusion oxasmaragdyrin, thismaragdyrin class compound of oxygen-containing sulfur-bearing can pass through [3+
2] synthetic strategy obtains, but the smaragdyrin class compound containing 5 pyrrole rings never obtains.Therefore, finding one kind can
The method for synthesizing stable armaticity ring expansion porphyrin compound becomes the focus of people's research.
Summary of the invention
Based on this, it is necessary to provide a kind of synthetic method of armaticity ring expansion porphyrin compound, this method can synthesize stabilization
Armaticity ring expansion porphyrin compound.
In addition, the application also provides the synthesis of a kind of fluorine boron ring expansion porphyrin compound and anti-aromaticity ring expansion porphyrin compound
Method and a kind of fluorine boron ring expansion porphyrin compound.
A kind of fluorine boron ring expansion porphyrin compound, shown in the structural formula such as formula (I) of the fluorine boron ring expansion porphyrin compound：
Ar is aryl.
One embodiment kind wherein, the Ar are 2,4,6- trimethylphenyls.
The synthetic method of above-mentioned fluorine boron ring expansion porphyrin compound, includes the following steps：
In protective gas atmosphere, it is anti-that alpha-brominated two pyrroles's alkene of fluorine boron and tripyrrole alkane are mixed into progress nucleophilic displacement of fluorine
It answers, obtains the fluorine boron ring expansion porphyrin compound, the structural formula of alpha-brominated two pyrroles's alkene of fluorine boron is as follows：
Ar is aryl,
The structural formula of the tripyrrole alkane is as follows：
Ar is aryl.
Described mix alpha-brominated two pyrroles's alkene of fluorine boron and tripyrrole alkane carries out nucleophilic displacement of fluorine in one of the embodiments,
The step of reaction is specially：
Alpha-brominated two pyrroles's alkene of fluorine boron, tripyrrole alkane, cesium carbonate and paraxylene are mixed, it is anti-to be heated to reflux state
It answers.
The method for synthesizing armaticity ring expansion porphyrin compound using fluorine boron ring expansion porphyrin compound described in any of the above embodiments,
Include the following steps：
In protective gas atmosphere, the fluorine boron ring expansion porphyrin compound and methanesulfonic acid are mixed and carry out boron removal reaction,
The compound of formula (II) is obtained, the structural formula of compound of the formula (II) is as follows：
Ar is aryl；
By the compound and triethylamine hybrid reaction of the formula (II), the compound of formula (III), the formula (III) are obtained
Structural formula of compound it is as follows：
Ar is aryl；
In protective gas atmosphere, the compound of the formula (III) and reducing agent are mixed and carry out reduction reaction, is obtained
Armaticity ring expansion porphyrin compound, shown in the structural formula such as formula (IV) of the armaticity ring expansion porphyrin compound：
Ar is aryl.
The fluorine boron ring expansion porphyrin compound and methanesulfonic acid mixing carry out the step of boron removal reaction in one of the embodiments,
It is rapid to be specially：
By the fluoboric acid ring expansion porphyrin compound, methanesulfonic acid and methylene chloride hybrid reaction.
The reducing agent is sodium borohydride in one of the embodiments,；The compound and reducing agent of the formula (III) are mixed
Closing the step of carrying out reduction reaction is specially：
By the compound of the formula (III), sodium borohydride, methylene chloride and methanol hybrid reaction.
A kind of armaticity ring expansion porphyrin compound, structural formula such as formula (IV) institute of the armaticity ring expansion porphyrin compound
Show：
Ar is aryl.
Utilize the side of fluorine boron ring expansion porphyrin compound described in any of the above embodiments synthesis anti-aromaticity ring expansion porphyrin compound
Method includes the following steps：
The fluorine boron ring expansion porphyrin compound and oxidant are mixed and carry out oxidation reaction, obtains anti-aromaticity ring expansion porphyrin
Compound, shown in the structural formula such as formula (V) of the anti-aromaticity ring expansion porphyrin compound：
Ar is aryl.
A kind of anti-aromaticity ring expansion porphyrin compound, the structural formula such as formula (V) of the anti-aromaticity ring expansion porphyrin compound
It is shown：
Ar is aryl.
The synthetic method of above-mentioned armaticity ring expansion porphyrin compound is original with the fluorine boron ring expansion porphyrin compound of stable structure
Material and methanesulfonic acid mixing carry out boron removal and react to obtain the compound of formula (II), and the compound of formula (II) is reacted with triethylamine again, obtained
To the compound of the stable anti-aromaticity formula (III) of oxidation state, the compound of formula (III) can be obtained again through reduction reaction
Armaticity ring expansion porphyrin compound shown in stable formula (IV).
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of fluorine boron ring expansion porphyrin compound prepared by embodiment 1；
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of anti-aromaticity ring expansion porphyrin compound prepared by embodiment 1；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the compound of formula (III) prepared by embodiment 1；
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of armaticity ring expansion porphyrin compound prepared by embodiment 1；
Fig. 5 be embodiment 1 prepare formula (I), (III), (IV) and (V) compound uv absorption spectra.
Specific embodiment
To facilitate the understanding of the present invention, below will to invention is more fully described, and give it is of the invention compared with
Good embodiment.But the invention can be realized in many different forms, however it is not limited to embodiment described herein.Phase
Instead, purpose of providing these embodiments is makes the disclosure of the present invention more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.Term as used herein "and/or" includes one or more phases
Any and all combinations of the listed item of pass.
The fluorine boron ring expansion porphyrin compound of one embodiment, structural formula are as follows：
Ar is aryl.
Further, 2 Ar, 4,6- trimethylphenyls.
The synthetic method of the above-mentioned fluorine boron ring expansion porphyrin compound of one embodiment, includes the following steps S110:
S110, in protective gas atmosphere, alpha-brominated two pyrroles's alkene of fluorine boron and tripyrrole alkane are mixed and carries out nucleophilic and takes
Generation reaction, obtains fluorine boron ring expansion porphyrin compound shown in formula (I).
Wherein, the structural formula of alpha-brominated two pyrroles's alkene of fluorine boron is as follows：
Ar is aryl.
The structural formula of tripyrrole alkane is as follows：
Ar is aryl.
Further, step S110 is specially：In protective gas atmosphere, by alpha-brominated two pyrroles's alkene of fluorine boron, tripyrrole
Alkane, cesium carbonate and paraxylene mixing, are heated to reflux state reaction.
Further, the reaction temperature of nucleophilic substitution is 140 DEG C, and the reaction time is 48 hours.
Further, the molar ratio of alpha-brominated two pyrroles's alkene of fluorine boron, tripyrrole alkane and cesium carbonate is 0.55:0.5:1.0.
Further, protective gas is inert gas.In the present embodiment, protective gas is argon gas.
The reaction equation of above-mentioned steps S110 is as follows：
Further, further include the steps that isolating and purifying after necleophilic reaction：
The reaction solution that necleophilic reaction is obtained is diluted with chloroform, using chloroform as eluant, eluent, through short silicagel column
After processing, vacuum distillation remove solvent, solvent is combined into the group of methylene chloride and n-hexane, using after silica gel column chromatography with two
Chloromethanes and recrystallizing methanol.
The synthetic method of above-mentioned fluorine boron ring expansion porphyrin compound passes through boronation before fluorine boron ring expansion porphyrin compound cyclization
First two pyrroles are locked, then using alpha-brominated two pyrroles's alkene of fluorine boron and tripyrrole alkane as raw material, carry out nucleophilic substitution, obtained steady
Fixed fluorine boron ring expansion porphyrin compound.
The armaticity ring expansion porphyrin compound of one embodiment, structural formula are as follows：
Ar is aryl.
Further, 2 Ar, 4,6- trimethylphenyls.
The synthetic method of the above-mentioned armaticity ring expansion porphyrin compound of one embodiment, include the following steps S210~
S230：
S210, fluorine boron ring expansion porphyrin compound is provided.
In the present embodiment, fluorine boron ring expansion porphyrin compound is prepared using above-mentioned steps S110.
It is appreciated that in other embodiments, above-mentioned fluorine boron ring expansion porphyrin compound can also use other methods system
It is standby, as long as fluorine boron ring expansion porphyrin compound shown in formula (I) can be obtained.
S220, in protective gas atmosphere, above-mentioned fluorine boron ring expansion porphyrin compound and methanesulfonic acid are mixed and carry out boron removal
Reaction, obtains the compound of formula (II).
Wherein, the structural formula of compound of formula (II) is as follows：
Ar is aryl.
Further, 2 Ar, 4,6- trimethylphenyls.
Further, step S220 is specially：In protective gas atmosphere, by above-mentioned fluorine boron ring expansion porphyrin compound, first
Sulfonic acid and methylene chloride hybrid reaction.
Further, the molal volume of fluorine boron ring expansion porphyrin compound and methanesulfonic acid ratio is 0.03mmol:0.1mL.
Further, the reaction temperature of boron removal reaction is 40 DEG C, and the reaction time is 5 hours.
Further, protective gas is inert gas.In the present embodiment, protective gas is argon gas.
The reaction equation of step S210 is as follows：
Further, further include the steps that isolating and purifying after boron removal reaction terminates：
The reaction solution that boron removal is reacted is washed with saturated sodium bicarbonate solution, washes, is extracted with dichloromethane, organic layer is used
Anhydrous sodium sulfate is dry.
S230, compound and triethylamine hybrid reaction by above-mentioned formula (II), obtain the compound of formula (III).
Wherein, the structural formula of compound of formula (III) is as follows：
Ar is aryl；
Further, 2 Ar, 4,6- trimethylphenyls.
Further, the molal volume of fluorine boron ring expansion porphyrin compound and triethylamine ratio is 0.03mmol:0.2mL.
Further, the reaction temperature of the compound of formula (II) and triethylamine hybrid reaction is room temperature, and the reaction time is 2 small
When.
The reaction equation of step S230 is as follows：
Further, the compound of formula (II) and triethylamine hybrid reaction further include the steps that isolating and purifying after terminating：
Silica gel post separation will be crossed after the compound of formula (II) and the washing of the reaction solution of triethylamine hybrid reaction, uses methylene chloride
It is recrystallized with the mixed solution of methanol.
S240, in protective gas atmosphere, the compound of above-mentioned formula (III) and reducing agent are mixed restore it is anti-
It answers, obtains armaticity ring expansion porphyrin compound.
Wherein, shown in the structural formula of armaticity ring expansion porphyrin compound such as formula (IV)：
Ar is aryl.
Further, 2 Ar, 4,6- trimethylphenyls.
Further, reducing agent is sodium borohydride.
When reducing agent is sodium borohydride, step S240 is specially：
In protective gas atmosphere, the compound of formula (III), sodium borohydride, methylene chloride and methanol are mixed and carried out
Reaction.Wherein the volume ratio of methylene chloride and methanol is 3:1.
Further, the molar ratio of the compound and sodium borohydride of formula (III) is 0.025:0.021.
Further, the reaction temperature of reduction reaction is room temperature, and the reaction time is 5 hours.
The reaction equation of step S240 is as follows：
Further, further include the steps that isolating and purifying after reduction reaction：
Silica gel chromatographic column chromatography purity is used after the reaction solution of reduction reaction is removed solvent.
The synthetic method of above-mentioned armaticity ring expansion porphyrin compound, using stable fluorine boron ring expansion porphyrin compound as raw material,
It reacts to obtain the compound of the formula (III) of the stable anti-aromaticity of oxidation state by boron removal, then also by the compound of formula (III)
Armaticity ring expansion porphyrin compound stable shown in formula (IV) can be obtained in original.
The anti-aromaticity ring expansion porphyrin compound of one embodiment, structural formula are as follows：
Ar is aryl.
Further, 2 Ar, 4,6- trimethylphenyls.
The synthetic method of the anti-aromaticity ring expansion porphyrin compound of one embodiment, includes the following steps S310~S320：
S310, formula fluorine boron ring expansion porphyrin compound is provided.
In the present embodiment, fluorine boron ring expansion porphyrin compound is prepared using above-mentioned steps S110.
It is appreciated that in other embodiments, above-mentioned fluorine boron ring expansion porphyrin compound can also use other methods system
It is standby, as long as being capable of fluorine boron ring expansion porphyrin compound shown in formula (I).
S320, above-mentioned fluorine boron ring expansion porphyrin compound and oxidant are mixed into progress oxidation reaction, obtains anti-aromaticity expansion
Ring porphyrin compound.
Wherein, shown in the structural formula of anti-aromaticity ring expansion porphyrin compound such as formula (V)：
Ar is aryl.
Further, 2 Ar, 4,6- trimethylphenyls.
Further, oxidant is manganese dioxide.
Further, when oxidant is manganese dioxide, step S320 is specially：
By fluorine boron ring expansion porphyrin compound, manganese dioxide and methylene chloride hybrid reaction.
Further, the molar ratio of fluorine boron ring expansion porphyrin compound and manganese dioxide is 0.07:0.4.
Further, the reaction temperature of oxidation reaction is room temperature, and the reaction time is 3 hours.
The reaction equation of step S320 is as follows：
Further, further include the steps that isolating and purifying after oxidation reaction：
The reaction solution of oxidation reaction is used into siliceous earth column separating-purifying.
The synthetic method of above-mentioned anti-aromaticity ring expansion porphyrin compound is original with stable fluorine boron ring expansion porphyrin compound
Material, is oxidized boron removal using manganese dioxide, the anti-aromaticity ring expansion porphyrin compound of stable structure can be obtained.
The following are specific embodiments.
Embodiment 1
(1) preparation of fluorine boron ring expansion porphyrin compound：
Tripyrrole alkane (253.9mg, 0.55mmol), alpha-brominated two pyrrole are sequentially added into dry Schlenk reaction tube
Cough up alkene (234.0mg, 0.5mmol), Cs2CO3(325.0mg, 1.0mmol), then in the guard mode of inert gas (argon gas)
Under, the super dry paraxylene of 10mL is injected in the reaction tube with syringe, finally places the reaction tube being sealed in oil bath
It is heated to reflux about 48 hours (detection raw material fully reacting).It is dilute with chloroform until temperature of reaction system is cooled to room temperature
It releases reaction solution and is evaporated under reduced pressure after the processing of too short silicagel column as eluant, eluent and removes solvent.Matched with methylene chloride and n-hexane
Solvent processed, carries out separating-purifying to residue using silica gel column chromatography and with methylene chloride and recrystallizing methanol, obtains green
Fluorine boron ring expansion porphyrin compound (38.3mg, yield 10%).
Obtained green fluorine boron ring expansion porphyrin compound is tested and analyzed, the result is shown in Figure 1：
1H NMR(500MHz,CDCl3):δ=10.30 (d, 2H, J=4.5Hz, β-H), 10.06 (d, 2H, J=4.0Hz,
β-H), 9.31 (d, 2H, J=4.0Hz, β-H), 9.08 (s, 2H, β-H), 8.86 (d, 2H, J=3.0Hz, β-H), 7.44 (s,
6H,Ar1- H), 2.73 (s, 9H, Me-H), 2.03 (s, 6H, Me-H), 1.94 (s, 12H, Me-H), -4.35 (t, J=11.0Hz,
2H,NH),-7.28(s,1H,NH)ppm.HR-MS(MALDI-TOF-MS):M/z=765.38, calcd for (C50H46N5BF2
)+=765.38 ([M]+).
(2) preparation of anti-aromaticity ring expansion porphyrin compound：
Fluorine boron shown in formula (I) is added into 50mL round-bottomed bottle and expands ring expansion porphyrin compound (54mg, 0.07mmol), MnO2
CH is added in (32.8mg, 0.4mmol)2Cl2(10mL) is stirred at room temperature 3 hours, and compound of reaction crosses siliceous earth column, obtains yellow
Negative side's tropism ring expansion porphyrin compound (49mg, yield 92%).
Obtained yellow negative side's tropism ring expansion porphyrin compound is tested and analyzed, as a result sees Fig. 2：
1H NMR(500MHz,CDCl3):δ=35.32 (s, 1H, NH), 6.37 (s, 2H, Ar-H), 6.31 (s, 4H, Ar-
), H 3.17 (d, J=4.0Hz, 2H, β-H), 3.03 (d, J=4.0Hz, 2H, β-H), 2.56 (d, J=4.0Hz, 2H, β-H),
2.50 (s, 12H, Me-H), 2.48 (s, 6H, Me-H), 2.43 (d, J=4.0Hz, 2H, β-H), 1.91 (s, 3H, Me-H), 1.87
(s,6H,Me-H),1.75(s,2H,β-H).λmax(ε[M-1cm-1])=376 (91990), 407 (78367), 642 (3806),
829(6316),1087(457),1318(378)nm.MS(ESI-TOF-MS):M/z=764.3738, calcd for
(C50H44N5BF2)+=764.3739 ([M]+).
(3) synthesis of the compound of formula (III)：
Into dry Schlenk reaction tube be added formula (I) shown in fluorine boron ring expansion porphyrin compound (23.0mg,
0.03mmol), then under the guard mode of inert gas (argon gas), with syringe by the super dry dichloro of 0.1mL methanesulfonic acid and 5mL
Methane is implanted sequentially in the reaction tube, finally by the reaction tube being sealed in 40 DEG C react 5 hours after, reaction solution saturated carbon
Sour hydrogen sodium solution washing, washing are extracted with dichloromethane, and organic layer is dry with anhydrous sodium sulfate, and 0.2mL triethylamine rear chamber is added
Temperature stirring 2 hours, crosses silica gel post separation, uses CH after washing2Cl2/ MeOH recrystallization, obtains the compound of the formula (III) of yellow
(19.1mg, yield 90%).
The compound of obtained yellow formula (III) is tested and analyzed, as a result sees Fig. 3：
1H NMR(500MHz,CDCl3):δ=32.57 (s, 1H, NH), 29.50 (s, 1H, NH), 6.50 (s, 2H, Ar-H),
6.44 (s, 4H, Ar-H), 3.88-3.87 (m, 4H, β-H), 3.64 (d, 2H, J=4.5Hz, β-H), 3.61 (d, 2H, J=
4.5Hz,β-H),2.75(s,2H,β-H),2.36(s,6H,Me-H),2.35(s,12H,Me-H),2.01(s,3H,Me-H),
1.97(s,6H,Me-H)ppm.λmax(ε[M-1cm-1])=400 (55689), 424 (53154), 1010 (790) nm.MS
(MALDI-TOF-MS):M/z=715.45, calcd for (C50H45N5)+=715.37 ([M]+).
(4) synthesis of armaticity ring expansion porphyrin compound：
In glove box, the compound (20.0mg, 0.025mmol) of formula (III), NaBH is added in Schlenk reaction tube4
(8.0mg, 0.21mmol), adds CH2Cl2/ MeOH (6/2mL) is allowed to dissolve, and reaction mixture stirs 5 hours at room temperature, drains molten
Agent is purified with silica gel column chromatography, obtains the armaticity ring expansion porphyrin compound (19.0mg, yield 95%) of green.
Obtained green armaticity ring expansion porphyrin compound is tested and analyzed, as a result sees Fig. 4：
1H NMR(500MHz,CDCl3):δ=9.36 (d, J=4.0Hz, 2H, β-H), 9.34 (d, J=4.0Hz, 2H, β-
), H 8.72 (d, J=4.0Hz, 2H, β-H), 8.46 (s, 2H, β-H), 8.34 (d, J=4.0Hz, 2H, β-H), 7.33 (s, 4H,
Ar-H),7.32(s,2H,Ar-H),2.65(s,9H,Me-H),2.01(s,6H,Me-H),1.91(s,12H,Me-H),-1.67
(br,4H,NH)ppm.λmax(ε[M-1cm-1])=346 (28460), 460 (220770), 566 (10750), 613 (10830),
653(11290),715(32290),812(3372)nm。
Referring to Fig. 5, being inhaled for the formula (I) of the preparation of embodiment 1, the ultraviolet light of the compound of formula (III), formula (IV), formula (V)
Receive map.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of fluorine boron ring expansion porphyrin compound, which is characterized in that the structural formula such as formula (I) of the fluorine boron ring expansion porphyrin compound
It is shown：
Ar is aryl.
2. fluorine boron ring expansion porphyrin compound according to claim 1, which is characterized in that the Ar is 2,4,6- trimethylbenzenes
Base.
3. the synthetic method of fluorine boron ring expansion porphyrin compound of any of claims 1 or 2, which is characterized in that include the following steps：
In protective gas atmosphere, alpha-brominated two pyrroles's alkene of fluorine boron and tripyrrole alkane are mixed and carry out nucleophilic substitution, is obtained
Structural formula to the fluorine boron ring expansion porphyrin compound, alpha-brominated two pyrroles's alkene of fluorine boron is as follows：
Ar is aryl,
The structural formula of the tripyrrole alkane is as follows：
Ar is aryl.
4. the synthetic method of fluorine boron ring expansion porphyrin compound according to claim 3, which is characterized in that it is described will be alpha-brominated
Two pyrroles's alkene of fluorine boron and tripyrrole alkane mix the step of carrying out nucleophilic substitution：
Alpha-brominated two pyrroles's alkene of fluorine boron, tripyrrole alkane, cesium carbonate and paraxylene are mixed, reflux state reaction is heated to.
5. using the method for the synthesis armaticity ring expansion porphyrin compound of fluorine boron ring expansion porphyrin compound described in as claimed in claim 1 or 22,
It is characterized by comprising the following steps：
In protective gas atmosphere, the fluorine boron ring expansion porphyrin compound and methanesulfonic acid are mixed and carry out boron removal reaction, is obtained
The structural formula of compound of the compound of formula (II), the formula (II) is as follows：
Ar is aryl；
By the compound and triethylamine hybrid reaction of the formula (II), the compound of formula (III), the change of the formula (III) are obtained
It is as follows to close object structural formula：
Ar is aryl；
In protective gas atmosphere, the compound of the formula (III) and reducing agent are mixed and carry out reduction reaction, obtains fragrance
Property ring expansion porphyrin compound, shown in the structural formula such as formula (IV) of the armaticity ring expansion porphyrin compound：
Ar is aryl.
6. the method for synthesis armaticity ring expansion porphyrin compound according to claim 5, which is characterized in that the fluorine boron expands
Ring porphyrin compound and methanesulfonic acid mix the step of carrying out boron removal reaction：
By the fluorine boron ring expansion porphyrin compound, methanesulfonic acid and methylene chloride hybrid reaction.
7. the method for synthesis armaticity ring expansion porphyrin compound according to claim 5 or 6, which is characterized in that described to go back
Former agent is sodium borohydride；The formula (III) compound and reducing agent mixing carry out reduction reaction the step of be specially：
The compound of the formula (III), sodium borohydride, methylene chloride and methanol are mixed and reacted.
8. a kind of armaticity ring expansion porphyrin compound, which is characterized in that the structural formula of the armaticity ring expansion porphyrin compound is such as
Shown in formula (IV)：
Ar is aryl.
9. utilizing the side of the synthesis anti-aromaticity ring expansion porphyrin compound of fluorine boron ring expansion porphyrin compound described in as claimed in claim 1 or 22
Method, which is characterized in that include the following steps：
The fluorine boron ring expansion porphyrin compound and oxidant are mixed and carry out oxidation reaction, obtains anti-aromaticity ring expansion porphyrin chemical combination
Object, shown in the structural formula such as formula (V) of the anti-aromaticity ring expansion porphyrin compound：
Ar is aryl.
10. a kind of anti-aromaticity ring expansion porphyrin compound, which is characterized in that the structure of the anti-aromaticity ring expansion porphyrin compound
Shown in formula such as formula (V)：
Ar is aryl.
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