CN109705027A - 1,2- bis- (pyridyl group) -3,4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane and preparation method thereof - Google Patents
1,2- bis- (pyridyl group) -3,4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane and preparation method thereof Download PDFInfo
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- CN109705027A CN109705027A CN201910105469.4A CN201910105469A CN109705027A CN 109705027 A CN109705027 A CN 109705027A CN 201910105469 A CN201910105469 A CN 201910105469A CN 109705027 A CN109705027 A CN 109705027A
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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 title claims abstract description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 125000004076 pyridyl group Chemical group 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- 238000001816 cooling Methods 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000005059 solid analysis Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 4
- 239000011521 glass Substances 0.000 description 21
- 239000013078 crystal Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229910000474 mercury oxide Inorganic materials 0.000 description 4
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 4
- 238000006552 photochemical reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- 238000007106 1,2-cycloaddition reaction Methods 0.000 description 2
- -1 298K Chemical compound 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NBDAHKQJXVLAID-UHFFFAOYSA-N 5-nitroisophthalic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC([N+]([O-])=O)=C1 NBDAHKQJXVLAID-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- WSXMFMCRLSKYBP-UHFFFAOYSA-N [C].CCCC Chemical group [C].CCCC WSXMFMCRLSKYBP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000399 optical microscopy Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Pyridine Compounds (AREA)
Abstract
The invention discloses one kind 1,2- bis- (pyridyl group) -3,4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane and preparation method thereof.Described 1,2- bis- (pyridyl group) -3, the preparation method of 4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane, the following steps are included: 1) take 3,5- bis- (2- pyridine vinyl) fluorobenzene, four nitric hydrate cadmiums and parachlorobenzoic-acid are dissolved in solvent, adjust pH≤6 of acquired solution, gained mixed liquor is placed in container, it is reacted in a heated condition after sealing, obtains intermediate 1；2) ultraviolet light for being 254~450nm with wavelength by intermediate 1, obtains intermediate 2；3) intermediate 2 is soaked in the acid solution of pH≤4, is filtered, collect filtrate, adjust its pH to alkalinity, there is solid precipitation, collect solid to get.The method of the present invention simple process is easy to operate, and yield is high；The chemical property of target product and each intermediate is stablized.
Description
Technical field
The present invention relates to the organic ligands for containing multiple pyridine groups, and in particular to 1,2- bis- (pyridyl group) -3,4-, bis- (4-
Pyridine vinyl -3- fluorobenzene) cyclobutane and preparation method thereof.
Background technique
Four-membered ring is synthesized using [2+2] photochemical reaction and its derivative has very important significance, but realizes it
Efficient photochemical transformation is more difficult.In recent years studies have shown that it is such be related to synthesize quaternary cyclobutane [2+2] photochemical reaction
In solid phase, especially the help of master plate molecule can significantly improve efficiency under the conditions of crystalline state.[2+2] photochemistry of solid phase is anti-
Should have high regioselective and highly-solid selectively, not need organic solvent, high conversion rate, therefore meet the reason of Green Chemistry
It reads.
Studied and improved solid state photoreaction of Schmidt ' the s criteria to solid-state [2+2] cycloaddition reaction of alkene
Topological criterion, and system summarize occur solid phase [2+2] cycloaddition light reaction specific spatial configuration and critical distance, specifically
Condition are as follows: the distance between 1, double bond center needs2, the double bond in adjacent molecule need to be arranged in parallel
(G.M.J.Schmidt,Pure Appl.Chem.1971,27,647-678.).Currently, the light dimerization reaction using alkene synthesizes
Cyclobutane has become research hotspot, and how efficiently controllable realization light dimerization reaction becomes a challenging job.
The correlation text of 1,2- bis- (pyridyl group) -3,4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane is had not yet to see
Offer report.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of 1, the 2- bis- (pyridyl group) of structure novel-(4- pyrroles of 3,4- bis-
Pyridine vinyl -3- fluorobenzene) cyclobutane and preparation method thereof.
The present invention relates to 1,2- bis- (pyridyl group) -3,4- bis- of structure shown in following formula (I)s (4- pyridine vinyl -3- fluorine
Benzene) cyclobutane:
The invention also includes the systems of above-mentioned 1,2- bis- (pyridyl group) -3,4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane
Preparation Method, comprising the following steps:
1) 3,5- bis- (2- pyridine vinyl) fluorobenzene, four nitric hydrate cadmium (Cd (NO are taken3)2·4H2) and parachlorobenzoic-acid O
It is dissolved in solvent, adjusts pH≤6 of acquired solution, gained mixed liquor is placed in container, reacts in a heated condition after sealing, cold
But, there is solid product precipitation, obtain intermediate 1；The solvent is water or water and is selected from methanol, ethyl alcohol and N, N- bis-
The combination of one or more of methylformamide；
2) ultraviolet light for being 254~450nm with wavelength by intermediate 1, obtains intermediate 2；
3) intermediate 2 is soaked in the acid solution of pH≤4, is filtered, collect filtrate, adjusted its pH to alkalinity, have solid
Body is precipitated, and collects solid to get described 1,2- bis- (pyridyl group) -3,4- bis- (the 4- pyridine vinyl -3- fluorobenzene) cyclobutane is arrived.
In the step 1) of above-mentioned preparation method, 3,5- bis- (2- pyridine vinyl) fluorobenzene, four nitric hydrate cadmiums and to chlorobenzene
The molar ratio of formic acid is stoichiometric ratio, and in the actual operation process, the dosage of four nitric hydrate cadmiums and parachlorobenzoic-acid can be slightly
Micro- excess, when the molar ratio of 3,5- bis- (2- pyridine vinyl) fluorobenzene, four nitric hydrate cadmiums and parachlorobenzoic-acid is 1:1:1,
The yield of reaction is higher.The dosage of the solvent can be determined as needed, specifically with (the 2- pyridine of 3, the 5- of 0.1mmol bis-
Vinyl) it calculates on the basis of fluorobenzene, the dosages of all raw material solvent for use for participating in reaction are usually 1~5mL；Preferred solvent is
Water.After by 3,5- bis- (2- pyridine vinyl) fluorobenzene, four nitric hydrate cadmiums and parachlorobenzoic-acid solvent, it can use existing
Conventional acid substance (such as nitric acid, hydrochloric acid, sulfuric acid or phosphoric acid) adjusts the pH value of acquired solution, preferably adjusting acquired solution
PH=2~4, be more preferably adjusted to pH=3~4.It is preferred that reaction carries out under conditions of >=80 DEG C, the time of reaction is controllable
It is made as >=12h, preferably 30~40h；More preferably reaction carries out under conditions of 100~120 DEG C, and the time reacted at this time is preferred
Control is in 30~36h.Reaction in the step is solvent-thermal method, wherein the container is usually heavy wall hard closed at one end
Glass tube, the sealing are usually to seal, and are sealed after preferably vacuumizing.The resulting intermediate 1 of the step is with crystal shape
Formula is precipitated.Raw material 3 involved in the step, 5- bis- (2- pyridine vinyl) fluorobenzene can refer to existing literature (W.X.Li et
Al.Inorg.Chem.57,13453-13460 (2018)) it is synthesized, it can also voluntarily be synthetically prepared.
In the step 2) of above-mentioned preparation method, when cracked or slight crack on intermediate 1, show that cycloaddition reaction has been sent out
It is raw, i.e., the existing formation of intermediate 2.Since intermediate 1 is crystal, particle is larger, and specific surface is smaller, from shortening irradiation time and drop
Low energy consumption angularly considers, preferably intermediate 1 is pulverized and last is irradiated again.More preferably it is ground to 200-300
It is irradiated again after mesh, according to the experience of applicant, the time irradiated with this condition is normally controlled in >=1h, preferably 2~
6h.In irradiation, distance of the light source away from powder is usually≤50mm, more preferably≤20mm.
In the step 3) of above-mentioned preparation method, the acid solution is selected from nitric acid solution, hydrochloric acid solution sulfuric acid solution
With the combination of one or more of phosphoric acid solution；It is straight that intermediate 2, which is soaked in the time in the acid solution of pH≤4,
Reach the time needed for destroying coordinate bond while unreacted 5- nitroisophthalic acid being precipitated, the experience of the applicant
Show that time control is more appropriate in 10-30min.In the step, existing conventional alkaline substance (such as sodium hydroxide, hydrogen can be used
Potassium oxide, sodium carbonate etc.) come adjust gained filtrate pH value, preferably adjust filtrate pH >=8；More preferably with alkaline matter
Aqueous solution adjust the pH value of filtrate.
Compared with prior art, present invention is characterized in that
1, the chemical property of intermediate involved in target product of the present invention and preparation method is sufficiently stable,
It, can long-term preservation under normal conditions without harsh preservation condition.
2, the method for the invention simple process is easy to operate, and reaction condition is mild, and yield is high.It can be achieved to take water as a solvent conjunction
At target product.
3, the fluorometric investigation carried out to target product shows that target product has excellent fluorescence property.This ligand may be used also
It is widely used in preparing fluorescent material.
Detailed description of the invention
Fig. 1 is the crystal structure figure of intermediate 1 obtained in the embodiment of the present invention 1；
Fig. 2 is the nuclear magnetic resonance spectroscopy spectrogram of final product made from the embodiment of the present invention 1；
Fig. 3 is the carbon-13 nmr spectra spectrogram of final product made from the embodiment of the present invention 1；
Fig. 4 is the Enantiomeric excess spectrogram of final product made from the embodiment of the present invention 1.
Specific embodiment
The present invention is described in further detail combined with specific embodiments below, content to better understand the invention, but
The present invention is not limited to following embodiments.
Embodiment 1
1) 3,5- bis- (2- pyridine vinyl) fluorobenzene 30.2mg (0.1mmol), Cd (NO is taken3)2·4H2O30.8mg
(0.1mmol) and parachlorobenzoic-acid 15.6mg (0.1mmol) are added in horminess glass tube closed at one end, are added into glass tube
Enter 4mL water, with the pH=3 of nitric acid (concentration 65%) regulation system, the other end of glass tube is sealed, then glass tube is placed in
Isothermal reaction 30h under the conditions of 100 DEG C is down to room temperature (rate of temperature fall is 5 DEG C/h), takes out, it is seen that glass tube after the reaction was completed
There is flaxen crystal to be precipitated on inner wall, which is intermediate 1 (120.8mg, yield 78%).
To being characterized as below for intermediate 1:
IR:v(KBr)/cm-13071 (w), 1614 (s), 1585 (s), 1532 (s), 1392 (s), 1269 (m), 1215
(m), 1165 (w), 1089 (w), 1014 (m), 969 (m), 877 (m), 845 (m), 770 (m), 663 (m), 534 (m), 439 (m)；
1H NMR(400MHz,d6- DMSO, 298K, TMS): δ=8.62 (d, 4H, Py-H), 7.98 (d, 2H), 7.79 (s,
1H), 7.61 (d, 4H, Py-H), 7.60 (d, 2H, CH=CH), 7.53 (d, 2H), 7.48 (d, 2H), 7.44 (d, 2H, CH=
CH)；
19F NMR(377MHz,d6-DMSO,298K,CFCl3): δ=113.130；
Elemental analysis: theoretical value (%): C, 79.45；H,5.00；N,9.27；
Measured value (%): C, 79.44；H,5.02；N,9.31.
Gained crystal is measured with agilent company SuperNova single crystal diffractometer to determine its monocrystalline knot simultaneously
Structure, gained crystallographic data are seen below shown in table 1, and part bond distance's bond angle data are as described in Table 2, the crystal knot of gained crystal
Composition is as shown in Figure 1.
The crystallographic data of 1. intermediate 1 of table:
aR1=Σ | | F0|-|Fc||/Σ|F0|.bwR2={ Σ w (F0 2-Fc 2)2/Σw(F0 2)2}1/2.cGOF={ Σ w
((F0 2-Fc 2)2)/(n-p)}1/2, where n=number of reflections and p=total number of
parameters refined.
The bond distance of 2. intermediate 1 of tableWith bond angle (o):
2) above-mentioned gained light yellow crystal is taken out in the air being placed under room temperature, is seen after a few hours with optical microscopy
The appearance of the crystal known to examining does not change, and is cleaned with ethyl alcohol, then place it on sheet glass be placed in wavelength be 254~
After irradiating for 24 hours under the high-power ultraviolet light of 450nm, it can obviously observe that slight crack occurs in its single-crystal surface by microscope.By
This is as it can be seen that intermediate 1 may have occurred [2+2] photochemical reaction under the irradiation of high-power ultraviolet light.
It separately takes above-mentioned gained light yellow crystal, grinds to 200 mesh, then this is ground into pulverized powder be placed in launch wavelength and be
2h (powder can be observed in irradiation process to darken) is irradiated under the ultraviolet lamp of 300nm, obtains intermediate 2, reaction process is such as
Shown in lower:
To being characterized as below for intermediate 2:
IR:v(KBr)/cm-12990 (w), 1614 (s), 1585 (s), 1520 (s), 1392 (s), 1269 (m), 1215
(m), 1165 (w), 1089 (w), 1010 (m), 969 (m), 857 (m), 845 (m), 778 (m), 663 (m), 534 (m), 439 (m)；
1H NMR (400MHz, d6- DMSO, 298K, TMS): δ=8.50 (d, 4H, Py-H), 8.39 (d, 4H, Py-H), δ=
7.98 (d, 2H), 7.48 (d, 2H), 7.47 (d, 4H, Py-H), 7.44 (d, 4H), 7.28 (d, 4H, Py-H), 7.24 (d, 2H, CH
=CH), 7.09 (s, 2H), 4.76 (d, 2H, CH-CH), 4.67 (d, 2H, CH-CH)；
19F NMR(377MHz,d6- DMSO, 298K, CFCl3): δ=113.820；
Elemental analysis: theoretical value (%): C, 79.45；H,5.00；N,9.27；
Measured value (%): C, 79.37；H,5.13；F,6.25；N,9.29.
The nuclear magnetic resonance map discovery of intermediate 2 and intermediate 1 is compared, the peak of δ=8.62ppm of intermediate 2 disappears completely
It loses, the peak of δ=4.76ppm and 4.67ppm occurs, that is, the signal peak for representing H atom on olefinic carbon disappears, and represents ring
The H atom signal peak of butane carbon atom occurs, and illustrates intermediate 1 after high-power ultraviolet light, [2+2] ring has occurred really
Addition photochemical reaction.
3) it will be placed in the nitric acid solution of pH=1 in intermediate 2 and impregnate 10min, there is Precipitation, filtered, collect filtrate,
Its pH=8 is adjusted with sodium hydrate aqueous solution (concentration 20wt%), there is yellow mercury oxide precipitation, is filtered, washing, after drying to obtain the final product
To yellow solid product (39.2mg, yield 65%).
Gained yellow solid product is characterized as below:
IR:v(KBr)/cm-12985 (s), 1639 (s), 1616 (s), 1602 (s), 1400 (m), 1459 (m), 1353
(m), 1179 (m), 1002 (m), 963 (m), 842 (w), 786 (m), 666 (m), 613 (m), 551 (m)；
1H NMR(400MHz,CDCl3, 298K, TMS): δ=8.56 (d, 4H, Py-H), 8.46 (d, 4H, Py-H), 7.30
(d, 4H, Py-H), 7.16 (d, 2H, CH=CH), 7.04 (d, 4H, Py-H), 7.04 (d, 4H), 6.87 (d, 2H, CH=CH),
6.80 (s, 2H), 4.50 (s, 4H, CH-CH)；Specific spectrogram is as shown in Figure 2；
13C NMR(100MHz,CDCl3, 298K): 164.834,161.930,150.274,149.950,147.917,
143.778,131.537,127.881,122.613,120.882,114.939,111.781,46.61；Specific spectrogram such as Fig. 3 institute
Show；
19F NMR(377MHz,CDCl3, 298K, CFCl3): -112.350；Specific spectrogram is as shown in Figure 4；
Elemental analysis: theoretical value (%): C, 79.45；H,5.00；N,9.27；
Measured value (%): C, 79.40；H,5.10；N,9.28.
Accordingly, it can be determined that yellow solid product obtained by the present embodiment is target product 1 of the present invention, 2- bis- (pyridyl group)-
3,4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane, shown in structural formula such as following formula (I):
Embodiment 2
1) 3,5- bis- (2- pyridine vinyl) fluorobenzene 30.2mg (0.1mmol), Cd (NO is taken3)2·4H2O30.8mg
(0.1mmol) and parachlorobenzoic-acid 15.6mg (0.1mmol) are added in horminess glass tube closed at one end, are added into glass tube
Enter 2mL water, with the pH=4 of nitric acid (concentration 69%) regulation system, the other end of glass tube is sealed, then glass tube is placed in
Isothermal reaction 36h under the conditions of 80 DEG C is down to room temperature (rate of temperature fall is 10 DEG C/h), takes out, it is seen that glass tube after the reaction was completed
There is the crystal of glassy yellow to be precipitated on inner wall, which is intermediate 1 (108.4mg, yield 70%)；
2) monocrystalline of gained intermediate 1 is taken, is ground to 200-300 mesh, then this is ground into pulverized powder is placed in launch wavelength and be
4h (powder can be observed in irradiation process to darken) is irradiated under the ultraviolet lamp of 254nm, obtains intermediate 2；
3) it will be placed in the nitric acid solution of pH=2 in intermediate 2 and impregnate 20min, there is Precipitation, filtered, collect filtrate,
Its pH=9 is adjusted with potassium hydroxide aqueous solution (concentration 10wt%), there is yellow mercury oxide precipitation, is filtered, washing, after drying to obtain the final product
To yellow solid product (24.1mg, yield 40%).
Infrared, nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra, nuclear magnetic resonance are carried out to yellow solid product obtained by the present embodiment
The characterizations such as fluorine spectrum, elemental analysis and single crystal structure analysis determine that products therefrom is target product 1,2- bis- (pyridyl group) -3,4- bis-
(4- pyridine vinyl -3- fluorobenzene) cyclobutane.
Embodiment 3
1) 3,5- bis- (2- pyridine vinyl) fluorobenzene 30.2mg (0.1mmol), Cd (NO is taken3)2·4H2O30.8mg
(0.1mmol) and parachlorobenzoic-acid 15.6mg (0.1mmol) are added in horminess glass tube closed at one end, are added into glass tube
Enter 5mL water, with the pH=1 of hydrochloric acid (concentration 36%) regulation system, the other end of glass tube is sealed, then glass tube is placed in
Isothermal reaction 12h under the conditions of 120 DEG C is down to room temperature (rate of temperature fall is 8 DEG C/h), takes out, it is seen that glass tube after the reaction was completed
There is the crystal of glassy yellow to be precipitated on inner wall, which is intermediate 1 (92.9mg, yield 60%)；
2) monocrystalline of gained intermediate 1 is taken, is ground to 200-300 mesh, then this is ground into pulverized powder is placed in launch wavelength and be
3h (powder can be observed in irradiation process to darken) is irradiated under the ultraviolet lamp of 350nm, obtains intermediate 2；
3) it will be placed in the sulfuric acid solution of pH=4 in intermediate 2 and impregnate 20min, there is Precipitation, filtered, collect filtrate,
Its pH=10 is adjusted with potassium hydroxide aqueous solution (concentration 10wt%), there is yellow mercury oxide precipitation, is filtered, washing is after dry
Obtain yellow solid product (18.1mg, yield 30.5%).
Infrared, nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra, nuclear magnetic resonance are carried out to yellow solid product obtained by the present embodiment
The characterizations such as fluorine spectrum, elemental analysis and single crystal structure analysis determine that products therefrom is target product 1,2- bis- (pyridyl group) -3,4- bis-
(4- pyridine vinyl -3- fluorobenzene) cyclobutane.
Embodiment 4
1) 3,5- bis- (2- pyridine vinyl) fluorobenzene 30.2mg (0.1mmol), Cd (NO is taken3)2·4H2O46.2mg
(0.15mmol) and parachlorobenzoic-acid 15.6mg (0.1mmol) are added in horminess glass tube closed at one end, into glass tube
3mL water is added, with the pH=6 of concentrated phosphoric acid regulation system, the other end of glass tube is sealed, then glass tube is placed in 110 DEG C of items
Isothermal reaction for 24 hours, after the reaction was completed, is down to room temperature (rate of temperature fall is 8 DEG C/h), is taken out, it is seen that on the inner wall of glass tube under part
There is the crystal of glassy yellow to be precipitated, which is intermediate 1 (123.9mg, yield 80%)；
2) monocrystalline of gained intermediate 1 is taken, is ground to 200-300 mesh, then this is ground into pulverized powder is placed in launch wavelength and be
6h (powder can be observed in irradiation process to darken) is irradiated under the ultraviolet lamp of 450nm, obtains intermediate 2；
3) it will be placed in the hydrochloric acid solution of pH=4 in intermediate 2 and impregnate 30min, there is Precipitation, filtered, collect filtrate,
Its pH=8 is adjusted with saturated sodium bicarbonate aqueous solution, there is yellow mercury oxide precipitation, is filtered, washing obtains yellow solid after dry
Product (21.4mg, yield 35.5%).
Infrared, nuclear magnetic resonance spectroscopy, carbon-13 nmr spectra, nuclear magnetic resonance are carried out to yellow solid product obtained by the present embodiment
The characterizations such as fluorine spectrum, elemental analysis and single crystal structure analysis determine that products therefrom is target product 1,2- bis- (pyridyl group) -3,4- bis-
(4- pyridine vinyl -3- fluorobenzene) cyclobutane.
Claims (10)
1. 1,2- bis- (pyridyl group) -3,4- bis- (4- pyridine vinyl -3- fluorobenzene) cyclobutane of structure shown in following formula (I)s:
The preparation side of 1,2- bis- (pyridyl group) -3,4- bis- described in claim 1 2. (4- pyridine vinyl -3- fluorobenzene) cyclobutane
Method, comprising the following steps:
1) it takes 3,5- bis- (2- pyridine vinyl) fluorobenzene, four nitric hydrate cadmiums and parachlorobenzoic-acid to be dissolved in solvent, adjusts gained
PH≤6 of solution, gained mixed liquor are placed in container, react in a heated condition after sealing, cooling, there is solid product precipitation,
Obtain intermediate 1；The solvent is for water or water and selected from one of methanol, ethyl alcohol and n,N-Dimethylformamide
Or two or more combination；
2) ultraviolet light for being 254~450nm with wavelength by intermediate 1, obtains intermediate 2；
3) intermediate 2 is soaked in the acid solution of pH≤4, is filtered, collected filtrate, adjust its pH to alkalinity, there is solid analysis
Out, solid is collected to get described 1,2- bis- (pyridyl group) -3,4- bis- (the 4- pyridine vinyl -3- fluorobenzene) cyclobutane is arrived.
3. preparation method according to claim 1, it is characterised in that: in step 1), adjust pH=2~4 of acquired solution.
4. preparation method according to claim 1, it is characterised in that: in step 1), reaction under conditions of >=80 DEG C into
Row.
5. preparation method according to claim 1, it is characterised in that: in step 1), time >=12h of reaction.
6. the preparation method according to claim 4, it is characterised in that: in step 1), react the condition at 100~120 DEG C
Lower progress.
7. preparation method according to claim 1, it is characterised in that: in step 2), time >=1h of irradiation.
8. preparation method according to claim 1, it is characterised in that: in step 3), intermediate 2 is soaked in pH≤4
Time >=10min in acid solution.
9. preparation method according to claim 1, it is characterised in that: in step 3), the acid solution is selected from nitre
The combination of one or more of acid solution, hydrochloric acid solution sulfuric acid solution and phosphoric acid solution.
10. preparation method according to claim 1, it is characterised in that: in step 3), adjust pH >=8 of filtrate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503388A (en) * | 2009-03-20 | 2009-08-12 | 苏州大学 | Preparation of 1,2,4-tetra (4-pyridinyl) cyclobutane |
| CN107936263A (en) * | 2017-12-20 | 2018-04-20 | 淮北师范大学 | A kind of coordination polymer with light reaction and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503388A (en) * | 2009-03-20 | 2009-08-12 | 苏州大学 | Preparation of 1,2,4-tetra (4-pyridinyl) cyclobutane |
| CN107936263A (en) * | 2017-12-20 | 2018-04-20 | 淮北师范大学 | A kind of coordination polymer with light reaction and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 胡飞龙: "烯基配位聚合物的自组装及固相[2+2]光环加成反应的研究", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》 * |
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| WO2023077654A1 (en) * | 2021-11-05 | 2023-05-11 | 苏州大学 | Photoinduced nonlinear expansion coordination polymer and preparation method therefor |
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