CN104557601B - For identifying the monomer of halide anion and polymer and preparation method - Google Patents
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Abstract
A kind of monomer for identifying halide anionN(to acetenyl) phenyl 2 X tetrafluorobenzamide (X=F, Cl, Br, I), polymer and monomer whose and the preparation method of polymer, the method uses p-aminophenyl acetylene and phenyl-hexafluoride formic acid to be predominant starting material, with N, N dimethyl 4 aminopyridine for catalyst, synthesize target micromolecular compound eventuallyN(to acetenyl) phenyl 2 X tetrafluorobenzamide, then with precious metals complex Rh+(2,5‑nbd)[(η6‑C6H5)B‑(C6H5)3] (triphenyl η6Phenyl boron 2,5 norbornadiene closes rhodium, Rh (nbd) BPh4) it is catalyst, by the method orienting coordination polymer, gatheredN(to acetenyl) phenyl 2 X tetrafluorobenzamide.In obtained small molecule monomer and polymer molecular structure, contain hydrogen bond donor the most simultaneously and halogen key donor, monomer and its polymer all identify halide anion so that hydrogen bond and halogen key are collaborative.Prepare simultaneously and there is reaction condition gentleness, course of reaction simply, be easily controlled, the product yield obtained relatively advantages of higher.
Description
Technical field
The present invention relates to, for identify halide anion, there is hydrogen bond and the monomer of halogen key donor and technical field of polymer thereof, be specifically related to a kind of for identifying halide anionN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide (X=F, Cl, Br, I) monomer and the preparation method and application of polymer thereof.
Background technology
High selectivity, strong affinity, the high sensitive and unique Anion Recognition responded are in nature or anion sensing process, there is extremely important effect, although the research about Anion Recognition achieves challenging progress in recent years, but the synthesis etc. at artificial molecule ion identification, MOLECULE DESIGN and anion receptor remains the research contents that chemical field is extremely challenging, therefore, the host-guest chemistry of Anion Recognition and applied research thereof are one of study hotspot and the focus in supramolecular chemistry field.
The functional group design of current little molecule or macromole anion receptor remains based on all kinds of-NH hydrogen bond donors, carry out the structure of Anion Recognition with halogen key weak interaction and be designed primarily for the exploitation of small molecule receptor, the most do not study and halogen key is incorporated in the synthesis of macromole receptor, more have no that hydrogen bond donor and halogen key donor are simultaneously introduced in the design synthesis of macromolecular skeleton structure by report, study hydrogen bond and halogen key works in coordination with the weak interaction identification to anion.Being used for macromole Anion Recognition system if hydrogen bond and the most important weak interaction of halogen key both organically combined, unique recognition effect will be served by band.
Recently, in Anion Recognition field, the research to macromole receptor has become an important development direction, and macromole receptor shows good sensitivity and selectivity because of the character of its uniqueness.But, compared with cation sensitive macromolecule, the research to polyanionic macromolecule receptor is later.Little molecule and macromole Anion Recognition receptor and the most basic difference of sensor are that the latter has signal and amplifies and high sensitivity response, especially for obtaining the anion receptor significantly sensitive based on certain chemical information, it is an alternative approach that the macromolecular compound of helical structure is prepared in design, because this structure can amplify the identification signal to object anion by changing its kinetics helical conformation.
Cis
(a)
With trans
(b)
Configuration polyphenylacetylene
Polyphenylacetylene is not only a kind of color development signal component, also it is receptor effective stereochemical structure support of carrying out Anion Recognition, it can the three dimensional structure of effective function of organization's group, the microcosmic spatial chemistry environment of its conformational change energy Effective Regulation host-guest interaction and Anion Recognition signal, this point is confirmed by document.nullPolyphenylacetylene can be divided into cis-configuration and anti-configuration in stereochemical structure，When support frame using cis-configuration as functional receptor，Occupy and be separated by two carbon atoms between adjacent two benzene ring building blocks of strand both sides，I.e. adjacent two phenyl ring of homonymy are apart from each other，Appropriately sized locus is had between adjacent two anion receptor function bases of phase keyed jointing on two such phenyl ring，Advantageously form many sites weak bond recognition mode of symmetry，Objectively providing " place to stay " (above formula a) for various anion objects，And in trans polyphenylacetylene strand，Benzene ring structure occupies the homonymy of whole strand，A carbon atom only it is spaced between adjacent two phenyl ring，The most necessarily make two adjacent two anion receptor function bases the most close，Even it is in " crowded " state，It is difficult to form suitable space (the above formula b) needed for multidigit point symmetry weak bond identification，It is unfavorable for that various anion is close and enter weak key action region and recognition reaction occurs.Additionally, the response recognition performance of macromole receptor is also closely related with the ionic radius of object anion rather than alkalescence, it means that on macromolecular skeleton, the density of functional group has material impact to the recognition performance of different anions.This patent is with cis polyphenylacetylene for functional receptor macromole support, and carries out design and the synthesis of functionalization little molecule polymerisable monomer based on this macromole, and then prepares macromole Anion Recognition receptor.At present, individually combine with hydrogen bond or halogen bond effect and identify that the functional receptor molecular studies report of anion is more, work in coordination with identify the documents and materials such as patent of anion ground function organic molecule and polymer thereof but without being simultaneously based on both the above weak interaction.
Summary of the invention
The technical problem to be solved is to provide a kind of monomer for identifying halide anion for shortcoming of the prior artN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide, also provides for the preparation method of this monomer and at the application process identifying halide anion.
Another mesh of the present invention also provides for the monomer for identifying halide anionNThe polymer of-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide, also provides for the preparation method of this polymer and at the application process identifying halide anion.
A kind of monomer for identifying halide anionN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide (X=F, Cl, Br, I), its structural formula is:
In formula, X is F, Cl, Br, I.
Its polymer being used for identifying the monomer of halide anion above-mentioned, structural formula is:
In formula, X is F, Cl, Br, I, m=500-600, and the number-average molecular weight of polymer is 1.8 × 105。
N-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide monomer and the syntheti c route of polymer thereof:
A kind of monomer for identifying halide anionN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide (X=F, Cl, Br, I) preparation method, the method uses p-aminophenyl acetylene and phenyl-hexafluoride formic acid to be predominant starting material, with N, N-dimethyl-4-aminopyridine is catalyst, has synthesized target micromolecular compound eventuallyN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide, then with precious metals complex Rh+(2,5-nbd)[(η6-C6H5)B-(C6H5)3] (triphenyl-η6-phenyl boron-2,5-norbornadiene closes rhodium, Rh (nbd) BPh4) it is catalyst, by the method orienting coordination polymer, gatheredN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide.In obtained small molecule monomer and polymer molecular structure, contain hydrogen bond donor and halogen key donor the most simultaneously.The method has reaction condition gentleness, course of reaction simply, is easily controlled, the product yield obtained relatively advantages of higher.
For identifying the monomer of halide anionNThe preparation method of-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide is as follows:
1.0mmol p-aminophenyl acetylene, the pentafluorobenzoic acid of 1.3mmol and the N of 0.2mmol, N-dimethyl-4-aminopyridine are dissolved in the 5 anhydrous CH of ml2Cl2Or in THF, it is subsequently adding 1.5mmol dimethylaminopropyl ethyl phosphoamide hydrochlorate EDC-HCl, at 23-25 ° of C stirring reaction 24-30h.
With CH2Cl2For solvent, reaction system being washed with water, divide and take organic layer, water layer is with CH2Cl2Extraction, washs with strong brine after being merged by gained organic layer, divides and takes organic layer and use anhydrous Na2SO4Dried filter, by filtrate decompression distillation and concentration, with ethyl acetate as eluant, by crude product concentrated solution on silica gel column chromatography isolated and purified, obtain target productN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide；
With THF as solvent, by reaction system decompression distillation, with ethyl acetate again solvent dilution bottoms, respectively Yi Shui and salt acid elution, divide and take organic layer, use anhydrous Na2SO4Dried filter, by filtrate decompression distillation and concentration, with ethyl acetate as eluant, by crude product concentrated solution on silica gel column chromatography isolated and purified, obtain target productN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide.
For identifying the poly-of halide anionNThe preparation method of-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide is as follows:
Under Ar gas shielded, by 2.69mmol'sN-(to acetenyl)-phenyl-2-chloro-tetrafluorobenzamide monomer is dissolved in that to add 4ml concentration the most again in the Shlenk bottle filling the 85.5 anhydrous THF of ml be 1.34 × 10-2mol/lRh(nbd)BPh4Anhydrous THF solution, under room temperature stirring reaction 24-30h after add 322 μm ol triphenylphosphines, the CH that will pour into after reaction system distillation and concentration2Cl2Middle precipitation, again uses CH by precipitate2Cl2Filter after washing and be vacuum dried, obtaining target product and gatherNThe chloro-tetrafluorobenzamide of-(to acetenyl)-phenyl-2-, in light yellow solid.
Both the above target product (monomer and polymer thereof) can by nuclear magnetic resoance spectrum hydrogen compose (1H NMR) and carbon spectrum (13C NMR) and infrared spectrum (FT-IR) modern physics method carry out detection characterize.GainedNThe performance assessment criteria of-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide and polymer thereof is as follows:
Outward appearance: monomer is faint yellow solid, polymer is light yellow solid powder.
Products obtained therefromNThe nuclear magnetic data of-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide and polymer thereof is as follows:
Fig. 1, Fig. 2 areNThe nuclear magnetic data collection of illustrative plates of-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide:
Shown in Fig. 1,1H NMR (400MHz, CDCl3, ppm), δ=7.37-8.48 (4H, Ph-H4), 6.72 (N-H), 2.92 (C ≡ C-H).
Shown in Fig. 2,13C NMR (400MHz, CDCl3 ,Ppm), δ=141.56 (amidocarbonylation C), (128.63-136.74 the C that be connected non-with carbonyl on pentafluorophenyl group), 101.71 (C being connected with carbonyl on pentafluorophenyl group), 105.97-125.99 (C on phenyl ring being connected with alkynyl in molecule), 65.13-68.77 (C ≡ C).
Fig. 3, Fig. 4 are poly-NThe nuclear magnetic data collection of illustrative plates of-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide:
Shown in Fig. 3,1H NMR (400MHz, CDCl3,
ppm), δ=7.89, 6.99, 6.57,
6.72(N-H); 6.32-8.52(Ph-H);4.91-6.06 (C=C-H on main polymer chain).
Shown in Fig. 4,13C NMR (400MHz, CDCl3 ,Ppm), δ=141.25-410.00 (amidocarbonylation C), (127.55-137.52 the C on phenyl-pentafluoride ring), (100.70 the C on phenyl ring being connected with carbonyl carbon), 107.98 (carbon on phenyl ring), 113.14-118.06 (C on main polymer chain).
Fig. 5, Fig. 6 are products obtained therefromN-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide and the ir data collection of illustrative plates of polymer thereof:
Fig. 5 is NThe infrared spectrum of-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide and data: 1006cm-1For the asymmetrical stretching vibration of C-F on phenyl ring；1355cm-1For the rocking vibration of C-H on phenyl ring；1518cm-1For the characteristic absorption of the stretching vibration of C-C in phenyl-pentafluoride ring；1631cm-1It is attributed to the rocking vibration of N-H；1762cm-1Stretching vibration for C=O absorbs by force position；2208cm-1Stretching vibration for alkynyl C ≡ C；3173 cm-1Absorb for the stretching vibration of C-H on phenyl ring；3483cm-1For the stretching vibration characteristic absorption position of C-H on alkynyl；3602cm-1Stretching vibration characteristic absorption for N-H.
Fig. 6 is poly-NThe infrared spectrum of-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide and data: 1015cm-1For the asymmetrical stretching vibration of C-F on phenyl ring；1527cm-1For the characteristic absorption of the stretching vibration of C-C in phenyl-pentafluoride ring；1644cm-1It is attributed to the rocking vibration of N-H；1756-1781cm-1Stretching vibration for amide C=O absorbs by force position；3174-3250 cm-1Absorb for the stretching vibration of C-H on phenyl ring；3259 is the stretching vibration of C-H on polymer molecule backbone；3564-3624cm-1Stretching vibration characteristic absorption for N-H.
May certify that from above nuclear magnetic resonance, NMR and ir data, two kinds of products prepared by this technical method are desired target productN-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide and polymer thereof.
Monomer and its polymer may be incorporated for the identification of halide anion, during using monomer as the identification receptor of halide anion, while the N-H group of anion and 2-X-tetrafluorobenzamide structure forms strong hydrogen bonding effect, halogen key weak interaction, i.e. two kinds weak key action collaborative identification halide anions can also be formed with the C-X group in 2-X-phenyl tetrafluoride structure.Unlike monomer, when macromole receptor using polymer as halide anion identification, polymer chain can spontaneous by it to same allosteric effect so that form two hydrogen bonds and two halogen keys between each halide anion and polymer, and can identify and combine substantial amounts of halide anion.
The invention have the characteristics that
(1) construction features of target product
This technological invention is designed and the target product preparedNIn-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide and polymer architecture thereof, have can as the amide structure unit of hydrogen bond donor, also have can as the fragrant C-F construction unit of halogen key donor, and the two with anion binding time, space geometry has concertedness, i.e.N-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide can combine anion with hydrogen bond and the two kinds of weak bond synergism identifications of halogen key simultaneously, and another target product using the method illustrated in the present invention to obtain gathersN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide is stereospecfic polymerization product (cis polymerization), and its construction unit has identical space geometry configuration with monomer, i.e. anion (as shown in Figure 7) can also be combined with hydrogen bond and the two kinds of weak bond synergism identifications of halogen key.
(2) chemical reaction condition of preparation process is gentle
The technology path preparing target product given by the present invention is relatively simple, and the reaction condition of every single step reaction is the gentleest, and total overall reaction is the most at room temperature carried out, consuming little energy, and course of reaction is safe and reliable, and productivity is of a relatively high.
(3) using value that target product is important
Designed by this technological invention and prepareNThe polymerizable construction unit of-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide is phenylacetylene group, polyphenylacetylene skeleton in its polymer architecture is not only a kind of color development signal component, also it is receptor effective stereochemical structure support of carrying out Anion Recognition, it can the three dimensional structure of effective function of organization's group, the microcosmic spatial chemistry environment of its conformational change energy Effective Regulation host-guest interaction and Anion Recognition signal.Therefore the target product prepared by the present invention has important using value at Anion Recognition and sensory field.
Accompanying drawing explanation
Fig. 1 is the product of embodiment 1N-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide1H NMR spectra；
Fig. 2 is the product of embodiment 1N-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide13C NMR spectra；
Fig. 3 is that the product of embodiment 1 gathersN-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide1H NMR spectra；
Fig. 4 is that the product of embodiment 1 gathersN-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide13C NMR spectra；
Fig. 5 is the product of embodiment 1NThe infrared spectrogram of-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide；
Fig. 6 is the product of embodiment 1Poly- NThe infrared spectrogram of-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide；
Fig. 7 is the present invention (polymer) hydrogen bond and the two kinds of weak bond synergism identifications of halogen key combine anionic sites diagram.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
1.0mmol p-aminophenyl acetylene, the pentafluorobenzoic acid of 1.3mmol and the N of 0.2mmol, N-dimethyl-4-aminopyridine are dissolved in the 5 anhydrous CH of ml2Cl2In, it is subsequently adding dimethylaminopropyl ethyl phosphoamide hydrochlorate (EDC-HCl) of 1.5mmol, 23 ° of C stirring reaction 24h.Reaction is with CH2Cl2For solvent, reaction system being washed with water, divide and take organic layer, water layer is with CH2Cl2Extract 3 times, wash with strong brine after gained organic layer is merged, divide and take organic layer and use anhydrous Na2SO4Dried filtration, by filtrate decompression distillation and concentration.With ethyl acetate as eluant, by crude product concentrated solution on silica gel column chromatography isolated and purified, obtain target productN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide (light yellow crystal, productivity 92%).
Under Ar gas shielded, by 2.69mmol'sN-(to acetenyl)-phenyl-phenyl-pentafluoride Methanamide monomer is dissolved in the Shlenk bottle filling the 85.5 anhydrous THF of ml, then adds that to add 4ml concentration the most again be 1.34 × 10-2mol/lRh(nbd)BPh4Anhydrous THF solution, under room temperature stirring reaction 30h, add 322 μm ol triphenylphosphines.Substantial amounts of CH is poured into by after reaction system distillation and concentration2Cl2In, precipitate is used again CH2Cl2Filter after washing and be vacuum dried, obtaining target product and gatherN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide (light yellow solid, productivity 95%).
Embodiment 2
By 1.0mmol p-aminophenyl acetylene, the chloro-tetrafluorobenzoic aid of 2-of 1.3mmol and the N of 0.2mmol, N-dimethyl-4-aminopyridine is dissolved in the 5 anhydrous CH of ml2Cl2In, it is subsequently adding dimethylaminopropyl ethyl phosphoamide hydrochlorate (EDC-HCl) of 1.5mmol, 25 ° of C stirring reaction 26h.Reaction is with CH2Cl2For solvent, reaction system being washed with water, divide and take organic layer, water layer is with CH2Cl2Extract 3 times, wash with strong brine after gained organic layer is merged, divide and take organic layer and use anhydrous Na2SO4Dried filtration, by filtrate decompression distillation and concentration.With ethyl acetate as eluant, by crude product concentrated solution on silica gel column chromatography isolated and purified, obtain target productNThe chloro-tetrafluorobenzamide of-(to acetenyl)-phenyl-2-(light yellow crystal, productivity 92%).
Under Ar gas shielded, by 2.69mmol'sN-(to acetenyl)-phenyl-2-chloro-tetrafluorobenzamide monomer is dissolved in the Shlenk bottle filling the 85.5 anhydrous THF of ml, and adding 4ml concentration the most again is 1.34 × 10-2mol/lRh(nbd)BPh4Anhydrous THF solution, under room temperature stirring reaction 26h, add 322 μm ol triphenylphosphines.Substantial amounts of CH is poured into by after reaction system distillation and concentration2Cl2In, precipitate is used again CH2Cl2Filter after washing and be vacuum dried, obtaining target product and gatherNThe chloro-tetrafluorobenzamide of-(to acetenyl)-phenyl-2-(light yellow solid, productivity 96%).
Embodiment 3
By 1.0mmol p-aminophenyl acetylene, the 2-I-tetrafluorobenzoic aid of 1.3mmol and the N of 0.2mmol, N-dimethyl-4-aminopyridine is dissolved in the 5 anhydrous THF of ml, is subsequently adding dimethylaminopropyl ethyl phosphoamide hydrochlorate (EDC-HCl) of 1.5mmol, 23 ° of C stirring reaction 30h.Reaction, with THF as solvent, by reaction system decompression distillation, with 50 ml ethyl acetate solvent dilution bottoms again, is washed with 20 ml water and 20ml hydrochloric acid (1 M aq. HCl) respectively, is divided and take organic layer, use anhydrous Na2SO4Dried filtration, by filtrate decompression distillation and concentration.With ethyl acetate as eluant, by crude product concentrated solution on silica gel column chromatography isolated and purified, obtain target productN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide (light yellow crystal, productivity about 92.5%).
Under Ar gas shielded, by 2.69mmol'sN-(to acetenyl)-phenyl-2-I-tetrafluorobenzamide monomer is dissolved in the Shlenk bottle filling the 85.5 anhydrous THF of ml, and adding 4ml concentration the most again is 1.34 × 10-2mol/lRh(nbd)BPh4Anhydrous THF solution, under room temperature stirring reaction 24h, add 322 μm ol triphenylphosphines.Substantial amounts of CH is poured into by after reaction system distillation and concentration2Cl2In, precipitate is used again CH2Cl2Filter after washing and be vacuum dried, obtaining target product and gatherN-(to acetenyl)-phenyl-2-I-tetrafluorobenzamide (light yellow solid, productivity 95%).
After above-described embodiment reaction terminates, find that the yield of target product is more stable, reached target.
Claims (4)
1. one kind for identifying the preparation method of monomer of halide anion, it is characterised in that: it is with aminobenzene acetylene and phenyl-hexafluoride formic acid as initiation material, is that catalyst finally synthesizes with N, N-dimethyl-4-aminopyridine, specifically comprises the following steps that
Aminobenzene acetylene, 2-X-tetrafluorobenzoic aid and N, N-dimethyl-4-aminopyridine are dissolved in anhydrous THF, are subsequently adding dimethylaminopropyl ethyl phosphoamide hydrochlorate EDC-HCl, at 23-25 ° of C stirring reaction 24-30h；
With THF as solvent, by reaction system decompression distillation, with ethyl acetate again solvent dilution bottoms, respectively Yi Shui and salt acid elution, divide and take organic layer, use anhydrous Na2SO4Dried filter, by filtrate decompression distillation and concentration, with ethyl acetate as eluant, by crude product concentrated solution on silica gel column chromatography isolated and purified, obtain target productN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide, its structural formula is:
In formula, X is F, Cl, Br, I.
The preparation method of the monomer for identifying halide anion the most according to claim 1, it is characterized in that: by 1.0mmol p-aminophenyl acetylene, the pentafluorobenzoic acid of 1.3mmol and the N of 0.2mmol, N-dimethyl-4-aminopyridine is dissolved in the 5 anhydrous THF of ml, it is subsequently adding 1.5mmol dimethylaminopropyl ethyl phosphoamide hydrochlorate EDC-HCl, at 23-25 ° of C stirring reaction 24-30h.
3. the preparation method of the polymer of the monomer of halide anion is identified according to being used for described in claim 1 and 2, it is characterised in that: under Ar gas shielded, willN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide monomer and anhydrous THF are mixed to form solution, and are contained in Shlenk bottle, then add Rh (nbd) BPh4Anhydrous THF solution, under room temperature stirring reaction 24-30h after add triphenylphosphine, after reaction system distillation and concentration, pour CH into2Cl2Middle precipitation, again uses CH by precipitate2Cl2Filter after washing and be vacuum dried, obtaining target product and gatherN-(to acetenyl)-phenyl-2-X-tetrafluorobenzamide, in light yellow solid, its structural formula is:
In formula, X is F, Cl, Br, I, and degree of polymerization m is 500-600.
The preparation method of the polymer of the monomer for identifying halide anion the most according to claim 3, it is characterised in that: under Ar gas shielded, by 2.69mmol'sN-(to acetenyl)-phenyl-2-chloro-tetrafluorobenzamide monomer is dissolved in the Shlenk bottle filling the 85.5 anhydrous THF of ml, and adding 4ml concentration the most again is 1.34 × 10-2mol/lRh(nbd)BPh4Anhydrous THF solution, under room temperature stirring reaction 24-30h after add 322 μm ol triphenylphosphines, after reaction system distillation and concentration, pour CH into2Cl2Middle precipitation, again uses CH by precipitate2Cl2Filter after washing and be vacuum dried, obtaining target product and gatherNThe chloro-tetrafluorobenzamide of-(to acetenyl)-phenyl-2-, in light yellow solid.
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| Cooperative Complexation of Amino Acid Derivatives to Platinum Acetylide-Based Bolaamphiphile;Feng Wang等;《Org. Lett.》;20141231;第16卷;Supporting Information第S3页 * |
| Effect of the Pendant Structure on Anion Signaling Property of Poly(phenylacetylene)s Conjugated to R-Amino Acids through Urea Groups;Toyoji Kakuchi等;《Macromolecules》;20091231;第42卷;第4431页Scheme1，第4433页表4左栏最后一段、右栏第一段 * |
| Size-Specific, Colorimetric Detection of Counteranions by Using Helical Poly(phenylacetylene) Conjugated to l-Leucine Groups through Urea Acceptors;Toyoji Kakuchi等;《Chem. Eur. J.》;20081231;第14卷;第10259–10266页 * |
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