含氟天麻素的合成

A本文报道了三个含氟天麻素及其衍生物的合成,即2-氟-4-羟甲苯基-β-D-葡萄吡喃糖苷,2-三氟甲基-4-羟甲苯基-β-D-葡萄吡喃糖苷,2,3,5,6-四氟-4-羟甲苯基-β-D-葡萄吡喃糖苷及其五乙酰衍生物等.这些新化合物的结构经元素分析,^1H和^1^9F NMR,IR,和MS等测试确证.     

The synthesis of a soluble,unsymmetrical phthalocyanine on a polymer support

A 1% crosslinked divinylbenzene-styrene copolymer was used in the preparation of the unsymmetrical 2-(6'-hydroxyhexoxy)-9,16,23-triisopropoxyphthalocyanine, soluble in common organic solvents.     

Preparation of a water-soluble fluorinated zinc phthalocyanine and its effect for photodynamic therapy

An amphiphilic fluorinated phthalocyanine, zinc tetracarboxyoctafluorophthalocyanine (ZnC4F8Pc) was synthesized and characterized. Its photodynamic efficiency for HeLa cells was compared with hydrophilic zinc octacarboxyphthalocyanine (ZnC8Pc) and hydrophobic zinc hexadecafluorophthalocyanine (ZnF16Pc). ZnC4F8Pc had a remarkable photodynamic effect among the phthalocyanines used. The effect is apparently caused by the fact that ZnC4F8Pc is mainly accumulated in the hydrophobic lipid membrane and is in the photoactive monomer form in HeLa cells.     

丙烯酸氟醇酯的合成

本文用不同方法合成了几种新的含氟醇及其丙烯酸酯和甲基丙烯酸酯RF(CH2)mOC(O)CR[1]=CH2[R1=H,Me;RF=Cl(CF2)2n,n=1,2,3,m=2;RF=CF3(CF2)2OCF(CF3)CF2OCF(CF3),m=1;RF=RfO(CF2)2SO2NR,m=2:Rf=Cl(CF2)8,R=Et;Rf=CF3(CF2)5,R=n-C3H7,Et;Rf=C2F5O(CF2)4,R=Me,Et],这些酯可以和丙烯酸正辛酯共聚,所得乳液是一种表面处理剂,能使织物具有一定防水,防油性能。     

The synthesis of fluorinated materials in microreactors

Synthetic utilities of microreactor for the synthesis of fluorinated materials are described. In particular, synthesis of silylenol ether of 4,4,4-trifluorobutan-2-one and its synthetic application at room temperature. Further, nitroaldol reactions and Michael addition reaction in microreactor are convenient ways for the syntheses of difluoromethylated materials.     

A convenient synthesis of a substituted phthalocyanine compound

A new substituted tetra-(4-octanethiol-5-nitro)phthalocyaninatocopper complex was synthesized by nucleophlic substitution of tetra-(4-bromo-5-nitro)phthalocyaninatocopper where the bromo activated by an ortho-nitro group is easily substituted by 1-octanethiol.     

The synthesis of vinyl naphthalenes with fluorinated side chains

Summary Methods for the synthesis of -fluoro--vinyl naphthalene and -difluoromethyl--vinylnaphthalene were developed.     

The synthesis and photophysicochemical properties of low-symmetry zinc phthalocyanine analogues

The synthesis of a low-symmetry derivative, zinc mono-carboxy substituted phthalocyanine, ZnPc-COOH (4) has been reported. The photochemical and photophysical properties of ZnPc-COOH (4), ZnTMPyPc (5), ZnttbPc (6) and a previously synthesized low-symmetry derivative, ZnttbIPc (7), in various organic solvents are reported. The red-shifting of the spectra of 4 and 5 (relative to that of unsubstituted zinc phthalocyanine, ZnPc) is a function of the electron-donating sulfur-containing substituents attached to the periphery of the molecule. High triplet quantum yields (Ф_T) generally occur in response to substitution on the zinc phthalocyanine ring periphery. The highest Ф_T values and triplet lifetimes (τ_T) occur in DMSO for all derivatives as a result of the solvent's high viscosity. The strongly electron-withdrawing imido fused ring of ZnttbIPc (7) stabilizes it against photo-oxidative degradation relative to the other derivatives.     

Enantioselective organocatalytic synthesis of fluorinated molecules

The enantioselective synthesis of fluorinated molecules has drawn much attention within the chemical community due to its unique stereoelectronic properties. The main aim of this review is to cover the most important organocatalytic enantioselective methodologies to obtain them. The review is divided into three parts: first, the direct introduction of a fluorine atom studied in the early 2000s. Second, the later use of Michael reactions to introduce fluorine-containing synthons. Finally, the simultaneously-developed trifluoromethylation reactions, giving the catalysts, mechanisms and reagents that have been used.     

Spectroscopic probing of the acid-base properties and photosensitization of a fluorinated phthalocyanine in organic solutions and liposomes

A perfluorinated derivative of phthalocyanine was synthesized as the free base, hexadeca-(2,2,2-trifluoroethoxy) phthalocyanine (H2F48Pc), and as a zinc complex, hexadeca-(2,2,2-trifluoroethoxy)-phthalocyaninatozinc (ZnF48Pc), and their spectroscopic and photochemical properties were studied. The absorption bands are shifted bathochromically relative to simple phthalocyanines, exhibiting the longest wavelength band near 735 nm (H2F48Pc) and 705 (ZnF48Pc). The solvatochromism of both compounds was modeled by Reichardt's ET(30) parameter and Kamlet, Abboud and Taft multiparameter approach. The former, simpler, model was found to be adequate. We found that H2F48Pc undergoes unique basic and acidic titrations in organic solvents. These titration processes are accompanied by spectral changes that are explained on the basis of the chromophore's symmetry. Singular value decomposition was employed to resolve the spectra into the contributions of the species at various stages of protonation and to obtain the equilibrium constants. Nuclear magnetic resonance spectra (1H, 19F and 13C) for the free base were obtained in a tetrahydrofurand8 solution. The carbon spectrum, taken as a function of temperature, provided evidence for the presence of a tautomerization process, which switches the two internal hydrogens between the four central nitrogen atoms. As far as we know, this is the first report of the measurement of the free energy of activation for such process (delta G = 10.6-11.4 kcal mol-1 between 217 and 330 K) for a phthalocyanine, in solution. Like most other phthalocyanines these two compounds also act as photosensitizers and as generators of singlet molecular oxygen. The absolute quantum yields (phi delta) for ZnF48Pc was 0.58 +/- 0.01 in benzene and 0.35 +/- 0.01 in lipid vesicles. H2F48Pc had lower yields, 0.16 and 0.005, respectively. Either protonation or deprotonation of the pyrrole nitrogens in H2F48Pc lowered the phi delta.     

Stereoselective synthesis of fluorinated 1,3-cis-diaminocyclopentanes

Several fluorinated 1,3-diaminocyclopentanes, previously reported to be useful RNA structural probes, can be prepared in a diastereoselective manner from a single bicyclic hydrazine precursor, in 3 to 9 steps.     

The synthesis of fluorinated aminophosphonic acid inhibitors of alanine racemase

The synthesis of β-trifluoro, β-difluoro, and β-monofluoro-1-aminoethanephosphonic acids is described utilizing fluorinated acetic acids as tarting materials.     

Hexafluorothioacetone based synthesis of fluorinated heterocycles

Cycloadducts of hexafluorothioacetone (HFTA) were prepared in high yield by a CsF catalyzed reaction between readily available 2,2,4,4-tetrakis-(trifluoromethyl)-1,3-dithietane (as a source of HFTA) with conjugated electron-rich hydrocarbon dienes, such as cyclopentadiene, 2,3-dimethylbuta-1,3-diene, cyclohexa-1,3-diene or (1Z,3Z)-cyclohepta-1,3-diene. Cyclohexa-1,4- and (1Z,5Z)-cycloocta-1,5-dienes, also undergo the reaction with in situ generated HFTA, but form the products of insertion of HFTA into the C-H bond of the diene as a result of ene-reaction. The highly selective reaction of HFTA with (1Z,3Z,5Z)-cyclohepta-1,3,5-triene and (1Z,3Z,5Z,7Z)-cycloocta-1,3,5,7-tetraene leads to the formation of cycloadducts derived from exclusive addition of thioacetone to the corresponding bicyclic isomers—bicyclo[4.1.0]hepta-2,4-diene or bicyclo[4.2.0]octa-2,4,7-triene, respectively. The corresponding cycloadducts of HFTA with 2,3-dimethylbutadiene-1,3-cyclohexa-1,3-cyclohexa-1,4-dienes and (1Z,3Z,5Z)-cyclohepta-1,3,5-triene were also prepared by direct reaction of sulfur/hexafluoropropene/KF and the corresponding hydrocarbon substrate at 35-45 °C in DMF.     

The photodegradation of a zinc phthalocyanine

A water-soluble zinc phthalocyanine (Pc), ZnPc (3), bearing 12 dimethylamino groups, which enhance the solubility of the macrocycle was synthesized and characterized. Photobleaching of the compound was examined both in vivo and in vitro. Laser irradiation causes photo-oxidation of the newly synthesized ZnPc. A photobleachable phthalocyanine can be an alternative in imaging; phthalocyanine dyes are used in imaging the cardiovascular system. Besides, it can be used in fluorescein angiography in some cases. When compared to stable ones, a photobleaching ZnPc (3) might be an attractive compound for imaging in medicine.     

The synthesis of highly fluorinated phthalonitrile resins and cure studies

The reactions of the potassium salts of 1,3- and 1,4-bis(2-hydroxy-hexafluoro-2-propyl) benzene $\text{1}$ and $\text{2}$ with tetrafluorophthalonitrile $\text{3}$ afforded three isomeric products in each case with reaction at the 4-position of $\text{3}$ predominating. When each mixture was submitted to the usual thermal conditions for phthalocyanine formation [1–5], the expected characteristic color change (blue or green) did not develop.Evidence was procured from our study which indicated that fluorine substituted on the phthalonitrile moieties hindered phthalocyanine formation. Instead, as an alternative reaction, some nucleophilic displacement of fluorine from the aromatic rings by the cyano substituents appeared to have occurred.     

Synthesis and X-ray structure of a fluorinated 1,1-dialkoxy-3-iminoisoindoline acetal,an elusive phthalocyanine precursor

The synthesis of a fluoroalkylated 1,1-dimethoxy-3-iminoisoindoline acetal, the first representative of the halogenated 3-imino-amino-1-acetal class is reported. In contrast to the protio compound, fluoroalkyl groups make the presence of a base unnecessary for its synthesis while stabilizing the amino tautomer as revealed by an X-ray structural analysis - the first atomic-level structural characterization of the 1,1-alkoxy-3-amino(imino) isoindoline scaffold. Dimers present in solid-state are H-bonded and define a motif similar to the stabilizing, reverse wobble one encountered in adenine-cytosine pairs of tRNA. The fluoro acetal forms easily both metallo- and metal-free phthalocyanines, supporting the proposal that acetals might be phthalocyanine intermediates.     

Simple and convenient synthesis of a fluorinated GM4 analogue

A series of fluorinated galactosides, dodecyl 2-deoxy-2-fluoro-β-d-galactopyranoside (2F Gal), dodecyl 4-deoxy-4-fluoro-β-d-galactopyranoside (4F Gal) and dodecyl 6-deoxy-6-fluoro-β-d-galactopyranoside (6F Gal), was chemically synthesized and introduced to B16 cells to serve as scaffolds for cellular enzyme glycosylation. Results showed that the presence of fluorine exercised significant effects on cell viability. Among the fluorinated galactosides used, 2F Gal was glycosylated to afford a GM4 analogue.     

The synthesis and mesomorphic properties of ferroelectric liquid crystals with a fluorinated asymmetric frame

A novel series of ferroelectric liquid crystals with a fluorinated asymmetric frame were synthesized by utilizing optically active (S)-2-, (S)-3-, (S)-4- and (S)-5-fluoroalkanols prepared from corresponding (R)-1,2-epoxyalkanes. Their mesomorphic and physical properties, such as spontaneous polarization, optic tilt angle and response time, were investigated systematically in a series of homologous compounds having the chiral centre at different positions on tails of various lengths. All the compounds exhibited the chiral smectic C phase in a wide range of temperatures and were found to possess a fast response time in spite of the small magnitude of the spontaneous polarization.     

Selective synthesis of triple-decker cyclohexylmethoxy-substituted europium phthalocyanine

Selective synthesis of substituded europium triphthalocyanine on the base of dilithium 2,3,9,10,16,17,23,24-octa(cyclohexylmethoxy)phthalocyanine was performed. The structure of the complex obtained was characterized by ¹H NMR spectroscopy, mass spectrometry, and UV-visible spectroscopy.