Reactivity of phthalocyanine precursors

Russian Chemical Bulletin - A higher reactivity of 4-nitrophthalonitrile as compared to phthalonitrile and 4-amino-phthalonitrile in the reaction with sodium methoxide in methanol was demonstrated...     

Ditolyldithiophosphato derivatives of phosphorus(III) and phosphorus(V)

O,O′-Ditolylphosphorodithioates of phosphorus(III), [(o-, m-, or p-CH₃C₆H₄O)₂PS₂] _n PCl_3−n , and phosphorus(V), [(o-, m-, or p-CH₃C₆H₄O)₂-PS₂] _n POCl_3−n , (n = 1, 2, and 3) were isolated as colorless viscous liquids by the reaction of PCl₃ and POCl₃ with sodium ditolylphosphorodithioate, (o-, m-, or p-CH₃C₆H₄O)₂PS₂Na, in 1:1, 1:2, and 1:3 molar ratios in toluene. These compounds were characterized by elemental analyses, molecular weight measurements, IR, and NMR (¹H, ³¹P, and ¹³C) spectroscopic studies, which indicated a less common monodentate linkage of dithiophosphate moieties in both phosphorus(III) and phosphorus(V) derivatives leading to a tetrahedral geometry around the phosphorus atom. Correspondence: Sushil K. Pandey, Department of Chemistry, University of Jammu, Baba Saheb Ambedkar Road, Jammu 180 006 (J & K), India.     

Ditolyldithiophosphato derivatives of phosphorus(III) and phosphorus(V)

O,O′-Ditolylphosphorodithioates of phosphorus(III), [(o-, m-, or p-CH₃C₆H₄O)₂PS₂] _n PCl_3−n , and phosphorus(V), [(o-, m-, or p-CH₃C₆H₄O)₂-PS₂] _n POCl_3−n , (n = 1, 2, and 3) were isolated as colorless viscous liquids by the reaction of PCl₃ and POCl₃ with sodium ditolylphosphorodithioate, (o-, m-, or p-CH₃C₆H₄O)₂PS₂Na, in 1:1, 1:2, and 1:3 molar ratios in toluene. These compounds were characterized by elemental analyses, molecular weight measurements, IR, and NMR (¹H, ³¹P, and ¹³C) spectroscopic studies, which indicated a less common monodentate linkage of dithiophosphate moieties in both phosphorus(III) and phosphorus(V) derivatives leading to a tetrahedral geometry around the phosphorus atom.     

Exploring skeletal diversity via ring contraction of glycal-derived scaffolds

Aryl ether C-glycoside scaffolds have been prepared from tri-O-acetyl-D-glucal by C-glycosylation followed by allylic substitution with phenols mediated by Pd(0). The aryl ethers were subjected to either [3,3]-sigmatropic rearrangement to produce 3-pyranyl-phenols or Au(III)-mediated ring contraction to create highly substituted tetrahydrofurans. [structure: see text]     

In pursuit of pestalotiopsin a via zirconocene-mediated ring contraction

[reaction: see text] An asymmetric route from the epimeric beta-hydroxy esters 4 and 5 to the densely functionalized (+)-10 and (-)-10, respectively, is described. Either cyclobutanol can be made available as the predominant product. The levorotatory antipode has been transformed into the advanced intermediate 21 bearing side chains destined to become incorporated into the cyclononene ring of the title compound (1).     

Photophysical properties of sulfonated dihydroxy phosphorus(V) tetrabenzotriazacorrole

The photosensitizing properties of a novel phthalocyanine analogue, sulfonated dihydroxy phosphorus(V) tetrabenzotriazacorrole [P(OH)2TBCSn] and a non-sulfonated one [P(OH)2TBC] are reported in this paper. Different from other phthalocyanine derivatives, P(OH)2TBCSn shows little aggregation in aqueous solution. The fluorescence quantum yield (PhiF) of P(OH)2TBCSn is lower than that of the non-sulfonated one. Studies of triplet state photophysics show that the presence of peripheral substituents on the macrocycle enhances the quantum yield of the triplet state. The sulfonated derivative, P(OH)2TBCSn, has a longer triplet lifetime (tauT = 0.234 ms) and higher singlet oxygen quantum yield (PhiDelta = 0.88) than P(OH)2TBC. Together with the ground-state absorption properties, the photosensitizing properties of the new compound suggest that it may be used as an excellent photosensitizer for photodynamic therapy (PDT).     

Hydrodesulfurization and ring contraction of sulfur heterocycles by nickel(0) complexes

Sulfur heterocycles, such as dibenzothiophene, phenoxathiin and phenothiazine, have been shown to undergo desulfurization with soluble, nickel(0)-derived reagents in either of two ways: (1) simple ring contraction; or (2) complete substitution of hydrogen for the sulfur. Thus, when treated with two equivalents of a 1:1 mixture of bis(1,5-cyclooctadiene)nickel(0) and 2,2′-bipyridyl, phenoxathiin yields dibenzofuran. If, however, one equivalent of LiAlH₄ is employed with the two equivalents of (COD)₂Ni and 2,2′-bipyridyl, this heterocycle gives a high yield of diphenyl ether.     

Synthesis of new 14-membered macrolide antibiotics via a novel ring contraction metathesis

[reaction: see text] A novel ring opening ring closing metathesis (ROM-RCM) was demonstrated for cyclic conjugated dienes, effecting the excision of a C(2)H(2) unit and a net ring contraction. Applying the ring contraction metathesis, new 14-membered ring macrolide antibiotics were synthesized in a single step from existing 16-membered ring macrolides. This new class of macrolide antibiotics will provide access to new therapeutics for the treatment of macrolide-resistant bacterial infections.     

Guanine-specific DNA oxidation photosensitized by the tetraphenylporphyrin phosphorus(V) complex via singlet oxygen generation and electron transfer

The photosensitized DNA damage caused by dihydroxoP(V)tetraphenylporphyrin (P(V)TPP), a cationic water-soluble porphyrin, was examined. The study of near-infrared emission measurements demonstrated the photosensitized singlet oxygen ((1)O(2)) generation by P(V)TPP (quantum yield: 0.28 in ethanol). The fluorescence quenching of P(V)TPP by DNA showed the electron transfer (ET) from nucleobases to photoexcited P(V)TPP. These results have shown that P(V)TPP has ability to damage DNA through dual mechanisms, (1)O(2) generation and ET. Under aerobic conditions, P(V)TPP photosensitized damage was more severe for single-stranded DNA compared to its double-stranded counterpart. Photoexcited P(V)TPP damaged every guanine residue in single-stranded DNA. HPLC measurements confirmed the formation of 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo), an oxidized product of 2'-deoxyguanosine, and showed that the yield of 8-oxodGuo in single-stranded DNA is larger than that in double-stranded DNA. The guanine-specific DNA damage and the enhancement in single-stranded DNA suggest that the (1)O(2) generation mainly contributes to the mechanism of DNA photodamage by P(V)TPP. Absorption spectrum measurements suggested the interaction between P(V)TPP and DNA. This interaction is expected to enhance the (1)O(2)-mediated DNA damage since the lifetime of (1)O(2) is very short. On the other hand, for double-stranded DNA, photosensitized damage at consecutive guanines was much less pronounced. Because the consecutive guanines act as a hole trap, this DNA-damaging pattern suggests the partial involvement of photoinduced ET. However, DNA damage by ET was not a main mechanism, possibly due to the reverse ET. In conclusion, P(V)TPP induces guanine specific photooxidation mainly via (1)O(2) generation. The interaction with DNA and the energy level of the photoexcited porphyrin may be advantageous for (1)O(2)-mediated DNA damage rather than ET mechanism.     

Organic iodine(V) compounds as terminal oxidants in iron(III) phthalocyanine catalyzed oxidation of alcohols

The pseudocyclic iodine(V) oxidants, such as esters of iodoxybenzoic acid (IBX-esters) and 2-iodylphenol ethers, can serve as stable and efficient sources of oxygen in catalytic oxidations, and their reactivity is similar to the commonly used thermally unstable and potentially explosive iodosylbenzene. In a specific example, primary or secondary benzylic alcohols are selectively oxidized by isopropyl IBX-ester in the presence of μ-oxo-(tetra-tert-butylphthalocyaninato)iron(III) (0.1 mol equiv) in dichloromethane at room temperature in 0.5-2 h to afford the respective carbonyl compounds in 100% conversion and preparative yields 91-95% after column chromatography.     

氯化二氯代四苯基卟啉磷合二氯甲烷的晶体结构

氯化二氯代四苯基叶啉磷（Dichloro（5，10，15，20－tetraphenylporphinato）－phosphorus（V）chloride，［PCl2TPP］Cl）是典型的非金属卟琳配合物．据文献报导［1］该配合物能够与噻吩类化合物反应，所得单体经电解氧化，可生成具有导电性的聚合物．因此，测定［PCl2TPP］Cl的分子结构有着十分重要的意义．1标题化合物的制备及单晶生长标题化合物技文献［2］合成．用于X－射线衍射的单晶样品是将标题化合物的二氯甲烷／正庚烷混合溶液静置数周后得到的．单晶为紫色，用于X－射线衍射测定的晶粒尺寸为0．38mm×0．38mm×0．28mm．…     

Triphenylphosphine-induced ring contraction of 1,2-dioxines

Triphenylphosphine inserts into the peroxide bond of 1,2-dioxines, initiating ring contraction with loss of triphenylphosphine oxide. This process yields dihydrofuran oxides in 54-97% yield from oxirenyl[2,3-c][1,2]dioxines and dihydrofurans from 3,6-dihydro-1,2-dioxines with inversion of stereochemistry at either the 2 or 5 position in the furan product.     

4H-1,4-benzothiazine derivatives via a novel lead tetraacetate induced ring contraction.

8-Chloro-3,4-dihydro-5-(2-thienyl)-2H-1,6-benzothiazocine underwent a facile lead tetraacetate induced ring contraction forming several 3-(2-thienyl)-4H-1,4-benzothiazine derivatives.     

From common carbohydrates to enantiopure cyclooctane polyols and glycomimetics via deoxygenative zirconocene ring contraction

D-Arabinose and D-glucose are transformed into the identical vinyl furanoside, whose role is to serve as the precursor to enantiopure cyclooctadienone 6. The key steps of this relay involve a zirconocene-promoted ring contraction and [3,3] sigmatropic rearrangement of an enynol. Subsequently defined are convenient synthetic routes to several cyclooctane-1,2,3-triols, 1,2,3,4,5-pentaols, and structurally related glycomimetics.     

Cyclic tetrapeptides via the ring contraction strategy: chemical techniques useful for their identification

Cyclic tetrapeptides are a class of natural products that have been shown to have broad ranging biological activities and good pharmacokinetic properties. In order to synthesise these highly strained compounds a ring contraction strategy had previously been reported. This strategy was further optimised and a suite of techniques, including the Edman degradation and mass spectrometry/mass spectrometry, were developed to enable characterisation of cyclic tetrapeptide isomers. An NMR solution structure of a cyclic tetrapeptide was also generated. To illustrate the success of this strategy a library of cyclic tetrapeptides was synthesised.     

The synthesis of phthalazin-1(2H)-ones and 3-hydroxyisobenzofuran-1(3H)-ones via the ring contraction of tropones

Phthalazin-1(2H)-ones and 3-hydroxyisobenzofuran-1(3H)-ones were synthesized by the reactions of tropones with hydrazines and alcohols, respectively, via the ring contraction.     

Synthesis of functionalized tetrahydro-1,3-diazepin-2-ones and 1-carbamoyl-1H-pyrroles via ring expansion and ring expansion/ring contraction of tetrahydropyrimidines

A general approach to 6-phenylthio-substituted 2,3,4,5-tetrahydro-1H-1,3-diazepin-2-ones based on the ring expansion reaction of 1,2,3,4-tetrahydropyrimidin-2-ones under the action of nucleophiles has been developed. The first step of the synthesis was preparation of N-[(2-benzoyloxy-1-tosyl)ethyl]urea by three-component condensation of 2-benzoyloxyethanal, urea and p-toluenesulfinic acid. Nucleophilic substitution of the tosyl group in the obtained sulfone with sodium enolates of α-phenylthioketones followed by cyclization-dehydration, and debenzoylation gave 4-hydroxymethyl-5-phenylthio-1,2,3,4-tetrahydropyrimidin-2-ones which were transformed into the 4-mesyloxymethyl-derivatives. Treatment of the latter with nucleophilic reagents, such as NaCN, sodium diethyl malonate, PhSNa, MeONa, NaBH(4), sodium succinimide, or potassium phthalimide, afforded the target multi-functionalized diazepinones. The obtained 6-phenylthio-diazepinones and their 6-tosyl-substituted analogues were converted into 3-substituted 1-carbamoyl-1H-pyrroles under acidic conditions as a result of ring contraction. Effective one-pot synthesis of the latter from 4-mesyloxymethyl-pyrimidines was realized using a ring expansion/ring contraction sequence.