Kinetics,catalysis, and mechanism of isomerization of N-[(benzotriazol-1-yl)methyl]anilines into the benzotriazol-2-yl derivatives

The ¹H NMR technique was applied for the measurement of the isomerization rates of N-ethyl-N-[(benzotriazol-1-yl)methyl]aniline ( 4 ) and 4-butyl-N-[(benzotriazol-1-yl)methyl]aniline ( 7 ) to the corresponding benzotriazol-2-yl isomers in dioxane-d₈ at 35°C. The rate constants obtained for pure dioxane-d₈ were 1.62 and 0.28 h^?1 for 4 and 7 , respectively. For both compounds, addition to acetic acid to the dioxane solutions accelerated the isomerizations whereas addition of triethylamine retarded it strongly. Addition of water slowed the isomerization of 4 but accelerated that of 7 : the different effects operating in the two cases are discussed and rationalized. © 1995 John Wiley & Sons, Inc.     

The cotype constant and an almost euclidean decomposition for finite-dimensional normed spaces

Every 2n-dimensional normed spaceE contains twon-dimensional subspacesE ₁ andE ₂ which are orthogonal with respect to the inner product induced by the John ellipsoid ofE and which satisfyd(E _i, l ₂ ⁿ )≦f(K ₂(E)), wheref(K ₂(E)) is some number that depends only on the cotype constant ofE, denotedK ₂(E). Supported in part by NSF grant DMS 8401906.     

Complexes of heteroscorpionate trispyrazolylborate ligands. Part XI. Weak CH/π interactions in crystals of hydrotris(3-phenylpyrazolyl)boratothallium(I) and hydrobis(5-methyl-3-phenylpyrazolyl)(3,5-dimethylpyrazol-yl)boratothallium(I) studied by X-ray crystallography

Thallium(I) complexes of heteroscorpionate hydrobis(3-phenyl-5-methylpyrazolyl)(3,5-dimethylpyrazol-yl)borate and hydrotris(3-phenylpyrazol-1-yl)borate were studied crystallographically. Both ligands were coordinated in κ³ fashion via N₂ atoms of pyrazol-1-yl moieties. Both compounds crystallize as centrosymmetric dimers in which weak CH/π intra- and interdimer interactions are responsible for arrangement in crystal structure.     

Stereochemistry of 1,2-oxaphospholanes. Part X. Synthesis,X-ray structure and NMR spectroscopy of (2S*,3R*,5R*)-2-methoxy-3,5-dimethyl-2-oxo-1,2-oxaphospholan-3-ol

The title compound (4a) was synthesized from a phosphite compound obtained from 4-hydroxy-2-pentanone and dimethylphosphorochloridite, after addition of an equivalent of water. Thecis-configuration of the P=O and C3-OH groups was established based on³¹P NMR chemical shifts. In chloroform, as well as in benzene solution, the most favorable conformations of the title compound are ₄ ⁵ T,⁴ E, and ₄ ⁵ T. The crystal and molecular structure of4a has been determined by single-crystal X-ray diffraction data, and refined toR=0.056. The five-membered ring has an envelope⁴ E (C₅) conformation, with the asymmetry parameter C ₅(4)=3.5°. Both the C5-CH₃ and the C3-CH₃ groups are equatorial. In the solid state, the molecules form dimers with hydrogen bonding between the hydroxyl groups and the phosphoryl oxygen atom of an adjacent molecule. A quantitative comparison of the structure of 4a with the structure of the related 2-mcthoxy-3,5,5-trimethyl-2-oxo-1,2-oxaphosphospholan-3-ol is given.     

Recent progress in biodegradable polymers and nanocomposite-based packaging materials for sustainable environment

Plastic-based materials are frequently used in packaging and can be seen universally in both the developed and developing societies. At present, most of the currently used food packaging materials are nondegradable and are creating serious environmental problems. New technologies are being explored and developed to study the complex interaction between the food packaging materials and food. For example, nanocomposite of cellulose constitutes environmentally friendly packaging, which is easily recycled by combustion and requires low power consumption in production. There are several such biodegradable materials which are available at a low price, have good mechanical properties and allow disposal in the soil. This is advantageous because biological degradation produces only carbon dioxide, water, and inorganic compounds to name a few. It has also been discovered that biodegradable plastics made of such materials can be disposed of together with organic waste. The widespread use of biopolymers in the place of standard plastics would help to reduce the weight of waste. Therefore, biodegradable materials take part in the natural cycle “from nature to nature” and play an important role for environmental sustainability. So, in this article, we briefly summarize the different characteristic of biodegradable polymers being used in food packaging applications.     

Convenient Synthesis of Julolidines Using Benzotriazole Methodology

Reaction of N,N-bis[(benzotriazol-1-yl)methyl]aniline (2) with 1-vinylpyrrolidin-2-one gives a mixture of diastereomeric 1,7-bis(2-oxopyrrolidin-1-yl)julolidines 3. After reduction of 3 with LAH, the predominant trans diastereomer of 1,7-di(pyrrolidin-1-yl)julolidine (4) is separated. Reaction of 2 with ethyl vinyl ether yields predominantly trans-1,7-di(benzotriazol-1-yl)julolidine (11). Stepwise synthesis from tetrahydroquinoline 15 gives access to julolidines with two different substituents on C-1 and C-7. Reaction of 1-[(benzotriazol-1-yl)methyl]-1,2,3,4-tetrahydroquinoline (25) with enolizable aldehydes gives a mixture of tetrahydroquinolines 26-29 which are converted into single julolidine products upon treatment with sodium hydride, LAH, or phenylmagnesium bromide. Reactions of 1,2,3,4-tetrahydroquinolines with benzotriazole and 2 molar equiv of enolizable aldehydes gives 1,2,3-trisubstituted julolidines 38-41, which with lithium aluminum hydride, sodium hydride, or a Grignard reagent produce single diastereomers of products 42, 43, and 45, respectively.     

Studies toward the synthesis of alpha-fluorinated phosphonates via tin-mediated cleavage of alpha-fluoro-alpha-(pyrimidin-2-ylsulfonyl)alkylphosphonates. Intramolecular cyclization of the alpha-phosphonyl radicals

Treatment of the alpha carbanions generated from several alpha-(pyrimidin-2-ylsulfonyl)alkylphosphonates with Selectfluor gave high yields of the alpha-fluoro-alpha-(pyrimidin-2-ylsulfonyl)alkylphoshonates, which were desulfonylated [Bu(3)SnH/2,2'-azobisisobutyronitrile (AIBN)/benzene or toluene/Delta] to give alpha-fluoroalkylphosphonates. "Catalytic" tin hydride, generated from tributyltin chloride and excess polymethylhydrosiloxane in the presence of potassium fluoride, also effected removal of the pi-deficient alpha-(pyrimidin-2-ylsulfonyl) group from the phosphonate esters. Substitution of Bu(3)SnD for Bu(3)SnH gave access to alpha-deuterium-labeled phosphonates. Prolonged treatment of alpha-(pyridin-2-ylsulfonyl)alkylphosphonate with excess Bu(3)SnH/AIBN or catalytic tin hydride also effected desulfonylation but in moderate yields. This represents a mild new methodology for removal of the synthetically useful pi-deficient heterocyclic sulfone moiety and an alternative route for the preparation of alpha-fluorinated phosphonates. Desulfonylation is suggested to proceed via attack of tin radical at an oxygen (or sulfur) atom of the sulfonyl group to give a stabilized alpha-phosphonyl radical intermediate. The latter was found to undergo 5-exo-trig ring closure to give the corresponding 2-methylcyclopentylphosphonates. Treatment of diethyl 1-bromohex-6-enylphosphonate with Bu(3)SnH/AIBN produced an analogous mixture of ring-closure products. Treatment of [(2-bromo-5- methoxyphenyl)(fluoro)(pyrimidin-2-ylsulfonyl)]methylphosphonate with Bu(3)SnH resulted in an intramolecular radical [1,5]-ipso substitution reaction and migration of the pyrimidinyl ring to give fluoro[5-methoxy-2-(pyrimidin-2-yl)phenyl]methylphosphonate.     

The modified `phosphine imide' reaction: a safe and soft alternative ureas synthesis

In this work we present a new way for the direct and general synthesis of urea compounds from primary amines by the modified `phosphine imide' reaction. A large panel of amine structures are compatible with the smooth reaction conditions. Particularly in the case of sensitive l-aminoesters, it is interesting to note that the stereochemistry at the asymmetric centre was unmodified in the reaction conditions.     

Oxidation state of vanadium introduced in dealuminated beta zeolite by impregnation with VIVOSO4 solution: influence of preparation parameters

Vanadium was introduced in dealuminated beta zeolite by impregnation with a VIVOSO4 aqueous solution at 353 K in air or argon (to prevent oxidation of VIV), leading to VSibeta and VSibeta-Ar zeolites, respectively. The samples were characterized by spectroscopy, XRD, and N2-physisorption. The oxidation state and environment of V in Sibeta zeolite depend on the preparation parameters (i.e., on the way the solid is recovered after impregnation and on the drying temperature). In solids recovered by centrifugation, washed with distilled water, and then dried overnight at 298 K in argon, vanadium is found as extra-lattice octahedral VIV ions as evidenced by EPR. In contrast, in solids not washed but directly dried overnight at 353 K in air or argon, vanadium is found in both cases as lattice tetrahedral VV ions. These ions are incorporated into vacant T sites associated with SiOH, SiO-, oxygen vacancies (OVs) or nonbridging oxygen (NBOs) defects as shown by diffuse reflectance UV-visible, 51V MAS NMR, FT-IR, and photoluminescence. The oxidation to VV ions is suggested to be due to an electron transfer from VO2+ to trigonal identical with Si+ defect sites followed by reaction of the resulting VO2+ ions with particular defects of vacant T sites. These processes occur already upon drying of V-impregnated Sibeta at 353 K. 51V MAS NMR allows detection of one kind of lattice tetrahedral V ions in VSibeta and two kinds in VSibeta-Ar. The formation of different kinds of tetrahedral V species is related to the presence in vacant T sites of Sibeta zeolite of different types of defect sites such as trigonal identical with Si+ defect or SiOH and SiO- groups.