bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies on organophosphorus compounds 61 substituent effects in organophosphorus esters
Authors: Yuan Chengye , Li Shusen , Hu Wenxiang , Fen Hainzhen
Published: January 2005

Examination of several model organophosphorus compounds, bicyclic phosphates (1), p‐substituted phenylphosphonates (2), and acidic alkylphosphonates (3) reveals that the polar substituent effect in organophosphorus esters parallels that of carbon compounds. No significant variation in polar effects of different alkyl groups with up to 10 carbon atoms is observed. As demonstrated by us, the commonly used Kabachnik polar constant σΦ for alkyl groups of organophosphorus compounds reflects the steric effect associated with steric hindrance to solvation of acidic anions. Therefore, a set of solvation steric parameters Eps has been calculated from pKa values of organophosphorus acids. This parameter can be applied to describe the structural effect on dissociation of organic acids and, after suitable modification, may reflect the steric effect of alkyl groups in hydrolytic reactions of organophosphorus esters.
Convenient synthesis of 1‐alkoxy‐di‐ and tetrahydrophosphinine 1‐oxides by ring enlargement
Authors: Keglevich Gyöurgy , Töuke Láaszlöa , Kováacs Attila , Töath Gáabor , Újszászy Kálmán
Published: January 2005

The double bond of the P‐alkoxy 3,4‐dimethyl‐2,5‐dihydro‐1H‐phosphole 1‐oxides reacts easily with dichlorocarbene to give two diastereomers of an unstable adduct useful in the synthesis of ring expanded products, such as 1,2‐dihydrophosphinine oxides or 1,2,3,6‐tetrahydrophosphinine oxides. The former can be prepared by thermolysis of the adducts, while the latter are obtained by cyclopropane ring opening effected by silver nitrate in an alcoholic solvent. The preparation of the double‐bond isomers of 1‐alkoxy‐tetrahydrophosphinine oxides containing only one methyl substituent in the ring is also described. The reaction of dihydro‐1H‐phosphole oxides with dichlorocarbene can be modified to give P‐alkoxy 1,4‐dihydrophosphinine oxides in an unexpected reaction.
Luminescent nitro derivatives of benzotriazolo[2,1a]benzotriazole
Authors: Lu Qi , Boyer Joseph H.
Published: January 2005

Fluorescence was enhanced and laser activity introduced by substitution in 5,11‐dehydro‐5H,11H‐benzotriazolo[2,1‐a]benzotriazole 6 to give 2‐nitro, 2,8‐dinitro, 2,4,8‐trinitro, and 2,4,8,10‐tetranitro derivatives 9a–d. Luminescence for compounds 6 and 9a–d and the 2,8‐dinitro‐3,9‐dimethyl and 2,3,8,9‐tetramethyl‐4,10‐dinitro derivatives 11a,b was erratically solvent dependent when examined in ethyl acetate, acetonitrile, and acetone and was most efficient in the 2,8‐dinitro derivative 9b [λf 479 nm (ethyl acetate) Φ 0.98, λf 501 nm (acetonitrile) Φ 0.58, and λf 494 nm (acetone) Φ 0.61] and in the tetranitro derivative 9d [λf 509 nm (acetonitrile) Φ 0.81 and λf 511 nm (acetone) Φ 0.66]. With laser activity at 560–590 nm (acetonitrile) the dye 9b was 30% as efficient as rhodamine 6G (ethanol) in power output. Luminescence was quenched by the reduction of nitro groups to give 2‐amino and 2,8‐diamino derivatives 9e,f and by the conversion of the tetranitro compound 9d to an unassigned diazido dinitro derivative 9g. Luminescence was not detected in 2,5‐dimethyl‐3,6‐dinitro‐1,3a‐4,6a‐tetraazapentalene 14 and ethyl 2,5‐dimethyl‐1,3a,4,6a‐tetraazapentalene‐3,6‐dicarboxylate 15. Azidoazobenzenes were obtained from 4‐methyl‐ and 4,5‐dimethyl‐1,2‐phenylene diamines via oxidation with lead dioxide to aminoazobenzene derivatives followed by treatment of the diazotized amines with sodium azide and thermolysis of azido intermediates to give 3,9‐dimethyl and 2,3,8,9‐tetramethyl derivatives 10a,b of the triazolotriazole 6. Nitration converted the triazole 6 to the 2,4,8‐trinitro derivative 9c and the alkyltriazoles to their dinitro derivatives 11a,b.
β‐Benzotriazolylethyl phosphates and phosphonic esters
Authors: Katritzky Alan R. , Mortikov Valery Yu. , Lam Jamshed N. , Sutharchanadevi Murugan , Francisco Manuel A.
Published: January 2005

β‐(1‐Benzotriazolyl)ethyl dibutyl phosphate and the 2‐benzotriazolyl analog were prepared from dibutyl phosphite and 1‐ and 2‐(β‐hydroxyethyl)benzotriazoles, respectively. Dialkyl β‐(N‐benzotriazolyl) ethylphosphonates were prepared from the corresponding dialkyl β‐bromoethylphosphonates. In both types of compounds, elimination of benzotriazole occurs in base; interestingly, such elimination is significantly faster in each series for the 2‐substituted benzotriazole than for the corresponding 1‐isomer.
An NMR study of a 13C‐labeled hypervalent (10‐C‐5) [1] pentacoordinate carbon species
Authors: Forbus T. R. , Martin J. C.
Published: January 2005

Removal of two electrons from 1,8‐bis(4‐methylphenylthio)‐9‐(2, 6‐dimethoxyphenyl‐1‐13C)‐10‐phenylanthracene (2) provides stable dication 1. Isotopic enrichment (85%) of 13C at the labeled site of the aromatic carbon, between the two sulfurs, makes possible the observation of spin‐spin coupling constants between this 13C‐carbon and the directly bonded equatorial ligand carbons. The magnitudes of these coupling constants (two 1JC1′C2′ = 61.9 Hz and one 1JC1′C9 = 56.3 Hz) suggest that this carbon is sp2 hybridized, with the postulated trigonal bipyramidal (TBP) geometry about this carbon center. The 13C NMR chemical shifts for the 10‐C‐5 carbon (δ 109.3) and for other carbons provide strong evidence against alternative structures for this dication. The data are consistent with the 10‐C‐5 species, with apical sulfonium ligands and equatorial carbons of the hypervalent TBP carbon species 1.
Electrochemical evidence for hypervalent (10‐C‐5) [1] pentacoordinate carbon
Authors: Forbus T. R. , Kahl J. L. , Faulkner L. R. , Martin J. C.
Published: January 2005

The electrochemical oxidation of 1,8‐bis(4‐methylphenylthio)‐9‐(2, 6‐dimethoxyphenyl)‐10‐phenylanthracene (2) is discussed. It undergoes facile, reversible two‐electron electrooxidation in two closely spaced one‐electron steps at E′ = 0.98 V and E′ = 1.02 V (vs. SCE). This behavior is discussed in terms of relief of three‐center antibonding interaction involving the 1‐, 8‐, and 9‐substituents of 2 with two sulfurs and a carbon of the 2,6‐dimethoxyphenyl group, which becomes a stabilized three‐center bonding interaction in dication 1. The central atom in the three‐center bond is a hypervalent pentacoordinate carbon atom.

A related two‐center antibonding interaction present in 1‐(4‐methylphenylthio)‐9‐(2,6‐dimethoxyphenyl)‐10‐phenylanthracene (5) is relieved by facile one‐electron oxidation (Ep = 1.14 V vs. SCE) forming 7. Removal of a second electron (Ep = 1.34 V vs. SCE) from anthracene 5 results in an unstable dication, 8.

Other analogous anthracene derivatives lacking both thioaryl groups (4) or the 9‐aryl group (4) prove much more difficult to oxidize, both showing oneelectron reversible oxidation potentials of 1.27 V (vs. SCE) similar to 9‐phenylanthracene (1.34 V vs. SCE) and 9,10‐diphenylanthracene (1.22 V vs. SCE).

These results provide strong evidence for the postulated structure of dication 2 which incorporates hypervalent pentacoordinate carbon, a 10‐C‐5 species [2,3].
Modified neglect of diatomic overlap calculations on boron‐nitrogen derivatives of nonbenzenoid aromatics. II. The analysis of the 130 possible nonfully boron‐nitrogen‐alternating isomers of pentaazapentaboraazulene
Authors: McFarland Jennifer D. , Zoellner Robert W.
Published: January 2005

Modified neglect of diatomic overlap (MNDO) calculations have been used to investigate the ground state properties of the 130 nonfully boron‐nitrogenalternating isomers of pentaazapentaboraazulene (PAPBAZ), N5B5H8. The two most stable of these nonfully boron‐nitrogen‐alternating isomers, 1,2,3a, 5,7‐pentaaza‐3,4,6,8,8a‐pentaboraazulene, (1,2,3a, 5,7‐PAPBAZ) (3), and 1,3,3a,5,7‐PAPBAZ (4) have strongly exothermic heats of formation (−142.5 and −142.4 kcal/mol, respectively), while the two least stable isomers, 1,6,7,8,8a‐PAPBAZ (131) and 1,2,3,3a,8a‐PAPBAZ (132), are calculated to have endothermic heats of formation (+95.43 and +96.31 kcal/mol, respectively). Each isomer optimized as a slightly to extremely nonplanar molecule, but each remained a bicyclic system containing a seven‐membered ring fused to a five‐membered ring. Thus, no ring‐opened structures were observed. An empirical relationship between the heat of formation and the number, position, and type of homonuclear (NN or BB) bonds present in the molecules could be established, but as the heat of formation for the molecules became more positive, the relationship became less strong. A general trend of diminishing energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) was observed as the heat of formation became more positive. In addition to a discussion of the structures of (3), (4), (131), and (132), the structures of 2,3a,4,6,8‐PAPBAZ (9), 2,3a,5,6,8‐PAPBAZ (11), 1,2,4,6,8‐PAPBAZ (15), 2,3a,4,7,8a‐PAPBAZ (19), 1,3a,4,5,8‐PAPBAZ (32), 1,2,3,5,7‐PAPBAZ (47), 1,3a,5,8,8a‐PAPBAZ (67), 1,3a,6,7,8a‐PAPBAZ (87), 3a,4,6,8,8a‐PAPBAZ (106), 1,2,3,5,6‐PAPBAZ (109), 1,2,3a,8,8a‐PAPBAZ (116), and 4,5,6,7,8‐PAPBAZ (130) are discussed in detail. Some of these molecules were chosen because they represent the minima and maxima, respectively, in heats of formation [(3), (4), (130), (131), and (132)], ionization potentials [(9) and (32)], differences in LUMO and HOMO energies [(106) and (32)], and dipole moments [(11) and (87)]. The remaining molecules were chosen because each represent the most stable system containing the following homonuclear chains: B‐B‐B (15), N‐N‐N (19), B‐B‐B‐B (47), N‐N‐N‐N (67), B‐B‐B‐B‐B (109), and N‐N‐N‐N‐N (116).
Reactions of Ph(ClCH2)SiH2 with fluoride ion sources: Formation of fluorine‐terminated siloxanes
Authors: Huhmann Jean L. , Corey Joyce Y.
Published: January 2005

The fluoride ion‐induced rearrangement of Ph(ClCH2)SiH2 was expected to provide either PhMeSiHF (migration of hydride) or (PhCH2)SiH2F (migration of phenyl). However, when Bu4N+F− (commercial TBAF) is added to Ph(ClCH2)SiH2, a mixture of fluorine‐terminated siloxanes, FPhMeSiO(PhMeSiO)xSiMePhF, is obtained. The presence of the Me group suggests a rapid anion‐induced migration of hydride to produce PhMeSiHF which reacts further with water present in TBAF samples. When the reaction mixture is cooled to 0°C or is monitored at the early stage of the reaction, the major products are PhMeSiF2, PhMeSi(OH)F, PhMeSi(OH)2, and FPhMeSiOSiMePhF which are proposed as the building blocks for the siloxanes. When dried CsF in CH3CN is used, the major products are PhMeSiF2 and PhMeSiH2 which are assumed to form from the fluoride ion‐induced disproportionation of PhMeSiHF. The reaction chemistry is rationalized in terms of hypervalent intermediates. The fluoride ion‐induced reactions of PhMeSiH2 and PhMeSiCl2 are also described and compared to those of Ph(ClCH2)SiH2.
Simple preparation of sterically congested 1,9‐disubstituted dibenzothiophenes and formation of their dithia dications via transannular S‐S interaction
Authors: Kimura Takeshi , Horie Yoji , Ogawa Satoshi , Furukawa Naomichi , Iwasaki Fujiko
Published: January 2005

4,6‐Disubstituted thianthrene‐5‐oxides reacted with n‐butyllithium to afford sterically crowded 1,9‐disubstituted dibenzothiophenes (3) in moderate yields. The structures of the phenylthio derivative 3a and its monooxide 6a were determined by X‐ray crystallographic analysis, which revealed that the distances between the two outer sulfur atoms are 3.012 Å (3a) and 3.016 Å (6a). 1,9‐Disubstituted dibenzothiophenes 3 and their monooxides 6 afforded the corresponding dithia dications on dissolution in conc. sulfuric acid. The lower oxidation potentials of compounds 3 compared with other dibenzothiophene derivatives reveal evidence for strong transannular interaction between the two outer sulfur atoms.
A facile synthesis of 2‐cyano‐4H‐3,1‐ benzothiazines and 2‐cyano‐4H‐3,1‐benzoxazines
Authors: Lee Hyunil , Kim Kyongtae
Published: January 2005

Treatment of the hydrochloride salts of 4‐chloro‐5‐(2‐halomethylaryl‐imino)‐5H‐1,2,3‐dithiazoles (2) with sodium cyanoborohydride in THF at room temperature gave 2‐cyano‐4H‐3,1‐benzothiazines (1) in good to moderate yields. 2‐Cyano‐4H‐3,1‐benzoxazines (4) were obtained in good to moderate yields by refluxing of 4‐chloro‐5‐(2‐hydroxymethylarylimino)‐5H‐1,2,3‐dithiazoles (3) with sodium hydride in THF. Intermolecular reaction of 5‐(p‐tolylimino)‐5H‐1,2,3‐dithiazole (12) with benzyl alcohol under the same conditions gave the acyclic analog of 4.
Preparation and X‐ray crystal structure analysis of cis‐2, 4‐bis(2, 4, 6‐tri‐t‐butylphenyl)‐1, 2, 4‐oxadiphosphetane 2, 4‐disulfide and cis/trans isomerization of the corresponding 1, 2, 4‐thiadiphosphetane derivative
Authors: Toyota Kozo , Ishikawa Yasuhisa , Shirabe Kotaro , Yoshifuji Masaaki , Okada Kengo , Hirotsu Ken
Published: January 2005

1,3‐Bis(2,4,6‐tri‐t‐butylphenyl)‐1,3‐diphosphaallene (1) reacted with elemental sulfur under wet reaction conditions to give cis‐ and trans‐2,4‐bis(2,4,6‐tri‐t‐butylphenyl)‐1,2,4‐thiadiphosphetane 2,4‐disulfide (cis‐2 and trans‐2) and cis‐2,4‐bis(2,4,6‐tri‐t‐butylphenyl)‐1,2,4‐oxadiphosphetane 2,4‐disulfide (cis‐3). The structure of cis‐3 was determined by X‐ray crystallography, and the cis/trans isomerization of 2 was studied.
A new rearrangement in phosphorus chemistry
Authors: Shevchenko Igor V. , Schmutzler Reinhard
Published: January 2005

The oxidation of 1,5‐dimethyl‐2,4‐bis(diethylamino)‐1,5‐diaza‐2,4‐diphosphorinan‐6‐one5with tetrachloroorthobenzoquinone (TOB) leads to the formation of the spirophosphorane9, which is unstable and undergoes an unusual spontaneous rearrangement into the isomeric methylenephosphinophosphorane11. The sulfuration of9and11gives the stable isomers12and19, exhibiting no tendency of mutual transformation. The mechanism of the isomerization of9into11is discussed. Some chemical properties of9and11have been investigated.
Synthesis of 1λ4,2‐diselenol‐1‐ylium salts
Authors: Reid David H. , Rose Beate G. , Jackson Michael G.
Published: January 2005

Seven bis‐(1λ4,2‐diselenol‐1‐ylium) tetrachloroferrates have been prepared by reaction of 1,3‐diketones or 1,3‐ketoaldehydes with hydrogen selenide and iron(III) chloride in ethanol saturated with hydrogen chloride. They decompose gradually in air. The corresponding 1λ4,2‐diselenol‐1‐ylium perchlorates have been prepared by reaction of the tetrachloroferrates with perchloric acid in acetic acid and are stable. The tetrachloroferrates react with benzenediazonium tetrafluoroborate to give 6,6aλ4‐diselena‐1,2‐diazapentalenes.
Synthesis of silyl, germyl, and phosphino‐substituted acylketenes from pivaloylethoxyacetylene
Authors: Lukashev Nikolai V. , Fil'chikov Aleksei A. , Kazankova Marina A. , Beletskaya Irina P.
Published: January 2005

The reaction of pivaloylethoxyacetylene with silicon halides, which has been found to occur as a 1,4‐addition, leads to allenic ethers, which readily eliminate ethyl halides and are converted to previously unknown types of ketenes—stable element‐substituted acylketenes. Germanium‐substituted acylketenes are also formed; however, clear evidence of 1,4‐addition of germanium halides was not obtained. In the reaction between Ph2PCl and pivaloylethoxyacetylene, phosphorus (III) substituted acylketenes initially formed underwent rapid [3 + 3] cyclodimerization.
Preparation and properties of some stable captodative diphosphenes carrying the N‐(9‐fluorenyl)‐N‐mesitylamino group as an electron‐donating new sterically protecting auxiliary
Authors: Abe Masatoshi , Toyota Kozo , Yoshifuji Masaaki
Published: January 2005

The N‐(9‐fluorenyl)‐N‐mesitylamino group was utilized as an electron‐donating new sterically protecting group and thus several captodative 1‐amino‐2‐aryldiphosphenes were prepared. The push‐pull substituent effect on the ‐PP‐ bond was demonstrated by 31P NMR, and the reactivities of the captodative diphosphenes were studied.
Deoxygenation of nitro and nitrosoaromatics by photolysis with t‐BuHgl/Kl. Regiochemistry of tert‐Butyl radical addition to nitrosoaromatics [1]
Authors: Russell Glen A. , Yao Ching‐Fa
Published: January 2005

Photolysis of nitroaromatics in the presence of t‐BuHgI/KI in Me2SO or DMF leads to products formed by t‐Bu• addition to the nitroso compounds. Similar products are formed in the dark in the presence of K2S2O8. Nitroso or nitrobenzene is converted into N,O‐di‐tert‐butylphenylhydroxylamine by a process involving N‐tert‐butylphenylhydroxylamine as an intermediate. In the presence of PTSA and KI, N‐tert‐butylphenylhydroxylamine predominates in Me2SO, but in DMF, the phenylhydroxylamine is reduced to N‐tert‐butylaniline. In a similar fashion, o‐nitrosotoluene is converted into o‐MeC6H4N(Bu‐t)OBu‐t, o‐MeC6H4N(Bu‐t)OH, and o‐MeC6H4NHBu‐t. p‐Nitroso‐N,N‐dimethylaniline forms the N,O‐di‐tert‐butylated derivative in the absence of acid but in the presence of PTSA/KI yields p‐Me2NC6H4NHBu‐t. Excellent yields of the N,O‐di‐tert‐butylated arylhydroxylamines are formed in DMF from the nitroaromatics with para Me2N, OH, I, Br, Cl, and ortho Ph or PhNH substituents. Nitrobenzenes with p‐CHO, p‐PhCO, or p‐CN substituents are deoxygenated to the nitroso compounds which react with t‐Bu• to form the tert‐butoxyamino radicals (ArṄOBu‐t). In Me2SO, the amino radicals react to form ArN(HgI)OBu‐t compounds which condense with the nitroso compounds to yield the azoxy compounds. With the p‐CN substituent, the azoxy compound is subsequently deoxygenated and tert‐butylated to yield p‐NCC6H4N(Bu‐t)NHC6H4CN‐p. In the presence of PTSA/KI, the amino radicals are reduced to p‐Y‐ArNHOBu‐t (Y = PhCO, CN). The compounds Y‐ArN(Bu‐t)OBu‐t undergo photochemical degradation to yield Y‐ArNHBu‐t with Y = p‐PhCO or p‐CN in a reaction that is inhibited by I−. With PTSA/H2O/KI in Me2SO, p‐Me2NC6H4N(t‐Bu)OBu‐t is converted into 4‐(N‐tert‐butylimino)‐2,5‐cyclohexadien‐1‐one, p‐Me2NC6H4NHBu‐t, and p‐tert‐butylamino‐m‐tert‐butoxy‐N,N‐dimethylaniline. o‐MeC6H4N(Bu‐t)OH reacts with PTSA/KI to form o‐MeC6H4N(Bu‐t)H in DMF or a mixture of the aniline and 4‐(N‐tert‐butylimino)‐3‐methyl‐2,5‐cyclohexadien‐1‐one in Me2SO. In the absence of KI, only the cyclohexadienone is formed in Me2SO.
A new range of heterocyclic telluronium salts based on 1,2,4,5‐bis(telluracyclopentano)benzene: Synthesis and spectroscopic considerations
Authors: Al‐Shirayda Hatif A.
Published: January 2005

The reactions of 1,2,4,5‐tetrakis(bromomethyl)‐benzene with sodium organotellurates (NaTeR) afford white telluronium salts of the type XRTe(CH2)2C6H2(CH2)2TeRX where R = p‐EtOC6H4 and p‐MeOC6H4 and X = Br.

Reactions of 1,2,4,5‐tetrakis(bromomethyl)‐benzene with elemental tellurium powder and an excess of sodium iodide in dimethyl sulfoxide (DMSO) give 1,2,4,5‐bis(1,1‐diiodotelluracyclopentano)benzene, C10H10Te2I4 as orange‐red crystals in poor yield, together with a yellow amorphous precipitate as the main product, the structure of which is still obscure.

Reduction of the bis(diiodide) compound gave a light and air sensitive ditelluride, C10H10Te2, which, on treatment with ethyl bromide, afforded a white telluronium salt of 1,2,4,5‐bis(1′‐bromo‐1′‐ethyl‐telluracyclopentano)benzene, C14H20Te2Br2. The synthesis, spectroscopic data, and solution properties of the prepared compounds are reported and discussed.
Spectroscopic studies and X‐ray crystal structures of charge‐transfer complexes of 1,4,7‐trithiacyclononane with diiodine
Authors: Cristiani Franco , Devillanova Francesco A. , Isaia Francesco , Lippolis Vito , Verani Gaetano , Demartin Francesco
Published: January 2005

1,4,7‐Trithiacyclononane ([9]aneS3) reacts with molecular diiodine in CH2Cl2 to form a 1:1 adduct. The formation constant and the thermodynamic parameters of this adduct have been determined by UV‐visible spectra of several solutions at the temperatures of 15, 20, 25, 30, and 35°C. The 13C NMR spectra show that adducts with higher ligand/diiodine molar ratios are formed. Two neutral charge‐transfer molecular compounds having formula 2[9]aneS3 · 4I2 (I) and [9]aneS3 · 3I2 · (II) have been obtained as crystals. The crystals of I are triclinic (a = 8.498(2) Å, b = 13.984(4) Å, c = 14.898(6) Å, α = 65.57(2)°, γ = 89.19(2)°, γ = 81.26(2)°, Z = 2, space group P1; R = 0.025) and contain units formed by two [9]aneS3 molecules connected by a diiodine molecule; one [9]aneS3 binds two other diiodine molecules, while the second binds only one other diiodine molecule. The crystals of II are monoclinic (a = 13.810(2) Å, b = 9.829(4) Å, c = 16.198(6) Å, β = 113.41(2)°, Z = 4, space group P21/c; R = 0.019) and contain molecules of [9]aneS3 binding three diiodine molecules. FT‐Raman spectra in the characteristic v(I–I) region, carried out on the solid adducts, are discussed in comparison with the structural parameters.
2‐Hydroperfluoropropyl azide—a versatile reagent for the oxidative fluorination of organic compounds of trivalent phosphorus
Authors: Lermontov Sergei A. , Sukhojenko Ivan I. , Popov Anatoli V. , Pushin Alexei N. , Martynov Ivan V. , Zefirov Nikolai S. , Stang Peter J.
Published: January 2005

2‐Hydroperfluoropropyl azide CF3CHFCF2N3, 1, an inexpensive, readily available, and stable (easy to store) compound, is suggested as an effective fluorinating reagent for different classes of trivalent organophosphorus compounds in accordance with the general scheme R3P → R3PF2. Generally, the reactions are performed without solvent, the highly volatile CF3 CHFCN being the main by‐product. The fluorination is usually an exothermic process, but slight heating is necessary in the case of alkyldifluorophosphites. The unusual Arbuzov rearrangement, accompanied by isomerization of an isobutyl or neopentyl group into a tert‐group, ROPF2 → t‐R′POF2, under the action of a catalytic amount of 1, was observed.
Synthesis of saccharidyl N,N‐bis(2‐chloroethyl)phosphoramidates and their antitumor activity
Authors: Chen Ru‐Yu , Chen Xiao‐Ru
Published: January 2005

In order to search for novel antitumor drugs with high activity and low toxicity, a series of new compounds, galactopyranosyl (or glucofuranosyl) N,N‐bis(2‐chloroethyl) phosphoramidates, have been synthesized. The structures of all compounds prepared were proved by 1H NMR, 31P NMR, IR, and MS spectroscopy and by elemental analyses. The existence of diastereoisomers was detected by 31P NMR and 1H NMR spectra. One of the two isomers of 3a and also one of 4b, i.e., 3a′ and 4b′, respectively, were obtained by recrystallization. The absolute configurations of 3a′ and 4b′ were determined by single‐crystal X‐ray diffraction analysis. The results of the preliminary biological tests indicated that some of these compounds have certain inhibitory activities against L1210 cells.
Synthesis and reactions of phenyliodonium bis(perfluoroalkanesulfonyl) methides
Authors: Zhu Shi‐Zheng
Published: January 2005

Phenyliodonium bis(perfluoroalkanesulfonyl) methides PhI+−C(SO2RF)2 (3) were prepared by the reaction of bis(perfluoroalkanesulfonyl)methanes with diacetoxyiodobenzene. The photochemical reactions of 3 with alkenes, methanol, bromine, and benzene gave the corresponding addition or insertion products. When 3 was irradiated in the presence of methyl sulfide, pyridine, and triphenylphosphine, it afforded the ylides containing the bis(perfluoroalkanesulfonyl)methylene functionality, Y+−C(SO2RF)2. In these reactions the bis(perfluoroalkanesulfonyl)carbene intermediate (RFSO2)2C: may be involved. Irradiation or heating of 3 in DMSO gave a 1 : 1 complex, the structure of which was confirmed by X‐ray diffraction analysis. Bis(perfluoroalkanesulfonyl)‐methylene dimethyloxosulfonium ylides Me2(O)S+−C(SO2RF)2 were obtained by air oxidation of bis(perfluoroalkanesulfonyl)methylene dimethylsulfonium ylides.
Cyclic sulfur nitrogen compounds and phosphorus reagents: Part XII. Reactions of S4N4 with (2‐pyridylamino) phosphines [1]
Authors: Mohan T. , Thomas C. J. , Rao M. N. Sudheendra , Aravamudan G. , Meetsma Auke , van de Grampel Johan C.
Published: January 2005

Tetrasulfurtetranitride, S4N4 reacts with (2‐pyridylamino)‐diphenylphosphine in MeCN at room temperature to form the cyclotrithiazene (NC5H4NH)‐Ph2PNS3N3 (1) in good yield. By contrast, the cyclophosphathiazenes Ph2PS2N3 (2) and 1,5(Ph2P)2S2N4 (3) are isolated from the same reaction mixture under reflux conditions. In solution, compound 1 is found to be transformed into 2. The reaction of S4N4 with (2‐pyridylamino)phenyl(dicyclohexylamino)phosphine in MeCN at room temperature affords Ph(DCA)PS2N3 (4) (DCA = dicylohexylamino) as the only reaction product. This on treatment with norbornadiene produces the addition product Ph(DCA)PS2N3·C7H8 ( 5 ).

The structure of 4 has been established by X‐ray diffraction. Its PSN ring adopts a skew boat conformation with SN bond lengths varying from 1.574(4) to 1.606(4) Å. The mean value of the endocyclic PN bonds amounts to 1.618(3) Å.
Dialkynyl selenides: Synthesis, 13C NMR spectra, and molecular orbital calculations
Authors: Murai Toshiaki , Shimizu Atsushi , Tatematsu Shūji , Ōno Kazuhiko , Kanda Takahiro , Kato Shinzi
Published: January 2005

Reactions of SeCl4 with lithium bis(trimethylsilyl)amide and terminal acetylenes in the presence of BuLi or AIBN afforded the corresponding dialkynyl selenides in moderate to high yields. The reaction may proceed via a selenium amide 7 and an alkynyl selenium amide 8. The comparison of 13C NMR spectra of dialkynyl selenides and tellurides has disclosed that the differences of the chemical shift of acetylenic carbons between Se and Te derivatives are consistent regardless of their substitution patterns. Ab initio molecular orbital calculations are reported for dialkynyl ether and chalcogenides. The calculated structures, charge distributions, and orbital energies are discussed.
The B6H14 problem: Generation of a catalogue of conceivable isomers
Authors: Fontain Eric
Published: January 2005

The structure‐generating feature of the computer program RAIN (reactions and intermediates networks) was used to produce the complete set of 48 conceivable B6H14 isomers with twofold constitutional symmetry. The constitutional isomers are built from BH units and contain up to two closed BBB three‐center bonds.
UV‐visible, IR, and 13C NMR studies on CT complexes between some thiohydantoins and molecular diiodine
Authors: Cristiani Franco , Devillanova Francesco A. , Garau Alessandra , Isaia Francesco , Lippolis Vito , Verani Gaetano
Published: January 2005

The reaction of some 5,5‐dimethyl‐2‐thiohydantoin derivatives (X = O, S; R, R′ = H, Me) with molecular diiodine has been studied in CH2Cl2 solution by different spectroscopic techniques. The formation constants (K) of the 1 : 1 molecular adducts and their thermodynamic parameters have been measured by UV‐visible spectroscopy. The results allow us to point out the different donor properties of C(2) = S thioketonic sulfur between the two series of compounds (X = O, S) and the influence of N(1) and N(3) methylation on the K's. From the analysis of the ν(NH) frequencies, it has been possible to show hydrogen bond interactions between the NH's and the S‐bonded iodine; this seems to be an important factor in determining the K values.
New perthiophosphonic acid anhydrides and the direct indication of the dimer‐monomer equilibrium. NMR and X‐Ray Studies
Authors: Beckmann Haiko , Großmann Gisbert , Ohms Gisela , Sieler Joachim
Published: January 2005

New perthiophosphonic acid anhydrides (R‐PS2)n with R = 2,4,6‐tri‐iso‐propylphenyl and 2,4‐di‐tert‐butyl‐6‐methylphenyl have been prepared. For the latter case, the isolation of the monomer (n = 1), the 2,4‐di‐tertbutyl‐6‐methylphenyl‐dithioxophosphorane, and both dimers (n = 2), cis‐ and trans‐2,4‐bis(2,4‐di‐tertbutyl‐6‐methylphenyl)‐2, 4‐dithioxo‐1, 3, 2, 4‐dithiadiphosphetane, has been determined. The new cis and trans dithiadiphosphetanes and dithioxophosphoranes as well as the known compounds (2,4,6‐trimethylphenyl‐PS2)2 and 2,4,6‐tri‐tert‐butylphenyl‐PS2 are characterized by solution and high resolution solid‐state 31P and 13C NMR spectroscopy. The existence of a dimer‐monomer equilibrium is directly proved by 2D exchange 31P NMR spectroscopy. It is shown that the reaction of the monomer with methanol is faster than the reaction of the dimer with methanol.
Reactions of triethylgermylpentafluorobenzene with some electrophilic agents
Authors: Bardin Vadim V. , Rogoza Ljudmila N. , Furin Georgii G.
Published: January 2005

Triethylgermylpentafluorobenzene C6F5GeEt3 reacts with CF3SO3H, HSO3Cl, Me3SiOSO2Cl, chlorine, bromine, Cl2/AlCl3, or Br2/AlBr3 with cleavage of the CarylGe bond. Cesium fluoride promotes electrophilic degermylation of C6F5GeEt3, possibly via the intermediate formation of a tetraorganylfluorogermanate.
Synthesis and rearrangement of triazinoquinazolines
Authors: Ibrahim Yehia A. , Elwahy Ahmed H. M.
Published: January 2005

Selective syntheses of triazino[4,3‐a]quinazolines 3a–e and their isomeric triazino[3,2‐b]quinazolines 4a–e by cyclization of the appropriate α‐keto acid hydrazones 2a–e under different reaction conditions are described. The angular triazinoquinazolines 3a–e were readily rearranged to the corresponding linear isomers 4a–e when heated in acetic anhydride in the presence of sodium acetate. This rearrangement was proposed to proceed via the intermediate isomeric triazino[3,4‐b]quinazolines 5a–e. The N‐methyl derivative 10 (of the intermediate 5b) was prepared and rearranged to 11, which is the N‐methyl derivative of 4b.
The reaction of vicinal triketones with cumulative phosphorus ylides. Synthesis of phosphoranylidenecyclobutanes
Authors: Soliman Fouad M. , El‐Kateb Ahmed A. , Hennawy Ibtisam T. , Abdel‐Malek Hoda A.
Published: January 2005

1,2,3‐Indantrione (1), diphenylpropanetrione(6), and alloxan (8) can be converted by reactions with ketenylidene‐(2a) and thioketenylidenetriphenylphosphorane (2b) into phosphoranylidenecyclobutanes (5, 7, and 9). The structures of the new cyclic compounds were confirmed on the basis of elemental analysis and spectral studies.
The synthesis and antitumor activity of novel 1,3,5,2‐trizaphosphorines linked with nitrogen mustards
Authors: Chen Ru‐Yu , Mao Li‐Juan
Published: January 2005

A series of novel derivatives of 2,5‐dihydro‐1,3,5,2‐triazaphosphorine has been synthesized and the structures of the most stable tautomers have been confirmed by 1H NMR and IR spectroscopy, MS, elemental analyses, and quantum chemistry calculations. We suggest that the thioenol form is more stable than the thione form which has been thought to be more stable up to the present time. The bioassay tests indicated that most of the new products have good antitumor activity.
Macrocycles containing bicyclophosphorane moieties [1]
Authors: Houalla Douraid , Bounja Zouhair , Skouta Saïd , Wolf Robert , Jaud Joel
Published: January 2005

The first stable macrocycles, 12–15, 16, 18, and 23, containing pentacovalent phosphorus have been obtained by an Atherton–Todd reaction between the bis(hydridobicyclophosphoranes) 3–7 and the corresponding binucleophile HO(CH2)2X(CH2)2OH. The tricyclic monophosphoranes 8–11 as well as the noncyclic derivative 20 have also been isolated. A pathway that accounts for the formation of all these compounds is proposed. The X‐ray crystal study of two 16‐membered rings, 14, 15, confirms the diequatorial placement of the macrocyclic frame on the trigonal bipyramidal phosphorus which retains the most favorable axial‐equatorial‐axial annelation of the bicyclic moiety. Comparison of these two molecular structures points out the effect of the nature of X on the conformation of the macrocycle.
Studies of silicon–nitrogen ring formation from tetrachlorodisilanes
Authors: Shibley John L. , West Robert , Powell Douglas R. , Tessier Claire A.
Published: January 2005

The addition of n equiv of MesNHLi (n = 1, 2, 3, 4) and m equiv of 12‐crown‐4 (m = 0.1, 1, 2, 3, 4) to (RsiCl2)2 (R = Mesityl; t‐Butyl) in THF at −78°C resulted in higher yields and improved selectivities of cyclodisilazanes and azadisilacyclopropanes. The reaction of 2 equiv of MesNDLi with (MesSiCl2)2 (I) yielded cis‐2‐chloro‐1,2,3,4‐tetramestylcyclodisilazane (2a) with 95% SiH deuteration. 2a was quantitatively chlorinated with retention of stereochemistry by N‐chlorosuccinimide to give the cis dichlorocyclodisilazane (3). Variable‐temperature 1H NMR studies from −70°C to 25°C in d8‐THF were performed on 1, 2a, 2b, and 3. 1 exhibited little variation throughout the temperature range, whereas 2a, 2b, and 3 showed several rotational isomers. trans‐2,3‐Bis(mesitylamino)‐1,2,3‐trimesitylazadisilacyclopropane was shown to isomerize to the cis isomer in the presence of n‐BuLi or MesNHLi. The molecular structures of 1 and 3 were determined by X‐ray crystallography. Compound 1 crystallized in the monoclinic space group P21/c, with cell parameters a = 16.599(2) Å b = 14.633(2) Å, c = 16.945(2) Å, β = 92.044(13)°, V = 4113.1(8) Å3, Z = 8, d (calcd) = 1.409 g/cm3, and R = 6.88%. Compound 3 ° C6H6 crystallized in the orthorhombic space group Pbca, with cell parameters a = 17.906(4) Å, b = 13.918(3) Å, c = 31.700(6) Å, V = 7900(3) Å3, Z = 8, d (calcd) = 1.194 g/cm3, and R = 7.52%.
Rearrangements of (chloromethyl)organylsilanes induced by Lewis acids or by Lewis bases: Regioselective methylenation of allylic systems
Authors: Eisch John J. , Chiu Chingchen S.
Published: January 2005

In order to study the scope and mechanisms of the migration of organyl groups from silicon to its adjacent methylene carbon, a series of derivatives of the type RSiMe2CH2Cl were synthesized, where R is vinyl, benzyl, methallyl, phenylethynyl, aryloxy, and N‐methylanilino. Attempts were then undertaken to induce such Si → C shifts by either the Lewis acid, methylaluminum dichloride, or the Lewis base, potassium fluoride. Under Lewis acidic conditions, only the benzyl and methylallyl groups could be induced to migrate; clearly, in the case of benzyl (and probably in the case of methallyl), migration was accompanied by allylic rearrangement to produce the o‐tolyl group. Under the agency of KF, all the groups investigated underwent rearrangement to produce FSiMe2CH2R. By a crossover experiment, it was shown that, when R = aryloxy, the rearrangement occurs intermolecularly. Experimental evidence indicates that all KF‐induced migrations are probably intermolecular and all MeAlCl2‐induced migrations considered here are intramolecular. The advantages for organosilicon synthesis of utilizing so‐called “relay substitution reactions” with the ClSiR2CH2Cl system are discussed:
equation image
With unsymmetrical allylic systems, regioselective methylenation now becomes possible, simply by inducing the Si → C rearrangement by MeAlCl2 or by KF.
Substitution reactions at silicon under strongly acidic conditions: Ligand metathesis between methyltrichlorosilane and octamethylcyclotetrasiloxane
Authors: Jiang Jianxiong , Brook Michael A. , Dickson James M.
Published: January 2005

A study of the reactions between methyltrichlorosilane (MeSiCl3) and octamethylcyclotetrasiloxane (D4) in the presence of trifluoromethanesulfonic acid (HOTf) showed that nucleophilic substitution in CHCl3 solution at the trifunctional silicon was surprisingly slow in comparison with the rate of equilibration/polymerization of D4. The reaction rate at MeSiCl3 was significantly faster with water present and faster still in THF. In these reactions, there was no evidence for SiOH groups (29Si NMR), even in the presence of excess water. The overriding criterion for relative reactivity toward nucleophilic substitution under strongly acidic conditions is the relative leaving group ability of the groups on silicon. Once MeSiCl3 begins to participate in the redistribution reactions, mono‐ 3 and tri‐ 5, but not di‐substituted 4 systems are formed (MeSiCl3−x(DnSiMe2Z (Z = OTf, Cl))x, x = 1, 3), likely through an intramolecular reaction. The mechanisms of nucleophilic substitution at silicon under these conditions are discussed.
Reactions of bis[bis(trimethylsilyl)methyl]germylene and the corresponding stannylene with diazidosilanes
Authors: Ohtaki Toshiyuki , Kabe Yoshio , Ando Wataru
Published: January 2005

The reactions of bis[bis(trimethylsilyl)methyl]‐germylene (1) and the corresponding stannylene (2) with di‐tert‐butyldiazidosilane gave N‐(azidosilyl)germanimine (4) and the stannanimine (5) in quantitative yields. The structures have been confirmed by single‐crystal X‐ray diffraction. Crystal data for 4: space group P1, Z = 2, a = 9.236 (1), b = 12.066 (1), c = 17.068 (1) Å, α = 98.45 (1), β = 90.43, γ = 110.27 (1)°. V = 1761.3 Å3, R = 0.051, and Rw = 0.069 based on 4218 reflections with |Fo2| ⩾ 3σ|Fo2|. For 5: space group P1, Z = 2, a = 9.183 (1), b = 12.193 (1), c = 17.292 (1) Å, α = 98.74 (1), β = 90.21, γ = 109.96 (1)°, V = 1795.5 Å3, R = 0.040, and Rw = 0.051 based on 4795 reflections. The similar reactions of 1 and 2 with 1,3‐diazidohexamethyltrisilane (16) provided azatrisilacyclobutanes quantitatively.
Reactions of iPr2NCP with methylating agents: Formation of the diamino‐2‐phosphaallylic cation ⊕
Authors: Grobe Joseph , Le Van Duc , Hegemann Marianne , Krebs Bernt , Läge Mechtild
Published: January 2005

The reaction of di(isopropyl)aminophosphaethyne 1 with iodomethane or the methyl ester of trifluormethylsulfonic acid (methyl triflate) yields the ionic 1λ3, 3λ3‐diphosphetene derivatives + X− (2a: X = I; 2b: X = CF3SO3). On the basis of NMR spectroscopic and X‐ray diffraction studies, the cation can be described as a combination of an amino‐2‐phosphaallylic cation and its methylated derivative.
Aminolysis of P‐trichloro‐N‐dichlorophosphorylmonophosphazene and the crystal structure of 1‐(dichlorophosphinyl)‐2‐chloro‐2,2‐bis(diisopropylamino)phosphazene
Authors: Kılıçc Zeynel , Gündüz Necla , Yıldız Mustafa , Kılıçc Adem , Mor Sevtap , Ercan Filiz , Hökelek Tuncer , Ülkü Dinçer
Published: January 2005

The reactions of Cl3PNP(O)Cl2 (1) with primary and secondary amines have been studied. The following monophosphazenes, (RRN)3PNP(O)(NRR)2, and bis(phosphinoyl)amines, [(RRN)2P(O)]2NH were isolated: NRR = NHCH2Ph, Net2, NH(CH2)2CH3 groups for monophosphazenes, and Net2, NH(CH2)2CH3 for phosphinoyl amines. The unexpected geminal phosphazene, Cl(RRN)2PNP(O)Cl2, {RRN = N[CH(CH3)2]2}, was also obtained in moderate yield. The spectral data (IR, 1H, 13C, and 31P NMR, and MS) are presented. The structure of 1‐(dichlorophosphinyl)‐2‐chloro‐2,2‐bis(diisopropylamino)phosphazene ( 5) was determined by X‐ray crystallography. The basicities of these and related compounds in nonaqueous nitrobenzene solution were obtained by potentiometric titration.
Conformational studies of 2‐anilino‐substituted 1,3,2‐oxazaphospholanes
Authors: Setzer William N. , Flair Mark N. , Yang Xiao‐Jing , Wu Chia‐Kuei , Meehan Edward J.
Published: January 2005

A series of 2‐anilino‐2‐thio‐1,3,2‐oxazaphospholanes derived from ephedrine has been synthesized and conformationally studied by proton NMR and X‐ray crystallography. The NMR data can be interpreted in terms of twist‐envelope conformations in which the anilino substituents on phosphorus adopt predominantly equatorial positions. X‐ray crystal structures of (2R,4S,5S)‐2‐anilino‐2‐thio‐3,4‐dimethyl‐5‐phenyl‐1,3‐2‐oxazaphospholane, (2R,4S,5S)‐2‐(4‐fluoroanilino)‐2‐thio‐3,4‐dimethyl‐5‐phenyl‐1,3,2‐oxazaphospholane, and (2R,4S,5S)‐2‐(4‐methoxyanilino)‐2‐thio‐3,4‐dimethyl‐5‐phenyl‐1,3,2‐oxazaphosholane have been carried out, and these compounds adopt envelop, twist‐envelope, and twist‐envelope conformations, respectively, with the anilino moieties equatorial.
Synthesis of the P‐sulfide derivatives of 3‐phosphabicyclo[3.1.0]hexanes and 1,2‐dihydrophosphinines
Authors: Keglevich György , Tőke László , Lovász Csaba , Újszászy Kálmán , Szalontai Gábor
Published: January 2005

Several 3‐phosphabicyclo[3.1.0]hexane 3‐oxides have been transformed into the corresponding sulfides by reaction with phosphorus pentasulfide. The 3‐phenyl derivative could also be prepared by deoxygenation of the oxide followed by reaction with elemental sulfur. Opening of the cyclopropane ring in phosphabicyclohexane sulfides afforded mixtures of 3‐ and 5‐methyl‐1,2‐dihydro‐phosphinine‐1‐sulfides. Because of better yields, preparation of these products by thionation of the dihydrophosphinine oxides is more appropriate. The new phosphorus heterocycles have been characterized by 31P, 13C, and 1H NMR and mass spectral data.
Charge‐transfer complexes between some S‐methylated derivatives of 5,5‐dimethyl‐2,4‐dithiohydantoin and molecular diiodine. A UV‐Visible, IR, FT‐Raman, and 13C NMR study
Authors: Cristiani Franco , Devillanova Francesco A. , Garau Alessandra , Isaia Francesco , Lippolis Vito , Verani Gaetano
Published: January 2005

Equilibrium constants (K) and thermodynamic parameters for the charge‐transfer complexes between diiodine and Δ3‐4‐S‐methyl‐5,5‐dimethylimidazolidine‐2‐thione (1), 2‐S‐methyl‐5,5‐dimethylimidazolidine‐4‐thione (2), and Δ1‐Δ3‐2S‐methyl‐4‐S‐methyl‐5,5‐dimethylimidazolidine (3) have been determined in CH2Cl2 by UV‐Visible spectroscopy. Depending on the solvent polarity, compound 2 exists as a Δ1 or Δ2 tautomer; both the tautomers are present in CH2Cl2. Compounds 1 and 2 act as good donors (K = 11,000 ± 800 and 640 ± 21 dm3 mol−1, 25°C, respectively) owing to the presence of a thioamidic group in the molecule, whereas in compound 3, the N‐coordination causes a strong reduction of the formation constant (K = 14.6 ± 0.8 dm3 mol−1, 25°C). The high difference between the stability constants of 1 and 2 has been ascribed to an intramolecular hydrogen bonding between NH and the bonded iodine, which can be possible only for 1. Additional spectroscopic data (FT‐Raman, NMR) enables a deeper understanding of the mutual interaction between donors and diiodine.
(Trialkylstannyl)cuprates: A spectroscopic and chemical investigation
Authors: Sharma Sunaina , Martin Robin A.
Published: January 2005

Low‐temperature 1H, 13C, and 119Sn NMR spectroscopic techniques were used to probe the nature of cuprates derived from Me3SnLi, CuCN, or CuBr · Me2S. In THF, addition of Me3SnLi and CuX (X = Br or CN) gives aggregated [Me3SnCu · LiX]n. When the ratio of stannyl anion to cuprous cation is 2 : 1, mixtures of (Me3Sn)3Cu2Li, (Me3Sn)2CuLi · LiX, and (Me3Sn)3CuLi2 are formed. This behavior is unlike either homo trialkylsilycyanocuprates, which form (R3Si)2Cu(CN)Li2 at 2 : 1 ratios of silyl anion to cuprous ion, or mixed trialkylstannyl‐ or trialkylsilyl‐cuprates, which exist as (R3M)Cu(R′)(CN)Li2 (M = Si or Sn and R′ = Me or Bu). (R3Sn)3CuLi2 is the major species when the stannyl anion to cuprous cation ratio reaches 3 : 1. On the other hand, the analogous magnesium cuprates are discrete species in solution and possess differential reactivity.
Dense energetic compounds of C, H, N, and O atoms IV nitro and azidofurazan derivatives
Authors: Gunasekaran Ananthakrishnan , Trudell Mark L. , Boyer Joseph H.
Published: January 2005

Both diaminofurazan 5 (DAF) and diaminoazofurazan 6 (DAAF) were converted to 5‐(4‐amino‐1,2,5‐oxadiazol‐3‐yl)‐1H‐[1,2,3]triazolo[4,5‐c][1,2,5]oxadiazol‐3‐yl‐1H‐[1,2,3]triazolo[4,5‐c][1,2,5]oxadiazolium inner salt 8 (AMOTO) (25 and 91%) in oxidations with iodobenzene diacetate and to dinitroazoxyfurazan 13 (DNAF) (4 and 15%) in oxidations with a mixture of ammonium persulfate and hydrogen peroxide in concentrated sulfuric acid. The intermediacy of diaminoazoxyfurazan 7 was supported by its conversion under similar treatment to DNAF (60%). Further oxidation by ammonium persulfate converted AMOTO 8 to 5,5′[azobis‐(1,2,5‐oxadiazole‐4,3 ‐ diyl)]bis[1H(1,2,3)triazolo ‐ [4,5‐c][1,2,5]oxadiazolium]bis(inner salt) 10. Diazidofurazan 19 (tentative assignment) was obtained from DAF 5 by tetrazotization followed by treatment with sodium azide. Aminoazido‐azofurazan 16 was obtained from diazotized DAAF by treatment with sodium azide and was converted to AMOTO 8 by an elimination of nitrogen at 25°C. Similar treatment converted tetrazotized DAAF to diazidoazofurazan 9 and 5‐(4‐azido‐1,2,5‐oxadiazol‐3‐yl) ‐ 1H ‐[1,2,3]‐triazolo[4,5‐c][1,2,5]‐oxadiazolium inner salt 15 (AZOTO) after evolution of nitrogen. Aminofurazan‐2‐ONN‐azoxyazidofurazan 17 (AAAF) was obtained from diazotized diaminoazoxyfurazan 7 by treatment with sodium azide. Excellent calculated detonation properties were obtained for DNAF 13, AZOTO 15, and AAAF 17.
Studies on phosphonium ylides XX. The behavior of Wittig reagents toward 1,4‐benzoquinone monoimines
Authors: Boulos Leila Sadek , Hennawy Ibtisam Tadros , Arsanious Mona Hizkial Nasr
Published: January 2005

Wittig reagents (1a–c) react with N‐(phenylsulfonyl)‐1,4‐benzoquinone monoimine 2a to give adducts 3a, 4a, and 4b. On the other hand, the reactions of 2b with the same ylides (1a–c) yield the new products 3b, 6a, and 6b, respectively. Mechanisms accounting for the formation of the new products are discussed and the probable structures of the products are presented, based on compatible analytical and spectral data.
The reactions of tellurium tetrachloride with acetone
Authors: Huang Chang‐Kai , Marhold Harold , O'Brien Daniel H. , Irgolic Kurt J.
Published: January 2005

The reactions of acetone with tellurium tetrachloride have been studied with the aid of proton, carbon‐13, and tellurium‐125 NMR spectroscopy. In the absence of a proton scavenger, such as sodium hydrogen carbonate, at ambient temperature, a 2 : 1 ratio of acetone to tellurium tetrachloride quickly forms mainly acetonyl tellurium trichloride. At higher temperatures and after longer periods, the initially formed acetonyl tellurium trichloride is converted to 2‐methyl‐4‐oxo‐2‐penten‐1‐yl tellurium trichloride through an acidcatalyzed aldol condensation. In the presence of sodium hydrogen carbonate, the condensation reaction is prevented, and an equilibrium mixture of acetonyl tellurium trichloride and bis(acetonyl) tellurium dichloride is formed.
Iodine‐induced E/Z isomerization of sterically protected 3,4‐diphosphinidenecyclobutenes and 1‐phosphaethenes
Authors: Toyota Kozo , Tashiro Katsuya , Abe Tetsuya , Yoshifuji Masaaki
Published: January 2005

Sterically protected (E,E)‐3,4‐bis(2,4,6‐tri‐t‐butylphenylphosphinidene)dialkylcyclobutenes were isomerized to the corresponding (E,Z) derivatives in the presence of catalytic amounts of iodine. Similar iodine‐induced isomerizations were observed in the case of (E)‐ and (Z)‐2‐phenyl‐1‐(2,4,6‐tri‐t‐butylphenyl)‐1‐phosphaethenes.
NAD(P)+–NAD(P)H models. 84. Stereochemistry controlled by the electronic effect from a sulfinyl group
Authors: Ohno Atsuyoshi , Yamazaki Norimasa , Tsutsumi Akihiro , Mikata Yuji , Okamura Mutsuo
Published: January 2005

2,3‐Dihydro‐2,2,4‐trimethylthieno[3,2‐b]pyridinium 1‐oxide iodide (1) has been reacted with various inorganic and organic hydride donors. It has been found that the stereochemistry of reaction is controlled by the orientation of the sulfinyl dipole, and the relative bulkiness of substituents plays no role in determining the reaction face: a reactive hydride donor prefers to attack at the anti‐face with respect to the sulfinyl dipole, whereas a less reactive hydride donor prefers to attack at the syn‐face.
Synthetic transformations of 1‐cyanomethylbenzotriazole
Authors: Katritzky Alan R. , Chen Jie , Yang Zhijun
Published: January 2005

Lithiation of 1‐cyanomethylbenzotriazole (4) with LDA and subsequent reactions with alkyl halides or carbonyl compounds afforded the corresponding 1‐(α‐cyanoalkyl)‐ and 1‐(α‐cyanoalkenyl)‐benzotriazoles. Bromination of 4 with NBS formed 1‐(bromocyanomethyl)benzotriazole. 1‐Cyanoalkylbenzotriazoles condensed with hydrazine hydrate to give 4‐amino‐3,5‐bis(benzotriazol‐1‐yl)triazoles which underwent deamination with sodium nitrite to yield 3,5‐bis(benzotriazol‐1‐yl)triazoles.