Synthese von vier- und achtgliedrigen Heterocyclen, die Schwefel, Stickstoff und Phosphor enthalten, und die Röntgenstrukturanalyse eines phosphorhaltigen achtgliedrigen SN-Ringes / Synthesis of Four- and Eight-Membered Heterocycles Containing Sulfur, Nitrogen and Phosphorus and the X-ray Structure of a Phosphorus-Containing Eight-Membered SN-Ring

1980 ◽  
Vol 35 (9) ◽  
pp. 1130-1136 ◽  
Author(s):  
Herbert W. Roesky ◽  
Sushil K. Mehrotra ◽  
Christoph Platte ◽  
Djamrnschid Amirzadeh-Asl ◽  
Bernhard Roth
Keyword(s):  
Tertiary Amine ◽  
Phosphorus Atom ◽  
Mass Spectra ◽  
Phosphorus Pentachloride ◽  
Membered Ring ◽  
Phosphonium Salts ◽  
Nitrogen And Phosphorus ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
Phosphorus Containing

Eight-membered rings of the composition [SO2(NR)2PR′]2 3a-d with R = CH3, C2H5, and R′ = CH3, C6H5, were prepared from substituted sulfamides and dichlorophosphanes in the presence of a tertiary amine. These molecules were characterized on the basis of 1H and 31P NMR investigations and of mass spectra. 3 a reacts with phosphorus pentachloride to yield the spirocyclic derivative 4 with the phosphorus atom in the center of two four-membered rings. Methyliodide reacts with 3 a and 3 b under opening of the eight- membered ring and formation of phosphonium salts. The structure of 3 b is discussed in detail. 8b crystallizes in the orthorhombic space group Pna 21 with a = 12.60(0), b = 13.27(1), c = 12.62(4) Å.

Zur Chemie der 1,3,5-Triaza-2-phosphorinan-4,6-dione. Teil IX. Umsetzungen einiger 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-dione mit Hexafluoraceton / Chemistry of the 1,3,5-Triaza-2-phosphorinan-4,6-diones. Part IX. Reaction of some 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-diones with Hexafluoroacetone

1995 ◽  
Vol 50 (12) ◽  
pp. 1785-1790 ◽  
Author(s):  
Ion Neda ◽  
Michael Farkens ◽  
Axel K. Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Crystal Structure ◽  
Phosphorus Atom ◽  
Mass Spectra ◽  
Membered Ring ◽  
The Other ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Phosphoryl Compound ◽  
Spirocyclic Compounds

The reactions of 2-(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (1), 2-bis(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2A3-phosphorinan- 4,6-dione (2), 2-methoxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (3) and 2-trimethylsiloxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (5) with hexafluoracetone are described. In the case of 2 and 3 the reaction furnished the spirocyclic compounds 7 and 8. 2-Bis(2-chloroethyl)amino-1,3,5-triphenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (4) did not react. In the case of 1 and 5 rearrangement reactions took place; the (2-chloroethyl)amino substituent of 1 reacted with one of two equivalents of hexafluoroacetone with formation of the spirocyclic phosphorane 6. The reaction of 5 with tetrabromoorthobenzoquinone gave the phosphoryl compound 9. Compounds 6 - 8 were characterized via their 1H-, 13C-, 19F- and 31P-NMR and mass spectra, compound 9 via its 1H-, 13C- and 31P-NMR and mass spectra. An X-ray crystal structure determination of 8 was conducted; in the six-membered ring the phosphorus atom lies 73 pm out of the plane of the other atoms, and displays trigonal bipyramidal coordination.

The X-Ray Crystal Structure of 1,2-3,4-Di-O-isopropylidene-4-C-methylthiomethoxy-β-L-arabino-hexoseptanos-5-ulose

1990 ◽  
Vol 43 (12) ◽  
pp. 2083 ◽  
Author(s):  
DC Craig ◽  
VJ James ◽  
JD Stevens
Keyword(s):  
Crystal Structure ◽  
Title Compound ◽  
Membered Ring ◽  
Boat Conformation ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray

The crystal structure of the title compound (1) has been determined by X-ray diffraction. Crystals of (1) are orthorhombic, space group P21212 with a 11.425(1), b 24.916(1), c 5.8952(3)Ǻ, Z 4. Refinement on 1675 observed reflections measured with Cu Kα radiation converged at R 0.034. The seven- membered ring adopts a boat conformation in which the pseudo plane of symmetry passes through the ring oxygen.

The crystal and molecular structure of tetrabenzocyclodecan-1,6-dione

1980 ◽  
Vol 58 (8) ◽  
pp. 777-779 ◽  
Author(s):  
T. Stanley Cameron ◽  
Christine Chan ◽  
David G. Morris ◽  
Alistair G. Shepherd
Keyword(s):  
Molecular Structure ◽  
Diffraction Analysis ◽  
Title Compound ◽  
Crystal And Molecular Structure ◽  
Membered Ring ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Nmr Spectrum ◽  
X Ray ◽  
C Nmr

The crystals belong to the orthorhombic space group C222, with a = 9.226, b = 12.092, c = 16.513 Å, Z = 4. A single crystal X-ray diffraction analysis has shown that the title compound, in which all carbon atoms are sp2 hybridized, exists with the ten membered ring in a slightly twisted tub conformation. The 13C nmr spectrum is also reported.

Darstellung und Charakterisierung von Spezies der Zusammensetzung η5-C5H5Cr(NO)2SR (R = C6H5, C6F5, t–C4H9) und [η5-C5H5CrNO]2(ER)2 (E = O, S, Se, Te, R = Alkyl, Aryl); Röntgenstrukturanalysen von [η5-C5H5(NO)Cr(μ-SeC6H5)2Cr(NO)-η5-C5H5] und [η5-C5H5(NO)Cr(μ-Se-n-C4H9)(μ-OH)Cr(NO)-η5-C5H5] / Synthesis and Characterization of Species of Composition η5-C5H5Cr(NO)2SR (R = C6H5, C6F5, t-C4H9) and [η5-C5H5CrNO]2(ER)2 (E = O, S, Se, Te, R = Alkyl, Aryl); Röntgenstrukturanalysen von [η5-C5H5(NO)Cr(μ-SeC6H5)2Cr(NO)-η5-C5H5] and [η5-C5H5(NO)Cr(μ-Se-n-C4H9)(μ-OH)Cr(NO)-η5-C5H5]

1982 ◽  
Vol 37 (1) ◽  
pp. 13-23 ◽  
Author(s):  
Johannes Rott ◽  
Ernst Guggolz ◽  
Albert Rettenmeier ◽  
Manfred L. Ziegler
Keyword(s):  
Mass Spectra ◽  
Membered Ring ◽  
Molecular Structures ◽  
Binuclear Complexes ◽  
Alkyl Aryl ◽  
X Ray ◽  
H Nmr ◽  
Crystal And Molecular Structures ◽  
Nmr Methods

The title compounds have been synthesized and characterized by elemental analysis, IR and 1H NMR methods and mass spectra. The crystal and molecular structures of the binuclear complexes [η-C5H5(NO)Cr(μ-SeC6H5)2Cr(NO)-η5-C5H5] and [η5-C5H5(NO)Crμ-Se-n-C4H9)(μ-OH)Cr(NO)-μ5-C5H5] have been determined by X-ray structure analysis. The latter is shown to have a four-membered ring consisting of two chromium atoms, one selenium, and one oxygen atom.

Beiträge zur Strukturchemie phosphorhaltiger Ketten und Ringe, IX [1]. Die Molekül- und Kristallstruktur von Tri-tert-butylcyclotriphosphanpentacarbonyl- chrom(O), [(t-BuP)3Cr(CO)5] / Structural Chemistry of Phosphorus-Containing Chains and Rings, IX [1]. The Molecular and Crystal Structure of Tri-tert-butylcydotriphosphane-pentacarbonyl-chromium (0), [(t-BuP)3Cr(CO)5]

1984 ◽  
Vol 39 (1) ◽  
pp. 37-42 ◽  
Author(s):  
Karl-Friedrich Tebbe ◽  
Magda Fehér
Keyword(s):  
Crystal Structure ◽  
Single Crystal ◽  
Least Squares ◽  
Direct Methods ◽  
Membered Ring ◽  
Free Molecule ◽  
Donor Ligand ◽  
Space Group ◽  
X Ray ◽  
Phosphorus Containing

The structure of [(t-BuP)3Cr(CO)5], C17CrH27O5P3, has been determined by single crystal X-ray techniques, solved by ‘direct methods', and refined to R = 0.048, wR = 0.050 for 3657 reflections by blocked least squares. The compound crystallizes in the space group P 21/c with a = 1664.9 pm, b = 916.5 pm , c = 3089.8 pm, β= 91.45° and Z = 8 formula units. The structure consists of two crystallographically independent but structurally nearly identical mononuclear [(t-BuP)3Cr(CO)5] complexes with the three-membered ring (t-BuP)3 as an unidentate σ-donor ligand. Compared to the free molecule (t-BuP)3 the cyclophosphane ligand is slightly distorted on account of its coordination to the Cr(CO)5-group.

Silaheterocycles 36 (1). Trichlorovinylsilane, lithium-tert-butyl, and 1,3-enynes: A versatile combination for the competitive formation of silacyclobutanes and silacyclobutenes

2000 ◽  
Vol 78 (11) ◽  
pp. 1445-1458 ◽  
Author(s):  
N Auner ◽  
M Grasmann ◽  
B Herrschaft ◽  
M Hummer
Keyword(s):  
Solid State ◽  
Triple Bond ◽  
Reaction Pathway ◽  
Membered Ring ◽  
State Structure ◽  
Orthorhombic Space Group ◽  
Multiple Bonds ◽  
X Ray ◽  
Tert Butyl ◽  
One Step

Equimolar amounts of trichlorovinylsilane (9), lithium-tert-butyl, and 1,3-enynes were reacted to yield the corresponding isomeric silacyclobutanes and silacyclobutenes competitively. As reaction pathway the mixture 9/tBuLi is discussed to give a silene equivalent, Cl2Si=CHCH2tBu (10), yielding the four-membered ring silacycles by formal [2 + 2] cycloaddition reactions of 10 with the C=C double or the C=C triple bond of the 1,3-enyne. The relative ratio of the products formed depends on the polarity of the multiple bonds in the enyne, which is mainly determined by the substituent pattern. Thus, from the organosubstituted 1,3-enynes R1 C=C-C(R2)=CR3R4 (R1 = Me, Et, SiMe3, Ph; R2 = H, Me, Ph; R3=Me, OMe, Ph; R4=H; and R1C=C-R' (R' = 1-cyclohexenyl, cyclohexanevinylidyne)) and 9/tBuLi the silacyclobutanes 12, 13, and 15 and the silacyclobutenes 14,16-24, and 27 (from 10 and 3-hexyne) are prepared in a one-step synthesis and isolated from the reaction mixtures. The silacyclobutanes and -butenes are thermally stable and can be distilled under vacuo up to temperatures of about 150°C without decomposition. The experimental results are confirmed qualitatively by semiempiric calculations at the AM-1 level and their analysis using FMO theory. The solid state structure of the silacyclobutene 19 (C17H30Cl2Si2) has been determined by single crystal X-ray diffractometry. 19 is orthorhombic, space group P212121, a = 1030.94(2) pm, b = 1244.6(2) pm, c = 1605.5(3) pm, Z = 4.Key words: neopentylsilene, dichloroneopentylsilene, silacyclobutenes, silacyclobutanes, 1,3-enynes.

Structure and conformation of hydroxylubimin, a sesquiterpenoid phytoalexin

1977 ◽  
Vol 55 (10) ◽  
pp. 1619-1623 ◽  
Author(s):  
George I. Birnbaum
Keyword(s):  
Structure Analysis ◽  
Direct Methods ◽  
Membered Ring ◽  
Side Chain ◽  
Equatorial Position ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Independent Molecules ◽  
Chiral Centers

In order to determine the orientation of the isopropenyl group and confirm the stereochemistry at other chiral centers in lubimin (1) and hydroxylubimin (2), two antifungal sesquiterpenes, an X-ray structure analysis of 2 was carried out. Crystals of 2 are orthorhombic, space group P212121, a = 6.190, b = 7.210, c = 63.082 Å, Z = 8. The structure was solved by direct methods and refined to R = 0.045. In both independent molecules the six-membered ring is chair-shaped with all four substituents equatorially oriented. The five-membered ring, attached by a spiro junction, is a half-chair with the isopropenyl substituent in an equatorial position. This side-chain is trans to the methyl-bearing carbon in the six-membered ring.

Zur Chemie der 1,3,5-Triaza-2-phosphorinan-4,6-dione. Teil X. Umsetzungen von 2-Hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ4- phosphorinan-4,6-dion mit Triazin-Derivaten sowie mit einigen Aldehyden / Chemistry of the 1,3,5-Triaza-2-phosphorinan-4,6-diones. Part X. Reactions of 2-Hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ4 -phosphorinan-4,6-dione with Triazine Derivatives and with Some Aldehydes

1995 ◽  
Vol 50 (12) ◽  
pp. 1833-1838 ◽  
Author(s):  
Ion Neda ◽  
Michael Farkens ◽  
Holger Thönnessen ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Structure Analysis ◽  
Mass Spectra ◽  
Nmr Spectra ◽  
Glyoxylic Acid ◽  
Crystal Structure Analysis ◽  
Membered Ring ◽  
X Ray ◽  
Triazine Derivatives

The reactions o f 2-hydro-1,3,5-trim ethyl-1,3,5-triaza-2-oxo-2λ4 -phosphorinan-4,6-dione 1 with the triazine derivatives, 1,3,5-trimethyl- and 1,3,5-tribenzyl-hexahydro-1,3,5-triazine, are described. The reaction of three equivalents of 1 with one equivalent of the triazine derivative gave 2 and 3. Both compounds were characterized via their 1H, 13C, and 31P NMR spectra, mass spectra and, in the case of 2, by an X-ray crystal structure analysis, which showed an almost planar six-membered ring; hydrogen bonds of the form N-H···O link the molecules in centrosymmetric pairs. The reactions of 1 with the aldehydes glyoxylic acid, 2-hydroxybenzaldehyde and 3,4,5-trimethoxybenzaldehyde gave addition products. The C (:O) group o f the aldehyde is inserted into the P -H bond o f 1. The resulting compounds 4 ,5 and 6 were characterized through their 1H, 13C, and 31P NMR spectra, and mass spectra.

2-Isothiocyanatobenzyltriphenylphosphonium bromides – new type of functionalized heterocumulenes suitable for synthesis of indole derivatives

1987 ◽  
Vol 52 (10) ◽  
pp. 2508-2520 ◽  
Author(s):  
Jozef Gonda ◽  
Pavol Kristian ◽  
Ján Imrich
Keyword(s):  
Nitrogen Atom ◽  
Sulfur Atom ◽  
Mass Spectra ◽  
Wittig Reaction ◽  
Indole Derivatives ◽  
Phosphonium Salts ◽  
X Ray Diffraction ◽  
X Ray ◽  
Electrophilic Reactions ◽  
New Type

Reaction of 2-bromomethylphenyl isothiocyanates with triphenylphosphine afforded triphenyl-(2-isothiocyanatobenzyl)phosphonium salts. Their reaction with bases liberated the corresponding carbanions which on intramolecular addition to the N=C=S group gave substituted 3-triphenylphosphoniumindolyl-2-thiolates. These compounds did not react in the Wittig reaction but underwent electrophilic reactions on the sulfur atom or on the indol nitrogen atom. According to a detailed analysis of 1H, 13C, 31P NMR and mass spectra, the indole derivatives exist predominantly in the betaine form. X-Ray diffraction analysis of the unsubstituted betaine, 3-triphenylphosphoniumindolyl-2-thiolate, agrees well with the spectral results.

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