scholarly journals Convenient Synthesis of Benziodazolone: New Reagents for Direct Esterification of Alcohols and Amidation of Amines

Molecules ◽  
2021 ◽  
Vol 26 (23) ◽  
pp. 7355
Author(s):  
Michael T. Shea ◽  
Gregory T. Rohde ◽  
Yulia A. Vlasenko ◽  
Pavel S. Postnikov ◽  
Mekhman S. Yusubov ◽  
...  
Keyword(s):  
Organic Synthesis ◽  
Room Temperature ◽  
Hypervalent Iodine ◽  
The Novel ◽  
Chlorobenzoic Acid ◽  
Direct Esterification ◽  
X Ray ◽  
Convenient Synthesis

Hypervalent iodine heterocycles represent one of the important classes of hypervalent iodine reagents with many applications in organic synthesis. This paper reports a simple and convenient synthesis of benziodazolones by the reaction of readily available iodobenzamides with m-chloroperoxybenzoic acid in acetonitrile at room temperature. The structure of one of these new iodine heterocycles was confirmed by X-ray analysis. In combination with PPh3 and pyridine, these benziodazolones can smoothly react with alcohols or amines to produce the corresponding esters or amides of 3-chlorobenzoic acid, respectively. It was found that the novel benziodazolone reagent reacts more efficiently than the analogous benziodoxolone reagent in this esterification.

scholarly journals Insertion of Phosphenium Ions into a Bicyclo[1.1.0]Tetraphosphabutane Iron Complex

Molecules ◽  
2021 ◽  
Vol 26 (13) ◽  
pp. 3920
Author(s):  
Martin Weber ◽  
Gábor Balázs ◽  
Alexander V. Virovets ◽  
Eugenia Peresypkina ◽  
Manfred Scheer
Keyword(s):  
Diffraction Analysis ◽  
Room Temperature ◽  
31P Nmr ◽  
Spectroscopic Studies ◽  
Iron Complex ◽  
The Novel ◽  
X Ray Diffraction ◽  
X Ray ◽  
Phosphenium Ions

By reacting [{Cp‴Fe(CO)2}2(µ,η1:1-P4)] (1) with in situ generated phosphenium ions [Ph2P][A] ([A]− = [OTf]− = [O3SCF3]−, [PF6]−), a mixture of two main products of the composition [{Cp‴Fe(CO)2}2(µ,η1:1-P5(C6H5)2)][PF6] (2a and 3a) could be identified by extensive 31P NMR spectroscopic studies at 193 K. Compound 3a was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.0]pentaphosphapentane unit. At room temperature, the novel compound [{Cp‴Fe}(µ,η4:1-P5Ph2){Cp‴(CO)2Fe}][PF6] (4) is formed by decarbonylation. Reacting 1 with in situ generated diphenyl arsenium ions gives short-lived intermediates at 193 K which disproportionate at room temperature into tetraphenyldiarsine and [{Cp‴Fe(CO)2}4(µ4,η1:1:1:1-P8)][OTf]2 (5) containing a tetracyclo[3.3.0.02,7.03,6]octaphosphaoctane ligand.

Synthesis and Structural Systematics of Nitrogen Base Adducts of Group 2 Salts. VII. Some Complexes of Group 2 Metal Halides With Aromatic N,N'-Bidentate Ligands

1996 ◽  
Vol 49 (1) ◽  
pp. 99 ◽  
Author(s):  
BW Skelton ◽  
AF Waters ◽  
AH White
Keyword(s):  
Room Temperature ◽  
The Novel ◽  
Bidentate Ligands ◽  
Nitrogen Base ◽  
One Dimensional ◽  
X Ray ◽  
L System ◽  
L Systems ◽  
Group 2 ◽  
Structural Characterizations

Syntheses and room-temperature single-crystal X-ray structural characterizations are recorded for a number of adducts of Group 2 halides with the aromatic N,N′- bidentate ligands L = 2,2'-bipyridine ( bpy ) and 1,10-phenanthroline ( phen ). One adduct of 1 : 1 MX2/L stoichiometry is recorded: [( bpy )Ca(μ-Br)(4/2)](∞ ׀ ∞) (1) is monoclinic, C 2/c, a l7.102(5), b 9.845(1), c 7.600(2) Ǻ, β 107.65(2)°, Z = 4 f.u .; conventional R on #1472; F ׀ at convergence was 0.057 for No 817 independent 'observed' ( I > 3σ(I)) reflections, the compound being a one-dimensional polymer… CaL (μ-Br)2CaL(μ-Br)2…, with six-coordinate calcium, cis-CaN2(μ-Br)4, on a twofold axis. 1 : 2 MX2/L systems have been described for two types of array: [( bpy )2CaI2] (2), orthorhombic, Pnca, a 16.914(4), b 13.80(1), c 9.290(4) Ǻ, Z = 4 f.u .; R 0.039 for No 1738, is discrete mononuclear, containing cis-CaN4I2 six-coordinate calcium, whereas the barium analogue is an infinite one-dimensional polymer, [( bpy )2Ba(μ-I)(4/2)](∞׀ ∞) (3), triclinic, Pī, a 11.318(2), b 11.078(2), c 9.206(4) Ǻ, α 80.87(2), β 77.52(2), γ 87.53(1)°, Z = 2 f.u .; R 0.032 for No 4154, with eight-coordinate (N2)2Ba(μ-I)4. The perchlorate analogue, [( bpy )2Ba(μ-OClO2O)(4/2)](∞ ׀ ∞) (4), although of similar stoichiometry, has a trans-rather than a cis-linked chain; it is monoclinic, P 21/c, a 6.606(2), b 18.661(7), c 19.440(8) Ǻ, β 109.45(4)°, Z = 4 f.u .; R 0.044 for No 4060, with μ-I replaced by O,O'-ClO4 bridging units and eight-coordinate barium, (N2)2BaO4. The 1 : 3 MX2/L system is represented (as its hemi( bipyridine ) 'solvate') by mononuclear [( bpy )3SrI2].0.5bpy (5), monoclinic, P 21/c, a 20.834(8), b 9.735(4), c 18.460(7) Ǻ, β 114.87(3)°, Z = 4 f.u .; R 0.039 for No 3711, containing eight-coordinate strontium, [(N2)3SrI2]; there is also an isomorphous calcium/ perchlorate analogue [( bpy )3Ca(OClO3)2].0.5bpy (6), a 21.413(6), b 9.813(4), c 18.659(2) Ǻ, β 115.67(2)°, R 0.057 for No 3090, in which unidentate O-ClO4 ligands replace the iodine about the metal atom. A 1 : 4 adduct is obtained with CaI2/phen; ionic [Ca( phen )4] I2 (7), triclinic, Pī , a 14.703(3), b 13.292(3), c 11.38(1) Ǻ, α 92.78(4), β 96.15(4), γ 105.22(2)°, Z = 2 f.u ., R 0.053 for No 3658, contains eight-coordinate Ca(N2)4 arrays, while the novel 1 : 5 adduct [ Ba ( phen )4] I2.MeCN (8) is triclinic, Pī , a 12.170(6), b 13.760(7), c 18 254(8) Ǻ, α 77.05(9), ,β 71.96(4), γ 70.83(9)°, Z = 2 f.u ., R 0.040 for No 4447, containing 10-coordinate barium, [ Ba (N2)5]. A 1 : 4 adduct formed with BaBr2 is [ BrBa( phen )4] Br.MeOH (9), triclinic, Pī , a 17.748(4), b 17.418(2), c 15.535(7) Ǻ, α 91.63(2), β 100.53(3), γ 115.39(1)°, Z = 4 f.u ., R 0.062 for No 4092, containing nine-coordinate barium, [ BrBa (N2)4].

A fourfold interpenetrating diamond-like three-dimensional zinc(II) coordination polymer: synthesis, crystal structure and physical properties

2019 ◽  
Vol 75 (5) ◽  
pp. 504-507 ◽  
Author(s):  
Hui-Ru Chen
Keyword(s):  
Crystal Structure ◽  
Room Temperature ◽  
Three Dimensional ◽  
Fluorescence Emission ◽  
Crystal Structure Analysis ◽  
The Novel ◽  
X Ray Diffraction ◽  
Metal Compounds ◽  
X Ray ◽  
Coordination Framework

Excellent fluorescence properties are exhibited by d 10 metal compounds. The novel three-dimensional ZnII coordination framework, poly[[{μ2-bis[4-(2-methyl-1H-imidazol-1-yl)phenyl] ether-κ2 N 3:N 3′}(μ2-furan-2,5-dicarboxylato-κ2 O 2:O 5)zinc(II)] 1.76-hydrate], {[Zn(C6H2O5)(C20H18N4O)]·1.76H2O} n , has been prepared and characterized using IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal structure analysis revealed that the compound exhibits a novel fourfold interpenetrating diamond-like network. This polymer also displays a strong fluorescence emission in the solid state at room temperature.

scholarly journals NMR and X-ray Studies Concerning Structure of 6,6’-(Oxybis(4,1-phenylene))bis-(2-allylpyridazin- 3(2H)-one)

2014 ◽  
Vol 22 (1) ◽  
pp. 25-38 ◽  
Author(s):  
Vasilichia Antoci ◽  
Mircea Apostu ◽  
Catalina Ciobanu ◽  
Dorina Mantu
Keyword(s):  
Phenyl Ring ◽  
Room Temperature ◽  
Heterocyclic System ◽  
Crystal Packing ◽  
Diphenyl Ether ◽  
The Novel ◽  
X Ray ◽  
Pyridazine Ring ◽  
Phenyl Rings ◽  
C Nmr

Abstract The structural NMR and X-ray studies of 6,6’-(Oxybis(4,1- phenylene))bis-(2-allylpyridazin-3(2H)-one), a bis-pyridazine derivative heterocycle, are reported in this study. Both 1H- and 13C- NMR confirm the proposed structure of compound. In order to establish unequivocally the structure of compound, the X-ray data analysis was performed. The compound crystallizes in the triclinic P-1(2) space group with a = 10.3699(7) Å, b = 10.6972(6) Å, c = 11.0449(4) Å, α = 87.941(5)°, β = 75.564(5)°, γ = 72.055(5)°, V= 1127.68 (12) Å3 and Z = 2. Molecular and crystal packing parameters for the novel heterocyclic system were obtained from intensity data collected at room temperature. The two phenyl rings (from the diphenyl ether moiety) are perpendicular one to each other and, on its turn, each phenyl ring is almost coplanar with the pyridazine ring

scholarly journals Heterocyclic Hypervalent Iodine(III) Compounds with Fused Benziodazole and Tetrazole Rings (I-Substituted Tetrazolo[1,5-b][1,2]Benziodazoles)

2020 ◽  
Author(s):  
Rajesh Kumar ◽  
Kapil Dev Sayala ◽  
Lejla Lejla Camdzic ◽  
Maxime Siegler ◽  
Avichal Vaish ◽  
...  
Keyword(s):  
Room Temperature ◽  
Hypervalent Iodine ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Reaction Conditions ◽  
Thermal Stabilities ◽  
X Ray ◽  
X Ray Crystallography ◽  
Derivatives Of ◽  
C Nmr

A series of heterocyclic hypervalent (HV) iodine(III) compounds containing fused tetrazole and benziodazole rings, i.e., derivatives of benziodazolotetrazole (BIAT) with various ligands (L) attached to the iodine atom (BIAT-L) were prepared and studied. They were characterized by <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy, ESI-HRMS, and X-ray crystallography. The thermal stabilities of all BIAT derivatives (L= Cl, OH, OAc, OMe) were studied and the degradation patterns as well as the enthalpies of degradation were measured by thermal gravimetric analysis coupled with differential scanning calorimetry. The reaction of various alkenes with BIAT-Cl in the presence of Cu(OTf)<sub>2</sub> at room temperature yielded chloro-tetrazolylated products. The oxidation of thioanisole with BIAT-Cl under various reaction conditions is also reported.

scholarly journals Pentamethylcyclopentadienylbis(ethen)eisen - ein 17e-Halbsandwichkomplex mit leicht verdrängbaren Ethenliganden / Pentamethylcyclopentadienylbis(ethene)iron - a 17e Halfsandwich Complex with Easily Displaceable Ethene Ligands

1995 ◽  
Vol 50 (3) ◽  
pp. 394-404 ◽  
Author(s):  
Klaus Jonas ◽  
Peter Klusmann ◽  
Richard Goddard
Keyword(s):  
Title Compound ◽  
Room Temperature ◽  
Iron Complexes ◽  
Starting Material ◽  
Dinuclear Complex ◽  
The Novel ◽  
Valuable Source ◽  
X Ray ◽  
Wide Range ◽  
Stabilizing Effect

The new room temperature stable halfsandw ich complex Cp*Fe(tmeda)Cl (2) has been synthesized by the 1:1 reaction of FeCl2(thf)1.5 with LiCp* in a mixture of THF and TMEDA at - 30 °C. 2 is an ideal starting material for the synthesis of a wide range of new iron complexes. Treatment of 2 with lithium sand in THF in the presence of COD or ethene followed by the addition of TMEDA yields the ferrates [Li(tmeda)][Cp*Fe(cod)] (3) or [Li(tmeda)][Cp*Fe(C2H4)2] (4). By delithiation with dichloroethane, 3 and 4 can be transformed into the novel 17 e iron complexes Cp*Fe(cod) (5) and Cp*Fe(C2H4)2 (6). 6 is extremely labile. Since the ethene ligands can be easily displaced, the title compound is a synthetically valuable source of the Cp*Fe fragment. Whereas the photochemically generated 17e dicarbonyl species CpFe(CO)2 rapidly recombines to give the dimer [CpFe(CO)2]2, the isoelectronic 6 is stable in ethene saturated pentane for several days at 0 °C. Without the stabilizing effect of ethene (in pure pentane or under vacuum ), 6 loses ethene to give the dinuclear complex (Cp*Fe)2(C2H4)2 (8) irreversibly. The structure of 8 has been characterized by X -ray analysis.

scholarly journals Heterocyclic Hypervalent Iodine(III) Compounds with Fused Benziodazole and Tetrazole Rings (I-Substituted Tetrazolo[1,5-b][1,2]Benziodazoles)

2020 ◽  
Author(s):  
Rajesh Kumar ◽  
Kapil Dev Sayala ◽  
Lejla Lejla Camdzic ◽  
Maxime Siegler ◽  
Avichal Vaish ◽  
...  
Keyword(s):  
Room Temperature ◽  
Hypervalent Iodine ◽  
Gravimetric Analysis ◽  
Scanning Calorimetry ◽  
Reaction Conditions ◽  
Thermal Stabilities ◽  
X Ray ◽  
X Ray Crystallography ◽  
Derivatives Of ◽  
C Nmr

A series of heterocyclic hypervalent (HV) iodine(III) compounds containing fused tetrazole and benziodazole rings, i.e., derivatives of benziodazolotetrazole (BIAT) with various ligands (L) attached to the iodine atom (BIAT-L) were prepared and studied. They were characterized by <sup>1</sup>H and <sup>13</sup>C NMR spectroscopy, ESI-HRMS, and X-ray crystallography. The thermal stabilities of all BIAT derivatives (L= Cl, OH, OAc, OMe) were studied and the degradation patterns as well as the enthalpies of degradation were measured by thermal gravimetric analysis coupled with differential scanning calorimetry. The reaction of various alkenes with BIAT-Cl in the presence of Cu(OTf)<sub>2</sub> at room temperature yielded chloro-tetrazolylated products. The oxidation of thioanisole with BIAT-Cl under various reaction conditions is also reported.

Benziodoxole-Derived Organosulfonates: The Strongest Hypervalent Iodine Electrophiles and Oxidants

Synlett ◽  
2019 ◽  
Vol 31 (04) ◽  
pp. 315-326 ◽  
Author(s):  
Viktor V. Zhdankin ◽  
Mekhman S. Yusubov ◽  
Pavel Postnikov ◽  
Akira Yoshimura
Keyword(s):  
Room Temperature ◽  
Trifluoromethanesulfonic Acid ◽  
High Reactivity ◽  
Hypervalent Iodine ◽  
Ionic Character ◽  
Primary Alcohols ◽  
Total Syntheses ◽  
X Ray ◽  
High Yields ◽  
Efficient Reagent

This account describes the development of organosulfonyloxy-substituted iodine(III) and iodine(V) benziodoxole derived reagents, which are thermally stable compounds with useful reactivity patterns. Iodine(III) benziodoxoles and pseudobenziodoxoles are powerful electrophiles and mild oxidants toward various unsaturated compounds. In particular, pseudocyclic benziodoxole-derived triflate (IBA-OTf) is an efficient reagent for oxidative heteroannulation reactions. Aldoximes react with nitriles in the presence of IBA-OTf at room temperature to give 1,2,4-oxadiazoles in high yields. Moreover, IBA-triflate is used as a catalyst in oxidative heteroannulations with m-chloroperoxybenzoic acid as the terminal oxidant. The iodine(V) benziodoxole derived tosylates, DMP-tosylate and IBX-tosylate, are superior oxidants for the oxidation of structurally diverse, synthetically useful alcohols, utilized as key precursors in the total syntheses of polyketide antibiotics and terpenes. And finally, the most powerful hypervalent iodine(V) oxidant, 2-iodoxybenzoic acid ditriflate (IBX·2HOTf), is prepared by treatment of IBX with trifluoromethanesulfonic acid. According to the X-ray data, the I–OTf bonds in IBX-ditriflate have ionic character, leading to the high reactivity of this reagent in various oxidations. In particular, IBX-ditriflate can oxidize polyfluorinated primary alcohols, which are generally extremely resistant to oxidation.1 Introduction2 Iodine(III) Benziodoxole Based Organosulfonates3 Pseudocyclic Iodine(III) Benziodoxole Triflate (IBA-triflate)4 Pseudocyclic Iodine(III) Benziodoxole Tosylates5 Iodine(V) Benziodoxole Derived Tosylates6 Iodine(V) Benziodoxole Derived Triflate (IBX-ditriflate)7 Conclusions

scholarly journals Synthesis of an Adduct-Type Organic Ionic Crystal with Solid-State Ionic Conductivity from A Thiocyanate-Based Ionic Liquid and B(C6F5)3

Crystals ◽  
2019 ◽  
Vol 9 (11) ◽  
pp. 567 ◽  
Author(s):  
Oki ◽  
Moriya
Keyword(s):  
Ionic Liquid ◽  
Solid State ◽  
Ionic Conductivity ◽  
Ionic Crystal ◽  
Crystalline State ◽  
Room Temperature ◽  
Sodium Thiocyanate ◽  
The Novel ◽  
X Ray ◽  
State Ionic

We synthesized the novel adduct-type organic ionic crystal [C3mim][SCN·B(C6F5)3] (1) by the reaction of 1–methyl–3–propylimidazolium thiocyanate ([C3mim][SCN]), which is a room temperature ionic liquid, and B(C6F5)3, a bulky Lewis acid. The formation of a coordinative B–N bond between the SCN anion and the B(C6F5)3 in 1 was revealed by single-crystal X-ray diffractometry. We showed that 1 displays ionic conductivity in the crystalline state and that doping 1 with sodium thiocyanate and B(C6F5)3 results in a dramatic increase in ionic conductivity compared to that of 1.

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