Reactions of oxalyl fluoride with electrophiles

The reactions of oxalyl fluoride with electrophiles in the presence of alkali metal fluoride were carried out. In the reaction with CF₃CH₂OTf (Tf=CF₃SO₂) or CH₃CH₂OTf, the synthesis of di-ether (ROCF₂CF₂OR) and mono-ether (ROCF₂COF) was achieved. The difference of the reactivities between these two compounds was discussed from the result of DFT calculations.     

The reactions of bisamides with oxalyl chloride

Alkylidenebisamides and alkylidenebiscarbamates were found to react with oxalyl chloride to give oxazolidinediones ( 2 ), a diazepinedione ( 3 ) or fragmentation products depending on the nature of the substituents (R' in formula 1 ).     

The reaction of carboxamidines with oxalyl chloride

The action of oxalyl chloride on amidines has given imidazoline-4,5-dione hydrochlorides. The reactions of the imidazoline-4,5-diones and their hydrochlorides with water, alcohols, and amines have been studied. In these reactions the imidazoline ring readily opens with the formation of derivatives of oxaminic acid.For Communication II, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 814–818, June, 1970.     

Reactions of amidines with oxalyl chloride. II

Unsubstituted, N-alkyl(aryl)- and N-chloroamidines react with oxalyl chloride to form imidazolidine-4, 5-diones. The hydrochlorides of 1-aryl-2-alkyl(aryl)imidazolidine-4, 5-diones decompose thermally to give N-arylimidoyl isocyanates which change immediately to 4-quinazolones.     

Reaction of substituted 5-aminopyrimidines with oxalyl chloride

Depending on the reaction conditions and the substituents, N-(2,4,6-substituted 5-pyrimidinyl)oxamyl chlorides and N,N-di(2,4,6-substituted 5-pyrimidinyl)oxamides are formed in the reaction of 5-aminopyrimidines with oxalyl chloride.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 536–538, April, 1976.     

Reactions of oxalyl chloride with 1,2-cycloalkanediols in the presence of triethylamine

The relationship between the product patterns and the configurations of 1,2-cycloheptane- and 1,2-cyclooctanediols 9 in the cyclocondensations with oxalyl chloride in the presence of triethylamine at 0 degrees C has been shown analogous to that obtained for 1,2-disubstituted acyclic ethylene glycols 1: cis-1,2-cyclooctanediol (9f) produced the cyclic oxalate 14f as the major product, while trans-1,2-cycloheptanediol (9e) and trans-1,2-cyclooctanediol (9g) formed the cyclic carbonates 12e, g as the major products. On the other hand, the cyclic oxalates 14a-d were formed as the major products from 1,2-cyclopentane- and 1,2-cyclohexanediols regardless of the configuration. These results can be accounted for by assuming the boat-like transition states for cyclizations of the half esters of comparatively rigid five- and six-membered diols 9a--d. The cyclic oxalates 14a, c may be directly formed through the resulting tetrahedral intermediates from cis-diols (9a,c), and the cyclic carbonates 12a,c as the minor products after ring inversion of the tetrahedral intermediates. The tetrahedral intermediates from the trans-isomers 9b, d cannot undergo ring inversion, producing no traces of the cyclic carbonates 12b, d.     

Dichlorination of olefins with diphenyl sulfoxide/oxalyl chloride

Abstract

The combination of diphenyl sulfoxide and oxalyl chloride was used to accomplish the dichlorination of olefins, in which chlorodiphenylsulfonium salt generated in situ was proposed to be the real active species as a chloronium ion source.     

Reaction of enamines of the isocholine and phenanthridine series with oxalyl chloride

Compounds of the 2,3-dioxopyrrolo[2, 1-a]isoquinoline and 2,3-dioxopyrrolo[1, 2-f]phenanthridine series were synthesized and the products of their condensation with o-phenylenediamine were obtained.Institute of Applied Chemistry, Ural Branch, Russian Academy of Sciences, Perm' 614600. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 946–949, July, 1994. Original submitted January 10, 1994.     

Chemistry of oxalyl derivatives of methyl ketones

It was established by IR, UV, and PMR spectroscopy that 2-phenacylidenebenzo-1,4-thiazin-3-ones are formed in the reaction of o-aminothiophenol with aroylpyruvic acids or 5-arylfuran-2,3-diones. 2-Carbomethoxy-2-phenacyl-1,3-benzothiazolines were isolated in the reaction of o-aminothiophenol with aroylpyruvic acid esters.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 755–757, June, 1977.     

Reaction of 5-substituted 4,6-dichloro-2-aminopyrimidines with oxalyl chloride

The reaction of 5-substituted 4,6-dichloro-2-aminopyrimidines with oxalyl chloride gives 2-isocyanatopyrimidines, the structures of which were proved by chemical means and the IR, PMR, and ³⁵Cl nuclear quadrupole resonance spectra. The intermediate pyrimidinyloxamic acid chlorides were not isolated; this is evidently explained by the low basicities of 2-amino-pyrimidines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1248–1251, September, 1977.     

The oxysulfenylation of alkenes with dimethyl sulfoxide/oxalyl chloride

A convenient method for the oxysulfenylation of alkenes using dimethyl sulfoxide/oxalyl chloride is described. Cycloalkenes give trans-adducts stereospecifically. The reactions of styrene are highly regioselective for Markovnikov adducts, whereas aliphatic alkenes lead to anti-Markovnikov adducts mainly.     

Reaction of oxalyl and malonyl chloride with 1,1-dimethyl-2-substituted hydrazides

Recently we reported the reaction of 1,1-dimethyl-4-substituted semicarbazides with phosgene to occur with formation of several new heterocyclic ring systems. Here we report the reaction of several semicarbazides, thiosemicarbazides and related acyl substituted hydrazides with oxalyl chloride and malonyl chloride. These reactions occur with the formation of heterocyclic products which are oxadiazolinones, imidazolidinetriones, 2-thioxoimidazolindine-4,5-diones, and 2-thioxo-1,3-diazine-4,6-diones (2-thioxopyrimidine-4,6-diones).     

Observation of dihalide elimination upon electron attachment to oxalyl chloride and oxalyl bromide, 300-550 K

Rate coefficients have been measured for electron attachment to oxalyl chloride [ClC(O)C(O)Cl] and oxalyl bromide [BrC(O)C(O)Br] in He gas at 133 Pa pressure over the temperature range of 300-550 K. With oxalyl chloride, the major ion product of attachment is Cl2(-) at all temperatures (66% at 300 K); its importance increases slightly as temperature increases. Two other product ions formed are Cl- (18% at 300 K) and the phosgene anion CCl2O- (16% at 300 K) and appear to arise from a common mechanism. With oxalyl bromide, the Br2(-) channel represents almost half of the ion product of attachment, independent of temperature. Br- accounts for the remainder. For oxalyl chloride, the attachment rate coefficient is small [(1.8 +/- 0.5) x 10(-8) cm3 s(-1) at 300 K], and increases with temperature. The attachment rate coefficient for oxalyl bromide [(1.3 +/- 0.4) x 10(-7) cm3 s(-1) at 300 K] is nearly collisional and increases only slightly with temperature. Stable parent anions C2Cl2O2(-) and C2Br2O2(-) and adduct anions Cl- (C2Cl2O2) and Br- (C2Br3O2) were observed but are not primary attachment products. G2 and G3 theories were applied to determine geometries of products and energetics of the electron attachment and ion-molecule reactions studied. Electron attachment to both oxalyl halide molecules leads to a shorter C-C bond and longer C-Cl bond in the anions formed. Trans and gauche conformers of the neutral and anionic oxalyl halide species have similar energies and are more stable than the cis conformer, which lies 100-200 meV higher in energy. For C2Cl2O2, C2Cl2O2(-), and C2Br2O2(-), the trans conformer is the most stable conformation. The calculations are ambiguous as to the oxalyl bromide geometry (trans or gauche), the result depending on the theoretical method and basis set. The cis conformers for C2Cl2O2 and C2Br2O2 are transition states. In contrast, the cis conformers of the anionic oxalyl halide molecules are stable, lying 131 meV above trans-C2Cl2O2(-) and 179 meV above trans-C2Br2O2(-). Chien et al. [J. Phys. Chem. A 103, 7918 (1999)] and Kim et al. [J. Chem. Phys. 122, 234313 (2005)] found that the potential energy surface for rotation about the C-C bond in C2Cl2O2 is "extremely flat." Our computational data indicate that the analogous torsional surfaces for C2Br2O2, C2Cl2O2(-), and C2Br2O2(-) are similarly flat. The electron affinity of oxalyl chloride, oxalyl bromide, and phosgene were calculated to be 1.91 eV (G3), and 2.00 eV (G2), and 1.17 eV (G3), respectively.     

The synthesis of macrocyclic ether-esters,thioether-esters,and ether-thiolesters with the oxalyl moiety

A new series of macrocyclic polyether-diesler compounds ( 3-12 ) have been prepared by treating various oligoethylene glyeols or mercaplans with oxalyl chloride. The compounds prepared were: 1,4,7,10,13-pentaoxacyclopentadecane-2,3-dione ( 3 ), 1,4,7,1 3-tetraoxa-10-thiacyclopenta-decane-2,3-dione ( 4 ), 1,4,10-lrioxa-7,13-dithiacyclopenladecane-2,3-dione ( 5 ), 1,4,7,10,13,16-hexaoxacyclooctadecane-2,3-dione ( 6 ), 1,4,7,10,13, 16-hexaoxacyclooctadecane-2,3,11,12-tetra-one ( 7 ), 1,4,10,13-tetraoxa-7,16-dithiacyclooctadecane-2,3,11,12-tetraone ( 8 ), 7,16-dioxa-1,4, 10,13-letralhiacyclooctadecane-2,3,11,12-tctraone ( 9 ), 1,4,7,10,13,16-hexathiacyclooctadecane-2,3,11,12-tetraone ( 10 ), 1,4,7,10,13,16,19-heptaoxacyclohencicosane-2,3-dione (11), and 1,4,7, 10,13,16,19,22-octaoxacyclolelracosane-2,3,14,15-letraone ( 12 ).     

CuCl-catalyzed reaction of zirconacyclopentenes with oxalyl chloride: a new pathway for the preparation of cyclopentenones

Zirconacyclopentenes, which are easily prepared from alkynes and EtMgBr (or ethylene) and Cp₂ZrCl₂, reacted with oxalyl chloride in the presence of catalytic amount of CuCl to give cyclopentenones in high yields. The reaction was performed conveniently in one pot from alkynes, EtMgBr, oxalyl chloride, and Cp₂ZrCl₂.     

Abundant polymorphism in a system with multiple hydrogen-bonding opportunities: oxalyl dihydrazide

To date, only one crystal structure has been reported in the literature for oxalyl dihydrazide [H(2)N.NH.CO.CO.NH.NH(2)]. In the present paper, we report the discovery of four new polymorphs of oxalyl dihydrazide, obtained by crystallization from solution under different conditions, including the use of different crystallization solvents. All polymorphs have the trans-trans-trans conformation of the N-N-C-C-N-N backbone, but the positions of the hydrogen atoms of the NH(2) groups relative to this backbone differ between the different polymorphs through variation of the torsion angle around each NH-NH(2) bond. The different polymorphs display a range of different hydrogen-bonding arrangements, constructed from different types of hydrogen-bonded array. The existence of several different potential hydrogen-bond donor and hydrogen-bond acceptor groups in the oxalyl dihydrazide molecule, together with the fact that the N-H bonds of the NH(2) groups adopt different orientations with respect to the molecular plane, leads to several possible geometric permutations for hydrogen-bonding arrangements in the solid state. It would not be surprising if even more polymorphs of oxalyl dihydrazide are discovered in the future.