Organomercury Compounds. 32. Syntheses of Fluorophenylmercurials by Decarboxylation

The organomercury compounds HgR₂ (R = 2-Cl,6-FC₆H₃, 2,6-F₂C₆H₃, 2,3,6-F₃C₆H₂, m-HC₆F₄, p-HC₆F₄, or C₆F₅) and RHg(O₂CR) (R = 2-Cl,6-C₆H₃, 2,6-F₂C₆H₃ or 2,3,6-F₃C₆H₂) have been obtained in moderate – good and low yields respectively from decarboxylation reactions of the corresponding mercury(II) fluorobenzoates in boiling pyridine. By contrast, mercury(II) 2,3,4-5-tetrafluorobenzoate gave a low yield of CO₂, a trace of Hg(o-HC₆F₄)₂ and a very low yield of o-HC₆F₄Hg(O₂CC₆F₄H-o). The ¹⁹⁹Hg NMR spectra of the diorganomercurials (R = 2-Cl,6-FC₆H₃, 2,6-F₂C₆H₃, 2,3,6-F₃C₆H₂, 2,4,6-F₃C₆H₂, 2,6-Cl₂C₆H₃, o-HC₆F₄, m-HC₆F₄, p-HC₆F₄ or C₆F₅) are discussed.     

Pseudochalkogenverbindungen. XXIV. Cyanamido-trimetaphosphimate

Pseudochalcogeno Compounds. XXIV. Cyanamido Trimetaphosphimates Synthesis and properties of sodium cyanamido trimetaphosphimates Na₃[P₃(NH)₃O_6?n(NCN)_n] (n:2,4) are reported. This compounds may be obtained by cautious hydrolysis of the corresponding hydrocyanamido-chloro-trimetaphosphimates, P₃N₃Cl_6?n(NHCN)_n. For sodium trimetaphosphimate, Na₃[P₃(NH)₃O₆] a simple, modified synthetic route is described. Possibilities of the formation of pseudochalcogeno-trimetaphosphimates of the type [P₃(NH) ₃O_6?n{C(CN)₂}_n]^3? (n = 2, 4) are discussed.     

Novel Copolymers of Styrene. 15. Phenoxy Ring-Substituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Electrophilic trisubstituted ethylenes, phenoxy ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂CH₃, where R is 4-(4-BrC₆H₅O), 2-(4-ClC₆H₅O), 3-(4-ClC₆H₅O), 4-(3-ClC₆H₅O), 4-(4-ClC₆H₅O), 4-(4-FC₆H₅O), 2-(3-CH₃OC₆H₅O), 2-(4-CH₃OC₆H₅O), 3-(4-CH₃OC₆H₅O), 4-(4-CH₃OC₆H₅O), 3-(4-CH₃C₆H₅O) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of phenoxy ring-substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r₁) for the monomers is 4-(4-CH₃OC₆H₅O) (6.07) > 3-(4-ClC₆H₅O) (3.38) > 3-(4-CH₃OC₆H₅O) (2.78) > 4-(3-ClC₆H₅O) (2.77) > 2-(4-ClC₆H₅O) (2.29) > 3-(4-CH₃C₆H₅O) (1.98) > 4-(4-FC₆H₅O) (1.92) > 4-(4-ClC₆H₅O) (1.89) > 2-(3-CH₃OC₆H₅O) (1.39) > 2-(4-CH₃OC₆H₅O) (0.90) > 4-(4-BrC₆H₅O) (0.77). Relatively high T_g of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (2.5-8.0% wt), which then decomposed in the 500-800°C range.     

Novel Copolymers of 4-Fluorostyrene. 10. Some Ring-substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₂CH=C(CN)₂ (where R is 4-C₆H₅O, 2-C₆H₅CH₂O, 3,4-(C₆H₅CH₂O)₂, 2-C₆H₅CH₂O-3-CH₃O, 3-C₆H₅CH₂O-4-CH₃O, 2-Cl-6-NO₂, 4-Cl-3-NO₂, 5-Cl-2-NO₂) and 4-fluorostyrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r ₁) for the monomers is 3,4-(C₆H₅CH₂O)₂(31.0) > 2-C₆H₅CH₂O-3-CH₃O (24.8) > 3-C₆H₅CH₂O-4-CH₃O (15.2) > 4-C₆H₅O (3.1) > 4-Cl-3-NO₂ (1.9) > 2-Cl-6-NO₂ (1.6) > 5-Cl-2-NO₂ (1.5) > 2-C₆H₅CH₂O (1.4). High T_g of the copolymers, in comparison with that of poly(4-fluorostyrene) indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 270-400°C range with residue, which then decomposition in 400–800°C range.     

Aminophosphane. XI. Einige Reaktionen des N-Diphenylphosphino-triphenyl-phosphazens

N-Diphenylphosphino-triphenylphosphazene possesses a highly reactive (C₆H₅)₂P group. At room temperature CH₃J adds to give (C₆H₅)₃P?N?P(C₆H₅)₂CH ₃J whilst phenylbromide did not react under similar conditions. The phosphorous halides (C₆H₅)₂PX(X = Cl, Br)add in a 1:1 mole ratio to yield (C₆H₅)₃P?N?P(C₆H₅)₂? PC₆H₅)₂X; this addition is also the preferred reaction with C₆H₅PCl₂, but PCl₃ is in part dehalogenated by (C₆H₅)₃P?N? P(C₆H₅)₂, and PSCl₃ desulfurized. The chalcogens O, S, Se, Te readily add to the P(III) atom of the base and this is also the case with BH₃. CS₂ forms the betaine (C₆H₅)₃ · · P?N? P(C₆H₅)₂? C(S)S. The IR and NMR spectra of the new compounds are discussed.     

Cationic Copolymerization of Propylene Oxide with Tetrahydrofuran. XI. Calculation of Individual Rate Constants

Rate constants (k₁ k₁₁, k₁₂, k₂₂, k₂₁ and k_t) for various steps involved in the copolymerization of propylene oxide (PO) with tetrahydrofuran (THF) have been calculated from reaction rate data obtained with the following catalyst system: (a) triphenyl-methyl cations ((C₆H₅)₃C⁺) associated with hexafluorophosphate (PF₆ ^?), hexafluoroarsenate (AsF₆ ^?) and hexafluoroantimonate (SbF₆ ^?) gegenions; (b) antimony pentachloride (SbCl₅); and, (c) boron trifluoride etherate, BF₃:(C₂H₅)₂O. The latter two systems were studied in the presence of cocatalysts. The effects of several parameters (the cocatalyst concentration and bulk size, the nature of the solvent, and the reaction temperature) on the rate constants are highlighted. The role of entropy in the initiation, propagation and termination steps is discussed in terms of solvation and desolvation processes. Based on termination activation energy considerations, the order of stability for the gegenions used in the copolymerization of PO with THF was found to be: AsF₆ ^? > SbF₆ ^? > HOBF₃ ^?PF₆ ^? > SbCl₆ ^?     

Front Cover: Reactivity of a Free Aluminylene towards Boron Lewis Acids: Accessing Aluminum-Boron-Bonded Species (Eur. J. Inorg. Chem. 25/2023)

The reactivity of the free aluminylene [N]-Al ( 1 ) ([N]=1,8-bis(3,5-di-tert-butylphenyl)-3,6-di-tert-butylcarbazolyl) towards boron Lewis acids is investigated. A facile oxidative addition reaction of 1 with Ph₂BOBPh₂ furnishes an exceedingly scarce example of the free alumaborane [N]-Al(BPh₂)(OBPh₂) ( 2 ) with an Al−B electron-sharing bond. By contrast, complexation of 1 with B(C₆F₅)₃ and HB(C₆F₅)₂ gives rise to the corresponding Lewis adducts [N]-Al→B(C₆F₅)₃ ( 3 ) and [N]-Al→BH(C₆F₅)₂ ( 4 ), respectively, with an Al→B dative bond. Crystallization of 4 in Et₂O produces the adduct [N]-Al(Et₂O)→BH(C₆F₅)₂ ( 5 ). Quantum chemical calculations are carried out to understand the formation of 2 as well as the bonding situation of 3 and 5 .     

Organoruthenaborane Chemistry. X. The SM2-catalysed formation of [ l-(η6-C6Me6)-isocloso-RuB9H9], and some B-phenylamino derivatives. NMR and X-ray diffraction studies

The action of SMe₂ on the ten-vertex nido-ruthenaborane [6-(η⁶-C₆Me₆)RuB₉H_l3] ( 1 ) provides a high-yield route to the unsubstituted isocloso-ruthenaborane [1-(η⁶-C₆Me₆)RuB₉H₉] (2). The benzene analogue [1-(η⁶-C₆Me₆)RuB₉H₉] is prepared similarly. By contrast, reaction of (1) with PhNH₂ gives a variety of B-phenylamino isocloso derivatives, including orange crystals of [1-(η⁶-C₆Me₆)-2-(PhNH)-isocloso-1-RuB 9 H₈] ( 3 ), red-orange [1-(η⁶-C₆Me₆)-2,3-(PhNH)₂-isocloso-1-RuB₉H₇] ( 4 ) and dark-red [1-(η⁶-C₆Me₆)-5,6,7-(PhNH)₃-isocloso-1-RuB₉H₆] ( 5 ). Detailed ¹H and ¹¹B nmr properties of these various compounds are described. The structure of ( 3 ) has been established by a single-crystal X-ray diffraction study of the solvate [1-(η⁶-C₆Me₆)-2-(PhNH)-isocloso-1-RuB₉H₈] · 1/2 CH₂Cl₂; the crystals were monoclinic, space group C2/c, with a = 1895.1(3), b = 1556.6(3), c = 1716.4(3) pm, β = 104.37(1)° and z = 8.     

Antimon-organo-Verbindungen. V. Zum Reaktionsverhalten des Phenylstibins

Organoantimony Compounds. V. The Reactivity of Phenyl Stibine C₆H₅SbH₂, synthesized by the reduction of C₆H₅SbCl₂ with LiBH₄, reacts with LiR under certain conditions forming (C₆H₅Sb)_n and H₂ or give by a partially elimination of H₂ stibides with a different structure. The latter react with alkyl and aryl halides forming tert. stibines which may be characterized as the corresponding dibromides. The preparation of C₆H₅SbNa₂ and its reaction with C₂H₅Br, Cl(CH₂)₄Cl and C₆H₅(Cl)C?N? N?C(Cl)C₆H₅ are described.     

Boron-nitrogen compounds. 94. Reactions of Dimethylaminoboranes with Pyrazole

Depending on the reaction conditions, the interaction of tris(dimethylamino)borane with pyrazole (Hpz) yields (CH₃)₂HNBpz₃ (III) or the pyrazaboles B₂pz₄[N(CH₃)₂]₂ (IV, cis and trans isomer), B₂pz₅N(CH₃)₂ (Va), or B₂pz₆. There is evidence that the reactions proceed via the extremely short-lived [(CH₃)₂N]₂ Bpz and, in particular, monomeric (CH₃)₂NBpz₂; the latter species can be identified in the mass spectrometer. In the system bis(dimethylamino)phenylborane/pyrazole the species (CH₃)₂HNB(C₆H₅)pz₂ and the pyrazabole B₂pz₃(C₆H₅)₂N(CH₃)₂ (VII, cis and trans isomer) were obtained. Also, some data on the pyrazabole B₂pz₂(C₆H₅)₂[N(CH₃)₂]₂ were collected although the compound could not be isolated in the pure state. The existence of the monomer (CH₃)₂NB(C₆H₅)pz could be established.     

The glycosides of Marsdenia erecta R. Br. I. Isolation, glycoside and aglycone. 325

Dried leaves of Marsdenia erecta R. Br. gave over 6% of a crude glycoside mixture, the main portion of which consisted of weakly polar material, soluble in ether or chloroform. By mild acid hydrolysis it yielded crude sugars and aglycones. The following four crist. sugars were isolated: D -cymarose, D -oleandrose and two bioses: pachybiose and marsectobiose (C₁₄H₂₄O₈, new). By PC. and TLC. the presence of digitoxose, canarose, thevetose and 3-O-methyl-6-deoxyallose could be demonstrated. The crude acyl-genin mixture contained β-sitosteryl-β-D -glucopyranoside and three highly hydroxylated pregnane derivatives: drevogenin-P, 17 β-marsdenin (C₂₁H₃₂O₆, new) and marsectohexol (C₂₁H₃₄O₆, new), all partly esterified with acetic, tiglic and benzoic acid. Five crist. acyl-genins (A1–A5) were isolated by chromatography, but most of them still were mixtures. After alkaline hydrolysis of the crude acyl-genins 6 acyl-free compounds were obtained. 4 of them were identical with the above mentioned substances, the other two: 17-iso-drevogenin-P and marsdenin (17 α-marsdenin) are formed from drevogenin-P and 17 β-marsdenin by isomerisation.     

Komplexchemie polyfunktioneller Liganden. XLVl. trans-Bis(methyldiphenylphosphin)-tetracarbonyl-chrom

Complex Chemistry of Polyfunctional Ligands. XLVI. trans-Bis(methyldiphenylphosphine) Tetracarbonyl Chromium The complex trans-Cr(CO)₄[CH₃P(C₆H₅)₂]₂ was produced photochemically from Cr(CO)₆ and CH₃P(C₆H₅)₂ in THF. Composition and geometric structure has been deduced from elemental analysis, mass, ¹³C-NMR, IR, FIR and Raman spectra.     

A 13C-NMR. Study of naphthalene chromium complexes. Correlation with reactivity: Nucleophilic aromatic substitution reactions

The ¹³C-NMR. spectra of the series of complexes η⁶-naphthalene · CrL₃ (L? CO ( 1 ), PF₃ ( 2 ), PF₂OMe ( 6 ), P(OMe)₃ ( 3 ), C₁₀H₈ (= 3 L) ( 4 ) and PMe₃ ( 5 )) are reported. Definite assignments of the ¹³C-NMR. resonances were made through the synthesis of [2, 3, 6, 7-²H₄]-naphthalene complexes. The coordinated ring ¹³C-resonance are found to undergo a smooth transition to higher field with increasing donor character of the coligands L. A correlation of the coordination shifts with the reactivity of the coordinated naphthalene is proposed. In complexes containing strong acceptor ligands the naphthalene is activated to attack by nucleophiles. Sequential treatment of complexes 1–4 , 6 and [C₁₀H₈FeC₅H₅]⁺[PF₆]^? ( 7 ) with stabilized carbanions and I₂ or Ce(IV)-salt yields α-substituted naphthalenes in the case of 1 , 2 , 6 and 7 but not in the case of 3 and 4 . Treatment of 3 with an excess of HBF₄ results not in the expected metal protonation but in a novel ligand transformation to yield 6 .     

Reactions of perfluoronitriles. III. Interactions with diphenylphosphine

Reaction of perfluoro-n-octanonitrile with diphenylphosphine gave two products: a primary adduct, C₇F₁₅C(NH)P(C₆H₅)₂, and the reduced adduct, C₇F₁₅CH(NH₂)P(C₆H₅)₂. Presence of water prevented the formation of the reduced compound; the latter was not produced by reduction of the primary adduct. Operative mechanisms are postulated; infrared and mass spectra are discussed.     

Novel Copolymers of Styrene. 4. Halophenoxy Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel electrophilic trisubstituted ethylenes, halophenoxy ring substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₄CH?C(CN)CONH₂,where R is 4-(4-bromophenoxy), 2-(4-chlorophenoxy), 3-(4-chlorophenoxy), 4-(3-chlorophenoxy), 4-(4-chlorophenoxy), and 4-(4-fluorophenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution in the presence of a radical initiator, AIBN at 70°C. The compositions of the copolymers were calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. Thus, the order of relative reactivity (1/r₁) is 4-(4-ClC₆H₄O) (2.01) > 4-(4-FC₆H₄O) (0.89) > 4-(4-BrC₆H₄O) (0.73) > 3-(4-ClC₆H₄O) (0.65) > 2-(4-ClC₆H₄O) (0.24) > 4-(3-ClC₆H₄O) (0.22). High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (10.4–15.0 wt%), which then decomposed in the 500-800°C range.     

Antimon-organo-Verbindungen. VI. Kristallines „Phenylantimon”︁ Bildung und Spaltung mit Natrium bzw. Lithiumbutyl

Organoantimony Compounds. VI. Crystalline Phenyl Antimony. Formation and Cleavage with Sodium and Lithium Butyl, respectively Reactions of C₆H₅SbH₂ with C₆H₅CH ? CH₂, C₆H₅C ? CH and other unsaturated compounds give the corresponding hydrogenated system and phenyl antimony as orange-red crystals and the formula (C₆H₅Sb)₆ · 1 C₆H₆ 1.1 reacts with sodium by cleavage of Sb–Sb bonds forming C₆H₅SbNa₂ and C₆H₅(Na)Sb–Sb(Na)C₆H₅. These stibides are suitable materials to prepare tert. stibines, distibines and cyclic stibines. The cleavage of 1 with butyllithium is a complicated reaction and gives beside other stibides also C₆H₅(C₄H₉)SbLi which can be characterized as (CH₃)₃Si–Sb(C₄H₉)C₆H₅. The ¹H-nmr data of the prepared stibines are discussed.     

The adamantane rearrangement of 1,2-trimethylenenorbornanes. Part IV. Hydride-ion abstraction in 1,2-exo-trimethylenenorbornane

In the AlBr₃-catalyzed adamantane rearrangement in CS₂ of 1,2-exo-trimethylenenorbornane ( 1 ) to 2-endo,6-endo-trimethylenenorbornane ( 3 ), hydride-ion abstraction occurs at C(6) from the exo-side. The k_H/k_D value for competition between 1 and 5 (D_exo-C(6)) was 1.58 ± 0.05, whereas no kinetic isotope effect was operative for competition between unlabeled 1 and 4 (D_endo-C(5)) and between 1 and 6 (D_endo-C(6)).     

Novel Copolymers of Styrene. 3. Some Ring-Substituted Butyl 2-Cyano-3-Phenyl-2-Propenoates

Novel trisubstituted ethylenes, ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂C₄H₉ (where R is 2-C₆H₅CH₂O, 3-C₆H₅CH₂O, 4-C₆H₅CH₂O, 4-CH₃COO, 3-CH₃CO, 4-CH₃CO, 4-CH₃CONH, 2-CN, 3-CN, 4-CN, 4-(CH₃)₂N, 4-(C₂H₅)₂N) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r₁) for the monomers is 4-C₆H₅CH₂O (6.39) > 2-C₆H₅CH₂O (2.06) > 3-CH₃CO (1.86) > 3-C₆H₅CH₂O (1.78) > 4-CH₃COO (1.58) > 3-CN (1.47) > 4-CN (1.21) > 4-(C₂H₅)₂N (1.19) > 4-(CH₃)₂N (1.18) > 2-CN (1.04) > 4-CH₃CO (0.71) > 4-CH₃CONH (0.63). Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3.6–9.5% wt), which then decomposed in the 500–800°C range.     

Homoatomic Rings,Chains and Macromolecules of Main Group Elements : edited by A.L. Rheingold. Elsevier Scientific Publishing Co., Amsterdam - Oxford - New York, 1977, xvi + 616 pages,Dfl. 195.00; U.S. $79.95.

Nucleophilic substitution is correlated with the frontier electron density parameter, the partial valence-inactive population (P^LUMO_A) for two series of polyene-M(CO)₃ complexes, AM(CO)₃ (A = C₆H₆Cr, C₅H₅Mn, C₄H₄Fe, C₃H₅Co and C₂H₄Ni) and [BFe(CO)₃]⁺ (B = C₅H₅, C₆H₇ and C₇H₉). In both series nucleophilic substitution by an S_N2 process is shown as probably occurring by initial attack at the metal atom.     

Activity and Osmotic Coefficients from the Emf of Liquid Membrane Cells. VIII. K.3[Co(CN)6], Mg3[Co(CN)6]2, and Ca3[Co(CN)6]2

The activity coefficients of K₃[Co(CN)₆], Mg₃[Co(CN)₆]₂, and Ca₃[Co(CN)₆]₂,are examined. The results highlight close similarity with the correspondinghexacyanoferrate (III) salts. On dilution, K₃[Co(CN)₆], like K₃[Fe(CN)₆], approachesthe limiting law from the upper side, while Mg₃[Co(CN)₆]₂ and Ca₃[Co(CN)₆]₂tend to the limiting law from the opposite side, like Mg₃[Fe(CN)₆]₂,Ca₃[Fe(CN)₆]₂, Sr₃[Fe(CN)₆]₂, and Ba₃[Fe(CN)₆]₂. Both kinds of behavior agreewith theory for a model of hard spheres bearing electric charges +1 and –3 or+2 and –3, respectively. The paramater values of the Pitzer equation for activityand osmotic coefficients are reported.