Synthesis and some heterocyclization reactions of new diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate and ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate

A new CF₂X-analogue of 1,1-bis(trifluoromethyl)-2,2-dicyanoethylene (X = P(O)(OEt)₂), diethyl (1,1-difluoro-3,3-dicyano-2-trifluoromethylallyl)phosphonate, has been synthesized from diethoxyphosphoryl pentafluoroacetone 1. A similar phosphoryl analogue of ethyl 3,3-dicyano-2-trifluoromethylacrylate, ethyl 3,3-dicyano-2-[(diethoxyphosphoryl)difluoromethyl]acrylate, has been obtained from ethyl 3-(diethoxyphosphoryl)-3,3-difluoro-2-oxopropionate 2. By heterocyclization of these new ethylenes with 3-methyl-2-pyrazoline-5-ones, 3(5)-aminopyrazoles, dimedone, 2-aminopyridines, 1-aryl-3-methyl-5-aminopyrazoles, 1,3,3-trimethylisoquinolines, as well as by condensation with anilines and ketones, the difluoromethylphosphonate-substituted derivatives of 1,4-dihydropyrano[2,3-c]pyrazole, 4,5-dihydropyrazolo[1,5-a]pyrimidine, 5,6,7,8-tetrahydro-4H-chromene, 2H-pyrido[1,2-a]pyrimidine, 4,7-dihydro-1H-pyrazolo[3,4-b]pyridine, 1,4-dihydropyridine, 4,5,6,7-tetrahydro-1H-[1]pyrindine, 1,4,5,6,7,8-hexahydroquinoline, and 6,7-dihydro-2H-pyrido[2,1-a]isoquinoline have been obtained in one stage.     

Synthesis and some heterocyclisation reactions of CF2H- and CF2Cl-substituted 1,1-dicyanoethylenes

New CF₂X-analogues of 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene (1) (X=H, Cl) were synthesised by the condensation of polyfluoroketones with malononitrile followed by dehydration using thionyl chloride (or phosphorus pentoxide). The heterocyclisation reactions of new CF₂X-analogues of 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene with amidines, 5-aminopyrazoles and 3-methyl-2-pyrazolin-5-ones were systematically investigated.     

Investigation of reactions of the organozinc reagents prepared from zinc and dialkyl dibromomalonates with the derivatives of 2-arylmethyleneindan-1,3-dione and 5-arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-dione

Organozinc compounds prepared from dialkyl dibromomalonates and zinc react with 2-arylmethyl-eneindan-4,6-diones, 5-arylmethylene-2,2-dimethyl-1,3-dioxane-4,6-diones, as well as with 2-[4-(1,3-dioxoindan-2-ylidenemethyl)phenyl]methyleneindan-1,3-dione and 5-[4-(2,2-dimethyl-4,6-dioxo-1,3-dioxane-2-ylidenemethyl)phenyl]methylene-2,2-dimethyl-1,3-dioxane-4,6-diones to form dialkyl 3-aryl-1′3′-dioxaspiro(cyclopropane-2,2′-indan)-1,1-dicarboxylates, dimethyl 3-aryl-6,6-dimethyl-5,7-dioxa-4,8-dioxaspiro[2,5]octan-2,2-dicarboxylates, dialkyl 2-{4-[3,3-bis (alkoxycarbonyl)-1′,3′-dioxaspiro(cyclopropane-2,2′-indan)-1-yl]phenyl}-1′,3′-dioxaspiro[cyclopropane-2,2′-indan]-1,1-dicarboxylates, and dialkyl 2-{4-[2,2-bis(alkoxycarbonyl)-6,6′-dimethyl-4,8-dioxo-5,7-dioxaspiro[2,5]oct-1-yl]phenyl}-6,6-dimethyl-4,8-dioxo-5,7-dioxaspiro[2,5]octan-1,1-dicarboxylate respectively.     

Reactions of polyfluorinated thietanes: Selective synthesis of 4-R-2,2-bis(trifluoromethyl)thietane-1-S-oxides and 2-substituted 5-fluoro-4-(trifluoromethyl)-2,3-dihydrothiophenes

Oxidation of 4-substituted 2,2-bis(trifluoromethyl)thietanes by m-chloroperoxybenzoic acid results in selective formation of the corresponding S-oxides in 65-86% yield. Oxidation of 4-C₂H₅S-2,2-bis(trifluoromethyl)thietane under mild conditions led to selective formation of 4-C₂H₅SO₂-2,2-bis(trifluoromethyl)thietane, which under more rigorous conditions was selectively converted into trans-4-C₂H₅SO₂-2,2-bis(trifluoromethyl)thietane-1-S-oxide. Reaction of 4-substituted 2,2-bis(trifluoromethyl)thietanes with activated aluminum powder results in a highly selective ring expansion process, producing the corresponding 5-fluoro-4-(trifluoromethyl)-2,3-dihydro-2-alkoxythiophenes in 58-93% yield. These compounds were also prepared in 61-85% yield using a “one-pot” procedure, starting from sulfur, hexafluoropropene and the corresponding vinyl ether without isolation of any intermediates. Both 2-i-C₃H₇O- and 2-t-C₄H₉O- 5-fluoro-4-(trifluoromethyl)-2,3-dihydrothiophenes were converted into 2-fluoro-3-trifluormethylthiophene by reaction with P₂O₅.     

Nucleophilic trifluoromethylation of RF-containing 4-quinolones, 8-aza- and 1-thiochromones with (trifluoromethyl)trimethylsilane

Reactions of N-substituted 2-polyfluoroalkyl-4-quinolones and 8-aza-5,7-dimethyl-2-polyfluoroalkylchromones with (trifluoromethyl)trimethylsilane proceed mainly as a 1,4-nucleophilic trifluoromethylation to give N-substituted 2,2-bis(polyfluoroalkyl)-2,3-dihydroquinolin-4(1H)-ones and 5,7-dimethyl-2,2-bis(polyfluoroalkyl)-2,3-dihydro-4H-pyrano[2,3-b]pyridin-4-ones after acid hydrolysis. Similar reaction with 2-trifluoromethyl-4H-thiochromen-4-one proceeds as a 1,2-addition to give 2,4-bis(trifluoromethyl)-4H-thiochromen-4-yl trimethylsilyl ether.     

Remarkable effect of metal fluoride catalyst on reaction of hexafluoropropene, sulfur and vinyl ethers. Convenient synthesis of 2,2-bis(trifluoromethyl)-4-R-thietanes, 3,3-bis(trifluoromethyl)-5-R-1,2-dithiolanes and 2,2-bis(trifluoromethyl)-4-R-1,3-dithiolanes

It was demonstrated that the outcome of the reaction of hexafluoropropene, sulfur and vinyl ether strongly depends on the catalyst and reaction conditions. The reaction of HFP and S_x leading to the formation of 2,2,4,4-tetrakis(trifluoromethyl)-1,3-dithietane (1) when it is catalyzed by CsF, proceeds under milder conditions and is easier to control compared to KF catalyzed process. The order of addition of reagents plays a crucial role on the outcome of the reaction. For example, the addition of vinyl ether to pregenerated solution of 1 in DMF solvent results in slow reaction, leading to the corresponding 2,2-bis(trifluoromethyl)-4-R-thietanes in 8-91% yield, and it is catalyzed by either by KF or CsF. The addition of second mole of sulfur to the solution of 2,2-bis(trifluoromethyl)-4-R-thietanes in the presence MF catalyst leads to insertion of sulfur into thietane ring with the formation of the corresponding cyclic disulfides—3,3-bis(trifluoromethyl)-5-R-1,2-dithietanes. On the other hand, the addition of second mole of sulfur to the solution of 1 in DMF in the presence of CsF catalyst, followed by addition of vinyl ether results in exothermic reaction, and it produces the corresponding 2,2-bis(trifluoromethyl)-4-alkoxy-1,3-dithiolanes in good yield.It was also demonstrated that 2,2-bis(trifluoromethyl)-4-R-thietanes can undergo disproportionation under action of fluoride anion, producing a mixture of the corresponding 1,2-dithiolane and CF₂C(CF₃)CH₂CFHOR. The nucleophilic attack of fluoride anion in this case proceeds selectively on the carbon of the thietane ring, bearing alkoxy group.The structure of 2,2-bis(trifluoromethyl)-4-R-thietanes forming as the result of 2 + 2 cycloaddition reaction between hexafluorothioacetone generated “in situ” from dimer 1 and vinyl ether was firmly supported by single crystal X-ray diffraction data, obtained for thietane bearing t-BuO-group.     

Highly conjugated (polypyridyl)metal-(porphinato)zinc(II) compounds: long-lived, high oscillator strength, excited-state absorbers having exceptional spectral coverage of the near-infrared

Transient dynamical studies of ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)2+ bis-hexafluorophosphate (Ru-PZn), osmium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)2+ bis-hexafluorophosphate (Os-PZn), ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)2+ bis-hexafluorophosphate (Ru-PZn-A), osmium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)2+ bis-hexafluorophosphate (Os-PZn-A), and ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-ruthenium(II)-15-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-bis(2,2';6',2' '-terpyridine)4+ tetrakis-hexafluorophosphate (Ru-PZn-Ru), and ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-osmium(II)-15-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-bis(2,2';6',2' '-terpyridine) tetrakis-hexafluorophosphate (Ru-PZn-Os) show that these highly conjugated supermolecular chromophores feature electronically excited states that absorb over broad NIR spectral windows with considerable oscillator strength and manifest lifetimes (1-50 mus) that are extraordinarily long relative to those of classic low band-gap organic materials. The excited-state absorptive domains of these strongly coupled multipigment ensembles can be extensively modulated. For sequential one-photon absorptive processes, these compounds evince large sigmae, sigmae/sigmag, and sigmae - sigmag values. As the combination of all these properties within single chromophoric entities have heretofore lacked precedent within the NIR, these and closely related structures may find particular utility in a variety of technologically important optical-limiting applications.     

Bis(trifluoromethyl)-containing 1-azatricycloheptanes

6-Substituted 7-halo-3,3-bis(trifluoromethyl)-2-azabicyclo[2.2.1]heptanes were synthesized by the addition of water, alcohols, and acetic acid to 3-halo-7,7-bis(trifluoromethyl)-1-azatricyclo[2.2.1.0^2,6]heptanes in the presence of H₂SO₄. 5,6-Disubstituted 3,3-bis(trifluoromethyl)-2-azabicyclo[2.2.1]heptanes were prepared by oxymercuration of 3,3-bis(trifluoromethyl)-2-azabicyclo[2.2.1]hept-5-ene.     

5-Amino-3,3-bis(trifluomethyl)-1-phenyl-4-cyano-4-pyrazoline

Conclusions The reaction of phenylhydrazine with 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene leads to 5-amino-3,3-bis(trifluoromethyl)-1-phenyl-4-cyano-4-pyrazoline, whose structure was proven by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2417–2419, October, 1988.     

Unusual frequency dispersion effects of the nonlinear optical response in highly conjugated (polypyridyl)metal-(porphinato)zinc(II) chromophores

The syntheses and electrooptic properties of a new family of nonlinear optical chromophores are reported. These species feature an ethyne-elaborated, highly polarizable porphyrinic component and metal polypyridyl complexes that serve as integral donor and acceptor elements. Examples of this structural motif include ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)(2+) bis-hexafluorophosphate (Ru-PZn); osmium(II) [5-(4'-ethynyl-(2,2';6',2'-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2'-terpyridine)(2+) bis-hexafluorophosphate (Os-PZn); ruthenium(II) [5-(4'-ethynyl-(2,2';6',2'-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phen-yl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)(2+) bis-hexafluorophosphate (Ru-PZn-A); osmium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))-15-(4'-nitrophenyl)ethynyl-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2' '-terpyridine)(2+) bis-hexafluorophosphate (Os-PZn-A); and ruthenium(II) [5-(4'-ethynyl-(2,2';6',2' '-terpyridinyl))osmium(II)-15-(4'-ethynyl-(2,2';6',2'-terpyridinyl))-10,20-bis (2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-bis(2,2';6',2'-terpyridine)(4+) tetrakis-hexafluorophosphate (Ru-PZn-Os). The frequency dependence of the dynamic hyperpolarizability of these compounds was determined from hyperRayleigh light scattering (HRS) measurements carried out at fundamental incident irradiation wavelengths (lambda(inc)) of 800, 1064, and 1300 nm. These data show that (i) coupled oscillator photophysics and metal-mediated cross-coupling can be exploited to elaborate high beta(0) supermolecules that exhibit significant excited-state electronic communication between their respective pigment building blocks; (ii) high-stability metal polypyridyl compounds constitute an attractive alternative to electron releasing dialkyl- and diarylamino groups, the most commonly used donor moieties in a wide range of established nonlinear optical dyes; (iii) this design strategy enables ready elaboration of chromophores having extraordinarily large dynamic hyperpolarizabilities (beta(lambda) values) at telecommunication relevant wavelengths; and (iv) porphyrin B- and Q-state-derived static hyperpolarizabilities (beta(0) values) can be designed to have the same or opposite sign in these species, thus providing a new means to regulate the magnitude of lambda(inc)-specific dynamic hyperpolarizabilities.     

Mononuclear, five-coordinate lanthanide amido and aryloxide complexes bearing tetradentate (N2O2) Schiff bases

Two monomeric, five-coordinate lanthanide complexes, [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]samarium[2,6-bis(tert-butyl)-4-methylphenoxide] and [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]erbium[2,6-bis(tert-butyl)-4-methylphenoxide], were isolated from the reactions of 2,6-bis(tert-butyl)-4-methylphenol with [bis-5,5'-(1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]lanthanide[bis(trimethylsilyl)amido] (lanthanide = Er(3+) and Sm(3+)). The purified phenoxides were recovered in excellent yields and analytical purity, and the reactions proceeded cleanly without Schiff-base degradation or cluster formation. Analogously, [bis-3,3'-(1,3-propanediyldiimino)-1-phenyl-2-butene-1-onato]erbium[bis(trimethylsilyl)amido] was also directly converted to [bis-3,3'-(1,3-propanediyldiimino)-1-phenyl-2-butene-1-onato]erbium[2,6-bis(tert-butyl)-4-methylphenoxide]; however, a less sterically demanding alcohol (i.e., ethanol) yielded a neutral trinuclear oxo alkoxide species with each dianionic Schiff base asymmetrically bridging through micro-oxo interactions. In this polynuclear cluster, each symmetry-related, seven-coordinate erbium(III) ion exhibits monocapped trigonal prismatic geometry, which assembles by sharing triangular capped faces. Single-crystal X-ray diffraction revealed square-pyramidal metal coordination in each five-coordinate lanthanide ion with varied S(4) ruffling of the "square base" donor atoms and the six-membered propylene diamine chelate ring adopting the boat conformation. To contrast the effect of subtle ligand changes, we also report the synthesis and characterization of [bis-5,5'-(2,2-dimethyl-1,3-propanediyldiimino)-2,2-dimethyl-4-hexene-3-onato]samarium[bis(trimethylsilyl)amido], having gem-dimethyl substituents appended to the propylene bridge central carbon. The six-membered diamine chelate ring in this compound adopts the chair conformation without metal-hydrocarbon interaction. Also presented are qualitative activity observations and polymerization data for the polymerization of rac-lactide and epsilon-caprolactone using the five-coordinate lanthanide amidos and phenoxides.     

Reactivity of fluorinated sulfur-containing heterocycles towards nucleophilic and oxidizing reagents

The reaction of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene, 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene and 2,2-bis(trifluoromethyl)-3,6-dihydro-4,5-dimethyl-2H-thiopyran with i-C₃H₇MgCl leads to the formation of ring opening products as the result of nucleophilic attack of the Grignard reagent on the sulfur atom. According to DFT calculations the reactivity of the sulphur-containing substrate correlates with the strain energy of the heterocycle. The oxidation of 3-thia-4,4-bis(trifluoromethyl)tricyclo[5.2.1.0^2,5]non-7-ene by hydrogen peroxide in hexafluoro-iso-propanol solvent resulted in formation of the corresponding sulfoxide however, the reaction with m-chloroperoxybenzoic acid produced the product of exhaustive oxidation of sulfur and the double bond. In sharp contrast, the oxidation of 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.1]hept-2-ene and 5,5-bis(trifluoromethyl)-6-thia-bicyclo[2.2.2]oct-2-ene by MCPBA (2d, 25 °C) proceeds with the preservation of the double bond, leading to the selective formation of the corresponding sulfones.     

Novel perfluoroalkenylphosphonates and iodoperfluoroalkenes from 3,3 -bis (trifluoromethyl) -1,1,2,4,4,4-hexafluoro-1-butylene and nonafluoro-n-butoxy-1,1,2-trifluoroethylene

The reaction of 3,3-bis(trifluoromethyl)-1,1,2,4,4,4-hexafluoro-1-butylene and nonafluoro-n-butoxy-1,1,2-trifluoroethylene with tris(trimethylsilyl)phosphite gave fluorotrimethylsilane and the respective (Z)-alkenylbis(trimethylsilyl)phosphonates. In one case hydrolysis afforded the free phosphonic acid (CF₃)₃CCF = CFP(O) (OH)₂. Using tri-n-butylphosphine and boron trifluoride etherate, 3,3-bis(trifluoromethyl)-1,1,2,4,4,4-hexafluoro-1-butylene and nonafluoro-n-butoxy-1,1,2-trifluoroethylene were converted into the corresponding phosphonium tetrafluoroborates, which when reacted further with iodine in the presence of Na₂CO₃ gave the iodo derivatives (CF₃)₃CCF = CFI and C₄F₉OCF = CFI.     

Bis(trifluoromethyl)-containing 1-azatricycloheptanes

Methods for the synthesis ofanti-3-halo-7, 7-bis(trifluoromethyl)-1-azatricyclo[2.2.1.0^2,6]heptanes by conjugated halogenation of 3,3-bis(trifluoromethyl)-2-azabicyclo[2.2.1]hept-5-ene have been developed. Hydrohalogenation of the synthesized 1-azatricyclic compounds gives exclusively 6,7-dihalo-3,3-bis(trifluoromethyl)-2-azabicyclo[2.2.1]heptanes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1649–1653, September, 1997.     

Hexafluoroacetone as protecting and activating reagent: reactions of hexafluoroacetone with α-keto acids

Hexafluoroacetone and α-keto acids react to give 5,5-bis(trifluoromethyl) substituted 2(5H)-furanones and/or 2,2-bis(trifluoromethyl)-1,3-dioxolan-4-ones depending upon the substituent pattern of the side chain of the acid. A fluoroanalogue of the natural product zymonic acid was obtained from ethyl 3,3,3-trifluoropyruvate and 2-oxosuccinic acid in one step.     

New thiourea organocatalysts and their application for the synthesis of 5-(1H-indol-3-yl)methyl-2,2-dimethyl-1,3-dioxane-4,6-diones a source of chiral 3-indoylmethyl ketenes

The stereoselective properties of modified thiourea organocatalysts were tested in the Friedel–Crafts alkylation of indole with 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones, which produces chiral 5-((1H-indol-3-yl)(aryl)methyl)-2,2-dimethyl-1,3-dioxane-4,6-diones. Based on a tentative reaction mechanism for ((S)-N-benzyl-2-(3-(3,5-bis(trifluoromethyl)phenyl)thioureido)-N,3,3-trimethylbutanamide organocatalysts, modifications were applied in four selected regions. Systematic structure-stereoselectivity relationship study allowed designing the best efficient organocatalyst for the investigated Friedel–Crafts alkylation of indole with 5-arylidene-2,2-dimethyl-1,3-dioxane-4,6-diones.     

Partially Fluorinated Heterocycles from 4,4-Bis(trifluoromethyl)-hetero-1,3-dienes <Emphasis Type="Italic">via</Emphasis> C–F Bond Activation – Synthesis of 2-Fluoro-3-(trifluoromethyl)furans

Summary. An efficient synthesis of 2-fluoro-3-(trifluoromethyl)furans was developed. Keystep of the reaction sequence is a [4 + 1] cycloaddition reaction of tin(II)chloride to 4,4-bis(trifluoromethyl)-1-oxabuta-1,3-dienes. At elevated temperatures the tin heterocycles are transformed into 1-aryl-4,4-difluoro-3-(trifluoromethyl)but-3-en-1-ones which on treatment with sodium hydride in dry DMF give 2-fluoro-3-(trifluoromethyl)furans. The single fluorine bound to C-(2) can be readily replaced by various N-, O-, S-, and C-nucleophiles and dinucleophiles.     

1-(2-Quinoxalyl)-, 1-[3,5-Di(trifluoromethyl)phenyl]-, 1-(2-Carboxyphenyl)-, and 1-Ethoxycarbonyl-4-oxo-4,5,6,7-tetrahydroindazoles

The corresponding 1-(2-quinoxalyl)-, 1-[3,5-di(trifluoromethyl)phenyl]-, and 1-ethoxycarbonyl-3-methyl-4-oxo-4,5,6,7-tetrahydroindazoles have been obtained from reactions of 2-acetyl-1,3-cyclohexanedione, its 5,5-dimethyl and 5-(2-furyl) derivatives, with 2-hydrazinoquinoxaline, 3,5-di(trifluoromethyl)phenylhydrazine, and ethoxycarbonylhydrazine. On interaction with ethoxycarbonylhydrazine the intermediate 2-[1-(-ethoxycarbonyl)hydrazino]ethylidene-1,3-cyclohexanediones were also isolated. From the potassium salt of 2-formyldimedone and 2-carboxyphenylhydrazine hydrochloride, 2-(2-carboxyphenyl)hydrazinomethylene-5,5-dimethyl-1,3-cyclohexanedione was obtained, the cyclization of which in ethanol in the presence of HCl led to 1-(2-carboxyphenyl)- and 1-(2-ethoxycarbonylphenyl)-6,6-dimethyl-4-oxo-4,5,6,7-tetrahydroindazole.     

Kondesationen mit hydrazin-N,N′-dicarbonsäurediamidin,XXIII [1] fluorierte β-diketone als reaktionspartner

Application of a 30% aqueous potassium carbonate solution for the condensation of 1,2-hydrazinedicaboxamidine with 1,1,1-trifluoro-2,4-pentanedione leads to the formation of 4,4′-dimethyl-6,6′-bis(trifluoromethyl)-2,2′-hydrazopyrimidine, with 1,1,1-trifluoro-2,4-hexanedione to 4,4′-diethyl-6,6′-bis-(trifluoromethyl)-2,2′-hydrazopyrimidine. 2-Guanidinoamino-4-methyl-6-trifluoromethylpyridine formed as an intermediate in this reacton may be isolated, while 4-ethyl-2-guanidinoamino-6-trifluoromethylpyrimidine undergoes cyclization to yield 2-amino-5-ethyl-7-trifluoromethyl-s-triazolo[1,5-a]pyrimidine.     

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with phenanthrenequinone and dibenzoyl

Reactions of 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydro-1,3,2-benzodioxaphosphepin-5-one with 9,10-phenanthrenequinone and dibenzoyl gave hydrolytically unstable spirophosphoranes with five- and seven-membered rings, 2-phenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-phenanthro[9,10-d][1,3,2]dioxaphosphol]-5-one and 2,4′,5′-triphenyl-4,4-bis(trifluoromethyl)-4,5-dihydrospiro[[1,3,2]benzodioxaphosphepine-2,2′-[1,3,2]dioxaphosphol]-5-one. The structure of the first of these was proved by X-ray analysis.