Band 41, Heft 2

Three different phases of bis(oxalato)platinate salts of bis(oxamide-oxime)platinum have been obtained by diffusion techniques and have been characterized by X-ray methods; α-phase: [Pt(C 2 O 4 ) 2 ][Pt(C 2 H 6 N 4 O 2 ) 2 ] · 2H 2 O, monoclinic P2 1 /n, a = 15.073(13), b = 3.660(1), c = 16.759(14) Å , β = 96.03(4)°, V = 919 Å 3 , Z = 2; β-phase: [Pt(C 2 O 4 ) 2 ][Pt(C 2 H 6 N 4 O 2 ) 2 ] · nH 2 O, monoclinic P2 1 /n, a = 6.718(1), b = 18.885(4), c = 7.412(2) Å, β = 107.06(2)°, V = 930 Å 3 , Z = 2; γ-phase: [Pt(C 2 O 4 ) 2 ][Pt(C 2 H 6 N 4 O 2 ) 2 ] · 3H 2 O, orthorhombic Pnca, a = 13.694(3), b = 19.210(5), c = 15.225(5) Å, V = 4005 Å 3 , Z = 8. The α-phase contains segregated stacks of the planar cations and anions, the β- and γ-phases mixed stacks. The well-refined structure of the γ-phase is discussed in detail and compared with the gross structural features of the α- and β-phases.

The first seleninylamine, t BuNSeO, was prepared from tert-butylamine, t BuNH 2 , and SeOCl 2 (3:1). The selenium diimide Se(NBu t ) 2 was isolated from the corresponding reaction of t BuNH 2 and SeCl 4 (6:1); it decomposes at ambient temperature to give cyclic Se 3 (NBu t ) 2 . The new compounds were characterized on the basis of their IR , 1 H and 13 C NMR and mass spectra.

The reactions o f the perfluorophosphaalkene F 3 CP = CF 2 (1) with HX compounds proceed via addition to the PC double bond yielding either secondary phosphanes F 3 CP(H)CF 2 X (X = OH, OR, NR 2 , PMe 2 ) or PX derivatives F 3 CP(X)CF 2 H (X = Cl, Br, SMe, SeMe, AsMe 2 ). The rate of reaction with H 2 O is strongly pH-dependent, but only at pH > 13 the opposite direction of addition is observed. Similar results are obtained for the addition of alcohols, for which the presence of OR - results in two effects: (i) Reversion of the addition direction to yield F 3 CP(OR)CF 2 H; (ii) HF elimination from F 3 CP(H)CF 2 OR to give substituted phosphaalkenes. With strong bases HNR 2 , the addition is followed immediately by HF elimination producing the surprisingly stable phosphaalkenes F 3 CP = C(F)NR 2 (R = Me, Et). Secondary phosphanes of the type F 3 CP(H)CF 2 X (X = OMe, OEt, PMe 2 ) are found to be suitable precursors for the preparation of novel heterosubstituted derivatives of 1 by elimination of HF with NMe 3 . New compounds were characterized by NMR, MS, GC/MS and GC/IR measurements.

The reactions between 1,2,4-thiadiazol-3,5-dicarbonitrile, S(CN) 4 , and sulfur chlorides (SCl 2 and S 2 Cl 2 ) in the presence of Adogen ® 464 (Aldrich) proceeds with formation of S 3 (CN) 4 Cl 2 (1) and S 3 (CN) 8 Cl 2 (2). These main products were characterized by X-ray structure determination of an adduct 1a and of 2. This adduct 1a was obtained by addition of the Lewis acid AsF 5 in liquid SO 2 . 1a crystallizes with one SO 2 molecule in the space group P2 1 /n with a = 1177.3(2), b = 1082.8(1), c = 1255.3(5) pm, β = 109.73(3)°, Z = 4, V = 1.5061 nm 3 . It contains two five-membered rings connected by a nitrogen atom. AsF 5 is coordinated to one of the ring nitrogen atoms [N(1)] adjacent to the sulfur atom S(1) and C(1)Cl-group. The other ring contains an S(2)-S(3) bond of length 207.7(4) pm. The rings are planar within experimental error. 2 crystallizes in the space group P2 1 /n with a = 782.12(6), b = 1498.1(5), c = 1217.8(2) pm, β = 102.43(1)°, Z = 4, V = 1.3934 nm 3 . 2 is formed by addition of one molecule of SCl 2 to two molecules of S(CN) 4 .

From a solution of a lithium-2-boratanaphthaline Li(XBC 9 H 7 ), 2a (X = Ph) and 2b (X = iPr 2 N), the crystalline metal derivatives Fe(XBC 9 H 7 ) 2 (4a, b), (tmeda)Li(XBC 9 H 7 ) (5 b), and D 2 Rh(XBC 9 H 7 ) (7b: D = C 2 H 4 ; 8b: 2 D = cod) can be prepared. The metal atoms Fe and Rh are hexahapto-bonded to the boron-containing moiety of the naphthaline-type skeleton. By a crystal structure determination, the Li-atom in 5b is found to be bonded in the same way.

The metallacycle [Br 3 WS 2 N 3 ] has been obtained from the reaction of S 4 N 4 with WBr 5 . The salt [Ph 4 P + ][Br 4 WS 2 N 3 - ] was formed from [Br 3 WS 2 N 3 ] by addition of Ph 4 PBr. It crystallizes in the orthorhombic space group Pbca with a = 1396.8(4), b = 1961.9(5), c = 2108.0(4) pm, and Z = 8. The following mean bond lengths were observed in the anion: W-N 184.2, W-Br 256.8, N-S 157.8 pm.

The reaction of metal loaded γ-Al 2 O 3 and SiO 2 with benzene-1,2-dicarbonitrile (2) resp. 1H-isoindole- 1,3(H )diimine (3) results in the β-modification of metallized phthalocyanines (1; metals: Cu(II), Co(II)). 1 is formed with an average yield of 48-64% in uniform distribution on the carriers from the reaction with 2. The sizes of the surface areas of the supports are not changed significantly by loading with 1. Non-uniform distribution or even unsupported crystals of 1 are found if the synthesis is carried out with 3.

The compounds t C 4 H 9 N=VR(O t C 4 H 9 ) 2 (R = CH 3 , n C 4 H 9 , CH 2 SiMe 3 , Mes) and t C 4 H 9 N = VMes 2 (O t C 4 H 9 ) have been prepared by reaction of tert-butyliminovanadium (V) chlorides with LiR; t C 4 H 9 N=V(CH 2 SiMe 3 ) 2 (O t C 4 H 9 ) and t C 4 H 9 N=VR 3 (R = CH 2 SiMe 3 , Mes) could only be characterized by NMR spectroscopy. The 1 H, 13 C and 51 V NMR spectra are discussed; the constants of 51 V , 14 N coupling have been determined.

Compounds RXHal 2 (X = P, As, Sb) react with Na 2 [M 2 (CO) 10 ] (M = Cr, Mo, W) to yield three types of products: A, [(CO) 5 M] 2 X-R containing trigonally planar coordinated X; C, [(CO) 5 M] 3 X-R containing coordinated metallacyclic ligands; B, [xxx] D, [(CO) 5 M] n (R)X = X (R) (n = 0, 1, 2, 3). The relation between these species, especially the one based on the valence tautomerism between A und B, is experimentally verified. Preparative, spectroscopic and X-Ray-structural results reveal a consistent picture of the relevant chemistry.

The reaction between the spiro-chlorophosphorane, [O = C (NMe) 2 ] 2 PX (X = Cl), and the related trimethylsiloxy compound (X = OSiMe 3 ) was expected to give rise to the formation of a μ-oxo-bis(spirophosphorane), [[O = C(NMe) 2 ] 2 P] 2 O. Instead, an isomer of the expected compound, with two N.Nʹ-dimethylurea bridges across a λ 5 P-O-λ 5 P bond system was obtained. The identity of the product was established by spectroscopic means (IR , NMR, mass spectroscopy), and by a single crystal X-ray diffraction study.

1 H and 13 C NMR spectroscopic parameter of in the phenyl rings substituted compounds of the type cis- and trans-bis(phenyl)bis(tri-n-butylphosphane)platinum(II) are reported and discussed with respect to correlations between coupling constants especially with platinum-195 and molecular configuration and substituent effects.

The synthesis of the title compounds 4a/b and their enolethers 4c/d respectively by hydrolysis of the α-methoxybenzylidene-pyrrolinones 3 is reported. Methylation by diazomethane preferentially yields the benzoylpyrroles 7. Analogously, hydrolysis of the α-methoxybenzylidene-pyrrolidinone 9 followed by methylation leads to the isomeric enolethers 10b and 11.

The [2](1,4)Anthraceno[2](2,6)pyridinophan-1,13-dien (5) and the corresponding [2.2]phane (7) were synthesized as models for exciplexes. The dithia[3.3]phanes(9) and (11) were prepared by cyclisation of the dithiols 13 and 16 with the dibromide 19. Oxidation of 9 to the disulfone 10 and vapour phase pyrolysis led to 7. Ring contraction of 9 by S-analogous Wittig ether rearrangement led to 20 which was converted to the diene 5 via oxidation to the disulfoxide 21 and pyrolytic elimination of methane sulfenic acid. Attempts to prepare 6 and 8 via similar routes from 11 failed. Electron absorption spectra and fluorescence spectra of 5 and 7 are discussed in terms of n-π interaction in 5 and π-π interaction in 7.

The full analysis of the 1 H NMR spectra of naloxone and naltrexone (hydrochloride salts, in 2 H 2 O solution) was performed by using an high-frequency (500 MHz) spectrometer and the recent technique of two-dimensional (2D ) homonuclear shift spectroscopy. The 1 H- 1 H connectivities allowed detection of correlated resonances and assignments of multiplets. The shapes of the contour levels of the COSY 45 spectra were also used to check the relative signs of coupling constants. The refinement of spectral parameters of some component spin-systems of the complex spectra was performed by computerized iterative simulation of patterns. The spectral analysis provided proton coupling constants that allowed to establish a slightly distorted-chair conformation of the piperidine ring in both compounds. The magnetic non-equivalence found for the protons bonded to C-17 atom (part of the N-alkyl fragment) was found to be larger in naltrexone than in the analogous naloxone. This fact, while no significant differences were observable in the chemical shifts of corresponding protons of the rigid molecular backbone of the two narcotic antagonists under study, was assigned to smaller degree of internal conformational flexibility of the N-methylcyclopropyl group in naltrexone with respect to that of the N-methylallyl group in naloxone. The above findings appeared in good agreement with our previously proposed views based on results from 13 C relaxation times studies, which suggested the possible correlation of the motional rates of the N-methyl-R group to the pharmacological activity of antagonist compounds. This would consist in a direct correlation between decreasing flexibility of the N-bonded fragment and increasing antagonistic potency.

Reaction of 2,3ʹ-bipyridine with dibromoalkanes affords both 1ʹ-bromoalkyl-2,3ʹ-bipyridinium bromides and 1ʹ,1‴-(alkanediyl)-bis-2,3ʹ-bipyridinium dibromides. The latter diquaternary salts react with dimethyl sulfate to afford 1ʹ,1‴-(alkanediyl)-bis-(1-methyl-2,3ʹ-bipyridinium) tetraquaternary salts which are reduced to diradical dications at potentials (E 0 ) of about -0.47 V to -0.62 V.

IR, UV and NMR data reveal that the dichlorination product of 3,5-di-tert-butylphenol is the keto tautomer (1a) of 3,5-di-tert-butyl-2,4-di-chlorophenol (3) instead of the ortho-quinol dichloride (2a), as assumed by Hewitt et al. (1972). According to the crystal structure determination, the first one of a monocyclic keto tautomer, 1a crystallizes in the space group P1̄ with Z = 4; a = 1052.6(3), b = 1202.6(4), c = 1207.4(4) pm, α = 90.52(4)°, β = 95.13(4)° and γ = 108.59(4)°. The structure was solved by direct methods and refined by full-matrix least squares to R = 0.094 for 2176 reflections (I > 3 · δ(I)). Bond lengths and angles show no unusual features; the conformation is discussed with respect to the acidity of the sp 3 -s CH bond. Suggestions for the mechanism of formation of 1a are presented.

6-Formyl-7-hydroxy-5-methoxy-2-methylchromone on bromination yields the 8-bromo derivative or the 8-bromo-6-formyl-5,7-dihydroxy derivative depending on the reaction condition. Cyclization of both leads to the corresponding 3-acetyl-, 3-benzoyl-, 3-carboxamido-, 3-carbethoxybenzodipyran derivatives. The 3-acetylbenzodipyran derivative when treated with ethyl acetoacetate or ethyl cyanoacetate in the presence of ammonium acetate yields the corresponding dihydropyranobenzopyranopyridine dione or the dihydropyranobenzopyranopyridine trione. The reaction of the 3-acetyl derivative with cyanoacetamide in the presence of ammonium acetate affords the substituted pyranobenzopyranopyridine dione. The 3-acetyl derivative undergoes self condensation to form the substituted benzopyranobenzopyran derivative.

Vacuum pyrolysis of 1,8-bis-(chloromethyl)naphthalene yields acenaphthylene and a little acenaphthene.

On tempering heterogeneous pellets of Cs 3 [IrBr 6 ] and NaI at 160 °C for several days, Cs 3 [IrI 6 ] is formed by solid state ligand exchange. Because of the slow diffusion rate of the halide ions within the NaI phase, the reaction has to be repeated several times in order to accomplish complete iodation. The embedding material is removed with anhydrous acetone or methanol. Cs 3 [IrI 6 ] is very slightly soluble in water and immediately hydrolyzed. The IR bands and Raman lines are assigned according to point group O h .

Z-Jasmone (1) was prepared from ethylene ketal of 0,0-diethyl-4-oxo-pentanephosphonate (2) in four steps in 36% overall yield. A key step in this synthesis is the oxygenation of the α-phosphonate carbanion generated from the monoalkylation product of 2 with Z-3-hexen-1-yl iodide (3).

Methyl N-isopropyl-4-nitrothiobenzimidate (1) exhibits reversible photochromism to a dark blue coloured species in the crystalline state only. Experimental evidence for a topochemically controlled nitro-aci-nitro tautomerism of 1 in the electronic excited state is presented.