Volume 31, Issue 6

The N-alkyliminoalanes [tert-C 4 H 9 NAIH] 4 , [tert-C 4 H 9 NAID] 4 , [iso-C 3 H 7 NAIH] 6 , [C 2 H 5 NAlH] 8 and [CH 3 NAIH] n have been prepared and intermediates such as Al 3 H 3 (N tert-C 4 H 9 )2(N tert-NHC 4 H 9 )2 and Al 8 H 10 (NC 2 H 5 ) 6 (NHC 2 H 5 ) 2 isolated. Cage structures and opened cages respectively are suggested on the basis of physical data. Halogenation of these iminoalanes by HgX 2 proceeds in a complicated manner, the products depending on the mole ratio used, the size of the alkylgroup and cage. HX formation during the halogenation is indicated by the formation of [Cl 2 AlNHR] 2 . Regioselectivity was observed for partial chlorination of [C 2 H 5 NAlH] 8 . Pyrolysis of [RNHAIHCl] 2 yields [tert-C 4 H 9 NAlCl] 4 and [iso-C 3 H 7 NAlCl] 4 .

A mixture of the two isomers of 1-chlorophospholene-1-oxide, obtained by a one-step, high-yield procedure reported previously 1 , upon reaction with P 4 S 10 was converted to a mixture of the two isomers of 1-chlorophospholene-1-sulfide which may be separated by spinning-band distillation. The thus obtained isomerically pure 1-chlorophospholene-1-sulfides were hydrolyzed to the corresponding 1-hydroxyphospholene-1-sulfides. These, as well as the precursor chloro compounds, were characterized by 1 H, 13 C, and 31 P NMR, mass spectrometry, and IR.

The hydrolysis of tris(organyloxy)boranes (boric acid esters) in organic solvents in the presence of KOH leading to potassium polyborates (free from water of crystallization) is studied as to the influences of (a) the reaction medium (ethanol or ligroine/ethanol), (b) the concentration of water, (c) the organyl group of the boric acid ester (methyl, isopropyl, or phenyl), (d) the time of stay of the precipitated insoluble polyborates under the mother liquor (15 to 61850 s), and (e) the temperature during precipitation and the time of stay (—18 to + 60°C). In the first stage of the reaction, during precipitation time, ester hydrolysis is followed by condensation, while aggregation and desorption processes occur between the time of precipitation and filtration.

From the reaction of bis-diphenylphosphino-methane and methyl bromide a diquaternized onium salt is obtained, which is converted into the carbodiphosphorane MePh 2 P=C=PPh 2 Me by sodium amide in THF. This bis-ylide was characterized by its reactions and its NMR spectra. With methyl chloride, the above diphosphine yielded the phosphino-phosphonium salt, which forms a phosphino-ylide upon dehydrohalogenation.

Gaseous methylsulfenylchloride, CH 3 SCl, reacts with active potassium fluoride at 100°C to give methyl(fluoromethyl)disulfane, CH 3 SSCH 2 F. This compound decomposes at room temperature to yield dimethyldisulfane and bis(fluoromethyl)disulfane. The new compounds have been identified by 1 H and 19 F NMR and mass spectra.

The 13 C NMR spectra of the ethylaluminium compounds [Al(C 2 H 5 ) x Cl 3 _ x ] 2 x = 1, 1,5, 2 and 3 are presented and factors governing the temperature dependence of the line shape are discussed. The exchange reaction of terminal ethyl groups for chlorine ligands and ethyl ligands, resp., in ethylaluminium-sesquichloride was investigated by fitting the calculated line shapes to the observed spectra. The energy of activation of this exchange process was determined as to be 12,3 ‡ 1,5 kcal/mole. The synthesis of 13 C 2 -[Al(C 2 H 5 )Cl 2 ] 2 is described.

Possible structures and the pertinent reaction pathways for the polymetalate ion present in a slightly soluble polymetalate having the analytical formula A 2 O · 2 MOs have been derived on the basis of theoretical considerations. Structure and kind of combination of the tetrameric units of one of the possibilities are in agreement with the results of X-ray structure analyses. First the previously proposed planar tetrametalate ion [M 4 O 12 (OH) 4 ] 4- -is formed by stepwise aggregation according to an addition mechanism. This species undergoes a rearrangement of the coordination sphere of two of the M atoms and is then subject to a polycondensation resulting in a polytetrametalate chain, [M 4 O 14 4- ] n .

The complexes K[OsX 4 acac], X = Cl, Br, I, are prepared by treatment of K 2 [OsX 6 ] with acetylacetone. The new compounds are characterized by their IR resp. visible and UV spectra which are highly resolved when measured on transparent pellets of the tetraethylammonium salts with KBr at 10 K. The influence of the different halide ligands on the bonding of the acac-group is discussed.

2,5,5-Triorgano-1,3,2-dioxaborolane-4-ones RB(—O—CO—CXY—O—) (2-6) can be prepared from α-hydroxycarboxylic acids XYC(OH)—COOH and dihalogenoorganoboranes RBHal 2 . They are much weaker Lewis acids than the 2-organo-1,3,2-dioxaborolane-4,5-diones RB(—O—CO—CO—O—) (1). The compounds 1 give 1:1 adducts with the bases DINO, MANO, PyO, and PSy, respectively; the crystal structure determination of 1f · DINO reveals a simple BO-coordination between the components. On electron impact, the chief fragmentation path is the elimination of CO 2 from compounds 1-6. The thermal degradation of 2-6 seems to be rather complicated in the liquid phase but is unique in the gaseous phase forming the compounds (RBO) 3 , CO, and XYC=O.

Kinetic parameters of the cis-trans isomerization in bis(5,5-dimethyl-2-hexenyl)-zinc have been determined by means of nuclear magnetic saturation transfer. Novel methods for the acquisition and analysis of saturation data are reported. The results are consistent with a dynamic allylic system passing through the secondary metal alkenyl form as an intermediate in the equilibrium of cis-trans isomers.

The bands of the room temperature absorption spectrum of (C 5 H 5 ) 3 U(IV)BH 4 have been identified on the basis of the complete energy matrix of the tetrahedral f 2 -system. Using the parameter set: F 2 = 181, F 4 = 33.5, F 6 = 3.8, ζ 5f = 1815, B 4 ° = —495 and B 6 ° = —292 cm -1 a good agreement between observed and calculated signals has been achieved.

The reduced, coordinatively unsaturated surface compounds of chromium, vanadium and molybdenum, supported on silicagel, react with O 2 under chemiluminescence; the extremely broad emission bands have their maxima at v = 15,0 kK (chromium), 18,6 kK (vanadium) and 20,6 kK (molybdenum). A general reaction mechanism is proposed based on the electronic structures of the starting, intermediate and final products. It allows an interpretation of the observed chemiluminescence phenomena in agreement with other experimental data; the desactivation of a CT excited peroxo complex of d o metal ion is postulated as source of radiation.

From the photochemical reaction of M(CO) 6 (M = Cr, Mo, W) and (CH 3 ) 2 -CH 2 in ether, yellow solids with the composition [(CH 3 ) 2 -CH 2 ] 2 M(CO) 4 are obtained in good yields. [(CH 3 ) 2 -CH 2 ] 2 M(CO)4 (M = Cr, Mo) are also accessible by the displacement of olefin from (norbornadiene) M(CO)4 by excess ylid in ether. Pale insoluble [(CH 3 ) 2 -CH 2 ] 3 Mo(CO) 3 is the sole product from the reaction of (cycloheptatriene)Mo(CO) 3 and excess ylid in ether.

The enthalpies of complex formation of EDTA and uramildiacetate (UDA) with univalent cations (H + , Li + , Na + , K + , Ag + and Tl + ) have been obtained by direct calorimetric measurements at ionic strength 0.1 (or 1) and 20°C. For comparison data for the formation of 1:1 UDA complexes with Mg 2+ , Ca 2+ , Ba 2+ and Sr 2+ have also been obtained. From these values and the stability constants the thermodynamic functions ΔG and ΔS are calculated. The results are compared with those of similar systems.

The reduction of the complexes C 5 H 5 Mn(CO) 2 L (L=P(C 6 H 5 ) 2 Cl, P(C 6 H 5 )(Et)Cl and P(C 6 H 5 )Cl 2 ) with Na in liquid NH 3 yields the complexes C 5 H 5 Mn(CO) 2 L′ (L′=P(C 6 H 5 ) 2 Na, P(C 6 H 5 )(Et)Na and P(C 6 H 5 )Na 2 ). The reaction of these complexes with CH 3 J and of CpMn(CO) 2 PØ 2 Na with H 2 O, CH 2 Cl 2 , CCl 4 , J 2 and CH 3 COCl are described. Furthermore it has been found, that n-butyl-lithium yields C 5 H 5 Mn(CO) 2 NMe 2 Li if reacted with C 5 H 5 Mn(CO) 2 NMe 2 H.

Whereas β-cyanoethylhydrazine (1) reacts with the β-ethoxy-α,β-unsaturated nitriles (2a—c) to yield the 5-amino-1-B-cyanoethylpyrazoles (8a—c), 1 reacts with anilinomethylenemalononitrile (2d) to yield 3-amino-1-B-cyanoethyl-4-cyanopyrazole (4; R=H; X=CN). 3a readily cyclised into the 5-amino-6,7-dihydropyrazolo[1,5-a]pyrimidine derivative (6) by the action of ethanolic guanidine. 6 was readily converted into the oxo derivative (7) by the action of acetic acid. 7 was also obtained by the action of 1% NaOH on 3a. On the other hand, 3b afforded a mixture of the pyrazolo[1,5-a]pyrimidine derivative (8) and the carboxylic acid (9) when treated with 1% NaOH solution. 3-Aminocrotononitrile (2e) reacted with 1 to yield the hydrazone derivative (12). The latter derivative was converted into the pyrazolo[1,5-a]pyrimidine derivative (14) by the action of acetic acid. On the other hand, the hydrochloride (15) was formed on treatment of 12 with acetic acid hydrochloric acid mixture. Compounds 8 a, b reacted with carbon disulphide to yield the pyrazolo[3,4-d]-6 (7 H)-m- thiazinethione derivatives (16a,b). The latter were readily converted into the pyrazolo-[3,4-d]pyrimidine derivatives (17 a, b) by the action of aqueous NaOH solution.

The synthesis of a number of dialkylbenzilidene anilines is described. Mesomorphic phases are found at or below room temperature. An efficient method for the preparation of the 4-n-alkylanilines and their benzilidene derivatives is described.

INDO calculations on various conformations in substituted allyl cations, anions and radicals indicate a new type of substituent effect in halogen substituted allyl radicals.

Syntheses and conversion of substituted azabicyclo[4,1,0]hepten are described.

The cis-trans-isomerism of the WITTIG hydrocarbon was investigated in solid state and solution by means of fluorescence spectroscopy. The fluorescence behavior of both isomers in 2-methyltetrahydrofurane was determined as a function of concentration, temperature, and wavelength of exciting radiation. Furthermore, irradiation experiments were undertaken with light of various wavelengths. The results obtained are in agreement with the assumption that the WITTIG hydrocarbon behaves with regard to the cis-trans-isomerism like a 1,3-butadien derivative, i.e. a thermal but no photochemical cis-trans-isomerisation can be detected. The enthalpy difference between the two isomers was estimated to ΔΗ = 250 ± 50 cal/mole. It could be shown that the fluorescence of the cis-isomer is quenched by the trans-isomer. This quenching occurs probably according to the resonance energy transfer mechanism.

The hypothesis of GLIKMAN and ZABRODA (Biochemistry [USSR] 84,, 239 [1969]) that the primary electron donor during photoreduction of manganese(III) in Mn(III)-hydroxychlorin compounds in oxygen free aqueous alkaline solutions is the axially bound OH - ion was tested with Mn(III)-2-a-hydroxyethyl-isochlorin e 4 . It has been shown that 1) the primary generation of OH radicals upon irradiation of the complex is highly improbable, 2) light is not essential for the reduction reaction, 3) the kinetics of photoreduction of the Mn(III)-compound in 2 N NaOH clearly is not compatible with OH radical formation.

The thermal decomposition of dialkyl tert-butylperoxy phosphates, in the presence and absence of solvents, yields the corresponding dialkyl phosphate, acetone, methanol, 2,2-dimethoxypropane, and methyl isopropenyl ether as the primary products. Prolonged heating of the product mixture produces trialkyl phosphates, (RO) 3 P(O), which arise from the thermal decomposition of dialkyl phosphates. Data are presented to support a mechanism involving the heterolytic cleavage of the peroxide linkage.

cis-Dichlorodipeptide esterplatinum complexesCl 2 Pt(MetGlyOEt),Cl 2 Pt(EthionylGlyOEt), Cl 2 Pt(GlyGlyOEt)2 and Cl 2 Pt(GlySerOEt) 2 are prepared from the α-amino acid complexes by peptide synthesis using platinum as an amino protecting group. cis-Cl 2 Pt(GlyGlyOEt)2 and cis-Cl 2 Pt(GlySerOEt)2 have been prepared also directly from K 2 PtCl 4 and the dipeptidesters. cis-Cl 2 Pt(GlyGlyOEt) 2 (2 a) and cis-Cl 2 Pt(NH 3 ) 2 (5) lead to a prefered inhibition of the DNA-synthesis of sarcoma 180, Yoshida-sarcoma and Walker-256-carcinosarcoma in vitro; RNA- and protein biosynthesis are influenced to a much lower degree. 2a and 5 cause filamentous growth in Escherichia coli B. The DNA polymerase deficient strain of E. coli, p 3478 pol A-, is more inhibited by 2 a and 5 than the non deficient strain W 3110 pol A + . Tumor growth of di-2-chloro-ethylmethylamine (HN 2 ) resistant sarcoma 180 and of Yoshida sarcoma is weakly inhibited, whereas Walker-256-carcinosarcoma is markedly inhibited; however 2a and 5 show similar inhibition of the same tumor.

Treatment of ethyl α-phenylthiocarbamylacetoacetate (1) with aromatic diazonium salts effects acetyl cleavage with the formation of ethyl α-phenylthiocarbamylglyoxalate arylhydrazones derivatives (2 a-e) which afford the anilinopyrazolones (5) and (7) on treatment with hydrazine or phenylhydrazine. The pyrazolones 5 a-e undergo aminoalkylation with formaldehyde and piperidine to give the N-Mannich bases 7 a-e, also obtained by treating the N-hydroxymethyl derivatives (9 a-e) with piperidine.

Diethyl bromomalonate (1) reacts with trimethylamine at 0°C to give the bromide salt of trimethylammoniummalonate (2), however, in the presence of methanol, ethanol or 1-butanol the bromide of ethyl trimethylammoniumacetate (3) is obtained under the loss of dialkyl carbonates. The analogous reaction of 1 with dimethylsulfide yields diethyl methylthiomalonate (5).

Cyclisation of the 4-phenylhydrazono derivatives of 2-thiazolidinone or 2-thiazolidinethione (1) with formaldehyde solution or with aromatic aldehydes yields 2-phenyl-2,3-dihydrothiazolo[4,3-c]-1,2,4-triazol-5-one or its 5-thiocarbonyl analogue (2). Condensing 2 with aromatic aldehydes afforded the corresponding 7-arylidene derivatives (8). The 5-arylidene derivatives of 4-anisylimino-2-thiazolidinethione (5) were obtained by condensing 4 with aromatic aldehydes. The potassium salt of 5 reacts readily with alkyl halides to yield the 5-arylidene derivatives of 4-anisylimino-2-alkylmercapto-2-thiazoline (6).

The γ-radiolysis of cellobiose (10 -2 M) in N 2 O saturated aqueous solution has been investigated and the G-values of the following 21 products containing six or less C-atoms have been measured (G-values in parentheses): glucose (2.1), gluconic acid (0.70), 4-ketoglucose (0.07), 5-keto-glucose (0.05), 4-deoxy-glucose (0.27), 5-deoxy-gluconic acid (0.18), 2-deoxy-gluconic acid (0.13), 3-deoxy-4-keto-glucose (0.23), 2-deoxy-5-keto-glucose (0.34), 4-deoxy-5-keto-glucose (0.14), 6-deoxy-5-keto-glucose (0.02), arabinose (0.07), ribose (0.015), 2-deoxy-ribose (0.17), 3-deoxy-pentulose (0.01), erythrose (0.015), threose (0.015), 2-deoxy-tetrose (0.01), butanone-(2)-diol(1.4) (0.01), dihydroxyacetone (0.01), carbon monoxide ( > 0.02). The formation of the major part (98%) of the measured products could be explained on the base of the following assumption: The first step of reaction sequence is abstraction of H atoms from C-Η bonds of the cellobiose by OH radicals. Radicals at C-1′, C-5′ and C-4 and their successors undergo in a second step four types of reactions: hydrolysis, rearrangement and H 2 O and CO elimination. In a third step the transformed radicals give rise to products by disproportionation reaction. Only two products out of 16 predicted under the above assumption are not observed. G-values for the attack at C-1′, C-5′ and C-4 are 1.4, 0.6 and 0.3 respectively.

1-Phenyl-4-thiohydantoin reacted with aryldiazonium salts to give the corresponding 5-arylazo-1-phenyl-4-thiohydantoin (1 a-f). On alkylation of 1 a, b,f with different alkyl halides, the corresponding 4-alkylmercapto derivatives (2a-f) were obtained. 2 a was hydrolysed with a mixture of ethanol-hydrochloric acid to give 5-phenylazo-1-phenyl-hydantoin (3). Treatment of 2 a, d with amines gave the products 4a—h. 4 a when refluxed with a mixture of acetic-hydrochloric acid, the product 3 was obtained, 1a, b reacted with formaldehyde and appropriate amine to give the corresponding Mannich bases 5 a-k. Also 1-phenyl-4-thiohydantoin when exposed to the Mannich reaction, 6a-e were obtained, 6 a when treated with benzenediazonium chloride, the colour substance 5 a was separated.

Using deuterium labelled compounds the mechanisms of methyl as well as methanol elimination from the title compounds have been established. It can be shown that in the case of 4-methoxy-methyl benzoic acid methyl ester the unusual methanol elimination from the [M-methyl]+ ion probably proceeds via the formation of a π-complex and a ring expansion reaction. In addition to this novel fragmentation some ortho-effects and other fragmentation reactions useful for an analytical identification of the ortho/para-isomers by means of mass spectrometry are discussed.

Two isomeric flavonolignans (Silymarins) have been isolated from the fruits of Silybum marianum L. Gaertn. and structurally elucidated mainly by means of NMR/mass spectroscopy and X-ray analysis respectively.

Single crystals of TlPb 2 Cl 5 and NH 4 Pb 2 Cl 5 were prepared. X-ray diffraction data confirm the space group C 2h 5 —P2 1/c (No. 14). Crystal structure determination shows a new typ, belonging to the PbCl 2 -structure.

MnGa 2 Se 4 and MnGa 2 Te 4 were prepared by direct synthesis from the elements at 900-1000°C. MnGa 2 Se 4 (Space group I 4, α = 5.676(2) Å, c = 10.760(3) Å, z = 2) is isotypic with CdGa 2 S 4 .

A new synthetic route for sulfinato complexes is reported: π-C 5 H 5 (CO) 3 WS(O) 2 CH 3 can very easily be prepared from π-C 5 H 5 (CO) 3 WH, CH 3 SO 2 Cl and N(C 2 H 5 ) 3 , a reaction in which sulfene (CH 2 =SO 2 ) -insertion into metal-hydrogen-bonding may be involved.

New intermetallic compounds of the ThCr 2 Si 2 -structure type have been prepared and their structures determined by single crystal data.

The oxygen partial pressure above supported, coordinatively unsaturated Cr II , V III , Mo II and Mn II species was measured with a ZrO 2 cell. Within this series the pressure ranges from 10 -6 to 10 -11 ppm O 2 , with the Mn II /SiO 2 systems exhibiting the lowest values of 10 -10.8 and 10 -11.3 . Other pertinent properties like chemiluminescence with O 2 and catalytic activity in ethylene polymerisation are also indicated. The manganese(II) absorption masses are thus particularly suitable for removal of traces of oxygen from liquids and gases in general but especially from polymerizable olefins.

Compounds Ü II M IV F 6 [Ü: Mn—Ni, Zn] crystallize in the LiSbF 6 - or in the ordered ReO 3 -structure respectively. The influence of the Jahn-Teller ions Cr 2+ and Cu 2+ on these structure types is studied.