New polyacetylenes from the sponge Siphonochalina sp.

Six new compounds, characterized by a long unsaturated alkyl chain (nC₂₂), were isolated from a marine sponge. All compounds except for one, possess an enyne terminus on one side of the molecule and either a terminal acetylene (in four) or a propargyl alcohol on the other end. Four of the compounds were unequivocally identified mainly by spectroscopic methods.Acetylenic compounds are well-known constituents of plants: only few, however, are known from marine organisms and to our knowledge only one group of compounds contains more than a single triple bond. Among the acetylene containing marine natural products are: A group of halogenated ethers, characterized by a straight-chain C-15 carbon skeleton and a terminal enyne function which has been isolated from algae¹ and a sea hare², carotenoids³, two steroids⁴, a sesquiterpene⁵ and polyketids^6,7.A diacetylene was found in a group of several n C-22 straight-chain compounds isolated from a marine sponge⁸. One of the compounds found in the latter sponge contains, again, the enyne terminus - an end group which turns out to be quite abundant in the above and the herewith discussed compounds.In our continuing search for bioactive compounds from marine organisms we have isolated from the sponge $\text{Siphonochalina sp}$.⁹ collected at several places in the southern part of the Gulf of Eilat (the Red Sea) six n C-22 straight-chain acetylenic compounds.Extraction of the freeze-dryed sponge (petrol ether, 4% dry weight) and subsequent repeated chromatographies (LH-20 and Silica gel)^10,11 gave six closely related new compounds, named in order of polarity, Δ¹⁵-docos-1-yne ($\text{1}$; RF^12a=0.65; 0.2% based on the dry weight of the animal), octahydrosiphonochalyne ($\text{2}$; Rf^12a=0.55; 0.4%), dihydrosiphonochalyne ($\text{4}$; Rf^12a=0.44; 0.1%) siphonochalyne ($\text{3}$; Rf^12b=0.34; 0.2%), dehydrosiphonochalynol ($\text{6}$; Rf^12b=0.55; 0.1%) and siphonochalynol ($\text{5}$; Rf^12b=0.43; 0.3%).     

The preperation and coordination properties of 1,4-diaza-3-methylbutadiene-2-ylpalladium(II) complexes with different substituents on the imino nitrogen atoms

The complexes trans-[PdCl{$\text{C(=NR)C}$(ME)=NR'} (PPh₃)₂] (R=C₆H₁₁,p-C₆H₄OMe; R$\text{.}\text{?}$=p-C₆H₄OMe, Me) containing a σ-bonded 1,4-diaza-3-menthyl-butadiene-2-yl group with different substituents on the nitrogen atoms have been prepared by two routes. The first involves initial methylation of the mixed isonitrile complex [PdCl₂(CNR)(CNR')]by HgMe₂, followed by reaction with PPh₃ ($\text{Pd}\text{PPh}{}_3$molar ratio $\text{1}\text{2}$). The second method involves condensation of primary aliphatic amines with the carbonyl group of the 1-azabut-1-en-3-one-2-yl moiety of the complex trans-[PdCl{$\text{C(=NR)C}$(Me) = 0} (PPh₃)₂]. The 1,4-diaza-3-methylbutadiene-2-yl derivatives act through their imino nitrogen atoms as chelating ligands towards anhydrous metal chlorides MCl₂ (M = Co, Ni, Cu, Zn). Magnetic moment measurements and the far-infrared and electronic spectra of these adducts indicate an essentially pseudo-tetrahedral configuration at M in the solid and in solution. With the ZnCl₂ adducts, the ¹H NMR pattern for the phenyl protons of the p-methoxyphenyl N-substituents dependss upon the position of the substituent i the 1,4-diazabutadiene chain.     

Trimethymetall-urotropinaddukte des aluminiums,galliums, indiums und thalliums

Reactions of urotropine (C₆H₁₂N₄) with trimethylmetal derivatives of Al, Ga, In und Tl in various ($\text{1}\text{1}$$\text{1}\text{4}$) molar ratios lead to stable and monomeric $\text{1}\text{1}$, $\text{1}\text{2}$ or $\text{1}\text{3}$ adducts in good yields, but no $\text{1}\text{4}$ addition product could be isolated. The vibrational spectra (IR and Raman) of all compounds are recorded and partly assigned. Some characteristic frequencies of the C₆N₄-skeletons clearly show the symmetry changes in the series of the $\text{1}\text{1}$ → $\text{1}\text{2}$ → $\text{1}\text{3}$ adducts (C_3ν → C_2ν → C_3ν). The X-ray structure determinations of C₆H₁₂N₄·.GaMe₃ (MeCH₃) and C₆H₁₂N₄·.2GaMe₃, are in good agreement with the vibrational spectra. Both compounds crystallize in monoclinic space groups (P2₁ and C2/c). The GaN distances are around 214 pm, and the values for the C₆N₄-skeletons are not significantly different from those for free urotropine.     

Two new C15 acetylenes from the marine red alga laurencia obtuse

Two new brominated C₁₅,-nonterpenoids which are unusual oxolane derivatives possessing a propargylic bromide side chain have been isolated from the red alga $\text{L. obtuse}$ and their structures were determined as 6 and 7. The ¹HNMR spectra of these new compounds are presented and assignments made.     

Synthesis and structural elucidation of some new heterocyclic β-diketone derivatives of boron

Some new β-diketone derivatives of boron having the general formula B₂O(OAc)_4?n[OC(R)$\text{C:CON(Ph)N:C}$ CH₃]_n (where n = 1 or 2; R = CH₃, C₂H₅, C₆H₅ and p-ClC₆H₄) have been synthesised by the reactions of oxy-bis(diacetatoborane) and substituted pyrazolones, such as 4-acyl-3-methyl-1-phenyl-2-pyrazolin-5-ones (acyl = acetyl, propionyl, benzoyl and p-chlorobenzoyl) in dry toluene solution in 1:1 and 1:2 molar ratios. These derivatives have been characterised by elemental analysis, molecular weight measurements. Structures have been proposed on the basis of chemical reactions, IR, ¹H and ¹¹B NMR spectral studies.In the derivatives B₂O(OAc)₃[OC(R)$\text{C:CON(Ph)N:C}$ CH₃] two of the three acetate groups are unidentate and the third is bridged between two boron atoms along with BOB linkage. Whereas the derivatives B₂O(OAc)₂[OC(R)$\text{C:CON(Ph)N:C}$ CH₃]₂ are the mixture of geometrical isomers.     

Extended hopane derivatives in sediments: identification by 1H NMR

The sedimentary C₃₂ hopanoic acid $\text{3a}$, one of the most abundant in nature and of probable bacterial origin, has been isolated for the first time as a single component and characterised by ¹H NMR. The 17αH,21βH configuration of the C₃₁ alkane has been similarly confirmed.     

v-Triazolines. part XXI. Spiro[bicyclo[2.2.1]hept-2-ene[54']1',2'.s'-triazole]derivatives from cyclopentadiene and 5-amino-4-methylene-v-triazolines

1R^*, 4R^*, 5S^*, 5'S^*-5'-Amino-1'-(4-nitrophenyl)-4',5'-dihydrospiro[bicyclo [2.2. 1]hept-2-ene[5.4]-1',2',3'-triazoles]$\text{2}$ have been obtained both by ?4 +2]-cycloaddition of cyclopentadiene to amino-methylene-1-(4-nitrophenyl)-4,5-dihydro-v-triazoles $\text{1}$ and by [3+2]-cycloaddition of 4-nitrophenylazide to 5-aminomethylene-2-norborenes $\text{4}$. The configuration has been fully established by X-ray crystallographic analysis. The course of the cycloaddition and the thermal behaviour of $\text{2}$ are discussed.     

Marine natural products: fistularin-1, -2 and -3 from the sponge Aplysina fistularis forma fulva

Three new high molecular weight bromotyrosine-related metabolites, $\text{3a}$, $\text{4a}$ and $\text{5a}$, were isolated from the sponge Aplysina ( Verongia) fistularis forma fulva, and their structures were determined from high resolution ¹H NMR and other spectroscopic data. The new metabolites are formally derived by combination of major segments of two known Aplysina metabolites $\text{1a}$ and $\text{2}$.     

An intramolecular diels-alder approach to quassinoids—a stereoselective construction of a-aromatic klaineanone

Thermolysis of a benzocyclobutene derivative ($\text{20}$) prepared from norcamphor produced stereoselectively a tetracyclic compound ($\text{2}$), which was converted to a lactone ($\text{21}$) having correct stereochemistry at C₇, C₈, C₉, C₁₁, C₁₃, and C₁₄ positions of (±)-klaineanone.     

Isolation and structure of sergeolide,a potent cytotoxic quassinoid from picrolemma pseudocoffea

Sergeolide $\text{2}$, isolated from the French Guyanan Simaroubaceae, Picrolemma pseudocoffea Ducke, is a novel quassinoid possessing the normal C₂₀ basic skeleton with a butenolide function attached to the A ring. Structure $\text{2}$ was established by interpretation of the 400 MHz ¹H-NMR and the ¹³C-NMR data. It is highly cytotoxic and is active against mouse leukemia P388. The previously known isobruceine B $\text{1}$ was also isolated.     

The crystal structure of tris(triphenylphosphine)gold(I)-[dodecahydrido-6-thia-nido-decaborate(1—)]

The crystal structure of tris(triphenylphosphine)gold(I)[dodecahydrido-6-thia-nido-decaborate(1—)], [(C₆H₅)₃P]₃AuB₉H₁₂S, has been determined using X-ray techniques and counter data. The compound is a salt consisting of [(C₆H₅)₃P]₃Au⁺ cations and B₉H₁₂S^? anions. The cation is trigonal and nearly planar with AuP distances of 2.382(5) Å and PAuP anglés of 119.3(36)°. The B₉H₁₂S^? thiaborane anion is an open icosahedral fragment with the S atom in the 6 position, on the periphery of the decaborane polyhedron. The structure is the same as that found in solution for the isoelectronic B₁₀H₁₄^2? anion. Crystals are triclinic, space group P$\text{1}$, with a = 13.086(12), b = 19.635(32), c = 11.180(8) Å, α = 103.60(16), β = 72.10(9), and γ = 94.76(15)°. The structure was refined by least squares to a conventional R of 0.077.     

Chirality and conformational changes in 4-phenylphenanthrenes and 1-phenylbenzo[c]phenanthrene derivatives

NMR data of several 4-phenylphenanthrenes (15, 16) have revealed that the crowding in these compounds does not lead to chirality at temperatures as low as ?90°. The easy rotation of the phenyl substituent observed by NMR implies that notwithstanding the phenanthrene moiety in average behaves as a planar part the phenyl group does not experience steric hindrance.The analysis of temperature-dependent NMR spectra of several derivatives of 1-phenylbenzo[c]phenanthrenes (17-20) indicated that in these compounds exchange processes do occur. By calculations of the free energies of activation from the NMR data two processes could be distinguished: rotation of the phenyl substituent at one side of the helical benzo[c]phenanthrene moiety, for which ΔG^XXX_rot , is ca. 13.0$\text{kcal}\text{mol}$ or slightly larger when bulky substituents are present at C₂, and racemisation by a rotation of the phenyl group around the opposite end of the benzo[c]phenanthrene skeleton with simultaneous inversion of the helical conformation. For this process ΔG^XXX_rac is ca. 16$\text{kcal}\text{mol}$. The results have been compared with comparable data of related compounds like 1.8-diphenylnaphthalene, hexahelicene, and 4-methylbenzo[c] phenanthrenes, and gave evidence for the remarkably small, space-demanding properties of the phenyl substituent in these compounds.     

Bridgehead nitrogen heterocycles from 2,4,6-triphenyl- pyrylium cation and thiosemicarbazide or thiocarbohydrazide

2,4,6-Triphenylpyrylium with thiosemicarbazide and thiocarbohydrazide, gives 2-pyrazolines $\text{3a}$ and $\text{3b}$ which undergo cyclization yielding pyrazolo(1,5-c]pyrimidine 5 and pyrazolo [2,3-d]-1,2,4-triazepine $\text{7}$ derivatives, respectively. Reaction of $\text{7}$ with phenacyl bromides gave 1,3-thiazolo[3,2-b]pyrazolo [2,3-d]-1,2,4-triazepin-4-iums $\text{10}$. Compound $\text{3a}$ on treatment with phenacyl bromides gave 1-(4'-aryl-thiazol-2'-yl)-2-pyrazoline derivatives $\text{6}$. Compound $\text{3b}$ reacts with acyl chlorides to give pyrazolo[1,5-c]pyrimidine derivatives $\text{14}$, and with aromatic aldehydes giving the 2-(Δ^2'1 pyrazolin-1-yl)-5-aryl-1,3,4-Δ²-thiadiazolines $\text{12}$ which were easily converted to the corresponding 2-(Δ²-pyrazolin-1-yl)-5-aryl-1,3,4-thiadiazoles $\text{13}$.     

Organotellurium derivatives: III. Synthesis of anionic complexes of 1-telluracyclopentane(IV) 11 diiodide

Complexes containing tetrahalotelluracyclopenzane anions of the type (R₄M₂)⁺[C₄H₈TeX₂X′₂]^2- (where R = CH₃, C₂H₅, C₃H₇, C₄H₉, C₆H₁₃, C₇H₁₅ or C₆H₅; M = N, P, As or Sb; X = Cl, Br, or I and X′ = I, Cl, Br, NCO, NCS, or N₃) have been synthesized, (i) by the interaction of 1-telluracyclopentane $\text{1}\text{1}$ diiodide with the corresponding tetraorganoammonium, -phosphonium, -arsonium, or -stibonium halides in nonaqueous solvents and (ii) via halogen exchange between complex anions and silver or alkali metal halides. The second method also yielded several pseudohalide and mixed halide-pseudohalide derivatives. The ionic nature of the new complex anions has been established by conductance and molecular weight measurements. NMR and IR spectra of some of the derivatives are discussed.     

Action of tert-butyl azidoformate on the conjugate bases of 1,2,3,4-tetrahydro-9H-carbazole and other indole derivatives

tert-Butyl azidoformate ($\text{2}$) reacts with the conjugate bases of $\text{3a}$, $\text{7a}$, $\text{9}$ (R¹ = R² = CH₃), and $\text{9}$ (R¹ = CH₃, R² = H) to give products [$\text{4}$, $\text{8}$, $\text{12}$, and $\text{14}$, respectively] in addition to the expected N-(tert-butoxycarbonyl)indole derivatives.     

Volume changes on mixing perfluoroalkanes with alkanes or ethers at 298.15 K

Excess molar volumes V^E at 298.15 K have been determined by means of a vibrating-tube densimeter for binary mixtures of n-hexane with a perfluoroalkane, C₅–C₈, and of perfluorohexane with a n-alkane, C₅–C₈, or an ether (diethyl, dipropyl, dibutyl, butyl methyl, and butyl ethyl ether). The systems perfluoropentane+hexane, perfluorohexane+pentane or hexane or diethyl ether have been investigated in the entire mole fraction range, while the other mixtures only in the miscibility regions. The observed V^E values are positive (up to 5.5 cm³ mol⁻¹) and among the largest known for non-electrolyte systems. Limiting partial molar volumes, $\text{V}\text{̄}\text{°}$, have been evaluated for each component of the examined mixtures. The behaviour of $\text{V}\text{̄}\text{°}$ has been discussed in terms of the scaled particle theory (SPT) and of a simple group additivity scheme based on surface interactions. An estimate has been made of the average separation distance of solvent from solute molecules.     

The structure and absolute configuration of heterophylloidine

The structure and absolute configuration of heterophylloidine, a new C₂₀-diterpenoid alkaloid isolated from $\text{Aconitum heterophylloides}$ Stapf, have been determined with the aid of ¹³C NMR spectral data and single-crystall X-ray analysis of the product obtained by treatment of heterophylloidine with aqueous hydrobromic acid.     

C2O(X3Σ−): absolute reaction rates measured by laser induced fluoresence

Absolute rate constants are reported for reactions of C₂O($\text{X}\text{?}$³Σ^?) under pseudo-first-order decay conditions. C₂O is generated by laser photodissociation of C₃O₂ at 266 nm, and detected by dye-laser induced fluorescence on the $\text{A}\text{?}$³Π_i-$\text{X}\text{?}$³Σ^? transition. Rate constants of (433 ± 12), (3.30 ± 0.12) and (1.12 ± 0.05) × 10^?13 cm³ molecule^?1 s^?1 are reported for reactions with NO, O₂ and isobutene. The NO value is approximate due to an apparent dark reaction between NO and C₃O₂. Upper limits of 1 × 10^?14 cm³ molecule^?1 s^?1 are reported for reactions with H₂, CO₂, C₃H₂ and C₂H₄. The C₂O + C₃O₂ reaction does not follow pseudo-first-order decay kinetics. Two explanations are proposed to explain this observation. Results are compared with previous relative rate measurements and are discussed in terms of their relevance to combustion chemistry.     

Microwave-optical double resonance in molecular ions. Co+

Microwave—optical double resonance signals have been detected in a mass-selected ion-beam spectrometer for ¹²C¹⁶O⁺. With the optical excitation of fluorescence from the R₁ ($\text{1}\text{2}$) line of the (0,0) band of the A²Π_{$\text{3}\text{2}$} ← X²∑ transition of 20350.6 cm^?1, the microwave resonances occurred at 118101.8 ± 0.2 MHz and at 117694 ± 2 MHz corresponding to the N= 1, J = $\text{3}\text{2}$ ← N = 0, J = $\text{1}\text{2}$ and the N = 1, J = $\text{1}\text{2}$ ← N = 0, J = $\text{1}\text{2}$ transitions.     

The chemistry and the stereochemistry of poly(N-alkyliminoalanes) : XVI. The crystal and molecular structure of the compound [HAlNCH(CH3)C6H5]6·13 C6H14

The crystal structure of [HAlNCH(CH₃)C₆H₅] ₆·$\text{1}\text{3}$ C₆H₁₄ has been determined by single crystal three-dimensional X-ray analysis. Block-matrix least-squares refinement led to conventional R factor of 0.08. The molecule is built up of a prismatic hexagonal framework, (AlN)₆. Average AlN distances are 1.893(6) and 1.981(7) Å in the six-membered rings and in transverse bonds, respectively. Crystal data: hexagonal, space group P6₃, a 22.296(5), c 18.144(4) Å, V 7811.2 ų, Z = 6, D_c 1.16 g cm^?3.