• Issue

    Angewandte Chemie International Edition in English: Volume 18, Issue 2

    91-172
    February 1979

Reviews

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Structure and Bonding in Cyclic Sulfur-Nitrogen Compounds

  • Pages: 91-97
  • First Published: February 1979
Structure and Bonding in Cyclic Sulfur-Nitrogen Compounds

The scope and variety of sulfur-nitrolgen rings become more comprehensible on adopting the coordination number of sulfur as a classification principle. In compounds of two-coordinate sulfur (and nitrogen) the π-electrons are largely delocalized; the coordination number and bond length can be correlated in some compounds of sulfur with higher coordination number.

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Empirical Parameters of Solvent Polarity as Linear Free-Energy Relationships

  • Pages: 98-110
  • First Published: February 1979

Effects of solvents on the rates of chemical reactions and on equilibria have long been known, but there are still no reliable methods for their description and prediction. Empirical parameters derived, e.g. from series of reactions, are of great value in this connection.

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New Applications of Computers in Chemistry

  • Pages: 111-123
  • First Published: February 1979
New Applications of Computers in Chemistry

The design of entirely new syntheses, and the classification and documentation of structures, substructures, and reactons are examples of new applications of computers to chemistry. The starting point is a mathematical model of constitutional chemistry based on the extension of the concept of isomerism to ensembles of molecules.

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Activation Analysis—Its Present State of Development and Its Importance as an Analytical Tool

  • Pages: 123-147
  • First Published: February 1979
Activation Analysis—Its Present State of Development and Its Importance as an Analytical Tool

The feasibility of simultaneous multielement determinations is one of the particular advantages of activation analysis. This trace analytical method can detect many elements and isotopes at concentrations below the ppb level.

Communications

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Synthesis of the Mast Cell Degranulating (MCD) Peptide from Bee Venom

  • Pages: 147-148
  • First Published: February 1979

Potential value in the therapy of rheumatism and other inflammation processes could attach to the MCD peptide from bee venom if it were available in larger quantities. The peptide consists of 22 amino acids and contains two disulfide bridges. Its first total synthesis has now been accomplished.

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Selective Electrochemical Removal of Protecting Groups in Nucleotide Synthesis

  • Pages: 148-149
  • First Published: February 1979
Selective Electrochemical Removal of Protecting Groups in Nucleotide Synthesis

Selective removal of an ester group from the completely protected nucleoside 3′-phosphate (2) by electrochemical reduction solves a serious problem of nucleotide synthesis. Reaction (2) → (3) requires a potential of −0.5 V; (2) → (1) can be accomplished by acid hydrolysis. At −1.2 V the remaining ester groups are removed from (1).

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Di-tert-Butyl Acetylenedicarboxylate and Its Cyclotrimerization

  • Pages: 149-150
  • First Published: February 1979

Di-tert—butylacetylenedicarboxylate (1)—surprisingly not synthesized before—is remarkable from a chemical standpoint. Its cyclotrimerization shows that the tert-butyl groups do not exert strong steric hindrance. Ready cleavage (without base) of the esters obtained from (1) is of advantage.

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Synthesis and Properties of Tetrabutylammonium Octaiododirhenate(III),[(n-C4H9)4N]2[Re2I8]

  • Pages: 150-151
  • First Published: February 1979

Salts of the anion [Re2I8]2−, containing a ReRe quadruple bond, have hitherto defied preparation. However, they are accessible by reaction in nonaqueous solution. The HI used should be free from water and iodine (XCL, Br).

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Long-Chain Alkylammonium Ions as Phase Transfer Reagents for the Synthesis of Mixed-Ligand Complexes of the Platinum Metals

  • Pages: 151-152
  • First Published: February 1979

Phase transfer reactions have great preparative potential in inorganic chemistry. Thus the first halo complexes of Os, Ir, Pt, and Re have now been synthesized in the presence of [(C12H25)3NH]HSO4; they contain not only fluorine but also bromine and iodine as ligands. The following anions are examples (XCL or Br):

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Detection of Large-Ring Sulfur Molecules in Liquid Sulfur: Simple Preparation of S12, α-S18, and S20 from S8

  • Pages: 152-153
  • First Published: February 1979

The molecular composition of liquid sulfur has been a topic of discussion for generations. It was known to contain the homocyclic species S6 and S7, as well as S8. The isolation of S12, α-S18, and S20, and the detection of Sx with x = 23—34 are new accomplishments.

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23Na-NMR Study of the Competition of Biogenic Amines with Sodium Ion for Binding to Lasalocid (X-537A)

  • Pages: 153-154
  • First Published: February 1979
23Na-NMR Study of the Competition of Biogenic Amines with Sodium Ion for Binding to Lasalocid (X-537A)

Lasalocid (X-537 A) (1), an ionophoric antibiotic, complexes both biogenic amines and inorganic cations. It has now been established that Na+ and serotonin bimaleate, 3-hydroxytyramine, or L-norepinephrine compete for binding to (1).

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Reversal of the Selectivity Principle in Free-Radical Addition to Alkenes

  • Pages: 154-155
  • First Published: February 1979

The selectivity of alkenes in radical reactions increases with increasing reactivity, i.e. the most selective alkenes are the most reactive ones. This result could be of interest, say in radical polymerization.

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A New Cationic Binuclear Trihydrido Complex Containing One Four-and One Five-Coordinate Platinum Atom

  • Pages: 155-156
  • First Published: February 1979
A New Cationic Binuclear Trihydrido Complex Containing One Four-and One Five-Coordinate Platinum Atom

Two Pt and three H atoms, together with four PPh3 groups, make up the cation of complex (1), RPh, which can be isolated as yellow, air-stable crystals. The remarkable structure was elucidated by NMR spectroscopy.

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Stable Aza- and Diazacyclopentadienylium Salts

  • Pages: 156-157
  • First Published: February 1979
Stable Aza- and Diazacyclopentadienylium Salts

Aza-analogues of the antiaromatic cyclopentadienyl cations are present in the salts (1) and (2). The antiaromatic character of the azacations is weaker than that of the parent cation; the donor groups contribute to stabilization.

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An Example of the Equilibrium Ethylenehydridometal ⇌ Ethylmetal Complex

  • Pages: 157-158
  • First Published: February 1979

An understanding of the processes involved in the insertion of olefins into MH bonds is important for many catalytic processes. Equilibrium between an ethylenehydrido-metal (1) and an ethyl-metal complex (2) in solution has been demonstrated for the first time.

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Stepwise Addition of a Lewis Acid and a Lewis Base to a Metal-Metal Bond

  • Pages: 158-159
  • First Published: February 1979
Stepwise Addition of a Lewis Acid and a Lewis Base to a Metal-Metal Bond

Cleavage of the CoCo bond in the complex is feasible without disrupting the binuclear structure. Thus a Lewis acid, e.g. CF3COOH, and a Lewis base. e.g. PMe3, can be added successively to (1).

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Hindered Rotation at the Triple Bond

  • Pages: 159-161
  • First Published: February 1979
Hindered Rotation at the Triple Bond

Rotation within the linear group can be hindered by substituents; the first example is bis(dimethyltriptycenyl)ethyne (1), RiRaCH3. Stuart-Briegleb space-filling models do not reproduce this effect.

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Surprising Transformation of Azulene by Cycloaddition with 1-(Diethylamino)propyne

  • Pages: 161-162
  • First Published: February 1979
Surprising Transformation of Azulene by Cycloaddition with 1-(Diethylamino)propyne

The cyclopentacyclononene derivative (3). the first compound to contain this ring system and also the first stable cyclononatetraene not to have an annelated benzene ring, has been synthesized from the “ethanoazulene” (1). This synthesis is possible because azulene reacts readily with the ynamine (2), to give the tricyclic species (4). Although 4,6,8-methylazulene initially gives the desired ring system (5), immediate transannular bonding occurs. The bracket in (1) prevents this reaction.

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Facile Ring Enlargement of Azulene to Give the Cyclopentacyclononene System by Dipolar Cycloaddition

  • Pages: 162-163
  • First Published: February 1979
Facile Ring Enlargement of Azulene to Give the Cyclopentacyclononene System by Dipolar Cycloaddition

The cyclopentacyclononene derivative (3). the first compound to contain this ring system and also the first stable cyclononatetraene not to have an annelated benzene ring, has been synthesized from the “ethanoazulene” (1). This synthesis is possible because azulene reacts readily with the ynamine (2), to give the tricyclic species (4). Although 4,6,8-methylazulene initially gives the desired ring system (5), immediate transannular bonding occurs. The bracket in (1) prevents this reaction.

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3-Bromo-3-methyl-2-trimethylsiloxy-1-butene—A New Cycloaddition Reagent

  • Pages: 163-164
  • First Published: February 1979
3-Bromo-3-methyl-2-trimethylsiloxy-1-butene—A New Cycloaddition Reagent

A facile entry to cycloheptenones and cyclopentanones is provided by the new cyclization reagent (1). Examples are the synthesis of Karahanaenone (2) from isoprene, and of(±)-α-cuparenone (4), R = p-CH3C6H4, from 1-isopropenyl-4-methylbenzene.

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Faclie Regeneration of Carbonyl Compounds from 1,3-Dithiane 1-Oxides via 1-Ethoxy-1,3-dithianium Salts

  • Pages: 165-166
  • First Published: February 1979
Faclie Regeneration of Carbonyl Compounds from 1,3-Dithiane 1-Oxides via 1-Ethoxy-1,3-dithianium Salts

Liberation of aldehydes RCHO from dithiane oxides (1) can be accomplished by transformation into the salts (3) and their cleavage with water. The reaction sequence (1)→(3) → RCHO is milder than the usual cleavage of (1) with acid.

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Bond Switch with Participation of π-Bonded SIV in Thiathiophthene-Analogous Systems

  • Pages: 166-167
  • First Published: February 1979
Bond Switch with Participation of π-Bonded SIV in Thiathiophthene-Analogous Systems

Dynamic bond switching at π-hypervalent sulfur has now been demonstrated. (1) and (2) rapidly equilibrate; this reaction involves the thiathiophtheneanalogous system (3).

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Synchronous Mechanism of the 1,1-Cycloaddition of Nitrile Ylides to CC Double Bonds

  • Pages: 167-168
  • First Published: February 1979
Synchronous Mechanism of the 1,1-Cycloaddition of Nitrile Ylides to CC Double Bonds

An insight into the mode of reaction of nitrile ylides such as (1) has come from the study of their intramolecular cyloaddition to double bonds. The formation of (2a) and (2b) in the ratio 9:1 is assessed as indicating a synchronous mechanism (RpCL—C6H4).

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Surn:x-wiley:05700833:media:ANIE197901681:tex2gif-stack-1 as Simultaneous End-on and Side-on Bonded Ligand in the Novel Transition-Metal Complex [Mo4(NO)4S13]4−

  • Pages: 168-169
  • First Published: February 1979
S as Simultaneous End-on and Side-on Bonded Ligand in the Novel Transition-Metal Complex [Mo4(NO)4S13]4−

Five different bonding states of sulfur are found in complex (1). It is a further example of the importance of Surn:x-wiley:05700833:media:ANIE197901681:tex2gif-stack-2 ligands in the stabilization of unusual coordination compounds of transition metals.

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Bis(chlorophenylphosphoranediyl)methane

  • Page: 169
  • First Published: February 1979
Bis(chlorophenylphosphoranediyl)methane

A new synthetic unit for phosphorus-carbon compounds has been discovered in the symmetrical “carbodiphosphorane” (2). It forms a 1:1 salt with HCL, and a dioxide (via elimination of RCL) with alcohols ROH.

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Flash Vacuum Thermolysis of Doubly Unsaturated Acyl Halides to Give Phenols

  • Page: 170
  • First Published: February 1979
Flash Vacuum Thermolysis of Doubly Unsaturated Acyl Halides to Give Phenols

The simplest dienylketene-phenol rearrangement has been achieved by vacuum flash thermolysis of sorboyl chloride at 6 × 10−5 torr/660°C. Other dienylketenes can also be generated under these conditions.