Technical Procedures for the Syntheses of Carotenoids and Related Compounds from 6-Oxo-isophorone: Syntheses of (3R,3′R)-Zeaxanthin. Part I

Starting from the readily available, optically active (4R)-4-hydroxy-2,2,6-trimethylcyclohexanone ( 1 ), a new technical synthesis of (3R,3′R)-zeaxanthin is described. According to a 2(C₉ + C₆) + C₁₀ = C₄₀ construction scheme, the ketone 1 was first transformed with (E)-3-methylpent-2-en-4-yn-1-ol ( 5 ) into a C₁₅-intermediate which, by a three-step sequence, could be converted into the known olefinic C₁₅-Wittig salt 4 . Optimized conditions for the final Wittig reaction of 4 with the C₁₀-dialdehyde 3 are discussed. Based on 1 , the overall yield of the entire technical process is ca. 40%.     

Transient absorption spectra of 2-hydroxybenzophenone photostabilizers

Transient absorption spectra (400–600 nm) of 2-hydroxybenzophenone and the methyl methacrylate copolymer of 2-hydroxy, 3-allyl, 4,4'-dimethoxybenzophenone following 355 nm excitation (7–480 ps delay) are reported. A short-lived, 435 nm transient (τ ≈ 10 ps in CH₂Cl₂) for both molecules is assigned to the lowest excited singlet before internal proton transfer. Weaker, broad T-T absorption is observed after 480 ps.     

Critical evaluation of additivity schemes for estimating heats of atomization

Additivity schemes for estimating heats of formation and heats of atomization of alkanes and halo- alkanes are scrutinized. A least squares analysis of the heats of atomization of alkanes leads to a revision of the values of the parameters. The improvement in the estimated heats of atomization over the values obtained with parameters previously suggested amounts to at least 100%. The reasons for the deviations from the experimental values are discussed. These parameters can be transfered to haloalkanes. Additional parameters necessary for estimating heats of atomization of haloalkanes are also obtained through least squares analyses.     

Structure determination of zinc iodide complexes formed in aqueous solution

Structures of the complexes formed in aqueous solutions between zinc(II) and iodide ions have been determined from large-angle X-ray scattering, Raman and far-IR measurements. The coordination in the hydrated Zn²⁺ hexaaqua ion and the first iodide complex, [ZnI]⁺, is octahedral, but is changed into tetrahedral in the higher complexes, [ZnI₂(H₂O)₂], [ZnI₃(H₂O)]^– and [ZnI₄]^2–. The Zn-I bond length is 2.635(4)Å in the [ZnI₄]^2– ion and slightly shorter, 2.592(6)Å, in the two lower tetrahedral complexes. In the octahedral [ZnI(H₂O)₅]⁺ complex the Zn-I bond length is 2.90(1)Å. The Zn-O bonding distances in the complexes are approximately the same as that in the hydrated Zn²⁺ ion, 2.10(1)Å.     

Ethylenediaminetetraacetato-monoperoxo complexes of vanadium(V)

Summary The monoperoxo complexes, M₂[VO(HEDTA)(O₂)]· 4H₂O, where M is K⁺ or NH ₄ ⁺ and H₄EDTA is ethylene-diaminetetraacetic acid, were prepared and characterized by Raman and i.r. spectra in the solid state and in aqueous solution. The single crystal X-ray study revealed a pentagonal bipyramidal anion structure with a tetradentate HEDTA(3—) ligand. The decomposition of complexes in aqueous solution to blue vanadium(IV) complexes as end products proceeds via a nonperoxo complex of vanadium.     

Glycosylidene Carbenes. Part 18. Insertion of glycosylidene carbenes into the Sn?H bond of tributyl- and triphenylstannane: A synthesis of stannoglycosides

Insertion of the glycosylidene carbenes, derived from the gluco- and the manno-diazirines 1 and 2 , into the Sn? H bond of R₃SnH (R = Bu or Ph) leads to the fully substituted stannoglycosides 3 – 8 (53–77%). The 1,2-cis-configurated products are formed preferentially (α-D /β -D ranges from 2.5:1 to 5.1:1 with 1 , and 1:1.3 to 1:4.2 with 2 ). Relative to CH₂Cl₂, THF favors formation of the equatorial Sn-glycosides. The stannylated (benzyloxy)glucals 9 and 10 were isolated as side products. The reaction of 1 with (Bu₃Sn)₂ yielded 9 (17% in CH₂Cl₂; 36% in CCl₄) together with the azines 11 and the benzyloxyglucal 12 . NMR Data of the Sn-glycosides 3 – 8 show evidence for an anomeric effect, ¹J(C(1),H) being larger in the axial and ¹J(Sn,C(1)) larger in the equatorial anomers.     

“Deuterated” Raney nickel: deuteration (reduction) of alkenes,carbonyl compounds and aromatic rings. Proton-deuterium exchange of “activated” aliphatic and aromatic ring hydrogens.

In the absence of deuterium gas, the reaction of deuterated Raney nickel with benzene derivatives, carbonyl compounds, alkenes and activated methylene groups gave either fully deuterated (reduced) products or led to hydrogen-deuterium exchange.     

Axial dispersion in coiled tubular reactors

A theoretical and experimental treatment of axial dispersion in coiled tubes is presented. The dispersion, δ, is related to the theoretical plate height divided by four times the radius of the tube (H/4r). This parameter, when plotted against the product of the Reynolds number and the Schmidt number (ReSc), accurately predicts maxima in dispersion curves. Variations in the boundary layer thickness and the velocity profile cause the dispersion to pass through a maximum at a constant value of log (De²Sc^1·14) equal to 6.13 for unretained solutes (De is the Dean number). A new measure of dispersion is proposed; the reduced dispersion, ? = 256/(Re^0.667Sc), is derived from the experimental behavior of dispersion at values of log (De²Sc^1·14) smaller than 6.13. The logarithm of ? is found to be approximately zero for 2.2 < log (De²Sc^1·14) < 6.1 and to decrease linearly with log (De²Sc^1·14) at higher values. Experiments with four solutes that have a wide range of molecular diffusivities are reported. Results agree with theory.     

Synthesis,Structures, and Properties of Layered Quaternary Chalcogenides of the General Formula ALnEQ4 (A = K,Rb; Ln = Ce,Pr, Eu; E = Si,Ge; Q = S,Se)

Four related quaternary compounds containing rare‐earth metals have been synthesized employing the molten flux method and metathesis. The reactions of Eu and Rb₂S₅ with Si and Ge in evacuated fused silica ampoules at 725 °C for 150 h yielded RbEuSiS₄ ( I ) and RbEuGeS₄ ( II ), respectively. On the other hand, a reaction between CeCl₃ and K₄Ge₄Se₁₀ at 650 °C for 148 h has yielded KCeGeSe₄ ( III ) and KPrSiSe₄( IV ) was obtained by the reaction of elemental Pr, Si and Se in KCl flux at 850 °C for 168 h. Crystal data for these compounds are as follows: I , orthorhombic, space group P2₁2₁2₁ (#19), a = 6.392(1), b = 6.634(2), c = 17.001(3) Å, α = β = γ = 90°, Z = 4; II , monoclinic, space group P2₁/m (#11), a = 6.498(2), b = 6.689(3), c = 8.964(3) Å, β = 108.647(6)°, Z = 2; III , monoclinic, space group P2₁ (#4), a = 6.852(2), b = 7.025(2), c = 9.017(3) Å, β = 108.116(2)°, Z = 2; IV , monoclinic, space group P2₁ (#4), a = 6.736(2), b = 6.943(2), c = 8.990(1) Å, β = 108.262(2)°, Z = 2. The crystal structures of I ‐ IV contain two‐dimensional corrugated anionic layers of the general formula, [LnEQ₄]^? (Ln = Ce, Pr, Eu; E = Si, Ge and Q = S, Se) alternately piled upon layers of alkali cations. In addition to structural elucidation, Raman and UV‐visible spectroscopy, and magnetic measurements for compound III (KCeGeSe₄) are also discussed.     

Characterization and crystal structures of copper(II), cobalt(II), and nickel(II) complexes with two kinds of piperidine carboxylic acids

Copper(II) complex with -piperidine-3-carboxylic acid ( -Hpipe-3):[Cu( -pipe-3)₂(H₂O)] and cobalt(II) and nickel(II) complexes with piperidine-4-carboxylic acid (Hpipe-4):[M(Hpipe-4)₂(H₂O)₄]Cl₂ (M: Co, Ni) have been prepared and characterized by means of IR and powder diffuse reflection spectra, thermal analysis, and magnetic susceptibility. The crystal structures of these complexes have been determined by X-ray diffraction. The crystal of [Cu( -pipe-3)₂(H₂O)] is orthorhombic with the space group Pbcn. The copper atom is in a square pyramidal geometry, ligated by two carboxylato oxygen atoms, two nitrogen atoms, and a water molecule. One molecule of this complex consists of either -piperidine-3-carboxylic acid or -piperidine-3-carboxylic acid. The crystals of [M(Hpipe-4)₂(H₂O)₄]Cl₂ are monoclinic with space group P2₁/n. In these complexes the metal atom is in an octahedral geometry ligated by two carboxylato oxygen atoms and four water molecules.