Intramolecular photoreactions of 6-(ω-alkenyl)-4-methoxy-2-pyrones

6-(ω-Alkenyl)-2-pyrones 3a-c and 8a, b were prepared and the photochemical reactions were investigated. Photosensitized reactions of 3b, c gave intramolecular [2+2]-cycloadducts 11b, c as tricyclic lactones, site-and regio-specifically. They are not frontier-orbital-controlled adducts. On the other hand, 3a, 8a, b afforded cyclobutenecarboxylic acids, 10a, 14a, b , respectively. The end-ester group at the side-chain is thought not to be effective for the intramolecular phptoaddition.     

Stereochemistry in cationic polymerization of alkenyl ethers. V. Stereochemistry of acetal additions as model reactions for the polymerization of alkenyl ethers

Acetal additions to β-substituted vinyl ethers having a variety of substituents (alkenyl ethers) were stereochemically investigated as model reactions for their cationic polymerization. The reactions catalyzed by BF₃O(C₂H₅)₂ in CH₂Cl₂ at O°C gave 1:1 adducts, the steric structure of which was determined by means of ¹³C-NMR spectroscopy. trans-Alkenyl ethers always gave adducts with a single structure stereospecifically, indicating that the intermediate carbocation attacks a trans-alkenyl ether from a definite direction independent of the bulkiness of substituents. On the other hand, cis-alkenyl ethers formed adducts with two steric structures, and the direction of cation addition was found to depend on the bulkiness of the alkoxy group involved. The above trends were in agreement with the results for poly(alkenyl ether)s and allowed detailed discussion of the stereochemistry of the propagation processes in alkenyl ether polymerizations.     

Mechanism of stereoregular polymerization of butadiene by homogeneous Ziegler-Natta catalysts. I. Effects of the species of transition metals

Butadiene was polymerized by catalysts of the type: metal acetylacetonate (metal: Ti to Ni in the periodic table)–triethylaluminum–aluminum halide, with various ratios of triethylaluminum to aluminum halide. The minimum cis content was observed with vanadium catalyst in all cases, while the minimum polymer yields were observed with the iron and the manganese catalysts. These transition metal effects are discussed in terms of the crystal field theory, and it is suggested that the electrostatic interaction between the nearly nonbonding electrons of transition metal atom and a butadiene molecule or a growing end of the polymeric chain plays an important role in the stereoregular polymerization of butadiene by homogeneous Ziegler-Natta catalysts.     

Synthesis of polystyenes with different stereoregularities by anionic polymerization

The stereoregularity of polystyrene prepared by anionic polymerization was determined by means of ¹³C-NMR spectroscopy. The stereoregularity changed with such polymerization conditions as catalyst, solvent, and temperature. Sodium naphthalene as catalyst gave a syndiotactic-rich polystyrene of 66–68% syndiotactic dyads independently of solvent and temperature, while potassium and cesium naphthalenes as catalyst produced polystyrenes with different stereoregularities ranging from syndiotactic-rich to isotactic-rich configurations, depending on solvent and temperature. The mechanism of anionic polymerization which caused the difference in stereoregularity was discussed from the viewpoint of growing ionic species.     

The cyclodextrin-quinone inclusion compounds in an aqueous solution at 77. K. I. 9,10-anthraquinone sulfonates and 1,4-naphthoquinones

The complex formation between cyclodextrins (-, -, -CD's and dimethyl-\-CD) and quinones (three 9, 10-anthraquinone sulphonates and two 1,4-naphthoquinones) in the water-ethylene glycol 1:1 mixture solution at 77 K was investigated using the n^* phosphorescence spectra and their excitation spectra and lifetimes of the quinones. It was concluded on the basis of the experimental results that the complexes have various structures according to the CD-quinone combination used. Vitamin K₃ was found to form the photodimer very efficiently in the presence of -CD. The assumed CD:quinone ratios of the complexes are given.     

A New Family of Indoaniline-Derived Calix[4]arenes: Synthesis and Optical Recognition Properties as a Chromogenic Receptor(1)

A new family of indoaniline-derived calix[4]arenes has been synthesized for the purpose of developing a new chromogenic receptor. A condensing reaction of calix[4]arene (1) with 4-(diethylamino)-2-methylaniline hydrochloride (2) in the presence of an oxidizing agent under alkaline conditions affords mono- (3), 1,2-bis- (4), 1,3-bis- (5), and tetrakisindoaniline-derived (6) calix[4]arenes after careful column chromatography. Compound 3 is crystallized from a CHCl(3)-MeOH solution, and the crystal structure was determined by X-ray analysis. The crystal is monoclinic, space group P2(1)/n, Z = 4, a = 19.507(6) ?, b = 18.591(6) ?, c = 8.524(2) ?, beta = 94.69(2) degrees. The final R value for 2406 reflections of F(o) > 3sigma(F(o)) is 0.085. A unique intramolecular hydrogen-bonding network involving the carbonyl oxygen of indoaniline for 3 implied that the quinone carbonyl group as an acceptor of the chromophore can easily be subjected to an electrostatic interaction in the lower rim. Indeed, 1,3-bis(indoaniline)-derived 2,4-bis((ethoxycarbonyl)methoxy)calix[4]arene 7, prepared by the reaction of 5 with ethyl bromoacetate in the presence of NaH, is capable of undergoing an efficient ion-dipole interaction between the binding cation and the two quinone carbonyl groups of the chromophores, so that a selective Ca(2+)-induced pronounced color change (wavelength change > 100 nm) occurs with an association constant on the order of 10(6) in 99% EtOH, making 7 of potential use as an optical sensor for Ca(2+) detection. The IR and NMR studies have indicated that Ca(2+) is encapsulated in the cavity made by the distally located OCH(2)CO(2) groups on the lower rim of the cone-shaped calix[4]arene segment. Interestingly, however, the shape of the cavity in which Ca(2+) has been encapsulated does not have a C(2) axis of symmetry, as inferred from the (1)H-(1)H COSY experiment. On the other hand, 1,2-bis(indoaniline)-derived analogue 8 shows no response with metal ions, which can be interpreted to mean the absence of a cavity for encapsulation on the lower rim.     

Stark and Zeeman spectroscopies of 4f 66s6p 7G1-6 levels in Sm I under external electric and magnetic fields

Systematic study of hyperfine structures, Zeeman and Stark effects in Sm I is performed for the lowest ⁷G_1-6 levels belonging to the configuration 4f ⁶6s6p by atomic-beam laser spectroscopy with fluorescence detection. The hyperfine coupling constants of ⁷G_2-6 levels are determined. From the Zeeman splittings for the 4f ⁶6s ^{2 7}F_2-6 ? 4f ⁶6s6p ⁷G_2-6 transitions, g-values are determined for the ⁷G_2.6 levels and the precision is improved by several orders of magnitude. From the Stark splittings for the ⁷F_0-3 ? ⁷G_1-3 transitions, tensor polarizabilities α ₂(J) are determined for the upper ⁷G_1-3 levels. Particularly for the ⁷G₁ level (15 650.55 cm^?1) which has close-lying opposite-parity level, the isotope dependence of α ₂(J) is clearly observed for the first time.     

New methods and reagents in organic synthesis. 56. Total syntheses of patellamides B and C,cytotoxic cyclic peptides from a tunicate 2. Their real structures have been determined by their syntheses.

The proposed structures of patellamides B and C, cytotoxic lipophilic cyclic peptides from a marine tunicate, have been revised on the basis of the spectral data of their partial hydrolysates, and their revised structures have been synthetically confirmed by the use of diphenyl phosphorazidate(DPPA) and diethyl phosphorocyanidate(DEPC).     

Diethyl phosphorocyanidated (DEPC). A novel reagent for the classical Strecker's α-amino nitrile synthesis

Diethyl phosphorocyanidate (DEPC) can be efficiently used for the synthesis of α-amino nitriles from carbonyl compounds and amines. The reaction may be called a modified Strecker synthesis.