Synthetic studies toward maytansinoids (2) a new strategy based on asymmetric induction by heteroconjugate addition of methyllithium onto pyranosyl hetero-olefins

The functionalized pyranosyl hetero-olefins $\text{4a}$, $\text{13}$ and $\text{15}$ received a remarkable diastereoselective addition of methyllithium to form $\text{threo}$ adducts, one of which was introduced into a possible synthetic intermediate as $\text{3}$ for maytansine ($\text{1}$) along Scheme I.     

Approximate empirical formula for X-ray intensity in radioactive nuclides

Known intensities of X-rays emitted from radioactive nuclides have been plotted against atomic number, and a distinct correlation has been found only for EC-decay type nuclides, as follows: 2.75 Z^1.06>X>0.507 Z^1.06, and X_{most probable}=1.18 Z^1.06, where X is the absolute percentage and Z is the atomic number of the decay product.     

Evaporation behavior of water from aqueous dispersions of multihollow particles prepared by the stepwise alkali/acid method

In order to clarify the formation mechanism of multihollow structures inside styrene–methacrylic acid copolymer particles prepared by the stepwise alkali/acid method, which we proposed in 1990, the evaporation behavior of water from aqueous dispersions of the original carboxylated particles and those after the alkali treatment and the stepwise alkali/acid treatments was examined. It is concluded that the particle after the alkali treatment had a number of small water pools inside. Received: 22 February 2001 Accepted: 20 June 2001     

X-ray crystal structure analyses and atomic charges of color former and developer. I. Color developers

The crystal and molecular structures of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A, BPA) (1), benzyl 4-hydroxybenzoate (2), 1,7-bis(4-hydroxyphenylthio)-3,5-dioxaheptane (3) and 4-hydroxyphenyl 4-isopropoxyphenyl sulfone (4) have been determined by X-ray crystal structure analysis. Theoretical calculations of the steric hindrance and semiempirical quantum chemical calculations to determine the color characteristics have been carried out. It is clear that the energy barriers for the variation of the orientation of phenol group in 1 to 4 are due to steric hindrance caused by the other moiety and the peak profiles are due to repulsive interactions of the other moiety. Net atomic charges on the hydrogen of the OH group are larger than those on the other atoms in the molecules. This high electron charge of the para orientation will cause the different thermosensitivity and stabilization.     

Fock representations of the affine Lie algebraA 1 (1)

The aim of this note is to show that the affine Lie algebraA ₁ ⁽¹⁾ has a natural family _, ,v of Fock representations on the spaceC[x _i,y _j;i andj ], parametrized by (,v) C ². By corresponding the highest weight _, of _, to each (,), the parameter spaceC ₂ forms a double cover of the weight spaceC₀C –₁ with singularities at linear forms of level –2; this number is (–1)-times the dual Coxeter number. Our results contain explicit realizations of irreducible non-integrable highest wieghtA ₁ ⁽¹⁾ -modules for generic (,v).     

Influence of nonionic emulsifier included inside carboxylated polymer particles on the formation of multihollow structure by the alkali/cooling method

The influence of nonionic emulsifier, included inside styrene-methacrylic acid copolymer [P(S-MAA)] particles during emulsion copolymerization, on the formation of multihollow structure inside the particles via the alkali/cooling method (proposed by the authors) was examined in comparison to emulsifier-free particles. It was clarified that the nonionic emulsifier included inside the P(S-MAA) particles eased the formation of multihollow structure.Part CCL of the series studies on suspension and emulsion     

Rapid ruthenium-catalyzed synthesis of pyranopyrandiones by reconstructive carbonylation of cyclopropenones involving C[bond]C bond cleavage

Pyranopyrandiones were prepared by a novel ruthenium-catalyzed carbonylative dimerization of cyclopropenones via C-C bond cleavage. For example, treatment of dipropylcyclopropenone with a catalytic amount of Ru3(CO)12 and NEt3 in THF under 15 atm of carbon monoxide at 140 degrees C for 20 h gave a novel functional monomer, 3,4,7,8-tetrapropylpyrano[6,5-e]pyran-2,6-dione, in an isolated yield of 81%. Unsymmetrically substituted pyranopyrandiones were also obtained by ruthenium-catalyzed carbonylative coupling of cyclopropenones with alkynes under similar reaction conditions.     

Liposomes prepared from synthetic amphiphiles. I. Their technetium labeling and stability

In order to apply liposomes prepared from synthetic amphiphiles containing amino acid residues to radiopharmaceuticals, their labeling with 99Tc or 99mTc and stability in saline or in serum were investigated. These liposomes were highly labeled by embedding stearylamine-diethylenetriamine pentaacetic acid as a ligand of technetium. The labeling was more efficient at pH 7.0 than at pH 4.0 or 8.5. Among these technetium-labeled liposomes tested, liposomes containing the alanine residue were stable in saline or in 50% serum at 37 degrees C for at least 24 h, in contrast to liposomes (phosphatidylcholine: cholesterol = 1:1 molar ratio) whose stability had been enhanced by adding cholesterol.     

Photo-initiated base-formation in a polymer matrix

It was found that amines were formed efficiently by the photolysis of O-acyloximes followed by hydrolysis in polystyrene films and the relationship between structures of O-acyloximes and yields of amines were investigated. O-phenylacetyl acetophenone oxime (PaApO), O-pivaloyl acetophenone oxime (PApO), and O-benzoyl acetophenone oxime (BApO) as monofunctional O-acyloximes and O,O′-succinyl diacetophenone oxime (SDApO) and O,O′-glutaryl diacetophenone oxime (GDApO) as bifunctional O-acyloximes were examined. The yields of amines for PaApO and SDApO under N₂ were ca. 70%, which was the highest among O-acyloximes examined in this experiment. On the other hand, the yields for PApO, BApO, and GDApO were less than 15% and it was verified that the hydrogen abstraction by imino radicals via 6-membered cyclic intermediates resulted in the lowering of yields. Although the effect of oxygen under photolysis on the yields of amine for PaApO was negligible under 50% conversion of PaApO, the yield decreased with further increase in the conversion and was 50% at 90% conversion. © 1994 John Wiley & Sons, Inc.