Vapour pressures and excess functions of N, N, N′, N′-tetramethylalkanediamine + cyclohexane. A group contribution study of the N---N proximity effect

The vapour pressuresof liquid cyclohexane + N, N, N′, N′-tetramethylalkanediamine, (CH₃)₂ N(CH₂)_uN(CH₃)₂ (u = 1,2) + cyclohexane mixtures were measured by a static method between 303.15 and 343.15 K at 10 K intervals. The excess molar enthalpies at 303.15 K were also measured.

The molar excess Gibbs energies, calculated from the vapour-liquid equilibrium data, and the molar excess enthalpies compare satisfactorily with group contribution (DISQUAC) predictions.

The proximity effect of N atoms produces a regular decrease of the interactional parameters.     

Synthesis of ferrocenyl-1,2-diketones and related compounds: Crystal and molecular structures of 1,2-diferrocenylethanedione and 1-ferrocenyl-2-(4-biphenylyl) ethanedione

Ferrocenyl-1,2-diketones FcCOCOR, 3, [Fc = (C₅H₅)Fe(C₅H₄)] can be prepared by oxidation of acylferrocenes FcCOCH₂R or, more efficiently, by oxidation of the isomeric ketones FcCH₂COR, 2. The ketones 2 are in turn readily synthesized from the salt (FcCH₂PPh₃)⁺I⁻ via the acylated salts [FcCH(COR)PPh₃]⁺I⁻. The haloacylferocenes FcCOCCl_x H_3−x (x = 1, 2, 3, of which the x = 2 example is synthetically equivalent to a diketone) are synthesized by Friedel—Crafts acylation of ferrocene using CCl_xH_3−xCOCl/AlCl₃, but the reaction proceeds via two parallel pathways, one giving the normal acyl derivatives FcCOCCl_xH_3−x and the other giving the reduced products FcCOCCl_x−1H_4−x. Two diketones FcCOCOFc 3b and FcCOCOC₆H₄Ph 3c have been structurally characterised by single-crystal X-ray diffraction.     

Total synthesis of (+)-zaragozic acid C

A total synthesis of (+)-zaragozic acid C is described. Key features of the synthesis are the use of a double Sharpless asymmetric dihydroxylation reaction of diene 6 to control stereochemistry at four contiguous stereocenters from C3 to C6; the introduction of the C1-side chain by reaction between the anion derived from the dithiane monosulfoxide 27 and the core aldehyde 12; a high yielding, acid-mediated simultaneous acetonide deprotection-dithiane removal-ketalization procedure leading exclusively to the 2, 8-dioxabicyclo[3.2.1]octane core 34; and a novel triple oxidation procedure allowing installation of the tricarboxylic acid.     

Potentiometric and visual titrations with bromamine-B

Bromamine-B is proposed as an oxidimetric titrant for potentiometric and visual end-point titrations of arsenic(II), hexacyanoferrate(II), antimony(III), hydroquinone, semicarbazide hydrochloride, isonicotinic acid hydrazide, hydrazine sulphate, ascorbic acid, phenylhydrazine hydrochloride and metol. Quinoline Yellow, naphthidine, dimethylnaphthidinedisulphonic acid, o-dianisidine, diphenylbenzidine, Variamine Blue, alpha-naphthoflavone, Amaranth, Methyl Orange and Methyl Red are proposed as indicators in macro and micro titrations of the reductants with bromamine-B. The transition potentials of Quinoline Yellow, naphthidine, dimethylnaphthidinedisulphonic acid, and o-dianisidine in the titration of ascorbic acid are reported. Arsenic(III) and hexacyanoferrate(II) are suggested for the standardization of bromamine-B solutions.     

Preparation and application of functional polymers—II. Preparation of vinyl ethers and thioethers using polymer-supported phosphonium salts

Insoluble polystyryldiphenyl-methoxymethyl- and methylthiomethyl-phosphonium chlorides have been prepared by treating polystyryldiphenylphosphine with chloromethylmethyl-ether and thioether respectively. These reagents were used for the conversion under mild conditions of carbonyl compounds into vinyl-ethers and thioethers, otherwise difficult to obtain; yields are high and work-up is easy. Moreover, methyl and ethyl β-styryl ethers were also prepared from the polymeric phosphorane by treatment with formate esters.     

Structural chemistry of azo complexes

Summary Complexes of Co^II, Ni^II, Cu^II, Pd^II, and Pt^IV with 2,4,5-trihydroxybenzoic acid and its substituted phenylazoderivatives have been prepared, together with some mixed-metal (Co, Cu or Ni, Cu) complexes of itsm-nitro,m-carboxy andm-hydroxyarylazo derivatives. The stereochemistries and the modes of bonding of the complexes were elucidated by spectral and magnetic susceptibility measurements.Abstracted from her Ph.D. thesis.     

Ion-Pair Formation in Pharmaceutical Analysis. Conductimetric Determination of Promazine, Chlorpromazine, Promethazine, Imipramine and Ciprofloxacin Hydrochlorides in Pure Form, Drug Formulations and Urine

 Potassium ferricyanide and sodium tetraphenylborate were used as titrants for the conductimetric determination of promazine HCl, chlorpromazine HCl, promethazine HCl, imipramine HCl and ciprofloxacin HCl through ion-associate complex formation. The molar combining ratio, effects of dilution of titrant, temperature and solvent were studied. The accuracy of the method is indicated by excellent recovery (99.50–99.96%). The sensitivity of the proposed method is discussed and the results are compared with the pharmacopoeial or the official methods. The suggested method has been applied for the analysis of the mentioned compounds in their pharmaceutical formulations and urine. Received March 1, 1998. Revision May 31, 1999.     

Effect of gamma-rays on the formation of color centers in copper-containing lead borate glasses

Absorption bands in the range of 350–950 nm, induced in copper-containing lead borate glasses by -rays were identified and characterized. The effect of irradiation dose, copper oxide and lead oxide contents on the intensity and position of the induced absorption bands were also considered. Several induced absorption bands were observed. At least two bands in the ranges of 740–780 and 850–870 nm could be identified. They are suggested to be associated with induced Cu⁽²⁺⁾ ions. The band in the 800–830 nm (1.6 eV) range is ascribed to the Pb⁽³⁺⁾ ion, whereas others in the ranges of 600–630 and 650–730 nm are associated with the intrinsic defects formed in the base glass.     

Reductive Amination of Aldehydes and Ketones with Sodium Triacetoxyborohydride. Studies on Direct and Indirect Reductive Amination Procedures(1)

Sodium triacetoxyborohydride is presented as a general reducing agent for the reductive amination of aldehydes and ketones. Procedures for using this mild and selective reagent have been developed for a wide variety of substrates. The scope of the reaction includes aliphatic acyclic and cyclic ketones, aliphatic and aromatic aldehydes, and primary and secondary amines including a variety of weakly basic and nonbasic amines. Limitations include reactions with aromatic and unsaturated ketones and some sterically hindered ketones and amines. 1,2-Dichloroethane (DCE) is the preferred reaction solvent, but reactions can also be carried out in tetrahydrofuran (THF) and occasionally in acetonitrile. Acetic acid may be used as catalyst with ketone reactions, but it is generally not needed with aldehydes. The procedure is carried out effectively in the presence of acid sensitive functional groups such as acetals and ketals; it can also be carried out in the presence of reducible functional groups such as C-C multiple bonds and cyano and nitro groups. Reactions are generally faster in DCE than in THF, and in both solvents, reactions are faster in the presence of AcOH. In comparison with other reductive amination procedures such as NaBH(3)CN/MeOH, borane-pyridine, and catalytic hydrogenation, NaBH(OAc)(3) gave consistently higher yields and fewer side products. In the reductive amination of some aldehydes with primary amines where dialkylation is a problem we adopted a stepwise procedure involving imine formation in MeOH followed by reduction with NaBH(4).