Polymerization via zwitterion. 24. Copolymerization of a cyclic acyl phosphonite with aromatic aldehydes

Summary Spontaneous copolymerizations of 2-phenyl-4-oxo-5, 6-benzo-1,3,2-dioxaphosphorinane, a new cyclic acyl phosphonite, (M_N) with p- and o-substituted aromatic aldehydes (M_E) gave 1∶2 (M_N ∶ M_E) alternating copolymers. This copolymerization took place without added catalyst affording copolymers via zwitterion . The intermediate of spiro acyloxyphosphorane was detected in situ by 31p NMR. The formation of a stabilized intermediate was taken as an important factor to control the 1∶2 composition. The scheme of the copolymerization involving a zwitterion was presented. For the comparison with the above system, copolymerizations of ethylene phenyl phosphonite with aromatic aldehydes were also examined.     

New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers) V. synthesis of α-tert-butyl-ω-isopropenylpolyisobutylene and α, ω-di(isopropenyl)polyisobutylene

Summary Polyisobutylenes carrying one or two terminal isopropenyl unsaturations have been obtained by complete dehydrochlorination of α-tert. -butyl-ω-tert. chloropolyisobutylene and α, ω-di(tert.-chloro) polyisobutylene, respectively. By the use of t-BuOK in refluxing THF only 1-olefin formed leading to a new macromer and a symmetrical telechelic diolefin. According to H¹ NMR spectroscopy the structure of this new telechelic polymer is:      

Enol esters XIII: Synthesis of isopropenyl esters by addition of carboxylic acids to propyne

The addition of long chain carboxylic acids to propyne under conditions of elevated temperature and pressure takes place in the presence of the zinc salt of the corresponding acid as indicated by the following equation. The reactor apparatus is described and the properties of a series of enol esters are listed. this series shows examples with chain length variations of the carboxylic acid moiety of the ester from 8 to 22 carbon atoms.     

Synthesis and characterization of aldehyde-capped polyisobutylenes

Summary The synthesis and characterization of linear mono- and ditelechelic polyisobutylenes (PIBs) carrying terminal primary aldehyde groups are described. The synthesis starts by chlorine terminated PIBs (PIB−Cl and Cl−PIB−Cl) prepared by inifering or living carbocationic polymerization. These starting materials were dehydrochlorinated to vinylidene (∼CH₂−C(CH₃)=CH₂) terminated PIBs and hydroformylated with CO/H₂ in the presence of a rhodium catalyst. According to NMR (500 MHz) and GPC analyses, the transformations are selective and demonstrably quantitative. The structures of these novel polymers are: I view of the rich chemistry of the aldehyde group, these materials are valuable intermediates.     

A new phosphorylation reaction of olefins. III. Derivatives of some unsaturated fatty materials

The reaction of olefins with phosphorus trichloride in the presence of aluminum chloride was recently reported to result in phosphorus-containing acids or acid chlorides of the type This new phosphorylation reaction was extended to fatty acid derivatives containing olefinic double bonds, such as methyl oleate, oleonitrile, oleamide, N,N-dimethyloleamide, olive oil, oleylacetamide and oleyl alcohol. Phosphorylated fatty derivatives were obtained in good yield in all cases. Presented at the AOCS meeting in New Orleans, La., 1962.     

Pine nut oil

Summary THE oil would seem to be made up about as follows: As a check upon the foregoing, the iodine number of the oil may be calculated therefrom. Figured from 31.6 per cent glyceryl linoleate and 56.7 per cent glyceryl oleate, the iodine number is 103.8. This checks well with that found, 102.1. It is possible to calculate the percentage of linolenic acid as well as those of linoleic and oleic from the iodine and thiocyanogen-iodine numbers: this calculation indicated 10.1 per cent glyceryl linolinate, 44.4 per cent linoleate, 33.7 per cent oleate. Figured from these the iodine value would be 132.4. This shows that linolenic acid cannot be present in any considerable quantity. Pine Seed Oil fromPinus monophylla must therefore be classed as a semi-drying oil. The author here wishes to acknowledge the assistance of Messrs. H. J. Svien, H. D. Addison and G. T. Vaala by whom the experimental work was carefully performed. Original Coutribution, received July 27, 1932.     

Characterization of chlorophyll pigments in ripening canola seed (Brassica napus)

This study characterizes the chlorophyll pigments in ripeningBrassica napus seed. Seed samples, collected weekly as the crop ripened, were analyzed by high-performance liquid chromatography to characterize chlorophyll pigment composition. Chlorophyll A, chlorophyll B, pheophytin A and pheophytin B were the predominant pigments, while pheophorbide A, methylpheophorbide A and pyropheophytin A were minor components. No differences in pigment composition were observed between the three cultivars tested or between early and late seeding dates. There were differences in pigment composition between the two years of the study, which may result either from seed aging during storage or from environmental influences. Pigment composition was dependent on seed maturity, with physiologically mature green seeds containing both chlorophylls and pheophytins, but fully mature seeds containing only chlorophylls. Pheophytins and the minor components appeared transiently, presumably formed from the chlorophylls and subsequently degraded. The ratio of chlorophyll A/B increased during seed ripening, with fully mature canola seed having a chlorophyll A/B ratio twice that of physiologically mature green seed. The “B” derivatives degraded faster than the “A” derivatives, suggesting enzymatic reactions. The initial steps in the chlorophyll breakdown pathway in canola seed appear to be:      

Puerto rican fatty oils

Summary The liquid fraction of Puerto Rican avocado pulp oil is decidedly a non-drying oil, iodine number 70.9. Its composition, according to our findings, is as follows: This work was supported by a grant from the Department of Agriculture and Commerce of Puerto Rico.     

The relationship of structure to properties in surfactants: V. Synthesis and properties of α,ω-bis (sodium p-sulfophenoxy)alkanes

A series of symmetrical surfactants containing two arylsulfonate groups in the molecule, of general structure, where n=4, 6, 8, 10 and 12, has been synthesized. The synthesis involves sulfonation of the corresponding diaryl ethers, isolation, purification, and characterization of the free para-disulfonic acids, followed by conversion of the latter to the disodium salts. The nuclear magnetic resonance (NMR) spectra of the products indicate that they are the para-sulfonated compounds substantially free of the ortho isomers. The Krafft points, surface tension-log concentration curves, critical micelle concentrations, and areas/molecule at the liquid/air interface have been determined. The surface area/molecule indicate that these compounds are lying flat in the liquid/air interface.     

Polymerization via zwitterion. 23. Terpolymerization among 2-phenyl-1,3,2-dioxaphospholane,methyl acrylate,and carbon disulfide

Summary The present paper describes the terpolymerization involving 2-phenyl-1,3,2-dioxaphospholane, methyl acrylate, and carbon disulfide, which took place without any added initiator in benzonitrile or dimethylformamide. The structure and composition of terpolymer were determined by NMR and IR spectra, as well as by elemental analysis. A reaction scheme proceeding via zwitterion was proposed (Eq. 2–5).     

6-Hydroxychroman-2-carboxylic acids: Novel antioxidants

6-Hydroxychroman-2-carboxylic acids (I) have been found to be effective antioxidants in animal fats, vegetable oils, and emulsion systems. Two new syntheses of these compounds have been developed. Structure-activity correlations for I with various substitutents at C₂, C₅, C₇, and C₈ in various test systems have been obtained. In addition, the homologous chroman acetic acids, which are also antioxidants, and a number of other derived compounds have been synthesized. The most effective antioxidant in this series is the tetramethyl compound I (R₂=R₅=R₇=R₈=CH₃). This compound has activity which compares well with the better commercial antioxidants. Presented in part at the AOCS Meeting, Mexico City, Mexico, April 1974.     

Activation of hydrochloric acid-CrCl3 · 6H2 solutions with N-alkyfamines

An economical procedure for the reactivation of aged CrCl₃ · 6H₂O solutions is required for the practical operation of Fe-Cr-redox cells. N-alkylamines of the general form (n=0, 1, 2, 3,...) are suited to this application. The best results were achieved with tetraethylene pentamine (n=3). The technique functions without energy addition for a considerable length of time and is easy to manage. The mechanism of the reactivation is discussed.     

Development of a phosphate-free home laundry detergent

A group of multifunctional surfactants was synthesized in order to arrive at materials which might function well in hard water. The salts of alkylaryl sulfopropionates, ; alkylaryl sulfonamides of taurine R-C₆H₄-SO₂NHCH₂CH₂SO₃Na; and the alkylaryl sulfonamide of aminoethylsulfuric acid R-C₆H₄-SO₂NHCH₂CH₂OSO₃Na were found to be quite effective. These compounds were synthesized via conventional routes and their biodegradability was established. These materials were formulated into the detergents with the aid of various organic and inorganic builders other than condensed phosphates. The detergency of these materials was evaluated with the aid of standard test cloths. Analogously formulated detergents based upon linear alkylbenzenesulfonate were also included for comparison in this evaluation study. It was found that a number of fairly satisfactory phosphate-free heavy duty detergent formulations could be developed. Presented at the AOCS Meeting, Houston, May 1971.     

American safflower seed oil

Summary The chemical and physical characteristics of a sample of hot pressed oil from saflower seed grown in Montana have been determined. This oil was found to contain 87.72 per cent of unsaturated acids, and 5.92 per cent of saturated acids. The composition of the oil has been determined with the following results, and, for comparison, results for sunflower seed and soy bean oils previously obtained, are also given. It will be observed that safflower oil contains a considerably larger proportion of linolic acid and less oleic acid than either of the other two oils, and this fact would account for its superior drying power.     

Self-organization of quantum-dot pairs by high-temperature droplet epitaxy

The spontaneously formation of epitaxial GaAs quantum-dot pairs was demonstrated on an AlGaAs surface using Ga droplets as a Ga nano-source. The dot pair formation was attributed to the anisotropy of surface diffusion during high-temperature droplet epitaxy.      

Partial specific volume and preferential hydration of low density lipoprotein subfractions

We have determined the partial specific volume ( ) for five low density lipoprotein (LDL) subfractions (n=5–7) and evaluated preferential hydration (n=2) for LDL subfraction 3 in normolipoproteinemic subjects in order to characterize these highly atherogenic components of the human plasma lipoprotein spectra. Values for at 1 g were determined by sixth place density measurements of the solvent and lipoprotein solutions and carbon, hydrogen and nitrogen (CHN) absolute mass of the lipoprotein concentrations. Mean values for were 0.9757±0.0019, 0.9701±0.0007, 0.9674±0.0016, 0.9616±0.0016 and 0.9550±0.0025 ml/g for subfractions 1, 2, 3, 4 and 5, respectively. However, molecular densities (σ) obtained from ϱ(rho)=1/ for respective LDL subfractions were 1.0249, 1.0308, 1.0337, 1.0399 and 1.0471 g/ml, respectively. The preferential hydration of lipoprotein subfraction 3 (n=2) in NaCl/H₂O solutions was 2.9–4.8 wt percent, whereas values were much lower (0.3–0.6 wt percent) in NaCl/NaBr/H₂O solvent system. Unhydrated densities for LDL subfraction 3 (n=2) at 1 g (sixth-place density meter) were 1.0287 and 1.0269 g/ml, whereas at 200,000 × g (used in D₂O flotation ηF^o vs ϱ determinations) both values were 1.0308 g/ml, indicating that these similar LDL fractions have 23 and 53% higher compressibility than the solvent at 200,000 × g force. It was observed that the linearity of ηF^o vs ϱ may not be valid for solvents NaCl/NaBr/H₂O of density as high as 1.4744 g/ml. Thus, flotation velocity data using extreme salt concentrations (1.4744 g/ml and higher) may be viewed with caution.     

One-pot Synthesis of Soluble Nanoscale CIGS Photoactive Functional Materials

Abstract  Promising alternatives for solar energy utilization are thin film technologies involving various new materials. This contribution describes an easy and inexpensive synthetic method that can be used to prepare soluble nanoscale triphenyl phosphine-coordinated CIGS (TPP-CIGS) photoactive functional materials. This complex is stable in the solid state under the irradiation of the ambient light, but its solution becomes a little bit unstable under the illumination of the low intensity laser. Graphic Abstract   Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Mild and highly regioselective synthesis of biaryl acids via Rh (I)-catalyzed cross-dehydrogenative coupling of benzoic acids using sodium chlorite as oxidant

A mild and efficient synthesis for the biaryl acids via rhodium-catalyzed cross-dehydrogenative coupling reaction has been developed. This novel protocol with sodium chlorite as an oxidant featured many advantages such as mild reaction conditions, high regioselectivity, tolerance of various functional groups, and good to excellent yields.

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Hydro-pyrolysis of lignocellulosic biomass over alumina supported Platinum,Mo<Subscript>2</Subscript>C and WC catalysts

In-line hydro-treatment of bio-oil vapor from fast pyrolysis of lignocellulosic biomass (hydro-pyrolysis of biomass) is studied as a method of upgrading the liquefied bio-oil for a possible precursor to green fuels. The nobel metal (Pt) and non-noble metal catalysts (Mo₂C and WC) were compared at 500 °C and atmospheric pressure which are same as the reaction conditions for fast pyrolysis of biomass. Results indicated that under the pyrolysis conditions, the major components, such as acids and carbonyls, of the fast pyrolysis bio-oil can be completely and partially hydrogenated to form hydrocarbons, an ideal fossil fuel blend, in the hydro-treated bio-oil. The carbide catalysts perform equally well as the Pt catalyst regarding to the aliphatic and aromatic hydrocarbon formation (ca. 60%), showing the feasibility of using the cheap non-noble catalysts for hydro-pyrolysis of biomass.

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