Preparations of 2,4-Disubstituted Oestradiols

1989 ◽  
Vol 42 (3) ◽  
pp. 421 ◽  
Author(s):  
DJ Pert ◽  
DD Ridley
Keyword(s):  
Sodium Methoxide ◽  
Major Product ◽  
Minor Amount ◽  
Alternative Routes ◽  
A Minor

2,4-Dibromoestra-1,3,S(10)-triene-3,17 β- diol 3-(2'-hydroxyethyl) ether (8) undergoes reaction with copper(11) chloride/sodium methoxide to afford a 4-bromo [2,3]- dioxan derivative (9) as the major product together with a minor amount of a 2-bromo [3,4]- dioxan derivative (10). These compounds were used to prepare a number of 2,4-disubstituted oestradiol derivatives. � Alternative routes to other 2,4-disubstituted oestradiols are described.

Photo-additions of aromatic hydrocarbons—indene and naphthalene with acrylonitrile

1969 ◽  
Vol 47 (5) ◽  
pp. 757-766 ◽  
Author(s):  
John J. McCullough ◽  
C. W. Huang
Keyword(s):  
Butyl Alcohol ◽  
Major Product ◽  
Minor Amount ◽  
Strong Base ◽  
Magnetic Resonance Data ◽  
Cis And Trans Isomers ◽  
Resonance Data ◽  
Ethanol Yields ◽  
A Minor ◽  
Cis And Trans

The photolyses of indene and naphthalene with acrylonitrile have been studied, and the products characterized. Indene reacts with acrylonitrile when the hydrocarbon absorbs light, or when a triplet sensitizer (acetophenone) is absorbing. Photolysis under the former conditions in ethanol yields 2-(1-indenylpropionitrile) (70%), 2-(3-indenylpropionitrile) (10%), and 6-cyano-2,3-benzobicyclo[3,2,0]hept-2-ene (20%). Base-catalyzed isomerizations of the substituted indenes are reported. On sensitization, cis- and trans-isomers of 7-cyano-2,3-benzobicyclo[3,2,0]hept-2-ene are formed, with a minor amount of indene dimer. The former isomers can be equilibrated with strong base. Adducts of 1,1-dimethyl- and 1,1-diphenylindene with acrylonitrile are also described, and nuclear magnetic resonance data reported. Naphthalene adds acrylonitrile on photolysis in t-butyl alcohol (pyrex filter) to afford trans-8-cyano-2,3-benzobicyclo-[4,2,0]-octa-2,4-diene (90%) and 1- and 2-naphthyl-2-propionitrile (10%). Sensitization with acetophenone gave no detectable products. Irradiation of the major product at 253.7 mμ through Vycor gave naphthalene. The preparative value of these reactions is considered and possible mechanisms are proposed.

scholarly journals Odour-active compounds in liquid malt extracts for the baking industry

2021 ◽  
Author(s):  
Nadine S. Rögner ◽  
Veronika Mall ◽  
Martin Steinhaus
Keyword(s):  
Threshold Value ◽  
Starting Material ◽  
Minor Amount ◽  
Malt Extract ◽  
Important Process ◽  
Gas Chromatography Olfactometry ◽  
Odour Threshold ◽  
A Minor ◽  
Baking Industry ◽  
Insight Into

AbstractAn odorant screening by gas chromatography–olfactometry (GC–O) and a crude aroma extract dilution analysis (AEDA) applied to the volatiles isolated from a light and a dark liquid malt extract (LME) by solvent extraction and solvent-assisted flavour evaporation (SAFE) identified 28 odorants. Fifteen major odorants were subsequently quantitated and odour activity values (OAVs) were calculated as ratio of the concentration to the respective odour threshold value (OTV). Important odorants in the light LME included 3-(methylsulfanyl)propanal (OAV 1500), (E)-β-damascenone (OAV 430), and 4-ethenyl-2-methoxyphenol (OAV 91). In the dark LME, sotolon (OAV 780), 3-(methylsulfanyl)propanal (OAV 550), (E)-β-damascenone (OAV 410), acetic acid (OAV 160), and maltol (OAV 120) were of particular importance. To get an insight into the changes during malt extract production, the quantitations were extended to the malt used as the starting material for both LMEs. Addition of a minor amount of water to malt before volatile extraction was shown to be effective to cover the free as well as the bound malt odorants. Results showed that some LME odorants originated from the starting material whereas others were formed during processing. Important process-induced LME odorants included (E)-β-damascenone and 4-ethenyl-2-methoxyphenol in the light LME as well as maltol, sotolon, (E)-β-damascenone, and 2-methoxyphenol in the dark LME. In summary, the odorant formation during LME production was shown to be more important than the transfer of odorants from the malt.

CLAY-INORGANIC STUDIES. II. HYDROXY ALUMINUM PHOSPHATE–MONTMORILLONITE COMPLEX

1975 ◽  
Vol 55 (2) ◽  
pp. 225-233 ◽  
Author(s):  
H. KODAMA ◽  
M. D. WEBBER
Keyword(s):  
Relative Humidity ◽  
Room Temperature ◽  
Aluminum Phosphate ◽  
Silicate Layer ◽  
Basal Spacing ◽  
Minor Amount ◽  
Chemical Compositions ◽  
A Minor ◽  
Positively Charged ◽  
Water Contents

Two specimens of hydroxy aluminum phosphate interlayer materials in montmorillonite clay were prepared with 7.20 meq Al and 11.29 meq H3PO4/g clay and with 14.40 meq Al and 22.58 meq H3PO4/g clay, and the resulting complexes studied by chemical and mineralogical methods. Both interlayer materials were slightly positively charged and except for different water contents their chemical compositions were almost identical. They contained Al, PO4 and H2O and a minor amount of Ca and approximated hydrous AlPO4∙nH2O. The mole ratios of Al:Ca:PO4:OH were 1.00:0.08:0.92:0.24 and 1.00:0.05:0.91:0.24, respectively. The interlayer materials appeared to be loosely packed and distributed sparsely in interspaces of the montmorillonite. The degree of packing was greater for the preparation with the larger amount of interlayer material. The materials increased the montmorillonite basal spacing to 23.3 Å under air-dry condition (30–40% relative humidity) but did not affect the lateral dimensions. The basal spacing varied somewhat with relative humidity at room temperature and decreased markedly as water was driven off by heating. Heat treatments between room temperature and 300 C sharply reduced the d001 spacings to 16.7 Å which persisted up to 700 C. It is postulated that the large basal spacings occur because the hydrated interlayer materials have a framework structure with tunnels along the c-axis. This being so, changes in the spacings with different humidities might result from the movement of water molecules among interstitial spaces existing around and between the loosely distributed molecules of interlayer material. The 16.7 Å spacing for the dehydrated phase corresponds to the sum of 7.0 Å, the edge dimension of an orthorhombic anhydrous AlPO4 and 9.7 Å, the silicate layer thickness.

scholarly journals Acetate represents a major product of heptanoate and octanoate β-oxidation in hepatocytes isolated from neonatal piglets

1996 ◽  
Vol 318 (1) ◽  
pp. 235-240 ◽  
Author(s):  
Xi LIN ◽  
Sean H. ADAMS ◽  
Jack ODLE
Keyword(s):  
Fatty Acid ◽  
Organic Acids ◽  
Chain Length ◽  
Ketone Bodies ◽  
Krebs Cycle ◽  
Major Product ◽  
Carbon Accounting ◽  
Minor Amount ◽  
Fatty Acid Carbon ◽  
Carboxyl Carbon

An experiment was conducted to explore the nature of the radiolabel distribution in acid-soluble products (ASPs) resulting from the oxidation of [1-14C]C7:0 or C8:0 by isolated piglet hepatocytes. The differences between odd and even chain-length and the impacts of valproate and malonate upon the rate of β-oxidation and ASP characteristics were tested. A minor amount of fatty acid carboxyl carbon (⩽ 10% of organic acids identified by radio-HPLC) accumulated in ketone bodies regardless of chain-length or inhibitor used. In all cases, acetate represented the major reservoir of carboxyl carbon, accounting for 60–70% of radiolabel in identified organic acids. Cells given [1-14C]C7:0 accumulated 85% more carboxyl carbon in Krebs cycle intermediates when compared with C8:0, while accumulation in acetate was unaffected. The results are consistent with the hypothesis that anaplerosis from odd-carbon fatty acids affects the oxidative fate of fatty acid carbon. The piglet appears unique in that non-ketogenic routes of fatty acid carbon flow (i.e. acetogenesis) predominate in the liver of this species.

Nucleophilic addition at u 3 -alkyne clusters leading to carbon-carbon bond formation

1982 ◽  
Vol 308 (1501) ◽  
pp. 59-66 ◽  
Keyword(s):  
Bond Formation ◽  
Organic Ligand ◽  
Major Product ◽  
Unsaturated Hydrocarbon ◽  
Terminal Alkynes ◽  
Hydrogen Atoms ◽  
Metal Atoms ◽  
Carbon Carbon Bond ◽  
Anionic Species ◽  
A Minor

Reactions of nucleophiles with triosmium carbonyl clusters, especially those containing unsaturated hydrocarbon ligands, are discussed. Attack may be at CO, the metal atoms, at carbon of the organic ligand, or, where there are acidic metal-bound hydrogen atoms, deprotonation to give anionic clusters may occur. New results on the reactions of LiBHEt3 with p3-alkyne clusters of type Os3(CO)10 (RC2R') are considered in the light of the range of possible sites of attack. Protonation of anionic species that are formed gives hydrogenation products with or without the loss of CO. Os3H2(CO)9(RC2R') is usually a minor product, while C-C coupling leads to Os3H(CO)9(CRCR'COH) (in general the major product) and to Os3H(CO)9- (CRCR'CH). With terminal alkynes RC2H H-atom transfer accompanies C-C coupling to give Os3H(CO)9(RC—C =C H 2) in substantial amounts. The initial site of hydride attack (CO, alkyne or metal) is considered in the context of low-temperature 1H n.m.r. results.

scholarly journals Vinyl ether hydrolysis. XIV. 2-Methoxy-2,3-dihydropyran: concurrent reaction of vinyl ether and acetal functional groups

1980 ◽  
Vol 58 (21) ◽  
pp. 2199-2202 ◽  
Author(s):  
R. A. Burt ◽  
Y. Chiang ◽  
A. J. Kresge
Keyword(s):  
Vinyl Ether ◽  
Isotope Effect ◽  
Reaction Rate ◽  
Functional Group ◽  
Minor Amount ◽  
Cyanoacetic Acid ◽  
Buffer Solutions ◽  
Hydrogen Isotope Effect ◽  
A Minor ◽  
Hydrolysis Of

The hydrolysis of 2-methoxy-2,3-dihydropyran shows a normal isotope effect (kH/kD > 1) under catalysis by the hydrogen ion and gives an accurately linear dependence of reaction rate upon undissociated acid concentration in cyanoacetic acid and formic acid buffer solutions. This substrate, therefore, unlike its higher homolog, 9-methoxyoxacyclonon-2-ene, provides no evidence in support of an anything but a normal mechanism for vinyl ether hydrolysis. Analysis of the hydrogen isotope effect suggests that a minor amount (8%) of this hydrolysis occurs via reaction of the acetal functional group.

scholarly journals Silica-Based Composites with Enhanced Rheological Properties Thanks to a Nanosized Graphite Functionalized with Serinol Pyrrole

2021 ◽  
Vol 11 (23) ◽  
pp. 11410
Author(s):  
Gea Prioglio ◽  
Silvia Agnelli ◽  
Stefano Pandini ◽  
Maurizio Galimberti
Keyword(s):  
Rheological Properties ◽  
High Surface ◽  
High Surface Area ◽  
Minor Amount ◽  
Carbon Filler ◽  
Hybrid Filler ◽  
Carbon Efficiency ◽  
Dynamic Rigidity ◽  
A Minor ◽  
New Generation

Silica-based rubber composites have tremendous importance, as they allow the reduction in hysteresis in demanding dynamic-mechanical applications such as tire compounds and hence have a lower environmental impact. However, they also present drawbacks such as poor rheological behavior. In this work, an innovative silica-based hybrid filler system was developed, obtaining a rubber composite with an improved set of properties. A nanosized high surface area graphite (HSAG) was functionalized with 2-(2,5-dimethyl-1H-pyrrol-1-yl)propane-1,3-diol, serinol pyrrole (SP), through a simple process characterized by a high carbon efficiency. The HSAG-SP adduct, with about nine parts of SP per hundred parts of carbon filler, was used to form a hybrid filler system with silica. An elastomeric composite, with poly(styrene-co-butadiene) from anionic polymerization and poly(1,4-cis-isoprene) from Hevea brasiliensis was prepared with 50 parts of silica, which was replaced in a minor amount (15%) by either pristine HSAG or HSAG-SP. The best set of composite properties was obtained with HSAG-SP: the same dynamic rigidity and hysteresis and tensile properties of the silica-based material and appreciably better rheological properties, particularly in terms of flowability. This work paves the way for a new generation of silica-based composites, with improved properties, based on a hybrid filler system with a nanosized edge functionalized graphite.

Base-catalyzed Degradations of Carbohydrates. IV. Formation of 2,3-Anhydro-2-methoxy-α-D-allopyranose Derivatives from 3-Deoxy-D-erythro-hex-2-enopyranoses

1973 ◽  
Vol 51 (3) ◽  
pp. 394-401 ◽  
Author(s):  
G. O. Aspinall ◽  
R. R. King
Keyword(s):  
Spectroscopic Data ◽  
Kojic Acid ◽  
Major Product ◽  
A Minor

1,4,6-Tri-O-acetyl-3-deoxy-2-O-methyl-α-D-erythro-hex-2-enopyranose (4) reacts with m-chloroperbenzoic acid to give the epoxide, 1,4,6-tri-O-acetyl-2,3-anhydro-2-methoxy-α-D-allopyranose (6), as the major product together with the perester, 4,6-di-O-acetyl-1,2-O-(1′-m-chloroperbenzoyloxy-ethylidene)-2-methoxy-α-D-glucopyranose (5), as a minor product. The structures of these novel compounds have been assigned on the basis of spectroscopic data and of transformations (i) to kojic acid diacetate and (ii) by oxidative degradations to substituted aldopentonolactones. Further examination of the products of the reaction of 1-O-acetyl-3-deoxy-2,4,6-tri-O-methyl-α-D-erythro-hex-2-enopyranose (1) with m-chloroperbenzoic acid has shown that the epoxide, 1-O-acetyl-2,3-anhydro-2-methoxy-4,6-di-O-methyl-α-D-allopyranose (15), is formed in addition to the previously characterized perester 2.

Combustion synthesis of Si3N4 powder

1997 ◽  
Vol 12 (3) ◽  
pp. 805-811 ◽  
Author(s):  
Wei-Chang Lee ◽  
Shyan-Lung Chung
Keyword(s):  
Reaction Mechanism ◽  
Combustion Synthesis ◽  
Combustion Temperature ◽  
Fine Particles ◽  
Minor Amount ◽  
Synthesis Reaction ◽  
Experimental Parameters ◽  
Combustion Synthesis Reaction ◽  
A Minor ◽  
Low Nitrogen

A combustion synthesis (SHS) process has been developed for the synthesis of Si3N4 powder under low nitrogen pressures. Si and NaN3 powders were used as the reactants, and NH4Cl powder was added as a catalytic agent. These powders were mixed and pressed into a cylindrical compact. The compact was wrapped up with an igniting agent (i.e., Ti + C), and the synthesis reaction was triggered by the combustion of the igniting agent. Addition of NH4Cl was found necessary for the combustion synthesis reaction under low nitrogen pressures (< 1.2 MPa). The product as synthesized is mostly in the form of agglomerated fine particles (0.1–1 μm in diameter) and is composed mainly of α-phase and a minor amount of β-phase. Effects of various experimental parameters (N2 pressure, NaN3, NH4Cl, and Si3N4 contents) on the product conversion and the combustion temperature were investigated. A possible reaction mechanism was proposed that explains the effects of the experimental parameters on the synthesis reaction.

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