Reduction of trichloromethylcarbinols. Hydrogenolysis of phenyl(trichloromethyl)carbinol and 1,1,1-trichloro-2-hydroxy-6-methyl-4- heptanone on metal surfaces

1969 ◽  
Vol 47 (9) ◽  
pp. 1521-1527 ◽  
Author(s):  
Eberhard Kiehlmann ◽  
Robert J. Bianchi ◽  
Wilkins Reeve
Keyword(s):  
Acidic Medium ◽  
Liquid Ammonia ◽  
High Yield ◽  
Main Reaction ◽  
Reaction Products ◽  
Large Excess ◽  
Reflux Time ◽  
Phenethyl Alcohol ◽  
Trichloromethyl Group ◽  
Sole Product

Reduction with zinc in neutral or acidic medium or catalytic hydrogenation of phenyl(trichloromethyl)-carbinol (1) gives β,β-dichlorostyrene (2), β-chlorostyrene (3), and phenyl(dichloromethyl)carbinol (4). β,β-Dichlorostyrene is the sole product of reduction of phenyl(trichloromethyl)carbinyl methyl ether with zinc and acetic acid. Lithium in liquid ammonia reduces the trichloromethyl group of 1 to give α-phenethyl alcohol (5) in low yield; acetophenone and β-phenethyl alcohol have been identified as byproducts of this reaction.Clemmensen reduction of 1,1,1-trichloro-2-hydroxy-6-methyl-4-heptanone (6) does not yield the expected 1,1,1-trichloro-6-methyl-2-heptanol; instead, 1,1-dichloro-6-methyl-1-hepten-4-one (7) and 1,1-dichloro-6-methyl-l-heptene (8) are formed as the main reaction products. Long reflux time, efficient stirring, and the employment of a large excess of amalgamated zinc and concentrated hydrochloric acid favor the formation of 8 while 7 is obtained in high yield when sulfuric acid is used instead of hydrochloric acid.A mechanism for the reduction of trichloromethylcarbinols (1 and 6) with zinc has been proposed, 7 being postulated as an intermediate in the formation of 8.

Microwave Radiation Applied in the N-Aryl-N′-Aminoеthylureas

2021 ◽  
pp. 125-141
Author(s):  
A.V. Kalistratova ◽  
M.S. Oshchepkov ◽  
M.S. Ivanova ◽  
L.V. Kovalenko ◽  
V.S. Boldyrev
Keyword(s):  
Microwave Radiation ◽  
Functional Groups ◽  
Aromatic Ring ◽  
Microwave Synthesis ◽  
High Yield ◽  
Main Reaction ◽  
Reaction Products ◽  
Active Compounds ◽  
Aryl Isocyanates ◽  
Research Show

The paper considers methods for the N-aryl-N'-aminoethylureas synthesis. The methods can be used as base products for the preparation of potential cytokinin active compounds with oxamate and oxamide functional groups. The previous studies showed that upon the interaction between aryl isocyanates and ethylenediamine, symmetric bisureas become the main reaction products, while the yield of the target 2-aminoethylureas is no more than 10 %. The high yield of N-aryl-N'-(oxamoylamino)ethylurea is also not provided by using one group aminoprotected ethylenediamine. Thus, when using Boc-protection, the yield of target products does not exceed 13 %. In this research, we used the methodology of microwave synthesis in acylation and aminolysis reactions. As a result, N-2-aminoethyl-N'-arylureas with various substituents in the aromatic ring were obtained in good yields. We compared the microwave radiation aminolysis of N,N'-bis(arylcarbamoyl)ethylenediamines, N-aryl-carbamoylimidazoles and diarylureas with ethylenediamine under microwave conditions. Findings of research show that reactions without microwaves proceed with the formation of only trace amounts of the target compounds, which are used for synthesis of structural analogs of phytoactive compounds, in the molecules of which carbamate and urea groups are replaced by oxamate ones

Flavan derivatives. XXIII. Preparation and synthetic applications of Flav-3-enes

1968 ◽  
Vol 21 (9) ◽  
pp. 2247 ◽  
Author(s):  
JW Clark-Lewis ◽  
RW Jemison
Keyword(s):  
Sodium Borohydride ◽  
Acidic Medium ◽  
Catalytic Reduction ◽  
Heterocyclic Ring ◽  
High Yield ◽  
Lithium Aluminium Hydride ◽  
Lower Field ◽  
Field Characteristic ◽  
Lithium Aluminium ◽  
New Synthesis

2'-Hydroxychalcones and α-alkoxy-2'-hydroxychalcones are converted by sodium borohydride in isopropanol into flav-3-enes and 3-alkoxyflav-3-enes in the convenient new synthesis which makes these flavenes readily available. Catalytic reduction of the flavenes gives the corresponding flavans or 3-alkoxyflavans in high yield, and the latter are obtained mainly in the 2,s-cis-form. The flavenes immediately give flavs lium cations in the cold when treated with acids in air, and oxidation of 5,7,3',4'-tetramethoxyflav-3-ene with benzoquinone in an acidic medium gave the flavylium salt, isolated as the ferrichloride. Reduction of 5,7,3',4'-tetramethoxy-flavylium chloride with lithium aluminium hydride gave 5,7,3',4'-tetramethoxy-flav-2-ene identical with the flavene obtained from (-)-epicatechin tetramethyl ether, and confirms an earlier investigation by Gramshaw, Johnson, and King. In its N.M.R. spectrum the heterocyclic-ring protons of this flav-2-ene give an ABX multiplet which is easily distinguished from the ABX multiplet at much lower field characteristic of flav-3-enes.

scholarly journals Chiral Amphiphilic Secondary Amine-Porphyrin Hybrids for Aqueous Organocatalysis

Molecules ◽  
2020 ◽  
Vol 25 (15) ◽  
pp. 3420 ◽  
Author(s):  
Aitor Arlegui ◽  
Pol Torres ◽  
Victor Cuesta ◽  
Joaquim Crusats ◽  
Albert Moyano
Keyword(s):  
Catalytic Activity ◽  
High Yield ◽  
Aldol Reactions ◽  
Free Base ◽  
Reaction Products ◽  
Chirality Transfer ◽  
Base Form ◽  
Low Degree ◽  
Acidic Conditions ◽  
Ph Dependent

Two chiral proline-derived amphiphilic 5-substituted-10,15,20-tris(4-sulfonatophenyl)porphyrins were prepared, and their pH-dependent supramolecular behavior was studied. In neutral aqueous solutions, the free-base form of the hybrids is highly soluble, allowing enamine-based organocatalysis to take place, whereas under acidic conditions, the porphyrinic protonated core of the hybrid leads to the formation of self-assembled structures, so that the hybrids flocculate and their catalytic activity is fully suppressed. The low degree of chirality transfer observed for aqueous Michael and aldol reactions strongly suggests that these reactions take place under true “in water” organocatalytic conditions. The highly insoluble catalyst aggregates can easily be separated from the reaction products by centrifugation of the acidic reaction mixtures, and after neutralization and desalting, the sodium salts of the sulfonated amine-porphyrin hybrids, retaining their full catalytic activity, can be recovered in high yield.

scholarly journals Use of Coal Bottom Ash and CaO-CaCl2-Activated GGBFS Binder in the Manufacturing of Artificial Fine Aggregates through Cold-Bonded Pelletization

Materials ◽  
2020 ◽  
Vol 13 (24) ◽  
pp. 5598
Author(s):  
Dongho Jeon ◽  
Woo Sung Yum ◽  
Haemin Song ◽  
Seyoon Yoon ◽  
Younghoon Bae ◽  
...  
Keyword(s):  
Early Stage ◽  
Bottom Ash ◽  
Relative Weight ◽  
Main Reaction ◽  
Reaction Products ◽  
Coal Bottom Ash ◽  
Heavy Metal Leaching ◽  
Granulated Blast Furnace Slag ◽  
Fine Aggregates ◽  
Cementless Binder

This study investigated the use of coal bottom ash (bottom ash) and CaO-CaCl2-activated ground granulated blast furnace slag (GGBFS) binder in the manufacturing of artificial fine aggregates using cold-bonded pelletization. Mixture samples were prepared with varying added contents of bottom ash of varying added contents of bottom ash relative to the weight of the cementless binder (= GGBFS + quicklime (CaO) + calcium chloride (CaCl2)). In the system, the added bottom ash was not simply an inert filler but was dissolved at an early stage. As the ionic concentrations of Ca and Si increased due to dissolved bottom ash, calcium silicate hydrate (C-S-H) formed both earlier and at higher levels, which increased the strength of the earlier stages. However, the added bottom ash did not affect the total quantities of main reaction products, C-S-H and hydrocalumite, in later phases (e.g., 28 days), but simply accelerated the binder reaction until it had occurred for 14 days. After considering both the mechanical strength and the pelletizing formability of all the mixtures, the proportion with 40 relative weight of bottom ash was selected for the manufacturing of pilot samples of aggregates. The produced fine aggregates had a water absorption rate of 9.83% and demonstrated a much smaller amount of heavy metal leaching than the raw bottom ash.

scholarly journals Hot Corrosion Behavior of BaLa2Ti3O10 Thermal Barrier Ceramics in V2O5 and Na2SO4 + V2O5 Molten Salts

Coatings ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 351 ◽  
Author(s):  
Hui Liu ◽  
Jin Cai ◽  
Jihong Zhu
Keyword(s):  
Corrosion Behavior ◽  
Hot Corrosion ◽  
Molten Salts ◽  
Main Reaction ◽  
Thermal Barrier ◽  
Dense Layer ◽  
Reaction Products ◽  
Corrosion Medium ◽  
Barrier Coating ◽  
Salt Corrosion

BaLa2Ti3O10 ceramics for thermal barrier coating (TBC) applications were fabricated, and exposed to V2O5 and Na2SO4 + V2O5 molten salts at 900 °C to investigate the hot corrosion behavior. After 4 h corrosion tests, the main reaction products resulting from V2O5 salt corrosion were LaVO4, TiO2, and Ba3V4O13, whereas those due to Na2SO4 + V2O5 corrosion consisted of LaVO4, TiO2, BaSO4 and some Ba3V4O13. The structures of reaction layers on the surfaces depended on the corrosion medium. In V2O5 salt, the layer was dense and had a thickness of 8–10 μm. While in Na2SO4 + V2O5 salt, it had a ~15 μm porous structure and a dense, thin band at the bottom. Beneath the dense layer or the band, no obvious molten salt was found. The mechanisms by which the reaction layer forms were discussed.

Darstellung von o-Phenylen-bis(dibromphosphan) — Reaktionsprodukte von o-Phenylen-bis(dichlorphosphan) / Synthesis of o-Phenylene-bis(dibromophosphane) — Reaction Products of o-Phenylene-bis(dichlorophosphane)

1984 ◽  
Vol 39 (12) ◽  
pp. 1706-1710 ◽  
Author(s):  
H.-J. Wörz ◽  
E. Quien ◽  
H. P. Latscha
Keyword(s):  
Hydrogen Peroxide ◽  
Hydrogen Bromide ◽  
Equimolar Amount ◽  
Reaction Products ◽  
Large Excess ◽  
Cyclic Anhydride ◽  
Complete Hydrolysis ◽  
Hydrolysis Of

o-Phenylene-bis(dibromophosphane) (1) is prepared by reaction of P ,P,P′,P′-tetrakis(dim ethylamino)-o-phenylenediphosphane with hydrogen bromide in ether. The reaction of o-phenylene- bis(dichlorophosphane) (2) with CH3OH in ether yields o-phenylene-bis(phosphonousacid- dimethylester) (3). The Michaelis-Arbuzov conversion of 3, either by heat or by catalytic amounts of CH3I in toluene, yields ophenylene-bis(methylphosphinic-acid-methylester) (4). The reduction of 2 must be carried out with a large excess of LiAlH4 (1:4) in ether to give o-phenylenediphosphane (5). The cyclic anhydride (6) of P.P′-dichloro-o-phenylenediphosphonous acid is formed when 2 is hydrolyzed in ether with an equimolar amount of water. Complete hydrolysis of 2 with an excess of water gives o-phenylenediphosphonous acid (7). With hydrogen peroxide o-phenylenediphosphonic acid (8) can be isolated.

Intermediate Products Analysis of Phenol Degradation in Aqueous Solution Caused by Pulsed Discharge

2012 ◽  
Vol 518-523 ◽  
pp. 3146-3149
Author(s):  
Sheng Lan ◽  
Zhen Xing Zhang ◽  
Yong Bin Yuan ◽  
Abdus Samee
Keyword(s):  
Aqueous Solution ◽  
Degradation Mechanism ◽  
Pulse Discharge ◽  
Phenol Degradation ◽  
Reaction Products ◽  
Pulsed Discharge ◽  
Dc Voltage ◽  
Intermediate Products ◽  
Phenethyl Alcohol ◽  
Products Analysis

Abstract. In this paper we have presented the degradation of Phenol in aqueous solution which is caused by pulse discharge. The reaction products in the wastewater dissolved phenol under pulsed discharge were tested using GC-MS. Based on the experimental results intermediate products include 2,4hydroxyphnel, polyhydroxy phenethyl alcohol and so on. The final products are carbon dioxide and water. In addition, the theoretical analysis has been conducted These results will be helpful for further studying degradation mechanism of wastewater dissolved phenol under pulsed discharge, using either AC or DC voltage.

scholarly journals Allyl type monomers for hard surface coating protection

2019 ◽  
Vol 140 ◽  
pp. 02007
Author(s):  
Larisa Popova ◽  
Anzhelika Tsyrulnikova ◽  
Sergey Vershilov ◽  
Julia Bazarnova ◽  
Ekaterina Aronova ◽  
...  
Keyword(s):  
Tetrabutylammonium Bromide ◽  
Environmental Safety ◽  
Carbon Chain ◽  
High Yield ◽  
Main Reaction ◽  
Fibrous Materials ◽  
Series Of Experiments ◽  
Work Up ◽  
Derivatives Of ◽  
Improve Mass Transfer

Based on the unsaturated derivatives of polyfluoroalkanols chemical products are used to protect solid and fibrous materials surface from the effects of water, oils and other pollutants. A method for obtaining allyl ethers of polyfluoroalkanols (polyfluoroalkoxypropenes) is based on the Williamson ether reaction. This method is a heterophase process. The use of solvents to improve mass transfer requires complementary measures to ensure industrial and environmental safety. It is more preferable to obtain the target ethers in water with PTC. A series of experiments using different chain length polyfluoroalkanols was studied by GLC. Kovats retention indexes of the target ethers were determined. It was found that in the case of lower homologues (CF3CH2OH, (CF3)2CHOH, HCF2CF2CH2OH), the addition of 5-15 vol.% 1,4-dioxane as a solubilizer provides a high yield of products. The application of PTC (tetrabutylammonium bromide) is indispensable for using polyfluoroalkanols with a longer carbon chain (C≥5). PTC invariably provides the almost complete conversion of polyfluoroalkanols. The decomposition process of TBAB becomes noticeable (GLC method) upon completion of the main reaction. Polyfluoroalkoxypropenes form azeotrope with water, which can be used in the work up process.

Physicochemical properties of a urea/zinc chloride eutectic mixture and its improved effect on the fast and high yield synthesis of indeno[2,1-c]quinolines

2020 ◽  
Vol 44 (19) ◽  
pp. 7987-7997
Author(s):  
Diana Peña-Solórzano ◽  
Vladimir V. Kouznetsov ◽  
Cristian Ochoa-Puentes
Keyword(s):  
Physicochemical Properties ◽  
Efficient Method ◽  
Zinc Chloride ◽  
Acidic Medium ◽  
Eutectic Mixture ◽  
Environmentally Friendly ◽  
High Yield

An environmentally friendly and efficient method for the synthesis of indeno[2,1-c]quinolines is developed using a urea/zinc chloride eutectic mixture as a green mildly acidic medium.

scholarly journals Chemical Denitrification with Mg0 Particles in Column Systems

2020 ◽  
Vol 12 (7) ◽  
pp. 2984 ◽  
Author(s):  
Alessio Siciliano ◽  
Giulia Maria Curcio ◽  
Carlo Limonti
Keyword(s):  
Kinetic Constant ◽  
Operating Parameter ◽  
Process Efficiency ◽  
Main Reaction ◽  
Main Reaction Product ◽  
Reaction Products ◽  
Metallic Elements ◽  
Reactive Material ◽  
Maximum Reaction Rate ◽  
Maximum Reaction

The removal of nitrate from aqueous environments through zero-valent metallic elements is an attractive technique that has gained increasing interest in recent years. In comparison to other metallic elements, zero-valent magnesium (ZVM) has numerous beneficial aspects. Nevertheless, the use of Mg0 particles for nitrate reduction in column systems has not been investigated yet. To overcome the lack of research, in the present study, a wide experimental activity was carried out to develop a chemical denitrification process through ZVM in batch column equipment. Several tests were executed to evaluate the effects of recirculation hydraulic velocity, pH, Mg0 amount, N-NO3− initial concentration and temperature on the process performance. The results show that the process efficiency is positively influenced by the recirculation velocity increase. In particular, the optimal condition was detected with a value of 1 m/min. The process pH was identified as the main operating parameter. At pH 3, abatements higher than 86.6% were reached for every initial nitrate concentration tested. In these conditions, nitrogen gas was detected as the main reaction product. The pH increase up to values of 5 and 7 caused a drastic denitrification decline with observed efficiencies below 26%. At pH 3, the ratio (RMN) between Mg0 and initial nitrate amount also plays a key role in the treatment performance. A characteristic value of about RMN = 0.333 gMg0/mgN-NO3− was found with which it is possible to reach the maximum reaction rate. Unexpectedly, the process was negatively affected by the increase in temperature from 20 to 40 °C. At 20 °C, the material showed satisfactory denitrification efficiencies in subsequent reuse cycles. With the optimal RMN ratio, removals up to 90% were detected by reusing the reactive material three times. By means of a kinetic analysis, a mathematical law able to describe the nitrate abatement curves was defined. Moreover, the relation between the observed kinetic constant and the operating parameters was recognized. Finally, the reaction pathways were proposed and the corrosion reaction products formed during the treatment were identified.

Sign in / Sign up

Export Citation Format

Share Document