Synthese und Eigenschaften von N-phosphorylierten Aminomethylen-dimethylphosphinoxiden und -sulfiden / Synthesis and Properties of N-Phosphorylated Aminomethylene-Dimethylphosphine Oxides and -Sulfides

1995 ◽  
Vol 50 (12) ◽  
pp. 1818-1832 ◽  
Author(s):  
Thomas Kaukorat ◽  
Ion Neda ◽  
Reinhard Schmutzler
Keyword(s):  
Hydrogen Peroxide ◽  
Phosphorus Atom ◽  
Addition Product ◽  
Molar Ratio ◽  
Oxidizing Agent ◽  
Reaction Conditions

In the reaction of N-methylaminomethylene-dimethylphosphine oxide and sulfide with diethylaminotrimethylsilane, N-methyl-N-trimethylsilyl-aminomethylene-dimethylphosphine oxide (1) and sulfide (2) were formed. These compounds were allowed to react with a series of P(III)C1 compounds to give the corresponding methylaminomethylene-bridged diphosphorus compounds (3 - 10) with phosphorus in the combination λ4P(V)/λ3P(III). In the oxidation of some of these compounds by the hydrogen peroxide-urea 1:1-adduct (NH2)2CO ·H2O2 or sulfur, the corresponding λ4P-CH2-N(Me)-λ4P-derivatives (11 - 16) were formed. Different reaction behaviour was observed depending on the substituent at λ4P or on the oxidizing agent. Reaction of 1 with trimethylsilylmethyl tetrafiuorophosphorane and with bromotriphenylphosphonium bromide furnished, besides trimethylhalosilane, the corresponding diphosphorus compounds (17 ) and (18) with phosphorus in the combination λ4P(V)/λ5P(V) (17) and λ4P(V)/λ4P(V)+ (18).Oxidation of N-diphenylphosphino-N-methyl-aminomethylene-dimethylphosphine oxide (3) by tetrachloro-o-benzoquinone led to the corresponding addition product in impure form. Reaction of 3 with hexafluoroacetone (HFA) yielded a mixture of two products which could not be separated. Both oxidation (>N-PPh2 → >N-P(:O)Ph2) and insertion of HFA into the P-N-bond (>N-PPh2 → >NC(CF3)2-O-PPh2) occurred. In the reaction of 1 with methyldichlorophosphine, both the mono- and disubstituted products, 22 and 23, were formed, independently of the reaction conditions and molar ratio of the starting compounds. The reaction of 1 with bis(diethylamino)chlorophosphine was unusual. Upon separation of both trimethylchlorosilane and dimethylaminotrimethylsilane, compounds 24 - 26 were formed, with the central phosphorus atom bearing one, two or three methylaminomethylene-dimethylphosphine oxide groups, respectively. Simultaneously, tris(diethylamino)phosphine was formed.

scholarly journals Epoxidation of allyl-glycidyl ether with hydrogen peroxide over Ti-SBA-15 catalyst and in methanol medium

2016 ◽  
Vol 18 (4) ◽  
pp. 9-14 ◽  
Author(s):  
Marika Walasek ◽  
Agnieszka Wróblewska
Keyword(s):  
Hydrogen Peroxide ◽  
Reaction Time ◽  
Glycidyl Ether ◽  
Diglycidyl Ether ◽  
Methanol Concentration ◽  
Molar Ratio ◽  
Oxidizing Agent ◽  
Aqueous Hydrogen Peroxide ◽  
Allyl Glycidyl Ether ◽  
Catalyst Content

Abstract This work presents the studies on the epoxidation of allyl-glycidyl ether (AGE) over the Ti-SBA-15 catalyst. In these studies an aqueous hydrogen peroxide was used as an oxidizing agent and as a solvent methanol was applied. The studies on the influence the following parameters: temperature (20–80°C), molar ratio of AGE/H2O2 (1:1.5–5:1), methanol concentration (10–90 wt%), catalyst content (1–9 wt%) and reaction time (15–240 min.) were carried out and the most favourable values of these parameters were chosen (temperature 80°C, molar ratio of AGE/H2O2 = 5:1, methanol concentration 30 wt%, catalyst content 3 wt% and the reaction time 240 min.). At these conditions the functions describing the process reached the following values: the selectivity of diglycidyl ether (DGE) 9.2 mol%, the conversion of AGE 13.9 mol% and the efficiency of H2O2 conversion 89.9 mol%.

Iodination of Organic Compounds with Elemental Iodine in the Presence of Hydrogen Peroxide in Ionic Liquid Media

2008 ◽  
Vol 61 (12) ◽  
pp. 946 ◽  
Author(s):  
Jasminka Pavlinac ◽  
Kenneth K. Laali ◽  
Marko Zupan ◽  
Stojan Stavber
Keyword(s):  
Hydrogen Peroxide ◽  
Ionic Liquid ◽  
Organic Compounds ◽  
Molar Ratio ◽  
Liquid Media ◽  
Reaction Conditions ◽  
Solid Form ◽  
Elemental Iodine ◽  
Solvent Free Reaction

Iodo-transformations using the reagent system I2/H2O2 were studied in the water miscible ionic liquid (IL) 1-butyl-3-methyl imidazolium tetrafluoroborate (bmimBF4) and in water immiscible IL, 1-butyl-3-methyl imidazolium hexafluorophosphate (bmimPF6). Two different forms of H2O2 as mediators of iodination were investigated, namely 30% aq. H2O2 and urea-H2O2 (UHP) in solid form. The role of the oxidant during the course of a reaction could be distinguished based on the amount of reagent required for the most efficient transformation. Two types of iodo-functionalizations through an electrophilic process were observed depending on the structure of the substrates. Whereas ring iodination took place in the case of dimethoxy- and trimethoxy-benzenes, with arylalkyl ketones the alkyl group α to the carbonyl was regioselectively iodinated. The results were further evaluated in comparison with iodination using the reagent system I2/H2O2 in water as medium, and under solvent-free reaction conditions, in terms of efficiency, selectivity, mechanism, and the ‘green’ aspects. The reusability/recycling of water immiscible bmimPF6 was investigated for 1,3,5-trimethoxy benzene (1b), which required a 1/0.5/0.6 molar ratio of substrat/I2/oxidant, and for 1,2,3-trimethoxy benzene (1f), which required a 1/1/1 ratio for complete iodine introduction. In addition, the efficiency of iodination was tested by varying the substrates, and employing the recycled hydrophobic IL bmimPF6.

The Oxidation of Rubber by Hydrogen Peroxide

1935 ◽  
Vol 8 (3) ◽  
pp. 352-359
Author(s):  
B. Kagan ◽  
N. Sukhareva
Keyword(s):  
Carbon Dioxide ◽  
Hydrogen Peroxide ◽  
Carbon Tetrachloride ◽  
Potassium Permanganate ◽  
Main Product ◽  
Addition Product ◽  
Oxidation Products ◽  
Oxidizing Agent ◽  
Small Admixture

Abstract It was noticed long ago that rubber changes during storage, and that it loses its valuable qualities. Many authors have tried to explain this phenomenon as a union of oxygen with rubber molecules. The most interesting work on this subject was the early work of Herbst (Ber., 39, 523 (1906)). Herbst blew air for 140 hours through benzene solutions of rubber and obtained two products, C10H16O3, as a main product, and C10H16O, as a very small admixture. Later Peachey and Leon (J. Soc. Chem. Ind., 31, 1103 (1912); 37, 55 (1918)) subjected rubber films to the action of oxygen and found that for each group of C10H16, four atoms of oxygen were added and one atom of carbon was liberated. These workers succeeded in separating several compounds with different degrees of oxidation, viz., C10H16O; C10H16O 4; C6H9O 2. Herbst thought that he had obtained an addition product of oxygen and rubber hydrocarbon, but Peachey considered that the compounds were the result of a splitting and depolymerization of the rubber molecules. Boswell (India-Rubber J., 54, 981, 987 (1922)) and his students investigated the phenomenon of oxidation of rubber and obtained different oxidation products for each oxidizing agent. A solution of rubber in carbon tetrachloride oxidized by means of potassium permanganate in the absence of air (in carbon dioxide) gave a product of the formula, C25H40O, which in turn was readily oxidized in air to C30H48O2. Using 3% hydrogen peroxide as an oxidizing agent, Boswell obtained a product with the formula, C30H48O, which in turn was easily oxidized to C25H40O2.

Research on Synthesis Regularity of Epoxysuccinic Acid

2013 ◽  
Vol 316-317 ◽  
pp. 942-945
Author(s):  
Qing He Gao ◽  
Yi Can Wang ◽  
Zhi Feng Hou ◽  
Hui Juan Qian ◽  
Yuan Zhang ◽  
...  
Keyword(s):  
Hydrogen Peroxide ◽  
Reaction Time ◽  
Maleic Anhydride ◽  
Reaction Temperature ◽  
Raw Material ◽  
Molar Ratio ◽  
Mass Ratio ◽  
Synthesis System ◽  
Reaction Conditions ◽  
Sodium Hydrate

The yield of epoxysuccinic acid was obtained by determining the content of unreacted maleic anhydride and tartaric acid as a by-product in synthesis system. This method could calculate the yield of epoxysuccinic acid precisely and overcome the disadvantage of obtaining inpure product by recrystallization method. Epoxysuccinic Acid was synthesized using maleic anhydride as raw material, hydrogen peroxide as oxidizer and tungstate as catalyst. The effects of reaction temperature, reaction time, ratio of materials, dosage of oxidizer and catalyst on epoxidation and hydrolysis reaction was investigated. The results showed that the yield of epoxysuccinic acid was 88% when the reaction conditions were as follows: reaction temperature 65°C, reaction time 1.5h, catalyst dosage 3%(based on mass of maleic anhydride), molar ratio of sodium hydrate to maleic anhydride 2:1, mass ratio of hydrogen peroxide to maleic anhydride 1:1.

scholarly journals Epoxidation of 1,5,9-cyclododecatriene with hydrogen peroxide under phase-transfer catalysis conditions: influence of selected parameters on the course of epoxidation

2021 ◽  
Vol 132 (2) ◽  
pp. 983-1001
Author(s):  
Grzegorz Lewandowski ◽  
Marcin Kujbida ◽  
Agnieszka Wróblewska
Keyword(s):  
Hydrogen Peroxide ◽  
Reaction Time ◽  
Catalytic System ◽  
Phase Transfer Catalysis ◽  
Phase Transfer ◽  
Environmentally Friendly ◽  
Molar Ratio ◽  
Oxidizing Agent ◽  
Catalyst Content

AbstractThis work presents the studies on the epoxidation of 1,5,9-cyclododecatriene (CDT) with hydrogen peroxide as the oxidizing agent, under conditions of the phase transfer catalysis (PTC), and with the following catalytic system: H2WO4/H3PO4/[CH3(CH2)7]3CH3N+HSO4− (compounds were mixed at the ratio of 2:1:1). The influence of the following parameters on the course of this process was investigated: catalyst content, molar ratio of H2O2:CDT, temperature and type of solvent. The highest yield of 1,2-epoxy-5,9-cyclododecadiene (ECDD) (54.9 mol%), at the conversion of CDT reached 72.3 mol%, was obtained at the temperature of 50 °C, for the catalyst content of 0.45 mol% (in relation to the introduced CDT), for the molar ratio of H2O2:CDT 1.5:1, with toluene as the solvent and after the reaction time of 30 min. Considering the he obtained results and numerous applications of ECDD, further research should be developed to provide a more efficient and environmentally friendly way of obtaining this compound. Graphic abstract

scholarly journals New method for synthesis of N-alkyl and N,N-dialkyl-O-ethyl and O-isopropylthiocarbamates by oxidation of ammonium salt of xhantogenic acid

2010 ◽  
Vol 64 (5) ◽  
pp. 401-409 ◽  
Author(s):  
Smiljka Milisavljevic ◽  
Aleksandar Marinkovic ◽  
Milutin Milosavljevic
Keyword(s):  
Hydrogen Peroxide ◽  
Ammonium Salt ◽  
Sodium Hypochlorite ◽  
Reaction Times ◽  
Synthetic Methods ◽  
Molar Ratio ◽  
Reaction Conditions ◽  
Optimal Method ◽  
Sodium Ethyl ◽  
Industrial Level

A synthesis of N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates by oxidation of ammonium salt of ethyl and isopropylxanthogenic acid in a presence of sodium hypochlorite and hydrogen peroxide were performed. Ammonium salt of ethyl and isopropylxanthogenic acid was obtained by the reaction of alkylammonium sulfate and sodium ethyl and isopropyl xanthate. Studies on a dependence of N-ethyl-O-isopropylthiocarbamate yield and purity with respect to reaction parameters (reaction time, molar ratio of oxidant and ethylamonium salt of isopropylxanthogenic acid) were performed. Optimal reaction conditions for synthesis of N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates were established. Synthesized compounds have been fully characterized by FTIR, 1H NMR and MS data, while purity has been determined by GC method. A plausible pathway for the N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates synthesis, in the presence of the oxidative agents sodium hypochlorite and hydrogen peroxide, was proposed. The presented synthetic methods has been developed at laboratory and applied at semi-industrial level. The developed optimal method provides a powerful and versatile method for the preparation of N-alkyl and N,N-dialkyl-O-ethyl and O-isopropyl thiocarbamates. This new optimized method offer several benefits, namely, simple operation, mild reaction conditions, bypass of hazardous organic solvents, moderately toxic and inexpensive reagents, and also short reaction times and high product yields.

scholarly journals Hydrogen Peroxide Oxidation of Coordinated Thiocyanate Ion in cis- and trans-[Coen2NH3NCS]2+: The Preparation and Properties of trans-[Coen2NH3CN]2+

1973 ◽  
Vol 51 (24) ◽  
pp. 4152-4158 ◽  
Author(s):  
Albert Richard Norris ◽  
James William Lennox Wilson
Keyword(s):  
Hydrogen Peroxide ◽  
Spectral Properties ◽  
Peroxide Oxidation ◽  
Reaction Conditions ◽  
Thiocyanate Ion ◽  
Hydrogen Peroxide Oxidation ◽  
Percent Conversion ◽  
Cis And Trans ◽  
In Cis

The hydrogen peroxide oxidation of thiocyanate ion in cis- and trans-[Coen2NH3NCS]2+ leads to the formation of the corresponding cis- and trans-cyanoammine- and diamminebis(ethylenediamine)cobalt-(III) complexes. The spectral properties of the previously unreported trans-[Coe2NH3CN]2+ are reported and compared to the spectral properties of the cis-isomer.Observations are made concerning the reaction conditions which favor a high percent conversion of trans-[Coen2NH3NCS]2+ to trans-[Coen2NH3CN]2+.

A review of lignin hydrogen peroxide oxidation chemistry with emphasis on aromatic aldehydes and acids

Holzforschung ◽  
2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Ajinkya More ◽  
Thomas Elder ◽  
Zhihua Jiang
Keyword(s):  
Hydrogen Peroxide ◽  
Oxidative Degradation ◽  
Reaction Medium ◽  
Dicarboxylic Acids ◽  
Aromatic Aldehydes ◽  
Product Distribution ◽  
Reaction Conditions ◽  
Alkaline Conditions ◽  
The Stability ◽  
Oxidation Chemistry

Abstract This review discusses the main factors that govern the oxidation processes of lignins into aromatic aldehydes and acids using hydrogen peroxide. Aromatic aldehydes and acids are produced in the oxidative degradation of lignin whereas mono and dicarboxylic acids are the main products. The stability of hydrogen peroxide under the reaction conditions is an important factor that needs to be addressed for selectively improving the yield of aromatic aldehydes. Hydrogen peroxide in the presence of heavy metal ions readily decomposes, leading to minor degradation of lignin. This degradation results in quinones which are highly reactive towards peroxide. Under these reaction conditions, the pH of the reaction medium defines the reaction mechanism and the product distribution. Under acidic conditions, hydrogen peroxide reacts electrophilically with electron rich aromatic and olefinic structures at comparatively higher temperatures. In contrast, under alkaline conditions it reacts nucleophilically with electron deficient carbonyl and conjugated carbonyl structures in lignin. The reaction pattern in the oxidation of lignin usually involves cleavage of the aromatic ring, the aliphatic side chain or other linkages which will be discussed in this review.

Study on the Synthesis of Isoamyl Acetate Catalyzed by Strong Acidic Cation Exchange Resin

2011 ◽  
Vol 396-398 ◽  
pp. 2411-2415 ◽  
Author(s):  
Ping Lan ◽  
Li Hong Lan ◽  
Tao Xie ◽  
An Ping Liao
Keyword(s):  
Acetic Acid ◽  
Reaction Time ◽  
Cation Exchanger ◽  
Cation Exchange Resin ◽  
Isoamyl Acetate ◽  
Molar Ratio ◽  
Esterification Reaction ◽  
Reaction Conditions ◽  
Optimum Reaction

Isoamyl acetate was synthesized from isoamylol and glacial acetic acid with strong acidic cation exchanger as catalyst. The effects of reaction conditions such as acid-alcohol ratio, reaction time, catalyst dosage to esterification reaction have been investigated and the optimum reaction conditions can be concluded as: the molar ratio of acetic acid to isoamylol 0.8:1, reaction time 2h, 25 % of catalyst (quality of acetic acid as benchmark). The conversion rate can reach up to 75.46%. The catalytic ability didn’t reduce significantly after reusing 10 times and the results showed that the catalyst exhibited preferably catalytic activity and reusability.

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