THE REACTION OF CHLORAL WITH HALOBENZENES AND WITH 2,4-DICHLOROPHENOL: SYNTHESIS OF HALOGENATED ETHYLBENZENES AND OF α-METHOXYPHENYLACETIC ACIDS

1966 ◽  
Vol 44 (5) ◽  
pp. 575-582 ◽  
Author(s):  
Wilkins Reeve ◽  
John P. Mutchler ◽  
Charles L. Liotta
Keyword(s):  
Carbon Disulfide ◽  
Potassium Hydroxide ◽  
Methoxy Group ◽  
Methylene Chloride ◽  
Aluminium Chloride ◽  
Molar Ratio ◽  
Side Chain ◽  
New Compounds ◽  
Hydroxy Groups

The Friedel–Crafts reaction of chloral with aromatic compounds to form aryltrichloromethylcarbinols is reviewed. The molar ratio of aluminium chloride to chloral is critical and varies from 0.15 to 2.0 depending on the solvent, steric considerations, and the reactivity of the aromatic ring. The reaction has been used to prepare several new compounds with carbon disulfide or excess aromatic compound as the solvent. From 2,4-dichlorophenol, an o-hydroxy-α-trichloromethylbenzyl alcohol is obtained. Both the phenolic and side-chain hydroxy groups of this alcohol are methylated with equal ease by dimethyl sulfate.It has now been found that changing the solvent from carbon disulfide to methylene chloride results in the hydroxy group of the initial carbinol also being replaced by chlorine. This role of the solvent in controlling the course of the reaction has not been observed previously.The trichloromethylcarbinols are converted into α-methoxy acids by treatment with methanolic potassium hydroxide. Sodium in liquid ammonia removes the α-methoxy group, as well as the halogens, from 3,5-dichloro-α,2-dimethoxyphenylacetic acid.

scholarly journals Darstellung und Eigenschaften von cyclo-Nonaschwefeloxid (S9O) und von cyclo-Dekaschwefeloxid (S10O) [1] / Preparation and Properties of cyclo-Nonasulfuroxide (S9O) and of cyclo-Decasulfuroxide (S10O) [1]

1985 ◽  
Vol 40 (5) ◽  
pp. 594-600 ◽  
Author(s):  
Ralf Steudel ◽  
Torsten Sandow ◽  
Jürgen Steidel
Keyword(s):  
Acetic Acid ◽  
Raman Spectrum ◽  
Oxygen Atom ◽  
Raman Spectra ◽  
Carbon Disulfide ◽  
Methylene Chloride ◽  
Molar Ratio ◽  
Infrared And Raman Spectra ◽  
Cyclic Molecules ◽  
First Time

Abstract The homocyclic oxides S9O (m.p. 33 °C, dec.) and S10O (m.p. 51 °C, dec.) have been prepared by oxidation of the corresponding sulfur rings S9 and S10 , respectively, by trifluoroperoxy acetic acid (molar ratio 1:2-3) in a carbon disulfide/methylene chloride mixture. According to infrared and Raman spectra, both compounds contain an exocyclic oxygen atom. S9O and S10O decompose at 25 °C to give SO2 and a polysulfuroxide SnO with >10 but both can be stored at -78 °C without decomposition. The SS bond distances are discussed on the basis of the Raman spectra. In addition, the Raman spectrum of solid S9 has been recorded for the first time. It shows that S9 crystallizes as two allotropes (α-and β-S9) both consisting of cyclic molecules of either C1 or C2 symmetry with bond distances of between 203 and 209 pm.

scholarly journals Reaktive E=C(p–p)π Systeme, XXXIV Addition von Alkoholen oder primären Aminen an Phosphaalkene F3CP=C(F)OR. Neue Trifluormethylphosphane und -phosphaalkene/Reactive E = C( p – p ) π-Systems, XXXIV Addition of Alcohols or Primary Amines to Phosphaalkenes F3CP= C(F)OR . Novel Trifluoromethylphosphanes and Phosphaalkenes

1993 ◽  
Vol 48 (1) ◽  
pp. 58-67 ◽  
Author(s):  
Joseph Grobe ◽  
Duc Le Van ◽  
Gudrun Lange
Keyword(s):  
High Resolution Mass Spectrometry ◽  
Molar Ratio ◽  
Primary Amines ◽  
The Novel ◽  
Experimental Conditions ◽  
Pull System ◽  
Fragment Ions ◽  
New Compounds ◽  
C Nmr

The course of the reactions o f fluorophosphaalkenes F3CP = C (F)OR [R = Me (1), Et (2)] with methanol or ethanol strongly depends on the experimental conditions. Thus at 70 °C a mixture of the 2-phosphapropionic acid ester F3CP (H )CO2R [R = Me (3), Et (4)] and trifluoromethylphosphane H2PCF3 is formed [molar ratio: 3 or 4 /H2 CF3 ≈1/1]. If the precursors F3CP (H )CO2R [R = Me (3), Et) are used as starting materials, the reaction with ROH under the same conditions affords 3 and 4, respectively, (90 to 95% yield) with only traces of H2PCF 3. In the presence o f iPr2NH these precursors react with R′OH to give the novel trifluoromethylphosphaalkenes F3CP = C (OR )OR [R /R′: Me/Me (6); E t/E t (7); Me/Et (8)]. With Et2NH , 3 undergoes an addition/elimination process yielding the interesting push/pull system Et2N(F)C = P-CO2Me (5). 1 and 2 react with primary amines R′NH2 (R′= tBu, Me) with stereoselective formation of the fairly labile phosphaalkenes F3CP = C(OR)NHR′ [R /R′: Me/tBu (9), Et/tBu(10), Me/Me (11)] with trans-positions for CF3 and NHR′.The new compounds 3 -11 were characterized by spectroscopic investigations (1H , 19F, 31P, 13C NMR ; IR, MS) and determination of M+ or typical fragment ions [M+ -OR ] by high resolution mass spectrometry.

scholarly journals “Newton’s cradle” proton relay with amide–imidic acid tautomerization in inverting cellulase visualized by neutron crystallography

2015 ◽  
Vol 1 (7) ◽  
pp. e1500263 ◽  
Author(s):  
Akihiko Nakamura ◽  
Takuya Ishida ◽  
Katsuhiro Kusaka ◽  
Taro Yamada ◽  
Shinya Fushinobu ◽  
...  
Keyword(s):  
Glycoside Hydrolases ◽  
Side Chain ◽  
Enzymatic Reactions ◽  
X Ray Diffraction ◽  
Peptide Bonds ◽  
Proton Relay ◽  
Newton’S Cradle ◽  
Dynamics Simulations ◽  
Hydrolysis Of

Hydrolysis of carbohydrates is a major bioreaction in nature, catalyzed by glycoside hydrolases (GHs). We used neutron diffraction and high-resolution x-ray diffraction analyses to investigate the hydrogen bond network in inverting cellulase PcCel45A, which is an endoglucanase belonging to subfamily C of GH family 45, isolated from the basidiomycete Phanerochaete chrysosporium. Examination of the enzyme and enzyme-ligand structures indicates a key role of multiple tautomerizations of asparagine residues and peptide bonds, which are finally connected to the other catalytic residue via typical side-chain hydrogen bonds, in forming the “Newton’s cradle”–like proton relay pathway of the catalytic cycle. Amide–imidic acid tautomerization of asparagine has not been taken into account in recent molecular dynamics simulations of not only cellulases but also general enzyme catalysis, and it may be necessary to reconsider our interpretation of many enzymatic reactions.

scholarly journals The Role of Arg13 in Protein Phosphatase M tPphA from Thermosynechococcus elongatus

2012 ◽  
Vol 2012 ◽  
pp. 1-7 ◽  
Author(s):  
Jiyong Su ◽  
Karl Forchhammer
Keyword(s):  
Amino Acid ◽  
Protein Phosphatase ◽  
Arginine Residue ◽  
Side Chain ◽  
Wild Type ◽  
Catalytic Center ◽  
Nitrophenyl Phosphate ◽  
Reduced Activity ◽  
Amino Acid Variants

A highly conserved arginine residue is close to the catalytic center of PPM/PP2C-type protein phosphatases. Different crystal structures of PPM/PP2C homologues revealed that the guanidinium side chain of this arginine residue can adopt variable conformations and may bind ligands, suggesting an important role of this residue during catalysis. In this paper, we randomly mutated Arginine 13 of tPphA, a PPM/PP2C-type phosphatase from Thermosynechococcus elongatus, and obtained 18 different amino acid variants. The generated variants were tested towards p-nitrophenyl phosphate and various phosphopeptides. Towards p-nitrophenyl phosphate as substrate, twelve variants showed 3–7 times higher Km values than wild-type tPphA and four variants (R13D, R13F, R13L, and R13W) completely lost activity. Strikingly, these variants were still able to dephosphorylate phosphopeptides, although with strongly reduced activity. The specific inability of some Arg-13 variants to hydrolyze p-nitrophenyl phosphate highlights the importance of additional substrate interactions apart from the substrate phosphate for catalysis. The properties of the R13 variants indicate that this residue assists in substrate binding.

Role of reduced precursor and solvolytic reagent molar ratio on preparation and properties of ionogel

2016 ◽  
Vol 242 ◽  
pp. 29-37 ◽  
Author(s):  
Abhishek Kumar Gupta ◽  
Yogendra Lal Verma ◽  
Manish Pratap Singh ◽  
Rajendra Kumar Singh
Keyword(s):  
Molar Ratio

Appearance, corrosion properties, and leach resistance of spruce and pine wood treated with Mea modified micronized copper preservative (MCu)

Holzforschung ◽  
2014 ◽  
Vol 68 (4) ◽  
pp. 477-486 ◽  
Author(s):  
Myung Jae Lee ◽  
Sedric Pankras ◽  
Paul Cooper
Keyword(s):  
Wood Species ◽  
Wood Preservative ◽  
Molar Ratio ◽  
Corrosion Properties ◽  
Pine Wood ◽  
Molar Ratios ◽  
Copper Leaching ◽  
Mold Resistance ◽  
Refractory Wood

Abstract Canadian refractory wood species treated with micronized copper (MCu) wood preservative become mottled and streaky in appearance. To overcome this issue, the MCu system was modified by adding small amounts of monoethanolamine (Mea). The modified systems were evaluated to clarify the role of Mea in terms of leaching, corrosion, and mold resistance of MCu systems. The mottled and streaky surface on treated spruce was prevented at Mea/Cu molar ratios between 0.7 and 1.5. Copper leaching remained modest and was only slightly higher than that of MCu alone up to a Mea/Cu molar ratio of 1.2. However, adding even a small amount of Mea to the MCu formulation increased fastener corrosion compared with MCu. Protonated Mea increased as more Mea was added and was identified as the main corrosion-causing electrolyte in the system.

Preparation of Some 2-(Methoxyphenyl)-2H-benzotriazoles and the Corresponding Hydroxyphenyl Compounds

1987 ◽  
Vol 40 (10) ◽  
pp. 1663 ◽  
Author(s):  
J Rosevear ◽  
JFK Wilshire
Keyword(s):  
Acetic Acid ◽  
Good Yield ◽  
Hydrobromic Acid ◽  
Methoxy Group ◽  
Methylene Chloride ◽  
Thiourea Dioxide ◽  
Boron Tribromide

The reaction of several substituted o- nitronitrosobenzenes with O- and p- anisidine , and 2,4- dimethoxyaniline in acetic acid gives in good yield the corresponding enitroazobenzenes which are readily reduced with thiourea dioxide ( formamidinesulfinic acid) to the corresponding 2-(methoxypheny1)-2H-benzotriazoles, demethylation of which furnished the corresponding 2- (hydroxypheny1)-2H-benzotriazoles. Demethylation of the dimethoxy derivatives was best accomplished with boron tribromide in methylene chloride, the methoxy group located ortho to the benzotriazole ring being demethylated more readily than is the para-methoxy group. The reaction of enitroazobenzenes containing a methoxy group with hydrobromic acid in acetic acid results in cleavage of the azo bond and also partial bromination to give o- nitroaniline and some of its brominated derivatives.

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