Organophosphorus Compounds. I. 2-Chloroalkylphosphonic Acids as Phosphorylating Agents

1963 ◽  
Vol 16 (4) ◽  
pp. 596 ◽  
Author(s):  
JA Maynard ◽  
JM Swan
Keyword(s):  
Magnetic Resonance ◽  
Proton Magnetic Resonance ◽  
Organophosphorus Compounds ◽  
Chloride Ion ◽  
The Other ◽  
High Yield ◽  
Neutral Solution ◽  
Phosphate Ion ◽  
Phosphorus Containing ◽  
Group 2

Alcohols and phenols are phosphorylated in high yield by reaction with various 2-chloroalkylphosphonic acids at 20-50�C in the presence of three or more molar equivalents of cyclohexylamine or triethylamine, the other products being the corresponding alk-1-ene and chloride ion. The reaction probably proceeds by attack of an ROH molecule on the phosphorus atom of a doubly-ionized phosphonate group. 2-Chlorodecyl-, 10-carboxy-2-chlorodecyl-, and 2-chloro-octylphosphonic acid decompose rapidly in neutral solution giving chloride ion, phosphate ion, and the corresponding alk-1-ene. In the absence of hydroxylic compounds, 2-chlorodecylphosphonic acid is decomposed by cyclohexylamine to dec-1-ene and a product which appears to be N-cyclohexylphosphoramidate; t-amines and also aniline cause dehydrohalogenation to dec-1-enylphosphonic acid. The proton magnetic resonance spectra of most of the phosphorus-containing substances described herein are recorded.

Metal – Aminopolycarboxylic Acid Complexes. II. Studies of Triethylenetetraaminehexaacetic Acid and its Lead(II) Complexes in Aqueous Solution by Proton Magnetic Resonance Spectroscopy

1971 ◽  
Vol 49 (12) ◽  
pp. 2086-2095 ◽  
Author(s):  
P. Letkeman ◽  
J. B. Westmore
Keyword(s):  
Magnetic Resonance ◽  
Proton Magnetic Resonance ◽  
Proton Magnetic Resonance Spectroscopy ◽  
Equilibrium Constants ◽  
The Other ◽  
Resonance Spectroscopy ◽  
Carboxylate Groups ◽  
Triethylenetetraaminehexaacetic Acid ◽  
Nitrogen Bonds ◽  
Aminopolycarboxylic Acid

Nuclear magnetic resonance (n.m.r.) spectroscopy was used to determine the preferred protonation sites in TTHA. For its 1:1 complex with Pb(II) the following equilibrium constants for protonation were obtained (triethylenetetraaminehexaacetic acid ≡ H6A)[Formula: see text]The non-protonated complex is considered to have four coplanar (or nearly coplanar) metal–nitrogen bonds with the center carboxylate groups coordinated above and below this plane, and with the terminal carboxylate groups playing only a small part in the coordinate bonding. The first and second protonations of the complex occur preferentially at the terminal and center nitrogen atoms, respectively, on the same side of the complex, accompanied by breaking of the respective metal–nitrogen bonds. This causes partial unwrapping of the complex from one side. Rapid interconversion between configurations in which unwrapping and rewrapping occurs first from one side of the molecule and then from the other leads to simplified n.m.r. spectra.

The effects of electronic buttressing on the conformations of some orthodisubstituted benzenes

1972 ◽  
Vol 25 (4) ◽  
pp. 811 ◽  
Author(s):  
RI Herrmann ◽  
ID Rae
Keyword(s):  
Magnetic Resonance ◽  
Benzene Ring ◽  
Aromatic Ring ◽  
Proton Magnetic Resonance ◽  
The Other ◽  
Magnetic Resonance Spectra

When one of a pair of substituents ortho to each other on a benzene ring is conjugated with an appropriate para substituent, it is pulled towards coplanarity with the aromatic ring and the other substituent has to take a greater share of the twisting necessary to avert steric conflict. This effect, termed electronic buttressing, is demonstrated in the proton magnetic resonance spectra of 5-dimethylamino-2- nitroanilines, 5-substituted methyl 2-nitrobenzoates, and 4-substituted 1,2-dinitrobenzenes. In this latter group the size of the effect is shown to depend on the conjugative ability of the 4-substituent.

Ribo-2′-deoxyribo hybrid dinucleoside monophosphates. Proton magnetic resonance studies of 3′,5′- and 2′,5′-uridylyl-2′-deoxythymidine

1978 ◽  
Vol 56 (4) ◽  
pp. 522-529 ◽  
Author(s):  
James Peeling ◽  
Frank E. Hruska ◽  
Peter C. Loewen
Keyword(s):  
Aqueous Solution ◽  
Magnetic Resonance ◽  
Proton Magnetic Resonance ◽  
Molecular Conformation ◽  
The Other ◽  
Magnetic Resonance Studies ◽  
Dinucleoside Monophosphates ◽  
Standard Techniques

This 1Hmr study initiates our examination of the conformations of dinucleoside monophosphates possessing ribo 2′- or 3′-nucleotidyl units linked to 5′-nucleotidyl units possessing the 2′-deoxyribo sugar. The syntheses of uridylyl-3′,5′-2′-deoxythymidine (3′,5′-UpdT) and its 2′,5′-isomer, 2′,5′-UpdT, were carried out with standard techniques. The 1Hmr data were obtained at frequencies up to 270 MHz and used to derive the dominant conformation of the dimers in aqueous solution. Comparison with data for the component mononucleotides reveals that dimerization does not lead to drastic changes in the molecular conformation. Literature data for dimers possessing only the ribo sugar (3′,5′-UpU) and the 2′-deoxyribo sugar (3′,5′-d(TpT)) are also presented. The results indicate that, at least for our dipyrimidine dimers, the molecular conformation of a particular fragment is not critically dependent on the nature (ribo or 2′-deoxyribo) of the other nucleotide unit.

THE ALCOHOLYSIS OF TRIALKYLALKOXYSILANES: PART II. THE PREPARATION AND CHEMISTRY OF METHYL 2,3,4-TRI-O-TRI-METHYLSILYL-α-D-GLUCOPYRANOSIDE

1965 ◽  
Vol 43 (7) ◽  
pp. 2004-2011 ◽  
Author(s):  
D. T Hurst ◽  
A. G. McInnes
Keyword(s):  
Magnetic Resonance ◽  
Acetic Anhydride ◽  
Proton Magnetic Resonance ◽  
Benzoyl Chloride ◽  
Phenyl Isocyanate ◽  
High Yield ◽  
Aqueous Methanol ◽  
Trimethylsilyl Group ◽  
Acidic Catalysts ◽  
Derivatives Of

The trimethylsilyl group on the 6-position of methyl 2,3,4,6-tetra-O-trimethylsilyl-α-D-glucopyranoside is preferentially removed by methanolysis, using basic or acidic catalysts, giving methyl 2,3,4-tri-O-trimethylsilyl-α-D-glucopyranoside in high yield (>80%). Reaction of the latter with acetic anhydride, benzoyl chloride, or phenyl isocyanate produces the corresponding 6-substituted derivatives in quantitative yield. The trimethylsilyl residues from the latter compounds are hydrolyzed by 50% aqueous methanol with the concomitant formation of 6-O-acetyl, 6-O-benzoyl, or 6-carbanilate derivatives of methyl α-D-glucopyranoside in excellent yield. Chemical and proton magnetic resonance (p.m.r.) studies established the structure of methyl 2,3,4-tri-O-trimethylsilyl-α-D-glucopyranoside, and of subsequent derivatives prepared from this compound. Infrared and p.m.r. evidence is offered to support conclusions regarding the conformation of the groups or atoms attached to C6 and C5 of the glucoside residue in some of these compounds.

Proton Magnetic Resonance Studies of Rotational Isomerism in Halotoluene Derivatives. IX. Rotational Barriers and Conformational Energy Differences in α,α,α′,α′,α″,α″, 2,4,6-Nonachloromesitylene

1973 ◽  
Vol 51 (13) ◽  
pp. 2110-2117 ◽  
Author(s):  
J. Peeling ◽  
B. W. Goodwin ◽  
T. Schaefer ◽  
J. B. Rowbotham
Keyword(s):  
Magnetic Resonance ◽  
Carbon Disulfide ◽  
Proton Magnetic Resonance ◽  
Methylene Chloride ◽  
Activation Parameters ◽  
Rotational Isomerism ◽  
Conformational Energy ◽  
The Other ◽  
Free Energies ◽  
Magnetic Resonance Studies

The activation parameters for the rotation of the dichloromethyl groups in the two conformations of α,α,α′,α′,α″,α″,2,4,6-nonachloromesitylene are reported for solutions in toluene-d8 and in methylene chloride. In addition, free energies of activation are given for solutions in bromochloromethane, tri-chloroethylene, and in carbon disulfide. The free energies of activation are lower in the toluene solution than in the other solutions. The entropies of activation are near zero, perhaps slightly negative. The symmetrical conformation is more stable than the unsymmetrical one in all the solvents.

THE PROTON MAGNETIC RESONANCE OF HgSO4∙1H2O

1967 ◽  
Vol 45 (11) ◽  
pp. 3737-3741 ◽  
Author(s):  
P. W. Lobo Jr. ◽  
J. P. Messa
Keyword(s):  
Hydrogen Bond ◽  
Magnetic Resonance ◽  
Water Molecule ◽  
Single Crystals ◽  
Proton Magnetic Resonance ◽  
Resonance Spectrum ◽  
Proton Magnetic Resonance Spectrum ◽  
The Other ◽  
X Ray ◽  
Crystallographic Axes

The proton magnetic resonance spectrum of single crystals of HgSO∙1H2O has been investigated. This crystal is of interest since, according to the X-ray structure analysis, it appears likely that one of the protons of the water molecule is hydrogen-bonded in the structure, while the other is free. Two non-equivalent sets of parallel H–H vectors have been observed in agreement with the crystal symmetry. The angles of one of the intramolecular H–H vectors with the crystallographic axes are α = 58°, β = 95°, and γ = 36°. The results are consistent with the suggestion that one of the protons does not form a hydrogen bond in the crystal.

Proton magnetic resonance spectra of the mannans of some new species of Hansenula and their phylogenetic significance

1970 ◽  
Vol 16 (6) ◽  
pp. 445-448 ◽  
Author(s):  
J. F. T. Spencer ◽  
P. A. J. Gorin ◽  
L. J. Wickerham
Keyword(s):  
New Species ◽  
Magnetic Resonance ◽  
Phylogenetic Relationships ◽  
Proton Magnetic Resonance ◽  
Hansenula Polymorpha ◽  
The Other ◽  
Phylogenetic Significance ◽  
Lower Content ◽  
Haploid Species ◽  
Magnetic Resonance Spectra

The proton magnetic resonance spectra of the mannose-containing polysaccharides from some new species of Hansenula were obtained and used as an aid in establishing their phylogenetic relationships to other members of the genus. The spectrum of the mannan from Hansenula dimennae is identical with that of the mannan from Hansenula californica. These two haploid species are taxonomically closely related and are adjacent on the same line of the phylogenetic diagram according to Wickerham. Hansenula saturnus var. subsufficiens mannan has a spectrum like those of the mannans of some strains of Hansenula mrakii and Hansenula beijerinckii. The new species Hansenula henricii, Hansenula nonfermentans, and Hansenula glucozyma all form mannans with spectra having characteristic signals at about τ4.24 and τ4.38, as do the spectra of the mannans formed by the other species on the same phylogenetic line, Hansenula polymorpha, Hansenula minuta, and Hansenula wickerhamii. These species have, relatively, DNA's with the highest guanine and cytosine percentages in the genus. Hansenula platypodis, a species which, unlike other Hansenula species, forms ascophores and anastomoses, has DNA with a lower content of guanine plus cytosine. The spectrum of H. platypodis mannan is like that of H. minuta mannan, with the exception of two small signals at τ4.44 and τ4.48 which do not occur in the spectrum of H. minuta mannan.

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