Transformation of Carbonyl or Thiocarbonyl Groups into Methylene Groups

2005 ◽  
pp. 1
Author(s):  
W. Kantlehner
Keyword(s):  
Methylene Groups

Synthesis and characterization of a series of 1-methyl-4-[2-aryl-1-diazenyl]piperazines and a series of ethyl 4-[2-aryl-1-diazenyl]-1-piperazinecarboxylates

2004 ◽  
Vol 82 (8) ◽  
pp. 1294-1303 ◽  
Author(s):  
Vanessa Renée Little ◽  
Keith Vaughan
Keyword(s):  
Free Energy ◽  
Chemical Shifts ◽  
Linear Free Energy Relationship ◽  
Piperazine Ring ◽  
Linear Free Energy ◽  
In Series ◽  
Methylene Groups ◽  
Diazonium Coupling ◽  
The Difference

1-Methylpiperazine was coupled with a series of diazonium salts to afford the 1-methyl-4-[2-aryl-1-diazenyl]piperazines (2), a new series of triazenes, which have been characterized by 1H and 13C NMR spectroscopy, IR spectroscopy, and elemental analysis. Assignment of the chemical shifts to specific protons and carbons in the piperazine ring was facilitated by comparison with the chemical shifts in the model compounds piperazine and 1-methylpiperazine and by a HETCOR experiment with the p-tolyl derivative (2i). A DEPT experiment with 1-methylpiperazine (6) was necessary to distinguish the methyl and methylene groups in 6, and a HETCOR spectrum of 6 enabled the correlation of proton and carbon chemical shifts. Line broadening of the signals from the ring methylene protons is attributed to restricted rotation around the N2-N3 bond of the triazene moiety in 2. The second series of triazenes, the ethyl 4-[2-phenyl-1-diazenyl]-1-piperazinecarboxylates (3), have been prepared by similar diazonium coupling to ethyl 1-piperazinecarboxylate and were similarly characterized. The chemical shifts of the piperazine ring protons are much closer together in series 3 than in series 2, resulting in distortion of the multiplets for these methylenes. It was noticed that the difference between these chemical shifts in 3 exhibited a linear free energy relationship with the Hammett substituent constants for the substituents in the aryl ring. Key words: triazene, piperazine, diazonium coupling, NMR, HETCOR, linear free energy relationship.

Hydroxyl-containing bis(sulfonates). Reaction of 1,4-dibromo-2,3-butanedione with water, methanol and sodium sulfite

2021 ◽  
pp. 1-12
Author(s):  
Gerasimos M. Tsivgoulis ◽  
Dimitris G. Vachliotis ◽  
Golfo G. Kordopati ◽  
Panayiotis V. Ioannou
Keyword(s):  
13C Nmr ◽  
Sodium Sulfite ◽  
The Other ◽  
Carbonyl Carbon ◽  
1H And 13C Nmr ◽  
Sodium Sulfonate ◽  
Pure Product ◽  
Methylene Groups ◽  
New Type ◽  
High Yields

Sulfonates are well-known substances with a variety of applications, e.g. as surfactants. On the other hand, bis(sulfonates) bearing hydroxyl or keto group(s) in between the sulfonate groups can be used with or without further modification as starting materials for the preparation of new type of molecules capable to form either complexes or in general supramolecular structures. The synthesis of three hydroxyl-bearing bis(sulfonates), 2-hydroxypropane-1,3-bis(sodium sulfonate) 4, DL-2,3-dihydroxybutane-1,4-bis(sodium sulfonate) 8, and sodium 2,3,4-trihydroxy-1-sulfonate 7 (as by-product) via the Strecker sulfonation are described. Interestingly, under similar conditions, sulfonation of 1,4-dibromo-2,3-butanedione 9 was found to be very complicated and no pure product could be isolated, despite previously reported results on sulfonation of α-halogenated ketones in high yields. There are indications that SO3 2 -  attacks at the carbonyl carbon of 9 followed by rearrangement and expulsion of SO4 2 - . 1,4-dibromo-2,3-butanedione 9, bearing two keto groups next to methylene groups, can potentially exist as enols or in the case of its solution in hydroxylic solvents in the form of hemiketals or geminal diols. This behavior of 9 when is dissolved in CDCl3, CD3OD and D2O was studied by means of UV-Vis, 1H and 13C NMR and the nature of the adducts formed was elucidated.

scholarly journals Semi-Crystalline Hydrophobic Polyamidoamines: A New Family of Technological Materials?

Polymers ◽  
2021 ◽  
Vol 13 (7) ◽  
pp. 1018
Author(s):  
Massimo Marcioni ◽  
Jenny Alongi ◽  
Elisabetta Ranucci ◽  
Mario Malinconico ◽  
Paola Laurienzo ◽  
...  
Keyword(s):  
Maximum Stress ◽  
Water Resistance ◽  
Prolonged Exposure ◽  
Water Soluble ◽  
Synthesis And Characterization ◽  
Molecular Weights ◽  
New Family ◽  
Methylene Groups ◽  
Methane Flame

The hitherto known polyamidoamines (PAAs) are not suitable as structural materials because they are usually water-soluble or swellable in water. This paper deals with the synthesis and characterization of semi-crystalline hydrophobic PAAs (H-PAAs) by combining different bis-sec-amines with bis-acrylamides obtained from C6–C12 bis-prim-amines. H-PAAs were initially obtained in a solution of benzyl alcohol, a solvent suitable for both monomers and polymers. Their number average molecular weights, M¯n, which were determined with 1H-NMR by evaluating the percentage of their terminal units, varied from 6000 to >10,000. The solubility, thermal properties, ignitability and water resistance of H-PAAs were determined. They were soluble in organic solvents, semi-crystalline and thermally stable. The most promising ones were also prepared using a bulk process, which has never been previously reported for PAA synthesis. In the form of films, these H-PAAs were apparently unaffected by water. The films underwent tensile and wettability tests. They showed similar Young moduli (260–263 MPa), whereas the maximum stress and the stress at break depended on the number of methylene groups of the starting bis-acrylamides. Their wettability was somewhat higher than that of common Nylons. Interestingly, none of the H-PAAs considered, either as films or powders, ignited after prolonged exposure to a methane flame.

Addition of methylene groups to Fe3(CO)9(μ3-Te)2

1991 ◽  
Vol 401 (3) ◽  
pp. 339-346 ◽  
Author(s):  
Pradeep Mathur ◽  
V.Dayal Reddy ◽  
Rakesh Bohra
Keyword(s):  
Methylene Groups

scholarly journals Demicellization of Polyethylene Oxide in Water Solution under Static Magnetic Field Exposure Studied by FTIR Spectroscopy

2013 ◽  
Vol 2013 ◽  
pp. 1-8 ◽  
Author(s):  
Emanuele Calabrò ◽  
Salvatore Magazù
Keyword(s):  
Magnetic Field ◽  
Aqueous Solution ◽  
Ftir Spectroscopy ◽  
Static Magnetic Field ◽  
Polyethylene Oxide ◽  
Water Solution ◽  
Infrared Region ◽  
Bending Vibrations ◽  
Field Exposure ◽  
Methylene Groups

FTIR spectroscopy was used to investigate the alterations of the vibration bands in the mid-infrared region of Polyethylene oxide in aqueous solution at 25 mg/mL concentration under exposure up to 4 h to a static magnetic field at 200 mT. FTIR spectroscopic analysis of PEO solution in the range 3500–1000 cm−1 evidenced the stretching vibrations of ether band, C–H symmetric-antisymmetric and bending vibrations of methylene groups, and the C–O–C stretching band. A significant decrease in intensity of symmetric and asymmetric stretching CH2 vibration bands occurred after 2 h and 4 h of exposure, followed by a significant decrease in intensity of scissoring bending in plane CH2 vibration around 1465 cm−1. Finally, the C–O–C stretching band around 1080 cm−1 increased in intensity after 4 h of exposure. This result can be attributed to the increase of formation of the intermolecular hydrogen bonding that occurred in PEO aqueous solution after SMF exposure, due to the reorientation of PEO chain after exposure to SMF. In this scenario, the observed decrease in intensity of CH2 vibration bands can be understood as well considering that the reorientation of PEO chain under the applied SMF induces PEO demicellization.

scholarly journals A Molecular Architectural Approach to Second-Order Nonlinear Optical Materials

1995 ◽  
Vol 392 ◽  
Author(s):  
Xiaoguang Yang ◽  
Duncan McBranch ◽  
Basil Swanson ◽  
Dequan Li
Keyword(s):  
Nonlinear Optical ◽  
Second Harmonic ◽  
Fused Silica ◽  
Second Order ◽  
Nonlinear Susceptibility ◽  
Design And Synthesis ◽  
Fundamental Wavelength ◽  
Assembled Monolayers ◽  
Methylene Groups ◽  
Nlo Chromophores

AbstractThe design and synthesis of a family of calix[4]arene-based nonlinear optical (NLO) chromophores are discussed. The calixarene chromophores are macrocyclic compounds consisting of four simple D-π-A units bridged by methylene groups. These molecules were synthesized such that four D-π-A units of the calix[4]arene were aligned along the same direction with the calixarene in a cone conformation. These nonlinear optical super-chromophores were subsequently fabricated into covalently bound self-assembled monolayers on the surfaces of fused silica and silicon. Spectroscopic second harmonic generation (SHG) measurements were carried out to determine the absolute value of the dominant element of the second-order nonlinear susceptibility, d33, and the average molecular alignment, ψ. We find a value of d33 = 60 pm/V at a fundamental wavelength of 890 nm, and ψ˜ 36° with respect to the surface normal.

Conversion of nor-ketones into prochiral terminal methylene groups: synthesis of (24E)- and (24Z)-[28-2H]ergosta-5,24(28)-dien-3β-ols

1985 ◽  
pp. 595-599 ◽  
Author(s):  
Mario Anastasia ◽  
Pietro Allevi ◽  
Pierangela Ciuffreda ◽  
Alberto Fiecchi ◽  
Pierluigi Gariboldi ◽  
...  
Keyword(s):  
Methylene Groups
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