Triazene derivatives of (1,x)-diazacycloalkanes. Part IV.1 Synthesis and characterization of 1-[2-aryl-1-diazenyl]-3-(3-[2-aryl-1-diazenyl]hexahydro-1-pyrimidinylmethyl)hexahydropyrimidines and 1-(5,5-dimethyl-3-[2-aryl-1-diazenyl]hexahydro-1-pyrimidinylmethyl)-5,5-dimethyl-3-[2-aryl-1-diazenyl]hexahydropyrimidines from the reaction of diazonium salts with mixtures of formaldehyde and 1,3-diaminopropanes

2005 ◽  
Vol 83 (8) ◽  
pp. 1071-1083 ◽  
Author(s):  
Shasta Moser ◽  
Ryan Church ◽  
M Brad Peori ◽  
Keith Vaughan
Keyword(s):  
High Resolution Mass Spectrometry ◽  
Diazonium Salts ◽  
X Ray ◽  
X Ray Crystallography ◽  
Ir And Nmr Spectroscopy ◽  
Analogous Manner ◽  
New Compounds ◽  
Bicyclic Molecules ◽  
Derivatives Of

Two new series of bistriazenes have been synthesized from a general reaction of diazonium salts with a mixture of a propanediamine and formaldehyde. Such reaction with 1,3-diaminopropane itself affords the 1-[2-aryl-1-diazenyl]-3-(3-[2-aryl-1-diazenyl]hexahydro-1-pyrimidinylmethyl)hexahydropyrimidines (6). 2,2-Dimethyl-1,3-diamino propane reacts in an analogous manner to give the 1-(5,5-dimethyl-3-[2-aryl-1-diazenyl]hexahydro-1-pyrimidinylmethyl)- 5,5-dimethyl-3-[2-aryl-1-diazenyl]hexahydropyrimidines (7). All new compounds have been characterized by IR and NMR spectroscopy, with elemental analysis or high resolution mass spectrometry of most of the new compounds. NMR assignments have been analyzed by a series of DEPT, COSY, and HSQC experiments. One example of each series has been unequivocally characterized by X-ray crystallography. The general conclusion of this study is that alkanediamines with three carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 18, in contrast to the case of ethylenediamine (spacer link has two carbon atoms), which affords cage-like molecules of type 17.Key words: bistriazene, hexahydropyrimidine, diazonium coupling, formaldehyde, diaminopropane, nuclear magnetic resonance.

Triazene derivatives of (1,x)-diazacycloalkanes. Part V.1 Synthesis and characterization of 4-ethyl-3-({6-ethyl-3-[2-aryl-1-diazenyl]hexahydro-1-pyrimidinyl}methyl)-1-[2-aryl-1-diazenyl)hexa- hydropyrimidines from the reaction of diazonium salts with mixtures of formaldehyde and 1,3-diaminopentane

2005 ◽  
Vol 83 (10) ◽  
pp. 1799-1807 ◽  
Author(s):  
Reid Tingley ◽  
M Brad Peori ◽  
Ryan Church ◽  
Keith Vaughan
Keyword(s):  
Diazonium Salts ◽  
X Ray Crystallography ◽  
Ir And Nmr Spectroscopy ◽  
New Compounds ◽  
Bicyclic Molecules ◽  
Derivatives Of ◽  
Methylene Group ◽  
Single Bonds

A new series of bistriazenes has been synthesized from a general reaction of diazonium salts with a mixture of 1,3-diaminopentane (DYTEK® EP diamine) and formaldehyde, which affords the 4-ethyl-3-({6-ethyl-3-[2-aryl-1-diazenyl]hexahydro-1-pyrimidinyl}methyl)-1-[2-aryl-1-diazenyl]hexahydropyrimidines (1). Each of the molecules of type 1 is built up of two equivalent 3-(aryldiazenyl)-6-ethylhexahydro-1-pyrimidinyl groups attached to a central methylene group. The importance of this study is in part due to the fact that the formaldehyde–1,3-diaminopentane system has not previously been investigated. All new compounds have been characterized by IR and NMR spectroscopy, with elemental analysis for selected compounds; one example from the series has been unequivocally characterized by X-ray crystallography. Although analysis of the NMR spectra is made somewhat difficult because of broadness and coalescence of signals due to the rotational dynamics of the N—N single bonds, it is possible to fully assign the proton spectra of all compounds and to detect 94% of all carbon signals. The fine structure within the proton spectra illustrate the diastereotopic nature of the methylene group protons because of the presence of a stereocenter in each hexahydropyrimidine ring. The general conclusion of this study is that alkanediamines with three carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 1, 2, and 3, in contrast to the case of ethylenediamine (spacer link has two carbon atoms), which affords molecules of type 7 that exemplify the bridged bicyclic bistriazene structure. The new compounds of series 1 represent an extension of a broad ranging study of the synthesis of new bistriazene derivatives of (1,x)-diazacycloalkanes.Key words: triazene, diazonium coupling, hexahydropyrimidine, diaminopentane, diazacycloalkanes, stereocenter, diastereotopic protons.

scholarly journals Synthesis and Crystal Structure of Unexpected (1S,4R,5R,6S)-4-Cyano-2,2,6-trimethyl-3-azabicyclo[3.3.1]nonan-6-yl Acetate

2017 ◽  
Vol 70 (12) ◽  
pp. 1269
Author(s):  
Steven Gareth Williams ◽  
Mohan Bhadbhade ◽  
Roger Bishop ◽  
Alison Thavary Ung
Keyword(s):  
Crystal Structure ◽  
Mass Spectrometry ◽  
High Resolution Mass Spectrometry ◽  
Unit Cell Parameters ◽  
Synthesis And Crystal Structure ◽  
X Ray ◽  
Cell Parameters ◽  
X Ray Crystallography ◽  
Ir And Nmr Spectroscopy ◽  
Resolution Mass

The reaction of (–)-β-pinene with KCN under a mild bridged Ritter reaction gave (1S,5R,6S)-2,2,6-trimethyl-3-aza-bicyclo[3.3.1]non-3-en-6-yl acetate that subsequently reacted to provide an unexpected (1S,4R,5R,6S)-4-cyano-2,2,6-trimethyl-3-azabicyclo[3.3.1]nonane-6-yl acetate. The structure of the compound was determined by high-resolution mass spectrometry, and IR and NMR spectroscopy and confirmed by single crystal X-ray crystallography. The compound crystallises in the monoclinic P21 space group, with unit cell parameters a 8.6120 (17), b 7.4570 (15), c 11.189 (2) Å, and β 110.16 (3)°.

Triazene derivatives of (1,x)-diazacycloalkanes. Part VII. Synthesis of a series of 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes from the reaction of diazonium salts with mixtures of formaldehyde and 1,4-diaminobutane

2006 ◽  
Vol 84 (10) ◽  
pp. 1434-1441
Author(s):  
Reid Tingley ◽  
Keith Vaughan
Keyword(s):  
Diazonium Salt ◽  
Diazonium Salts ◽  
The Novel ◽  
Cage Structure ◽  
X Ray Crystallography ◽  
New Compounds ◽  
Type 3 ◽  
Bicyclic Molecules

A new series of bistriazenes, the 1-aryl-2-[3-(3-[2-aryl-1-diazenyl]-1,3-diazepan-1-ylmethyl)-1,3-diazepan-1-yl]-1-diazenes (8), has been synthesized from the reaction of diazonium salts with a mixture of 1,4-diaminobutane and formaldehyde. All new compounds of series 8 have been characterized by IR and NMR spectroscopy, and the elemental composition of selected examples has been verified by elemental analysis. The connectivity of the series has been unequivocally determined by X-ray crystallography. The new bistriazenes are important because the structure contains the novel saturated heterocycle, 1,3-diazepane. The general conclusion of this study is that alkanediamines with three or four carbon atoms in the spacer link between the nitrogen atoms give rise to the linear bicyclic molecules of type 2, in contrast to the case of ethylenediamine (two carbon atoms in spacer link), which affords molecules of type 3, which exemplify the cage structure of type 1.Key words: diazonium salt, triazene, bistriazene, diazepane, formaldehyde, nuclear magnetic resonance.

Synthesis and characterization of a series of 4-methyl-1-[2-aryl-1-diazenyl]-1,4-diazepanes and 1,4-di-[2-aryl-1-diazenyl]-1,4-diazepanes

2004 ◽  
Vol 82 (12) ◽  
pp. 1725-1735 ◽  
Author(s):  
Shasta Lee Moser ◽  
Keith Vaughan
Keyword(s):  
Nmr Assignments ◽  
Diazonium Salt ◽  
Variable Temperature ◽  
2D Nmr ◽  
Diazonium Salts ◽  
X Ray Diffraction ◽  
X Ray ◽  
New Compounds ◽  
C Nmr

1-Methylhomopiperazine was coupled with a series of diazonium salts to afford the 4-methyl-1-[2-aryl-1-diazenyl]-1,4-diazepanes (6), a new series of triazenes. These compounds are, in the main, stable crystalline solids (some of the series are stable oils), and they have been characterized by 1H and 13C NMR spectroscopy, IR spectroscopy, and mass spectrometry. NMR assignments were determined by 2D NMR and variable-temperature NMR experiments and by comparison with model compounds. A second series of new compounds, namely, 1,4-di-[2-aryl-1-diazenyl]-1,4-diazepanes (5), were prepared by coupling unsubstituted homopiperazine (1,4-diazepane) with 2 molar equivalents of the diazonium salt and were similarly characterized. The crystal and molecular structure of the parent member of this bis-triazene series (5, X = H) has been determined by single-crystal X-ray diffraction analysis.Key words: triazene, bis-triazene, diazenyl, bis-diazenyl, diazonium salt, NMR, diazepane.

Triazene derivatives of (1,x)-diazacycloalkanes. Part III. Synthesis and characterization of a series of 1,4-di[2-aryl-1-diazenyl]piperazines

2005 ◽  
Vol 83 (5) ◽  
pp. 471-476 ◽  
Author(s):  
Vanessa Renée Little ◽  
Reid Tingley ◽  
Keith Vaughan
Keyword(s):  
Mass Measurement ◽  
Variable Temperature ◽  
Molar Ratio ◽  
Diazonium Salts ◽  
Piperazine Ring ◽  
Nmr Data ◽  
Ir And Nmr Spectroscopy ◽  
Reported Data ◽  
Derivatives Of

Reaction of a series of diazonium salts with piperazine in a 2:1 molar ratio affords excellent yields of the 1,4-di-[2-aryl-1-diazenyl]piperazines (3), which have been characterized by IR and NMR spectroscopy. Structural characterization is supported by elemental analysis or by mass spectrometry with accurate mass measurement of the molecular ion. The protons of the piperazine ring hydrogens give rise to a sharp singlet at ca. 4 ppm in the NMR spectra, indicating that the conformational equilibrium in the piperazine ring is rapid on the NMR timescale. The four equivalent carbon atoms of the piperazine ring resonate in the range 46–48 ppm. A variable temperature NMR experiment suggests that there is restricted rotation around the N2—N3 bond of the triazene moiety in 3. The NMR data compares favorably with previous reported data for 1-aryldiazenyl-4-methylpiperazines (1) and 1,4-di-(2-aryldiazen-1-yl)homopiperazines (2b).Key words: triazene, piperazine, diazonium coupling, NMR.

scholarly journals Mechanistic Insights into the Chaperoning of Human Lysosomal-Galactosidase Activity: Highly Functionalized Aminocyclopentanes and C-5a-Substituted Derivatives of 4-epi-Isofagomine

Molecules ◽  
2020 ◽  
Vol 25 (17) ◽  
pp. 4025
Author(s):  
Patrick Weber ◽  
Martin Thonhofer ◽  
Summer Averill ◽  
Gideon J. Davies ◽  
Andres Gonzalez Santana ◽  
...  
Keyword(s):  
Lysosomal Storage Diseases ◽  
Hydroxyl Group ◽  
Glycosidase Inhibitors ◽  
Lysosomal Storage ◽  
X Ray ◽  
Pharmacological Chaperones ◽  
X Ray Crystallography ◽  
Structure Activity ◽  
New Compounds ◽  
Derivatives Of

Glycosidase inhibitors have shown great potential as pharmacological chaperones for lysosomal storage diseases. In light of this, a series of new cyclopentanoid β-galactosidase inhibitors were prepared and their inhibitory and pharmacological chaperoning activities determined and compared with those of lipophilic analogs of the potent β-d-galactosidase inhibitor 4-epi-isofagomine. Structure-activity relationships were investigated by X-ray crystallography as well as by alterations in the cyclopentane moiety such as deoxygenation and replacement by fluorine of a “strategic” hydroxyl group. New compounds have revealed highly promising activities with a range of β-galactosidase-compromised human cell lines and may serve as leads towards new pharmacological chaperones for GM1-gangliosidosis and Morquio B disease.

The synthesis and characterization of 3,3-disubstituted pent-4-enals and their 2,2-(trimethylenedithio)pent-4-enal precursors, including the X-ray crystal structure of (R)-3-ethyl-3-phenyl-2,2-(trimethylenedithio)pent-4-enal

1985 ◽  
Vol 63 (5) ◽  
pp. 1035-1040 ◽  
Author(s):  
Charles G. Young ◽  
Brian R. James ◽  
Steven J. Rettig
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Crystal And Molecular Structure ◽  
Synthesis And Characterization ◽  
Intramolecular Rearrangement ◽  
X Ray ◽  
X Ray Crystallography ◽  
New Compounds ◽  
Allylic Bromide

A variety of 3,3-disubstituted pent-4-enals (5a, R = Me, R′ = Et; 5b, R = Me, R′ = Ph; 5c, R = Et, R′ = Ph) has been prepared by the Raney nickel desulfurization of the corresponding 3,3-disubstituted 2,2-(trimethylenedithio)pent-4-enal precursors 4a–4c. The precursor compounds were prepared by the alkylation of 2-formyl-1,3-dithiane with the appropriate 3,3-disubstituted allylic bromide. The new compounds have been characterized by elemental analysis, infrared and nmr spectroscopy, and mass spectrometry. The crystal and molecular structure of (R)-4c has also been determined by X-ray crystallography. At temperatures of ca. 130 °C, compounds 4a–4c undergo intramolecular rearrangement to form the tri-substituted alkenes 6a–6c, which have also been characterized by the present study.

scholarly journals Synthesis and Characterization of a Linear [Mn3(O2CMe)4(py)8]2+Complex

2010 ◽  
Vol 2010 ◽  
pp. 1-7
Author(s):  
Eleni E. Moushi ◽  
Christos Kizas ◽  
Vassilios Nastopoulos ◽  
Anastasios J. Tasiopoulos
Keyword(s):  
Magnetic Susceptibility ◽  
Exchange Interactions ◽  
Synthesis And Characterization ◽  
Antiferromagnetic Exchange ◽  
X Ray ◽  
X Ray Crystallography ◽  
Ground Spin State ◽  
New Compounds ◽  
Microcrystalline Powder

Two new compounds that consist of the linear trinuclear manganese(II) cation [Mn3(O2CMe)4(py)8]2+cocrystallizing with different counteranions (I3-, [1]; ClO4-, [2]) are reported. Complex1was prepared from the reaction of [Mn(O2CMe)2]⋅4H2O withI2in MeCO2H/py, whereas complex2was isolated from the reaction of [Mn3O(O2CMe)6(py)3]⋅py with [Mn(ClO4)2]⋅6H2O in MeCN/py. The crystal structures of both compounds were determined by single crystal X-ray crystallography. Magnetic susceptibility studies that were performed in microcrystalline powder of1in the 2–300 K range revealed the presence of antiferromagnetic exchange interactions that resulted in anS=5/2ground spin state.

Oxide, Sulfide, Selenide, and Borane Derivatives of Indenylphosphines

2003 ◽  
Vol 56 (11) ◽  
pp. 1153 ◽  
Author(s):  
Julian J. Adams ◽  
David E. Berry ◽  
Owen J. Curnow ◽  
Glen M. Fern ◽  
Michelle L. Hamilton ◽  
...  
Keyword(s):  
Solid State ◽  
13C Nmr Spectroscopy ◽  
State Structure ◽  
Solid State Structure ◽  
X Ray ◽  
X Ray Crystallography ◽  
Isolation And Characterization ◽  
Linear Relationships ◽  
Derivatives Of

We report the preparation, isolation and characterization of oxide, sulfide, selenide, and borane derivatives of a series of indenylphosphines. Some members of the series had already been prepared, and we have completed the series. We have prepared (indenyl)xPh3-xPO (x = 1–3) for the oxide series, (indenyl)xPh3-xPS (x = 3) for the sulfides, (indenyl)xPh3-xPSe (x = 1,2) for the selenides, and (indenyl)xPh3-xPBH3 (x = 1–3) for the boranes. Linear relationships of the 31P NMR chemical shift with the number of indenyl groups were observed. The compounds were also characterized by 1H and 13C NMR spectroscopy and mass spectrometry. The solid-state structure of diindenylphenylphosphine selenide was determined by X-ray crystallography and found to be isomorphous with diindenylphenylphosphine sulfide. The solid-state structure of triindenylphosphine sulfide was also determined by X-ray crystallography and the indenyl groups were confirmed to all be the inden-3-yl isomer. Additionally, pentacarbonyl(triindenylphosphine)molybdenum(0), 1,3-bis(diphenylphosphino)indene diborane, and rac-bis(1-(diphenylphosphino)indenyl)ironII) diborane were prepared, isolated, and characterized.

Synthese und Charakterisierung von Halogen-phosphor(III)- Derivaten des 8-Hydroxychinolins. Röntgenstrukturanalyse von 8-[Phenyl(chloro)-phosphito]-chinolin/ Synthesis and Characterization of Halogen-phosphorus(III) Derivatives of 8-Hydroxyquinoline. X -Ray Structure Analysis of 8-[Phenyl(chloro)phosphito]-quinoline

1993 ◽  
Vol 48 (1) ◽  
pp. 85-89 ◽  
Author(s):  
Lin Yang ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Nmr Spectroscopy ◽  
Single Crystal ◽  
Diffraction Study ◽  
Elemental Analysis ◽  
Synthesis And Characterization ◽  
X Ray Diffraction ◽  
X Ray ◽  
New Compounds ◽  
Derivatives Of

The reaction of 8 -trimethylsiloxyquinoline, 2 with PCl3, PhPCl2, and PhPF2 has furnished the corresponding 8 -quinolyl halophosphite derivatives, 3-5 . The synthesis of two metal complexes, 8 and 9, of 4 with Au(I) and Pt(II) is described. The new compounds were characterized by elemental analysis and by 1H and 31P NMR spectroscopy. A single crystal X-ray diffraction study of 4 has been conducted; a short intramolecular P ··· N contact (230.9 pm) and a long P-Cl bond (218.7 pm) were observed.

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