Synthesis and Structure of 2,2,2- Nitrilotriacetyl Chloride with a Flat NC3 Pyramide

Klapötke, Thomas M.; Krumm, Burkhard; Moll, Richard

doi:10.5560/znb.2013-3042

Cited by 5 publications

(5 citation statements)

References 8 publications

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“…All organic manipulations were carried out using standard Schlenk techniques and lithiations were performed in a nitrogen glovebox unless otherwise noted. [32]. Compounds 1 and 5 were also reported previously [21].…”

Section: General Considerationssupporting

confidence: 69%

“…The synthesis of tris(2-X-phenylamino)ethyl)amine ligands proceeds via standard coupling and reduction techniques with nitrilotriacetic acid (NTA) as the starting material (Scheme 1). The NTA is first treated with phosphorus pentachloride to yield nitrilotriacetyl chloride [22]. The acid chloride is then coupled with 2-(methylthio)aniline or 2-(phenylthio)aniline using trimethylamine as a sacrificial base to yield 2,2',2"-nitrilotris(N-(2-(methylthio)phenyl)acetamide (1), as previously reported [21], and 2,2',2"-nitrilotris(N-(2-(phenylthio)phenyl)acetamide (2).…”

Section: Ligand Synthesesmentioning

confidence: 99%

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A modular synthesis of tris(aryl)tren ligands: Synthesis, structure and lithiation chemistry

Mdluli

Hubbard

Javier-Jimenez

et al. 2017

Inorganica Chimica Acta

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A modular synthesis of tris(aryl)tren ligands has been demonstrated via the condensation of nitrilotracetyl chloride with different anilines followed by reduction. Varying the aniline in the condensation step from 2-methylthioaniline, to 2-phenylthioaniline, to 2-chloroaniline, generates 2,2',2"-nitrilotris(N-(2-(methylthio)phenyl)acetamide (1), 2,2',2"-nitrilotris(N-(2-(phenylthio)phenyl)acetamide (2) and 2,2',2"-nitrilotris(N-2-chlorophenyl)acetamide (3) respectively. The 2-chloroaniline synthesis is complicated by the production of N-(2chlorophenyl)-3,5-dioxo-1-piperazine-N-(2-chlorophenyl)acetamide (4), but can be adjusted to produce only 3. The reduction of complexes 1-3 proceeds with lithium aluminum hydride for 1 and 2 and with borane for 3 to yield the tris(aryl)tren ligands tris-(2-(2-(methylthio)phenylamino)ethyl)amine (5), tris-(2-(2-(phenylthio)phenylamino)ethyl)amine (6), and tris-(2-(2-chlorophenylamino)ethyl)amine (7). All three of these ligands can be deprotonated with tert-butyllithium for 5 and 7, and n-butyllithium for 6 to generate their trilithium complexes, 8, 9 and 10 for 5, 6 and 7 respectively, with 10 forming two different solvates (10a and 10b). All complexes are characterized by 1 H and 13 C NMR and the solid state structures of complexes 2, 3, 4, 7, 8, 9, 10a and 10b are described.

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Section: General Considerationssupporting

confidence: 69%

Section: Ligand Synthesesmentioning

confidence: 99%

A modular synthesis of tris(aryl)tren ligands: Synthesis, structure and lithiation chemistry

Mdluli

Hubbard

Javier-Jimenez

et al. 2017

Inorganica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Tris-(2-(2-(methylthio)phenylamino)ethyl)amine was synthesized via standard coupling and reduction techniques using nitrilotriacetic acid (NTA) as the starting material (Scheme 1). The NTA is first converted to nitrilotriacetyl chloride with phosphorus pentachloride [21], which is then coupled to 2-(methylthio)aniline to yield 2,2',2"-nitrilotris(N-(2-(methylthio)phenyl)acetamide (1). The tris-amide is then reduced with lithium aluminum hydride to generate the desired tren-based N 4 S 3 ligand (2).…”

Section: Ligand Synthesesmentioning

confidence: 99%

A tripodal aminothioether ligand scaffold: Synthesis and coordination to zirconium and hafnium

et al. 2017

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The heptadentate ligand, tris-(2-(2-(methylthio)phenylamino)ethyl)amine (2), has been synthesized from the condensation of nitrilotriacetyl chloride with 2-(methylthio)aniline, to generate 2,2',2"-nitrilotris(N-(2-(methylthio)phenyl)acetamide) (1), followed by a lithium aluminum hydride reduction. The zirconium (3) and hafnium (4) complexes of this ligand were generated via transamination reactions. Both complexes are isostructural, exhibiting a hexadentate N 4 S 2 coordination from the ligand, with one diethylamido ligand also bound. The solid state structures of all compounds are reported.

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“…Noticeably, the COCl-terminated silica also provides a significant OH signal (∼3200 cm –1 ), as shown in Figure A, indicating that the −COCl group is moisture sensitive, which could cause the −COCl modified silica substrate to revert to the COOH-terminated form . The SFG spectra obtained from the surfaces terminated with −COOH and −COCl are similar; in particular, −C–Cl stretching (∼771 cm –1 ) is not detectable and not within the IR range of 4000–1000 cm –1 . − Therefore, to increase the NP attachment as much as possible and prevent the reversion of −COCl to −COOH, amide bond formation was performed immediately after obtaining the −COCl terminated silica substrate, as mentioned earlier in the Experimental section. In Figure B, the peak observed at ∼1748 cm –1 ( ssp ) can be assigned to the CO stretching of the −COCl group.…”

Section: Resultsmentioning

confidence: 91%

Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy

et al. 2018

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Successive surface reactions on hydrophilic silica substrates were designed and performed to immobilize ethanolamine-modified magnetic ferrite-based nanoparticle (NP) for surface characterization. The various surfaces were monitored using sum-frequency generation (SFG) spectroscopy. The surface of the hydrophilic quartz substrate was first converted to a vinyl-terminated surface by utilizing a silanization reaction, and then, the surface functional groups were converted to carboxylic-terminated groups via a thiol–ene reaction. The appearance and disappearance of the vinyl (CH2) peak at ∼2990 cm–1 in the SFG spectra were examined to confirm the success of the silanization and thiol–ene reactions, respectively. Acyl chloride (−COCl) formation from carboxy (−COOH) functional group was then performed for further attachment of magnetic amine-functionalized magnesium ferrite nanoparticles (NPs) via amide bond formation. The scattered NPs attached on the modified silica substrate was then used to study the changes in the spectral profile of the ethanolamine modifier of the NPs for in situ lead(II) (Pb2+) adsorption at the solid–liquid interface using SFG spectroscopy. However, due to the limited number of NPs attached and sensitivity of SFG spectroscopy toward expected change in the modifier spectroscopically, no significant change was observed in the SFG spectrum of the modified silica with magnetic NPs during exposure to Pb2+ solution. Nevertheless, SFG spectroscopy as a surface technique successfully monitored the modifications from a clean fused substrate to −COCl formation that was used to immobilize the decorated magnetic nanoparticles. The method developed in this study can provide a reference for many surface or interfacial studies important for selective attachment of adsorbed organic or inorganic materials or particles.

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Synthesis and Structure of 2,2,2- Nitrilotriacetyl Chloride with a Flat NC3 Pyramide

Cited by 5 publications

References 8 publications

A modular synthesis of tris(aryl)tren ligands: Synthesis, structure and lithiation chemistry

A modular synthesis of tris(aryl)tren ligands: Synthesis, structure and lithiation chemistry

A tripodal aminothioether ligand scaffold: Synthesis and coordination to zirconium and hafnium

Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy

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