Synthesis of a monophosphorus analog of hexamethylenetetramine

Daigle, Donald J.; Pepperman, Armand B.; Vail, Sidney L.

doi:10.1002/jhet.5570110326

Cited by 236 publications

(150 citation statements)

References 8 publications

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“…[5,22,23] In contrast to other tertiary aminoalkylphosphanes where alkylation takes place on phosphorus, pta is alkylated smoothly on one of its nitrogen atoms. [24] The charge and steric bulk of such ligands are changed by quaternarization and this is reflected also in their water-solubility. [25] Coordination properties of alkyl-pta derivatives and catalytic applications of their complexes received less attention than those of pta.…”

Section: Introductionmentioning

confidence: 99%

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

Udvardy

Bényei

Kathó

2012

Journal of Organometallic Chemistry

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New air-stable, water-soluble Ru(II)-phosphane complexes were synthesized in high purity by the reaction of cis-[RuCl2(dmso)4] with 2 equivalents of 1,3,5-triaza-7-phosphaadamantane (pta) and its N-methyl and N-benzyl derivatives (pta-Me and pta-Bn, respectively). All new complexes were characterized by elementary analysis and spectroscopic methods (NMR, ESI  1 and the new complexes actively catalyzed the isomerization of allylic alcohols. MS) and the molecular structures of cis-cis-trans-[RuCl2(dmso)2(pta)2], cis-cis-trans-

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Section: Introductionmentioning

confidence: 99%

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

Udvardy

Bényei

Kathó

2012

Journal of Organometallic Chemistry

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“…Among other properties, similarity of pta to urotropine is shown also by the finding that dilute aqueous acids protonate one of the nitrogens of both compounds [20], while no P-protonated pta is known. Furthermore, reaction of both urotropine and pta with alkyl halides yield N-alkylated (azonia) products [18]. This is in contrast to the easy P-alkylation of alkyl phosphanes.…”

Section: Introductionmentioning

confidence: 94%

“…Conversely, it is the phosphorus analog of 1,3,5,7-tetraazaadamantane (urotropine); indeed, urotropine may serve as starting material for the synthesis of pta [18,19]. Among other properties, similarity of pta to urotropine is shown also by the finding that dilute aqueous acids protonate one of the nitrogens of both compounds [20], while no P-protonated pta is known.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and structure of stable water-soluble phosphonium alkanoate zwitterions derived from 1,3,5-triaza-7-phosphaadamantane

Udvardy

Purgel²,

Szarvas

et al. 2015

Struct Chem

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1,3,5-Triaza-7-phosphaadamantane (pta) was shown to form phosphonium-alkanoate zwitterions with unsaturated dicarboxylic acids in water in the absence of strong acids. Solid state structures of the phosphonium salt (1) derived from maleic or fumaric acids and that of the zwitterionic product (2) of the reaction of pta with citraconic and mesaconic acids were determined by single crystal X-ray diffraction. DFT calculations gave insight into the mechanism of the reaction, including the relative reactivity of the four dicarboxylic acids, and revealed the reasons for the lack of phosphonium salt formation by pta in strongly acidic aqueous solutions.

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“…The hydrophilic phosphine ligand, 1,3,5-triaza-7-phosphaadamantane, was prepared according to the literature. 22 The tetramer precursor ruthenium complex [Cp*Ru(m 3 -Cl)] 4 23 and the chlorine initiator [H-(MMA) 2 -Cl] 24 were also prepared according to published procedures. Toluene (Kishida Kagaku, Osaka, Japan; purity 499%) was dried and purified by passing through purification columns (Solvent Dispensing System, SG Water USA, NH, USA; Glass Contour) and sparged with dry nitrogen for more than 15 min immediately before use.…”

Section: Experimental Procedures Materialsmentioning

confidence: 99%

Aqueous metal-catalyzed living radical polymerization: highly active water-assisted catalysis

Ouchi

Yoda

Terashima

et al. 2011

Polym J

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Catalytic aqueous living radical polymerization was achieved through a ligand design for a ruthenium-based catalyst. A phenolic phosphine ligand [PPh 2 (pPhOH)] was combined with a pentamethylcyclopentadienyl (Cp*)-based tetrameric ruthenium precursor, and the resulting complex showed a high catalytic activity for aqueous living radical polymerizations of hydrophilic methacrylates (for example, poly(ethylene glycol) methacrylate and 2-hydroxyethyl methacrylate) in conjunction with a chlorine initiator [H-(MMA) 2 -Cl]. The catalytic system allowed very fast living polymerizations, block copolymerizations and syntheses of high-molecular-weight polymers (DP n B1000) with narrow-molecular-weight distributions. Importantly, the activity was high enough to control the polymerization using a catalytic amount of the complex, even though the polymerizations were performed at low temperature (40 1C). Such advanced catalysis was achieved by not only simple hydrophilicity of the ligand but also by a water-assisted dynamic transformation from the original coordinatively saturated form [Cp*RuCl(PR 3 ) 2 ; 18e; PR 3 ¼phosphine] into an unsaturated and active form [Cp*RuCl(PR 3 ); 16e]. Water molecule(s) may also coordinate for further stabilization as demonstrated by 31 P NMR analyses.

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Synthesis of a monophosphorus analog of hexamethylenetetramine

Cited by 236 publications

References 8 publications

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

The dual role of cis-[RuCl2(dmso)4] in the synthesis of new water-soluble Ru(II)–phosphane complexes and in the catalysis of redox isomerization of allylic alcohols in aqueous–organic biphasic systems

Synthesis and structure of stable water-soluble phosphonium alkanoate zwitterions derived from 1,3,5-triaza-7-phosphaadamantane

Aqueous metal-catalyzed living radical polymerization: highly active water-assisted catalysis

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