Trimethylammonium Iodide Research Articles

Chemistry of dimethylaminomethylporphyrins. New synthesis of meso-methylporphyrins via triphenylporphyrinylmethylphosphonium iodides

Reaction of various trimethyl(porphyrinylmethyl) ammonium iodides (generated in situ from the corresponding meso-dimethylaminomethylporphyrins and iodomethane) with triphenylphosphine afforded triphenylporphyrinylmethylphosphonium iodides which, when subjected to mild basic hydrolysis, gave meso-methylporphyrins in high yields.

Immunomodulatory activity of amphiphilic antimicrobials on mouse macrophages

A quaternary ammonium salt (1-methyldodecyl)-trimethylammonium iodide, a structurally analogous amine oxide (1-methyldodecyl)-dimethylamine- N-oxide and the amine oxide lacking long alkyl chain trimethylamine- N-oxide were tested for their immunomodulatory activity. Inbred mice strain C57/BL6 were pretreated for 7 days by the compounds under study. The activity of elicited peritoneal macrophages was also tested. Both compounds have a long alkyl chain. In concentrations of 10 −6M there was a significant increase of the phagocytic, candidacidal and lysozyme activities of the cells. We also observed a suppressed peroxidase activity. The colicidal activity of both the peritoneal and spleen cells were not affected. The amine oxide lacking the long alkyl chain has the same effect at high concentration. A similarity between the effects of the amphiphilic compounds on the macrophages and their antimicrobial efficacy elicits the conclusion that both activities are caused by their ability to interact with the cell membranes.

Effects of a 5-HT3 antagonist on peripheral 5-hydroxytryptamine-induced anorexia

Since antagonizing peripheral 5-HT2receptors incompletely blocks the anorexia induced by systemically administered 5-HT, another 5-HT receptor subtype is implicated in this effect. To determine whether the 5-HT3 receptor is the additional type involved, the specific, peripheral 5-HT3 antagonist [[3-(1-Methyl-1H-mdol-3-yl)-1,2,4-oxadiazol-5-yl]methyl]trimethyl-ammonium iodide (MIO) was used. After an overnight fast, rats were injected with MIO followed 1 h later by 5 mg/kg of 5-HT. There was a dose-dependent potentiation by MIO of the 5-HT-induced anorexia that peaked at a dose of 2.5 mg/kg of MIO. However, MIO by itself failed to induce an anorexia Although the 5-HT3 receptor is implicated in 5-HT-induced anorexia, it is suggested that its activation counters the effects of 5-HT in the mediation of the anorexia.

Renewable Perfluorosulfonated Ionomer Carbon Paste Electrode for Competitive Homogeneous Electrochemical Immunoassays Using a Redox Cationic Labeled Hapten

A Nafion-loaded carbon paste electrode (CPE) was prepared and its square wave voltammetric response at a fresh surface was optimized using (ferrocenylmethyl)-trimethylammonium iodide (1) as a model of a cation that accumulates irreversibly. Low current responses could be obtained reproducibly without preconditioning at a CPE loaded with 1-octanol and neutralized Nafion. Use of the former made the method more sensitive, and use of the latter gave lower background currents and stable analytical response over a long period of Nafion-loaded CPE use. Under optimized conditions and using a 5 min accumulation period, the modified electrode gave a linear current response over the range of 5 nM to 1.5 microM 1, a detection limit of 5 nM 1 and a relative standard deviation of 5% for 0.5 microM 1. Using these optimized conditions, the competitive homogeneous immunoassay of phenytoin as a model hapten was carried out with cobaltocenium-labeled phenytoin as tracer. Clinical serum samples (5 microL) of phenytoin at therapeutic concentrations (20-80 microM) could be analyzed using this method.

Structure and Dynamic Behavior of Crowded Cis Vicinal [(N,N-Dimethylamino)cyclopentyl]trimethylammonium Salts and Related Compounds

Carbon-13 NMR spectra of [cis-2-(N,N-dimethylamino)cyclopentyl]trimethylammonium iodide (4a) and triflate (4b) in acetone-d6 and in CD3NO2 show inversion of the amine with rotation about the ring−N...

Development of a novel series of trialkoxyaryl derivatives as specific and competitive antagonists of platelet activating factor.

The synthesis and structure-activity relationship (SAR) analysis of a novel series of trialkoxyaryl derivatives, as specific and competitive inhibitors of platelet activating factor (PAF), are described. Molecular modeling comparisons of PAF with the known antagonists Ginkgolide B and L-652731 led to the selection of N-[2-[(3,4,5-trimethoxybenzoyl)oxy]ethyl]-N,N,N-trimethylammonium iodide (1) from the Wellcome registry of compounds and to the synthesis of the lead compound N-[2-[[4-(hexyloxy)-3,5-dimethoxybenzoyl]oxy]ethyl]-N,N,N- trimethylammonium iodide (3, pKb 5.43). Further SAR considerations directed the design to 2-(hexyloxy)-1,3-dimethoxy-5-[4-(4-methylthiazol-5-yl)butyl] benzene (38) (pKb 7.14), a novel, specific, and competitive inhibitor of the PAF receptor in rabbit-washed platelets.

Reactions of β-fluorovinamidinium salt with bifunctional hetero nucleophiles. A new synthetic route to fluorinated heterocycles

β-Fluorovinamidinium salt ( 2), readily prepared fromN-(2, 3, 3-trifluoro-1-propenyl)trimethyl-ammonium iodide ( 1) and diethylamine, reacted with bifunctional hetero nucleophiles such as amidine and guanidine hydrochlorides in the presence of a base to afford regiospecifically monofluorinated pyrimidines 4 in good yields. The one-pot procedure starting from 1 was applicable for synthesizing heterocyclic compounds 4 in almost comparable yields.

Ferrocenyl salts as synthons: new ferrocenyl-1,3-dikentones

Reaction of (ferrocenylmethyl)trimethylammonium iodide with the mono-sodium salts of a range of acyclic 1,3-diketones leads smoothly to 2-(ferrocenylmethyl)-1,3-diketones [(C5H5)Fe(C5H4)CH2]CH(COR1)(COR2), but with the corresponding tetrabutylammonium salts deacylation occurs. With the sodium salt of cyclohexane-1,3-dione, disubstitution occurs to give (2,6-dioxocyclohexane-1,1-diyl)bismethyleneferrocene, [(C5H5)Fe(C5H4CH2)]2C[(CO)2(CH2)3]. The lithium salt of acetylferrocene reacts with a range of monocarboxylic esters to provide 1-ferrocenyl-1,3-diketones [(C5H5)Fe(C5H4)]COCH2COR, but simple esters of dicarboxylic acids either do not react, or undergo only monosubstitution.

Structures of (ferrocenylmethyl)trimethylammonium iodide and hexa-N-methylferrocene-1,1'-diylbis(methylammonium iodide)

(Ferrocenylmethyl)trimethylammonium iodide (1), [C 14- H20FeN][I], Mr = 385.07, monoclinic, P2dc, a = 8.6236 (5), b = 13.5926 (10), c = 12.8623 (6) A, ~ = 102.792 (4)° , V = 1470.3 (2) A 3, Z = 4, T = 293K, F(000) = 760, Dx = 1.74 gcm -3, Mo Ks, A -- 0.71069 ,~, # = 3.08mm -l, R = 0.024 for 4075 observations [I > 30(/)]. The [{(CsHs)Fe(CsH4)I-CH2N(CH3)3] + cation is involved in a three-dimensional network of C--H...I- interactions (both the cation and anion residing in general positions). The shortest C.-.I distances are 3.954 (2), 3.992 (2) and 4.009 (3) A. Hexa-Nmethylferrocene- 1,1'-diylbis(methylammonium iodide) (2), [C18H30FeN2].2[I], Mr = 584.10, monoclinic, C2/c, a = 27.1457(12), b -- 12.3446(6), c = 14.5295 (10) ,A,, /3 = 115.909 (4) °, V = 4379.5 (4) A, 3, Z = 8, T = 293 K, F(000) = 2264, Dx -- 1.772gcm -3, MoKa, A = 0.71069A, # = 3.48mm -I, R = 0.031 for 4482 observations [I > 30(/)]. In (2), the [Fe{(CsHa)CH2-N(CH3)3}2] 2÷ cation (which has approximate twofold symmetry) and one of the anions reside in general positions. Another iodide resides on a twofold axis, while a third iodide lies on an inversion centre. A more extensive three-dimensional network of C--H---I- interactions is present in (2) than in (1) and involves all three of the iodide anions. The shortest C--.I- contacts are 3.733 (4) and 3.848 (4) A~ and involve the iodide which resides in a general position (all three iodides have C...I contacts < 4.1 A).

Intercalation of Ferrocene and Its Derivatives into VxNb1−xOPO4 (x = 0, 0.06, 0.11, and 0.21) Interlayer Spaces

Abstract Ferrocene, FcH [Fc = (C5H5)Fe(C5H4)], (ferrocenylalkyl)trimethylammonium iodides, [Fc(CH2)nNMe3]+I− (n = 1 or 2), and 1,2-diferrocenylethane, FcCH2CH2Fc, have been intercalated into the V0.21Nb0.79OPO4 interlayer space. The V(V) ion is reduced by the iodide ion and/or the Fc centers, the Nb(V) ion being not reduced. The long-axis direction of the guest molecules is arranged approximately parallel to the swelling V0.21Nb0.79OPO4 sheet. Some Fc centers of FcCH2CH2Fc and FcCH2CH2NMe3+ are not oxidized in spite of their proximity to the metal ion site of the V0.21Nb0.79OPO4 lattice because most of the V sites are isolated from other V sites owing to the low V contents. Ferrocenylalkylamines, FcCH2NMe2 and FcCH2CH2NH2, have been intercalated into the VxNb1−xOPO4 (x = 0, 0.06, 0.11, and 0.21) interlayer spaces, accompanied with the protonated amino groups and the Nb(V) and reduced V(IV) sites. ESR signals of the V0.06Nb0.94OPO4 intercalation compounds exhibit hyperfine structures due to the V(IV) nucleus (I = 7/2). With the increase of the V content in the host lattice, ESR signals are further broadened owing to the dipole–dipole and/or exchange interactions among the V(IV) sites.

Effect of the choline acetyltransferase inhibitor (2-benzoylethyl)- trimethylammonium iodide (BETA) on human placental prostaglandin release and phospholipase A 2 activity

We investigated the effect of an inhibitor of acetylcholine (ACh) synthesis, (2-benzoylethyl)trimethylammonium iodide (BETA), on prostaglandin (PG)E2 and PGF2 alpha release from incubated placental explants in the presence or absence of ACh or arachidonic acid (AA). BETA alone (100 microM) significantly reduced both PGE2 and PGF2 alpha release. However, this inhibitory effect of BETA was not reversed in the presence of ACh (10 microM to 1 mM). The addition of AA (10 to 100 microM) increased both PGE2 and PGF2 alpha release, and simultaneously overcame the inhibition of PGE2 but not PGF2 alpha release by BETA. These results are compatible with the hypothesis that BETA may be inhibiting the phospholipase A2 (PLA2) step rather than prostaglandin H synthase (PGHS) step in the enzymatic pathway of PG generation. This hypothesis was supported by evidence showing a lack of effect of BETA (10 and 100 microM) on ovine placental microsome PGHS activity. Moreover, human placental homogenate PLA2 activity was reversibly inhibited by BETA (100 microM). In the presence of BETA (100 microM), addition of exogenous ACh (100 microM) had no significant effect on placental PLA2 activity. These results indicate that the inhibitory effect of BETA on placental PG release was unlikely to be via an action on ACh synthesis, but rather via a reversible effect on PLA2 activity.

Ferrocene-metallocyclam conjugates: new redox systems whose two-electron activity can be modulated through the medium

The two conjugate systems 1 and 2, in which a ferrocene subunit and a nickel-cyclam fragment are covalently linked, have been prepared and investigated for their redox behavior, using voltammetric techniques. I has been synthesized through the reaction of Ni II with the free ligand 3, prepared from the reaction of (ferrocenylmethyl)trimethylammonium iodide with a 5-fold excess of cyclam. 2 has been obtained by a very convenient one-pot template procedure, in which ferrocenesulfonamide acts as a locking fragment in closing an open-chain tetraamine, in the presence of formaldehyde.

A New Facile and Efficient Method for the Preparation of (Z)-α-Fluoro-β-(dialkylamino) acrylaldehydes from (Polyfuoro-1-propenyl)trimethylammonium Iodide

Treatment of (Z)-(2,3,3-trifluoro-1-propenyl)trimethylammonium iodide, available in three steps from 2,2,3,3-tetrafluoropropyl o-nitrobenzenesulfonate, with various secondary amines in aqueous dimethyl sulfoxide at 40-70°C gave rise to the corresponding Z isomers of α-fluoro-β-(dialkylamino)acrylaldehydes in good yields, together with a small amount of (Z)-α-fluoro-β-(dimethylamino)-acrylaldehyde.

A solution and solid state conformation of 2-diphenylphosphinoyl-1,3-dioxanes. The nature of O-C-P anomeric interactions.

Diastereoisomeric 2-diphenylphosphinoyl-1,3-dioxanes 1–4 were synthesized either via the Arbuzov reaction of isopropyl diphenylphosphinite with (1,3-dioxan-2-yl) trimethylammonium iodides or via the transacetalization reaction between 1,3-diols and diphenyl (diethoxymethyl) phosphine oxide. The latter reaction afforded less thermodynamically stable isomers of 3 and 4 in a good yield (44 and 56%, respectively). The magnitude of the anomeric effect in this system determined according to the Franck's equation was found to be 19.7 kJ/mol. Both the NMR and X-ray structural data concerning cis-4,6-dimethyl-1,3-dioxane derivatives 4 suggest that the anomeric effect could stem from several interaction, including the n o-δ * C-P negative hyper-conjugation and intramolecular hydrogen bond formation.

Extremely simple route to β-fluoro vinamidinium salts: A novel reaction of (polyfluoro-1-propenyl)trimethylammonium iodides with primary or secondary amines

(2,3,3-Trifluoro-1-propenyl)trimethylammonium iodides readily underwent demethylation-allylic substitution followed by N-N exchange reaction at ambient temperature or at 70 °C by the action of various secondary amines or several primary amines to give the corresponding β-fluorinated vinamidinium salts in good yields.

Reaction of (polyfluoroalkyl)trimethylammonium salts with hydroxide ion

(Polyfluoroalkyl)trimethylammonium iodides ( 1a–d), R fCF 2CH 2N +Me 3I − (R f −, a = HCF 2, b = CF 3, c = H(CF 2) 3, d = H(CF 2) 5), reacted easily with an equimolar amount of sodiumhydroxide in water at 20°C to give Z isomers of (polyfluoro-1-alkenyl)trimethylammoniumiodides ( 2a–d), R fCFCHN +Me 3I −, quantitatively. However, treatment of 1 with 3 equimolaramounts of sodium hydroxide yielded different products depending on the length of the R fchain: la gave (2-oxo-3,3-difluoropropyl)trimethylammonium iodide ( 3a), which had a greattendency to form the hydrate 4a; 1b produced a mixture of the analogous ketone 3b and betaine 6; 1c and 1d afforded the corresponding 1 H,ω H-perfluoroalkanes 7c and 7d, respectively,together with 6.

Trimethyl(maleimidophenyl)ammonium iodides and their copolymers

AbstractNew quaternary ammonium monomers derived from N‐(dimethylaminophenyl)‐maleimides were prepared and characterized. Their copolymerization with vinyl compounds and modification of the polymers of the starting imides with methyl iodides yielded copolymers containing trimethyl(maleimidophenyl)ammonium units. Membranes based on crosslinked imide copolymers were prepared, and their properties were determined after quaternization of the tertiary amino groups.

ChemInform Abstract: Synthesis of 5‐Fluoromethyl‐2,3‐dihydro‐1,4‐dithiins.

5-Trifluoromethyl- and 5-difluoromethyl-2,3-dihydro-1,4-dithiins were synthesized by reaction of (2,2,3,3,3-pentafluoropropyl)- and (2,2,3,3-tetrafluoropropyl)trimethylammonium iodide with sodium hydroxide, followed by treatment with the sodium salt of 1,2-ethanedithiol

ChemInform Abstract: The Reaction of Quaternary Ammonium Salts Derived from 2‐Aryl‐3‐(N,N‐dimethylamino)‐1‐propenes with Some Enolate Anions.

AbstractCoupling of the (2‐aryl‐1‐propen‐3‐yl)trimethylammonium iodides (I) with the anions derived from the active methylene compounds (II) yields the carboxylates (III).

Synthesis of 5-Fluoromethyl-2,3-dihydro-1,4-dithiins

5-Trifluoromethyl- and 5-difluoromethyl-2,3-dihydro-1,4-dithiins were synthesized by reaction of (2,2,3,3,3-pentafluoropropyl)- and (2,2,3,3-tetrafluoropropyl)trimethylammonium iodide with sodium hydroxide, followed by treatment with the sodium salt of 1,2-ethanedithiol.