Bis Diethyl Research Articles

Functional Derivatives of Sterically Hindered Amines. Polyalkylpiperidine Diesters

Several diesters of dicarboxylic acids with pendant polyalkylpiperidine structural units were prepared from α-bromo and α,α'-dibromo substituted aliphatic dicarboxylic acid diesters by a nucleophilic replacement reaction with 2,2,6,6-tetramethyl-4-hydroxypiperidine, 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, and 2,2,6,6-tetramethyl-4-aminopiperidine, by a nucleophilic addition of amino derivative to the α,β-unsaturated dicarboxylic acid diester and by an acid catalyzed condensation of 2,2,6,6-tetramethyl-4-oxopiperidine with diethyl bis(hydroxymethyl)malonate.

Sulfenylation of α‐phosphoryl sulfides. Chemical evidence for intermediate formation of α‐phosphoryl trithioorthoformate [1

Abstract1‐Lithio‐1‐(diethoxyphosphoryl)methyl methyl sulfide 1‐Li was reacted with diphenyl disulfide in a tetrahydrofuran solution to give predominantly diethyl methylthio(phenylthio)methylphosphonate 2 accompanied by a small amount of diethyl bis‐(phenylthio)methyl phosphonate 3. The latter was the main product when the reaction was performed in the absence of the solvent. The formation of 3 was explained through the desulfenylation of the transiently formed diethyl methylthiobis(phenylthio)methylphosphonate 4 with lithium benzenethiolate and confirmed by 31P NMR measurements at low temperature.

New α-Amino Acids for Peptides of Biological Interest: 2-[2′-(Methylthio)Ethyl]Methionine Derivatives

Abstract Synthetic route to N- and C-protected derivatives of the new α,α-disubstituted achiral methionine analogue 2-[2′-(methylthio)ethyl]methionine is described starting from diethyl bis(2-methylthioethyl)malonate.

Degradation Kinetics and Mechanisms of Moricizine Hydrochloride in Acidic Medium

AbstractThe degradation kinetics of moricizine hydrochloride (1) were examined over a pH range of 0.6 to 6.0 at an ionic strength of 0.3 and 60°C. The disappearance of intact 1 was followed by a stability‐indicating HPLC assay. The degradation products, which had approximate solubilities of <100 μg/mL, precipitated in aqueous solution. The precipitate was collected for HPLC analysis and identification of degradation products. Degradation of 1 was catalyzed by acetate and phosphate buffers and was pH dependent, with the pH of the minimum rate constant located between 2.8 and 3.2. At pH 0.6‐2.0, 1 degraded via amide hydrolysis to yield first ethyl (10H‐phenothiazin‐2‐yl) carbamate (2), an amide hydrolysis product, which further oxidized in parallel to give ethyl (3‐oxo‐3H‐phenothiazin‐2‐yl) carbamate (3), ethyl (10H‐phenothiazin‐2‐yl) carbamate S‐oxide (4), and diethyl (3, 10′‐bi‐10H‐phenothiazine‐2,2′‐diyl)bis(carbamate) (5), the dimer of the amide hydrolysis product. At pH 2.2‐6.0, 1 degraded via a reverse Mannich reaction, to form the reverse Mannich product ethyl [10‐(1‐oxo‐2‐propenyl)‐10H‐phenothiazin‐2‐yl] carbamate (6), and by parallel reaction via the described amide hydrolysis pathway. The dimer of the amide hydrolysis product was not detectable at pH >2.8. At pH >4.0, the reverse Mannich product was the predominant degradation product. Degradation of 1 was subject to positive and negative kinetic salt effects at pH 1.0 and 4.0, respectively. Arrhenius plots determined at pH 1.0 and 6.0 were linear between 37 and 70°C. Predicted shelf lives at room temperature (22 °C) at pH 1.0 and 6.0 were identical to the shelf lives determined experimentally.

ChemInform Abstract: Phosphorus‐Nitrogen Compounds. Part 67. The Reactions of Octachlorocyclotetraphosphazatetraene with Diethyl Bis(hydroxymethyl) malonate. Comparison of Product Type and of the 31P, 1H and 13C NMR Spectra with Those of the Derivatives of Propane‐1,3‐diol and 2,2‐ Dimethylpropane‐1,3‐diol.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Phosphorus‐Nitrogen Compounds. Part 65. Reactions of Hexachlorocyclotriphosphazatriene with Diethyl Bis(hydroxymethyl) malonate. Comparison of Product Type and of the 31P, 1H and 13C Nuclear Magnetic Resonance Spectra with the Spiro Derivatives of Propane‐1,3‐diol and 2,2‐Dimethylpropane‐1,3‐diol.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

PHOSPHORUS-NITROGEN COMPOUNDS. PART 67.1THE REACTIONS OF OCTACHLOROCYCLO-TETRAPHOSPHAZATETRAENE WITH DIETHYL BIS(HYDROXYMETHYL)MALONATE. COMPARISON OF PRODUCT TYPE AND OF THE31P,1H AND13C NUCLEAR MAGNETIC RESONANCE SPECTRA WITH THOSE OF THE DERIVATIVES OF PROPANE-1,3-DIOL AND 2,2-DIMETHYLPROPANE-1,3-DIOL

Abstract The reactions of octachlorocyclotetraphosphazatetraene, N4P4Cl8, with diethyl bis(hydroxymethyl)-malonate, (HOCH2)2C(CO2Et)2, gave the following isolated and characterized derivatives: N4P4Cl6-[(OCH2)2C(CO2Et)2], N4P4Cl4[(OCH2)2 C(CO2Et)2]2, (two isomers), N4P4Cl2[(OCH2)2C(CO2Et)2]3 and N4P4[(OCH2)2C(CO2Et)2]4. 31P, 1H and 13C n.m.r. spectroscopic investigations showed all derivatives to have spiro structures. The isomeric bis derivatives have 2,2,4,4- and 2,2,6,6-structures. A comparison is made of product type and of the nuclear magnetic resonance spectra with those of the derivatives of propane-1,3-diol and 2,2-dimethylpropane-1,3-diol.

PHOSPHORUS-NITROGEN COMPOUNDS. PART 65.1 THE REACTIONS OF HEXACHLOROCYCLOTRI-PHOSPHAZATRIENE WITH DIETHYL BIS- (HYDROXYMETHYL)MALONATE. COMPARISON OF PRODUCT TYPE AND OF THE 31P, 1H AND 13C NUCLEAR MAGNETIC RESONANCE SPECTRA WITH THE SPIRO DERIVATIVES OF PROPANE- 1,3-DIOL AND 2,2-DIMETHYL-PROPANE-1,3-DIOL

Abstract The reactions of hexachlorocyclotriphosphazatriene with diethyl bis(hydroxymethyl)malonate give the following spiro derivatives: mono, N3P4Cl4[(OCH2)2 C(CO2 Et)2], bis, N3P3Cl3[(OCH2)2C(CO 2Et)2]2 and tris, N3P3[(OCH2)2C(CO2Et)2]3. A comparison is made of the products obtained by the above diol with those from propane-1.3-diol and 2,2-dimethylpropane-l,3-diol. The 31P, 1H and 13C n.m.r. spectra of the spiro derivatives of the above three diols are compared.

ChemInform Abstract: Synthesis of Acylphosphonites.

AbstractTreatment of diethyl bis(ethoxy)methylphosphonite (I) with the acyl chlorides (II) yields the acylphosphonites (III) and the phosphinate (IV).

Biologically oriented organic sulfur chemistry. 22. 2-(3-Chloropropyl)-5-chloropentanol as a prototype for synthesis of functionalized polysulfides and prodrugs

A synthetic approach based on 2-(3-chloropropyl)-5-chloropentanol is reported that permits synthesis of trisulfides containing either Cl or four other groups. The carbinol 5 was prepared by converting diethyl bis-(3-chloropropyl)malonate with Me/sub 3/SiI to the malonic acid, which was decarboxylated (with some remediable lactonization to followed by reduction. The carbinol 5 was converted via the triflate to a thiosulfonate, which thioalkylated Na/sub 2/S to give a trisulfide containing four Cl atoms. Replacement of the four Cl atoms of the carbinol 5 with PhCh/sub 2/S groups, followed by formation of the tosylate (the triflate polymerized) and then of the thiosulfonate, permitted synthesis of a tetrakis(benzylthio) trisulfide that illustrates tetrafunctionalization. Several intermediates are potential progenitors of prodrugs, although an effort to use bis(quaternary ammonium salts) prepared from 5 in this way was unpromising owing (chiefly) to very sparing solubilities.

Facile synthesis of β-alkyl-substituted esters from α,β-unsaturated aldehydes

β-Alkyl-substituted carboxylates were synthesized in good yields from α,β-unsaturated aldehydes by using the 1:1 carbonyl adducts with diethyl bis (trimethylsilyl) phosphite.

The crystal and molecular structure of bis[diethyl bis-(1-pyrazolyl)borato]nickel(II): evidence for apical positioning of the methylene hydrogen in the square planar nickel complex

The crystal and molecular structure of bis[diethyl bis-(1-pyrazolyl)borato]nickel(II): evidence for apical positioning of the methylene hydrogen in the square planar nickel complex

Retrograde amnesic effects of diethyl ether and bis(trifluoroethyl) ether.

Retrograde amnesic effects of diethyl ether and bis(trifluoroethyl) ether.

Preliminary Evaluation of Animal Systemic Insecticides

When 17 compounds were found to be active as systemic insecticides in preliminary laboratory tests with guinea pigs, tests were conducted by treating small numbers of cattle with these compounds and Bayer 23129 ( O,O -dimethyl S -2(ethylthio) ethyl phosphorodithioate) to determine their systemic effect against cattle grubs ( Hypoderma spp.). Bayer 29493, Dowco 105, and Stauffer R-2371 gave 95% to 100% control of grubs at dosages tolerated by the cattle. The rest were ineffective or inconsistently effective or effective at dosages toxic to cattle. The chemical names of the effective compounds are Bayer 29493 ( O,O -dimcthyl O -(4-methylthio- m -tolyl) phosphorothioate), Dowco 105 ( O -(4- tert -butyl-2-dllorophenyl) O -methyl ethylphosphoramidothioate), and Stauffer R-2371 ( O,O -diethyl bis-(4-chlorophenyl) methyl phosphorodithioate).