A New Route to Monoalkylhydrazines

Electrophilic amination of primary amines with N-(dietho-xyphosphoroyl)-O-(p-nitrophenylsulfonyl)-hydroxylamine 1, followed by dephosphorylation of the phosphorohydrazidate 2 with p-toluenesulfonic acid monohydrate in ethanol, represents a novel approach to monoalkylhydrazines.     

A New Route to Resorcinols

A convenient preparation of resorcinol derivatives from α-phenylsulfinyllactones and α, β-unsaturated ketones is described.     

A New Route to Heterosilsesquioxane Frameworks

The substitution of an O atom in the Cy₈Si₈O₁₂ framework by a heteroatom or a heteroatom-containing group (Z) provides a simple route to discrete heterosilsesquioxane frameworks 1 . In this reaction the Cy₈Si₈O₁₂ framework is initially opened with triflic acid and then treated with different nucleophiles (Cy=cyclohexyl; Z=NPh, SO₄, nBuBO₂, CrO₄).     

A New Route to 3-Phosphonylpyrazoles

The regioselective synthesis of 3-diethoxyphosphonopyrazoles has been accomplished through the addition of aryl or alkyl hydrazines to (3-ethoxyacryloyl)phosphonic acid diethyl ester. An example of hydrolysis of the pyrazolephosphonic ester to the corresponding acid is described.     

A New Route to 1,2,3-Propanetrithiol

A new procedure was developed for preparing 1,2,3-propanetrithiol from available initial compounds. 1,2,3-Trichloroethane reacts with sodium disulfide prepared by dissolving sulfur in the system NaOH-N₂H₄ · H₂O-H₂O to give a disulfide dendrimeric polymer, thiokol, in almost quantitative yield. This polymer is subjected to reductive cleavage with an alkaline solution of hydrazine hydrate, which is followed by acidification with HCl. The yield of 1,2,3-propanetrithiol exceeds 60%. The synthesis can be performed as a one-pot procedure.     

A New Route to Metal Azides

Beside several other applications, metal azides can be used for the synthesis of nitridophosphates and binary nitrides. Herein we present a novel synthetic access to azides: Several metals, such as main‐group, transition metals, and rare‐earth metals, react with silver azide in liquid ammonia as a solvent giving the corresponding metal azides. In this work Mn(N₃)₂, Sn(N₃)₂, and Eu(N₃)₂, as well as their ammonia complexes were synthesized for the first time through low‐temperature methods. Also a simpler access to Zn(N₃)₂ was possible. At room temperature and the respective vapor pressure of NH₃, it became possible to grow single crystals of the dinuclear holmium azide [Ho₂(μ‐NH₂)₃(NH₃)₁₀](N₃)₃?1.25 NH₃. We are confident that this new route could lead to novel metal azides as well as nitrides of the main‐group, the transition, and the rare‐earth metals upon careful decomposition.     

A New Route to Silyl-substituted Cyclobutenones and Silylketenes

2-Silyl-cyclobutene(di)ones are obtained by an addition/substitution approach on dimethyl squarate using silyl anions. The acetal and in particular the thioacetal derivatives readily undergo electrocyclic ring opening to reactive silyl(vinyl)ketenes.     

A New Route to 2-Aminoalkanephosphonic Acids

The phosphonic acids and their esters, which are more resistant to hydrolysis than phosphates, could find wide application in biochemistry as regulators for metabolic processes¹.     

A New Synthetic Route to Selected Indenones

Indenones are useful intermediates in the synthesis of several natural products, e.g. gibberellins (1) and steroid hormones with a C-nor-D-home system (2). Despite the nernerous methods for indenone synthesized, or the yields was much lower as mentioned in earlier reports (1)(4). One of the difficulties of the usual methods is the required electrophilic cyclization meta to a methoxyl substiruent. House (5) deals with these difficulties in more detail. In our method the synthesis of 6-methoxyinde-nones is effected by substitution dara to methoxyl function.     

A New Synthetic Route to 5-Isoxazolamines

5-Isoxaz0lamineshavebeenusedasintermediatesforthesynthesis0fderivatives0fantihistaminic,analgetic,antibacterial,insecticidal,herbicidalandfungicidalactivity'.Usuallytheyaresynthesizedbytheintramolecularcondensation0fhydr0xylamineand0-nitrilegr0up'.Otherapproaches,suchasreductivecyclizati0nofZ-a-cyano-6-nitroethylenesandIithiumaIuminumhydridereduction0f3-cyanooxazoleshaveals0beenrepoFted'-'.HerewerepoFtanewsyntheticrouteofthesecompounds.Ohn0andNaruse7havereportedthatthereactionof2-chlorocycl…