The preparation and some reactions of 1,3,2-thiazaphospholidine-2-ones

1,3,2-Thiazaphospholidine-2-ones have been prepared by rearrangement of the corresponding 1,3,2-oxazaphospholidine-2-thiones. The stereochemical course of ring opening reactions has been investigated.     

The preparation and reactions of polymeric azides. II. The preparation and reactions of various polymeric azides

Polymeric haloethyl acrylates, methacrylates, and methacrylamides, poly(vinyl chloride), poly-(epichlorohydrin), and halohydrins prepared from poly(glycidyl methacrylate), poly(butadiene), and poly(pentenamer) were converted to the corresponding azides. These azides reacted with a variety of acetylenic and olefinic derivatives to give, in most cases, good conversions to the corresponding triazole derivatives.     

The preparation and reactions of esters of dichloromethaneboronic acid

Dichloromethaneboronic acid is obtained in impure form from the reaction of dichloromethyllithium with trimethylborate. Reaction with the appropriate alcohols furnishes the 1,3 propandiol ester and the diisopropyl ester. Diisopropyldichloromethaneboronate reacts with organolithium or organomagnesium reagents to give substitution products which can be oxidized to aldehydes.     

The preparation of nitrocyclododecane and some of its reactions

Summary Nitrocyclododecane was prepared by nitrating cyclododecane with nitric acid, and some of its reactions were studied.     

The preparation and some reactions of 2, 3, 5, 6-tetrachlorophenylmagnesium chloride

The reaction of pentachlorobenzene with metallic magnesium in THF at 10–15°C gives after hydrolysis 1, 2, 4, 5-tetrachlorobenzene (76%) and pentachlorobenzene (8%); after trimethylsilylation, 1, 2, 4, 5-tetrachloro-3-(trimethylsilyl)benzene (74%), pentachloro(trimethylsilyl)benzene (8%) and 1, 2, 4, 5-tetrachlorobenzene (6%); after iodination, 1, 2, 4, 5-tetrachloroiodobenzene (44%), pentachloroiodobenzene (12%) and 1, 2, 4, 5-tetrachlorobenzene (9%); and finally after carbonation, 2, 3, 5, 6-tetrachlorobenzoic acid (58%). These products indicate that in the Grignard reaction a mixture of largely 2, 3, 5, 6-tetrachlorophenylmagnesium chloride and some pentachlorophenylmagnesium chloride is formed. The formation pentachlorophenylmagnesium chloride is explained on the basis of metal—hydrogen exchange reaction between 2, 3, 5, 6-tetrachlorophenylmagnesium chloride and the unreacted pentachlorobenzene.     

The preparation and reactions of C(α),N-dilithiocarboalkoxyhydrazones

C(α),N-Carboalkoxyhydrazones were metalated with an excess of lithium diisopropylamide (LDA), and the resulting dianions were condensed with methyl iodide, an unsubstituted ketone, a benzoate ester, salicylates, a benzoylacetate, or ethyl chloroformate.     

The preparation and reactions of 1-lithio-alkylamino-1-lithio-oxy-allene derivatives

The reaction of secondary α-keto-amide 2,4,6-tri-iso-propylbenzenesulphonylhydrazones with n-butyl-lithium generated, via a modified Shapiro reaction, the title carbanions (RCH=CC(O^-)N?R¹]. These reacted at carbon with deuterium oxide, aldehydes, and ketones and are therefore most useful for the introduction of acrylate functionality.     

The reactivity of TiO2 with different preparation histories in solid-state reactions in CaSO2-TiO2 systems

Influences of the preparation histories of TiO₂ on its reactivity in solid-state reactions in CaSO₂-TiO₂ systems were studied by means of TG, DTA and isothermal kinetic experiments.In order to estimate the reactivities of solids, it was necessary to note the behaviors in the initial reaction step in the selected reaction system. It was concluded that the reactivity of TiO₂ was dependent on the structure difference due to the different preparation histories, and the greater the stability of the anatase form, up to higher temperature, the higher the reactivity of TiO₂.

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Zusammenfassung Der Einfluß der Herstellungsgeschichten von TiO₂ auf seine Reaktivität bei der Festphasenreaktion im System CaSO₄-TiO₂ wurde durch TG, DTA und isotherme kinetische Versuche untersucht.Zur Abschätzung der Reaktivität der Festkörper mußte ihr Verhalten während des Anfangsschrittes der Reaktion im gewählten System beobachtet werden. Es wurde gefolgert, daß die Reaktivität des TiO₂ von den durch verschiedene Herstellungsgeschichten verursachten Strukturdifferenzen abhängt und bis zu höheren Temperaturen umso stabiler in der Anatas-Form ist, je höher die Reaktivität des TiO₂ ist.

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Résumé On a étudié par TG, ATD et expériences cinétiques isothermes l'influence du mode de préparation de TiO₂ sur sa réactivité lors de la réaction en phase solide des systèmes CaSO₄-TiO₂.Afin d'estimer la réactivité des solides, il a été nécessaire d'observer leurs comportements lors de l'étape initiale de la réaction dans le système réactionnel choisi. On en a conclu que la réactivité de TiO₂ dépend des différences de structure dues aux différents modes de préparation et que ce composé est d'autant plus stable, à températures élevées, sous la forme d'anatase, que la réactivité de TiO₂ est forte.

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C , TiO₂ CaSO₄-TiO₂. , . , TiO₂ , TiO₂.

     

The preparation of organomagnesium fluorides by organometallic exchange reactions

The preparation of alkyl- and aryl-magnesium fluorides by the reaction of dialkyl- and diaryl-magnesium compounds with fluorinating agents, such as BF₃ etherate, SiF₄, Bu₃SnF, Ph₃SiF and Et₂AlF in tetrahydrofuran were studied. Methyl-, ethyl-, and phenyl-magnesium fluoride were prepared in high yield by the reactions of dimethyl-, diethyl-, and diphenyl-magnesium with boron trifluoride diethyl etherate in tetrahydrofuran. Methylmagnesium fluoride was prepared in quantitative yield by the reaction of dimethylmagnesium with silicon tetrafluoride in tetrahydrofuran and butylmagnesium fluoride was prepared in quantitative yield by the reaction of tributyltin fluoride in THF with dibutylmagnesium. Other combinations of R₂Mg compounds and fluorinating agents resulted in the formation of less pure products.     

烯丙基二异雪松基硼烷的制备及其与羰基化合物的不对称反应

本文以(-)-α-雪松烯为原料, 制备了烯丙基二异雪松基硼烷(Icd~2B-CH~2CH=CH~2). 该手性硼烷很容易与醛反应生成相应的烯丙基取代的手性仲醇, 光学产率在60%e.e.左右. 与潜手性酮反应的光学产率低于30%e.e..     

Preparation and reactions of polymeric azides. III. The preparation and reactions of polymeric phosphine imines

Polymeric azides reacted with triphenylphosphine to give the corresponding phosphine imines, which reacted with bases, aldehydes, and isocyanates to give amines, imines, and carbodiimides, respectively.     

5-Bromo-2-pyridylzinc reagent; direct preparation and its coupling reactions

A facile synthetic route to the direct preparation of 5-bromo-2-pyridylzinc iodide has been developed. Treatment of 5-bromo-2-iodopyridine with active zinc gave rise to the selective oxidative addition to C-I bond under mild conditions. The resulting organozinc iodide has been used in the variety of coupling reactions affording the corresponding cross-coupling product.     

One-step preparation of 3-alkoxypyrazine-2-carbonitriles from pyrazine-2,3-dicarbonitriles and related reactions

A series of 5,6-disubstituted 3-alkoxypyrazine-2-carbonitriles ( 2a-i ) were prepared from 5,6-disubstituted pyrazine-2,3-dicarbonitriles ( 1a-d ) by direct substitution with alcohols. Treatment of 1 with amines gave either pyrrolopyrazines ( 3a,b ) or substitution products ( 4,5 ). In a low temperature range, 1 afforded imidates and related compounds ( 6–11 ). The preference among these reactions depended on the 5,6-substituents and on the reaction conditions.