Reactions of Carbohydrates in Liquid Ammonia. II. Apparatus and Methods. Alkyl, Acyl and Certain Metallic and Non-metallic Derivatives of Diacetoneglucose

1934 ◽  
Vol 56 (11) ◽  
pp. 2449-2454 ◽  
Author(s):  
Irving E. Muskat
Keyword(s):  
Liquid Ammonia ◽  
Derivatives Of

SiF-NH-Funktionelle Cyclodisilazane – Synthese und Reaktivität / SiF-NH-Functional Cyclodisilazane – Synthesis and Reactivity

2003 ◽  
Vol 58 (10) ◽  
pp. 939-949 ◽  
Author(s):  
Clemens Reiche ◽  
Uwe Klingebiel ◽  
Mathias Noltemeyer
Keyword(s):  
Crystal Structures ◽  
Liquid Ammonia ◽  
Lithium Derivative ◽  
Derivatives Of

Dichlorosilanes with bulky substituents R(Me3C)SiCl2 react with liquid ammonia to give geminal silyldiamines [R(Me3C)Si(NH2)2, 1: R = CH2 Me, 2: R = CHMe2]. In the reaction of the monolithium derivatives of these compounds with halosilanes 1-amino-1.3-disilazanes are obtained [(NH2)(Me3C)RSi-NH-SiR1R2R3; 3: R = CMe3, R1 = R2 = R3 = Me; 4: R = R1 = CMe3, R2 = R3 = Me; 5: R = R1 = R2 = CMe3, R3 = H; 6: R = R1 = CMe3, R2 = Me, R3 = F; 7: R = CHMe2, R1 = R2 = R3 = Me]. If monolithiated diamines are treated with trifluorosilanes cyclisation occurs to give (NH-Si(CMe3)2-NH-SiFR)cyclodisilazanes [R = N(SiMe3)(CMe3) (8); R = N(SiMe2CMe3)2 (9)]. 50% of the educts are recovered. The spirocyclic compound 10 is isolated from the reaction of the dilithiated 1-amino-1.3-disilazane 3 with F3SiN(SiMe2CMe3)2. NH-SiF-Functional cyclodisilazanes can be obtained in the reaction of the dilithium derivative of compound 4 with trifluorosilanes [(N(SiMe2CMe3)-Si(CMe3)2-NH-SiFR), R = Ph (11); R = CMe3 (12)]. The lithium derivative of 12 crystallises with TMEDA as adduct 13. In the reaction of the lithiated compound 12 with Me3SiCl, LiCl elimination and substitution of the N-atom is observed (14). The treatment of 13 with PhCHO leads to a 1.3-diaza-5-oxa-2.4-disila-cyclohexane (15 a, b). Starting from lithiated 12 the methoxysubstituted cyclodisiloxane 16 is accessible in the reaction with MeOH. As result of its reactivity towards Me2SiF2 the fluorosilyl-substituted cyclodisilazane 17 is obtained. Crystal structures of 9-11 and 13 have been determined.

On the Mechanism of the Amination of 3-Substituted Derivatives of 1,2,4-Triazine with Potassium Amide in Liquid Ammonia

Heterocycles ◽  
1978 ◽  
Vol 9 (10) ◽  
pp. 1490
Author(s):  
Bingzhu Yin ◽  
Andrzej Rykowski ◽  
Pawel Nantka-Namirski ◽  
Henk van der Plas
Keyword(s):  
Liquid Ammonia ◽  
Derivatives Of

Synthesis, Characterization, and Chemistry of Dimethyl Sulfide Derivatives of closo-B10H102-

2002 ◽  
Vol 67 (7) ◽  
pp. 1007-1024 ◽  
Author(s):  
Heather D. Hall ◽  
Bradley D. Ulrich ◽  
Roman G. Kultyshev ◽  
Jianping Liu ◽  
Shengming Liu ◽  
...  
Keyword(s):  
Alkali Metal ◽  
Single Crystal ◽  
Diffraction Analysis ◽  
Liquid Ammonia ◽  
Dimethyl Sulfide ◽  
X Ray Diffraction ◽  
Chiral Column ◽  
X Ray ◽  
Derivatives Of

The reaction of Cs2[B10H10] with DMSO in acid produces the disubstituted 1,10-, 1,6-, and 2,7(8)-isomers of (Me2S)2B10H8 as well as the monosubstituted [(Me2S)B10H9]- anion. Through a modified procedure, the trisubstituted compound 1,10-(Me2S)2-2-(MeS)B10H7 was prepared and characterized. The 1,10-(Me2S)2B10H8 isomer was converted to the enantiomers 2,7-(Me2S)2B10H8 and 2,8-(Me2S)2B10H8 which were separated on a chiral column. The 1,6-(Me2S)2B10H8 isomer was converted to a mixture of 1,10-(Me2S)2B10H8 and 2,3-(Me2S)2B10H8. These polyhedral rearrangements are believed to occur through the diamond-square-diamond mechanism. The 1,6- and 1,10-(Me2S)2B10H8 isomers were reduced with alkali metal in liquid ammonia to produce the dianions [1,6-(MeS)2B10H8]2- and [1,10-(MeS)2B10H8]2-, respectively. Sodium ethanethiolate was used for the reduction of [1-(Me2S)B10H9]- and 1,10-(Me2S)2B10H8 to form [1-(MeS)B10H9]2- and [1-(MeS)-10-(Me2S)B10H8]-, respectively. The structures of 1,10-(Me2S)2B10H8, 1,6-(Me2S)2B10H8, 2,8-(Me2S)2B10H8, 2,3-(Me2S)2B10H8, 1,10-(Me2S)2-2-(MeS)B10H7, [1-(MeS)-10-(Me2S)B10H8]-, and [1,6-(MeS)2B10H8]2- were determined by single-crystal X-ray diffraction analysis.

Tricyclic psychotropic agents containing two chalcogen atoms in the central ring: Synthesis of 11-(dimethylaminoalkyl) derivatives of 11H-dibenzo[b,e]-1,4-dioxepin and 11H-dibenzo[b,e]-1,4-dithiepin

1982 ◽  
Vol 47 (1) ◽  
pp. 72-87 ◽  
Author(s):  
Karel Šindelář ◽  
Jiří Holubek ◽  
Miroslav Ryska ◽  
Emil Svátek ◽  
Antonín Dlabač ◽  
...  
Keyword(s):  
Liquid Ammonia ◽  
Sodium Hydride ◽  
Central Ring ◽  
Simultaneous Formation ◽  
Alternative Synthesis ◽  
Psychotropic Agents ◽  
Reserpine Hypothermia ◽  
The One ◽  
High Degree ◽  
Derivatives Of

1-[2-(2-Fluorophenoxy)phenyl]-4-dimethylaminobutanol (XI) was synthesized from 2-(2-fluorophenoxy)benzoic acid (VIII) in three steps and cyclized with sodium hydride in dimethylformamide to the title compound V. Reaction of 5-chloro-2-(methylthio)thiophenol (XIV) with sodium and liquid ammonia afforded benzene-1,2-dithiol (XIII) which was treated with 2-bromobenzyl bromide and gave 11H-dibenzo[b,e]-1,4-dithiepin (II). An alternative synthesis of compound II consisted in the cyclization of 2-(2-bromophenylthiomethyl)thiophenol (XVIII) and was accompanied by the simultaneous formation of 6H, 12H-dibenzo[b,f]-1,5-dithiocin (XIX) and thianthrene (XX). Reaction of compound II with n-butyllithium and the following treatment with dimethylaminoalkyl chlorides or with carbon dioxide resulted on the one hand in two further title compounds VI and VII, and in the carboxylic acid XXI on the other. 2-Chloro-11H-dibenzo[b,e]-1,4-dithiepin (XXII) was obtained by a further synthesis alternative using in the first step the cyclization of 2-(4-chloro-2-chloromethylphenylthio)thiophenol (XXV). Compound VI and VII showed a high degree of activity in the test of antagonization of reserpine hypothermia in mice.

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