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  • 1
    Publication Date: 1983-01-01
    Print ISSN: 0040-4039
    Electronic ISSN: 1873-3581
    Topics: Chemistry and Pharmacology
    Published by Elsevier
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  • 2
    Publication Date: 1973-01-01
    Print ISSN: 0040-4039
    Electronic ISSN: 1873-3581
    Topics: Chemistry and Pharmacology
    Published by Elsevier
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 106 (1973), S. 1752-1757 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemical Reactions in Fused Salts, XV. Synthesis and Reactions of Carbonyl Halides and PseudohalidesA new method of preparation of carbonyl diisocyanate, chlorocarbonyl isocyanate and carbonyl diisothiocyanate in molten salts as a solvent is described. Carbonyl pseudohalides undergo redistribution reaction with carbonyl halides by which reaction fluoro- and chlorocarbonyl pseudohalides are obtained. The preparation of chlorocarbonyl fluoride is also performed advantageously by this redistribution reaction. Fluorocarbonyl isocyanate adds hydrogen halides forming iminodicarboxylic acid halides, FCO—NH—COX.
    Notes: Neue Darstellungsmethoden für Carbonyldiisocyanat, Chlorcarbonylisocyanat und Carbonyldiisothiocyanat in geschmolzenen Salzen als Lösungsmittel werden beschrieben. Carbonylpseudohalogenide gehen Kommutierungsreaktionen mit Carbonylhalogeniden ein, wodurch Fluor- bzw. Chlorcarbonylpseudohalogenide leicht zugänglich werden.  -  Die Kommutierung ermöglicht auch einen vorteilhaften Zugang zum Chlorcarbonylfluorid.  -  Durch Addition von Halogenwasserstoffen an Fluorcarbonylisocyanat werden die entsprechenden Iminodicarbonsäurehalogenide, FCO—NH—COX, dargestellt.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 103 (1970), S. 3939-3941 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1285-1296 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Partially Halogenated and Silylated 1,3-Dithietane 1,1,3,3-Tetraoxides and a New Stable Sulfene-Amine AdductTwo new convenient syntheses of 2,2,4,4-tetrachloro-1,3-dithietane-1,1,3,3-tetraoxide (3a) and the corresponding tetrabromo compound (3b), starting from 1,3-dithietane 1,1,3,3-tetraoxide (1) (disulfene) are described. 2-Chloro-(10a), 2-bromo-(10b), 2,4-dichloro-(11) and 2,2,4-trichloro-1,3-dithietane 1,1,3,3-tetraoxide (12) are obtained as the first examples of partially halogenated disulfenes, starting from 2,4-bis(trimethylsilyl)- (6a) and 2,4-bis(tert-butyldimethylsilyl)-1,3-dithietane 1,1,3,3-tetraoxide (6b), respectively [produced from 1 with tert-butyldimethylsilyl nonafluorobutanesulfonate (5b)]. The reaction of 6a with elementary chlorine leads to 2,4-bis[methylbis(trichloromethyl)silyl]-1,3-dithietane 1,1,3,3-tetraoxide (6c). 10a, 11, and 12 can be easily brominated to the mixed perhalogenated derivatives, e. g. 2,2,4-tribromo-4-chloro-1,3-dithietane 1,1,3,3-tetraoxide (13). Preparation and properties of an adduct 17 between chloro(chloromethyl-sulfonyl)sulfene and trimethylamine are described, which is the third stable representative of this class of compounds.
    Notes: Zwei neue, einfache Synthesen des 2,2,4,4-Tetrachlor-1,3-dithietan-1,1,3,3-tetraoxids (3a) und der entsprechenden Tetrabromverbindung (3b), ausgehend von 1,3-Dithietan-1,1,3,3-tetraoxid (1) (Disulfen) werden beschrieben. Aus 2,4-Bis(trimethylsily)- (6a) und 2,4-Bis(tert-butyldimethylsilyl)-1,3-dithietan-1,1,3,3-tetraoxid (6b) [hergestellt aus 1 mit Nonafluorbutansulfonsäure-(tert-butyldimethylsilyl)ester (5b)] gelingt die Darstellung von 2-Chlor- (10a), 2-Brom-(10b), 2,4-Dichlor-(11) und 2,2,4-Trichlor-1,3-dithietan-1,1,3,3-tetraoxid (12) als erste Vertreter partiell halogenierter Disulfene. Die Umsetzung von 6a mit elementarem Chlor führt zu 2,4-Bis-[methylbis(trichlormethyl)silyl]-1,3-dithietan-1,1,3,3-tetraoxid (6c). 10a, 11 und 12 lassen sich leicht zu den gemischt perhalogenierten Derivaten wie 2,2,4-Tribrom-4-chlor-1,3-dithietan-1,1,3,3-tetraoxid (13) bromieren. Die Darstellung und Eigenschaften eines Addukts 17 aus Chlor-(chlormethylsulfonyl)sulfen und Trimethylamin als drittem, stabilem Vertreter dieser Verbindungsklasse werden beschrieben.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 919-925 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of Trifluoroacetyl IsocyanateTrifluoroacetyl isocyanate (1) can readily be obtained from trimethylsilyl isocyanate and trifluoroacetyl chloride. 1 reacts with trifluoroacetamide forming N,N′-bis(trifluoroacetyl)urea (2), which can also be obtained from trifluoroacetyl chloride and urea or N,N′-bis(trimethylsilyl)urea, respectively. 1 reacts with ammonia or various amines forming the trifluoroacetyl-substituted ureas 3-6, and hydrazine 7. From 1 and trifluoroacetic acid hexafluorodiacetamide (8) could be obtained. 1 reacts with tert-butylalcohol forming tert-butyl (trifluoroacetyl)-carbamate (9). From 1 and N,N-dimethylformamide N,N-dimethyl-N′-(trifluoroacetyl)formamidine (10) could be obtained as well as N-(trifluoroacetyl)pyrrole-2-carboxamide (11) from pyrrole.
    Notes: (Trifluoracetyl)isocyanat (1) erhält man günstig aus (Trimethylsilyl)isocyanat und Trifluoracetylchlorid. 1 reagiert mit Trifluoracetamid zu N,N′-Bis(trifluoracetyl)harnstoff (2), der auch aus Trifluoracetylchlorid und Harnstoff bzw. N,N′-Bis(trimethylsilyl)harnstoff erhalten wurde. Mit Ammoniak und verschiedenen Aminen reagiert 1 zu den trifluoracetylsubstituierten Harnstoffen 3-6 und dem Hydrazin 7. Aus 1 und Trifluoressigsäure wird Hexafluordiacetamid 8 erhalten. 1 reagiert mit tert-Butylalkohol zu tert-Butyl-(trifluoracetyl)carbamat (9). Aus 1 und N,N-Dimethylformamid bildet sich N,N-Dimethyl-N′-(trifluoracetyl)formamidin (10) und aus Pyrrol das N-(Trifluoracetyl)pyrrol-2-carboxamid (11).
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 3334-3339 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaction of Pentafluoro-2-aza-1-propene with Perfluorinated CarbenesPerfluorinated carbenes like :CF2 and :C(CF3)2 do not react with perfluoro-2-aza-1-propene (1) to yield the expected aziridines 2 and 8, respectively. Assuming the intermediacy of bis(trifluoromethyl)amide anion (4) the formation of the well known dimer of 1, (CF3)2N—CF=N—CF3 (3), can be explained as well as the formation of (CF3)2N—CF2H (5) and (CF3)2N—CF2Br (6). From 1,1,1,3,3,3-hexafluoro-2-propanimine (10) and :C(CF3)2 we did not obtain the aziridine 11 but (CF3)2C=N—CH(CF3)2 (12), which is formed by insertion into the NH-bond.  -  The structure of C4Cl8N2, which is formed as a by-product of the synthesis of perchloro-2-aza-1-propene, has been determined: Cl2C=N—CCl2—CCl2—N=CCl2.
    Notes: Perfluorierte Carbene wie :CF2 und :C(CF3)2 reagieren mit Perfluor-2-aza-1-propen (1) nicht zu den erwarteten Aziridinen 2 und 8. Unter Annahme eines Bis(trifluormethyl)amid-Anions (4) läßt sich sowohl die Bildung des bekannten Dimeren von 1, (CF3)2N—CF=N—CF3 (3), als auch die von (CF3)2N—CF2H (5) und (CF3)2N—CF2Br (6) erklären. Auch aus 1,1,1,3,3,3-Hexafluor-2-propanimin (10) entsteht mit :C(CF3)2 nicht das Aziridin 11, sondern (CF3)2C=N—CH(CF3)2 (12) nach Insertion in die NH-Bindung.  -  Die Konstitution des bei der Synthese von Perchlor-2-aza-1-propen als Nebenprodukt entstandenen C4Cl8N2 wurde bestimmt: Cl2C=N—CCl2—CCl2—N=CCl2.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 115 (1982), S. 2892-2897 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Chemistry of (Trifluoromethyl)sulfinylamine, CF3NSO, and Related CompoundsCF3NSF2 (1) reacts with PCl5 to yield CF3NSCl2 (2) which is converted to the title compound 4 with Ag2O as is well known. 4 can also be obtained from CF3NCl2 (3) and SOCl2, and it reacts with XeF2 to form CF3NSOF2 (5) and with HCl to yield CF3NH2 (6). All reactions were also carried out with the corresponding C2F5 compounds (1a—6a). The hydrochloride of 6a decomposes via (C2F5)2NH. HCl (11) yielding CF3CF2—N=CFCF3 (13) in contrast to 6a, which forms CF3CN (14). CF3—NSN—CF3 (8) can be obtained directly from 4 or from 2 and 3 or 2 and 6, respectively. CF3—NSN—C2F5 (9) and C2F5—NSN—C2F5 (10) are formed in the reaction of 2a with 6.1 reacts with BBr3 to form (trifluoromethyl)imidosulfur dibromide (7).
    Notes: CF3NSF2 (1) reagiert mit PCl5zu CF3NSCl2 (2) und dieses in bekannter Weise mit Ag2O zur Titelverbindung CF3NSO (4). 4 bildet sich auch aus CF3NCl2 (3) und SOCl2. Es reagiert mit XeF2 zu CF3NSOF2 (5) und mit HCl zu CF3NH2 (6). Alle Reaktionen wurden auch mit den entsprechenden C2F5-Verbindungen (1a-6a) durchgeführt. Das Hydrochlorid von 6a zersetzt sich über (C2F5)2NH · HCl (11) zu CF3CF2—N=CFCF3 (13), wogegen 6a CF3CN (14) ergibt. CF3-NSN-CF3 (8) läßt sich direkt aus 4 oder aus 2 und 3 bzw. 2 und 6 erhalten. CF3—NSN—C2F5 (9) bzw. C2F5—NSN—C2F5 (10) bilden sich bei der Reaktion von 2a mit 6.1 reagiert mit BBr3 zu (Trifluormethyl)imidoschwefeldibromid (7).
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 116 (1983), S. 1623-1630 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis and Properties of New Perhalogenated 1,3-Dithietane S-OxidesNew perchlorinated and perfluorinated 1,3-dithietanes (4, 6, 7, 12, 14, 15), which are partially oxidized at the sulfur atoms, are described. Pyrolysis of the 1,3-dioxides 7 and 15 leads to the sulfoxides 8 and 16, X2C = S = O (X = Cl, F). respectively. Two new oxidizing agents are used: trifluoromethane- and nonafluorobutanepersulfonic acid.
    Notes: Die neuen perchlorierten und perfluorierten, am Schwefel partiell oxidierten 1,3-Dithietane 4, 6, 7, 12, 14 und 15 werden beschrieben. Pyrolysen der 1,3-Dioxide 7 und 15 führen zu den Sulfoxiden 8 bzw. 16, X2C = S = O (X = Cl, F). Zwei neue Oxidationsmittel werden angewendet: Trifluormethan- und Nonafluorbutanpersulfonsäure.
    Additional Material: 1 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 106 (1973), S. 587-593 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cleavage Reactions of Trimethylsilyl Cyanide, a New Synthesis of O-(Trimethylsilyl)-cyanohydrinesThe cleavage of trimethylsilyl cyanide with phosgene yields tricyano(trimethylsiloxy)methane. Oxalyl dichloride and trifluoroacetyl chloride react under formation of 1,1,2,2-tetracyano-1,2-bis(trimethylsiloxy)ethane and dicyano(trifluoromethyl)(trimethylsiloxy)methane, respectively. Not only halogen atoms are exchanged by the cyano group but also the carbonyl group reacts with trimethylsilyl cyanide analogously to the synthesis of cyanohydrines. A number of typical O-(trimethylsilyl)cyanohydrines was obtained for the first time.
    Notes: Die Spaltung des Trimethylsilylcyanids mit Phosgen ergibt Tricyan(trimethylsiloxy)methan. Oxalyldichlorid reagiert zum 1,1,2,2-Tetracyan-1,2-bis(trimethylsiloxy)äthan und Trifluoracetylchlorid zum Dicyan(trifluormethyl)(trimethylsiloxy)methan. Nicht nur Halogenatome werden gegen die Cyangruppe ausgetauscht, sondern auch die Carbonylgruppe reagiert mit Trimethylsilylcyanid analog der Cyanhydrinsynthese. Eine Anzahl typischer O-(Trimethylsilyl)cyanhydrine wurde erstmals dargestellt.
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