Walter Maringgele

Zur Borylierung von Benzol und Naphthalin durch Dehalogenierungsprodukte von Dichlor(diisopropylamino)boran

Abstract The formation of the compounds C 6 H 6 · x BN(i-C 3 H 7 ) 2 ( x = 1–6) from the reaction of dichloro(diisopropylamino)borane with sodium/potassium alloy in 1,2-dimethoxyethane, has been confirmed by mass spectrometric studies (high resolution, field ionisation and collision activation using “linked scan” analysis). The compounds with x = 2 and x = 3 were separated from the reaction mixture and identified as compounds C 6 H 6 · 2BN(i-C 3 H 7 ) 2 (Ia) and C 6 H 6 · 3BN(i-C 3 H 7 ) 2 (II) by NMR ( 1 H, 11 B, 13 C and 15 N). Hydrolysis of the naphthalene derivative, C 10 H 8 ·2BN(i-C 3 H 7 ) 2 (III) in alkaline medium gives 1-methyl-2-propene-1-yl-benzene (IV) and 1-allyl-2-methylbenzene (V), which suggests that this moiety has structure IIIb (2,10-bis(diisopropylamino)-1,5-dihydro-1,5-epiborano-benzo[ c ]borepin) rather than that of isomeric IIIa (1,2-bis(diisopropylamino)-1,1 a ,2,8 b -tetrahydro-borireno[2,3- b ][3]benzoborepin).

Umsetzung von metall- und metalloidverbindungen mit mehrfunktionellen molekülen : XIV. Darstellung monomerer cyanoborane☆

Abstract Monomeric cyanoboranes are obtained by reaction of bis(amino)haloboranes and amino(halo)organylboranes with AgCN. 1 H, 11 B NMR, IR and mass spectra are reported together with analytical data.

Reaktionen subvalenter verbindungen des siliciums mit benzol und mit biphenyl

Abstract Subvalent species of silicon have been generated by the dehalogenation of dichloro-bis(2,6-dimethyl-piperidino)silane (I), dichloro-bis(diethylamino)silane and dichloro(diisopropylamino)methylsilane (VI) with Na/K alloy in hexane containing benzene or biphenyl. From the reaction mixtures products formed by insertion into CH bonds of the aromatic compounds, have been isolated or detected as the aryl substituted aminosilanes (II, IV, VII and IX) and the bis(aminosilanyl)phenylenes (V and VIII). Furthermore benzo[ d ]-1,3-dihydro-1,2,3-trisiloles (III, IX and XII) were formed upon 1,2-substitution of the aromatic rings. Additional products are tris(diethylamino)silane ( B ) and the 1,3-diphenyltrisilane derivative X. Compounds I, II, III, VI, XI and XII were characterized by their elemental analyses and spectroscopic data (MS, NMR: 1 H, 13 C, 29 Si). Compounds IV, V, VII, VIII, IX and X have been detected by MS and in part characterized by NMR and IR data. An X-ray structure analysis has been performed of I.

Umsetzungen von metall- und metalloidverbindungen mit mehrfunktionellen molekülen : XXXV. Cyclische ureidoborane

Abstract Reactions of N,N ′-diorganylureas and N,N ′-diorganylthioureas, respectively, with halo-organylboranes lead to hydrogen halide and mixtures of two reaction products. The mixtures consist of 1,3,5-triaza-2-boracyclohexane-dione-4,6 and -dithione-4,6 (A), and 1,3,5-triaza-2,6-dibora-cyclohexanone-4 and -thione-4 (B), respectively. In the case of II and V 1-oxa-3,5-diaza-2,6-dibora-cyclohexanone-4 is obtained as a by-product. Further by-products are in the case of the reaction of N,N ′-dimethylthiourea with trihaloboranes 1,3,5-trimethyl-2,4,6- trihaloborazines and in the synthesis of XIX cyclohexylisothiocyanate. Haloboranes split the N,N ′-diorganylureas and N,N ′-diorganylthioureas partially into isocyanate and isothiocyanate and primary amine. This explains the formation of the above-mentioned heterocycles A and B. XXII–XXVII exist, as indicated by v (CN) in their infrared spectra and by the 11 B NMR spectra, as 6-organyl-imino-1-thia-3,5-diaza-2,4-diboracyclohexanes. The compounds are characterized analytically and spectroscopically (NMR: 1H , 11B ; MS; IR).

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 12. Mitteilung

N-Trimethylsilylamides react with aminohalogenoboranes in nearly quantitative yield to monomeric amido(bis)aminoboranes. From the reaction of N-substituted acylamides with bis(amino)halogenoboranes and dialkoxyhalogenoboranes respectively and triethylamine corresponding amido-bis(amino)-and amido-bis(alkoxy)boranes were obtained in high yields. In certain cases equilibria between monomeric and dimeric forms are observed.1H,11R, and19F.-n.m.r. spectra, mass spectra and characteristic i.r. group frequencies are reported.

Reaktionen der Enthalogenierungsprodukte von Dichlor(diisopropylamino)boran mit Olefinen in n-Hexan

Reactions of vinyltrimethylsilane, propene, 3,3-dimethyl-1-butene, 1-butene, 3-methyl-1-butene, 1-pentene, 4,4-dimethyl-1-pentene, cyclopentene, cyclohexene and cyclooctene with dichloro(diisopropylamino)borane and Na/K-alloy in n-hexane yield the 1,2-diboretanes I-VII, IX, XI and the 1,2,3-triborolanes VIII, X, XII. By-products XIV and XVI–XVIII were found in the mass-spectra. In reaction to VII the 1,2,3,4-tetrakis(diisopropylamino)tetraborane(6) (XIX) was isolated as by-product. Vinyl-3-cyclohexene reacts under the same conditions to give the triborolane (XIII). The compounds I–XIII, XV and XIX were characterized by elemental analyses and spectroscopic data (MS; NMR: 1H, 13C, 11B, 29Si), X, XII, XIII and XIX also by X-ray structure analyses.

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 22. Mitt.: Die Reaktion von Trimethylsilylcarbonsäureamiden mit Halogen(diorganyl)boranen

Trimethylsilylacetamide and trimethylsilyltrifluoroacetamide react with halogenodiorganylboranes to monomeric or dimeric amidoboranes depending on the organyl substituents. The compounds were characterized analytically and spectroscopically (NMR:1H,19F,11B; MS; IR).

Umsetzung von Metall- und Metalloidverbindungen mit mehrfunktionellen Molekülen, 8. Mitt.

N-substituted halogenoacetamides react with halogenoboranes to the title compounds. The corresponding N-substituted halogenoimines result as byproducts. The importance of inductive and steric effects of the substituents is shown by the fact, that certain N-substituted halogenoacetamides react under formation of N-substituted halogenoimines only.1H-,11B-, and19F-NMR spectra, mass spectra and characteristic IR group frequencies are reported.

Umsetzung von Metall und metalloidverbindungen mit mehrfunktionellen molekülen : XXX. Synthese von offenkettigen und cyclischen sulfonamidoboranen

Depending upon the electronic behaviour of the substituent R in nitroso compounds R−N=O, either adducts with halogenoborane derivates are formed, or addition of a boron—halogen bond across the N=O double bond can take place. Accordingly N-nitrosoamines form adducts with trichloroborane and organoboranes, while from the reactions of 1,1-dichloronitrosoethane and BCl3 or BBr3 dimeric alkylideneiminoxyboranes are obtained under elimination of Cl2 and Br2 resp.Abstract N-organyl-N-trimethylsilyl-sulfonamides react with halogenodiorganyl-, bis(amino)halogeno- and phenyldimethylamino-chlorborane in quantitative yield to the corresponding sulfonamidoboranes I – XXII, The compounds XXIII – XXVIII, which have the diorganylboryl-grouping in ω-position to the sulfonamidogroup, are obtained by reaction of N-methyl-N.(β-hydroxyethyl)-n-perfluorobutylsulfonamide with halogeno-diorganyl-, bis(amino)halogeno- and organyl-amino-halogenoboranes resp. The bis(sulfonamido)boranes (IXXX and XXX) are byproducts of such reactions. The sulfonamidoboranes XXXI – XXXIII, which are derived from unsubstituted sulfonamide, are formed in the reaction of n-perfluorobutyl-sulfonamide and halogenodiorganylborane. N-(β -hydroxyethyl)-n-perfluorobutylsulfonamide reacts with halogenodiorganylborane in mole ratio 1 : 2 to the bis(diorganyl-boryl)-perfluorobutyl-oxyethylsulfonamides XXXIV – XXXVI. N-(β-dimethylboryloxy-i-propyl)-n- perfluorosulfonamide XXXVII is obtained by reaction of bromodimathylborane with N-(β-hydroxy-i-propyl)-n-perfluorobutylsulfonamide. The reaction of N, N-bis(β-hydroxy-ethyl)-n-perfluorobutylsulfonamide with dichloro-n-butyl-and dichloroophenylborane resp., leads to the 1.4.6.5-aza-dioxaboracyclooctanderivatives XXXVIII – XXXIX. N-(β-hydroxyethyl)-n-perfluorobutylsulfonamide and N-(β-hydroxy-i-propyl)-n-perfluorobutyl-sulfonamide resp. react with dihalogeno-organylboranes forming the corresponding 1.3.2-oxa-azabora-cyclopentane-derivatives XL and XLVIII. The compounds are characterized analytically and spectroscopically (NMR: 1 H, 11 B; MS).

Umsetzung von metall- und metalloidverbindungen mit mehrfunktionellen molekülen : X. N-alkyl-N-ω-cyanoalkyl-amino(diorganyl)borane

Abstract N -Alkyl- N -ω-cyanoalkylamino(trimethyl)silanes react with halogendi-(organyl)-boranes and chloro-bis(dimethylamino)borane resp., with formation of halogentrimethylsilane and the monomeric title compounds. The compounds were characterized analytically and spectroscopically (NMR: 1 H, 11 B; MS; IR)