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Über das Verhalten von silicium- und zinnorganischen Verbindungen bei der Synthese von Heterocyclen
(1977)
The isocyanates of silicon (CH3)2Si(NCO)2 and Si(NCO)4 react with CH3N[Sn(CH3)3]2 and N[Sn(CH3)3]3 to yield the cyclic derivatives 2a-2b as well as the spiro compound 3. The structures of the compounds are discussed on the basis of 1H NMR and IR data. Mass spectra are not conclusive for assigning a certain structure. SO2(NCO)2 and (CH3)3Si-S-Si(CH3)3 form a cyclic compound 4 which contains two sulfur atoms of coordination number two and four. The results of the mass spectra can be interpreted by assuming that a rearrangement occurred. 4 hydrolyses under formation of 5.
1 reacts with SCl2 to yield 2. The methylsilane derivatives [OC–NCH3–CO–NCH3-SO2–N]nSi(CH3)4-n for n = 2, 3 and 4 are readily prepared from 1 and (CH3)2SiCl2, CH3SiCl3 and SiCl4. The IR and mass spectra are reported.
CH3P(S)(NCO)2 reacts with [(CH3)3Si]2N-CH3, [(CH3)3SiNCH3]2CO and [(CH3)3Sn]3N to give the cyclic compounds 2a-2c. The structures are discussed on the basis of NMR and IR data. In 2 a and 2 b the (CH3)3Si-groups are easily and quantitatively replaced by protons with water under formation of (CH3)3Si-O-Si(CH3)3. By the reaction of CH3P(S)(NCO)2 with [(CH3)3Si]2S 4 is obtained, a cyclic compound with a sulfur atom of coordination number 2.
FP(S)(NCS)2 was used to investigate the scope of these reactions. With [(CH3)3Si]2NCH3 and FP(S)(NCS)2 5 is obtained, which reacts with S2Cl2 to yield 6, a bridged disulfur compound. This method may be useful for the systematic investigation of new cyclic compounds.
Arsenhaltige Heterocyclen
(1978)
In the reaction of N,N'-bis-trimethylsilyl-dimethylurea with As[N(CH3)2]3 a four membered ring O = C(NCH3)2AsN(CH3)2 1 could be isolated. 1 was not obtained by cleavage of the Si-N-bonds with the corresponding chloride. In contrast CH3N[CONCH3Si(CH3)3]2 reacts with AsCb to yield the six-membered ring CH3N(CON-CH3)2ASCl 2. The four-membered ring which contains an arsenic-halogen bond seems to be unstable. In the adamantane-type compound, AS4(NCH3)6, one methylamine could be eliminated by CF3SO3H to give AS4(NCH3)5(OSO2CF3)2 3. 1H, 19F NMR as well as mass spectroscopy have been used in the characterization of the products obtained.
As[N(CH3)2]3 reacts with the following isocyanates: FSO2NCO, n-C4F9SO2NCO, SO2(NCO)2 and (CH3)3SiNCO. The products which result from reaction of FSO2NCO and n-C4F9SO2NCO are the acyclic tri- and bisubstituted arsines [xxx]
In contrast, SO2(NCO)2 and (CH3)3SiNCO form eight- and four-membered ring compounds, where the skeleton consists of the atoms As2S2N4 (3) and As2N2 (4). The new compounds were characterized by NMR and mass spectra.
The reactions of N,N′ -bis(pentafluorophenyl)sulfurdiimide with [(CH3)3Sn]2NCH3, [(CH3)3Sn]3N and [(CH3)3Sn]2NC6F5 yiels the 1:1 adducts 1-3. 1H and 19 F NMR investigations show, that fluorine atoms in the ortho position of the phenyl ring coordinate to the tin atom. This causes an increase of electron density at tin. A similar interpretation is given for the adduct 4 of N,N′-bis(p-chlorophenylsulfonyl)sulfurdiimide and [(CH3)3Sn]2NCH3, where an oxygen atom of the sulfonyl group is bonded to tin.
Substituted amides react with tridiloromethanesulfenyl chloride in the presence of triethylamine to following compounds: S=PCl2NCH3SCCl3, S=PFCl2NCH3SCCl3, S =PFClNCH3SCCl3, S=PF2NCH3SCCl3, O = PCl2NCH3SCCl3, O= PFClNCH3SCCl3, O = PF2NCH3SCCl3, FSO2NCH3SCCl3 and CF3SO2-NCH3SCCl3. The properties of these substances are described. They were characteriszed by elemental analyses, IR- and mass spectra. 19F-, 1H- and 31P-NMR spectra are reported and discussed.
By reacting S = PX2NHCH3 or O = PX2NHCH3 (X = F and/or Cl) with S = PF2Br in the presence of triethylamine the following compounds are prepared: S = PCl2NCH3F2P = S, S = PFClNCH3F2P = S, O = PCl2NCH3F2P = S and O = PFClNCH3F2P = S. Also, the infrared, proton NMR, fluorine NMR, phosphorus NMR, and mass spectral data of these compounds are presented and discussed.
Pyrosulfonyldifluoride reacts with waterfree hydrazine in a molar ratio of 2 : 3 to give hydrazine -1,2-bis(sulfonylfluoride) in a low yield.. The reaction of N-fluorosulfonylamide and SOCl2 yields NH4⊕⊖ N(SO2F)2. This salt is converted to (C6H5)4P⊕⊖N(SO2F)2 in water by (C6H5)4PCl. (CH3)2NNH2 reacts with PSF3, PSF2Br, PSF2CH3 or PSF2C2H5 to yield the following compounds: (CH3)2NNHPSF2, (CH3)2NN (PSF2)2, (CH3)2NNHPSFCH3 and (CH3)2NNHPSFC2H5. The properties and the chemical behaviour of these substances are described. Results of ir-spectra, as well as 31P-, 19F- and 1H-nmr- and mass-spectra and elemental analysis characterize the compounds.
Eight-membered rings of the composition [SO2(NR)2PR′]2 3a-d with R = CH3, C2H5, and R′ = CH3, C6H5, were prepared from substituted sulfamides and dichlorophosphanes in the presence of a tertiary amine. These molecules were characterized on the basis of 1H and 31P NMR investigations and of mass spectra. 3 a reacts with phosphorus pentachloride to yield the spirocyclic derivative 4 with the phosphorus atom in the center of two four-membered rings. Methyliodide reacts with 3 a and 3 b under opening of the eight- membered ring and formation of phosphonium salts. The structure of 3 b is discussed in detail. 8b crystallizes in the orthorhombic space group Pna 21 with a = 12.60(0), b = 13.27(1), c = 12.62(4) Å.