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- Biochemie und Chemie (23)
The synthesis of [Ph4As+]2[Cl4Re(NS)(NSCl)2-] · CH2Cl2 (4) from the reaction of S4N4, Cl4ReN, and Ph4AsCl is reported. CH2Cl2 is used as solvent. The reaction of S4N4 with Re2Cl10 similarly leads to the salt [Ph4As+][Cl2ReNS-] (5) in a smaller yield. 4 crystallizes in the triclinic space group P1̅ with Z = 2, a - 10.434(2), b = 12.1454(6), c = 21.125(2) Å, a = 81.210(6), β = 86.70(1), γ = 76.624(8)°.
By substitution of a halogen atom in cyclic phosphazenes by isocyanate or isothiocyanate new members of this class of compounds are synthesized. These compounds are fairly stable against hydrolysis. Reaction of the new compounds with amines yields
P3N3F5NHC(O)N(CH3)2 and P3N3F5NHC(S)N(CH3)2. With elemental chlorine P3N3F5N = CCl2 is formed. Numerous IR, NMR and mass spectra data of the new compounds are reported.
Two routes for the preparation of (CH3)2SnS2N2 are given, which are kinetically controlled reactions. The molecule (CH3)2SnS2N2 was characterized by X-ray analysis. It is an interesting starting material for the preparation of S2N2CO and S3N2O. The latter reacts with iminosulfur oxides and isocyanates under the formation of S3N3SO2F and S3N3SO2CF3. The structure of S3N3SO2F was established by X-ray analysis. The bonding properties are discussed.
The cleavage of thin-nitrogen derivatives with S3N2Cl2 yields also five membered sulfurnitrogen rings. The structure and properties of P3N3F5NS3N2 and C3N3F2NS3N2 are reported. Six, eight and ten membered rings are formed by the reactions of (CH3)3Si–N = S = N–Si (CH3)3 with FSO2–N=S=O, these are S4N4O2 and S5N5+S3N3O4, respectively. The cation S5N5+ is a planar molecule, while the oxygen containing species are puckered. In S4N4O2 the oxygens are attached to one sulfur atom, which has a tetrahedral configuration.
The structure of the silicon containing cyclic and bicyclic rings (CH3)2Si(NSN)2Si(CH3)2 and CH3Si(NSN)3SiCH3 were determined.
R-P(Se)F2- (R = CH3, C2H5, C3H11, C6H5, N(CH3)2, N(C2H5)2, NHSi(CH3)3) and R-P(Se)FCl-compounds (R = CH3, C2H5) can be prepared by reaction of R-P(Se)Cl2-derivatives with antimony(III)fluoride under reduced pressure. In some cases the oxidation of fluorophophines with elemental selenium is successful. The isolated compounds are colourless volatile liquids which are sensitive to air and moisture. The chemical properties are described.
1H-, 19F-, 31P-NMR-, IR- and Raman-spectroscopic data are given. Main stretching frequencies are discussed by comparison with similar oxygen- and sulphur-compounds.
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.
P3N3F5NHNH2 reacts with P3N3F5Br to yield the symmetric hydrazide P3N3F5-NHNHP3N3F5. Compounds of the type P3N3F5NHNHC(O)CX3 and P3N3F5NHN = CX2 are readily prepared from P3N3F5NHNH2 and carbonic acid chlorides and respectively aldehydes and ketones.
The reaction product of P3N3F5NHNH2 and CH3CH2CHO gives a dimeric derivate. Its structure was proofed by molecular weight, IR- and mass spectra.
The preparations of the following compounds are described: O = PF2N = PCl2N = PCl3, O = PF2N = PCl2N = PCl2N (CH3) 2, O = PF2N=PCl2N = PCl2N (C2H5) 2, O = PF2N = PCl2N (CH3) 2, O = PF2N = PCl2N (C2H5)2, O = PF2N = PCl2N (CH3) Si (CH3)3, O = PF2N = PCl2NCS, O = PFClN = PCl2N (CH3)2, O = PFClN = PCl2N (C2H5)2, O = PFClN = PCl [N (C2H5)2]2 and O =P (C6H5) FN = PCl3. They were characterized by 1H-, 19F- and 31P-nmr spectroscopy. Analytical, ir and mass spectral data are reported. The properties of these substances are compared with the corresponding thiophosphorylderivatives.
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.
The preparation of (CH3)3SnSPSFC2H5, Pb(SPSFCH3)2, Pb(SPSFC2H5)2 and CH3HgSPSFCH3 is described. On the basis of NMR the structure was formulated as ... All the complexes are colourless and monomeric in solution. The magnetic and reflectance spectra of Cr(S2PFCH3)3, Mn(S2PFC2H5)2, Co(S2PFCH3)2, Ni(S2PFCH3)2 and Ni(S2PFC2H5)2 are reported and interpreted.
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.
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.
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.
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.
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.
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.
N-Sulfonylsulfimide
(1978)
(CF3SO2NSO2)2 (1), a compound with a four-membered ring, was prepared from CF3SO2NSO and SO3. 1 as well as (FSO2NSO2)2 form 1:1 adducts with S4N4 , pyridine and pyridine carbonitrile-4 (2a-2f). By comparison with FSO2NCOS4N4 it was shown that a dipolar type of addition had occured. In contrast the reaction of 1 and (FSO2NSO2)2 with aromatic nitriles yields 1:2 cycloaddition products (3a-3g) which were characterized on the basis of mass spectra. The six-membered rings of 4a-4b which contain carbon, nitrogen and sulfur atoms were obtained from the reaction of isocyanates with (FSO2NSO2)2 or (CF3SO2NSO2)2. 4-BrC6H4NCO and SO3 react in a similar way to yield 5. The starting materials are extremely sensitive to moisture while most of the adducts can be handled in open air without decomposition.
Über Reaktionen von 3-trifluormethylphenylsubstituierten silicium-und zinnorganischen Verbindungen
(1978)
Several routes were investigated for the preparation of 3-CF3C6H4N[Si(CH3)3]2 2 and 3-CF3C6H4N[Sn(CH3)3]2 3. The latter compound reacts with 3-CF3C6H4NCO to yield [3-CF3C6H4(CH3)3SnN]2CO 4. A substituted urea 5 is also formed from [(CH3)3Si]2NCH3 and 3-CF3C6H4NCO. 5 is used for the preparation of cyclic compounds, with S2Cl2 the ten-membered ring (3-CF3C6H4NCONCH3S2)2 6 is formed. 5 and HN(SO2Cl)2 yield the six-membered ring 3-CF3C6H4NCONCH3(SO2)2NH 7. SeOCl2 and 5 react under formation of a spiro compound (S-CF3C6H4NCONCH3)2Se 8. The compounds were characterized on the basis of mass and 19F NMR spectra.
The title compound N,N-bis(trimethylstannyl)trifluoromethanesulfonamide (1) reacts with S2Cl2, SOCl2 and SO2Cl2 in a molar ratio 2:1 to yield the compounds S2Cl2 a twelve-membered ring 6. These are the largest neutral sulfur-nitrogen rings of coordination number two at the sulfur atoms known to date. 3 reacts with SOCI2 under migration of a methyl group from the tin to a sulfur atom to yield CF3SO2(R3Sn)NS(CH3)NSO2CF3 (7). 2,2,4,4-Tetramethyl-1,3-bis(trifluormethylsulfonyl)cyclodisilazan and 7 are formed by the reaction of 3 with R2SiCl2- The analogous four-membered germanium compound 8 is obtained from 1 and R2GeCl2. While the pyrolysis of 1 yields only the six-membered cyclotristannazan 9, the six-membered germanium analog is only formed in minor amounts. By treating 9 with R3SiCl the ring is decomposed to give 10. A six-membered ring is formed from the reaction of 1 with ClR2SiOSiR2Cl 11. The structure of 6 is discussed in detail. 6 crystallizes in the monoclinic space group C2/c with a = 24.408(5), b = 7.377(2), c = 16.715(3) Å, β = 117.16(3)° and Z = 4. It has a chair conformation which is different from the isoelectronic S12-structure.
The kinetically stable triazatriphosphorinyl and tetraazatetra-phosphorocinyl azides 3 and 4 are prepared from the corresponding chlorides 1, 2 with sodium azide. 3 and 4 react with phosphanes to yield the λ5 -diphosphazenes 5a-d. By the reaction of 1 or 2 with KCN the nitriles 6 and 7 are formed. -The new compounds are characterized on the basis of IR and mass spectra.
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.
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.
S4N3Cl reacts with sulfonic acids and imido- bissulfonyl derivatives under HCl-evolution to the following compounds: S4N3SO3CF3, S4N3N (SO2F)2, S4NSO3CH3HSO3CH3, S4N3N (SO2CF3) SO2Cl and S4N3N (SO2CF3) SO2F, They are yellow solids which decompose when heated below the melting point. The compounds are formed in nearly quantitative yield and have been characterized by elemental analysis, nmr and electronic spectra.