Primary and secondary aminoalkylphosphanes R2N-(CH2)m-PH2 (R2 = Me2, nBu2, C5H10, C4H8O, 2-(1-Methyl-2-pyrrolidinyl); m = 2, 3, 6, 10, 11; 1-6) or [R2N-(CH2)m]2PH (7, R2 = C5H10; m = 2) are accessible by aminoalkylation of PH3 with ω̃ -chloroalkylamines R2N-(CH2)m-Cl in the superbasic medium DMSO/KOH (DMSO = dimethylsulfoxide). By selective N-quaternization of 1, 2, 4-6 with R'I (R' = Me, CnH2n+1; n = 6-8, 12, 16, 18) in the two-phase system CH2Cl2/H2O novel primary phosphanes [R'R2N-(CH2)m-PH2]+I- (11-16f) with quaternary ammonium groups in the alkyl side chain are obtained. The water solubility of 11-16f decreases with increasing chain length (n) of R′ 11 (R = R' = Me; m = 2) shows a trans conformation at the C2H4 bridge according to an X-ray structural analysis. Protonation of 1, 2, 4, 5 with HCl affords the water-soluble hydrochlorides [HR2N-(CH2)m-PH2]+Cl- (19-22). The cationic primary phosphanes 11-16f are stable towards oxygen. By oxidation of 11 with one or two equivalents of H2O2 the primary phosphane oxide [Me3N-(CH2)2-P(O)H2]+I- (23) or the phosphonous acid [Me3N-(CH2)2- P(O)(OH)H]+I- (23a) are formed. Hofmann degradation of 11 or 16c with KOH yields phosphirane in good yields. Reaction of 1, 2, 4-6 (L) with Fe2(CO)9 at ambient temperature yields stable complexes (CO)4FeL (26-30). Under more rigorous conditions Fe3 clusters (31, 32) with free R2N groups are obtained.

triclinic, Pi, u = 1015.5(2), b = 1045.4(4), c = 1700.7(3) pm, 3~ = 105.34(2), p = 90.93(2), 7 = 98.65(10)'. V = 1.7184(6) nm', 2 = 2, P~~,~, , = 2.055 Mgm-3, p(MoK,) = 3.240 mm-', 44Y4 independent reflections were used for the solution and refinement of (3), , 8 = 86.27(3), = 82.91(3)'. V=1,7471(6)nm',Z=2,p,,,,,= 2.364Mgn1-~,p(Mo,,)= 2.743mm-', 4465 independent reflections were used for the solution and refinement of the structure. R1 = 0.0757, wR2 = 0.1992. wR2 = [x w(F: ~ FZ)'/ Z K~] ' " . R1 = C(llFol -l~ll/ZIFol) b) Further details of the crystal structure investigations may be obtained from the Fachinformationszentrum Karlsruhe. Gesellschaft fur wissenschaftlich-technische Information mbH, D-76344 Eggenstein-Leopoldshafen (FRG), on quoting the depository number CSD-57077, the names of the authors. and the journal citation.

4-Hydroxy-3-phenylsulfanyl-2-quinolones 2 and 4-hydroxy-3-sulfonyl-2-quinolones 7, which are readily accessible from 4-hydroxy-2-quinolones 1 and diphenyldisulfide or thiophenol, can be converted to 4-azido-3-phenylsulfanyl-2-quinolones 10 or 4-azido-3-phenylsulfonyl-2-quinolones 12 via 4-chloro-3-phenylsulfanyl-2-quinolones 5 or 4-chloro-3-phenylsulfonyl-2-quinolones 9, respectively. Thermolysis of the azides 1 0 and 1 2 results in a cyclization reaction to give quinolino [3,4-b] Organic azides with reactive ortho-groups such as aryl-, heteroaryl-or acyl groups are known to decompose on thermolysis or photolysis followed by a cyclization to heterocycles, either via a nitrene or an electrocyclic mechanism [2]. Mainly, this cyclization type leads to five-membered heterocycles. Two typical examples are the attack of the azide nitrogen either to the 2-position of a phenyl ring in ortho-position to the azide forming indoles [3], or by attack of the azide nitrogen to e.g. the oxygen atom of a carbonyl group in ortho-position to the azide forming isoxazoles [4]. Only in a few cases, the formation of six-membered heterocycles is reported [2], e.g. with a benzyl substituent in ortho-position of the azido group; in this way we obtained from 4-azido-3-benzyl-2-quinolones in good yields dibenzo [b,h][1,6]naphthyridin-6-ones [5]. S i m i l a r l y, the phenylsulfanyl group, Ph-S, or their oxidized variants, the phenylsulfoxide group, Ph-SO, and the phenylsulfonyl group, Ph-SO 2 , seemed to be good candidates for such a thermal azide cyclization.Recently a direct sulfenylation of 4-hydroxy-2-quinolones by the action of diphenyl disulfide has been developed in our group [6,7]. This reaction sequence was used, in this contribution, in order to obtain 4-azido-2-quinolones with phenylsulfanyl groups in 3-position as suitable starting materials for the planned thermal cyclization of azides to six-membered heterocycles. The reaction of 4-hydroxy-2-quinolones 1 with diphenyl disulfide was carried out as described in references [6,7] under basic conditions. During the reaction the thiophenolate anion was formed, which was oxidized by oxygen back to diphenyl disulfide. In contrast to the earlier described method [7], we obtained better results when the air for oxidation was not bubbled through the reaction mixture, but compressed air was blown onto the mixture with a tube ending above the surface of the reaction mixture. This was because the inlet pipe often was clogged when air was bubbled through the mixture. In this way the amount of employed diphenyl disulfide could be reduced to a halfmolar amount and the 3-phenylsulfanyl-2-quinolones 2a-c were obtained in good to excellent yields. There is also the possibility to obtain the thioethers 2 from thiophenol and 3-chloro-4-hydroxyquinolones 4 in pyridine as basic solvent in excellent yields, however this method needs two more steps.

Primary phosphines, RPH2, may be synthesized selectively by alkylation of phosphine, PH3, with alkyl halides RX (R = Me, Et, n-Bu, 2-Bu, C16H33, CH2=CH–CH2, Ph–CH2, 2-Py–CH2–CH2; X = Cl, Br) and concentrated aqueous KOH as auxilliary base in dimethylsulfoxide as a solvent or in two phase systems employing phase transfer catalysts. Under more rigorous conditions secondary phosphines R2PH (R = Me, n-Bu, CH2=CH–CH2) are also accessible in good yields. Using 1,3-dibromo(chloro)-propane or -butane diprimary phosphines H2P–(CH2)2–CHR–PH2 (R = H, Me) are obtained, while 1,4-dibromopentane in a high yield cyclization reaction leads to 2-methylphospholane (12) with a chiral C-atom in a-position.

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