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The reaction of 1,1-bis(diphenylphosphino)methane with substituted o-quinones afforded the novel 6-[bis(diphenylphosphoryl)methyl]-, and 6-bis(diphenyl phosphoryl)methylidene derivatives. Moreover, 1,1-bis(diphenylphosphino)methane reacts with 3,4,5,6-tetrabromo-o-benzoquinone to give only the new 6-[bis(diphenylphosphoryl)methyl] derivative. Mechanisms accounting for the formation of the new products are discussed. The antimicrobial activity of some of the newly synthesized compounds was also examined.

The reaction of 5(4H)-pyrazolone with phosphorus ylides afforded new triphenylphosphanylidene alkanone derivatives. Moreover, its benzylidene derivative reacted with Wittig–Horner reagents to give the corresponding dialkoxyphosphoryl, alkyl phosphonate, and heterocyclic products. Treatment of pyrazole-4-carbaldehyde with Wittig–Horner reagents and trialkyl phosphites gave the respective alkyl phosphonate adducts. Mechanisms accounting for the formation of the new products are discussed. The biological activity of some of the newly synthesized compounds was also examined.

The reaction of 1,2-bis(diphenylphosphino)ethane with substituted o-benzo-quinones afforded new bis(6-hydroxycyclohexa-2,4-dienone) derivatives. Treatment of the same reagent with o-naphthoquinone, phenanthrenequinone, and acenaphthenequinone gave the respective bis(diphenylphosphoryl)ethylidenes or diacenaphthylenone derivatives. On the other hand, p-quinones react with 1,2-bis(diphenylphosphino)methane to yield the corresponding 4-hydroxycyclohexa-2,5-dien-1-ones. Possible reaction mechanisms are considered and the structural assignments are based on compatible analytical and spectroscopic data.

3-(Hydroxyimino)pentane-2,4-dione reacts with phosphonium ylides, Wittig–Horner reagents, trialkyl phosphites, and Lawesson's reagents to give the olefinic and cyclic products, the phosphonate adducts, the dialkyl phosphate products, the phosphinodithioic acid, and 2,4-dithione products, respectively. Furthermore, the reaction of 3-(phenylimino)pentane-2,4-dione with Wittig, Wittig–Horner reagents and trialkyl phosphite resulted in the formation of 2,5-diendioate, diethoxy phosphoryl hexanoate and the phosphate products. Possible reaction mechanisms are considered and the structural assignments are based on analytical and spectroscopic results. The antibacterial and antifungal activities for some of the new compounds are also reported.

1,1′-(Azodicarbonyl)dipiperidine reacts with tris(dimethylamino)phosphine, trialkyl phosphites, phosphorus ylides, and Lawesson's reagents to give the phosphorodihydrazidic amide, oxadiazole, dihydropyridazine, ethylenic, and thicarbonyl products, respectively. The antibacterial and antifungal activities for the new compounds are reported. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Biological Evaluation.

1,3,2,4-Dithiadiphosphetane-2,4-disulfide and its p-phenoxy derivatives react with 2-indanone-, 1-indanone-oxime, and tetralone oxime at different reaction temperatures to give 1,3,2-dithiaphosphetane-2-sulfide, dimeric compounds, 1-thioxo-1H-inden- phosphinodithioic acid, and 1,3,5,2-trithiaphosphorine. Compatible analytical and spectroscopic results were obtained for all the new compounds.

The reaction of 2,6-bis(benzylidene)cyclohexanones with dialkylphosphonates and tris(dialkylamino)phosphines afforded the new benzoxaphosphole derivatives (5a–5d) and (9a–9f). The biological activity of the newly synthesized compounds was also examined. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic results. The structure of the new benzoxaphosphole 5a was confirmed by a single crystal X-ray determination.

1,2,3,4-tetrahydro-1-naphthylidene-malononitrile (1) reacts with carbethoxymethylene and carbmethoxymethylene- triphenylphosphoranes (2a, 2b) to give the new phospho-ranylidenecyclopentaylidene products (4a, 4b, and 5), respectively. The treatment of (1) with phosphorus ylide 2c afforded the new phosphonium ylide 6. Moreover, the application of reagent (2d) on (1) renders compound 7. On the other hand, when N-phenyliminotriphenylphosphorane (3) reacts with (1), the corresponding adduct (8) was obtained together with triphenylphosphine. Mechanisms accounting for the formation of new products are discussed, and probable structures of products are presented based on analytical and spectroscopic data.

Thiohydantoin 1 reacts with 2-oxovinylidenetriphenylphosphorane (2) to give 1-methyl-2-thioxo-6-(triphenyl-λ5-phosphoranylidene)-hexahydro-furo[2,3-d]imidazol-5-one (5). On the other hand, when 1 reacts with phosphorus ylides 3a–d, the respective olefinic adducts 6a, 6b, 8, and the dimeric product 7 were obtained together with triphenyl-phosphine oxide. Moreover, the application of reagent 4 on 1 renders the new product 4-methyl-2,3-diphenyl-2,3,4,6-tetrahydro-1-oxa-1,3,4,6-tetra-azapentalene-5-thione. Mechanisms accounting for the formation of the products are presented based on analytical and spectroscopic data.

3,4-Diphenyl-5-cyanopyridazine-6-thione (1) reacts with carbethoxy-methylene and carbmethoxymethylene-triphenylphosphoranes (2a,b) to give both the olefinic compounds (3a,b) and 3,4-diphenyl-6-alkoxyfuro-[3,2-c]-pyridazines (4a,b) respectively. Treatment of 1 with phosphorus ylide (2c) afforded only the new furopyridazine (4c). On the other hand, when (1) reacts with diphenylmethylenetriphenylphosphorane (2d), adduct (5) was obtained together with triphenylphosphine. Moreover, application of reagent (2e) on (1) renders the new product 3,4-diphenyl-6-(phenylimino)-5-cyanopyridazine (6). Mechanisms accounting for the formation of the new products are discussed and the probable structures of the products are presented based on analytical and spectroscopic data.

Wittig-Homer reagent 1a reacts with 2-nitroso-1-naphthol 3 to give the olefinic adduct 5, the alkylated product 4 and the dimeric compound 6. When 2-nitroso-1-naphthol 3 reacts with Wittig- Homer reagents 1b,c. the corresponding phosphonate adducts 8a,b together with compounds 4 and 6 were obtained. Oxovinylidenetriphenylphosphorane 2 reacts with 3 to give the corresponding phosphoranylidenecyclobutylidene adduct 10 and triphenylphosphine oxide. The structural assignments of the new products are based on compatible analytical and spectroscopic results.

Wittig-Horner reagents (1a–c) react with o-quinone diimine (2a) to give the respective phosphonate adducts (3a–c) and the alkylated product 4. The reaction of p-quinone diimine (2b) with the same reagents yield adducts 5, 6 and 7, respectively. Structural reasoning for the new compounds was based on compatible analytical and spectral data. The mechanism that accounts for formation of adducts 3 is illustrated in Scheme 2.

Cyanomethylenetriphenylphosphorane (1) reacted with 1,4-naphthoquinone 1 to give the new ylid-phosphorane adduct 4 and the dimeric product 5. Reaction of acenaphthenequinone (2) with phosphorus ylide I afforded compounds 6 and 7. On the other hand, ylide I reacts with phenanthrenequinone (3) yielding adducts 8, 9 and 10, respectively. Structural reasoning for the new products was based on compatible analytical and spectral data (IR, 1H, 31P-NMR and MS). The mechanism that accounts for the formation of the new adducts is discussed.

Wittig-Horner reagents (2a-c) react with 5-(4-pyridyl)-2-thiono-1,3,4-oxadiazole (1) yielding the new adducts (3a-c). Structural reasoning for compounds 3 was based on compatible analytical and spectral data. The mechanism that accounts for the formation of 3 is discussed.

Naphthalenone 1 reacts with tris(dialkylamino)phosphines 3 in refluxing benzene to give the corresponding 1,2-dihydro-2-dialkylamino-1,1-diphenylnaphth[1,2-d-][1, 2]oxaphosphine-2-oxides (7a, b). Reaction of 1 with 3a in boiling methanol affords the oxaphosphole 8 and adduct 9. The oxaphosphine 11 is obtained upon reacting 1 with ethyldiphenylphosphinite (10). Naphthalenone 2 reacts with 3a to give triaminodioxyphosphorane 13. Pyrolysis of 13 yields 2 and aminophosphine 3a. Upon reacting 2 with 10, adduct 14 is obtained. Structural assignments are based on analytical, chemical and spectroscopic evidence.

Methylenetriphenylphosphoranes (IIa, b) react with 1,4-naphthoquinonemonobenzenesulfonimine (I) yielding the new azapropane adduct IIIa together with the dimeric adducts IIIb, IIIc, and IIId. Structures of the new products were established by analytical and spectroscopic (IR, 1H NMR, 31P NMR, 13C NMR, and MS) results. A mechanism is proposed to explain the formation of compounds III.

Tris(dimethylamino)phosphine (IIIa) and/or Bis-dimethylaminophenyl-phosphine (IIIb) react with 9,10-dihydro(9-dicyanomethylene)phenanthrene-10-one (Ib) to produce 1:1 adducts which have the aminophosphonium dipolar ion structure (V) in the crystalline state and in solutions. The 1:1 adduct isolated from the reaction of IIIb with 9,10-phenanthrenequinonemonoimine (Ic) has a similar dipolar structure (XII) in the crystalline state. Solutions of the latter contained the same molecular species (XII) in equilibrium with a cyclic aminophospholene species (XIII). Only decomposition products could be observed from the reaction of IIIa with Ic. The products in this case were the phosphoroamidate (X), 9,10-phenanthrenequinone (Ia) and phenanthroxazine XI. A mechanism is proposed to explain the formation of these compounds.

Depending upon the type of Wittig reagents, naphthalenone 1 reacts with reagents 3a and 3b to give adducts 4 and 5 respectively. Reaction of 1 with phosphacumulene 6 gives the phosphorane 7. On the other hand, naphthalenone 2 reacts with 3a and 3b to give adducts 8 and 9. The identity of the new compounds is established from analytical and spectroscopic evidences.

The reaction of carbmethoxymethylene (1a)-, carbethoxymethylene (1b)-, acetylmethylene (1c)-, and benzoylmethylene (1d)-triphenylphosphoranes with N,N′-2,5-cyclohexadiene-1,4-diylidenebis (methanesulfonamide) (IIa) and its 2-chloro-derivatives IIb afforded the new ylid-phosphoranes IIIa-g via 1,2-addition reaction. Structural reasoning for compounds 111 was based on compatible analytical and spectral data (IR, 1H NMR, 31P NMR, 13C NMR, and MS). The mechanism that accounts for formation of adducts III is discussed.

Methylenetriphenylphosphoranes (2a-b) react with N,N′-2,5-cyclohexadiene-1,4-diylidenebis [benzamide] (1) yielding the new ylid-phosphorane adducts 3a and 3b, respectively. Quinoneimine 1 is reduced mainly to p, -Phenylenedibenzamide (7) when treated with ylid 2c under similar conditions. Structures of the new products were established by analytical and Spectroscopic (IR, 1H NMR, 31P NMR, 13C NMR, and MS) results. A mechanism is proposed to explain the formation of compounds 3.

Simple, rapid and highly sensitive iodimetric amplification methods are described for the micro- and submicro-determination of antimony(III) in antibilharzial compounds. The methods are based on oxidation of the sample with an excess of periodate in acetate buffered medium, masking of the unreacted periodate with molybdate, and finally, iodimetric titration of the iodate that is released. Specific reactions have been found to occur for the four different compounds analysed owing to the presence, in the same molecule, of one or two antimony(III) and α-diol functions, both of which are oxidised quantitatively and simultaneously by periodate. Thus 3-, 9-, 15- and 18-fold amplification is achieved with triphenylstibine, tartar emetic, stibophen and diantimony piperazine tartrate, respectively. The total mean recovery is 99·49 per cent.