Search

3-Imino-1-methyl-indolin-2-one (2a) reacts with phosphorus hexamethyltriamide 1(1:1 mol) in dry toluene at room temperature to give the dimeric spirophospholane 4a. On the other hand, the reaction of 3-(4-arylimino)-1-methylindoline-2-ones 2b–2c with trisdimethylaminophosphine 1 in boiling toluene gave phosphoramides 4b and 4c. Furthermore, 1-benzyl-3-(4-arylimino)indolin-2-ones 3a–3c react with aminophosphine 1 in excess as solvent at 110 °C for 6–8 h to give phosphonamides 5a–5c. Possible reaction mechanism are considered and the structural assignments are based on spectroscopic data and x-ray analysis.

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.

Trisdimethylaminophosphine reacts with 2-benzamido-N-arylidene-3-aryl-acrylohydrazide to give phosphoryl benzamide and phosphoryl-cyano-benzamide adducts depending on the reaction conditions. Moreover, 1-aryliden-amino-2-phenyl-4-aryliden-2-imidazolin-5-ones react with trisdialkylaminophosphines to yield tetraalkylphosphonic diamide adducts. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic evidence and X-ray analysis.

4-Benzylidene-2-phenyl-5(4H)-oxazolones react with Wittig-Horner reagents in the presence of alcoholic sodium alkoxide to give novel dioxopyrrolidinephosphonates, diethyl [3-(benzoylamino)- 1-cyano-2-oxo-4-phenylbut-3-en-1-yl]phosphonate and phosphonoalkenoate derivatives. Both the phosphonate adducts and the ester products were also isolated from the reaction of oxazolones with triethyl phosphonoacetate using alcoholic sodium ethoxide and/or sodium hydride as a base. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic results. The biological evaluation of the new compounds is reported.

The reaction of 5-aroyl-1,2,4-triazin-6(1H)-ones 2a, 2b with methoxycarbonyl-, ethoxycarbonyl-, methylenetriphenylphosphorane ( 1a,1b ) gave olefinic adducts 4a-4d , pyranotriazine products 5a-5d , and triphenylphosphine oxide. Moreover, benzoylmethylenetriphenylphosphorane ( 1c ) reacts with 5-[(4-methoxyphenyl) carbonyl]-3-phenyl-1,2,4-triazin-6(1H)-one ( 2b ) to yield 4e and triphenylphosphine oxide. On the other hand, the application of phosphorus ylides on 5-[(hydroxyimino) (4-methoxyphenyl)methyl]-3-phenyl-1,2,4-triazin-6(1H)-one ( 3b ) render the new product tetraazabenzocyclohepten-8-one oxide 6 , and triphenylphosphine oxide. Trimethylphosphonoacatate 7 reacts with 5-aroyl-1,2,4-triazin-6(1H)-ones 2a, 2b to afford 5,6-dihydro-5-hydroxy-3,5-diarylpyrano[3,2-e][1,2, 4]-triazin-7-ones 8a, 8b and alkylated adducts 9a, 9b . Moreover, 5-[(hydroxyimino)aryl methyl]-3-phenyl-1,2,4-triazin-6(1H)-ones 3a, 3b react with Wittig-Horner reagent to give alkylated products 10a, 10b and isoxazolo [4,5-e]-1,2,4-tr...

The reaction of 3-amino-2-phenyl-4(3H)-quinazolinone with oxovinylidenetriphenylphosphorane afforded 5-phenylpyrazolo[1,5-c] quinazoline-2(3H)-one and triphenylphosphine oxide. On the other hand, when quinazolinone reacts with phosphorus ylides, the corresponding phosphorane adducts were obtained. Moreover, quinazolinone reacts with trisdialkylaminophosphines to give the new (dialkylamino)oxophosphonium dipolar products. Possible reaction mechanisms are considered and the structural assignments are based on analytical and spectroscopic results.

The reaction of dibenzoyldiazine with phosphorus ylides afforded the new 2-[(benzoylhydrazono)phenylalkyl]but-2-enedioic acid dialkylesters. Moreover, ethyl-2(triphenylphosphoranylidene)propionate reacts with dibenzoyldiazine to give the olefinic compound and triphenylphosphine oxide. On the other hand, oxovinylidene-triphenylphosphorane reacts with dibenzoyldiazine to give a new phosphorane adduct. Trialkyl phosphites react with dibenzoyldiazine to yield the dialkyl phosphonate products. The reaction of dibenzoylhydrazide with Wittig reagents gave rise to the new 3,7-diphenylpyrazolo[1,2-α]pyrazole-1,5-diones. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic results.

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.

N-Phenyliminophosphorane (1) reacts with 9,10-phenanthrenequinone (2a) to give the new products 2-phenylphenanthro[9,10-d][1,3,2]dioxazole (4a) and (10Z)-10-(phenylimino)-9(10H) phenanthrenone (4b). The reaction of 1 with 1,2-naphthoquinone (2b) afforded both the dioxazole derivative 5a and the known 2-anilino-naphthoquinone-1,4-anil (5b). On the other hand, 2,6-di-tert-butyl-2,3-diphenyl-2,3-dihydro-1,2,3-benzoxadiazole (6) was obtained from the reaction of (2c) with phosphinimine (1). Application of reagent 1 on 2d and 2e renders (6E)-2,3,4,5-tetrahalogeno-6-(phenylimino)-2,4-cyclohexadien-1-one 7a and 7b, respectively. Moreover, p-quinones (3a–3c) react with phosphinimine (1) to yield products 8, 9 and 10, respectively. 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.

Dimeric spirophospholane (III), phosphoramides (V), and phosphonamides (VII) are obtained in reactions of isatin imines (I), (IV), (VII) with iminophosphine.

The reaction of 1,3-diphenyl-2-(phenylimino)-3-(ylidenemethyl-acetate)-1-propanone (5) with trisdialkylaminophosphines (6a,b) in refluxing toluene afforded the new oxazaphospholene products (7a–b). On the other hand, the cyclic azaphospholene adducts 8a–b were isolated from the reaction of 5 with 6a,b without solvent. Trialkyl phosphites 1b–c react with compound 5 to give the respective dialkyl phosphate products (9a,b). Moreover, trisdialkylaminophosphines (6a,b) react with 2a and 2b to give the dipolar adducts 10a,b and the phosphonate products 11a,b, respectively. Possible reaction mechanisms are considered, and the structural assignments are based on compatible analytical and spectroscopic results. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:511–517, 2001

5-{[(1E)-(4-methoxyphenyl)methylene]amino}-1,3,4-thiadiazole-2-thiol (1a) reacts with trialkyl phosphites (2a–c) to give the respective dialkyl phosphonate adducts (4a–c). On the other hand, the reactions of trisdialkylaminophosphines (3a,b) with 1a, 5-{[(1E)-(4-phenyl)methylene]amino}-1,3,4-thiadiazole-2-thiol (1b) yield the corresponding open dipolar structures 6a–c. In the case of the reaction of triethyl phosphite (2a) with 1b, both the dialkyl phosphonate adduct (7) and the dipolar product (8a) are obtained. Moreover, triisopropyl phosphite (2c) reacts with 1b to give both the S-alkyl and the N-alkyl phosphonate adducts (9a,b), respectively. Mechanisms are proposed to explain the formation of the new products, and their structures were confirmed on the basis of elemental analysis and spectral studies. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:594–601, 2001

Carbomethoxymethylene and carbethoxymethylene triphenylphosphoranes (1a, b) react with 1,2-naphthoquinone-1-benzimide (8) to give the corresponding 1-benzoylimino-1H-naphthalen-2-ylidene-acetic esters 9a,b and 2-(1-benzoylamino-naphthalen-2-yl)-but-2-enedioic esters 10a,b together with 1-benzamido-2-naphthol (11). Application of Wittig-Horner reagents 4a,b on 8 at room temperature and in the presence of alcoholic sodium alkoxide renders 2-(1-benzoylamino-naphthalen-2-yl)-3-phosphonylsuccinic esters 12a,b. Conducting the reaction in refluxing toluene and in the presence of sodium hydride led to the formation of 2-benzamido-naphthol-1-ethyl ether (13). 1-Benzamido-2-naphthol (11) was also isolated from both reaction media. Trimethyl and dimethyl phosphites (7a,b) react with 8 to 14 as the sole product. 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.

The reaction of methoxycarbonylmethylene 2b- and ethoxycarbonylmethylene 2c-triphenylphosphoranes with substituted 2-amino-1,4-naphthoquinones 1a-c afforded the new pyrroline-ylidphosphoranes 3b-3g via 1,2- and 1,4-addition reactions. On the other hand, 2-dimethylamino-1,4-naphthoquinone 1d reacts with cyanomethylenetriphenylphosphorane 2d to give adduct 4. Mechanisms accounting for the formation of the new products are discussed.

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 reagents (1a–c) react with N-(phenylsulfonyl)-1,4-benzoquinone monoimine 2a to give adducts 3a, 4a, and 4b. On the other hand, the reactions of 2b with the same ylides (1a–c) yield the new products 3b, 6a, and 6b, respectively. Mechanisms accounting for the formation of the new products are discussed and the probable structures of the products are presented, based on compatible analytical and spectral data.

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.

2, 4-Bis-(4-methoxyphenyl)-1, 3, 2, 4-dithiadiphosphetane-2, 4-disulfide [Lawesson reagent (LR)] 1 reacts with p-quinone monoimine-2a to give the novel benzo-1,3,2-oxathiaphosphol-5-(methanesulfonamido)-2-(4-methoxyphenyl)-2-sulfide 4. On the other hand, the reaction of 2b and 3 with LR 1 leads to the formation of the benzo- and the naphtho-1,3,2-dithiaphosphol-5 -(benzenesulfonamido)- 2- (4-methoxyphenyl) -2-sulfide 5, 6. Thiation of 2a, 2b, and 3 with P4S10 yields phenoxathiin derivatives 8a, 8b, and 9, respectively. The identity of the new products is established from analytical and spectroscopic evidence.

Diethyl phosphite 2a reacts with N- (phenylsulfonyl) - 1,4 - benzoquinone monoimine 1a to give 1,4-diethyl [(2-hydroxy-5-[(phenylsulfonyl) amino ] phenyl] [sphosphonate 3a, diethyl (1-hydroxy -4- [ ( phenylsulfonyl ) imino ] -2,5-cyclohexadiene )] phosphonate 3b and amide 3c , respectively. When quinone monoimine 1a was reacted with dimethyl and diisopropyl phosphites (2b,c), the corresonding dialkyl phosphonate adducts (bd3e) and (bd3f) were obtained. Whereas quinone monoimine (bd1b) is reduced mainly to amide (bd4b) when treated with diethyl phosphite (bd2a) , it reacts with dimethyl phosphite (bd2b) to give the dialkyl phosphonate adduct (bd4a) together with amide (bd4b) . Possible reaction mechanism are considered and the structural assignments are based on compatible analytical and spectroscopic results.

Trimethyl phosphite (2a) reacts with N-(phenylsulfonyl)-1,4-benzoquinone monoimine (1a) to give the respective phosphonate 3c, phosphates 3d, 3e and the alkylated products 3a and 3b. The reaction of triethyl phosphite (2b) with the same quinone imine 1a yields only the phosphate adduct 3f and the amide 3g. Triisopropyl phosphite (2c) reacts with 1a to form the alkylated product 3h. Trimethyl phosphite (2a) gives the phosphate 4a on reaction with N-(methylsulfonyl)- 1,4-benzoquinone monoimine (1b). In case of the reaction of triethyl and triisopropyl phosphites (2b, c) with 1b only the respective alkylated products 4b–d are obtained. A mechanism is proposed to explain the formation of the new adducts.

Trimethyl phosphite (2a) reacts with N-(phenylsulfonyl)-1,4-benzoquinone monoimine (1a) to give the respective phosphonate 3c, phosphates 3d, 3e and the alkylated products 3a and 3b. The reaction of triethyl phosphite (2b) with the same quinone imine 1a yields only the phosphate adduct 3f and the amide 3g. Triisopropyl phosphite (2c) reacts with 1a to form the alkylated product 3h. Trimethyl phosphite (2a) gives the phosphate 4a on reaction with N-(methylsulfonyl)- 1,4-benzoquinone monoimine (1b). In case of the reaction of triethyl and triisopropyl phosphites (2b, c) with 1b only the respective alkylated products 4b–d are obtained. A mechanism is proposed to explain the formation of the new adducts.

2, 4-Bis-(4-methoxyphenyl)-1, 3, 2, 4-dithiadiphosphetane-2, 4-disulfide [Lawesson reagent (LR)] 1 reacts with p-quinone monoimine-2a to give the novel benzo-1,3,2-oxathiaphosphol-5-(methanesulfonamido)-2-(4-methoxyphenyl)-2-sulfide 4. On the other hand, the reaction of 2b and 3 with LR 1 leads to the formation of the benzo- and the naphtho-1,3,2-dithiaphosphol-5 -(benzenesulfonamido)- 2- (4-methoxyphenyl) -2-sulfide 5, 6. Thiation of 2a, 2b, and 3 with P4S10 yields phenoxathiin derivatives 8a, 8b, and 9, respectively. The identity of the new products is established from analytical and spectroscopic evidence.

Carbomethoxymethylene and carbethoxymethylene triphenylphosphoranes (1a, b) react with 1,2-naphthoquinone-1-benzimide (8) to give the corresponding 1-benzoylimino-1H-naphthalen-2-ylidene-acetic esters 9a,b and 2-(1-benzoylamino-naphthalen-2-yl)-but-2-enedioic esters 10a,b together with 1-benzamido-2-naphthol (11). Application of Wittig-Horner reagents 4a,b on 8 at room temperature and in the presence of alcoholic sodium alkoxide renders 2-(1-benzoylamino-naphthalen-2-yl)-3-phosphonylsuccinic esters 12a,b. Conducting the reaction in refluxing toluene and in the presence of sodium hydride led to the formation of 2-benzamido-naphthol-1-ethyl ether (13). 1-Benzamido-2-naphthol (11) was also isolated from both reaction media. Trimethyl and dimethyl phosphites (7a,b) react with 8 to 14 as the sole product. 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.

The reaction of 1,3-diphenyl-2-(phenylimino)-3-(ylidenemethyl-acetate)-1-propanone (5) with trisdialkylaminophosphines (6a,b) in refluxing toluene afforded the new oxazaphospholene products (7a–b). On the other hand, the cyclic azaphospholene adducts 8a–b were isolated from the reaction of 5 with 6a,b without solvent. Trialkyl phosphites 1b–c react with compound 5 to give the respective dialkyl phosphate products (9a,b). Moreover, trisdialkylaminophosphines (6a,b) react with 2a and 2b to give the dipolar adducts 10a,b and the phosphonate products 11a,b, respectively. Possible reaction mechanisms are considered, and the structural assignments are based on compatible analytical and spectroscopic results. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:511–517, 2001

N-Phenyliminophosphorane (1) reacts with 9,10-phenanthrenequinone (2a) to give the new products 2-phenylphenanthro[9,10-d][1,3,2]dioxazole (4a) and (10Z)-10-(phenylimino)-9(10H) phenanthrenone (4b). The reaction of 1 with 1,2-naphthoquinone (2b) afforded both the dioxazole derivative 5a and the known 2-anilino-naphthoquinone-1,4-anil (5b). On the other hand, 2,6-di-tert-butyl-2,3-diphenyl-2,3-dihydro-1,2,3-benzoxadiazole (6) was obtained from the reaction of (2c) with phosphinimine (1). Application of reagent 1 on 2d and 2e renders (6E)-2,3,4,5-tetrahalogeno-6-(phenylimino)-2,4-cyclohexadien-1-one 7a and 7b, respectively. Moreover, p-quinones (3a–3c) react with phosphinimine (1) to yield products 8, 9 and 10, respectively. 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.

Trisdimethylaminophosphine reacts with 2-benzamido-N-arylidene-3-aryl-acrylohydrazide to give phosphoryl benzamide and phosphoryl-cyano-benzamide adducts depending on the reaction conditions. Moreover, 1-aryliden-amino-2-phenyl-4-aryliden-2-imidazolin-5-ones react with trisdialkylaminophosphines to yield tetraalkylphosphonic diamide adducts. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic evidence and X-ray analysis.

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.

The reactivity of the novel compound ethyl (2-phenylquinazolin-4-oxy)-acetate (1), towards carbon electrophiles and nitrogen nucleophiles is described. Reaction of (2-phenylquinazolin-4-oxy)acetic hydrazine (5) with carbon electrophiles is also investigated. Futhermore, the behaviour of 4-chloro-2-phenylquinazoline (6) towards a variety of nitrogen and carbon nucleophiles is studied.

The reaction of methylenetriphenylphosphoranes (1) with N,N′-3,5-cyclohexadiene-1,2-diylidenebis [benzamide] (2) afforded new ylid-phosphoranes of type 3. The mechanism that accounts for formation of adducts 3 is discussed. Structural reasoning for compounds 3 was based on compatible analytical, chemical and spectroscopic results.

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.