Search

Novel synthetic route for phosphanylidene-benzothiophenethione, benzothiaphosphinine-4-thione, triphenylphosphoranylidenecyclobutane and benzodithiolylidenephosphonate derivatives has been proposed...

The reactions of bis(diphenylphosphino)alkanes with benzophenone, bis(piperidinocarbonyl)diazene, isatin, and quinoxaline1,4-di- N-oxide have been studied and the products characterised by elemental analysis and spectroscopic measurements.

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.

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.

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.

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

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.

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.

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.

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.

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.

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.

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.

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.

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.

The reaction of 2-benzylidene-1,3-diphenylpropanetrione (1a) with phosphorus ylides 2a–c afforded the new phosphonium ylides 4a–c. Trialkyl phosphites 3a–c react with 1a to give the respective dialkyl phosphonate products 5a–c. On the other hand, the olefinic compounds 6 and 7 were isolated from the reaction of 1b with Wittig reagents 2. Moreover, trialkyl phosphites reacted with 1b to give products 8a–c. Possible reaction mechanisms are considered, and the structural assignments are based on analytical and spectroscopic evidence. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:57–64, 2000