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Organophosphorus Compounds, XXVI* the Reaction of Diazoketones with Trialkyl Phosphites

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Organophosphorus Compounds, XXVI* the Reaction of Diazoketones with Trialkyl Phosphites Organophosphorus Compounds, XXVI* The Reaction of Diazoketones with Trialkyl Phosphites M. M. S i d k y , F. M. S o l im a n , an d A. A. E l K a t e b National Research Centre, Dokki, Cairo, Egypt (Z. Naturforsch. 32 b, 1287-1290 [1977]; received May 25, 1977) Diazoketones, Phosphites, Hydrazones, Azines Diazoketones 1, 8 , 10 and 14 react with trialkyl phosphites to give different products depending upon the structure of the diazo compound, the type of the solvent and the nature of the phosphite ester used. Possible reaction mechanisms are discussed and the structural assignements are based on analytical, chemical and spectroscopic results. Though the action of triphenylphosphine on dia­ the corresponding diazo-compound (1) (m.p., mixed zoketones, leading to phosphazines, has been ob­ m.p. and comparative IR spectra). served frequently1-4, no information in the litera­ A possible explanation for the production of ture seems to be known regarding the behaviour of l,3-indandione-2-hydrazone (4) is presented in these diazo compounds towards trialkyl phosphites. Scheme 1. Initial attack by the phosphite-phos- We have found that when 2-diazo-l,3 indandione (1), was allowed to react with trimethyl-, triethyl-, or triisopropyl phosphite, in benzene or acetonitrile solution, one and the same product was isolated in 0 £ c - n 2 . WOI3 P - (^j[^):=N-N-P(0R)3 I R = CH3 II each case. This was identified as 1,3-indandione-2- 0 0 R = C2 H5 or hydrazone (4) for the following reasons: I) The 2 a 1 R = C3 H7-i yellow crystalline product 4 gave correct combustion values corresponding to the formula C 9 H 6N2O2. II) The IR absorption spectrum of 4, in KBr, lacked ? H.OH the intense band in the 2110-2070 cm-1 region; >N-tteP(0R)3 ■£.N-N-P(0R)3 characteristic for the diazo-group stretching vibra­ H-0 J tion5. However, strong absorption bands at 3300 2 b 1 OH HCi Reduction V- -(R0)3 P=0 H-0H XOH N-NH2 0 Scheme 1 cm-1 and 3150 cm-1 (NH2)6 were present in the IR spectrum of 4. Ill) Treatment of 4 with hydrochloric phorus on 1 would give an unstable phosphorazine acid in methanol afforded bis-indandione (6), most like 2. Addition of elements of water (unavoidable probably via an intermediate formation of triketo- moisture) to the latter product would give the hydrindine hydrate (5)7-8. IV) Treatment of com­ transient intermediate 3 with pentacovalent phos­ pound 4 with mercuric oxide in THF, regenerated phorus. This collapses to yield 4. In favour of this * Dedicated to Prof. Dr. A. Schönberg on the occasion idea is the finding that compound 4 and triphenyl­ of his 85. birthday. phosphine oxide are obtained upon treatment of phosphazine (7) with acetic acid in ethanol solution; Requests for reprints should be sent to Dr. M. Sidky, a behaviour which recalls that of other phosphazines National Research Centre, Sh. E]-Tahrir, Dokki-Cairo, E gypt. towards hydrolysis9-13. Dieses Werk wurde im Jahr 2013 vom Verlag Zeitschrift für Naturforschung This work has been digitalized and published in 2013 by Verlag Zeitschrift in Zusammenarbeit mit der Max-Planck-Gesellschaft zur Förderung der für Naturforschung in cooperation with the Max Planck Society for the Wissenschaften e.V. digitalisiert und unter folgender Lizenz veröffentlicht: Advancement of Science under a Creative Commons Attribution Creative Commons Namensnennung 4.0 Lizenz. 4.0 International License. 1288 M. M. Sidky et al. • Organophosphorus Compounds 0 anthraquinone Q^>>N-N-P(C 6H5 )3 * ♦ (C6 H5 )3P-0 N-N=P(0R)3 i 0 7 ogo I 0 0 u Similarly, the reaction of 7-diazo-8-acenaphthe- 15 none ( 8 ) with the same phosphite reagents, gave acenaphthenequinonemonohydrazone (9) almost i J2 0 z 0 ^ — j - N 2 16 phosphite interaction was conducted in acetonitrile. 8 9 No reaction was observed with triethyl or triiso- propyl in benzene even after 24 h. However, using quantitatively. The identity of 9 was verified by acetonitrile, as a reaction medium, yielded anthra­ comparison of its physical properties with a reference quinone. sample14. It is evident from the results of the present in­ On the other hand, however, the reaction of vestigation that diazoketones 1, 8 ,10 and 14 behave 3-diazooxindole (10) with trimethyl, triethyl, or towards trialkyl phosphites in a manner quite dif­ triisopropyl phosphite, in benzene or acetonitrile, led ferent from PPI 13. In the latter case, stable phos- to the formation of the azine 13. The latter com­ phazines were isolated. We believe, however, that pound was identical (m.p., mixed m.p. and com­ the reaction of trialkyl phosphites with the diazo­ parative IR spectra) with an authentic specimen, ketones of the present study involves an initial prepared by hydrolysis of isatine-3-hydrazone15. phosphorazine formation, which suffers further trans­ The formation of azine 13 suggested either hydroly­ formation yielding the observed products. sis of an intermediate phosphorazine 11 to the Noteworthy to mention is that the reaction of 2-diazo-l,3-indandione (1) with trialkyl phosphites now represents a newly developed method for pre­ paring l,3-indandione-2-hydrazone (4), not available by methods known for hydrazone-formation. Experimental Materials and equipment All melting points are uncorrected. The benzene (thiophenefree) and petroleum ether (b.p. 60-80 °C) were dried over sodium. The trialkyl phosphites 17-18 were purified by treatment with sodium ribbon followed by fractional distillation. IR spectra were hydrazone 12 followed by disproportionation of the recorded in KBr discs, with a Carl Zeiss Infracord Spectrophotometer Model UR 10. The diazoketones latter or direct disproportionation of the phos­ 1, 8 , 10 and 14 were prepared by established proce­ phorazine 11 to give the azine13-16. dures. Treatment of 10-diazoanthrone (14) with the same phosphite esters gave different products de­ Action of trialkyl phosphites on 2-diazo-l,3-indandione (1) pending upon the nature of the phosphite ester A solution of the trialkyl phosphite (0.012 mole) used and/or the prevailing experimental condi­ in benzene (5 ml) was added dropwise to a suspen­ tions. sion of 1 (0.01 mole ) 19 in benzene and the mixture Thus, whilst the reaction of 14 with trimethyl kept at room temperature for 24 h. After removal phosphite, in benzene at room temperature, gave of the volatile materials under reduced pressure, the solid product, so obtained, was crystallized from anthraquinone, anthraquinone-azine (16) was main­ ethanol to give yellow crystals of 1,3-indandione- ly obtained when the 10-diazoanthrone-trimethyl 2-hydrazone (4), melting point 200 °C (75%). M. M. Sidky et al. • Organophosphorus Compounds 1289 Analysis for C9H&N2O2 Action of trialkyl phosphites on 3-diazooxindole 10 Calcd C 61.36 H 3.40 N 16.09, A mixture of 10 (0.01 mole), benzene (or aceton­ Found C 61.11 H 3.60 N 15.95. itrile) (10 ml) and the trialkyl phosphite (0.012 mole) was kept at room temperature for 24 h. After Compound 4 was also formed when the above removal of the volatile materials under reduced described procedure was performed in acetonitrile. pressure, the solid residue, left behind, was crystal­ lized from pyridine to give oxindole-azine 13 (m.p. Formation of bis-indandione-1,3-dione (6) from 4 and mixed m.p. 255 °C) (68%)15. A mixture of l,3-indandione-2-hydrazone (4) (0.17 g) in aqueous methanol (6 ml 50%) and HC1 Reaction of trimethyl phosphite with 10-diazoanthron (0.5 ml sp.gr. 1.18) was refluxed for 3h. The dark (14) brown precipitate formed, was collected and crys­ tallized from benzene to give 6 (m.p. and mixed a) In benzene: A mixture of trimethyl phosphite m.p. 297 °C)8. (0.012 mole) and 10-diazoanthrone (0.01 mole)3 in benzene (10 ml) was stirred at room temperature for 72 h. After removal of the volatile materials Oxidation of 1,3-indandione-2-hydrazone (4) under reduced pressure, the residue was washed A mixture of 4 (0.001 mole) and yellow mercuric several times with light petroleum. The solid oxide (0.0012 mole) in tetrahydrofuran (40 ml) was product was then crystallized from toluene to give stirred at room temperature for 24 h. The mixture yellow crystals of anthraquinone (m.p. and mixed was then filtered, and the filtrate was evaporated to m.p. 282 °C) (58%). dryness. The resulting solid material (yield 62%) crystallized from methanol to give yellow crystals b) In acetonitrile: This was carried out in the identified as 2-diazo-l,3-indandione (1) (m.p., manner described above. The solid product that mixed m.p. and comparative IR spectra). was isolated from the reaction mixture was crystal­ lized from pyridine and identified as anthraquinone- azine (16) (m.p. and mixed m.p. 330 °C) (64%)3. Action of acetic acid on phosphazine 7 A mixture of the phosphazine 7 (0.2 g) 1 and aqueous ethyl alcohol (5 ml 80%) containing one Action of triethyl phosphite on 10-diazoanthrone (14) drop of glacial acetic acid was boiled for 1/2 h. a) In benzene: Triethyl phosphite (0.012 mole) The yellow precipitate formed was collected and was added dropwise to compound 14 (0.01 mole) crystallized from ethanol to give 1,3-indandione- in benzene (10 ml). The mixture was kept at room 2-hydrazone (4) (m.p. and mixed m.p. 200 °C). temperature for 72 h and the solvent was evaporated in vacuo. The residual solid was washed with light Reaction of trialkyl phosphites wit 7-diazo-8- petroleum and crystallized from CCI4 to give un­ acenaphthenone (8) changed 14 (m.p.
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