Synthesis of New Heterocyclic Compounds Derived From 5,10- dihydrophenophosphazine

Synthesis of New Heterocyclic Compounds Derived From 5,10- dihydrophenophosphazine
Suad M. Al – Araji., Moayad abood Gban*
Department of Chemistry, College of Science, University of Baghdad, Baghdad, Iraq.
*Email:moayad.kban@yahoo.com
Iraqi Journal of Science, 2015, Vol 56, No.1A, pp: 12-24
http://www.iasj.net/iasj?func=fulltext&aId=99208

Iraqi Journal of Science

المجلة العراقية للعلوم

 

 




Abstract:
This work comprises the synthesis of 18 new N- substituted 5,10- dihydrophenophosphazine.The diphenylamine was chosen as the starting material , which was reacted with phosphorus trichloride at elevated temperature (200-220)0C for 6 hrs, followed by treating the reaction mixture with water to yield 5,10- dihydrophenophosphazine-10-oxide(1), this was reacted with ethylchloroacetat to obtain ethyl(5,10-dihydrophenophosphazine-10- oxide)acetate(2). Compound (2) was converted to acid hydrazide by treating with hydrazine hydrate( 98% ) to obtain 5-(5,10-dihydrophenophosphazine) acetohydrazide-10-oxide (3). The acid hydrazid was used to react with phenylisocyanat , phenylthioisocyanat to give (4,7) respectively which were used to prepare different heterocyclic compounds. Compound (5) was performed by the intramolecular cyclization of (4) in the presence of NaOH(2N).Compound (8) was synthesized by interaction of (7) with NaOH(2N).Compound (6) and (9) were obtaind upon the reaction of semicarbazide (4) and thiosemicarbazide (7) with phosphoric acid at 1200C. Compound (3) undergoes the character condensation reaction with different aromatic aldehyde in ethanol gave the shiff bases (10-18).
5-N-Ethyl (5, 10-dihydrophenophosphazine-10-oxide) acetate (2)
Amixture of 5,10-dihydrophenophosphazine-10-oxide(1),(5g,0.027mol) ethylchloroacetate (3.5ml,0.027 mol) in dry acetone (5 ml) and anhydrous K2CO3 (0.5 g) was refluxed for 24 h, then cooled ,filtered and solvent removed under reduced pressure. The resulting solid was monitored by (T.L.C) and recrystallized from ethanol.

Result and discussion
5,10-dihydrophenophosphazine-10-oxide(1) was prepared by the reaction of diphenylamine and phosphorus trichloride at 2200C followed by hydrolysis of the mixture with hot water [11] show figure 1.Compound(1) was treated with ethylchloroacetate to give N- ethyl(5,10dihydrophenophosphazine- 10-oxide)acetate(2)which was characterized by T.L.C, m.p , 1HNMR and FTIR spectrum figure 2 showed stretching bands at (3186- 3093) cm -1 for aromatic (C-H)., 2977 cm-1 for aliphatic (C-H) ., 2322 cm-1 (P-H).,1751cm-1 for ester(C=O).,(1612-1591-1520) cm-1 for (C=C) aromatic and bending band at 1465 cm-1 for (N-H) [12-14] see table2.

 

 

Iraqi Journal of Science

المجلة العراقية للعلوم

University of Baghdad, College of Science, Department of Chemistry, Karada, Baghdad,








KARADA

A view above karrada - view is taken to Baghdad's Karrada over from a military plane,

- منظر ماخوذ لبغداد من فوق الكرادة من طائرة عسكرية

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Synthesis, characterization and reactivity of a six-membered cyclic glycerol carbonate bearing a free hydroxyl group

Five- and six-membered cyclic carbonates have recently become popular as starting materials for the synthesis of polycarbonates via ring opening polymerization or synthesis of environmentally friendly non-isocyanate polyurethanes. In many cases a five-membered glycerol carbonate has been used in these applications. However, the simplest derivative of glycerol, a six-membered cyclic glycerol carbonate (5-hydroxy-1,3-dioxan-2-one), has not been reported so far. In this work, for the first time, we report a procedure for the synthesis of this monomer from glycerol. The product was characterized by ¹H NMR, ¹³C NMR, and FTIR spectroscopy and X-ray diffraction measurements. Further, the synthesis of bis(2-oxo-1,3-dioxan-5-yl) sebacate, a biscyclic six-membered carbonate, was described. The reactivities of 5-hydroxy-1,3-dioxan-2-one and its biscyclic ester derivative were investigated. No ring opening polymerization of both the monomers was observed, instead an isomerization to appropriate five-membered cyclic carbonates occurred. Unfortunately, the protection of the hydroxyl group 2with an ester type substituent does not protect it against isomerisation

Synthesis, characterization and reactivity of a six-membered cyclic glycerol carbonate bearing a free hydroxyl group

M. Tryznowski,*^a   Z. Żołek-Tryznowska,^b   A. Świderska^a and  P. G. Parzuchowski^a  

*Corresponding authors

^aFaculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
E-mail: tryznowski@ch.pw.edu.pl

^bFaculty of Production Engineering, Warsaw University of Technology, Narbutta 85, 02-524 Warsaw, Poland

Green Chem., 2015, Advance Article

DOI: 10.1039/C5GC01688F.......http://pubs.rsc.org/en/Content/ArticleLanding/2015/GC/C5GC01688F?utm_source=feedburner&utm_medium=feed&utm_campaign=Feed%3A+rss%2FGC+%28RSC+-+Green+Chem.+latest+articles%29#!divAbstract

Paweł Parzuchowski

Warsaw University of Technology Faculty of Chemistry ul. Noakowskiego 3, 00-664 Warszawa, Poland Phone: +48 22 234 7317. E-mail: pparzuch@ch.pw.edu.pl

faculty of Chemistry, Warsaw University of Technology, Noakowskiego

//////faculty of Chemistry, Warsaw University of Technology, Noakowskiego







 Mozambique • Inhambane

more.......
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Fused [small beta]-carbolines

Visible-light photoredox catalysis: direct synthesis of fused [small beta]-carbolines through an oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade in batch and flow microreactors

Org. Chem. Front., 2015, 2,1308-1312
DOI: 10.1039/C5QO00207A, Research Article

D. Chandrasekhar, Satheesh Borra, Jeevak Sopanrao Kapure, Ghule Shailendra Shivaji, Gannoju Srinivasulu, Ram Awatar Maurya
Fused [small beta]-carbolines were synthesized via a visible light photoredox catalyzed oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade in batch and flow microreactors.

http://pubs.rsc.org/en/Content/ArticleLanding/2015/QO/C5QO00207A#!divAbstract

Fused β-carbolines were synthesized via a visible light photoredox catalyzed oxidation/[3 + 2] cycloaddition/oxidative aromatization reaction cascade in batch and flow microreactors.

Several structurally diverse heterocyclic scaffolds were obtained in good yields by coupling of tetrahydro-β-carbolines with a variety of dipolarophiles under photoredox multiple C–C bond forming events.

The photoredox coupling of tetrahydro-β-carboline with 1,4-benzoquinone was significantly faster in continuous flow microreactors and the desired products were obtained in higher yields compared to batch reactors.

Synthetic procedures General experimental procedures for the synthesis of N-alkylated of tetrahydro-β-carbolines 1a-f: In a 25 mL round bottom flask, tryptoline (86 mg, 0.5 mmol), α-halo carbonyls (0.5 mmol), Et3N (50 mg, 0.5 mmol) and CH2Cl2 (5 mL) was taken and the reaction mixture was stirred at ambient temperature for 2 h. Next the reaction mixture was diluted with CH2Cl2 (15 mL) and washed with water. The organic layer was dried over anhydrous Na2SO4 and evaporated to yield a crude product which was purified by silica-gel column chromatography using ethyl acetate/hexane in increasing polarity to yield compounds 1a-f.

General experimental procedures for the visible light photoredox catalyzed coupling of Nalkylated of tetrahydro-β-carbolines 1a-f with dipolarophiles 2a-g under batch conditions: In a 25 mL round bottom flask, tetrahydro-β-carbolines 1a-f (0.1 mmol), dipolarophiles 2a-g (0.1 mmol), [Ru(bpy)3Cl2]·6H2O (0.5 mol%) and MeCN (5 mL) was taken. The reaction vessel was kept at a distance of 10 cm (approx.) from a visible light source (11W white LED bulb) and the reaction mixture was stirred in open air condition until the reaction was complete (TLC). Next the reaction mixture was concentrated to give a crude product which was purified Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers. This journal is © the Partner Organisations 2015 by silica-gel column chromatography using ethyl acetate/hexane in increasing polarity to yield compounds 3a-n

General experimental procedures for the visible light photoredox catalyzed coupling of Nalkylated of tetrahydro-β-carbolines 1a with dipolarophiles 2a in flow microreactors: A solution of tetrahydro-β-carboline 1a (0.2 mmol) and dipolarophile 2a (0.2 mmol) in MeCN (5 mL) was kept in one syringe and the solutions of photocatalyst [Ru(bpy)3Cl2]·6H2O (0.001 mmol in 5 mL MeCN) and t-BuOOH (2 mmol in 2 mL MeCN) were taken in two separate syringes. All the three solutions were pumped via two syringe pumps and mixed on an Xjunction and flown through the capillary microreactor wrapped over a visible light source (11W white LED bulb). Under stable conditions, exactly 6 mL of the reaction mixture was collected, concentrated to yield a crude product which was purified by silica-gel column chromatography using ethyl acetate/hexane in increasing polarity to yield compounds 3a

     

D. Chandrasekhar,^a   Satheesh Borra,^a  Jeevak Sopanrao Kapure,^b   Ghule Shailendra Shivaji,^b  Gannoju Srinivasulu^b and   Ram Awatar Maurya*^ac  

*Corresponding authors

^aDivision of Medicinal Chemistry and Pharmacology, CSIR-Indian Institute of Chemical Technology, Hyderabad-500007, India
E-mail: ramaurya@iict.res.in

^bNational Institute of Pharmaceutical Education and Research, Balanagar, Hyderabad-500035, India

^cAcademy of Scientific and Innovative Research, New Delhi 110025, India

Org. Chem. Front., 2015,2, 1308-1312

DOI: 10.1039/C5QO00207A

Ram Awatar Maurya

PhD

INSPIRE FACULTY

Indian Institute of Chemical T..., Hyderabad · Medicinal Chemistry and Pharmacology Division (IICT)

RESEARCH EXPERIENCE

 Mar 2012–Jun 2012, PostDoc Position

• Pohang University of Science and Technology · Department of Chemical Engineering · Prof Dong Pyo Kim
  South Korea · Andong
• Sep 2009–Feb 2012, Post Doctoral Fellow
  Chungnam National University
  South Korea · Daejeon

 

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