Synthesis and characterization of benzyl and benzoyl

Polyhedron 25 (2006) 3526–3532 www.elsevier.com/locate/poly

Synthesis and characterization of benzyl and benzoyl substituted oxime-phosphazenes E. C ¸ il *, M. Arslan, A.O. Go¨rgu¨lu¨ Chemistry Department, Firat University, Arts and Science Faculty Chemistry, TR-23169 Elazig, Turkey Received 15 November 2005; accepted 3 July 2006 Available online 25 July 2006

Abstract Two oxime-cyclophosphazenes were prepared from hexakis(4-formylphenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphenoxy)cyclotriphosphazene (7). The reactions of these oximes with benzyl chloride, benzenesulfanoyl chloride, benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride were studied. Hexa and pentasubstituted compounds were obtained from the reaction of hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene (3) with benzyl chloride (4) and benzoyl chloride, respectively. However, the oxime groups on 3 rearranged to nitrile (5) in the reaction of 3 with benzenesulfanoyl chloride and 1-napthalenesulfanoyl chloride. Hexasubstituted compounds were also obtained from the reactions of hexakis(4-[(1)-N-hydroxyethaneimidoyl]phenoxy)cyclotriphosphazene (8) with benzoyl chloride (10), 4-methoxybenzoyl chloride (11) and 2-chlorobenzoyl chloride (12). A trisubstituted compound was obtained from the reaction of 8 with benzyl chloride (9). All the products were generally obtained in high yields. Pure and defined products could not be obtained from the reaction of 3 with 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. The structures of the compounds were defined by elemental analysis, IR, 1H, 13C and 31P NMR spectroscopy. 2006 Elsevier Ltd. All rights reserved. Keywords: Hexachlorocyclotriphosphazene; Phosphazene; Oxime; Oxime derivatives; Oxime-phosphazenes

1. Introduction Phosphazenes are the best known and most intensively studied phosphorus–nitrogen compounds [1–5]. These compounds possess a number of characteristics such as biomedical properties and applications [6–9]. Cyclophosphazene derivatives, substituted with aziridine groups, and polyphosphazene-platinum (II) conjugates were investigated as biomedical products due to their strong antitumor activity [10,11]. Antimicrobial and biological effects of some phosphazenes on bacterial and yeast cells have been studied [12–14]. On the other hand, it is known that phosphorus and nitrogen compounds are effective flame retardants for fibre materials [15]. Some other applications *

Corresponding author. Tel.: +90 4242 370000/6625; fax: +90 4242 330062. E-mail address: [email protected] (E. C ¸ il). 0277-5387/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.poly.2006.07.009

include model compounds for polyphosphazenes, starting materials for the preparation of cyclolinear and/or cyclomatrix phosphazene substrates, commercial polymers with carbon backbones containing pendant cyclophosphazene groups, inorganic hydraulic fluids and lubricants, biologically important substrates such as anticancer agents, insect chemosterilants, pesticides and fertilizers, supports for catalysts, dyes and crown ether phase transfer catalysts for nucleophilic substitution reactions, core substrates for dendrimers, thermal initiators for anionic polymerization reactions and photosensitive materials [16]. The literature contains reports on the synthesis of different linear, cyclic or poly phosphazenes [17–29]. There are also a large number of literature reports on the reactions of the functional groups on phosphazene substituents [10,30]. Typical examples of these include coupling reactions of trimeric phosphazene azides with aryloxy, alkoxy and dialkylamino cosubstituents [31], N-vinylic phosphazenes

E. Çil et al. / Polyhedron 25 (2006) 3526–3532

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with azodicarboxylic and acetylenic esters [32], oxime-phosphazene derivatives with alkyl and acyl substituents [33,34], polymers from 4-formylphenoxy [35,36], maleic [37] and 3,4-methylenedioxyphenoxy substituents [38]. In this paper, we have prepared oxime-cyclophosphazenes from hexakis(4-formylphenoxy)cyclotriphosphazene and hexakis(4-acetylphenoxy)cyclotriphosphazene, and have studied their reactions with benzyl and benzoyl halides such as benzyl chloride, benzenesulfanoyl chloride, benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. We hope that this original work is potentially an useful addition to the literature and can lead to some high polymer works.

pyridine (15 mL) for 3 h. After the reaction was complete, the mixture was allowed to cool and was slowly poured into water (100 mL) and reprecipitated twice from water. The white solid 3 was washed with alcohol and dried at 50 C in a vacuum. Yield: 83% (18.33 g). IR (cm 1): 3340 mOH, 1187 mP@N, 949 mP–O–C. 1H NMR (in acetone-d): 6.86 (d) H2 (4JPOCCH: 8.45), 7.28 (d) H3 (5JPOCCCH: 8.50), 7.96 (s) H5, 10.17 (s) H6, 7.20 (w) H2 (is.), 7.77 (w) H3 (is.); H2:H3:H5:H6 = 2:2:1:1. 13C NMR: 121.50 C2, 121.33 C2 (is.), 129.00 C3, 129.37 C3 (is.), 131.00 C4, 131.00 C4 (is.), 148.19 C5, 151.70 C1.

2. Experimental

A solution of 0.70 mL (0.77 g, 6.08 mmol) benzyl chloride in acetone (10 mL) was slowly added dropwise to a stirred and cooled (0–5 C) mixture of 3 (0.80 g, 0.84 mmol) and K2CO3 (2.00 g, 14.47 mmol) in acetone (30 mL). The reaction was carried out at room temperature for 1 h and then was refluxed for 48 h. After the reaction was complete, the precipitate was filtered off and the solvent was removed. An oily product was obtained. It was dissolved in a very small amount of acetone and was precipitated with hexane. The solvent was removed under vacuum over 96 h. A white solid 4 formed. Yield: 66% (0.83 g). IR (cm 1): 1183 mP@N, 1024 mN–O–C, 952 mP–O–C. 1H NMR (in DMSO-d): 6.95 (d) H2, 7.2–7.6 (m) H3, H8, H9, H10, 8.30 (s) H5, 5.20 (s) H6. 13C NMR: 150.95 C1, 148.49 C5, 147.60 C5 (is.), 137.79 C7, 137.85 C7 (is.), 129.64 C4, 129.28 C4 (is.), 128.78 C9, 128.69 C10, 128.63 C8, 128.32 C3, 121.31 C2, 121.00 C2 (is.), 76.04 C6. (The solvents could not be removed completely, so there are very very weak peaks at 0.8 and 1.3 ppm.)

2.1. General remarks Solvents and other liquids used in the experimental works were dried by conventional methods. Hexachlorocyclotriphosphazene [N3P3Cl6] (1) was recrystallized from hexane. Other chemicals were used as purchased. Hexakis(4-formylphenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphenoxy)cyclotriphosphazene (8) were prepared as described by Carriedo and et al. [25]. The reactions of [N3P3Cl6] with the phenols were carried out under the dry nitrogen. The IR spectra were recorded on an ATI Unicam Mattson 1000 FTIR spectrometer. 1H, 13C and 31P NMR spectra were recorded using a Bruker DPX-300 spectrometer operating at 300.13, 75.46 and 121.49 MHz, respectively. The 1H and 13C NMR chemical shifts were measured using SiMe4 as an internal standard and the 31P chemical shifts were measured using 85% H3PO4 as an external standard. Chemical shifts downfield from the standard were assigned positive d values. Microanalysis was carried out by a LECO 932 CHNS-O apparatus. 2.2. Synthesis of compound 2 A mixture of 1 (10.34 g, 29.74 mmol), 4-hydroxybenzaldehyde (22.05 g, 180.56 mmol) and K2CO3 (50.00 g, 361.76 mmol) was stirred in THF (250 mL) at 0 C and then reacted at ambient temperature for 48 h. The solvent was removed under vacuum. The residue was extracted with CH2Cl2 (4 · 75 mL). After the solvent was removed, a white solid 2 formed in 92% (23.57 g) yield. IR (cm 1): 1706 mC@O, 1184 mP@N, 962 mP–O–C. 1H NMR (in CDCl3-d, for numbering see Scheme 2, coupling constants J (Hz), is.: isomer, s: singlet, w: weak): 7.10 (d) H2 (4JPOCCH: 8.50), 7.60 (d) H3 (5JPOCCCH: 8.56), 9.90 (s) H5; H2:H3:H5 = 2:2:1. 13C NMR: 121.60 C2, 131.40 C3, 134.14 C4, 154.80 C1, 190.83 C5. 2.3. Synthesis of compound 3 A mixture of 2 (20.00 g, 23.21 mmol) and hydroxylaminehydrochloride (10.00 g, 143.90 mmol) was refluxed in

2.4. Reaction of 3 with benzyl chloride

2.5. Reaction of 3 with benzenesulfanoyl chloride A solution of 0.55 mL (0.76 g, 4.29 mmol) benzenesulfanoyl chloride in acetone (10 mL), 3 (0.60 g, 0.63 mmol) and Et3N (2 mL) in acetone (30 mL) was used for 4. The reaction was carried out at room temperature for 12 h and then was refluxed for 48 h. Compound 5 was obtained. The orange colour solid 5 was washed with alcohol and dried at 50 C in a vacuum for 48 h. Yield: 68% (0.36 g). IR (cm 1): 2230 mCN, 1188 mP@N, 950 mP–O–C. 1H NMR (in DMSO-d): 7.15 (d) H2, 7.85 (d) H3. 13C NMR: 152.88 C1, 135.07 C3, 121.99 C2, 118.85 C4, 109.37 C5. 2.6. Reaction of 3 with 1-napthalenesulfanoyl chloride A solution of 1.00 g (4.41 mmol) 1-napthalenesulfanoyl chloride in acetone (10 mL), 3 (0.60 g, 0.63 mmol) and Et3N (2 mL) in acetone (30 mL) was used for 4. The reaction was carried out at room temperature for 12 h and then was refluxed for 60 h. Compound 5 was obtained. The orange colour solid 5 was washed with alcohol and dried at 50 C in a vacuum for 48 h. Yield: 85% (0.45 g).

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2.7. Reaction of 3 with benzoyl chloride A solution of 0.55 mL (0.66 g, 4.73 mmol) benzoyl chloride in acetone (10 mL), 3 (0.60 g, 0.63 mmol) in acetone (30 mL) and Et3N (2 mL) was used for the preparation of 6 for 4. The reaction was carried out at room temperature for 12 h. After the reaction was complete, the precipitate was filtered off, the liquid mixture was slowly poured into water (100 mL) and the solid product was obtained. It was reprecipitated twice from water, then it was dissolved in hot alcohol and any impurities were filtered off. The white solid 6 was crystallized from alcohol and dried at 50 C in a vacuum for 48 h. Yield: 27% (0.25 g). IR (cm 1): 3410 mOH, 1746 mC@O, 1181 mP@N, 1082 mN–O–C, 955 mP–O–C. 1H NMR (in DMSO-d): 6.90–8.30 (m) H2, H3, H8, H9, H10, H12, H13, 8.90 (s) H5, H15, 11.30 (s) H16. 13C NMR: 167.80 C6, 163.55 C5, 157.32 C15, 153.28 C1, 152.27 C11, 135.00 C10, 134.00 C4, 132.00 C14, 128.08–129.7 C3, C7, C8, C9, C13, 121.95 C2, 121.67 C12. 2.8. Synthesis of compound 7 A mixture of 1 (7.00 g, 20.13 mmol), 4-hydroxyacetophenone (16.72 g, 122.80 mmol) and K2CO3 (34.00 g, 245.99 mmol) was refluxed in acetone (250 mL) for 3 h. The solvent was evaporated in a vacuum and the residue was extracted with CH2Cl2 (4 · 75 mL). After the evaporation of the solvent in a vacuum, a white solid 7 formed in 87% (16.50 g) yield. IR (cm 1): 1685 mC@O, 1188 mP@N, 949 mP–O–C. 1H NMR (in DMSO-d): 7.05 (d) H2, 7.85 (d) H3, 2.45 (s) H6, H2:H3:H6 = 2:2:3. 13C NMR: 27.04 C6, 120.96 C2,131.20 C3, 134.54 C4, 153.27 C1, 197.00 C5. 2.9. Synthesis of compound 8 Hydroxylaminehydrochloride (4.50 g, 64.75 mmol) and 7 (10.00 g, 10.57 mmol) were used for the preparation of 8, as for 3. After the reaction was complete, the mixture was allowed to cool and the mixture was slowly poured into water (100 mL) and reprecipitated twice from water. The white solid 8 was obtained in 99% (10.89 g) yield. IR (cm 1): 3460 mOH, 1208 mP@N, 960 mP–O–C. 1H NMR (in DMSO-d): 6.85 (d) H2, 7.50 (d) H3, 2.10 (s) H6, 11.25 (s) H7, H2:H3:H6:H7 = 2:2:3:1. 13C NMR: 11.90 C6, 120.93 C2, 127.36 C3, 134.64 C4, 150.39 C1, 152.51 C5. 2.10. Reaction of 8 with benzyl chloride A solution of 0.50 mL (0.55 g, 4.34 mmol) benzyl chloride in acetone (10 mL), 8 (0.60 g, 0.58 mmol) and K2CO3 (2.00 g, 14.47 mmol) in acetone (30 mL) was used for the preparation of 9, as for 4. The oily product 9 was obtained and dried under vacuum for 48 h. Yield: 80% (0.60 g). IR (cm 1): 3295 mOH, 1183 mP@N, 1014 mN–O–C, 955 mP–O–C. 1H NMR (in DMSO-d): 11.30 (s) H18, 6.85 H2, 7.70 (m) (H3, H9, H10, H11, H13, H14), 5.20(s) H7, 2.10 (s) H17, 2.15 (s) H6. 13C NMR: 153.97 C16, 152.48

C5, 150.76 C12, 150.31 C1, 138.25 C8, 134.66 C15, 133.44 C4, 128.79 C10, 128.48 C11, 128.22 C9, 127.73 C14, 127.37 C3, 120.95 C2, C13, 75.94 C7, 12.82 and 11.88 C17, C6. 2.11. Reaction of 8 with benzoyl chloride A solution of 0.70 mL (0.74 g, 5.22 mmol) benzoyl chloride in acetone (10 mL), 8 (0.60 g, 0.58 mmol) and Et3N (2 mL) in acetone (30 mL) was used for the preparation of 10, as for 4. The reaction was carried out at room temperature for 12 h and then was refluxed for 24 h. After the reaction was complete, the mixture was allowed to cool and the mixture was slowly poured into water (100 mL) and reprecipitated twice from water. The white solid 10 was crystallized from alcohol. Yield: 88% (0.85 g). IR (cm 1): 1747 mC@O, 1173 mP@N, 1063 mN–O–C, 962 mP–O–C. 1H NMR (in DMSO-d): 7.10 (d) H2, 7.75 (d) H3, 8.01 (d) H9, 7.70 (t) H11, 7.50 (t) H10. 13C NMR: 163.40 C7, 163.19 C5, 151.75 C1, 151.78 C1 (is.), 134.12 C11, 132.6 C4, 132.40 C4 (is.), 129.60 C9, 129.35 C10, 129.18 C3, 128.87 C8, 121.32 C2, 14.64 C6. 2.12. Reaction of 8 with 4-methoxybenzoyl chloride A solution of 0.70 g (4.10 mmol) 4-methoxybenzoyl chloride in acetone (10 mL), 8 (0.60 g, 0.58 mmol) and Et3N (2 mL) in acetone (30 mL) was used for the preparation of 11, as for 4. The reaction was carried out at room temperature for 24 h. The white solid 11 was washed with hot alcohol and acetone. Yield: 80% (0.85 g). IR (cm 1): 1741 mC@O, 1210 mP@N, 1023 mN–O–C, 951 mP–O–C. 1H NMR (in DMSO-d): 6.87 (d) H10, 7.12 (d) H2, 7.70 (d) H3, 7.90 (d) H9, 2.43 (s) H6, 3.85 (s) H12. 13C NMR: 163.79 C7, 162.83 C5, C11, 151.72 C1, 151.78 C1 (is.), 132.22 C4, 132.40 C4 (is.), 131.73 C9, 129.07 C3, 121.25 C2, 120.88 C8, 114.58 C10, 55.93 C12, 14.52 C6. 2.13. Reaction of 8 with 2-chlorobenzoyl chloride A solution of 0.60 mL (0.82 g, 4.73 mmol) 2-chlorobenzoyl chloride in acetone (10 mL), 8 (0.60 g, 0.58 mmol) and Et3N (2 mL) in acetone (30 mL) was used for the preparation of 12, as for 4. The reaction was carried out at room temperature for 12 h and then was refluxed for 8 h. The white solid 12 was washed with hot alcohol. Yield: 76% (0.82 g). IR (cm 1): 1741 mC@O, 1210 mP@N, 1032 mN–O–C, 953 mP–O–C. 1H NMR (in DMSO-d): 7.10–7.88 HAr, 2.42 (s) H6. 13C NMR: 14.99 C6, 121.33 C2, 151.77 C1, 162.75 C5, 163.83 C7, 133.95 C9, 132.38 C4, 131.92 C11, 131.53 C8, 131.28 C13, 129.33 C10, 129.22 C3, 127.87 C12. 3. Results and discussion The reaction of 1 with 6 equivalent of 4-hydroxybenzaldehyde and 4-hydroxyacetophenone in the presence of K2CO3 in THF gave hexakis(4-formylphenoxy)cyclotriphosphazene (2) and hexakis(4-acetylphenoxy)cyclo-


triphosphazene (7). Oxime compounds hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene (3) and hexakis(4-[(1)-N-hydroxyethaneimidoyl]phenoxy)cyclotriphosphazene (8) were synthesized from the reactions of 2 and 7 with hydroxlaminehydrochloride in pyridine, respectively. Hexa and pentasubstituted compounds were obtained from the reaction of hexakis(4-[(hydroxyimino)methyl] phenoxy)cyclotriphosphazene (3) with benzyl chloride and benzoyl chloride in acetone (in the presence of K2CO3 for benzyl chloride, and Et3N for benzoyl chloride) via replacement of all the oxime protons with benzyl and benzoyl groups, respectively. However, the oxime groups on 3 rearranged to nitrile (5) in the reaction of 3 with benzenesulfanoyl chloride and 1-napthalenesulfanoyl chloride via dehydration of the oximes [39,40]. Compound 5 was previously synthesized by Carriedo. N3P3(OC6H4-CN)6 was directly obtained from the reaction of N3P3Cl6 with 4-cyanophenol and characterized by elemental analysis and 1H, 13C and 31P NMR spectra (25). The analysis results of 5 are in good accordance with the literature values (25). Similar compounds, N3P3(OPh)5(OC6H4–CN–p) and N3P3(OC6H4–R–4)5(OC6H4–CN–4) (R@H or tBu), were synthesized by Allcock et al. [41] and Carriedo et al. [42], respectively. Hexasubstituted compounds were obtained from the reactions of 8 with benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. A trisubstituted compound was obtained from the reaction of 8 with benzyl chloride in acetone (in the presence of K2CO3 for benzyl chloride, and triethylamine for benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride). The reactions are shown in Scheme 1. All the products were generally obtained in high yields. Pure and defined products could not be obtained from the reaction of 3 with 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. The structures of the compounds were defined by elemental analysis, IR and 1H, 13C and 31P NMR spectroscopy (structures 2–12 are shown in Scheme 2). Physical properties and analytical data for 2–12 are shown in Table 1. Compounds 2–12 were synthesized in high yields except for 4 HO-C6H4-C(O)H

and 6. The solvents used for the purification of compounds 4, 5, 6 and 9 could not be removed completely, so weak peaks of trace amounts of solvents were observed at 0.8 and 1.3 ppm for 4, 1.3 and 2.4 ppm for 5, 0.8, 1.3 and 4.4 ppm for 6 and 9 in the 1H NMR spectra. Similarly, solvent peaks were observed at 18 and 25 ppm for 4, 20 and 29 ppm for 5, 19 and 57 ppm for 6 and 8 and 30 ppm for 9 in the 13C NMR spectra. Thus the presence of these trace amounts of solvent affect the elemental analysis, in particular the carbon value. The characteristic stretching peaks in the IR spectra of the phosphazenes have been assigned in the experimental section. The P@N stretching vibrations, which are observed between 1173 and 1210 cm 1, are characteristic of cyclophosphazenes. Compared to 1, which appeared at 1218 cm 1, these peaks are shifted to longer wavelengths for 2–12. The OH stretching vibrations in the IR spectra of 3, 6, 8 and 9 indicate oxime compounds. While 3 and 8 are initial oximes, all hydrogen atoms of the OH groups of 6 and 9 could not be replaced by the benzoyl and benzyl substituents, respectively. The NMR data for 2–12 are presented in the experimental section. The 31P NMR shifts of 2–12 change between 7.51 and 17.21 ppm. Although there is only one peak in the 31P NMR spectra of 1, 2, 5, 6, 7, 9, 10 and 12 at 20.12, 8.33, 7.51, 8.36, 8.05, 9.00, 8.88 and 8.84 ppm, respectively, two peaks, with very weak second signals, are observed at d = 17.21, 17.26, d = 8.67, 8.57, d = 9.04, 9.01 and d = 8.89, 8.79 ppm for 3, 4, 8 and 11, respectively. It is assumed that the weak peaks are due to the cyn and anti isomerism of the –C@N– groups. The effects of the cyn and anti isomerism are also observed in the 13C NMR spectra of 3, 4 and 11. This data demonstrates that compounds 3, 4, 8 and 11 consist of a mixture of two isomers, but the others have one isomer. Although there are different phosphorus environments in the molecule of 6, the main peak is observed as a singlet. It is understood that the phosphorus peaks are not affected by these changes because the substituted groups are far away from the phosphorus atoms.

HO-C6H4-C(O)CH3

N3P3Cl 6

(1) N3P3(O-C6H4-C(O)CH3)6 (7)

N3P3(O-C6H4-C(O)H)6 (2)

H2NOH.HCl

H2NOH.HCl N3P3(O-C6H4-CH=NOH)6 (3) R-Cl

R'-S(O)2Cl

N3P3(O-C6H4-C(CH3)=NOH) 6 (8) R-Cl

N3P3(O-C6H4-CN)6 (5)

N3P3(O-C6H4-CH=NOR)6 (4)

N3P3(O-C6H4-C(CH3)=NOR) 3(O-C6H4-C(CH3)=NOH)3 (9)

N3P3(O-C6H4-CH=NOR)5(O-C6H4-CH=NOH) (6)

3529

N3P3(O-C6H4-C(CH3)=NOR) 6 (10-12)

R= CH2-C6H5(4,9), C(O)-C6H5(6,10), C(O)-C6H4-OCH3(11), C(O)-C6H4-Cl(12) R'=C6H5 or C10H7

Scheme 1. General pathway of the reactions.

3530


O

5

4

N3P 3

3

1

O

2

OH 6

3

1

O

6

2

(2)

CN 5

O

N3 P 3 O

N

4

6 7

3

1

N3 P 3

8

2

(5) O

5

4 O

O

N

6

14

7

3

1

6

2

6

10

(4)

3

1

O

9

N3P 3

6

(3)

5

4

N

5

4

N3P 3

8

N

OH 16

13

11

O

15

12

2 9

(6)

5

10

6

O N3P 3

4 O

CH3 6

1

2

N3P3

17

10 9

15 O

8 7

2

O

(9) H3C 4

N 3P3

O

6

5

O N

1

13

3

6

CH3 O

4

N3P3 O

3

1 2

5

N

11

O

7 O

10

(10)

6

(11)

11

6

CH3 10

Cl 4

N3P3 O

5

N O

3

1

11

9 7

12

8 13

2

O

(12)

N OH 18

14

12

O

9

2

16

3

7 8

3

CH3

11

N

3

1

6

(8)

CH3

5

4

2

6

(7)

OH 7

3

1

O

N

5

4

N 3P 3

3

6

O

5

CH3

6

Scheme 2. The structures of the compounds 2–12.

CH3 12

10

8 9

6

E. Çil et al. / Polyhedron 25 (2006) 3526–3532 Table 1 Physical properties and analytical data of 2–12 Yield (%) 2

92

3

83

4

66

5

94

6

27

7

87

8

99

9

80

10

88

11

80

12

76

C H N C H N C H N C H N C H N C H N C H N C H N C H N C H N C H N

Found

Calcd.

58.52 3.39 4.51 53.43 3.75 12.98 66.56 4.78 7.70 58.29 2.96 13.33 61.70 3.87 8.07 60.93 4.50 4.40 55.67 4.69 11.98 62.23 5.01 8.60 61.43 4.34 6.76 59.81 4.36 5.79 57.38 3.41 5.58

58.55 3.514 4.88 53.00 3.81 13.25 67.60 4.86 8.45 59.80 2.87 14.94 62.80 3.83 8.56 60.96 4.48 4.44 55.66 4.67 12.17 63.44 5.09 9.65 62.10 4.37 7.59 60.64 4.60 6.85 57.89 3.56 6.75

The 1H and 13C NMR data also confirm the structures of 2–12 (Scheme 2). In the 1H NMR spectra (Table 1), the OH protons are observed at 10.17, 11.30, 11.25 and 11.30 ppm for 3, 6, 8 and 9, respectively. It is understood from the integral intensities that there are six OH protons in 3 and 8, which are the original oxime-phosphazenes, one OH proton in 6 and three OH protons in 9. This observation for 6 and 9 indicates that benzoyl or benzyl groups

3531

have not replaced all the OH protons in 3 and 8. The aldehyde proton for 2 appears at 9.90 ppm. The azomethine protons for 3, 4 and 6 are observed at 7.96 (H5), 8.30 (H5) and 8.90 (H5, H15) ppm, respectively. The aromatic protons for all the compounds appear between 6.85 and 8.30 ppm. Detailed 13P NMR spectral data are shown in Table 2. The aldehyde carbon atom for 2 and the ketone carbon atom for 7 are observed at 190.83 and 197.00 ppm, at the lowest downfield position of the carbon atoms. Compared to 3 and 8, the azomethine carbon atoms in the substituted moiety of the molecules are shifted to lower downfield for compounds 6, 10, 11 and 12, except for 4 and 9 in which the benzyl group releases an electron to the molecule. The azomethine resonances do not change or show very little change in the non-substituted moiety of 9. 4. Conclusion Hexa and pentasubstituted compounds were obtained from the reaction of hexakis(4-[(hydroxyimino)methyl]phenoxy)cyclotriphosphazene (3) with benzyl chloride and benzoyl chloride via replacement of all the oxime protons with benzyl and benzoyl groups, respectively. However, the oxime groups in 3 rearranged to nitrile (5) in the reaction of 3 with benzenesulfanoyl chloride and 1-napthalenesulfanoyl chloride via dehydration of the oxime groups. Hexasubstituted compounds were obtained from the reactions of 8 with benzoyl chloride, 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. A trisubstituted compound was obtained from the reaction of 8 with benzyl chloride. Pure and defined products could not be obtained from the reaction of 3 with 4-methoxybenzoyl chloride and 2-chlorobenzoyl chloride. Acknowledgement We thank the Firat University Research Fund for support (Project No: FUBAP 923). References

Table 2 The 31P NMR data of 1–12

1 2 3 4 5 6 7 8 9 10 11 12

Major isomer

Minor isomer

ppm

Rel. intensity (%)

ppm

Rel. intensity (%)

82 62

17.26 8.57

18 38

79

9.01

21

79

8.79

21

20.12 8.33 17.21 8.67 7.51 8.36 8.05 9.04 9.00 8.88 8.89 8.84

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