J. CHEM. SOC. PERKIN TRANS. I 1988 Reactivity and Chemoselectivity of Primary 2-p-Enamino-h5-phosphazenes towards Electrophi les Jose Barluenga," Fernando Lopez, and Francisco Palacios. Departamento de Quimica Organometalica, Universidad de Oviedo, 3307 1 Oviedo, Spain Felix H. Can0 and Maria de la Concepcion Foces-Foces lnstituto de Quimica Fisica 'Rocasolano', Serrano 719,28006Madrid, Spain The multifunctional character of Z-p-enamino-hs-phosphazenes (2) towards several electrophiles is shown. Thus, while hydrogen or alkyl halides react through the P=N double bond, affording p-enaminophosphonium salts (3)and (4), in the presence of a base, alkylation of the enamine moiety (6) occurs. Ethyl chloroformate acts as acylating agent of the enaminic nitrogen and with bromine and triet hy lam ine, a-bromoenaminop hosp hazenes (8) are obtained.Enamines' are known to be useful intermediates in carbon- carbon and carbon-heteroatom bond formation yet their synthesis and reactivity has been little studied. In the last few years some primary enamines having electron-withdrawing substituents, e.g., sulphonyl,2 nitro,3 imin~,~ and cyan^,^ have been prepared and their use in organic synthesis shown. (2 1 Recently we described the first synthesis of primary 2-p-enamino-h5-phosphazenes6 (2) via a-lithiation of alkyldiaryl- i iv,iiih5-phosphazenes (1) followed by reaction with arenenitriles, as bsol; 1II,IV, well as their utility as key intermediates in the synthesis of phosphorus-containing heterocyclic compounds.' The ability of compounds (2) to react through both reactive centres, h5-phosphazene' and enamine,' a feature which has already been observed in the preparation of l-a~a-4h~-phosphinines,~" prompted us to explore the chemoselectivity of (2) towards several reagents.In a previous paper6 we reported the reactions of h5-phosphazene derivatives of (2) with CO,, and CS,. Here, we report our results on the reactivity of (2) with other electrophiles (Schemes I and 2). Results and Discussion Treatment of compound (2a) with HI resulted in nitrogen protonation giving compound (3) (m.p. 164-165 "C, 6, +21.2 p.p.m.). Although the 13C n.m.r. spectrum confirmed that the framework of the enamine functionality remained intact, it did not allow the site of protonation (1 and/or 5-position) to be determined.A single crystal X-ray analysis unequivocally established the structure of (3) and showed that selective protonation occurred at the h5-phosphazene nitrogen (P-N bond length 1.622 A). The bond angles for the C=C double bond are 125.7' and 122" and the torsion angles for the P-C=C-N and P-C=C-CAr are 16.3" and -162.4" respectively, values which corresponds with the appropriate sp2 hybridization and 2-stereochemistry. The high basicity' of h5-phosphazenes could explain the nucleophilic attack by the P=N linkage rather than the primary enamino nitrogen atom. Likewise, alkyl halides e.g., methyl iodide and ethyl bromo- acetate, reacted with compound (2) to afford the N-alkyl- arylamino phosphonium salts (4) regioselectively in excellent yields.The high shift values of the 31P n.m.r. signals and the P-H (9.4 Hz) and P-C (5.9 Hz) coupling constants observed in H- and 3C-n.m.r., respectively, for the methyl and methylene groups of the alkylating agent are fully consistent with the phosphonium salt structure (4). The reaction of compound (2) with ethyl chloroformate led, as in the case of p-imino enamines,'' to exclusive ethoxy- (6) Scheme 1. Reagents and conditions: i, BuLi-THF, -70 "C; ii, R'CN; iii, H,O; iv, R3X. CI-)("NHPh R' NHC02 Et (3) R2 = H CKy (5) (4)a;R2 = Me b;R2 = CH,CO,E t (21-Ph2Br PEt3N bsol;NPh -Et3NH B r R1 NH2 (7) (81 Scheme 2. carbonylation of the enamino nitrogen and formation of the phosphonium salt (5);the chemical shift at 21.3 p.p.m.similar to that found in compound (3)was assigned to the phosphorus and the doublets observed at 9.9 ('JPH 7.1 Hz) and 4.5 ('JPH 9.7 Hz) p.p.m. were assigned to the phenyl substituted amino and p-enamino hydrogens, respectively. The reactivity of the p-enamino carbon of (2) was also investigated and it was found that metallation of (2) with butyl- 2330 J. CHEM. SOC. PERKIN TRANS. I 1988 Table 1. Selected physical data for the compounds (2)--(8) 5 Compound (2b) R' c-C6H1 1 R2 R3 M.p. ("C) 157-158 Yield () 82 1.r. (Nujol) 1650 "ma,. (cm-9 CDCI, (p.p.m.) A r 6, 6, 4.26 (d, 'JpH 71.2 (d, lJPc 22.0 Hz, XH); 115.5 Hz, C-l), 6, +4.7 5.93 (s, 1 H, NH) 168.4 (C-2) 164-165 98 1 640,3 200, 4.53 (d, 1 H, 56.9 (d, lJPc +21.2 3 280, 3 440 'JpH22.1 Hz, 112.2 Hz, C-l), =CH), 6.16 (s,1 H, NH) 164.3 (d, ,.Ipc 1.1 Hz,C-2) Oil 98 1 630,3 160, 3.39 (d, 3 H, 39.3 (d, ,JPc 5.9 +36.0 3 300, 3 440 ,JPH9.4 Hz, Hz Me), 60.7 (d, Me), 4.2 (d, 1 H, lJPc 119.6 Hz, ,JPH17.3 Hz, C-1), 163.8 (C-2) ==CH), 6.06 (s, 1 H, NH) Oil 97 1600,l 710, 4.24 (d, 1 H, 52.0 (d, ,JPc8.8 +37.0 2 500,3 300 'JpH18.3 Hz, Hz, CH,), 58.9 SH), 4.55 (d, 2 H, 3JpH12.0 (d, Jpc 11 5.9 Hz, C-l), 165.0 (d, Hz, CH,), 6.79 'JPc 0.7 Hz, (s, 1 H, NH) 'JX 1.2 Hz, CO) C-2), 168.9 (d, Oil 97 1 590,l 700, 3 160 4.55 (d, 1 H, 'JpH 19.7 Hz, 57.2(d, 1Jpc116.5 4-21.3 Hz,C-l), 153.0 =CH), 6.83 (s, (CO), 165.2 (C-2) 1 H, NH), 9.87 (d, 1 H, 'JpH7.9 Hz, NH) 6a) (6b) 4-MeC,H4 c-C6H 1 1 Me Me 138-139" 152-153 90 (87)b 86 (83)b 1 620,3 320, 3 400, 3 460 1.39 (d, 3 H, 3Jp~15.7 Hz, 13.5 (d, 15.7 Hz, Me), + 15.4 Me), 4.0 (s, 1 H, NH) 73.9 (d, 'JPc 119.7 Hz, C-1), 164.4 (d, 'J, 3.9 Hz, C-2) Me CH,Ph 102-103" 105-106 85 (79)b 90 (83)b 1 610, 3 480 3.28 (d, 2 H, 3JpH 18.9 Hz, 32.6 (d, 2Jpc 15.6 Hz, C- 1 l), 74.4 (d, + 15.7 CH,) lJPc123.8 Hz, C-1), 166.9 (d, 'JpC3.2 Hz, C-2) CH,Ph 165-166 87 (80)b 1 610, 3 440 3.22 (d, 2 H, 3Jp~18.9 HZ, 34.9 (d, ,JpC 14.0 HZ, C-1 I), 83.0 (d, +14.5 CH,) Jpc 116.6 Hz, C-l), 162.1 (d, CH,=CHCH, Oil 92 (87)b 1 600,3 300, 3 460 2.47 (dd, 2 H, 3JpH18.9, 3JHH 32.4 (d, ,JPc 18.9 Hz,C-l1),81.3(d, ,JpC 5.4 Hz, C-2) +14.5 6.3 Hz, CH,), lJPc 118.1 Hz, 4.28 (m,2 H, 4.0 (s, 1 H, NH), (C-ll), 137.2 (d, C-l), 112.9 SH,), 4.95 3Jpc9.0 Hz, (m,1 H, =CH) C-12), 161.2 (d, ,JX 5.2 Hz, C-2) CH,=CHCH, Oil 88 (75)b 1 640,3 320, 3 480 2.57 (dd, 2 H, 5.5 Hz, CH,), 'JPH18.9, 'JH, 30.6 (d, 'JPc 15.2 HZ, C-l), 75.5 (d, 'Jpc 121.7 Hz, +15.5 NH), 4.76 (m, 5.63 (m, 1 H, 4.16 (s, 1 H, 2 H, =CH2), =CH) C-1),114.2(C-13), 136.8 (d, 3JX 7.1 (d, 'Jpc 3.1 Hz, Hz, C-12), 166.2 c-2) J.CHEM. SOC. PERKIN TRANS. I 1988 233 1 Table 1. (continued) CDC1, (p.p.m.) A1.r. (Nujol) Compound R' R2 R3 M.p. ("C) Yield () v,,,, (cm-I) 6, 6, 6, (7) 4-MeC6H, 160-161 97 1 620,3 240, 9.0 (d, 1 H, 'JPH 88.4 (d, lJPc +28.4 3 400 7.9 Hz, NH) 119.7 Hz, C-l), 164.4 (d, 'J, 22.1 Hz, C-2) (8) 4-MeC6H, 123-124 95 (90)' 1 590, 3 440 2.31 (s, 3 H, Me) 63.6 (d, 'JPc119.7 + 13.5 Hz, C-1), 163.4 (d, 'Jpc 8.3 Hz, C-2) 'Lit.,6 138-139 "C and 102-103 "C respectively.From method B. From method B. Microanalytical data correlate well with the proposed structures: solids: C _+ 0.19. H _+ 0.16, N amp; 0.21; oils, C i-0.36, H amp; 0.28,N amp; 0.42. I I I IQ I Figure. An ORTEP view of the salt of (3), showing the numbering scheme used in the crystallographic work, together with the H-bonding network. i, ii stand for the symmetry operations (1/2 -x, 1/2 + y, 1/2 -z) and (1/2 -x, -1/2 + y, 1/2 -z) respectively lithium followed by addition of an alkyl halide leads treatment of the h5-phosphazene-derived anion with nitrile and regioselectively to C-alkylation, a result which parallels that subsequent quenching with the corresponding alkyl halide.reported for p-imino enamines.' Compounds (6)were formed The same regioselectivity was encountered when bromine in high yields and show the 'H-and 13C-n.m.r. signals expected was employed as the electrophile; thus, the reaction of for the alkyl group attached to the p-enamino carbon; compound (2) with bromine led to a-bromination and furthermore, (6a) and (6c) are identical with compounds hydrobromination of the P=N double bond to afford the previously reported from the reaction of ethyldiphenyl-h5- phosphonium salt (7) (m.p. 160-161 "C, 8p +28.4 p.p.m.);phosphazenes.6 It is worth noting that the conversion of (1) into compound (7) was in turn dehydrohalogenated to the p-(6) can be accomplished in a high yield, one-pot reaction by enamino-h5-phosphazene derivative (8) (m.p.123-124 "C, 6, + 13.5 p.p.m.) by treatment with triethylamine. Compound (8) could be synthesized in one step, without affecting the overall yield, by running the bromination reaction of (2) in the presence of trie thylamine. In conclusion, we have shown that primary Z-P-enamino-h5- phosphazenes (2) react at three centres when treated with different electrophiles. Thus, protonation and alkylation occur in the same way as that observed for simple h5-phosphazenes (position 1) whilst with halogenating agents, e.g., bromine, typical enamine behaviour (position 3) is shown.However, the ambident character of the metallated enamine moiety of (2) leads to regioselective C-alkylation and N-acylation in the reaction with alkyl and acyl halides, respectively (positions 3 and 5). Experimental General.-M.p.s were taken on samples in open capillary tubes using a Buchi melting-point apparatus and are un-corrected. N.m.r. spectra were obtained using a Varian FT-80 n.m.r. spectrometer with deuteriated chloroform as solvent; chemical shifts are reported in p.p.m. downfield from an internal SiMe, (TMS) for 'H- and 3C-n.m.r. or from H3PO4 85 in the case of the 31Pn.m.r. 1.r. spectra were recorded in Nujol on a Perkin-Elmer 298 spectrophotometer. Microanalyses were performed on a Perkin-Elmer Model 240 instrument and mass spectra were obtained using a Hewlett-Packard 5930A spectrometer.Compounds (2) were obtained according to the literature methods6 and the same process was applied in the synthesis of (2) in which R' = c-C,H, ,. Synthesis of (Z)-(p-Amino-p-p-toIylvinyl)diphenyl(phenyl-amino)phosphonium Iodide (3).-A stoicheiometric amount of HI was bubbled, under an argon atmosphere through a solution of compound (2a) (2.04 g, 5 mmol). The precipitate of (3) which formed immediately was filtered off and recrystallised from a mixture of toluenexhloroform to give pure (3) (2.6 g, 98); v,,,. 1 640, 3 200, 3 280, and 3 440 cm-'; 6, 2.35 (s, 3 H, Me), 4.53 (d, 1 H, ,JPH22.1 Hz,=CH), 6.16 (s, 1 H,NH), and 6.57- 8.35 (m, 14 H, ArH, NH,); 6,20.9 (Me), 56.9 (d, 'Jpc112.2 Hz, C-l), 119.2-133.9 (21-C, Arc), 138.9 (C-7), 141.1 (C-6), and 162.3 (d, ,JPc1.1 Hz, C-2); 6, +21.2 p.p.m.Synthesis of Enaminophosphonium Halides (4): General Procedure.-(Z)-(P-Amino-P-p-tolylvinyl)(methylphenyl-amino)diphenylphosphonium iodide. (4a). Methyl iodide (5 mmol) was added dropwise to a solution of compound (2a) in dry THF (30 ml) and the solution stirred for 2 h. The solvent was evaporated off to produce compound (4a) quantitatively; vmax,1 630, 3 160, 3 300, and 3 440 cm-'; 6, 2.31 (s, 3 H, Me), 3.39 (d, 3 H, 3Jp~9.4 Hz, Me), 4.2 (d, 1 H, 2JpH17.3 Hz, XH), 6.06 (s, 1 H, NH), and 7.k7.91 (m, 19 H ArH, NH); 6c 19.7 (Me), 39.3 (d, ,JPc5.9 Hz, Me), 60.7 (d, lJPc119.6 Hz, C-l), 118.6132.8 (21-C, Arc), 140.2 (C-6), 140.5 (C-7), and 163.8 (C-2); 6, + 36.8 p.p.m.Synthesis of (2)-(p-Ethoxycarbonylamino-p-p-tolylviny1)di-phenyZ(pheny1amino)phosphonium Chloride (5).-This was prepared by the same method as compound (4). For (5) v,,,. 1 700 and 3 160 cm-'; 6, 1.31 (t, 3 H, 3J~~6.3 Hz, Me), 2.4 (s, 3 H, Me),4.2 (q,2 H, 3JHH 19.7Hz,6.3 Hz, CH2),4.55 (d, 1 H, 2JpH XH), 6.83 (s, 1 H, NH), 6.95-8.10 (m, 19 ArH), and 9.87 (d, 1 H, 'JpH 7.9 Hz, NH); 13.9 (Me), 20.0 (Me), 57.2 (d, lJPc116.5 Hz, C-1), 59.0 (CH,), 117.6-130.5 (21 C, Arc), 138.0 (C-6), 140.1 (C-3), 151.6 (C-7), 153.0 (CO), and 165.2 (C-2); tip +21.3 p.p.m. J. CHEM. SOC. PERKIN TRANS. I 1988 Table 2. Final atomic co-ordinates xju Ylb s/c 0.094 98(2) 0.130 24(6) 0.180 04(2) 0.184 4(1) 0.358 7(3) 0.082 4( 1) 0.199 8(3) 0.254 9(8) 0.139 2(3) 0.243 3(3) 0.420 O(8) 0.076 7(3) 0.290 5(3) 0.483 l(8) 0.121 9(3) 0.301 3(3) 0.472 7(9) 0.178 6(3) 0.144 9(4) 0.507 3(9) 0.097 2(4) 0.170 3(4) 0.641 9(9) 0.115 4(5) 0.140 6(5) 0.754 l(10) 0.1 18 9(5) 0.085 O(5) 0.738 5(12) 0.106 4(7) 0.0588(5) 0.606 9( 13) 0.089 l(8) 0.088 l(4) 0.490 6(9) 0.085 4(5) 0.137 6(4) 0.271 l(10) 0.014 5(4) 0.104 O(4) 0.157 9(11) 0.016 3(5) 0.064 l(4) 0.099 l(12) -0.035 5(5) 0.056 5(4) 0.151 6(13) -0.088 9(5) 0.089 l(5) 0.260 9( 16) -0.091 5(5) 0.130 l(5) 0.323 4( 14) -0.039 7(4) 0.236 2(3) 0.134 6(9) 0.150 3(5) 0.250 3(5) 0.065 9( 12) 0.1 10 4(5) 0.287 4(6) -0.051 7(13) 0.129 l(6) 0.307 O( 5) -0.099 7( 12) 0.185 4(6) 0.291 9(6) -0.032 4( 15) 0.223 6(6) 0.257 2(5) 0.083 7( 13) 0.206 9(5) 0.330 3(3) 0.567 5(8) 0.107 9(3) 0.385 6(3) 0.595 3(9) 0.151 5(4) 0.421 3(4) 0.680 l(11) 0.133 4(5) 0.404 8(4) 0.737 4( 10) 0.082 l(5) 0.350 6(4) 0.709 9( 12) 0.040 O(5) 0.313 4(4) 0.627 4( 11) 0.052 O(4) 0.445 3(6) 0.824 7( 16) 0.089 2(8) 0.5000 0.282 O(29) 0.250 0 0.524 8( 10) 0.021 l(29) 0.247 5( 12) 0.540 2( 14) 0.175 9(36) 0.242 4( 14) * Means population parameters = 0.50 Synthesis of x-Alkyl-P-enamino-h5-phosphazenes(6): Gene-ral Procedure.-( 2)-4-Cyclohexyl- 3-methyl- 1,2,2-triphenyl-1,5-diaza-2h5-phosphapenta-1,3-diene(6b). Method A.Compound (2b) (5 mmol) dry THF (40 ml) was added to BuLi (5 mmol) at -20 "C under argon and the mixture was stirred for 0.5 h during which time the temperature decreased to -70deg;C.Methyl iodide (5 mmol) was added dropwise and the mixture was left to reach room temperature and then hydrolysed with ice-water. Aqueous work-up afforded an oil that was re-crystallised from hexane-dichloromethane to give (6b) (1.8 g, 86).Method B. A solution of N-phenyl methyldiphenyl-h5- phosphazene (5 mmol) in THF was added to BuLi (5 mmol) at -20 "C and the mixture stirred for 0.5 h after which cyclohexanecarbonitrile (5 mmol) at -70 "C was added. Once room temperature had been reached methyl iodide again at -70 "C was added. Aqueous work-up and purification as indicated in method A yielded (6b) (1.7 g, 83); v,,,. 1 620, 3 320,3 400, and 3 460 cm-'; 6,0.55-1.87 (m, 11 H, C-C,H, ,), 1.39 (d, 3 H, 3Jp~15.7 Hz, Me), 4.0 (s, 1 H, NH), and 6.2-7.83 (m, 15 H ArH, NH); 6,13.55 (d, ,JPc15.7 Hz, Me), 25.9 (C-5, C- 6), 29.9 (C-4), 41.2 (d, 3Jpc 12.6 Hz, C-3), 73.9 (d, 'Jpc, 119.7 Hz, C-1), 116.5-133.2 (14 c,Arc), 150.34 (d, *JPc3.1 Hz, C-7), and 164.4 (d, 2Jpc3.9 Hz, C-2); 6, + 15.4 p.p.m.Synthesis of (Z)-(p-Amino-a-bromo-p-p-tolylviny1)diphenyl-(pheny1amino)phosphonium Bromide (7).-Bromine (5 mmol) in benzene (10 ml) was added dropwise to a solution of (2a) (5 mmol) in dry benzene (40 ml) over a period of 0.5 h. The mixture was stirred for 6 h and then evaporated to afford a solid which J. CHEM. SOC. PERKIN TRANS. I 1988 Table 3. Selected bond distances (A) and bond angles (") for compound (31 P-N( 1) 1.622( 8) P-C( 2) 1.724( 10) P-C( 11) P-C(21) N( 1)-C(31) N(4)-C(3) C(2)-C(3)C(3)-C(4 1 ) 1.870( 10) 1.792(8) 1.42 1( 12) 1.33 1 ( 12) 1.3 84(9) 1.476( 1 3) N( 1)-P-C(2) N( 1)-P-C( 11) 1 13.3(5) 101.8(4) N( 1)-P-C(2 1) 111.3(4) C( 1 1)-P-C(2) C(21)-P-C(2) 1 12.2(4) 109.3(4) C( 11)-P-C(21) 108.8(5) P-N(1)-C(31) 12 1.4(7) P-C(2)-C(3) N(4)-C(3)-C(2) 125.7(7) 122.0(8) N(4)-C(3)-C(4 1) 1 17.9(7) C(2)-C(3)-C(41) 120.2( 7) was recrystallised from toluenehloroform to give (7) (2.7 g, 97);v,,,. 1 620, 3 240, and 3 400 cm-'; tiH 2.0 (s, 3 H, Me), 6.2-7.97 (m, 19 H ArH, NH,), and 9.0 (d, 1 H, ,JPH7.9 Hz); 6, 21.1 (Me), 88.4 (d, 'JPc119.7 Hz, C-l), 121.0-133.4(21 C, Arc), 138.9 (C-7), 140.2 (C-6), and 164.4 (d, ,JPc 22.1 Hz, C-2); 6, +28.4 p.p.m.; m/z 566568 (M+).Synthesis of' (Z)-3-Bromo-1,2,2-triphenyZ-4-p-tolyI-1,5-diaza-2h5-phosphapenta-l,3-diene(8).-Method A. Bromine (5 mmol) was added to a mixture of (7) (5 mmol) and triethylamine (5 mmol) in toluene. After 8 h of vigorous stirring at room temperature the triethylamine bromohydrate was filtered off and the mother liquor was evaporated at reduced pressure, to yield a solid which was recrystallised from hexane-dichloro- methane (2.3 g, 95). Method B. The procedure was as indicated for method A, using compound (2a) instead of the brominated derivative (7), in a one-pot reaction with bromine and triethylamine to give the products (8) (2.2 g, 90); v,,,.1 590 and 3 440 cm-'; SH2.3 1 (s, 3 H, Me) and 6.35-8.08 (m, 14 H ArH, NH,); 6,21.3 (Me), 63.6 (d, 'JPc119.7 Hz, C-l), 117.9-133.5 (21 C, Arc), 136.8 (d, 3J,, 12.6Hz, C-3), 139.6 (C-6), 150.7(C-7),and 163.4 (d, 2Jpc8.3 Hz, C-2); 6, + 13.5 p.p.m.; m/z 48-88 (M+). Crystal Data for Compound (3).--(C,,H,,N,P 'I-} -+CI,CH,. Space group C2/c, Z = 8, D,= 1.381 g ~m-~, a = 24.415 7(9), b = 9.318 0(2), c = 25.343 2(11) A, p = 116.893(3)" (from a least-squares fit to the h,k,I and 28 values of 83 reflexions of 8 up to 45' with Cu-K, radiation), p = 107.55 cm-' (min. and max. transmission factors were 0.762-1.334).' A pale yellow rhombic prism of 0.17 x 0.17 x 0.27 mm was used in the analysis. Data Cofktionand Processing.-Philips PW 1 100 diffracto- meter, 0/28 scans, width 1 So,graphite monochromated Cu-K, radiation, 8 up to 65", 1 min/reflex.Stability checked every 90 min, using two standard reflexions, with no variation detected. Usual Lorentz and polarization corrections were applied. The number of total independent and observed, with 30(I), 30(I), 3.50(1) criteria were 4 277 (3 068), 4 631 (3 823), and 4 069 (2 420) respectively. Structure Solution and Re$nement.-Patterson and/or Direct Methods' were used for the solution and weighted full matrix Table 4. Selected torsion angles (") C(2)-P-N( 1)-C(31) -5 1.7(9) C(ll)-P-N(l)-C(31) -172.4(8) C(1 l)-P-C(2)-C(3) 64.5(9) C(ll)-P-C(2l)-C(26) 84.9(9) P-C( 2)-C( 3)-N(4) 16.3( 12) P-C(2)-C( 3)-C(4 1 ) -162.4(6) P-N(1)-C(31)-C(32) -19.1(15) C(26)-C(2 1)-P-C(2) -37.9( 10) C(22)-C(21)-P-N( 1) 23.0( 10) C( 16)-C( 1 1)-P-N( 1) -78.5(9) C( 12)-C( 1 1)-P-C(2) -14.3(10) C(2)-C(3)-C(41 )-C(42) -160.6(8) N(4)-C(3)-C(4 1 )-C(42) 20.6( 12) C (2)-C( 3)-N (4)-H (4B) 13(7) Table 5.Hydrogen interactions (A, "). Italic numbering indicates the symmetry operation Compound (i = 1/2 -x, 1/2 + y, 1/2 -z) X-H Y X-H X...y H...Y X-H...Y * * I 1.02(16) 3.558(20) 2.67( 15) 146(9)N( 1)-H( 1) I; i 0.78(8) 3.681(7) 2.96(8) 161(11)N(4)-H(4A) N(l) 0.92(11) 3.144(12) 2.38(9) 140(7)N(4)-H(4B) * least-squares for the refinement, working on Fobs.with one block full matrix.13 After the isotropic cycles an empirical absorption correction was applied in the iodide-containing salts.The thermal models were anisotropic for the non-hydrogen atoms and isotropic for the hydrogen atoms, which were sought from difference synthesis. Weights were chosen through empirical functions on Fobs. and sin 8/hso as to give no trends in ( wA2F), versus Fobs.and/or sin B/h.Scattering factors were taken from the International Tables for X-Ray Crystallo- graphy.14 394 Parameters; final R and R, indices were 0.071 and 0.078; the final residual density was within k2.2 etk3, the maximum being near the P and N(l) atoms; the maximum thermal value was U33(C15), 0.16(1) A'. The disordered Cl,CH, molecule of crystallization was kept with the fixed population in the last cycles of refinement, isotropically. Its H- atoms could not be located.Final atomic co-ordinates for the non-hydrogen atoms are given in Table 2, with numbering given in the Figure.' Tables 3 and 4 give the main geometrical features. Table 5 shows the H-bonding network. Thermal parameters and H-atom co-ordinates are available on request from The Cambridge Crystallographic Data Centre.* * See 'Instructions for Authors (1988),' J. Chem. Soc.. Perkin Trans. I, 1988, Issue 1. References 1 P. M. Hickmott, Tetrahedron, 1982, 38, 1975. 2 B. F. Feringa, J. Chem. Soc., Chem. Commun., 1985,466. 3 I. Tokumitzu and T. Hayashi, J. Org. Chem., 1985, 50, 1547. 4 (a)J. Barluenga, B. Olano, and S. Fustero, J. Org. Chem., 1983, 48, 2255. (b) J. Barluenga, J. Jardon, V. Rubio, and V. Gotor, J. Org.Chem., 1983, 48, 1379. 5 A. Corsaro, U. Chiachio, A. Compagnini, and G. Purrello, J. Chem. Soc., Perkin Trans. 1, 1980, 1635. 6 J. Barluenga, F. Lopez, and F. Palacios, J.Chem. Res. 1985,(S),21 1; (M), 2541. 7 (a)J. Barluenga, F. Lopez, and F. Palacios, J. Chem. SOC.,Chem. Commun., 1985, 1681. (6) J. Barluenga, F. Lopez, and F. Palacios, Tetrahedron Lett., 1987, 2875. 8 E. V. Abel and S. A. Mucklejohn, Phosphorus Sulfur, 1981,9, 235. 9 (a) M. I. Kabachnik, Phosphorus, 1971, 1, 117. (b) R. A. Shaw, Phosphorus Sulfur, 1979, 5, 363. 10 J. Barluenga, J. Jardon, and V. Gotor, J. Org. Chem., 1985,50, 802. 11 N. Walker and D. Stuart, lsquo;Difabs,rsquo; Acta Crystallogr., Sect. A, 1983, 39, 158-166. 12 P. Main, S. J. Fiske, S. E. Hull, L. Lessinger, G. Germain, J. P. Declercq, and M. M. Woolfson. lsquo;Multan 80 System,rsquo; University of York, 1980. J. CHEM.SOC. PERKIN TRANS. I 1988 13 J. M. Stewart, P. A. Machin, C. W. Dickinson, H. L. Ammon, H. Heck and H. Flack. lsquo;The X-Ray Systemrsquo; Technical report TR-446, Computer Science Center, University of Maryland, 1976. 14 International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, England, 1974, vol. IV. 15 C. K. Johnson, ORTEP, Report ORNL-3794, Oak Ridge National Laboratory, Tennessee, U.S.A., 1965. Received 1st June 1987; Paper 71950
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