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4-( Diphenylphosphino)Phenyl]-1 -Isocyanoethane (10)

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4-( Diphenylphosphino)Phenyl]-1 -Isocyanoethane (10) PDF hosted at the Radboud Repository of the Radboud University Nijmegen The following full text is a publisher's version. For additional information about this publication click this link. http://hdl.handle.net/2066/16401 Please be advised that this information was generated on 2021-10-02 and may be subject to change. 112 A. J. Naaktgeboren et al. / Synthesis of diphenylphosphine-substitutedpolyf( 1 -phenylethyl) iminomethylene] in the spectrum of the reaction mixture having reacted phenyl-l-methylpyrimidinium iodide14 (Id) were prepared as overnight (see above), are assigned to the N —CH 3 and the described in the literature. H —C= signals of 9 (R 1 = H), respectively11,12. This was confirmed when after an overnight reaction the ‘H-NMR General procedure for measuring the 1 H-NMR spectra in N2DA-D20 spectra of the solutions of lb, lc and Id in N 2D4 D 20 were To 50 mg of the quaternized compound 1 being cooled at —30°, measured. In the case of lc and Id in the low field region a about 0.5 ml of precooled ( — 30°) deuterated hydrazine hydrate peak is observed between 5 7.03-7.09 i.e. the HC= in 9 (Merck, 80% N2D4 D20, deuteration ratio >99%) was added. (R 1 = H) where in the case of lb this low-field singlet is A yellow-orange coloured solution was obtained. TMS was added absent but a peak is observed in the high field region at 5 1.87 as internal standard. A sample of this solution was introduced in a i.e. the CH 3 in 9 (R 1 = C H 3)13. 1 H-NMR tube being cooled at ~ —30°. The measurements started 10-15 min after addition. The three pyrazoles 8b, 8c and 8d which were isolated from The pyrazoles 8a-d being obtained in the hydrazinolysis were the analogous reaction of the pyrimidinium salts lb, lc and isolated as described previously3. Id, are all deuterated at position 4. It was observed further that the 3,5-dimethyl-4-D-pyrazole (8c) also contains deu­ terium in the methyl group as proved by the presence of Acknowledgement peaks at m/e = M, M + 1, M + 2, M + 3, M + 4 and M + 5 in the mass spectrum. Apparently, in the open-chain One of the authors (M. S. Brouwer) wishes to thank the compounds 3, 4 and 5 the methyl group participates in the management of Philips Duphar B.V., Weesp, The Nether­ tautomerism since the alternative possibility - a H/D ex­ lands, for giving him the opportunity to carry out this work change in the methyl group of 3,5-dimethyl-4-D-pyrazole - at the Laboratory of Organic Chemistry, Agricultural does not take place under these mild conditions. University, Wageningen, The Netherlands. We are indebted to Drs. C. A. Landheer for measuring the mass spectra. Experimental part 12 It cannot be excluded that 9 undergoes hydrazinolysis in the presence of hydrazine leading to a replacement of the N(CH3) The 1 H-NMR spectra were recorded on a Jeol JNM-C60 H spectro­ group. See: The Chemistry of the Carbon-Nitrogen double meter, using TMS (5 = 0) as internal standard. In the case of adduct bond (1970) p. 81, 82, Ed. S. Patai. However, it does not change measurements the apparatus was equipped with a JES-VT-3 the assignments. variable temperature controller. Measurements of D contents were 13 Compare Sadler system 5390 M: (CH3)2N—CH =N —C6H4- carried out on an AEI-MS 902 mass spectrometer. pC 1; N -C H 3 5 2.95 and -C H = 5 7.35. See also 8325 M: (CH3)2N—C(CH3)=N —C6H4-/jC1; N -C H 3 5 3.00 and Preparation of the starting materials -C (C H 3) = 5 1.78. 1-Methylpyrimidinium iodide (la) 1,2-dimethylpyrimidinium 14 E. A. Oostveen and H. C. van der Plas, Reel. Trav. Chim. iodide4 (lb), 1,4,6-trimethylpyrimidinium iodide3 (lc) and 4- Pays-Bas 93. 233 (1974). Poly(iminomethylenes). 7 1. Synthesis of diphenylphosphine-substituted poly[(l-phenylethyl)iminomethylene] A. J. Naaktgeboren, R. J. M. Nolte and W. Drenth Department of Organic Chemistry of the University, Croesestraat 79, Utrecht, The Netherlands (Received August 31st, 1977) Abstract. Polymer-anchored phosphine functions were obtained in two ways: by diphenylphosphina- tion of poly[[l-(4-bromophenyl)ethyl]iminomethylene] and by polymerization of l-[4(diphenyl- phosphino)phenyl]-l-isocyanoethane. The synthesis of the monomers and polymers is described. Introduction Many efforts have been made at anchoring homogeneous ' Part 6: R. J. M. Nolle, J. A. J. van Zomeren and J. W. Zwikker, catalysts on insoluble supports. For this purpose materials submitted for publication. like silica2 and polystyrene3,4 have frequently been used. 2 K. G. A Hum, R. D. Hancock, /. V. Howell, S. McKenzie, R. C. This immobilization of a catalyst sometimes diminishes Pitkethlv and P. J. Robinson, J. Organometal. Chem. 87, 203 side-reactions5 and extends its lifetime. (1975). The anchoring of homogeneous catalysts on the usual types 3 J. C. Bailor, Jr., Catal. Rev.-Sci. Eng. 10, 17 (1974). of polymeric supports suffers from a number of disadvan­ 4 K. G. Allum, R. D. Hancock, /. V. Howell, R. C. Pitkethly and tages. In most cases the secondary structure of the polymers P. J. Robinson, J. Organometal. Chem. 87, 189 (1975). and the surroundings of the catalytic centres are unknown. 5 R. H. Grubbs, C. Gibbons, L. C. Kroll, W. D. Bonds, Jr. and C. H. Brubaker, Jr., J. Amer. Chem. Soc. 95, 2373 (1973). Often, the accessibility of the complexes is reduced, giving 6 G. Bernard, Y. Chauvin and D. Commereuc, Bull. Soc. Chim. rise to lower activities6. The degree of introduction of phos­ Fr. 1163 and 1168 (1976). phine groups, often used as interfaces between polymer and M. J. Farrall and J. M. Fréchet, J. Org. Chem. 41, 3877 (1976). metal ion, appears to be low: 1 per 3-20 polymer side H R. H. Grubbs and S. H. Su, J. Organometal. Chem. 122, 151 chains7,8. Moreover, the polymers usually contain some (1976). Recueil, Journal o f the Royal Netherlands Chemical Society, 97/4, april 1978 113 residual chlorine or bromine. In earlier papers Millich9 and Just like functionalized polystyrene resins, polymer 5 suffers we10,11 showed that poly(iminomethylenes) have the con­ from two disadvantages: the distribution of phosphorus figuration of a tightly coiled helix with side-chains pro­ over the polymer chain is unknown and the presence of truding from a rodlike main chain. This property gives bromine can affect the behaviour of the support, e.g. by poly(iminomethylenes) major advantages for catalyst at­ quaternization of phosphine with a possibility of cross- tachment: the catalytic centres are more accessible and the linking3. Therefore, we decided to synthesize also a poly- secondary structure is more uniform and better defined. (iminomethylene) with a phosphine function in each The chirality of the main chain might be attractive for repeating unit (Scheme 2). asymmetric catalysis. In this paper we describe the synthesis of two types of tri- ii phenylphosphine containing poly(iminomethylenes). The 1 — PhjP - Ph2P' C-CHj first type was made by diphenylphosphination of poly[[ 1 - 8 (4-bromo-phenyl)ethyl]iminomethylene]. The second type was synthesized by polymerization of a triphenylphosphine containing isocyanide. Applications of these polymers in catalysis will be described in subsequent papers of this H H H H H Ph2P C-N—C Ph?P C—N-C Ph7P C-N-C=0 series. CH3 \ / CH3 CH3 L 10 Results and discussion 11 Millich has described the synthesis of 1-phenylethyl iso­ Scheme 2 cyanide and its polymerization by means of an acid-coated glass catalyst12. We have synthesized l-(4-bromophenyl)- Protection of the carbonyl function in 4-bromoaceto­ ethyl isocyanide, (3), in an analogous way starting from phenone, 1, by 1,2-ethanediol gave the acetal 6. Its product 4-bromoacetophenone (Scheme 1). Polymerization of 3 was of lithiation can be used as a synthon for coupling with many types of reagent. Reaction of this synthon with chloro­ H H H C - N - C - 0 diphenylphosphine gave the substituted triphenylphosphine 7. This compound w^s hydrolyzed to give 8 which was directly converted to yV-formyl[l-[4-(diphenylphosphino)- phenyl]ethyl]amine, 9, via a Leuckart synthesis15. Initial attempts to synthesize 9 through reaction of the Grignard or lithium derivative of 2 with chlorodiphenylphosphine failed. II II H N N C—N-C The isocyanide 10 was obtained in a yield of 75-85% by 1 HC-CKU h c - c h 3 0r\ / CH-j dehydration of 9 using either phosphoryl chloride1'1 or A n perchloromethyl formate17, both in combination with V triethylamine. Direct synthesis of 10 from isocyanide 3 by H Br PPh- reaction with butyllithium and chlorodiphenylphosphine m n gave unsatisfactory results. 5 The pale-yellow crystals of 10 were moderately soluble in Scheme 1 ethanol and diethyl ether, and soluble in tetrahydrofuran, acetone, chloroform and dichloromethane. In chlorinated accomplished by nickel chloride13. The intrinsic viscosity of hydrocarbons slow decomposition was observed. In the the polymer obtained, (4), was 0.31 dl/g. If we use the values infrared spectrum of 10 strong absorptions were visible at of the Mark-Houwink constants determined for poly[(1 - 2142 and 1430 cm-1 indicative of the isocyanide and phenylethyl)iminomethylene]14 to estimate the molecular phenylphosphine functions. The structures of 10 and its weight, a value of 40,000 is calculated. precursors 8 and 9 were supported by elemental analysis, The introduction of diphenylphosphine functions into ‘H-, 13C-, 31P-NMR and mass spectroscopy.
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