Hencsei, Pál

Nagy, József

Zimonyi-Hegedűs, Emese

English

Periodica Polytechnica (Budapest University of Technology and Economics)

PREPARATION AND SPECTROSCOPIC INVESTIGATION OF N-SILYL-PHENYLENEDIAMINES By J. NAGY, P. HE~CSEI and E. ZElIO:'YYI-HEGEDUS Department of Inorganic Chemistry, Technical University, Budapest (Received }Iarch 21, 1974) Introduction In the course of the study on the Si-N bond, aftEr the N-silyl-pirroles and anilinosilanes, preparation lJ,r and IR spectroscopic investigations phenylene-diamines silylized on nitrogen followed, to be reviewed in the present paper. The following compounds are discussed: N,N'-bis-(trimethylsilyl)-ortho-phenylenediamine (I), N ,N' -bis-( trimethylsilyl)-metaphcnylenediamine (II), N ,N' -bis-(trimethylsilyl)-paraphenylenediamine (Ill), and N,N,N' ,N' -tetra-kis-( trimethylsilyl)-para-phenylenediamine (IV). Literary Survey on Phenylenediamines Few papers have been published on silyl-phenylenediamines so far. Some authors investigated these compounds but their works contain very few data. BIRKOFER et al. [1] reported on the preparation of the silicon derivatives of ortho-phenylenediamine. The reactions were carried out in toluene starting from ortho-phenylenediamine and trimethylchlorosilane in the presenc(> of triethylamine at a yield of 95 %. KLEBE [2] reported of the preparation of meta- and paraderivatives by the same method but in benzene solution. STEWART et al. [3] prepared the ortho-derivative from ortho-phenylenediamine with hexamethyldisilazane in the presence of trimcthylchlorosilane in catalytic quantity, in absolute tetrahydrofuranc, at a yield of 83%. This paper also contains some NMR and IR data of N,N'-bis-(trimethylsilyl)-ortho-phenylene-diamine. Apart from the l'eferences these compounds are mentioned in some patents [4] but these give no further information of preparation and physical and chemical properties. N ,N,N' ,N' -tetrakis-(trimethylsilyl)-para-phenylene-diamine are mentioned in two papers by GERSON et al [5, 6] where the ESR spectrum of the compound is also reviewed. VhTKE et al. [7] published the preparation and IR spectrum of the tetrasilyl-derivative. This compound was prepared from para-phenylenediamine with trimethyl-diethylamino-silane in the presence of (NH.t)2S0" as catalyst, the product had a yield of 72%. The data of silyl-phenylenediamines found in the literature are compiled in Table 1. 1* 276 m.p. QC b.p. °C/Hgmm 20 nD spectra data J. ;YAGY et al. Table I Data published on silyl-phenylenediamines I. 23 32-34,5 137/14 106-08/1,8-2 XMR, IR II. i HI. 103-05 1,5266 The Preparation of the Compounds IV. 96 112-16/0,25 IR,Raman, ESR Silyl-phenylenediamines were prepared from the respective phenylenedi-amines dissolved in organic solvents together with triethylamine as acid acceptor, and to this mixture trimethylchlorosilane was added. For the pre-paration of ortho-, meta- and para-derivatives toluene, benzene, and xylene was used as solvents. To 1 mole of phenylenediamine 2 moles of trim ethyl-chlorosilane and 2 moles of triethylamine were taken. The crude ortho- and meta-derivatives were purified by fractionated vacuum distillation, the para-derivative was recrystallized from carbon tetrachloride. The yields were: I: 70%, Il.: 80%, Ill.: 50% in this order. The tetrakis-silyl compound was pre-pared by the method reported in [7]. The purity of the products was checked in various ways: by C-H analysis, gas chromatography, ebullioscopic deter-mination of the molecular weight in carbon tetrachloride and by measured and calculated molecular refraction. The physical and chemical data of each compound are sho'wn in Table Il. m.p.OC b.p. °C/Hgmm 25 nD d~5 g/ml MRD (exp) MRD (calc) Table IT Physical-chemical'data-of-silyl-phenylenediamines, I. H. HI. 104,5 134/14 105-06/0,]5 1,5051 1,5278 0,9268 0,9616 80,82 80,83 79,66 79,66 Spectroscopy IV. 95,5 115-16/0,2 The DV absorption spectra of the compounds were recorded on a Spektro-mom 201 spectrophotometer. Cyclohexane (n-hexane in the case of compound IV) was used as solvent. The cell lengths were 0,2 and 1 cm, the concentrations Iz\VESTIGATIOS OF z\-SILYL-PHESYLESEDlkUISES log£ ~.5 2 3,5 2,5 2 -1,5 1 o-C5H4 [Ni-iSl(CH 3)3J2 2 o-CSH4 (eH2)2 277 o·~co 210 220 230 240 250 260 270 280 290 300 310 320 330 'Mnm) Fig. 1. DV absorption spectra of ::'\_::'\'-bis-(trimethylsilyl)-ortho-phenylenediamine and ortho-phenylenediamine i - - , J.:J 1 1 ~ I 1 2 O,5\L---~--~ ____ ~ __ -J ____ ~ __ ~ ____ ~ __ ~ ____ ~ __ -L ____ ~ __ ~ ____ ~1 ~. 200 2'0 220 230 240 250 250 270 280 290 3eO 310 320 330 :,(nm) Fig. 2. 'CV absorption spectra of ::.\,::'\'-bis-(trimethylsilyl)-meta-phcnylenediamine and meta-phenylenediamine ranged from 10-2 to 10-5 mole/I. The DY ab:oorption :opectruill of phenylenedia-mine 'was al:oo recorded for the evaluation of the spectra. The spectra and the data for the absorption maxima are shown in Fig 1 to 3 and in Table HI. 278 log.£ 4,5 ~ I 3 4 r 3.5 3 2,5 1,5 1 p-C6H"[NH5i(CH3)3JZ 2 p-C6 H4 (NH2)2 3 p-C6 H4 [N (51(CH3)3)2J2 J. lYAGY ., al. i I. 0,51 L --L--L-~-~-~-~--::-'-:---:~--::.l.---::L::----::'-::--:-''-:--:-''~''. 200 210 220 230 21,0 250 260 270 280 290 300 310 320 330 A(nm) Fig. 3. UV ltbsorption spectra of N,1'I'-bis-(trimethylsilyl)-para-phenylenediamine, N,N,N'.:\ '-tetrakis-(trimethylsilyl)-para-phenylenediamine and para-phenylenediamine Table HI DV absorption data of silyl-phenylenediamines i. nm l'~ cnl- 1 I. 24,5 40816 10500 29·1 34014 3690 n. 225 44444 18600 250 inf. 40000 6260 296 33784, 344,0 Ill. 257 38911 9,1-10 320 31250 2380 IV. 239 41841 10 HO 279 inf. 3584,2 910 314 31847 480 N,N'-bis-(tertiary-buthyl)-phenylenediamine canDot he prepared he-cause of steric hindrance and only few spectra of the N ,N' -dimethyl-phenylene-diamines" are known so we compared the spectra to these of phenylene-diamines. The IR spectra were recorded on a UR-20 spectrophotometer. Recordings were performed on specimens in 0,02 mm tubes and between two plates in layers. The IR data and the assignations are shown in Table IV. I,'TESTIGATIOS OF S-SIL YL-PHESYLESEDLDIISES Table IV IR spectroscopic data of silyl-phenylenediamines 1. 3372 s I' ~H 3072 w I' (=CH) 3040 ill )' (=CH) 2964 vs l'asCH3 2905 ill "sCH3 1620 s l' CC 1604 vs " CC 1590 vs )' CC 1508 vs l' CC 1498 vs l' CC 1463 ill l' CC 1406 s OasCHa(Si) 1305 vs l' CN 1255 vs OsCH3(Si) 1102 ill p(=CH) 1047 s p(=CH) 860 vs gasCH3(Si) vs m w 835 vs ga,CHiSi) 780 s gsCH3(Si) 745 vs i'< =CH) 690 S "a,SiCa 622 l' SiN very strong strong medi~m weak i 11. 3385 s v ~H 3080 w I' (=CH) 3044 ill " (=CH) 2962 vs )'asCHa 2905 S l'sCH3 1613 vs pCC 1595 s I' CC 1506 vs v CC 1455 ill v CC 1400 s oa,CHiSi) 1306 s " CN 1255 vs 05 CHi Si) 1093 w p(=CH) 1079 w p(=CH) 855 vs gasCHiSi) 843 vs gasCHiSi) 768 s gsCHiSi). i' (= CH) 692 ill "asSiCa. ;' CC 620 m J' Si); Discussion 3382 ill 3050 w 3035 w 2960 w 2860 w 1635 s 1522 vs 1455 w 1450 w 1313 m 1266 s 1070 w 1015 w HI. " NH I' (=CH) I' (=CH) )'asCHa )'sCH1 V CC I' CC V CC r)asCHa(Si) I' CN OsCH3(Si) p(=CH) p(=CH) 835 vs gasCH3(Si). y(=CH) 800 m gsCH3(Si) 730 s gsCH3(Si) 518 s l' SiN (?) 279 From thc study of the ITV spectra of ortho- andmeta-phenylcnediamines and their silyl derivatives it was stated that the spectra showed small differences, only a small bathochromic shift was found in the case of thc silyl derivatives compared to phenylenediamines. The bathochromic shift was more considerable in the spectra of para-phenylenediamine and bis-(trimethyl-silyl)-para-phenylenediamine and the rU::l of the spectra was quite different in the case of the tetrakis-silyl derivatiyc. IR data have following conclusions. The valence vibration J!NH is assigned to the maximum about the -wave number 3400. This single maximum found ill this region affirms that the compounds contain only monosubstituted amino-groups and they have no unsubstituted NH2 groups. The maxima cor-responding to vibrations j!( = CH) and ,,(CC) show up according to the differ-ently substituted (ortho-, meta-, and para-) benzene ring: 745 (ortho-), 768 and 692 (meta-) and 835 (para-) wave numbers. The valence vibration of the Si-N bond was assigned to 622 and 620 cm -1 values. In connection with N-silyl-pyrroles, BURGER and BURCZYK [8] showed the I' Si-N vibration to 280 J . .:\AGY et al. appear around 600 cm -1. Assignation is uncertain in compound In where single maximum is found at 518 cm -1 in the IR spectrum. From the DY and IR spectra of N-silyl-phenylenediamines an interaction can be stated to arise between nitrogen and silicon, inducing the formation of delocalized systems. This assumption is tu be supported by quantum chemieal calculations. The authors wish to thank Dr. T. G.,(BOR for recording the IR spectra. Summary The preparation of ::\".silyl-phenyjenediamin~s is :reported. The UY and IR absorption spectra were recorded and evalnated. Inferences were drawn on the structure of the molecules. References 1. BIRKOFER, L.-KUIILTHAL H. P.-RITTEll, A.: Chem. Ber. 93, 2810 (1960) 2. KLEBE, J. F.: J. Polymer Sci. B2, 1079 (1964) 3. STEWART, H. F.-KoEPSELL, D. G.-- WEST, R.: J. Am. Chem. Soc. 92, 84·6 (1970) 4. "G. S. 3,172.874 (1965), Fr. 1,-t37,751 (1966), E S. 3,303.157 (1967), Ger. ~,026.399 (1970) 5. GERSO]);, F.-KRY]);ITZ, D.-BoCK, H.: Angew. Chem., Int. Ed. Engl. 8,767(1969) 6. GERSO]);, F.-KRY]);ITZ, "G.-BOCK, H.: Helv. Chim. Acta, 52, 2512 (1969) 7. WITKE, K.-REICH, P.-l(IUEGS31A]);X, H.: Z. anorg. allg. Chem. 380, 16·1· (l971) 8. BtRGER, H.-BDRCZYK, K.: Z. anorg. allg. Chem. 381, 176 (1971) Dr. 16zsef NAGY Dr. Pal HEl'ICSEI Emese ZDIOl'IYI-HEGEDUS 1 H·1521 Budap'" 

PREPARATION AND SPECTROSCOPIC INVESTIGATION OF N-SILYL-PHENYLENEDIAMINES

https://pp.bme.hu/ch/article/download/3203/2308

PREPARATION AND SPECTROSCOPIC INVESTIGATION OF N-SILYL-PHENYLENEDIAMINES

Abstract

Similar works

Full text

Available Versions

Periodica Polytechnica (Budapest University of Technology and Economics)