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Scientific Paper
SYNTHESIS AND CHARACTERISATION OF N-FUNCTIONALIZED ENETETRAMINES, AND THEIR PROPERTIES
Yetkin Gök,a* Engin Çetinkaya,b Ismail Özdemir,a Bekir Çetinkaya,b
and Michael F. Lappertc
Inönü University, Faculty Science and Art, Department of Chemistry, 44069 Malatya,Türkiye
b Ege University, Department of Chemistry, 35100 Bornova-Izmir, Türkiye
c University of Sussex, Chem Lab., Brighton 9QJ, E Sussex, England
Received 22-12-03
Abstract
Two general routes are described for the synthesis of the title compounds from the reaction of, either the dimethyl acetal of N,N’-dimethylformamide and an appropriate N,N’bis(secondary amine), or sodium hydride (or potassium tert-butoxide) and 4,5-dihydroimidazolium salts. N-Functionalized enetetramines (3, 8) having 2-methoxyethyl or allyl substituent on the N-atom have been made. The reaction of this enetetramines with S8 and Se, gave the corresponding cyclic chalcogeno ureas derivatives (4, 5). Treatment of potassium tert-butoxide with 1,1’-ethylene-3,3’-diallyldiimidazolidinium dibromide (7) afforded, either the enetetramine (8), or, alternatively, the amino-Claisen isomer (9). All new compounds were identified by 1H, 13C NMR, FT-IR and micro analysis.
Key words: enetetramines, imidazole, amino-Claisen rearrangement
Introduction
The chemical behavior of the carbon-carbon double bond in tetrasubstituted ethylene derivatives is greatly influenced by the electron-donating or withdrawing power of its four substituents. Alkenes with four electron-donating substituents react as strong nucleophiles and this trend is particularly pronounced in tetraaminoethylenes. These compounds are referred to as enetetramines (electron-rich olefins).1,2 Although an extensive chemistry of enetetramines of the type I (R = R’ or R ? R’) and II (Figure 1) has been developed,3 relatively little is known of chemistry of analogues.
r(CH2)n^
(H2C)m)=(    (CH2)m ""--N          N-"
R'          R'
I                                                    II
Figure 1. Exobicyclic and endotricyclic enetetramines.
R        R'
^N          NT
R'          R
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The general route to compound I involves interaction of the appropriate N,N’-disubstituted-1,2-diaminoetane, NH(R)(CH2)2NRH (R=a primary alkyl or an unhindered aryl group) with the dimethyl acetal of N,N-dimethylformamide (DMFDMA) in an inert atmospher, eqn 1.
2HN(R)(CH2)2N(R)H   +   2CH(NMe2)(OMe)2   ^f^    I (R=R')    +    2Me2NH    +   4MeOH         (1)
The equilibrium is driven to the right by continuous removal by distillation of MeOH and Me2NH. The reaction has been extended to (i) six-membered bicyclic analogues of I and (ii) compounds II.5,6 Symmetrical tetraarylenetetramines (I, R= an unhindered aryl group, eg. R= Ph) have been prepared by a similar procedure (EtOH elimination) from the orthoester CH(OEt)3 and HN(R)(CH2)2NRH or by heating PhN(CH2)2N(Ph)C(H)CCl3 (CHCl3 elimination).7
Our group described a useful alternative method for preparing compounds I and II from sodium hydride and a 4,5-dihydroimidazolium halide, eqn. (2) [e.g. For I or II, n=m= 2, R= CH2Ph].6
R                                                                R          R'
^N                                        THF             ^N          N^
2      +) X-     + 2 NaH     ----^-»          )=(      I                                  (2)
^N                                     -2 NaX          ^N          NT
R                                       "H2                  R'          R
This procedure has the advantages that it requires extremely mild conditions, affords the products in high yield and is particularly suitable for unsymmetrical enetetramines, e.g. I and II (R * R’).
R          R
R'
I' Figure 2. The rearrangement of I.
The biimidazolidinylidene I (R=R’= allyl) was not accessible using the procedure of eqn. (1) and, if formed, spontaneously rearranged to the isomer I’ (R=R’= allyl) (Figure 2).8 This thermal amino-Claisen rearrangement was believed to be [3,3]-sigmatropic, because the corresponding thermal transformation of the tetracrotyl analogue I (R=R’= CH2CH=CHMe) regiospecifically yielded I’ [R= CH2CH=CHMe, R’= CH(Me)CH=CH2], while its photochemical isomerisation gave, not only the latter,
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but also the isomer I’ (R=R’= crotyl). In a preliminary publication we noted, that a similar I›I’ isomerisation (8›9, iii in Scheme 2) occured for the case of R= -CH2CH2-, R’= CH2CH=CH2.
For some years we have used to enetetramines (electron-rich olefins) such as I as a sources of carbenetransition metal complexes.9 In this paper we report straightforward preparation of a series (i) N-functionalized enetetramines (3, 8) having 2-methoxyethyl or allyl substituent on the N-atom, (ii) the cyclic chalcogeno ureas (4, 5) and (iii) the thermal degradation product 9 of the enetetramine 8.
Results and Discussion
The enetetramines 3 can be prepared from the interaction of the DMFDMA with the appropriate secondary diamine (eqn. 1) or sodium hydride (or potassium tert-butoxide) with 4,5-dihydroimidazolium salts in an inert atmospher (eqn. 2). These methods are illustrated in Scheme 1 and Scheme 2 for the case of the N-functionalized enetetramines (3a, R=R’= CH2CH2OMe; 3b, R= CH2CH2OCH3, R’= CH3; 3c, R= Ph, R’= CH2CH=CH2; 8, R= -CH2CH2-, R’= CH2CH=CH2). The identify of these compounds has been confirmed by CHN analyses, FT-IR, 1H and 13C NMR spektroscopy.
The starting materials for the enetetramine 3a was made by the literature procedure from ClCH2CH2OCH3 and H2N(CH2)2NH2.9 The enetetramine 3a was prepared from DMFDMA and H3CO(CH2)2HN(CH2)2NH(CH2)2OCH3, as for eqn. (1).4 The starting materials (2b, 2c, 7) for enetetramines 3b, 3c and 8 readily prepared from appropriate alkyl halide. The hydrogen atom attached to C(2) of imidazolium salt has considerable protic character (as evident from 1H NMR data) and hence the high reactivity to the base-induced protic acid elimination is not surprising. Thus, they reacted smoothly and good yield with an excess (ca. 20%) sodium hydride or potassium tert-butoxide in tetrahyrofuran at ambient temperature within 9-18h.
The 1,1’-dimethyl-3,3’-di(2-methoxyethyl)-2,2’-biimidazolidinylidene (3b) was obtained as a mixture of cis/trans-isomers as evident from the observed two peaks at 129.5 and 129.7 ppm for ? (13CC=C) in the 13C NMR spectra of 3b. 1,1’-Diphenyl-3,3’-diallyl-2,2’-biimidazolidinylidene (3c) was similarly obtained as a mixture of cis/trans-
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isomers. It is clearly notice that ? (13CC=C) move to higher field upon attachment of the OMe group.
R
1    R' R
+\
2    R"
X-
(i)
(ii)
R          R1
^N          NT
R'         R
(iii)
(iv)
R
[     )=s R'      4
R
L    /^ R'
Se
a     R,R'= CH2CH2OCH3
b     R= CH3, R'= CH2CH2OCH3
c     R= C6H5, R'= CH2CH=CH2
Scheme 1. Synthesis of N-functionalized enetetramines and their cylic chalcogeno urea derivatives. Reaction conditions: (i) CH(OCH3)2N(CH3)2, 100-120 °C; (ii) NaH (KOBut), THF, 25 °C; (iii) S8, toluene, 110 °C; (iv) Se, toluene, 110 °C.
The cyclic chalcogeno ureas were prepared from enetetramines 3 and appropriate Group VI elements in good yields according to the procedure indicated in scheme 1 and described in experimental section. This behavior is typical for reactive enetetramines I and II.
Both, thio urea and selenourea exhibited a characteristic ?C=S and ?C=Se band at 1450-1502 cm-1which corresponded well with 1500 cm-1 found for the functionalized derivatives. 13C chemical shifts, which provide a useful diagnostic tool for urea compounds, show that C=S (or C=Se) is substautially deshielded. Values of ? (13C=X, X= S or Se) are in the range 180-184 ppm and similar the those found for non-functionalized derivatives
Treatment of potassium tert-butoxide with compound 7 afforded, either the enetetramine 8, or, alternatively, the isomer 9 depending on the nature of the allyl substituent at nitrogen (Scheme 2). When compound 7 reacted with potassium tert-butoxide in THF at ambient temperature within 9 h, the enetetramine 8 was obtained. The enetetramine 8 exhibit a characteristic ? (13CC=C) peak at 160.8 ppm. The 13C data showed that (8) contained one type of allyl group.
As for eqn. 2, when compound 7 was heated with potassium tert-butoxide in THF under reflux for 1 h, a regiospecific rearrangement was observed compound 9 was formed as, the result of a [3,3]-sigmatropic amino-Claisen type rearrangement. The 13C
3
5
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data were particularly informative, as they showed that (9) contained two types of allyl group (Figure 3).
I       I
^-N        NT
(i)
I          I
I +> <¦'+!
CH2=CHCH2    CH2CH=CH2
7
2Br-
(ii)
(iii)
I                         I
L     )"(     J       8
^N        NT
CH2=CHCH2    CH2CH=CH2
I          I
^N /   NT
CH2=CHCH2
CH2CH=CH2
Scheme 2. Synthesis of enetetramines 8 and its thermal degradation product 9. Reaction conditions: (i)BrCH2CH=CH2, DMF, 25 °C; (ii) KOBut, ButOH, 25 °C; (iii) KOBut, THF, 60 °C.
l 6.0
-N /    NT   ' CH2=CHCH2 iH2CH=CH2
i
3.5
5.5
5.0              4.5              4.0              3.5              3.0
Figure 3. 1H NMR spectrum of compound 9.
2.5
In conclusion from readily available starting materials, such as 1-alkyl-2-imidazoline four new N-functionalized enetetramines, six chalcogeno ureas derivatives and one rearanged isomer of 1,1’-ethylen-3,3’di(alyl)-2,2’biimidazolidinylidene have been prepared and characterized.
6
9
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Experimental
All manipulations of air/or moisture-sensitive compounds were carried out under an argon atmosphere by using standard Schlenk techniques. Solvents were dried and freshly distilled under argon before use. IR absorption spectra were obtained from a Matson 1000-FTIR spectrometer in KBr discs, in the range of 400-4000 cm-1. 1H-NMR (400 MHz) and 13C-NMR (100 MHz) spectra were recorded on a Bruker DPX FT NMR spectrometer (CDCl3 or C6D6 and TMS as internal standard).
1,3,1’,3’-Tetra(2-methoxyethyl)-2,2’-biimidazolidinylidene (3a). A stirred solution of N,N-dimethylformamide dimethyl acetal (9.3 mL, 70 mmol) and 1,2-bis(2-methoxyethylamino)etane (11.2 g, 63.6 mmol) in dry toluene (20 mL) was heated for 3 h at 90 °C under an argon atmosphere. The reaction mixture was then heated at 120 °C under distillation conditions, allowing the produced dimethylamine and methanol to be removed. From the resultant product, unreacted starting materials were eliminated by evaporation in vacuo. Oily residue was distilled in vacuum (130-140 °C/0.15 mmHg) (6.62 g, 56%). 1H NMR (C6D6) ?: 2.48 (s, 6H,CH3), 2.74 (t, J 6.5 Hz, 4H, CH2CH2OCH3), 2.96 (t, J 6.5 Hz, 4H, CH2CH2OCH3), 3.12 (s, 6H, OCH3), 3.39 (t, J 5.5 Hz, 8H, 4,5-CH2). 13C NMR (C6D6) ?: 42.4 (CH3), 53.2, 54.9, 74.0 (CH2CH2OCH3), 74.0 (4,5-CH2), 129.5, 129.7 (C=C).
1,1’-Dimethyl-3,3’-di(2-methoxyethyl)-2,2’-biimidazolidinylidene (3b). 1-methyl-3-(2-methoxyethyl)-4,5-dihydroimidazolium iodide (9 g, 33.33 mmol) was added to a suspension of sodium hydride (1.2 g, 50 mmol) in THF (50 mL). The mixture was stirred at 20 °C for 18 h then heated at 60 °C for 1 h, and the volatiles were removed under reduced pressure. Toluene (15 mL) was added to the resultant oily residue and the suspension was filtered. After removal of the solvent from the filtrate, the residue was distilled in vacuo (90-100 /0.15 mmHg) (4.16 g; 88%). 1H NMR (C6D6) ?: 2.98 (s, 8H, 4,5-CH2), 3.12 (s, 12H, OCH3), 3.21 (t, J 5.7 Hz, 8H, CH2CH2OCH3), 3.42 (t, J 5.7 Hz, 8H, CH2CH2OCH3). 13C NMR (C6D6) ?: 46.6, 47.9, 52.3 (CH2CH2OCH3), 52.5 (4,5-CH2), 128.2 (C=C).
1,1’-Diphenyl-3,3’-diallyl-2,2’-biimidazolidinylidene (3c). This compound was prepared from 1-phenyl-3-allyl-4,5-dihydroimidazolium iodide (3.3 g, 12.3 mmol) and potassium tert-butoxide (42.2 mL, 0.3 M). The compound 3c was recrystallised from
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pentane (5 mL) and Et20 (7 mL) at -25 °C, yield (1.07 g; 55%), mp 68-69 °C. Anal. Calcd for C24H28N4: C 77.38, H 7.58, N 15.04. Found: C 77.34, H 7.12, N 14.93. *H NMR (C6D6) ?: 2.53 (t, J 62 Hz, 4H, 4,5-CH2), 2.53 (t, J 62 Hz, 4H, 4,5-CH2), 3.70 (d, J 6.1 Hz, 4H, CH2=CHCH2), 4.49 (m, 4H, CH2=CHCH2), 5.58 (m, 2H, CH2=CHCH2), 6.87-7.75 (m, 10H, CHs). 13C NMR (C6D6) ?: 48.8, 49.2, 51.4, 54.4 (4,5-CH2), 55.2, 118.3, 136.5 (CH2=CHCH2), 116.3, 118.9, 119.4, 121.1, 121.1, 136.2 (C6H5), 144.4, 146.1 (C=C).
Reaction of Group VI Elements (S8 and Se) With iV-Functionalized Eneteramines 3. General Procedure for Preparation of Compounds 4 and 5. A mixture of enetetramine 3 (1 mmol) an sulfur, S8 (2 mmol) in toluene (10 mL) was heated under reflux for 2h. Then, the mixture was filtered to remove unreacted sulfur and all volatiles were removed in vacuo. The crude solid was crystallized from toluene/n-hexane (1/2) upon cooling to -20 °C.
Using a similar procedure, enetetramine (3), (1 mmol) and selenium (2 mmol) afforded l,3-dialkylimidazolidin-2-selenone (5).
1,3-Di(2-methoxyethyl)imidazolidin-2-thione (4a). This compound was prepared from l,3,l’,3’-tetra(2-methoxyethyl)-2,2’-biimidazolidinylidene 3a (0.42 g, 1.12 mmol) and sulfur, S8 (0.07 g, 2.18 mmol), yield (0.21 g, 41%), mp 46-47 °C. Anal. Calcd for C9Hi8N202S: C 49.09, H 9.09, N 12.77. Found C 49.31, H 9.23, N 12.70. IR, ?: 1480 (C=S). lH NMR (CDC13) ?: 3.35 (s, 6H, OCH3), 3.60 (t, 4H, J 5 Hz, CH2CH2OCH3), 3.68 (s, 4H, 4,5-CH2), 3.81 (t, 4H, J 5 Hz, CH2CH2OCH3). 13C NMR (CDC13), ?: 58.8 (4,5-CH2), 47.7, 48.0, 71.4 (CH2CH2OCH3), 182.5 (C=S).
1-Methyl-3-(2-methoxyethyl)imidazolidin-2-thione (4b). This compound was prepared from l,l’-dimethyl-3,3’-di(2-methoxyethyl)-2,2’-biimidazolidinylidene 3b (0.43 g, 1.36 mmol) and sulfur, S8 (0.08 g, 2.50 mmol), yield (0.33 g, 68%), mp 38-39 °C. Anal. Calcd for C7Hi4N2OS: C 48.25, H 8.11, N 16.09, S 18.37. Found C 48.36, H 8.11, N 15.96, S 18.46. IR, ?: 1502.4 (C=S). *H NMR (CDC13) ?: 3.13 (s, 3H, CH3\ 3.34 (s, 3H, OCH3\ 3.47-3.82 (m, 4H, CH2CH2OCH3\ 3.47-3.82 (m, 4H, 4,5-CH2). 13C NMR (CDCI3) ?: 35.0 (CH3), 47.7, 47.8 (4,5-CH2), 49.0, 58.8, 71.4 (CH2CH2OCH3), 182.9 (C=S).
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l-Phenyl-3-allylimidazolidin-2-thione (4c). This compound was prepared from l,l’-diphenyl-3,3’-diallyl-2,2’-biimidazolidinylidene 3c (0.65 g, 1.74 mmol) and sulfur, S8 (0.11 g, 3.43 mmol), yield (0.12 g, 32%), mp 40-41 °C. Anal. Calcd for Ci2Hi4N2S: C 66.05, H 6.42, N 12.84, S 14.67. Found: C 66.01, H 6.31, N 12.73, S 14.44. IR, ?: 1487 (C=S). lH NMR (CDC13) ?: 3.65 (t, 2H, J 9 Hz, 4,5-CH2); 3.99 (t, 2H, J 9 Hz, 4,5-CH2), 4.35 (d)-5.87 (m)-5.29 (m) (5H, CH2CH=CH2), 7.21-7.60 (m, 5H, CH). 13C NMR (CDCI3) ?: 46.9, 49.9 (4,5-CH2), 57.7, 119.6, 126.0 (CH2CH=CH2), 127.2, 129.7, 133.2, 142.0 (C6H5), 183.3 (C=S).
l,3-Di(2-methoxyethyl)imidazolidin-2-selenone (5a). This compound was prepared from l,3,l’,3’-tetra(2-methoxyethyl)-2,2’-biimidazolidinylidene 3a (0.60 g, 1.61 mmol) and selenium (0.3 g, 3.22 mmol), yield (0.3 g, 60%), mp 49-50 °C. Anal. Calcd for C9Hi8N202Se: C 37.83, H 6.35, N 12.61. Found: C 37.69, H 6.11, N 12.71. IR, ?: 1564 (C=Se). lH NMR (CDC13) ?: 3.18 (s, 3H, CH3), 3.29 (s, 3H, OCH3), 3.50-3.88 (m, 4H, CH2CH2OCU3X 3.50-3.88 (m, 4H, 4,5-CH2). 13C NMR (CDC13) ?: 37.1 (CH3), 49.9, 50.0 (4,5-CH2), 49.2, 59.2, 72.0 (CH2CH2OCH3), 181.4 (C=Se).
l-Methyl-3-(2-methoxyethyl)imidazolidin-2-selenone (5b). This compound was prepared from l,l’-dimethyl-3,3’-di(2-methoxyethyl)-2,2’-biimidazolidinylidene 3b (0.35 g, 1.10 mmol) and selenium (0.18 g, 2.27 mmol), yield (0.44 g, 85%), mp 61-62 °C. Anal. Calcd for C7Hi4N2OSe: C 40.76, H 6.84, N 10.56. Found: C 40.90, H 6.60, N 10.62. IR, ?: 1514 (C=Se). 'H NMR (CDC13) ?: 3.35 (s, 6H, OCH3), 3.64 (t, 4H, J 5 Hz, CH2CH2OCH3), 3.71 (s, 4H, 4,5-CH2), 3.90 (t, 4H, J 5 Hz, CH2CH2OCH3). 13C NMR (CDCI3) ?: 61.0 (4,5-CH2), 51.3, 51.7, 74.0 (CH2CH2OCH3), 182.9 (C=Se).
l-Phenyl-3-allylimidazolidin-2-selenone (5c). This compound was prepared from l,l’-diphenyl-3,3’-diallyl-2,2’-biimidazolidinylidene 3c (0.44 g, 1.18 mmol) and selenium (0.19 g, 2.40 mmol), yield (0.53 g, 86%), mp 62-63 °C. Anal. Calcd for Ci2Hi4N2Se: C 54.34, H 5.32, N 10.56. Found: C 54.45, H 5.08, N 10.53. IR, ?: 1488.9 (C=Se). lH NMR (CDC13) ?: 3.63 (t, 2H, J 9 Hz, 4,5-CH2); 3.93 (t, 2H, J 9 Hz, 4,5-CH2), 4.43 (d)-5.85 (m)-5.27 (m) (5H, CH2CH=CH2), 7.19-7.49 (m, 5H, CHs). 13C NMR (CDC13) ?: 47.3, 50.9 (4,5-CH2), 52.9, 119.3, 126.1 (CH2CH=CH2), 127.2, 129.2, 132.3, 141.8 (C6H5), 180.8 (C=Se).
l,l’-Ethylenediimidazolidine (6). A stirred solution of diethylethane-l,2-diamine 1 (0.44 g, 3.01 mmol) in N,N-dimethylformamide dimethyl acetal (0.71 g, 6.07 mmol)
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was heated for 3 h at 90 °C under an argon atmosphere. The reaction mixture was then heated at 120 °C under distillation conditions, allowing removal of the produced dimethylamine and methanol. From the resultant product, unreacted starting materials were evaporated in vacuo. The yellow precipitate of 6 was recrystallized from toluene and n-hexane at -20 °C (0.41 g, 82%). 1H NMR (C6H6) ?: 2.38 (s, 4H, CH2CH2), 2.55 (t, 4H, J 9.3 Hz, 4,5-CH2), 3.68 (t, 4H, J 9.3 Hz, 4,5-CH2), 6.45 (s, 2H, 2-CH). 13C NMR (CDCl3) ?: 46.5 (CH2CH2), 48.8, 55.6 (4,5-CH2), 158.3 (2-CH).
3,3’-Diallyl-1,1’-ethylenediimidazolidinium dibromide (7). To a solution of 1,1’-ethylenediimidazoline 6 (5.05 g, 30.4 mmol) in DMF (20 mL) allyl bromide (6 mL,
69.4 mmol) was added and the mixture stirred at room temperature for 1 h. Et2O (5 mL) was added the reaction mixture. A yellow solid precipitated in this period. The product was filtered, washed twice with dried Et2O and dried in vacuo (12.87 g, 95%), mp 129-130 °C. Anal. Calcd for C14H24N4Br2: C 41.20, H 5.93, N 13.99. Found: C 41.18, H 5.95, N 13.78. 1H NMR (C6D6) ?: 4.03 (t, J 3.5 Hz, 4H, 4,5-CH2), 4.08 (s, 4H, CH2CH2), 4.17 (d, J 6.4 Hz, 4H, CH2=CHCH2), 4.38 (t, J 3.5 Hz, 4H, 4,5-CH2), 5.37 (m, 4H, CH2=CHCH2), 5.83 (m, 2H, CH2=CHCH2), 10.05 (s, 2H, 2-CH). 13C NMR (C6D6) ?:
48.5 (CH2CH2), 40.8, 49.5 (4,5-CH2), 45.2, 122.2, 129.4 (CH2=CHCH2), 158.7 (2-CH).
1,1’-Ethylene-3,3’di(alyl)-2,2’biimidazolidinylidene (8). 3,3’-diallyl-1,1’-ethylenediimidazolidinium dibromide 7 (1.6 g, 3.9 mmol) was added to a suspension of potassium tert-butoxide (1 g, 8.9 mmol) in tert-butanol (20 mL). The mixture was stirred at 20 °C for 10 h. The volatiles were removed under reduced pressure. Pentane (15 mL) was added to the resultant oily residue and product was precipitated. The crude product was recrystallised from pentane (5 mL) and Et2O (7 mL) at –25 °C (0.28 g, 30%), mp 73-75 °C. Anal. Calcd for C14H22N4: C 68.26, H 9.00, N, 22.74. Found: C 68.15, H 8.88, N 22.63. 1H NMR (C6D6) ?: 2.71 (t, J 7.6 Hz, 4H, 4,5-CH2), 2.98 (t, J 7.6 Hz, 4H, 4,5-CH2), 3.09 (s, 4H, CH2CH2), 3.68 (d, J 5.9 Hz, 4H, CH2=CHCH2), 5.00 (m, 4H, CH2=CHCH2), 5.54 (m, 2H, CH2=CHCH2). 13C NMR (C6D6) ?: 41.1, 41.5 (4,5-CH2), 42.3 (CH2CH2), 45.0, 47.3, 116.6, 134.5 (CH2=CHCH2), 160.8 (C=C).
1,1’-Ethylene-2-imidazolinyl-2,3-dialylimidazolidine (9). 3,3’-dialyl-1,1’-ethylenediimidazolidinium dibromide 7 (9.37 g, 22.9 mmol) was added to a suspension of potassium tert-butoxide (7 g, 62.3 mmol) in THF (50 mL). The mixture was stirred at 20 °C for 12 h and heated for 1 h at 60 °C. The volatiles were removed under reduced
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446
Acta Chim. Slov. 2004, 51, 437-446.
pressure. The oily residue was distilled in vacuo (94-95 °C/0.01 mmHg) (2.99 g, 53%). 13C NMR (CDCl3) ?: 35.9 (fC), 44.9 (nC), 47.8 (aC), 48.2 (lC), 49.7 (mC), 52.1 (bC), 52.5 (iC), 53.0 (cC), 80.4 (eC), 115.0 (kC), 116.3 (hC), 135.7 (gC), 138.3 (jC), 164.3 (dC).
Acknowledgements
The authors wishes to thank Inonu University Science Foundation (BAP) with the support.
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Povzetek
Opisana sta dva splošna načina sinteze naslovnih spojin iz N,N’-dimetilformamida dimetil acetala in ustreznega N,N’-bis(sekundarnega amina), oziroma natrijevega hidrida (ali kalijevega t-butoksida) in 4,5-dihidroimidazolijevih soli. Pripravili smo N-funkcionalizirane entetramine (3, 8) z 2-metoksietil- ali alil- substituentom na N-atomu. Reakcija teh entetraminov z S8 in Se so dale ustrezne ciklične halkogeno sečnine (4, 5). Obdelava kalijevega t-butoksida z 1,1’-etilen-3,3’-dialildiimidazolidinijevim dibromidom (7) je dala entetramin (8) oziroma amino-Claisen-ov isomer (9). Vse nove spojine so identificirane z 1H, 13C NMR, FT-IR in mikro analizo.
Y. Gök, E. Çetinkaya, I. Özdemir, B. Çetinkaya, M. F. Lappert: Synthesis and Characterisation of N-…