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FULL PAPER

Multistep Reversible Redox Systems, LXIII[e]

2,5-Disubstituted N,N9-Dicyanoquinone Diimines (DCNQIs) 2
Syntheses, and Redox Properties
Siegfried Hünig*a, Robert Baub, Martina Kemmera, Hubert Meixnera[2], Tobias Metzenthinb, Karl Petersc,
Klaus Sinzgera[3], and Juris Gulbisa[4]

Institut für Organische Chemie der Universität Würzburga,
Am Hubland, D-97074 Würzburg, Germany
University of Southern California, Chemistry Departmentb,
Los Angeles, CA 90089, USA
MPI für Festkörperforschungc,
Heisenbergstr. 1, D-70506 Stuttgart, Germany

Received August 4, 1997

Keywords: DCNQIs / Quinones / Substituent effects / Voltammetry / Crystal structures

Quinones 1a2q and DCNQIs 2a2g have been synthesized voltammetry). Linear correlations have been found between
in order to investigate substituent effects. It was necessary to E2 (OX/SEM) data of 1 and 2 with (σm + σp)/2 and between
employ novel synthetic routes for the introduction of iodine E2 of 1 and 2. Correlations have also been found between E2
into 1f (7), the trifluoromethyl group into 1g2i, deuterium and the LUMO energies of 1 and 2. The crystal structure of
into 1m2p, and especially for the chloride/fluoride exchange quinone 1i shows some special interactions due to the two
of 1j to 1k, and 1l. With few exceptions both 1 and 2 undergo CF3 groups, whereas the structures of DCNQIs 2d and 2g
reversible electron transfer in two steps including thermody- link up with those evaluated earlier.
namically very stable radical cations (lg KSEM > 10, cyclic

Within the series of new quinoid derivatives [5] 2,5-disub- in reasonable yields. Quantitative demethylation of 4a2c
stituted N,N9-dicyano-1,4-benzoquinone diimines 2 with subsequent oxidation then afforded the expected qui-
(DCNQIs) have gained special importance due to the ex- nones 1a2c in high purity and yield (Scheme 2). The use
ceptional conducting properties of their radical anion of a superior iodination reagent, benzyltriethylammonium
salts [6]. In addition to the derivatives already reported [5] we dichloroiodate (BTMA-ICl2), has recently been reported [8].
now describe syntheses and properties of DCNQIs 2, to- Although a yield of 90% of 1c from 1,4-dimethoxybenzene
gether with, where necessary, their precursors, quinones 1 in acetic acid was originally reported, we were unable to
(Scheme 1). The charge-transfer (CT) complexes and rad- reproduce these results (ca. 59% yield) , however, isolated
ical anion salts derived from these DCNQIs will also be 79% of 1c using dichloromethane as the solvent.
presented.
Scheme 1 Scheme 2

Syntheses of Haloquinones 1a2f The halogen/methoxy-substituted quinones 1d [9] and
Iodonation of the substituted 1,4-dimethoxybenzenes 1e [10] have already been described. However, we replaced
3a2c, using the well-established reagent iodine/mercury ox- the cumbersome route to 1d [9] by a simple one-step ap-
ide [7] yielded the expected dihalogenated derivatives 4a2c proach from the inexpensive amine 5. The yield was rather
low, but this was compensated by the high purity of 1d (no
[e]
Part LXII: Ref. [1]. isomers, Scheme 3).

Eur. J. Org. Chem. 1998, 3352348  WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1998 14342193X/98/020220335 $ 17.501.50/0 335

1998. Syntheses of Trifluoromethyl-Substituted Quinones 1g2i The synthesis of quinones 1g2i requires appropriate aro- matic precursors carrying one or two trifluoromethyl groups. may may be produced either from gaseous CF3I (using an auto. (b) Introduction of the CF3 group into without rotational symmetry that fits into the general crys- the aromatic ring by ipso substitution of haloaromatics tal lattice I4a/a of the radical anion salts of 2 [6]. Instead. A convenient alterna- tive is based on halogen exchange 6 R 7 and direct oxida- tive demethylation [12] of 7 to quinone 1f (Scheme 3). and 14. Substituting 4c by the corresponding dibenzyl ether 15 paves the way to hydroquinone 16 and quinone 1i. 13. Org. Scheme 3 Scheme 4 Direct iodination of 1. However. Hünig et al.g. the starting material (16%). Unfortunately. debenzylation does not proceed by catalytic hydrogen- ation although this procedure does remove impurities (de- halogenation) of the crude product. SF4 or ET2NSF3 (DAST). SMe) Synthesis of Halomethyl Quinones 1j and 1l group into CF3 by e. The complications associated 18 by exchange of the chlorine in 17 by fluorine.4-dimeth- procedure to be suited for our purpose (Scheme 4). For the preparation of 1l we therefore chose to synthesise as does oxidation of 9 to 1g. However. From these results it is not sur. the halogen exchange product 8 (10%) and the corresponding diphenyl derivative (5%). It is al- ready known [11] that consecutive formation of the corre- sponding biphenyl derivative prevails. or more conveniently [14] from structure. substitution to 9 occurs rather smoothly. 3352348 . How- ever. Starting from 8.4-trimethoxybenzene by both of the methods discussed above was not successful. For these precursors two general routes [13] have to be considered: (a) Transformation of a CX3 (X 5 Cl.4-dimeth- oxybenzene (4c) affords a mixture of 12. also yield radical anion salts of 2 with the same crystal clave) and copper. in the first step (10 R Oxidation of 18 affords the expected quinone 1l in an equiv- 11) a complex reaction mixture (57%) was formed which alent process to 17. the benzylic protecting groups 15 are smoothly cleaved to hydroquinone 16 by the established reagent EtSH/Et2OBF3 [15].FULL PAPER S. J.2. a using (trifluoromethyl)copper. oxybenzene 17 [16] is smoothly oxidized to quinone 1j [17]. CF3CO2Na/CuI by decarboxylation. and easily oxidized to 1h. This short-lived intermediate 2CH2F group. Since this approach requires rather unusual starting materials this The methoxy group in 1 and 2 is the only substituent route was excluded. which may be introduced via 2CH2Cl.5-diodo-1. contained besides 11 (65%). demethylation of 12 either using boron tribromide or by oxidative cleavage with CeIV is not pos- sible. We found the latter The easily accessible bis(chloromethylated) 1. Chem. Scheme 5 prising that trifluoromethylation of 2. Of the with 7 (vide supra) mean that use of the bromoderivative several reported methods for this halogen exchange treat- 10 is advisable for the introduction of the trifluoromethyl ment of 17 potassium fluoride in polyethylene glycol in the group. 336 Eur. The expected product 11 could indeed be isolated presence of potassium iodide [18] worked best (Scheme 5).

DCNQI 2q was prepared from 2. including the highly sensitive 2i (R1. Hydrolysis of e. [25]]. CD3I (> 99. where all 20. Even after careful recrystallization. 2i (16%) still contains some of these impurities.Multistep Reversible Redox Systems. Although the published preparation for this re- agent [27] could not be reproduced [28]. Chem. Redox Properties of Quinones 1 and DCNQI 2 In an extension of earlier work [6] both quinones 1 and DCNQIs 2 were studied using cyclic voltammetry under the same conditions. Obviously.N9-dicy- ano-1. 3352348 337 .N) 5 2255 cm21. Inspired by these results.g. ref. However. and 1l where the working electrode (Pt) is already blocked Eur. ν(C5N) 5 1525 cm21. Dilithiation of e. The latter is easily accessible by the established route [26] from 13C-cyana- mide. 1j and 1l2q are smoothly transformed properties [6] [19]. Therefore. from perdeuterated p-xylene using deuterated reagents in This is especially true for semiquinone radical anions of 1j all steps [24]. in accordance with earlier results [5].g. albeit by a different approach [20]. LXIII FULL PAPER Syntheses of Quinones 1m2q Labelled with Isotopes Syntheses of DCNQIs 2a2q Deuterated quinones 1m2p are important precursors for According to our general procedure [5] outlined in Scheme the production of DCNQI copper salts which have unique 7 quinones 1a2h. 22. reaction of 13C- bromocyan with ammonia in ethanol starting from 278°C afforded a nearly quantitative yield of 13C-cyanamide. R1/R3 5 CH2Cl and CH2F cause decompo- The dideuterated quinone 1m has already been prepared sition on introduction of the second electron into 2jSEM. This ideal behavior is followed by nearly all quinones 1 and DCNQIs 2. and 28 afforded the corresponding quinones relevant data are collected.4 have re- cently been prepared. into the corresponding DCNQIs 2. the second reduction step of quinones 1 is not fully reversible. probably Oxidative cleavage of the hydroquinone dimethyl ethers due to aggregational effects. 26 is also rather difficult to achieve (cf.N) 5 2180 cm21. The amount of deuterium in the reagent formation constants KSEM are given. in Table 1. Scheme 6 Difficulties are only observed with the rather sensitive 2i [ν(C. ν(C5N) 5 1555 cm21] which is contaminated with either the reduction product N. According to Scheme 8. only approximated semiquinone 1j2m in high yield. J. mers of deuterated 2. [23]). ref.4-addition product 30 [ν(C. Org.5%) is fully transferred to the products (MS). R3 5 CF3) as exem- plified by Figure 1.4-diaminobenzene 29 or the 1. all possible iso.5-dimethylbenzoquinone-1. Scheme 7 According to Scheme 6 the most reliable method for in- troducing either deuterium (> 95%) or CD3 groups (via ICD3) into aromatic rings is halogen/lithium exchange which works smoothly not only for 21 and 23 but also for the persubstituted derivatives 19 and 27 [21]. 24. 1998.4-benzo- quinone by the same route (70%) except that 13C-enriched bis(trimethylsilyl)carbodiimide was employed.5-dimethyl-1. two reversible one-electron transfers at E2 and E1 are expected. 25 [22] is less rapid and resulted only in 85% deuteration of 26. cf. The very low energy LUMO of 2i (vide infra) points to both the strong reducibility and nucleophilicity of 2i.

well within the limits of error for these semiempirical 338 Eur. Potentials E1 and E2 from cyclovoltammograms of quino- nes 1 and DCNQIs 2 in CH2Cl2 versus Ag/AgCl/MeCN. It has already beeen demonstrated [30] that the Scheme 9 Coulomb integral Jmm of the two electrons in the HOMO of the reduced form is basically responsible for ∆HR of the equilibrium OX 1 RED v 2 SEM.02 0.16 ø14 Figure 1.35 0.74 0.3 eV) their difference amounts to only 0.7 b Br/I 10.23 0.36[c] 0.19 0.2-quinonei.06 0.08 mV/eV and demon- strongly diminished concentration in the second reduction strate again the weaker substituent effect with increasing wave.98 10. In 1RED with X 5 2O2 the negative charge is bet. Both classes of com. Scheme 8 Table 1.7 c I/I 10. 1998.19 ø15 100 mV/s (ferrocene 5 539 mV) h CF3/OCH3 20.30 ø15 i CF3/CF3 10.33 0. 2 2 l[b] CH2F/CH2F 20.30 ø14 c I/I 10.44 0. A quantitative corre- lation between Jmm from SCF calculations and log KSEM from CV data has already been derived for other two-step redox systems [31].15 0.01 0.79 13. 3352348 .25 0. The gradients differ by 0.7 d Cl/MeO 10. J.5 [a] Quasi reversible.2 g CF3/CH3 10. Figure 2 demonstrates an excellent linear correlation (r 5 0.74 20.74 11.47 20.91 irr.59 10. although even the latter shows very good. polymerization creasing acceptor strength of the substrates.31 0.00 0.42 irr. especially in aprotic solvents.83 0. Therefore quinones 1j and 1l are expected to tron affinities.59 21.50 irr.82 indicates that the differences for mines 32l are formed in this way. Chem.79 10. 103 compared to the KSEM values of the corresponding qui- nones 1.14 0.222.74 10.9 21.00 0.74 20.25 0. n 5 number of formally transferred electrons. This is the corresponding E2 potentials.21 ø13 e Br/MeO 20.6 h CF3/OCH3 10. In the region where the two curves nearly In full accord with earlier observations [5] [6].74 ±0. These differences are probably mainly due to after only one scan.77 0.02 0.84 10. This substitu- etc.56 20. 1lRED and 2jRED. 2 2 l[b] CH2F/CH2F 10.13 0.22 0.63 0.59 10.33 21. nBu4N1BF 42. In Figure 3 these data are correlated with group than chloride. the latter.43 20. Hünig et al.68 0.45 ø13 b Br/I 10. Since experimental data are not available for decompose more readily than DCNQIs 2j (or 2l) on re.56 10.66 21. scan rate g CF3/CH3 20. the first reduction potentials (E2) become smaller with in- pounds are highly reactive (dimerization.2-Quinonemethides 31j and 31l or the 1. electron affinities.5 e Br/MeO 10. fluoride is a much worse leaving were calculated. nBu4N1BF 42.25 ø13 d Cl/MeO 20. Org.54 10.27 ø14 CH2Cl2 versus Ag/AgCl/CH3CN. Koopman9s electron affinities (2εLUMO [eV]) duction. consistent with the relative decomposition rates 1RED > The two linear correlations shown in Figure 3 are both 1lRED and 2jRED >> 2l.33 20. [29]).03 0. R3 5 CF3) in f I/OCH3 20.64 0.74 20.55 0.20 0.65 0. log KSEM 5 semiquinone formation constant (ferrocene 5 539 mV) 1 R1/R2 E2 [V] n E1 [V][a] n lg KSEM a Cl/I 10.4 i CF3/CF3 10.FULL PAPER S.993) between E2 (quinone) and E2 (DCNQI) for 1a2o and 2a2o together with all corresponding derivatives pub- lished so far.40 0.43 0.01 0.74 11. KSEM values meet (at 2.1 j[b] CH2Cl/Cl2Cl 10.35 20.01 0.05 of the DCNQIs 2 are smaller by a factor of approximately V.06 0.84 10.54 10. 2 [b] In MeCN.20 0.9 f I/OCH3 10. 2 [c] Not fully reversible.74 20. Furthermore.42 11. 2 2 2 R1/R3 E2 [V] n E1 [V] n lg KSEM a Cl/I 10. 1. ent effect may either originate from differing solvation ener- ter available for the extraction of Y2 than with X 5 gies of OX and SEM (∆∆Gsolv) or from the differing elec- 2N2CN2.35 0.01 0. π-systems.97 0.13 0.53 0. The gradient a 5 0. It seems probable from Scheme 9 that smaller Coulomb repulsions in the more extended DCNQI a halide ion is expelled from 1jRED. Cyclovoltammogram of DCNQI 2i (R1.77 0.37 20.18 ø15 j[b] CH2Cl/CH2Cl 20.

2. 3352348 339 .Multistep Reversible Redox Systems. MeO/MeO there exists a linear correlation between the first reduction which had to be excluded from the correlation E2 5 a (σm potentials E2 of disubstituted quinones together with their 1 σp)/2 1 b to obtain r 5 0. With the exception of DCNQI derivatives and (σm 1 σp)/2 [32]. Chem. From these results different solvation energies for the systems under discussion become very improbable. (e) excluded from the calculated correlation Figure 3. LXIII FULL PAPER Figure 2.5-disubstituted derivatives (O) published Figure 4. Correlation of the potentials E2 (quinone) and E2 An excellent correlation is obtained again even for such (DCNQI) for 1a2o and 2a2o (h) together with those of all other extreme electron attracting substituents as CF3/CF3. the deviating substituents are bent and may prefer ented in this paper are collected in Figure 4 and 5 and to adopt different conformations in OX and SEM as sug- complement this previously published data. MeS/MeS. Plot of the first reduction potentials E2 of 2. leaving intrinsic (electronic) factors as the most plausible On the other hand stronger deviations are observed for reason for the observed effects. (e) excluded from the calcu- lated correlation correlations. (s) for- mer data [6]. (s) former data [6]. The dependence upon the Eur. (h) data from this paper. Plot of the first reduction potentials E2 of the correspond- ing DCNQIs versus the Hammett parameter (σm 1 σp)/2.993. Correlation of the potentials E2 (23 quinones and DCNQIs) with Koopman9s electron affinities (negative LUMO energies) calculated with the AM1 program Figure 5.5-disubsti- tuted quinones versus the Hammett parameter (σm 1 σp)/2. 1998. The results pres. gested by AM1 calculations [3]. J. CH3/F. As already demonstrated the combinations CH3/F. Org. (h) data from this paper. allyl/allyl.

5 230.78 εσn1 217. obviously not be the case if the differences of σm and σp become large (e. Orbital energies for LUMO.36 21. DCNQIs [28] [34] and indicates slight deviations from the plemented program package MOPAC 6. The deviation of the two N2CN stituted DCNQIs [33].83 22.92 218. Bond lengths and angles compare well with those of the unsubstituted DCNQI [34] and its 2.g.N) 3 103 [a] 229. (e) excluded from the gorithm by which the canonical molecular orbitals can be calculated correlation transformed into a set of localized orbitals.57 parameter (σm 1 σp)/2 implies that σm and σp affect the qN (C. 340 Eur.5-disubstituted DCNQIs (R1. As expected. J. In connection with the extension of the agreement with the experimental ones given in Table 1.0 27. Orbital coefficients of the LUMOs of 1. right.62 OX εσn2 222.28 218. The molecular ge- ometry of 2d is presented in Figure 8.0 now contains ideal sp3 and sp2 hybridizations. σ n1 and σ n2.46 222. In 2.25 218. the σ-orbitals of the nitrile nitrogen atoms may be safely iden- tified. Table 2.2 244.4 220.02 222.FULL PAPER S. however.92 218. However.24 222.N9-dicyano-5-methoxy-1.15 21.5 221. duction potentials E2 were estimated to be 0.4 114. OCH3/CF3).03 222. 3352348 .59 22.9 245.41 222. From these calculations the first re- (a 5 0. the highest potential so far observed for 2.63 V (2h.36 21. Some Crystal Structures of Quinoid Compounds Figure 7. (C202N21) by 2 pm.13 218.1 210.c plane of the unit cell. stituent effects can be derived from the LUMO orbital coef. (a) 2-Chloro-N.4 qN (5N<) 3 103 [a] 270.57 SEM εσn2 217. The relevant data are collected in Table 2. those for 2m (CH3/CH3) [33].28 218.03 222.88 23. respectively.15 222.5-dimethyl derivative [28].31 εσn1 222. 1998. the next higher molecule thereby always being placed with its cyano group above the ring of the lower one (Figure 8. Figure 6.5- ficients in positions 2(5) of 1. Org.40 22.4-benzoquinone.5-disubstituted CF3 groups (2i) the partial charge qN at the nitrile groups TCNQs [32] the substituent effects are definitely even smaller even becomes positive.27 218.37. π-system these coefficients decrease appreciably in the above mentioned order. Two orbitals. HOMO.4-benzoquinone Diimine (2d): The crystals of DCNQI 2d belong to the space group Cc in which the molecules are arranged parallel to the b.5-disub. With two the steeper gradient in Figure 4. AM1 calculations were performed for groups from linearity by 8° corresponds to those in other five of the newly snythesized DCNQIs. in 2d the C32C4 bond is elongated by 3 pm due to the 5- Semiempirical Calculations for Some DQNQIs methoxy group which even stretches the nitrile bond In connection with earlier MO calculations for 2. Chem. are found which are nearly colinear with the two nitrile groups in a DCNQI molecule. Hünig et al. The order of this sensitivity to sub. R3) for OX and SEM (radical anion).4-benzoquinone We concentrated on the X-ray analysis of 2d. charge densities at the nitrile and imino nitrogen atoms (qN) R1/R3 CD3/CD3 I/OCH3 CF3/OCH3 CF3/CH3 CF3/CF3 εLUMO 22. The newly im.28 222. Figure 6).12 218.89 21. left). σ-n [eV]. The electron-withdrawing ef- In general the substituent effects are stronger in quinones fect of the other substituents is reflected in lower HOMO.62 qN (C. than in the corresponding DCNQIs as can be derived from SOMO and σ-n energies for both OX and SEM. the data for 2o (CD3/CD3) coincide with OMe). Plot of the first reduction potentials E2 of TCNQs[32] AM1 parameters for halogens as well as a localization al- versus the Hammett parameter (σm 1 σp)/2. Data from AM1 calculations of 2. DCNQI and disubstituted DCNQIs. DCNQI (center) and TCNQ (right) according to AM1 calcu- lations because of our interest in the arrangement of the bent methoxy group and the structural effect of the rather bulky trifluoromethyl group. 1c and 2g (left).7 εHSOMO 20. This will.N) 3 103 [a] 2209 2194 2183 2184 2160 qN (5N<) 3 103 [a] 2235 2206 2200 2213 2193 potentials with the same weight. independent of the nature of the substituents. These potentials are in very good TCNQ (Figure 7). In this way.

4-benzoquinone. Both 2. right: view onto the planes of two molecules of 2g along the two atoms. a post-doctoral grant from the Fonds der Chemischen slightly larger [∆(ΣVS) 5 5. J. Ludwigshafen Eur. The shortest distances are axis. Therefore. This means that the two CF3 groups are interlocked like cogwheels.4-benzoquinone (1i): Crys. dTC 5 3. Both the unsubstituted DCNQI [34] and the 2. Frank- molecules of 1i (4 3 CF3. fluoro and hydro- gen atoms are not shown for clarity. Left: view onto the b plane of the unit cell of 2. cell contains two molecules of 1i which can be transformed Within the crystal lattices no distances are shorter than into one another by a twofold helical twist parallel to the x the usual van der Waals data.2-b]thio- phene (2. (c) 2-Methyl-5-trifluoromethyl-DCNQI (2g): The unsym- metrically substituted DCNQI 2g forms crystals from the space group R3. next molecule as demonstrated in Figure 10.5-Br2DCNTT) [39] crystallize in the monoclinic space group P21/c. As dem. right: view on the plane of two neighboring molecules along the shortest cell axis b The crystal structure of 2g (R3) represents a third pack- ing type for DCNQIs and related acceptors which until now has not been observed. stacking axis c Figure 9. Quinone 1i forms layers along the a/b plane. Å3 [36]) the volume of the unit cell of 1i exceeds that of acknowledged.3221. the intermolecu- lar C2C distances of neighboring CF3 groups (4.2 Å3] than for chloranil (8 3 Cl: Industrie (to T.Multistep Reversible Redox Systems. The less dense pack- ing of 1i is also reflected in the larger intermolecular dis- tances in crystals of 1i [d(C5O···C5O) 5 2.2 Å) than the sum of the van der Waals radii of the (R3). Obviously the crystal lattices of these donors The same type of packing is found for chloranil which are not determined by a common electronic interaction in also adopts the space group P21/a [35].67 Å] compared to chloranil with 2.5-Me2DCNQI [40] and the afore- mentioned 2-Cl-5-MeO-DCNQI (2d) (space groups Pnma and Cc respectively) are found with similar arranged molec- ular layers. The unit ated.4 Å3 [36]) is only furt/Main.2624. Although the sum of contrast to DCNQI CT complexes and radical cation salts. For similar reasons the positions of the hydrogen (b) 2.36 is smaller than the average packing coefficients CK 5 from X-ray data and some bond lengths 0. The coefficient ∆(ΣVS)/∆VC 5 cell (space group Cc). Org.77 Å) are well below the “rotational diameter” (5. Due to disorder the data for a DCNQI molecule 2g are taken from the data containing two CF3 groups which oc- cupy the crystal position only by 50% (center of inversion in 2g). Left: shortest distances between neighboring molecules carbonyl carbon atom of the next. tween the carbonyl oxygen atom of one molecule and the Figure 10.123.6520. the van der Waals volumes of the substituents from two Financial support by the Fonds der Chemischen Industrie. right: geometry of 2-Cl. respectively. being even shorter of 2-methyl-5-trifluoromethyl-DCNQI (2g) in the crystal lattice (3. 4 3 H: 164. LXIII FULL PAPER Figure 8.) and a DAAD grant (to J.95 Å.13 Å.5-Bis(trifluoromethyl)-1. However.c projection of the unit chloranil by ∆VC 5 14.85 Å and 3.5-bis(cyanimino)-2. M.5-bis(tri- fluoromethyl)-1. atoms at the methyl group and at C3/C6 could not be evalu- tals of quinone 1i belong to the space group P21/a.5-MeO-DCNQI (2b) 0. Its unit cell contains nine molecules of 2g.6 Å) of a CF3 group. demonstrating the shortest di- stances between two molecules within one layer. We are also grateful to the BASF AG.77 [37] for organic compounds. 1998. found between a CF3 group and the NCN moiety of the onstrated by Figure 9 the shortest distances are found be.5-MeO-DCNQI (2b): b. The C2F bond lengths (1. rotation of these CF3 groups is expected either to be coupled or to pass an energy barrier when jumping into the next low energy position after rotation by 120°.5-dihydrothieno[3.33 Å) coincide with rel- evant data from the literature [38].6 Å3. 3352348 341 .225. Left: 2-Cl. G. Chem.) are gratefully 159.

44 (2 q.89. 1 H. About half of treated with ultrasound (10 min) and heated for 30 min to 90°C. 2 1H NMR (CDCl3. 6-H).2 mmol) in THF (50 ml) was added n- butyllithium (131 mmol.76 (s. 72273°C from methanol (40 ml). 1480 was repeated 2 or 3 times.83. 3 342 Eur. 100 The filter cake of CuI was removed in portions which were sus- mmol).p. 138°C. After drying with MgSO4. 1510 (C5C).28. 112. After 2 h at room temp.17. 6-H).p.3 MHz. Chem. 2 C9H11IO3 (294.88 (3 s. 200 MHz): δ 5 3.81 g.87. C-3). From methanol (2 3) 1a chemicals. 56.39 (s.1 g) yielded 9 (8. 7. CuI (22. 21. m. 200 MHz): δ 5 3. m. C-6).77.18 (s.95 (s.33 g. g. 4-OCH3).4 g.4. (4. Table 3. 29%) colorless needles. 57. was added to the cooled mixture which was then filtered through 1-Chloro-4-iodo-2. the solvent was removed at this temperature. H 3. 2 amide (300 ml).18 (s.3 g. for the donation of some valuable mmol) and HgO (13. C-2.): δ 5 57.7 pended in MTB or DE (100 ml) and filtered again.19.13. iodine (25. 1-. 4. dimethyl acet- 298 (100) [M1(35Cl) 2 CH3). 84. C 28. 121. 2 IR (KBr): ν̃ 5 3000 cm21.36. Trifluoromethylated 1. m/z (%): 344 (95) [M1 (81Br)]. Experimental Section 1050. 1630. calcd. C-1.96 (s. 375 (44) [M1 2 CH3]. 1-.FULL PAPER S.18 (s. 3. ref.6 MHz. 1015. 123.0 mmol). 1020. 1260.5-trimethoxybenzene (7): To 2-bromo-1. 3-H): 2 13C NMR (CDCl3.95 (s. a solution of iodine (16. -4).9 mmol). 2 Gen- eral Procedure 2 (GP2): GP2 was based on a patent [14]. 2 13 C NMR (CDCl3. -5). the solvent was distilled until the temperature ene (324 h) and then decolorized by washing with solutions of NaI of the mixture increased to 1522153°C. 2 IR (KBr): ν̃ 5 2800 cm21 (C2H). 1210 (C2O). 97. 200 MHz): δ 5 3. found C 24. 7. 1-. m. toluene (100 ml). 1. The organic phase was extracted with water (3 3 30 ml) and dried with Na2SO4. 250 MHz): δ 5 2. C-1. -6). 121. iodine (4. 2 MS (70 eV). C-2). and HgO (23. 1. Org. 2 1H NMR (CDCl3. and 1l [50] C-6). C. 2g [49]. 1415.1): calcd. 2 1H NMR (CDCl3.11.0 mmol). C 32. The crude product re- 760.26 (d. 6-H. 1195 (C2O). 3 H.5  in hexane) at 270°C. X-ray data for 2d [49]. C-5).87. 7. Hünig et al. chloro-2-methyl-1. 745. H 2. 1440.33 (s.20.4. found C 36.5 g. 9 H.20 (s. 2 MS (70 eV). 1337. 329 (54) [M1 (81Br) 2 CH3]. [1].76 H 3. iodine (I2) and yellow mercury oxide [7] were flask equipped with a stirrer and a Claisen bridge. 2 H.33 (s. UV.5-trimeth- oxybenzene (6. 153.96. -4). 283 (74) [M1(35Cl) 2 CH3]. 1. 342 (100) [M1 (79Br)]. 114. CF3CO2Na (24. 152.0 g. 1350. 838. 1470 (C5C).3g. 20.06 (q. 114°C.5): calcd. 152. H 2.79 g.06 (s.25 (3 q.p. 1 H. 2. C-3). Leverkusen. s. H 2. m. 3-H).5-dimethoxybenzene (4a): GP1 with 2-chloro. H 2. OCH3). 1 H.26 (d. m/z (%): 300 (32) [M1(37Cl)]. J. amounts of sodium trifluoroacetate and copper(I) iodide were sus- cedure 1 (GP1): Equivalent amounts of the appropriate 1.55 (2 q. 1450.8 g. 1 H. 2 IR (KBr): ν̃ 5 2810 cm21 (C2H). 4- cf. 1438. 2 1H NMR (CDCl3. 131 mmol) in THF (50 ml) was slowly added. 85.50 (s. dimethyl acetamide.22 (s. 4-OCH3). the corresponding Iodinated 1. Colorless crystals of 1c.01. 1-Iodo-2. water (3 3 50 ml) and dried with Na2SO4. 741. 153. C-1). Colorless needles of 1a (13. 60. 6. 1-Bromo-4-iodo-2. 2 MS (70 eV). 1H NMR. 6-H). 6. C-3). The bromo. 823. 4-OCH3). 2 IR (KBr): ν̃ 5 2820 cm21 (C2H).42 (s. 1 H.p.26 (s.80. 1265. 2880.: corrected. 16. C-5). 18. 2 3 OCH3). 70°C (m. 1205 (C2O). MTB or DE (50 ml) recrystallized from methanol.p.46 (d. 151.36. 50.0). 2 1H NMR (CDCl3.79 d.or iodo-substituted hydroquinone ether.4-dimethoxybenzene (8. 845. 180 1). 1425. 86. found C 31. The brown crude product (12. 2 IR. 50. 67%) as colorless crystals. 116. 2 C8H8I2O2 (390.65. 1998. C-4).41 (s. 52%). 3352348 .): δ 5 57. a Buchner funnel (diameter 7 cm) covered with silica gel (223 cm).p. 2885 (CH). 847.4-di. CV. 3-H). 144.4-Dimethoxybenzene Derivatives. the residue was crystallized from ethanol (70 ml) yield to 7 (12.7 g. [11]: 70°C).4-Diiodo-2.7 g. 6-H). 100.5 g. 2 C8H8O2BrI (343. obtained according to C-5). the mixture was cooled to 70°C and the solvent by distillation under reduced pressure and the brown residue removed in vacuo until 30250 ml remained. ref.0 mmol).p. C-2).5-dimethoxybenzene (4c): GP1 with 2-iodo-1.78. 3. and the Bayer AG.80 C8H8O2ClI (298. 835. mained after removal of the solvent under reduced pressure. 150. C-4). C 36. 3 H. m. 2 13C NMR 1.0 mmol). 13 C NMR. it was distilled off to remove traces of water.89 (d. 2 General Pro. pended under argon in dry toluene in a three-necked round-bottom methoxybenzene. 7. C-3.): δ 5 7. the mixture was extracted with diethyl ether (3 3 100 ml). After addition of dry The brown mixture was continuously extracted with refluxing tolu. 1475 C5C). General: M.4-Dimethoxy2-methyl-5-trifluoromethylbenzene (9): GP2 with 5- (CDCl3. 3-.69. This procedure g. 1340.4-Dimethoxybenzene Derivatives.82 (s.98. C-6). 1270. 2 13C NMR (CDCl3. 1425.4-dimethoxybenzene (10. 51%). 1065. 1058.17 (s.04 (2 s.0): calcd. 123. 100. 327 (56) [M1 (79Br) 2 CH3]. 113. C 24.44. 50. and addition of 2  HCl (30 ml) and H2O (100 ml).8 g. 169°C.0 1600. 1 H. ref. 83. The organic phases were extraced with (C5C).94 (2 s. 100 mmol). 3. m/z (%): 390 (100) [M1].4-dimethoxybenzene (17. 57. 835. After stirring for 628 h and NaHSO3. 1-. 18.19 (s. 63 MHz): δ 5 56. iodine (12.00 g. 72. [8] in 72% yield.9 mmol). HgO (4.34 (d. 2970. After evaporation of the solvent. H 2. 57.71. After stirring for 1 h at 270°C. mmol). OCH3).4-di- methoxybenzene (5. OCH3). 1010. 120 mmol). 2940.5-dimethoxybenzene (4b): GP1 with 5-bromo.14 (d. 250 MHz): δ 5 3. 2 3 OCH3).6 MHz. C-2). 60. H 2.7 g.07.96 (2 s. found C 28.71. 110 mmol).9 g. 150.

1102111°C. 6 H. 1200. m.0 mmol) in THF (20 ml) was J13C-19F 5 272 Hz. 56. 2830 (CH).5. 300mmol) CuI (38. 2 C10H11D3O2 (169. 8:1) yielded 12 (3. The mixture was slowly warmed to room temp. CH3). 890.5-bis(trideuteriomethyl)benzene (24): By adap- 31.94 (d. 1. 1035. After warm. . 8. 2960. (28): By analogy to the undeuterated compound [44] bromination of 150.37.69 (s. 1 H. CF3). C-2). 173 (2. H 8. H 8. 172 (0. C-1. m. Chem.24 (q. 151. CF3). 6. 935.4-dimethoxy-2. 1590. 2 13C NMR (CDCl3. found C 71. 8 OCH3). 171 (0.2): calcd.73. 2810 (CH).63) [M1 2 2]. m. dimethyl acetamide (300 ml).4-Dideuterio-2. 1290.39) [M1 2 1]. 88%). OCH3). phase with DE (3 3 100 ml). TMEDA (12. 2945. found C 69.2): [51] calcd. 200 mmol). 2220.p. C-6). 200 mmol). 10. 400 mmol). 157 (100) [M1 2 CH3].4 g.1 g. 9:1) of 0.5-bis(trideuteriomethyl)benzene (27).4-Dimethoxy-2.66 (s.94. warmed to 250°C and cooled again to 270°C before trideuterio- 115. (CDCl3. -5). The solvent was evaporated and obtained. 2 1H crude product from ethanol (50ml) afforded a colorless mixture NMR (CDCl3.p.6-dimethylbenzene (20): By analogy to ref. By adapting methoxy-3.55 (q. 3. 2935. C-3. 2. 2935. 250 -4). C 54. H 8. 800.75 g.84 (s. were obtained. m/z (%): 168 (49.24 (s. 2885. 113. 2 H. 3-.95 (q. 2 C10H12D2O2 (168. 124. 3. OCH3). 1252126°C (undeuterated: 85%.00 (q.89 (q.2): [51] calcd.11.3 Hz. 70 ml. 7. 124.55. -5). 1280. 1252126°C [44]). The suspension was 55. OCH3).5-dimethylbenzene (19.80 (q. H 3..Multistep Reversible Redox Systems.54 g. 26%) as colorless crystals.. the mixture was acidified (70 eV). -4). 2930. 2 IR (KBr): ν̃ 5 3020 cm21. m. 6. 2220. (CD). [42] [43] n-butyllithium (2.29.7 g.86 (s. (100 ml).6-dibromo- C10H8F6O2 (274.2): calcd.2): calcd. [M1 2 CH3].5 mmol) in DE (230 ml). C 68.8 g. 6-H). 2. 50%) contained (1H g. LXIII FULL PAPER H.6 g. [carboxy-D]acetic acid (98% dried with Na2SO4. 6 H.4-dimethoxybenzene 1-. OCH3). 200 mmol) in THF (19. The crude product (7.02 (s.7%. 2 (CDCl3. 635.81. 2 MS added.26 (s. 113.00 (s. < 0. 55. CF3CO2Na (54. 2 1H NMR (CDCl3.06) [M1]. -5).73 (s.2): [51] calcd. OCH3). MHz): δ 5 2. 2980. 111.56 (s. found C 51. 58%). 97.59-hexamethoxydiphenyl ether 16. 56.4. OCH3). 2840 (CH). 123. 73274°C. [D4]methanol (. 168 (0.1 g. C-1. 1030.69 (3 q. 720. 152. 2 1. 159 (100) 166 (1. 2220.9 Hz. 1.6-bis(trideuteriomethyl)benzene J13C-19F 5 31.5  in hexane) was 110 mmol) was added at 278°C to n-butyllithium (1. 1510 (C5C). (54. H 5. was regained [carboxy-D]acetic acid (98% D.62 (d. OCH3). (21.-4).25 (5%). 63 MHz): δ 5 56. which contained (1H NMR) 10 (16%).5  in hexane) was added at 255°C to 3. 5%). 142. ref. 151. 1030.38 [M1 2 1].79) [M1].48 (q. Flash chromatography (PE/CH2Cl. 63 MHz): δ 5 16. found C 68. C-1.44 g. 153 (100) [M1 2 CH3]. 6 H. H 8.41. -6).16 (s. the residue recrystallized from ethanol (30ml) to yield 20 (3.5. CF3).92.05. 2 24 (5. 110. drying with Na2SO4 and evaporation of the solvent afforded the crude product.32 reaction time.40 (s. added at 255°C to 27 (7. -4).p.48. 1505 (C5C). CH3).36.96 g. 116. Work up according to 22 yielded 24 (8.7 C10H8D6O2 (172. After cooling When room temp. 122.34 (dq. was 3 50 ml) and dried with Na2SO4. 2-iodo-1. OCH3). and then refluxed (30 min).5 ml) was added.09 250 MHz): δ 5 3. 5. 109°C.06 H.55. m. 1. Deuteration of CD3 > 99. m. 2 C10H6D8O2 tions 3 and 6 > 93%. 2 13C NMR 1]. 2880. 3-H). 81%) of 3. After stirring at room temp. Hz. 11 (65%).4-Dimethoxy-2. C-5).83. -4).71 (dq. was added. The dibromo-1. 99%.8 g. 63 (CDCl3. 2 with 2  HCl (30 ml) and water (100 ml). 123.9 g. C-2. H 4.55 (q.07. 250 MHz): δ 5 2. 3-. H 2. 113. 63 MHz): δ 5 56.83 (s. C-2. 1510 (C5C). 1455. CH3). 51.38 g.04. 3-H). 3.69. 2060.43 g. 2875. The jelly-like mixture was stirred at 240°C 1. [21] n-butyllithium (2. washing with water. 2220.58 (s. 3-. 2200.3 Hz.26.80 (q. C-6). -5).3  in cyclo- Eur.0 mmol.62 (s.28 (s. m. 2 IR (KBr): ν̃ 5 3020 NMR) 12 (75%).13. OCH3). Deuterated Hydroquinone Derivatives. C 70. H. 1205. OCH3).24 (t.4-Dideuterio-2. 2890. OCH3). C 71.O9-bis(N. 122. 6. 2835.8 g. dimethyl acetamide (500 ml). CH3). -4). CuI (38.7 mmol) was ium (57. toluene (100 ml). 175 mmol) J13C-19F 5 272 Hz.64 (d.p. 1390. 154 (100) [M1 2 cm21. 1500 (150 ml).14 (s. The colorless suspension was cooled to 270°C before [D4]methanol (> 99% D.90 (s. J13C-19F 5 31. 124.59. Deuteration of positions 3 and 6 > 95% 2 13C NMR Deuterations of positions 3 and 6 > 97%. 63 MHz): δ 5 (10%) and probably 2. Flash chromatography (PE/ 615. 2 IR (KBr): ν̃ 5 3080 cm21. 109°C. 1455. C-2. Deuterations of 2 CD3 > 97%. 8 h and then stirred for 3 h. 2 1H NMR CH3]. bromo-1. 250 MHz): δ 5 3.49-bis(trifluoro. (30 ml) was added. 20%). refluxed (30 min) and mmol) in diethyl ether (DE) (230 ml).81 g yielded 11 (2 s. 6 H. C-1. C-3. the organic phase was washed with water (3 tion from ethanol (20 ml). 84%). 1390. 1370. Extraction of the organic C10H11F3O2 (220.53. 6 H. 3.4-dimethoxy-5-trifluoromethylbenzene cm21. 785.5-bis(trifluoromethyl)benzene (12): GP2 with 4c (30 min) and trideuteriomethyl iodide (29.0 g. [21] n-butyllith. warmed to room temp.0 suspension was warmed to room temp. 100 mmol). J13C-19F 5 5.42 g. C 50. [22]. 151. 23. m/z (%): 274 (97) [M1 2 CH3].23. m. J13C-19F 5 5. After removal of the solvent and recrystalliza- D. 63 MHz): δ 5 56. 123. 221 (75) [M1 2 CH3].81. J13C-19F 5 30.4-Trimethoxy-5-trifluoromethylbenzene (11): GP2 with 2- From ethanol (70 ml) colorless crystals of 22 (7. H 8.81 (s.13 g. 2055 (CD). 151.01) [M1]. 278°C n-butyllithium (22. 90%) as colorless needles. dissolved in DE (100 ml) and THF C10H11F3O3 (236. 2 1H NMR (CDCl3. 24.35 (s. 2040 (CD). 11. 610. -6).5 g. m/z (%): 174 4). found C 43. (2 h).2 mmol. 113.00.6 ml) was added.69 (s. 5 ml) was added. C-3.5-trimethoxybenzene (10. 75. 1365.43 g) as colorless crystals. H 8. C-2. H 5. C-3). C-3.39 (q. 3 H. 9 H. 1610.52. 1 H. J13C-19F 5 273 Hz.5  in hexane. 2050 (13. 3. 55.5-di. 2 MS (70 eV).0 ml. 1280.05 (q. C-3). MS (70 eV). 3352348 343 . found C 54. 1430. 7.N9-di- 1. 151. 69%) from ethanol (80 ml). J13C-D 5 24 Hz. 6-H). -6). C-2. 50. 3-. 6.04 1302131°C (1312132°C [41]).p. C-2. -5). C-2).p. 6-H). 6-H).2.3 Hz. C-5). C-1. 2 1. and probably 2. 6-H).4-dimethoxybenzene (23). 56. 6. 2 1H NMR (CDCl3. -5).5 Hz. 2200. C-1.05 (q.5-dimethoxy-3.3 Hz.0 mmol). 2 MS (70 eV).85 (2 s.54.91 (q. 108. C 43.7 Hz. m/z (%): 172 (52.18 MHz): δ 5 56. 1102111°C.34 (s.09 (s.97. 29. 69. 2 H. added to a solution of 2-bromo-5-methyl-1.22 (s. 1 H.00 (s.29.85. 2200. 3-.4-dimethoxy-2. 2 IR (KBr): ν̃ 5 2980 cm21. 1500 (C5C). 122.04) [M1 2 2]. 2835. 109.46 (dq.82.66) [M1 2 MHz): δ 5 3.53 (q. 250 MHz): δ 5 3.5% D. m/z (%): 236 (100) [M1]. 6-H). H 4. methyl iodide (> 99. 6 H. 2100.40. 132. 830. 20. 2800 (CH).85. 2 13C NMR (CDCl3. toluene 2930. J13C-19F 5 5. [51] found C 71. 890. methyl)diphenyl ether (14. 1050.2): calcd. -6). 167 (5. 1998.16) [M1 2 1]. H (174. 2 H.4-Dimethoxy-2-methyl-5-trideuteriomethylbenzene (22): At ethylcarbamate) (26): In an adaption to ref.40 (s. 2 13C NMR (CDCl3. 2110. ml) was added and the reaction mixture washed with water and ing the mixture to room temperature. 124. C-1. Org. m/z (%): 220 (62) [M1]. Deuteration of 2 CD3 > 99%. Recrystallization of the (C5C).4. CH3). 2. 28 (3. 1085. 250 1195. 205 (100) [M1 2 CH3]. CF3CO2Na (40. -6). J.7 ml.35. 2980. 63 MHz): δ 5 15. 2 MS (70 eV).99.58. C-3.78 (s. J13C-19F 5 1. 6.59-tetramethoxy-4. Deuterations of posi. 2 MS and hexane (100 ml) were cooled to 290°C before 2.0 mmol) in THF (100 ml).48) [M1]. 2 1H NMR (CDCl3.5  in hexane. 8. tion of ref. (13. 2975.5-Bis(trideuteriomethyl)hydroquinone-O.p.01 g. 6 to 270°C.60 (d. 6-H). 2 13C NMR (CDCl3.6. CH3).49. 50. 1180. (q.81 (s. 6 H. 2 MS (70 eV).8 mmol) afforded 28 (8.76.62. 56. 2 13C NMR (CDCl3. OCH3). 2825 (CH). (0. CH2Cl2.90 (3 s. OCH3). 3. < 0.p. 26. 7. H 8. J13C-D 5 23. (t.82 (2 q. 6. 2 IR (KBr): ν̃ 5 3000 m/z (%): 169 (51.5-dibromo- (70 eV).

0 mmol) in acetonitrile (100 ml).31 g. (3. 2835 (CH). 250 MHz): δ 5 2. 48. C-6). 48. 1 H. 2 C6H2O2BrI (312. C-3.97 g. Chem. 850. (s.4 mmol) in THF (120 ml) was slowly added and after stirring 2 GP3(b) with the crude hydroquinone (2. C-5). oxyaniline (3.07).88). CH2Cl2 (50ml). 1:1) of the crude product afforded 1g (5. Brown stirred mixture was slowly warmed to room temp. 146.p. 45%). 4J 5 1. 1350.p. 2 1H NMR found C 22.02. (CH3CN): λmax (lg ε) 5 250 nm (4.61.4-Benzoquinones by Oxidation of Aromatic Precursors.75. 2 IR (CCl4): ν̃ 5 3060 cm21.0 g.) of chromium(IV) 2-Iodo-5-methoxy-1. 176.57 (s. 1540 (C5C). 0. 2970.37 g (59%). 2 MS (70 eV). 30 ml. CeIV reagent (63. 177°C.72 (d.3 oxide in H2SO4 (33%) was then slowly added.41 mmol).00 (s.01 (s. 250 MHz): δ 5 s.62 (s. 28% based on 10). 100%) in acetone/ (1 h. 1450.20 (s.FULL PAPER S.PE/ (150 ml) to afford 1a (7.1 Hz. 3. 2 13C NMR (CDCl3. 2 Gen. 278°C) trideuteriomethyl iodide (12. ca.65 g. -4). m/z (%): 17.61 (q. 2 C6H2O2I2 (359. 3020. 11. (b) The hydroquinones were dissolved in an acetone/water mg. 1660 (C5O).5 mmol) in min). (s. 35. CeIV reagent (53.28 (s. CrO3/H2SO4 (2 . 63 MHz): δ 5 56. m/z (%): 264 (M) [M1].O9-bis(N. BBr3 (18. 1360. gen phosphate in water (200 ml) was added to 5-chloro-2-meth- ane was added at 278°C a concentrated solution of the 1.3 (10. (C5C). 7. 186.96 970. C-5).76 (d. 2 UV (CH3CN): λmax (lg ε) 5 241 nm (4.81 (d. 353 (3.p.56. 2 13C NMR (CDCl3. 33. 12 H. 1645 (C5O). 7. 960. 322 (sh. 181. 133. (CDCl3.p.09). CH2Cl2.0 mmol) and potassium hydro- eral Procedure 3 (GP3): (a) To 2. 1160..15 g. CH3).90ml.29 (s. C-5). CH2CH3). Hünig et al. The water (100 ml).51 (s. (5:1) mixture. 137. (2 s. 98. 1450.3 fra).88. The organic phase was washed with water and 13 C NMR (CDCl3. C8H5F3O2 (190.10 (d. m. 3-H). After washing with water. 2 MS (70 eV). 200 ml acetone/water. After stirring (30 min). 144. m. 3. 154°C. ε) 5 238 nm (3. OCH3).5 h.54. 2890. CF3).59 (s.6 Hz. C 26. 3-. 2 1H NMR (CDCl3. [9]. m/z (%): 314 (59) [M1(81Br)]. C-4). 55 ν̃ 5 3065 cm21 (5C2H).4): calcd. 143.9 MHz): δ 5 119. 8 H. The crude quinone was crystallized from ethanol g. C-6). 162 (100) [M1 2 CO]. C-2).99). CH2CH3).40 mmol).5 mmol). 116 mmol) in 2 UV (CH3CN): λmax (lg ε) 5 240 nm (3.84. 1680. 4J1H-19F 5 1.42. 125 mmol). 2 H. which was directly transformed into 1l by GP3(b) (vide in. C-3). 2 MS (70 eV). 2 of the solvent yielded the crude quinone. m. [46] m. 2 UV (CH3CN): λmax (lg ε) 5 243 nm (3. 370 water (100 ml). C-5). 1665 (C5O).86).5 mmol) in CH2Cl2 (80 ml). C-4). 925.62 (d. 20. 6.76 (d. 134. C 50. 7.90 (s.71 (subl. 3-H). 1120.80 (s.85.5 mmol.6 g. Evaporation of the solvent yielded the crude 6). (2. 268 (100) [M1 (35Cl)]. OCH3). 178.08 (q. C-2).p. 1270. C-2). 1420. 370 (CCl4): ν̃ 5 3055 cm21.62 g. orange crystals. 2 mmol). found C 32. IR (KBr): ν̃ 5 3050 cm21. 1 H. 2 UV (CH3CN): λmax (lg 26 (8. 1650 (C5O). 2 IR C). 1 H. Washing the organic phase with water. 1998. 1645 (C5O). Flash chromatography (SiO2. 177.50 (q.00.75 (s.3 mmol.00 g. 144. 3 H. 910. C-1. 6. 62. 105. 1430. 1 H. On evaporation of the crystallization from methanol (40 ml) flash chromatography (silica solvent the crude hydroquinones remained which were directly oxi. The red residue was crystallized from ethanol (50 ml) to 2-Methoxy-5-trifluoromethyl-1. 62.03.85).41 (s. 103°C 7. 2 IR (KBr): ν̃ 5 2960 cm21. 191°C.04). J13C-19F 5 5.65. H 0. 17. 1160. H 2. yield yellow plates of 1c (1. 131. 4. GP3(b) with the crude hydroquinone (9.0 Hz. 1260. 12.p. 3 H.0 mmol) in CH2Cl2 (80 ml).22). J 5 7.85 g) was crystallized from ethanol (200 ml. 50. 1015.. (30 min).18 (t.N9-diethylcarbamate) (25. crude 1c (1. 37°C. 200 MHz): δ 5 7. C-3). 1210. After stirring 2.0 g.1): calcd. 15. 85°C. 1732174°C). 1540 (C5 crystallization from hexane (30ml). -5).80 (s. 308 (3. 1190. 6. CrO3/H2SO4 (2 . OCH3). [12] an aqueous 1600. of BBr3 in dichlorometh.01 (q. 2 MS (70 eV). 2 MS (70 eV). 314 (3. 2 chloromethane.86 (s. m.50 (s. 22. 1340.5 mmol. C-4). 250 MHz): nitrile. 1595 (C5C).5 g.0): calcd.30. C-1). 1165. 6-H). CrO3/H2SO4 (2 . 75. 1190.58). 2 1H NMR (CDCl3. 178. CeIV reagent (55. brick-red crystals. and then acidi. 1012102°C).70 (q. [45]).6 in CH2Cl2 (100 ml).60).4-benzoquinone (1b): GP3(a): With 4b (6.4-benzoquinone (1d): A solution of potass- 1. 2-Chloro-5-iodo-1. 0. 344 Eur. with cold DE (2 3 10 ml) the red residue became yellow. 3 H.4 g.5-Diiodo-1. 7. 0°C). C 31.4-benzoquinone (1f): GP4 with 7 (13. 144. 250 MHz): δ 5 7.43 (s. 20°C) the violet solution turned red.9): calcd. 360 (100) [M1]. H 0. 3-H).p.p. ref. 2 IR (KBr): contaminated by products 10 and 8 (vide supra. 1435. the solvent removed on washing onto ice (200 g) and extracted with DE. J13C-19F 5 275 Hz.8 g. 122. solution of 2. m. 63 MHz): δ 5 15. m/z (%): 270 (35) [M1 (37Cl)].51 g. 2960. 44. After stirring (30 mmol) in acetonitrile (100 ml). 10%). 1570.4-dimeth. 177. H 0. 7. 2 UV 312 (55) [M1(79Br)]. 850. (1.0 mmol) in acetonitrile (100 ml). 2 H. 1365. found C 20. 2920. 1310.9 MHz): δ 5 119. C-1. 6-H). 1575 (C5C).76 g. 91%). 294 (3. 3-. 1:4. 6-H). m/z (%): 361 (7) [M1 1 1 H]. 3-H). 2 IR (KBr): ν̃ 5 3050 cm21 drying with Na2SO4 and evaporation of the solvent afforded crude (5C2H).77).4-benzoquinone (1c): GP3(a) 4c (2. 2 C7H5IO3 (264.4-benzoquinone (1g): GP4 with 9 100%). On stirring oxybenzene.47 (s. 1 h.90. m. 1 H.8 g. H 2. (C5O).50 g. 3.6 g. C-1). 100%).47 (q. 3. 6-H). 33. the mixture was extracted with dichloromethane. of cerium(IV) ammonium nitrate was 990.p. 2 13C NMR (CDCl3. 68 (25).1 equiv.4 Hz. 85 ml.1 Hz.47 g.55. 1 H. (s. gel. H 1.39 2-Bromo-5-iodo-1. C 23. Evaporation product yielded 1f (5.32 g. CH3). 60 MHz): δ 5 1. ium nitrosodisulfonate (13. yellow plates.72 (dq. 143. J13C-19F 5 32. 225°C) to fied with 2  HCl (50 ml). hexane/hexane 98:2. 2-Chloro-5-methoxy-1. 3352348 . 6-H). C-2). 200 MHz): δ 5 7. C-6). H 0. 287 (3. 83%). 1732174°C (ref. C-3).1 190 (86) [M1]. 101 mmol) in water (100 ml).7 equiv.23 quinone. 2 1H NMR (CDCl3.51 g. 1 H. 2925 (CH). 159. 1660 (C5O).76). BBr3 (1. m. 2970. 1610 (3. 1 H. -6). 2910 (CH). C-1). 2 1H NMR (CDCl3. The organic water (100 ml).17  in CH2Cl2. 13. Flash chromatography (SiO2. yellow crystals. the clear solution was poured tracted with CHCl3 (2 3 100 ml). 6.20 ml.11 mol) in THF (80 ml). 2 1H NMR (CDCl3/TMS. 2920.08). 1000. 2. 2 1H NMR (CDCl3.5 ml. H 1. g. General Procedure 4 (GP4): According to ref. 1575. H 1 H. 2-Methyl-5-trifluoromethyl-1. whereby a colorless precipitate was formed (cf.06 g. 134. At 0°C a 2  solution (0. 7. H 0. 810. CH2Cl2) yielded a yellow microcrystalline powder of 1d (660 dized.9 g) from petroleum ether (PE) (50270°C) 8. 900. The mixture was ex- After stirring for 15 h at room temp. 1230.9): calcd. m.53 (q. C-3).80 mmol). orange crystals.65. 1350.89). 72%).16 (s. found C 50.20 (s.59 (d.5 equiv. 122 (96). H). ref. δ 5 3.92 (d. BBr3 (3. mmol) in acetonitrile (110 ml). 2 C6H2O2ClI (270.29.99 (d. 295 (3. J 5 7. J. 180. 236 (49) [M1 2 CO]. -4).72. found C 26. 1560 (C5C). 4J 5 1.71). 135. 363 (3. 2 13C NMR (CDCl3. 6-H). GP3(b): With the crude hydroquinone (5. 1660. PE/CH2Cl2. acetone/water (200 ml). 120. 50. 2940. 2860 (CH).4 Hz. 176.51 (s.85. 1430.4-benzoquinone (1h): GP4 with 11 afford 1b (4. 1265.77. C 20.76). 62%) after 2 IR (KBr): ν̃ 5 3050 cm21 (C2H).0 mmol) in CH2Cl2 (50 ml).41. 1695 MHz): δ 5 119. C-2. 1370. the mixture was extracted with di.4-benzoquinone (1a): GP3(a) with 4a (10.20 (s. CH2Cl2) of the crude phase was washed with water and dried with MgSO4.6 Hz. After the organic phase was dried with NasSO4. yielded 1h (5.0 g. 3005. 2 UV (CH3CN): λmax (lg ε) 5 237 nm added to a solution of the hydroquinone dimethyl ether in aceto. 1380. C- dried with MgSO4. Flash chromatography (SiO2. Org.222.36 (q. hydroquinone-O.

-4). 4J 5 1. 12 h). 128. 3-.6-dimethyl-1. Chem. From the cooled reaction mixture the precipitate was iso- g. m. 2 (b) NaOH (4. -6).14. C-3. C8H2F6O2 (244.20) 6-H). 2 C8H5F3O3 2. m. 2 1H NMR (CDCl3. 1250. 2. C 67. 10. 1375. 6. 160 mmol).4 Hz). 2 13C NMR (CDCl3. 1513 (C5C). 63.1 ref. 5.96 (d. polyethyl. C5O). C 69.4-dimethoxybenzene [16] (17.p.69. 49%). 181.92 (dq. CuI (25. [15] the colorless solid (9. C 39. 33. C-1. bar H2. ene glycol 400 (16. m/z (%): 142 (72. CH3). C-1. J13C-19F 5 31. 20°C).40 g). g. 20. 3-. 2 1H NMR (CDCl3. 2 13C NMR (CD3OD.5-Dideuterio-3. 57.49 (s.3 g. -6). After stirring (2 h. 127. C- C8H6F2O2 (172. Eur. 6-H). 2 1H NMR (CDCl3/TMS): δ 5 5.78 g. H 3. m.59 (s. 250 MHz): δ 5 1. 150.01 g. 2JC-F 5 17. -4).94 (dq. JC-F 5 17.59 (d. (24. After removing the NMR (CDCl3.18) [M1 2 2]. 122 (20) [M/2 1 CF3].95 (s. 2950. 2 UV H).)]. 63 MHz): δ 5 133.10 g. 122 (100) [M1/2]. 2 H. J13C-19F 5 [M1 2 1].p. The benzyl bromide (32. 865. 1160. -4). 4 H. C-1. OCH2C6H5). C-2. 1232124°C.5-Bis(fluormethyl)-1.0 Hz. -4). 1152116°C.5 mmol) in acetonitrile (30 ml). 2 1H NMR (q.5-bis(chloromethyl)-1. 305 (2.p. 2 IR (KBr): ν̃ 5 3030 cm21 (CH). 22. CF3). OCH2Ph). 6. 3-. CH2F. m. 137 (0. C-2. 2 13C 1862187°C. 1030. 350 mmol).57) [M1].52) [M1 2 1]. 1350. 134.0 g. 264 mmol).31 g (41%). found C 70.9 Hz). 71 (72) [M1/2 1 CD3].p. 1260. 930. 10 mmol) in acetic acid (40 ml) at 0210°C. 1650 (C5O).5 arom. 2 IR (KBr): ν̃ 5 this temperature.55 (m. 1225. 9 mmol. C-3. 145. 0. 1430.42 (CH3CN): λmax (lg ε) 5 238 nm (4. 1240. 250 MHz): δ 5 7.83. 2 13C NMR (CDCl3. 93%) as yellow crystals. NMR (CDCl3/TMS): δ 5 78. 3.73) [M1]. m. 2 1H NMR (CDCl3. Flash chromatography (SiO2. 121.2 (KBr): ν̃ 5 3030 cm21.1 (d.40.1 g. 4J1H-19F 5 1.3%. 154°C (subl. 250 MHz): δ 5 5. 145. found C 47. 635. 1010. 68 (68) [M1/2 1 CH3]. (12.06. H 5. [18] 2. 1590 heated in an inert atmosphere for 10 h to 80°C. 2 IR (KBr): ν̃ 5 3060 cm21 δ 5 1. C). CH3). 66. 2 MS (70 eV). 725. 2 IR 149. 1165. the mixture was 25. 1237.1 g. J13C-19F 5 175 Hz. KF (9.1): [51] calcd.1 toluene (75 ml).13): calcd. Deuteration of positions 3 and 6 > 95%. 1. 2 H. 216 (52) [M1 2 CO]. 1020. HNO3 was slowly added to 18 (2.61 (q.1): [51] calcd. 6-H).47) Na2SO4 and removal of the solvent and reagents at 1 Torr yielded [M1 2 2].4-benzoquinone (1l): By analogy to (206. 133.83 (s. 690. 2 found C 69. 2 MS (70 Hz). 63 MHz): δ 5 120. 2942 (CH). 123. 1600 (C5 mmol) in acetone/water (40 ml).05 (t. 2 CO]. 820. nonedibenzyl ether (15. 178 (23) [M1 2 CO]. C-2. 6. 187. 145. C-6). 63 MHz): δ 5 15. 2:1) yielded 2.85 (t. 2 MS (70 hydrolyzed with ice-cold water. 2 JH-F 5 46. lated and recrystallized from toluene to yield 2. -4). C 46.08 g. 2 C8H2D6O2 (142. 4.46 After refluxing for 4 d. 122.2 (s. KI (1. C-3).29 (d. 1640 (C5O). By catalytic hydrogenation in ethanol the crude product 1375.40 (2 s. 2 63 MHz): δ 5 72. 7.05. Org. 100. 6-H).40 g. 3-. 136.24 g. 2JH-F 5 49. 3JC-F 5 7.07 (s. C. Work up (GP3) yielded an oker-colored solid 2960 cm21 (CH). 63 MHz): (5. 140 (0. J13C-19F 5 5. 2 IR (KBr): 6. 135. 1 H.83 (s.p. 125°C.50 (s. 1650 (C5O). 0. Extraction with DE. 2-Methyl-5-trideuteriomethyl-1. 160°C (subl. 75°C.06 (s. -6). the mixture was diluted 2.53 (q.90 (s. 2 1H monitored by TLC (SiO2.1 Hz). 71 (100) [M1/2].84 for 1 h. H 5. 176 (27) [M1 2 H 5.82. -5). 4J 5 1.4-benzoquinone (1m): GP4 with 20 mmol).6 Hz. Dimethylacetamide (150 ml) was added and the mmol) in water (50 ml).34. 158 mmol) and ethanol (200 ml) and treated with curred (30250 ml) which was completed by addition of PE. C 55. 132.92.39. -6).6 5 95%. H (4.31 g.6 CF3).10 g. 158. C-2.7 (d. OCH2].11. 110 (29) [M1/2]. -6). -5). 910.58).3 Hz. C 59.45. 250 MHz): δ 5 4.33 g.Multistep Reversible Redox Systems. 2 C8H6D2O2 (138.82.7 Hz.04.5 mmol) in methanol (200 ml).1): calcd.p. δ 5 115. 12 H.84 g. 180. 690. 88%) as yellow needles. m. 12. C-3. From ethanol (40 ml) the crude product afforded (2. The crude hydroquinone was dissolved in 2  with MgSO4 and the solution concentrated until precipitation oc- NaOH (79 ml. H). H 6.7%.00. 960.5-Bis(trideuteriomethyl)-1. 22. 6-H). J.23 (d. OCH2C6H5). 1998. the mixture was poured into ice-cold water. 2 13C NMR ([D6]acetone. C-2.9 g.4-dimethoxybenzene (18): By adaption of 24 (1. 3 H. 152.3 Hz. 1595 (C5C). 1670 (C5O). a yellowish solid (5.96 ([D6]acetone. 3-. 610.08.44) [M1 2 2]. 930. 2. PE/EA. J13C-D 5 (49. 138 (1.26 (q. 1350.1): [51] calcd. From ethanol (60 ml) the crude prod- J13C-19F 5 31. 2 13C δ 5 56.5-bis(trifluoromethyl)hydroquinone [3. 6-H).10 mol) in water ν̃ 5 3054 cm21. 2 GP2 with 15 (17. H 6. [16] [17] conc. CF3) uct afforded 1n (3. 910. (0. eV). 128.4 (s. 133. C-2).4 Hz.18. 124. 2270 (CD). 299922837 (C2H). -5).6 arom. 2 MS (70 eV). 111.5 Hz.56. 132 mmol) The organic phase was extracted with water (2 3 100 ml) and dried in CH2Cl2 (50 ml).01 (q.11 g. 4 (CDCl3. 1430.4-benzoquinone (1o): (a) GP4 with 2. 2 H. 6 H. 2 IR (KBr): ν̃ 5 3061 cm21.5-Bis(fluoromethyl)-1.1 Hz).).28 ml. 1160. 3. -5).1 mmol) in water (30ml). 4 H. toluene. 660. 2 13C NMR (CDCl3. CeIV reagent (12. m/z (%): 206 (26) [M1]. -5).0 2.60 (s. 3.09 H.22 (q.6 MHz): 4 1 (d.3 mmol) in CH2Cl2 (100ml). m. 2 GP3 with the hydroquinone 16 (3.92.60 (s.0 g. H 1. (%): 244 (89) [M1]. The reaction was (C5C).7 (d. Deuteration in positions 3. CF2CO2Na (35. 30. 187.18). 141 organic phase was dried with MgSO4 and the solvent evaporated.3 (d. 2 1H NMR (12. 2 H. 83%) as yellow needles. 6 H.5 g) was only purified [150ml. OCH3). OH). 51%) as colorless crystal. 1170.89.72 (s. (OMe).93 (q.6 Hz. 630.4-benzoquinone (1n): GP4 22 2 H. 2 C8H5D3O2 (139.8 mmol) in acetonitrile (50ml). C 69.24. 2 1H NMR (CDCl3/TMS): δ 5 3.9 g. LXIII FULL PAPER J H-19F 5 1.0 mmol) in water (70 ml).1 OCH2Ph). 180. 133. C-3.81 (s. 114 (33) [M1 275 Hz. product yielded 10 (1.98. H 0.33. 132 mmol) in (3. 111 (56) [M1 2 CO]. 144. H). C-5). C-1. 760. 1035.0 mmol) in acetonitrile (70 ml) CeIV reagent (36.3 g. -6). From ethanol (20 ml) the crude 40.7 g.14. CH2F. CH3).18 (s. C-1.51 (s. 137 (6. 6-H).4-benzoquinone (1i): GP3(a) with 4c with ice-cold water (150 ml) and extracted with DE (3 3 50 ml). H 2. 4JH-F 5 2. CH3).4 Hz). OCH3). 61%) as colorless needles. C5O. the mixture was continuously extracted with DE (500ml.20): calcd. The 187. -4). C-1.75). 7. 136 (0.41 g) was < 0. J13C-19F 5 272 Hz. C-3. 14109. 86.32 (q.6-C.00 g.5 g). 930. (s. 2 13C NMR acetonitrile under reduced pressure and addition of water (150 ml). found C 39.1): calcd. NMR (CDCl3/TMS): δ 5 56. -4).53 (s. 63 MHz): δ 5 15.6 Hz). arom. 250 MHz): 78%) yellow plates. H 3. C).88 g.1 (OCH3). CH2F. CeIV reagent (31. drying with eV).30. 790. 4J 5 1. 3352348 345 . -5). 125.p.80 g. By analogy to ref. 3JC-F 5 17. J13C-19F 5 31. 1345. 1211 (30 ml) was added to 26 (8.6 Hz. 108. 865. H 5. Deuteration The residue (6. 1360. m/z (%): 139 (100) [M1].9 g. 69 (100) [CF 31].48. BBr3 (33. 81. 134.45 (2 d.2527.2 g. H 2. 1300.57 (3 d.51.5-diiodohydroqui- 1649 (C5C. 2 H.5 g Pd/C (10% Pd). 2 H. Deuteration J13C-19F 5 5. 1 H.0 mmol).37.27 (q.90) [M1 2 1].07 (s.52 (q.4 arom. 4 h). From ethanol the crude product yielded 1m mixture distilled until it reached 1522153°C and stirred (8 h) at (2. H 5. ref.56 C).5-Bis(trifluoromethyl)-1. 189 mmol) in ethanol (100 ml) by refluxing remaining solid was recrystallized from methanol to afford 1l (0. 27. 185. 2 MS (70 eV). arom. After 1 h.62. 1JC-F 5 173.05 (dq. J13C-19F 5 3.95 (s. 1232124°C. C-2.p. 2920 (CH).81 (m. (CDCl3.2 g) was recrystallized from methanol to yield 18 of both CD3 5 99. 2 C10H12F2O2 (202. 2 13C suspended in ethanethiol (85 ml) and treated at 0°C with BF3·Et2O NMR (CDCl3.83. 1045. found C 67. mmol). CrO3/H2SO4 (2 .62. 9.59 (q.80 (q. (d. 3- (CH). 250 MHz): δ 5 6.7 g. 8.89 (s.58.6 Hz. 1200. m/z (%): 138 (83.79 (q. C-1. m.0 Hz.1 Hz. 1275. m/z of CD3 5 99.1 Hz. 1 H. 6. 40 mmol) and acetonitrile (10ml) were 1242125°C. found C 55. 6. found C 59. Rf 5 0.

2 MS (70 eV).29). 1 H.FULL PAPER S.p. 1285.69.56).28).47 (OCH3). 250 MHz): anti: δ 5 4.21. 23%].55. 7. 2 C9H5N4BrO (265. 1600 (C5C). 1040. 2f (1. 72%).5 mmol) in acetonitrile (50 ml) CeIV re. 370 sh (4. 645.56.N). 1535 (C5N). (lg ε) 5 355 (4. 360 (76) [M1(81Br)]. 1445. anti: δ 5 57.78. 69%). 316 (100) [M1 (35Cl)].92 (OCH3).04 (s. 1010. 7. J13C-D 5 24. 2. 137.00 (t.0 mmol) in CH2Cl2 (120 ml) 16 h. 3-H). 6-H). 1540 (C5N). anti: δ 5 59. H 0. 134. Due to m/z (%): 144 (100.6 MHz): δ 5 16. 1555 (C5C).53.4-benzoquinone [10] (1e. 1540 (C5N). 77%]. 2 C9H5ClIN4O (220.).84. 1295. 13 C NMR: Solubility too low. 189 GP5 with 1f (2.87 (C-3).10 (s. 2 4220 h at 20°C. 3-H) [anti-2f. 3 H. eV). 2 IR (KBr): bility signals of lower intensity could not be recorded.05 g. 340 sh (4. H 0. 805. 77 (60) [C3HN2].35 g. From (OCH3). 2 1H NMR (CDCl3.74 (C-1). 209°C (dec. 1 H. 2165 (C.17.83 (s. m. 890. a solution of the 1. after one crystallization. 1160.N9-dicyano-5-methoxy-1. 264 (32) [M1 (79Br)].p. 145. the mixture was immediately ex. 805. 12. 1 H. syn: δ 5 57. 990.62. 142 (0. 7. 9. 43%) yellow crystals. C 23. C 30. The organic phase was washed with water. OCH3). (dec. C-3.45.0 g. 7.78 mmol) in CH2Cl2 (20 ml). 1590 42%).60) [M1 2 1]. H 0. 105. 2 UV (CH3CN): λmax 6. 350 (4. 2170 (C.26). 2 UV (CH3CN): λmax (lg ε) 5 250 nm (4. m. 100. From (36) [M1(35Cl) 2 I].07 (s. 399 sh MHz): δ 5 2. 2 I].00 g. 8. 6. 25. 200 MHz): δ 5 2-Chloro-N. 127 (78) [I]. 2180 (C.18. 4. 1430. N 20. 975. 1545 (C5C).1): calcd. 250 MHz): δ 5 7.64.28. m. 73%). CH3). m/z (%): 318 (36) N. 2 IR (KBr): ν̃ 5 3040 cm21 (5C2H).44).64.40 (C-3). 154°C (60 ml)/methylcyclohexane (100 ml) deep red needles of 2c (476 mg. Chem. 6-H).) in dichloro. toluene (50 ml)/methylcyclohexane (160 ml) red-violet crystals of N 17.47 mmol) in CH2Cl2 (100 ml). 72 (82) [M1/2]. N 15. 3. H 2.N). 2 IR (KBr): ν̃ 5 3020 cm21 (C5C). 2 IR (KBr): GP4 with 28 (3. 1 H. 77 (100) [C4HN2].22 GP5 with 1a (3. 2 IR (KBr): ν̃ 5 3040 cm21 (CH).73 (C- (4. 178. 3.74 (s. H 1. 2 IR (KBr): ν̃ 5 2260 cm21 (CD). 6-H). (C-2). OCH3). 1105.5): calcd. C 40.48.66.4-benzoquinone Diimine (2e): equiv. m. 6- evaporated. 4. 200 MHz): δ 5 112. 1 H. 2 MS (70 eV).74. The 1395. 1090. 130 (144.39). 6. 126.8 mmol) in water (50 ml). 8 h). hydrolysis with ice-cold water. imine (2g): GP5 with 1g (4.N).8 2). 81 Br 2 CN]. 7. 7 h. 2165 (C. 1225. 7. 127.5-Dideuterio-3.4-benzoquinone (1p): 2d (615 mg. 1998. 299 (30) [M1 1 2 NMR spectra of 2b could not be recorded. 1. 171. N 13. 6. 155 (72) [M1 (79Br) 2 OCH3].67 g. 3-H). 890. 154 (19) [M1 2 2 I].26 (s. with the 2-Chloro-N.N9-Dicyano-2.50 g. 132. found C 66.19 (C-2). m/z (%): H 2 CH3].4-benzoquinone (1 equiv. OCH3). N 18.4-benzoquinone Diimines. (100) [M1 (37Cl) 2 35Cl 2 OCH3CN). C 34. m. m/z (%): 266 (46) [M1 (81Br)]. 350 (4.61 mmol) in CH2Cl2 (50 ml). 2 1H NMR (100) [M1 (81Br) 2 79Br 2 OCH3 2 CN].39. 2 UV crude product (3.00 g. 1230. N 25. 2 13C NMR (CDCl3. ν̃ 5 3020 cm21 (5C2H). 2 C8H2N4ClI (316.39 346 Eur. 6- (3. no depression. 254 (76)[M1(81Br) 2 found C 34.47 (C-6).53 (C-2). H 5. 1 H. 1 H. 2170 (C. CH2Cl/PE. 1000. 820. C-1.29. 185°C (dec.62.67 (s. 39%). 43. the solvent eva. 370 sh (4. 910. the crude quinone yielded 1p (2. J.55.02 (q. H 1. Flash chromatography (SiO2. HCl and extracted with be recorded. found C 23. 2 2 2]. CH2Cl2). 312 (49) [M1]. 1 H. 2 MS (70 eV). 233°C (dec. 101.1): (CDCl3.32).21). was crystallized from toluene (150 ml)/methylcyclohexane (220 ml) methane was slowly added. N 21. C 66.21.08 g) sequently. N 25.84.38 (s. neutralized (pH 5 425) with conc. 2 C8H2N4BrI (360.31 g. H 1.03 (s.68 sh (4.23.) were isolated. 132. 1:1) yielded 10 (1.04 (s. From toluene cyclohexane yielded orange crystals of 2g (2.00) [M1]. (lg ε) 5 327 nm (4. C 26. 3-H). GP5 with 1d (660 mg.36.71.74 (s.89.) were obtained. H 1. (C5C). 6-H). 890. 1555 (C5N). -6). 9. 3-H).95.19).p. 3-H).32). 1030. 1555 (C5C).p.79 (s. 1320.25). Due to the very low solubility m/z (%): 314 (100) [M1 2 2 H]. Hünig et al.0): calcd. 1560 1 H. 130 ε) 5 210 (4. OCH3). mixed m.). 250 MHz): δ 5 4. dried with MgSO4 and the solvent (CDCl3. 6-H). H 0. 1555 (C5N).4-benzoquinone Diimine (2c): GP5 16 h. 1 H. 935.74 (C-6). m/z (%): 408 (100) [M1].04).p. 3 H. From toluene (50ml)/methylcyclohexane (100 ml) red-brown needles of 2. OCH3).6-bis(trideuteriomethyl)-1. while monitoring by DC (SiO2.69 g. 3. Sub. C-2. 2 1H NMR (CDCl3.4-benzoquinone Diimine (2b): 3020 cm21 (CH).75 g.91. GP3(b) in acetone/water (120 ml) with CrO3/H2SO4 (2 . N 13. 180°C (dec. 1290. The organic phase was washed with 340 sh (4. 1175.12 Hz. 1325. 281 (32) [M1 CH2Cl2. found C 49. 2175 (C.64 (s. 379 sh (4. 56%). -5). 810.10 (C-6). 355 (4. 1 H. 113. H 2.49).) in GP5 with 2-bromo-5-methoxy-1. 795.p. In most cases the pure DCNQI derivative was obtained H).0 mmol) in CH2Cl2 (100 ml).N9-dicyano-5-methoxy-1.5-Disubstituted N. 3352348 .50 g) yielded from toluene (100ml)/methylcyclo. 340 (4.N). 1630 (C5O). 168. (CH3CN): λmax (lg ε) 5 304 nm sh (3. H 0. 7. Org.N9-Dicyano-2-methyl-5-trifluoromethyl-1. 2 1H NMR water until pH ø 5 was attained.38).64. 2 calcd. The crude hydroquinone was oxidized according to C8H2N4I2 (408. dry dichloromethane. found C 40. 6. H 0. 3 H.25 (C-1.p. 2 General Procedure 5 (GP5): Bis(trimethylsilyl)carbodiimide (5 2-Bromo-N. 20 h.40. 2 IR (KBr): ν̃ 5 2-Bromo-N. C 48. hexane (400 ml) red-brown crystals of 2b (3. whereby an orange color develops. 281 (8) [M1 (35Cl) 2 35Cl].32 (s.p.p. (dec. 4. 137.83 (s. 1220. 1175.40 g) from methyl- with 1c (1. 1030.19.00 g. 1560 (C5C). 440 (2. Overall deuteration 5 97%. 3-H) [syn-2f.N9-Dicyano-1. m. -4). 61%). 2175 (C.94). 8. 2 MS (70 eV). 250 MHz): anti: δ 5 1252126°C. 850.57 (4. yellow crystals.93 (C-3).60). 1235. 1045.92 (s.34). 362 (83) [M1 (81Br)]. 188.13 g.46 (s. N 15. Crystallization of the crude product (3. signals of lower intensity could not H). syn: δ 5 (C5C). GP5 with 1b (4.) were added at 0°C to titanium tetrachloride (5 equiv.).39).4-benzoquinone Diimine (2f): [M1 (37Cl)].66 (s. N 17. 365 sh (4.58 (s.24). agent (24.62.04 (s. The crude product (1.28). 1175.93 (s. 13. From ethanol (15 ml) 1220. 2 13C NMR (CDCl3. 3 H.4-benzoquinone Diimine (2a): 112.77 (C-6).50. 16 h.99. N.4-benzoquinone Di- calcd. 2 UV (CH3CN): λmax (lg ε) 5 260 nm (3. 2 UV (CH3CN): λmax (lg ε) 5 293 nm (3. The reaction mixture was stirred for to afford brown needles of 2e (840 mg.33 toluene (150 ml)/methylcyclohexane (300 ml) deep red crystals of (OCH3). found C 30. 1040.22.) were obtained.N). 2 C9H5IN4O (312. 2. 129. 124°C. 1640. 250 2 UV (CH3CN): λmax (lg ε) 5 335 sh (4.76. 6-H). found C 26. 1545 (C5N). 1580 4. 256 sh NMR (CDCl3. 18.22). 1 H. 3 H.38 (s.68.38) [M1 low solubility signals of lower intensity could not be recorded. 6. 1 H. 430 (3.41 (C-4).N). Due to low solubility.86). 2 porated. 780. -4). 17. 2 UV (CH3CN): λmax (5C2H).N).14. 3 H.05 ml. 3 H. 3-H). 1 H.N9-dicyano-5-iodo-1. 226°C 2 1H NMR (CDCl3.p. m. 127 (54) [I].46. OCH3).65. 364 (4.N9-Dicyano-2-iodo-5-methoxy-1.31).5-diiodo-1. 143 (5.N9-dicyano-5-iodo-1. 660. 102.50 g. 1 H. 113.1 mmol).49 (s.4-benzoquinone Diimine (2d): product from procedure (a). syn: δ 5 4. 2 13C NMR (CDCl3. 2 UV (CH3CN): λmax (lg [M1 (81Br) 2 81Br 2 OCH3].1): [51] calcd.80 mmol) in CH2Cl2 (60 ml). 92%).22 (C. 1 H. 2 C8D8O2 MS (70 eV). m.) were isolated. H 6. syn: δ 5 62. m. After IR (KBr): ν̃ 5 3035 cm21 (5C2H).17).1 mmol) in CH2Cl2 (50 ml.N). 14 h.62 (s.50 g.9): N. CH3). m/z (%): 222 (25) [M1 (35Cl) 2 35Cl 2 OCH3]. 103. 63 MHz): δ 5 133.740. 2 13C 685.03 (C. 2 MS (70 eV).N). 2 MS (70 ν̃ 5 3040 cm21 (5C2H).93.6): calcd.06 (s.81). N 18. 211 (37) 1240. Due to low solu- 2a (2. 210°C (dec. tracted with dichloromethane.

623. methylcyclohexane (280 ml) orange-red.43. 735.N).. 497%].00mmol) in CH2Cl2 (70 ml).p.4): calcd. 925. [27] Br13CN (13.06 (s.N9-[13C]Dicyano-2.9 (d.1 ml.4-benzoquinone diimine (2k) and 30. 3352348 347 . 19%) yellow lyl)-[13C]carbodiimide (17.25 g. 146. found C 41. 2 IR (KBr): ν̃ 5 3020 cm21 (5C2H).44 g. Fraction 1: 2l (170 mg.N9-dicyano-1. found C (4. C 50. 78%). H 4. N. 787. CH2Cl.4-benzoquinone Diimine (100 ml). 728.4-benzoquinone [16] [17] 1j were isolated. C-3). 1003. 1520 (C5N).17. 70%).30.41. m/z (%): 189 (63) [M1 N 22. 2 UV (CH3CN): λmax (lg ε) 5 343 nm (4. 201°C (dec.2): calcd. 12 mmol) in CH2Cl2 (50 ml). 112. OCH3). 603. 112. N 22. H 1.N). 4JH-H 5 1. [48]. 2JC-F 5 18. toluene yielded yellow crystals of 2j (2. 2 13C NMR (CDCl3/TMS): δ 5 78. (254. 3-. 1555 (C5N).0 mmol) in dry CH2Cl2 (10 ml). 1 2 H]. N 23.p. LXIII FULL PAPER (d. 16 h.5 (C.78 (s.74 (s.p. 1630. 1380. 2 H. 2 13C NMR (CDCl3/ TMS): δ 5 39. [25])]. 16 h. 28°C (75285%. 169.97.75. 62. 172.02 g.4-benzoquinone Di- 2 1H NMR (CDCl3. toluene) until 1l was consumed (20240 (140ml) [26]. 16 h. 346 2 C10H2D6N4 (190. ν(C5C): 1525 cm21 (cf. After 30 min.53 (s. 192 (C. 189°C [28]).01 6. bis(trimethylsilyl)carbodiimide ml). 650. 1998. 1578 (C5C). m. 860. N 25. The crude product (5. 1030. 4 H.90 (d. 159 (95) [M1 2 HCN].64 (s. 16 h.76.6 Hz).). 1360. 127.2): calcd. off and washed with DE. 3 H. 1568 (C5N).17. 124. 4.48. N 30. 28°C for BrCN [47]). 650.17.0 mmol) in CH2Cl2 2. Crystallization from acetonitrile (150 ml) yielded bronze- mg.9 g. z (%): 188 (73) [M1 1 2 H].1): calcd.0mmol).46 g. 189°C (dec. 620.37. 5. C 41.66. 1573 (C5C). 63%). C 47.46. 1525 (C5N).p. 3-H). 1 H. found: C 47. The found C 63.0 mmol) in CH2Cl2 (100 ml). 173. N 21. 2 UV (CH3CN): λmax (lg ε) 5 316 nm sh (4219).40 sonic bath. 835. 2 MS (70 eV).p.08 (s. 1580 (C5C).51. N 29. Precipitated NH4Br was filtered off and washed with DE (3 3 50 After stirring for 2 h at room temp. removed and the solvent evaporated to yield [13C]cyanamide (5.99. 1035.N). 5-C). 292 (100) 63.11 g. 2980 4-C). 1530.28. m.5-bis(fluoromethyl)-1. 2 C10H5D3N4 (187. 3040. C NMR (CDCl3/TMS): δ 5 4.11.p.54. 2 C10H6D2N4 (186. g.p. 740.17. 144. 162 (71) [M1 2 DCN]. 190 (100) [M1].4-benzoquinone Diimine (2q): (2-. C 54. 3020. 1000.N9-dicyano-2-fluoromethyl-1. 1 H. From acetonitrile (100ml) umber-colored plates (d. 1340. 1602 (C5C). 1290.37. 4 H. 910. 270 mol) in ethanol (2l): At 0°C Et3N·3 HF in CH2Cl2 (5 ml) was slowly added to (70 ml) at 278°C in a pressure vessel and stirred for 16 h at 20°C. 1175.N9-Dicyano-2.4 25. ν̃ 5 3010 cm21 (C2H).2 (b) GP5 with a different ratio of reagents: 2. Ad. N 29. 131 mmol) in N.1 mmol) in CH2Cl2 (100 ml). 1372139°C.0 mmol) in CH2Cl2 (3 ml) was added at 0°C and the reaction at 0°C to trimethylsilyl chloride (34.49. 1152.6-dimethyl-1. 2160 (C. 4.7 Hz). N 19. (7.62 (s. 7. 2 C10H5F3N4O (C. 187 (100) [M1]. 2 C10H2F6N4 (292. 84%).09. without decomposition. 2 MS (70 eV). 3 H.50 g. N 30. 2945 (C2H).98. 136°C. 1287. 1345.45.5-dideuterio-3. N 29. 186 (100) [M1]. adapting ref. 680.5 Hz). 176°C. g. 250 MHz): δ 5 4.4-benzoquinone Di- dition of hot methylcyclohexane until the solution turned slightly imine (2o) [47]: GP5 with 1o (6.5-bis(trideuteriomethyl)-1.0 mmol) was added to the yellow solution in an ultra. N 25.). N 29.5 h. H 4. 1028. 200:1).N9-Dicyano-2-methoxy-5-trifluoromethyl-1.5-Dimethyl- 2180 (C. N 19. 2 IR (KBr): ν̃ 5 2255 cm21 (C2D). The main crystal fraction contained colored plates of 2o (1. Org. 2177. From acetonitrile orange scales of 2p (2. 1573 (C5C). (C5N).3 (C. m/z (%): 294 (28) [M1 1 2 H]. 2 IR (KBr): a mixture of 2i and its dihydro derivative [ν(C. 1555 (C5N).7 N.5-dideuterio3.N).p.39 g.55. 2 H. 1-.N9-Dicyano-2. N 22. C-6).60 g.4-benzoquinone (1. TiCl4 TMS): δ 5 5. m. 164 (74) [M1 2 DCN].52. m. 760.2): calcd. H 4. 1030. 2940 (CH).N9-Dicyano-2.4 (1-. 643.N). 1278. 2 1H NMR (CDCl3/ 1.0mmol) in CH2Cl2 (50 ml). 1410. Yield 75%. CH2F. 7. were isolated. 2JH-F 5 46 Hz.N): 2255 cm21. 2170 (C.30. 16 h. 1183. 128.6 (s. m. m. H 4. 2970 (C2H).21. 1525. 825.04.1): calcd. H 1.30 g.93.24).23 imine (2h): GP5 with 1h (5. 2 1H (100) [M1]. 15. J.5-bis(trifluoromethyl)-1. found: (C2H). 5-C. 920.4-benzoquinone Di. 2112 (13C. m. found C 50. 2175 358 sh (4. 80%). C 64.N). 80%). 20. 873. 633. N N. titanium tetrachloride (2. crude product (0.08. CH2F. H 2.p.N9-Dicyano-2. 1425. 1000. 2 IR (KBr): ν̃ 5 3052.11. 1l (0. 1223. 1028.16. Crystallization from 1558 (C5C).2 Hz). m/ g.51. 2 C10H8N4 (184. (2. 6-C.10.p.3 (3-. 2127. 915. 1330.30). 2 IR (KBr): ν̃ 5 3034. found C 64. OCH3).31. H 0.5-bis(chloromethyl)-1.6 Hz). Work up acccording to GP5. From the concentrated solution (40 ml) further NH4Br was (2. 2167 (C. 3-H). From the organic phase bis(trimethylsi- toluene/acetic acid. 1160. 3. 765. 180°C (dec. 16.14.75. m. C-4).45. 14. 1240.0 mmol).45. m/z (%): 194 (17) [M1 1 2 H]. 6-C). 74%).39. 35.4-benzoquinone Diimine DE (50 ml) was added to ammonia (4. H 1275. 2 MS (70 eV). 918. 78%) (2j): GP5 with 2. 2 IR (KBr): ν̃ 5 3060 cm21. H 4. (CH3CN): λmax (lg ε) 5 330 nm (4. 1298.26. 425 (3. bis(trimethylsilyl)-[13C]carbodiimide (4.12. From acetonitrile (250ml) bronze-colored plates of 2m (2. [M1].45 g) afforded from toluene (90 ml)/ 2170 (C. 172. 1571 (C5N). 7. 270 mmol) in DE monitored by TLC (SiO2. N 23. were isolated (unlabelled: 3 JC-F 5 12.N9-Dicyano-2-methyl-5-trideuteriomethyl-1. H 4. 180°C (dec. 344 sh (4. 2-.15 g. 254 (100) [M1].46).N).66 g. Eur. CH2Cl).91. 1200. (%): 192 (84) [M1 1 2 H]. b. 2 MS (70 eV).30). C 47.N9-Dicyano-2. H N.N). A deep red precipitate formed.p. found C 62. C 63. C 54.78 g. 159 (58) [M1 2 N. imine (2n) [47]: GP5 with 1n (2. C-2).04. microcrystalline 2h (4. H 2. 16 h. 2165 (C. ref. m/z (%): 240 (20) [M1 1 2 H]. 800.26). H (a) Br13CN was obtained from K13CN (15% 13C) and bromine by 2. 51%]. 1395. isolated. 2 IR (KBr): ν̃ 5 3055 cm21 (CH). 2 Fraction 2: Mixture of 4-chloromethyl. 1580 (C5C). 1130.51. (2i): GP5 with 1i (1. 2 C10H5F3N4 (238.).12.2): calcd.). 1030. 6-H) [anti-2g. C 65. H 1.57. 770. 144. 2 MS (70 eV). H 4.41.6-quinoid. 1 H.p.69.21.36 g. 58261°C/20 Torr. 1762178°C. H 2. found C 65.1 (s. 1523 (C5N). 2 MS (70 eV).6-bis(trideuteriomethyl)-1.N).91 (s.25.48 g.0 mmol) in CH2Cl2 (100 turbid and cooling of the mixture yielded a violet powder of 2i (228 ml). H 2.6 g.5-dimethyl-1.70 (t. 4JH-H 5 1. 2 UV 4. 2 IR (KBr): ν̃ 5 2250 cm21 (C2D).4-benzoquinone Diimine DCN].55 (m.N). N 29. 186 (100) [M1 2 2 CN]. 2 C10H6Cl2N4 (253. 1603 (C5C). 40. 2 IR (KBr): ν̃ 5 2160 cm21 m/z (%): 256 (55) [M1 1 2 H]. of 2g (1. 2 MS (70 eV). 4-C). 160 (50) [M1 2 HCN].0 mmol) in CH2Cl2 (100 ml). H 4.46. Chem. imine (2m): GP5 with 1m (2. 6. N. 890.72). 7.N).1): calcd. m. J9C-F 5 177.80. 6-H) [syn-2g. m. 4 h. 1530 (C5N). 1165.Multistep Reversible Redox Systems. 238 (77) [M1]. 18.8 (d.24). m. After stirring at 20°C (2 h).50 (q. 3022. 923.17.2): calcd. C 64.37 g. From acetonitrile (300 ml) bronze-colored scales of 2n (3. found C 48.01 1113. 1085. was powder. 10. N 30.47.18. N.16. 1 H. 945. the precipitate was filtered min). 158 (43) [M1 2 DCN]. N.28 g.5-Bis(chloromethyl)-N. H 4. 2 C10H6F2N4 (220. quinoid H). Flash chromatography (SiO2.21. 16%). 1410. 4.11 (s. 25.N).59.60 g. 2 C10D8N4 (192.62 (d. m/z 2180 (C.4-ben- zoquinone Diimine (2p): GP5 with 1p (2. N 30.4-benzoquinone Di- 2. 670. 98%) which was dissolved in DE (50 ml) and added within 1 h g. 330 (4. the dichloro derivative 2j (190 mg) which could not be separated C-1). 1535. 850. 4JH-F 5 1.2): calcd.86 g) was just dissolved in boiling toluene. In a variation of ref.69 g.5 Hz.

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