Dicyanomethylene compounds as cyanation reagents

Article abstract of DOI:10.1515/znb-2002-0412

Ethenetetracarbonitrile (2, in benzene solution) and 1,3-dioxoindan-2-ylidene propanedinitrile (4, in ethanol or acetonitrile solution) act on N-aryl-2,3-dihydro-1H-benz[d,e]isoquinolines 6a-d and N-aryl-6,7-dihydro-5H-dibenz[c,e]azepines 11a-d via hydrid

Full text of DOI:10.1515/znb-2002-0412

Dicyanomethylene Compounds as Cyanation Reagents [1]*
Dietrich Döppa, Sabine Jüschkea, and Gerald Henkelb
a
Fachgebiet Organische Chemie und
b
Fachgebiet Festkörperchemie, Institut für Chemie, Gerhard-Mercator-Universität
Duisburg, D-47048 Duisburg, Germany
Reprint requests to Prof.Dr.D.Döpp, Fax +49(0)203-3794192.
E-mail: doepp@uni-duisburg.de
Dedicated to Professor W. S. Veeman on the occasion of his 60th birthday
Z.Naturforsch. 57b, 460Ð470 (2002); received February 1, 2002
Dihydroisoquinolines, Bridged Functional Biphenyls, Cyclic Iminium Ions
Ethenetetracarbonitrile (2, in benzene solution) and 1,3-dioxoindan-2-ylidene propanedini-
trile (4, in ethanol or acetonitrile solution) act on N-aryl-2,3-dihydro-1H-benz[d,e]isoquino-
lines 6a-d and N-aryl-6,7-dihydro-5H-dibenz[c,e]azepines 11a-d via hydride abstraction fol-
lowed by addition of cyanide to the iminium carbon atom forming the corresponding 1- and
5-carbonitriles 9a-d and 13a-d, respectively, in moderate to medium yields.Additionally, the
known 1,3-dihydroxy-2H-inden-2-ylidenepropanedinitrile 15 and a novel dispirocyclopro-
pane (17) are formed from 4 in the reaction with 6 in acetonitrile and ethanol, respectively.
The structures of 17 and 6-(4-methylphenyl)-6,7-dihydro-5H-dibenz[c,e]azepine-5-carbonit-
rile have been unambiguously confirmed by single-crystal X-ray crystallography.
Introduction
N,N-Dialkylanilines undergo a para-tricyanovi-
nylation (TCV) reaction when exposed to ethene-
tetracarbonitrile (2)[2]. N-Phenylisoindoline (1,
Ar = Ph) or other N-phenylisoindolines even with
free para-position on the phenyl group do not
show significant para-tricyanovinylation with 2, in-
stead, a complex sequence of steps ultimately
leading to 3 is observed [3].This behaviour is most
likely due to the sensitivity of positions 1 and 3 in
1 to formal (stepwise or concerted) hydride ab-
straction or C-H homolyses [3].In contrast, 1,3-
dioxoindan-2-ylidene propanedinitrile (4) does
show a TCV-analogous reaction with the above-
mentioned isoindolines and at the same time a
multistep-sequence of events ultimately leading to
substitution of 1-H and 3-H of the isoindole de-
rived from 1 by 2-cyano-1,4-naphthoquinon-1-yl
[3], a residue accessible by electron-transfer medi-
ated rearrangement [4] of 4.The structures of pro-
ducts 3 and 5 have been confirmed for 3 (Ar = 3-
CH3C6H4)) and 5 (Ar = 4-H3COC6H4) by single
crystal structural analyses [3, 5].
Scheme 1.
These intriguing transformations led us to inves-
tigate the reactions of dihydro-benz[d,e]isoquino-
lines 6 and dihydrodibenz[c,e]azepines (11) bear-
ing a selection of N-aryl substituents with the
acceptor systems 2 and 4.Both donor systems ( 6,
11) feature benzylic activation of the α-carbon
* Presented in part at the 5th Conference on Iminium
Salts (ImSaT-5), Stimpfach-Rechenberg (Germany),
September 11Ð13, 2001.
0932Ð0776/2002/0400Ð0460 $06.00 ” 2002 Verlag der Zeitschrift für Naturforschung, Tübingen · www.znaturforsch.com
D
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D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
461
atoms as in 1 and should therefore be reactive at
these positions towards 2 and 4.
Results and Discussion
The heterocyclic donors 6a-d [6] and 11a-d [7]
were prepared according to published procedures.
Treatment of 6a with three molar equivalents of
ethenetetracarbonitrile (2) in benzene as solvent
at room temperature resulted in a green coloura-
tion of the solution which later became dark
brown.While a yellow colour of the CT complex
from 2 and the solvent was persistent and detecta-
ble at all times (λmax = 384 nm, [8]), monitoring of
the reaction by visible spectroscopy failed since at
lower concentrations no significant colour changes
were observed any more.Concentration of the
preparative runs resulted in formation of a precip-
Scheme 2.
itate which by washing with ethyl acetate yielded
a dark-blue solid which did not melt below 300 ∞C,
showed CN absorptions at 2216 and 2254 cmÐ1
,
CH2-resonances in going from 6 to 9: Due to the
introduction of a stereogenic centre at C-1, the C-
3 methylene protons now show an AB pattern
while 1-H gives rise to a singlet.
A plausible rationale for the introduction of a
cyano group at C-1 is depicted in Scheme 2.A net
hydride abstraction [2, 13] by 2 from 6 forms the
cyclic iminium ion 7 and tetracyanoethanide 8a.
was insoluble in all common solvents and was not
characterized further.The formation of polymers
from 2 in the presence of alcohols, phenols and
amines has been observed [9] and most of the nit-
rile groups seem to be involved in the polymeriza-
tion [10, 11].
The remaining soluble materials were subjected
to preparative layer chromatography.From the
one significant zone and by crystallization from
ethanol, the α-aminonitrile 9a (see below for char-
acterization) was obtained in 7% yield.It was
found to be air-sensitive, thus in all further cases
the work-up was carried out as quickly as possible
to minimize losses.Since 1-H is activated by its
benzyl-like position and any C-1 centered radical
would be highly stabilized including a captodative
[12] contribution, this sensitivity is quite plausible.
While an increase in reaction temperature to 50 ∞C
did not lead to any improvement, by keeping the
temperature as close as possible to the freezing
point of the mixture by external ice/water cooling,
the yield of 9a could be raised to 54%.Similar
results were obtained for the analogous com-
pounds 9b-d from 6b-d (see Scheme 2).All yields
given in this study refer to converted starting
material.
The structures of 9a-d were delineated from
their spectroscopic properties (see Experimental
Section).The salient feature is the change in the
Scheme 3.
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462
D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
The latter may deliver a cyanide ion to 7 directly tigation of minor zones, but certainly not in quan-
within the ion pair, since release of CN- into the tities sufficient for full characterization.
non-anionstabilizing solvent seems less likely.The
The weaker acceptor 4, being easily accessible
fate of 10a is not clear at present, formation of [15] from indane-1,2,3-trione, was expected to re-
intractable polymers is a likely possibility, since it act similarly to 2 with the heterocyclic donors 6a-
is more reactive towards bases than 2, water (for d.Due to insufficient solubility of 4 in benzene,
example during work-up and chromatography) the reaction was carried out both in dry ethanol
initiates HCN-elimination and produces hitherto and in acetonitrile at room temperature.In the
unidentified materials [14].Products derived from
former solvent, nearly three days were required to
6 with higher molecular weight, structurally analo- achieve conversions of 85Ð90% for 6a-c and 53%
gous to 3, may be present in the reaction mixtures for 6d and low to medium yields of compounds
in very small amounts as indicated from MS inves- 9a-d (see Scheme 2).In acetonitrile, nearly quanti-
a)
Fig.1.a) Structure of compound 17 in the crystal.The crystallographic numbering does not match the systematic
˚
numbering.Selected bond lengths [A ]: C(9)-C(10) 1.517(3), C(9)-C(11) 1.533(3), C(10)-C(11) 1.539(3),
C(10)-C(21) = C(10)-C(20) = 1.460(3); selected angles [∞]: C(20)-C(10)-C(21) 111.9(2), C(12)-C(11)-C(19) 105.8(1),
C(1)-C(9)-C(8) 104.4(1); b) detail of crystal structure of 17·MeCN viewed along the y-axis.
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D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
463
˚
tative conversions were achieved already after A) than the two other C-C bonds of the three-
three hours, but yields of 9a-d tended to be low or membered ring.In the crystal lattice of 17·MeCN
moderate.In addition, 1,3-dihydroxyindan-2-yli-
denepropanedinitrile (15) was formed in yields stacking the indanylidene units (Fig.1b).
varying between 12 and 19%.A rationale for the 1,3-Dihydrobenz[c,e]azepines 11a-d may be re-
the solvent molecules reside in tubes formed by
formation of this known [16] byproduct is abstrac- garded as 1,2-phenylene homologues of isoindo-
tion of a proton by the carbanion 8b resulting from lines 1 and are thus expected to show a reactivity
hydride abstraction, see Scheme 3.
towards 2 and 4 similar to that of 1.To our sur-
In ethanol solution, on the other hand, 15 is not a prise, however, again solely α-cyanation forming
significant byproduct, although protonation of any carbonitriles 13a-d was observed when 11a-d was
8b formed should be favourable.Instead, a new
allowed to react with either 2 in benzene or its
compound was regularly detected and identified as analogue 4 in ethanol.
the cyclopropane 17.Aside of the simple 1H and
The structural assignment rests largely on the
13C NMR spectra demonstrating the presence of 1H and 13C NMR spectra: Due to the creation of
two equivalent dioxoindanylidene units and two a stereogenic centre at C-5, the 4H singlets for the
equivalent CN groups, the structure of 17 was un- methylene protons in 11a-d give way to a 1H sin-
ambiguously corroborated by a single crystal struc- glet for 5-H and an AB-quartet for 7-CH2.Also,
ture determination of its 1:1 stoichiometric solvate these spectra in total reflect the reduction of sym-
with acetonitrile (Figs 1 and 2).This compound,
metry in 13 with respect to 11 (see Experimental
being the formal 1,3-dioxoindan-2-ylidene adduct Section).Rigorous structure proof comes from the
to the C=C double bond of 4 may be formed from single crystal X-ray structural analysis of 13b (see
the carbanion 8b by conjugate addition to 4, fol- Fig.3 and Table 1).
lowed by intramolecular displacement of malodini-
trile anion (Scheme 3).For a review on the forma-
tion of polycyano cyclopropanes, see ref.[17].
The central seven-membered ring is confined
into a twist-form, and the planes of the two phenyl
rings in the biphenyl moiety form a twist angle of
The C2v- symmetry of 17 in solution is reduced ð 42.7∞.The (relative) configuration of 13b is rel-
to C1 in the crystal (see Fig.2). The C(9)-C(21) (5R, aS), the unit cell consists of two molecules
˚
bond (1.517 A) is significantly shorter (by 0.002 each of the (5R, aS)- and (5S, aR)-enantiomers.
Fig.2. Structure of 17 in the
crystal.View perpendicular to
the plane of the three-memb-
ered ring
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464
D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
Fig.3.Structure of com-
pound 13b in the crystal.
Since the cyclic benzofused substrates 6 and 11
˚
Table 1.Selected bond lengths [A ] and angles [∞] of com-
pound 13b (C22H18N2) in the crystal.The crystallo-
graphic numbering does not correspond to systematic
numbering.
might be especially favourable for α-hydride ab-
straction, and the N-phenyl derivatives 6a and 11a
did not show much of para-tricyanovinylation with
2 or an analogous reaction with 4, the question
was addressed whether such a reaction would take
place on 4-unsubstituted N-benzylanilines at all.
Using substrates 18a,b attack of 4 at the free para-
position took place; however, the primary 1:1 ad-
ducts 19a,b only underwent prototropy to form
20a,b.Subsequent coloration and HCN elimina-
tion took place upon melting.Any products of α-
cyanation at the benzylic carbon atom could not
be detected.
˚
Bond lengths [A]
Bond angles [∞]
C(1)ÐC(6)
C(6)ÐC(7)
C(7)ÐC(12)
1.406(2)
1.485(2)
1.405(2)
C(1)ÐC(6)ÐC(7)
120.3(1)
120.0(1)
120.8(1)
114.0(1)
116.3(1)
112.6(1)
121.4(1)
111.5(1)
110.9(1)
122.0(1)
120.6(1)
C(6)ÐC(7)ÐC(12)
C(7)ÐC(12)ÐC(13)
C(12)ÐC(13)ÐN(1)
C(13)ÐN(1)ÐC(21)
N(1)ÐC(21)ÐC(1)
C(6)ÐC(1)ÐC(21)
N(1)ÐC(21)ÐC(22)
C(1)ÐC(21)ÐC(22)
C(13)ÐN(1)ÐC(14)
C(14)ÐN(1)ÐC(21)
C(12)ÐC(13) 1.512(2)
C(13)ÐN(1)
N(1)ÐC(21)
C(21)ÐC(1)
C(21)ÐC(22) 1.501(2)
C(22)ÐN(2)
1.473(2)
1.452(2)
1.522(2)
1.145(2)
Scheme 5.
Conclusion
Under favourable conditions, as with com-
Scheme 4.
pounds 6 and 11 bearing activated α-positions, eth-
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D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
465
Starting materials
enetetracarbonitrile (2) and 1,3-dioxo-2-indanyli-
dene propanedinitrile (4) react by net cyanation,
most likely by initial hydride abstraction and sub-
sequent transfer of a cyanide ion to the amine-
derived iminium ion.Scope and limitations of this
process have not been explored yet, and no opti-
mization has so far been attempted.Nevertheless
this reaction sequence may be developed into an-
other method of α-cyanation of tertiary amines.
Ethenetetracarbonitrile (2), Merck, was sublimed
prior to use, m.p.198 Ð200 ∞C (lit.[2a] 200 Ð
202 ∞C).
(1.3-Dioxoindan-2-ylidene)propanedinitrile (4)
was prepared according to Chatterjee [15b], m.p.
279Ð282 ∞C (lit.[15b] 280 Ð285 ∞C).
1,8-Bis(hydroxymethyl)naphthalene was pre-
This ought to be seen in the context that α- pared according to Boekelheide and Vick [24] in
51% yield, m.p. 158Ð160 ∞C (lit.[24] 157 Ð
aminonitriles may be regarded as stabilized imi-
nium ions [18].Several related α-cyanations using
trimethylsilylcyanide as a cyanide source for imi-
nium ions generated by photooxidation [19Ð22],
or action of other oxidants [18] on tertiary amines
to generate iminium ions which are then reacted
with cyanide ions [18] have been reported.Sodium
borohydride reduction of pyridinium ions in the
presence of sodium cyanide to generate 1,2,3,6-
158 ∞C). Ð This material was converted [25] into
1,8-bis(bromomethyl)-naphthalene, m.p.129
133 ∞C (lit.[25] 131 Ð133 ∞C).
Ð
This compound (instead of the corresponding
bis(chloromethyl) analogue) was used to prepare
the 2-aryl-2,3-dihydro-1H-benz[d,e]isoquinolines
6a-d: Samples of 100 mg (3.2 mmol) and equimo-
lar amounts of the corresponding aniline were re-
fluxed in 10 ml of toluene in the presence of 0.47 g
tetrahydropyridine 2-carbonitriles is a comple- (8.0 mmol) of triethylamine. Thereafter the mix-
ture was treated with 2 M NaOH and extracted
with CHCl3.After drying and concentration the
residue was crystallized from methanol (6a) or
ethanol (6b-d).
2-Phenyl-2,3-dihydro-1H-benz[d,e]isoquinoline
(6a): Yield 05.2 g (66%), m.p.58 Ð59 ∞C (lit.[6]
57Ð59 ∞C).
mentary technique of α-cyanation [23].In the ex-
amples presented in this study, the same reagent
is functioning as dehydrogenating agent and as cy-
anide ion source.
Experimental Section
M.p.’s have been determined on a Kofler hot
stage microscope. Ð IR-spectra were recorded on
Perkin Elmer 283 and 983 instruments.Weak
(strong) bands have been indicated by w (s) after
the wavenumber. Ð A Bruker WM 300 instrument
2-(4-Methylphenyl)-2,3-dihydro-1H-benz[d,e]-
isoquinoline (6b): Yield 05.7 g (69%) m.p.148
Ð
150 ∞C (lit.[6] 146 Ð148 ∞C).
2-(4-Methoxyphenyl)-2,3-dihydro-1H-benz[d,e]-
isoquinoline (6c): Yield 05.4 g (61%), m.p.107
Ð
1
has been used to determine H (300.13 MHz) and
108 ∞C (lit.[6] 106 Ð107 ∞C).
13C (75.47 MHz) NMR spectra. Assignment of
carbon resonances has been supported by DEPT
experiments.Abbreaviations indicating signal
multiplicity: s singlet, d doublet, t triplet, m
multiplet. Ð Mass spectra have been obtained with
a Varian MAT 311 doubly focussing instrument
using electron impact ionization (70 eV). Ð Ele-
mental analyses have been determined on a Carlo
Erba Model 1106 Elemental Analyzer.Analytical
thin-layer chromatography: Al-sheets coated with
Merck silica gel 60 F254. Ð Preparative layer chro-
matography (plc): Glass plates 48 ¥ 20 cm covered
with slurry applied and air dried layers of Merck
silica gel PF254.Detection of zones by fluorescence
quenching after 254 nm excitation.Zones were re-
moved from the plates and extracted with cold
acetone.
2-(4-Chlorophenyl)-2,3-dihydro-1H-benz[d,e]-
isoquinoline (6d): Yield 0.51 g (57%), m. p. 116Ð
118 ∞C (lit.[6] 117 Ð119 ∞C).
2,2Ј-Bis(hydroxymethyl)biphenyl, prepared ac-
cording to Rieche, Höft and Schultze [7], had m.
p.113 ∞C (lit.[7] 112 ∞C).This was converted into
2,2Ј-bis(bromomethyl)-biphenyl by treating with a
doubled molar amount of phosphorus tribromide
at 20 ∞C, followed by hydrolysis.Crystallization
from petroleum ether gave a 78% yield as col-
ourless crystals, m.p.88 Ð90 ∞C (lit.[26] 89 Ð
92 ∞C).To prepare [7] compounds 11, samples of
340 mg (1.0 mmol) of the dibromide and 1.0 mmol
of the corresponding aniline were heated to reflux
in 10 ml of toluene containing 0.2 ml of triethyla-
mine for 2 h.The mixture was treated with 2 M
NaOH and the organic layer was dried and con-
centrated.The residues were crystallized from eth-
anol to give 2.2 g (81%) 11a, 1.4 g (49%) 11b,
2.63 g (87%) 11c, and 1.53 g (50%) of 11d.
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466
D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
6-Phenyl-6,7-dihydro-5H-dibenz[c,e]azepine
5Ј-H), 7.31 (m, 4H), 7.43 (m, 2H), 7.53 (m, 2H)
(11a): M.p. 84Ð86 ∞C (lit.[7] 895. Ð90.0 ∞C). Ð IR (all biphenylylene-H). Ð 13C (75.47 MHz, CDCl3):
(KBr pellet): ν = 2939, 2834 (CH2), 1591, 1564, δ = 52.27 (2¥ CH2); 116.07, 127.74, 128.10, 128.39,
1492 s, 1469, 1379, 1210, 821s, 757s cmÐ1. Ð H 128.95, 129.49 (all 2 aryl-CH each); 122.94 (4Ј-C);
1
NMR (300.13 MHz, CDCl3): δ = 4.12 (s, 4H, 2 ¥ 134.46 and 140.57 (C-4a, C-7a, C-11a, C-11b);
CH2), 6.79 (m, 1H, 4Ј-H), 6.79 (m, 2H, 2Ј-, 6Ј-H); 148.02 (C-1Ј). Ð MS (EI, 70 eV): m/z (%) = 305
7.22Ð7.35 (m, 6H), 7.42 (m, 2H), 7.52 (m, 2H) (all (100) [M+], 304 (98) [M+-H], 178 (32), 166 (42),
aryl-H). Ð 13C NMR (75.47 MHz, CDCl3): δ = 165 (42), 140 (21), 138 (40), 111 (21) [ClC6H4 ].
+
52.13 (2 ¥ CH2), 118.17 (4Ј-C); 114.93, 127.66, C20H16ClN (305.8): calcd. C 78.55, H 5.28, N 4.58;
128.04, 128.23, 129.14, 129.57 (2 aryl-CH each); found: C 78.50, H 5.31, N 4.63.
134.84, 140.68 C-4a, C-7a, C-11a, C-11b), 149.47
Reactions of 2-aryl-2,3-dihydro-1H-benz[d,e]-
(1Ј-C). Ð MS (EI, 70 eV): m/z (%) = 271 (95) isoquinolines (6a,d) with ethenetetracarbonitrile
[M+], 270 (100) [M+-1], 194 (5) [M+-C6H5], 178 (2), general procedure: To a chilled solution of
(24), 165 (33), 152 (8) [biphenylylene+] 135.5 (7) 384 mg (3.0 mmol) of 2 in 10 ml of benzene a pre-
[M++], 104 (43), 77 (35). Ð C20H17N (271.3): calcd. cooled solution of 6a-d in 10 ml of was added
C 88.52, H 6.32, N 5.16; found: C 88.51, H 6.35, dropwise, which caused a spontaneous change of
N 5.11.
6-(4-Methylphenyl)-6,7-dihydro-5H-dibenz[c,e]-
colour from yellow to dark green.The mixture was
stirred for 18 h and allowed to warm up to room
azepine (11b): M.p. 110Ð111 ∞C (lit.[7] 104 Ð temp.After concentration, the residue was sepa-
105 ∞C). Ð IR (KBr pellet): 2909, 2855 (CH2), rated from a not identified deep blue solid by ex-
1614, 1516 s, 804 s, 756 s cmÐ1. Ð 1H NMR (300.13 traction with ethyl acetate.The extract was con-
MHz, CDCl3): δ = 2.26 (s, 3H, CH3), 4.06 (s, 4H, centrated to a few ml and subjected to plc using
2 ¥ CH2), 6.89 (m, 2H, 3Ј-, 5Ј-H), 7.06 (m, 2H, cyclohexane/ethyl acetate 5:1.The fastest moving
2Ј-, 6Ј-H), 7.30 (m, 4H), 7.40 (m, 2H), 7.51 (m, 2H) zones (Rf values given) were removed while still
(all biphenylylene-H). Ð 13C NMR (75.47 MHz), moist, extracted with ethyl acetate and the extracts
CDCl3): δ = 20.35 (CH3), 52.49 (2¥ CH2); 115.35, were concentrated.Crystallization from ethanol
127.59, 127.98, 128.14, 129.55, 129.64 (all aryl-CH gave colourless crystals, 114 mg (42%) of 9a, Rf =
each); 134.88, 140.69 (C-4a, C-7a, C-11a, C-11b), 0.36; 153 mg (54%) of 9b, Rf = 0.43; 108 mg (36%)
147.46 (1Ј-C). Ð MS (EI, 70 eV): m/z (%) = 285 of 9c, Rf = 0,16; 137 mg (45%) of 9d, Rf = 0.29.
(98) [M+], 284 (100)[M+-1], 178 (22), 165 (27), 118
(29), 91 (29) [C7H7 ]. Ð C21H13N (285.4): calcd. 1-carbonitrile (9a): M.p.130 Ð132 ∞C. Ð IR (KBr
C 88.38, H 6.71, N 4.91; found C 88.28, H 6.76, pellet): ν = 2210w (CN), 1600, 1580, 1500, 805, 760
N 4.94.
6-(4-Methoxyphenyl)-6,7-dihydro-5H-dibenz-
2-Phenyl-2,3-dihydro-1H-benz[d,e]isoquinoline-
+
1
cmÐ1. Ð H NMR (300.13 MHz, CDCl3): δ = 4.87
and 4.76 (AB-system, |2JAB| = 15.4 Hz, 3-CH2), δ =
[c,e]azepine (11c): M.p. 148Ð149 ∞C (lit.[7] 148 Ð 5.81 (s, 1H, 1-H); 7.10 (m, 1H), 7.26 (m, 2H), 7.35Ð
149 ∞C). Ð IR (KBr pellet): ν = 2935, 2385 (CH2), 7.55 (m, 6H), 7.81 (m, 1H), 7.90 (m, 1H) (all aryl-
1511 s, 1249, 1036, 822, 770 cmÐ1. Ð 1H NMR H). Ð 13C NMR (75.47 MHz, CDCl3): δ = 49.37
(300.13 MHz, CDCl3): δ = 3.74 (s, 3H, OCH3), 4.02 (C-3), 54.96 (C-1), 116.70 (CN); 119.04 (C-2Ј, C-
(s, 4H, 2 ¥ CH2), 6.84 (m, 2H, 2Ј-, 6Ј-H), 6.94 (m, 6Ј); 123.00, 123.08, 123,32, 125.71, 126.26, 126.74,
2H, 3Ј-, 5Ј-H); 7.30 (m, 4H), 7.41 (m, 2H), 7.50 (m, 128.94, (all aryl-CH); 129.60 (C-3Ј, C-5Ј); 126.45,
2H) (all biphenylylene-H). 13C NMR (75.47 MHz, 127.45, 130.91, 133.39, 148.27 (all quart. aryl-C). Ð
CDCl3): δ = 53.36 (2 ¥ CH2), 55.58 (OCH3); MS (EI, 70 eV): m/z (%) = 270 (88) [M+], 269
114.50, 117.40, 127.57, 127.99, 128.16, 129.55 (2 (100), 244 (73), 243 (77) [M+-HCN], 166 (65), 77
aryl-CH each); 134.81, 140.74 (C-4a, C-7a, C-11a, (37) [Phenyl+]. Ð C19H14N2 (270.3): calcd. C 84.42,
C-11b), 144.23 (1Ј-C), 152.93 (4Ј-C). Ð MS (EI, 70 H 5.22, N 10.36; found C 84.10, H 5.45, N 9.96.
eV): m/z (%) = 301 (100) [M+], 300 (74) [M+-1];
286 (14) [M+-CH3] 179 (26), 178 (21), 134 (18), 120 isoquinoline-1-carbonitrile (9b):
(15). Ð C21H19NO (301.4): calcd. C 83.69, H 6.35, 146 ∞C. Ð IR (KBr pellet): ν = 2210w (CN), 1600,
2-(4-Methylphenyl)-2,3-dihydro-1H-benz[d,e]-
M.p. 145Ð
N 4.65; found C 83.66, H 6.32, N 4.58.
1575, 1510 (aryl), 1210, 950, 825, 815, 785 cmÐ1. Ð
6-(4-Chlorophenyl)-6,7-dihydro-5H-dibenz[c,e]- 1H NMR (300.13 MHz, CDCl3): δ = 2.29 (s, 3H
azepine (11d): M.p. 146Ð147 ∞C (lit.[7] 147 Ð CH3); δ = 4.75 and 4.63 (AB system,|2JAB|= 15.4
149 ∞C). Ð IR (KBr pellet): ν = 2939, 2834 (CH2), Hz, 3-CH2), 5.71 (s, 1H, 1-H); 7.13 (m, 4H), 7.26
1591, 1564, 1492s, 1460, 1379, 1210s, 821, 757s cmÐ1. Ð (m, 1H), 7.29Ð7.46 (m, 3H), 7.79 (m, 1H), 7.82 (m,
1H NMR (300.13 MHz, CDCl3): δ = 4.06 (s, 4H, 2 1H) (all aryl-H). Ð 13C NMR (75.47 MHz, CDCl3):
¥ CH2), 6.88 (m, 2H, 2Ј-, 6Ј-H), 7.20 (m, 2H, 3Ј-, δ = 20.93 (CH3), 49.47 (C-3), 55.36 (C-1), 116.19
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D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
467
(CN), 119.16 (2Ј-C,6Ј-C), 130.08 (3Ј-C, 5Ј-C); (13%) of 15; from 6b: 7 mg (3%) of donor 6b and
122.92, 123.23, 125.61, 126.16, 126.60, 128.80 (aryl- 52 mg (19%) of 9b, m.p.145 Ð146 ∞C, along with
CH); 126.37, 127.53, 131.02, 132.66, 133.29, 145.90 80 mg (19%) of 15; from 6c: 129 mg (43%) of 9c,
(all quart.aryl-C). Ð MS (EI, 70 eV): m/z (%) = m.p.122 ∞C, along with 61 mg (15%) of 15; from
284 (65) [M+], 283 (79) [M+-H], 258 (67), 257 (100) 6d: 6 mg (2%) unchanged 6d, and 90 mg (30%) 9d,
+
[M+-HCN], 166 (44), 91 (14) [C7H7 ]. Ð C20H16N2 m.p.126 Ð128 ∞C, along with 50 mg (12%) of 15.
(284.4): calcd. C 84.48, H 5.67, N 9.85; found C
84.48, H 5.72, N 9.82.
(1,3-Dihydroxy-2H-inden-2-ylidene)propanedi-
nitrile (15): Subl.p.285
∞C (lit.[15] mp..>
2-(4-Methoxyphenyl)-2,3-dihydro-1H-benz[d,e]- 300 ∞C). Ð IR (KBr pellet): ν = 3269 (broad, OH),
isoquinoline-1-carbonitrile (9c): M.p.122 ∞C. Ð 2229s (CN), 1572, 1452, 1430, 1297, 1248, 988, 961,
IR (KBr pellet): 2220w (CN), 1510, 1240, 1080, 810 773 cmÐ1. Ð H NMR (300.13 MHz, (CD3)2SO):
1
1
cmÐ1. Ð H NMR (300.13 MHz, CDCl3): δ = 3.79 δ = 7.86 (m, 2H) and 8.36 (m, 2H) (habitus of an
(s, 3H, OCH3), δ = 4.81 and 4.55 (AB system, AAЈBB’-system, 4 aryl-H), 11.50 (very broad, 2H,
|2JAB| = 15.4 Hz, 3-CH2), 5.62 (s, 1H, 1-H); 6.93 OH). Ð 13C NMR (75.47 MHz, (CD3)2SO): δ =
(m, 2H), 7.85 (m, 2H), 7.34Ð7.51 (m, 4H), 7.85 (m, 92.03 (C(CN)2), 115.67 (CN), 124.00 (aryl-CH),
1H), 7.87 (m, 1H) all aryl-H). Ð 13C NMR (75.47 128.13 (3aЈ-C, 7aЈ-C), 130.22 (aryl-CH), 153.46 (1Ј-
MHz, CDCl3): δ = 49.47 (CH2), 55.50 (OMe), C, 3Ј-C). Ð MS (EI, 70 eV): m/z (%) = 210 (100)
55.66 (C-1), 114.81 (C-2Ј, C-6Ј), 116.18 (CN), [M+], 183 (8) [M+-HCN], 155 (30), 127 (64), 105
121.57 (C-3Ј, C-5Ј); 122.95, 123.23, 125.66, 126.23, (18). Ð C12H6N2O2 (210.2): calcd. C 68.54, H 2.88,
126.68, 128.88 (aryl-CH); 126.41, 127.79, 131.30, N 13.32; found C 68.54, H 2.92, N 13.25.
133.41, 142.04, 156.16 (all quart. aryl-C). Ð MS
Reaction of 6 with 4 in ethanol, general pro-
(EI, 70 eV): m/z (%) = 300 (67) [M+], 299 (56), 274 cedure: A solution of 1.0 mmol of 6 and 420 mg
(70), 273 (100) [M+-HCN], 166 (21). Ð C20H16N2O (2.0 mmol) of 4 in 100 ml of dry ethanol was
(300.3): calcd. C 79.98, H 5.37, N 9.33; found: C stirred at room temperature for three days, during
79.88, H 5.44, N 9.36.
2-(4-Chlorophenyl)-2,3-dihydro-1H-benz[d,e]-
which time the colour changed from yellow to red
and a fine colourless precipitate formed, which
isoquinoline-1-carbonitrile (9d): Colourless crys- was collected and recrystallized from acetonitrile
tals, 137 mg (45%). Ð M.p.126 Ð128 ∞C. Ð IR to give colourless needles of 17.The mother liquor
(KBr pellet): 2230w (CN), 1590, 1510, 1500 (aryl), was separated by plc using cyclohexane/ethyl ace-
1
1230, 810, 770 cmÐ1. Ð H NMR (300.13 MHz, tate (5:1).The significant zones ( Rf values given
CDCl3): δ = 4.71 and 4.60, (AB system, |2J|= 15.4 below) were recovered while still moist and
Hz, 3-H2), 5.70 (s, 1H, 1-H); 7.07 (m, 2H), 7.25Ð worked up quickly.The following quantities of ma-
7.30 (m, 3H), 7.35Ð7.46 (m, 3H), 7.74 (m, 1H), terials have been obtained:
7.81 (m, 1H), (all aryl-H). Ð 13C NMR (75.47
From 6a: 211 mg (60%) of 17; Rf = 0.48: 32 mg
MHz, CDCl3): δ = 49.20 (CH2), 54.58 (C-1), 115.97 (13%) of 6a; Rf = 0.33: 101 mg (43%) of 9a, m. p.
(CN), 120.07 (C-2Ј, C-6Ј), 129.48 (C-3Ј, C-5Ј); 130Ð132 ∞C. Ð From 6b: 190 mg (54%) of 17, Rf =
123.01, 123.35, 125.67, 126.23, 126.79, 128.97 (all 0.52: 39 mg (15%) 6b; Rf = 0.38: 157 mg 9b, m. p.
aryl-CH); 126.17, 126.88, 128.04, 130.31, 133.23, 145Ð146 ∞C.From 6c: No 17; Rf = 0.33: 28 mg
146.71 (all quart. aryl-C). Ð MS (EI, 70 eV): m/z (10%) 6c; Rf = 0.23: 59 mg (22%) 9c, m. p.
(%) = 304 (99) [M+], 303 (100) [M+-1], 277 (90) 122 ∞C. Ð From 6d: 161 mg (46%) 17; Rf = 0.64:
[M+-HCN], 276 (90), 268 (22) [M+-HCl], 267 (22), 132 mg (47%) of 6d; Rf = 0.47: 40 mg (25%) 9d,
241 (27), 166 (52), 139 (28). Ð C19H13ClN2 (304.8): m.p.126 Ð128 ∞C.
calcd. C 74.87, H 4.30, N 9.19; found 74.85, H 4.40,
N 9.12.
1,1Љ,3,3Љ-Tetraoxo-[indane-2-spiro-1Ј-cyclopro-
pane-2Ј-spiro-2Љ-indane]-3Ј,3Ј-dicarbonitrile (17):
Reaction of 6 with 4 in acetonitrile, general pro- M.p.239 Ð242 ∞C (from acetonitrile). Ð IR (KBr
cedure: To a solution of 1.0 mmol of 6 in 50 ml pellet): ν = 2255w (CN), 1728 (C=O), 1593, 1245,
acetonitrile 420 mg (2.0 mmol) of 4 were added. 1098, 819, 767, 753 cmÐ1
Ð
1H NMR (300.13
Within two minutes, the initially yellow solution MHz, DMSO-D6): δ = 7.90 (narrow m, 8H, aryl-
first turned red and then green and was stirred for H). Ð 13C NMR (75.47 MHz, DMSO-D6): δ =
3 h at 20 ∞C, after which time a colourless precipi- 22.42 (3Ј-C), 48.12 (spiro-C), 109.79 (CN), 122.81
tate of 15 was collected and crystallized from ace- and 135.54 (aryl-CH), 141.87 (quart. aryl-C),
tonitrile.By plc of the original filtrate starting
185.83 (C=O). Ð MS (EI, 70 eV): m/z (%) =
material 6 and 1-carbonitriles 9 were recovered as 354 (18) [M+ +2], 352 (63) [M+], 324 (25) [M+
-
follows: From the run using 6a: no 6a; 51 mg CO], 296 (33) [M+ Ð 2CO], 282 (11), 268 (22)
(19%) of 9a, m.p.130 Ð132 ∞C together with 55 mg [M+ Ð 3CO], 239 (13), 104 (100) [C6H4CO+], 76
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468
D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
+
(87) [C6H4 ]. Ð C21H8N2O4 · CH3CN (393.3): (CH3), 52.05 (CH2), 56.25 (C-5), 118.08 (CN);
calcd. C 70.23, H 2.83, N 10.68; found C 69.80, 117.21, 128.11, 128.59, 128.90, 129.22, 129.38,
H 2.78, N 10.22.
129.56, 130.02, 130.06 (2C), 130.20, 130.27 (all aryl-
Reactions of compounds 11 with ethenetetracar- C-H); 130.62, 133.71, 139.54, 140.08, 146.30 (all
bonitrile (2): Solutions (1.0 mmol each) of 11a-d in quart.aryl-C). Ð MS (EI, 70 eV): m/z (%) = 310
100 ml of benzene were treated with 260 mg (100) [M+], 309 (65) [M+-1], 284 (33) [M+-CN], 204
(2.0 mmol) of 2 and stirred at 20 ∞C for 48 h, dur- (13), 203 (12), 191 (16), 165 (21), 120 (25), 118
+
ing which time the original colour changed from (15), 91 (25) [C7H7 ]. Ð C22H18N2 (310.4): calcd.
yellow to green.After concentration the solid resi-
due was treated with few ml of ethyl acetate.In
all cases, except the run with 11a, a colourless solid
C 85.12, H 5.86, N 9.03; found C 85.01, H 5.94,
N 8.96.
6-(4-Methoxyphenyl)-6,7-dihydro-5H-dibenz[c,e]-
residue consisting of the carbonitriles 13b,c or d azepine-5-carbonitrile (13c): M.p.195
was filtered off.This was later combined with the (acetonitrile). Ð IR (KBr pellet): ν = 2957 (CH3),
same materials obtained by plc and crystallized 2933 and 2837 (CH2), 2218w (CN), 1510s, 1246s,
Ð196 ∞C
1
from the solvent listed.
1043, 819, 766 cmÐ1. Ð H NMR (300.13 MHz,
From 11a were obtained: no solid; Rf = 0.52: CDCl3): δ = 3.78 (s, 3H, OCH3), δ = 4.16 and 3.91
8.0 mg (3%) of 11a; Rf = 0.36: 124 mg (43%) of (AB system, |2J|= 12.5 Hz, 7-CH2), 5.25 (s, 1H, 5-
13a.
H), 6.87 (m, 2H, 2Ј-, 6Ј-H), 7.05 (m, 2H, 3Ј-, 5Ј-H),
From 11b were obtained: 82 mg solid 13b; Rf = 7.34Ð7.48 (m, 4H) and 7.48Ð7.64 (m, 4H), (biphe-
0.58: 16 mg (6%) of 11b; Rf = 0.28: 60 mg of 13b, nylylene-H). Ð 13C NMR (75.47 MHz, CDCl3). δ =
combined yield 142 mg (46%).
53.40 (CH2), 55.56 (OCH3), 56.91 (C-5), 118.09
From 11c were obtained: 62 mg solid 13c; Rf (CN); 114.69, 120.56, 128.03, 128.53, 128.79,
0.43: 6 mg (2%) of 11c; Rf = 0.32: 40 mg of 13c, 129.10, 129.24 (2C), 129.88, 130.15 (all aryl-CH);
combined yield 102 mg (31%).
133.64, 139.47, 140.03, 142.82, 155.17 (all quart.
From 11d were obtained: 124 mg of solid 13d; aryl-C). Ð MS (EI, 70 eV): m/z (%) = 326 (100)
Rf = 0.67: 32 mg (11%) of 11d; Rf = 0.49: 15 mg of [M+], 325 (55) [M+-1], 311 (14), 300 (29) [M+-CN],
13d, combined yield 139 mg (42%).
286 (56), 204 (34), 203 (20), 191 (15), 178 (16),
177 (16), 166 (17), 165 (24), 136 (25), 108 (27). Ð
6-Phenyl-6,7-dihydro-5H-dibenz[c,e]azepine-5-
carbonitrile (13a): M.p.175 Ð176 ∞C (from etha- C22H18N2O (326.4): calcd. C 80.95, H 5.56, N 8.58;
nol). Ð IR (KBr pellet): ν = 2929 and 2860 (CH2), found C 80.80, H 5.62, N 8.59.
2226w (CN), 1594, 1499, 1374, 1219, 763s, 749s, 692
6-(4-Chlorophenyl)-6,7-dihydro-5H-dibenz[c,e]-
1
cmÐ1. Ð H NMR (300.13 MHz, CDCl3): δ = 3.95 azepine-5-carbonitrile (13d): M.p.217 Ð219 ∞C
and 4.40, (AB system, |2J| = 12.5 Hz, 7-CH2), δ = (acetonitrile). Ð IR (KBr pellet): ν = 2925 (CH2),
5.47 (s, 1H, 5-H); 6.95 (m, 1H, 4Ј-H); 7.04 (m, 2H), 2212w (CN), 1591, 1492s, 1222, 811, 761, 750, 741
7.30Ð7.49 (m, 6H), 7.49Ð7.65 (m, 3H), (all aryl- cmÐ1. Ð H NMR (300.13 MHz, CDCl3): δ = 4.34
1
H). Ð 13C (75.47 MHz, CDCl3): 51.39 (CH2), 55.79 and 3.95 (AB system, |2J|= 12.5 Hz, CH2), 5.39 (s,
(C-5), 117.89 (CN), 120.64 (C-4Ј); 116.30, 128.08, 1H, 5-H), 6.96 (m, 2H, 2Ј-, 6Ј-H), 7.30 (m, 2H, 3Ј-
128.58, 128.89, 129.21, 129.41, 129.51 (2C), 129.61, , 5Ј-H), 7.32Ð7.50 (m, 4H) und 7.60 (m, 4H, all
130.16, 130.24 (all aryl-CH), 130.00, 133.53, 139.45, biphenylylene-H). Ð 13C NMR (75.47 MHz,
139.99 (all quart. aryl-C), 148.20 (1Ј-C). Ð MS (EI, CDCl3): δ = 51.71 (CH2), 55.77 (C-5), 117.71 (CN),
70 eV): m/z (%) = 296 (100) [M+], 295 (74) [M+- 125.79 (4Ј-C), 117.51, 128.13, 128.63, 128.95,
1], 270 (30) [M+-CN], 204 (16), 203 (14), 191 (23), 129.27, 129.39 (2C), 129.53 (2C), 130.37 (all aryl-
190 (18), 165 (32), 106 (33), 104 (29), 93 (18), 77 CH), 129.89, 133.13, 139.93, (quart. aryl-C), 146.23
(42). Ð C21H16N2 (296.4): calcd. C 85.11, H 5.44, (C-1Ј). Ð MS (EI, 70 eV): m/z (%) = 330 (100)
N 9.45; found C 84.98, H 5.49, N 9.40.
[M+], 329 (53) [M+-1], 304 (29) [M+-CN] 204 (25),
203 (14), 191 (38), 166 (25), 165 (29), 140 (26), 138
6-(4-Methylphenyl)-6,7-dihydro-5H-dibenz[c,e]-
azepine-5-carbonitrile (13b): M.p.222 Ð225 ∞C (23), 127 (14), 111 (15) [C6H4Cl+]. Ð C21H15N2Cl
(acetonitrile). Ð IR (KBr pellet): ν = 2918, 2863 (330.8): Calcd. C 76.23, H 4.58, N 8.46; found C
(CH2), 2224w (CN), 1612, 1513s, 1383, 1205, 797, 76.18, H 4.64, N 8.39.
1
762 cmÐ1. Ð H NMR (300.13 MHz, CDCl3): δ =
Reaction of N-alkyl-N-benzylanilines 18a,b with
2.31 (s, 3H, CH3), δ = 4.31 and 3.93 (AB system, 4 in ethanol: A solution of 420 mg (2.0 mmol) of
|2J|= 12.5 Hz, 7-CH2), 5.40 (s, 1H, 5-H); 6.96 (m, 4 in 80 ml of ethanol was treated with a) 200 mg
2H, 2Ј-, 6Ј-H), 7.14 (m, 2H, 3Ј-, 5Ј-H); 7.33Ð7.46 (1.0 mmol) of N-benzyl-N-methylaniline, b)
(m, 4H) and 7.51Ð7.63 (m, 4H) (all biphenylylene- 210 mg (1.0 mmol) of N-benzyl-N-ethylaniline and
H). Ð 13C NMR (75.47 MHz, CDCl3): δ = 20.51 stirred at 20 ∞C for 94 h (a) and 120 h (b), respec-
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D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
469
tivily, during which time the colour of the solution C26H19N3O2 (405.4): calcd. C 77.02, H 4.73, N
changed from yellow to light red and a light yellow 10.36; found C 76.93, H 4.74, N 10.37.
precipitate started to separate.Concentration of
the solution gave more of this material.Recrystal-
lization gave 269 mg 19a (66%) and 380 mg (91%) 153 ∞C (from methanol, with dec.and colouration
[4-(N-Benzyl-N-ethylamino)phenyl]-(1,3-dioxo-
indan-2-yl)propanedinitrile (19b): M.p.150
Ð
19b, respectively, as light yellow crystals.
[4-(N-Benzyl-N-methylamino)phenyl]-(1,3-di-
oxoindan-2-yl)propanedinitrile (19a): M.p.149
to purple). Ð IR (KBr pellet): ν = 2252w (CN),
1712 (C = O), 1609, 1518, 1357, 1290, 742 cmÐ1. Ð
3
Ð
1H NMR (300.13 MHz, CDCl3): δ = 1.13 (t, J =
3
152 ∞C (from ethanol, with dec.and colouration to
7.1 Hz, 3H, CH3), 3.44 (q, J = 7.1 Hz, 2H, CH2),
purple). Ð IR (KBr pellet): ν = 2242w (CN), 1753, 3.78 (s, 1H, indanyl-2-H); 6.55 (m, 2H), 7.07 (m,
1
1713 (C = O), 1613, 1526, 1244, 744 cmÐ1. Ð H 2H), 7.25 (m, 5H), 7.63 (m, 2H), 7.91 (m, 2H), all
NMR (300.13 MHz, CDCl3): δ = 2.97 (s, 3H, CH3), aryl-H. The 7.91 and 7.63 multiplets have the habi-
3.79 (s, 1H, indanyl-2-H), 4.47 (s, 2H, Ph-CH2); tus of an AAЈBB’ system as have parts of the 7.25
6.57 (m, 2H), 7.07 (m, 2H), 7.24 (m, 3H), 7.28 (m, and 6.55 ppm multiplets. Ð 13C NMR (75.47 MHz,
2H), 7.84 (m, 2H), 7.93 (m, 2H), all aryl-H, the CDCl3): δ = 12.00 (CH3), 39.37 (C(CN)2), 45.33
latter two m and those at 6.57 and 7.28 appear (CH3-CH2), 53.65 (Ph-CH2), 56.57 (indanyl-C-2),
as symmetric AAЈBB’systems. Ð 13C NMR (75.47 113.29 (CN); 112.03, 123.89, 126.35, 128.22, 128.73,
MHz, CDCl3): δ = 38.54 (CH3), 39.30 (C(CN)2), 136.57 (all for 2C each, aryl-CH); 127.11 (phenyl-
55.98 (CH2), 56.46 (indanyl-2-H); 112.06, 123.84, 4-CH); 114.00, 137.99, 142.04, 149.47 (all quart.
126.42, 128.11, 128.70, 136.57 (all 2C, aryl-CH); aryl-C); 192.06 (2¥ C = O). Ð MS (EI, 70 eV): m/
127.15 (phenyl-C-4); 113.25 (CN); 114.34, 137.74, z (%) = 392 (1) [M+ Ð HCN], 367 (3) [M+- 2 CN?],
+
141.96, 150.44 (all quart. aryl-C); 192.01 (2¥ C = 211 (19), 196 (19), 91 (100) [C7H7 ].
Ð
O).MS (EI, 70 eV): m/z (%) = 405 (0.5) [M+], 378 C27H21N3O2 (419.5): calcd. C 77.31, H 5.06, N
+
(59) [M+
Ð
HCN], 91 (100) [C7H7 ].
Ð
10.01; found C 77.29, H 5.05, N 10.08.
Table 2.Crystal data and structure refinement for 13b and 17 · MeCN.
13b
17 · MeCN
Chemical formula
Formula weight
C22H18N2
310.38
C23H11N3O4
393.35
Temperature
150 K
150 K
˚
˚
0.71073 A
Wavelength (Mo-Kα)
Crystal system, space group
Unit cell dimensions
0.71073 A
¯
monoclinic, P21/n
triclinic, P1
a = 9.309 (9) A
˚
˚
˚
a = 12.410 (2) A
˚
b = 10.415 (2) A
b = 9.668 (6) A
˚
˚
c = 12.470 (2) A
c = 10.915 (9) A
α = 95.29 (7)∞
ꢀ = 112.10 (7)∞
ꢀ = 95.83 (2)∞
γ = 90.60 (7)∞
3
3
˚
˚
Volume
1603.4 A
905.2 A
Z, calculated density
Absorption coefficient
F (000)
4, 1.286 Mg/m3
2, 1.443 Mg/m3
0.076 mmÐ1
0.102 mmÐ1
656
404
Crystal size
0.47 ¥ 0.35 ¥ 0.33 mm
0.77 ¥ 0.29 x.0.23 mm
Theta range
2.21 to 27.00∞
2.02 to 26.99∞
Limiting indices
0>h<15, Ð13>k<13, Ð15>1<15
7124 / 3505 [R(int) = 0.0213]
100.0%
0>h<11, Ð12>k<12, Ð13>1<12
3952 / 3952 [R(int) = 0.0000]
100.0%
Reflections collected / unique
Completeness to theta = 27.00 deg
Absorption correction
Max. and min. transmission
Refinement method
Data / restraints / parameters
Goodness-of-fit on F2
Final R Indices [I>2σ(I)]
R Indices (all data)
Extinction coefficient
Largest diff.peak and hole
psi-scan
psi-scan
0.997 and 0.966
full-matrix least-squares (F2)
3505 / 0 / 219
0.989 and 0.938
full-matrix least-squares (F2)
3952 / 0 / 273
1.041
1.060
R1 = 0.0393, wR2 = 0.0976
R1 = 0.0466, wR2 = 0.1035
0.0106 (14)
R1 = 0.0446, wR2 = 0.1117
R1 = 0.0565, wR2 = 0.1214
0.018 (3)
Ð3
Ð3
˚
˚
02. 99 and Ð0.301 eA
0.323 and Ð0.266 eA
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470
D.Döpp et al. · Dicyanomethylene Compounds as Cyanation Reagents
Crystal structure determination: Data collection
X-ray data of both structures have been depos-
was performed using a Siemens P4 four-circle dif- ited at the Cambridge Crystallographic Data
fractometer with rotating anode generator, graphite Centre (13b: CCDC 177254; 17: CCDC 177253).
monochromator and scintillation counter, λ = Copies of the data can be obtained free of charge
˚
0.71073 A (Mo-Kα).Both structures were solved
on application to CCDC, 12 Union Road, Cam-
bridge CD21EZ, U.K. [Fax (internat.) +44-1223/
with direct methods using SHELXS-97.Structure
refinements were performed against F2 using 336033; E-mail: deposit@ccdc.cam.ac.uk].
SHELXL-97.For both compounds empirical ab-
sorption corrections were applied.All non-hy-
Acknowledgement
drogen atoms were refined using anisotropic dis-
placement parameters.The hydrogen atoms were
Financial support by Fonds der Chemischen In-
positioned with idealized geometry and refined with dustrie is gratefully acknowledged.
isotropic displacement parameters (see Table 2).
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