Flash preparation of carbenoids: A different performance of cyanogen bromide

Article abstract of DOI:10.13005/ojc/300477

Cyanogen halides are known substances for the cyanating reaction. There are a few evidences for bromination reaction too. On the other hand carbenes are known as very important substances due to their remarkable reactions. Unfortunately carbenes at room temperature are very unstable and there is not a simple method for preparation of them. In most cases the isolation is not possible. We have reported a new reliable and fast preparation method of almost stable carbenoids. The mechanism of the formation has been discussed.

Full text of DOI:10.13005/ojc/300477

ISSN: 0970-020 X
CODEN: OJCHEG
2014, Vol. 30, No. (4):
Pg. 2081-2089
ORIENTAL JOURNAL OF CHEMISTRY
An International Open Free Access, Peer Reviewed Research Journal
www.orientjchem.org
Flash Preparation of Carbenoids:
A Different Performance of Cyanogen Bromide
MOHAMMAD JALILZADEH HEDAYATI1* and NADER NOROOZI PESYAN2
1Department of Chemistry, Faculty of Science, Ahar Branch, Islamic Azad University, Ahar, Iran.
2Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran.
*Corresponding author E-mail: m-jalilzadeh@iau-ahar.ac.ir
http://dx.doi.org/10.13005/ojc/300477
(Received: August 01, 2014; Accepted: September 01, 2014)
ABSTRACT
Cyanogen halides are known substances for the cyanating reaction. There are a few
evidences for bromination reaction too. On the other hand carbenes are known as very important
substances due to their remarkable reactions. Unfortunately carbenes at room temperature are
very unstable and there is not a simple method for preparation of them. In most cases the isolation
is not possible. We have reported a new reliable and fast preparation method of almost stable
carbenoids. The mechanism of the formation has been discussed.
Key words: Carbene, Carbenoid, Cyanogen halides, Active carbons.
INTRODUCTION
solid that decomposes in the presence of moisture
and has a very small liquid range (mp 50–53 °C,
bp 61–62 °C). It is cheap and can be synthesized
by the reaction of sodium cyanide with bromine in
aqueous medium4. CNBr produces electrophilic
cyanide. Therefore, it is attacked by nucleophiles
such as amines, alcohols and thiols.
Cyanogen halides are known as
important synthetic substances since they are
strong cyanating agents. For instance cyanogen
iodide reacts with the tertiary amine ring of
marcfortine A to give cyano and iodocyano
substituted products1. Also cyanogen iodide has
been used as a reagent for disulfide bond formation
in peptides2.
Primary and secondary amines react with
CNBr to give mono- and dialkylcyanamides5,6,7
.
CNBr is a very useful reagent for the preparation of
aryl nitriles. It condenses with toluene in the
presence of AlCl3 to give p-toluonitrile8. CNBr is
known to convert carboxylic acids to nitriles at
Cyanogen bromide is a very useful and
extensively used reagent for the synthesis of
cyanamides3. It is a colorless or white crystalline

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HEDAYATI & PESYAN, Orient. J. Chem., Vol. 30(4), 2081-2089 (2014)
higher temperature under sealed-tube conditions.
The reaction involves the intermediacy of a
carboxylic cyanic anhydride. In anhydrous benzene,
RESULTSAND DISCUSSION
In this paper a new reaction of active
the carboxylic cyanic anhydride may be trapped carbons (1a-j) with cyanogen bromide in the
and, in the presence of pyridine, symmetrical presence of an organic base (triethyl amine or
anhydrides may be produced in yields of 78–95%9. pyridine in some cases) has been described.
Von Braun found that a dialkyl thioether is cleaved Generated active carbenoids (2a-j) are shown in
by CNBr, at a somewhat elevated temperature (60– Scheme 2. Recently, we have performed the
70 °C, sealed tube), to an alkyl thiocyanate and an condensation of (thio)barbituric acids (1a-d) with
alkyl bromide10.More recently, this reaction has been aldehydes 22 and ketones 23 in the presence of BrCN
used for the selective cleavage of methionine and Et3N afforded spiro[furo[2,3-d]pyrimidine-6,5_-
peptides11 and other peptides12. Reaction between pyrimidine]pentaones and active carbenoid salt (2a-
cyanogen bromide and some 3-amino-1,1- d). In the reaction of 5,5-dimethylcyclohexane-1,3-
diphenylpropanes, variously substituted at C-1, dione (dimedone, 1e) under same condition the
leads either to N-cyano derivatives or to similar scaffold structures have been produced as
tetrahydrofurans13. Cyanogen bromide is a capable expected 24. Also we have investigated the
reagent for the synthesis of cyanamides 3, cyanates condensation of Meldrum’s acid (1f) with aldehydes
14, and also used to selective cleavage of the in the presence of BrCN and Et3N under the same
methionyl peptide bonds in ribonuclease 15 and etc. condition. In this reaction, full-substituted
Nonetheless this compound also is useful to cyclopropanes and the salt of 2f were obtained 25,26
.
simultaneity brominating and cyanating; the
bromination and cyanation of imidazoles 16, free
radical reaction with alkanes that result in
bromination of alkanes and -bromination of -
Et3N
Z
W
Z
W
Br
C
N
(or Pyridine)
Et3NH
1g-j
2g-j
Br
17
Y
Y
aminoenones 18. By the way the Von Braun reaction
is an organic reaction in which a tertiary amine
reacts with cyanogen bromide to an
organocyanamide19.The reaction of tertiary amines
with CNBr yield disubstituted cyanamides and an
alkyl bromide20.The bromodealkylation reaction has
also been used to cleave the ring system of aziridine
compounds21. Routine reactions of Cyanogen
bromide have been presented in scheme 1. Although
cyanogen bromide is a well known reagent, it has
never been used as a carbenoid generator before.
X
X
X
X
Et3N
HBr
C
N
(or Pyridine)
O
O
O
O
Et3NH
1a-f
2a-f
Br
X-Y-X= NH-CO-NH (a); MeN-CO-NMe (b); HN-CSNH (c); MeN-CO-NH (d); CH2-CMe2-CH2 (e); O-CMe2-O (f)
Z,W= CN,CN (g); EtO-CO, CO2Et (h); EtO-CO, CN (i); MeCO,CO2Et (j)
Scheme 2: Reaction of active carbons with
cyanogen bromide in the presence of TEA
On the other hand based on our earlier
experiments, we decided to investigate on the
possibility of the reaction of non-cyclic active
carbons. For this reason some reactions of cyanogen
bromide and triethyl amine with acyclic active
carbons (1g-j) were performed 25,26. Although we
did not attain triethylammonium 2-bromo-1,3-
diethoxy-1,3-dioxopropan-2-ide (2h) obtained from
diethyl malonate reaction (and other acyclic active
carbon), we have succeeded in obtaining
triethylammonium bromodicyanomethanide (2g) in
the latter case malononitrile. Perhaps it is due to the
stronger electron-attracting nature of cyanide group
versus ester and/or simple carbonyl groups. By the
way cyanide group has less steric hindrance than
ester or carbonyl groups.
Substances
Products
CN
N
H
N
R
R
R
R
O
O
R
R
OH
Me
R
R
OCN
CN
S
S
Scheme 1: Common reactions
of cyanogen bromide

HEDAYATI & PESYAN, Orient. J. Chem., Vol. 30(4), 2081-2089 (2014)
2083
Proposed mechanism has been explained
in Scheme 3. On the basis of the well established
chemistry of pyrimidines27 and according to the
mechanism of the bromination of 1-alkyl imidazoles
by cyanogen bromide28 it is reasonable to assume
that active carbons 1a-f reacted with cyanogen
bromide and formed alkyl carbonobromidoimidate
3a-f. Intramolecular rearrangement of 3a-f afforded
4a-f followed by loss of HCN. Triethylamine as a
base captured the acidic methylene proton of 4a-f
and salts of 2a-f were formed. The salt of
triethylammonium hydrobromide was also
observed. Unfortunately, all attempts failed to
separate or characterize 3a-f and 4a-f intermediates
as representatives.
In the case of malononitrile a similar
mechanism has been suggested (scheme 4).
O
O
O
O
O
Et3N, BrCN
- HCN
H
HN
NH
OH
HN
NH
HN
NH
HN
NH
HN
NH
Et3N
O
O
O
O
O
O
O
O
O
Br
H
Br
4
3
Br
N
2a
1a
Br
N
Et3NH
Scheme 3: Proposed mechanism of 2a formation
CN
N
Path a
NC
CN
NC
C
H
N
N
NC
H
BrCN
Br
C
5
H
Br
Path b
(-HCN)
NC
CN
NC
CN
NC
CN
Et3N
Et3NH
Et3NH
H
6
2g
Br
Br
Scheme 4: Proposed mechanism of 2g formation
It is reasonable to assume that the
characterized in direct reaction of 1g with
triethylamine through path b.
compound 1g reacts directly with cyanogen
bromide to form 2,2-dicyanoacetimidoyl bromide
(5) intermediate through path a. Intramolecular
rearrangement of this intermediate produces 2-
bromomalononitrile (6) intermediate. Finally,
triethylamine as a base captures the acidic proton
affording 2g. Malononitrile (1g) directly reacts with
triethylamine to form the salt of triethylammonium
dicyanomethanide in the absence of cyanogen
bromide (path b). The salt of triethylammonium
dicyanomethanide was also separated and
All attempts to isolation of 5 and 6 were
unsuccessful unfortunately.According to our search,
there is no report about compound 2g in literatures.
The salt of 2g was isolated and characterized by
spectroscopy techniques. Other evidence for the
formation and confirmation of 2g (the existence of
bromine atom in this salt structure) was performed
by Beilstein test and the wet silver nitrate test
(precipitate of pale yellow silver bromide).

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The IR spectrum of 2g shows the proton at ´ 8.93 ppm and a singlet for two amide
frequency of NH+ stretching at the broad range of protons at ´ 9.38 ppm on barbituric acid ring moiety.
2500-3300 cm-1, frequency of CN and C-Br The IR spectrum of 2a indicated no CN bond
stretching at 2167 and 565 cm-1, respectively. The stretching absorption. The 13C NMR spectrum of 2a
1HNMR spectrum of this compound shows showed five distinct peaks. The peak at  9.09 and
(integration in parenthesis) a triplet at ´ 1.39 ppm 46.19 ppm are of methyl and methylene carbons in
(9H) and a multiplet (a quartet approximately) at triethylammonium salt moiety, respectively and the
3.14 ppm (6H) are corresponding to methyl and peak at 72.27 ppm corresponds to C-5 on barbituric
methylene protons in triethylammonium salt moiety, acid ring. Two peaks at ´ 152.02 and 161.26 ppm
respectively. A broad singlet at ´ 9.78 ppm (1H) is of correspond to the carbonyl groups on barbituric acid
NH+ in this salt. 13C NMR spectrum of this salt shows ring moiety, respectively. Other evidence for the
four distinct peaks that confirm the structure of 2g.
formation of 2a-f (the existence of bromine atom in
The structure of the 2a-f was deduced from their IR, these molecules) was performed by Beilstein test
1H NMR, 13C NMR spectra and CHN analysis. and the wet silver nitrate test29 (precipitate of pale
Representatively, the 1H NMR spectrum of 2a yellow silver bromide). During isolation and
consisted of a triplet for three methyl protons at ´ identification of 2a-f interestingly there is not any
1.16 ppm, a quartet for the corresponding methylene evidence of cyanide peak in IR spectra (scheme 5).
protons at 3.08 ppm, a broad singlet for ammonium
Y
Y
X
X
Et3N, BrCN
X
X
NC
CN
NC
CN
CN
O
O
O
O
1g
7
CN
1a-f
8a-f
Scheme 5: Reaction path through cyanation of active carbon
In the case of Barbituric acid’s salts, 2b keto 1-en 1-ol (12j) form and not in beta dicarbonyl
plays an important role and its nucleophilicity is (1j) form. Whereas cyclic compounds like Barbituric
stronger than that of 2a and 2c.The 2a and 2c have acid, Dimedone and Meldrum’s acid (1a-f) have
aromatic nature with delocalizing of the negative been founded mainly in keto form. A similar
charge while 2b has not.
equilibrium is not seen in malononitrile (scheme 7).
Bromodicyanomethanide (2g) is the main form. Any
Acyclic compounds with the exception of symptom of other resonance forms is not seen in
malononitrile behave in different way. Reason of 13CNMR spectra of 2g as expected. Also as seen in
this different behavior is not clearly recognized. figure 2, three distinctive peaks for 2a and two peaks
Perhaps it is due to the enol-keto equilibrium for ammonium ion are shown in 13CNMR spectrum.
occurred in acyclic beta-dicarbonyl or beta- There is not any symptom of existence of enol form
cyanocarbonyl compounds (scheme 6). For for 2a.
example ethyl aceto acetate mainly exists in beta-
O
O
O
O
O
O
O
OH
Et3N
O
O
O
O
11j
10j
9j
12j
Minor form
Major form
Major form
Scheme 6: Resonance forms in ethyl aceto acetate 1j and 1-ethoxy-1,3-dioxobutan-2-ide (9j)

HEDAYATI & PESYAN, Orient. J. Chem., Vol. 30(4), 2081-2089 (2014)
2085
Reaction of diethyl malonate (DEM) (1h),
ethyl cyanoacetate (ECA) (1i) and ethyl
acetoacetate (EAA) (1j) with cyanogen bromide in
acetone formed diethyl bromomalonate (13h) and
ethyl bromoacetoacetate (13j) in moderate yield,
respectively. Triethylammonium hydrobromide salt
was observed in all reaction products (scheme 8).
a peak at ´ 13.85 and 63.21 ppm are of methyl and
methylene carbon atoms, at ´ 42.40 and 164.58
ppm corresponds to the methine and carbonyl
carbon atoms respectively. Diethyl cyanomalonate,
8h has been synthesized previously by the reaction
of ethyl cyanoacetate, 1i with ethyl chloroformate
in acetone30. We performed the reaction of 1h with
cyanogen bromide according to method of
reference 30 (formation of 8h was not observed).
The 1H NMR spectrum of diethyl
bromomalonate, 13h show a triplet at ´ 1.31 and a
quartet at ´ 4.29 ppm are of to equivalent methyl
and methylene protons, respectively. A singlet at ´
4.82 corresponds to the CHBr proton. The peak
integration ratios 1.0:4.0:6.0 are of methine, two
methylene and two methyl protons, respectively.
These ratios are in good agreement with the
structure of 13h.The 13C NMR spectrum of 13h show
N
N
N
N
2g
H
H
Scheme 7: Possible resonance
form of dicyanomethanide (2g)
Z
W
Z
W
Et
Et
N
CN
Br
CN
Z
W
13h,13j
8j
14
Et3N, BrCN
/Acetone , rt
1g-j
NC
CO2Me
Z
W
Et3NH
Br
15i
2g
Z,W= CN,CN (g); EtO-CO, CO2Et (h); EtO-CO, CN (i); MeCO,CO2Et (j)
Scheme 8: Acyclic compounds reaction with cyanogen bromide
In contrast, our experiments indicated that
the reaction of 1h with cyanogen bromide leads to
diethyl bromomalonate, 13h and N,N-
diethylcyanamide (14) in acetone (Scheme 9).
CN
Et
Et
Et3N
+
BrCN
Br
N
+
EtBr
N
Et
Et
14
16
CN
Scheme 9: Formation mechanism of 14
Expectedly, triethylamine attacks the NC+
cyanogen bromide obtaining
triethylcyanoammonium bromide salt (16) (Scheme
9). According to Scheme 9, the ethyl bromide and
14 were observed based on von Braun reaction
through analyzing the crude reaction mixture by
of

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HEDAYATI & PESYAN, Orient. J. Chem., Vol. 30(4), 2081-2089 (2014)
GC-Mass analyses. The reaction of ethyl Entrapping of free carbenes by polar carbon-carbon
cyanoacetate, 1i with cyanogen bromide in ether double bonds (producing cyclopropane structure)
indicated no significant product(s). In contrast, in is one of the most famous reactions used to
acetone as a polar aprotic solvent ethyl 2- identification of carbenes. Entrapping includes the
isopropylidenecyanoacetate (15i) was afforded by shuttle attack of carbene to polar carbon-carbon
means of the condensation of 1i with acetone in double bond. Two moles of malenonitrie were
32% yield (Scheme 8). No 13i and 8i were observed reacted with aldehydes 17k-z as knovenagel
in this reaction.
condensation (insitu performing of 18k-z). On the
other hand malononitrile was reacted with
The structure of 15i was characterized by trithylamine and cyanogen bromide as described
1HNMR, 13CNMR and GC-Mass analysis. before. Negative charge of 2g attacks to polar
Interestingly, ethyl bromoacetoacetate, 13j or ethyl double bond of 18k-z as shown in the scheme 10.
cyanoacetoacetate, 8j were found in the reaction of Final cyclopropane products 19k-z were isolated
1
ethyl acetoacetate, 1j and cyanogen bromide in and identified by HNMR, 13CNMR and IR data.
ether as solvent (Scheme 8).
Existence of free carbene was maintained by
results.The same method for entrapping of carbenes
For assurance of existence of free in the case of cyclic substrates resulted similar
carbenoid, in the case of malononitrile we have cyclopropanes as expected.
performed some of well-known carbenes reactions.
Et3N, RCHO 17
path B: knovenagel condensation
NC
R
NC
CN
18
NC
R
NC
NC
NC
1g
2g
19
NC
CN
Br
Et3N, BrCN
path A: Carbenoid generation
NC
k
l
m
n
o
R= C6H5 ( ), R= o-O2N-C6H4 ( ), R= m-O2N-C6H4 ( ), R= p-Br-C6H4 ( ), R= p-Cl-C6H4 ( ),
p
q
r
s
R= 3,4,5-Tri-CH3O-C6H2 ( ), R= m-PhO-C6H4 ( ), R= p-CH3O-C6H4 ( ), R= p-NC-C6H4 ( ),
R= o-Naphthyl (t), R= 2-Furyl (u), R= 2-Pyridyl (v), R= 9-Anthranyl (w), R= 2-Pyrrolyl (x),
R= p-OH-C6H4 (y), R= m-OH-C6H4 (z)
Scheme 10: Insitu generation of carbene based on malononitrile
EXPERIMENTAL
General procedures
The data are reported as (s=singlet, d=doublet,
t=triplet, q=quartet, m=multiplet or unresolved,
bs=broad singlet, coupling constant(s) in Hz,
Melting points were measured with a digital melting integration). All reactions were monitored by TLC
point apparatus (Electrothermal) and were with silica gel-coated plates (solvent system of most
uncorrected. IR spectra were determined in the cases is AcOEt:AcOH/ 80:20/ v:v). Elemental
region 4000- 400 cm-1 on a NEXUS 670 FT IR analyses were performed using a VarioEL III
spectrometer by preparing KBr pellets. The 1HNMR analyzer (Tabriz University, Tabriz, Iran). The mass
and 13CNMR spectra were recorded on Bruker 300 analysis performed using mass spectrometer
FT-NMR at 300 and 75 MHz, respectively (Urmia (Agilent Technology (HP) type, MS Model: 5973 ,ion
University, Urmia, Iran).1HNMR and 13CNMR spectra source temperature was 230 ºC (Tehran University,
were obtained on solution in DMSO-d6 and/or in Tehran, Iran).
CDCl3 as solvents using TMS as internal standard.

HEDAYATI & PESYAN, Orient. J. Chem., Vol. 30(4), 2081-2089 (2014)
2087
Synthesis of 2, Method A: In a 25 mL round bottom
flask equipped by a magnetically stirrer, dissolved
0.12 g (0.96 mmol) cyanogen bromide (BrCN) in 4
mL ethanol at 0 °C. Then separately, 0.15 g (0.96
mmol) barbituric acid were dissolved in 10 mL
ethanol in an Erlenmeyer, 0.75 mL triethylamine
was added into solution and then was transferred it
into a separatory funnel, then it was added drop
wise into solution of BrCN in round bottom flask at
0 °C.The progression of reaction was monitored by
thin layer chromatography (TLC). After a few
minutes, the white-cream solid precipitate, filtered
off, washed with few mL ethanol and dried.
72.3, 46.2, 9.1; Anal. Calcd. for C10H18N3O3Br: C,
38.9; N, 13.63; H, 5.84. Found: C, 39.04; N, 13.66; H,
5.92 %. MS, m/z 308 (M+, 0), 154 (7), 128 (base
peak, 100), 101 (15), 86 (60), 72 (5), 58 (16), 42
(98).
Triethylammonium-1,3-dimethyl-5-bromo-2,4,6-
trioxohexahydropyrimidin-5-ide (2b)
White solid (45%); mp 152-154 °C
(decamps.). FT-IR (KBr) 3200, 2980, 1670, 526 cm-
1; 1H NMR (DMSO-d6, 300 MHz) ´ 1.17 (t, 9H), 2.80
(s, 6H), 3.08 (q, 6H), 8.95 (bs, 1H); 13C NMR (DMSO-
d6, 75 MHz) ´ 161.9, 157.1, 73.4, 46.1, 30.2, 9.1;
Anal. Calcd. for C12H22N3O3Br: C, 42.87; N, 12.50; H,
6.60. Found: C, 42.65; N, 12.43; H, 6.52%.
Method B
In a 10 mL with Teflon-faced screw cap
tube equipped by a magnetically stirrer, dissolved,
0.132 g (2 mmol) malononitrile, 0.202 g (2 mmol)
triethylamine in 5mL ethanol and then 0.210 g (2
mmol) cyanogen bromide (BrCN) was added into
solution at 0 °C. White-Cream color solid precipitate
in less than five minutes, filtered off and washed
with few mL ethanol and dried.
Triethylammonium-5-bromo-4,6-dioxo-2-
thioxohexahydropyrimidin-5-ide (2c)
White solid (50%);mp = 159-161 °C;FT-IR
(KBr) 3408, 3070, 2975, 2937, 2677, 1648 (C=O),
1612, 590, 526 (C-Br) cm-1; 1H NMR (DMSO-d6,300
MHz) ´ 1.16 (t, 9H, 3CH3), 3.07 (q, 6H, 3CH2), 10.17
(bs, 1H, NH ammonium), 10.35 (bs, 2H, 2NH TBA);
13C NMR (DMSO-d6, 75 MHz) ´ 174.7, 164.3, 79.7,
46.2, 9.1; Anal. Calcd. for C10H18N3O2SBr: C, 37.05;
N, 12.97; H, 5.56. Found: C, 37.10; N, 13.05; H, 5.51
%.
Synthesis of cyclopropane structures
In a 10 mL with Teflon-faced screw cap
tube equipped by a magnetically stirrer, dissolved,
0.265 g (4 mmol) malononitrile, 0.400 g (4 mmol)
triethylamine and 2 mmol aldehydes in 7mL ethanol
and then 0.210 g (2 mmol) cyanogen bromide
(BrCN) was added into solution at 0 °C. temprator
was raised to 70 °C. Cream color solid precipitate
after a few minutes, filtered off and washed with
few ml ethanol and dried.
Triethylammonium-2-bromo-5,5-dimethylcyclo
hexane-1,3-dione-2-ide (2e)
Colorless crystalline solid (62%); mp= 75-
76 °C;FTIR (KBr, Cm-1) vmax:3417, 2958, 2870, 2678,
2495, 1644, 1610, 1509, 472; 1H NMR (CDCl3, 300
MHz)  7.27 (bs, 1H), 3.02 (q, J=7.5 Hz, 6H), 2.18
(s, 4H), 1.17 (t, J=7.5 Hz, 9H), 0.87 (s, 6H); 13C NMR
(CDCl3, 75 MHz) ´ 8.7, 28.3, 31.7, 46.2, 50.2, 96.7,
186.0.
The physical and spectral data of the
selected compounds are follows as representatives.
Spectral data for intermediate compounds (which
prepared for study of mechanism) have not been
described. Do not hesitate to ask for full
supplementary data or more information.
Triethylammonium 5-bromo-2,2-dimethyl-4,6-
dioxo-1,3- dioxan-5-ide (2f)
White crystalline solid (45%), mp 252–253
°C; IR (KBr) 3448 (OH), 2995, 2944, 2738, 2678
(CH-aliph.), 1752 (C=O), 1033 (C–O), 752 (C–Br)
cm-1; 1H NMR (CDCl3, 300 MHz) ´ 10.10 (bs), 3.09
(q, 6H), 1.54 (s, 6H), 1.27 (s, 9H); 13C NMR (CDCl3,
75 MHz)  164.0, 102.2, 46.4, 27.5, 25.6, 8.7.
Triethylammonium-5-bromo-2,4,6-trioxohexahy
dropyrimidin-5-ide (2a)
White solid (50%); mp = 155-158 °C
(decomps.); FT-IR (KBr) 3130, 2985, 2816, 1658
1
(C=O), 603, 524 (C-Br) cm-1; H NMR (DMSO-d6,
300 MHz)  1.16 (t, 9H, 3CH3), 3.08 (q, 6H, 3CH2),
8.93 (bs, 1H, NH ammonium), 9.38 (s, 2H, 2NH
BA); 13C NMR (DMSO-d6, 75 MHz) ´ 161.3, 152.0,
Triethylammonium bromodicyanomethanide (2g)
White crystalline solid (60); FT-IR (KBr)
3420, 3047, 2987, 2947, 2804, 2738, 2678, 2491,

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1
2167, 1475, 1035, 565 cm-1; H NMR (CDCl3, 300 3-(2-nitrophenyl)cyclopropane-1,1,2,2-
MHz)  1.39 (t, 9H, J = 7.2 Hz), 3.14 (m, 6H), 9.78 tetracarbonitrile (19l)
(bs, 1H); 13C NMR (CDCl3, 75 MHz) ´ 141.6, 121.6,
46.6, 8.8.
White crystalline solid (60%), mp 215-216
°C (decompds.);FT-IR (KBr) 3108, 3089, 3031, 2924,
2866, 2258, 1610, 1530, 1346, 851, 794, 736, 702
cm-1; 1H NMR (Acetone-d6, 300 MHz) ´ 5.45 (s, 1H),
Diethyl bromomalonate (13h)
The experimental procedure for the 7.96 (t, 1H, J = 7.5 Hz), 8.07 (t, 1H, J = 7.5 Hz), 8.37
reaction of 1h, 1i and 1j with cyanogen bromide (d, 1H, J = 7.5 Hz), 8.51 (d, 1H, J = 7.5 Hz); 13C NMR
and triethylamine in acetone and other solvents (Acetone-d6, 75 MHz) ´ 147.9, 135.3, 132.7, 132.6,
were similar to the barbituric acid experimental 126.6, 122.0, 110.2, 108.8, 41.7, 23.8.
procedure (method A). Colorless oily liquid (38%).
FT-IR (KBr) 2985, 1743, 1150 cm-1; 1H NMR (DMSO- 3-(3,4,5-Trimethoxyphenyl)cyclopropane-1,1,2,2-
d6, 300 MHz):  1.31 (t, 6H), 4.29 (q, 4H), 4.82 (s, tetracarbonitrile (19p)
1H). 13C NMR (DMSO-d6,, 75 MHz); ´ 164.6, 63.2,
W
hite crystalline solid (68%), mp 227-229
42.4, 13.9; GCMS m/z: (RT, 3.96 min.), 241 (M+2), °C (decompds.);FT-IR (KBr) 3047, 2997, 2943, 2842,
239 (M), 212 (2), 193 (10), 166 (18), 140 (30), 138 2260, 1592, 1512, 1468, 1421, 1251, 1127, 993
(42), 120 (20), 29 (100, base peak).
cm-1; 1H NMR (Acetone-d6, 300 MHz) ´ 3.77 (s, 3H),
3.87 (s, 6H), 4.96 (s, 1H), 7.31 (s, 2H); 13C NMR
3-phenylcyclopropane-1,1,2,2-tetracarbonitrile (Acetone- d6, 75MHz)  153.9, 139.8, 121.4, 110.7,
(19k)
109.1, 107.2, 59.8, 55.9, 42.9, 22.9.
ACKNOWLEDGEMENTS
White crystalline solid (65%), mp 225-227
°C (decompds.) (lit.229-230 °C10);FT-IR (KBr) 3046,
3013, 2928, 2264, 1640, 1374, 1231, 741, 701, 662
cm-1; 1H NMR (DMSO-d6, 300 MHz) ´ 5.29 (s, 1H),
The Authors gratefully acknowledge
7.47 (m, 3H), 7.78 (m, 2H); 13C NMR (DMSO-d6, 75 financial support by the Research Council of Islamic
MHz)  130.4, 130.0, 129.4, 127.3, 111.4, 109.9, Azad University-Ahar Branch.
42.2, 23.6.
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