Transformation of Contact-Explosives Primary Amines and Iodine(III) into a Successful Chemical Reaction under Solvent-Free Ball Milling Conditions

Article abstract of DOI:10.1002/adsc.201500914

Any synthetic transformation using contact-explosives primary amines and hypervalent iodine(III) (phenyliodine diacetate) in constrained media (extreme conditions) is practically impossible. Herein, we report a method of controlling the explosion into a successful chemical reaction using the acid-salt NaHSO₄. As a proof-of-concept, we considered mechanochemical (ball-milling) cross dehydrogenative coupling (CDC) reaction for the amidation of aldehydes via C-H activation. An isothermal titration calorimetric (ITC) study was helpful to understand the enthalpy changes during the reactions before and after addition of NaHSO₄.

Full text of DOI:10.1002/adsc.201500914

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DOI: 10.1002/adsc.201500914
Transformation of Contact-Explosives Primary Amines and
Iodine(III) into a Successful Chemical Reaction under
Solvent-Free Ball Milling Conditions
Tapas Kumar Achara and Prasenjit Mala,*
a
School of Chemical Sciences, National Institute of Science Education and Research (NISER) Bhubaneswar, PO
Bhimpur-Padanpur, Via Jatni, District Khurda, Odisha – 752050, India
E-mail: pmal@niser.ac.in
Received: September 29, 2015; Published online: December 9, 2015
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201500914.
À
Abstract: Any synthetic transformation using con- of aldehydes via C H activation. An isothermal ti-
tact-explosives primary amines and hypervalent iodi- tration calorimetric (ITC) study was helpful to un-
ne(III) (phenyliodine diacetate) in constrained derstand the enthalpy changes during the reactions
media (extreme conditions) is practically impossible. before and after addition of NaHSO4.
Herein, we report a method of controlling the explo-
sion into a successful chemical reaction using the
acid-salt NaHSO4. As a proof-of-concept, we consid- Keywords: ball milling; cross dehydrogenative cou-
ered mechanochemical (ball-milling) cross dehydro- pling (CDC) reaction; contact explosive; hypervalent
genative coupling (CDC) reaction for the amidation iodine; phenyliodine diacetate (PIDA)
Introduction
Recently, ball-milling mechanochemistry[8] has
gained significant interest as an alternative technology
The behavior of a chemical system is known to be in organic synthesis.[9] This mechanochemical method-
controlled by the environment. In 1867, to reduce ology has huge significance to green processes, is time
safety problems when transporting nitroglycerine, efficient, environmentally benign and has shown to be
Alfred Nobel mixed an absorbent clay ꢀKieselguhrꢁ economical. Towards quantitative conversion, less by-
with nitroglycerine to diminish the sensitivity.[1] En- products and minimum purification bring extra impor-
capsulation within a cavity of a container molecule, is tance to this method.[10] The mechanochemical synthe-
known to prevent oligomerization of a reactive spe- ses of small organic molecules,[9b,10c] including hyper-
cies like cyclotrisiloxane[2] or cyclobutadiene.[3] Also, valent iodine-mediated synthesis[11] are well explored.
we reported with Nitschke that white phosphorus was
air-stable upon incarceration within a tetrahedral met-
allo-supramolecular capsule.[4] The iodine-ammonia Results and Discussion
combination is known as a contact explosive[5] in con-
strained media. Similarly, hypervalent iodine com- We report here a mechanochemical cross dehydrogen-
pounds, as oxidizers,[6] form charge transfer complexes ative coupling (CDC)[12] for the oxidative amidation[13]
[14]
with fuel-amines[7] and cause highly exothermic reac- of aryl aldehydes via C H activation using phenyl-
À
tions. Under solvent-free conditions (constrained iodine diacetate (PIDA)[15] and benzylamines. The
media) the reactants experience maximum possible acid-salt sodium bisulfate (NaHSO4) was used to con-
contacts among themselves and create an extreme sit- trol the reactivity of the contact-explosive (Figure 1).
uation for contact-explosives. Therefore, a violent
exothermic reaction takes place for hypervalent io- atom-economic approach for C N bond construction.
dine(III) reagents and electron-rich amines under sol- Making a C N bond is an important transformation
vent-free conditions. To the best of our knowledge, no in organic synthesis as it constitutes the structural
synthetic applications using hypervalent iodine(III) backbone of proteins and peptides through amide
reagents and primary amines in a constrained media linkages. Common methods for oxidative amidation
The CDC reaction has proven to be a powerful and
À
À
have been reported as yet.
involve: coupling of carboxylic acids and amines in
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Tapas Kumar Achar and Prasenjit Mal
Figure 1. Mechanochemical cross dehydrogenative coupling (CDC); newly formed bond is shown as a red-thick line. a) This
work. b) Uncontrollable reaction in the absence of NaHSO4. c) NaHSO4-mediated explosion-free and successful reaction. d)
Photographs of reaction mixture after explosion (left) and subsequent to making it explosion-free (right).
the presence of a coupling agent,[16] acylation of
Table 1 represents the optimization of the reaction
amines with activated carboxylic acids, etc.[17] Recent- conditions. Mechanochemical CDC for the synthesis
ly we reported the metal- and solvent-free oxidative of N-benzyl-4-bromobenzamide (3a) was done suc-
À
amidation of aldehydes with N-chloramines via C H cessfully using 4-bromobenzaldehyde (1.0 equiv., 1a),
activation under neat and ball-milling conditions benzylamine (1.1 equiv., 2a), PIDA (2.0 equiv.) and
using TBAI (tetrabutyl ammonium iodide)-TBHP NaHSO4 (2.0 equiv.). During optimization, the prog-
(tert-butyl hydroperoxide) combinations.[18]
ress of the reaction was monitored using thin layer
1
À
For C N bond construction, hypervalent iodine chromatography (TLC) or H NMR (see the Support-
compounds are also considered as useful reagents.[19] ing Information).
However, an immediate explosion was observed and
Amide derivatives were obtained in good to excel-
the reaction mixture became brownish during the lent yields (Figure 2) under the optimized conditions.
mixing of benzaldehydes, benzylamines and PIDA Higher yields of amides were observed with the aro-
under solvent-free ball-milling conditions (Caution!! matic aldehydes containing electron-withdrawing (3a–
see Experimental Section) (Figure 1d, left). Conse- 3c, 3f–3o, 3q–3s, 3u–3x, 3z and 3aa) than electron-do-
quently, it was found that acetic acid generated (from nating groups (3d, 3e, 3t, 3y). Amides from halogen-
PIDA) could control the reactivity of the amine substituted benzaldehydes (3a, 3f, 3h, 3j, 3n, 3o, 3r
through protonation and a 47% yield of the amide and 3w) were also isolated in convincing yields. Ac-
was obtained (Figure 1b). The same reaction was cordingly, various amines like benzylamine (3a–h,
found to be explosion free in the presence of exter- 3o,p), 4-fluorobenzylamine (3i–k and 3aa), 2-phenyl-
nally-added acetic acid (yield 41%, Table 1). Like- ethanamine (3q–u), 2-chlorobenzylamine (3l–n) and
wise, use of an acid-salt such as NaHSO4 (Figure 1c) [3,5-bis(trifluoromethyl)phenyl]methanamine (3v–z)
as additive afforded an 84% yield of 3a.
derivatives also facilitated excellent yields of the
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Transformation of Contact-Explosives Primary Amines Iodine(III)
Table 1. Optimization of reaction condition for the synthesis
of 3a as shown in Figure 1.[a]
Entry
PIDA (equiv.)
Additive (equiv.)
Yield [%]
1
2
3
4
5
6
7
8
9
10
1.1
2.0
1.1
1.1
1.1
2
2
2
2
2
NaHSO4 (1)
NaHSO4 (2)
NaH2PO4 (1)
NaCl (1)
NaHCO3 (1.2)
KH2PO4 (2)
AcOH (2)
H2SO4 (2)
PTSA (2)
TBAHS (2)
44
84 (67)
15
Trace
23
19
41
11
<5
~5
[a]
Reactions were performed with 1.0 equiv. of 1a and
1.1 equiv. of 2a.
Yields (based on recovered aldehydes after chromato-
[b]
graphic purification) are shown.
amides. In addition, reactions were performed under
solvent-free conditions and therefore highly volatile
aliphatic amines were not considered for this study.
Control experiments (Figure 3) were performed to
shed some light on the mechanism of the reaction.
Reaction of 4-nitrobenzaldehyde (1b) with a secon-
dary amine (dibenzylamine, 4) led to corresponding
amide in 13% yield (Figure 3 a) and the majority of
the aldehydes remained unreacted. More reactive sec-
ondary amines possibly destroyed PIDA and the reac-
tion became uncontrollable using NaHSO4. Oligomer-
[20]
ic iodosylbenzene sulfate
6
[(PhIO)3SO3)]n
is
known to be synthesized from grinding of PIDA with
NaHSO4.[21] Mechanochemical milling of 6 and imine
5 (synthesized separately from 1a and 2a) did not
Figure 2. Compound identification numbers and yields are
result in any amide (Figure 3b). Separately, 1a, 2a and shown for the synthesized compounds.
6 under ball-milling also led to explosions (Caution!!)
(Figure 3d). More examples of unsuccessful one-pot
milling reactions were: (i) imine 5, PIDA, NaHSO4
and K2CO3 (14%, Figure 3c), (ii) imine 5 and PIDA
The role of NaHSO4 towards the successful and ex-
(0%, Figure 3e) because PIDA was unable to perform plosion-free mechanochemical CDC reactions was
oxo transfer reactions, and (iii) 5, NaHSO4 and PIDA clarified. The acid-salt NaHSO4 is widely used in the
(5%, Figure 3f). From these observations, it was ra- poultry industry to decrease basic-ammonia and bac-
tionalized that the iodosylbenzene sulfate
6
terial levels in litter.[24] In aqueous solution, NaHSO4
[(PhIO)3SO3)]n was not the active reagent and imine acts as a medium-strong acid. A solution of 1.0M
5 was not the intermediate[22] for this transformation. NaHSO4 in water shows pH<1.0 and the bisulfate
Expectedly, the oxidative amidation proceeded via anion has a pKa value of ~1.99. The pKa of benzyl-
+
a hemiaminal intermediate (Figure 4a).[23]
amine is 9.38 (through dissociation of NH ) and
À
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Tapas Kumar Achar and Prasenjit Mal
Figure 3. a)–f) Control experiments to understand the mechanism of the reaction.
Figure 4. a) Plausible mechanism for the CDC reaction. b) Unsuccessful amidation under optimized conditions. c) Determi-
nation of enthalpy changes from the reaction of benzylamine and PIDA, both in the absence and the presence of acetic acid
(AcOH).
comparable to that of ammonia (9.21).[25] Ammonia
generally reacts with NaHSO4 to form salts.[24]
Similarly, NaHSO4 may form an acid-base complex
with basic amines to realize the explosion-free oxida-
tive amidation. Also, in the presence of concentrated
H2SO4, benzylamine did not react with either alde-
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Transformation of Contact-Explosives Primary Amines Iodine(III)
hyde or PIDA. The stronger protic acid H2SO4 (pKa: ronment can be protected through the sequestration
À
À10) could completely deactivate the amine upon
of hazardous substances. This study also highlights the
NH+ protonation. However, using the weaker organic progress of C H bond activation chemistry for the
acid p-toluenesulfonic acid (pKa: À2.8), the amide formation of amides and should find wide application
(3a) was isolated in <5% yield. Pyrrolidine (pKa: in the context of both natural product synthesis and
11.27 conjugate acid in water) and 4-methoxybenzyl- pharmaceuticals using mechanochemistry.
amine are stronger bases than benzylamine and the
À
explosion could not be controlled using NaHSO4. Ac-
cordingly, no amidation products were isolated using Experimental Section
pyrrolidine or 4-methoxybenzylamine (3ab–3af, Fig-
ure 4b). Also, a gram-scale synthesis of amide was General Methods
done successfully using the proposed methodology
The ball milling (21 Hz) experiments were performed in the
(see large-scale synthesis paragraph in the Experi-
open atmosphere. Column chromatographic purifications of
mental Section).
compounds were done using silica-gel (mesh 100–200) and
An isothermal titration calorimetric analysis (ITC,
see the Supporting Information) analysis (see also iso-
thermal titration calorimetric (ITC) study in the Ex-
perimental Section) was performed to estimate the
enthalpy of the reaction (DH) from the reaction of
PIDA and benzylamine in acetonitrile both in the ab-
sence (DH1) and in the presence (DH2) of acetic acid
(Figure 4c). The acetic acid could control the reaction
and DDH (DH1ÀDH2) of the reaction was 3.26”
105 kcalmolÀ1.
Amidation reactions using primary amines and io-
dine(III) reported by Tiwari and co-workers were
done in an ionic liquid.[22] Higher concentrations of
primary amine destroyed PIDA during fast addition
and that resulted in poor yields of amides. A two-fold
increase in the yield of amide was achieved upon
dropwise addition of amine with constant stirring to
the PIDA solution in ionic liquids. The high polarity
of ionic liquids and the high-dilution effect, coopera-
tively, could stop the immediate explosion of primary
amines and iodine(III). However, in this work under
solvent-free ball-milling conditions the maximum pos-
sible concentration puts the system under high stress
and thus it could lead to uncontrollable oxidation
more easily. As a result an explosion was observed
immediately in the absence of NaHSO4.
hexane-ethyl acetate mixtures as eluent, unless otherwise
mentioned. NMR spectra were recorded on a 400 MHz in-
strument at 258C. The chemical shift values are reported in
parts per million (ppm) and referred to the residual chloro-
form (7.26 ppm for 1H and 77.16 for 13C) and deuterium
1
oxide (4.79 ppm for H). The peak patterns are designated
as follows: s, singlet; d, doublet; t, triplet; q, quartet; m,
multiplet; dd, doublet of doublets; td, triplet of doublets; br
s, broad singlet. The coupling constants (J) are reported in
hertz (Hz). High-resolution mass spectrometry (HR-MS)
was conducted on an ESI-TOF (time of flight) mass spec-
trometer. The isothermal titration calorimetric (ITC) experi-
ment was performed in a MicroCal iTC200 isothermal titra-
tion calorimeter. Infrared spectral data are reported in
wavenumber (cmÀ1). Melting points of the compounds were
determined using a digital melting point apparatus and are
uncorrected.
Caution: When PIDA and primary amines were mixed
under solvent-free conditions, an immediate explosion was
observed. In the presence of NaHSO4, no explosion was ob-
served under similar conditions. Still, general safety con-
cerns in the laboratory should be carefully exercised and it
is highly recommended that all reactions should be carried
out in a well-ventilated fume hood behind a blast shield.
Large Scale Synthesis
The recommended loading of the reactant materials should
be less than one third of the jar volume. In a 25-mL stainless
steel milling jar, two balls (15 mm dia), PIDA (1.74 g,
5.4 mmol), NaHSO4 (746 mg, 5.4 mmol), 4-bromobenzalde-
hyde (500 mg, 2.7 mmol) and benzylamine (324 mL,
2.9 mmol) were added sequentially and milled for 2 h.
Work-up and subsequent purification (see the Suppoorting
Information) led to 4-bromobenzaldehyde (1a; yield:
167 mg) and product 3a; yield: 406 mg (78%).
Conclusions
In summary, the present work describes an unprece-
dented approach in which either an acid or acid-salt
(NaHSO4) could transform an explosive reaction mix-
ture into a successful chemical reaction. A concept is
proposed in which, by selecting appropriate condi-
tions, it is now possible to perform a highly exother-
mic reaction in the ambient laboratory atmosphere.
We anticipate that stopping an explosion of the con-
tact-explosives primary amines-phenyliodine diacetate
Isothermal Titration Calorimetric (ITC) Study
In acetonitrile, 200 mL of 2.08”10À7 M solution of benzyl-
amine were titrated with 1.36”10À7 M of PIDA solution.
system and the safety benefits of using them are sub- Using 0.5 mL per titration, 40 titrations were performed.
stantial: (i) a new research area can be initiated using
this concept; (ii) this approach could be used directly
to diffuse dangerous chemical weapons; (iii) the envi-
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(s), 870 (s), 697 (s) cmÀ1; HR-MS (ESI-TOF): m/z=
257.0924, calcd. for C14H13N2O3 (M+H+): 257.0921.
Synthesis of Oligomeric Iodosylbenzene Sulfate
[(PhIO)3SO3]n (6)[26]
N-Benzyl-4-cyanobenzamide (3c): Rf =0.32 (ethyl acetate/
hexane=1:4); white solid; yield: 89% (89 mg, 71%); mp
1
154–1568C (lit.[29] 150–1518C); H NMR (400 MHz, CDCl3):
d=7.87 (d, J=8 Hz, 2H), 7.69 (d, J=8 Hz, 2H), 7.37–7.29
(m, 5H), 6.67 (br s, 1H), 4.62 (d, J=4 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=165.7, 138.3, 137.6, 132.5, 129.0,
˜
128.0, 128.0, 127.8, 118.0, 115.2, 44.4; IR (KBr) n=3316 (w),
2923 (s), 2218 (s), 1643 (m), 1550 (s), 1422 (s), 1311 (s), 864
(s), 721 (s) cmÀ1; IR (KBr): n=3315 (w), 3090 (s), 3064 (s),
˜
Phenyliodine diacetate (400 mg, 1.24 mmol) was added to
NaHSO4·H2O (176 mg, 1.03 mmol) in an agate mortar. Then
the mixture was ground for 10 min and the resulting mass
was transferred to a beaker and dissolved in 5 mL of water.
After 5 min, a clear yellow solution was formed and allowed
to settle for 2 h. After that the yellow precipitate was fil-
tered off and washed with cold water and dried to afford
a yellow crystalline compound (yield: 135 mg). The filtrate
was left for slow evaporation and an additional 92 mg of
3028 (s), 2923 (s), 2231 (s), 1644 (s), 1547 (m), 1496 (m),
1286 (m), 857 (m), 697 (m) cmÀ1; HR-MS (ESI-TOF): m/z=
237.1041, calcd. for C15H13N2O (M+H+): 237.1022.
N-benzyl-4-methylbenzamide (3d): Rf =0.40 (ethyl ace-
tate/hexane=1:4); white solid; yield: 72% (77 mg, 59%);
mp 133–1368C (lit.[27] 131–1348C); 1H NMR (400 MHz,
CDCl3): d=7.69 (d, J=8.1 Hz, 6H), 7.37–7.27 (m, 16H),
7.21 (d, J=8.0 Hz, 6H), 6.58 (s, 3H), 4.61 (d, J=5.6 Hz,
7H), 2.39 (s, 9H); 13C NMR (101 MHz, CDCl3): d=167.43,
142.02, 138.47, 131.63, 129.31, 128.83, 128.65, 127.97, 127.65,
127.61, 127.10, 77.48, 77.16, 76.84, 44.12, 21.53; IR (KBr):
compound
6 was isolated; total yield: 227 mg (74%).
1H NMR (400 MHz, D2O): d=8.09 (d, J=8 Hz, 2H), 7.71
(t, J=7.5 Hz, 1H), 7.55 (t, J=7.8 Hz, 2H); 13C NMR
(100 MHz, D2O): d=134.3, 133.1, 131.5, 123.5.
˜
n=3311 (m), 3085 (s), 3054 (s), 3028 (s), 1639 (m), 1546
(m), 1420 (s), 1323 (s), 1058 (s), 841 (s), 721 (s) cmÀ1; HR-
MS (ESI-TOF): m/z=226.1247, calcd. for C15H16NO (M+
H+): 226.1226.
General Procedure for the Preparation of Amides
under Ball-Milling
N-Benzyl-4-methoxybenzamide (3e): Rf =0.20 (ethyl ace-
tate/hexane=1:4); white solid; yield: 74% (69 mg, 56%);
mp 118–1218C (lit.[30] 124–1268C); 1H NMR (400 MHz,
CDCl3): d=7.76 (d, J=8 Hz, 2H), 7.40–7.28 (m, 5H), 6.92
(d, J=8 Hz, 2H), 6.31 (br s, 1H), 4.64 (d, J=8 Hz, 2H),
3.84 (s, 3H); 13C NMR (100 MHz, CDCl3): d=166.9, 162.3,
138.5, 128.9, 128.9, 128.0, 127.7, 126.7, 113.9, 55.5, 44.2; IR
In a 10-mL stainless steel milling jar, benzylamine (65 mL,
0.59 mmol) was added to the mixture of 4-bromobenzalde-
hyde (100 mg, 0.54 mmol), PIDA (348 mg, 1 mmol),
NaHSO4 (149 mg, 1 mmol) and one grinding ball (15 mm di-
ameter, stainless steel). The progress of the reaction under
milling conditions was monitored by thin layer chromatogra-
˜
(KBr): n=3521 (w), 3295 (m), 3054 (s), 1633 (m), 1537 (m),
1505 (s), 1256 (s), 846 (m), 726 (m) cmÀ1; HR-MS (ESI-
TOF): m/z=242.1198, calcd. for C15H16NO2 (M+H+):
242.1176.
1
phy (TLC) or H NMR. After completion of the reaction,
the mixture was dissolved in dichloromethane and the prod-
uct (N-benzyl-4-bromobenzamide) was purified by column
chromatography. Isolated materials: 20 mg of 4-bromoben-
zaldehyde (1a) were recovered as unreacted material togeth-
er with 3a; yield: 105 mg (84% based on recovered 1a).
The isolated yields given below (after column chromatog-
raphy) were calculated based on recovered starting material.
However, in parenthesis the yields are calculated based on
aldehydes used for the reaction.
N-Benzyl-4-chlorobenzamide (3f): Rf =0.25 (ethyl acetate/
hexane=1:4); white solid; yield: 79% (76 mg, 62%); mp
1
157–1628C (lit.[27] 163–1668C); H NMR (400 MHz, CDCl3):
d=7.79 (d, J=8 Hz, 2H), 7.43 (d, J=8 Hz, 2H), 7.37–7.27
(m, 5H), 6.51 (br s, 1H), 4.645 (d, J=4 Hz, 2H). 13C NMR
(100 MHz, CDCl3): d=167.5, 138.2, 134.4, 131.6, 128.9,
˜
128.7, 128.0, 127.7, 127.1, 44.2; IR (KBr): n=3324 (m), 3059
(s), 3030 (s), 2928 (s), 1643 (s), 1603 (s), 1576 (s), 1542 (m),
1452 (s), 1418 (s), 1312 (s), 1259 (s), 1028 (s), 727 (s), 694
(m), 666 (s) cmÀ1; HR-MS (ESI-TOF): m/z=246.0672,
calcd. for C14H13ClNO (M+H+): 246.0686.
N-Benzyl-3-nitrobenzamide (3g): Rf =0.17 (ethyl acetate/
hexane=1:4); white solid; yield: 87% (81 mg, 68%); mp 99–
1028C (lit.[31] 95–968C); 1H NMR (400 MHz, CDCl3): d=
8.60 (s, 1H), 8.34 (d, J=8 Hz, 1H), 8.17 (d, J=8 Hz, 1H),
7.63 (dt, J=11.7, 6.0 Hz, 1H), 7.36–7.31 (m, 5H), 6.75, 6.65
(br s, 1H), 4.655 (d, J=4 Hz, 2H). 13C NMR (100 MHz,
CDCl3): d=165.0, 148.3, 137.6, 136.1, 133.4, 130.0, 129.0,
N-Benzyl-4-bromobenzamide (3a): Rf =0.30 (ethyl ace-
tate/hexane=1:4); white solid; yield: 84% (73 mg, 67%);
mp 155–1598C (lit.[27] 160–1628C); 1H NMR (400 MHz,
CDCl3): d=7.66 (d, J=8 Hz, 2H), 7.56 (d, J=8 Hz, 2H),
7.35–7.31 (m, 5H), 6.42 (br s, 1H), 4.63 (d, J=8 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=166.5, 138.0, 133.3, 131.9,
˜
129.0, 128.7, 128.1, 127.9, 126.4, 44.4; IR (KBr): n=3308
(m), 3081 (s), 2919 (s), 2848 (s), 1640 (m), 1548 (m), 1416
(s), 1256 (s), 847 (s) cmÀ1; HR-MS (ESI-TOF): m/z=
290.0176, calcd. for C14H13BrNO (M+H+): 290.0175.
N-Benzyl-4-nitrobenzamide (3b): Rf =0.32 (ethyl acetate/
hexane=1:4); white solid; yield: 92% (87 mg, 73%); mp
˜
128.1, 128.0, 126.2, 121.9, 44.6; IR (KBr): n=3301 (w), 3086
1
141–1448C (lit.[28] 1428C); H NMR (400 MHz, CDCl3): d=
(s), 2926 (s), 1642 (m), 1528 (m), 1349 (m), 1159 (s), 1081
(s), 909 (s), 814 (s), 699 (m) cmÀ1; HR-MS (ESI-TOF):
m/z=257.0931, calcd. for C14H13N2O3 (M+H+): 257.0921.
N-Benzyl-3-bromobenzamide (3h):[32] Rf =0.30 (ethyl ace-
tate/hexane=1:4); white solid; yield: 76% (69 mg, 63%);
mp 112–1168C; 1H NMR (400 MHz, CDCl3): d=7.93 (s,
8.26 (d, J=8 Hz, 2H), 7.94 (d, J=8 Hz, 2H), 7.37–7.34 (m,
5H), 6.60 (br s, 1H), 4.65 (d, J=8 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=165.4, 149.7, 140.0, 137.5, 129.0,
˜
128.3, 128.1, 128.1, 123.9, 44.6; IR (KBr): n=3280 (m), 2922
(m), 2839 (s), 1633 (m), 1597 (m), 1515 (m), 1345 (m), 1105
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Adv. Synth. Catal. 2015, 357, 3977 – 3985

FULL PAPERS
Transformation of Contact-Explosives Primary Amines Iodine(III)
1H), 7.71 (d, J=8 Hz, 1H), 7.62 (d, J=8 Hz, 1H), 7.38–7.27
(m, 6H), 6.43 br (s, 1H), 4.635 (d, J=4 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=166.1, 137.9, 136.4, 134.6, 130.3,
127.86, 127.43, 118.09, 115.36, 77.48, 77.16, 76.84, 42.54; IR
˜
(KBr): n=3415 (w), 2923 (s), 2848 (s), 2230 (s), 1648 (m),
1543 (s), 1288 (s), 858(s), 750 (m) cmÀ1; HR-MS (ESI-TOF):
m/z=271.0640, calcd. for C15H12ClN2O (M+H+): 271.0632.
4-Bromo-N-(2-chlorobenzyl)benzamide (3n): Rf =0.37
(ethyl acetate/hexane=1:4); white solid; yield 84% (83 mg,
˜
130.3, 129.0, 128.1, 127.9, 125.7, 122.9, 44.4; IR (KBr): n=
3320 (m), 3063 (s), 3028 (s), 2925 (s), 1638 (m), 1562 (m),
1542 (m), 1471 (s), 1454 (s), 1315 (s), 1071 (s), 996 (s), 894
(s), 744 (m), 698 (m) cmÀ1; HR-MS (ESI-TOF): m/z=
290.0189, calcd. for C14H13BrNO (M+H+): 290.0175.
1
68%); mp 138–1398C; H NMR (400 MHz, CDCl3): d=7.65
(d, J=8 Hz, 2H), 7.56 (d, J=8 Hz, 2H), 7.46 (dd, J=6,
4 Hz, 1H), 7.39 (dd, J=8, 4 Hz, 1H), 7.27–7.24 (m, 2H),
6.56 (br s, 1H), 4.72 (d, J=8 Hz, 2H); 13C NMR (100 MHz,
CDCl3): d=166.5, 135.4, 133.9, 133.2, 132.0, 130.7, 129.8,
4-Cyano-N-(4-fluorobenzyl)benzamide
(3i):
Rf =0.20
(ethyl acetate/hexane=1:4); white solid; yield: 92%
(100 mg, 74%); mp 109–1118C; 1H NMR (400 MHz,
CDCl3): d=7.88 (d, J=8 Hz, 2H), 7.72 (d, J=8 Hz, 2H),
7.31 (dd, J=10, 6 Hz, 2H), 7.03 (dd, J=12, 5 Hz, 2H), 6.59
(br s, 1H), 4.60 (d, J=8 Hz, 2H); 13C NMR (100 MHz,
˜
129.3, 128.7, 127.4, 126.4, 42.3; IR (KBr) n=3320 (m), 3068
(s), 1633 (m), 1590 (s), 1539 (m), 1482 (m), 1318 (m), 1070
(s), 1009 (s), 847 (s), 749 (m) cmÀ1; HR-MS (ESI-TOF):
m/z=323.9794, calcd. for C14H12BrClNO (M+H+):
323.9785.
1
CDCl3): d=165.7, 162.5 (d, JC,F =245 Hz), 138.2, 133.5 (d,
3
4JC,F =3 Hz), 132.6, 129.8 (d, JC,F =8 Hz), 127.8, 118.0, 115.9
2
˜
(d, JC,F =21 Hz), 115.3, 43.7; IR (KBr): n=3265 9 m), 3094
N-Benzyl-2,3,4,5,6-pentafluorobenzamide (3o): Rf =0.45
(ethyl acetate/hexane=1:4); white solid; yield: 78% (63 mg,
(m), 2922 (m), 2852 (s), 2230 (m), 1633 (m), 1556 (m), 1512
(m), 1428 (s), 1251 (s), 1220 (m), 1154 (s), 1059 (s), 861 (m),
840 (m), 807 (m), 731 (s), cmÀ1; HR-MS (ESI-TOF): m/z=
255.0925, calcd. for C15H12FN2O (M+H+): 255.0928.
1
59%); mp 2158C; H NMR (400 MHz, CDCl3): d=7.38–7.29
(m, 5H), 6.42 (br s, 1H), 4.61 (d, J=8 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=157.5, 145.7–145.4 (m), 143.9–143.5
(m), 143.2–142.9 (m), 141.3–141.0, 139.2–138.8 (m), 136.7–
136.3 (m), 129.0, 128.1, 127.8, 111.7–111.3 (m), 44.5; IR
4-Bromo-N-(4-fluorobenzyl)benzamide (3j): Rf =0.35
(ethyl acetate/hexane=1:4); white solid; yield: 83% (80 mg,
1
69%); mp 128–1318C; H NMR (400 MHz, CDCl3): d=7.63
˜
(KBr): n=3235 (m), 3068 (m), 2953 (m), 1652 (m), 1566 (s),
(d, J=8.5 Hz, 2H), 7.53 (d, J=8.5 Hz, 2H), 7.28 (dd, J=8.3,
5.5 Hz, 2H), 7.01 (t, J=8.6 Hz, 2H), 6.65 (br s, 1H), 4.55 (d,
J=5.7 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=166.6,
1494 (m), 1059 (s), 988 (m), 875 (s), 746 (s) cmÀ1; HR-MS
(ESI-TOF): m/z=302.0588, calcd. for C14H9F5NO (M+H+):
302.0599.
1
4
162.4 (d, JC,F =244 Hz), 133.9 (d, JC,F =3 Hz), 133.1, 131.9,
N-Benzylpyrene-1-carboxamide (3p): Rf =0.32 (ethyl ace-
tate/hexane=1:4); white solid; yield: 81% (49 mg, 48%);
mp 1058C; 4:3 mixture of rotamers; 1H NMR (400 MHz,
CDCl3): d=8.57 (dd, J=9.2, 3.5 Hz, 1H), 8.28–8.16 (m,
2H), 8.16–7.93 (m, 6H), 7.84–7.71 (m, 3H), 7.52–7.37 (m,
8H), 7.37–7.27 (m, 8H), 6.60 (s, 1H), 6.49 (s, 1H), 4.87–4.73
(m, 2H), 4.71–4.54 (m, 3H); 13C NMR (100 MHz, CDCl3):
d=169.9, 167.4, 138.3, 138.3, 134.4, 132.6, 131.6, 131.2, 130.8,
130.8, 128.9, 128.9, 128.8, 128.7, 128.6, 128.1, 128.0, 127. 8,
127.7, 127.2, 127.1, 126.4, 125.9, 125.8, 124.8, 124.6, 124.5,
129.7 (d, 3JC,F =8 Hz), 128.7, 126.4, 115.7 (d, JC,F =21 Hz),
2
˜
43.5; IR (KBr): n=3315 (m), 3081 (s), 1638 (m), 1548 (m),
1227 (s), 841 (s), 801 (s), 711 (s) cmÀ1; HR-MS (ESI-TOF):
m/z=308.0099, calcd. for C14H12BrFNO (M+H+): 308.0081.
N-(4-Fluorobenzyl)-4-nitrobenzamide
(3k):
Rf =0.30
(ethyl acetate/hexane=1:4); white solid; yield: 86% (85 mg,
1
67%); mp 129–1328C; H NMR (400 MHz, CDCl3): d=8.27
(d, J=8 Hz, 2H), 7.94 (d, J=8 Hz, 2H), 7.33 (s, 2H), 7.04
(t, J=8.1 Hz, 2H), 6.57 (br s, 1H), 4.625 (d, J=4 Hz, 2H);
1
13C NMR (100 MHz, CDCl3): d=165.4, 162.5 (d, JC,F
=
=
˜
124.4, 77.9, 77.2, 76.8, 44.8, 44.2; IR (KBr): n=3288 (m),
4
3
245 Hz), 149.8, 139.9, 133.4 (d, JC,F =3 Hz), 129.9 (d, JC,F
3063 (s), 3030 (s), 2923 (s), 1635 (m), 1537 (m), 1490 (s),
1291 (m), 848 (s), 695 (m) cmÀ1; HR-MS (ESI-TOF): m/z=
336.1393, calcd. for C24H18NO (M+H+): 336.1383.
2
9 Hz), 128.3, 124.0, 115.9 (d, JC,F =22 Hz), 43.8; IR (KBr):
˜
n=3271 (m), 3077 (s), 2923 (m), 2853 (m), 1644 (m), 1600
(m), 1548 (m), 1510 (m), 1349 (m), 1219 (m), 1156 (s), 1064
(s), 981 (s), 824 (m), 723 (m) cmÀ1; HR-MS (ESI-TOF):
m/z=275.0829, calcd. for C14H12FN2O3 (M+H+): 275.0826.
N-(2-Chlorobenzyl)-4-nitrobenzamide (3l): Rf =0.45 (ethyl
acetate/hexane=1:4); white solid; yield: 87% (93 mg, 69%);
4-Cyano-N-phenethylbenzamide (3q): Rf =0.18 (ethyl ace-
tate/hexane=1:4); white solid; yield: 94% (91 mg, 68%);
1
mp 115–1178C; H NMR (400 MHz, CDCl3): d=7.77 (d, J=
8 Hz, 2H), 7.70 (d, J=8 Hz, 2H), 7.35–7.32 (m, 2H), 7.28–
7.22 (m, 3H), 6.21 (br s, 1H), 3.76–3.71 (m, 2H), 2.95 (t, J=
6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=165.8, 138.6,
132.5, 128.9, 128.9, 127.6, 126.9, 118.1, 115.1, 41.4, 35.6; IR
1
mp 163–1668C; H NMR (400 MHz, CDCl3): d=8.27 (d, J=
8 Hz, 2H), 7.93 (d, J=8 Hz, 2H), 7.48–7.38 (m, 2H), 7.29–
7.25 (m, 2H), 6.69 (br s, 1H), 4.745 (d, J=4 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=165.3, 149.6, 139.8, 134.9,
133.8, 130.8, 129.7, 129.5, 128.2, 127.3, 123.8, 42.5; IR (KBr):
˜
(KBr): n=3306 (w), 3085 (s), 2923 (s), 2852 (s), 2228 (s),
1633 (m), 1543 (m), 1497 (s), 1313 (s), 857 (s), 753 (s) cmÀ1
;
HR-MS (ESI-TOF): m/z=251.1192, calcd. for C16H15N2O
˜
n=3331 (m), 3063 (s), 2920 (m), 2857 (s), 1644 (m), 1598
(M+H+): 251.1178.
(m), 1523 (m), 1345 (m), 1300 (m), 1015 (s), 752 (s) cmÀ1
;
4-Bromo-N-phenethylbenzamide (3r): Rf =0.35 (ethyl ace-
tate/hexane=1:4); white solid; yield: 87% (71 mg, 62%);
mp 113–1168C (lit.[33] 143–1448C); 1H NMR (400 MHz,
CDCl3): d=7.55 (s, 4H), 7.35–7.32 (m, 2H), 7.27–7.22 (m,
3H), 6.08 (br s, 1H), 3.71 (dd, J=12, 8 Hz, 2H), 2.93 (t, J=
6.9 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=166.6, 138.8,
133.5, 131.9, 131.8, 128.9, 128.5, 126.8, 126.2, 41.3, 35.7; IR
HR-MS (ESI-TOF): m/z=291.0537, calcd. for C14H12ClN2O3
(M+H+): 291.0531.
N-(2-Chlorobenzyl)-4-cyanobenzamide (3m): Rf =0.30
(ethyl acetate/hexane=1:4); white solid; yield; 88% (92 mg,
1
64%); mp 132–1358C; H NMR (400 MHz, CDCl3): d=7.87
(d, J=8.3 Hz, 2H), 7.72 (d, J=8.2 Hz, 2H), 7.51–7.43 (m,
1H), 7.43–7.36 (m, 1H), 7.30–7.25 (m, 2H), 6.70 (s, 1H),
4.73 (d, J=5.9 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=
165.67, 138.29, 135.10, 133.94, 132.61, 130.83, 129.86, 129.55,
˜
(KBr): n=3419 (w), 2923 (s), 2848 (s), 1639 (m), 1542 (s),
1482 (s), 1317 (s), 1068 (s), 1009 (s), 755 (s) cmÀ1; HR-MS
Adv. Synth. Catal. 2015, 357, 3977 – 3985
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3983

FULL PAPERS
Tapas Kumar Achar and Prasenjit Mal
(ESI-TOF): m/z=304.0348, calcd. for C15H15BrNO (M+
H+): 304.0331.
N-[3,5-Bis(trifluoromethyl)benzyl]-4-nitrobenzamide (3x):
Rf =0.27 (ethyl acetate/hexane=1:4); white solid; yield:
89% (133 mg, 73%); mp 165–1678C; 1H NMR (400 MHz,
CDCl3): d=8.32 (d, J=8 Hz, 2H), 7.98 (d, J=8 Hz, 2H),
7.82 (s, 3H), 6.72 (br s, 1H), 4.795 (d, J=4 Hz, 2H);
13C NMR (100 MHz, CDCl3): d=165.8, 150.1, 140.4, 139.2,
132.4 (q, JC.F =66 Hz), 128.4, 128.2 (d, JC.F =3 Hz), 123.2 (q,
4-Nitro-N-phenethylbenzamide (3s): Rf =0.20 (ethyl ace-
tate/hexane=1:4); white solid; yield: 93% (95 mg, 76%);
1
mp 152–1568C (lit.[34] 1518C); H NMR (400 MHz, CDCl3):
d=8.24 (d, J=8 Hz, 2H), 7.83 (d, J=8 Hz, 2H), 7.34–7.22
(m, 5H), 6.31 (br s, 1H), 3.74 (dd, J=12, 6 Hz, 2H), 2.96 (t,
J=6.6 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=165.6,
149.6, 140.3, 138.6, 128.9, 128.8, 128.1, 126.9, 123.9, 41.5,
J
C.F =542 Hz), 124.2, 122.0 (q, JC.F =8 Hz), 43.6; IR (KBr):
˜
n=3298 (m), 3056 (s), 2989 (s), 2929 (s), 2851 (s), 1644 (m),
1600 (m), 1519 (m), 1352 (m), 1282 (m), 1124 (m), 985 (s),
896 (s), 870 (s), 738 (m) cmÀ1; HR-MS (ESI-TOF): m/z=
393.0673, calcd. for C16H11F6N2O3 (M+H+): 393.0668.
˜
35.5; IR (KBr): n=3328 (m), 3063 (s), 2923 (s), 1643 (m),
1597 (m), 1541 (m), 1517 (m), 1452 (s), 1352 (s), 1193 (s),
867 (s), 753 (s) cmÀ1; HR-MS (ESI-TOF): m/z=271.1077,
calcd. for C15H15N2O3 (M+H+): 271.1077.
N-[3,5-Bis(trifluoromethyl)benzyl]-4-methylbenzamide
(3y): Rf =0.40 (ethyl acetate/hexane=1:4); white solid;
yield: 82% (147 mg, 70%); mp 107–1088C; 1H NMR
(400 MHz, CDCl3): d)7.95–7.54 (m, 5H), 7.23 (s, 2H), 6.91
(s, 1H), 4.72 (s, 2H), 2.39 (s, 3H). 13C NMR (100 MHz,
CDCl3): d=167.8, 142.7, 141.4, 132.1 (q, JC,F =67 Hz), 130.9,
4-Methyl-N-phenethylbenzamide (3t): Rf =0.25 (ethyl ace-
tate/hexane=1:4); white solid; yield: 79% (99 mg, 71%);
1
mp 82–848C (lit.[35] 76–778C); H NMR (400 MHz, CDCl3):
d=7.60 (d, J=8 Hz, 2H), 7.33 (d, J=8 Hz, 2H), 7.27–7.21
(m, 5H), 6.15 (br s, 1H), 3.72 (dd, J=12, 8 Hz, 2H), 2.94 (t,
J=6.8 Hz, 2H), 2.39 (s, 3H); 13CNMR (100 MHz, CDCl3):
d=167.5, 141.9, 139.1, 131.9, 129.3, 128.9, 128.8, 126.9, 126.7,
129.5, 127.9, 127.1, 123.3 (q, JC,F =542 Hz), 121.5 (q, JC,F
=
˜
7 Hz), 43.2, 21.5; IR (KBr): n=3303 (w), 3047 (s), 2934 (s),
1634 (m), 1538 (m), 1505 (m), 1380 (m), 1355 (m), 1278 (m),
1173 (m), 1133 (m), 889 (m), 837 (m), 705 (m), 682 (m)
˜
41.2, 35.8, 21.5; IR (KBr): n=3313 (m), 3026 (s), 2937 (s),
1637 (m), 1534 (m), 1307 (m), 1199 (s), 836 (s), 749 (s), 697
(m) cmÀ1; HR-MS (ESI-TOF): m/z=262.1211, calcd. for
C16H17NNaO (M+Na+): 262.1202.
cmÀ1
;
HR-MS (ESI-TOF): m/z=362.0986, calcd. for
C17H14F6NO (M+H+): 362.0974.
N-[3,5-Bis(trifluoromethyl)benzyl]-3-nitrobenzamide (3z):
Rf =0.27 (ethyl acetate/hexane=1:4); white solid; yield:
88% (138 mg, 76%); mp 152–1558C; 1H NMR (400 MHz,
CDCl3): d=8.63 (s, 1H), 8.40 (d, J=8 Hz, 1H), 8.21 (d, J=
8 Hz, 1H), 7.83 (s, 3H), 7.69 (t, J=8 Hz, 1H), 6.82 (br s,
1H), 4.805 (d, J=4 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=165.3, 148.4, 140.5, 135.3, 133.5, 132.4 (q, JC,F =66.5 Hz),
130.3, 128.2 (d, JC,F =3 Hz), 126.7, 123.3 (q, JC,F =536 Hz),
3-Nitro-N-phenethylbenzamide (3u): Rf =0.20 (ethyl ace-
tate/hexane=1:4); white solid; yield: 90% (97 mg, 78%);
mp 118–1208C; 1H NMR (400 MHz, CDCl3): d=8.51 (s,
1H), 8.35 (d, J=8 Hz, 1H), 8.08 (d, J=8 Hz, 1H), 7.63 (t,
J=8 Hz, 1H), 7.32 (dt, J=17, 7.8 Hz, 5H), 6.28 (br s, 1H),
3.77 (dd, J=12, 6 Hz, 2H), 2.98 (t, J=6 Hz, 2H); 13C NMR
(100 MHz, CDCl3): d=165.1, 148.3, 138.6, 136.4, 133.1,
130.0, 128.9, 128.9, 126.9, 126.1, 121.8, 41.5, 35.6; IR (KBr):
˜
122.0 (q, JC,F =10 Hz), 43.7; IR (KBr): n=3315 (w), 3087
˜
n=3305 (m), 3085 (s), 3032 (s), 2923 (s), 1644 (m), 1530
(m), 2924 (m), 2853 (s), 1645 (m), 1531 (s), 1351 (s), 1278
(s), 1174 (m), 1133 (m), 898 (s), 705 (s) cmÀ1; HR-MS (ESI-
TOF): m/z=393.0680, calcd. for C16H11F6N2O3 (M+H+):
393.0668.
(m), 1350 (m), 1322 (m), 906 (s), 814 (s), 719 (s) cmÀ1; HR-
MS (ESI-TOF): m/z=271.1088, calcd. for C15H15N2O3 (M+
H+): 271.1077.
N-[3,5-Bis(trifluoromethyl)benzyl]-4-cyanobenzamide
(3v): Rf =0.32 (ethyl acetate/hexane=1:4); white solid;
yield: 85% (143 mg, 72%); mp 166–1708C; 1H NMR
(400 MHz, CDCl3): d=7.91 (d, J=8 Hz, 2H), 7.82–7.81 (m,
3H), 7.77 (d, J=8 Hz, 2H), 6.70 (br s, 1H), 4.775 (d, J=
4 Hz, 2H); 13C NMR (100 MHz, CDCl3): d=166.0, 140.5,
137.6, 132.8, 132.4 (q, JC,F =79.5 Hz), 128.1 (d, JC,F =3 Hz),
127.9, 123.3 (q, JC,F =543 Hz), 122.0 (q, JC,F =7 Hz), 117.9,
N-(4-Fluorobenzyl)-3-nitrobenzamide (3aa): Rf =0.20
(ethyl acetate/hexane=1:4); white solid; yield: 84% (93 mg,
73%); mp 119–1218C; H NMR (400 MHz, CDCl3): d=8.59
1
(s, 1H), 8.36 (d, J=7.3 Hz, 1H), 8.18 (d, J=7.1 Hz, 1H),
7.65 (t, J=7.6 Hz, 1H), 7.34 (s, 2H), 7.05 (t, J=7.5 Hz, 2H),
6.57 (brs, 1H), 4.64 (d, J=4.4 Hz, 2H); 13C NMR (100 MHz,
CDCl3): d=165.0, 162.5 (d, 1JC,F =245 Hz), 148.3, 135.9,
133.5 (d, 4JC,F =3 Hz), 133.4, 130.0, 129.9 (d, 3JC,F =8 Hz),
2
˜
126.4, 121.9, 115.9 (d, JC,F =21 Hz), 43.8; IR (KBr): n=3290
˜
115.8, 43.5; IR (KBr): n=3407 (w), 3249 (m), 3050 (s), 2920
(w), 3087 (s), 1640 (m), 1557 (m), 1525 (s), 1509 (s), 1350
(s), 1320 (m), 1216 (m), 1157 (s), 1095 (s), 820 (m), 673 (s)
(s), 2851 (s), 2234 (s), 1642 (m), 1543 (m), 1307 (s), 1278
(m), 1160 (s), 1116 (m), 985 (s), 703 (s) cmÀ1; HR-MS (ESI-
TOF): m/z=373.0770, calcd. for C17H11F6N2O (M+H+):
373.0770.
cmÀ1
;
HR-MS (ESI-TOF): m/z=275.0829, calcd. for
C14H12FN2O3 (M+H+): 275.0826.
N-[3,5-Bis(trifluoromethyl)benzyl]-4-chlorobenzamide
(3w): Rf =0.40 (ethyl acetate/hexane=1:4); white solid;
yield: 83% (124 mg, 65%); mp 137–1418C; 1H NMR
(400 MHz, CDCl3): d=7.80 (s, 3H), 7.75 (d, J=8.4 Hz, 2H),
7.44 (d, J=8.4 Hz, 2H), 6.58 (s, 1H), 4.76 (d, J=6.0 Hz,
2H); 13C NMR (100 MHz, CDCl3): d=166.7, 140.9, 138.5,
Acknowledgements
We are thankful to DST (New Delhi, India), (Grant no. INT/
FINLAND/P-06 and SR/S1/IC-59/2010) for financial sup-
port. TKA is thankful to UGC (India) for a fellowship.
132.3 (q, JC,F =66 Hz), 132.1, 129.2, 128.6, 128.0 (d, JC,F
=
3 Hz), 123.3 (q, JC,F =542 Hz), 121.8 (q, JC,F =8 Hz), 43.4; IR
˜
(KBr): n=3286 (w), 3076 (m), 2927 (s), 1640 (s), 1538 (m),
1487 (m), 1278 (s), 1173 (s), 1132 (s), 845 (m), 705 (s) cmÀ1
HR-MS (ESI-TOF): m/z=382.0451, calcd. for
C16H11ClF6NO (M+H+): 382.0428.
;
3984
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ꢂ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2015, 357, 3977 – 3985

FULL PAPERS
Transformation of Contact-Explosives Primary Amines Iodine(III)
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