Tetranitroacetimidic acid: A high oxygen oxidizer and potential replacement for ammonium perchlorate

Article abstract of DOI:10.1021/ja5074036

Considerable work has been focused on developing replacements for ammonium perchlorate (AP), a primary choice for solid rocket and missile propellants, due to environmental concerns resulting from the release of perchlorate into groundwater systems, which has been linked to thyroid cancer. Additionally, the generation of hydrochloric acid contributes to high concentrations of acid rain and to ozone layer depletion. En route to synthesizing salts that contain cationic FOX-7, a novel, high oxygen-containing oxidizer, tetranitroacetimidic acid (TNAA), has been synthesized and fully characterized. The properties of TNAA were found to be exceptional, with a calculated specific impulse exceeding that of AP, leading to its high potential as a replacement for AP. TNAA can be synthesized easily in a one-step process by the nitration of FOX-7 in high yield (>93%). The synthesis, properties, and chemical reactivity of TNAA have been examined.

Full text of DOI:10.1021/ja5074036

Subscriber access provided by Penn State | University Libraries
Communication
Tetranitroacetimidic acid (TNAA) – A High Oxygen Oxidizer
and Potential Replacement for Ammonium Perchlorate
Thao T. Vo, Damon A. Parrish, and Jean'ne M. Shreeve
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja5074036 • Publication Date (Web): 08 Aug 2014
Downloaded from http://pubs.acs.org on August 11, 2014
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.

Page 1 of 6
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Tetranitroacetimidic acid (TNAA) – A High Oxygen Oxidizer
and Potential Replacement for Ammonium Perchlorate
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Thao T. Vo§, Damon A. Parrish‡, and Jean’ne M. Shreeve*,
§
Department of Chemistry, University of Idaho, Moscow, Idaho 83844‐2343, United States
Naval Research Laboratory, 4555 Overlook Avenue, Washington, D. C. 20375, United States
Supporting Information Placeholder
ABSTRACT: Considerable work has been focused on developing replacements for ammonium perchlorate, a primary choice for
solid rocket and missile propellants, due to environmental concerns resulting from the release of perchlorate into ground water
systems, which have been linked to thyroid cancer. Additionally, the generation of hydrochloric acid contributes to high
concentrations of acid rain and to ozone layer depletion. En route to synthesizing salts which contain cationic FOX‐7, a novel,
high oxygen‐containing oxidizer, tetranitroacetimidic acid (TNAA), has been synthesized and fully characterized. The properties
of TNAA were found to be exceptional with a calculated specific impulse exceeding that of ammonium perchlorate (AP), leading
to its high potential as a replacement for AP. TNAA can be synthesized easily in a one step process by the nitration of FOX‐7 in
high yield (>93%). The synthesis, properties, and chemical reactivity of TNAA have been examined.
Ammonium perchlorate (AP) has long been the primary
choice as an oxidizer in propellants for rockets and
missiles.1,2 However, significant global efforts to replace AP
stems from environmental concerns due to the release of
perchlorate into ground water systems and the generation of
hydrogen chloride during burning – enhancing acid rain and
depletion of the ozone layer.3 The contamination in soil and
water has driven major health concerns as perchlorates can
affect normal thyroid functions by competing with the
binding sites of iodine and is linked to thyroid cancer.4 In
addition, a major disadvantage of AP is that the chlorine
content causes a smoke that can be easily detected by radar
or when the humidity is high, a white smoke can be seen
easily.5 Therefore, considerable effort has been made to
replace AP in propellant formulations. Among the chlorine‐
free oxidizers developed, ammonium dinitroamide (ADN)
and hydrazinium nitroformate (HNF) have risen as potential
replacements for AP since their properties are comparable
and the reduced introduction of harmful contaminants into
the environment make them appealing.4,6,7 However, both
suffer from drawbacks due to their sensitivity towards impact
and friction and ADN’s high hygroscopic nature.5,8 Therefore,
further research is required to develop oxidizers that are
stable, environmentally friendly and readily synthesized (in
good yields) to become suitable for replacing AP.
FOX‐7 and HFOX cations.10 This work demonstrated the
amphoteric properties of FOX‐7 and HFOX and gave rise to
new potential building blocks for energetic salts. Among the
acids examined, the reaction of FOX‐7 with fuming nitric
acid led to the formation of the title compound,
tetranitroacetimidic acid (TNAA), rather than the
anticipated nitrate salt. Few examples of the conversion of
gem‐dinitro substrates to trinitromethyl complexes have
been reported which makes the chemical formation of TNAA
of interest.11 Following characterization of TNAA, this
exciting new molecule was found to have applications as an
efficient oxidizer with properties exceeding those of AP and
comparable to ADN and HNF. Now we describe our
contributions to the new chemistry of FOX‐7 and to the
development of a likely new oxidizer through the synthesis
and full characterization of TNAA concomitantly with its
potential application as a suitable replacement for AP.
Tetranitroacetimidic acid, TNAA (2), was synthesized by
the reaction of FOX‐7 (1) with an excess of fuming nitric acid
to leave colorless crystals after removal of the excess acid in
vacuo (Scheme 1). Unlike the cationic salts of FOX‐7
obtained with other strong acids,10 compound 2 is stable at
room temperature for long periods and is non‐hygroscopic.
Scheme 1. Synthesis of 2.
For some time our group has been interested in expanding
the chemistry of 1,1‐diamino‐2,2‐dinitroethene (FOX‐7),9 an
insensitive energetic material which has attracted
considerable attention as a potential replacement for some
commonly used sensitive explosives.1 We recently examined
the reactivity of FOX‐7 and its hydrazine derivative, 1‐amino‐
1‐hydrazino‐2,2‐dinitroethene (HFOX), with a variety of
strong acids which led to the first isolated salts that contain
The colorless crystals may yellow slightly over time. TNAA is
only slightly soluble in most organic solvents, but can be
partially dissolved in ethyl acetate and dichloromethane. It is
unstable in acetonitrile as became evident when dissolved in
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 6
deuterated acetonitrile for NMR studies. The compound
that formation of the trinitromethyl moiety could result from
1
2
3
4
5
6
7
8
began to decompose, generating heat, and bubbles of a
brown gas (nitrogen dioxide). Decomposition also occurs in
DMSO.
two potential routes: 1) an attack on a nitronium ion by the
nitrovinyl carbon with concomitant loss of a proton from the
amino nitrogen or 2) nitration of the amine nitrogen;
however, the reaction order is unknown.12
The structure of 2 was determined by single crystal X‐ray
analysis (Figure 1). It crystallizes in the monoclinic space
In our current work, 3 may have formed, but due to the
lack of a scavenging agent to take up the resulting water, the
latter may react further with the amine intermediate (3),
leading to 2. It should be noted that in the preparation of 2, it
is important to use freshly distilled fuming nitric acid and to
remove all the excess acid prior to exposing the sample to air.
If residual amounts of the acid remain, 2 slowly transforms to
nitrourea (4) as was confirmed by single crystal X‐ray
analysis. Surprisingly, no crystal data for nitrourea were
found in the records of the Cambridge Crystallographic Data
Center. Its crystal structure data is given in the Supporting
Information. Formation of 2 is also dependent on the
concentration of the nitric acid. When 1 was treated with
commercially available 65% nitric acid (~16 M) and allowed
to stir overnight, brown gas (nitrogen dioxide) was found
over the solution inside the reaction flask. The reaction was
quenched with ice and the product was extracted with
dichloromethane to yield amidinoformic acid (5). The
formation of 5 was previously reported by reacting 1 with a
variety of organic peroxides such as 30% hydrogen peroxide
(H2O2), Caro’s acid (H2SO5) or peroxytrifluoroacetic acid
(CF3CO3H) (Scheme 3).13a
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Figure 1. Thermal ellipsoids plot (50%) ‐ single crystal X‐ray
structure of 2.
group P21/c system with four molecules per unit cell. The C‐C
bond distance (1.53 Å) agrees with the average bond distance
for a single C‐C bond (1.54 Å). Upon closer examination of
the C2‐N3 and C2‐O16 bond distances, the C‐N bond
distance of 2 (1.31 Å) is slightly shorter than the average bond
distance for a single C‐N bond (1.47 Å) and slightly longer
than C=N (1.22 Å). Also, the C‐O bond distance of 1.29 Å is
slightly longer than that of C=O (1.23 Å), suggesting that 2
may exist as an equilibrium between the two forms as shown
in Figure 2. Mass spectroscopy (EI) was also used to verify
the structure of 2. The parent peak at 239 amu, a signal at
240 amu assigned to M++1 and a strong signal at 150 amu
assigned to the trinitromethyl group [‐C(NO2)3] were
observed. The amino derivative of 2, compound 3, was
synthesized earlier by nitrating 1 with a mixture of nitric
Scheme 3. Synthesis of 5 from 1 with organic peroxides.
Based on the literature precedence for the formation of 5, it
is likely that the same proposed mechanism is suitable when
FOX‐7 is reacted with 65% HNO3 rather than with the
peroxide (Scheme 4). The loss of HNO2 leads to intermediate
7 which can undergo a nitro
̶
nitrito rearrangement13b to form
Figure 2. Possible equilibrium between two forms of 2 based
on bond lengths.
Table 1. Physical properties of AP, ADN and TNAA
AP
NH4ClO4
‐‐‐
ADNa
HNFb
2
acid, trifluoroacetic anhydride, and trifluoroacetic acid
(Scheme 2).11 However, 3 was isolated as an oil and found to
be very unstable at room temperature. Characterization of 3
has not been reported. Indirect structural deduction of 3 was
accomplished by reacting it with ammonia in acetonitrile to
obtain the stable products ammonium trinitromethanide and
mononitroguanidine.11
Formula
Tmc (°C)
Tdecd (°C)
ISe (J)
NH4N(NO2)2
N2H5C(NO2)3
C2HN5O8
93
159
3–5
64–72
52
45
26
129
131
4
28
38
52
13
91
137
19
20
29
60
30
> 200
15f
FSg (N)
Ni%
> 360h
11
Oj%
54
26
1.95
156
OBk %
dl (gcm‐3)
Ispo (s)
1.81
1.86
1.87m(1.84)n
209
202p
265q
Scheme 2. Reaction of 1 with a mixture of nitric acid,
trifluoroacetic anhydride (TFAA), and trifluoroacetic
acid (TFA) to form compound 3.
a) [Ref. 3] b) [Ref. 8]. c) Melting temperature. d) Decomposition
temperature [onset]. e) Impact sensitivity. f) Ref. 1. g) Friction sensitivity.
h) Measured FS. i) Nitrogen content. j) Oxygen content. k) Oxygen
balance. l) Density. m) Measured density. n) Crystal density. o) Specific
impulse [values were obtained from Explo5 v6.01 and calculated at an
isobaric pressure of 70 bar and initial temperature of 3,300 K]. p)
Calculated via Explo 5 v6.01. q) [Ref. 5].
8 in step 3 of Scheme 4. Nucleophilic attack of the nitrite ion
with intermediate
8 followed by the displacement of
The
nitration
of
1,1,‐diamino‐2,2,‐dinitroethylene
dinitrogen trioxide leads to the formation of product 5 (step
derivatives examined by Baum and co‐workers suggested
ACS Paragon Plus Environment

Page 3 of 6 Journal of the American Chemical Society
Scheme 4. Proposed mechanism for formation of 5 from 1 with 65% HNO3.
1
2
3
4
5
6
7
8
9
3). The lack of formation of 2 with 65% HNO3 may be a result
of the quenching step with water. When the reaction was
attempted without quenching, the excess acid was removed
under vacuum to give an unknown white solid. Therefore,
the water content present in 65% HNO3 compared to fuming
HNO3 may play a significant role in the formation of
compound 5 versus 2.
Attempts to extend this acid chemistry to HFOX with
fuming nitric acid under neat conditions resulted in
combustion of HFOX after the addition of the second drop of
nitric acid. Subsequently HFOX was suspended in
acetonitrile and cooled in an ice bath before addition of
nitric acid. When the excess acid and solvent was removed,
white needles were obtained. Upon repeating this reaction
several times, the final product exploded at reduced pressure.
Because of safety concerns, this chemistry was no longer
pursued. Any attempts to study this chemistry should be
accomplished with extreme caution keeping in mind that
HFOX itself can spontaneously detonate.
Compound 2 is a very attractive and promising stable
oxidizer (MP 91°C and Td (onset) 137 °C ) with a majority of its
properties (calculated via Explo5 v6.01) exceeding that of AP
(Table 1). It was also found to have properties that were
comparable to ADN and HNF. Compared to AP, 2 has a
significantly enhanced nitrogen and oxygen content and
higher positive oxygen balance due to the trinitromethyl
group. The oxygen balance is a measure of the amount of
oxygen available for combustion of energetic materials.
Positive OBs indicate there is more than enough oxygen to
convert all carbon to carbon monoxide and all hydrogen to
water whereas negative values indicate that the oxygen
content is insufficient for complete oxidation. The specific
impulse (Isp) is a measure of a propellant’s efficiency.
Compared to AP, 2 has a higher specific impulse (209 s) and
trinitromethanide (10), first reported in 1920, was isolated.14
Interestingly the crystal structure of 10 had not been
recorded at the Cambridge Crystallographic Data Centre.
Suitable crystals of 10 were isolated and single crystal X‐ray
analysis was obtained to complete the structural analysis (see
Supporting Information). The reactivity of 2 with simple
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 5. Reaction of 2 with P4O10 and Olah’s reagent.
bases was then examined. When sodium hydroxide was
added to a suspension of 2 in water, sodium carbonate and
sodium nitroform were isolated. Similar results were
observed when sodium bicarbonate, ammonia or
guanidinium carbonate was reacted with 2 where the
corresponding trinitromethanide salt was isolated and
verified by elemental and crystal structure analysis. These
results indicated the highly reactive nature of the amide
moiety with bases.
Compound 2 with acids was also examined. By studying a
variety of weak and strong acids [i.e., trifluoroacetic acid
(pKa = 0.5), hydrochloric acid (pKa = ‐7), and perchloric acid
(pKa = ‐10)], it was found that 2 only reacted with triflic acid
(CF3SO3H; pKa = ‐15). When 2 was stirred with an excess of
°
triflic acid under neat conditions for 30 minutes at 25 C,
colorless crystals were obtained after the removal of the
majority of the acid over an extended period in vacuo. These
hygroscopic crystals were identified as the cocrystal salt 11
containing a 1:1 ratio of 1‐amino‐2,2,2‐trinitroethaniminium
triflate and triflate hydrate via single crystal X‐ray analysis
(Scheme 6; Figure 3). They can be stored at room
temperature under vacuum for several weeks without
is slightly more stable towards impact (19 J) with
a
comparable density. In comparison to ADN, 2 is significantly
more stable towards impact with enhanced or comparable
properties. It is interesting to note that the calculated ISP value
(Explo 5 v6.01) of a fuel mixture comprised of HTPB/TNAA/Al
(12/68/20) is 261 s which shows that TNAA is even more
effective in a mixed fuel system (HTPB = hydroxyl-terminated
polybutadiene). However, the thermal stability and friction
sensitivity of 2 are not competitive with AP and is slightly
less than that of ADN. Enhancing these two properties may
make 2 even more appealing and a better substitute for AP.
Therefore we were prompted to study the chemical reactivity
of 2 to understand and enhance the molecular structure to
obtain the desired properties.
The unique structure of 2 and the likely existence of the
two forms (Figure 2) may explain its challenging reaction
chemistry. Our initial studies began with examining the
reactivity of the hydroxyl group in 2. Attempts to dimerize
compound 2 with P4O10 were unsuccessful (Scheme 5,
structure 9). In an effort to replace the hydroxyl group by
fluorine with Olah’s reagent (pyridine/HF), no fluorinated
product was observed and rather the long known pyridinium
Scheme 6. Reaction of 2 with CF3SO3H.
decomposition. In addition to X‐ray crystal structure, the
structure of 11 was also supported by 13C and 19F NMR,
elemental analysis. The cocrystal salt (11) crystallizes in a
triclinic space group P‐1 with two molecules per unit cell and
has a crystal density of 1.48 gcm‐3. The C‐C bond distance
(C1‐C2, 1.53 Å) agrees with the average bond distanc for a
ACS Paragon Plus Environment

Journal of the American Chemical Society
ASSOCIATED CONTENT
Page 4 of 6
1
2
Supporting Information
Experimental procedures, characterization data (single
crystal X‐ray), and heat of formation calculations. This
material is available free of charge via the Internet at
http://pubs.acs.org.
3
4
5
6
7
8
Figure 3. Single crystal X‐ray structure of salt 11 ‐ thermal
ellipsoids plot (50%).
AUTHOR INFORMATION
9
Corresponding Author
single C‐C (1.54 Å) bond. Examining the bond distance of
C2‐N1 (1.29) and C2‐N2 (1.30), the C‐N bond distance is
shorter than the average bond distance for a single C‐N
single bond (1.47 Å) and longer than the average C=N
double bond (1.22 Å) suggesting that the positive charge is
delocalized over the atoms N1‐C2‐N2.10
The unexpected reduction of the N‐NO2 group of 2 in the
formation of the trinitroethaniminium cation in 11 is
supported by the literature for the unique ability of triflic
acid to reduce the nitro group in nitrobenzyl alcohol.15
However, further investigation is necessary to understand
the mechanistic transformation of the 1‐amino‐2,2,2‐
trinitroethaniminium cation.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
jshreeve@uidaho.edu
ACKNOWLEDGMENT
The authors gratefully acknowledge the support of ONR
(N00014‐12‐1‐0536 and N00014‐11‐AF‐0‐0002), and the
Defense Threat Reduction Agency (HDTRA 1‐11‐1‐0034). We
are indebted to Mr. Scott Economu and Dr. Brendan
Twamley for considerable assistance with crystal structuring.
REFERENCES
(1)Klapötke, T.
M. Chemistry
of
High‐Energy
Materials; Walter de Gruyter GmbH & Co. KG:Berlin/New
York, 2011; pp 179–184.
(2) Klapötke, T. M.; Gökçinar, E. Turk. J. Chem. 2010, 34,
953–967.
(3) Nagamachi, M. Y.; Oliveira, J. I. S.; Kawamoto, A. M.;
Dutram, R. C. L. J. Aerosp. Technol. Manag., 2009, 1, 153–160
(4) Mandal, A. K.; Kunjir, G. M.; Singh, J.; Adhav, S. S.;
Singh, S. K.; Pandey, R. K.; Bhattacharya, B.; Kantam, M. L.
Cent. Eur. J. Energetic Mater. 2014, 11, 83–97.
(5) Silva, G. D.; Rufino, S. C.; Iha, K. J. Aerosp. Technol.
Manag. 2013, 5, 139–144.
(6) Jadhav, H. S.; Talawar, M. B.; Dhavale, D. D.; Asthana, S.
N.; Krishnamurthy, V. N. Indian J. Chem. Tech. 2005, 12, 187–
192.
(7) Dendage, P. S.; Sarwade, D. B.; Asthana, S. N.; Singh, H. J.
Energ. Mater. 2001, 19, 41–78.
(8) Joo, Y.‐H.; Min, B. S. New J. Chem. 2014, 38, 50–54.
(9) (a) Garg, S.; Gao, H.; Joo, Y.‐H.; Parrish, D. A.; Shreeve, J.
M. J. Am. Chem. Soc. 2010, 132, 8888–8890 and references
cited therein. (b) Garg, S.; Gao, H.; Parrish, D. A.; Shreeve, J.
M. Inorg. Chem. 2011, 50, 390–395 and references cited
therein. (c) Gao, H.; Shreeve, J. M. Chem. Rev. 2011, 111, 7377–
7436. (d) Gao, H.; Joo, Y.‐H.; Parrish, D. A.; Vo, T.; Shreeve, J.
M. Chem. Eur. J. 2011, 17, 4613–4618. (e) Vo, T. T.; Parrish, D.
A.; Shreeve, J. M. Inorg. Chem. 2012, 51, 1963–1968 and
references cited therein. (f) Vo, T. T.; Zhang, J.; Parrish, D. A.;
Twamley, B.; Shreeve, J. M. J. Am. Chem. Soc. 2013, 135, 11787–
11790.
The existence of the 1‐amino‐2,2,2‐trinitroethaniminium
cation in 11 is interesting due to its appeal as a precursor for
energetic salts. Typical cations used for energetic salts have
high nitrogen and low oxygen content; however, the cation
of 11 has both high nitrogen and oxygen content, making it
an ideal building block for energetic salts. The density of
trinitroethaniminium triflate of cocrystal salt 11 was
calculated (by literature method)16 to be 2.09 gcm‐3 with a
detonation pressure (P), detonation velocity (V), and Isp
(calcluated via Explo 5 v6.01), of 25 Gpa, 7208 ms‐1 and 247 s
respectively. The low energetic performance is expected as
the counter ion is non‐energetic. When the 1‐amino‐2,2,2‐
trinitroethaniminium cation is parlayed with dinitroamide
‐
[N(NO2)2 ] (12), the density (calculated)16 was found to be
2.06 gcm‐3 with high detonation performances (V = 9053 ms‐1;
P = 36 Gpa), exceeding the values of FOX‐7 (V = 8771 ms‐1, P
=
35 GPa) and RDX (cyclo‐1,3,5‐trimethylene‐2,4,6‐
trinitramine; V = 8864 ms‐1, P = 36 GPa) (see Supporting
Information). Further investigation is required to enhance
the stability of 11 with anions that are suitable to stabilize the
1‐amino‐2,2,2‐trinitroethaniminium cation, which may give
rise to interesting and powerful energetic salts.
In summary, the chemical reactivity of FOX‐7 has been
expanded via the synthesis and characterization of a new
oxidizer, TNAA (2), which results from a simple single step
process from FOX‐7 in high yield (> 93%). This novel
molecule has a high potential for replacing AP as an oxidizer
for applications in solid rocket propellants and missiles.
Compound 2 is more stable towards impact than AP and
DNA with enhanced or comparable properties. The reaction
chemistry of 2 leads to some interesting insights in its
synthesis and reactivity such as the formation of 11. The 1‐
amino‐2,2,2‐trinitroethaniminium cation of 11 represents a
very promising energetic precursor for energetic salts due to
its high nitrogen and oxygen content. Compound 2 exhibits
an interesting molecular structure that adds to the examples
of transformation of the gem‐dinitro system to
trinitromethyl‐containing materials. As is the case for FOX‐7,
the chemical reactivity of 2 needs further investigation in
order to fully explore its reaction chemistry.
(10) Vo, T. T.; Parrish, D. A.; Shreeve, J. M. Private
Communication.
(11) Hervé, G.; Jacob, G.; Latypov, N. Tetrahedron, 2005, 61,
6743–6748.
(12) Baum, K.; Nguyen, N. V.; Gilardi, R.; Flippen‐Anderson, J.
L.; George, C. J. Org. Chem. 1992, 57, 3026–3030.
(13) (a) Hervé, G.; Jacob, G. Tetrahedron, 2007, 63, 953–959.
(b) Amin, M. R.; Dekker, L.; Hibbert, D. B.; Ridd, J. H.;
Sandall, J. P. B. J. Chem. Soc., Chem. Commun. 1986, 658 –
659.
(14) Schmidt, E.; Fischer, H. Ber. Dtsch. Chem. Ges., 1920, 53,
1529 – 1537.
ACS Paragon Plus Environment

Page 5 of 6
Journal of the American Chemical Society
(15) Austin, R. P.; Ridd, J. H. J. Chem. Soc., Perkin Trans.2,
1994, 1411–1414.
(16) (a) Ye, C.; Shreeve, J. M. J. Phys. Chem. A. 2007, 111, 1456–
1461. b) Gao, H.; Ye, C.; Piekarski, C. M.; Shreeve, J. M. J.
Phys. Chem. C, 2007, 111, 10718–10731.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 6 of 6
Insert Table of Contents artwork here
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
6
ACS Paragon Plus Environment