Anti-migration and Combustion Catalytic Performances of Ferrocenyl Compounds of Anilines and Alkylamines Synthesized by Click Reaction

Article abstract of DOI:10.1002/zaac.202000322

To enhance anti-migratory performance and combustion catalytic activities of neutral ferrocene-based burning rate catalysts (BRCs), nine ferrocenyl 1,2,3-triazolyl compounds of anilines and aliphatic amines (Fc-ATAZs, 1–9) were synthesized by click reaction and characterized by NMR, UV/Vis, FT-IR, and MS. TG and DSC studies confirmed that the Fc-ATAZs are highly thermal stable. Cyclic voltammetry results implied that 1 and 6 are reversible redox systems. The anti-migration and anti-volatility tests showed that the Fc-ATAZs are low-migratory and low-volatile compounds.Combustion catalytic activity results of the Fc-ATAZs revealed that they are highly active for promoting thermal disintegration of AP, RDX and HMX. Compounds 3, 2 and 8 can increase released heats of AP, RDX and HMX, respectively, by 132 %, 112 % and 36 %, respectively, being the highest in each case. Most of them are more active than the reported analogs derived from phenols and benzoic acids. They, except 9, are more active than catocene and can be used as potential BRCs in composite solid propellants.

Full text of DOI:10.1002/zaac.202000322

Journal of Inorganic and General Chemistry
DOI: 10.1002/zaac.202000322
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
Anti-migration and Combustion Catalytic Performances of
Ferrocenyl Compounds of Anilines and Alkylamines Synthesized
by Click Reaction
Xiaoling Shi,[a] Wenqian Cheng,[a] Liping Jiang,[b] Fuqiang Bi,[b] Jizhen Li,[b] and Guofang Zhang*[a]
Abstract. To enhance anti-migratory performance and combustion
catalytic activities of neutral ferrocene-based burning rate catalysts
tivity results of the Fc-ATAZs revealed that they are highly active for
promoting thermal disintegration of AP, RDX and HMX. Compounds
(BRCs), nine ferrocenyl 1,2,3-triazolyl compounds of anilines and ali- 3, 2 and 8 can increase released heats of AP, RDX and HMX, respec-
phatic amines (Fc-ATAZs, 1–9) were synthesized by click reaction and
characterized by NMR, UV/Vis, FT-IR, and MS. TG and DSC studies
confirmed that the Fc-ATAZs are highly thermal stable. Cyclic voltam-
tively, by 132%, 112% and 36%, respectively, being the highest in
each case. Most of them are more active than the reported analogs
derived from phenols and benzoic acids. They, except 9, are more
metry results implied that 1 and 6 are reversible redox systems. The active than catocene and can be used as potential BRCs in composite
anti-migration and anti-volatility tests showed that the Fc-ATAZs are
low-migratory and low-volatile compounds.Combustion catalytic ac-
solid propellants.
gration tendency and acceptable synthetic costs.[3] Although
catocene is currently applied broadly in composite solid pro-
pellants as BRC, some unavoidable problems still exist. It was
reported that the mixture of catocene and ultra ammonia per-
chlorate (AP) exhibited highly electrostatic sensitivity during
the propellant curing and in some cases gave rise to dangerous
issues.[3a] Catocene can migrate slowly to the surface of the
propellant grain to form a brown shell, which can be ignited
easily. The enlargement of the burning area will increase gas
pressure in the combustion chamber and lead to unsteady com-
bustion process of the propellants, and lastly could pose a po-
tential explosion danger towards the solid rocket engine.[4]
In last few decades researchers have taken great efforts to
overcome high-migration and high-volatility problems of the
marketed ferrocene-based BRCs by means of diverse ap-
proaches including, for examples, developing ferrocenyl
group-grafted polymers and dendrimers, introducing concepts
of coordination chemistry and ionic liquid, increasing molecu-
lar weights of the ferrocene-based BRCs by synthesizing poly-
nuclear ferrocene derivatives, incorporating polar atoms (O
and/or N) in the alkylferrocene molecules to improve their mo-
lecular polarity and interaction with other components in the
propellants.[5–9] The famous one is butacene, which was syn-
thesized by grafting ferrocenylalkylsilyl groups to hydroxyl-
terminated polybutadiene (HTPB) main chain to form a pre-
polymer, which can be cross-linked with TDI to form elasto-
mers in the propellants. In this case, butadiene played roles as
both ferrocene-based BRC and modified binder in a composite
solid propellant and has been marketed in European and Latin
America.[5] Researchers also modified HTPB polymeric mol-
ecules with ferrocenyl groups by other methods and the com-
posite propellants containing ferrocene-modified HTPB pre-
polymers exhibited excellent combustion properties.[6a,6b]
F. J Xiao and L. Wang et al. synthesized ferrocenyl group-
Introduction
Ferrocene is a classic organometallics and its discovery was
known as a milestone in the history of organometallic chemis-
try due to its high thermal and chemical stabilities, excellent
electrochemical properties and easy modification.[1] Ferrocene
and its derivatives have been widely applied in industry, agri-
culture, medicine, aerospace and other fields.[1] One of their
important applications is to use them as combustion modifiers
in car and rocket engines to improve combustion efficiency
of fuels. Alkylferrocenes are usually utilized as additives in
composite solid propellants to enhance combustion rates and
decrease pressure index of the propellants.[2] Initially, mononu-
clear ferrocenyl compounds such as n-butylferrocene (NBF)
and tert-butylferrocene (TBF) were employed in the propel-
lants as burning rate catalysts (BRCs). It is found, however,
that these compounds exhibit high-volatility during fabrication
of the propellants and high-migratory trends during long-time
storage of the propellants, due to their lower molecular
weights.
Then a series of dinuclear ferrocenyl derivatives including
2,2-bis(ethylferrocenyl)propane (catocene), 2,2-bis(butylferro-
cenyl)propane (BBFPr) and 2,2-bis(butylferrocenyl)pentane
(BBFPe) were developed, among them catocene was commer-
cialized due to its excellent combustion efficiency, lower mi-
* Prof. Dr. G. Zhang
Fax: +86-29-81530830
E-Mail: gfzhang@snnu.edu.cn
[a] Key Laboratory of Applied Surface and Colloid Chemistry, MOE/
School of Chemistry and Chemical Engineering
Shaanxi Normal University
Xi’an, 710119, P. R. China
[b] Xi’an Modern Chemistry Research Institute
Xi’an, 710065, P. R. China
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.202000322 or from the au-
thor.
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were conducted on a Bruker Avance 400 MHz spectrometer. High-
incorporated polymers and dendrimers and found that they are
low- and even non-migratory ferrocenyl derivatives.[6c–6f]
H. Y. Zhao, Y. F. Yuan and our groups prepared transition-metal
coordination compounds derived from ferrocenyl-containing
ligands and found that the new complexes show no migration
properties and high catalytic activity in the AP thermal decom-
position.[7] C. Morales-Verdejo and co-workers obtained a few
homo- and hetero-nuclear metallocenes, which are good anti-
migration BRC candidates.[8]
resolution ESI-MS were acquired on a Bruker maXis spectrometer.
UV/Vis absorption spectra were performed on a UV-2450 spectro-
photometer. Elemental analyses were achieved using a Vario EL III
Elemental Analyzer. TG and DSC studies were executed on Q50 and
HS-1 models, respectively, under N2 (50 mL min–1) at 5 °C·min–1 with
sample mass between 2.95–3.05 mg. Cyclic voltammetry (CV) studies
were recorded using a CHI660C analyzer, on which a platinum work-
ing electrode and an Ag/Ag+ reference electrode were used. The tested
compounds were solved in deoxygened 0.1 mol·L–1 nBu4NPF6-DMSO
In the last decade our group developed a large number of supporting electrolyte before the measurement.
ionic ferrocenyl compounds to retard high-migration issues of
Synthesis of Compounds 1–9: Owing to the similar preparation
alkylferrocenes by introduction the concept of ionic liquids.[9]
Recently, by means of the well known copper-catalyzed azide
alkyne cycloaddition (CuAAC) approach,[10] we synthesized
a series of ferrocene-functionalized 1,2,3-triazolyl compounds
with phenols and benzoic acids as starting materials, and we
found that they show excellent anti-migration ability and can
be described as non-migratory ferrocenyl compounds.[11] On
comparison with a OH or a COOH group, a NH2 group can
generally introduce two ferrocenyl 1,2,3-triazolyl units into a
new compound by the synthetic method we used for the syn-
thesis of the ferrocenyl compounds of phenols and benzoic
acids[11] and more nitrogen and iron contents are favorable for
enhancing catalytic activity of a ferrocene-based BRC. Herein
we designed and synthesized nine novel ferrocenyl derivatives
(Fc-ATAZs) with anilines or alkylamines as precursors
(Scheme 1). The molecular structures of the Fc-ATAZs were
characterized completely by 1H NMR, 13C NMR, UV/Vis
spectroscopes, FT-IR, high-resolution MS and elemental analy-
sis. Their thermal stability was measured by DSC and TG.
Electrochemical properties were investigated by cyclic voltam-
metry (CV). Migration and volatility tendency were evaluated
by the method we used, with ferrocene (Fc) and catocene as
references.[11] Their effects on the thermal disintegration of
method of 1–9, N,N-bis(1-ferrocenylmethyl-1H-1,2,3-triazol-4-yl-
methyl) aniline (1) was taken as an example:[11] In a 100 mL round-
bottom flask, 50 mL dried DMF and aniline 1.39 g (15.0 mmol) were
added, then 7.91 g (50.0 mmol) K2CO3 was added stepwise and stirred
at 70 °C for 2 h. Then 2.94 mL (37.5 mmol) propargyl bromide was
added dropwise, the mixture was then stirred and heated for 8 h. The
reaction mixture was cooled to room temperature and filtered. The
DMF in the filtrate was then removed completely by using rotary
evaporator under vacuum. The purified N,N-dipro-2-ynylaniline was
collected by column chromatography using n-hexane/ethyl acetate
(v:v) 5:2 as eluent. In 70 mL methanol 1.01 g (6.0 mmol) N,N-dipro-2-
ynylaniline and 2.92 g (12.1 mmol) azidomethylferrocene were added,
followed by a solution of 0.69 g (2.82 mmol) CuSO4 5H2O in 20 mL
water. Aqueous solution of 0.58 g (2.82 mmol) sodium ascorbate pre-
pared freshly was added and stirred for 24 h at room temperature.
After removal of the solvents under vacuum, the desired product 1 was
collected by using chromatographic technique with dichloromethane/
methanol (v:v) 3:1 as elute.
N,N-bis(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmethyl) aniline
(1): Yellow powder. Yield: 3.33 g (85.2%). M. p.: 152.6–154.1 °C.
FT-IR (KBr): ν˜ = 3316 w, 3087 m, 2935 w, 1681 w, 1591 s, 1501 vs,
1445 m, 1376 m, 1314 s, 1224 s, 1162 m, 1106 m, 1044 s, 989 m, 940
m, 822 vs, 732 s, 683 m, 483 vs. cm–1.1H NMR (400 MHz, CDCl3):
δ = 7.28 (s, 2 H), 7.18 (t, 2 H), 6.85 (d, 2 H), 6.72 (t, 1 H), 5.19 (s, 4
main oxidizers including AP, RDX and HMX were obtained H), 4.61 (s, 4 H), 4.19 (t, 8 H), 4.18 (t, 8 H), 4.13 (s, 10 H). 13C NMR
(101 MHz, CDCl3): δ = 147.96 (NCC5H5), 145.31 (NCCH), 129.28
(NCCH), 121.40, 117.75, 113.68 (C6H5), 81.18, 68.93, 68.88 (C5H4),
68.74 (C5H5), 49.99 (C5H4CH2), 46.89 (CCH2N). MS (m/z, ESI+),
by DSC and/or TG techniques.
652.1552 [M
+
H+]. C34H33Fe2N7+H: 652.1574. C34H33Fe2N7
(651.14): calcd. C, 62.69; H, 5.11; N, 15.05%; found: C, 62.54; H,
5.24; N, 15.10%.
N,N,NЈ,NЈ-tetrakis(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmeth-
yl) o-dianiline (2): Yellow powder. Yield: 6.51 g (88.6 %). M. p.:
112.0–113.5 °C. FT-IR (KBr): ν˜ = 3402 w, 3087 m, 2935 w, 2938 w,
1646 w, 1487 m, 1432 m, 1328 s, 1217 s, 1113 s, 1044 vs, 919 m, 822
1
vs, 739 m, 483 vs. cm–1. H NMR (400 MHz, CDCl3): δ = 7.32 (s, 4
H), 6.75 (s, 4 H), 5.13 (s, 8 H), 4.45 (s, 8 H), 4.19–4.07 (m, 36 H).
13C NMR (101 MHz, CDCl3): δ = 144.35 (NCCH), 142.33 (NCC5),
122.81 (NCCH), 122.73, 121.66 (C6H4), 81.68, 68.84, 68.76 (C5H4),
68.58 (C5H5), 49.78 (C5H4CH2), 45.56 (CCH2N). MS (m/z, ESI+),
1247.2412 [M + Na+ ], 701.4944 (M-(FcCH2 C2 N3 HCH2
+FcCH2N3H2)). C62H60Fe4N14+Na: 1247.2421, for C37H33Fe2N8:
701.1527. C62H60Fe4N14(1224.25): calcd. C,60.81; H, 4.94; N,
16.01%; found: C, 60.91; H, 4.82; N, 16.08%.
Scheme 1. Molecular structures of the Fc-ATAZs compounds 1–9 of
aniline and alkylamines.
Experimental Section
N,N,NЈ,NЈ-tetrakis(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmeth-
yl) m-dianiline (3): Yellow powder. Yield: 6.13 g (83.4%). M. p.:
Materials and Equipment: Azidomethylferrocene was synthesized as
that described previously.[10b] RDX, AP and HMX were offered by 106.4–107.5 °C. FT-IR (KBr): ν˜ = 3094 m, 2928 w, 1715 w, 1591 s,
Xi’an Modern Chemistry Research Institute. 1H and 13C NMR spectra
1494 m, 1445 m, 1321 s, 1217 m, 1182 s, 1106 m, 1037 s, 926 m, 808
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vs, 697 w, 497 vs. cm–1. H NMR (400 MHz, CDCl3): δ = 7.44 (s, 4
N,N,NЈ,NЈ,NЈЈ-pentakis(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-
ylmethyl) diethylenetriamine (8): Light brown powder. Yield: 6.36 g
H), 4.22 (s, 8 H), 4.16 (s, 8 H), 4.13 (s, 20 H). 13C NMR (101 MHz, (80.6%). M. p.: 81.5–83.5 °C. FT-IR (KBr): ν˜ = 3406 w, 3087 m,
CDCl3): δ = 149.09 (NCCH), 145.45 (NCC5), 129.85, 121.88 (NCCH), 2921 m, 2824 m, 1626 m, 1432 m, 1321 s, 1217 m, 1099 m, 1050 vs,
H), 6.94 (t, 1 H), 6.38 (s, 1 H), 6.20 (d, 2 H), 5.19 (s, 8 H), 4.51 (s, 8
103.78, 99.28 (C6H4), 81.42, 68.89, 68.87 (C5H4), 68.80 (C5H5), 49.91 1002 s, 926 w, 815 vs, 711 w, 490 vs. cm–1. 1H NMR (400 MHz,
(C5H4CH2), 46.90 (CCH2N). MS (m/z, ESI+), 1247.2419 [M + Na+],
701.4942 (M-(FcCH2C2N3HCH2 +FcCH2N3H2)). C62H60Fe4N14+Na:
CDCl3): δ = 7.56 (d, 4 H), 7.43 (d, 1 H), 5.22 (s, 10 H), 4.25 (s, 10
H), 4.14 (d, 35 H), 3.62 (s, 10 H), 2.70–2.41 (m, 8 H). 13C NMR
1247.2421, for C37H33Fe2N8: 701.1527. C62H60Fe4N14 (1224.25): (101 MHz, CDCl3): δ = 144.16 (NCCH2), 122.91 (NCHC), 81.47
calcd. C, 60.81; H, 4.94; N, 16.01%; found: C, 60.76; H, 4.99; N,
16.06%.
(C5H4), 68.86 (C5H5), 51.88, 51.56 (C5H4CH2), 49.84 (NCCH2), 49.03
(NCH2CH2), 48.10 (NCH2CH2). MS (m/z, ESI+), 1499.3478 [M + H+],
1258.3176 (M-FcCH2N3). C74H78Fe5N18+H: 1499.3482, for
N,N,NЈ,NЈ-tetrakis(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmeth-
C63H67Fe4N15+H: 1258.3135. C74H78Fe5N18 (1498.34): calcd. C,
yl) p-dianiline (4): Light brown powder. Yield: 6.02 g (81.8 %). 59.30; H, 5.25; N, 16.82%; found: C, 59.12; H, 5.40; N, 16.71%.
M. p.: 176.1–177.4 °C. FT-IR (KBr): ν˜ = 3094 m, 2921 w, 2845 w,
O,N,N-tris(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmethyl)-2-
aminoethanol (9): Yellow powder. Yield: 4.32 g (80.2 %). M. p.:
44.9–46.5 °C. FT-IR (KBr): ν˜ = 3087 w, 2921 s, 2845 m, 1633 m,
1445 m, 1328 m, 1210 m, 1106 s, 1044 vs, 989 s, 815 s, 711 w, 482
1646 m, 1522 vs, 1438 m, 1363 m, 1314 s, 1217 s, 1113 m, 1030 s,
933 m, 815 vs, 718 m, 490 vs. cm–1.1H NMR (400 MHz, [D6]DMSO):
δ = 7.84 (d, 4 H), 6.72 (s, 4 H), 5.22 (s, 8 H), 4.40 (s, 8 H), 4.27 (s,
8 H), 4.14 (s, 28 H). 13C NMR (101 MHz, CDCl3): δ = 145.11
(NCCH), 141.67 (NCC5), 121.88 (NCCH), 116.97 (C6H4), 81.39,
68.89 (C5H4), 68.72 (C5H5), 53.50, 49.90 (C5H4CH2), 47.32 (CCH2N).
MS (m/z, ESI+), 1247.2436 [M + Na+]. C62H60Fe4N14+Na: 1247.2421.
C62H60Fe4N14 (1224.25): calcd. C, 60.81; H, 4.94; N, 16.01%; found:
C, 60.56; H, 5.19; N, 15.81%.
1
vs. cm–1. H NMR (400 MHz, CDCl3): δ = 7.53 (s, 2 H), 7.46 (s, 1
H),), 4.26 (s, 6 H), 4.17 (m, 21 H), 3.72 (s, 4 H), 3.62 (t, 2 H), 2.68
(t, 2 H). 13C NMR (101 MHz, CDCl3): δ = 144.99, 144.23 (NCCH2),
122.68, 121.95 (NCHC), 81.23, 80.88 (C5H4), 69.05 (OCH2CH2),
68.97, 68.95, 68.87, 68.76 (C5H5), 64.47 (OCH2), 52.60 (NCH2), 50.00
(C5H4CH2), 49.93 (NCH2CH2), 48.36 (NCH2). MS (m/z, ESI+),
921.1802 [M + Na+], 701.4944 (M-FcC). C44H46Fe3N10O+Na:
921.1802, for C33H37Fe2N10O: 701.1851. C44H46Fe3N10O (898.19):
calcd. C, 58.82; H, 5.16; N, 15.59%; found: C, 58.70; H, 5.22; N,
15.52%.
N,N,NЈ,NЈ-tetrakis(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmeth-
yl) benzidine (5): Yellow powder. Yield: 6.95 g (89.1 %). M. p.:
127.9–130.1 °C. FT-IR (KBr): ν˜ = 3406 m, 3073 m, 2921 w, 1605 s,
1508 vs, 1438 m, 1376 m, 1307 m, 1217 s, 1099 m, 1044 s, 995 m,
1
933 m, 808 s, 476 s cm–1. H NMR (400 MHz, CDCl3): δ = 7.34 (s,
Supporting Information (see footnote on the first page of this article):
DSC and TG curves of 1–9. FT-IR spectra of 1–9; UV/Vis and of 1–
9 in CH3CN; Cyclic voltammograms of 6 in 0.1 m nBu4PF6-DMSO at
different scan rates; Photo of the simulated composite propellant sam-
ples containing 1, 3, 5, 7, ferrocene and catocene after 1–4 weeks
migration at 50 °C; DSC curves of AP and AP + 1–5 wt.-% 1; DSC
curves of RDX and RDX with 1–5 wt.-% 1; DSC curves of HMX and
HMX with 1–5 wt.-% 1; DSC curves of HMX and HMX + 1 wt.-%
1–9; Table of the redox potentials of the ferrocene/ferrocium couples
from cyclic voltammetry of compounds 1–9 in 0.1 m nBu4PF6-DMSO
2 H), 7.31 (s, 2 H), 7.30 (s, 4 H), 5.20 (s, 8 H), 4.63 (s, 8 H), 4.20 (s,
8 H), 4.17 (s, 8 H), 4.13 (s, 20 H). 13C NMR (101 MHz, CDCl3): δ =
146.58 (NCCH), 145.28 (NCC5), 130.52 (NCCH), 127.08, 121.45,
114.10 (C6H4), 81.17, 68.94, 68.88 (C5H4), 68.73 (C5H5), 50.00
(C5H4CH2), 46.99 (CCH2N). MS (m/z, ESI+), 1323.2747 [M + Na+].
C
68H64Fe4N14+Na: 1323.2734. C68H64Fe4N14 (1300.28): calcd. C,
62.79; H, 4.96; N, 15.08%; found: C, 62.73; H, 4.90; N, 15.01%.
N-(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmethyl) o-nitroaniline
(6): Orange yellow powder. Yield: 2.12 g (84.8 %). M. p.: 139.8–
141.2 °C. FT-IR (KBr): ν˜ = 3373 m, 3157 w, 3087 w, 1620 s, 1572 s,
1502 s, 1474 m, 1411 m, 1355 m, 1257 vs, 1222 s, 1160 s, 1162 m,
1104 w, 1048 m, 1044 s, 810 m, 748 m, 580 w, 503 m, 482 m cm–1.
1H NMR (400 MHz,CDCl3): δ = 8.33 (s, 1 H), 8.18 (d, 2 H), 7.42 (t,
1 H), 7.38 (s, 1 H), 6.96 (d, 1 H), 6.69 (t, 1 H), 5.28 (s, 2 H), 4.63 (d,
2 H), 4. 26 (s, 2 H), 4. 21 (s, 2 H), 4. 17 (s, 5 H). 13C NMR (101 MHz,
CDCl3): δ = 144.81 (NCCH), 144.65 (NCC5), 136.33 (NCCH), 132.46,
126.84, 121.06, 116.06, 114.11 (C6H4), 80.63, 69.15 (C5H4), 68.93
(C5H5), 50.24 (C5H4CH2), 39.08 (CCH2N). MS (m/z, ESI+), 417.0882
(M +). C20H19FeN5O2: 417.0888. C20H19FeN5O2 (417.09): calcd. C,
57.57; H, 4.59; N, 16.78%; found: C, 57.45; H, 4.66; N, 16.69%.
1
and compound 6 at scanning rates of 0.1–0.3 V/s as well as H NMR,
13C NMR and ESI-MS spectra of 1–9.
Results and Discussion
Synthesis and Characterization
The novel ferrocenyl 1,2,3-triazolyl compounds Fc-ATAZs
(1–9) were prepared by the traditional CuAAC-based synthetic
strategy. However, stronger bases such as NaOH or NaH
should be used instead of K2CO3 for the synthesis of prop-
N,N,NЈ,NЈ-tetrakis(1-Ferrocenylmethyl-1H-1,2,3-triazol-4-ylmeth- argyl-containing intermediates of compounds 7–9. Notably,
yl) ethylenediamine (7): Yellow powder. Yield: 6.36 g (90.2 %).
M. p.: 139.0–141.5 °C. FT-IR (KBr): ν˜ = 3094 m, 2935 w, 2817 m,
1654 w, 1549 w, 1438 m, 1328 s, 1217 s, 1113 m, 1037 vs, 1002 m,
only one H atom of the NH2 group in o-nitroaniline was substi-
tuted by propargyl group during the reaction even if stronger
and more equivalent of bases or propargyl bromide were used
in the reaction, a similar situation has been encountered in the
reaction of picric acid with propargyl bromide, where no reac-
tion was detected.[11] The strong acidity of the precursors
maybe responsible for their inertness in the reaction. The DSC
curves of the Fc-ATAZs (Figure S1, Supporting Information)
showed that the new compounds are highly thermal-stable,
with the initial thermal decomposition peaks being higher than
1
919 w, 815 vs, 704 w, 490 vs. cm–1. H NMR (400 MHz, CDCl3): δ
= 7.60 (s, 4 H), 5.24 (s, 8 H), 4.26 (s, 8 H), 4.16 (s, 28 H), 3.65 (s, 8
H), 2.61 (s, 4 H). 13C NMR (101 MHz, CDCl3): δ = 144.20 (NCCH),
122.90 (NCCH), 81.41, 68.91 (C5H4), 68.86 (C5H5), 50.88 (C5H4CH2),
49.89 (NCH2CH2), 48.19 (NCCH2N). MS (m/z, ESI+), 1177.2602 [M
+ H+], 898.2133 (M-FcCH2C2N3HC). C58H60Fe4N14+H: 1177.2601,
for C44H48Fe3N11: 898.2142. C58H60Fe4N14 (1176.25): calcd. C, 59.21;
H, 5.14; N, 16.67%; found: C, 59.10; H, 5.06; N, 16.80%.
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220 °C. Their thermal stability were further verified by their for 4), respectively, suggested that compounds 1 and 6 display
TG curves (Figure S2, Supporting Information). In their FT-IR reversible ferrocene/ferrocenium waves. It is additionally
spectra, the strong intensity absorption peaks in the range of noted that the oxidation potentials of the Fc-ATAZs are much
1216–1222 cm–1 can be ascribed to the stretching vibrations of higher than those of TBF, NBF and catocene, suggested that
C–N bonds. The strong bands around 1600 cm–1 are assigned the new compounds exhibit higher anti-oxidative ability on
to the stretching vibrations of benzene ring skeletons. The ab- comparison with these neutral ferrocenes in DMSO. The
sorption peaks located in the regions of 3096–3089, 1114– strong electron-withdrawing nitro groups in 6 exert negligible
1096, 824–820 and 500–488 cm–1 confirmed the appearance effect on the redox potentials of the ferrocenyl group in 6. The
of ferrocenyl groups in each new compound. The medium and electrochemical behavior of the new ferrocenyl compounds
strong bands in the range of 923–936 and 1039–1050 cm–1, may give us a deep insight into the catalytic activity and elec-
respectively, suggested the formation of characteristic 1,2,3- tron-transfer mechanisms of ferrocene-based BRCs towards
triazolyl rings in the new compounds (Figure S3, Supporting thermal decomposition of AP during combustion. Moreover,
Information). In the FT-IR spectrum of compound 6 it is found effect of scan rates on the CV of 6 was investigated with dif-
that the characteristic stretching vibration of N–H bond is at ferent scan rates between 0.1–0.3 V·s–1 and the results are
3370 cm–1, and that the asymmetric and symmetric stretching shown in Figure S5 (Supporting Information). It was found
vibrations of the NO2 group are at 1570 and 1355 cm–1, that peak currents (anode and cathode) were linearly dependent
1
respectively. In their H NMR spectra, the chemical shifts of on the square roots of scan rates, implying a diffusion-con-
the proton atoms of the 1,2,3-triazolyl groups locate between trolled process in the electrochemical property of the tested
7.60 and 7.26 ppm. In their 13C NMR spectra, carbon atoms compound, as observed for electrochemical properties of the
of the ferrocenyl groups resonated in the range of 68–81 ppm. ferrocenyl compounds reported earlier.[13]
The high solution mass spectra of the new compounds indi-
cated consistency of their calculated and determined molecular
weights, which confirmed that the as-synthesized compounds
are the target compounds 1–9.
In the UV/Vis absorption spectra of the new compounds 1–
9 in DMSO (Figure S4, Supporting Information), the strong
absorption bands around 290 nm can be assigned to the π–π*
transitions of phenyl and cyclopentadienyl groups, the shoul-
ders and the strong peaks between 314 and 332 nm are ap-
pointed to the charge–transfer bands of the ferrocenyl groups.
The wide absorption bands spanning 330 nm to 550 nm peaked
around 430 nm are ascribed to the π–π* transitions of the chro-
mophores of the ferrocenyl groups. The common weak absorp-
tions of the Fe (II) ions, assigned to their d–d transitions,
peaked in the range of 440–450 nm, are totally overlapped by
the strong π–π* transitions of the ferrocenyl groups.[12] The
strong electron-withdrawing nitro group in compound 6
weaken strongly the absorption bands of the ferrocenyl group
around 320 nm.
Figure 1. Cyclic voltammograms of 1–9 in 0.1 mol·L–1 nBu4NPF6-
DMSO with a scanning rate of 0.1 V·s–1.
Electrochemical Behavior
Anti-migratory and Anti-volatility Studies
For a BRC, it is believed that during combustion catalysis at
Alkylferrocenes, such as NBF, TBF and catocene, as addi-
least an electron gain and loss process is involved. Moreover, tives move slowly to the surface of a composite solid propel-
electrochemical property of a ferrocenyl compound is usually lant grain during its prolonged storage and thus cause
studied due to electrochemical activity of the ferrocenyl group. concentration increase on the surface, which would give rise
Electrochemical behavior of compounds 1–9 is therefore in- to unexpected problems and even danger during combustion
vestigated. CV curves of 1–9 in DMSO in the presence of of the propellant. For retarding high-migration problem of alk-
a
c
0.10 m Bu4NBF4 are illustrated in Figure 1 and Ep , Ep , ΔEp, ylferrocenes, we synthesized nine ferrocene-containing 1,2,3-
a
c
Ep1/2, and Ip /Ip are listed in Table S1 (Supporting Infor- triazolyl compounds with aniline and alkylamine derivatives
mation). Only one pair of redox peak for each ferrocenyl com- as precursors. Anti-migration performance of the compounds
pound appears in their CV curves although they are multinu- 1, 3, 5, and 7 were measured with Fc and catocene as refer-
clear ferrocenyl compounds except compound 6, indicative of ences. Sample preparation and anti-migration determination
a simultaneous transfer of more electrons occurred in these are similar to that described,[11] From the photos shown in Fig-
compounds, due mainly to no conjugation being found in the ures S6–S11 (Supporting Information). it is noted that both
a
c
new compounds. The Ep1/2, ΔEp and Ip /Ip in the ranges of catocene and Fc diffused significantly after only one week test,
a
c
428–560 mV, 87–168 mV, and 1.08–1.22 (except Ip /Ip = 3.49 while the tested four Fc-ATAZs showed marginable movement
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after four weeks aging. No evident migration of the tested
compounds is due mainly to the strong hydrogen bonding be-
tween nitrogen atoms of 1,2,3-trizolyl groups of the com-
pounds and NH4+ of AP and the terminal OH groups of HTPB
prepolymer, and secondarily to the weak interactions between
the novel ferrocene derivatives and the propellant compo-
nents.[14] The migration distances vs. aging time are illustrated
in Figure 2. It is observed that both Fc and catocene moved to
both sides obviously (2.5 cm and 1.7 cm, respectively) after
four weeks migration. However, the tested four Fc-ATAZs kept
almost no migration over a four-week period (Ͻ 0.2 cm), in-
timating that the new ferrocenes exhibit high anti-migration
behavior, as we observed earlier for other ferrocenyl deriva-
tives with similar molecular structures.[11]
Figure 3. TG curves of 1–9 and Cat (catocene) at 70 °C for 24 h.
The combustion behavior of AP has therefore close correlation
with combustion process of composite solid propellants. Re-
searchers in the BRC field often study catalytic activity of a
BRC towards AP thermal degradation and the results are of
reference value for their combustion performance in a solid
propellant.[15]
In last decades researchers discovered that AP and Al pow-
der have a few shortcomings during combustion. These draw-
backs include releasing strong smoke and corrosive chlorine
gas during their combustion and will cause decrease of signal
receiving abilities of IR sensors and increase detecting pos-
sibilities by enemy radars. In this situation, other oxidizers,
mostly RDX or HMX, are suggested to be used to partly sub-
stitute AP and Al powder to overcome their shortcomings.
Therefore, thermal degradation behavior of RDX and HMX
with the new compounds as additives was additionally evalu-
ated.
Addition content of the new Fc-ATAZs in these three oxidiz-
ers was optimized with compound 1 as references. The test
results, shown in Figures S12–S14 (Supporting Information),
suggested that the optimal concentrations of the Fc-ATAZs in
AP, RDX and HMX are 5 wt%, 5 wt% and 1 wt%, respec-
tively. Therefore, in AP and RDX the new compounds each
was added in 5 wt%, and in HMX each of them was used in
1 wt%.
DSC curves of the pure AP and its mixtures were displayed
in Figure 4. It was observed that the thermal disintegration of
AP is composed of three stages: phase-transition peaked at
244 °C, low-temperature decomposition (LTD) peaked at
293 °C and high-temperature decomposition (HTD) peaked at
406.6 °C. Similarly, the DSC curves of the mixtures each exhi-
bits three steps, too. The phase-transition peak temperature of
AP shifts right a few degree in the mixtures, indicating that
the new ferrocenes exerted no significant effect on AP phase
transition. However, in DSC curves of AP + 5 wt% 1–9, small
exothermal peaks ranged from 188 to 202 °C appear, which
can be ascribed to the heat release peaks formed by the cata-
lytic effect of the in-situ produced nano iron oxides through
Figure 2. Migration distances of the simulated composite propellant
samples containing 1, 3, 5, 7 after 1–4 weeks migration at 50 °C. [Fc
(ferrocene) and Cat (catocene) were used as references].
It is well known that neutral alkylferrocene-based BRCs
with small molecular weights exhibit evident volatility during
curing of composite propellants using the alkylferrocenes as
BRCs and thus leads to deposition on the inner shell of the
rocket engines and uneven distribution within the propellant
grain. Moreover, the sublimation and volatility behavior of the
alkylferrocenes during fabrication probably give rise to unex-
pected issues and even danger.[3–5] A ferrocene-based BRC
should have high anti-volatility. Therefore, TG technique was
employed to evaluate anti-volatility performance of the new
Fc-ATAZs and catocene (as reference) at 70 °C for 24 h. The
results are shown in Figure 3. It can be seen that catocene exhi-
bits ca 4.50% weight-loss after 24 h, intimating that catocene
is a relatively high-volatile ferrocenyl compound. By contrast,
the novel Fc-ATAZs showed marginable weight-loss, among
them 7 exhibiting the highest weight-loss (0.71%), suggesting
that the new ferrocenyl compounds exhibit much high anti-
volatility ability upon comparison with catocene. Again, the
TG analysis verified that introduction of 1,2,3-triazolyl group
into ferrocenyl derivatives can effectively improve anti-mi-
gration and anti-volatility ability of ferrocene-based BRCs.
Catalytic Performances
AP is one of the main components in a AP-based composite redox reactions of ferrocenes with AP.[16] These types of in-
solid propellant and its weight percentage is about 70 wt%. situ formed nano iron oxides have been mentioned by others
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who studied on the combustion of AP with ferrocene-function- advance of AP with the new ferrocenes as additives. The TG
alized additives.[15d,17] The peak of high decomposition tem- results verified again that the Fc-ATAZs exert favorable effect
perature (HDT) stage of AP at 406.6 °C move dramatically to on the AP thermal degradation.
lower temperature when the Fc-ATAZs are used as additives.
It was noted that DSC curve of each mixture shows two exo-
thermal peaks, the former being 306-312 °C, and the latter be-
ing 342–360 °C.
Figure 5. TG curves of AP and mixtures AP + 5 wt% 1–9.
DCS curves of RDX and its mixtures with new ferrocenes
1–9 are illustrated in Figure 6. The DSC curve of pure RDX
exhibits only one exothermic peak at 237 °C. The curves of
the mixtures each, however, has two exothermic peaks, located
in the range of 191–207 °C and 226–235 °C, respectively. In
each DSC curve, the first peak appeared mainly before the
endothermic peak of RDX and another one showed after the
endothermic peak of RDX, which have been observed in our
reported DSC curves earlier,[11] which is due to the partial
polymerization of RDX molecules in the samples. The advance
of the peak temperature of RDX suggested that the new ferro-
cenyl compounds as additives can considerably accelerate the
thermal degradation of RDX. The released heat increased from
–831 J·g–1(RDX) to –1261 to –1648 J·g–1(mixtures) dramati-
Figure 4. DSC curves of AP and mixtures AP + 5 wt% 1–9.
The results revealed that the Fc-ATAZs as additives exert
great effect on the thermal degradation of AP and accelerate
decomposition rate of AP, as we observed previously.[9,11] The
appearance of two peaks at HTD stage of AP in each DSC
curve figures out that the decomposition mechanism of the
mixtures is probably different from that of pure AP. The re-
leased heats of the mixtures are from –1180 to –1730 J·g–1,
with 5 wt% 3 +AP being the highest, which is by 123.2%
higher than that of pure AP (–746 J·g–1) and higher by 32.8%
than the released heat of 5 wt% catocene +AP (–1303 J·g–1).
Additionally, it was also noted that the heats released by the
mixtures 5 wt% 1–5 +AP are all higher than that of the mix-
ture containing AP and 5 wt% O,OЈ,OЈЈ-trikis-(ferro-
cenylmethyl-1H-1,2,3-triazol-4-ylmethyl) pyrogallol ether
(–1478 J·g–1), which released the highest heat among the mix-
tures earlier.[11] The results demonstrated that the ferrocenyl
1.2.3-triazolyl compounds derived from anilines are more
active than those from phenols and benzoic acids towards the
AP decomposition. It was also found that the heats released by
the mixtures of 5 wt% 7–9 + AP are lower than those of
5 wt% 1–5 +AP, hinting that the ferrocenyl compounds de-
rived from alkylamines are unfavorable in the combustion ca-
talysis towards AP thermal disintegration on comparison with
those of the anilines.
From TG curve of AP illustrated in Figure 5, it was ob-
served that AP began its weight-loss from 268 °C and ceased
its thermal degradation at 395 °C. When 5 wt% Fc-ATAZs
was doped in AP, the mixtures began their weight-loss from
lower temperatures and ceased their thermal disintegration in
the range of 241–251 °C, which are lower by 44–54 °C than
that of AP itself, indicative of the decomposition temperature Figure 6. DSC curves of RDX and mixtures RDX + 5 wt% 1–9.
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[2] a) R. B. Tong, Y. L. Zhao, L. Wang, H. J. Yu, F. J. Ren, M. Sa-
cally, intimating that the novel ferrocenyl compounds have
marked effects on the thermal disintegration of RDX.
leem, J. Organomet. Chem. 2014, 755, 16–32; b) M. Usman, L.
Wang, H. J. Yu, F. Haq, M. Haroon, R. Summe Ullah, A. Khan,
S. Fahad, A. Nazir, T. Elshaarani, J. Organomet. Chem. 2018,
872, 40–53; c) W. D. Zhou, L. Wang, H. J. Yu, R. B. Tong, Q.
Chen, J. H. Wang, X. P. Yang, A. Zain ul, M. Saleem, Appl. Or-
ganomet. Chem. 2016, 30, 796–805.
As illustrated in Figure S15 (Supporting Information), all
mixtures exhibit lower peak temperatures than HMX itself, and
the heats released by all mixtures (–1155 to –1425 J·g–1) are
higher by 10–36% than that of HMX (–1046 J·g–1). Taking
both peak temperature and released heat into account, all Fc-
ATAZs compounds exert positive effect on the thermal disinte-
gration of HMX. If the released heats of the mixtures of HMX
+ 1 wt% 1–9 are compared with those reported previously, it
was found that HMX can release more heat with 1–9 as addi-
tives than with the ferrocenyl compounds derived from phenols
and benzoic acids as additives.[11] In the reported compounds
previously, some compounds even made negative effect on the
HMX thermal degradation, with released heats being lower
than that of HMX itself.[11] At lower temperatures, ferrocene
compounds are difficult to be oxidized into iron oxides by both
RDX and HMX, since they are classic nitramines. Therefore
the new compounds exerted no significant effect on the decom-
position peak temperatures of RDX and HMX, which explains
why shifts of the decomposition peak temperatures of both oxi-
dizers are within a few degrees.
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Conclusions
In summary, nine ferrocenyl 1,2,3-triazolyl compounds de-
rived from anilines and aliphatic amines were synthesized,
aiming to enhancing anti-migratory abilities of the usual neu-
tral ferrocene-based BRCs, and ameliorating the combustion
catalytic activities of their analogues derived from phenols and
benzoic acids. The evaluation results concluded that the new
ferrocenes are highly thermal stable. The new compounds are
of almost no migration and low volatility by the introduction
of polar nitrogen atoms into their molecules. And the novel
ferrocenyl compounds show highly catalytic activity in the
thermal degradation of AP, RDX and HMX, and are more
active than their analogues derived from phenols and benzoic
acids reported previously. Currently, the synthesis of ferro-
cenyl 1,2,3-triazolyl compounds derived from nitrogen-rich
energetic compounds such as imidazoles, pyrazoles and 1,2,4-
triazoles and evaluation of their combustion catalytic proper-
ties are underway in our laboratory.
Acknowledgements
[10] a) R. K. Iha, K. L. Wooley, A. M. Nystrom, D. J. Burke, M. J.
Kade, C. J. Hawker, Chem. Rev. 2009, 109, 5620–5686; b) F. Am-
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This work was supported by the XiЈan Modern Chemistry Research
Institute (contracts no. 204-J-2019–0387, 204-J-2020–1237) and the
National Natural Science Foundation of China (21401124, 21602129).
[11] W. Q. Cheng, X. L. Shi, Y. Zhang, Y. J. Jian, G. F. Zhang, Inorg.
Keywords: Ferrocenyl 1,2,3-triazolyl compounds;
Anti-migration; Combustion catalysis; High temperature
chemistry; Thermodynamics
Chim. Acta 2020, 502, 119374.
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X. Shi, W. Cheng, L. Jiang, F. Bi, J. Li, G. Zhang* ........ 1–9
Anti-migration and Combustion Catalytic Performances of
Ferrocenyl Compounds of Anilines and Alkylamines Synthe-
sized by Click Reaction
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