Synthesis of Novel Silanes Functionalized with Mono-and Bis-Fluoroalkylated [1,2,3]-Triazoles

Article abstract of DOI:10.1080/10426507.2015.1032411

In the current work, a series of mono-fluoroalkylated [1,2,3]-triazole precursors was prepared by the 1,3-dipolar cycloaddition reaction of allyl azide and perfluoroalkylethoxyl propynes, in which the CuSO₄ and sodium ascorbate were used as the catalyst. Using these precursors as unsaturated substrates, a series of novel mono-fluoroalkyldichloromethyl silanes were successfully synthesized via hydrosilylation between C=C and Si-H bonds. Furthermore, to construct fluorosilanes with two or more stacked fluoroalkyl groups in one molecule, silanes with bis-fluoroalkylated [1,2,3]-triazoles as pendants were synthesized afterwards.

Full text of DOI:10.1080/10426507.2015.1032411

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Phosphorus, Sulfur, and Silicon and the Related
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Synthesis of novel silanes functionalized with mono-
and bis-fluoroalkylated [1,2,3]-triazoles
Lu Caia, Yanhua Yuana, Zhanxiong Liab & Wanjun Wangc
a College of Textile and Clothing Engineering, Soochow University, Suzhou 215021, China
b State Key Laboratory of Disaster Prevention & Mitigation of Explosion & Impact, Nanjing
210007, China
c Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai 200032,
China
Accepted author version posted online: 18 Apr 2015.
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To cite this article: Lu Cai, Yanhua Yuan, Zhanxiong Li & Wanjun Wang (2015): Synthesis of novel silanes functionalized
with mono- and bis-fluoroalkylated [1,2,3]-triazoles, Phosphorus, Sulfur, and Silicon and the Related Elements, DOI:
10.1080/10426507.2015.1032411
To link to this article: http://dx.doi.org/10.1080/10426507.2015.1032411
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Synthesis of novel silanes functionalized with mono- and bis-fluoroalkylated
[1,2,3]-triazoles
Lu Cai a, Yanhua Yuan a, Zhanxiong Li , a, b, Wanjun Wang ,c
a College of Textile and Clothing Engineering, Soochow University, Suzhou 215021, China
b State Key Laboratory of Disaster Prevention & Mitigation of Explosion & Impact, Nanjing
210007, China
c Shanghai Institute of Organic Chemistry, Chinese Academy of Science, Shanghai 200032,
China
Abstract
In the current work, a series of mono-fluoroalkylated [1,2,3]-triazole precursors was prepared by
the 1,3-dipolar cycloaddition reaction of allyl azide and perfluoroalkylethoxyl propynes, in
which the CuSO4 and sodium ascorbate were used as the catalyst. Using these precursors as
unsaturated substrates, a series of novel mono-fluoroalkyldichloromethyl silanes were
successfully synthesized via hydrosilylation between C=C and Si-H bonds. Furthermore, to
construct fluorosilanes with two or more stacked fluoroalkyl groups in one molecule, silanes
with bis-fluoroalkylated [1,2,3]-triazoles as pendants were synthesized afterwards.
* Corresponding Author. Tel: +86-512-67061190; Fax: +86-512-67246786.
E-mail address: lizhanxiong@suda.edu.cn (Z. X. Li).
* Corresponding Author. Tel: +86-21-54925321; Fax: +86-21-64166128.
E-mail address: wangwj@sioc.ac.cn (W. J. Wang).
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Keywords: 1,3-dipolar cycloaddition; Hydrosilylation; Triazole; Fluoroalkylated silane;
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1. Introduction
Little interest and attention was paid to the Huisgen 1,3-dipolar cycloaddition reaction of organic
azides and alkynes [1-2], until the pivotal discovery by the groups of Medal and Sharpless in
2002 [3-4]. Soon after, the study of the reaction experienced a rapid development. The copper (I)
catalyst was reported to dramatically accelerate the reaction under mild conditions with a high
regioselectivity [5-9]. Since then, the copper (I)-catalyzed azide-alkyne cycloaddition (CuAAC)
reaction, forming [1,2,3]-triazole bridging groups, has become a robust and reliable method for
the functionalization of a wide variety of molecules [10-11]. With the characteristics of high
efficiency, selectivity, wide substrate scope and devoid of side reactions [12-13], numerous
applications have been found in medicine [14-18], materials and surface science [19],
bioconjugation [20-21].
At the same time, many compounds possessing fluoroalkyl segments have garnered considerable
interest due to the special properties of the fluorine atom, namely the electronegativity of
fluorine and the high polar C-F bond [22-23]. They offer superior performance with good
physical and chemical properties, low surface energy, high optical clarity, low refractive index,
high thermal resistance and high lubricativity [24-26], which render them particularly attractive
in many fields, such as coatings [27], waterproofing of textiles [28], antifouling properties of
paints for boats [29], as well as antibacterial materials [30].
Fluorosilicone materials, which combine the properties of fluoroalkyl and organosilicone, have
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been put into many applications, such as fluorinated mesoporous silica materials [31],
superhydrophobic membranes [32], hollow fiber membranes [33], and highly heat-resistant
surface [34]. Actually, the synthesis of fluoroalkyl functionalized silanes has been reported by
many researchers. Yoshino’s group synthesized a fluorinated silane with a biphenyl as bridging
group to combine fluoroalkyl and silane [34]; Ameduri made fluoroalkyl olefins react directly
with trichlorosilane to obtain fluoroalkyl functionalized silanes with C-C bridging group [35];
Shao designed and synthesized a perfluorooctylated silane coupling agent with quaternary
ammonium as the bridging group [30]; Li’s group synthesized a novel trifluoromethylphenyl
silane coupling agent with a phenyl bridging group via Grignard Reaction [36].
Herein, the mono- and bis-fluoroalkylated [1,2,3]-triazoles were prepared by CuAAC reaction of
allyl azide and perfluoroalkyl terminal alkynes, in which the CuSO4 and sodium ascorbate were
used as catalysts. Then a series of novel mono- and bis-fluoroalkyldichloromethyl silanes were
successfully synthesized via hydrosilylation between C=C and Si-H bond with chloroplatinic
acid as catalyst. In these newly synthesized fluorinated silanes, the triazoles were firstly used to
bond fluoroalkyl groups with silanes as heterocyclic bridging group.
2. Results and discussion
Synthesis of silanes functionalized with mono-fluoroalkylated [1,2,3]-triazoles
Perfluoroalkylethoxyl propynes 2a-2c were synthesized according to reference [37], and allyl
azide 3 was prepared according to reference [38] with a boiling point of 90-92 ºC (The boiling
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point reported in the reference [38] was 93-95 ºC).
The reaction of perfluorobutylethoxyl propyne 2a and allyl azide 3 was carried out as a model
reaction to optimize the 1,3-dipolar cycloaddition reaction conditions (see Table 1). First, CuI
was used as the catalyst and the t-BuOH/H2O were used as mixed solvents. However, the
reaction was not initiated and no product was obtained (see Table 1, Entry 1). It is well known
that CuSO4/sodium ascorbate and CuI are the common used catalysts in the copper (I)-catalyzed
azide-alkyne cycloaddition (CuAAC) reaction, and it has been reported that the formation of Cu
(I) acetylide is the key step of the CuAAC reaction, amine additives, for example, triethylamine,
could accelerate the formation of Cu (I) acetylide [39]. So triethylamine was added in our study,
but the yield was still unsatisfactory (see Table 1, Entry 2). If t-butanol was substituted by THF
and the reaction temperature was improved, the effect was also not obvious (see Table 1, Entry 3).
It indicated that CuI couldn’t act as an effective catalyst in the current reaction system. So we
turned to utilize CuSO4 and sodium ascorbate as the catalysts. In this section, it was found that
CuSO4 and sodium ascorbate could act as efficient catalysts with optimistic yield (see Table 1,
Entry 4).
Next, silanes functionalized with mono-fluoroalkylated [1,2,3]-triazoles were obtained by the
hydrosilylation reaction of dichloromethylsilane and mono-fluoroalkylated [1,2,3]-triazole
precursors with chloroplatinic acid as catalyst. The catalytic mechanism has been reported by
Chalk-Harrod [40]. The detailed synthetic route to target compounds 5a-5c is shown in Scheme
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1.
Synthesis of silanes functionalized with bis-fluoroalkylated [1,2,3]-triazoles
Based on the successful synthetic method of mono-fluoroalkyl functionalized silanes, silanes
substituted with more than one fluoroalkyl group were designed. These fluorinated silanes would
obtain lower surface energy with the denser fluorines gathering on the surface of materials
[41-42]. To achieve this purpose, a series of bis-perfluoroalkyl terminal alkynes 8a-8c were
obtained according to reference [43], and the 1,3 dipolar-cycloaddition reactions of allyl azide 3
1
and bis-perfluoroalkyl terminal alkynes 8a-8c were carried out subsequently. H NMR
spectroscopy confirmed the successful reactions since the signals of alkynyl (δ=2.31 ppm) was
disappeared, and the triazole proton (δ=7.52 ppm) was clearly detected. Then silanes
functionalized with bis-fluoroalkylated [1,2,3]-triazoles were obtained by the hydrosilylation
reaction between dichloromethylsilane and bis-fluoroalkylated [1,2,3]-triazole precursors. The
synthetic paths of target compounds 10a-10c are shown in Scheme 2.
3. Experimental
3.1 Materials and methods
Propargyl bromide, allyl bromide and toluene were purified by distillation before using. Other
chemicals were obtained from commercial sources and used without further purification. FT-IR
1
13
spectra were obtained with NICOLET 5700 spectrometer on KBr disks. H NMR and C NMR
spectra were recorded on an INOVA-400 spectrometer in CDCl3 with Me4Si as internal standard.
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19F NMR spectra were obtained on Bruker DPX 400 spectrometer in CDCl3 with CFCl3 as
internal reference. All the chemical shifts were expressed in ppm, and coupling constants (J)
were given in Hz. Mass spectra were recorded on a Finnigan-MAT-8430 instrument using ESI
ionization. The Supplemental Materials contains sample 1H, 13C and 19F NMR spectra for 4, 5, 8,
9 and 10 (Figures S 1 – S 15)
3.2 Synthesis procedure
3.2.1 General Procedure For The Synthesis of Compounds (4a-4c) To a 100 mL three-necked
round flask, perfluoroalkylethoxyl propyne (30 mmol) was added to a mixed solvent of t-BuOH
(30 mL) and dieonized water (15 mL), followed by adding CuSO4•5H2O (0.75 g, 3.00 mmol)
and sodium ascorbate (1.19 g, 6.00 mmol). Then the mixture was stirred for 30 min, after that
allyl azide (2.74 g, 33 mmol) was added dropwise. The reaction was stirred vigorously for 24 h
at 40 ºC. The mixture was diluted with deionized water (20 mL) and extracted with ether (3×20
mL). The combined organic layer was washed with saturated brine (3×20 mL) and deionized
water (3×20 mL), dried by magnesium sulfate, and concentrated. Purification was performed by
flash column chromatography on silica gel (200-300 mesh) with ether/hexane (50:50) as eluant
reagent.
1-allyl-4-(2-perfluorobutylethoxy)methyl-[1,2,3]-triazole (4a) Pale yellow liquid, yield 70%;
1H NMR (400 MHz, CDCl3): δ 7.62 (s, 1H, Ctriazole-H), 6.04 (ddt, 1H, J=16.6, 10.2, 6.3Hz,
CH2=CH), 5.49 (d, 1H, CHH=CH), 5.11 (d, 1H, J=6.2Hz, CHH=CH), 4.68 (s, 2H, Ctriazole-CH2),
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4.05 (t, 2H, J=6.6Hz, Ntriazole-CH2), 3.85 (t, 2H, J=6.6Hz, C4F9CH2CH2), 2.44 (dt, 2H, J=18.6,
6.5Hz, C4F9CH2); 13C NMR (100 MHz, CDCl3): δ 144.5, 131.0, 122.3, 120.3, 64.5, 62.46, 52.6,
31.4; 19F NMR (300 MHz, CDCl3): δ -81.1, -113.7 -124.6, -126.7; FT-IR (KBr): 3137.4,
3092.8, 2903.3, 1644.8, 1240.6, 1209.6, 1135.4, 1105.2 cm-1; MS (ESI) m/z: 386.7 [M+H]+.
1-allyl-4-(2-perfluorohexylethoxy)methyl-[1,2,3]-triazole (4b) Pale yellow liquid, yield 68%;
1H NMR (400 MHz, CDCl3): δ 7.58 (s, 1H, Ctriazole-H), 6.04 (ddt, 1H, J=16.4, 10.2, 6.2Hz,
CH2=CH), 5.36 (d, 1H, CHH=CH), 5.01 (d, 1H, J=6.2Hz, CHH=CH), 4.68 (s, 2H, Ctriazole-CH2),
3.95 (t, 2H, J=6.2Hz, Ntriazole-CH2), 3.81 (t, 2H, J=7.6Hz, C6F13CH2CH2), 2.51 (dt, 2H, J=18.9,
13
6.8Hz, C6F13CH2); C NMR (100 MHz, CDCl3): δ 144.6, 131.1, 122.3, 120.2, 64.5, 62.3, 52.7,
31.3; 19F NMR (300 MHz, CDCl3): δ -81.1, -117.0, -122.1, -122.9, -123.3, -126.3; FT-IR (KBr):
3137.3, 3092.7, 2913.4, 1647.8, 1241.6, 1219.6, 1156.7, 1104.4 cm-1; MS (ESI) m/z: 486.6
[M+H]+.
1
1-allyl-4-(2-perfluorooctylethoxy)methyl-[1,2,3]-triazole (4c) Pale yellow oil, yield 68%; H
NMR (400 MHz, CDCl3): δ 7.56 (s, 1H, Ctriazole-H), 6.04 (ddt, 1H, J=16.5, 10.5, 6.2Hz,
CH2=CH), 5.35 (d, 1H, CHH=CH), 5.00 (d, 1H, J=6.2Hz, CHH=CH), 4.68 (s, 2H, Ctriazole-CH2),
4.01 (t, 2H, J=6.5Hz, Ntriazole-CH2), 3.84 (t, 2H, J=6.7Hz, C8F17CH2CH2), 2.41 (dt, 2H, J=18.8,
13
6.5Hz, C8F17CH2). C NMR (100 MHz, CDCl3): δ 144.8, 131.0, 122.4, 120.3, 64.5, 62.3, 52.7,
19
31.3; F NMR (300 MHz, CDCl3): δ -81.1, -113.6, -122.2 to -122.9, -123.0, -123.7, -126.2;
FT-IR (KBr): 3136.3, 3091.4, 2921.4, 1644.6, 1240.5, 1209.9, 1146.3, 1103.5 cm-1; MS (ESI)
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m/z: 586.5 [M+H]+.
3.2.2 General Procedure For The Synthesis of Compounds (5a-5c) To a 50 mL three-necked
round flask, 1-allyl-4-(2-perfluoroalkylethoxy)methyl-[1,2,3]-triazole (0.02 mol) and tolune (10
mL) were added and stirred for 10 min at 70 ºC, followed by addition of one drop of Karstedt’s
catalyst. Then the dichloromethylsilane (2.30 g, 0.02 mol) was added dropwise and the reaction
mixture was stirred at 70 ºC for 4 h. The solvent was removed under reduced pressure to give the
resulting product.
γ-(4-perfluorobutylethyoxylmethyl-[1,2,3]-triazolo)propyl-dichloro-methyl silane (5a) Pale
1
yellow oil, yield 95%; H NMR (400 MHz, CDCl3): δ 7.82 (s, 1H, Ctriazole-H), 4.85 (s, 2H,
Ctriazole-CH2), 4.06 (t, 2H, J=6.2Hz, Ntriazole-CH2), 3.89 (t, 2H, J=6.6Hz, C4F9CH2CH2), 2.45 (dt,
2H, J=18.6, 6.5Hz, C4F9CH2), 1.82 (m, 2H, SiCH2CH2), 1.15 (m, 2H, SiCH2), 0.78 (s, 3H,
SiCH3); 13C NMR (100 MHz, CDCl3): δ 144.8, 122.4, 64.5, 62.3, 52.6, 31.3, 24.8, 14.2, 0.3; 19F
NMR (300 MHz, CDCl3): δ -81.1, -113.5, -124.6, -126.1; FT-IR (KBr): 3138.8, 3092.8, 2970.2,
1260.5, 1240.6, 1209.6, 1133.4 cm-1; MS (ESI), m/z: 500.4 [M+H]+; Anal. Calcd for
C13H16Cl2F9N3OSi: C, 31.21; H, 3.22; N, 8.40; found: C, 31.18; H, 3.32; N, 8.32.
γ-(4-perfluorohexylethyoxylmethyl-[1,2,3]-triazolo)propyl-dichloro-methyl silane (5b) Pale
1
yellow oil, yield 96%; H NMR (400 MHz, CDCl3): δ 7.81 (s, 1H, Ctriazole-H), 4.86 (s, 2H,
Ctriazole-CH2), 3.98 (t, 2H, J=6.2Hz, Ntriazole-CH2), 3.89 (t, 2H, J=6.6Hz, C6F13CH2CH2), 2.43 (dt,
2H, J=18.8, 6.5Hz, C6F13CH2), 1.83 (m, 2H, SiCH2CH2), 1.19 (m, 2H, SiCH2), 0.80 (s, 3H,
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SiCH3); 13C NMR (100 MHz, CDCl3): δ 144.8, 122.30 64.5, 62.3, 52.5, 31.3, 24.8, 14.2, 0.3. 19F
NMR (300 MHz, CDCl3): δ -81.1, -117.1, -122.2, -123.0, -123.3, -126.3; FT-IR (KBr): 3137.6,
3094.7, 2916.7, 1261.5, 1241.6, 1219.6, 1151.1, 1099.4 cm-1; MS (ESI) m/z: 600.5 [M+H]+;
Anal. Calcd for C15H16Cl2F13N3OSi: C, 30.01; H, 2.69; N, 7.00; found: C, 30.12; H, 2.78; N,
6.99.
γ-(4-perfluorooctylethyoxylmethyl-[1,2,3]-triazolo)propyl-dichloro-methyl silane (5c) Pale
1
yellow oil, yield 93%; H NMR (400 MHz, CDCl3): δ 7.82 (s, 1H, Ctriazole-H), 4.86 (s, 2H,
Ctriazole-CH2), 3.98 (t, 2H, J=6.2Hz, Ntriazole-CH2), 3.82 (t, 2H, J=6.6Hz, C8F17CH2CH2), 2.41 (t,
2H, J=18.8, 6.5Hz, C8F17CH2), 1.85 (m, 2H, SiCH2CH2), 1.24 (m, 2H, SiCH2), 0.82 (s, 3H,
SiCH3); 13C NMR (100 MHz, CDCl3): δ 144.8, 122.4, 64.5, 62.3, 52.7, 31.4, 24.8, 14.2, 0.3; 19F
NMR (300 MHz, CDCl3): δ -81.1, -113.6, -122.2 to -122.8, -122.9, -123.7, -126.2; FT-IR (KBr):
3137.6, 3094.7, 2964.0, 1260.5, 1241.6, 1209.6, 1145.9 cm-1; MS (ESI) m/z: 700.6 [M+H]+;
Anal. Calcd for C17H16Cl2F17N3OSi: C, 29.16; H, 2.30; N, 6.00; found: C, 29.33; H, 2.44; N,
6.12.
3.2.4 General Procedure For The Synthesis of Compounds (9a-9c)
To
a
50
mL
three-necked
round
flask,
bis[1-(1H,1H,2H,2H-perfluoroalkyl)]-2-(prop-2-yn-1-ylthio)succinate (10 mmol) was added to a
mixture solvent of t-BuOH (20 mL) and deionized water (10 mL), followed by adding
CuSO4•5H2O (0.25 g, 1.00 mmol) and sodium ascorbate (0.40 g, 2.00 mmol). Then the mixture
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was stirred for 30 min, after that allyl azide (0.91 g, 11.00 mmol) was added dropwise. The
reaction was stirred vigorously for 24 h at 40 ºC. The mixture was diluted with deionized water
and extracted with ether (3×30 mL). The combined organic layer was wash with saturated brine
(3×20 mL) and deionized water (3×20 mL), dried by magnesium sulfate, and concentrated.
Purification was performed by flash column chromatography on silica gel (200-300 mesh) with
ether/hexane (50:50) as eluant reagent.
1-allyl-4-{bis[1-(1H,1H,2H,2H-perfluorohexyl)]-2-(prop-2-yn-1-ylthio)succinate}-[1,2,3]-tri
1
azole (9a) Pale yellow oil, yield 72%; H NMR (400 MHz, CDCl3): δ 7.51 (s, 1H, Ctriazole-H),
6.02 (ddt, 1H, J=16.5, 10.2, 6.2Hz, CH2=CH), 5.36 (d, 1H, CHH=CH), 4.97 (d, 1H, J=6.2Hz,
CHH=CH), 4.42 (m, 4H, C4F9CH2CH2), 4.13 (m, 2H, CH2=CHCH2), 3.98 (m, 1H, COOCH),
3.72 (m, 2H, Ctriazole-CH2), 3.01 (m, 2H, COOCH2), 2.53 (m, 4H, C4F9CH2CH2); 13C NMR (100
MHz, CDCl3): δ 170.7, 169.9, 144.2, 131.0, 121.9, 120.4, 60.4, 52.8, 41.0, 35.7, 26.3, 25. 6; 19F
NMR (300 MHz CDCl3): δ -81.10, -113.92, -124.60, -126.06; FT-IR (KBr): 3137.6, 2980.3,
1743.7, 1646.2, 1240.5, 1209.5, 1156.0, 1099.9, 1046.2, 946.4 cm-1; MS (ESI) m/z: 764.8
[M+H]+.
1-allyl-4-{bis[1-(1H,1H,2H,2H-perfluorooctyl)]-2-(prop-2-yn-1-ylthio)succinate}-[1,2,3]-tria
zole (9b) Pale yellow oil, yield 68%; 1H NMR (400 MHz, CDCl3): δ 7.52 (s, 1H, Ctriazole-H), 6.03
(ddt, 1H, J=16.5, 10.2, 6.2Hz, CH2=CH), 5.35 (d, 1H, CHH=CH), 4.97 (d, 1H, J=6.2Hz,
CHH=CH), 4.41 (m, 4H, C6F13CH2CH2), 4.11 (m, 2H, CH2=CHCH2), 3.98 (m, 1H, COOCH),
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13
3.72 (m, 2H, Ctriazole-CH2), 3.01 (m, 2H, COOCH2), 2.53 (m, 4H, C6F13CH2); C NMR (100
19
MHz, CDCl3): δ 170.7, 169.9, 144.2, 131.0, 121.9, 120.3, 60.4, 52.8, 41.0, 35.8, 26.2, 21.0; F
NMR (300 MHz， CDCl3): δ -80.2, -117.1, -122.1, -123.4, -123.3, -126.4; FT-IR (KBr): 3137.2.,
2993.3, 1743.7, 1646.4, 1240.5, 1222.5, 1158.0, 1099.9, 1048.7, 948.1 cm-1; MS (ESI) m/z:
964.7 [M+H]+.
1-allyl-4-{bis[1-(1H,1H,2H,2H-perfluorodecyl)]-2-(prop-2-yn-1-ylthio)succinate}-[1,2,3]-tria
zole (9c) Pale yellow oil, yield 37%; 1H NMR (400 MHz, CDCl3): δ 7.51 (s, 1H, Ctriazole-H), 6.04
(ddt, 1H, J=16.5, 10.2, 6.2Hz, CH2=CH), 5.36 (d, 1H, CHH=CH), 4.96 (d, 1H, J=6.2Hz,
CHH=CH), 4.45 (m, 4H, C8F17CH2CH2), 4.11 (m, 2H, CH2=CHCH2), 3.98 (m, 1H, COOCH),
13
3.73 (m, 2H, Ctriazole-CH2), 3.05 (m, 2H, COOCH2), 2.54 (m, 4H, C8F17CH2); C NMR (100
19
MHz, CDCl3): δ 170.7, 169.9, 144.2, 131.0, 121.9, 120.3, 60.3, 52.8, 41.0, 35.8, 26.2, 28.2. F
NMR (300 MHz，CDCl3): δ -80.9, -113.8, -121.7 to -122.1, -122.8, -123.7, -126.2; FT-IR (KBr):
3140.0, 2921.7, 1739.4, 1646.0, 1240.5, 1206.5, 1143.7, 1099.9, 1048.1 cm-1; MS (ESI) m/z:
1164.8 [M+H]+.
3.2.9 General Procedure For The Synthesis of Compounds (10a-10c)
To
a
50
mL
three-necked
round
flask,
1-allyl-4-{bis[1-(1H,1H,2H,2H-perfluoroalkyl)]-2-(prop-2-yn-1-ylthio)succinate}-[1,2,3]-triazol
e (5.20 mmol) and tolune (10 mL) were added together and stirred for 10min at 70 ºC, followed
by addition of one drop of Karstedt’s catalyst. Then the dichloromethylsilane (5.98 g, 5.20 mmol)
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was added dropwise and the reaction mixture was stirred at 70 ºC for 4 h. The solvent was
removed under reduced pressure to give the resulting product as yellow oil.
γ-[4-{bis[1-(1H,1H,2H,2H-perfluorohexyl)]-2-(prop-2-yn-1-ylthio)succinate}-[1,2,3]-triazolo
]propyl-dichloro-methyl silane (10a) Pale yellow oil, yield 97%; 1H NMR (400 MHz, CDCl3):
δ 7.78 (s, 1H, Ctriazole-H), 4.30 (m, 4H, C4F9CH2CH2), 4.06 (m, 2H, SiCH2CH2CH2), 3.96 (m, 1H,
COOCH), 3.82 (m, 2H, Ctriazole-CH2), 3.02 (m, 2H, COOCH2), 2.56 (m, 4H, C4F9CH2), 1.40 (m,
13
2H, SiCH2CH2), 0.68 (m, 2H, SiCH2), 0.07 (s, 3H, SiCH3); C NMR (100 MHz, CDCl3): δ
170.7, 169.9, 144.1, 121.9, 60.4, 52.9, 41.1, 35.8, 30.1, 26.4, 25.0, 14.3, 0.3; 19F NMR (300 MHz，
CDCl3): δ -81.1, -113.9, -124.6, -126.0; FT-IR (KBr): 3138.8, 2970.2, 1743.2, 1260.5, 1240.6,
1209.5, 531.8 cm-1; MS (ESI) m/z: 878.8 [M+H]+; Anal. Calcd for C23H23Cl2F18N3O4SSi: C,
31.45; H, 2.64; N, 4.78; found: C, 31.30; H, 2.51; N, 4.63.
γ-[4-{bis[1-(1H,1H,2H,2H-perfluorooctyl)]-2-(prop-2-yn-1-ylthio)succinate}-[1,2,3]-triazolo]
1
propyl-dichloro-methyl silane (10b) Yellow liquid, yield 95%; H NMR (400 MHz, CDCl3): δ
7.80 (s, 1H, Ctriazole-H), 4.39 (m, 4H, C6F13CH2CH2), 4.10 (m, 2H, SiCH2CH2CH2), 4.01 (m, 1H,
COOCH), 3.74 (m, 2H, Ctriazole-CH2), 3.07 (m, 2H, COOCH2), 2.54 (m, 4H, C6F13CH2), 1.38 (m,
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2H, SiCH2CH2), 0.72 (m, 2H, SiCH2), 0.06 (s, 3H, SiCH3); C NMR (100 MHz, CDCl3): δ
170.7, 169.9, 144.2, 121.9, 60.4, 52.8, 41.1, 35.8, 28.4, 26.4, 25.3, 14.6, 0.3; 19F NMR (300 MHz，
CDCl3): δ -81.0, -117.2, -122.1, -123.1, -123.1, -126.4; FT-IR (KBr): 3136.2, 2992.2, 1744.2,
1260.5, 1240.6, 1209.5, 531.8 cm-1; MS (ESI) m/z: 1078.7 [M+H]+; Anal. Calcd for
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C27H23Cl2F26N3O4SSi: C, 30.07; H, 2.15; N, 3.90; found: C, 30.15; H, 2.28; N, 3.94.
γ-[4-{bis[1-(1H,1H,2H,2H-perfluorodecyl)]-2-(prop-2-yn-1-ylthio)succinate}-[1,2,3]-triazolo
1
]propyl-dichloro-methyl silane (10c) Yellow oil, yield 96%; H NMR (400 MHz, CDCl3): δ
7.81 (s, 1H, Ctriazole-H), 4.39 (m, 4H, C8F17CH2CH2), 4.11 (m, 2H, SiCH2CH2CH2), 4.02 (m, 1H,
COOCH), 3.72 (m, 2H, Ctriazole-CH2), 3.03 (m, 2H, COOCH2), 2.54 (m, 4H, C8F17CH2), 1.40 (m,
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2H, SiCH2CH2), 0.70 (m, 2H, SiCH2), 0.06 (s, 3H, SiCH3); C NMR (100 MHz, CDCl3): δ
170.7, 169.9, 144.2, 121.9, 60.4, 52.8, 41.1, 35.7, 30.3, 26.4, 25.3, 14.6, 0.3; 19F NMR (300 MHz，
CDCl3): δ -80.9, -113.8, -121.7 to -122.1, -122.8, -123. 6, -126.2; FT-IR (KBr): 3138.3, 2993.4,
1743.6, 1260.5, 1240.8, 1209.5, 531.6 cm-1; MS (ESI) m/z: 1278.9 [M+H]+; Anal. Calcd for
C31H23Cl2F34N3O4SSi: C, 29.12; H, 1.81; N, 3.29; found: C, 29.26; H, 1.97; N, 3.33.
4. Conclusions
We have successfully synthesized a series of novel silanes functionalized with mono- and
bis-fluoroalkylated [1,2,3]-triazoles via CuAAC reaction followed by hydrosilylation reaction.
The obtained bis-fluoroalkylated [1,2,3]-triazolosilanes were deemed to possess better
performance in surface treatment due to the densely stacked fluoroalkyl groups. The triazole
bridging group can provide the antibacterial property after quaternization.
Acknowledgements
We gratefully acknowledge for the financial supports by National Natural Science Foundation of
China (No. 51273140), the State Key Laboratory of Disaster Prevention & Mitigation of
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Explosion & Impact (No. DPMEIKF201305) and a Project Funded by the Priority Academic
Program Development of Jiangsu Higher Education Institutions.
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Table 1 Reaction conditions of perfluorobutylethoxyl propyne 2a with allyl azide 3
Entry
Conditions
Temperature/ºC
Yield/%
1
2
3
4
CuI; t-BuOH:H2O=2:1a; 24h
CuI; Et3N; t-BuOH:H2O=2:1; 24h
CuI; Et3N; THF:H2O=2:1; 24h
40
40
50
None
23
48
CuSO4; NaAsc; t-BuOH:H2O=2:1; 24h
40
70
a The ratio indicated volumetric ratio.
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Scheme 1 Synthesis of mono-fluoroalkyl functionalized silanes
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Scheme 2 Synthesis of bis-fluoroalkyl functionalized silanes
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