Regioselective ring opening of [(perfluoroalkyl)methyl] oxiranes with N-nucleophiles

Article abstract of DOI:10.1016/j.jfluchem.2005.06.002

The reactions of C₈F₁₇CH₂CHCH₂O with some primary and secondary aliphatic amines affording selective ring opening at C_β are reported. The reactions with secondary amines HNR¹R² (R¹ = R² = Et; R¹ = Bu^t, R² = CH₂CH₂O(CO)C(CH ₃)CH₂; R¹ = Et, R² = CH ₂CH₂OH; R¹ = R² = CH ₂CH₂OH) gave the corresponding C₈F ₁₇CH₂CH(OH)CH₂NR¹R² derivatives. For R¹ = Et, R² = CH₂CH ₂OH; R¹ = R² = CH₂CH₂OH, the reactions proceed through the selective nucleophilic attack of the NH moiety with no evidence of reactivity of the OH group. The reactions with the primary amines, allylamine and n-hexamethylenediamine, gave different products depending on reaction conditions.

Full text of DOI:10.1016/j.jfluchem.2005.06.002

Journal of Fluorine Chemistry 126 (2005) 1274–1280
www.elsevier.com/locate/fluor
Regioselective ring opening of [(perfluoroalkyl)methyl]
oxiranes with N-nucleophiles
a
L. Conte a, F. Maniero a, A. Zaggia a, R. Bertani a, , G. Gambaretto ,
*
A. Berton b, R. Seraglia b
a
`
Dipartimento dei Processi Chimici dell’Ingegneria, Universita di Padova, Via Marzolo 9, 35131 Padova, Italy
b Istituto Scienze e Tecnologie Molecolari, C.N.R., Sezione di Padova, Via Marzolo 1, 35131 Padova, Italy
Received 24 February 2005; received in revised form 3 June 2005; accepted 6 June 2005
Available online 12 September 2005
Abstract
The reactions of
with some primary and secondary aliphatic amines affording selective ring opening at Cb are reported.
The reactions with secondary amines HNR1R2 (R1 = R2 = Et; R1 = But, R2 = CH2CH2O(CO)C(CH3) CH2; R1 = Et, R2 = CH2CH2OH;
R1 = R2 = CH2CH2OH) gave the corresponding C8F17CH2–CH(OH)–CH2–NR1R2 derivatives. For R1 = Et, R2 = CH2CH2OH;
R1 = R2 = CH2CH2OH, the reactions proceed through the selective nucleophilic attack of the NH moiety with no evidence of reactivity
of the OH group. The reactions with the primary amines, allylamine and n-hexamethylenediamine, gave different products depending on
reaction conditions.
# 2005 Elsevier B.V. All rights reserved.
Keywords: [(Perfuoroalkyl)methyl]oxiranes; F-Alkyl oxiranes; Ring opening; Primary and secondary aliphatic amines; Aminoalcohols; Fluorinated
surfactants
1. Introduction
with complete regioselectivity [1b]. F-Alkyl a-hydroxy
acids are prepared by ring opening oxidative reaction of
F-alkyl oxiranes in the presence of HNO3 [3].
Fluorinated oxiranes [1] are very important industrial
intermediates for various polymeric materials employed
for a wide variety of special purposes, from polymers
for contact lenses with improved oxygen transport, to
hydrophobic coatings and surface property modifiers
[2]. Fluoroalkyloxiranes can be easily transformed into
various products through nucleophilic ring opening
processes [1].
To our knowledge, only few reactions of perfluoroalkyl
epoxides have been reported with N-nucleophiles:
(i) morpholine, possessing
a
strongly nucleophilic
nitrogen, gave nucleophilic attack selectively at both
the terminal C-atoms in diepoxides of the type
(n = 4, 6) to yield
the corresponding dihydroxylated bis morpholinyl
derivatives [4]; (ii) hydrazine hydrate reacted with
O- and S-nucleophiles have been reported to react under
acid and base catalysis conditions with complete regios-
electivity of ring opening [1b]. Alkanols, alkane diols and
hydroxyalkyl (meth)acrylates are reported to give ring
opening of (perfluoroalkyl)methyl oxiranes in the presence
of Lewis acids [1b]. Thiourea reacts with perfluoroalkyl
epoxides under non-catalysed conditions to afford thiiranes
at ꢀ10 8C and at room temperature
to give the monoalkylated hydrazinoalcohol derivative
C8F17CH2CH(OH)CH2NHNH2, as the major product [5];
and (iii) aqueous ammonia (28%) reacted with F-alkylated
oxiranes to give the corresponding aminodiol derivatives
RFCH2CH(OH)CH2NHCH2CH(OH)CH2RF, formed by the
action of NH2 on the primary carbon atom of the starting
F-alkyl oxirane, followed by the action of –NH2 of the
* Corresponding author. Tel.: +39 049 8275731; fax: +39 049 8275525.
E-mail address: roberta.bertani@unipd.it (R. Bertani).
0022-1139/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2005.06.002

L. Conte et al. / Journal of Fluorine Chemistry 126 (2005) 1274–1280
1275
aminoalcohol intermediate, on the primary carbon atom of
an another starting F-alkyl oxirane [6].
perfluoroalkyl iodide C8F17I with allyl alcohol in the
presence of Na2S2O5 and AIBN [2,20-azobis(2-methylpro-
pionitrile)] as initiators in a biphasic system forming the
corresponding iodo-alcohol according to the procedure
reported by Brace for the addition of perfluoroalkyl iodides
to allylic compounds [16]. Free radical addition of RFI to
allylic compounds requires longer reaction time and more
initiator with respect to terminal alkenes and norbornene, in
order to obtain a high conversion avoiding ‘‘degradative
chain transfer’’ processes that represent a termination step.
In spite of these difficulties, the experimental conditions
suitable to obtain quite good conversion and yields have
been previously studied [17]. Subsequent epoxidation of the
iodo-alcohol mediated by NaOH gives the corresponding
oxirane in high yield [18] (Scheme 1).
Recently, highly efficient cleavage of aliphatic epoxides
with alcohols, aniline and thiophenol in the presence of
catalytic amount of BPh3 [7], with aromatic and aliphatic
amines in the presence of Zn(II) chloride [8] and of
ruthenium catalysts [9] have been reported.
Steric, polar and resonance effects can contribute to the
regioselectivity that is observed in the ring cleavage
reactions of unsymmetrical-substituted oxiranes [10a–c].
In the case of a monoalkyl-substituted oxirane, such as 2-
methyl oxirane, basic reagents such as sodium methoxide or
ammonia yield, predominantly, products of nucleophilic
attack at Cb (i.e. the least substituted carbon), while under
acidic conditions a greater proportion of attack occurs at Ca.
On the contrary, 2-phenyl oxiran is preferentially attacked at
the primary position by methoxide anion, while in the case
of attack by amines, both products can be obtained [10d–f].
The preparation of [(perfluoroalkyl)methyl] oxiranes was
previously reported to occur from 2-bromo-2-F-alkylethyl
acetates and from 2-bromo-2-F-alkylethanols by reactions
with concentrated NaOH and a phase transfer catalyst or
with KF in triethylene glycol [19a]. The one step synthesis
of perfluoroalkyl oxiranes was reported to occur starting
from perfluoroalkyl halides and allylic alcohols (in the
presence of K2CO3) catalyzed by PdCl2(PPh3)2 [19b].
The synthesis here described can be performed with very
good yield and was tested even with significantly large
reactant quantities. Furthermore, the high yield results
guaranteed by the use of the isopropyl alcohol, were
significantly reduced if the reaction is performed in the
presence of methanol or ethanol.
1-Perfluoroalkyl
epoxy
ethers
of
the
type
are reported to react with Lewis acids
to give different ring opening products, depending upon the
structure and the experimental conditions. In all cases,
except when a phenyl group stabilizes, the Cb secondary
carbenium ion, the Ca–O bond is broken leading to additon,
trasposition or cyclization products [11]. Consistent with the
above mechanistic concepts are the observations that in an
oxirane an electron withdrawing group with no conjugative
effect, such as a trifluoromethyl group, inhibits reaction at
that carbon to which it is attached [12].
Recently, the chemoselective preparation of perfluor-
oalkylated epoxides from branched iodoacetate and iodo-
hydrin precursors was also reported [20].
Recently, the mild cleavage of aliphatic epoxides with
substitutedanilinesoveraluminawasreportedinacompletely
regioselective fashion affording the compound formed by Cb
attack as the only product [13]. Mild and efficient aminolysis
of oxiranes was reported to occur in the presence of metal
salts (such as LiClO4, Mg(ClO4)2, NaClO4, CaCl2, ZnCl2,
LiBF4) as catalysts at room temperature [14].
2.2. Reactions of
with amines
The epoxide 1 was reacted with some primary and
secondary aliphatic amines with complete regioselectivity in
the ring opening according to Eq. (1) giving rise to the
corresponding amino alcohol derivatives 2–6.
Here we report the ring opening in (perfluoroalkyl)methyl
oxirane
with some primary and sec-
ondary aliphatic amines in order to prepare new amphiphilic
compounds suitable for paper treatment, capable of imparting
water repelling and oil resistance [15]. As a matter of fact,
aliphatic amines can be considered as models for polymeric
systems of technological interest as coatings, such as
polyethylenimines H–(NHCH2CH2)n–NH2 and –(NHCH2-
CH2)x–[N(CH2CH2NH2)CH2CH2]y–. Furthermore, the exp-
erimental conditions suitable to perform addition of one or
more fluorinated moieties to primary amines are discussed.
(1)
2. Results and discussion
The reaction of 1 with diethylamine and 2-(t-butylami-
no)ethyl methacrylate occurred only by mixing upon heating
to afford the corresponding products 2 and 3 in good yields.
Compounds 2 and 3 have been characterised by elemental
analysis, IR and NMR spectroscopic determinations. In
2.1. Synthesis of the epoxide
The [(perfluoroalkyl)methyl] oxirane
,
1, was prepared according to Scheme 1 by reaction of the

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L. Conte et al. / Journal of Fluorine Chemistry 126 (2005) 1274–1280
The values of contact angles and surface tension for 700
have been determined. Surface free energy of the solid was
calculated using the contact angles according to the method
proposed by Owens and Wendt [219b] who extended the
Fowkes concept [21a]. The QH O and QCH I for 700 are,
2
2 2
respectively, 114.7 ꢁ 28 and 108.3 ꢁ 78. The dispersion and
the polar components of the surface free energy of water are
26.0 and 48.5 mN mꢀ1, respectively, and those of diiodo-
methane are 46.8 and 2.3 mN mꢀ1, respectively [21b],
with a total surface energy of 6.92 mN mꢀ1. These values
must be compared with the corresponding QH O and QCH I
values obtained for poly(tetrafluoroethylene), which are
1088 and 888, respectively, with a total surface energy of
19.1 mN mꢀ1, significantly higher than the value calculated
for 700. The contact angle values must be as large as possible
to indicate hydrophobic and oleophobic properties (in any
Scheme 1.
particular, the 13C NMR data confirmed the selective form-
ation of the product obtained by regioselective attack of the
amine moiety to the Cb atom of the epoxide ring. The reaction
with 2-(t-butylamino)ethyl methacrylate was performed in
the presence of a catalytic amount of hydroquinone in order
to avoid polymerization processes of the amine.
2
2 2
The reaction of 1 with allylamine was performed by
heating at 90 8C for 5 h; GC/MS analysis of the reaction
mixture indicates the formation of two products in about
60/35 ratio, corresponding to 4 and [C8F17CH2–CH(OH)–
CH2]2NCH2CH CH2, 40, the latter being obtained by
subsequent addition of two epoxide moieties to the primary
amine. The formation of [C8F17CH2–CH(OH)–CH2]2-
NCH2CH CH2 was confirmed by mass spectrometric
analysis of the reaction mixture.
case larger than 908; QH O ꢂ 1508 corresponds to super-
2
hydrophobic behavior) while the total surface energy value
must be as small as possible.
3. Experimental
3.1. General
Reaction of 1 with 2-(ethylamino)ethan-1-ol gave selec-
tively product 5 obtained by addition of the NH moiety, not
OH, to the Cb carbon of the epoxide. The reaction occurred
only upon heating the reagents obtaining the desired product
in very good yield. Also reaction of 1 with diethanolamine
occurred through the selective attach of the NH moiety,
affording quantitatively the product 6, bearing three OH
groups, suitable for interaction with hydrophilic surfaces.
1 reacted also with the diamine hexamethylenediamine
yielding the corresponding diamino-dialcohol derivative 7
(Eq. (2)).
Perfluorooctyl iodide was a commercial grade reagent
(Elf Atochem S.A.). Diethylamine, 2-(t-butylamino)ethyl-
methacrilate, allylamine, 2-(ethylamino)ethan-1-ol, dietha-
nolamine, hexamethylenediamine and AIBN [2,20-azobis(2-
methylpropionitrile)] were purchased from Aldrich Chemi-
cal Co. All other reagents employed were common
laboratory materials. All the chemical reagents were used
as received. Reactions were performed under inert atmo-
sphere (N2). GLC analyses of the reaction mixtures were
performed using a Carlo Erba GC6000 VEGA2 instrument
(2.5 m ꢃ 2 mm stainless steel column packed with RTZ 100
Silicoport P200-20). Typical operative conditions were:
temperature programme 508, 208 minꢀ1 to 250 8C; He as gas
carrier 24 ml minꢀ1
.
(2)
GCMS spectra were measured on a Carlo Erba
Instruments MFC 500/QMD1000 using a silica fused
capillary PS264 column (30 m ꢃ 0.2 mm) and on a Finnigan
Mat TSQ7000 (capillary column 30 m ꢃ 0.3 mm). Typical
conditions were: temperature programme 608 for 2 min,
Compound 7 was characterized by elemental analysis, IR
spectroscopy and NMR spectrometry. The mass spectro-
metric analysis by MALDI technique confirmed the forma-
tion of 7 accompanied by a small (<10%) amount of the
ter-adduct [C8F17CH2CH(OH)CH2]2N(CH2)6NHCH2CH-
(OH)CH2F17C8, 70, characterized by the presence of the
signals at m/z 1544 in the MALDI determination.
108 minꢀ1 to 280 8C; He as gas carrier 1 ml minꢀ1
.
FT IR spectra were measured using a Nicolet Avatar
spectrophotometer.
1H and 13C {1H} NMR spectra were recorded on a Bruker
200 AC spectrometer operating at 200.1 and 50.3 MHz,
respectively. Peak positions are relative to Me4Si and were
calibrated against the residual solvent resonance (1H) or the
deuterated solvent multiplet (13C). 19F NMR measurements
were recorded on a Bruker 200 AC spectrometer operating at
188.3 MHz. Peak positions are reported relative to CFCl3.
The electrospray ionisation mass spectrum of 6 was
recorded on a LCQ DECA (Finningam MAT) instrument,
Compound [C8F17CH2CH(OH)CH2]2N(CH2)6N[CH2-
CH(OH)CH2F17C8]2, 700 is the only product formed when
the reaction of the diamine H2N–(CH2)6–NH2, is performed
at 120 8C and for longer time (8 h) in the presence of four
equivalents of 1, as clearly indicated by the MALDI analysis
of the solid product obtained.

L. Conte et al. / Journal of Fluorine Chemistry 126 (2005) 1274–1280
1277
operating in positive ion mode. The instrumental conditions
used were the following: source potential 4 kV, capillary
temperature 270 8C, sheath gas (N2) flow rate 40 arbitrary
units. One milligram of samples was dissolved in 1 ml of
acetone. Five microlitres of the initial solution were diluted
to 1 ml with CH3CN. The final solution was directly
introduced into the ESI ion source by a syringe pump at a
1H NMR (CD3COCD3): d 3.2 (m, CHO, 1H); 2.5 (m,
CF2CH2, 2H); 3.0 (m, CH2O, 1H); 3.3 (m, CH2O, 1H).
19F NMR (CD3COCD3):
d
ꢀ82.8 (t, CF3,
3JFF = 10.0 Hz); ꢀ113.9 (m, CF2CH2); ꢀ123.3, ꢀ124.2,
ꢀ124.7, ꢀ127.8 (m, CF2). 13C NMR (CD3COCD3): d 45.1
3
(s, CH2), 44.6 (t, CH, JCF = 5.6 Hz), 35.2 (t, CH2CF2,
2JCF = 21.7 Hz), 115–125 (m, CF2, CF3).
flow rate of 10 ml minꢀ1
.
MALDI mass measurements were performed on a
REFLEX time-of-flight instrument (Bruker-Franzen Analy-
tik, Bremen, Germany) equipped with a SCOUT ion source,
operating in positive reflectron mode. Ions, formed by a
pulsed UV laser beam (nitrogen laser, l = 337 nm) were
acceleratedto25 kV. Pulsedionextraction(PIE)wasobtained
applying a voltage of about 14 kV to the second grid for
200 ns. 2,5-Dihydroxybenzoic acid (DHB) (10 mg mlꢀ1 in
acetone) was used as matrix. Five microlitres of sample
solution (2 mg/mL in CHCl3) was mixed with 5 mL of matrix
solution. One microlitre of the resulting mixture were deposi-
ted on the stainless steel sample holder and allowed to dry
before introduction into the mass spectrometer. External mass
calibration was made using the [M + H]+ and [M + 2H]2+ ions
of bovine insulin at m/z 5734 and 2867, respectively.
3.3. Reaction of
with diethylamine
57.2 g of 1 (0.1 mol) were reacted with diethylamine at
85 8C for 12 h. Diethylamine (8.8 g, 0.1 mol) was added into
three steps (3 g at the beginning, 3 g after 7 h and 3 g after a
further hour). Residual diethylamine was distilled at 55 8C.
The GC/MS analysis of the reaction mixture showed the
presence of a unique peak at retention time of 9.4 min.
Compound 2 was distilled at 108–110 8C, 4–7 mbar. M.P.
45 8C. Yield: 52.1 g (79%).
El. Anal. Calcd. for C15H16F17ON, C, 32.8; H, 2.9; N, 2.5.
Found: C, 33.0; H, 2.9; N, 2.6.
Mass spectrum (m/z, rel.ab%): 549 ([C8F17CH2CH(OH)-
CH2N(C2H5)2]ꢄ+, 5); 534 ([C8F17CH2CH(OH)CH2N(C2H5)-
CH2]+, 5); 531 ([C8F17CH CHCH2N(C2H5)2]ꢄ+, 2); 520
([C8F17CH2CH(OH)CH2N(C2H5)]+, 2); 116 ([CH(OH)-
CH2N(C2H5)2]+, 20); 86 ([(C2H5)2NCH2]+, 100); 58
([(C2H5)CH3N]+, 20).
The surface free energies were determined using a Kruss
G10/DSA10 goniometer interfaced to image-capture soft-
ware. Measurements were made with de-ionised water and
diiodomethane taking an average of ten 15 mL drops with
each type of liquid.
IR (neat): nOH 3431 s br; nCF 1205 s cmꢀ1
.
1H NMR (CD3COCD3): d 1.6 (t, CH3, 3JHH = 6.2 Hz, 6H);
2.7–3.2 (m, CH2, 8H); 4.6 (m, CH, 1H); 5.0 (s, OH, 1H).
19F NMR (CD3COCD3): d ꢀ82.3 (t, CF3, 3JFF = 9.4 Hz);
ꢀ113.1 (t, CF2CH2); ꢀ122.3, ꢀ122.8, ꢀ122.5, ꢀ124.3,
ꢀ127.2 (m, CF2).
3.2. Synthesis of
In a 2-L round-bottomed flask equipped with a reflux
condenser connected with the atmosphere through a drying
tube and a mechanic stirrer, 1000 g (1.8 mol) of C8F17I,
800 g of a 24% water solution of Na2S2O5 and 9.0 g of AIBN
were introduced. When the temperature of the reaction
mixture reached 80 8C, 150 g (2.6 mol) of allyl alcohol were
added dropwise in an hour. The reaction mixture was heated
for additional 2 h at 80 8C. Then the reaction mixture was
cooled to room temperature and 500 g of water were added.
A white solid formed, which was filtered off, washed with
water and identified as C8F17CH2CHICH2OH.
13C NMR (CD3COCD3): d 11.0 (s, CH3), 47.1 (s, NCH2),
2
59.8 (s, NCH2), 61.6 (CH), 35.5 (t, CH2CF2, JCF
21.0 Hz), 102–128 (m, CF2, CF3).
=
3.4. Reaction of
2-(t-butylamino)ethyl methacrilate
with
2-(t-Butylamino)ethyl methacrilate (11.2 g, 0.1 mol)
have been reacted with 28.5 g (0.1 mol) of 1 at 150 8C
for 17 h in the presence of a catalytic amount of
hydroquinone. The reaction mixture turned to brown. The
product was distilled at 140–145 8C (1 mbar). The GC/MS
analysis of the reaction mixture showed the presence a
unique peak at retention time of 29.2 min.
The undried product (1350 g) was reacted with 380 g of
40% NaOH water solution containing 230 g of isopropyl
alcohol at room temperature for 45 min under stirring.
Then 300 g of water and 300 g of CHCl3 were added.
From the organic phase after three extractions (3 ꢃ 100 ml),
the final epoxide was distilled at 100 8C (17 mbar). Yield:
783.0 g (90%). A GC/MS analysis of the product showed a
unique peak at retention time of 4.9 min.
Yield: 33.3 g (84%). El. Anal. Calcd. for C21H24F17O3N,
C, 38.1; H, 3.7; N, 2.1. Found: C, 38.0; H, 3.5; N, 2.0.
Mass spectrum (m/z, rel.ab%): 661 ([C8F17CH2CH(OH)-
CH2N(CBut)(CH2CH2OCOC(CH3)CH2]ꢄ+, 0.1); 646 ([C8-
F17CH2CH(OH)CH2N(CBut)(CH2CH2OCOCCH2]+, 0.2);
506 ([C8F17CH2CH(OH)CH2NHCH2]+, 20); 198 ([CH2-
C(CH3)CO2CH2CH2NHC(CH3)3CH]+, 90); 142 ([CH2-
C(CH3)CO2CH2CH2NHCH2]+, 100); 113 ([CH2-
C(CH3)CO2CH2CH2]+, 72); 69 ([CH2C(CH3)CO]+, 60);
57 ([C(CH3)3]+, 70); 41 ([C3H5]+, 35).
El. Anal. Calcd. for C11H5F17O: C, 27.7; H, 1.1; Found:
C, 27.5; H, 1.1. Mass spectrum (m/z, rel.ab%): 476
([C8F17CH2CH(O)CH2]ꢄ+, 5); 57 ([CH2CH(O)CH2]+, 70);
107 ([CF2CH2CH(O)CH2]+, 100).
IR (neat): nCH 3058 m, 3011 m, 2925 m; nCF 1205 s; nCOC
.
908 cmꢀ1

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L. Conte et al. / Journal of Fluorine Chemistry 126 (2005) 1274–1280
IR (neat): nOH 3435 s br; nCO 1720 s; nC C 1639 m; nCF
1206 s cmꢀ1
13C NMR (CD3COCD3): d 63.6, 62.7, 62.0, 61.1 (s,
NCH2 e CH), 36.0 (t, JCF = 20.7 Hz, CH2CF2), 135.4
3
.
1H NMR (CD3COCD3): d 1.1 (s, But, 9H); 2.0 (m, CH3,
3H); 2.7–3.0 (m, NCH2 and CH2CF2, 6H); 4.1 (m, CH and
OCH2, 3H); 6.1 and 5.6 (m, CH2, 2H), 4.7 (s, br, OH, 1H).
(CH ), 118.0 (CH2 ), 125–110 (m, CF2, CF3).
Product 40 was obtained in a separate experiment by
reacting 6.0 g (0.1 mol) of allylamine with 1 (23.8 g,
0.05 mol) at 90 8C for 8 h. Yield 2.5 g (87%). El. Anal.
Calcd. for C25H17F34O2N, C, 29.7; H, 1.7; N, 1.4. Found: C,
30.1; H, 1.5; N, 1.2.
3
19F NMR (CD3COCD3): d ꢀ82.5 (t, JFF = 11.3 Hz,
CF3); ꢀ113.7 (t, CF2CH2); ꢀ122.9, ꢀ123.2, ꢀ124.1,
ꢀ124.7, ꢀ127.6 (m, CF2).
13C NMR (CD3COCD3): d 17.8 (s, CH3), 55.3 (s, NCH2),
2
35.8 (t, JCF = 21.1 Hz, CH2CF2), 26.9 (s, CCH3), 54.0
3.6. Reaction of with
2-(ethylamino)ethan-1-ol
(CCH3), 65.4 (s, CH2O), 167.1 (s, CO), 137.0 (s, C ), 125.7
(s, CH2 ), 58.0 (s, NCH2), 63.3 (CHOH), 105–110 (m, CF2,
CF3).
2-(Ethylamino)ethanol (9.0 g, 0.1 mol) were heated at
85 8C and reacted with 47.6 g of 1 (0.1 mol) added dropwise
during 2 h. The reaction mixture was reacted for further 3 h.
Then the final product, compound 5, was distilled at 162 8C
(42 mbar). The GC/MS analysis showed the formation of a
unique product at 17.6 min.
3.5. Reaction of
with allylamine
Allylamine (2.8 g, 0.05 mol) was reacted with an
equimolar amount of 1 (23.8 g, 0.05 mol) at 90 8C for
5 h. The product was distilled at 168–178 8C (1 mbar). The
GC/MS analysis of the reaction mixture showed the
presence of two significant peaks at 19.9 and 27.3 min, in
60/35 ratio, respectively, which were identified as product 4
and 40 on the basis of the mass spectra. Compound 4 was
purified by further distillation at 140–142 8C (1 mbar).
Yield: 184.0 g (67%). El. Anal. Calcd. for C14H12F17ON,
C, 31.5; H, 2.3; N, 2.6. Found: C, 33.0; H, 2.1; N, 2.5.
Mass spectrum (m/z, rel.ab%): 533 ([C8F17CH2CH(OH)-
CH2NHCH2CHCH2]ꢄ+, 2); 532 ([C8F17CH2CH(OH)CH2-
NCH2CHCH2]+, 2); 506 ([C8F17CH2CH(OH)CH2NCH3]+,
2); 488 ([C8F17CH2CHCHNCH3]+, 3); 463 ([C8F17CH2CH-
(OH)]+, 1); 70 ([C3H5NHCH2]ꢄ+, 100); 41 ([C3H5]+, 35).
Yield: 52.2 g (92%). El. Anal. Calcd. for C15H16F17-
O2N, C, 31.9; H, 2.9; N, 2.5. Found: C, 32.1; H, 2.5; N,
2.2.
Mass spectrum (m/z, rel.ab%): 565 ([C8F17CH2CH(OH)-
CH2N(CH2CH3)(CH2CH2OH)]ꢄ+, 5); 534 ([C8F17CH2-
CH(OH)CH2N(C2H5)CH2]+, 15); 132 ([C6H14NO2])]ꢄ+,
15); 102 ([C5H12NO]ꢄ+, 100); 58 ([C3H8N]+, 25).
IR (neat): nOH 3384 br; nCF 1202 s cmꢀ1
.
1H NMR (CD3COCD3): d 1.0 (t, CH3, JHH = 6.3 Hz,
3H); 2.0–2.7 (m, CH2, 6H); 3.5 (m, CH2, 2H); 4.0 (m, CH
and CH2, 3H), 4.5 (s, br, OH, 1H).
3
3
19F NMR (CD3COCD3): d ꢀ82.4 (t, JFF = 10.0 Hz,
CF3); ꢀ113.6 (t, CF2CH2); ꢀ122.8, ꢀ123.1, ꢀ123.9,
ꢀ124.7, ꢀ127.4 (m, CF2).
IR (KBr): nOH 3400 br; nCF 1202 s; nC C 1648 m cmꢀ1
.
1H NMR (CD3COCD3): d 4.2 (m, CH, 1H); 4.3 (s, br, OH,
1H), 5.9 (m, CH , 1H); 5.1 (m, CH2 , 2H); 3.3–3.1 (m,
CH2, 4H); 2.7 (td, CH2, 3JHH = 0.3 Hz, 3JHF = 1.0 Hz, 2H);
13C NMR (CD3COCD3): d 11.5 (CH3), 49.0, 60.3 and
61.0 (NCH2), 58.4 (CH2OH), 36.4 (t, CH2CF2,
2JCF = 21.1 Hz), 62.9 (CHOH), 102–128 (m, CF2, CF3).
3.4 (br, NH, 1H).
19F NMR (CD3COCD3): d ꢀ82.6 (t, CF3, JFF
3
=
10.6 Hz); ꢀ113.9 (t, CF2CH2); ꢀ122.8, ꢀ123.5, ꢀ124.8,
3.7. Reaction of
diethanolamine
with
ꢀ127.5 (m, CF2).
2
55.6 (s, NCH2CH), 36.9 (t, JCF = 20.6 Hz, CH2CF2), 52.0
3
13C NMR (CD3COCD3): d 68.2 (t, CH, JCF = 2.6 Hz),
Diethanolamine (21.0 g, 0.2 mol) were heated at 85 8C
and reacted with 47.6 g of 1 (0.1 mol). The reaction mixture
was reacted for 6 h. A solid product formed which was
identified as 6; mp 92–93 8C.
Yield: 67.2 g (98%). El. Anal. Calcd. for C15H14F17O3N,
C, 31.1; H, 2.4; N, 2.4. Found: C, 30.8; H, 2.2; N, 2.2.
Mass spectrum (ESI, m/z, rel.ab%): 582 ([C8F17CH2-
CH(OH)CH2N(CH2CH2OH)2H]ꢄ+, 100); 564 ([C8F17CH2-
CH(OH)CH2N(CH2CH2)(CH2CH2OH)]ꢄ+, 45); 520 ([C8F17-
CH2CH(OH)CH2N(CH2CH3)]ꢄ+, 10).
IR (KBr): nOH 3386 br; nCF 1204 s cmꢀ1
.
1H NMR (CD3COCD3): d 2.6 (m, CH2, 6H); 3.6 (m, CH2,
6H); 4.2 (s, br, OH and CH, 4H).
19F NMR (CD3COCD3): d ꢀ82.5 (t, 3JFF = 9.8 Hz, CF3);
ꢀ113.6 (t, CF2CH2); ꢀ122.9, ꢀ123.2, ꢀ124.0, ꢀ124.7,
ꢀ127.5 (m, CF2).
(CH2), 137.3 (CH ), 116.0 (CH2 ), 100–130 (m, CF2, CF3).
The product [C8F17CH2CH(OH)CH2]2NCH2CH CH2, 40,
was distilled at 205–207 8C (1 mbar). Yield: 6.9 g (24%).
Mass spectrum (m/z, rel.ab%): 573 ([C8F17CH2-
CH(OH)CH2N(CH2CHCH2)2]+; 546 ([C8F17CH2CH(OH)-
CH2N(CH2)CH2CHCH2]+, 100), 5); 490 ([C8F17C3H5NO]+,
15); 69 ([C3H5NCH2]ꢄ+, 30); 41 ([C3H5]+, 60).
IR (KBr): nOH 3400 br; nCF 1210 s; nC C 1644 m cmꢀ1
.
1H NMR (CD3COCD3): d 5.2 (m, CH2 , 4H); 4.2 (m, CH,
2H); 4.3 (s, br, OH, 2H), 5.9 (m, CH , 2H); 3.3 (m, NCH2,
3
4H); 2.7 (m, CH2, 4H); 2.4 (td, CH2, JHH = 0.4 Hz,
3JHF = 1.1 Hz, 4H).
19F NMR (CD3COCD3): d ꢀ82.5 (t, CF3, JFF = 9.9 Hz);
3
ꢀ114.0 (t, CF2CH2); ꢀ122.9, ꢀ123.2, ꢀ123.2, ꢀ125.0,
ꢀ127.6 (m, CF2).

L. Conte et al. / Journal of Fluorine Chemistry 126 (2005) 1274–1280
1279
13C NMR (CD3COCD3): d 59.1 (NCH2), 61.1 (CH2OH),
3
36.6 (t, CH2CF2, JCF = 20.5 Hz), 64.1 (CHOH), 63.4
(NCH2), 128–106 (m, CF2, CF3).
Mass spectrum (MALDI): 2020, [M]ꢄ+; 1543
[M ꢀ CH2C(OH)CH2C8F17]+. IR (KBr): nOH 3397 m br;
1
nCF 1220 s cmꢀ1. H NMR (CD3COCD3): d 1.2 (m, CH2,
8H); 2.0–2.6 (m, CH2, 20H); 4.0 (m, CH, 4H); 4.2 (s, br, OH,
4H).
3.8. Reaction of
n-hexamethylendiamine
with
19F NMR (CD3COCD3): d ꢀ83.2 (t, CF3, 3JFF = 9.2 Hz);
ꢀ114.2 (t, CF2CH2); ꢀ123.3, ꢀ123.7, ꢀ124.6, ꢀ125.3,
ꢀ128.2 (m, CF2).
95.2 g of 1 (0.2 mol) were reacted with hexamethylen-
diamine (11.6 g, 0.1 mol) at 100 8C for 3 h. The obtained
product was dissolved in hot THF. Upon cooling, a light
yellow solid precipitated, which was filtered off and
identified as compound 7.
13C NMR (CD3COCD3):
d
36.0 (t, CH2CF2,
2JCF = 19.5 Hz), 56.0 and 55.7 (CHOH), 62.6, 63.7 and
61.6 (NCH2), 27.4 and 27.1 (CH2); 105–125 (m, CF2, CF3).
Yield: 70.5 g (66%). El. Anal. Calcd. for C28H26F34O2N2,
C, 31.5; H, 2.4; N, 2.6. Found: C, 30.9; H, 2.2; N, 2.7.
Mass spectrum (MALDI): 1068, [M]ꢄ+; 649
[M ꢀ C8F17]+; 635 [M ꢀ C8F17–CH2]ꢄ+; 591 [M ꢀ C8F17–
C3H6O]+; 576 [M ꢀ C8F17–C3H6ONH]ꢄ+; 562 [M ꢀ C8F17–
C3H6ONH–CH2]+; 548 [M ꢀ C8F17–C3H6ONH–2CH2]ꢄ+;
419 [C8F17]+; 319 [C6F13]+.
4. Conclusions
Regioselective ring opening was observed in the
reactions of with some primary and secondary aliphatic
amines, which can be considered as models for polymers,
giving rise to the products selectively formed by nucleo-
philic attack on the Cb in the epoxide ring. The process could
represent an interesting method for the controlled introduc-
tion of perfluorinated chains onto monomeric and polymeric
systems bearing amino groups in the aim to prepare new
amphiphilic compounds suitable for surface treatments.
IR (KBr): nOH 3380 m br; nNH 3130 m br; nCF
1204 s cmꢀ1
.
1H NMR (CD3COCD3): d 1.4 (m, CH2, 8H); 2.4–3.2 (m,
CH2, 12H); 4.4 (m, CH, 2H); 4.2 (s, br, NH, 2H); 4.5 (s, br,
OH, 2H). 19F NMR (CD3COCD3): d ꢀ82.3 (t, CF3,
3JFF = 9.6 Hz); ꢀ113.9 (t, CF2CH2); ꢀ123.0, ꢀ123.9,
ꢀ124.7, ꢀ127.4 (m, CF2).
13C NMR (CD3COCD3):
d
37.0 (t, CH2CF2,
Acknowledgements
2JCF = 20.5 Hz), 68.4 (CHOH), 55.2 (NCH2), 48.4 (CH2),
27.2 (CH2); 115–125 (m, CF2, CF3).
The authors acknowledge the MIUR (PRIN2003) for
financial support.
From the THF solution, by taking to dryness, a yellow
product was obtained, which was characterised as [C8F17-
CH2CH(OH)CH2]2NCH2(CH2)4CH2NHCH2CH(OH)CH2-
C8F17, 70. Yield: 9.7 g (6.2%). El. Anal. Calcd. for C39H30-
F51O3N2, C, 30.3; H, 2.0; N, 1.8. Found: C, 30.2; H, 1.8; N,
1.7.
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