Fluorinated epoxides: 5. Highly selective synthesis of diepoxides from α,ω-diiodoperfluoroalkanes. Regioselectivity of nucleophilic epoxide-ring opening and new amphiphilic compounds and monomers

Journal of Fluorine Chemistry 102 (2000) 349±361

Fluorinated epoxides

5. Highly selective synthesis of diepoxides from

a,o-diiodoper¯uoroalkanes. Regioselectivity of nucleophilic

epoxide-ring opening and new amphiphilic compounds and monomers^$

1

*

Â

Ï

Â

Vladimõr Cõrkva, Manuel Gaboyard , Oldrich Paleta

Department of Organic Chemistry, Prague Institute of Chemical Technology, Technicka 5, 16628 Prague 6, Czech Republic

Received 15 August 1999; received in revised form 26 August 1999; accepted 27 September 1999

Dedicated to Professor Paul Tarrant on the occasion of his 85th birthday

Abstract

An improved procedure for the radical addition of a,o-diiodoper¯uoroalkanes I±(CF₂CF₂)_n±I (n 2, 3) to allyl acetate that afford the

corresponding bis-adducts AcOCH₂CHICH₂(CF₂CF₂)_nCH₂CHI±CH₂OAc (2a±2b) has been developed. The primary bis-adducts 2a±2b

suffered a subsequent rearrangement in the addition mixture to afford semi-rearranged adducts AcOCH₂CHICH₂±(CF₂CF₂)_n±CH₂CH±

(OAc)CH₂I (3a±3b) in an amount of ca. 15% rel. at reaction temperatures. Both adducts 2a±2b and rearranged adducts 3a±3b were

converted to diepoxides CH₂(±O±)CHCH₂(CF₂CF₂)_nCH₂CH±(±O±)CH₂(4a±4b) with high chemoselectivity in two ways: the selectivity of

the direct epoxidation of 2a±2b and/or 3a±3b with potassium hydroxide was extremely dependent on the solvent; the second method

included hydrolysis of 2a±2b and/or 3a±3b to bis-iodohydrins 5a±5b and 6a±6b that were easily transformed to the diepoxides 4a±4b.

Ring-opening reactions of bis-epoxides 4a±4b with hydroxy compounds in the presence of boron tri¯uoride etherate took place at the

terminal carbon atom of both epoxide rings with complete regioselectivity. A convenient transformation of the diepoxides to the

corresponding amphiphilic tetrols (14a±14b) via dioxolane intermediates was accomplished with overall yields of 57±65% . Base-catalyzed

ring-opening by methacrylic acid was not completely regioselective (89% terminal attack on both oxirane rings) and afforded a mixture of

regioisomeric bis-methacrylates (16a±16b and 17a±17b) bearing two hydroxyl groups. In contrast, epoxide ring-opening with morpholine

Keywords: Radical addition of a,o-diiodoper¯uoroalkanes; Rearrangement of a-iodoacetates; Bis-iodohydrins; Epoxidation; Nucleophilic rearrangement of

¯uoroalkyloxiranes; Diepoxy¯uoroalkanes; Nucleophilic oxirane ring opening; Amphiphilic compounds; a,o-Bis(2,2-dimethyl-1,3-dioxolan-4-yl)¯uoroalk-

anes; Fluoroalkanetetrols; Dihydroxy¯uoroalkane-a,o-diyl bis-methacrylates; a,o-Bis(morpholin-4-yl)¯uoroalkanediols

1. Introduction

applications. Unfortunately, this review has not included a

series of recent papers [5±13] from the Journal of Fluorine

Chemistry which correct some previous results [5,10],

improve procedures to some important synthetic intermedi-

ates [6±11,13] and extend variety of useful products for

potential practical applications prepared on the basis of the

radical additions [9,12,14,15]. A careful spectral analysis of

the reaction mixture in additions of per¯uoroalkyl iodides to

allyl acetate, that were originally carried out previously

[4,16±18], led to the discovery of a novel rearrangement

[5,8]. The new and improved knowledge presented in the

recent papers [5,8±12] were employed with advantage in this

paper.

Some years ago, P. Tarrant had emphasized in a review [3]

that ¯uorocarbon iodides have been useful reagents for the

preparation of a variety compounds by several fundamental

reactions including radical additions. Recently, N.O. Brace

summarized in a recent review [4] free radical chemistry of

per¯uoroalkyl iodides in the synthesis of organic substances

of a large variety of structures with emphasis on practical

^$Part 1, [1]. Part 2, [2]. Part 3, [11]. Part 4, [12].

^*Corresponding author. Fax: 42-2-2431-1082.

E-mail address: oldrich.paleta@vscht.cz (O. Paleta).

1

Analogously to the chemistry of per¯uoroalkyl iodides

[3,4], the chemistry of diiodoper¯uoroalkanes can lead to a

Â

Present address: Ecole Nationale Superieure de Chimie de Montpellier,

34296 Montpellier Cedex 5, France.

PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 3 0 1 - 2

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

350

variety of mono- and bifunctional compounds, e.g. special

amphiphilic compounds, substituted diols for polyesters or

polyurethanes [14,15,19±21], bifunctional monomers and

curing and crosslinking agents for polymers including coat-

ings [22]. While the chemistry of per¯uoroalkyl iodides has

been extensively studied [4,8 and references therein], the

reports on the chemistry of a,o-diiodoper¯uoroalkanes are

relatively scarce. Among radical additions of the reagents to

ole®ns, e.g. the additions to ethylene and propene [7,23], b-

bromostyrene [24], vinyl acetate [25] or allyl-substituted

steroide compound [26] have been published. In addition,

several papers have reported additions of diiodoper¯uor-

oalkanes to allyl acetate: the addition reaction of some a,o-

diiodoper¯uoro-alkanes [16,17,25] has been described pre-

viously, but the structures of products were assigned, as

usual in that time, only on the basis of elemental analyses

and refractive indexes and/or boiling points; in a more

recent study [7], the addition products were not puri®ed

and characterized; recently, the additions with diiodoper-

¯uoroalkanes were described [8] in details and main and by-

products were characterized. The last reaction afforded

mixtures of mono- and bis-adducts. In this paper, a proce-

dure has been developed affording almost pure bis-adducts.

Diepoxides, in which the oxirane rings are connected by a

¯uorinated or per¯uorinated alkane-a,o-diyl, i.e.

±

(CH₂)_n(CF₂)_m(CH₂)_n± (n 0, 1; m 4, 6, 8), are quite

rarely reported in the literature: the ®rst type (n 0,

m 4) was obtained by a several-step synthesis from per-

¯uorodicarboxylate [27], while the second type (n 1,

m 4) was obtained by a direct epoxidation of the bis-

adduct to allyl acetate [16]. Concerning reactions of these

diepoxides, we have not found any characterized compound

prepared from the diepoxides.

Scheme 1. Products of radical addition of diiodoperfluoroalkanes to allyl

acetate.

initially and subsequently react with the second molecule of

allyl acetate to form bis-adducts 2a±2b (Scheme 1) [8]. The

relative amount of mono- and bis-adducts can be strongly

in¯uenced by a solvent: the reaction in butyronitrile leads to

almost exclusive formation of bis-adducts, while without

solvent the end reaction mixture contained 25±33% of

mono-adducts 1a±1b (Table 1). In contrast to previous

report [8], no 2 : 1 telomers were detected in the mixture

probably owing to a lower reaction temperature and lower

reactivity of relatively bigger molecules 2a±2b. The primary

adducts 1a±1b and 2a±2b undergo a subsequent rearrange-

ment [5,8]. The amount of rearranged products is dependent

on reaction temperature, but after some time an equilibrium

is established [5]. In this study the content of semi-rear-

2. Results and discussion

2.1. Radical additions of a,o-diiodoperfluoroalkanes to

allyl acetate

The reactions of diiodides I±(CF₂)_n±I (n 4, 6) were

initiated with dibenzoyl peroxide [7,8,16]. They are step-

wise processes in which mono-adducts 1a±1b are formed

Table 1

Composition of mono- and bis-adducts obtained in the radical addition of diiodoperfluoroalkanes to allyl acetate

Starting

diiodide

Solvent

Conversion

(%)

Composition of adducts (%)^b

Ratio of

bis-adducts

Mono-adduct

Bis-adducts

2/3 (% rel.)

1

2

3

a

I±(CF₂CF₂)₂±I

I±(CF₂CF₂)₃±I

±

98

1a

1b

33

4

2a

2b

67

0

Butyronitrile

a

±

82.5

75

3a

3b

13.5

0

86/14

84/16

25

2

Butyronitrile

82.5

15.5

^a[8].

^bCalculated from ¹⁹F NMR spectra.

Table 2

Selectivity of the formation of epoxides 4a±4b from diacetates 2a±2b (AcOCH₂CHICH₂±Q_F±CH₂CHI±CH₂OAc), 3a±3b or diiodohydrins 5a±5b, 6a±6b by potassium hydroxide in solvents

Starting compound

Q_F

Solvent^a

Time (h)

Conversion (%)

Reaction mixture composition^b(% rel.)

Diepoxide yield (%)

Purity

Diepoxide

Unsaturated

4a±4b

ester 11a±11b

alcohol 9a±9b

2a

2b

5a

5b

C₄F₈

C₆F₁₂

C₄F₈

C₆F₁₂

100

86^c

100

84^d

100

86^f

Hexane

5

0

98

99

98

99

98

±

4a

4b

4a

4b

0

Et₂O

5

25

62

86

88

25

86

87

95

94

95

94

51

25

9

24

13

5

15

50

71^h

72

10

72^h

72

73^h

74

76^h

76

Hexane/Et₂O (1 : 1)

Hexane/Et₂O (4 : 1)

Hexane

5

8

4

5

50^e

9^e

8^e

±

25^e

5^e

5

Hexane/Et₂O (4 : 1)

Et₂O

5

0.5

Et₂O

±

6

100

84^g

±

5^e

6^e

Et₂O

±

^aMixing at room temperature.

^bGC analyses with calibration.

^cIsomer 3a, 14% rel.

^dIsomer 3b,16% rel.

^eThe structures of 9b and 11b were not confirmed.

^fIsomer 6a, 14% rel.

^gIsomer 6b, 16% rel.

^hPurity 99%.

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

352

Table 3

of by-product. No by-products have been reported in pre-

vious papers using pentane or hexane [9,16].

Optimization of the solvent mixture for epoxidation of diiododiacetates

2a±2b and 3a±3b

We employed our experience [11] in the optimization of a

solvent system for the preparation of diepoxides 4a±4b

using powdered potassium hydroxide (Tables 2 and 3,

Scheme 2) that appeared to be a better base than sodium

hydroxide in the epoxidations [11]. However, solvent-che-

moselectivity relation appeared to be rather different from

that observed in the preparation of per¯uoroalkylated oxi-

ranes on the basis of additions of per¯uoroalkyl iodides

[11]: diethyl ether again caused the formation of about 75%

rel. of by-products 9a and 11a in the epoxidation, but

epoxidation in hexane, the best solvent for the preparation

of monoepoxides from the iodoacetates [11] gave surpris-

ingly no product or low yield (Table 2). Therefore, a mixed

solvent containing diethyl ether was optimized (Table 3).

Petroleum ether and hexane as the main component

appeared to be the best among other hydrocarbons, but

the latter gave better chemoselectivity (Tables 2 and 3).

By this methodology, the amount of the by-products 9 and

11 was reduced to about 13% rel. (Table 2), which is a more

worse result than that for the preparation of monoepoxides

where the relative amount of by-products was suppressed to

about 2% rel. [11]. Both initial bis-adducts 2a±2b and

rearranged bis-adducts 3a±3b were converted to the diep-

oxides 4a±4b which is an analogous observation to that for

the formation of monoepoxides [11].

Solvent mixture

Vol. : Vol.

Reaction mixture composition (%)

Diepoxide 4a

Diacetates 2a, 3a

Petroleum ether/diethyl ether

4 : 1

5 : 1

6 : 1

7 : 1

8 : 1

82

84

80

74

66

0

<1

ca. 2

14

Hexane/diethyl ether

1 : 1

2 : 1

3 : 1

4 : 1

5 : 1

6 : 1

62

60

74

86

67

69

0

5

0

ranged compounds 3a±3b was relatively low (14 and 16%

rel.) owing to a lower reaction temperature and short reac-

tion time. When the reaction was carried out below 1008C

no rearranged product was observed during 1 h reaction

time (Section 3.2).

2.2. Preparation of diepoxides 4a±4b and formation of

by-products 9 and 11

2.2.1. From diiodoalkanediyl diacetates 2a±2b and 3a±3b

We have reported in our recent paper [11] that the

chemoselectivity of the transformation of per¯uoroalkyl

iodide adducts onto allyl acetate to the corresponding

epoxides is extremely dependent on the solvent used. The

amount of by-products formed in diethyl ether, that was

found as the least convenient solvent [11], was up to 75%

rel. The previous papers using this procedure [18,25] have

not mentioned the formation of any amount of by-products.

We have also found [11] that the chemoselectivity of

epoxidation is the best in hexane giving only ca. 2% rel.

2.2.2. From diiododiols 5a±5b and 6a±6b

To avoid the formation of by-products and to obtain pure

diepoxides, a two step synthesis of the diepoxides was

accomplished. The mixtures of products 2 and 3 were ®rst

converted to the corresponding iodohydrins 5 and 6

(Scheme 2) in 84±86% preparative yields by reesteri®cation

with acidic methanol. The iodohydrins 5 and 6 (Scheme 2)

were subsequently epoxidized in 64±74% preparative yields

using powdered potassium hydroxide in diethyl ether, i.e. by

analogous procedure previously reported [25] for the pre-

paration of monoepoxides. By using iodohydrins 5 and 6 as

Scheme 2. Preparation of diepoxides 4a±4b from bis-adducts 2a±2b and rearranged bis-adducts 3a±3b.

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

353

Scheme 3. Probable reaction sequence in the formation of by-products in the epoxidation of adducts 2a±2b and 3a±3b.

substrates instead of iodoacetates 2 and 3, the relative

amount of by-products 9 was suppressed to 5±6% rel.

(Table 2) and unsaturated esters 11 were not detected

in the reaction mixture at all. No unsaturated by-products

were reported in the previous paper [25] for an analogous

reaction.

bis-iodohydrins 5 are used as substrates and short reaction

time applied (Table 2). Thus, unsaturated by-products gen-

erally accompany diepoxides 4 prepared by the above

reactions in higher relative amount than in structurally

analogous monoepoxides [11]. As the formation of the

by-products was studied in our preceding paper [11], we

veri®ed the by-products only for one of the bis-adducts, i.e.

2a (Scheme 3).

2.2.3. Formation of by-products 9 and 11

The amount of by-products 9 and 11 is strongly depen-

dent on the substrate and solvent used (Table 3): in diethyl

ether or hexane the by-products strongly dominate when

diiododiacetates are used as substrates (Table 2), which is a

sharp contrast to the preparation of monoepoxides from

iodoacetates reported recently [11]. The amounts of by-

products are strongly reduced when bis-iodohydrins 5 are

employed in diethyl ether. The reason of the formation of

by-products 9 and 11 (Scheme 3) is the acidity of the a-bond

C±H relatively to the per¯uorinated chain (for a discussion

on the reactions by which the by-products are formed see the

preceding paper [11]).This bond can be attacked directly in

the iodoacetate 2 (as well as in rearranged adduct 3 [11]) to

afford unsaturated epoxyacetate 11 that subsequently

affords allylic epoxyalkenol 9 by hydrolysis. The a-bond

C±H is also attacked by hydroxyl anion in the diepoxides

4 to start a rearrangement leading to epoxyalkenol 9

(Scheme 3). This subsequent side transformation of diep-

oxides 4 to the corresponding epoxyalkenols 9 is much

slower than the formation of the diepoxides 4, but cannot be

completely suppressed in the reaction system even when

2.3. Nucleophilic ring-opening reactions in diepoxides

4a±4b

It has been shown in our preceding paper ([12] and

references therein) that the regioselectivity of the epox-

ide-ring opening in 2-[(per¯uoroalkyl)methyl]oxiranes is

dependent on the type of a catalyst applied. Both mechan-

isms for acid-catalyzed (boron tri¯uoride etherate, magne-

sium perchlorate) and triethylamine-catalyzed reactions

were discussed to explain different regioselectivity. As

diepoxides 4a±4b are two-fold analogues of 2-[(per¯uor-

oalkyl)methyl]oxiranes, a similar reactivity toward nucleo-

philes and similar regioselectivity [12] of reactions can be

expected.

2.3.1. Acid-catalyzed ring opening, reaction with alkanols

The reported Lewis-acid catalyzed reactions of per¯uor-

oalkylated epoxides with hydroxy compounds have pro-

ceeded with complete regioselectivity [12,28±30].

The same result has been observed for the reactions of

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

354

Scheme 4. Nucleophilic reactions of diepoxides 4a±4b.

diepoxides 4a±4b with methanol in the presence of boron

tri¯uoride etherate (Scheme 4): the oxygen of hydroxy

groups attacked both terminal carbon atoms at the epoxide

rings with complete regioselectivity to afford dihydroxy bis-

ethers 12a±12b; no regioisomers were found in the reaction

mixtures by ¹⁹F NMR (the sensitivity of the method is about

1% rel. [31,32]. a,o-Dialkoxydiols 12a±12b can further be

transformed to bifunctional monomers as bis-(meth)-acry-

lates [9,12,14] or used directly for poly(urethanes), bis-

(meth)acrylates etc. As the ring opening in the diepoxides

4a±4b can be performed with monohydroxy compounds of

different structure ([12] and references therein), e.g. oli-

goethylene glycol monoalkyl ethers or hydroxyalkyl

(meth)acrylates [12], the synthesis that starts from a,o-

diiodoper¯uoroakanes can afford a number of interesting

compounds for various practical applications including

hydrophilic biocompatible polymers.

yields and subsequently re-acetalized with methanol and

hydrochloric acid to tetrols 14a±14b in 63±70% preparative

yields. The tetrols 14a±14b can be applied for the prepara-

tion of new dendrimeric compounds, or as crosslinking

agents for polymers. Heating of bis-dioxolanyl derivative

13a in wet ethyl acetate caused partial hydrolysis to dioxo-

lanyldiol 15a.

2.3.3. Ring opening in the presence of a base and with

morpholine, preparation of amphiphilic bis-methacrylates

16 and 17

It has been known [12] that the nucleophilicity of hydro-

xylic oxygen in (meth)acrylic acids is low to cause a ring

opening in per¯uoroalkyl epoxides under acid catalysis. A

similar reactivity was observed for non-¯uorinated epox-

ides, where tertiary amines were used as catalysts [39±41].

In the case of ¯uoroalkyl epoxides, the ring opening was

performed in the presence of potassium methacrylate

[42,43], triphenylphosphane [42,43] or triethylamine

[12,44]. Before base-catalyzed ring opening the reaction

was not regioselective with 10±17% rel. of the inner carbon

attack [12,42±44]. According to the previous experience, we

used triethyl amine as a catalyst for the ring opening. As

previously observed for monoepoxides [12,42±44], the ring

opening in the diepoxides 4a±4b was also not completely

regioselective (Scheme 4): the attack of the terminal carbons

occurred from 89% rel. to afford major regioisomers

2.3.2. Transformation to tetrols 14a±14b

We have recently developed a novel method for the

transformation of ¯uoroalkylated epoxides to the corre-

sponding vicinal diols [12,14,15], because the yields of

the direct acid-catalyzed reaction or were not very satisfac-

tory [28,33,34], or required special conditions [35±38]. In

this method, the epoxides 4a±4b were ®rst transformed to

the corresponding bis-1,3-dioxolanyl derivatives 13a±13b

by acid-catalyzed reaction with acetone [12] in 90±92%

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

355

16a±16b. The attack at the inner carbon atom (11% rel.,

products 17a±17b) has been previously explained in the

terms of the HSAB concept [12]. Thus, base-catalyzed ring

opening of ¯uoroalkylated epoxides [12] or diepoxides

prepared by the addition to allyl acetate or allylic alcohol

afford mixture of the corresponding amphiphilic methacry-

lates [12] or bis-methacrylates with the regioisomers formed

by the terminal attack highly prevailing (83±90% rel.).

Amphiphilic bis-methacrylates as mixtures of 16a±16b

and 17a±17b can be used as special crosslinking agents

including hydrophilic biocompatible copolymers.

In contrast to (meth)acrylate quasi-oxyanions acting in

the above epoxide ring-opening reactions [12], morpholine

possessing a strongly nucleophilic nitrogen reacted with

complete regioselectivity: the nucleophilic attack occurred

at the both terminal carbon atoms in diepoxides 4a±4b to

afford dihydroxylated bis-morpholinyl 18a±18b (Scheme

4). The same regioselectivity has been reported [9] for the

analogous reaction of morpholine with 2-[(per¯uoroalkyl)-

methyl]oxiranes. The different regioselectivity in ring-

opening reactions of oxyanions and secondary amines

can be caused by different hardness of these two nucleo-

philic centers, nitrogen being a softer nucleophile, as dis-

cussed in our preceding paper [12].

ether was dried with sodium and distilled over sodium;

hexane (Fluka) and morpholine (Lachema) was distilled

prior to use and stored over molecular sieves; methacrylic

acid (Aldrich); petroleum ether, chloroform, methanol,

acetone and toluene were puri®ed according to standard

procedures [45].

3.2. General procedure for the radical addition of

diiodoperfluoroalkanes to allyl acetate

The reactions were carried out in a two-necked round-

bottom ¯ask (250 ml) equipped with a long re¯ux condenser

and magnetic spinbar on a oil bath.

Method A: The ¯ask was charged with a mixture of

diiodoper¯uoroalkane, allyl acetate and butyronitrile that

was heated up to ca. 1158C. Then, dibenzoyl peroxide was

added portionwise to the mixture through the neck and

heating was stopped. A slight foam at the mixture surface

appeared indicating start of the reaction, by which the

temperature in ¯ask increased up to 1258C. The amber

solution became clear after 5 min reaction indicating almost

completion of the reaction. The mixture was stirred for

30 min until the temperature fell down to 908C. Volatile

components were distilled off in vacuum by oil pump

(0.5 mm Hg, 1308C bath temperature) to afford crude

product consisting of compounds 1, 2 and 3 (Table 1).

For analytical purposes and further transformations, the

mono-adducts 1 and di-adducts 2 and 3 were separated

by simple column chromatography (silica gel; hexane,

chloroform).

3. Experimental details

3.1. General comments

Boiling points were not corrected. GC analyses were

performed on Micromat HRGC 412 (Nordion Analytical;

25 m glass capillary column, SE-30) and a Chrom 5 instru-

Method B: The same reactants as in Method A, but

without butyronitrile as a solvent, were used and the reac-

tion was carried out according to [8]. The mixture was

warmed up to ca. 908C and the peroxide was added in

several portions to keep reaction temperature below 1008C

during 1 h reaction time. After removing volatile compo-

nents as above, the crude product contained compounds 1

and 2 (Table 1), which were easily separated by simple

column chromatography (see Method A).

Â

ment (Laboratornõ pùõstroje, Prague; FID, 380 cm Â 0.3 cm

column packed with silicon elastomer E-301 on Chromaton

N-AW-DMCS (Lachema, Brno); nitrogen was used as

carrier gas, detector/injector temperatures were 260/

2558C); the GC apparatus was connected to a Hewlett±

Packard integrator (model 3390). NMR spectra were

recorded on a Bruker 400 AM (FT, ¹⁹F at 376.5 MHz)

and a Bruker WP 80 SY (FT, ¹⁹F at 75 MHz) instruments

using TMS and CFCl₃as the internal standards. Chemical

shifts are quoted in ppm (s: singlet, bs: broad singlet, d:

doublet, t: triplet, q: quadruplet, m: multiplet), coupling

constants J in Hz, solvent CDCl₃.

3.2.1. From 1,4-diiodoperfluorobutane

Method A: 1,4-Diiodoper¯uorobutane (68.1 g, 0.15 mol),

allyl acetate (30 g, 0.3 mol), dibenzoyl peroxide (1.81 g,

7.5 mmol), butyronitrile (31.1 g, 0.45 mol). On the conver-

sion of 98%, the crude product consisted of a mixture

of mono-adduct 1a (4%) and diadducts 2a and 3a (96%,

Table 1), yield 94.7 g (95%).

The chemicals used were as follows: silica gel L40/100

(Merck); potassium hydroxide pellets were ground to pow-

der before use; boron tri¯uoride etherate (Lachema) was

distilled before use; 1,4- and 1,6-diiodoper¯uoroalkanes

were obtained from Asahi Glass Co., Japan, and were

worked-up with alkaline thiosulphate solution; dibenzoyl

peroxide (Fluka) was precipitated from its chloroform

solution by methanol and dried in vacuo; 2,2-diphenyl-1-

picrylhydrazyl (Aldrich); allyl acetate (Aldrich), butyroni-

trile (Aldrich) and were used without puri®cation; triethyl-

amine (Aldrich) was distilled before use (88±898C); diethyl

2,7-Diiodo-4,4,5,5,6,6,7,7-octa¯uoroheptyl acetate (1a):

1

for H and ¹⁹F NMR and MS spectra see [8].

(2,9-Diiodo-4,4,5,5,6,6,7,7-octa¯uorodecane-1,10-diyl)

1

diacetate (2a, ca. 86% rel.): for H and ¹⁹F NMR and MS

spectra see [8].

(2,10-Diiodo-4,4,5,5,6,6,7,7-octa¯uorodecane-1,9-diyl)

diacetate (3a, ca. 14% rel.) [CH₃COOCH₂CHICH₂(CF₂)₄-

1

CH₂CH(OCOCH₃)CH₂I]: H NMR (CDCl₃) d: 2.07, 2.10

(2s, 6H, CH₃); 2.40±2.60 (m, 2H, CH₂CF₂); 3.25±3.45 (m,

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

356

2H, CH₂I); 4.20±4.35 (m, 2H, CH₂O); 4.35±4.50 (m, 1H,

CHI); 5.12 (m, 1H, CHO) ppm.

¹⁹F NMR (CDCl₃): The same spectrum as for 2a.

3.3.2. From mixtures of diacetates 2a±2b and rearranged

diacetates 3a±3b (14 and 16% rel.) by reaction with

potassium hydroxide in solvents

Preparative reactions: The reactions were performed in

the same manner as in Section 3.3.1. For results see Table 2.

Optimization of the solvent mixture for epoxidations: A

round-bottom ¯ask (50 ml) was charged with a mixture of

diacetates 2a and 2b (1.31 g, 2 mmol), powdered potassium

hydroxide (0.6 g, 10 mmol) and solvent (25 ml). The het-

erogenous mixture was re¯uxed while stirring by mechanic

stirrer with spirals from stainless wire for 5 h. Then, the

mixture was ®ltered, solvents were evaporated on rotary

evaporator and the residue was analyzed by GC (for results

see Table 3).1,2;9,10-Diepoxy-4,4,5,5,6,6,7,7-octa¯uorode-

cane (4a) [(CH₂(O)CHCH₂CF₂CF₂)₂]: Analysis Ð Found:

C, 38.0; H, 3.30; F, 48.8%. C₁₀H₁₀F₈O₂, requires: C, 38.23;

H, 3.21; F, 48.38%; M, 314.2.

3.2.2. From 1,6-diiodoperfluorohexane

Method A: 1,6-Diiodoper¯uorohexane (68.1 g, 0.12 mol),

allyl acetate (30 g, 0.3 mol), dibenzoyl peroxide (1.81 g,

7.5 mmol), butyronitrile (31.1 g, 0.45 mol). On the conver-

sion of 98%, the crude product consisted of a mixture

of mono-adduct 1b (2%) and diadducts 2b and 3b (98%,

Table 1), yield 88.4 g (92%).

2,9-Diiodo-4,4,5,5,6,6,7,7,8,8,9, 9-dodeca¯uorononyl

1

acetate (1b): for H and ¹⁹F NMR and MS spectra see

[8].

(2,11-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorodode-

F

cane-1,12-diyl) diacetate (2b, ca. 84% rel.): for ¹H and ¹⁹

NMR and MS spectra see [8].

(2,12-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorodode-

cane-1,11-diyl) diacetate (3b, ca. 16%) [CH₃COOCH_2-

CHICH₂(CF₂)₆CH₂CH(OCOCH₃)CH₂I]: ¹H NMR (CDCl₃)

d: 2.07, 2.10 (2s, 6H, CH₃); 2.60±3.00 (m, 2H, CH₂CF₂);

¹H NMR (CDCl₃) d: 2.1±2.45 (m, 2H, CH₂CF₂); 2.55 (dd,

H_A, CH₂O, ²J_HH 5, ³J_HH 2); 2.83 (t, H_B, CH₂O, ²J_HH

³J_HH 4); 3.17±3.21 (m, 1H,CHO) ppm.

¹³C NMR (CDCl₃) d: 35.19 (t, CH₂CF₂,²J_CF 22); 44.82

2

4.20±4.35 (m, 2H, CH₂O); 4.35±4.50 (m, 1H, CHI) ppm. ¹⁹

F

(t, CHCH₂CF₂, J_CF 5); 45.75 (s, CH₂O) ppm.¹⁹F NMR

NMR (CDCl₃) d: 113.75 (m, 4F, CF₂CH₂); 122.07 (m,

4F, CH₂C₂F₄CF₂); 123.93 (m, 4F, CH₂CF₂CF₂) ppm.

(CDCl₃) d: 112.99 (m, 4F, CF₂CH₂); 123.89 (m, 4F,

CH₂CF₂CF₂) ppm. 1,2;11,12-Diepoxy-4,4,5,5,6,6,7,7,8,8,-

9,9-dodeca¯uorododecane (4b) [(CH₂(O)CHCH₂CF₂CF₂-

CF₂)₂]: Analysis Ð Found: C, 34.4; H, 2.52; F, 55.3%.

C₁₂H₁₀F₁₂O₂, requires: C, 34.80; H, 2.43; F, 55.04%; M,

414.2.

3.3. Preparation of diepoxides 4a±4b from diacetates 2a±

2band 3a±3b

¹H NMR (CDCl₃) d: 2.10±2.45 (m, 2H, CH₂CF₂); 2.52

3.3.1. From individual non-rearranged diacetates 2a±2b

by reaction with potassium hydroxide in solvents (Table 2)

A round-bottom ¯ask (500 ml) was charged with diace-

tate 2a or 2b (13.1 or 15.1 g, respectively; 0.02 mol),

powdered potassium hydroxide (5.6 g, 0.10 mol), hexane

(200 ml) and diethyl ether (50 ml). The heterogenous mix-

ture was re¯uxed while stirring by mechanic stirrer with

spirals from stainless wire for 5 h (conversion 99%). Then,

the mixture was ®ltered, solvents were evaporated on rotary

evaporator, and yield of pure diepoxides (or, respectively)

were obtained by distillation on oil pump: 4a, 5.4 g (86%),

purity 99%. bp 90±928C/0.5 mm Hg (lit. value [16]: 110±

1128C/5 mm Hg); 4b: 7.1 g (85%), bp 104±1068C/0.5 mm

Hg, purity 99%. The distillation residue also contained

unsaturated by-products. In the reaction of the starting

diacetate 2a the following by-products were isolated and

identi®ed as mixtures of cis and trans isomers: epoxy-

acetate 11a (0.6 g, 9% rel., bp 81±838C/0.1 mm Hg, purity

98%) and epoxy-alcohol 9a (0.3 g, 5% rel., bp 75±788C/

0.2 mm Hg, purity 98%). In the case of diacetate 2b the by-

products epoxy-alcohol 9b (11,12-epoxy-4,4,5,5,6,6,7,7,-

8,8,9,9-dodeca¯uorododec-2-en-1-ol) and epoxy-acetate

11b [(11,12-epoxy-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorodo-

dec-2-ene-1-yl) acetate] were not isolated and their struc-

tures were approximately assigned on the basis of NMR

spectra of reaction mixture (and their similarity with 9a,

11a) and similarity of gas chromatograms with the mixture

of products in the reaction of 2a.

2

3

(dd, H_A, CH₂O, J_HH 5, J_HH 2); 2.81 (t, H_B, CH₂O,

²J_HH ³J_HH 4); 3.13±3.21 (m, 1H, CHO) ppm.

¹⁹F NMR (CDCl₃) d: 113.83 (m, 4F, CF₂CH₂); 122.12

(m, 4F, CH₂C₂F₄CF₂); 124.04 (m, 4F, CH₂CF₂CF₂) ppm.

9,10-Epoxy-4,4,5,5,6,6,7,7-octa¯uorodec-2-en-1-ol (9a)

[CH₂(O)CHCH₂CF₂CF₂-CF₂CF₂CH=CHCH₂OH]: Analy-

sis Ð Found: C, 38.1; H, 3.2; F, 48.5%. C₁₀H₁₀F₈O₂,

requires: C, 38.23; H, 3.21; F, 48.38%; M, 314.18.

trans isomer (89% rel.): ¹H NMR (CDCl₃) d: 2.02 (s, 3H,

CH₃); 2.10±2.40 (m, 2H, CH₂CF₂); 2.52 (q, 2H, CH₂O);

2.79 (s, 1H,OH); 3.15 (m, 1H, CHO); 4.21 (m, 2H, CH₂OH);

6.30±6.38 (m, H_A, CH=CH); 6.38±6.45 (m, H_B, CH=CH)

2

ppm. ¹³C NMR (CDCl₃) d: 35.09 (t, CH₂CF₂, J_CF 22);

3

44.80 (t, CHO, J_CF 5); 45.60 (s, CH₂O); 60.88 (s,

2

CH₂OH); 141.09 (t, CHCF₂, J_CF 22 Hz); 170.16 (s,

C=O) ppm. ¹⁹F NMR (CDCl₃) d: 108.25 (m, 1F, CF₂CH);

112.20 (m, 1F, CF₂CH); 112.90 (m, 2F, CF₂CH₂);

113.15 (m, 2F, CF₂CH₂); 123.86 (m, 4F, CH₂CF₂CF₂)

ppm.

1

cis isomer (11% rel.): H NMR (CDCl₃) d: 2.02 (s, 3H,

CH₃); 2.10±2.40 (m, 2H, CH₂CF₂); 2.52 (q, 2H, CH₂O);

2.79 (s, 1H, OH); 3.15 (m, 1H, CHO); 4.35 (m, 2H,

CH₂OH); 6.49 (m, 2H, CH=CH) ppm. ¹³C NMR (CDCl₃)

d: 20.21 (s, CH₃); 35.09 (t, CH₂CF₂,²J_CF 22); 44.80 (t,

CHO,³J_CF 5); 45.60 (s, CH₂O); 61.92 (s, CH₂OAc);

2

144.50 (t, CHCF₂, J_CF 22 H); 170.16 (s, C=O) ppm.

¹⁹F NMR (CDCl₃): the same as for the trans isomer.

Â

V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

357

(9,10-Epoxy-4,4,5,5,6,6,7,7-octa¯uorodec-2-ene-1-yl)

acetate (11a) [CH₂(O)CHCH₂CF₂CF₂CF₂CF₂CH=CH-

CH₂OCOCH₃]: Analysis Ð Found: C, 40.4; H, 3.43; F,

43.0%. C₁₂H₁₂F₈O₃, requires: C, 40.46; H, 3.40; F, 42.67%;

M, 356.2.

CH₂CF₂); 3.31 (dd, H_A, CH₂I, ²J_HH 10 Hz, ³J_HH 6 Hz);

2

3

3.42 (dd, H_B, CH₂I, J_HH 10 Hz, J_HH 4 Hz); 3.80 (m,

2H, CH₂O); 4.00±4.10 (m, 1H, CHO); 4.40 (m, 1H, CHI)

ppm. ¹⁹F NMR (CDCl₃) d: the same as for 5a.

trans isomer (81% rel): ¹H NMR (CDCl₃) d: 2.05 (s, 3H,

CH₃); 2.10±2.40 (m, 2H, CH₂CF₂); 2.79 (q, 2H, CH₂O);

3.15 (m, 1H, CHO); 4.65 (m, 2H, CH₂OAc); 5.70±6.00 (m,

2H, CH=CH) ppm. ¹³C NMR (CDCl₃) d: 20.21 (s, CH₃);

3.4.1.2. Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodecafluorodo-

decanediols (5b and 6b). The same procedure as in Section

3.4.1.1 was used; a mixture of diiododiacetates 2b (84%

rel.) and 3b (15.1 g, 20 mmol) was reacted. The mixture of

products 5b and 6b (purity ca. 96%) was obtained in an yield

of 10.2 g (85%). For analytical purposes the mixture of

products was purified by column chromatography (silica

gel, toluene/methylene chloride).

2

3

35.09 (t, CH₂CF₂, J_CF 22); 44.80 (t, CHO, J_CF 5);

45.60 (s, CH₂O); 61.92 (s, CH₂OAc); 135.46 (t, CHCF₂,

²J_CF 22); 170.16 (s, C=O) ppm. ¹⁹F NMR (CDCl₃) d:

108.90 (m, 1F, CF₂CH); 112.90 (m, 1F, CF₂CH₂);

113.15 (m, 2F, CF₂CH₂); 123.86 (m, 4F, CH₂CF₂CF₂)

ppm.

Analysis (5b and 6b) Ð Found: C, 21.8.1; H, 1.83; F,

34.7; I, 38.0%. C₁₂H₁₂F₁₂I₂O₂, requires: C, 21.51; H, 1.80;

F, 34.0; I, 37.9%; M, 670.0.2,11-Diiodo-4,4,5,5,6,6,7,7,8,-

8,9,9-dodeca¯uorododecane-1,12-diol (84% rel., 5b) [(HO-

CH₂CHICH₂CF₂CF₂CF₂)₂]: ¹³C NMR (CDCl₃) d: 22.68 (s,

1

cis isomer (19% rel.): H NMR (CDCl₃) d: 2.05 (s, 3H,

CH₃); 2.10±2.40 (m, 2H, CH₂CF₂); 2.79 (q, 2H, CH₂O);

3.15 (m, 1H, CHO); 4.80 (m, 2H, CH₂OAc); 6.05±6.20 (m,

2H, CH=CH) ppm. ¹³C NMR (CDCl₃) d: 20.21 (s, CH₃);

2

CHI); 38.30 (t, CH₂Q_F, J_CF 21 Hz); 68.64 (s, CH₂O)

35.09 (t, CH₂CF₂, J_CF 22); 44.80 (t, CHO, J_CF 5 );

45.60 (s, CH₂O); 61.92 (s, CH₂OAc); 138.58 (t, CHCF₂,

²J_CF 22); 170.16 (s, C=O) ppm. ¹⁹F NMR (CDCl₃): the

same as for the trans isomer.

ppm. ¹H NMR (CDCl₃) d: 2.15 (s, 1H, OH); 2.69±2.84 (m,

1H, CH₂CF₂); 2.93±3.08 (m, 1H, CH₂CF₂); 3.78 (dd, H_A,

2

3

2

3

CH₂O, J_HH 12 Hz, J_HH 5 Hz); 3.83 (dd, H_B, CH₂O,

3

²J_HH 12 Hz, J_HH 5 Hz); 4.44 (kv, 1H, CHI) ppm. ¹⁹F

NMR (CDCl₃) d: 113.83 (m, 4F, CF₂CH₂); 122.12 (m,

4F, CH₂C₂F₄CF₂); 124.04 (m, 4F, CH₂CF₂CF₂) ppm.1,12-

Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorododecane-2,11-

diol (16% rel., 6b) (HOCH₂CHICH₂(CF₂)₆CH₂CHOH-

CH₂I): ¹³C NMR (CDCl₃) d: 14.76 (s, CH₂I); 38.30 (t,

3.4. Preparation of diepoxides 4a±4b from diiodohydrins

5a±5b and 6a±6b (Table 2)

3.4.1. Preparation of diiodohydrins 5a±5b and 6a±6b from

mixtures of diacetates 2a±2b and rearranged diacetates

3a±3b (14 and 16% rel.) by acid reesterification with

methanol

2

CH₂Q_F, J_CF 21 Hz); 65.45 (s, CHO); 68.64 (s, CH₂O)

ppm. ¹H NMR (CDCl₃) d: 2.15 (s, 1H, OH); 2.30±2.50 (m,

2H, CH₂CF₂); 3.32±3.40 (m, 1H, CH₂I); 4.05±4.12 (m, 1H,

CHO); 4.44 (q, 1H, CHI) ppm. ¹⁹F NMR (CDCl₃) d: the

same as for 5b

3.4.1.1. Diiodo-4,4,5,5,6,6,7,7-octafluorodecanediols (5a

and 6a). A mixture of diiododiacetates 2a and 3a (86

and 14% rel. 13.1 g, 20 mmol), methanol (39.5 g,

1.2 mol) and concentrated hydrochloric acid (4 drops)

was refluxed for 6 h when the conversion was ca. 98%

(checked by GC). Then, volatile components were distilled

off in vacuum (0.5 mm Hg) on a distillation apparatus with

oil pump to give almost pure mixture (ca. 97%) of 5a and 6a

in an yield of 9.25 g (86%) was obtained. For analytical

purposes the mixture of products was purified by column

chromatography (silica gel, toluene/methylene chloride).

Analysis (5a and 6a) Ð Found: C, 21.2.1; H, 2.24; I,

44.1%. C₁₀H₁₂F₈I₂O₂, requires: C, 21.07; H, 12.08; I,

44.51%; M, 570.0.

2,9-Diiodo-4,4,5,5,6,6, 7,7-octa¯uorodecane-1,10-diol

(86% rel., 5a) [(HOCH₂CHICH₂±CF₂CF₂)₂]: ¹H NMR

(CDCl₃) d: 2.57 (s, 1H, OH); 2.60±2.87 (m, 1H, CH₂CF₂);

2.87±3.10 (m, 1H, CH₂CF₂); 3.80 (m, 2H, CH₂O); 4.40 (m,

1H, CHI) ppm. ¹⁹F NMR (CDCl₃) d: 113.54 (m, 4F,

CF₂CH₂); 123.89 (m, 4F, CH₂CF₂CF₂) ppm.

3.4.2. Preparation of diiodohydrins 5a±5b from diacetates

2a±2b by acid reesterification with methanol (Table 2)

3.4.2.1. 2,9-Diiodo-4,4,5,5,6,6,7,7-octafluorodecane-1,10-

diol (5a). The same procedure as in Section 3.4.1.1 was

applied; a mixture of diiododiacetate 2a (4.6 g, 7 mmol),

methanol (13.2 g, 0.4 mol) and concentrated hydrochloric

acid (2 drops) was refluxed for 6 h when the conversion was

ca. 98% (checked by GC). After removing volatile

components, almost pure mixture (ca. 95%) of 5a in an

yield of 3.05 g (83%) was obtained. For analytical purposes

the product was purified by column chromatography (silica

gel, toluene/methylene chloride).

3.4.2.2. 1,12-Diiodo-4,4,5,5,6,6,7,7,8,8,9,9-dodecafluor-

ododecane-2,11-diol (5b). The same procedure as in

Section 3.4.2.1 was applied; a mixture of diiododiacetate

2b (5.1 g, 6.8 mmol), methanol (13.2 g, 0.4 mol) and

concentrated hydrochloric acid (2 drops) was refluxed for

6 h when the conversion was ca. 98% (checked by GC).

After removing volatile components, almost pure mixture

(ca. 95%) of 5b in an yield of 3.25 g (82%) was obtained.

2,10-Diiodo-4,4,5,5,6,6,7, 7-octa¯uorodecane-1,9-diol

(14% rel., 6a) (HOCH₂CHICH₂±(CF₂)₄CH₂CHOHCH₂I):

¹H NMR (CDCl₃) d: 2.30±2.60 (2m, 2H, CH₂CF₂); 2.57 (s,

1H, OH); 2.60±2.87 (m, 1H, CH₂CF₂); 2.87±3.10 (m, 1H,

Â

V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

358

For analytical purposes the product was purified by column

chromatography (silica gel, toluene/methylene chloride).

3.5.2. 1,12-Dimethoxy-4,4,5,5,6,6,7,7,8,8,9,9-dode-

cafluorododecane-2,11-diol (12b)

The same procedure as in Section 3.5.1 was applied;

diepoxide 4b (0.434 g, 1.05 mmol), boron tri¯uoride ethe-

rate (4 drops). With the complete conversion of the starting

diepoxide and after precipitation from toluene solution the

product 12b was obtained in an yield of 0.40 g (80%), mp

90±928C. Analysis Ð Found: C, 34.8; H, 3.70; F, 48.0%.

3.4.3. Preparation of diepoxides 4a±4b from diiodohydrins

5a±5b and 6a±6b by reaction with potassium hydroxide

(Table 2)

3.4.3.1. 1,2;9,10-diepoxy-4,4,5,5,6,6,7,7-octafluorodecane

(4a). In a round-bottom flask equipped with a reflux

condenser with a drying tube, a mixture of diiodohydrins

5a (86% rel.) and 6a (2.2 g, 4 mmol), powdered potassium

hydroxide (1.2 g, 0.02 mol) and diethyl ether (20 ml) was

refluxed while stirring intensively with magnetic spinbar for

30 min when the conversion was ca. 98% (checked by GC).

After filtration, the ether was removed from the filtrate

under reduced pressure and the residue was distilled in

vacuum to afford diepoxide 4a in an yield of 0.95 g

(74%), bp 88±908C/0.5 mm Hg, which contained

unsaturated alcohol 11a (ca. 6%, GC and ¹⁹F NMR).

C₁₄H₁₈F₁₂O₄, requires: C, 35.15; H, 3.79; F, 47.65%; M,

478.3. ¹³C NMR (CDCl₃) d: 35.43 (t, CH₂CF₂, J_CF

2

21 Hz); 59.84 (s, CH₃O); 64.92 (s, CHO); 76.53 (s,

CH₂O) ppm. ¹H NMR (CDCl₃) d: 2.20±2.40 (2m, 2H,

CH₂CF₂); 2.47 (s, 1H, OH); 3.40 (dd, H_A, CH₂O,

3

²J_HH 9.5 Hz, J_HH 6 Hz); 3.42 (s, 3H, CH₃); 3.50

2

3

(dd, H_B, CH₂O, J_HH 9.5 Hz, J_HH 4 Hz); 4.29 (m,

1H, CHO) ppm. ¹⁹F NMR (CDCl₃) d: 113.22 (m, 4F,

CF₂CH₂); 122.12 (m, 4F, CH₂C₂F₄CF₂); 124.18 (m, 4F,

CH₂CF₂CF₂) ppm.

3.6. Transformation of diepoxides 4a and 4b to bis-

dioxolanyl derivatives (products 13a±13b)

3.4.3.2. 1,2;11,12-Diepoxy-4,4,5,5,6,6,7,7,8,8,9,9-dode-

cafluorododecane (4b). The same procedure as above

[diiodohydrins 5b (84% rel.) and 6b (2.92 g, 4 mmol)]

was applied to obtain diepoxide 4b in an yield of 1.16 g

(66%), bp 103±1058C/0.5 mm Hg, which contained

unsaturated alcohol 11b (ca. 6%, GC and ¹⁹F NMR).

3.6.1. Reaction of 1,2;9,10-diepoxy-4,4,5,5,6,6,7,7-

octafluorodecane (4a) with acetone (product 13a)

In a round-bottom ¯ask equipped with a re¯ux condenser

with a drying tube (MgSO₄), a mixture of diepoxide 4a

(0.347 g, 1.10 mmol), acetone (10 ml), and boron tri¯uoride

etherate (4 drops) was re¯uxed while stirring intensively

with magnetic spinbar for 1 h when the conversion was ca.

98% (checked by GC). Then, acetone and volatile compo-

nents were removed on rotary evaporator and crude product

13a as a white solid was obtained (0.45 g, 94%). Recrys-

tallization of this product was unsuccessful. For analytical

purposes, 13a was puri®ed by simple column chromato-

graphy (silica gel; hexane, chloroform), mp 62±658C.

An attempt of recrystallization in boiling ethyl acetate led

to the formation of dioxolanyldiol 15a, mp 95±978C. The

partial hydrolysis of the starting 13a was caused by traces of

water and acetic acid in ethyl acetate.

3.4.4. Preparation of diepoxides 4a±4b from diiodohydrins

5a±5b by reaction with potassium hydroxide (Table 2)

The same procedures and same amounts of reactants were

employed as in Section 3.4.3. For results see Table 2.

3.5. Ring opening of diepoxides 4a and 4b with methanol

(products 12a and 12b)

3.5.1. 1,10-dimethoxy-4,4,5,5,6,6,7,7-octafluorodecane-

2,9-diol (12a)

In a round-bottom ¯ask equipped with a re¯ux condenser

with a drying tube (MgSO₄), a mixture of diepoxide 4a

(0.325 g, 1.03 mmol), methanol (7.9 g, 0.25 mol) and boron

tri¯uoride etherate (2 drops) was re¯uxed while stirring

intensively with magnetic spinbar for 4 h when the conver-

sion was complete (checked by GC). After evaporation of

methanol on rotary evaporation, crude 12a as a white solid

was obtained that was dissolved in boiling toluene and

precipitated with petroleum ether to afford pure dimethox-

ydiol 12a in an yield of 0.21 g (54%), mp 87±898C. Analysis

Ð Found: C, 37.8; H, 4.70; F, 39.7%. C₁₂H₁₈F₈O₄, requires:

C, 38.10; H, 4.80; F, 40.16%; M, 378.25. ¹³C NMR (CDCl₃)

d: 35.42 (t, CH₂CF₂, ²J_CF 21 Hz); 59.75 (s, CH₃O); 64.68

(s, CHO); 76.64 (s, CH₂O) ppm. ¹H NMR (CDCl₃) d: 2.20±

2.40 (2m, 2H, CH₂CF₂); 2.76 (s, 1H, OH); 3.37 (dd, H_A,

1,6-Bis(2,2-dimethyl-1,3-dioxolan-4-yl)-2,2,3,3,4,4,5,5-

octa¯uorohexane (13a): Analysis Ð Found: C, 40.2; H,

5.37; F, 36.1%. C₁₆H₂₂F₈O₄, requires: C, 40.65; H, 5.15; F,

35.30%; M, 430.3. ¹³C NMR (DMSO) d: 25.52, 26.55 (2s,

2

CH₃); 34.31 (t, CH₂Q_F, J_CF 21 Hz); 68.48 (s, CH₂O);

1

68.67 (s, CHO); 108.72 (s, C) ppm. H NMR (DMSO) d:

1.29, 1.34 (2s, 6H, CH₃); 2.30±2.60 (m, 2H, CH₂CF₂); 3.63

2

3

(dd, H_A, CH₂O, J_HH 8 Hz, J_HH 7 Hz); 4.09 (dd, H_B,

2

3

CH₂O, J_HH 8 Hz, J_HH 6 Hz); 4.37 (kv, 1H, CHO)

ppm. ¹⁹F NMR (DMSO) d: 112.01 (m, 4F, CF₂CH₂);

123.00 (m, 4F, CH₂CF₂CF₂) ppm

8-(2,2-Dimethyl-1,3-dioxolan-4-yl)-4,4,5,5,6,6,7,7-octa-

¯uorooctane-1,2-diol (15a). Analysis Ð Found: C, 39.6; H,

4.37; F, 39.4%. C₁₃H₁₈F₈O₄, requires: C, 40.00; H, 4.65; F,

38.93%; M, 390.3. ¹³C NMR (DMSO) d: 25.58, 26.60 (2s,

2

3

CH₂O, J_HH 10 Hz, J_HH 6.5 Hz); 3.41 (s, 3H, CH₃);

3.48 (dd, H_B, CH₂O, ²J_HH 10 Hz, ³J_HH 4 Hz); 4.26 (m,

1H, CHO) ppm. ¹⁹F NMR (CDCl₃) d: 113.33 (m, 4F,

CF₂CH₂); 124.06 (m, 4F, CH₂CF₂CF₂) ppm.

2

CH₃); 34.34 (t, CH₂Q_F, J_CF 21 Hz); 65.05 (s, CHO);

65.26 (s, CH₂O); 68.54 (s, CH₂O); 68.73 (s, CHO); 108.80

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V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

359

(s, C) ppm. ¹H NMR (DMSO) d: 1.29, 1.34 (2s, 6H, CH₃);

2.00±2.20 (m, 1H, CH₂CF₂); 2.30±2.50 (m, 1H, CH₂CF₂);

3.24 (dd, H_A, CH₂O, ²J_HH 11 Hz, ³J_HH 7 Hz); 3.39 (dd,

H_B, CH₂O, ²J_HH 11 Hz, ³J_HH 5 Hz); 3.62 (t, H_A, CH₂O,

²J_HH ³J_HH 7.5 Hz); 3.85 (m, 1H, CHO); 4.09 (t, H_B,

ppm. ¹⁹F NMR (DMSO) d: 113.20 (m, 4F, CF₂CH₂);

123.79 (m, 4F, CH₂CF₂CF₂) ppm.

3.7.2. 4,4,5,5,6,6,7,7,8,8,9,9-Dodecafluorododecane-

1,2,11,12-tetrol (14b)

2

CH₂O, J_HH ³J_HH 7.5 Hz); 4.37 (m, 1H, CHO) ppm.

The same procedure as in Section 3.7.1 was applied to

crude bis-dioxolane (13b) (0.53 g, 1 mmol). After removing

acetone and volatile components and precipitation, pure

crude 14b as a white solid (0.30 g, 67%) was obtained, mp

103±1058C. Analysis Ð Found: C, 31.7; H, 2.9; F, 51.1%.

¹⁹F NMR (DMSO) d: 113.01 (m, 4F, CF₂CH₂); 123.70

(m, 4F, CH₂CF₂CF₂) ppm.

3.6.2. Reaction of1,2;11,12-diepoxy-4,4,5,5,6,6,7,7,8,8,9,9-

dodecafluorododecane (4b) with acetone(1,8-bis(2,2-

dimethyl-1,3-dioxolan-4-yl)-2,2,3,3,4,4,5,5,6,6,7,7-

dodecafluorooctane, 13b)

C₁₂H₁₄F₁₂O₄, requires: C, 32.01; H, 3.13; F, 50.61%; M,

2

450.2. ¹³C NMR (DMSO) d: 34.08 (t, CH₂Q_F, J_CF

1

21 Hz); 65.01 (s, CHO); 65.18 (s, CH₂O) ppm. H NMR

(DMSO) d: 2.00±2.20 (m, 1H, CH₂CF₂); 2.30±2.50 (m, 1H,

CH₂CF₂); 3.24 (dd, H_A, CH₂O, ²J_HH 11 Hz,

The same procedure as in Section 3.7.1 was applied;

diepoxide 4b (0.425 g, 1.02 mmol). After removing acetone

and volatile components, crude 13b as a white solid (0.52 g,

95%) was obtained. For analytical purposes, 13b was

puri®ed by simple column chromatography (silica gel;

hexane, chloroform), mp 72±758C. An attempt of recrys-

tallization of the crude product in boiling ethyl acetate led to

the total hydrolysis of the dioxolane rings to tetrol 14b (see

Section 3.7.2). Analysis Ð Found: C, 40.1; H, 4.01; F,

43.5%. C₁₈HF₁₂O₄, requires: C, 40.76; H, 4.18; F, 42.97%;

M, 530.5. C₁₈H₂₂O₄F₁₂M 530.35) calculated/found

40.76/37.47 %C, 4.18/3.85 %H, 42.97/43.65 %F. ¹³C

NMR (DMSO) d: 25.51, 26.52 (2s, CH₃); 34.17 (t, CH₂Q_F,

²J_CF 21 Hz); 68.43 (s, CH₂O); 68.59 (s, CHO); 108.81 (s,

2

3

³J_HH 7 Hz); 3.40 (dd, H_B, CH₂O, J_HH 11 Hz, J_HH

5 Hz); 3.85 (m, 1H, CHO); 4.45 (2s, 2H, OH) ppm. ¹⁹F

NMR (DMSO) d: 112.98 (m, 4F, CF₂CH₂); 121.69 (m,

4F, CH₂C₂F₄CF₂); 123.75 (m, 4F, CH₂CF₂CF₂) ppm.

3.8. Base catalyzed ring opening of diepoxides 4a and 4b

with methacrylic acid (products 16a±16b, and 17a±17b)

3.8.1. Reaction of 1,2;9,10-diepoxy-4,4,5,5,6,6,7,7-

octafluorodecane (4a) (products 16a and 17a)

In a round-bottom ¯ask equipped with a re¯ux condenser

with a drying tube (MgSO₄), a mixture of diepoxide 4a

(0.317 g, 1.01 mmol), methacrylic acid (1.70 g,

19.7 mmol), triethylamine (5 drops) and diphenyl picryl

hydrazyl (15 mg) was heated to 1008C while stirring inten-

sively with magnetic spinbar for 2 h when the conversion

was ca. 98% (checked by GC). Then, the excess of

methacrylic acid was distilled off in vacuum in a distillation

apparatus with oil pump (0.5 mm Hg, 1008C bath tempera-

ture) to afford crude product (16a and 17a) as a brown solid.

Pure mixture of regioisomeric products was obtained 16a

and 17a (89 and 11% rel.) by their precipitation from boiling

toluene solution using petroleum ether, the yield was

0.205 g (41%), mp 75±788C. Analysis (16a and 17a) Ð

Found: C, 43.8; H, 4.47; F, 31.7%. C₁₈H₂₂F₈O₆, requires: C,

43.45; H, 4.56; F, 31.24%; M, 486.4.

1

C) ppm. H NMR (DMSO) d: 1.29, 1.34 (2s, 6H, CH₃);

2.20±2.70 (m, 2H, CH₂CF₂); 3.63 (t, H_A, CH₂O,

2

²J_HH ³J_HH 7 Hz); 4.09 (t, H_B, CH₂O, J_HH 8 Hz,

³J_HH 6 Hz); 4.37 (m, 1H, CHO) ppm. ¹⁹F NMR (DMSO)

d:

CH₂C₂F₄CF₂); 123.50 (m, 4F, CH₂CF₂CF₂) ppm.

112.00 (m, 4F, CF₂CH₂);

121.00 (m, 4F,

3.7. Alcoholysis of bis-dioxolanylderivatives 13a and

13b

3.7.1. 4,4,5,5,6,6,7,7-Octafluorodecane-1,2,9,10-tetrol

(14a)

In a round-bottom ¯ask equipped with a re¯ux condenser,

a mixture of crude bis-dioxolanyl derivatives 13a (0.45 g,

1.05 mmol), methanol (10 ml) and concentrated hydrochlo-

ric acid (4 drops) was re¯uxed while stirring for 1 h when

the conversion was ca. 98% (checked by GC). Volatile

components were removed under reduced pressure on rotary

evaporator to obtain crude 14a as a white solid. This solid

was dissolved in boiling ethyl acetate and precipitated with

petroleum ether to obtain pure 14a in an yield of 0.28 g

(74%), mp 101±1038C. Analysis Ð Found: C, 33.9; H, 3.9;

F, 43.1%. C₁₀H₁₄F₈O₄, requires: C, 34.29; H, 4.03; F,

43.38%; M, 350.2. ¹³C NMR (DMSO) d: 34.27 (t, CH₂Q_F,

²J_CF 21 Hz); 65.29 (s, CHO); 65.29 (s, CH₂O) ppm.¹H

NMR (DMSO) d: 2.00±2.20 (m, 1H, CH₂CF₂); 2.30±2.50

(2, 9-Dihydroxy-4, 4,5, 5, 6,6,7, 7-octa¯uorodecan-1,10-

diyl) dimethacrylate (16a, 89% rel.) [(CH₂=C(CH₃)COO-

CH₂CHOHCH₂CF₂CF₂)₂]: ¹³C NMR (CDCl₃) d: 18.83 (s,

2

CH₃); 35.69 (t, CH₂CF₂, J_CF 21 Hz); 64.75 (s, CHO);

68.50 (s, CH₂OMA); 127.19 (s, CH₂=); 136.38 (s, C=);

1

167.98 (s, C=O) ppm. H NMR (CDCl₃) d: 1.97 (s, 3H,

CH₃); 2.20±2.50 (m, 2H, CH₂CF₂); 2.65 (s, 1H, OH); 4.19

(dd, H_A, CH₂OMA, ²J_HH 12 Hz, ³J_HH 6 Hz); 4.27 (dd,

2

3

H_B, CH₂OMA, J_HH 12 Hz, J_HH 4 Hz); 4.42 (m, 1H,

CHO); 5.64 (s, H_cis, CH₂=); 6.16 (s, H_trans, CH₂=) ppm. ¹⁹

F

NMR (CDCl₃) d: 112.85 (m, 4F, CF₂CH₂); 123.86 (m,

4F, CH₂CF₂CF₂) ppm.

(2,10-Dihydroxy-4, 4,5,5,6, 6, 7, 7-octa¯uorodecan-1,9-

diyl) dimethacrylate (17a, 11% rel.) (CH₂C(CH₃)COOCH_2-

CHOHCH₂(CF₂)₄CH₂CH(OCOC(CH₃)CH₂)CH₂OH): ¹³C

2

(m, 1H, CH₂CF₂); 3.24 (dd, H_A, CH₂O, J_HH 11 Hz,

2

³J_HH 7 Hz); 3.39 (dd, H_B, CH₂O, J_HH 11 Hz,

³J_HH 5 Hz); 3.86 (m, 1H, CHO); 4.92 (2s, 2H, OH)

Â

V. Cõrkva et al. / Journal of Fluorine Chemistry 102 (2000) 349±361

360

NMR (CDCl₃) d: 18.83 (s, CH₃); 32.65 (t, CH₂CF₂,

5.75%. C₁₈H₂₈F₈N₂O₄, requires: C, 44.26; H, 5.78; F, 31.10;

N, 5.73%; M, 488.4. ¹³C NMR (CDCl₃) d: 36.77 (t, CH₂Q_F,

²J_CF 21 Hz); 54.14 (s, CH₂N); 60.89 (s, CHO); 64.88 (s,

2

²J_CF 21 Hz); 35.69 (t, CH₂CF₂, J_CF 21 Hz); 46.41

(s, CH₂O); 64.75 (s, CHO); 69.17 (s, CHOMA); 68.50 (s,

CH₂OMA); 127.19 (s, CH₂=); 136.38 (s, C=); 167.98 (s,

1

CH₂N); 67.54 (s, CH₂O) ppm. H NMR (CDCl₃) d: 2.00±

1

C=O) ppm. H NMR (CDCl₃) d: 1.97 (s, 3H, CH₃); 2.20±

2.20 (m, 1H, CH₂CF₂); 2.20±2.37 (m, 1H, CH₂CF₂); 2.32±

2.50 (m, 4H, CH₂N); 2.67 (m, 2H, CH₂N); 3.64 (s, 1H, OH);

3.72 (m, 4H, CH₂O); 4.14 (m, 1H, CHO) ppm. ¹⁹F NMR

(CDCl₃) d: 112.82 (m, 4F, CF₂CH₂); 124.06 (m, 4F,

CH₂CF₂CF₂) ppm.

2.50 (m, 2H, CH₂CF₂); 2.50±2.60 (m, 2H, CH₂CF₂); 2.65 (s,

1H, OH); 3.76 (dd, H_A, CH₂O, ²J_HH 12 Hz, ³J_HH 5 Hz);

3.82 (dd, H_B, CH₂O, ²J_HH 12 Hz, ³J_HH 4 Hz); 4.19 (dd,

3

H_A, CH₂OMA, ²J_HH 12 Hz, J_HH 6 Hz); 4.27 (dd, H_B,

2

3

CH₂OMA, J_HH 12 Hz, J_HH 4 Hz); 4.42 (m, 1H,

CHO); 5.37 (m, 1H, CHOMA); 5.64 (s, H_cis, CH₂=);

6.16 (s, H_trans, CH₂=) ppm. ¹⁹F NMR (CDCl₃) d: the same

as for 16a.

3.9.2. 1,12-Bis(morpholin-4-yl)-4,4,5,5,6,6,7,7,8,8,9,9-

dodecafluorododecane-2,11-diol (18b)

The same procedure as in Section 3.9.1 was applied;

diepoxide 4b (0.453 g, 1.09 mmol), 90 min reaction. The

crude 18b as a yellow solid (0.52 g, 95%) was obtained.

Pure product 18b was obtained by its precipitation from

boiling toluene solution using petroleum ether, the yield was

0.48 g (75%), mp 102±1058C. Analysis Ð Found: C, 40.3;

H, 4.69; F, 39.2; N, 4.74%. C₂₀H₂₈F₁₂N₂O₄, requires: C,

40.82; H, 4.78; F, 38.73; N, 4.76%; M, 588.4. ¹³C NMR

3.8.2. Reaction of 1,2;11,12-diepoxy-4,4,5,5,6,6,7,-

7,8,8,9,9-dodecafluorododecane (4b) (products 16b and

17b)

The same procedure as in Section 3.8.1 was applied;

diepoxide 4b (0.459 g, 1.11 mmol), methacrylic acid (2.0 g,

23.2 mmol), 3 h reaction at 1008C. With ca. 97% conversion

of the starting diepoxide and after repeated crystallization

(toluene/petroleum ether) the product (16b and 17b, ca.

90% rel.) was obtained in an yield of 0.26 g (40%), mp 80±

828C. Analysis (16b and 17b) Ð Found: F, 38.2%.

C₂₀H₂₂F₁₂O₆, requires: F, 38.86%; M, 586.4. (2,11-Dihy-

droxy-4,4,5,5,6,6,7,7,8,8,9,9-dodeca¯uorododecan-1,12-

diyl) dimethacrylate (16b, ca. 90% rel.) [(CH₂=

2

(CDCl₃) d: 36.84 (t, CH₂Q_F, J_CF 21 Hz); 54.22 (s,

CH₂N); 60.89 (s, CHO); 64.94 (s, CH₂N); 67.59 (s,

CH₂O) ppm. ¹H NMR (CDCl₃) d: 2.00±2.20 (m, 1H,

CH₂CF₂); 2.20±2.37 (m, 1H, CH₂CF₂); 2.32±2,55 (m,

4H, CH₂N); 2.69 (m, 2H, CH₂N); 3.64 (s, 1H, OH); 3.72

(m, 4H, CH₂O); 4.15 (m, 1H, CHO) ppm. ¹⁹F NMR (CDCl₃)

d: 112.70 (m, 4F, CF₂CH₂); 122.10 (m, 4F, CH₂C₂F₄-

CF₂); 124.10 (m, 4F, CH₂CF₂CF₂) ppm.

C(CH₃)COOCH₂CHOHCH₂CF₂CF₂CF₂)₂]: ¹³C NMR

2

(CDCl₃) d: 18.95 (s, CH₃); 35.64 (t, CH₂CF₂, J_CF

21 Hz); 64.77 (s, CHO); 68.49 (s, CH₂OMA); 127.26 (s,

1

CH₂=); 136.34 (s, C=); 167.96 (s, C=O) ppm. H NMR

Acknowledgements

(CDCl₃) d: 1.97 (s, 3H, CH₃); 2.20±2.50 (m, 2H, CH₂CF₂);

2

2.45 (s, 1H, OH); 4.19 (dd, H_A, CH₂OMA, J_HH 12 Hz,

The authors thank heartily the Asahi Glass Company,

Japan for the kind gift of diiodoper¯uoroalkanes. The

research was supported by the Grant Agency of the Czech

Republic (Grant No. 203/98/1174 and 106/001296) and the

grant of the Ministry of Education of the Czech Republic

(Project LB98233). Elemental analyses and measurements

of some NMR spectra were carried out in the Central

Laboratories of the Prague Institute of Chemical Technol-

ogy; the authors thank their staff members for the kind

assistance.

2

³J_HH 6 Hz); 4.29 (dd, H_B, CH₂OMA, J_HH 12 Hz,

³J_HH 4 Hz); 4.42 (m, 1H, CHO); 5.65 (s, H_cis, CH₂=);

6.15 (s, H_trans, CH₂=) ppm. ¹⁹F NMR (DMSO) d: 113.00

(m, 4F, CF₂CH₂); 121.80 (m, 4F, CH₂C₂F₄CF₂); 124.00

(m, 4F, CH₂CF₂CF₂) ppm.

3.9. Ring opening of diepoxides 4a and 4b with

morpholine

3.9.1. 1,10-Bis(morpholin-4-yl)-4,4,5,5,6,6,7,7-

octafluorodecane-2,9-diol (18a)

References

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obtained by its precipitation from boiling toluene solution

using petroleum ether, the yield was 0.43 g (61%), mp 95±

978C. Analysis Ð Found: C, 43.9; H, 5.69; F, 31.6; N,

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Article Doi

Fluorinated epoxides: 5. Highly selective synthesis of diepoxides from α,ω-diiodoperfluoroalkanes. Regioselectivity of nucleophilic epoxide-ring opening and new amphiphilic compounds and monomers

DOI: 10.1016/S0022-1139(99)00301-2

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