JP4300293B2 - Fluorine-containing unsaturated thiol derivative - Google Patents

Description

The present invention relates to a novel fluorine-containing compound used as a surfactant or a synthetic intermediate thereof.

  In general, diacetylene-containing compounds are known to form more stable copolymers when irradiated with ultraviolet rays, and diacetylene compounds having a functional group such as a carboxylic acid, a hydroxyl group, and a thiol group at one end thereof Has also been synthesized. In addition, it has been reported that a compound having a thiol and diacetylene bond can be used as a gold surface coating for the gold surface coating (see, for example, Non-Patent Document 1 and Patent Documents 1 to 3).

Lee et al. Have also succeeded in synthesizing F (CF ₂ ) _m (CH ₂ ) _n SH (m = 1 to 4, n = 9 to 15), and synthesized a compound in which the thiol is replaced with a hydroxyl group. ing. However, a compound in which a carbon-carbon triple bond or a double bond is introduced into these has not been obtained yet. Similarly, Calas et al. Have succeeded in synthesizing a compound in which F (CF ₂ ) _m (CH ₂ ) _n SH (m = 6, 8, n = 2, 11) and its thiol are replaced with hydroxyl groups, A carbon-carbon triple bond or a double bond introduced is not synthesized (see Non-Patent Documents 2 to 3).

On the other hand, Lu et al., Among compounds represented by Rf—C≡C—R and Rf— (CH═CH) ₂ —R, Rf is Cl (CF ₂ ) _n (n = 2, 4, 8). , CF ₃ and C ₂ F ₅
R is selected from n-C _n H _m (n, m = 3, 7; 5, 11; 6, 13; 8, 17) and (CH ₂ ) _n OH (n = 6, 9). Although it has been reported that a compound composed of a combination with a selected group has been obtained (see Non-Patent Document 4), it has not been successfully converted into a thiol derivative.

Further, Fried et al. Considered that when a fluorine atom is introduced into unstable prostheclinin (PGI ₂ ) and thromboxane (TXA ₂ ) in the prostaglandin research process, a stable structure is assumed. A compound in which methylene (CH ₂ ) sandwiched between triple bonds or double bonds is substituted with CF ₂ is synthesized (see Non-Patent Document 5), but no fluorine compound other than CF ₂ is introduced.

JP 2001-253867 A Japanese Patent Laid-Open No. 2001-253484 JP 2001-247540 A Tetrahedron. Lett. 1994, p9501 J. et al. Fluorine Chem. 93 (1999) p107-115. J. et al. Fluorine Chem. , 104 (2000) p173-183 Tetrahedron, 51 (43), 11765-11774 (1995) J. et al. Am. Chem. Soc. 109, p3684-3692 (1987)

  The object of the present invention is to have a fluorine-containing organic group, a carbon-carbon unsaturated bond (double bond or triple bond) and a sulfur atom (SH, S or SS) in the same molecule, and to have a good surface activity. It is to provide a novel compound having or useful as a synthesis intermediate thereof.

  As a result of intensive research on solving the above problems, the present inventors have bonded a monovalent fluorine-containing organic group to one end of a carbon-carbon double bond or a triple bond, and a sulfur atom (SH, It has been found that an organic group-bonded compound containing S, SS) can be obtained in a relatively high yield, and the present invention has been completed.

That is, according to the present invention, the fluorine-containing unsaturated thiol derivative represented by the general formula (1) or (2) having a fluorine atom, a sulfur atom, and a carbon-carbon double bond or triple bond in the same molecule. Is provided.
R ¹ -XR ² (1)
R ¹ -XR ³ -SSR ³ -XR ¹ (2)
[Wherein R ¹ represents a perfluoroalkyl group having 2 to 25 carbon atoms, R ² represents an alkyl group having 2 to 25 carbon atoms having SH, R ³ represents an alkylene group having 2 to 25 carbon atoms, and X represents , C≡C or (CH═CH) _n (where n = 2). ]

According to the present invention, there is provided a novel compound having both a fluorine-containing organic group, an unsaturated bond (double bond or triple bond) and a sulfur atom (SH or SS or S) in the same molecule.
The fluorine-containing unsaturated thiol derivative of the method of the present invention is effective as a surfactant, widely used in cosmetics, agricultural chemicals, industrial chemicals, etc., and as a synthetic intermediate for surfactants used in various technical fields. Is also useful.

The fluorine-containing unsaturated thiol derivative of the present invention can be represented by the following general formula (1) or general formula (2).
R ¹ -XR ² (1)
R ¹ -XR ³ -SSR ³ -XR ¹ (2)
In the general formula (1) or (2), R ¹ is a perfluoroalkyl group having 2 to 25 carbon atoms, R ² is an alkyl group having 2 to 25 carbon atoms having SH, and R ³ is carbon number. 2 to 25 alkylene groups are shown.
Further, X has two consecutive C≡C, which is a carbon-carbon triple bond showing an acetylene bond, or CH═CH, which is a carbon-carbon double bond showing an ethylene bond. The configuration of this double bond may be any of the stereoisomers of E or Z, and may be either the S-cis conformation or the S-trans conformation. Further, in the case of a conjugated diene, the two double bonds may be any of EE, EZ, and ZZ, and the double bonds may be in either the S-cis conformation or the S-trans conformation.

In the fluorine-containing unsaturated thiol derivative of the present invention, the number of carbon atoms contained in each organic group represented by R ^{1 to} R ³ is 2 to 100, preferably 50 or less, more preferably 25 or less. It is. The organic groups constituting R ^{1 to} R ³ include various types shown below.
First, the aliphatic group includes chain (including branched) and cyclic groups, and further includes saturated and unsaturated groups. The chain aliphatic group includes an alkyl group and an alkenyl group. Cycloaliphatic groups include cycloalkyl groups and cycloalkenyl groups. In the alkyl group, the number of carbon atoms constituting the main chain is preferably 2 to 60, more preferably 2 to 25. In the alkenyl group, the number of carbon atoms constituting the main chain is preferably 2 to 50, more preferably 2 to 25. In the cycloalkyl group and the cycloalkenyl group, the number of rings can be one or more (2 to 4, preferably 2 to 3). The number of carbon atoms constituting the molecule is 5 to 60, preferably 6 to 25.

  Specific examples of the organic group include, for example, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, and n-to. Xyl, isohexyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl, otatadecyl, eicosyl, cyclopentyl, cyclohexyl , Adamantyl, vinyl, propenyl, butenyl, acrylic, methacryl, octynyl, dodecenyl, undecenyl, cyclohexenyl and the like.

  These organic groups may have an inert substituent that does not participate in the synthesis reaction of the present invention. Examples of such a substituent include a substituted or unsubstituted aryl group, a carbonyl group, an alkoxy group, an alkoxy group. Examples include carbonyl group, acyl group, acyloxy group, alkyl or arylsulfonyl group, nitro group, halogen (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like.

In addition, the organic group can contain a heteroatom in the main chain of the organic group. The heteroatom includes an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom and the like.

Furthermore, the organic group may contain a metal atom. In this case, the metal atoms include alkali metals such as lithium, sodium, potassium, rubidium and cesium, alkaline earth metals such as beryllium, magnesium, calcium, strontium and barium, metals such as boron, aluminum, titanium, tin and iron Atoms can be mentioned. These metal atoms are usually contained in the organic group in a bond form such as a carbon-metal bond or an ionic bond.

The organic group of the fluorine-containing unsaturated thiol derivative in the present invention further includes the following.
The saccharide is not particularly limited, but is usually a monosaccharide, an amino sugar, or an oligosaccharide. Examples of monosaccharides include pentose, hexose, deoxyhexose, heptose, and amino sugar. Examples include apiose, hamamelose, streptose, sedoheptulose, coliose, glucosamine, galactosamine, 2-deoxy-2-methylaminoglucose and the like. Examples of oligosaccharides include non-reducing oligosaccharides and reducing oligosaccharides, and specific examples include sucrose, trehalose, gentianose, raffinose, lactose, cellobiose, maltose, and gentiobiose.

As the amines, the number of elements in the compound usually contained is composed of 50 or less carbon atoms, 20 or less oxygen atoms, 30 or less nitrogen atoms, and 5 or less sulfur atoms, preferably carbon. Number 35 or less, oxygen number 5 or less, nitrogen number 15 or less, sulfur number 3 or less, more preferably those having a carbon number of 2 to 20, an oxygen number of 3 or less, a nitrogen number of 2 to 10, and a sulfur number of 1 or less. .

  Specific amino acids include glycine, alanine, valine, leucine, isoleucine, serine, threonine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, ornithine, arginine, histidine, hydroxylysine, cysteine, cystine, methionine, phenylalanine. , Tyrosine, tryptophan, proline, 4-hydroxyproline, tricolominic acid, ibotenic acid, kisscaric acid, canavanine, kainic acid, domoic acid, 1-aminocyclopropanecarboxylic acid, 2- (methylenecyclopropyl) glycine, hypoglycine A, 3 -Cyanoalanine, Avenaic acid, Mugineic acid, Mimosine, Levodopa, β-hydroxy-γ-methylflutamic acid, 5-hydroxytryptophan, pantothenic acid, laminin, betacyanin Examples thereof include amines having a sulfonic acid group such as taurine.

  The amines may be substituted with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and one or more of them may be substituted. Further, the phosphoric acid group and the amino alcohol may be bonded. Examples of amino alcohols include choline, ethanolamine, and serine.

Although it does not restrict | limit especially as peptides, Usually, it is a nitrogen-containing polymer, Polypeptides, such as a polycondensation compound or protein by 2 or more amino acids, myoglobin, hemoglobin, etc. are mentioned.

Nucleic acids include nucleosides, nucleotides, or polymer chains of nucleotide units. A nucleoside is a cytosine, thymine, adenine, or guanine base linked to a 2-deoxyribose or ribose sugar, a nucleotide is a nucleoside sugar linked to a phosphate group, and a thymine is also uracil. included.

The fluorine-containing unsaturated thiol derivative of the present invention can be produced using, for example, the synthesis route shown below. In addition, R < ⁴ > -R < ⁸ > in a formula means an organic group all.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist. FIG. 1 shows all the steps for synthesizing the target compound from the raw materials described in the Examples. In addition, all the compound numbers in an Example are the compounds shown in FIG.

(Synthesis of Compound 1)
P-Toluenesulfonic acid was added to an anhydrous methylene chloride solution of 8-bromooctanol and dihydropyran under ice cooling. After stirring at room temperature for 18 hours, it was diluted with methylene chloride. This was washed in turn with water and saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 5: 95) to obtain Compound 1 at 92 to 99%.

(Synthesis of Compound 2)
An anhydrous dimethyl sulfoxide solution of Compound 1 was added to an anhydrous dimethyl sulfoxide solution of lithium acetylide / ethylenediamine under ice cooling. After stirring at the same temperature for 3 hours, ice water was added, the mixture was extracted with hexane, washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 5: 95) to obtain Compound 2 at 65 to 85%.

(Synthesis of Compound 3)
Hydrosulfuric acid sodium and sodium hydrogencarbonate were added to an acetonitrile aqueous solution of compound 2 and perfluorooctyl iodide, and the mixture was stirred at room temperature for 4 hours. This was diluted with water and extracted with ether. Then, it wash | cleaned with the saturated salt solution and was made to dry with anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 5: 95) to obtain 71 to 91% of compound 3 (mixture of E form and Z form).

(Synthesis of Compound 4)
An anhydrous diethyl ether solution of Compound 3 was added to a solution of t-butoxy potassium in anhydrous diethyl ether cooled to −20 ° C., and the mixture was stirred at the same temperature for 1 hour and further at 0 ° C. for 2 hours. This was neutralized with aqueous hydrochloric acid and extracted with ether. Then, it wash | cleaned with the saturated salt solution and was made to dry with anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 9) to obtain Compound 4 at 87 to 99%.

(Synthesis of Compound 5)
P-Toluenesulfonic acid was added to a methanol solution of compound 4 and stirred at room temperature for 24 hours. Water was added to this, followed by extraction with ether. After filtration, the solvent was distilled off and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 3: 7) to obtain Compound 5 at 82 to 99%.

(Synthesis of Compound 6)
Carbon tetrabromide and triphenylphosphine were added to an anhydrous tetrahydrofuran solution of compound 5, and the mixture was stirred at room temperature for 2 hours. This was concentrated under reduced pressure and then purified by column chromatography (silica gel, ethyl acetate: hexane = 5: 95) to obtain Compound 6 at 67-87%.

(Synthesis of Compound 7)
To an anhydrous N, N-dimethylformamide solution of potassium thioacetate, an N, N-dimethylformamide solution of Compound 6 was added dropwise and stirred at room temperature for 18 hours. Ice water was added thereto, and the mixture was extracted with methylene chloride. After filtration, the solvent was distilled off to obtain Compound 7 at 80 to 95%.

Compound 7 was identified by 1H or ¹⁹ F-NMR spectrum.
1H-NMR (TMS, CDCl3): 1.28-1.47 (m, 8H), 1.50-1.64 (m, 4H), 2.32 (s, 3H), 2.35 (m, 2H), 2.87 (t, J = 7.3 Hz, 2H).
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.64 (t, J = 9.71 Hz, 3F), −95.58 (m, 2F), −120.49 (m, 2F), −121.88 (M, 4F), -122.65 (m, 4F), -126.03 (m, 2F).

(Synthesis of Compound 8)
A 30% aqueous sodium hydroxide solution was added dropwise to the acetone solution of compound 7 and the mixture was stirred at room temperature for 2 hours. This was neutralized with 10% aqueous hydrochloric acid and extracted with methylene chloride. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 3: 7) to obtain Compound 8 at 80 to 95%. This reaction formula is shown in (9).

The resulting compound 8 was identified by 1H or ¹⁹ F-NMR spectrum.
1H-NMR (TMS, CDCl3): 1.28-1.47 (m, 9H), 1.50-1.64 (m, 4H), 2.35 (m, 2H), 2.50 (t, J = 7.5 Hz, 2H).
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.64 (t, J = 9.71 Hz, 3F), −95.58 (m, 2F), −120.49 (m, 2F), −121.88 (M, 4F), -122.55 to -122.74 (m, 4F), -126.03 (m, 2F).

(Synthesis of Compound 9)
Compound 6 was dissolved in ethanol, 70% sodium hydrosulfide was added thereto, and the atmosphere was purged with argon, followed by sonication at 50 to 55 ° C. for 9 hours. The resulting reaction solution was diluted with methylene chloride, acidified with dilute hydrochloric acid, extracted with methylene chloride, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 1) to obtain compounds 8 and 9 at 34 to 54% and 22 to 44%, respectively.

The obtained compound 9 was identified by 1H or ¹⁹ F-NMR spectrum.
1H-NMR (TMS, CDCl3): 1.28-1.47 (m, 16H), 1.50-1.64 (m, 8H), 2.35 (m, 4H), 2.68 (t, J = 7.5 Hz, 4H).
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.64 (t, J = 9.71 Hz, 6F), −95.58 (m, 4F), −120.49 (m, 4F), −121.88 (M, 8F), -122.55 to -122.74 (m, 8F), -126.03 (m, 4F).

(Synthesis of Compound 10)
Compound 3 (mixture of E-form and Z-form) was separated into 3E (E-form of Compound 3) and 3Z (Z-form of Compound 3) by flash column chromatography, and the following operation was performed.
A 1.6 M n-butyllithium hexane solution (4 to 5 equivalents) was added to an anhydrous tetrahydrofuran solution of compound 3E cooled to -78 ° C. After 1 hour, methanol was added and the temperature was slowly raised to 0 ° C., then a saturated aqueous ammonium chloride solution was added, the mixture was extracted with ethyl acetate, washed with saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 15: 85) to obtain Compound 10 at 71 to 91%.

(Synthesis of Compound 11)
Carbon tetrabromide and triphenylphosphine were added to an anhydrous tetrahydrofuran solution of compound 10, and the mixture was stirred at room temperature for 2 hours. This was concentrated under reduced pressure, and then purified by column chromatography (silica gel, ethyl acetate: hexane = 5: 95) to obtain Compound 11 at 70 to 90%.

(Synthesis of Compound 12)
An anhydrous N, N-dimethylformamide solution of Compound 11 was added dropwise to an anhydrous N, N-dimethylformamide solution of potassium thioacetate and stirred at room temperature for 18 hours. Ice water was added thereto, and the mixture was extracted with methylene chloride. After filtration, the solvent was distilled off to obtain Compound 12 at 78 to 98%.

Compound 12 was identified by 1H or ¹⁹ F-NMR spectrum.
1H-NMR (TMS, CDCl3): 1.20-1.50 (m, 10H), 1.52-1.63 (m, 2H), 2.25-2.37 (m, 2H); 32 (s, 3H), 2.87 (t, J = 6.5 Hz, 2H), 5.48 (dd, J = 15.4, 12.8 Hz, 1H), 6.11 (dtt, J = 11 .9, 7.8, 2.Hz, 1H).
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.66 (t, J = 10.04 Hz, 3F), −106.54 (m, 2F), −121.35 (m, 2F), −121.90 (M, 4F), -122.65 (m, 2F), -123.50 (m, 2F), -126.06 (m, 2F).

(Synthesis of Compound 13)
A 30% aqueous sodium hydroxide solution was added dropwise to the acetone solution of compound 12, and the mixture was stirred at room temperature for 2 hours. This was neutralized with 10% aqueous hydrochloric acid and extracted with methylene chloride. After filtration, the solvent was distilled off and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 3: 7) to obtain Compound 13 at 80 to 95%.

The resulting product 13 was identified by 1H or ¹⁹ F-NMR spectrum.
1H-NMR (TMS, CDCl3): 1.20-1.50 (m, 11H), 1.52-1.63 (m, 2H), 2.35 (m, 2H), 2.50 (t, J = 7.5 Hz, 2H), 5.48 (dd, J = 15.4, 12.8 Hz, 1H), 6.11 (dtt, J = 11.9, 7.8, 2.Hz, 1H) .
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.66 (t, J = 10.04 Hz, 3F), −106.54 (m, 2F), −121.35 (m, 2F), −121.90 (M, 4F), -122.65 (m, 2F), -123.50 (m, 2F), -126.06 (m, 2F).

(Synthesis of Compound 14)
Compound 11 was dissolved in ethanol, 70% sodium hydrosulfide was added thereto, and the mixture was purged with argon, followed by sonication at 50 to 55 ° C. for 9 hours. The resulting reaction solution was diluted with methylene chloride, acidified with dilute hydrochloric acid, extracted with methylene chloride, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 1) to obtain compounds 13 and 14 at 35 to 55% and 2 to 45%, respectively.

The resulting product 14 was identified by 1H or ¹⁹ F-NMR spectrum.
1H-NMR (TMS, CDCl3): 1.20-1.50 (m, 10H), 1.52-1.63 (m, 2H), 2.35 (m, 2H), 2.50 (t, J = 7.5 Hz, 2H), 5.48 (dd, J = 15.4, 12.8 Hz, 1H), 6.11 (dtt, J = 11.9, 7.8, 2.Hz, 1H) .
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.66 (t, J = 10.04 Hz, 3F), −106.54 (m, 2F), −121.35 (m, 2F), −121.90 (M, 4F), -122.65 (m, 2F), -123.50 (m, 2F), -126.06 (m, 2F).

(Synthesis of Compound 15)
An equivalent amount of acetic acid, acetic anhydride, triphenylphosphine, and a catalytic amount of bisbenzylideneacetone palladium were sequentially added to a toluene solution of Compound 5, and the mixture was heated at 110 ° C. for 15 hours. After the solvent was distilled off, the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 5: 95) to obtain Compound 15 at 55 to 85%.

(Synthesis of Compound 16)
To a tetrahydrofuran solution of compound 15 was added 10% aqueous sodium hydroxide solution, and the mixture was stirred at room temperature for 1 day. This was neutralized, extracted with methylene chloride, washed with saturated brine, and dried over anhydrous magnesium sulfate. The filtration solvent was distilled off and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 10: 90) to obtain Compound 16 at 75 to 95%.

(Synthesis of Compound 17)
Carbon tetrabromide and triphenylphosphine were added to an anhydrous tetrahydrofuran solution of compound 16, and the mixture was stirred at room temperature for 2 hours. This was concentrated under reduced pressure, and then purified by column chromatography (silica gel, ethyl acetate: hexane = 5: 95) to obtain Compound 17 at 65 to 85%.

(Synthesis of Compounds 18 and 19)
Compound 17 was dissolved in ethanol, 70% sodium hydrosulfide was added thereto, and the mixture was purged with argon, followed by sonication at 50 to 55 ° C. for 9 hours. The resulting reaction solution was diluted with methylene chloride, acidified with dilute hydrochloric acid, extracted with methylene chloride, and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by column chromatography (silica gel, ethyl acetate: hexane = 1: 1) to obtain compounds 18 and 19 at 30 to 55% and 20 to 45%, respectively.

The resulting products 18 and 19 were identified by 1H or ¹⁹ F-NMR spectra.
Compound 18:
1H-NMR (TMS, CDCl3): 1.25-1.31 (m, 7H), 1.52-1.53 (m, 2H), 2.50 (t, J = 7.5 Hz, 2H), 3.92 (t, J = 6.5 Hz, 2H), 5.62 (dt, J = 15.0, 6.5 Hz, 1H), 6.08 (dd, J = 15.0, 9.8 Hz) 1H), 6.75 (ddt, J = 15.4, 9.8, 2.0 Hz, 1H), 7.05-7.20 (m, 1H).
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.64 (t, J = 9.71 Hz, 3F), −111.88 (m, 2F), −121.31 (m, 2F), −121.80 (M, 4F), -122.60 (m, 2F), -123.27 (m, 2F), -125.97 (m, 2F).
Compound 19:
1H-NMR (TMS, CDCl3): 1.25-1.31 (m, 12H), 1.52-1.53 (m, 4H), 2.68 (t, J = 7.5 Hz, 4H), 3.92 (t, J = 6.5 Hz, 4H), 5.62 (dt, J = 15.0, 6.5 Hz, 2H), 6.08 (dd, J = 15.0, 9.8 Hz) 2H), 6.75 (ddt, J = 15.4, 9.8, 2.0 Hz, 2H), 7.05-7.20 (m, 2H).
19F-NMR (CFCl ₃ , CDCl ₃ ): −80.64 (t, J = 9.71 Hz, 6F), −111.88 (m, 4F), −121.31 (m, 4F), −121.80 (M, 8F), -122.60 (m, 4F), -123.27 (m, 4F), -125.97 (m, 4F).

  Since the fluorine-containing unsaturated thiol derivative obtained in the present invention has a good surface activity, it can be widely used in a wide range of fields such as cosmetics, agricultural chemicals, industrial chemicals and household products.

It is a chemical reaction formula showing a synthetic route of an example of a fluorine-containing unsaturated thiol derivative in the present invention.

Claims (1)

The following general formula (1) or (2)
R ¹ -XR ² (1)
R ¹ -XR ³ -SSR ³ -XR ¹ (2)
[Wherein R ¹ represents a perfluoroalkyl group having 2 to 25 carbon atoms, R ² represents an alkyl group having 2 to 25 carbon atoms having SH, R ³ represents an alkylene group having 2 to 25 carbon atoms, and X represents , C≡C or (CH═CH) _n (where n = 2). ] The fluorine-containing unsaturated thiol derivative represented by this.

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