JP5663926B2 - Trifluorovinyloxy-N-monoalkylaniline compound and method for producing the same - Google Patents

Description

  The present invention relates to a trifluorovinyloxy-N-monoalkylaniline compound and a method for producing the same. More specifically, the present invention relates to a trifluorovinyloxy-N-monoalkylaniline compound capable of forming reaction sites at both ends of the polymer main chain of the fluorinated polyether compound and a method for producing the same.

In the halogenated anilide compounds of the following fluorine-containing polyether compounds derived from monohalogenoanilines, the viscosity (25 ° C) differs greatly depending on the presence or absence of hydrogen bonding between the primary anilide compound and the secondary anilide compound, and the secondary anilide compound. It has been confirmed by preliminary studies by the present inventors that the viscosity of the monohalogenated anilide compound is significantly lower than that of the primary monohalogenated anilide compound.

WO 90/15042 A2

Polymer 41 6213 (2000) Tetrahedron Letters 36 6373 (1995) Tetrahedron Letters 38 (5831) (1997) J. Am. Chem. Soc. 128, 7055 (2006) J. Polymer Sci .; Part A: Poly. Chem. 31 3465 (1993)

The present inventors, as a compound capable of forming reactive sites of the polymer main chain terminal of the fluorine-containing polyether compound has examined Aniri emission compound having trifluoride lobby Niro dimethylvinylsiloxy groups (-OCF = CF _2), As described in Non-Patent Document 1, when trifluorovinyloxyaniline, which is a known compound, is used, viscosity reduction of the fluorinated polyether compound having it at both ends of the polymer main chain is not achieved. Have confirmed.

  An object of the present invention is to provide a trifluorovinyloxyaniline compound and a method for producing the same, which can reduce the viscosity of a fluorine-containing polyether compound into which a trifluorovinyloxyaniline compound is introduced as a reaction site at both ends of a polymer main chain. There is.

(ここで、R¹は炭素数1〜3のアルキル基である)で表わされるトリフルオロビニロキシ-N-モノアルキルアニリン化合物、好ましくはトリフルオロビニロキシ-N-モノメチルアニリンが提供される。 According to the present invention, the general formula [I]

There is provided a trifluorovinyloxy-N-monoalkylaniline compound represented by (wherein R ¹ is an alkyl group having 1 to 3 carbon atoms), preferably trifluorovinyloxy-N-monomethylaniline.

  Such a trifluorovinyloxy-N-monoalkylaniline compound is a method for N-monoalkylating trifluorovinyloxyaniline or (2-bromotetrafluoroethoxy) aniline, which is a precursor of trifluorovinyloxyaniline, to N -Manufactured by a method of dealkylating after monoalkylation.

を形成させると、該含フッ素ポリエーテル化合物の低粘度化を達成せしめ、RIM成形なども可能とさせる。 A fluorinated polyether compound in which a trifluorovinyloxyaniline compound is introduced as a reaction site at both ends of the polymer main chain using the trifluorovinyloxy-N-monoalkylaniline compound according to the present invention, for example,

When this is formed, the viscosity of the fluorine-containing polyether compound can be reduced, and RIM molding or the like can be achieved.

で表わされ、ここでR¹は炭素数1〜3のアルキル基、すなわちメチル基、エチル基、n-プロピル基またはイソプロピル基であり、特に製造の容易さの点からはメチル基であることが好ましい。 The trifluorovinyloxy-N-monoalkylaniline compound according to the present invention has the general formula [I]

Where R ¹ is an alkyl group having 1 to 3 carbon atoms, that is, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group, and particularly a methyl group from the viewpoint of ease of production. Is preferred.

  Trifluorovinyloxy-N-monoalkylaniline compounds are methods for N-monoalkylating o-, m- or p-trifluorovinyloxyanilines, or precursors of trifluorovinyloxyanilines (2-bromo Tetrafluoroethoxy) aniline can be produced by N-monoalkylation followed by deFBrification reaction.

  N-alkylation of a trifluorovinyloxyaniline compound or (2-bromotetrafluoroethoxy) aniline compound can be easily produced by N-alkylation with an alkylating agent such as alkyl iodide or dialkyl sulfuric acid. it can. However, since the reaction mixture obtained as a result of this reaction is a mixture of N-monoalkyl, N, N-dialkyl and unreacted raw materials, N-monoalkyl is removed from the reaction mixture by distillation, liquid chromatography, etc. An operation to separate the body is required. As one of the separation operation methods, the N-monoalkyl product can be isolated by acetylating the N-monoalkyl product and then hydrolyzing the acetyl group.

  In N-monoalkylation of trifluorovinyloxyaniline or (2-bromotetrafluoroethoxy) aniline, it is more preferable from the viewpoint of yield to adopt a selective N-alkylation method. Examples of such a selective N-alkylation method include a method described in Non-Patent Document 2 or 3, that is, a method via a sulfonamide. Specifically, as shown in the examples below, trifluorovinyloxyaniline or (2-bromotetrafluoroethoxy) aniline is converted to 2-nitrobenzenesulfonyl chloride or nitrobenzene in the presence of a tertiary amine such as pyridine or triethylamine. After sulfonamidation with 2,4-dinitrobenzenesulfonyl chloride, N-alkylation with alkyl halide in aprotic polar solvent such as N, N-dimethylformamide, and finally N, N-dimethylformamide Selective N-monoalkylation can be achieved by reaction with thiophenol or mercaptoacetic acid under basic conditions in an aprotic solvent such as chloroform.

  The trifluorovinyloxyaniline or (2-bromotetrafluoroethoxy) aniline to be N-alkylated is produced by a known method. For example, Non-Patent Document 1 describes a method for producing trifluorovinyloxyaniline from acetamidophenol, and Patent Document 1 discloses trifluorovinyloxyaniline and (2-bromo) starting from methyl hydroxybenzoate. Non-Patent Document 4 describes a method for producing trifluorovinyloxyaniline using bromo (trifluorovinyloxy) benzene derived from bromophenol as a raw material. ing.

On the other hand, the deFBrification reaction of (2-bromotetrafluoroethoxy) -N-monoalkylaniline can be carried out by reacting zinc in an aprotic polar solvent such as acetonitrile or 1,2-dimethoxyethane. it can.
-OCF ₂ CF ₂ Br + Zn → -OCF = CF ₂ + ZnFBr

The trifluorovinyloxy-N-monoalkylaniline compound of the present invention can form a fluorine-containing polyether compound by reacting with a fluorine-containing polyether dicarboxylic acid difluoride compound as shown in the following reaction formula.

  This fluorine-containing polyether compound having a terminal trifluorovinyloxy group is obtained by curing with a trifunctional compound such as 1,1,1-tris (4-trifluorovinyloxyphenyl) ethane (Non-patent Document 5). An elastomeric molding can be provided.

  Next, the present invention will be described with reference to examples.

Reference example 1
Synthesis of 4- (2-bromotetrafluoroethoxy) aniline and 4- (trifluorovinyloxy) aniline
(1) To a solution consisting of 100 g (0.657 mol) of methyl 4-hydroxybenzoate and 300 ml of methanol, 43.4 g (0.657 mol) of potassium hydroxide (purity 85%) was added little by little while cooling the reaction vessel with ice water. The reaction was continued for another 3 hours. After removing methanol under reduced pressure, it was dried under reduced pressure at 140 ° C. and 27 Pa for 8 hours. 119 g (95% yield) of potassium salt of methyl 4-hydroxybenzoate was obtained as a colorless solid.
(2) In a solution of 50 g (0.26 mol) of potassium 4-hydroxybenzoate in 150 ml of dimethyl sulfoxide, 89 g (0.34 mol) of 1,2-dibromotetrafluoroethane was added at 60 ° C. in a nitrogen atmosphere. It was added dropwise over 1 hour. After completion of dropping, the reaction was further carried out at 70 ° C. for 2 hours and 90 ° C. for 30 minutes. The reaction mixture was cooled to room temperature, 150 ml of water was added, and the product was extracted with dichloromethane. Thereafter, usual post-treatment was performed to obtain 84 g of a crude product. This was distilled under reduced pressure to obtain 81 g (yield: 93%) of methyl 4- (2-bromotetrafluoroethoxy) benzoate (boiling point: 75-77 ° C., 13 Pa) as a colorless liquid.
(3) Alkaline solution consisting of 70 g (0.211 mol) of methyl 4- (2-bromotetrafluoroethoxy) benzoate and 100 ml of methanol and 18.1 g (0.274 mol) of potassium hydroxide (purity 85%) and 100 ml of methanol Was added at room temperature and the reaction was continued for another 4 hours. To the obtained solution, 110 ml of water and 43 g of concentrated hydrochloric acid were added, and the contents were mixed well. The liberated product was extracted with diethyl ether, and then subjected to usual work-up to obtain 65.8 g (yield 98%) of 4- (2-bromotetrafluoroethoxy) benzoic acid as a colorless solid.
(4) A mixture of 65.6 g (0.207 mol) 4- (2-bromotetrafluoroethoxy) benzoic acid, 32.1 g (0.270 mol) thionyl chloride, 2.0 g (0.027 mol) dimethylformamide and 160 ml chloroform was prepared at 50 ° C. The reaction was performed for 2 hours. After distilling off chloroform and unreacted thionyl chloride under reduced pressure, the residue was further distilled under reduced pressure. 67.3 g (yield 97%) of 4- (2-bromotetrafluoroethoxy) benzoyl chloride (boiling point 68-72 ° C., 9 Pa) was obtained as a colorless liquid.
(5) To a solution consisting of 67.3 g (0.201 mol) 4- (2-bromotetrafluoroethoxy) benzoyl chloride and 200 ml tetrahydrofuran, an aqueous solution consisting of 43.1 g (0.663 mol) sodium azide and 140 ml water was added. It was added while cooling. After continuing the reaction for 1.5 hours, 200 ml of water was added, and the product was extracted with dichloromethane. Thereafter, usual post-treatment was performed to obtain 67.8 g (yield 99%) of [4- (2-bromotetrafluoroethoxy) phenyl] azidomethanone as a colorless liquid.
(6) A solution comprising 67.7 g (0.198 mol) of [4- (2-bromotetrafluoroethoxy) phenyl] azidomethanone and 650 ml of toluene solvent was reacted at 100 ° C. for 1.5 hours. Toluene was distilled off under reduced pressure, and then the residue was distilled under reduced pressure. 53.8 g (yield 87%) of 4-isocyanato- (2-bromotetrafluoroethoxy) benzene (boiling point 54-56 ° C., 33 Pa) was obtained as a colorless liquid.
(7) A mixture consisting of 41.3 g (0.132 mol) of 4-isocyanato- (2-bromotetrafluoroethoxy) benzene, 74 ml of concentrated hydrochloric acid and 150 ml of 1,2-dimethoxyethane was reacted at 80 ° C. for 2 hours. To the obtained reaction mixture, an alkaline aqueous solution consisting of 56 g of potassium hydroxide (purity 85%) and 500 ml of water was added. The product was extracted with diethyl ether and then subjected to normal workup. Further, distillation under reduced pressure was carried out to obtain 33.6 g (yield 88%) of 4- (2-bromotetrafluoroethoxy) aniline (boiling point 65 to 68 ° C., 53 Pa) as a colorless liquid.
(8) A mixture consisting of 18.0 g (63 mmol) of 4- (2-bromotetrafluoroethoxy) aniline, 5.3 g (81 mmol) of Zn and 300 ml of 1,2-dimethoxyethane was heated to reflux overnight under a nitrogen atmosphere. After cooling, the reaction mixture was filtered, 500 ml of a saturated aqueous sodium hydrogen carbonate solution was added to the filtrate, and this was extracted with dichloromethane, followed by normal workup. Distillation under reduced pressure yielded 8.8 g (yield 75%) of 4- (trifluorovinyloxy) aniline (boiling point 85 to 90 ° C., 133 Pa) as a colorless liquid.

Example 1
(1) 5.0 g (26 mmol) of 4-trifluorovinyloxyaniline, 7.1 g (32 mmol) of 2-nitrobenzenesulfonyl chloride and 2.5 g (32 mmol) of pyridine in 100 ml of dichloromethane solvent at room temperature for 1 hour Reacted. After completion of the reaction, 9.7 g (yield 98%) of N- (4′-trifluorovinyloxyphenyl) -2-nitrobenzenesulfonamide was obtained by an ordinary post-treatment method.
(2) 9.7 g (26 mmol) of N- (4′-trifluorovinyloxyphenyl) -2-nitrobenzenesulfonamide, 4.8 g (34 mol) of methyl iodide and 18 g (130 mmol) of potassium carbonate were added to 100 ml of N , N'-dimethylformamide solvent was allowed to react at room temperature for 1 hour. After completion of the reaction, 9.7 g (yield 95%) of N- (4′-trifluorovinyloxyphenyl) -N-methyl-2-nitrobenzenesulfonamide was obtained by an ordinary post-treatment method.
(3) N- (4'-trifluorovinyloxyphenyl) -N-methyl-2-nitrobenzenesulfonamide 9.7 g (25 mmol), mercaptoacetic acid 3.0 g (50 mmol) and lithium hydroxide monohydrate 4.2 g (100 mmol) was reacted in 100 ml N, N′-dimethylformamide solvent at 60 ° C. for 2 hours. After completion of the reaction, 4.1 g (yield 80%) of 4-trifluorovinyloxy-N-methylaniline having a boiling point of 59 to 62 ° C. (133 Pa) was obtained by a usual post-treatment method.
¹ H-NMR (CDCl ₃ , 300 MHz) δ: 2.8 ppm (singlet, 3H, N—CH ₃ )
3.7ppm (brs, 1H, NH)
6.6ppm (doublet, 2H, Ar)
7.0ppm (doublet, 2H, Ar)
¹⁹ F-NMR (CDCl ₃ , 300 MHz) δ: -122 ppm (dd, 1F, trans -CF = C F ₂ )
-129ppm (dd, 1F, cis -CF = C F ₂ )
-134ppm (dd, 1F, -C F = CF ₂ )
Infrared absorption spectrum (neat) γ: 3430cm ^-1
3090cm ^-1
2900cm ^-1
1840cm ^-1
1600cm ^-1

Example 2
(1) To a solution consisting of 41.6 g (144 mmol) of 4- (2-bromotetrafluoroethoxy) aniline, 16.3 g (207 mmol) of pyridine and 250 ml of chloroform, 38.1 g (172 mmol) of 2-nitrobenzenesulfonyl chloride was added, The reaction was performed at room temperature for 1 hour. The usual post-reaction treatment gave 66.9 g (98% yield) of N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide as an orange solid.
(2) 26 g of methyl iodide in a solution consisting of 66.9 g (141 mmol) of N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide, 97 g (705 mmol) of potassium carbonate and 400 ml of dimethylformamide (183 mmol) was added and the reaction was allowed to proceed for 2 hours at room temperature. After usual reaction post-treatment, 68.4 g (99% yield) of N-methyl-N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide was obtained as a yellow solid.
(3) N-methyl-N- [4- (2-bromotetrafluoroethoxy) phenyl] -2-nitrobenzenesulfonamide 55.5 g (114 mmol), lithium hydroxide monohydrate 19.1 g (456 mmol) and To a solution consisting of 400 ml of dimethylformamide was added 21.0 g (228 mmol) of mercaptoacetic acid and reacted at 60 ° C. for 2 hours. After carrying out the usual post-reaction treatment, the reaction product was distilled to give 4- (2-bromotetrafluoroethoxy) -N-methylaniline (boiling point 60-67 ° C., 13 Pa) as a pale yellow liquid, 28.5 g (Yield 83%).
(4) A mixture of 9.6 g (32 mmol) of 4- (2-bromotetrafluoroethoxy) -N-methylaniline, 2.5 g of Zn (38 mmol) and 150 ml of 1,2-dimethoxyethane was stirred overnight under a nitrogen atmosphere. Heated to reflux. After cooling, the reaction mixture was filtered, 300 ml of saturated aqueous sodium hydrogen carbonate solution was added to the filtrate, and this was extracted with diethyl ether, followed by normal workup. By performing distillation under reduced pressure, 5.9 g (yield 91%) of 4- (trifluorovinyloxy) -N-methylaniline (boiling point 59 to 62 ° C., 133 Pa) was obtained as a colorless liquid.

を、含フッ素系溶媒(住友3M製品HFE-7100)90mlに溶解し、そこにトリエチルアミン1.9g(19ミリモル)およびジエチルエーテル36mlを加えた。これに、実施例１で得られた4-トリフルオロビニロキシ-N-メチルアニリン2.4g(12ミリモル)を加え、30℃で3時間反応を行った。得られた反応混合物を飽和食塩水に加え、分離した有機層を1.5重量％水酸化カリウム水溶液で洗浄した後、無水硫酸マグネシウムで乾燥、ロ過した。減圧下でロ液から含フッ素系溶媒およびジエチルエーテルを留去した後、得られた粘稠な液体をジエチルエーテルで数回洗浄し、次いで減圧下でジエチルエーテルを完全に留去した。このようにして、含フッ素ポリエーテル化合物

を、僅かに黄色味を帯びた透明な液体として60g得た。E型粘度計(東機産業製TEV-22)により粘度を測定したところ、13Pa・s(25℃)であった。
¹⁹F-NMR(ケミカルシフトはCFCl₃基準)： -125ppm(F^b)
-147ppm(F^c)
-124ppm(F^d)
-131ppm(F^e)
-139ppm(F^f)
¹H-NMR(ケミカルシフトはTMS基準)： 7.0ppm(H^a)
6.9ppm(H^b)
3.1ppm(H^c)
IR(neat)： 1834cm^-1(C=C)
1703cm^-1(C=O)
1509cm^-1(Ar) Reference example 2
Fluorine-containing dicarboxylic acid fluoride (l + m = 120) 78 g (about 4.5 mmol)

Was dissolved in 90 ml of a fluorine-containing solvent (Sumitomo 3M product HFE-7100), and 1.9 g (19 mmol) of triethylamine and 36 ml of diethyl ether were added thereto. To this, 2.4 g (12 mmol) of 4-trifluorovinyloxy-N-methylaniline obtained in Example 1 was added and reacted at 30 ° C. for 3 hours. The obtained reaction mixture was added to saturated brine, and the separated organic layer was washed with 1.5 wt% aqueous potassium hydroxide solution, dried over anhydrous magnesium sulfate and filtered. After distilling off the fluorine-containing solvent and diethyl ether from the filtrate under reduced pressure, the resulting viscous liquid was washed several times with diethyl ether, and then diethyl ether was completely distilled off under reduced pressure. Thus, a fluorine-containing polyether compound

Was obtained as a slightly yellowish transparent liquid. When the viscosity was measured with an E-type viscometer (TEV-22 manufactured by Toki Sangyo), it was 13 Pa · s (25 ° C.).
¹⁹ F-NMR (chemical shift based on CFCl ₃ ): -125 ppm (F ^b )
-147ppm (F ^c )
-124ppm (F ^d )
-131ppm (F ^e )
-139ppm (F ^f )
¹ H-NMR (chemical shift is based on TMS): 7.0 ppm (H ^a )
6.9ppm (H ^b )
3.1ppm (H ^c)
IR (neat): 1834cm ^-1 (C = C)
1703cm ^-1 (C = O)
1509cm ^-1 (Ar)

Claims (4)

General formula [I]

(Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms), a trifluorovinyloxy-N-monoalkylaniline compound represented by: The trifluorovinyloxy-N-monoalkylaniline compound according to claim ¹ , wherein R ¹ in the general formula [I] is a methyl group. The method for producing a trifluorovinyloxy-N-monoalkylaniline compound according to claim 1, wherein the trifluorovinyloxyaniline is N-monoalkylated using alkyl iodide or dialkyl sulfuric acid . 2. The trifluorovinyloxy-N according to claim 1, wherein (2-bromotetrafluoroethoxy) aniline is N-monoalkylated using alkyl iodide or dialkyl sulfuric acid and then deFBrylated. -Method for producing monoalkylaniline compound.