JPH0119368B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the following formula It relates to (3,3,3-trifluoropropyl)styrene represented by: The present inventors have been intensively researching the effective use of 3,3,3-trifluoropropene, and have previously filed applications for a series of 3,3,3-trifluoropropyl aromatic compounds. This time, we have discovered that a 3,3,3-trifluoropropyl group can be added to phenethyl chloride in a similar manner, and have arrived at the present invention. The present invention uses phenethyl chloride as a starting material and reacts it with 3,3,3-trifluoropropene to produce (3,3,3-trifluoropropyl)phenethyl chloride (hereinafter referred to as a compound). (3,3,3-trifluoropropyl)styrene (hereinafter referred to as the compound) is obtained by dehydrochlorinating this. Each reaction will be explained in detail below. Method for Synthesizing the Compound The compound can be synthesized using phenethyl chloride and 3,3,3-trifluoropropene as raw materials in the presence of an acid catalyst as shown in the reaction formula below. BF ₃ is preferred as the acid catalyst. The reaction may be carried out in a continuous or batch manner, and the synthesis may be carried out under relatively mild temperature conditions. As an example, a case of batch type will be explained. Phenethyl chloride, 3,3,3-trifluoropropene and BF ₃ are charged into a stainless steel autoclave and reacted at a predetermined reaction temperature for 0.5 to 30 hours. Reaction temperature is 0~150℃
is the preferred range. Further, when reacting an equivalent amount of phenethyl chloride and 3,3,3-trifluoropropylene, it is preferable to use 0.5 equivalent or more of BF ₃ per equivalent of phenethyl chloride. After the reaction is completed, residual gas is purged from the autoclave, and the contents of BF ₃ are then removed by neutralization, washing with water, etc. to obtain a liquid reaction mixture exhibiting a yellowish brown color.
This reaction mixture is subjected to precision distillation under reduced pressure to obtain (3,3,3-trifluoropropyl)phenethyl chloride. The resulting distillate is obtained as a mixture of isomers. However, p(3,3,3-trifluoropropyl)phenethyl chloride can be obtained by performing the precision distillation process more precisely. Method for synthesizing the compound The compound can be easily obtained by dehydrochlorinating the compound. The reaction formula is shown below. (3, 3,
A mixture of (3-trifluoropropyl)phenethyl chloride isomers yields a mixture of (3,3,3-trifluoropropyl)styrene isomers and also p-
p-(3,3,3-trifluoropropyl)styrene is obtained from (3,3,3-trifluoropropyl)phenethyl chloride. The dehydrochlorination reaction can be carried out, for example, by adding the compound to a methanol solution of potassium hydroxide and refluxing the mixture for 0.5 to 2 hours. After the reaction is complete, methanol is distilled off and then extracted with ether.
A reaction mixture is obtained by distilling off the ether. The compound is obtained by precision distilling this reaction mixture under reduced pressure. p-(3,3,3-trifluoropropyl)styrene can also be obtained in the same manner. Since the compound and p-(3,3,3-trifluoropropyl)styrene have polymerization ability, 3,
It is useful as a raw material for polystyrene having 3,3-trifluoropropyl groups. The present invention will be explained in more detail with reference to Examples below. However, the present invention is not limited to the following examples. Example 1 In a stainless steel autoclave with a capacity of 20, 2500 g (17.73 M) of phenethyl chloride and 3,3,
1702g (17.73M) of 3-trifluoropropene was charged. Furthermore, BF ₃ was pressurized until the internal pressure reached 33 Kg/cm ² ·G, and the mixture was reacted at a temperature of 40° C. for 17 hours with stirring. After the reaction was completed, residual gas was purged, and the contents were then poured into a 10% aqueous sodium carbonate solution. This was washed with water and dried according to a conventional method to obtain 4110 g of a yellowish brown reaction mixture. This reaction mixture was examined by gas chromatography and gas chromatography mass spectrometry, and found to have the composition shown in Table 1.

【table】

[Table] Next, this reaction mixture was fractionated under reduced pressure to obtain a boiling point of 91~
2060g of fraction at 96°C/1.5mmHg was obtained. The analysis results shown below revealed that this fraction was (3,3,3-trifluoropropyl)phenethyl chloride. a Gas chromatography
Gas chromatography peak area (%) Mono-(3,3,3-trifluoropropyl)
Phenethyl chloride Peak A 38.0 Peak B 14.7 Peak C 47.3 b Gas chromatography mass spectrometry (20 eV) Figure 1 shows the mass spectrum. Peaks A, B, and C all have m/e=236. c ¹ H-NMR (60MHz, CCl ₄ solution, TMS standard) Figure 2 shows the ¹ H-NMR spectrum. d Infrared absorption spectrum Figure 3 shows the infrared absorption spectrum. Example 2 During the distillation in Example 1, the boiling point was 96°C/1.5
103 g of mmHg fraction was obtained. This fraction corresponds to peak C in gas chromatography, and the analysis results shown below indicate that the purity is over 99%.
-(3,3,3-trifluoropropyl)phenethyl chloride. a NMR ¹ H-NMR (60 MHz, CCl ₄ solution, TMS standard) Figure 4 shows the ¹ H-NMR spectrum ¹⁹ F-NMR (56.4 MHz, CDCl ₃ solution, benzotrifluoride external standard) δ + 2.58 ppm (t , -CF ₃ , J _HF = 10.2Hz) ^13C -NMR (90MHz, CDCl ₃ solution, TMS standard) δ137.7ppm δ136.6 (C ₁ , C ₄ ) δ129.2 δ128.5 (C ₂ , C ₃ , C ₅ , C ₆ ) δ44.9 δ38.8 (Ar- C H ₂ C H ₂ -Cl) δ35.6 (q, C F ₃ ) δ27.9 δ27.8 (Ar- C H ₂ C H ₂ -CF ₃ ) b Infrared absorption spectrum The spectrum is shown in Figure 5. Example 3 2 equipped with a reflux capacitor
(3,3,
3-trifluoropropyl) phenethyl chloride 200g (0.846M), potassium hydroxide 94g
(1.692M) and 600 ml of methanol were charged and reacted for 1.5 hours under reflux conditions. After the reaction is complete,
The precipitated potassium chloride was separated, and methanol was distilled off from the liquid. Next, 300 ml of ether was added to extract the organic matter, and the ether was distilled off to obtain 153 g of a colorless and transparent reaction mixture. The reaction mixture was examined using gas chromatography and gas chromatography mass spectrometry, and the composition was as shown in Table 2.

[Table] This reaction mixture was precisely distilled under reduced pressure to obtain a boiling point of 69.
A fraction of ~72°C/4.5mmHg was obtained. This fraction was found to be (3,3,3-trifluoropropyl)styrene based on the analysis results shown below. a Gas chromatography Peak area (%) (3,3,3-trifluoropropylstyrene) Peak 59.5 Peak 14.3 Peak 26.2 b Gas chromatography mass spectrometry (20 eV) The spectrum is shown in Figure 6. Both peaks are m/e=200. ^c1H -NMR (60MHz, _CCl4 solution, TMS standard) The spectrum is shown in FIG. d Infrared absorption spectrum The spectrum is shown in Figure 8. Example 4 10 g of p-(3,3,3-trifluoropropyl)phenethyl chloride obtained in Example 2
(0.0423M), 4.7g (0.0846M) of potassium hydroxide, and 30ml of methanol were charged into a 100ml round bottom flask equipped with a reflux condenser, and reacted under reflux conditions for 1 hour. After the reaction was completed, the precipitated potassium chloride was separated, and methanol was distilled off from the liquid. Next, 50 ml of ether was added to extract the organic matter, and when the ether was distilled off, 7.4 g of a colorless and transparent reaction mixture was obtained. This reaction mixture was distilled under reduced pressure to obtain 4.6 g of a fraction with a boiling point of 52-53°C/1.2 mmHg. This fraction corresponds to a peak in gas chromatography. The analysis results shown below show that p-(3,3,3-
It turned out to be trifluoropropyl) styrene. ^a1H -NMR (60MHz, _CCl4 solution, TMS standard) The spectrum is shown in FIG. b Infrared absorption spectrum The spectrum is shown in Figure 10.

[Brief explanation of drawings]

Figures 1, 2, and 3 are monographs, respectively.
Mass spectrum of (3,3,3-trifluoropropyl)phenethyl chloride, ¹ H-NMR,
Figures 4 and 5 show the ¹ H-NMR spectrum and infrared absorption spectrum of p-(3,3,3-trifluoropropyl)phenethyl chloride, respectively, and Figure 6 shows the infrared absorption spectrum.
Figures 7 and 8 are the mass spectra of (3,3,3-trifluoropropyl)styrene, respectively;
¹ H-NMR and infrared absorption spectra are shown, and Figures 9 and 10 show p-(3,3,3-
¹ H-NMR of trifluoropropyl)styrene,
Infrared absorption spectrum is shown.

Claims (1)

[Claims] 1. The following general formula (3,3,3-trifluoropropyl)styrene represented by: 2 3,3,3-trifluoroprpylstyrene is p-(3,3,3,-trifluoroprupyl)
3,3,3-trifluoropropylstyrene according to claim 1, which is styrene.