JPS6340796B2 - - Google Patents

Description

[Detailed description of the invention]

1. Industrial Application Field The present invention relates to a fluorine-containing allylsilane compound and a method for producing the same. 2. Prior Art In recent years, fluorine-containing compounds have attracted much attention in various fields such as medicines, agricultural chemicals, and various surface treatment agents. However, one major problem is that
The question is how to selectively introduce fluorine into the desired position within the molecule, and so far there have been no methods for selectively introducing fluorine with ease and high yield. Almost no fluorine-containing organic compounds obtained by this method are known. 3. Purpose of the invention The purpose of the present invention is to solve the above problems and _to
An object of the present invention is to provide a fluorine-containing allylsilane compound having a fluorine-containing group such as fluorine-containing group at a desired position and making it possible to incorporate the fluorine-containing group into the molecule of another compound, and a method for producing the same. . 4. Structure of the invention That is, the present invention has the following general formula: (However, R _f is a fluorine-containing alkyl group with 10 or less carbon atoms or a fluorine-containing alkenyl group with 10 or less carbon atoms, and R ₁ is an alkyl group with 10 or less carbon atoms, an alkenyl group with 10 or less carbon atoms. , represents an aryl group or an aralkyl group.These groups may further have a substituent introduced therein. This fluorine-containing allylsilane compound is a herbicide,
It is useful as physiologically active substances such as insecticides, or as intermediates in their building blocks. Further, the present invention provides a method for easily obtaining the fluorine-containing allylsilane compound with high yield, using the general formula: (R ¹ ) ₃ SiCH ₂ MX (where R ¹ is the number of unsubstituted or substituted carbon atoms). Alkyl group of 10 or less, alkenyl group of 10 or less carbon atoms, aryl group or aralkyl group, M
is an element of group a of the periodic table such as an alkaline earth metal atom, an element of group b of the periodic table, or an element of group b of the periodic table,
X represents a halogen atom. ) and a silane metal halide represented by the general formula: R _f COOR ² (however, R _f is a fluorine-containing alkyl group having 10 or less carbon atoms or a fluorine-containing alkenyl group having 10 or less carbon atoms, R ² represents an alkyl group having 10 or less carbon atoms or an alkenyl group having 10 or less carbon atoms. Substituents may be introduced into these groups. , general formula: (However, R ¹ and R _f are the same as above.) A fluorine-containing carbinol represented by is obtained, and one molecule of (R ¹ ) ₃ SiOH is obtained from this fluorine-containing carbinol.
(However, R ¹ is the same as above.) is eliminated, and the general formula: (However, R ¹ and R _f are the same as those described above.) This invention relates to a method for producing a fluorine-containing allylsilane compound, which is characterized by obtaining a fluorine-containing allylsilane compound represented by the following formula. In the fluorine-containing allylsilane compound according to the present invention represented by the above general formula, applicable
R _f (The fluorine-containing aliphatic group has the general formula: CF ₃ (CF ₂ ) _o − or (CF ₃ ) ₂ CF (CF ₂ ) _o −
Examples include fluorine-containing aliphatic groups represented by: This includes CF ₃ −, CF ₃ CF ₂ −, CF ₃ (CF ₂ ) ₂ −, CF ₃
(CF ₂ ) ₃ −, CF ₃ (CF ₂ ) ₄ −, CF ₃ (CF ₂ ) ₅ −,
(CF ₃ ) ₂ CF−, (CF ₃ ) ₂ CFCF ₂ −, (CF ₃ ) ₂ CF
(CF ₂ ) ₂ −, (CF ₃ ) ₂ CF(CF ₂ ) ₃ −, etc. In addition to these alkyl groups, unsaturated groups, especially alkenyl groups, such as _CF2 =CF- _CF2- , _CF3 -CF=CF-
etc. are also applicable. However, the number of carbon atoms of the fluorine-containing aliphatic group to be applied is 10 or less in consideration of solubility in a solvent. Further, the above-mentioned fluorine-containing aliphatic group is not limited to the perfluoroalkyl group or alkenyl group listed above, but also includes a hydrogen atom bonded to a part of the molecular chain, such as CF ₃ (CF ₂ ) ₂ CH ₂ CF ₂ − is also applicable. Furthermore, in addition to the above R _f , aromatic group-substituted iodides, such as C ₆ H ₅ −CF ₂ −, C ₆ H ₅ −
(CF ₂ ) ₂ − etc. may also be used. In addition, the above R ¹ includes a methyl group, an ethyl group,
An alkyl group such as a propyl group, isopropyl group, butyl group, or isobutyl group, or an alkenyl group partially having an unsaturated bond can be used, but the number of carbon atoms should be 10 or less. In addition to these, an aryl group or an aralkyl group (the substituent in this case may be the above-mentioned alkyl group) can also be applied as R ¹ . On the other hand, as the metal halide of silane used in the above manufacturing method for obtaining the fluorine-containing allylsilane compound ((R ² ) ₃ SiCH ₂ MX) according to the present invention,
R ¹ is the same as above, and M is a periodic table a of alkaline earth metal atoms such as magnesium.
Group B elements of the periodic table such as cerium, yttrium, and ytterbium, and group B elements of the periodic table such as manganese are applicable. Further, examples of the halogen X include chlorine atom and bromine atom. The above fluorine-containing carboxylic acid ester (R _f
COOR ² ), R _f can be the same various fluorine-containing aliphatic groups as mentioned above, and R ²
The same aliphatic or aromatic hydrocarbon groups as R ¹ described above can be used as R 1 . In addition, when removing the above-mentioned (R ¹ ) ₃ SiOH, an acid or alkali is added to the fluorine-containing carbinol. All you have to do is make it work. Usable acids include sulfuric acid, phosphoric acid, and trifluoroacetic acid, and usable alkali is KH. Next, the present invention will be explained based on a specific example of the following formula applied to the introduction of CF ₃ group into the allylsilane skeleton. First, ethyl trifluoroacetate, which is available at a low price as a CF ₃ source, is reacted with Grignard reagent 1 obtained from chloromethyltrimethylsilane and magnesium to form carbinol 2, and then Peterson elimination is carried out. By carrying out this process, β-trifluoromethylallylsilane 3 can be obtained in a good yield (for example, 60%). This reaction can be expressed by the following formula (however, the (CH ₃ ) ₃ Si- group is abbreviated as TMS). However, in this reaction, when removing TMSOH, it is necessary to use the
It is desirable to act with concentrated H ₂ SO ₄ under Hg).
If such heating and depressurization are not performed,
The TMS group that should remain in product 3 may also be eliminated. Fluorine-containing allylsilane 3 obtained by the above reaction
has a boiling point of 106.5 to 107.0°C, is very stable at room temperature and pressure, and can withstand long-term storage. Purification can also be easily carried out by distillation. 5 Examples Next, specific examples of the present invention will be described.
The examples below are not intended to limit the invention;
Various modifications can be made based on the technical idea. Example 1 Mg (9.72g,
0.4mol) and ether (300ml),
(CH ₃ ) ₃ SiCH ₂ MgCl was synthesized by slowly dropping (CH ₃ ) ₃ SiCH ₂ C (49.1 g, 0.4 mol). CF ₃ CO ₂ C ₂ H ₅ in this Grignard solution
(28.4g, 0.2mol) was added dropwise over 1 hour,
Stirred at room temperature for 1 hour. After the reaction, the reaction was stopped with 1NHCl solution, and the resulting oil layer was separated. After distilling off the solvent, the product (37.9
g) was obtained with a yield of 70%. The boiling point (BP) of this product was 85.0-86.0°C/14 mmHg. Moreover, the analytical data of this product was as follows. ¹⁹ F NMR (external standard CF ₃ CO ₂ H): 4.0 (CF ₃ ) ¹ H NMR (CDCl ₃ ): τ9.96 to 9.88 (Si(CH ₃ ) ₃ ), 9.99 to 8.81 (CH ₂ ×
2), 8.50 (OH) IR: 3600cm ^-1 (OH) Elemental analysis: C44.17, H8.06 Calculated value C (44.08), H (8.51) A 3-necked flask (25ml) containing concentrated sulfuric acid (5ml)
ml), set the distillation device and dropping funnel, and
(1.53 g, 5.1 mol) was slowly added dropwise, and the produced allylsilane 3 was trapped under reduced pressure. Redistill the product to yield allylsilane (6.8g)
78% achieved a BP of 55 to 97 mmHg. The analytical data for this product were as follows. ¹⁹ F NMR: −8.4 (CF ₃ ) ¹ H NMR: τ9.93 (Si(CH ₃ ) ₃ ), 9.39 (CH ₂ ) 5.07,
4.55

[Formula] IR: 1650cm ^-1 (C=C)

Claims (1)

[Claims] 1. General formula: (However, R _f is a fluorine-containing alkyl group having 10 or less carbon atoms or a fluorine-containing alkenyl group having 10 or less carbon atoms, R ¹ is an alkyl group having 10 or less carbon atoms,
Indicates an alkenyl group, aryl group, or aralkyl group having 10 or less carbon atoms. ) A fluorine-containing allylsilane compound characterized by the following: 2 General formula: (R ¹ ) ₃ SiCH ₂ MX (However, R ¹ is an alkyl group having 10 or less carbon atoms,
An alkenyl group, an aryl group or an aralkyl group having 10 or less carbon atoms, M represents an element of group a of the periodic table or an element of group b or Vb of the periodic table, and X represents a halogen atom. ) and a silane metal halide represented by the general formula: R _f COOR ² (where R _f is a fluorine-containing alkyl group having 10 or less carbon atoms or a fluorine-containing alkenyl group having 10 or less carbon atoms, R ² represents an alkyl group having up to 10 carbon atoms or an alkenyl group having up to 10 carbon atoms.) is reacted with a fluorine-containing carboxylic acid ester represented by the general formula: (However, R ¹ and R _f are the same as above.) A fluorine-containing carbinol represented by is obtained, and one molecule of (R ¹ ) ₃ SiOH is obtained from this fluorine-containing carbinol.
(However, R ¹ is the same as above.) is eliminated, and the general formula: (However, R ¹ and R _f are the same as those described above.) A method for producing a fluorine-containing allylsilane compound, which comprises obtaining a fluorine-containing allylsilane compound represented by the following. 3. The method according to claim 2, wherein (R ¹ ) ₃ SiOH is removed by causing acid or alkali to act on fluorine-containing carbinol.