WO2011062033A1 - 芳香族ジフルオロ酢酸エステルの製造方法 - Google Patents
芳香族ジフルオロ酢酸エステルの製造方法 Download PDFInfo
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- WO2011062033A1 WO2011062033A1 PCT/JP2010/068920 JP2010068920W WO2011062033A1 WO 2011062033 A1 WO2011062033 A1 WO 2011062033A1 JP 2010068920 W JP2010068920 W JP 2010068920W WO 2011062033 A1 WO2011062033 A1 WO 2011062033A1
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- 0 C[*+](C)C(C(*)=O)(F)F Chemical compound C[*+](C)C(C(*)=O)(F)F 0.000 description 6
- SNHMUERNLJLMHN-UHFFFAOYSA-N Ic1ccccc1 Chemical compound Ic1ccccc1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- XOKDXPVXJWTSRM-UHFFFAOYSA-N N#Cc(cc1)ccc1I Chemical compound N#Cc(cc1)ccc1I XOKDXPVXJWTSRM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
- C07B37/04—Substitution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
Definitions
- the present invention relates to a method for producing an aromatic compound having a difluoroacetate group.
- the present invention has been made in consideration of the above situation, and the following production method and the like, that is, iodobenzene having an electron withdrawing group (polar functional group) and ⁇ -silyldifluoroacetic acid ester are converted into metal halides.
- each R 1 independently represents an electron withdrawing group
- each R 2 independently represents a monovalent organic group.
- m represents an integer of 1 to 3
- n represents an integer of 0 to (5-m).
- R 3 represents a monovalent organic group
- R 4 is independently selected from the group consisting of a methyl group, an ethyl group, a propyl group, an isopropyl group, and a phenyl group, each of which may be substituted. It represents at least one selected.
- each R 1 independently represents an electron withdrawing group
- each R 2 independently represents a monovalent organic group
- R 3 represents a monovalent organic group.
- m represents an integer of 1 to 3
- n represents an integer of 0 to (5-m).
- examples of the metal halide include potassium fluoride and copper iodide.
- examples of R 1 include a bonding group at the ortho position and / or the meta position, and specifically, a cyano group, a nitro group, or a substituted group.
- examples thereof include at least one selected from the group consisting of a good alkyl acetate group, an optionally substituted alkylcarbonyl group, a halogen group, and an optionally substituted phenyl group.
- R 2 examples include at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, and an alkynyl group.
- examples of R 3 include at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, and an alkynyl group.
- examples of the compound represented by the general formula (2) include the following general formula (5): [In General Formula (5), R 3 represents a monovalent organic group, and X represents a halogen group (for example, a chlorine atom). ] And the following general formula (6): [In General Formula (6), each R 4 independently represents at least one selected from the group consisting of an optionally substituted methyl group, ethyl group, propyl group, isopropyl group and phenyl group; Represents a halogen group (for example, a chlorine atom). ]
- the compound obtained by making it react with the compound represented by these is mentioned.
- examples of the reaction include a reaction performed in the presence of magnesium.
- the present invention it is possible to provide a method for producing a compound having a difluoromethylene group at a lower cost and in a higher yield.
- the method of the present invention can produce, for example, aromatic difluoroacetic acid ester and aromatic difluoroacetic acid at low cost and high yield.
- the method for producing an aromatic difluoroacetic acid ester according to the present invention (hereinafter sometimes referred to as the production method of the present invention) is represented by the compound represented by the general formula (1) and the general formula (2).
- This is a method for producing a compound represented by the general formula (3) (that is, an aromatic difluoroacetic acid ester) by reacting with a compound obtained in the presence of a metal halide.
- each R 1 independently represents an electron withdrawing group.
- the electron withdrawing group is not limited, but preferred examples include —CN, —NO 2 , —C (O) OC 2 H 5 , COCH 3 , —Br and —Ph (phenyl group). , —CN group and —C (O) OC 2 H 5 are more preferred.
- R 1 is not limited, but is preferably a group bonded to a carbon atom at the ortho position and / or the meta position of the iodobenzene ring.
- the number (m) of R 1 bonded to the iodobenzene ring is an integer of 1 to 3, preferably 1.
- -CN, -NO 2 , -C (O) OC 2 H 5 , -COCH 3 , -Br or -Ph bonded to the para position of the iodobenzene ring, and the ortho position of the iodobenzene ring
- a preferred embodiment is one in which —NO 2 is bound to
- R 2 each independently represents a monovalent organic group. Although it does not limit as monovalent organic group, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group etc. are mentioned preferably, Among these, an alkyl group is more preferable.
- the alkyl group as R 2 is not limited, but is preferably a straight chain or branched alkyl group having 1 to 16 carbon atoms, and the alkyl group may be formed on any carbon atom thereof, for example, a halogen atom, an alkoxy group.
- a group, a haloalkoxy group, an alkylamino group, an alkylthio group, a cyano group, an aminocarbonyl group (CONH 2 ), and an aryl group may be substituted with any number and in any combination.
- the number (n) of R 2 bonded to the iodobenzene ring is an integer of 0 to (5-m), preferably an integer of 0 to 2.
- R 2 is not limited, but is preferably bonded to the meta position.
- R 3 represents a monovalent organic group. Although it does not limit as monovalent organic group, for example, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group etc. are mentioned preferably, Among these, an alkyl group is more preferable and an ethyl group is especially preferable.
- the alkyl group as R 3 is not limited, but is preferably a straight chain or branched alkyl group having 1 to 16 carbon atoms, and the alkyl group may be formed on any carbon atom thereof, for example, a halogen atom, an alkoxy group.
- a group, a haloalkoxy group, an alkylamino group, an alkylthio group, a cyano group, an aminocarbonyl group (CONH 2 ), and an aryl group may be substituted with any number and in any combination.
- each R 4 is preferably independently an optionally substituted methyl group, ethyl group, propyl group, isopropyl group, phenyl group or the like, and more preferably a methyl group or an ethyl group.
- a methyl group is preferable, and a methyl group is particularly preferable. Note that the mode of substitution is not limited, and may be substitution by any number and any combination.
- the compound represented by the general formula (2) can be obtained, for example, by a reaction between the compound represented by the general formula (5) and the compound represented by the general formula (6).
- R 3 represents a monovalent organic group, and specifically, the contents described for the general formula (2) can be similarly applied.
- X represents a halogen group, for example, Cl, Br, I etc. are preferable, More preferably, it is Cl (chlorine atom).
- the reaction between the compound represented by the general formula (5) and the compound represented by the general formula (6) is carried out in an inert gas atmosphere such as nitrogen and argon in an inert solvent under the reaction conditions. What is necessary is just to mix, and it is not limited.
- Preferred examples of the solvent include those described below as solvents that can be used in the production method of the present invention.
- the reaction temperature is preferably 20 to 50 ° C.
- the mixing time (stirring time) is preferably 1 to 2 hours
- the reaction pressure may be around normal pressure.
- the reaction is not limited, but is preferably performed in the presence of magnesium from the viewpoint that the reaction can be promoted.
- a method such as extraction and purification of the product compound (compound represented by the general formula (2)) from the reaction system is not particularly limited, and conventionally known methods such as extraction and purification can be appropriately employed.
- the metal halide used for the reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2) is not limited, but for example, potassium fluoride.
- Preferred examples include (KF) and copper iodide (CuI).
- potassium fluoride is more preferable because the yield of the reaction product can be further increased.
- the amount of metal halide used is not limited, but for example, it is preferably used in an amount of 0.2 to 4 equivalents in terms of moles relative to the compound represented by the general formula (1) that is a raw material compound.
- the amount is preferably 0.2 to 1.2 equivalents.
- the amount is preferably 1 to 1.2 equivalents
- copper iodide is used, the amount is preferably 0.2 to 1 equivalents.
- the solvent that can be used in the production method of the present invention is not limited as long as it is inert under the reaction conditions of the reaction of the compounds of the general formulas (1) and (2).
- Solvent eg, pentane, hexane, heptane, etc.
- aromatic hydrocarbons eg, benzene, toluene, xylene, etc.
- nitriles eg, acetonitrile, propionitrile, phenylacetonitrile, isobutyronitrile, benzonitrile, etc.
- Acid amides for example, dimethylformamide, dimethylacetamide, methylformamide, formamide, hexamethylphosphoric triamide, N-methylpyrrolidone, etc.
- lower ethers for example, tetrahydrofuran, 1,2-dimethoxyethane, 1,4 -Dioxane, diethyl ether, 1,2-epoxy ester Emissions, 1,
- these solvents can be used in combination.
- the amount of the solvent is about 1 to 100 parts by weight, preferably 1 to 10 parts by weight with respect to 1 part by weight of the starting material.
- the solvent to be used is preferably one from which water has been removed as much as possible, but it is not necessarily required to have been completely removed.
- the amount of water that is usually mixed in industrially available solvents is not particularly problematic in the practice of the production method of the present invention, and can therefore be used as it is without removing the water.
- the raw material compounds represented by the above general formulas (1) and (2) may be mixed in a solvent in the presence of the metal halide.
- the amount of the raw material compound used it is preferable to use 1 to 2 equivalents, more preferably, of the compound represented by the general formula (2) in terms of moles relative to the compound represented by the general formula (1). 1.2 to 1.5 equivalents.
- the mixing and reaction of the raw material compounds are preferably performed in an inert gas atmosphere such as nitrogen and argon, the reaction temperature is preferably 40 to 80 ° C., and the mixing time (stirring time) is The reaction pressure is preferably 5 to 20 hours, and the reaction pressure may be around normal pressure.
- various reaction promotion methods generally performed in the Grignard reaction can be applied as necessary for the purpose of promoting the reaction.
- halogens such as bromine or iodine, Grignard reagents, organic halides such as ethyl bromide, methyl iodide, methylene iodide, ethyl iodide and ⁇ -bromoethyl ether, or ethyl orthosilicate. And the like, and a method of stirring or irradiating ultrasonic waves.
- the compound (product compound) obtained by the production method of the present invention that is, the aromatic difluoroacetate is a compound represented by the general formula (3) as described above.
- the contents described for the general formulas (1) and (2) can be similarly applied to R 1 , R 2 and R 3 , and m and n.
- methods such as extraction and purification of the product compound from the reaction system are not particularly limited, and conventionally known methods such as extraction and purification can be appropriately employed.
- the present invention further provides a method for producing a compound represented by the general formula (4) (ie, aromatic difluoroacetic acid) by hydrolyzing the compound represented by the general formula (3). it can.
- a compound represented by the general formula (4) ie, aromatic difluoroacetic acid
- the hydrolysis reaction of the compound represented by the general formula (3) can be carried out by appropriately adopting known hydrolysis reaction methods and conditions, and is not limited, but, for example, inert such as nitrogen and argon
- the reaction is preferably carried out in a gas atmosphere, the reaction temperature is preferably 20 to 100 ° C., the reaction time (stirring time) is preferably 1 to 40 hours, and the reaction pressure may be around normal pressure.
- a method such as extraction and purification of the product compound (compound represented by the general formula (4)) from the reaction system is not particularly limited, and conventionally known methods such as extraction and purification can be appropriately employed.
- the compound represented by the general formula (4) (that is, aromatic difluoroacetic acid) is not limited, but for example, by decarboxylating a difluoroacetic acid group (—CF 2 CO 2 H) in the compound, It can be derived into a compound having a difluoromethyl group (—CF 2 H) (aromatic difluoromethyl compound).
- this decarboxylation reaction is not limited, for example, it may be carried out in an inert gas atmosphere such as nitrogen and argon in an inert solvent under the reaction conditions, and is not limited.
- an inert gas atmosphere such as nitrogen and argon in an inert solvent under the reaction conditions, and is not limited.
- As said solvent what was mentioned above as a solvent which can be used for the manufacturing method of this invention can be illustrated preferably.
- the reaction temperature is preferably 120 to 230 ° C.
- the reaction time is preferably 5 to 48 hours
- the reaction pressure may be around normal pressure.
- the decarboxylation reaction is preferably performed in the presence of a metal halide, particularly potassium fluoride, because the reaction efficiency and yield can be further increased.
- the amount of potassium fluoride used is not limited, but it is preferably used in an amount of 1 to 10 equivalents, more preferably 5 etc. in terms of moles relative to the compound represented by the general formula (4) before decarboxylation. Amount.
- the method for extracting and purifying the product compound (aromatic difluoromethyl compound) from the reaction system is not particularly limited, and conventionally known methods such as extraction and purification can be appropriately employed.
- difluorotrimethylsilanyl acetic acid ethyl ester (Me 3 Si—CF 2 CO 2 Et; compound 3a) used in this example was used.
- magnesium (486 mg, 20.0 mmol), chlorotriethylsilane (Et 3 SiCl; 6.03 g, 40.0 mmol), and DMF (30 mL) are placed in a two-necked reaction tube under a nitrogen atmosphere. While the reaction vessel was cooled in a water bath, ethyl chlorodifluoroacetate (Compound 3; 1.57 g, 10.0 mmol) was added, followed by stirring at room temperature for 1.5 hours. The reaction mixture was extracted with diethyl ether, washed with water, and the organic layer was dried over anhydrous sodium sulfate.
- difluorotriethylsilanyl acetic acid ethyl ester (Et 3 Si—CF 2 CO 2 Et; compound 3b) was also obtained in this example.
- 2,2-difluoro-2- (4-nitrophenyl) acetic acid ethyl ester (compound 2b; 147 mg, 0.6 mmol) and 1N NaOH aqueous solution (3 mL) were placed in an eggplant flask and stirred at room temperature for 19 hours. did. After the reaction, the reaction mixture was neutralized with 5% aqueous HCl aqueous solution, extracted with ethyl acetate, washed with water, and the organic layer was dried over anhydrous sodium sulfate.
- 2- (4-acetylphenyl) -2,2-difluoroacetic acid ethyl ester (compound 2e; 436.0 mg, 1.8 mmol) and 1N NaOH aqueous solution (3.0 mL) were added to an eggplant flask and the mixture was stirred at 100 ° C. for 1.5 hours. Stir. After the reaction, the reaction mixture was neutralized with 5% aqueous HCl aqueous solution, extracted with ethyl acetate, washed with water, and the organic layer was dried over anhydrous sodium sulfate.
- the present invention it is possible to provide a method for producing a compound having a difluoromethylene group at a lower cost and in a higher yield.
- the method of the present invention is very useful in that, for example, aromatic difluoroacetic acid esters and aromatic difluoroacetic acid can be produced at low cost and in high yield.
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Abstract
Description
で表される化合物と下記一般式(2):
〔一般式(2)中、R3は一価の有機基を表し、R4はそれぞれ独立して置換されていてもよいメチル基、エチル基、プロピル基、イソプロピル基及びフェニル基からなる群より選ばれる少なくとも1種を表す。〕
で表される化合物とを金属ハロゲン化物の存在下で反応させることによる、下記一般式(3):
で表される化合物の製造方法。
で表される化合物の製造方法。
さらに、R3としては、例えば、アルキル基、シクロアルキル基、アリール基、アルケニル基、及びアルキニル基からなる群より選ばれる少なくとも1種が挙げられる。
本発明の製造方法においては、必要に応じ、反応を促進する目的で、グリニャール反応で一般的に行われている各種の反応促進法を適用することもできる。そのような方法として、例えば、臭素またはヨウ素などのハロゲン、グリニャール試薬、臭化エチル、ヨウ化メチル、ヨウ化メチレン、ヨウ化エチル及びβ-ブロムエチルエーテル等の有機ハロゲン化物、あるいはオルト珪酸エチル等を反応系に添加する方法や、攪拌又は超音波を照射する方法等を挙げることができる。
本発明の製造方法において、反応系からの生成化合物の抽出及び精製等の方法は、特に限定はされず、従来公知の抽出及び精製等の方法が適宜採用できる。
1H-NMR(CDCl3, TMS) δ4.32 (2H, q, J = 7.0 Hz), 1.35 (3H, t, J = 7.0 Hz), 0.237 (9H, s)
19F-NMR(CDCl3, C6F6) δ 38.5 (2F, s)
Mass m/e: (m/z) (%) 181 (6), 153 (10), 125 (6), 103 (8), 77 (26), 73 (100)
1H-NMR(CDCl3, TMS) δ 4.31 (2H, q, J = 7.1 Hz), 1.35 (3H, t, J = 7.1 Hz), 1.02 (9H, t, J= 8.0 Hz), 0.77 (6H, q, J = 8.0 Hz)
19F-NMR(CDCl3, C6F6) δ 42.9 (2F, s)
Mass m/e: (m/z) (%) 209 (20), 131 (12), 115 (38), 87 (100)
1H-NMR(CDCl3, TMS) δ7.78 (2H, d, J = 8.8 Hz), 7.74 (2H, d, J = 8.8 Hz), 4.34 (2H, q, J= 7.0 Hz), 1.31 (3H, t, J = 7.0 Hz)
19F-NMR(CDCl3, C6F6) δ 56.8 (2F, s)
Mass m/e: (m/z) (%) 225 (M+, 2), 181 (2), 152 (100), 126 (4), 102 (8), 75 (4)
1H-NMR(CDCl3, TMS) δ 7.80 (2H, d, J = 9.2 Hz), 7.77 (2H, d, J = 9.2 Hz),
19F-NMR(CDCl3, C6F6) δ 56.3 (2F, s)
19F-NMR(CDCl3, C6F6) δ 56.8 (2F, s)
Mass m/e: (m/z) (%) 225 (M+, 2), 181 (2), 152 (100), 126 (4), 102 (8), 75 (4)
1H-NMR(CDCl3, TMS) δ 8.33 (2H, d, J = 9.0 Hz), 7.82 (2H, d, J = 9.0 Hz), 4.33 (2H, q, J= 7.0Hz), 1.32 (1H, t, J = 7.0 Hz)
19F-NMR(CDCl3, C6F6) δ 57.2 (2F, s)
Mass m/e: (m/z) (%) 172 (100), 156 (16), 142 (16), 126 (42), 107 (5), 75 (4)
1H-NMR(CDCl3, TMS) δ 8.34 (2H, d, J = 8.8 Hz), 7.85 (2H, d, J = 8.8 Hz)
19F-NMR(CDCl3, C6F6) δ 56.7 (2F, s)
1H-NMR(CDCl3, TMS) δ 8.20 (1H, d, J = 8.0 Hz), 7.98 (1H, d, J = 8.0 Hz), 7.83 (1H, t, J= 8.0Hz), 7.75 (1H, t, J = 8.0 Hz)
19F-NMR(CDCl3, C6F6) δ 61.3 (2F, s)
1H-NMR(CDCl3, TMS) δ 8.13 (2H, d, J = 8.2 Hz), 7.68 (2H, d, J = 8.2 Hz), 4.41 (2H, q, J= 7.2 Hz), 4.30 (2H, q, J = 7.2 Hz), 1.41 (3H, J = 7.2 Hz), 1.30 (3H, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 57.2 (2F, s)
Mass m/e: (m/z) (%) 272 (M+, 2), 227 (15), 199 (100), 171 (34), 126 (14)
1H-NMR(CDCl3, TMS) δ 8.13 (2H, d, J = 8.0 Hz), 7.71 (2H, d, J = 8.0 Hz), 4.41 (2H, q, J= 7.2Hz), 1.40 (3H, t, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 56.6 (2F, s)
1H-NMR(CDCl3, TMS) δ 8.05 (2H, d, J = 8.4 Hz), 7.75 (2H, d, J = 8.4 Hz), 2.65 (3H, s)
19F-NMR(CDCl3, C6F6) δ 56.6 (2F, s)
1H-NMR(CDCl3, TMS) δ 7.60 (2H, d, J = 8.6 Hz), 7.48 (2H, d, J = 8.6 Hz), 4.30 (2H, q, J= 7.2 Hz), 1.31 (3H, t, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 57.6 (2F, s)
Mass m/e: (m/z) (%) 280 (M+2, 12), 278 (M+, 12), 207 (94), 205 (100), 126 (32), 75 (8)
1H-NMR(CDCl3, TMS) δ 7.61 (2H, d, J = 8.8 Hz), 7.50 (2H, d, J = 8.8 Hz)
19F-NMR(CDCl3, C6F6) δ 56.7 (2F, s)
1H-NMR(CDCl3, TMS) δ 7.38-7.70 (9H, m), 4.35 (2H, q, J = 7.2 Hz), 1.33 (3H, t, J = 7.2Hz)
19F-NMR(CDCl3, C6F6) δ 58.3 (2F, s)
Mass m/e: (m/z) (%) 276 (M+, 21), 203 (100), 183 (6), 152 (6)
1H-NMR(CDCl3, TMS) δ7.37-7.714 (9H, m)
19F-NMR(CDCl3, C6F6) δ 56.9 (2F, s)
1H-NMR(CDCl3, TMS) δ 7.61 (2H, d, J = 9.2 Hz) 7.44-7.52 (3H, m), 4.30 (2H, q, J = 7.2Hz), 1.31 (3H, t, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 57.8 (2F, s)
Mass m/e: (m/z) (%) 200 (M+, 8), 127 (100), 77 (6)
1H-NMR(CDCl3, TMS) δ 7.52 (2H, d, J = 8.8 Hz), 6.93 (2H, d, J = 8.8 Hz),4.29 (2H, q, J= 7.2 Hz), 4.06 (2H, q, J = 7.0 Hz), 1.43 (3H, t, J = 7.0 Hz), 1.30 (3H, t, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 59.2 (2F, s)
Mass m/e: (m/z) (%) 244 (M+, 12), 171 (98), 143 (100), 126 (4)
1H-NMR(CDCl3, TMS) δ7.78 (2H, d, J = 8.8 Hz), 7.74 (2H, d, J = 8.8 Hz), 4.34 (2H, q, J= 7.0 Hz), 1.31 (3H, t, J = 7.0 Hz)
19F-NMR(CDCl3, C6F6) δ 56.8 (2F, s)
Mass m/e: (m/z) (%) 225 (M+, 2), 181 (2), 152 (100), 126 (4), 102 (8), 75 (4)
1H-NMR(CDCl3, TMS) δ 8.33 (2H, d, J = 9.0 Hz), 7.82 (2H, d, J = 9.0 Hz), 4.33 (2H, q, J= 7.0Hz), 1.32 (1H, t, J = 7.0 Hz)
19F-NMR(CDCl3, C6F6) δ 57.2 (2F, s)
Mass m/e: (m/z) (%) 172 (100), 156 (16), 142 (16), 126 (42), 107 (5), 75 (4)
1H-NMR(CDCl3, TMS) δ 8.15 (1H, d, J = 7.8 Hz), 7.96 (1H, d, J = 7.8 Hz), 7.80 (1H, t, J= 7.8Hz), 7.72 (1H, t, J = 7.8 Hz), 4.39 (2H, q, J = 7.2 Hz), 1.35 (3H, t, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 61.8 (2F, s)
Mass m/e: (m/z) (%) 200 (4), 199 (5), 172 (100), 156 (68), 143 (96), 126 (62), 95 (79)
1H-NMR(CDCl3, TMS) δ 8.13 (2H, d, J = 8.2 Hz), 7.68 (2H, d, J = 8.2 Hz), 4.41 (2H, q, J= 7.2 Hz), 4.30 (2H, q, J = 7.2 Hz), 1.41 (3H, J = 7.2 Hz), 1.30 (3H, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 57.2 (2F, s)
Mass m/e: (m/z) (%) 272 (M+, 2), 227 (15), 199 (100), 171 (34), 126 (14)
1H-NMR(CDCl3, TMS) δ 8.04 (2H, d, J = 8.4 Hz), 7.72 (2H, d, J = 8.4 Hz), 4.31 (2H, q, J= 7.2 Hz), 2.64 (3H, s), 1.31 (3H, t, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 57.2 (2F, s)
Mass m/e: (m/z) (%) 242 (M+, 13), 227 (59), 199 (20), 169 (100), 154 (13), 126 (34)
1H-NMR(CDCl3, TMS) δ 7.60 (2H, d, J = 8.6 Hz), 7.48 (2H, d, J = 8.6 Hz), 4.30 (2H, q, J= 7.2 Hz), 1.31 (3H, t, J = 7.2 Hz)
19F-NMR(CDCl3, C6F6) δ 57.6 (2F, s)
Mass m/e: (m/z) (%) 280 (M+2, 12), 278 (M, 12), 207 (94), 205 (100), 126 (32), 75 (8)
1H-NMR(CDCl3, TMS) δ 7.38-7.70 (9H, m), 4.35 (2H, q, J = 7.2 Hz), 1.33 (3H, t, J = 7.2Hz)
19F-NMR(CDCl3, C6F6) δ 58.3 (2F, s)
Mass m/e: (m/z) (%) 276 (M+, 21), 203 (100), 183 (6), 152 (6)
Claims (10)
- 下記一般式(1):
で表される化合物と下記一般式(2):
で表される化合物とを金属ハロゲン化物の存在下で反応させることによる、下記一般式(3):
で表される化合物の製造方法。 - 前記金属ハロゲン化物がフッ化カリウム又はヨウ化銅である、請求項1に記載の方法。
- 前記R1が、オルト位及び/又はメタ位の結合基である、請求項1~3のいずれか1項に記載の方法。
- 前記R1が、シアノ基、ニトロ基、置換されていてもよいアルキル酢酸エステル基、置換されていてもよいアルキルカルボニル基、ハロゲン基、及び置換されていてもよいフェニル基からなる群より選ばれる少なくとも1種である、請求項1~4のいずれか1項に記載の方法。
- 前記R2が、アルキル基、シクロアルキル基、アリール基、アルケニル基、及びアルキニル基からなる群より選ばれる少なくとも1種である、請求項1~5のいずれか1項に記載の方法。
- 前記R3が、アルキル基、シクロアルキル基、アリール基、アルケニル基、及びアルキニル基からなる群より選ばれる少なくとも1種である、請求項1~6のいずれか1項に記載の方法。
- 前記Xが塩素原子である、請求項8に記載の方法。
- 前記一般式(5)で表される化合物と前記一般式(6)で表される化合物との反応が、マグネシウムの存在下で行われる、請求項8又は9に記載の方法。
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JP2002047293A (ja) * | 2000-08-01 | 2002-02-12 | Central Glass Co Ltd | 2−トリアルキルシリル2,2−ジフルオロ酢酸エステルの製造方法 |
JP2009263316A (ja) | 2008-04-30 | 2009-11-12 | Konishi Kagaku Ind Co Ltd | 不完全縮合オリゴシルセスキオキサンの製造方法 |
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JP2002047293A (ja) * | 2000-08-01 | 2002-02-12 | Central Glass Co Ltd | 2−トリアルキルシリル2,2−ジフルオロ酢酸エステルの製造方法 |
JP2009263316A (ja) | 2008-04-30 | 2009-11-12 | Konishi Kagaku Ind Co Ltd | 不完全縮合オリゴシルセスキオキサンの製造方法 |
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EP2502898A1 (en) | 2012-09-26 |
US20120220795A1 (en) | 2012-08-30 |
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