JPH0142940B2 - - Google Patents
Info
- Publication number
- JPH0142940B2 JPH0142940B2 JP5735484A JP5735484A JPH0142940B2 JP H0142940 B2 JPH0142940 B2 JP H0142940B2 JP 5735484 A JP5735484 A JP 5735484A JP 5735484 A JP5735484 A JP 5735484A JP H0142940 B2 JPH0142940 B2 JP H0142940B2
- Authority
- JP
- Japan
- Prior art keywords
- cyano
- mol
- tetrafluorophenol
- doublet
- tetrafluorophenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000001257 hydrogen Chemical group 0.000 claims description 2
- 229910052739 hydrogen Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- JJUQENYUEZBNLS-UHFFFAOYSA-N 2,3,5,6-tetrafluoro-4-hydroxybenzonitrile Chemical compound OC1=C(F)C(F)=C(C#N)C(F)=C1F JJUQENYUEZBNLS-UHFFFAOYSA-N 0.000 description 6
- -1 4-cyano-2, 3,5,6-tetrafluorophenyl methacrylic ester Chemical compound 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 235000019341 magnesium sulphate Nutrition 0.000 description 5
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YXWJGZQOGXGSSC-UHFFFAOYSA-N 2,3,4,5,6-pentafluorobenzonitrile Chemical compound FC1=C(F)C(F)=C(C#N)C(F)=C1F YXWJGZQOGXGSSC-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006222 acrylic ester polymer Polymers 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NAHAJNUUPUGXOB-UHFFFAOYSA-N (4-cyano-2,3,5,6-tetrafluorophenyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=C(F)C(F)=C(C#N)C(F)=C1F NAHAJNUUPUGXOB-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は下記一般式（）で示される新規な４
−シアノ−２，３，５，６−テトラフルオロフエ
ニルアクリル酸エステルまたは４−シアノ−２，
３，５，６−テトラフルオロフエニルメタクリル
酸エステル〔以下、新規（メタ）アクリル酸エス
テル類とする。〕に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel 4 compound represented by the following general formula ().
-cyano-2,3,5,6-tetrafluorophenyl acrylate or 4-cyano-2,
3,5,6-tetrafluorophenyl methacrylic ester [hereinafter referred to as new (meth)acrylic esters. ]Regarding.
〔式中Ｒはメチル基（CH3）または水素(H)を表わ
す。〕
本発明の上記一般式（）で示される新規（メ
タ）アクリル酸エステル類は重合性にすぐれ、ホ
モポリマーあるいはコポリマーの原料とすること
ができ、種々の有用な含フツ素（メタ）アクリル
酸類ポリマーとなりうる。即ち、含フツ素（メ
タ）アクリル酸エステル類ポリマーは、通常のフ
ツ素が含有していない（メタ）アクリル酸エステ
ル類ポリマーと異なる特殊な機能がえられ、接着
剤、コーテイング剤あるいはレジスト等に有用で
ある。 [In the formula, R represents a methyl group (CH 3 ) or hydrogen (H). ] The novel (meth)acrylic esters of the present invention represented by the above general formula () have excellent polymerizability and can be used as raw materials for homopolymers or copolymers, and are useful in various useful fluorine-containing (meth)acrylic acids. Can be a polymer. In other words, fluorine-containing (meth)acrylic ester polymers have special functions different from ordinary fluorine-free (meth)acrylic ester polymers, and are useful for adhesives, coating agents, resists, etc. Useful.
本発明における４−シアノ−２，３，５，６−
テトラフルオロフエニル（メタ）アクリル酸エス
テル類の製造法は、今まで全く報告されていな
い。一方、フツ素を含有していないフエノール類
と不飽和有機酸クロライドからフエニル有機酸エ
ステル類を合成する方法は、たとえば、Pier
Luigi Magagniniら、Gazz.Chim.Ital.、96、
1035（1966）、Gene Sumrellら、J.Am.Chem.
Soc.、81、4310（1959）あるいはAllen R.Banks、
J.Org.Chem.、42、3965（1977）等に記載されて
いる。 4-cyano-2,3,5,6- in the present invention
No method for producing tetrafluorophenyl (meth)acrylic acid esters has been reported so far. On the other hand, methods for synthesizing phenyl organic acid esters from fluorine-free phenols and unsaturated organic acid chlorides are known, for example, from Pier
Luigi Magagnini et al., Gazz.Chim.Ital., 96 ,
1035 (1966), Gene Sumrell et al., J.Am.Chem.
Soc., 81 , 4310 (1959) or Allen R. Banks,
J.Org.Chem., 42 , 3965 (1977), etc.
本発明者らが新規（メタ）アクリル酸エステル
類の製造法を検討した結果、４−シアノ−２，
３，５，６−テトラフルオロフエノールあるいは
そのアルカリ塩とメタクリル酸クロライドから４
−シアノ−２，３，５，６−テトラフルオロメタ
クリル酸エステルまたは４−シアノ−２，３，
５，６−テトラフルオロフエノールあるいはその
アルカリ塩とアクリル酸クロライドから４−シア
ノ−２，３，５，６−テトラフルオロアクリル酸
エステルが容易に製造できることを見い出した。 As a result of the present inventors' investigation into the production method of novel (meth)acrylic acid esters, 4-cyano-2,
4 from 3,5,6-tetrafluorophenol or its alkali salt and methacrylic acid chloride
-cyano-2,3,5,6-tetrafluoromethacrylic acid ester or 4-cyano-2,3,
It has been found that 4-cyano-2,3,5,6-tetrafluoroacrylic acid ester can be easily produced from 5,6-tetrafluorophenol or its alkali salt and acrylic acid chloride.
以下、本発明における新規物質の製造方法を実
施例により具体的に説明し、えられたこれらの新
規物質を構造決定するための分析結果をも同時に
示す。 Hereinafter, the method for producing the novel substances according to the present invention will be explained in detail with reference to Examples, and the analysis results for determining the structures of these novel substances obtained will also be shown at the same time.
実施例 １
〔４−シアノ−２，３，５，６−テトラフルオ
ロフエノールの合成〕
ペンタフルオロベンゾニトリル250ｇ（1.295モ
ル）、水酸化カリウム171ｇ（3.05モル）および溶
媒としての２−メチル−２−プロパノール500ml
を三ツ口フラスコに仕込んだ。窒素ガス雰囲気の
撹拌下70℃で20時間反応を行つた。その後２−メ
チル−２−プロパノールを蒸発乾固させ、内容物
を水250c.c.に溶解させた。Example 1 [Synthesis of 4-cyano-2,3,5,6-tetrafluorophenol] 250 g (1.295 mol) of pentafluorobenzonitrile, 171 g (3.05 mol) of potassium hydroxide and 2-methyl-2- as a solvent. Propanol 500ml
was charged into a three-necked flask. The reaction was carried out at 70°C for 20 hours under stirring in a nitrogen gas atmosphere. Thereafter, the 2-methyl-2-propanol was evaporated to dryness and the contents were dissolved in 250 c.c. of water.
次に６規定の硫酸を滴下しPH２に調整した水溶
液にエーテル500c.c.を加え、有機物質を抽出し、
分液した。この抽出操作を２回繰り返した。エー
テル層を硫酸マグネシウムで乾燥後、エーテルを
蒸発乾固で除去してえられた結晶をベンゼンで再
結晶することによつて４−シアノ−２，３，５，
６−テトラフルオロフエノールをえた。（対ペン
タフルオロベンゾニトリル収率81.3モル％）
m.p.128〜９℃
19F NMR（溶媒：アセトン−d6、外部標準物
質；トリフルオロ酢酸）
δ＝61.4ppm（doublet−multiplet、2F）
δ＝84.7ppm（doublet−multiplet、2F）
実施例 ２
四塩化炭素200c.c.中に４−シアノ−２，３，５，
６−テトラフルオロフエノール19.1ｇ（0.100モ
ル）およびメタクリル酸クロライド13.0ｇ
（0.125モル）を溶解させ、更に３Å（オングスト
ローム）のモレキユラーシーブ20ｇを加えた。還
流下48時間撹拌を続けた。ついで冷却後、反応混
合物を過し、モレキユラーシーブを分離し、
液を硫酸マグネシウムで乾燥させた後ロータリー
エバポレーターで蒸発乾固し、４−シアノ−２，
３，５，６−テトラフルオロフエニルメタクリル
酸エステル21.7ｇ（対４−シアノ−２，３，５，
６−テトラフルオロフエノール収率83.8％、純度
96.5％）をえた。 Next, add 500 c.c. of ether to the aqueous solution adjusted to pH 2 by adding 6N sulfuric acid dropwise to extract organic substances.
The liquid was separated. This extraction operation was repeated twice. After drying the ether layer with magnesium sulfate, the ether was removed by evaporation to dryness, and the resulting crystals were recrystallized with benzene to give 4-cyano-2,3,5,
6-Tetrafluorophenol was obtained. (Yield 81.3 mol% relative to pentafluorobenzonitrile) mp128-9℃ 19 F NMR (solvent: acetone- d6 , external standard material: trifluoroacetic acid) δ=61.4ppm (doublet-multiplet, 2F) δ=84.7ppm (doublet-multiplet, 2F) Example 2 4-cyano-2,3,5,
19.1 g (0.100 mol) of 6-tetrafluorophenol and 13.0 g of methacrylic acid chloride
(0.125 mol) was dissolved, and 20 g of 3 Å (angstrom) molecular sieve was added. Stirring was continued under reflux for 48 hours. After cooling, the reaction mixture was filtered to separate the molecular sieve.
The liquid was dried with magnesium sulfate and then evaporated to dryness using a rotary evaporator to obtain 4-cyano-2,
21.7 g of 3,5,6-tetrafluorophenyl methacrylate (vs. 4-cyano-2,3,5,
6-Tetrafluorophenol yield 83.8%, purity
96.5%).
下記にえられたこの新規物質の構造決定のため
の分析結果を示した。 The analytical results for determining the structure of this new substance are shown below.
ベンゼンで再結晶した４−シアノ−２，３，５，
６−テトラフルオロフエニルメタクリル酸エステ
ル
Γ融 点 87〜88℃
Γ元素分析値
Ｃ(%) Ｈ(%) Ｆ(%) Ｎ(%)
理論値 50.97 1.93 29.34 5.41
分析値 50.8 1.98 29.1 5.44
Γ 1H NMR（溶媒；CCI4、内部標準物質；
TMS）
CH3 δ＝2.1ppm（Singlet、3H）
CH2 δ＝5.9ppm（Singlet、1H）
δ＝6.4ppm（Singlet、1H）
Γ 19F NMR（溶媒；アセトン−d6、外部標準物
質；トリフルオロ酢酸）
δ＝58.8ppm（doublet−doublet、
JAB,A′B′≒21Hz、
JAB′,A′B≒10Hz、2F）
δ＝75.3ppm（doublet−doublet、
JBA,B′A′≒21Hz、
JBA′,B′A≒10Hz、2F）
Γ質量分析スペクトル
EI ｍ／ｅ＝259（M+）
Γ赤外吸収スペクトル（KBr）
2250cm-1（νc≡N）
1760cm-1（νc=p）
1650cm-1（νc=c）
1500cm-1（νF−ベンゼン核ｃ＝ｃ）
実施例 ３
水酸化ナトリウム0.94ｇ（0.0236モル）が溶解
しているメタノール50c.c.中に４−シアノ−２，
３，５，６−テトラフルオロフエノール3.0ｇ
（0.0157モル）を加え溶解させ、氷冷して０℃に
保ちこの溶液にメタクリル酸クロライド1.80ｇ
（0.0173モル）をゆつくり滴下した。滴下終了後
さらにこの温度に保ち２時間撹拌を続け、その後
純水50mlを加え、また、20％水酸化ナトリウム水
溶液でPHを10に調整し、白色結晶を生成させた。
この白色結晶を過し、水で洗浄し、その後乾燥
させて４−シアノ−２，３，５，６−テトラフル
オロフエニルメタクリル酸エステル1.35ｇ（純度
98％、対４−シアノ−２，３，５，６−テトラフ
ルオロフエノール収率32モル％）をえた。えられ
た新規物質の構造決定のための分析結果は実施例
２と同じであつた。4-cyano-2,3,5, recrystallized from benzene
6-Tetrafluorophenyl methacrylate Γ Melting point 87-88℃ Γ Elemental analysis value C (%) H (%) F (%) N (%) Theoretical value 50.97 1.93 29.34 5.41 Analysis value 50.8 1.98 29.1 5.44 Γ 1 H NMR (solvent; CCI 4 , internal standard;
TMS) CH 3 δ=2.1ppm (Singlet, 3H) CH 2 δ=5.9ppm (Singlet, 1H) δ=6.4ppm (Singlet, 1H) Γ 19 F NMR (solvent: acetone-d 6 , external standard: Fluoroacetic acid) δ=58.8ppm (doublet−doublet, J AB,A ′ B ′≒21Hz, J AB ′ ,A ′ B ≒10Hz, 2F) δ=75.3ppm (doublet−doublet, J BA,B ′ A ′ ≒21Hz, J BA ′ ,B ′ A ≒10Hz, 2F) Γ Mass spectrometry spectrum EI m/e=259 (M + ) Γ Infrared absorption spectrum (KBr) 2250cm -1 (ν c ≡ N ) 1760cm -1 ( ν c=p ) 1650 cm -1 (ν c=c ) 1500 cm -1 (νF - benzene nucleus c=c) Example 3 In 50 c.c. of methanol in which 0.94 g (0.0236 mol) of sodium hydroxide is dissolved 4-cyano-2,
3,5,6-tetrafluorophenol 3.0g
(0.0157 mol) was added and dissolved, cooled on ice and kept at 0°C. To this solution was added 1.80 g of methacrylic acid chloride.
(0.0173 mol) was slowly added dropwise. After the dropwise addition was completed, the temperature was kept at this temperature and stirring was continued for 2 hours, and then 50 ml of pure water was added, and the pH was adjusted to 10 with a 20% aqueous sodium hydroxide solution to form white crystals.
The white crystals were filtered, washed with water, and then dried to obtain 1.35 g of 4-cyano-2,3,5,6-tetrafluorophenyl methacrylate (purity:
A yield of 98% and 32 mol% of 4-cyano-2,3,5,6-tetrafluorophenol was obtained. The analysis results for determining the structure of the obtained new substance were the same as in Example 2.
実施例 ４
ベンゼン30mlに４−シアノ−２，３，５，６−
テトラフルオロフエノール3.0ｇ（0.0157モル）
およびメタクリル酸クロライド1.80ｇ（0.0173モ
ル）を溶解させ、さらに塩化水素トラツプ剤とし
て炭酸カルシウム1.73ｇ（0.0173モル）を加え、
還流下32時間撹拌を続けた。放冷後反応混合物を
過し、炭酸カルシウムを分離した後、液を硫
酸マグネシウムで乾燥させた後ロータリーエバポ
レーターで蒸発乾固し、４−シアノ−２，３，
５，６−テトラフルオロフエニルメタクリル酸エ
ステル2.6ｇ（収率63.9％、純度95.4％）をえた。
えられた新規物質の構造決定のための分析結果は
実施例２と同じであつた。Example 4 4-cyano-2,3,5,6- in 30ml of benzene
Tetrafluorophenol 3.0g (0.0157mol)
and 1.80 g (0.0173 mol) of methacrylic acid chloride were dissolved, and 1.73 g (0.0173 mol) of calcium carbonate was added as a hydrogen chloride trapping agent.
Stirring was continued under reflux for 32 hours. After cooling, the reaction mixture was filtered to separate calcium carbonate, the liquid was dried over magnesium sulfate, and then evaporated to dryness using a rotary evaporator to give 4-cyano-2,3,
2.6 g of 5,6-tetrafluorophenyl methacrylate (yield 63.9%, purity 95.4%) was obtained.
The analysis results for determining the structure of the obtained new substance were the same as in Example 2.
実施例 ５
四塩化炭素200c.c.中に４−シアノ−２，３，５，
６−テトラフルオロフエノール19.1ｇ（0.100モ
ル）およびアクリル酸クロライド11.3ｇ（0.125
モル）を溶解させ、さらに３Åのモレキユラーシ
ーブ20ｇを加えた。還流下38時間撹拌を続けた。
放冷後、反応混合物を過しモレキユラーシーブ
を分離し、液を硫酸マグネシウムで乾燥させた
後ロータリーエバポレーターで蒸発乾固し、融点
を有する４−シアノ−２，３，５，６−テトラフ
ルオロフエニルアクリル酸エステル15.2ｇ（対４
−シアノ−２，３，５，６−テトラフルオロフエ
ノール収率62.0％、純度96.4％）をえた。Example 5 4-cyano-2,3,5, in 200 c.c. of carbon tetrachloride
19.1 g (0.100 mol) of 6-tetrafluorophenol and 11.3 g (0.125 mol) of acrylic acid chloride
20 g of 3 Å molecular sieve was added. Stirring was continued under reflux for 38 hours.
After cooling, the reaction mixture was filtered to separate the molecular sieve, the liquid was dried over magnesium sulfate, and then evaporated to dryness on a rotary evaporator to obtain 4-cyano-2,3,5,6-tetra having a melting point. Fluorophenyl acrylic acid ester 15.2g (for 4
-cyano-2,3,5,6-tetrafluorophenol (yield 62.0%, purity 96.4%) was obtained.
下記にえられたこの新規物質の構造決定のため
の分析結果を示した。 The analytical results for determining the structure of this new substance are shown below.
Γ沸 点 62℃（２mmHg）
Γ融 点 21〜23℃
Γ元素分析値
Ｃ(%) Ｈ(%) Ｆ(%) Ｎ(%)
理論値 48.98 1.22 31.02 5.71
分析値 48.9 1.25 30.8 5.77
Γ 1H NMR（溶媒；CCl4、内部標準物質；
TMS）
δ＝5.9〜7.0ppm（multiplet、3H）
Γ 19F NMR（溶媒；アセトン−d6、外部標準物
質；トリフルオロ酢酸）
δ＝58.7ppm（broad doublet、Ｊ＝21Hz、
2F）
δ＝75.2ppm（broad doublet、Ｊ＝21Hz、
2F）
Γ質量分析スペクトル
EI ｍ／ｅ＝245（M+）
Γ赤外吸収スペクトル（neat）
2250cm-1（νc≡N）
1770cm-1（νc=p）
1630cm-1（νc=c）
1500cm-1（νF−ベンゼン核ｃ＝ｃ）
実施例 ６
ベンゼン30mlに４−シアノ−２，３，５，６−
テトラフルオロフエノール3.82ｇ（0.020モル）
およびアクリル酸クロライド2.26ｇ（0.025モル）
を溶解させ、さらに塩化水素トラツプ剤として炭
酸カルシウム2.5ｇ（0.025モル）を加え、還流下
40時間撹拌を続けた。放冷後反応混合物を過
し、炭酸カルシウムを分離した後、液を硫酸マ
グネシウムで乾燥させた後ロータリーエバポレー
ターで蒸発乾固し、４−シアノ−２，３，５，６
−テトラフルオロフエニルアクリル酸エステル
2.8ｇ（収率57.1％、純度95.8％）をえた。えれら
れた新規物質の構造決定のための分析結果は実施
例５と同じであつた。Γ boiling point 62℃ (2mmHg) Γ melting point 21~23℃ Γ elemental analysis value C (%) H (%) F (%) N (%) Theoretical value 48.98 1.22 31.02 5.71 Analysis value 48.9 1.25 30.8 5.77 Γ 1 H NMR (solvent; CCl 4 , internal standard;
TMS) δ = 5.9 to 7.0 ppm (multiplet, 3H) Γ 19 F NMR (solvent: acetone-d 6 , external standard material: trifluoroacetic acid) δ = 58.7 ppm (broad doublet, J = 21 Hz,
2F) δ=75.2ppm (broad doublet, J=21Hz,
2F) Γ Mass spectrometry spectrum EI m/e=245 (M + ) Γ Infrared absorption spectrum (neat) 2250cm -1 (ν c ≡ N ) 1770cm -1 (ν c=p ) 1630cm -1 (ν c=c ) 1500cm -1 (νF-benzene nucleus c=c) Example 6 4-cyano-2,3,5,6- in 30ml of benzene
Tetrafluorophenol 3.82g (0.020mol)
and acrylic acid chloride 2.26 g (0.025 mol)
2.5 g (0.025 mol) of calcium carbonate was added as a hydrogen chloride trapping agent, and the mixture was heated under reflux.
Stirring was continued for 40 hours. After cooling, the reaction mixture was filtered to separate calcium carbonate, and the liquid was dried over magnesium sulfate and evaporated to dryness using a rotary evaporator to obtain 4-cyano-2,3,5,6.
-tetrafluorophenyl acrylate ester
2.8g (yield 57.1%, purity 95.8%) was obtained. The analysis results for determining the structure of the obtained new substance were the same as in Example 5.
Claims (1)
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5735484A JPS60202854A (en) | 1984-03-27 | 1984-03-27 | 4-cyano-2,3,5,6-tetrafluorophenyl acrylic acid ester or 4-cyano-2,3,5,6-tetrafluorophenyl methacrylic acid ester |
| US06/708,289 US4572805A (en) | 1984-03-27 | 1985-03-05 | 2,3,5,6-Tetrafluorophenyl (meth) acrylates and method for production thereof |
| CA000476118A CA1247128A (en) | 1984-03-27 | 1985-03-08 | 2,3,5,6-tetrafluorophenyl (meth) acrylates and method for production thereof |
| DE8585301932T DE3563531D1 (en) | 1984-03-27 | 1985-03-20 | 2,3,5,6-tetrafluorophenyl (meth)acrylates and their production |
| EP85301932A EP0160379B1 (en) | 1984-03-27 | 1985-03-20 | 2,3,5,6-tetrafluorophenyl (meth)acrylates and their production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5735484A JPS60202854A (en) | 1984-03-27 | 1984-03-27 | 4-cyano-2,3,5,6-tetrafluorophenyl acrylic acid ester or 4-cyano-2,3,5,6-tetrafluorophenyl methacrylic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60202854A JPS60202854A (en) | 1985-10-14 |
| JPH0142940B2 true JPH0142940B2 (en) | 1989-09-18 |
Family
ID=13053237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5735484A Granted JPS60202854A (en) | 1984-03-27 | 1984-03-27 | 4-cyano-2,3,5,6-tetrafluorophenyl acrylic acid ester or 4-cyano-2,3,5,6-tetrafluorophenyl methacrylic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60202854A (en) |
-
1984
- 1984-03-27 JP JP5735484A patent/JPS60202854A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60202854A (en) | 1985-10-14 |
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