JPH0236561B2 - - Google Patents
Info
- Publication number
- JPH0236561B2 JPH0236561B2 JP57035932A JP3593282A JPH0236561B2 JP H0236561 B2 JPH0236561 B2 JP H0236561B2 JP 57035932 A JP57035932 A JP 57035932A JP 3593282 A JP3593282 A JP 3593282A JP H0236561 B2 JPH0236561 B2 JP H0236561B2
- Authority
- JP
- Japan
- Prior art keywords
- palladium
- general formula
- reaction mixture
- mmol
- trifluoropropene
- 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 - Lifetime
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- VLSRKCIBHNJFHA-UHFFFAOYSA-N 2-(trifluoromethyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C(F)(F)F VLSRKCIBHNJFHA-UHFFFAOYSA-N 0.000 claims description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 9
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 21
- 239000011541 reaction mixture Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- QKBKGNDTLQFSEU-UHFFFAOYSA-N 2-bromo-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C(Br)=C QKBKGNDTLQFSEU-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal amides Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002940 palladium Chemical class 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 3
- KTQBOMAVUDZQFO-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-yl prop-2-enoate Chemical compound FC(F)(F)C(C)OC(=O)C=C KTQBOMAVUDZQFO-UHFFFAOYSA-N 0.000 description 2
- XFOCTDPLVDZSGA-UHFFFAOYSA-N 2,3-dibromo-1,1,1-trifluoropropane Chemical compound FC(F)(F)C(Br)CBr XFOCTDPLVDZSGA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 description 1
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VIJMMQUAJQEELS-UHFFFAOYSA-N n,n-bis(ethenyl)ethenamine Chemical compound C=CN(C=C)C=C VIJMMQUAJQEELS-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は一般式
（式中、Ｙは水酸基、アルコキシ基、アリールオ
キシ基又は第二級アミノ基である。）で表わされ
るα−トリフルオロメチルアクリル酸およびその
誘導体の製造方法に関する。[Detailed Description of the Invention] The present invention relates to the general formula (In the formula, Y is a hydroxyl group, an alkoxy group, an aryloxy group, or a secondary amino group.) The present invention relates to a method for producing α-trifluoromethylacrylic acid and its derivatives.
本発明の前記一般式（）で表わされるα−ト
リフルオロメチルアクリル酸およびその誘導体は
重合させることにより含フツ素ポリアクリル酸誘
導体に誘導することができる。含フツ素ポリアク
リル酸類はLSI製造用レジストとして有用であ
る。 The α-trifluoromethylacrylic acid and its derivatives represented by the general formula () of the present invention can be induced into fluorine-containing polyacrylic acid derivatives by polymerization. Fluorine-containing polyacrylic acids are useful as resists for LSI manufacturing.
従来、前記一般式（）で表わされるα−トリ
フルオロメチルアクリル酸類を製造する方法とし
ては、(1)トリフルオロアセトンをシアノヒドリン
とし、アセチル化した後熱分解してα−トリフル
オロアクリロニトリルを合成し、これを加水分解
し、塩化水素を付加した後さらに加水分解及び脱
水反応を行なうことによりα−トリフルオロアク
リル酸を合成する方法〔M.W.Buxton、M.
Stacey、andJ.C.Tatlow、J.Chem Soc.、367
（1954）．参照〕、及び(2)３，３，３−トリフルオ
ロイソプロペニルリチウムと二酸化炭素との反応
によつてα−トリフルオロアクリル酸を合成する
方法〔F.G.Drekasmith O.J.Stewart、and P.
Tarrat J.Org.Chem.、33、280（1967）．参照〕が
知られている。しかし、前者は工程が長くしかも
全収率も10％以下であり、工業的には到底採用で
きる方法ではない。後者は危険な発火性のブチル
リチウムを用いるため無水条件が必要であり、し
かも反応は−110℃という極低温で行なわなけれ
ばならないため工業的合成に適していない。 Conventionally, as a method for producing α-trifluoromethylacrylic acids represented by the general formula (), (1) trifluoroacetone is converted into cyanohydrin, acetylated, and then thermally decomposed to synthesize α-trifluoroacrylonitrile. , a method for synthesizing α-trifluoroacrylic acid by hydrolyzing this, adding hydrogen chloride, and then performing further hydrolysis and dehydration reactions [MWBuxton, M.
Stacey, and J.C. Tatlow, J.Chem Soc., 367
(1954). Reference] and (2) Method for synthesizing α-trifluoroacrylic acid by reaction of 3,3,3-trifluoroisopropenyllithium with carbon dioxide [FGDrekasmith OJStewart, and P.
Tarrat J.Org.Chem., 33 , 280 (1967). Reference] is known. However, the former method requires a long process and has a total yield of less than 10%, so it is definitely not a method that can be adopted industrially. The latter is not suitable for industrial synthesis because it uses dangerous flammable butyllithium, requires anhydrous conditions, and the reaction must be carried out at an extremely low temperature of -110°C.
本発明者等は従来法の欠点を克服すべく検討し
た結果、２−ハロ−３、３、３−トリフルオロプ
ロペンから一挙にα−トリフルオロメチルアクリ
ル酸およびその誘導体を合成する工業的方法を見
出し本発明を完成した。 As a result of studies aimed at overcoming the drawbacks of conventional methods, the present inventors have developed an industrial method for synthesizing α-trifluoromethylacrylic acid and its derivatives from 2-halo-3,3,3-trifluoropropene all at once. Heading The invention has been completed.
本発明は塩基及びパラジウム触媒の存在下、一
般式
（式中、Ｘは塩素、臭素又はヨウ素原子である。）
で表わされる２−ハロ−３，３，３−トリフルオ
ロプロペン、一般式
HY −（）
（式中、Ｙは水酸基、アルコキシ基、アリールオ
キシ基又は第二級アミノ基である。）で表わされ
る化合物及び一酸化炭素を反応させ、前記一般式
（）で表わされるα−トリフルオロメチルアク
リル酸およびその誘導体を製造するものである。 In the present invention, in the presence of a base and a palladium catalyst, the general formula (In the formula, X is a chlorine, bromine or iodine atom.)
2-halo-3,3,3-trifluoropropene, represented by the general formula HY -() (wherein Y is a hydroxyl group, an alkoxy group, an aryloxy group, or a secondary amino group) The compound and carbon monoxide are reacted to produce α-trifluoromethylacrylic acid and its derivatives represented by the above general formula ().
本発明の原料である前記一般式（）で表わさ
れる２−ハロ−３，３，３−トリフルオロプロペ
ンは、３，３，３−トリフルオロプロペンに塩
素、臭素あるいはヨウ素を付加させることによつ
て得られる１，１，１−トリフルオロ−２，３−
ジハロプロパン〔参考文献A.L.Henne and M.
Nager、J.Amer.Chem.Soc.、73、1042（1951）．
参照）を脱ハロゲン化水素させることによつて容
易に製造することができる。また、本発明を実施
する際は１，１，１−トリフルオロ−２，３−ジ
ハロプロパンを用いて、系中で直接前記一般式
（）で表わされる２−ハロ−３，３，３−トリ
フルオロプロパンに変換して用いることもでき
る。 2-halo-3,3,3-trifluoropropene represented by the general formula (), which is a raw material of the present invention, can be obtained by adding chlorine, bromine or iodine to 3,3,3-trifluoropropene. 1,1,1-trifluoro-2,3- obtained by
Dihalopropane [Reference ALHenne and M.
Nager, J.Amer.Chem.Soc., 73 , 1042 (1951).
(see) can be easily produced by dehydrohalogenating. In addition, when carrying out the present invention, 1,1,1-trifluoro-2,3-dihalopropane is used directly in the system to 2-halo-3,3,3 represented by the general formula (). - It can also be used by converting it into trifluoropropane.
本発明は塩基の存在下に行なうことを必須要件
とする。塩基としては、アルカリ金属の水素化
物、水酸化物、炭酸塩、炭酸水素塩、アルカリ金
属アミド、トリエチルアミン、Ｎ，Ｎ−ジメチル
アニリン、ピリジン等が挙げられる。塩基の使用
量は前記一般式（）の化合物に対して等モルで
よい。また、１，１，１−トリフルオロ−２，３
−ジハロプロパンを用いる場合には２倍モル用い
るのが好ましい。 The present invention requires that the reaction be carried out in the presence of a base. Examples of the base include alkali metal hydrides, hydroxides, carbonates, hydrogen carbonates, alkali metal amides, triethylamine, N,N-dimethylaniline, pyridine, and the like. The amount of the base to be used may be equimolar to the compound of the general formula (). Also, 1,1,1-trifluoro-2,3
- When using dihalopropane, it is preferable to use twice the mole.
更に本発明はパラジウム触媒の存在下に行なう
ことを必須要件とする。パラジウム触媒として
は、パラジウム黒、パラジウム炭素、及び酢酸パ
ラジウム、塩化パラジウム等のパラジウム塩に三
級ホスフインを添加した触媒、及びジクロロビス
（トリフエニルホスフイン）パラジウム、テトラ
キス（トリフエニルホスフイン）パラジウム等の
パラジウム錯体、更にこれらのパラジウム錯体を
担体に担持したもの等を例示することができる。
触媒の使用量は前記一般式（）の化合物に対し
て1/1000〜1/10モル範囲で用いることができる。 Furthermore, the present invention requires that the reaction be carried out in the presence of a palladium catalyst. Examples of palladium catalysts include palladium black, palladium on carbon, catalysts in which tertiary phosphine is added to palladium salts such as palladium acetate and palladium chloride, and dichlorobis(triphenylphosphine)palladium and tetrakis(triphenylphosphine)palladium. Examples include palladium complexes and those in which these palladium complexes are supported on carriers.
The amount of the catalyst used can be in the range of 1/1000 to 1/10 mole based on the compound of the general formula ().
本発明は常圧でも進行するが反応時間、収率の
点から10〜200気圧の範囲で行なうのが好ましい。
溶媒は必ずしも必要ではないが、一般的に溶媒を
用いた方が収率が良いので好ましい。溶媒として
は、反応に直接関与しないもの、例えば塩化メチ
レン、クロロホルム、アセトニトリル、エーテ
ル、テトラヒドロフラン、ジメトキシエタン、ジ
グライム、ベンゼン、トルエン、Ｎ，Ｎ−ジメチ
ルホルムアミド、ジメチルスルホキシド、ヘキサ
メチルホスホリツクトリアミド等を使用すること
が出来る。反応温度は室温から200℃の範囲で行
なうことができる。 Although the present invention proceeds at normal pressure, it is preferably carried out at a pressure in the range of 10 to 200 atmospheres from the viewpoint of reaction time and yield.
Although a solvent is not necessarily required, it is generally preferable to use a solvent because the yield is better. As a solvent, those not directly involved in the reaction, such as methylene chloride, chloroform, acetonitrile, ether, tetrahydrofuran, dimethoxyethane, diglyme, benzene, toluene, N,N-dimethylformamide, dimethylsulfoxide, hexamethylphosphoric triamide, etc. It can be used. The reaction temperature can be carried out in the range from room temperature to 200°C.
実施例 １
ジクロロビス（トリフエニルホスフイン）パラ
ジウム351.0mg（0.50ｍmol）、２−ブロモー３，
３，３−トリフルオロプロペン8.75ｇ（50ｍ
mol）、水0.9ｇ（50ｍmol）、トリエチルアミン
7.58ｇ（75ｍmol）及び溶媒のテトラヒドロフラ
ン50mlを200mlのオートクレーブに入れ、30気圧
の一酸化炭素圧下60℃で18時間加熱撹拌した。反
応混合物に1N−塩酸を加えエチルエーテルで抽
出を行なつた後、ノナンを内部基準とする反応混
合物のGLC分析により、２−トリフルオロメチ
ルアクリル酸を収率60％で得た。反応混合物を蒸
留することにより、沸点79〜81℃／40mmHgを有
する純粋なα−トリフルオロメチルアクリル酸
3.90ｇ（収率56％）を得た。Example 1 Dichlorobis(triphenylphosphine)palladium 351.0mg (0.50mmol), 2-bromo 3,
3,3-trifluoropropene 8.75g (50m
mol), water 0.9g (50mmol), triethylamine
7.58 g (75 mmol) and 50 ml of tetrahydrofuran as a solvent were placed in a 200 ml autoclave, and the mixture was heated and stirred at 60° C. for 18 hours under a carbon monoxide pressure of 30 atmospheres. After adding 1N hydrochloric acid to the reaction mixture and performing extraction with ethyl ether, 2-trifluoromethylacrylic acid was obtained in a yield of 60% by GLC analysis of the reaction mixture using nonane as an internal standard. By distilling the reaction mixture, pure α-trifluoromethylacrylic acid with boiling point 79-81℃/40mmHg
3.90g (yield 56%) was obtained.
融点：52.5〜53.0℃
1H NMR（CDCl3：TMS）：δ6.52（四重線、Ｊ＝
1.3Hz，1H）、6.80（四重線、Ｊ＝1.8Hz、1H）、
9.46（一重線、1H）．
19F NMR（CDCl3：CFCl3）：δ−66.54
IR（KBr）：3600〜2400（νOH）、1710（νc＝ｃ）cm
-1.
質量スペクトル：ｍ／ｅ M+140（67）、123（40）、
120(12)、101（26）、95（26）、76（73）、75（56）、
73
（13）、69（100）、53(11)、45（54）、31（17）、27(
12)、
26（14）．
実施例 ２
ジクロロビス（トリフエニルホスフイン）パラ
ジウム70.2mg（0.10ｍmol）、２ブロモ−３，３，
３−トリフルオロプロペン1.75ｇ（10ｍmol）、
水0.18（10ｍmol）、トリエチルアミン1.52ｇ（15
ｍmol）及び溶媒のＮ，Ｎ−ジメチルホルムアミ
ド10mlを50mlのオートクレーブに入れ40気圧の一
酸化炭素圧下、60℃で18時間加熱撹拌した。反応
混合物に1N−塩酸を加えて、酢酸エチルで抽出
を行なつた後、ノナンを内部基準とする反応混合
物のGLC分析により、α−トリフルオロメチル
アクリル酸を収率78％で得た。GLC分取により
純粋なα−トリフルオロメチルアクリル酸を単離
した。Melting point: 52.5-53.0℃ 1 H NMR (CDCl 3 :TMS): δ6.52 (quartet, J=
1.3Hz, 1H), 6.80 (quartet, J=1.8Hz, 1H),
9.46 (single line, 1H). 19F NMR ( CDCl3 : CFCl3 ): δ-66.54 IR (KBr): 3600-2400 ( νOH ), 1710 (νc=c) cm
-1 . Mass spectrum: m/e M + 140 (67), 123 (40),
120(12), 101(26), 95(26), 76(73), 75(56),
73
(13), 69 (100), 53 (11), 45 (54), 31 (17), 27 (
12),
26(14). Example 2 Dichlorobis(triphenylphosphine)palladium 70.2mg (0.10mmol), 2bromo-3,3,
3-trifluoropropene 1.75g (10mmol),
Water 0.18 (10 mmol), triethylamine 1.52 g (15
mmol) and 10 ml of N,N-dimethylformamide as a solvent were placed in a 50 ml autoclave and heated and stirred at 60° C. for 18 hours under 40 atmospheres of carbon monoxide pressure. After adding 1N hydrochloric acid to the reaction mixture and performing extraction with ethyl acetate, α-trifluoromethylacrylic acid was obtained in a yield of 78% by GLC analysis of the reaction mixture using nonane as an internal standard. Pure α-trifluoromethylacrylic acid was isolated by preparative GLC.
実施例 ３
ジクロロビス（トリフエニルホスフイン）パラ
ジウム70.2mg（0.10ｍmol）、２ブロモー３，３，
３−トリフルオロプロペン1.75ｇ（10ｍmol）、
水0.18ｇ（10ｍmol）、トリエチルアミン1.52ｇ
（15ｍmol）及び溶媒のテトラヒドロフラン10ml
を50mlのオートクレーブに入れ35気圧の一酸化炭
素圧下、60℃で18時間加熱攬拌した。反応混合物
に1N−塩酸を加えてエチルエーテルで抽出を行
なつた後、ノナンを内部基準とする反応混合物の
GLC分析よりα−トリフルオロメチルアクリル
酸を収率60％で得た。Example 3 Dichlorobis(triphenylphosphine)palladium 70.2mg (0.10mmol), 2bromo3,3,
3-trifluoropropene 1.75g (10mmol),
Water 0.18g (10mmol), triethylamine 1.52g
(15 mmol) and solvent tetrahydrofuran 10 ml
was placed in a 50 ml autoclave and heated and stirred at 60°C for 18 hours under a carbon monoxide pressure of 35 atmospheres. After adding 1N hydrochloric acid to the reaction mixture and extracting with ethyl ether, the reaction mixture was extracted using nonane as an internal standard.
Based on GLC analysis, α-trifluoromethylacrylic acid was obtained in a yield of 60%.
実施例 ４
ジクロロビス（トリフルニルホスフイン）パラ
ジウム70.2mg（0.10ｍmol）、２，３−ジブロモー
１，１，１−トリフルオロプロパン2.56ｇ（10ｍ
mol）、水0.18ｇ（10ｍmol）、トリエチルアミン
3.03ｇ（30ｍmol）及び溶媒のテトラヒドロフラ
ン10mlを50mlのオートクレーブに入れ50気圧の一
酸化炭素圧下、60℃で18時間加熱撹拌した。反応
混合物に1N−塩酸を加えて、エチルエーテルで
抽出を行なつた後ノナンを内部基準とする反応混
合物のGLC分析により、α−トリフルオロメチ
ルアクリル酸を収率48％で得た。Example 4 Dichlorobis(triflunylphosphine)palladium 70.2 mg (0.10 mmol), 2,3-dibromo-1,1,1-trifluoropropane 2.56 g (10 m
mol), water 0.18g (10mmol), triethylamine
3.03 g (30 mmol) and 10 ml of tetrahydrofuran as a solvent were placed in a 50 ml autoclave and heated and stirred at 60° C. for 18 hours under 50 atmospheres of carbon monoxide pressure. After adding 1N hydrochloric acid to the reaction mixture and performing extraction with ethyl ether, α-trifluoromethylacrylic acid was obtained in a yield of 48% by GLC analysis of the reaction mixture using nonane as an internal standard.
実施例 ５
ジクロロビス（トリフエニルホスフイン）パラ
ジウム70.2mg（0.10ｍmol）、２，３−ジブロモー
１，１，１−トリフルオロプロパン2.56ｇ（10ｍ
mol）、ジエチルアミン0.73ｇ（10ｍmol）、トリ
エチルアミン2.53ｇ（25ｍmol）及び溶媒のテト
ラヒドロフラン10mlを50mlのオートクレーブに入
れ50気圧の一酸化炭素気圧、100℃で７時間加熱
撹拌した。反応混合物をエチルエーテルで抽出を
行なつた後、トルエンを内部基準とする反応混合
物のGLC分析により、α−トリフルオロメチル
−Ｎ，Ｎ−ジメチルアクリルアミドを収率43％で
得た。GLC分取により純粋なα−トリフルオロ
メチル−Ｎ，Ｎ−ジエチルアクリルアミドを単離
した。Example 5 Dichlorobis(triphenylphosphine)palladium 70.2 mg (0.10 mmol), 2,3-dibromo-1,1,1-trifluoropropane 2.56 g (10 m
mol), 0.73 g (10 mmol) of diethylamine, 2.53 g (25 mmol) of triethylamine, and 10 ml of tetrahydrofuran as a solvent were placed in a 50 ml autoclave and heated and stirred at 100° C. for 7 hours under 50 atmospheres of carbon monoxide. After the reaction mixture was extracted with ethyl ether, α-trifluoromethyl-N,N-dimethylacrylamide was obtained in a yield of 43% by GLC analysis of the reaction mixture using toluene as an internal standard. Pure α-trifluoromethyl-N,N-diethylacrylamide was isolated by preparative GLC.
1H NMR（CDCl3：TMS）：δ1.15（三重線、Ｊ＝
7.0Hz、6H）、3.40（四重線、Ｊ＝7.0Hz、4H）、
5.58〜5.65（多重線、1H）5.89〜6.00（多重線、
1H）．
19F NMR（CDCl3：CFCl3）：−65.73（三重線、
1.3Hz）
IR（neat）：3120（νc=c-H、1640（νc=p）cm-1.
実施例 ６
ジクロロビス（トリフエニルホスフイン）パラ
ジウム70.2mg（0.10ｍmol）、２−ブロモ−３，
３，３−トリフルオロプロペン1.75ｇ（10ｍ
mol）、エチルアルコール0.46ｇ（10ｍmol）、ト
リエチルアミン1.01ｇ（10ｍmol））及び溶媒の
ベンゼン20mlを50mlのオートクレーブに入れ、10
気圧の一酸化炭素圧下、80℃で15時間加熱撹拌し
た。トルエンを内部基準とする反応混合物の
GLC分析により、α−トリフルオロメチルアク
リル酸エチル及び３，３，３−トリフルオロ−２
−エトキシメチルプロピオン酸エチルが各々41％
及び47％の収率で得た。GLC分取により純粋な
α−トリフルオロメチルアクリル酸エチルを単離
した。 1 H NMR (CDCl 3 :TMS): δ1.15 (triplet line, J=
7.0Hz, 6H), 3.40 (quartet, J=7.0Hz, 4H),
5.58~5.65 (multiplet, 1H) 5.89~6.00 (multiplet,
1H). 19F NMR ( CDCl3 : CFCl3 ): -65.73 (triple line,
1.3Hz) IR (neat): 3120 (ν c=cH , 1640 (ν c=p ) cm -1 . Example 6 Dichlorobis(triphenylphosphine)palladium 70.2 mg (0.10 mmol), 2-bromo-3,
3,3-trifluoropropene 1.75g (10m
mol), ethyl alcohol 0.46g (10mmol), triethylamine 1.01g (10mmol)) and the solvent benzene 20ml in a 50ml autoclave,
The mixture was heated and stirred at 80° C. for 15 hours under carbon monoxide pressure. of the reaction mixture with toluene as the internal standard.
By GLC analysis, α-trifluoromethylethyl acrylate and 3,3,3-trifluoro-2
-Ethyl ethoxymethylpropionate 41% each
and a yield of 47%. Pure ethyl α-trifluoromethylacrylate was isolated by preparative GLC.
1H NMR（CDCl3：TMS）：δ1.31（三重線、Ｊ＝
7.0Hz、3H）4.26（四重線、Ｊ＝7.0Hz、2H）、
6.34〜6.42（多重線、1H）、6.60〜6.68（多重線、
1H）．
19F NMR（CDCl3：CFCl3）：δ−66.27（三重線、
Ｊ＝1.5Hz）．
IR（neat）：3150（νc=c-H）、1735（νc=p）、1645（
ｃ＝
ｃ）cm-1.
質量スペクトル：ｍ／ｅ M+168（０）、123
（100）、101（14）、99(10)、95（16）、69（22）、29
（29）、28（19）、27(12)．
元素分析：実測値（％） 計算値（％）
Ｃ：42.40 42.87
Ｈ： 4.15 4.20
実施例 ７
ジクロロビス（トリフエニルホスフイン）パラ
ジウム210.6mg（0.30ｍmol）、２−ブロモ−3.3，
３−トリフルオロプロペン1.75ｇ（10ｍmol）、
エチルアルコール0.46ｇ（10ｍmol）、トリエチ
レンアミン1.52ｇ（15ｍmol）及び溶媒のテトラ
ヒドロフラン10mlを50mlのオートクレーブに入れ
45気圧の一酸化炭素圧下、60℃で16時間加熱撹拌
した。トルエンを内部煩準とする反応混合物の
GLC分析により、α−トリフルオロメチルアク
リル酸エチル及び３，３，３−トリフルオロ−２
−エトキシメチルプロピオン酸エチルが各々43％
及び46％の収率で得られた。 1 H NMR (CDCl 3 :TMS): δ1.31 (triple line, J=
7.0Hz, 3H) 4.26 (quartet, J=7.0Hz, 2H),
6.34~6.42 (multiplet, 1H), 6.60~6.68 (multiplet,
1H). 19F NMR ( CDCl3 : CFCl3 ): δ-66.27 (triplet line,
J=1.5Hz). IR (neat): 3150 (ν c=cH ), 1735 (ν c=p ), 1645 (
c=
c) cm -1 . Mass spectrum: m/e M + 168 (0), 123
(100), 101 (14), 99 (10), 95 (16), 69 (22), 29
(29), 28(19), 27(12). Elemental analysis: Actual value (%) Calculated value (%) C: 42.40 42.87 H: 4.15 4.20 Example 7 Dichlorobis(triphenylphosphine)palladium 210.6mg (0.30mmol), 2-bromo-3.3,
3-trifluoropropene 1.75g (10mmol),
Put 0.46 g (10 mmol) of ethyl alcohol, 1.52 g (15 mmol) of triethylene amine, and 10 ml of tetrahydrofuran (solvent) into a 50 ml autoclave.
The mixture was heated and stirred at 60° C. for 16 hours under a carbon monoxide pressure of 45 atm. of the reaction mixture with toluene as the internal standard.
By GLC analysis, α-trifluoromethylethyl acrylate and 3,3,3-trifluoro-2
-Ethyl ethoxymethylpropionate 43% each
and a yield of 46%.
Claims (1)
ロプロペン、一般式 HY で表わされる化合物及び一酸化炭素を反応させる
ことからなる、一般式 で表わされるα−トリフルオロメチルアクリル酸
およびその誘導体の製造方法（式中、Ｘは塩素、
臭素又はヨウ素原子であり、Ｙは水酸基、アルコ
キシ基、アリールオキシ基又は第二級アミノ基で
ある。）。[Claims] 1. In the presence of a base and a palladium catalyst, the general formula 2-halo-3,3,3-trifluoropropene represented by the general formula HY, a compound represented by the general formula HY, and carbon monoxide are reacted. Method for producing α-trifluoromethylacrylic acid and its derivatives represented by (wherein, X is chlorine,
It is a bromine or iodine atom, and Y is a hydroxyl group, an alkoxy group, an aryloxy group, or a secondary amino group. ).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57035932A JPS58154529A (en) | 1982-03-09 | 1982-03-09 | Preparation of alpha-trifluoromethylacrylic acid and its derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57035932A JPS58154529A (en) | 1982-03-09 | 1982-03-09 | Preparation of alpha-trifluoromethylacrylic acid and its derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58154529A JPS58154529A (en) | 1983-09-14 |
| JPH0236561B2 true JPH0236561B2 (en) | 1990-08-17 |
Family
ID=12455795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57035932A Granted JPS58154529A (en) | 1982-03-09 | 1982-03-09 | Preparation of alpha-trifluoromethylacrylic acid and its derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58154529A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6094933A (en) * | 1983-10-31 | 1985-05-28 | Sagami Chem Res Center | Production of alpha-perfluoroalkylacrylic acid |
| JP2533506B2 (en) * | 1986-07-11 | 1996-09-11 | 財団法人 相模中央化学研究所 | Process for producing fluorine-containing carboxylic acid ester |
| JP2508763B2 (en) * | 1986-11-07 | 1996-06-19 | 東ソー株式会社 | Method for producing fluorine-containing carboxylic acid ester |
| JP2004292340A (en) * | 2003-03-26 | 2004-10-21 | Tosoh F-Tech Inc | alpha-PENTAFLUOROETHYLACRYLIC ACID DERIVATIVE AND METHOD FOR PRODUCING THE SAME |
| JP4947875B2 (en) * | 2003-03-26 | 2012-06-06 | 東ソ−・エフテック株式会社 | Oxyperfluoroalkylpropionic acid derivative and method for producing the same |
| JP4500571B2 (en) * | 2003-03-26 | 2010-07-14 | 東ソ−・エフテック株式会社 | Production method of fluorine-containing acrylic ester |
| JP2004292339A (en) * | 2003-03-26 | 2004-10-21 | Tosoh F-Tech Inc | Method for producing fluorine-containing acrylic ester |
| EP1637514B1 (en) * | 2003-03-26 | 2014-05-07 | Tosoh F-Tech, Inc. | Method for producing fluorine-containing acrylate |
| JP4625652B2 (en) * | 2004-05-13 | 2011-02-02 | 東ソー株式会社 | Method for producing 2-perfluoroalkyl acrylate |
| JP4786895B2 (en) * | 2004-10-22 | 2011-10-05 | 東ソ−・エフテック株式会社 | Method for producing fluorine-containing acrylic ester |
| JP4862374B2 (en) * | 2005-12-05 | 2012-01-25 | セントラル硝子株式会社 | Method for producing 4,4,4-trifluorobutenoic acid |
| HUE048141T2 (en) * | 2012-08-30 | 2020-07-28 | Daikin Ind Ltd | Method for producing a-fluoroacrylic acid ester |
| CN103058851B (en) * | 2012-11-06 | 2015-02-11 | 西安近代化学研究所 | Method for preparing 2-(trifluoromethyl) acrylic acid |
-
1982
- 1982-03-09 JP JP57035932A patent/JPS58154529A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58154529A (en) | 1983-09-14 |
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