JPH04117374A - Polyfluoroalkyl group-containing butenolide derivative and production thereof - Google Patents
Polyfluoroalkyl group-containing butenolide derivative and production thereofInfo
- Publication number
- JPH04117374A JPH04117374A JP23456990A JP23456990A JPH04117374A JP H04117374 A JPH04117374 A JP H04117374A JP 23456990 A JP23456990 A JP 23456990A JP 23456990 A JP23456990 A JP 23456990A JP H04117374 A JPH04117374 A JP H04117374A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- butenolide
- peroxide
- polyfluoroalkyl group
- group
- 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.)
- Pending
Links
- SQEBMLCQNJOCBG-HVHJFMEUSA-N (5s)-3-(hydroxymethyl)-5-methoxy-4-methyl-5-[(e)-2-phenylethenyl]furan-2-one Chemical class C=1C=CC=CC=1/C=C/[C@]1(OC)OC(=O)C(CO)=C1C SQEBMLCQNJOCBG-HVHJFMEUSA-N 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- 150000002240 furans Chemical class 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- FBMORZZOJSDNRQ-UHFFFAOYSA-N Demethoxy,B,HCl-Adriamycin Natural products C1C2C(=C)CCCC2(C)CC2(O)C1=C(C)C(=O)O2 FBMORZZOJSDNRQ-UHFFFAOYSA-N 0.000 abstract description 10
- JUTMAMXOAOYKHT-UHFFFAOYSA-N karrikinolide Natural products C1=COC=C2OC(=O)C(C)=C21 JUTMAMXOAOYKHT-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 3
- ILBCDLOQMRDXLN-UHFFFAOYSA-N furan-2-yloxy(trimethyl)silane Chemical compound C[Si](C)(C)OC1=CC=CO1 ILBCDLOQMRDXLN-UHFFFAOYSA-N 0.000 abstract description 3
- YGVPAHRKSAVCPT-UHFFFAOYSA-N triethyl(furan-2-yloxy)silane Chemical compound CC[Si](CC)(CC)OC1=CC=CO1 YGVPAHRKSAVCPT-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- UHASMEVRHWRZKF-UHFFFAOYSA-N [2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propanoyl] 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)OC(F)(C(F)(F)F)C(=O)OOC(=O)C(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F UHASMEVRHWRZKF-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- HJRXHKBZNQULJQ-UHFFFAOYSA-N 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane Chemical compound FC(F)(F)C(F)(F)C(Cl)(Cl)Cl HJRXHKBZNQULJQ-UHFFFAOYSA-N 0.000 description 1
- UGCSPKPEHQEOSR-UHFFFAOYSA-N 1,1,2,2-tetrachloro-1,2-difluoroethane Chemical compound FC(Cl)(Cl)C(F)(Cl)Cl UGCSPKPEHQEOSR-UHFFFAOYSA-N 0.000 description 1
- LVULLLDMOZXHRF-UHFFFAOYSA-N 1,2,2,3-tetrachloro-1,1,3,3-tetrafluoropropane Chemical compound FC(F)(Cl)C(Cl)(Cl)C(F)(F)Cl LVULLLDMOZXHRF-UHFFFAOYSA-N 0.000 description 1
- KTULQNFKNLFOHL-UHFFFAOYSA-N 1,2-dibromo-1,1,2,3,3,3-hexafluoropropane Chemical compound FC(F)(F)C(F)(Br)C(F)(F)Br KTULQNFKNLFOHL-UHFFFAOYSA-N 0.000 description 1
- OVZATIUQXBLIQT-UHFFFAOYSA-N 1,2-dibromo-1-chloro-1,2,2-trifluoroethane Chemical compound FC(F)(Br)C(F)(Cl)Br OVZATIUQXBLIQT-UHFFFAOYSA-N 0.000 description 1
- 102100022210 COX assembly mitochondrial protein 2 homolog Human genes 0.000 description 1
- 101000900446 Homo sapiens COX assembly mitochondrial protein 2 homolog Proteins 0.000 description 1
- 150000001265 acyl fluorides Chemical class 0.000 description 1
- -1 acyl fluorite Chemical compound 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- ZJRXSAYFZMGQFP-UHFFFAOYSA-N barium peroxide Chemical compound [Ba+2].[O-][O-] ZJRXSAYFZMGQFP-UHFFFAOYSA-N 0.000 description 1
- VIHAEDVKXSOUAT-UHFFFAOYSA-N but-2-en-4-olide Chemical compound O=C1OCC=C1 VIHAEDVKXSOUAT-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- KVBKAPANDHPRDG-UHFFFAOYSA-N dibromotetrafluoroethane Chemical compound FC(F)(Br)C(F)(F)Br KVBKAPANDHPRDG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、新規なポリフルオロアルキル基含有ブテノラ
イド誘導体及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel polyfluoroalkyl group-containing butenolide derivative and a method for producing the same.
〈従来の技術〉
有機化合物中に、ポリフルオロアルキル基を含有する化
合物は、耐熱性、撥水撥油性、生理活性等の有用な性質
を示すものとして注目をあつめている。特にブテノライ
ド類中に、ポリフルオロアルキル基が導入されたポリフ
ルオロアルキル基含有ブテノライド誘導体は、医薬、農
薬更には界面活性剤等の合成中間体として有用であると
考えられ注目されている。しかしながら前記ポリフルオ
ロアルキル基含有ブテノライド誘導体及びその製造方法
は殆ど知られていないのが現状である。<Prior Art> Among organic compounds, compounds containing polyfluoroalkyl groups are attracting attention as they exhibit useful properties such as heat resistance, water and oil repellency, and physiological activity. In particular, polyfluoroalkyl group-containing butenolide derivatives in which polyfluoroalkyl groups are introduced into butenolides are attracting attention because they are thought to be useful as synthetic intermediates for medicines, agricultural chemicals, and even surfactants. However, at present, little is known about the polyfluoroalkyl group-containing butenolide derivatives and the method for producing them.
〈発明が解決しようとする課題〉
本発明の目的は、医薬、農薬更には界面活性剤等の合成
中間体として利用可能なポリフルオロアルキル基含有ブ
テノライド誘導体及びその製造方法を提供することにあ
る。<Problems to be Solved by the Invention> An object of the present invention is to provide a polyfluoroalkyl group-containing butenolide derivative that can be used as a synthetic intermediate for medicines, agricultural chemicals, and surfactants, and a method for producing the same.
本発明の別の目的は、反応触媒及び特殊な装置を用いず
、高収率かつ容易にポリフルオロアルキル基含有ブテノ
ライド誘導体を製造する方法を提供することにある。Another object of the present invention is to provide a method for easily producing a polyfluoroalkyl group-containing butenolide derivative in high yield without using a reaction catalyst or special equipment.
く課題を解決するための、手段〉
本発明によれば、下記一般式（１）
（式中ｎは、０〜８の整数を示す）で表わされるポリフ
ルオロアルキル基含有ブテノライド誘導体が提供される
。Means for Solving the Problems> According to the present invention, a polyfluoroalkyl group-containing butenolide derivative represented by the following general formula (1) (wherein n represents an integer of 0 to 8) is provided. .
また本発明によれば、
下記一般式（Ｉｆ）
（式中ｎは、０〜８の整数を示す）で表わされる過酸化
ポリフルオロアルカノイルと、
下記一般式（ＩＩＩ）
（式中Ｒ１、Ｒ２及びＲ１は、炭素数１〜４のアルキル
基又はフェニル基を示す）で表わされるフラン類とを反
応させることを特徴とする前記一般式（Ｉ）で表わされ
るポリフルオロアルキル基含有ブテノライド誘導体の製
造方法が提供される。According to the present invention, a polyfluoroalkanoyl peroxide represented by the following general formula (If) (in which n represents an integer of 0 to 8) and the following general formula (III) (in which R1, R2 and R1 is an alkyl group having 1 to 4 carbon atoms or a phenyl group). is provided.
以下本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明のポリフルオロアルキル基含有ブテノライド誘導
体は、下記一般式（Ｉ）で表わすことができ、
式中ｎはＯ〜８の整数を示す。この際ｎが９以上の場合
には、溶媒に対する溶解性が低下するので使用できない
。前記一般式（１）で表わされるポリフルオロアルキル
基含有ブテノライド誘導体としては、具体的には、例え
ば、５−（ペルフルオロ−１′−メチル−２′−オキサ
ペンチル）ブテノライド、５−（ペルフルオロ−１’
、４’ −ジメチル−２’ 、５’−ジオキサオクチル
）ブテノライド、５−（ペルフルオロ−１’ 、４’
、７’−トリメチル−２’ 、５’ 、８’ −トリオ
キサウンデシル）ブテノライド、５−（ペルフルオロ−
１’ 、４’ 、７’ 、１０’ −テトラメチル−２
′５’、８’ １１’ −テトラオキサテトラデシ
ル）ブテノライド、５−（ペルフルオロ−１’ 、４’
７’ １０’、１３’ −ペンタメチル−２′５’
、８’ １１’、１４’−ペンタオキサヘプタデシル
）ブテノライド等を好ましく挙げることができる。The polyfluoroalkyl group-containing butenolide derivative of the present invention can be represented by the following general formula (I), where n represents an integer of 0 to 8. In this case, if n is 9 or more, it cannot be used because the solubility in the solvent decreases. Specific examples of the polyfluoroalkyl group-containing butenolide derivative represented by the general formula (1) include 5-(perfluoro-1'-methyl-2'-oxapentyl)butenolide, 5-(perfluoro-1 '
, 4'-dimethyl-2', 5'-dioxaoctyl)butenolide, 5-(perfluoro-1', 4')
, 7'-trimethyl-2', 5', 8'-trioxaundecyl)butenolide, 5-(perfluoro-
1', 4', 7', 10'-tetramethyl-2
'5',8'11'-tetraoxatetradecyl)butenolide,5-(perfluoro-1',4'
7'10',13'-pentamethyl-2'5'
, 8'11',14'-pentaoxaheptadecyl) butenolide and the like can be preferably mentioned.
本発明におけるポリフルオロアルキル基含有ブテノライ
ド誘導体の製造方法は、特定の過酸化ポリフルオロアル
カノイルと特定のフラン類とを、反応させることを特徴
とする。The method for producing a polyfluoroalkyl group-containing butenolide derivative in the present invention is characterized by reacting a specific polyfluoroalkanoyl peroxide with a specific furan.
本発明の製造方法において原料成分として用いる過酸化
ポリフルオロアルカノイルは下記−線式％式％
式中ｎはＯ〜８の整数を示す。この際ｎが９以上の場合
には、溶媒の存在下において反応させる際に前記過酸化
ポリフルオロアルカノイルの溶解性に問題が生じるので
使用できない。前記一般式（ＩＩ）で表わされる過酸化
ポリフルオロアルカノイル中の
を具体的に列挙すると、
である。The polyfluoroalkanoyl peroxide used as a raw material component in the production method of the present invention is represented by the following -linear % formula % where n represents an integer of O to 8. In this case, if n is 9 or more, it cannot be used because a problem arises in the solubility of the polyfluoroalkanoyl peroxide when reacting in the presence of a solvent. A specific list of the polyfluoroalkanoyl peroxides represented by the general formula (II) is as follows.
前記過酸化ポリフルオロアルカノイルを調製するには、
例えば、下記−数式（ＩＶ）
（式中ｎは０〜８の整数を示す）で表わされるアシルフ
ルオリドを、水酸化ナトリウム、水酸化カリウム、炭酸
水素ナトリウム、炭酸水素カリウム、炭酸ナトリウム、
炭酸カリウム及びこれらの混合物等からなる群より選択
される化合物の存在下にて、過酸化水素と反応させる方
法若しくは前記−数式（ＩＶ）で表わされるアシルフル
オリトを過酸化ナトリウム、過酸化カリウム、過酸化バ
リウム及びこれらの混合物等からなる群より選択される
化合物と反応させる方法等により得る事ができる。To prepare the polyfluoroalkanoyl peroxide,
For example, an acyl fluoride represented by the following formula (IV) (wherein n represents an integer of 0 to 8) can be converted into sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate,
A method of reacting with hydrogen peroxide in the presence of a compound selected from the group consisting of potassium carbonate, mixtures thereof, etc., or - a method of reacting an acyl fluorite represented by formula (IV) with sodium peroxide, potassium peroxide, It can be obtained by a method of reacting with a compound selected from the group consisting of barium peroxide, mixtures thereof, and the like.
この際、反応温度は、反応を速やかに行うために一３０
〜１００℃とするのが好ましく、また反応時間は、５分
〜１０時間の範囲とするのが経済的にも好ましい。At this time, the reaction temperature was set at -30° C. to quickly carry out the reaction.
The temperature is preferably 100° C. to 100° C., and the reaction time is preferably 5 minutes to 10 hours from an economic standpoint.
本発明の製造方法において、前記過酸化ポリフルオロア
ルカノイルと反応させるフラン類は、下記−数式（ＤＩ
）で表わすことができ、式中Ｒ工、Ｒ２及びＲ３は、炭
素数１〜４のアルキル基又はフェニル基を示す。この際
Ｒ１、Ｒ２及びＲ３の少くとも１つが炭素数５以上のア
ルキル基の場合には、製造が困難である。なお、この際
２ （５Ｈ）−フラノンを用いても、全くポリフルオロ
アルキル基は導入されないので、前記−数式（ｍ）で表
わされるフラン類を用いる必要がある。In the production method of the present invention, the furan to be reacted with the polyfluoroalkanoyl peroxide is expressed by the following formula (DI
), where R, R2 and R3 represent an alkyl group having 1 to 4 carbon atoms or a phenyl group. In this case, if at least one of R1, R2 and R3 is an alkyl group having 5 or more carbon atoms, production is difficult. In this case, even if 2 (5H)-furanone is used, no polyfluoroalkyl group is introduced, so it is necessary to use furans represented by the above-mentioned formula (m).
前記−数式（ＩＩ）で表わされるフラン類としては、例
えば２−トリメチルシロキシフラン、２−トリエチルシ
ロキシフラン、２−ジフェニル−ｔ−ブチルシロキシフ
ラン等を好ましく挙げることができる。Preferred examples of the furans represented by formula (II) include 2-trimethylsiloxyfuran, 2-triethylsiloxyfuran, and 2-diphenyl-t-butylsiloxyfuran.
本発明の製造方法において、前記過酸化ポリフルオロア
ルカノイルと前記フラン類との仕込みモル比は、１：０
．２〜１ｏが好ましく、特に１：０．５〜５であること
が好ましい。前記フラン類の仕込みモル比が０．２未満
の場合には、生成するポリフルオロアルキル基含有ブテ
ノライド誘導体の収率が低下し、また１０を超える場合
には反応終了後において未反応のブテノライド類が多量
に残存し、目的とする生成物の単離が困難となるので好
ましくない。また、反応は常圧で行なうことが可能であ
り、且つ反応温度は一２０〜１５０℃の範囲が好ましく
、０〜１００℃の範囲が特に好ましい。前記反応温度が
一２０℃未満の場合には反応時間に長時間を要し、１５
０℃を超えると反応時の圧力が高くなり、反応操作が困
難であるので好ましくない。更に反応時間は３０分〜２
０時間の範囲が好ましく、工業的には３〜１０時間の範
囲とするのが特に好ましい。In the production method of the present invention, the molar ratio of the polyfluoroalkanoyl peroxide and the furans is 1:0.
．． The ratio is preferably 2 to 1o, particularly preferably 1:0.5 to 5. If the charging molar ratio of the furans is less than 0.2, the yield of the polyfluoroalkyl group-containing butenolide derivative to be produced will decrease, and if it exceeds 10, unreacted butenolides will be removed after the reaction is completed. This is not preferred because a large amount remains, making it difficult to isolate the desired product. Further, the reaction can be carried out at normal pressure, and the reaction temperature is preferably in the range of -20 to 150°C, particularly preferably in the range of 0 to 100°C. If the reaction temperature is less than 120°C, the reaction time will take a long time, and the
If the temperature exceeds 0°C, the pressure during the reaction will be high and the reaction operation will be difficult, which is not preferable. Furthermore, the reaction time is 30 minutes to 2
A range of 0 hours is preferred, and a range of 3 to 10 hours is particularly preferred industrially.
本発明の製造方法では、前記種々の反応条件下において
、前記過酸化ポリフルオロアルカノイルと前記フラン類
とを反応させることにより、目的とするポリフルオロア
ルキル基含有ブテノライド誘導体を製造することができ
るが、前記過酸化ポリフルオロアルカノイルの取扱いを
容易にし、また反応をより円滑に行なうために溶媒を用
いて反応させるのが好ましい。前記溶媒としては、ハロ
ゲン化脂肪族溶媒が好ましく、具体的には例えば、２−
クロロ−１，２−ジブロモ−１，１，２−トリフルオロ
エタン、１，２−ジブロモへキサフルオロプロパン、１
，２−ジブロモテトラフルオロエタン、１，１−ジフル
オロテトラクロロエタン、１．２−ジフルオロテトラク
ロロエタン、フルオロトリクロロメタン、ヘプタフルオ
ロ−２，３゜３−トリクロロブタン、１，１，１，３−
テトラクロロテトラフルオロプロパン、１，１．１−ト
リクロロペンタフルオロプロパン、１．１．２−トリク
ロロトリフルオロエタン等を好ましく挙げることができ
、工業的には、１，１．２−トリクロロトリフルオロエ
タンが特に好ましい。また前記溶媒の仕込み量は、前記
過酸化ポリフルオロアルカノイルの濃度が前記溶媒に対
して１〜３０重量％の範囲となるように調整するのが望
ましい。In the production method of the present invention, the desired polyfluoroalkyl group-containing butenolide derivative can be produced by reacting the polyfluoroalkanoyl peroxide and the furans under the various reaction conditions. In order to facilitate the handling of the polyfluoroalkanoyl peroxide and to carry out the reaction more smoothly, it is preferable to carry out the reaction using a solvent. The solvent is preferably a halogenated aliphatic solvent, specifically, for example, 2-
Chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane, 1
, 2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3°3-trichlorobutane, 1,1,1,3-
Preferred examples include tetrachlorotetrafluoropropane, 1,1.1-trichloropentafluoropropane, 1.1.2-trichlorotrifluoroethane, etc., and 1,1.2-trichlorotrifluoroethane is used industrially. is particularly preferred. Further, the amount of the solvent to be charged is desirably adjusted so that the concentration of the polyfluoroalkanoyl peroxide is in the range of 1 to 30% by weight based on the solvent.
本発明の製造方法により得られる反応生成物は蒸留、カ
ラムクロマトグラフィー等の公知の方法で精製すること
が可能である。The reaction product obtained by the production method of the present invention can be purified by known methods such as distillation and column chromatography.
〈発明の効果〉
本発明のポリフルオロアルキル基含有ブテノライド誘導
体は新規な化合物であり、医薬、農薬更には界面活性剤
等の合成中間体として利用することができる。また本発
明の製造方法においては、短時間で高収率かつ容易に、
しかも反応触媒及び特殊な装置を使用せずにポリフルオ
ロアルキル基含有ブテノライド誘導体を製造することが
できる。<Effects of the Invention> The polyfluoroalkyl group-containing butenolide derivative of the present invention is a novel compound and can be used as a synthetic intermediate for medicines, agricultural chemicals, and even surfactants. In addition, in the production method of the present invention, in a short time, with high yield, and easily,
Moreover, a polyfluoroalkyl group-containing butenolide derivative can be produced without using a reaction catalyst or special equipment.
〈実施例〉
以下本発明を実施例により更に詳しく説明するが、本発
明はこれらに限定されるものではない。<Examples> The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.
失胤叢よ
過酸化ペルフルオロ−２−メチル−３−オキサヘキサノ
イル７．９０ｇを含む１，１．２−トリクロロトリフル
オロエタン溶液９０ｇ中に、２−トリメチルシロキシフ
ラン３ 、７２ ｇ （２４ｍｍｏｌ）を、添加混合し
、窒素気流下にて、４０℃で、５時間反応を行った。反
応終了後、反応混合物を、５％水酸化ナトリウム水溶液
及び水でそれぞれ２回洗浄を行なったのち、硫酸マグネ
シウムを用いて乾燥した。次いで蒸留を行ない、下記構
造式で示す、５−（ペルフルオロ−１′−メチル−２′
−オキサペンチル）ブテノライドを収率７８％で得た。Into 90 g of 1,1,2-trichlorotrifluoroethane solution containing 7.90 g of perfluoro-2-methyl-3-oxahexanoyl peroxide, 3.72 g (24 mmol) of 2-trimethylsiloxyfuran was added. , were added and mixed, and the reaction was carried out at 40° C. for 5 hours under a nitrogen stream. After the reaction was completed, the reaction mixture was washed twice with a 5% aqueous sodium hydroxide solution and twice with water, and then dried using magnesium sulfate. Next, distillation is performed to obtain 5-(perfluoro-1'-methyl-2'
-oxapentyl)butenolide was obtained in a yield of 78%.
（以下、収率は全て過酸化物に対する収率である。）得
られた化合物についての各種分析結果を以下に示す。(Hereinafter, all yields are based on peroxide.) Various analysis results of the obtained compounds are shown below.
ＭＳ ｒａ／ｚ ３６８
Ｅｘａｃｔ ＭＡＳＳ ｍ／ｚ ３６７．９９０９
（実測値）Ｃ，Ｈ３Ｐ工、Ｏ，； ３６７．９９０５（
理論値）ＩＲ（ｃｍ−’ ）１８００ （Ｃ＝ｏ） 、
１３２０ （ＣＦ３）、１３４０ （ＣＦ３）−１２３
０（ＣＦ２）
１Ｈ−ＮＭＲ（ＣＤＣＩ３） δ５．３１（ＩＨ，ｎ
＋）、６．４０，７．５１（ＡＢｑ。MS ra/z 368 Exact MASS m/z 367.9909
(Actual measurement value) C, H3P engineering, O,; 367.9905 (
Theoretical value) IR (cm-') 1800 (C=o),
1320 (CF3), 1340 (CF3)-123
0 (CF2) 1H-NMR (CDCI3) δ5.31 (IH, n
+), 6.40, 7.51 (ABq.
Ｊ＝５．３Ｈｚ）
１” Ｃ−ＮＭＲ（ＣＤＣＩ、 ）δ７６．５０．１２
５．１０．１４５．８０．１７０．５０”Ｆ−ＮＭＲ（
ＣＤＣＩ３；ｅｘｔ、ｃＦ、ｃＯＯＨ）δ −２，０〜
−９，０（８Ｆ） 、−５１，０（ＩＦ） 、−５４，
１（２Ｆ）去ＪＬＩλ
過酸化ペルフルオロ−２−メチル−３−オキサヘキサノ
イルを過酸化ペルフルオロ−２，５−ジメチル−３，６
−シオキサヘキサノイルに代えた以外は実施例１と同様
に反応及び精製を行ない。J=5.3Hz) 1” C-NMR (CDCI, )δ76.50.12
5.10.145.80.170.50"F-NMR (
CDCI3; ext, cF, cOOH) δ -2,0~
-9,0 (8F), -51,0 (IF), -54,
1 (2F) left JLIλ perfluoro-2-methyl-3-oxahexanoyl peroxide to perfluoro-2,5-dimethyl-3,6 peroxide
The reaction and purification were carried out in the same manner as in Example 1 except that -thioxahexanoyl was used instead.
下記構造式で示す、５−（ペルフルオロ−１′４′−ジ
メチル−２’ 、５’ −ジオキサオクチル）ブテノラ
イドを収率９４％で得た。5-(perfluoro-1'4'-dimethyl-2',5'-dioxaoctyl)butenolide shown by the following structural formula was obtained in a yield of 94%.
各分析結果を以下に示す。The results of each analysis are shown below.
ＭＳ ｍ／ｚ ５３４（Ｍ”）
Ｅｘａｃｔ ＭＡＳＳ ＊／ｚ ５３３．９７６１
（実測値）Ｃ１□Ｈ３Ｆ１７０４； ５３３．９７５８
（理論値）ＩＲ（ｃｍ−１）１８００（Ｃ＝Ｏ）、１２
２０（ＣＦよ）１Ｈ−ＮＭＲ（ＣＤＣＩ、 ） ６５
．３２（ＬＨ，＋ａ）、６．４７，７．５６（ＡＢｑ、
２Ｈ。MS m/z 534 (M”) Exact MASS */z 533.9761
(Actual measurement value) C1□H3F1704; 533.9758
(Theoretical value) IR (cm-1) 1800 (C=O), 12
20 (CF) 1H-NMR (CDCI, ) 65
．． 32 (LH, +a), 6.47, 7.56 (ABq,
2H.
Ｊ＝５．７Ｈｚ）
１３Ｃ−ＮＭＲ（ＣＤＣＩ、）δ８２．７２．１２５．
９０．１４７．６３．１７０．０５去ｔ３
過酸化ペルフルオロ−２−メチル−３−オキサヘキサノ
イルを過酸化ペルフルオロ−２，５，８−トリメチル−
３，６，９−）−リオキサドデカノイルに代えた以外は
実施例１と同様に反応及び精製を行ない１．５−（ペル
フルオロ−１’ 、４’７′−トリメチル−２’ 、５
’ 、８’ −トリオキサウンデシル）ブテノライドを
収率９４％で得た。J=5.7Hz) 13C-NMR (CDCI,) δ82.72.125.
90.147.63.170.05 t3 Perfluoro-2-methyl-3-oxahexanoyl peroxide was converted to perfluoro-2,5,8-trimethyl-peroxide.
The reaction and purification were carried out in the same manner as in Example 1 except that 3,6,9-)-rioxadodecanoyl was used.
',8'-trioxaundecyl)butenolide was obtained in a yield of 94%.
各分析結果を以下に示す。The results of each analysis are shown below.
ＭＳ ｍＨｚ ７００（Ｍ”）
Ｅｘａｃｔ ＭＡＳＳ ｍＨｚ ６９９．９６１０
（実測値）Ｃ工、Ｈ，Ｆ２３０． ； ６９９．９６
１１（理論値）ＩＲ（ｃｍ−′″）１８００（Ｃ＝Ｏ）
、１２３０（ＣＦｚ）、１３２０（ＣＦ３）。MS mHz 700 (M”) Exact MASS mHz 699.9610
(Actual measurement value) C work, H, F230. ; 699.96
11 (theoretical value) IR (cm-''') 1800 (C=O)
, 1230 (CFz), 1320 (CF3).
１３４０（ＣＦ３）
１Ｈ−ＮＭＲ（ＣＤＣＩ、 ） ６５．２２（ＬＨ，ｍ
）、６．５０，７．７０（ＡＢｑ、２Ｈ。1340 (CF3) 1H-NMR (CDCI, ) 65.22 (LH, m
), 6.50, 7.70 (ABq, 2H.
Ｊ＝５．２Ｈｚ）
１３Ｃ−ＮＭＲ（ＣＤＣＩ３） ６８２．１０，１２５
．４４，１４７．０９，１６９．９８”Ｆ−ＮＭＲ（Ｃ
ＤＣ１３；ｅｘｔ、ＣＦ３ＣＯ０Ｈ）δ−２，５〜−９
，５（１８Ｆ） 、−５４，０（２Ｆ） 、−６７，１
（２Ｆ）去」１１（
過酸化ペルフルオロ−２−メチル−３−オキサヘキサノ
イルを過酸化ペルフルオロ−２，５，８゜１１−テトラ
メチル−３，６，９，１２−テトラオキサペンタデカノ
イルに代えた以外は実施例１と同様に反応及び精製を行
ない、下記構造式で示す、５−（ペルフルオロ−１’
、４’ 、７’ 、１０′−テトラメチル−２’ 、５
’ 、８’ 、１１’−テトラオキサテトラデシル）ブ
テノライドを収率８６％で得た。J=5.2Hz) 13C-NMR (CDCI3) 682.10,125
．． 44,147.09,169.98"F-NMR (C
DC13; ext, CF3CO0H) δ-2,5 to -9
,5(18F) ,-54,0(2F) ,-67,1
(2F) 11 (Perfluoro-2-methyl-3-oxahexanoyl peroxide to perfluoro-2,5,8゜11-tetramethyl-3,6,9,12-tetraoxapentadecanoyl The reaction and purification were carried out in the same manner as in Example 1 except for the following changes, and 5-(perfluoro-1'
, 4', 7', 10'-tetramethyl-2', 5
',8',11'-tetraoxatetradecyl)butenolide was obtained in a yield of 86%.
各分析結果を以下に示す。The results of each analysis are shown below.
ＭＳ ８６６（Ｍ”）
Ｅｘａｃｔ ＭＡＳＳ ｍＨｚ ８６５．９４６１
（実測値）Ｃ１，Ｈ，Ｆ２．Ｏ，； ８６５，９４６７
（理論値）ＩＲ（ｃｍ−’） １８００（Ｃ＝Ｏ）、
１３４０（ＣＦ３）、１３２０（ＣＦ３）。MS 866 (M”) Exact MASS mHz 865.9461
(Actual measurements) C1, H, F2. O,; 865,9467
(Theoretical value) IR (cm-') 1800 (C=O),
1340 (CF3), 1320 (CF3).
１２３０（ＣＦ２）
” Ｈ−ＮＭＲ（ＣＤＣＩ、 ）６５．２９（ｎ＋、Ｉ
Ｈ） 、６．４０，７．８８（ＡＢｑ、２Ｈ。1230 (CF2) ” H-NMR (CDCI, ) 65.29 (n+, I
H), 6.40, 7.88 (ABq, 2H.
Ｊ＝５．３Ｈｚ）
” ３Ｃ−ＮＭＲ（ＣＤＣＩ、 ）δ８２．８９．１２
５．００．１４７．９８．１６７．３３”Ｆ−ＮＭＲ（
ＣＤＣＩ、 ；ｅｘｔ、ＣＦ３ＣＯ０Ｈ）δ−２，１〜
−９，９（２３Ｆ） 、−５３，９（２Ｆ） 、−５６
，０（ＩＦ）−６７，９（３Ｆ）J=5.3Hz) 3C-NMR (CDCI, )δ82.89.12
5.00.147.98.167.33”F-NMR (
CDCI, ;ext, CF3CO0H) δ-2,1~
-9,9 (23F), -53,9 (2F), -56
,0(IF)-67,9(3F)
Claims (1)
ルオロアルキル基含有ブテノライド誘導体。 ２）下記一般式（II） ▲数式、化学式、表等があります▼・・・・（II） （式中ｎは、０〜８の整数を示す）で表わされる過酸化
ポリフルオロアルカノイルと、 下記一般式（III） ▲数式、化学式、表等があります▼・・・（III） （式中Ｒ＿１、Ｒ＿２及びＲ＿３は、炭素数１〜４のア
ルキル基又はフェニル基を示す）で表わされるフラン類
とを反応させることを特徴とする請求項１記載のポリフ
ルオロアルキル基含有ブテノライド誘導体の製造方法。[Claims] 1) Polyfluoroalkyl represented by the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (in the formula, n represents an integer from 0 to 8) Group-containing butenolide derivatives. 2) The following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(II) (In the formula, n represents an integer from 0 to 8) Polyfluoroalkanoyl peroxide and the following: General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(III) (In the formula, R_1, R_2 and R_3 represent an alkyl group or a phenyl group having 1 to 4 carbon atoms) Furans 2. The method for producing a polyfluoroalkyl group-containing butenolide derivative according to claim 1, which comprises reacting with a polyfluoroalkyl group-containing butenolide derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23456990A JPH04117374A (en) | 1990-09-06 | 1990-09-06 | Polyfluoroalkyl group-containing butenolide derivative and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23456990A JPH04117374A (en) | 1990-09-06 | 1990-09-06 | Polyfluoroalkyl group-containing butenolide derivative and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04117374A true JPH04117374A (en) | 1992-04-17 |
Family
ID=16973072
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23456990A Pending JPH04117374A (en) | 1990-09-06 | 1990-09-06 | Polyfluoroalkyl group-containing butenolide derivative and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04117374A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100441007B1 (en) * | 2001-11-27 | 2004-07-21 | 삼성전자주식회사 | Refrigerator |
| US8850842B2 (en) | 2003-03-28 | 2014-10-07 | Lg Electronics Inc. | Refrigerator |
-
1990
- 1990-09-06 JP JP23456990A patent/JPH04117374A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100441007B1 (en) * | 2001-11-27 | 2004-07-21 | 삼성전자주식회사 | Refrigerator |
| US8850842B2 (en) | 2003-03-28 | 2014-10-07 | Lg Electronics Inc. | Refrigerator |
| US8850843B2 (en) | 2003-03-28 | 2014-10-07 | Lg Electronics Inc. | Refrigerator |
| US8850841B2 (en) | 2003-03-28 | 2014-10-07 | Lg Electronics Inc. | Refrigerator |
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