JPH04159273A - Fluoroalkyl group-containing tetrahydrofuran derivative and its production - Google Patents
Fluoroalkyl group-containing tetrahydrofuran derivative and its productionInfo
- Publication number
- JPH04159273A JPH04159273A JP28418290A JP28418290A JPH04159273A JP H04159273 A JPH04159273 A JP H04159273A JP 28418290 A JP28418290 A JP 28418290A JP 28418290 A JP28418290 A JP 28418290A JP H04159273 A JPH04159273 A JP H04159273A
- Authority
- JP
- Japan
- Prior art keywords
- fluoroalkyl group
- formula
- tetrahydrofuran derivative
- integer
- containing tetrahydrofuran
- 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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims description 33
- 125000003709 fluoroalkyl group Chemical group 0.000 title claims description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002978 peroxides Chemical class 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 4
- 239000002904 solvent Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000005871 repellent Substances 0.000 abstract description 4
- 230000002940 repellent Effects 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
- HBYDRXVFGDTGBN-UHFFFAOYSA-N 3-(trifluoromethyl)oxolane Chemical compound FC(F)(F)C1CCOC1 HBYDRXVFGDTGBN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- JUTIIYKOQPDNEV-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl 2,2,3,3,4,4,4-heptafluorobutaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)F JUTIIYKOQPDNEV-UHFFFAOYSA-N 0.000 description 5
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-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
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000000047 product Substances 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
- IQJADVFBZGJGSI-UHFFFAOYSA-N 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane Chemical compound FC(F)(Cl)C(F)(F)C(Cl)(Cl)Cl IQJADVFBZGJGSI-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
- 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
- LFCQGZXAGWRTAL-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoyl 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptaneperoxoate Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LFCQGZXAGWRTAL-UHFFFAOYSA-N 0.000 description 1
- PBYGGJOUDQSPDM-UHFFFAOYSA-N 2-nonyloxolane Chemical compound CCCCCCCCCC1CCCO1 PBYGGJOUDQSPDM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 group 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 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- -1 alkanoyl peroxide Chemical class 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
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 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〉
一本発明は、フルオロアルキル基含有テトラヒドロフラ
ン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 fluoroalkyl group-containing tetrahydrofuran derivative and a method for producing the same.
〈従来の技術〉
有機化合物中に、フルオロアルキル基を含有する化合物
は、撥水撥油性、生理活性等の有用な性質を示すものと
して注目を集めている。特にテトラヒドロフランにフル
オロアルキル基が導入された化合物は、撥水撥油剤、界
面活性剤、医薬、農薬等の合成中間体として有用である
と考えられている。フルオロアルキル基が導入されたテ
トラヒドロフラン誘導体としては、２位に−ＣＦ、 Ｃ
ＦＨＣＦ、が導入された化合物が、Ｊ、 Ｆｌｕｏｒｉ
ｎｅ Ｃｈｅｍ、ｉｆｌＬ４０９〜４１９ （Ｉ９９０
）において開示されている。しかしながら、テトラヒド
ロフランの３位にフルオロアルキル基が導入されたテト
ラヒドロフラン誘導体及びその製造方法に関しては、全
く知られていないのが現状である。<Prior Art> Among organic compounds, compounds containing a fluoroalkyl group are attracting attention as they exhibit useful properties such as water and oil repellency and physiological activity. In particular, compounds in which a fluoroalkyl group is introduced into tetrahydrofuran are considered to be useful as synthetic intermediates for water and oil repellents, surfactants, medicines, agricultural chemicals, and the like. As a tetrahydrofuran derivative into which a fluoroalkyl group is introduced, -CF, C
A compound into which FHCF was introduced was published in J. Fluori
ne Chem, iflL409~419 (I990
). However, at present, nothing is known about a tetrahydrofuran derivative in which a fluoroalkyl group is introduced at the 3-position of tetrahydrofuran and a method for producing the same.
〈発明が解決しようとする課題〉
本発明め目的は、撥水撥油剤、界面活性剤、医薬、農薬
等の合成中間体として利用可能なフルオロアルキル基含
有テトラヒドロフラン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 fluoroalkyl group-containing tetrahydrofuran derivative that can be used as a synthetic intermediate for water and oil repellents, surfactants, medicines, agricultural chemicals, etc., and a method for producing the same. It is in.
本発明の別の目的は、反応触媒及び特殊な装置を用いず
、高収率かつ容易にフルオロアルキル基含有テトラヒド
ロフラン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 fluoroalkyl group-containing tetrahydrofuran derivative in high yield without using a reaction catalyst or special equipment.
〈課題を解決するための手段〉 本発明によれば、下記一般式（Ｉ） しＦ、 Ｌｌ’。〈Means for solving problems〉 According to the present invention, the following general formula (I) F, Ll'.
を示す（但しＸは、フッ素原子、塩素原子又は水素原子
を示し、ｎは１〜１ｏの整数を、ｍはＯ〜８の整数を示
す）コで表わされるフルオロアルキル基含有テトラヒド
ロフラン誘導体が提供されるる。(wherein, X represents a fluorine atom, a chlorine atom, or a hydrogen atom, n represents an integer of 1 to 1o, and m represents an integer of O to 8). Ruru.
また本発明によれば、下記一般式（ＩＩ）を示す（但し
Ｘは、フッ素原子、塩素原子又は水素原子を示し、ｎは
１〜１０の整数を、ｍはＯ〜８の整数を示す）］で表わ
されるフルオロアルカノイルペルオキシドと、２，５−
ジヒドロフランとを反応させることを特徴とする前記一
般式（Ｉ）で表わされるフルオロアルキル基含有テトラ
ヒドロフラン誘導体の製造方法が提供される。According to the present invention, the following general formula (II) is represented (wherein, X represents a fluorine atom, a chlorine atom, or a hydrogen atom, n represents an integer of 1 to 10, and m represents an integer of O to 8). ] and 2,5-
There is provided a method for producing a fluoroalkyl group-containing tetrahydrofuran derivative represented by the general formula (I), which comprises reacting the derivative with dihydrofuran.
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.
本発明のフルオロアルキル基含有テトラヒドロフラン誘
導体は、下記一般式（Ｉ）で表わすことができ、
を示す（但しＸは、フッ素原子、塩素原子又は水素原子
を示し、ｎは１〜１０の整数を、ｍは０〜８の整数を示
す）。この際ｎが１１以上の整数若しくはｍが９以上の
整数の場合には、溶媒に対する溶解性が低下するので使
用できない。The fluoroalkyl group-containing tetrahydrofuran derivative of the present invention can be represented by the following general formula (I), where X represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n represents an integer of 1 to 10. m represents an integer from 0 to 8). In this case, if n is an integer of 11 or more, or if m is an integer of 9 or more, the solubility in the solvent will decrease, so they cannot be used.
前記一般式（Ｉ）で表わされるフルオロアルキル基含有
テトラヒドロフラン誘導体のＲＦを具体的に列挙すると
、ＣＦ、−、Ｆ（ＣＦ２＋２゜Ｆ（ＣＦ２−）−、、Ｆ
（ＣＦ２−）−、、Ｆ（ＣＦ、＋、。The RF of the fluoroalkyl group-containing tetrahydrofuran derivative represented by the general formula (I) is specifically listed as follows: CF, -, F(CF2+2°F(CF2-)-, F
(CF2−)−,,F(CF,+,.
Ｆ（ＣＦ２＋、、Ｆ（ＣＦ２−）、、Ｆ（ＣＦ２＋ｅ。F(CF2+,,F(CF2-),,F(CF2+e.
ｐ （ｃ Ｆ２ ＋ ＊ 、Ｆ （ｃ Ｆ２＋ １゜、
ＨＣＦ、−。p (c F2 + *, F (c F2+ 1°,
HCF, -.
Ｈ（ＣＦ２＋２．Ｈ（ＣＦ、＋３．Ｈ（ＣＦ２＋４゜Ｈ
（ｃ Ｆ ｍす５．Ｈ（ＣＦ、＋６．Ｈ（ＣＦ２＋、。H(CF2+2.H(CF,+3.H(CF2+4゜H)
(c F msu5.H(CF, +6.H(CF2+,.
Ｈ（ＣＦ、＋−，、Ｈ（ＣＦ２−）−、、Ｈ（ＣＦ２＋
、。。H(CF, +-,, H(CF2-)-,, H(CF2+
,. .
ＣｌＣＦ２−、Ｃ１（ＣＦ２＋２．Ｃ１（ＣＦ２−）−
、。ClCF2-, C1(CF2+2.C1(CF2-)-
,.
ｃ ｌ （ＣＦ２−）−、、Ｃｌ （ＣＦ２−３−、、
Ｃｌ （ＣＦ２＋、。c l (CF2-)-, Cl (CF2-3-,,
Cl (CF2+,.
Ｃｌ （ＣＦ２−）−、、Ｃ１（ＣＦ２＋、、Ｃｌ （
ＣＦ２＋、。Cl(CF2−)−,,C1(CF2+,,Cl(
CF2+,.
である。It is.
前記一般式（Ｉ）で表わされるフルオロアルキル基含有
テトラヒドロフラン誘導体としては例えば、３−トリフ
ルオロメチルテトラヒドロフラン。Examples of the fluoroalkyl group-containing tetrahydrofuran derivative represented by the general formula (I) include 3-trifluoromethyltetrahydrofuran.
３−ペルフルオロエチルテトラヒドロフラン、３−ペル
フルオロプロピルテトラヒドロフラン、３−ペルフルオ
ロブチルテトラヒドロフラン、３−ペルフルオロペンチ
ルテトラヒドロフラン、３−ペルフルオロへキシルテト
ラヒドロフラン、３−ベルフルオロへブチルテトラヒド
ロフラン、３−ベルフルオロオクチルテトラヒドロフラ
ン、３−ベルフルオロノニルテトラヒドロフラン、３−
ペルフルオロデシルテトラヒドロフラン、３−（ペルフ
ルオロ−１′−メチル−２′−オキサペンチル）テトラ
ヒドロフラン、３−（ペルフルオロ−１’ 、４’ −
ジメチル−２’ 、５’ −ジオキサオクチル）テトラ
ヒドロフラン、３−（ペルフルオロ−１’ 、４’ 、
７’−トリメチル−２７，５／ 。3-Perfluoroethyltetrahydrofuran, 3-perfluoropropyltetrahydrofuran, 3-perfluorobutyltetrahydrofuran, 3-perfluoropentyltetrahydrofuran, 3-perfluorohexyltetrahydrofuran, 3-perfluorohexyltetrahydrofuran, 3-perfluorooctyltetrahydrofuran, 3-perfluoro Nonyltetrahydrofuran, 3-
Perfluorodecyltetrahydrofuran, 3-(perfluoro-1'-methyl-2'-oxapentyl)tetrahydrofuran, 3-(perfluoro-1',4'-
dimethyl-2',5'-dioxaoctyl)tetrahydrofuran, 3-(perfluoro-1',4',
7'-trimethyl-27,5/.
８１−トリオキサウンデシル）テトラヒドロフラ１′
ン等を好ましく挙げることができる。81-trioxaundecyl)tetrahydrofura 1'
Preferred examples include the following.
本発明のフルオロアルキル基含有テトラヒドロフラン誘
導体の製造方法においては特定のフルオロアルカノイル
ペルオキシドと２，５−ジヒドロフランとを反応させる
ことを特徴とする。The method for producing a fluoroalkyl group-containing tetrahydrofuran derivative of the present invention is characterized by reacting a specific fluoroalkanoyl peroxide with 2,5-dihydrofuran.
本発明の製造方法において用いるフルオロアルカノイル
ペルオキシドは下記一般式（ＩＩ）で表わすことができ
、
を示す（但しＸは、フッ素原子、塩素原子又は水素原子
を示し、ｎは１〜１０の整数を、ｍはＯ〜８の整数を示
す）。この際ｎが１１以上の場合若しくはｍが９以上の
場合には溶媒に対する溶解性が低下し、溶媒の存在下に
おいて反応させる際に前記一般式（ＩＩ）にて示される
フルオロアルカノイルペルオキシドの溶解性に問題が生
じるので使用できない。前記一般式（ｎ）で表わされる
フルオロアルカノイルペルオキシドのＲ２は、具体的に
は、前記一般式（Ｉ）で表わされるフルオロアルキル基
含有テトラヒドロフラン誘導体におけるＲ、と同様であ
る。The fluoroalkanoyl peroxide used in the production method of the present invention can be represented by the following general formula (II), where X represents a fluorine atom, a chlorine atom, or a hydrogen atom, and n represents an integer of 1 to 10. m represents an integer from 0 to 8). In this case, when n is 11 or more or when m is 9 or more, the solubility in the solvent decreases, and the solubility of the fluoroalkanoyl peroxide represented by the general formula (II) when reacting in the presence of a solvent decreases. It cannot be used because it causes problems. Specifically, R2 in the fluoroalkanoyl peroxide represented by the general formula (n) is the same as R in the fluoroalkyl group-containing tetrahydrofuran derivative represented by the general formula (I).
本発明のフルオロアルキル基含有テトラヒドロフラン誘
導体の製造方法において、前記フルオロアルカノイルペ
ルオキシドと２，５−ジヒドロフランとを反応させる際
の仕込みモル比は、１：０．５〜１０が好ましく、特に
ｉ：ｏ、ｓ〜５とするのが好ましい。前記２，５−ジヒ
ドロフランの仕込みモル比が０．５未満の場合には生成
するフルオロアルキル基含有テトラヒドロフラン誘導体
の収率が低下し、また１０を超えると反応終了後に未反
応の２，５−ジヒドロフランが多量に残存し、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
３０〜１５０℃の範囲とするのが望ましい。前記反応温
度が一３０℃未満の場合には反応に長時間を要し、１５
０℃を超えると反応時の圧力が高くなり、反応操作が困
難となるので好ましくない。更に反応時間は３０分〜２
０時間の範囲とすることが好ましい。In the method for producing a fluoroalkyl group-containing tetrahydrofuran derivative of the present invention, the molar ratio of the fluoroalkanoyl peroxide and 2,5-dihydrofuran is preferably 1:0.5 to 10, particularly i:o. , s~5. If the molar ratio of the 2,5-dihydrofuran charged is less than 0.5, the yield of the fluoroalkyl group-containing tetrahydrofuran derivative produced will decrease, and if it exceeds 10, unreacted 2,5-dihydrofuran will be removed after the reaction is completed. This is not preferred because a large amount of dihydrofuran 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 -30 to 150°C. When the reaction temperature is less than 130°C, the reaction takes a long time and
If the temperature exceeds 0°C, the pressure during the reaction will become high and the reaction operation will become difficult, which is not preferable. Furthermore, the reaction time is 30 minutes to 2
It is preferable to set it as the range of 0 hours.
本発明の製造方法では、前記種々の反応条件下において
、前記フルオロアルカノイルペルオキシドと２，５−ジ
ヒドロフランとを反応させることにより目的とするフル
オロアルキル基含有テトラヒドロフラン誘導体を得るこ
とができるが、前記フルオロアルカノイルペルオキシド
の取り扱い及び反応をより速やかに行なうために溶媒を
用いることが好ましい。前記溶媒としてはハロゲン系脂
肪族溶媒が特に好ましく、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用いることができ、特に工業的
には、１，１．２−トリクロロトリフルオロエタンを好
ましく挙げることができる。前記溶媒を使用する場合の
前記フルオロアルカノイルペルオキシドの濃度は、溶媒
全体に対して１〜５０重量％程度であることが望ましい
。In the production method of the present invention, the desired fluoroalkyl group-containing tetrahydrofuran derivative can be obtained by reacting the fluoroalkanoyl peroxide with 2,5-dihydrofuran under the various reaction conditions. It is preferred to use a solvent to more quickly handle and react the alkanoyl peroxide. As the solvent, halogenated aliphatic solvents are particularly preferable, and 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-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, etc. can be used. From an industrial perspective, 1,1,2-trichlorotrifluoroethane is particularly preferred. When the solvent is used, the concentration of the fluoroalkanoyl peroxide is preferably about 1 to 50% by weight based on the entire solvent.
本発明の製造方法により得ら九る反応生成物は、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
とができる。The reaction product obtained by the production method of the present invention can be obtained by distillation,
It can be purified by known methods such as column chromatography.
〈発明の効果〉
本発明のフルオロアルキル基含有テトラヒドロフラン誘
導体は、撥水撥油剤、界面活性剤、医薬、農薬等の合成
中間体として利用することができる。<Effects of the Invention> The fluoroalkyl group-containing tetrahydrofuran derivative of the present invention can be used as a synthetic intermediate for water and oil repellents, surfactants, medicines, agricultural chemicals, and the like.
また本発明のＭ進方法では、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フルオロ
アルキル基含有テトラヒドロフラン誘導体を製造するこ
とができる。Further, according to the M-adic method of the present invention, a fluoroalkyl group-containing tetrahydrofuran derivative can be easily produced in a short time, in high yield, and 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.
失に析よ
２．５−ジヒドロフランＬｏｇ （０，１４ｍｏＱ）を
１．ｌ、２−トリクロロトリフルオロエタン１２０ｇに
溶解させた後、得られた溶液を３０℃に保ち、ジ（ペル
フルオロブチリル）ペルオキシド４３ｇ （０，１ｍｏ
ｎ）を含む１，１．２−トリクロロトリフルオロエタン
溶液８２６ｇを加えた。次いで窒素雰囲気下にて、同温
度で５時間撹拌を行なった。反応終了後、飽和食塩水を
加え、有機層について、０．５％水酸化ナトリウム水溶
液及び水でそれぞれ洗浄した後、硫酸マグネシウムを用
いて乾燥した。溶媒留去後、減圧蒸留して、下記構造式
で示される３−ペルフルオロプロピルテトラヒドロフラ
ンを収率５０％で得た。得られた化合物の沸点”Ｈ−Ｎ
ＭＲ，”Ｃ−ＮＭＲ。Calculate 2.5-dihydrofuran Log (0,14moQ) at 1. After dissolving in 120 g of l,2-trichlorotrifluoroethane, the resulting solution was kept at 30 °C and 43 g of di(perfluorobutyryl) peroxide (0,1 mo
826 g of a 1,1.2-trichlorotrifluoroethane solution containing n) was added. Next, stirring was performed at the same temperature for 5 hours under a nitrogen atmosphere. After the reaction was completed, saturated brine was added, and the organic layer was washed with a 0.5% aqueous sodium hydroxide solution and water, and then dried using magnesium sulfate. After distilling off the solvent, the residue was distilled under reduced pressure to obtain 3-perfluoropropyltetrahydrofuran represented by the following structural formula in a yield of 50%. The boiling point of the obtained compound “H-N
MR, “C-NMR.
”Ｆ−ＮＭＲ，ＩＲ，ＭＲ及び元素分析の各分析結果を
以下に示す。The results of F-NMR, IR, MR, and elemental analysis are shown below.
沸点 ４０〜ｂ
’Ｈ−ＮＭＲ（ＣＤＣＩ３）δ＝２．１３（２Ｈ，ｄｔ
、Ｊ＝８．５Ｈｚ、７．３Ｈｚ）。Boiling point 40~b'H-NMR (CDCI3) δ = 2.13 (2H, dt
, J=8.5Hz, 7.3Hz).
３．００ （ＬＨ，ｍ）、３．７０〜４．１８（４Ｈ
，ｍ）
”Ｃ−ＮＭＲ（ＣＤＣＩ、） δ＝２６．２゜４１．
２ （ｔ、Ｊ ＯＣＦ ＝２２．５Ｈｚ）。3.00 (LH, m), 3.70-4.18 (4H
, m) "C-NMR (CDCI,) δ=26.2°41.
2 (t, J OCF =22.5Hz).
６６．８，６８．２
”Ｆ−ＮＭＲ（ＣＤＣ１，： ｅ Ｘ ｔ、ＣＦ３Ｃｏ
２Ｈ）δ＝−５０，５（２Ｆ）、−４２，０（２Ｆ）。66.8, 68.2 "F-NMR (CDC1,: e X t, CF3Co
2H) δ = -50,5 (2F), -42,0 (2F).
−４，６（３Ｆ）
ＩＲ（■−”）１３５０（ＣＦ、）、１２３０ （Ｃ
Ｆ２）ＭＳ （ＥＩ）ｍ／ｚ ２３９ （Ｍ”
−１）。-4,6 (3F) IR (■-”) 1350 (CF, ), 1230 (C
F2) MS (EI) m/z 239 (M”
-1).
１９１、 ｊ４５．９１
元素分析
計算値 Ｃ：３５．０１％ Ｈ：２．９４％実測値 Ｃ
：３４．１８％ Ｈ：３．１８％寒庭旌え
ジ（ペルフルオロブチリル）ペルオキシドをジ（ペルフ
ルオロヘプタノイル）ペルオキシドに代えた以外は実施
例１と同様に反応を行ない、下記構造式で示される３−
ペルフルオロへキシルテトラヒドロフランを４５％の収
率で得た。各分析結果を以下に示す。191, j45.91 Elemental analysis calculated value C: 35.01% H: 2.94% actual value C
: 34.18% H: 3.18% The reaction was carried out in the same manner as in Example 1, except that di(perfluorobutyryl) peroxide was replaced with di(perfluoroheptanoyl) peroxide, and the reaction was carried out in the same manner as in Example 1 to obtain a product shown by the structural formula below. 3-
Perfluorohexyltetrahydrofuran was obtained with a yield of 45%. The results of each analysis are shown below.
”Ｈ−ＮＭＲ（ＣＤＣ１，）δ＝２．１４（２Ｈ，ｄｔ
、Ｊ＝８．５Ｈｚ、７．３Ｈｚ）。"H-NMR (CDC1,) δ = 2.14 (2H, dt
, J=8.5Hz, 7.3Hz).
３．０２ （ＬＨ，ｍ）、３．７０〜４．１８（４Ｈ，
ｍ）？
Ｉ Ｒ（Ｑｌ−１）１３５０ （ＣＦ３）、１２３０
（ＣＦ２）ＭＳ （ＥＩ）ｍ／ｚ ３’８９ （Ｍ”
−１）元素分析
計算値 Ｃ：３０．７９％ Ｈ：１．８１％実測値 Ｃ
：３０，５５％ Ｈ：２．０６％失凰孤主
ジ（ペルフルオロブチリル）ペルオキシドをジ（ペルフ
ルオロ−２−メチル−３−オキサヘキサノイル）ペルオ
キシドに代えた以外は実施例１と同様に反応を行ない、
下記構造式で示される３−（ペルフルオロ−１′−メチ
ル−２′−オキサペンチル）テトラヒドロフランを４７
％の収率で得た。各分析結果を以下に示す。3.02 (LH, m), 3.70-4.18 (4H,
m)? I R (Ql-1) 1350 (CF3), 1230
(CF2) MS (EI) m/z 3'89 (M”
-1) Elemental analysis calculated value C: 30.79% H: 1.81% actual value C
: 30,55% H: 2.06% Loss of alcohol The reaction was carried out in the same manner as in Example 1, except that di(perfluorobutyryl) peroxide was replaced with di(perfluoro-2-methyl-3-oxahexanoyl) peroxide. do the
47 3-(perfluoro-1'-methyl-2'-oxapentyl)tetrahydrofuran shown by the following structural formula
% yield. The results of each analysis are shown below.
”Ｈ−ＮＭＲ（ＣＤＣｌ２）δ＝２．１２（２Ｈ，ｄ
ｔ、Ｊ＝８．４Ｈｚ、７．２Ｈｚ）。"H-NMR (CDCl2) δ = 2.12 (2H, d
t, J = 8.4Hz, 7.2Hz).
２．９８ （ＬＨ，ｍ）、３．７０〜４．２０（４Ｈ＋
ｍ ） ｔ
Ｉ Ｒ（ＣＭ−Ｊ １３５０ （ＣＦ３）、１２２０
（ＣＦ２）ＭＳ （ＥＩ）ｍ／ｚ ３５５ （Ｍ”
１） 。2.98 (LH, m), 3.70-4.20 (4H+
m ) t I R (CM-J 1350 (CF3), 1220
(CF2) MS (EI) m/z 355 (M”
1).
元素分析
計算値 Ｃ：３０．３５％ Ｈ：１．９８％実測値 Ｃ
：３０．０９％ Ｈ：２．１５％失亀史土
ジ（ペルフルオロブチリル）ペルオキシドをジ１、（ペ
ルフルオロ−２，５−ジメチル−３，６−シオキサノナ
ノイル）ペルオキシドに代えた以外は実施例１と同様に
反応を行ない、下記構造式で示される３−（ペルフルオ
ロ−１’ 、４’ −ジメチル−２′、５′−ジオキサ
オクチル）テトラヒドロフランを４１％の収率で得た。Elemental analysis calculated value C: 30.35% H: 1.98% Actual value C
:30.09% H:2.15% Shikameshido Di(perfluorobutyryl) peroxide was replaced with di1,(perfluoro-2,5-dimethyl-3,6-sioxanonanoyl) peroxide. The reaction was carried out in the same manner as in Example 1 to obtain 3-(perfluoro-1',4'-dimethyl-2',5'-dioxaoctyl)tetrahydrofuran represented by the following structural formula in a yield of 41%.
各分析結果を以下に示す。The results of each analysis are shown below.
１Ｈ−ＮＭＲ（ＣＤＣ１，）δ＝２．１２（２Ｈ，ｄ
ｔ、Ｊ＝８．５Ｈｚ、７．３Ｈｚ）。1H-NMR (CDC1,) δ = 2.12 (2H, d
t, J = 8.5Hz, 7.3Hz).
３．００ （ＩＨ，ｍ）、３．７０−４．２０（４Ｈ，
ｍ）
ＩＲ（ａｎ−１）１３５０（ＣＦ３）、１２２０ （Ｃ
Ｆ２）ＭＳ （ＥＩ）ｍ／ｚ ５２１ （Ｍ”−１）
元素分析
計算値 Ｃ：２７．６０％ Ｈ：１．３５％実測値 Ｃ
：２８．０６％ Ｈ： １．４２％失族剪旦
ジ（ペルフルオロブチリル）ペルオキシドをジ（ペルフ
ルオロ−２，５，８−トリメチル−３゜６．９−トリオ
キサドデカノイル）ペルオキシドに代えた以外は実施例
１と同様に反応を行ない、下記構造式で示される３−（
ペルフルオロ−１′。3.00 (IH, m), 3.70-4.20 (4H,
m) IR (an-1) 1350 (CF3), 1220 (C
F2) MS (EI) m/z 521 (M”-1)
Elemental analysis calculated value C: 27.60% H: 1.35% Actual value C
: 28.06% H: 1.42% Di(perfluorobutyryl) peroxide was replaced with di(perfluoro-2,5,8-trimethyl-3°6.9-trioxadodecanoyl) peroxide. Other than that, the reaction was carried out in the same manner as in Example 1, and 3-( shown by the following structural formula)
Perfluoro-1'.
４’ 、７’ −）−ジメチル−２’ 、５’ 、８’
−トリオキサウンデシル）テトラヒドロフランを３３
％の収率で得た。各分析結果を以下に示す。4', 7'-)-dimethyl-2', 5', 8'
-trioxaundecyl)tetrahydrofuran 33
% yield. The results of each analysis are shown below.
”Ｈ−ＮＭＲ（ＣＤＣｌ２）δ＝２．１２（２Ｈ，ｄｔ
、Ｊ＝８．４Ｈｚ、７．２Ｈｚ）。"H-NMR (CDCl2) δ = 2.12 (2H, dt
, J=8.4Hz, 7.2Hz).
２．９８ （ＬＨ，ｍ）、３．７０〜４．２０（４Ｈ，
ｍ）
Ｉ Ｒ（（！ｌ−”） １３５０（ＣＦ３）、 １２２
０ （ＣＦ、）ＭＳ （ＥＩ）ｍ／ｚ ６８７ （Ｍ
”−１）元素分析2.98 (LH, m), 3.70-4.20 (4H,
m) I R((!l-”) 1350(CF3), 122
0 (CF,)MS (EI)m/z 687 (M
”-1) Elemental analysis
Claims (1)
式、表等があります▼を示す（但しＸは、フッ素原子、
塩素原子又は水素原子を示し、ｎは１〜１０の整数を、
ｍは０〜８の整数を示す）］で表わされるフルオロアル
キル基含有テトラヒドロフラン誘導体。 ２）下記一般式（II） ▲数式、化学式、表等があります▼・・・（II） ［式中Ｒ＿Ｆは、Ｃ＿ｎＦ＿２＿ｎＸ又は▲数式、化学
式、表等があります▼を示す（但しＸは、フッ素原子、
塩素原子又は水素原子を示し、ｎは１〜１０の整数を、
ｍは０〜８の整数を示す）］で表わされるフルオロアル
カノイルペルオキシドと、２，５−ジヒドロフランとを
反応させることを特徴とする請求項１記載のフルオロア
ルキル基含有テトラヒドロフラン誘導体の製造方法。[Claims] 1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, R_F indicates C_nF_2_nX or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is a fluorine atom,
represents a chlorine atom or a hydrogen atom, n is an integer of 1 to 10,
m is an integer of 0 to 8)] A fluoroalkyl group-containing tetrahydrofuran derivative. 2) The following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the formula, R_F indicates C_nF_2_nX or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, X is fluorine atom,
represents a chlorine atom or a hydrogen atom, n is an integer of 1 to 10,
2. The method for producing a fluoroalkyl group-containing tetrahydrofuran derivative according to claim 1, which comprises reacting a fluoroalkanoyl peroxide represented by [m is an integer of 0 to 8] with 2,5-dihydrofuran.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28418290A JPH04159273A (en) | 1990-10-24 | 1990-10-24 | Fluoroalkyl group-containing tetrahydrofuran derivative and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28418290A JPH04159273A (en) | 1990-10-24 | 1990-10-24 | Fluoroalkyl group-containing tetrahydrofuran derivative and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04159273A true JPH04159273A (en) | 1992-06-02 |
Family
ID=17675240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28418290A Pending JPH04159273A (en) | 1990-10-24 | 1990-10-24 | Fluoroalkyl group-containing tetrahydrofuran derivative and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04159273A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019159652A1 (en) | 2018-02-16 | 2019-08-22 | ダイキン工業株式会社 | Perfluoro diacyl peroxide, solution, polymerization initiator, polymer preparation method, and perfluoro acyl chloride |
-
1990
- 1990-10-24 JP JP28418290A patent/JPH04159273A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019159652A1 (en) | 2018-02-16 | 2019-08-22 | ダイキン工業株式会社 | Perfluoro diacyl peroxide, solution, polymerization initiator, polymer preparation method, and perfluoro acyl chloride |
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