JPH0477490A - Fluorine-containing phosphonate compound and its preparation - Google Patents
Fluorine-containing phosphonate compound and its preparationInfo
- Publication number
- JPH0477490A JPH0477490A JP19134490A JP19134490A JPH0477490A JP H0477490 A JPH0477490 A JP H0477490A JP 19134490 A JP19134490 A JP 19134490A JP 19134490 A JP19134490 A JP 19134490A JP H0477490 A JPH0477490 A JP H0477490A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- fluorine
- formulas
- tables
- compound
- 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
- -1 phosphonate compound Chemical class 0.000 title claims description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 12
- 229910052731 fluorine Inorganic materials 0.000 title claims description 12
- 239000011737 fluorine Substances 0.000 title claims description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 7
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 6
- 229960003857 proglumide Drugs 0.000 claims description 4
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 3
- 150000003018 phosphorus compounds Chemical class 0.000 claims 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 abstract description 5
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002917 insecticide Substances 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野ン
本発明は、農医薬の重要な中間体である新規な含フッ素
フォスフォネート化合物およびその製造法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a novel fluorine-containing phosphonate compound that is an important intermediate for agricultural medicines and a method for producing the same.
〈従来の技術〉
含フッ素フォスフォネート化合物は、農医薬上重要な中
間体になりうるものであるが、これまで簡便な製造法は
知られていなかった。<Prior Art> Fluorine-containing phosphonate compounds can be important agricultural and pharmaceutical intermediates, but no simple manufacturing method has been known so far.
〈発明が解決しようとする課題〉
入手容易な化合物から、短段階で含フッ素フォスフォネ
ート化合物を製造する。<Problems to be Solved by the Invention> To produce a fluorine-containing phosphonate compound in a short period of time from easily available compounds.
く課題を解決するための手段〉
本発明者らは、このような状況に鑑み、入手容易な化合
物から、短段階で、含フッ素フォスフォネート化合物を
製造できる方法を種々検討−た結果、本発明を完成する
に至った。すなわち、本発明は、
１１） 一般式ＣＩ）
（式中、Ｒはメチル基またはエチ／ｌ／基を表わす。）
で示される含フッ素フォスフォネート化合物（以下、本
発明化合物と称する）、
（２１式（Ｉｔ）
ＢｒＣＦｇ Ｈ
で示されるプロミド化合物とトリエチルフォスファイト
とを反応させる式（■′）
ＢｒＣＦ２ Ｈ
で示される本発明化合物の製造法（以下、製造法Ａと称
する。）および（８）式（ｎ）で示されるプロミド化合
物とジメチルフォスファイトまたはジエチルフォスファ
イトとを、塩基の存在下に反応させる一般式（１）で示
される本発明化合物の製造法（以下、製造法Ｂと称する
。）である。Means for Solving the Problems In view of the above circumstances, the present inventors have investigated various methods for producing fluorine-containing phosphonate compounds in a short period of time from readily available compounds, and have developed the present invention. The invention was completed. That is, the present invention provides: 11) A fluorine-containing phosphonate compound (hereinafter referred to as the compound of the present invention) represented by the general formula CI) (wherein R represents a methyl group or an ethyl/l/group); 21 Formula (It) Formula (■') for reacting a bromide compound represented by BrCFg H with triethyl phosphite A method for producing the present compound represented by BrCF2 H (hereinafter referred to as manufacturing method A) and (8) A method for producing the compound of the present invention represented by general formula (1), in which a bromide compound represented by formula (n) and dimethyl phosphite or diethyl phosphite are reacted in the presence of a base (hereinafter referred to as manufacturing method B). ).
製造法人の反応、すなわち、プロミド化合物（Ｉｔ）と
トリエチルフォスファイトとの反応では、溶媒は特に必
要とせず、両者を混合して加熱することによって、本発
明化合物を得ることができる。反応温度は、通常８０℃
〜１５０℃で、反応時間は、通常、４時間〜１５時間で
行なわれる。トリエチルフォスファイトのモル比は、通
常、プロミド化合物（Ｉｆ）に対し、０．８〜１．８倍
・−４劃する。In the reaction of the manufacturing company, that is, the reaction between the promide compound (It) and triethyl phosphite, no solvent is particularly required, and the compound of the present invention can be obtained by mixing the two and heating them. The reaction temperature is usually 80℃
The reaction time is usually 4 hours to 15 hours at a temperature of 150°C to 150°C. The molar ratio of triethyl phosphite is usually 0.8 to 1.8 times -4 to that of the promide compound (If).
製造法Ｂの反応を行なうに際して用いられる塩基として
は、たとえば水素化す） ＩＪウム、水素化カリウム、
ナトリウムメチラート、ナトリウムエチラート、ｎ−ブ
チルリチウム、金属す） リウム等があげられる。本反
応は、通常、溶媒の存在下に行なわれ、井≠今噴福溶謀
としては、たとえばテトラ上１゛ロフラン、トルエン等
がよく用いられるが、もちろんこれらに限定されない。The bases used in the reaction of production method B include, for example, IJium hydride, potassium hydride,
Examples include sodium methylate, sodium ethylate, n-butyllithium, and metal lithium. This reaction is usually carried out in the presence of a solvent, and as a solvent, for example, tetrahydrofuran, toluene, etc. are often used, but the solvent is of course not limited to these.
反応温度は、通常、０℃〜５０℃であシ、ジメチルフォ
スファイトまたはジエチルフォスファイトのモル比は、
通常、ゾロミド化合物に対し、１〜１．５倍、塩基は、
通常、ジメチルフォスファイトまたはジによっても異な
るが、通常、１時間〜１５時め
間で怜寺＋壱る。The reaction temperature is usually 0°C to 50°C, and the molar ratio of dimethylphosphite or diethylphosphite is:
Usually, the base is 1 to 1.5 times as much as the zolomide compound.
Usually, it takes about 1 hour to 15 hours, although it varies depending on the dimethyl phosphite or dimethyl phosphite.
本発明化合物は、たとえば次式に示した変換によって、
含フツ素アミド化合物（１）や含フツ素エステル化合物
（Ｖ）へ容易に変換することができる。前者は殺虫剤と
して有用なインブチルアミド糸化合物（ＩＶ）の重要な
中間体になる。The compound of the present invention can be obtained, for example, by the transformation shown in the following formula:
It can be easily converted into a fluorine-containing amide compound (1) or a fluorine-containing ester compound (V). The former is an important intermediate for inbutyramide thread compound (IV), which is useful as an insecticide.
酸
（ＩＩ）
（Ｖ）
（上記式中、Ｒはメチル基′またはエチル基を表わし、
Ｒ′は低級アルキル基を表わす。）（Ｆ／）
（上記式中、Ｒはメチル基またはエチル基を表わす。）
なお、本発明における出発化合物である式（ＩＩ）で示
されるプロミド化合物は、文献記載の方法（Ｃｈｅｍｉ
ｃａｌ Ａｂｓｔｒａｃｔｓ Ｂ ｓ巻７８４６８５（
１９７５））に従って容易に合成することができる。Acid (II) (V) (In the above formula, R represents a methyl group' or an ethyl group,
R' represents a lower alkyl group. ) (F/) (In the above formula, R represents a methyl group or an ethyl group.) The bromide compound represented by formula (II), which is the starting compound in the present invention, can be prepared by the method described in the literature (Chemi
cal Abstracts B s volume 784685 (
(1975)).
〈実施例〉 次に実施例で本発明をさらに詳細に説明する。<Example> Next, the present invention will be explained in more detail with reference to Examples.
実施例１
１．４−ジブロモ−１，１，２−）リフルオロ−２−ブ
テン８．Ｏｆとトリエチルフォスファイト６、１ ｄと
を、１００℃で１０時間攪拌した。この間留出する臭化
エチルを除外した。反応液を減圧下に蒸留し、１−プロ
モー１ 、１ 、２−）リフルオロ−４−（ジエチルフ
ォスフォノ）−２−ブテンを無色オイルで得た。Example 1 1.4-dibromo-1,1,2-)refluoro-2-butene8. Of and triethyl phosphite 6,1 d were stirred at 100°C for 10 hours. During this period, the distilled ethyl bromide was excluded. The reaction solution was distilled under reduced pressure to obtain 1-promo-1,1,2-)refluoro-4-(diethylphosphono)-2-butene as a colorless oil.
得量 ５．ｆＭ（５７％）
沸点 ８Ｏ−＝−８５℃（０，７謳Ｈｐ ）’ＨＮＭＲ
（ＣＤ０１ｇ ） δ＝１．８１（ｔ、６Ｈ）、２．
６７（ｄｄｑ、２Ｈ）、４．１（ｍ、ｓＨ）、５．２６
Ｐ−５，９（ｍ、ＩＨ）
実施例２
６０％水素化ナトリウム０．５０ ｔを無水テトラヒド
ロフラン１５ｍに溶かし、この溶液に、２０℃で、ジメ
チルフォスファイト１，４４りを加え、水素ガヌの発泡
がおさまるまで同温度で撹拌した。反応ｇｉｔ−０℃ま
で冷却し、これに１．４−ジブロモ−１，１，２−）リ
フルオロ−２−ブテン８．５ｆをｉ下した。ついで２０
℃まで昇温し、同温度で１２時間攪拌した。反応液を、
水冷した５％塩酸水にあけ、酢酸エチルで抽出した。水
層を食塩で飽和後、再び酢酸エチルで抽出した。酢酸エ
チｚ’ｍｔを合わせ、食塩水で洗浄後、硫酸マグネシウ
ムで乾燥した。溶媒留去の後、減圧下に蒸留を行ない、
１−プロモー１．１．２−トリフルオロ−４−（ジメチ
ルフォスフォノ）−２−ブテン２．７１ｆを無色オイル
で得た。Yield 5. fM (57%) Boiling point 8O-=-85℃ (0.7 HP)'HNMR
(CD01g) δ=1.81 (t, 6H), 2.
67 (ddq, 2H), 4.1 (m, sH), 5.26
P-5,9 (m, IH) Example 2 0.50 t of 60% sodium hydride was dissolved in 15 ml of anhydrous tetrahydrofuran, 1.44 t of dimethyl phosphite was added to this solution at 20°C, and hydrogen The mixture was stirred at the same temperature until the foaming subsided. The reaction mixture was cooled to −0° C., and 8.5 f of 1,4-dibromo-1,1,2-)refluoro-2-butene was added thereto. Then 20
The temperature was raised to ℃ and stirred at the same temperature for 12 hours. The reaction solution,
The mixture was poured into water-cooled 5% hydrochloric acid and extracted with ethyl acetate. The aqueous layer was saturated with sodium chloride, and then extracted again with ethyl acetate. Ethyl acetate z'mt was combined, washed with brine, and dried over magnesium sulfate. After removing the solvent, distillation is performed under reduced pressure.
1-promo 1.1.2-trifluoro-4-(dimethylphosphono)-2-butene 2.71f was obtained as a colorless oil.
収率 ７８％ 沸点 ６５〜７０℃（０，５１１１Ｈ
ｒ ）〈発明の効果〉
本発明によれば、入手容易な化合物から、短段階で、含
フッ素フォスフォネート化合物を製造することができる
。Yield 78% Boiling point 65-70℃ (0,5111H
r) <Effects of the Invention> According to the present invention, a fluorine-containing phosphonate compound can be produced from easily available compounds in a short period of time.
Claims (3)
とを反応させることを特徴とする式 ▲数式、化学式、表等があります▼ で示される含フッ素フォスフォネート化合物の製造法。(2) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A fluorine-containing phosphorous compound characterized by reacting a promide compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Method for producing nate compounds.
たはジエチルフォスフアイトとを、塩基の存在下に反応
させることを特徴とする一般式 ▲数式、化学式、表等があります▼ （式中、Ｒはメチル基またはエチル基を表わす。） で示される含フッ素フォスフォネート化合物の製造法。(3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A general formula characterized by reacting a promide compound represented by the formula with dimethyl phosphite or diethyl phosphite in the presence of a base ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a methyl group or an ethyl group.) A method for producing a fluorine-containing phosphonate compound represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19134490A JPH0477490A (en) | 1990-07-18 | 1990-07-18 | Fluorine-containing phosphonate compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19134490A JPH0477490A (en) | 1990-07-18 | 1990-07-18 | Fluorine-containing phosphonate compound and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0477490A true JPH0477490A (en) | 1992-03-11 |
Family
ID=16273009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19134490A Pending JPH0477490A (en) | 1990-07-18 | 1990-07-18 | Fluorine-containing phosphonate compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0477490A (en) |
-
1990
- 1990-07-18 JP JP19134490A patent/JPH0477490A/en active Pending
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