JPS59210096A - Dialkylphosphonate derivatives and their production method - Google Patents
Dialkylphosphonate derivatives and their production methodInfo
- Publication number
- JPS59210096A JPS59210096A JP8278383A JP8278383A JPS59210096A JP S59210096 A JPS59210096 A JP S59210096A JP 8278383 A JP8278383 A JP 8278383A JP 8278383 A JP8278383 A JP 8278383A JP S59210096 A JPS59210096 A JP S59210096A
- Authority
- JP
- Japan
- Prior art keywords
- dihydroquinoline
- ethoxycarbonyl
- dialkylphosphonate
- ppm
- derivatives
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- -1 alkali metal salt Chemical class 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001350 alkyl halides Chemical class 0.000 abstract description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000000417 fungicide Substances 0.000 abstract description 3
- 230000000855 fungicidal effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 2
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical class C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241001480061 Blumeria graminis Species 0.000 description 1
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 1
- 101100536577 Caenorhabditis elegans cct-4 gene Proteins 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000207199 Citrus Species 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 241000221301 Puccinia graminis Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000000160 carbon, hydrogen and nitrogen elemental analysis Methods 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はジアルキルホスホナート誘導体及びその製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to dialkylphosphonate derivatives and methods for their production.
本発明の化合物は新規な化合物であり殺菌剤としては有
用である。The compounds of the present invention are novel compounds and are useful as fungicides.
０−ＣｏＣ２Ｈ。0-CoC2H.
Ｒ３は、低級アルキル基を示す。）で示されるジアルキ
ルホスホナート誘導体（以下本発明化合物という。）、
及び一般式
で表わされる４−アルキル−１−エトキシカルボニル−
ｉ、 ２− ジヒドロキノリン−２−ジアルキルホスホ
ナート（■）をアルカリ金属塩とし、次いでＲ，Ｘ（式
中Ｒ２は、前記に同じ。Ｘｉ、ｊ：ハロゲンを示す。）
で表わされるハロゲン化アルキルと反応させることを特
徴とする一般式
で表わされるジアルキルホスホナート誘導体の製造法を
提供するものである。次に本発明化合物の製造法を更に
詳しく述べる。R3 represents a lower alkyl group. ) (hereinafter referred to as the compound of the present invention),
and 4-alkyl-1-ethoxycarbonyl- represented by the general formula
i, 2-dihydroquinoline-2-dialkylphosphonate (■) as an alkali metal salt, and then R,X (in the formula, R2 is the same as above. Xi, j: represents a halogen).
The present invention provides a method for producing a dialkylphosphonate derivative represented by the general formula, which comprises reacting with an alkyl halide represented by the following formula. Next, the method for producing the compound of the present invention will be described in more detail.
本発明化合物の製造に用いる原料である４−アルキル−
１−エトキシカルボニル−１，２−ジヒドロキノリン−
２−ジアルキルホスホナート（■）は、テトラヘドロン
レターズ（Ｔｅｔｒａｈｅａｒｏｎ Ｌｅｔｔｅｒｓ
。4-alkyl- which is a raw material used in the production of the compound of the present invention
1-Ethoxycarbonyl-1,2-dihydroquinoline-
2-Dialkylphosphonate (■)
.
２３巻、１６号、１７０９−１７１２頁（１９８２））
に記載されている様にキノリンとクロル炭酸エチルを反
応させ次いでヨウ化ナトリウム存在下に亜リン酸トリア
ルキルを反応させ一般式
される１−エトキシカルボニル−１，２−ジヒドロキノ
リン−２−ジアルキルホスホナート（曲とし、次いで該
化合物をアルカリ金属塩としＲ，Ｘ （式中Ｒ１は、前
記に同じ）で表わされるハロゲン化アルキルと反応させ
ることにより得られる。Volume 23, No. 16, pp. 1709-1712 (1982))
1-ethoxycarbonyl-1,2-dihydroquinoline-2-dialkylphosphor of the general formula is obtained by reacting quinoline with ethyl chlorocarbonate and then reacting trialkyl phosphite in the presence of sodium iodide as described in . It is obtained by converting the compound into an alkali metal salt and reacting it with an alkyl halide represented by R,X (wherein R1 is the same as above).
この一般式（ＩＩ）の化合物をはｉｆ当景のアルカリ金
属と反応させて１，２−ジヒドロキノリン誘導体のアル
カリ金属塩に導びき、次いでほぼ当量のハロゲン化アル
キルと反応させることにより本発明化合物０）を製造す
ることができる。The compound of the general formula (II) is reacted with an alkali metal of interest to form an alkali metal salt of a 1,2-dihydroquinoline derivative, and then reacted with an approximately equivalent amount of an alkyl halide to form a compound of the present invention. 0) can be produced.
反応に際しては、一般に溶媒の存在下で行うことが好ま
しい。The reaction is generally preferably carried out in the presence of a solvent.
溶媒としては、例えばエーテル、インフロビルエーテル
、テトラヒドロフラン、ジオキサン、ベンゼ右 トルエ
〉、くシレン箕仕立Ｅ先こ吐たミ字＝等が用いられる。Examples of solvents that can be used include ether, inflovir ether, tetrahydrofuran, dioxane, benzene, and the like.
アルカリ金属としては、例えばナトリウム、カリウム、
リチウム、又はｎ−ブチルリチウム等及びそのアルキル
化合物又は水素化ナトリウム、ナトリウムアミド、リチ
ウムジイソプロピルアミド等が用いられる。Examples of alkali metals include sodium, potassium,
Lithium, n-butyllithium, etc. and its alkyl compounds, sodium hydride, sodium amide, lithium diisopropylamide, etc. are used.
反応温度は通常約−８０℃〜室温の間を選択する。The reaction temperature is usually selected between about -80°C and room temperature.
次に実施例でもって本発明の詳細な説明するが本発明は
、これら実施例のみに限定されるものではない。Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
実施例１
冷却器、窒素吸き込み管、ラバーセプタムを付した１０
０−の３日フラスコに１−エトキシカルボニル−４−メ
チル−１，２−ジヒドロキノリン−２−ジエチルホスホ
ナート１ ｇｒ、テトラヒドロフラン１５ゴを取シトラ
イアイスーアセトン浴にて一７８°Ｃに冷却した。マグ
ネチノクスターラーで攪拌しつつ、フラスコ内を窒素で
十分置換した。Example 1 10 with cooler, nitrogen suction tube and rubber septum
1 gr of 1-ethoxycarbonyl-4-methyl-1,2-dihydroquinoline-2-diethylphosphonate and 15 g of tetrahydrofuran were placed in a 3-day flask and cooled to -78°C in a citrus ice-acetone bath. . While stirring with a magnetic stirrer, the inside of the flask was sufficiently purged with nitrogen.
次いでｔ５９Ｍｎ−ブチルリチウム−ｎ−ヘキサン溶液
１．７８ ＃ｌｔを加え、３０分間攪拌した。Then, 1.78 #lt of t59M n-butyllithium-n-hexane solution was added and stirred for 30 minutes.
その後、ヨウ化メチル０．１８７を加え２０分間攪拌し
、ドライアイス−アセトン浴を取り除き室温まで昇温し
、１時間攪拌した。Thereafter, 0.187 g of methyl iodide was added and stirred for 20 minutes, the dry ice-acetone bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 1 hour.
反応終了後、テトラヒドロフランを留去し残留物に５チ
炭酸水素ナトリウム水溶液２５ｍ１を加え生成物をジ
クロロメタンで抽出した。ジクロロメタン溶液を無水硫
酸マグネシウムで乾燥後、ジクロロメタンを留去した。After the reaction was completed, tetrahydrofuran was distilled off, 25 ml of an aqueous sodium bicarbonate solution was added to the residue, and the product was extracted with dichloromethane. After drying the dichloromethane solution over anhydrous magnesium sulfate, dichloromethane was distilled off.
残留物をカラムクロマトグラフィ（シリカゲル、酢酸エ
チル：ｎ−ヘキサン−４：１展開溶媒）で精製して４．
４−ジメチル−１−エトキシカルボニル−１，４−ジヒ
ドロキノリン−２−ジエチルホスホナー） ０．８１
ｇｒを得た。ぺ５１．５１７２）
赤外線吸収スペクトル（ＮａＣ７）
２９８０（０−Ｈ）、１７２０（Ｃ−０）。The residue was purified by column chromatography (silica gel, ethyl acetate:n-hexane-4:1 developing solvent).4.
4-dimethyl-1-ethoxycarbonyl-1,4-dihydroquinoline-2-diethylphosphoner) 0.81
I got gr. 51.5172) Infrared absorption spectrum (NaC7) 2980 (0-H), 1720 (C-0).
１ｚ６ｏ（ｐ−０）、１０５０．１０２０（ｐ −ｏ
−ｃ ） ｔｙｒｒ−’
核磁気共鳴吸収スペクトル（ｃａｔ、 、内部標準ＴＭ
Ｓ ）
δ １．１０〜１．６０ （ｍ） ｐｐｍ （１５Ｈ
）δ ｌ ７０〜４．６０ （ｍ） ｐｐｍ （６Ｈ
）δ ”０（ａ）ｐｐｍ （ＩＨ）
δ ７．００〜７．４０ （ｍ） ｐｐｍ （３Ｈ）
δ ７．７０〜＆００（ｍ） ｐｐｍ （ＩＨ）元素
分析（Ｃ，８Ｈ，、Ｎｏ、Ｐとして）ＣＨＮ
分析値（チ） ５．ａ７９ ７．５６ 五６９理論
値（チ） ５ａ８５ ７．１３ ３．８１Ｇｏ−ＭＥ
３Ｓによる分子量 ６６７
次に４．４−ジメチル−１−エトキシカルボニル−１，
４−ジヒドロキノリン−２−ジエチルホスホナートの殺
菌剤としての使用例を示す。４４−ジメチル−１−エト
キシカルボニル−１，４−ジヒドロキノリン−２−ジエ
チルホスホナートを１０チのメタノール水溶液に溶解し
、さらにツイーン２０〔商品名、花王アトラス■製 〕
を添加３００ ｐｐｍの濃度の薬剤を調製した。３００
ｐｐｍの薬剤を小麦苗に噴霧し、６０時間後に黒サビ
病菌（Ｐｕｃｃｉｎｉａ ｇｒａｍｉｎｉｓ ｔｒｊ−
ｔｉｓ ｒａｃｅ）を接種し温室内で育てた。２週間後
に観察したところ病害は、全く認められなかった。また
ウドンコ病菌（Ｅｒｙｓｉｐｈｅ ｇｒａｍｉｎｉｓ）
に対しても効果が認められた。1z6o(p-0), 1050.1020(p-o
-c) tyrr-' Nuclear magnetic resonance absorption spectrum (cat, , internal standard TM
S) δ 1.10-1.60 (m) ppm (15H
) δ l 70-4.60 (m) ppm (6H
)δ ”0(a)ppm (IH) δ 7.00~7.40 (m) ppm (3H)
δ 7.70~&00(m) ppm (IH) elemental analysis (as C, 8H,, No, P) CHN analysis value (chi) 5. a79 7.56 569 theoretical value (chi) 5a85 7.13 3.81Go-ME
Molecular weight according to 3S 667 Next, 4,4-dimethyl-1-ethoxycarbonyl-1,
An example of the use of 4-dihydroquinoline-2-diethylphosphonate as a fungicide is shown. 44-dimethyl-1-ethoxycarbonyl-1,4-dihydroquinoline-2-diethylphosphonate was dissolved in 10 g of methanol aqueous solution, and then Tween 20 [trade name, manufactured by Kao Atlas ■]
The drug was prepared at a concentration of 300 ppm. 300
ppm of the chemical was sprayed on wheat seedlings, and 60 hours later, Puccinia graminis trj-
tis race) and grown in a greenhouse. When observed two weeks later, no disease was observed. Also, powdery mildew fungus (Erysiphe graminis)
It was also found to be effective.
実施例２
実施例１と同一の反応装置に１−エトキシカルボニル−
４−メチル−１，２−ジヒドロキノリン−２−ジエチル
ホスホナート１ ｇｒ、テトラヒドロフラン１５−を取
シ、ドライアイス−アセトン浴にて一７８℃に冷却した
。マグネテソクスターラーで攪拌しつつ、フラスコ内を
窒素で十分置換した。Example 2 In the same reactor as Example 1, 1-ethoxycarbonyl-
1 gr of 4-methyl-1,2-dihydroquinoline-2-diethylphosphonate and 15 g of tetrahydrofuran were removed and cooled to -78°C in a dry ice-acetone bath. While stirring with a magnetic stirrer, the inside of the flask was sufficiently purged with nitrogen.
次いで１．５５Ｍｎ−ブチルリチウム−ヘキサン溶液を
１．８３７加え、３０分間攪拌した。その後、臭化エチ
ル（１２１７を加え、２０分間攪拌し、ドライアイス−
アセトン浴を取シ除き室温まで昇温し、１時間攪拌した
。Next, 1.837 ml of 1.55M n-butyllithium-hexane solution was added and stirred for 30 minutes. Then, ethyl bromide (1217) was added, stirred for 20 minutes, and dried on dry ice.
The acetone bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 1 hour.
反応終了後、実施例１と同一の操作を行い、ヒドロキノ
リン−２−ジエチルホスホナート０、５５ ｇｒを得九
（垢’１．５１８６）赤外線吸収スペクトル（Ｎａｃ
！Ａ）
２９７０（０−Ｈ）、１７１６（０−０）。After the reaction was completed, the same operation as in Example 1 was carried out to obtain 0.55 gr of hydroquinoline-2-diethylphosphonate.
! A) 2970 (0-H), 1716 (0-0).
１２５０（Ｐ−０）、１０５０，１０２０（ｐ−ｏ−ｃ
）グ１
核磁気共鳴吸収スペクトル（ｃａｔ４．内部標準ＴＭＳ
）
ａ ａ６０〜１．９０（？ｎ）ｐｐｍ（１７Ｈ）δ
ｘ４ｓ 〜４．４８（ｍ）ｐｐｍ（６１（）δ ６．１
２ ’ （ｄ） ｐｐｍ （Ｉ Ｈ）δ ６．
７３〜７． ！＋ ３ （ｔｒＬ） ｐｐｍ （５Ｈ）
δ ７．５７〜７．９６ （ｍ） ｐｐｍ （Ｉ Ｈ）
元素分析値（ＣＩ９Ｈ２ｇＮＯ５Ｆ）
ＯＨＮ
分析値（チ） ５９．８０ ７．４４ 五７
１理論値（％） ５９．８３ ７．４０ ＆
６７０Ｃ−ＭＳＳによる分子量 ３８１
実施例３
実施例１と同一の反応装置に１−エトキシカルボニル−
１，２−ジヒドロキノリン−２−ジイソプルホスホナー
ト１ ｇｒ、テトラヒドロフラン２０ｍを取りドライア
イス−アセトン浴にて一７８°Ｃに冷却した。マグネチ
ックスターラーで攪拌しつつ、フラスコ内を窒素で十分
置換した。1250 (P-0), 1050, 1020 (p-o-c
)G1 Nuclear magnetic resonance absorption spectrum (cat4. Internal standard TMS
) a a60~1.90(?n)ppm(17H)δ
x4s ~4.48 (m) ppm (61 () δ 6.1
2' (d) ppm (I H) δ 6.
73-7. ! + 3 (trL) ppm (5H)
δ 7.57-7.96 (m) ppm (IH)
Elemental analysis value (CI9H2gNO5F) OHN Analysis value (chi) 59.80 7.44 57
1 Theoretical value (%) 59.83 7.40 &
Molecular weight by 670C-MSS 381 Example 3 In the same reactor as Example 1, 1-ethoxycarbonyl-
1 gr of 1,2-dihydroquinoline-2-diisopurphosphonate and 20 ml of tetrahydrofuran were taken and cooled to -78°C in a dry ice-acetone bath. While stirring with a magnetic stirrer, the inside of the flask was sufficiently purged with nitrogen.
次いで１．５９ Ｍ −ｎ−ブチルリチウム−ｎ−へキ
サン溶液２．０３ ｍｌを加え３０分間攪拌した。さら
にヨウ化メチル０．１７ｍを加え２０分間攪拌しドライ
アイス−アセトン浴を取シ除き室温まで昇温し１時間攪
拌した。Next, 2.03 ml of 1.59 M n-butyllithium-n-hexane solution was added and stirred for 30 minutes. Furthermore, 0.17 m of methyl iodide was added and stirred for 20 minutes, and the dry ice-acetone bath was removed, the temperature was raised to room temperature, and the mixture was stirred for 1 hour.
再びドライアイス−アセトン浴にて一７８°Ｃに冷却し
１．５９Ｍ ｎ−ブチルリチウム−ｎ−へキサン溶液
２．＋３３７．ヨウ化メチルを０．１７ ｍｌ加え同様
の反応を行った。Cool again to -78°C in a dry ice-acetone bath and add a 1.59M n-butyllithium-n-hexane solution2. +337. A similar reaction was carried out by adding 0.17 ml of methyl iodide.
反応終了後は、実施例１と同一の操作を行い４．４−ジ
メチル−１−エトキシカルボニル−１，４−ジヒドロキ
ノリン−２−ジイソプロピルホスホｆ−ト（１５ｇｒを
得た。（、ｎＪ５ ｔｓｏ４ｓ）赤外線吸収スペクト
ル（ｒｉａｃｔ）
２９７５（Ｃ−Ｈ）、１７２０（０−０）。After the reaction was completed, the same operation as in Example 1 was performed to obtain 4,4-dimethyl-1-ethoxycarbonyl-1,4-dihydroquinoline-2-diisopropylphosphonate (15 gr. (, nJ5 tso4s) Infrared absorption spectrum (react) 2975 (C-H), 1720 (0-0).
１２６Ｃ１（Ｐ−０）、＋ｏ＋ｏ、９８０（Ｐ−Ｑ −
０） ｒｙＦ’
核磁気共鳴吸収スペクトル（ＣＣｔ４内部標準ＴＭＳ
）δ １． ＯＯ〜１．８８ （ｍ） ｐｐｍ （２１
Ｈ）δ ４．００〜５．００（ｍ）ｐｐｒｎ（４Ｈ）δ
６．５５ （ｍ） ｐｐｍ（Ｉ Ｈ）δ ６
．９５〜７．４５ （ｍ） ｐｐｍ （３Ｔ（）δ ７
．６ｏ〜ａｏｏ（ｍ）ｐｐｍ（１ｎ）元素分析値（Ｃ２
，Ｈ３ｏＮＯ，Ｐとして）ＯＨＮ
分析値（坤 ６０．８１ ７．６０ ５．５７理
論値（％） ６０．７５ ７．６５ ３．５４
Ｇ Ｏ−ＭＳＦ！による分子量 ３９５特許出願人
東洋曹達工業株式会社
手続補正書
１ＪｆＦｌ−の表示
昭和５８年特許願第 ０８２７８３ 弓２発明の名称
ジアルキルボスホナー１〜誘導体及びその製造法６・袖
正をする者
ｉＪＩ ｆ’ｌ＝との関係 特許出願人電話番号（５８
５）ろろ１１
４補ＩＥ命令の１ヨイｑ
自発
６補正の対象
［明細書の発明の詳細な説明の欄」
７補正の内容
（１）明細書、８頁５行
ｒＥｒｙｓｉｐｈｅ ＱｒａｒｒｌｉｎｉｓＪを
ｒＥｒｙｓｉｐｌｅ ｇｒａｍｉｎｉｓＪと訂正す
る。126C1 (P-0), +o+o, 980 (P-Q -
0) ryF' nuclear magnetic resonance absorption spectrum (CCt4 internal standard TMS
)δ 1. OO~1.88 (m) ppm (21
H) δ 4.00-5.00 (m) pprn(4H) δ
6.55 (m) ppm (I H) δ 6
．． 95-7.45 (m) ppm (3T()δ 7
．． 6o~aoo(m) ppm(1n) Elemental analysis value (C2
, H3oNO, P) OHN Analytical value (Kon 60.81 7.60 5.57 Theoretical value (%) 60.75 7.65 3.54
GO-MSF! Molecular weight by 395 patent applicant
Toyo Soda Kogyo Co., Ltd. Procedural Amendment 1 JfFl- Indication 1982 Patent Application No. 082783 Bow 2 Name of the Invention Dialkylboschoner 1 - Derivatives and their Manufacturing Process 6 / Relationship with Sleeve Straightener iJI f'l= Patent Applicant phone number (58
5) Roro 11 4th Supplement IE instruction 1yoiq Spontaneous 6 Subject of amendment [Detailed description of invention column in specification] 7 Contents of amendment (1) Specification, page 8, line 5 rErysiphe QrarrlinisJ to rErysiple graminisJ correct.
（２）明細書、１１頁８行 ｒ （ｍ） Ｊを ｒ（ｄン」と訂正する。(2) Specification, page 11, line 8 r (m) J Correct it as r(d-n).
Claims (1)
ホナート誘導体。 １ アルキル基を示す。）で表わされる４−アルキル−１−
エトキシカルボニル−１，２−ジヒドロキノリン−２−
ジアルキルホスホナートをアルカリ金属塩とし、次いで
Ｒ，Ｘ （式中Ｒ２は、前記に同じ、Ｘは）・ロゲンを
示す。）で表わされるハロゲン化アルキルと反応させる
ととを特徴とする一般式 キル基を示す。）で表わされるシアルギルホスホナート
誘導体の製造法。[Claims] Omari 0002H. Indicates a lower alkyl group. ) A dialkylphosphonate derivative represented by 1 Indicates an alkyl group. ) 4-alkyl-1-
Ethoxycarbonyl-1,2-dihydroquinoline-2-
The dialkylphosphonate is used as an alkali metal salt, and then R, ) represents a general formula kyl group characterized by reacting with a halogenated alkyl group. ) A method for producing a sialgyl phosphonate derivative represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8278383A JPH0240078B2 (en) | 1983-05-13 | 1983-05-13 | JIARUKIRUHOSUHONAATOJUDOTAIOYOBISONOSEIZOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8278383A JPH0240078B2 (en) | 1983-05-13 | 1983-05-13 | JIARUKIRUHOSUHONAATOJUDOTAIOYOBISONOSEIZOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59210096A true JPS59210096A (en) | 1984-11-28 |
| JPH0240078B2 JPH0240078B2 (en) | 1990-09-10 |
Family
ID=13784010
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8278383A Expired - Lifetime JPH0240078B2 (en) | 1983-05-13 | 1983-05-13 | JIARUKIRUHOSUHONAATOJUDOTAIOYOBISONOSEIZOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0240078B2 (en) |
-
1983
- 1983-05-13 JP JP8278383A patent/JPH0240078B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0240078B2 (en) | 1990-09-10 |
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