JPS62205074A - Production of 4-alkoxy-2-butenyl lactone - Google Patents
Production of 4-alkoxy-2-butenyl lactoneInfo
- Publication number
- JPS62205074A JPS62205074A JP4785186A JP4785186A JPS62205074A JP S62205074 A JPS62205074 A JP S62205074A JP 4785186 A JP4785186 A JP 4785186A JP 4785186 A JP4785186 A JP 4785186A JP S62205074 A JPS62205074 A JP S62205074A
- Authority
- JP
- Japan
- Prior art keywords
- lactone
- butenyl
- compound
- formula
- methylene chloride
- 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 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- -1 4-methoxy-2-butenyl lactone Chemical class 0.000 claims abstract description 11
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 239000007858 starting material Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- ZYTSUANFIPZBDM-UHFFFAOYSA-N (2,5-dimethoxy-2h-furan-5-yl)methanol Chemical compound COC1OC(CO)(OC)C=C1 ZYTSUANFIPZBDM-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 239000002728 pyrethroid Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 3
- 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 2
- YDVNLQGCLLPHAH-UHFFFAOYSA-N dichloromethane;hydrate Chemical compound O.ClCCl YDVNLQGCLLPHAH-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PPRRVDHSOLNCBW-UHFFFAOYSA-N 1-(2,5-dihydrofuran-2-yl)ethanol Chemical compound OC(C)C1OCC=C1 PPRRVDHSOLNCBW-UHFFFAOYSA-N 0.000 description 1
- MWXWHUXLVXOXBZ-UHFFFAOYSA-N 1-(furan-2-yl)propan-1-ol Chemical compound CCC(O)C1=CC=CO1 MWXWHUXLVXOXBZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は２−ブテニルラクトンの誘導体の製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing a 2-butenyl lactone derivative.
（従来の技術）
２−ブテニルラクトン誘導体は有機合成上、有用な化合
物であり、例元ばピレスロイドを合成するうえでも非常
に有用な中間体である。(Prior Art) 2-Butenyl lactone derivatives are useful compounds in organic synthesis, and are very useful intermediates in the synthesis of pyrethroids, for example.
従来、４−置換−２−ブテニルラクトン誘導体を得る方
法としでは Ｊ ｏｕｒｎｍｌ ｏｆ Ｏｒｌ（ａｎｉ
ｃＣｈｅｍｉｓｔｒｙ、 ａｓ １９７４＠ １９７３
に記載されている光反応などの合成方法が知られている
が、いまだ収率、再現性等の点で満足すべき方法は見出
されていない。Conventionally, the method for obtaining 4-substituted-2-butenyl lactone derivatives was as follows:
cChemistry, as 1974@1973
Synthesis methods such as the photoreaction described in 2003 are known, but no method has yet been found that is satisfactory in terms of yield, reproducibility, etc.
（発明が解決しようとする問題点）
本発明の目的は収率、再現性等の点で優れた２−ブテニ
ルラクトン誘導体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 method for producing 2-butenyl lactone derivatives that is excellent in terms of yield, reproducibility, and the like.
（問題点を解決するための手段）
本発明は一般式
（Ｒ’はＣ，＝、のアルキル基、Ｒ２，Ｒ３はそれぞれ
異なっていてもよ（、水素またはＣ１，６のアルキル基
を示す）で表わされる化合物を過ヨ・ン素酸またはその
塩と反応させることを特徴とする一般式（Ｒ’は上記に
同じ）で表わされる４−アルコキシ−２−ブテニルラク
トンの製造方法に係る。(Means for Solving the Problems) The present invention is based on the general formula (R' is a C,=, alkyl group, R2 and R3 may be different from each other (represents hydrogen or a C1,6 alkyl group)) The present invention relates to a method for producing 4-alkoxy-2-butenyl lactone represented by the general formula (R' is the same as above), which comprises reacting the compound represented by periodic acid or a salt thereof.
上記においてＣ、、、のフルキル基としては例えばメチ
ル、エチル、イソプロピル、ブチル、ヘキシル基等を挙
げることができる。In the above, examples of the furkyl group represented by C, . . . include methyl, ethyl, isopropyl, butyl, hexyl, and the like.
本発明の目的化合物は医薬、農薬等の合成中間体として
有用な化合物であり、例えばピレスロイドの合成中間体
として非常に有用である。The object compound of the present invention is a compound useful as a synthetic intermediate for medicines, agricultural chemicals, etc., and is very useful as a synthetic intermediate for pyrethroids, for example.
本発明の出発原料（Ｈ）は例えば下記の方法により製造
される。The starting material (H) of the present invention is produced, for example, by the following method.
（ＩＩＩ） （ＩＩ）化
合物（ＩＩＩ）としては例えば７１Ｊフリルアルコール
、ａ−メチルフルフリルアルコール、ａ−エチルフルフ
リルアルコール、ａ、ａ−ツメチルフルフリルアルコー
ル等を挙げることができる。(III) (II) Examples of compound (III) include 71J furyl alcohol, a-methylfurfuryl alcohol, a-ethylfurfuryl alcohol, a,a-trimethylfurfuryl alcohol, and the like.
過ヨウ素酸の塩としては、例えばナトリウム塩、カリウ
ム塩、アンモニウム塩などの塩が用いられる。As the salt of periodic acid, for example, salts such as sodium salt, potassium salt, and ammonium salt are used.
本発明において化合物（ＩＩ）と過ヨウ素酸またはその
塩の反応は溶媒の存在下に行うのが好ましい。In the present invention, the reaction between compound (II) and periodic acid or a salt thereof is preferably carried out in the presence of a solvent.
過ヨウ素酸またはその塩は、通常化合物（ｎ）の１モル
に対して約１〜５モル反応させるのが好ましい、使用さ
れる溶媒としては例えばベンゼン、トルエン等の芳香族
炭化水素、塩化メチレン、ジクロルエタン等のへロデン
化炭化水素、ノオキサン、エチルエーテル等のエーテル
類、ｎ−ヘキサン、ｎ−へブタン等の脂肪族炭化水素な
どの有ｆｉ溶媒と水との混合溶１＆系およＶ２層溶媒系
が好ましい。Periodic acid or its salt is preferably reacted in an amount of about 1 to 5 moles per mole of compound (n). Examples of solvents used include aromatic hydrocarbons such as benzene and toluene, methylene chloride, Mixed solutions of water and fi-containing solvents such as helodenated hydrocarbons such as dichloroethane, ethers such as nooxane and ethyl ether, and aliphatic hydrocarbons such as n-hexane and n-hebutane, 1& system and V2 layer solvents system is preferred.
反応温度は特に限定されないが、余りに低温であれば、
混合溶媒や、２７１！ｌＮ＃媒系での水相が固結してし
まうし、余りに高温であれば出発物質や目的化合物が熱
分解を起こすので、通常的−１０℃〜６０℃、好ましく
は約θ℃〜３０℃とするのが良い。The reaction temperature is not particularly limited, but if it is too low,
Mixed solvent, 271! The aqueous phase in the lN# medium system will solidify, and if the temperature is too high, the starting materials and target compounds will thermally decompose, so the temperature is usually -10°C to 60°C, preferably about θ°C to 30°C. It is better to
本発明の目的化合物（１）は例えば濃縮、抽出、蒸留、
クロマトグラフィー等の公知の手段により精製すること
ができる。The target compound (1) of the present invention can be obtained by, for example, concentration, extraction, distillation,
It can be purified by known means such as chromatography.
（′ｉＡ 施 例） 以下に本発明を実施例によって説明する。('iA implementation example) The present invention will be explained below by way of examples.
実施例１
２．５−ジメトキシ−２−ヒドロキシメチル−２，５−
ジヒドロフラン２０９ｍｇと塩化ノチレン２輪ｌの混合
溶液に、過ヨウ素ｆ？！３３０ｍｇを溶解した水溶液２
ｍｌを更に混合し、０ ”０〜１０℃にて３時間反応さ
せた０反応終了後、重曹水で中和し、塩化メチレン相を
蒸留すると、目的物である４−７トキシー２−ブテニル
ラクトンが９２％の収率で得られた。このもののＮＭＲ
スペクトルは以下の通りで、その構造と一致した。Example 1 2,5-dimethoxy-2-hydroxymethyl-2,5-
Add periodine f? to a mixed solution of 209 mg of dihydrofuran and 2 liters of notylene chloride. ! Aqueous solution 2 in which 330mg was dissolved
ml was further mixed and reacted at 0 to 10°C for 3 hours. After the reaction was completed, the mixture was neutralized with aqueous sodium bicarbonate, and the methylene chloride phase was distilled to yield the target product, 4-7 toxy-2-butenyl lactone. Obtained with a yield of 92%. NMR of this product
The spectrum was as shown below and was consistent with its structure.
Ｎ Ｍ Ｒ（ＣＤ ＣＩ３） δ ｐｐ輸３．５
５ （ｓ、 ３１１）、 ５．８４ （ｂｒｓ、 Ｈ
ｌ）？６．１８ （ｄｄ、 １ｌｌ）、 ７．１８ （
ｄｄ、 ［）実施例２
２．５−ジメトキシ−２−ヒドロキンメチル−２，５−
ジヒドロフラン２１１ｍｇと１．２−ジクロルエタン１
ｍｌの混合溶液に、過ヨウ素ｆｉ３６１ｍｇを溶解した
水Ｓ液２ｓＺを更に混合し、Ｏ℃〜１０℃にて６時間反
応させた０反応終了後、重曹水で中和し、塩化メチヒン
相を蒸留すると、目的物の４−メトキン−２−ブテニル
ラクトンが７５％の収率で得られた。NMR (CD CI3) δ pp import 3.5
5 (s, 311), 5.84 (brs, H
l)? 6.18 (dd, 1ll), 7.18 (
dd, [) Example 2 2,5-dimethoxy-2-hydroquinemethyl-2,5-
211 mg of dihydrofuran and 1 part of 1,2-dichloroethane
ml of the mixed solution was further mixed with water S solution 2sZ in which 361 mg of periodine fi was dissolved, and reacted at 0°C to 10°C for 6 hours. After the reaction was completed, it was neutralized with aqueous sodium bicarbonate, and the methihine chloride phase was distilled. Then, the target product, 4-methquin-2-butenyl lactone, was obtained with a yield of 75%.
このもののＮＭＲスペクトルは実施例１のものと一致し
た。The NMR spectrum of this product matched that of Example 1.
実施例３
２．５−ジメトキシ−２−ヒドロキシメチル−２，５−
ジヒドロ７ラン１１フｌ１１ｇとジオキサン２社のｔｎ
合溶液に、過ヨウ素酸ナトリウム２２０糟ｇを溶解した
水溶液２ｍＮを更に混合し、０℃〜１０℃にて２００時
間反応せた０反応終了後、減圧で濃縮し、その残渣を水
−塩化メチレンで溶解、抽出し、塩化メチレン相を蒸留
すると、目的物の４−メトキシ−２−ブテニルラクトン
が８０％の収率で得られた。このもののＮＭＲスペクト
ルは実施例１のものト一致した。Example 3 2,5-dimethoxy-2-hydroxymethyl-2,5-
Dihydro 7ran 11 fl 11 g and dioxane 2 companies' tn
The combined solution was further mixed with 2 mN of an aqueous solution in which 220 g of sodium periodate was dissolved, and reacted at 0°C to 10°C for 200 hours. After the reaction was completed, it was concentrated under reduced pressure, and the residue was diluted with water-methylene chloride. When the methylene chloride phase was distilled, the desired product, 4-methoxy-2-butenyl lactone, was obtained in a yield of 80%. The NMR spectrum of this product matched that of Example 1.
実施例４
２．５−ジメトキシ−２−ヒドロキシメチル−２，５−
ジヒドロ７ラン２０２＋ｕｒと酢酸エチル２ｍｌの混合
溶液に、過ヨウ素Ｐ１１３５０＋ａｇを溶解した水溶液
２−を更に混合し、２０℃〜４０℃にて２時間反応させ
た。Example 4 2,5-dimethoxy-2-hydroxymethyl-2,5-
An aqueous solution 2- in which periodine P11350+ag was dissolved was further mixed with a mixed solution of dihydro 7ran 202+ur and 2 ml of ethyl acetate, and reacted at 20°C to 40°C for 2 hours.
反応終了後、重曹水で中和し、塩化エチル相を蒸留する
と、目的物の４−７トキシー２−ブテニルラクトンが６
５％の収率で得られた。このもののＮＭＲスペクトルは
実施例１のものと一致した。After the reaction is completed, it is neutralized with aqueous sodium bicarbonate, and the ethyl chloride phase is distilled to produce 4-7 toxy-2-butenyl lactone, the target product.
Obtained with a yield of 5%. The NMR spectrum of this product matched that of Example 1.
実施例５
２．５−ツメトキシー２−（１−ヒドロキシエチル）−
２，５−ジヒドロフラン１９０槌ｇとエチルエーテル２
社の混合溶液に、過ヨウ素酸３４０＋＊ｇを溶解した水
溶液４ｔａｌを更に混合し、Ｏ℃〜１０℃にて１．５時
間反応させた０反応終了後、重曹水で中和し、エチルエ
ーテル相を蒸留すると、目的物の４−７トキシー２−ブ
テニルラクトンが７８％の収率で得られた。このものの
ＮＭＲスペクトルは実施例１のものと一致した。Example 5 2.5-Tumethoxy 2-(1-hydroxyethyl)-
2,5-dihydrofuran 190 g and ethyl ether 2
4 tal of an aqueous solution in which 340+*g of periodic acid was dissolved was further mixed with the mixed solution of the same company, and reacted for 1.5 hours at 0°C to 10°C. After the completion of the reaction, neutralization was performed with aqueous sodium bicarbonate, Distillation of the phase yielded the desired product, 4-7toxy-2-butenyl lactone, in a yield of 78%. The NMR spectrum of this product matched that of Example 1.
実施例６
２．５−ジメトキシ−２−ヒドロキシメチル−２，５−
ジヒドロフラン２１０Ｂと塩化メチレン２ｔａｌの混合
溶液に、過ヨウ素ＰＩｌｆＪリウム３６０輪ｇを溶解し
た水溶液２社を更に混合し、θ℃〜１０℃にて２００時
間反応せた０反応終了後、塩化メチレン相を蒸留すると
、目的物の４−メトキシ−２−ブテニルラクトンが８６
％の収率で得られた。このもののＮＭＲスペクトルは実
施例１のものと一致した。Example 6 2,5-dimethoxy-2-hydroxymethyl-2,5-
A mixed solution of dihydrofuran 210B and 2 tal of methylene chloride was further mixed with two aqueous solutions in which 360 g of periodine PIlfJ was dissolved and reacted at θ°C to 10°C for 200 hours. After the completion of the reaction, the methylene chloride phase was When distilled, the target product, 4-methoxy-2-butenyl lactone, is distilled into 86
% yield. The NMR spectrum of this product matched that of Example 1.
実施例７
２．５−ジメトキシ−２−ヒドロキシメチル−２，５−
ジヒドロ７ラン１１０ＩＩ１ｇとツタノール４−１の混
合溶、液に、過ヨウ素酸ナトリウム２１０＋＊１１を溶
解した水溶液２ｔ＆１を更に混合し、−１０℃〜０℃に
て２００時間反応せた。反応終了後、減圧で濃縮し、そ
の残渣を水−塩化メチレンで溶解、抽出し、塩化メチレ
ン相を蒸留すると、目的物の４−メトキシ−２−ブテニ
ルラクトンが９０％の収率で得られた。Example 7 2,5-dimethoxy-2-hydroxymethyl-2,5-
An aqueous solution of 2t&1 in which sodium periodate 210+*11 was dissolved was further mixed with the mixed solution of 1g of dihydro 7ran 110II and 4-1 of tutanol, and reacted at -10°C to 0°C for 200 hours. After the reaction was completed, it was concentrated under reduced pressure, the residue was dissolved and extracted with water-methylene chloride, and the methylene chloride phase was distilled to obtain the target product, 4-methoxy-2-butenyl lactone, in a yield of 90%.
このもののＮＭＲスペクトルは実施例１のものと一致し
た。The NMR spectrum of this product matched that of Example 1.
実施例８
２．５−ジイソプロビルオキシ−２−ヒドロキシメチル
−２，５−ジヒドロ７ラン２：１０Ｂと塩化メチレン２
Ｉ１１１の混合溶液に、過ヨウ素酸３３０■を溶解した
水溶９２ｍ１を更に混合し、０℃〜１０℃にて６時間反
応させた６反応終了後、重曹水で中和し、塩化メチレン
相を蒸留すると、目的物の４−イソプロピルオキシ−２
−１テニルラクトンが７２％の収率で得られた。このも
ののＮＭＲスペクトルは以下の通りで、その構造と一致
した。Example 8 2,5-diisopropyloxy-2-hydroxymethyl-2,5-dihydro 7ran 2:10B and methylene chloride 2
92 ml of an aqueous solution containing 330 μm of periodic acid dissolved in the mixed solution of I111 was further mixed and reacted at 0°C to 10°C for 6 hours. After the completion of the 6 reactions, neutralization was carried out with aqueous sodium bicarbonate, and the methylene chloride phase was distilled. Then, the target product 4-isopropyloxy-2
-1 thenyl lactone was obtained with a yield of 72%. The NMR spectrum of this product was as shown below, and was consistent with its structure.
Ｎ Ｍ Ｒ（ＣＤ ＣＩ、） δ ｐｐｍ１．２６
（ｄ、 ６Ｈ）、 ４．１０ （ｍｔ １８）、 ６．
０３ （ｓ、 ＩＨ）。NMR (CD CI,) δ ppm1.26
(d, 6H), 4.10 (mt 18), 6.
03 (s, IH).
６．１８ （ｄ、 ＩＩＩ）、 ７．２１ （ｄ、 １
８）実施例９
２．５−ジメトキシ−２−（１−ヒドロキシプロピル）
−２，５−ジヒドロ７ラン５４−ｇと塩化メチレン２Ｉ
Ｉ＋１の混合溶液に、過ヨウ素酸９６Ｂを溶解した水溶
液２ｍｌを更に混合し、０℃〜１０℃にて４ Ｉｌ、？
間反応させた。反応終了後、重曹水で中和し、塩化メチ
レン相を蒸留すると、目的物の４−メトキシ−２−ブテ
ニルラクトンが７９％の収率で得られた。このもののＮ
ＭＲスペクトルは’ｌ＆ｍ例１のモノト一致しな。6.18 (d, III), 7.21 (d, 1
8) Example 9 2.5-dimethoxy-2-(1-hydroxypropyl)
-2,5-dihydro7rane 54-g and methylene chloride 2I
2 ml of an aqueous solution in which periodic acid 96B was dissolved was further mixed with the mixed solution of I+1, and 4 Il, ? was added at 0°C to 10°C.
It was allowed to react for a while. After the reaction was completed, the mixture was neutralized with an aqueous sodium bicarbonate solution and the methylene chloride phase was distilled to obtain the target product, 4-methoxy-2-butenyl lactone, in a yield of 79%. N of this
The MR spectrum does not match that of Example 1.
実施例１０
２．５−ジメトキシ−２−（１−ヒドロキシプロピル）
−２，５−ジヒドロ７ラン５６−ｇとメタ／−ル２■ｌ
の混合溶液に、過ヨウ素酸ナトリウム９４鯵ｇを溶解し
た水溶液２ｍｌを更に混合し、θ℃〜ｌＯ℃にて２１時
間反応させた。反応終了後、減圧で濃縮し、残渣を水−
塩化メチレンにて溶解、抽出し、塩化メチレン相を蒸留
すると、目的物の４−メトキシ−２−ブテニルラクトン
が７０％の収率で得られた。Example 10 2.5-dimethoxy-2-(1-hydroxypropyl)
-2,5-dihydro7rane 56 g and methanol 2 l
To the mixed solution was further mixed 2 ml of an aqueous solution in which 94 g of sodium periodate was dissolved, and the mixture was reacted at θ°C to 10°C for 21 hours. After the reaction was completed, it was concentrated under reduced pressure and the residue was dissolved in water.
The mixture was dissolved in methylene chloride, extracted, and the methylene chloride phase was distilled to obtain the target product, 4-methoxy-2-butenyl lactone, in a yield of 70%.
このもののＮＭＲスペクトルは実施例１のものと一致し
た。The NMR spectrum of this product matched that of Example 1.
実施例１１
２．５−ジメトキシ−２−（１−ヒドロキシ−１−メチ
ル一二チル）−２，５−ジヒドロ７ラン５９■ｇと塩化
メチレン２社の混合溶禅に、過ヨウ素酸１０３ｍｇを溶
解した水溶液２ｍｆを更に混合し、０℃〜１０℃にて４
時間反応させた０反応終了後、重曹水で中和し、塩化メ
チレン相を蒸留すると、目的物の４−７トキシー２−ブ
テニルラクトンが７５％の収率テ得られた。このものの
ＮＭＲスペクトルは実施例１のものと一致した。Example 11 103 mg of periodic acid was added to a mixed solution of 59 g of 2,5-dimethoxy-2-(1-hydroxy-1-methyl-1-dithyl)-2,5-dihydro7ran and two methylene chloride companies. Further mix 2 mf of the dissolved aqueous solution and heat at 0°C to 10°C for 40 minutes.
After the reaction was completed for 0 hours, the mixture was neutralized with an aqueous sodium bicarbonate solution, and the methylene chloride phase was distilled to obtain the target product, 4-7 toxy-2-butenyl lactone, in a yield of 75%. The NMR spectrum of this product matched that of Example 1.
（以 上）(that's all)
Claims (1)
３はそれぞれ異なつていてもよく、水素またはＣ＿１＿
〜＿６のアルキル基を示す）で表わされる化合物を過ヨ
ウ素酸またはその塩と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▼（ I ） （Ｒ＾１は上記に同じ）で表わされる４−アルコキシ−
２−ブテニルラクトンの製造方法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) (R^1 is an alkyl group of C_1_-_6, R^2, R^
3 may be different, hydrogen or C_1_
There are general formulas ▲mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting a compound represented by ~__6 alkyl group) with periodic acid or its salt▼(I) (R^1 is the same as above) ) 4-alkoxy-
Method for producing 2-butenyl lactone.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4785186A JPH0696567B2 (en) | 1986-03-05 | 1986-03-05 | Method for producing 4-alkoxy-2-butenyl lactone |
| FR8702981A FR2595358B1 (en) | 1986-03-05 | 1987-03-05 | PROCESS FOR THE PREPARATION OF 4-ALCOXY-2-BUTENYL-1-LACTONES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4785186A JPH0696567B2 (en) | 1986-03-05 | 1986-03-05 | Method for producing 4-alkoxy-2-butenyl lactone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62205074A true JPS62205074A (en) | 1987-09-09 |
| JPH0696567B2 JPH0696567B2 (en) | 1994-11-30 |
Family
ID=12786871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4785186A Expired - Lifetime JPH0696567B2 (en) | 1986-03-05 | 1986-03-05 | Method for producing 4-alkoxy-2-butenyl lactone |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0696567B2 (en) |
| FR (1) | FR2595358B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3905243A1 (en) * | 1989-02-21 | 1990-08-23 | Basf Ag | METHOD FOR PRODUCING LACTONES |
-
1986
- 1986-03-05 JP JP4785186A patent/JPH0696567B2/en not_active Expired - Lifetime
-
1987
- 1987-03-05 FR FR8702981A patent/FR2595358B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| FR2595358A1 (en) | 1987-09-11 |
| JPH0696567B2 (en) | 1994-11-30 |
| FR2595358B1 (en) | 1990-11-16 |
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