JPH0377878A - Production of 2-furylcarbinol derivative - Google Patents
Production of 2-furylcarbinol derivativeInfo
- Publication number
- JPH0377878A JPH0377878A JP21314689A JP21314689A JPH0377878A JP H0377878 A JPH0377878 A JP H0377878A JP 21314689 A JP21314689 A JP 21314689A JP 21314689 A JP21314689 A JP 21314689A JP H0377878 A JPH0377878 A JP H0377878A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- zinc
- pref
- reaction
- water
- 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
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical class OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011701 zinc Substances 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 14
- -1 ammonium halide Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims 3
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 150000003180 prostaglandins Chemical class 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- BLHZUMDWLLFLJC-UHFFFAOYSA-N 4-methylfuran-2-carbaldehyde Chemical compound CC1=COC(C=O)=C1 BLHZUMDWLLFLJC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- FVFIZQMCIUNSPY-UHFFFAOYSA-N 3-(2-methylpropyl)furan-2-carbaldehyde Chemical compound CC(C)CC=1C=COC=1C=O FVFIZQMCIUNSPY-UHFFFAOYSA-N 0.000 description 1
- VJISCMXRLFHAKO-UHFFFAOYSA-N 4-butylfuran-2-carbaldehyde Chemical compound CCCCC1=COC(C=O)=C1 VJISCMXRLFHAKO-UHFFFAOYSA-N 0.000 description 1
- KYOQLZOZPDVYCB-UHFFFAOYSA-N 4-ethylfuran-2-carbaldehyde Chemical compound CCC1=COC(C=O)=C1 KYOQLZOZPDVYCB-UHFFFAOYSA-N 0.000 description 1
- RNFIHRJWAKWIEM-UHFFFAOYSA-N 4-propan-2-ylfuran-2-carbaldehyde Chemical compound CC(C)C1=COC(C=O)=C1 RNFIHRJWAKWIEM-UHFFFAOYSA-N 0.000 description 1
- MLNFKFQKOYSGRY-UHFFFAOYSA-N 4-propylfuran-2-carbaldehyde Chemical compound CCCC1=COC(C=O)=C1 MLNFKFQKOYSGRY-UHFFFAOYSA-N 0.000 description 1
- GKJMGRNQNUBUMM-UHFFFAOYSA-N 5-(3-methylphenyl)-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound CC1=CC=CC(C=2NNC(=S)N=2)=C1 GKJMGRNQNUBUMM-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- YTRIOKYQEVFKGU-UHFFFAOYSA-M benzyl(tripropyl)azanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CC1=CC=CC=C1 YTRIOKYQEVFKGU-UHFFFAOYSA-M 0.000 description 1
- SXGBREZGMJVYRL-UHFFFAOYSA-N butan-1-amine;hydrobromide Chemical compound [Br-].CCCC[NH3+] SXGBREZGMJVYRL-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Furan Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は医農薬の中間体、とりわけプロスタグランデイ
ン中間体として有用な２−フリルカルビノール誘導体の
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing 2-furylcarbinol derivatives useful as intermediates for pharmaceuticals and agrochemicals, particularly as prostaglandin intermediates.
〈従来の技術〉
従来、上記２−フリルカルビノール誘導体の製造法とし
ては例えば、４−（２−フリル）−４−ヒドロキシ−１
−ブチンとハロゲン化アルキルとを反応させる方法（特
開昭６２−２９５６８号公報）が知られている。<Prior art> Conventionally, as a method for producing the above-mentioned 2-furyl carbinol derivative, for example, 4-(2-furyl)-4-hydroxy-1
- A method of reacting butyne with an alkyl halide (JP-A-62-29568) is known.
〈発明が解決しようとする課題〉 しかしながら上記の方法ではリチウムアミド。<Problem that the invention seeks to solve> However, the above method uses lithium amide.
またはブチルリチウム等発火の危険性が高く取扱が困難
な試薬を使用するため、工業的には必ずしも満足できる
ものとは言い鼎い。Also, since it uses reagents such as butyl lithium that have a high risk of ignition and are difficult to handle, it is not necessarily satisfactory from an industrial perspective.
本発明の目的はプロスタグランデイン等の中間体である
２−フリルカルビノール誘導体を工業的にも有利に製造
することである。An object of the present invention is to industrially advantageously produce 2-furylcarbinol derivatives, which are intermediates for prostaglandin and the like.
く課題を解決するための手段〉
本発明者らはプロスタグランデインの中間体の？！造法
を捷供すべく種々検討した結果、フルフラー・九類と容
易に合成可能なアセチレン性ハロゲノエステル類とを反
応させることにより、工業的にも有利に２−フリルカル
ビノール誘導体が製造できることを見出し本発明に至ワ
た。Means for Solving the Problems> The present inventors have developed a method for solving the problems of prostaglandin intermediates. ! As a result of various studies to develop a production method, it was discovered that 2-furylcarbinol derivatives can be produced industrially advantageously by reacting Furfurur Group 9 with easily synthesized acetylenic halogenoesters. This led to the present invention.
すなわち、本発明は一般式（１）
（式中、ＲＩは水素原子または低級アルキル基を表わす
。）
で示されるフルフラール類と、−数式（１Ｎ）Ｘ−ＣＨ
，−Ｃ二Ｇ−（ＣＨ，）元ＣＯＯ臥（ＩＩ）（式中、Ｘ
はハロゲン原子を表わし、Ｒおは水素原子または低級ア
ルキル基を表わす、ｎは２ヘ−４の整数を表わす。）
で示されるアセチ１／ン性ハロゲノエステル類とを。That is, the present invention provides a furfural compound represented by the general formula (1) (wherein RI represents a hydrogen atom or a lower alkyl group) and a compound represented by the formula (1N)X-CH
, -C2G-(CH,) element COO(II) (wherein, X
represents a halogen atom, R represents a hydrogen atom or a lower alkyl group, and n represents an integer of 2-4. ) and the acetinic halogenoesters shown in the following.
亜鉛及び水の存在下に反応させることを特徴とする一般
式（Ｉｆｆ）
ｎ
（式中、Ｒ，、Ｌ及びｎは前記と同２二意味を表わすい
）
で示される２−フリルカルビノール誘導体の製造法であ
る、
以下１本発明について詳細に説明する。A 2-furyl carbinol derivative represented by the general formula (Iff) n (wherein R, , L and n have the same meanings as above), which is characterized by being reacted in the presence of zinc and water. The present invention, which is a manufacturing method, will be described in detail below.
本発明で使用される上記−数式（１）のフルフラール類
としては、４−メチルフルフラール、４−エチルフルフ
ラール、４−ｎ−プロピルフルフラール、４−イソプロ
ピルフルフラール、４−ｎ−ブチルフルフラール、４−
イソブチルフルフラール、４−ｔ、ｃｒｔ、−ブチルフ
ルフラール等が例示されるや
これらのフルフラール類（１）は通常、−数式［１Ｎ）
で示されるアセチレン性ハロゲノｊ６ステル類に対して
１〜４倍当量、好ましくは１〜２倍当量使用される。The furfurals of formula (1) used in the present invention include 4-methylfurfural, 4-ethylfurfural, 4-n-propylfurfural, 4-isopropylfurfural, 4-n-butylfurfural, 4-
Examples include isobutylfurfural, 4-t, crt, -butylfurfural, etc. These furfurals (1) usually have the formula [1N]
It is used in an amount of 1 to 4 times, preferably 1 to 2 times, relative to the acetylenic halide j6 ester represented by the formula.
一般式（ＩＩ）で示されるアセチレン性ハロゲノエステ
ル類としてば ６−ブロモ−１または６−クロロ−４−
ヘキシン酸メチル、７−ブロモ−または７−クロロ−５
−ヘプチン酸メチル、８−ブーモー、またば８−クロロ
−６−オクチン酸メチル等が例示される。Examples of acetylenic halogenoesters represented by general formula (II) include 6-bromo-1 or 6-chloro-4-
Methyl hexinate, 7-bromo- or 7-chloro-5
Examples include methyl -heptate, 8-boumo, and methyl 8-chloro-6-octinate.
亜鉛としては９通常粉末または微粉末のものが使用され
る。Zinc is usually used in the form of powder or fine powder.
亜鉛は通常、−軟式ｌ０で示されるアセチレン性ハロゲ
ノエステル類に対して１〜３倍当量。Zinc is usually 1 to 3 times equivalent to the acetylenic halide represented by -soft l0.
好ましくは１〜２倍当量使用される。Preferably, 1 to 2 equivalents are used.
水は通常７−数式（ＩＮ）で示されるアセチレン性ハロ
ゲノエステル類に対して１〜５０侑重量使用されるが、
その使用量はｔＧ−に制限されるもので１．Ｊ、ない。Water is usually used in an amount of 1 to 50 weight per acetylenic halogenoester represented by the formula (IN),
Its usage is limited to tG-1. J.No.
本発明においてはノ１（以り１に有機溶媒を共存させて
もよ（、かかる−ζｌａン宕媒としては、ｎ−ヘキサン
等の脂１１ｈ族系、（・刀・只ン ４−シレン等の芳香
族系炭化水素。あるいｊよジ云チルエーテルもしくはテ
トラヒドロフラン等のエーテル系溶媒が挙げられる。In the present invention, organic solvents may be present in No. 1 (in other words, organic solvents may be present in No. 1), such -ζlan solvents include fatty 11h group systems such as n-hexane, (, sword, 4-silene, etc.). aromatic hydrocarbons, and ether solvents such as dithyl ether or tetrahydrofuran.
これらの有機溶媒は通常９−数式（ｎ）で示されるアセ
チレン性ハロゲノエステル類に対して０゜１〜３０倍重
量使用されるが、その使用量は特に制限されない。These organic solvents are usually used in an amount of 0.1 to 30 times the weight of the acetylenic halide represented by formula (n), but the amount used is not particularly limited.
本発明においては塩化アンモニウムまたは臭化アンモニ
ウム等のハロゲン化アンモニウムを共存させても良く２
その使用量は通常水に対して０．０５−＝１倍重量、好
ましくは０，１〜１倍重量である。In the present invention, ammonium halides such as ammonium chloride or ammonium bromide may be present.
The amount used is usually 0.05 to 1 times the weight of water, preferably 0.1 to 1 times the weight of water.
また、ハロゲン化°アンモニウムに代えて酸を使用する
こともできる。Moreover, an acid can also be used in place of the ammonium halide.
かかる酸としては、塩酸、リン酸等の鉱酸、または酢酸
等の有機酸が使用され、その使用量は特に制限されない
が、好ましくは一般式（Ｉ［）で示されるアセチレン性
ハロゲノエステル類に対して０．０１〜ｌＯ倍モルであ
る。As such acids, mineral acids such as hydrochloric acid and phosphoric acid, or organic acids such as acetic acid are used, and the amount used is not particularly limited, but it is preferable to use acetylenic halogenoesters represented by the general formula (I[). It is 0.01 to 10 times the mole.
さらに２本発明においては有機第４級アンモニウム塩を
使用することもできる。Furthermore, in the present invention, organic quaternary ammonium salts can also be used.
かかる有機第４級アンモニウム塩としては例えば、テト
ラ−ｎ−ブチルアンモニウムプロミド。Examples of such organic quaternary ammonium salts include tetra-n-butylammonium bromide.
テトラ−ｎ−ブチルアンモニウムクロリド、テトラ−ｎ
−ペンチルアンモニウムプロミド、テトラ−ｎ−ペンチ
ルアンモニウムアイオダイド、ベンジルトリエチルアン
モニウムプロミド、ベンジルトリプロピルアンモニウム
クロリド、ベンジルトリプロピルアンモニウムアイオダ
イド５ ドデシルトリメチルアンモニウムプロミド、セ
チルトリメチルアンモニウムクロリド等が挙げられる。Tetra-n-butylammonium chloride, tetra-n
-pentylammonium bromide, tetra-n-pentylammonium iodide, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium iodide 5 Dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, and the like.
本発明の反応温度は１通常５〜９５℃９好ましくは１０
〜８０℃、より好ましくは２０〜６０℃で行われ９反応
の終点は通常、−数式（ＩＩ）で示されるアセチレン性
ハロゲノエステル類を反応系から検出できなくなった時
点をもって決定される。The reaction temperature of the present invention is usually 5 to 95°C, 9 preferably 10
The reaction is carried out at ~80°C, preferably 20~60°C, and the end point of the reaction is usually determined at the point at which the acetylenic halogenoester represented by formula (II) can no longer be detected from the reaction system.
反応終了後１反応混合物を通常の後処理５例えば濾過、
抽出１分液等の後、シリカゲルカラムクロマトグラフィ
ーによる精製により、目的化合物である一般式（ＩＩＩ
）で示される２−フリルカルビノール誘導体を得ること
ができる。After completion of the reaction 1. The reaction mixture is subjected to conventional post-treatments 5. e.g. filtration,
After extraction and separation, purification by silica gel column chromatography yields the target compound of the general formula (III
) can be obtained.
〈発明の効果〉
本発明によれば従来の合成法で用いていた発火危険性の
高い試薬を使用することなく、フルフラールＩｔ（１）
と、容易に合成可能なアセチレン性ハロゲノエステル類
（Ｉｔ）とを、亜鉛と水の存在下２−フリルカルビノー
ル誘導体を工業的にも有利に製造することができる。<Effects of the Invention> According to the present invention, furfural It(1) can be produced without using reagents with a high risk of ignition used in conventional synthesis methods.
2-furylcarbinol derivatives can be industrially advantageously produced from the easily synthesized acetylenic halogenoesters (It) in the presence of zinc and water.
該誘導体は医農薬、とりわけプロスタグランデイン中間
体として有用である。The derivatives are useful as medicines and agrochemicals, especially as prostaglandin intermediates.
〈実施例〉 以下、実施例により本発明をさらに詳細に説明する。<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
窒素雰囲気下、フルフラール０．８８ ｇ 、 ）ル
エン０．８７ ｇ 、亜鉛粉０．７８ ｇ 、テトラ−
ｎ−ブチルアンモニウムプロミド０．２６ｇ及び水７．
８ｇの混合物に３０〜３５℃で塩化アンモニウム１．１
３ｇを加えた。Example 1 Under nitrogen atmosphere, furfural 0.88 g, ) toluene 0.87 g, zinc powder 0.78 g, tetra-
0.26 g of n-butylammonium bromide and water7.
Ammonium chloride 1.1 to 8 g mixture at 30-35 °C
Added 3g.
反応液を２５℃まで冷却し、２５〜３０℃で７−ブロモ
−５−ヘプチン酸メチル１ｇを３０分〜１時間かけて加
えた０滴下終了後、同温度で５時間撹拌した。The reaction solution was cooled to 25° C., and 1 g of methyl 7-bromo-5-heptate was added over 30 minutes to 1 hour at 25 to 30° C. After completion of the dropwise addition, the mixture was stirred at the same temperature for 5 hours.
反応終了後９反応液にトルエン２００■！を加えて濾過
し、有機層を少量の５％炭酸水素ナトリウム水溶液、飽
和食塩水で洗浄後、硫酸マグネシウムで乾燥し、溶媒を
減圧下に留去して粗生成物を得た。更にこれをシリカゲ
ルクロマトグラフィーにより精製して８−（２−フリル
）−８−ヒドロキシ−５−オクチン酸メチル０．６２ｇ
を得た。After the reaction is complete, add 200cm of toluene to the reaction solution! The organic layer was washed with a small amount of 5% aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. This was further purified by silica gel chromatography to obtain 0.62 g of methyl 8-(2-furyl)-8-hydroxy-5-octoate.
I got it.
実施例２
窒素雰囲気下、フルフラール０．８８ ｇ 、 ）ル
エン０．８７ ｇ 、亜鉛粉０．７８ ｇ 、テトラ−
ｎ−ブチルアンモニウムプロミド０．２６ ｇ 、水７
．８ｇ及び酢酸０．２０ｇの混合物に、３０〜３５℃で
７−ブロモ−５−へブチン酸メチル１ｇを３０分〜１時
間かけて加えた０滴下終了後、同温度で４時間撹拌した
。Example 2 Under nitrogen atmosphere, furfural 0.88 g, ) toluene 0.87 g, zinc powder 0.78 g, tetra-
n-butylammonium bromide 0.26 g, water 7
．． To a mixture of 8 g of acetic acid and 0.20 g of acetic acid, 1 g of methyl 7-bromo-5-hebutate was added over 30 minutes to 1 hour at 30 to 35°C. After completion of the dropwise addition, the mixture was stirred at the same temperature for 4 hours.
反応終了後、実施例１に準じて後処理を行い。After the reaction was completed, post-treatment was performed according to Example 1.
８−（２−フリル）−８−ヒドロキシ−５−オクチン酸
メチル０．７１ｇを得た。0.71 g of methyl 8-(2-furyl)-8-hydroxy-5-octinoate was obtained.
実施例３
７−ブロモー５−ヘプチン酸メチルに代えて８−ブロモ
ー６−オクチン酸メチルを用いる以外は実施例１に準じ
て反応及び後処理をして、９−（２−フリル）−９−ヒ
ドロキシ−６−ノニン酸メチル０．６７ ｇを得た。Example 3 The reaction and post-treatment were carried out according to Example 1 except that methyl 8-bromo-6-octate was used in place of methyl 7-bromo-5-heptate to produce 9-(2-furyl)-9- 0.67 g of methyl hydroxy-6-nonynoate was obtained.
実施例４
フルフラールに代えて４−メチルフルフラールを用いる
以外は実施例１に準じて反応及び後処理して、８−（４
−メチル−２−フリル）−８−ヒドロキシ−５−オクチ
ン酸メチル０．５１ ｇを得た。Example 4 The reaction and post-treatment were carried out in accordance with Example 1 except that 4-methylfurfural was used instead of furfural to produce 8-(4
0.51 g of methyl-8-hydroxy-5-octinoate (methyl-2-furyl)-8-hydroxy-5-octinoate was obtained.
Claims (4)
す。） で示されるフルフラール類と、一般式 ▲数式、化学式、表等があります▼ （式中、Ｘはハロゲン原子を表わし、Ｒ＿２は水素原子
または低級アルギル基を表わす。ｎは２〜４の整数を表
わす。） で示されるアセチレン性ハロゲノエステル類とを、亜鉛
及び水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＿１、Ｒ＿２及びｎは前記と同じ意味を表わ
す。） で示される２−フリルカルビノール誘導体の製造法。(1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents a hydrogen atom or a lower alkyl group.) There are furfurals represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, X represents a halogen atom, R_2 represents a hydrogen atom or a lower argyl group, and n represents an integer of 2 to 4.) in the presence of zinc and water. A method for producing a 2-furyl carbinol derivative represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1, R_2 and n represent the same meanings as above.) .
求項１記載の製造法。(2) The method according to claim 1, wherein the reaction is carried out in the presence of ammonium halide.
項２または３記載の製造法。(4) The production method according to claim 2 or 3, wherein the reaction is carried out in the presence of a quaternary ammonium salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21314689A JP2906062B2 (en) | 1989-08-18 | 1989-08-18 | Method for producing 2-furylcarbinol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21314689A JP2906062B2 (en) | 1989-08-18 | 1989-08-18 | Method for producing 2-furylcarbinol derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0377878A true JPH0377878A (en) | 1991-04-03 |
| JP2906062B2 JP2906062B2 (en) | 1999-06-14 |
Family
ID=16634341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21314689A Expired - Lifetime JP2906062B2 (en) | 1989-08-18 | 1989-08-18 | Method for producing 2-furylcarbinol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2906062B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897795B2 (en) | 2008-04-09 | 2011-03-01 | Scinopharm Taiwan Ltd. | Process for the preparation of prostaglandin analogues and intermediates thereof |
-
1989
- 1989-08-18 JP JP21314689A patent/JP2906062B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7897795B2 (en) | 2008-04-09 | 2011-03-01 | Scinopharm Taiwan Ltd. | Process for the preparation of prostaglandin analogues and intermediates thereof |
| US8436194B2 (en) | 2008-04-09 | 2013-05-07 | Scinopharm Taiwan, Ltd. | Process for the preparation of prostaglandin analogues and intermediates thereof |
| US8742143B2 (en) | 2008-04-09 | 2014-06-03 | Scinopharm Taiwan, Ltd. | Process for the preparation of prostaglandin analogues |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2906062B2 (en) | 1999-06-14 |
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