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
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Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21314689A Expired - Lifetime JP2906062B2 (en) | 1989-08-18 | 1989-08-18 | Method for producing 2-furylcarbinol derivative |
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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
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---|---|
JP2906062B2 (en) | 1999-06-14 |
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