JPH0124791B2 - - Google Patents
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- Publication number
- JPH0124791B2 JPH0124791B2 JP55185540A JP18554080A JPH0124791B2 JP H0124791 B2 JPH0124791 B2 JP H0124791B2 JP 55185540 A JP55185540 A JP 55185540A JP 18554080 A JP18554080 A JP 18554080A JP H0124791 B2 JPH0124791 B2 JP H0124791B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- benzyl
- butyrolactone
- mmol
- tetrahydropyranoxy
- 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.)
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Pyrane Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、ムギネ酸、2′−デオキシムギネ酸等
のムギネ酸類の新規な製造法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing mugineic acids such as mugineic acid and 2'-deoxymuginic acid.
植物が、その成長及び生命を維持するために、
多くの元素を必要とすることが知られている。例
えば、鉄は、クロロフイルの生合成に必要であ
り、鉄の不足は、鉄性黄変病をひき起こす。 In order for plants to maintain their growth and life,
It is known that many elements are required. For example, iron is required for chlorophyll biosynthesis, and iron deficiency causes iron yellowing disease.
最近、稲の根の水耕液からムギネ酸(11)が、小麦
から2′−デオキシムギネ酸(12)が、また、からす麦
からアペニン酸（13）が発見された。 Recently, mugineic acid (11) was discovered in the hydroponic solution of rice roots, 2'-deoxymuginic acid (12) was discovered in wheat, and apenic acid (13) was discovered in barley.
また、最近の研究によれば、ムギネ酸又は2′デ
オキシムギネ酸を、水耕栽培の水溶液中に添加す
ることによつて、稲のクロロフイル含量を増加さ
せることができることが、明らかになつつた。 Furthermore, recent research has revealed that the chlorophyll content of rice can be increased by adding mugineic acid or 2'deoxymuginic acid to an aqueous solution for hydroponic cultivation.
更に、これらの化合物を詳細に研究したとこ
ろ、低分子量であるにもかかわらず、銅等の金属
に配位し、キレート化合物を形成することが、明
らかになつた。このような観点からみれば、これ
らのムギネ酸類は、最小の分子量を有するキレー
ト剤であつて、将来、多くの新しい用途が期待さ
れる重要な化合物であるといえる。 Furthermore, detailed studies of these compounds revealed that, despite their low molecular weight, they coordinate with metals such as copper to form chelate compounds. From this point of view, these mugineic acids are chelating agents with the smallest molecular weight, and can be said to be important compounds that are expected to have many new uses in the future.
ムギネ酸類の合成は、ラセミ化を避けるため、
温和な条件で反応させることが必要である。更に
ヒドロキシル基、イミノ基又はカルボキシル基の
保護基も、その導入及び除去が温和な条件で行え
るものであることが必要である。 In the synthesis of mugineic acids, in order to avoid racemization,
It is necessary to carry out the reaction under mild conditions. Furthermore, it is necessary that the protective group for a hydroxyl group, imino group or carboxyl group can be introduced and removed under mild conditions.
本発明は、鋭意研究の結果、かかる困難を克服
して、ムギネ酸類の全合成に成功した。 As a result of intensive research, the present invention has overcome these difficulties and succeeded in total synthesis of mugineic acids.
ムギネ酸類は、次のような工程によつて合成さ
れる。 Mugineic acids are synthesized through the following steps.
α−ヒドロキシ−γ−ブチロラクトン（14）の
ヒドロキシ基をテトラヒドロピラニル化した後、
開環すると同時にカルボキシル基をベンジル化
し、α−テトラヒドロピラノキシ−γ−ヒドロキ
シ酪酸ベンジル（15）を作る。 After tetrahydropyranylation of the hydroxy group of α-hydroxy-γ-butyrolactone (14),
Upon ring opening, the carboxyl group is benzylated to produce benzyl α-tetrahydropyranoxy-γ-hydroxybutyrate (15).
更に、その末端の第１アルコールをピリジニウ
ムクロロクロメートによりアルデヒド（16）に酸
化し、α−アミノ−γ−ブチロラクトン誘導体
（17）とカプリングし、γ−アミノ−α−テトラ
ヒドロピラノキシ酪酸ベンジル誘導体（18）を作
る。 Furthermore, the terminal primary alcohol was oxidized to aldehyde (16) with pyridinium chlorochromate, and coupled with α-amino-γ-butyrolactone derivative (17), resulting in benzyl γ-amino-α-tetrahydropyranoxybutyrate derivative ( 18) Make.
イミノ基を保護した後（19）、開環すると同時
にカルボキシル基をベンジルエステル化し、γ−
ヒドロキシ酪酸エステル誘導体（20）を作る。 After protecting the imino group (19), the carboxyl group was benzyl esterified at the same time as ring opening, and γ-
Make a hydroxybutyric acid ester derivative (20).
更に、その末端の第１アルコールをピリジニウ
ムクロロクロメートによりアルデヒド（21）に酸
化し、例えば、アゼチジン−２−カルボン酸エス
テル（22）とカプリングし、イミノ基、ヒドロキ
シル基及びカルボキシル基を保護した2′−デオキ
シムギネ酸（23）を作る。 Furthermore, the terminal primary alcohol is oxidized to an aldehyde (21) with pyridinium chlorochromate, and coupled with, for example, azetidine-2-carboxylic acid ester (22), the imino group, hydroxyl group, and carboxyl group are protected. -Produces deoxymuginic acid (23).
次いで、ベンジル基をPb−Ｃを触媒として微
量のHClの存在下、水素で還元除去し、更にテト
ラヒドロピラニル基及びtert.ブトキシカルボニル
基をトリフルオロ酢酸により除去して、２−デオ
キシムギネ酸(12)を得る。 Next, the benzyl group was removed by reduction with hydrogen in the presence of a trace amount of HCl using Pb-C as a catalyst, and the tetrahydropyranyl group and tert.butoxycarbonyl group were removed with trifluoroacetic acid to obtain 2-deoxymuginic acid (12 ) is obtained.
なお、α−アミノ−γ−ブチロラクトン誘導体
（17）の代りに、α−アミノ−β−ヒドロキシ−
γ−ブチロラクトン誘導体（24）を用いれば、ム
ギネ酸(11)を得ることができる。 Note that instead of the α-amino-γ-butyrolactone derivative (17), α-amino-β-hydroxy-
By using the γ-butyrolactone derivative (24), mugineic acid (11) can be obtained.
実施例 １
Ｌ−α−ヒドロキシ−γ−ブチロラクトン2.02
ｇ（19.8ミリモル）と、２，３−ジヒドロピラン
2.02ｇ、24ミリモルの乾燥塩化メチレン溶液10ml
を、触媒量のＰ−トルエンスルホン酸（１水塩と
して10mg、0.05ミリモル）の存在下で、0C、窒素
の雰囲気中で、30分間撹はんした。反応混合物に
炭酸水素ナトリウム粉末100mgを加えて急冷し、
直接シリカゲルを用いたカラムクロマトグラフに
かけ、エチルエーテル＋ｎヘキサン（３：２）に
より展開し、α−テトラヒドロピラノキシ−γ−
ブチロラクトン（25）3.50ｇを得た。（収率約95
％）
実施例 ２
α−テトラヒドロピラノキシ−γ−ブチロラク
トン（25）425mg（2.28ミリモル）を、2.5％
KOH6.0ml（2.28ミリモル）とジオキサン6.0mlの
混合溶媒に溶解し、窒素雰囲気中、室温で14時間
撹はんした。得られた反応混合物から溶媒を減圧
で吸引除去し、残つた油状物質を、DMFと水の
４：１の混合溶媒10mlに溶解した。この溶液に、
ベンジルブロマイド469mg、（2.74ミリモル、1.2
ミリグラム当量）を加え、次いで、触媒として18
−クラウン−6.30mg（0.114ミリモル、0.05ミリグ
ラム当量）を加え、５時間撹はんした。得られた
反応混合物を水に注ぎ、エーテルで３回抽出し
た。抽出液を集め、MgSO4上で乾燥し、減圧で
濃縮し、油状物質を得た。これをシリコ（Silic）
CC7を用いたカラムクロマトグラムにより、エチ
ルエーテル＋ｎヘキサン（１：１）で展開し、無
色の油状物質として、α−テトラヒドロピラノキ
シ−γ−ヒドロキシ酪酸ベンジル（26）537mgを
得た。（収率約80％）
実施例 ３
ピリジニウムクロロクロメイト2.26ｇ（10.5ミ
リモル）を乾燥塩化メチレン10mlに懸濁させ、こ
れに室温下、窒素雰囲気中、α−テトラヒドロピ
ラノキシ−γ−ヒドロキシ酪酸ベンジル（26）の
塩化メチレン溶液を加えた。反応混合物を２時間
撹はん後、ろ過後、溶媒を減圧留去して油状物質
を得た。これを、展開剤としてシリコ−CC7を用
いたカラムクロマトグラフにより、エーテル、ｎ
ヘキサン（２：１）で展開し、３−ホルミル−２
−テトラヒドロピラノキシ−プロピオン酸ベンジ
ル（27）444mgを得た。（収率76％）。 Example 1 L-α-hydroxy-γ-butyrolactone 2.02
g (19.8 mmol) and 2,3-dihydropyran
2.02 g, 24 mmol of dry methylene chloride solution in 10 ml
was stirred for 30 minutes at 0 C in an atmosphere of nitrogen in the presence of a catalytic amount of P-toluenesulfonic acid (10 mg as monohydrate, 0.05 mmol). Add 100 mg of sodium hydrogen carbonate powder to the reaction mixture and quench it.
Direct column chromatography using silica gel and development with ethyl ether + n-hexane (3:2) yielded α-tetrahydropyranoxy-γ-
3.50 g of butyrolactone (25) was obtained. (yield approx. 95
%) Example 2 425 mg (2.28 mmol) of α-tetrahydropyranoxy-γ-butyrolactone (25) at 2.5%
It was dissolved in a mixed solvent of 6.0 ml (2.28 mmol) of KOH and 6.0 ml of dioxane, and stirred at room temperature in a nitrogen atmosphere for 14 hours. The solvent was removed from the resulting reaction mixture under reduced pressure and the remaining oil was dissolved in 10 ml of a 4:1 mixed solvent of DMF and water. In this solution,
Benzyl bromide 469 mg, (2.74 mmol, 1.2
milligram equivalents) and then add 18 milligram equivalents as a catalyst.
- Crown - 6.30 mg (0.114 mmol, 0.05 milligram equivalent) was added and stirred for 5 hours. The resulting reaction mixture was poured into water and extracted three times with ether. The extracts were combined, dried over MgSO 4 and concentrated in vacuo to give an oil. This is Silic
A column chromatogram using CC7 was developed with ethyl ether + n-hexane (1:1) to obtain 537 mg of benzyl α-tetrahydropyranoxy-γ-hydroxybutyrate (26) as a colorless oil. (yield approx. 80%) Example 3 2.26 g (10.5 mmol) of pyridinium chlorochromate was suspended in 10 ml of dry methylene chloride, and mixed with methylene chloride of benzyl α-tetrahydropyranoxy-γ-hydroxybutyrate (26) at room temperature in a nitrogen atmosphere. solution was added. The reaction mixture was stirred for 2 hours, filtered, and the solvent was distilled off under reduced pressure to obtain an oily substance. This was analyzed by column chromatography using silico-CC7 as a developing agent.
Developed with hexane (2:1) and 3-formyl-2
444 mg of benzyl -tetrahydropyranoxy-propionate (27) was obtained. (yield 76%).
実施例 ４
α−アミノ−γ−ブチロラクトンのトリフルオ
ロ酢酸塩（28）930mg（4.32ミリモル、1.5ミリグ
ラム当量）を溶解した乾燥メタノール溶液20ml
に、０℃、窒素の雰囲気中で、３−ホルミル−２
−テトラヒドロピラノキシ−プロピオン酸ベンジ
ル（27）846mg（2.88ミリモル）を溶解したメタ
ノール溶液５mlを加え次いで、シアノホウ水素化
ナトリウム189mgを加えて、30分撹はんした。そ
の後、室温まで温め、14時間撹はんした。反応混
合物に水10mlを加えて、メタノールを減圧下で吸
引除去した。その後、水層をCHCl3で３回抽出
し、MgSO4上で乾燥し、溶媒を減圧で吸引除去
して油状物質を得た。これを、シリコCC7を用い
たカラムクロマトグラムにより、エチルエーテル
で展開し、α−テトラヒドロピラノキシ−γ−テ
トラヒドロフラノアミノ酪酸ベンジル（29）977
mgを得た（収率90％）。 Example 4 20 ml of a dry methanol solution containing 930 mg (4.32 mmol, 1.5 milligram equivalent) of trifluoroacetate of α-amino-γ-butyrolactone (28)
3-formyl-2 at 0°C in a nitrogen atmosphere
5 ml of a methanol solution in which 846 mg (2.88 mmol) of benzyl -tetrahydropyranoxy-propionate (27) was dissolved was added, followed by 189 mg of sodium cyanoborohydride, and the mixture was stirred for 30 minutes. Thereafter, it was warmed to room temperature and stirred for 14 hours. 10 ml of water was added to the reaction mixture and methanol was removed by suction under reduced pressure. The aqueous layer was then extracted three times with CHCl 3 , dried over MgSO 4 and the solvent was removed under vacuum to obtain an oil. This was analyzed by column chromatography using Silico CC7 and developed with ethyl ether.
mg (90% yield).
実施例 ５
α−アミノ−γ−ブチロラクトン誘導体（29）
340mg（0.90ミリモル）と、ジ−tert.ブチル−ジ
カーボネート294mg（1.35ミリモル）の乾燥塩化
エチレン溶液に、触媒量のトリエチルアミン4.5
mg（0.045ミリモル）を加え、室温、窒素雰囲気
中で、20時間撹はんした。 Example 5 α-amino-γ-butyrolactone derivative (29)
340 mg (0.90 mmol) of di-tert.butyl dicarbonate and 294 mg (1.35 mmol) of di-tert.butyl dicarbonate in a solution of dry ethylene chloride in a catalytic amount of 4.5 mg triethylamine.
mg (0.045 mmol) and stirred at room temperature in a nitrogen atmosphere for 20 hours.
反応混合物から、溶媒を減圧吸引除去し、濃縮
して、シリカゲルを用いたカラムクロマトグラフ
により、エチルエーテル＋ｎヘキサン（４：１）
で展開して、tert.ブトキシカルボニル誘導体
（30）387mgを得た。（収率90％）
実施例 ６
α−アミノ−γ−ブチロラクトン（30）460mg
（0.96ミリモル）を、2.5％KOH5.06ml（1.92ミリ
モル）とLiAlH4を加えて蒸留したばかりのジオ
キサン５mlの混合物に溶解し、窒素雰囲気中、室
温で14時間撹はんした。得られた反応溶液を減圧
で濃縮し、DMFと水（４：１）の混合溶媒18ml
に溶解した。この溶液に、ベンジルブロマイド
393mg（2.3ミリモル）と、触媒として18−クラウ
ン−6.24mg（0.096ミリモル）とを加え、室温で
６時間撹はんした。得られた反応溶液に、60mlの
水を加え、エチルエーテルで、４回抽出した。得
られた抽出液をMgSO上で乾燥した後減圧で濃縮
し、シリコCC7を用いたカラムクロマトグラムに
よりエチルエーテル・ｎヘキサン（３：１）で展
開して、油状のα−アミノ−γ−ヒドロキシ酪酸
ベンジル（31）を得た。（収率約60％）
実施例 ７
ピリジニウムクロロクロメイト681mg（3.16ミ
リモル）を乾燥塩化メチレン５ml中に懸濁させ、
これに、室温下、窒素雰囲気中、α−アミノ−γ
−ヒドロキシ酪酸ベンジル（31）の塩化メチレン
溶液を加えた。反応混合物を２時間撹はん後、30
mlのエーテルを加え、MgSO（５ｇ）を加えて撹
はんした後、ろ過後、溶媒を減圧留去して、油状
物質を得た。これを、展開剤としてシリコCC7を
用いたカラムクロマトグラフにより、ホモセリン
アルデヒド誘導体（32）277mgを得た。（収率75
％）
実施例 ８
アゼチジン−２−カルボン酸ベンジルのトリフ
ルオロ酢酸塩（33）46mg（0.15ミリモル）を溶解
した乾燥メタノール１mlに、０℃、窒素の雰囲気
中で、α−アミノ−β−ホルミルプロピオン酸ベ
ンジル誘導体（32）50mg（0.91ミリモル）を溶解
したメタノール溶液を加え、次いで、シアノホウ
水素化ナトリウム7.0mg（1.1ミリモル）を加え
た。１時間後に室温まで温め、16時間撹はんし
た。反応混合物を水５c.c.の中に注ぎ急冷し、メタ
ノールを減圧で吸引除去した。粗生成物を水層か
らCHClで３回抽出し、抽出物を集めてMgSO上
で乾燥し、溶媒を減圧で吸引除去ぢて油状物を
得、これをシリコCC7を用いたカラムクロマトグ
ラムにより、エチルエーテル・ｎヘキサン（１：
１）で展開し、α−アミノ−γ−イミノ酪酸ベン
ジル誘導体（34）41mgを得た。（収率約60％）
実施例 ９
ヒドロキシル基がテトラヒドロプラニル化さ
れ、イミノ基がtert.ブトキシカルボニル化され、
三つのカルボキシル基がベンジルエステル化され
ている2′−デオキシムギネ酸（34）43mg（0.0567
ミリモル）の撹はん懸濁液を1μl以下HClと６mg
のPd−Ｃの存在下で、１気圧の水素で処理し、
14時間撹はんした。反応混合物をろ過し、減圧蒸
発して、無定形固体33mgを得た。この固体の
NMRを調べたところ、ベンジル基が消失してい
ることが確かめられた。 The solvent was removed from the reaction mixture under reduced pressure, concentrated, and purified by column chromatography using silica gel (ethyl ether + n-hexane (4:1)).
387 mg of tert.butoxycarbonyl derivative (30) was obtained. (yield 90%) Example 6 α-amino-γ-butyrolactone (30) 460 mg
(0.96 mmol) was dissolved in a mixture of 5.06 ml (1.92 mmol) of 2.5% KOH and 5 ml of freshly distilled dioxane with LiAlH 4 and stirred at room temperature under a nitrogen atmosphere for 14 hours. The obtained reaction solution was concentrated under reduced pressure, and 18 ml of a mixed solvent of DMF and water (4:1) was added.
dissolved in. Add benzyl bromide to this solution.
393 mg (2.3 mmol) and 6.24 mg (0.096 mmol) of 18-crown as a catalyst were added and stirred at room temperature for 6 hours. 60 ml of water was added to the resulting reaction solution, and the mixture was extracted four times with ethyl ether. The obtained extract was dried over MgSO, concentrated under reduced pressure, and subjected to column chromatography using Silico CC7, developed with ethyl ether/n-hexane (3:1) to obtain an oily α-amino-γ-hydroxy Benzyl butyrate (31) was obtained. (yield approx. 60%) Example 7 681 mg (3.16 mmol) of pyridinium chlorochromate are suspended in 5 ml of dry methylene chloride,
To this, α-amino-γ was added at room temperature in a nitrogen atmosphere.
A solution of benzyl hydroxybutyrate (31) in methylene chloride was added. After stirring the reaction mixture for 2 hours,
ml of ether was added, and MgSO (5 g) was added and stirred. After filtration, the solvent was distilled off under reduced pressure to obtain an oily substance. This was subjected to column chromatography using Silico CC7 as a developing agent to obtain 277 mg of homoserine aldehyde derivative (32). (yield 75
%) Example 8 46 mg (0.15 mmol) of trifluoroacetate of benzyl azetidine-2-carboxylate (33) was dissolved in 1 ml of dry methanol at 0°C in a nitrogen atmosphere. A methanol solution containing 50 mg (0.91 mmol) of derivative (32) was added, followed by 7.0 mg (1.1 mmol) of sodium cyanoborohydride. After 1 hour, the mixture was warmed to room temperature and stirred for 16 hours. The reaction mixture was quenched by pouring into 5 c.c. of water, and the methanol was removed by suction under reduced pressure. The crude product was extracted from the aqueous layer three times with CHCl, the extracts were combined and dried over MgSO, and the solvent was removed under reduced pressure to obtain an oil, which was analyzed by column chromatography using Silico CC7. Ethyl ether/n-hexane (1:
1) to obtain 41 mg of benzyl α-amino-γ-iminobutyric acid derivative (34). (yield approx. 60%) Example 9 The hydroxyl group is tetrahydropranylated, the imino group is tert.butoxycarbonylated,
43 mg (0.0567
A stirred suspension of 1 mmol or less of HCl and 6 mg
treated with 1 atm of hydrogen in the presence of Pd-C,
Stirred for 14 hours. The reaction mixture was filtered and evaporated under reduced pressure to yield 33 mg of amorphous solid. This solid
NMR analysis confirmed that the benzyl group had disappeared.
この粗生成物を、トリフルオロ酢酸１と反応
させ溶解した。30分静置反応を完結させた後、水
を加えて10mlに希釈し、ダウエツクス50W−５イ
オン交換樹脂で処理し、アンモニア水で溶出さ
せ、2′−デオキシムギネ酸のアンモニア塩の溶液
とした。 This crude product was reacted with trifluoroacetic acid 1 and dissolved. After the reaction was allowed to stand for 30 minutes, it was diluted to 10 ml with water, treated with Dowex 50W-5 ion exchange resin, and eluted with aqueous ammonia to obtain a solution of ammonia salt of 2'-deoxymuginic acid.
この溶液を、減圧で蒸発、乾燥させ、粗2′−デ
オキシムギネ酸21mgを得た。セフアデツクスＧ−
10を用いたカラムクロマトグラフにより、水で展
開し2′−デオキシムギネ酸(12)を得た。得られた
2′−デオキシムギネ酸の融点は196〜199℃〔α〕
−66.6゜で天然物と同一であつた。 This solution was evaporated and dried under reduced pressure to obtain 21 mg of crude 2'-deoxymuginic acid. Safedex G-
Column chromatography using 10 and developing with water gave 2'-deoxymuginic acid (12). obtained
The melting point of 2'-deoxymuginic acid is 196-199℃ [α]
-66.6°, which was the same as the natural product.
Claims (1)
るに当たり、α−ヒドロキシ−γ−ブチロラクト
ンのヒドロキシ基をテトラヒドロピラニル化した
後、開環すると同時にカルボキシル基をベンジル
エステル化し、得られたα−テトラヒドロピラノ
キシ−γ−ヒドロキシ酪酸ベンジルを酸化して、
α−テトラヒドロピラノキシ−β−ホルミルプロ
ピオン酸ベンジルを得、これと、β位にテトラヒ
ドロピラノキシ基を有するか有しないα−アミノ
−γ−ブチロラクトンとカプリングし、得られた
化合物のイミノ基をtert.ブトキシカルボニル化
し、ブチロラクトン環を開環すると同時にカルボ
キシル基をベンジルエステル化し、更に、他端の
第１アルコール基を酸化しアルデヒド基として、
一般式(2)とカプリングし、次いでヒドロキシ基、
カルボキシル基およびイミノ基の保護基を除くこ
とを特徴とするムギネ酸類の製造法。 ここで、Ｒは、水素又はヒドロキシル基を表
す。 [Scope of Claims] 1. In synthesizing the mugineic acids represented by the following general formula (1), the hydroxy group of α-hydroxy-γ-butyrolactone is tetrahydropyranylated, and at the same time as the ring is opened, the carboxyl group is benzylated. esterification and oxidizing the obtained benzyl α-tetrahydropyranoxy-γ-hydroxybutyrate,
Benzyl α-tetrahydropyranoxy-β-formylpropionate is obtained, and this is coupled with α-amino-γ-butyrolactone having or not having a tetrahydropyranoxy group at the β position, and the imino group of the obtained compound is tert.butoxycarbonylation, opening the butyrolactone ring and at the same time benzyl esterifying the carboxyl group, further oxidizing the primary alcohol group at the other end to form an aldehyde group,
Coupling with general formula (2), then hydroxy group,
A method for producing mugineic acids, which comprises removing protective groups for carboxyl groups and imino groups. Here, R represents hydrogen or a hydroxyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55185540A JPS57112385A (en) | 1980-12-29 | 1980-12-29 | Production of mugineic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP55185540A JPS57112385A (en) | 1980-12-29 | 1980-12-29 | Production of mugineic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57112385A JPS57112385A (en) | 1982-07-13 |
| JPH0124791B2 true JPH0124791B2 (en) | 1989-05-15 |
Family
ID=16172587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP55185540A Granted JPS57112385A (en) | 1980-12-29 | 1980-12-29 | Production of mugineic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57112385A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK229876A (en) * | 1975-06-11 | 1976-12-12 | Merck & Co Inc | PROCEDURE FOR MAKING ESTERS OF ALFA-METHYL-3,4-DIHYDROXYPHENYLALANINE |
-
1980
- 1980-12-29 JP JP55185540A patent/JPS57112385A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57112385A (en) | 1982-07-13 |
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