JPS60239431A - Production of 3,3'-dialkoxybenzyl - Google Patents
Production of 3,3'-dialkoxybenzylInfo
- Publication number
- JPS60239431A JPS60239431A JP59094840A JP9484084A JPS60239431A JP S60239431 A JPS60239431 A JP S60239431A JP 59094840 A JP59094840 A JP 59094840A JP 9484084 A JP9484084 A JP 9484084A JP S60239431 A JPS60239431 A JP S60239431A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- dialkoxybenzoin
- solvent
- copper sulfate
- substance
- 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.)
- Pending
Links
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は８−アルコキシベンズアルデヒドを縮合して３
，３′−ジアルコキシベンゾインとなし、これを酸化し
て８，８′−ジアルコキシベンジルを製造する方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for condensing 8-alkoxybenzaldehyde to
, 3'-dialkoxybenzoin and oxidize it to produce 8,8'-dialkoxybenzyl.
８．８′−ジアルコキシベンジルはアクリレートの光重
合開始剤、高分子添加剤（ポリエステル）。8.8'-Dialkoxybenzyl is a photopolymerization initiator for acrylate and a polymer additive (polyester).
医薬品合成の中間体として有用な物質である。It is a useful substance as an intermediate in pharmaceutical synthesis.
従来８，８′−ジアルコキシベンジルの装造に関する文
献は少なく、僅かに下記の２例が知られているのみであ
る。Ｂｅｒ、 鶴、 ８７４ｆｌ （１９２２） Ｇ：
は３−メトキシベンズアルデヒドをシアン化カリウムの
存在下６６％エタノール中で煮沸縮合反応させ、得られ
た８、８′−ジメトキシベンゾインをエタノ−Ｉし中で
フエーりング液を用いて酸化し３，８′−ジメトキシベ
ンゾインを得ているが、この収率は４９％と低い。Conventionally, there are few documents regarding the preparation of 8,8'-dialkoxybenzyl, and only the following two examples are known. Ber, Tsuru, 874fl (1922) G:
3-methoxybenzaldehyde was subjected to a boiling condensation reaction in 66% ethanol in the presence of potassium cyanide, and the resulting 8,8'-dimethoxybenzoin was oxidized using Fehling's solution in ethanol-I to give 3,8' -dimethoxybenzoin was obtained, but the yield was as low as 49%.
また、丁ｅｔｒａ ｈｅｄｙｏｎ Ｌｅｔｔｅｒｓ１９
８１．２２ （４０） ８９５９〜６０には８−メトキ
シペンシイフレクロライドをテトラヒドロフラン中で、
ヨウ化サマリウムの存在−ＦＧこ、カップリングさせて
８，８′−ジメトキシベンジ〃を合成する方法が記載さ
れて（・る。この反応ζよ一段反応で、収率も７８％と
高（・力（、ヨウイヒサマ１）ラムが高価であり工業的
【こ有利な方法とは云えなり・。Also, hedion Letters19
81.22 (40) In 8959-60, 8-methoxypensyphlechloride in tetrahydrofuran,
A method for synthesizing 8,8'-dimethoxybendi by coupling the presence of samarium iodide with FG has been described (・). This reaction ζ is a one-step reaction, and the yield is as high as 78% (・Rum is expensive and industrial [this is not an advantageous method].
この様な状況に鑑み本発明者らは８−アルコキシベンズ
アルデヒドを原料として８，３′−ジアルコキシベンジ
ルを製造する方法を二つい°て研究を重ねた結果、縮合
反応の溶媒とし′Ｃ２０〜５０％Ｃ２０ル５０
ること、酸化反応り溶媒にピリジン水を用（・ること、
硫酸銅の存在Ｆをこ空気酸化することなどの知見を得、
これ◆こ基づいて本発明を完成した。In view of this situation, the present inventors conducted research on two methods for producing 8,3'-dialkoxybenzyl using 8-alkoxybenzaldehyde as a raw material. %C20 50 In the oxidation reaction, pyridine water was used as a solvent.
Obtained knowledge such as air oxidation of the presence of copper sulfate,
Based on this, the present invention was completed.
即ち本発明の目的は工業的に有利な３，８′−ジアルコ
キシベンジルの製造方法を提供する瘉こあ？、その姿旨
は３−アルコキシベンズアルデヒドを縮合サセて、３，
８’−ジアルコキシベンゾインとなし、これを酸化して
３，８′−ジアルコキシベンジルＩしを合成するに際し
、縮合反応の溶媒とし゛（２０〜５０％アルコール水を
用い、アルカリ金属シアン化物り存在ＦＧこ５０〜８０
℃に保持して反応させること、オヨヒ８，３′ージアル
コ午ンペ／ゾインの酸化反応の溶媒としてピリジン水を
用し・、硫酸鋼の存在Ｆに空気酸化することを特徴とす
る８，８′−シアＭコキシベンジルの製造法である。That is, an object of the present invention is to provide an industrially advantageous method for producing 3,8'-dialkoxybenzyl. , its gist is that 3-alkoxybenzaldehyde is condensed and 3,
8'-Dialkoxybenzoin is oxidized to synthesize 3,8'-dialkoxybenzyl I as a solvent for the condensation reaction (20-50% alcohol water is used, and alkali metal cyanide is present). FG 50-80
8,8 characterized in that the reaction is carried out while being maintained at ℃, pyridine water is used as a solvent for the oxidation reaction of 8,3'-dialkone/zoin, and air oxidation is carried out in the presence of sulfuric acid steel. This is a method for producing '-sia M koxybenzyl.
本発明の対象となる３，８・−ジアルコキシベンジルは
３−アルコキシベンズアルデヒドを原料として下記の弐
に従って＠：ぺする。3,8--Dialkoxybenzyl, which is a subject of the present invention, is produced using 3-alkoxybenzaldehyde as a raw material according to the following procedure.
ここを二ＲはＣ＋ − Ｃ４のアルキル基を示し、アル
コキシ基の例とし・ではメトキシ、エト午シ，イソプロ
ポキシ、ｎ−プロポキシ、ｎ−ブトキシおよびｔ−ブト
キシが挙げられる。Here, 2R represents a C+-C4 alkyl group, and examples of alkoxy groups include methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy and t-butoxy.
縮合反応の溶媒としではメタノ−Ｉし，エタノール、イ
ソプロパツール、ｎ−ｊロノ（ノールナトの水溶液を用
い、いずれも２０〜５０％水溶液が適当である。２０％
未満では反応収率が低く反応速度が遅い。５０％を超え
ると反応速度は速くなるが分解速度も速く従って収率低
下の原因となる。As the solvent for the condensation reaction, an aqueous solution of methanol, isopropanol, and nj rono (nornato) is used, and a 20 to 50% aqueous solution is suitable for each.20%
If it is less than that, the reaction yield will be low and the reaction rate will be slow. When it exceeds 50%, the reaction rate increases, but the decomposition rate also increases, which causes a decrease in yield.
この時昏こ用いるアルカリ金属シアン化物としてはシア
ン化リチウム、シアン化カリウム、シアン化ナトリウム
等が挙げられるが、収率その他にはさしたる影響がない
ので経済的にはシアン化ナトリウムを用いるのが得策で
ある。Examples of the alkali metal cyanide used at this time include lithium cyanide, potassium cyanide, and sodium cyanide, but it is economically advisable to use sodium cyanide as it does not have a significant effect on yield or other aspects. .
使用喰は３−アルコキシベンズアルデヒドに対し８〜５
Ｑ ｗｔ％，望ましくは５〜９Ｑ ｗｔ％が良い。The amount used is 8 to 5 for 3-alkoxybenzaldehyde.
Q wt%, preferably 5 to 9 Q wt%.
少い場合は、反応が遅く収率が低い。多い場合は経済的
でないし、収率も低下する。If the amount is small, the reaction will be slow and the yield will be low. If the amount is too large, it is not economical and the yield also decreases.
酸化反応に使用するピリジン水は４０〜８０％濃度のも
のが好ましい。４０％未満では反応速度が遅く、８０％
を超えると硫酸銅つ分散が悪くなり収率低下をきたす。The pyridine water used in the oxidation reaction preferably has a concentration of 40 to 80%. If it is less than 40%, the reaction rate is slow, and if it is less than 80%
If the amount exceeds this amount, the dispersion of copper sulfate becomes poor and the yield decreases.
この時用いる硫酸鋼の喰は８−メトキシベンズアルデヒ
ドに対し、１０〜ｌＱＱｍｏ１％．望ましくは８０〜７
０ｍｏ１％が良い。また空気酸化するには適当番二分敵
させて液中に吹込めばよく特暴こ限定されるものではな
い。The content of the sulfuric acid steel used at this time is 10 to 1QQmo1% relative to 8-methoxybenzaldehyde. Preferably 80-7
0mo1% is good. In addition, air oxidation can be carried out by blowing into the liquid in an appropriate amount of air, and is not limited to specific air.
反応温度は８０〜１１０℃の範囲に保持して行なうのが
適当であり、これより低（・と反応速度力（遅く、高い
と加圧容器が必要となるので工業的Ｇこ有利ではない。It is appropriate to maintain the reaction temperature in the range of 80 to 110°C; lower than this and the reaction rate is slow, and higher is not advantageous for industrial use since a pressurized vessel is required.
本発明で実施することにより８−アルコキシベンズアル
デヒドを原料として高収率（綜合収率８０％以．ｈ ）
で８７３′−アフレコキシペンジルを得ることができ、
工業上の利用価値はきわめて大き（・。By implementing the present invention, high yield is achieved using 8-alkoxybenzaldehyde as a raw material (total yield of 80% or more.h)
873′-afrekoxypenzyl can be obtained with
The industrial value is extremely large (・.
以下実施例を示して本発明をｔ＋こ詳細をこ説明する。The present invention will be explained in detail below with reference to Examples.
実施例１
８−メトキシベンズアルデヒド１３６ ｇ （ １．０
モアｖＬ エタノール１６８ｇＪｄよびボ８８１ ｇを
１４のフラスコ舎こ入れ、これ會こシアン化ナト■Ｊウ
ムｔａ．ｅｇ（ ０．２８ モル） ラフ４加Ｌ、６２
− ６４ ’Ｃ テ４．５時＋［反応させた。反応液
を冷却し、塩化メチレフ８００ｇで２回抽出した債、得
られた塩化メチレン相を水で水洗し、塩化メチレンは留
去した。缶残曇こ粘稠液が１５０ｇ得られたつこれを高
速液体クロマトグラフィーで分析したところ８，８′−
ジメトキシベンゾイノ１１３．７ ｇ （０，４１８モ
ル）を含んでいた。Example 1 136 g of 8-methoxybenzaldehyde (1.0
Put 168 g of ethanol and 881 g of ethanol into 14 flasks, and then add sodium cyanide. eg (0.28 mol) Rough 4+L, 62
- 64 'C Te 4.5 o'clock + [Reacted. The reaction solution was cooled and extracted twice with 800 g of methylene chloride. The resulting methylene chloride phase was washed with water, and the methylene chloride was distilled off. 150g of cloudy viscous liquid remaining in the can was obtained, which was analyzed by high performance liquid chromatography and found to be 8,8'-
It contained 113.7 g (0,418 mol) of dimethoxybenzoino.
＋９．ｄｌ’−ジメトキシベンゾイノの収率は８３．６
％であった。+9. The yield of dl'-dimethoxybenzoino is 83.6
%Met.
８７８′−ジメトキシベンゾインを含む粘稠液にピリジ
ン２１８ｇ、硫酸銅の五水和物（ＣｕＳＯ４−５Ｈ２０
）１０６ ｇおよび水９０ｇを添加し、９４℃に昇温し
１ 同温度で空気を１２０〜ｘａｏ ｍｊ／ｍｉｎの割
合で５〜６時間流して酸化したつ
反応終了後、本２８０ｇを添加し、室温まで冷却し、晶
析した８７３′−ジメトキシベンジルをＰａした。得ら
れたケーキを高速液体クロマトグラフィーで分析したと
ころ、８，３’−ジメトキシベンジル１１Ｌ５ ｇ （
０，４１７モルンを含んでいた。A viscous liquid containing 878'-dimethoxybenzoin was mixed with 218 g of pyridine and copper sulfate pentahydrate (CuSO4-5H20).
) and 90 g of water were added, the temperature was raised to 94°C, and oxidized by flowing air at the same temperature for 5 to 6 hours at a rate of 120 to xao mj/min. After the reaction was completed, 280 g of this product was added, After cooling to room temperature, the crystallized 873'-dimethoxybenzyl was subjected to Pa. When the obtained cake was analyzed by high performance liquid chromatography, it was found that 8,3'-dimethoxybenzyl 11L5 g (
It contained 0,417 mornes.
８７８′−ジメトキシベンジルの収率は９９．７％であ
り、８−メトキシベンズアルデヒドに対して、８８．４
％であった。The yield of 878'-dimethoxybenzyl was 99.7%, and the yield was 88.4% based on 8-methoxybenzaldehyde.
%Met.
得られたケーキをアＩレコール等で積装すること台こよ
り淡黄色結晶を得た。融点は８２〜８８℃、高速液体ク
ロマトグラフィーによる純度は９９．９％であった。The resulting cake was loaded with an aircol or the like to obtain pale yellow crystals. The melting point was 82-88°C, and the purity as determined by high performance liquid chromatography was 99.9%.
実施例２
３−メトキシベンズアルデヒドのかわりをこ、３−エト
キシベンズアルデヒド１５０ ｇ （１，０モＶ）を使
用した以外は実施例１と同様にし−（８，３’−ジェト
キシベンゾイノ１２０．６ ｇ （０，４０２モ／Ｌ／
）を得た。収率は８０，４％であった。ついで、同様に
酸化して８，３′−ジェトキシベンジル１１８．６ ｇ
（０，８９８モル）を得た。収率は９９．０％であり
、３−エトキシベンズアルデヒドに対して、 ７９．６
％であった。Example 2 Same as Example 1 except that 150 g (1,0 moV) of 3-ethoxybenzaldehyde was used instead of 3-methoxybenzaldehyde. g (0,402mo/L/
) was obtained. The yield was 80.4%. Then, it was oxidized in the same way to give 118.6 g of 8,3'-jethoxybenzyl.
(0,898 mol) was obtained. The yield was 99.0%, based on 3-ethoxybenzaldehyde, 79.6
%Met.
実施例３〜５
禰合反応の溶媒に使用したエタノールのかわりに表１に
示すアルコールを使用した以外は実施例１と同様に反応
させ、表１に示す結果を得たっ表 １
実施例６
シアン化ナトリウムのかわり蚤こ、シアン化カリウム１
８４ ｇ （０，２８モル）を使用した以外は実施例１
と同様に反応させ、３，８’−ジメトキシベンジルＩＩ
ＬＯｇ （０，４１５モル）を得た。収率は８−エトキ
シベンズアルデヒドを二対して８３．０％であった。Examples 3 to 5 The reaction was carried out in the same manner as in Example 1, except that the alcohol shown in Table 1 was used instead of the ethanol used as the solvent for the coalescence reaction, and the results shown in Table 1 were obtained. Table 1 Example 6 Cyanide Potassium cyanide 1 instead of sodium chloride
Example 1 except that 84 g (0.28 mol) was used
3,8'-dimethoxybenzyl II
LOg (0,415 mol) was obtained. The yield was 83.0% based on 8-ethoxybenzaldehyde.
出願人 製鉄化学工業株式会社 代表者 佐々木 浩Applicant: Steel Chemical Industry Co., Ltd. Representative Hiroshi Sasaki
Claims (1)
８，３’−ジアルコキシベンゾインとなし、これを酸化
して８，３′−ジアルコキシベンジルを合成するに際し
、縮合反応の溶媒とし°て２０〜５０％アルコール水を
用い、アｌレカリ金属シアン化物の存在ドに５０〜８０
℃に保持しＣ反応させること、勘よび３，３′−ジアル
コキシベンゾインの酸化反応の溶媒としてピリジン水を
用い、硫酸銅の存在下に空気酸化することを特徴とする
８、３′−ジアルコキシベンジルの製造法。 （２） アルコキシ基がメトキシ基である特許請求の範
囲（１）記載の方法。 （８） アルコールがエタノールである特許請求の範囲
（１）記載の方法。 （４） アルカリ金属のシアン化物がシアン化ナトリウ
ムで鼠る待ｉｆｆ請求の範囲（１）記載の方法。 （５） ピリジン水が４０〜８０％とリジン水である特
許請求の範囲（１）記載の方法。 （６） ８０〜１１０℃ に保持して空気酸化する特許
請求の範囲（１）記載の方法。[Claims] (l) By condensing 3-1 lucoxybenzaldehyde,
8,3'-dialkoxybenzoin and oxidize it to synthesize 8,3'-dialkoxybenzyl, using 20 to 50% alcohol water as a solvent for the condensation reaction. 50-80 for presence of monsters
8,3'-di-alkoxybenzoin is maintained at a temperature of 3,3'-dialkoxybenzoin for C reaction, pyridine water is used as a solvent for the oxidation reaction of 3,3'-dialkoxybenzoin, and air oxidation is carried out in the presence of copper sulfate. Method for producing alkoxybenzyl. (2) The method according to claim (1), wherein the alkoxy group is a methoxy group. (8) The method according to claim (1), wherein the alcohol is ethanol. (4) The method according to claim (1), wherein the alkali metal cyanide is mixed with sodium cyanide. (5) The method according to claim (1), wherein the pyridine water is 40 to 80% lysine water. (6) The method according to claim (1), wherein air oxidation is carried out while maintaining the temperature at 80 to 110°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59094840A JPS60239431A (en) | 1984-05-11 | 1984-05-11 | Production of 3,3'-dialkoxybenzyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59094840A JPS60239431A (en) | 1984-05-11 | 1984-05-11 | Production of 3,3'-dialkoxybenzyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60239431A true JPS60239431A (en) | 1985-11-28 |
Family
ID=14121235
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59094840A Pending JPS60239431A (en) | 1984-05-11 | 1984-05-11 | Production of 3,3'-dialkoxybenzyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60239431A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04364151A (en) * | 1991-06-10 | 1992-12-16 | Teijin Ltd | Production of benzyl-4,4'-dicarboxylic acid and its ester |
| JP2010189362A (en) * | 2009-02-20 | 2010-09-02 | Ne Chemcat Corp | Method for producing benzyl compound |
-
1984
- 1984-05-11 JP JP59094840A patent/JPS60239431A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04364151A (en) * | 1991-06-10 | 1992-12-16 | Teijin Ltd | Production of benzyl-4,4'-dicarboxylic acid and its ester |
| JP2010189362A (en) * | 2009-02-20 | 2010-09-02 | Ne Chemcat Corp | Method for producing benzyl compound |
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