JPH0548210B2 - - Google Patents
Info
- Publication number
- JPH0548210B2 JPH0548210B2 JP60228462A JP22846285A JPH0548210B2 JP H0548210 B2 JPH0548210 B2 JP H0548210B2 JP 60228462 A JP60228462 A JP 60228462A JP 22846285 A JP22846285 A JP 22846285A JP H0548210 B2 JPH0548210 B2 JP H0548210B2
- Authority
- JP
- Japan
- Prior art keywords
- sodium borohydride
- ester
- mmol
- carboxylic acid
- alcohol
- 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.)
- Expired - Lifetime
Links
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 20
- 239000012279 sodium borohydride Substances 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 16
- 150000002148 esters Chemical class 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 235000005074 zinc chloride Nutrition 0.000 claims description 10
- 239000011592 zinc chloride Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 150000003512 tertiary amines Chemical class 0.000 claims description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 5
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- -1 primary alcohols Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 229940095102 methyl benzoate Drugs 0.000 description 2
- ZQWPRMPSCMSAJU-UHFFFAOYSA-N methyl cyclohexanecarboxylate Chemical compound COC(=O)C1CCCCC1 ZQWPRMPSCMSAJU-UHFFFAOYSA-N 0.000 description 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 description 2
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- SWGQITQOBPXVRC-UHFFFAOYSA-N methyl 2-bromobenzoate Chemical compound COC(=O)C1=CC=CC=C1Br SWGQITQOBPXVRC-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、アルコール特に１級アルコールの製
造に関するものであり、より詳しくは脂肪族もし
くは芳香族カルボン酸又はそのエステルの３級ア
ミンの存在下、水素化ホウ素ナトリウムと塩化亜
鉛により還元することによつてアルコールを製造
する方法に関するものである。
アルコールは久しく工業用化学薬品として知ら
れており、種々の製品の製造のために大量に使用
されている。さらに中には医薬・農薬の重要な中
間体も多数有り、製造法は数多く報告されてい
る。
カルボン酸エステルを水素化アルミニウムリチ
ウムにより還元し、アルコールに導く方法は、古
くから実験室レベルで知られた方法であるが危険
性や高価格のため、工業的に用いることはできな
い。そのため水素化アルミニウムリチウムのかわ
りに廉価で危険性の少ない水素化ホウ素ナトリウ
ムを用いる努力がなされてきた。水素化ホウ素ナ
トリウム単独でカルボン酸エステルを還元するこ
とはできないため、低級アルコールを滴下し、還
元能力を増強する方法が報告されている。しかし
ながらこの方法は水素化ホウ素ナトリウム大過剰
必要であつたり、反応系が泡立ち、大量で利用す
ることは難しい。また水素化ホウ素ナトリウムと
各種金属塩との組み合わせでエステルを還元する
方法も種々の報告されている。たとえば、コロニ
ツシユは（J.Kollonitsch、et al.、Nature
（London）173、125（1954）．175、346（1955））ハ
ロゲン化リチウムと水素化ホウ素ナトリウムの組
み合わせによりエステルを還元している。又、ブ
ラウンらは（H.C.Brown、et al.、J.Am.Chem.
Soc.、77、6209（1955））各種の多価金属ハライド
の存在下、水素化ホウ素ナトリウムの還元を検討
し無水塩化アルミニウムが良い添加剤であると報
告している。しかしながら彼らは添加剤として塩
化亜鉛を用いた場合は水素化ホウ素ナトリウムで
エステルを還元することはできないと報告してい
る。
本発明は従来不可能とされていた水素化ホウ素
ナトリウムと塩化亜鉛の組み合わせによるカルボ
ン酸又はそのエステルの還元方法を工業的に可能
とし、さらに先行技術の問題点・特に工業的利用
価値をたかめるものである。たとえば、先行技術
で最も良いとされていた水素化ホウ素ナトリウム
と無水塩化アルミニウムの組み合わせは溶媒とし
て工業的に好ましくないジグライム（ジエチレン
グリコールジメチルエーテル）を用いている。
又、無水塩化アルミニウムは塩化亜鉛に比べて大
量の取り扱いが困難であり、またルイス酸性が強
く副反応を生じる場合もあり不安定なエステルの
還元に適さない。
本発明の目的は、中性条件下で短い反応時間、
簡便な処理操作により高収率でアルコールを製造
するための改良された方法を提供することにあ
る。これは安価で工業的に利用価値の高いアルコ
ールの製造方法である。
ところで、水素化ホウ素ナトリウムと塩化亜鉛
のみではカルボン酸又はそのエステルは低収率で
しけ還元されない。しかしながら我々は鋭意研究
を続けた結果驚くべきことにこの条件に３級アミ
ンを存在させると短時間で、しかも高収率でアル
コールが得られることを見出し本発明を完成し
た。
本発明に用いられるカルボン酸又はそのエステ
ルは、次の一般式で表わされる。
ここでR1はアルキル、シクロアルキル、アリ
ール又はアラルキルであり、枝分かれしていても
よくまた不活性な置換基（たとえばハロゲン原
子、ヒドロキシ基、アルコキシ基、アミノ基等）
で置換されていてもよい。R2はカルボン酸の場
合は水素原子、カルボン酸エステルの場合は枝分
かれしていてもよいアルキル、又はアラルキルが
あげられる。また、R1とR2が結合してもよい。
上記のカルボン酸エステルの例としては、メチ
ルベンゾエート、エチルベンゾエート、メチル２
−メチルベンゾエート、メチル４−メトキシベン
ゾエート、エチルフエニルアセテート、メチル２
−ブロモベンゾエート、エチル２−フエニルチオ
ベンゾエート、ベンジルアセテート、エチルアセ
テート、メチルヘキサノエート、メチルシクロヘ
キサンカルボキシレート、メチルステアレートな
どがあげられる。
一方、カルボン酸の例としては安息香酸、フエ
ニルプロピオン酸等があげられる。
本発明でもちいる３級アミンは次の一般式で表
わされる。
ここでR3、R4およびR5は同一又は異なるアル
キル、アリールで、そのうち２つが共同して窒素
原子と共に環を形成してもよい。R3、R4および
R5は枝分かれしてもよい。代表的な３級アミン
としては、トリメチルアミン、トリエチルアミ
ン、Ｎ，Ｎ−ジメチルアニリン、Ｎ，Ｎ−ジエチ
ルアニリン、Ｎ−メチルピペリジン等があげられ
る。
本発明の目的化合物であるアルコールは上記一
般式（）で表わされるカルボン酸又はそのエス
テルから本発明方法により製造されるアルコー
ル、R1CH2OHおよびR2OHの両方とも含む。
本発明の方法の実施においては、温度の範囲は
０℃〜150℃が適当であり、好ましくは50℃〜80
℃である。反応時間は10分〜24時間、好ましくは
30分〜３時間が良い。本反応で用いられる溶媒
は、THF（テトラヒドロフラン）、DME（ジメト
キシエタン）などエーテル系溶媒が好ましく、そ
の内テトラヒドロフランが最も好ましい。反応は
原料であるカルボン酸又はそのエステルに対して
水素化ホウ素ナトリウム0.5〜4.0倍モル量、好ま
しくは1.0〜2.0倍モル量、塩化亜鉛0.25〜2.0倍モ
ル量、好ましくは0.5〜1.0倍モル量及び３級アミ
ン0.25〜2.0倍モル量好ましくは0.5〜1.0倍モル量
を用いて実施される。反応終了後希塩酸、塩化ア
ンモニウム溶液又はアンモニア水を加えて反応を
停止させ不溶物をろ別後溶媒を減圧留去してアル
コールを得ることができる。
実施例 １
安息香酸メチル2.72ｇ（20ｍmol）をテトラヒ
ドロフラン15mlに溶解させ、水素化ホウ素ナトリ
ウム1.52ｇ（40ｍmol）、塩化亜鉛2.72ｇ（20ｍ
mol）及びＮ，Ｎ−ジメチルアニリン1.21ｇ（10
ｍmol）を加え、還流下２時間撹はんした。反応
混合物を冷却し飽和塩化アンモニウム溶液を加え
過剰の還元剤を分解した。不溶物をろ別し、ろ液
を減圧留去後、蒸留によりベンジルアルコール
1.77ｇ（収率82％）を無色油状物として得た。
（bp：105−106℃／20mmHg）
実施例 ２
ステアリン酸メチル2.98ｇ（10ｍmol）をテト
ラヒドロフラン7.5mlに溶解させ、水素化ホウ素
ナトリウム0.76ｇ（20ｍmol）、塩化亜鉛1.36ｇ
（10ｍmol）及びＮ，Ｎ−ジメチルアニリン1.21
ｇ（10ｍmol）を加え還流下２時間撹はんした。
反応混合物を冷却し、氷冷した6N−塩酸中に注
いだ。析出した固体をエーテルで抽出し、飽和食
塩水で洗浄後無水硫酸ナトリウムで乾燥した。溶
媒を減圧留去後再結晶により精製し１−オクタデ
カノール2.65ｇ（収率99％）を無色結晶として得
た。
（mp：60−61℃）
実施例 ３
安息香酸2.44ｇ（20ｍmol）のテトラヒドロフ
ラン15ml溶液中に水素化ホウ素ナトリウム1.52ｇ
（40ｍmol）、塩化亜鉛2.72ｇ（20ｍmol）及び、
Ｎ，Ｎ−ジメチルアニリン4.84ｇ（40ｍmol）を
加え、還流下２時間撹はんした。反応混合物を冷
却し氷冷した6N−塩酸中に注ぎ、クロロホルム
で２回抽出した。クロロホルム層を飽和食塩水で
洗浄し無水硫酸ナトリウムにて乾燥した。溶媒を
減圧留去し残さを状留して1.06ｇ（49％）のベン
ジルアルコールを無色油状物として得た。
（bp105−106℃／20mmHg）
実施例 ４
実施例１及び２と同様に以下の化合物を得た。
The present invention relates to the production of alcohols, particularly primary alcohols, more particularly by reduction of aliphatic or aromatic carboxylic acids or esters thereof with sodium borohydride and zinc chloride in the presence of tertiary amines. The invention relates to a method for producing alcohol. Alcohol has long been known as an industrial chemical and is used in large quantities for the production of various products. Furthermore, there are many important intermediates for pharmaceuticals and agricultural chemicals, and many manufacturing methods have been reported. The method of reducing a carboxylic acid ester with lithium aluminum hydride to lead to alcohol is a method that has long been known at the laboratory level, but cannot be used industrially due to the danger and high cost. Therefore, efforts have been made to use sodium borohydride, which is cheaper and less dangerous, in place of lithium aluminum hydride. Since sodium borohydride alone cannot reduce carboxylic acid esters, a method has been reported in which a lower alcohol is added dropwise to enhance the reducing ability. However, this method requires a large excess of sodium borohydride and the reaction system foams, making it difficult to use in large quantities. Various methods have also been reported for reducing esters using a combination of sodium borohydride and various metal salts. For example, Kollonisch (J. Kollonitsch, et al., Nature
(London) 173 , 125 (1954). 175 , 346 (1955)) reduced the ester by a combination of lithium halide and sodium borohydride. Also, H.C.Brown, et al., J.Am.Chem.
Soc., 77 , 6209 (1955)) investigated the reduction of sodium borohydride in the presence of various polyvalent metal halides and reported that anhydrous aluminum chloride was a good additive. However, they reported that it was not possible to reduce the ester with sodium borohydride when using zinc chloride as an additive. The present invention makes it possible industrially to reduce a carboxylic acid or its ester using a combination of sodium borohydride and zinc chloride, which was thought to be impossible in the past, and also addresses the problems of the prior art and particularly enhances its industrial utility value. It is. For example, the best combination of sodium borohydride and anhydrous aluminum chloride in the prior art uses diglyme (diethylene glycol dimethyl ether), which is industrially undesirable, as a solvent.
Furthermore, anhydrous aluminum chloride is difficult to handle in large quantities compared to zinc chloride, and is also highly Lewis acidic and may cause side reactions, making it unsuitable for reducing unstable esters. The purpose of the present invention is to achieve short reaction times under neutral conditions,
The object of the present invention is to provide an improved method for producing alcohol in high yield through simple processing operations. This is an inexpensive and industrially useful method for producing alcohol. By the way, carboxylic acid or its ester cannot be reduced in low yield with only sodium borohydride and zinc chloride. However, as a result of intensive research, we surprisingly found that when a tertiary amine is present under these conditions, alcohol can be obtained in a short time and in high yield, and we have completed the present invention. The carboxylic acid or ester thereof used in the present invention is represented by the following general formula. Here, R 1 is alkyl, cycloalkyl, aryl, or aralkyl, which may be branched and an inert substituent (e.g., halogen atom, hydroxy group, alkoxy group, amino group, etc.)
may be replaced with . Examples of R 2 include a hydrogen atom in the case of a carboxylic acid, and an optionally branched alkyl or aralkyl in the case of a carboxylic ester. Furthermore, R 1 and R 2 may be combined. Examples of the above carboxylic acid esters include methyl benzoate, ethyl benzoate, methyl 2
-Methyl benzoate, methyl 4-methoxybenzoate, ethyl phenyl acetate, methyl 2
-bromobenzoate, ethyl 2-phenylthiobenzoate, benzyl acetate, ethyl acetate, methylhexanoate, methylcyclohexanecarboxylate, methyl stearate and the like. On the other hand, examples of carboxylic acids include benzoic acid and phenylpropionic acid. The tertiary amine used in the present invention is represented by the following general formula. Here, R 3 , R 4 and R 5 are the same or different alkyl or aryl, and two of them may jointly form a ring with the nitrogen atom. R 3 , R 4 and
R 5 may be branched. Typical tertiary amines include trimethylamine, triethylamine, N,N-dimethylaniline, N,N-diethylaniline, and N-methylpiperidine. The alcohol which is the object compound of the present invention includes both R 1 CH 2 OH and R 2 OH, which are alcohols produced by the method of the present invention from the carboxylic acid represented by the above general formula () or its ester. In carrying out the method of the invention, the temperature range is suitably between 0°C and 150°C, preferably between 50°C and 80°C.
It is ℃. Reaction time is 10 minutes to 24 hours, preferably
30 minutes to 3 hours is good. The solvent used in this reaction is preferably an ether solvent such as THF (tetrahydrofuran) or DME (dimethoxyethane), of which tetrahydrofuran is most preferred. The reaction is carried out using 0.5 to 4.0 times the molar amount of sodium borohydride, preferably 1.0 to 2.0 times the molar amount, and 0.25 to 2.0 times the molar amount of zinc chloride, preferably 0.5 to 1.0 times the molar amount of the carboxylic acid or its ester as a raw material. and tertiary amine in a molar amount of 0.25 to 2.0 times, preferably 0.5 to 1.0 times in molar amount. After completion of the reaction, dilute hydrochloric acid, ammonium chloride solution or aqueous ammonia is added to stop the reaction, insoluble matter is filtered off and the solvent is distilled off under reduced pressure to obtain alcohol. Example 1 2.72 g (20 mmol) of methyl benzoate was dissolved in 15 ml of tetrahydrofuran, 1.52 g (40 mmol) of sodium borohydride, and 2.72 g (20 mmol) of zinc chloride.
mol) and N,N-dimethylaniline 1.21 g (10
mmol) and stirred under reflux for 2 hours. The reaction mixture was cooled and saturated ammonium chloride solution was added to decompose excess reducing agent. After filtering out insoluble matter and distilling the filtrate under reduced pressure, benzyl alcohol is distilled off.
1.77 g (82% yield) was obtained as a colorless oil. (bp: 105-106℃/20mmHg) Example 2 2.98g (10mmol) of methyl stearate was dissolved in 7.5ml of tetrahydrofuran, 0.76g (20mmol) of sodium borohydride, and 1.36g of zinc chloride.
(10 mmol) and N,N-dimethylaniline 1.21
g (10 mmol) was added thereto, and the mixture was stirred under reflux for 2 hours.
The reaction mixture was cooled and poured into ice-cold 6N hydrochloric acid. The precipitated solid was extracted with ether, washed with saturated brine, and dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by recrystallization to obtain 2.65 g (yield 99%) of 1-octadecanol as colorless crystals. (mp: 60-61°C) Example 3 1.52 g of sodium borohydride in a solution of 2.44 g (20 mmol) of benzoic acid in 15 ml of tetrahydrofuran.
(40 mmol), zinc chloride 2.72 g (20 mmol) and
4.84 g (40 mmol) of N,N-dimethylaniline was added, and the mixture was stirred under reflux for 2 hours. The reaction mixture was cooled, poured into ice-cold 6N hydrochloric acid, and extracted twice with chloroform. The chloroform layer was washed with saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the residue was distilled to give 1.06 g (49%) of benzyl alcohol as a colorless oil.
(bp105-106°C/20mmHg) Example 4 The following compound was obtained in the same manner as in Examples 1 and 2.
【表】【table】
Claims (1)
カルボン酸又はそのエステルを水素化ホウ素ナト
リウムと塩化亜鉛により還元することを特徴とす
るアルコールの製造方法。1. A method for producing alcohol, which comprises reducing an aliphatic or aromatic carboxylic acid or its ester with sodium borohydride and zinc chloride in the presence of a tertiary amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60228462A JPS6287529A (en) | 1985-10-14 | 1985-10-14 | Production of alcohol or such |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60228462A JPS6287529A (en) | 1985-10-14 | 1985-10-14 | Production of alcohol or such |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6287529A JPS6287529A (en) | 1987-04-22 |
| JPH0548210B2 true JPH0548210B2 (en) | 1993-07-20 |
Family
ID=16876861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60228462A Granted JPS6287529A (en) | 1985-10-14 | 1985-10-14 | Production of alcohol or such |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6287529A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011170220A (en) * | 2010-02-22 | 2011-09-01 | Dainippon Printing Co Ltd | Hologram label |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4995456B2 (en) * | 2005-12-05 | 2012-08-08 | 出光興産株式会社 | Process for producing substituted adamantylethanol |
-
1985
- 1985-10-14 JP JP60228462A patent/JPS6287529A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011170220A (en) * | 2010-02-22 | 2011-09-01 | Dainippon Printing Co Ltd | Hologram label |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6287529A (en) | 1987-04-22 |
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