JPH0454177A - Production of gamma-alkyl-gamma-lactone - Google Patents
Production of gamma-alkyl-gamma-lactoneInfo
- Publication number
- JPH0454177A JPH0454177A JP2161843A JP16184390A JPH0454177A JP H0454177 A JPH0454177 A JP H0454177A JP 2161843 A JP2161843 A JP 2161843A JP 16184390 A JP16184390 A JP 16184390A JP H0454177 A JPH0454177 A JP H0454177A
- Authority
- JP
- Japan
- Prior art keywords
- acrylic acid
- gamma
- alcohol
- zinc
- lactone
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 etc. Chemical compound 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 6
- 150000003333 secondary alcohols Chemical class 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 229940102001 zinc bromide Drugs 0.000 abstract description 5
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 abstract description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000011592 zinc chloride Substances 0.000 abstract description 2
- 235000005074 zinc chloride Nutrition 0.000 abstract description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 11
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PHXATPHONSXBIL-UHFFFAOYSA-N xi-gamma-Undecalactone Chemical compound CCCCCCCC1CCC(=O)O1 PHXATPHONSXBIL-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- 125000000457 gamma-lactone group Chemical group 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004721 gamma keto acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 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
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、香料として、あるいは香料、医薬品、農薬な
どの出発原料として有用なγ−アルキル−γ−ラクトン
の新しい製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a new method for producing γ-alkyl-γ-lactones useful as fragrances or as starting materials for fragrances, pharmaceuticals, agricultural chemicals, and the like.
［従来の技術］
従来、γ−アルキル−γ−ラクトンの製造方法としては
、
（１）γ−ケト酸を還元する方法（Ｚｈｕｒ Ｏｂｓｃ
ｈｃｈｅｉＫｈｉｍ、 ３１，９８４（１９６１））（
２）γ−アルキル不飽和カルボン酸を硫酸と加熱する方
法（特公昭３８−４０６０号公報）等、種々知られてい
る。[Prior Art] Conventionally, methods for producing γ-alkyl-γ-lactone include (1) a method of reducing γ-keto acid (Zhur Obsc
hcheiKhim, 31,984 (1961)) (
2) Various methods are known, such as a method of heating γ-alkyl unsaturated carboxylic acid with sulfuric acid (Japanese Patent Publication No. 38-4060).
しかし、これらの方法には、原料の人手か困難である、
原料が高価である等の問題かあった。However, these methods require manual labor or difficulty in raw materials,
There were problems such as the raw materials being expensive.
これに対し、入手が容易な原料を用いる方法として、ア
ルコールとアクリル酸又はアクリル酸メチルとのラジカ
ル付加反応による方法か提案されている（Ｉｚｖｅｓｔ
、 Ａｋａｄ、 Ｎａｕｋ、 ５ＳＳＲ，Ｏｔ、ｄ、
ＫｈｉｍＮａｕｋ、、 １８７ｘ（１９６２）） 。し
かし、この方法のような単なる加熱反応では、γ−アル
キル−γ−ラクトンの収率が２０〜３０％程度と極めて
悪いという問題がある。この収率の低さは、原料アルコ
ールをアクリル酸又はアクリル酸メチルに対して１０倍
モル以上という大過剰用いることにより改善することが
できるが、この場合には原料アルコールの回収、再生等
が煩雑で生産性が悪く、経済的に不利となる。そこで、
かかる問題点を伴わずに収率及び生産性を向上させる方
法として、反応液中にスルホン酸類を添加する（特公昭
５３−３６４６６号公報）、すン酸塩及び／又は硫酸塩
を添加する（特公昭５２４２７９４号公報）等の方法が
知られている。On the other hand, as a method using easily available raw materials, a method using a radical addition reaction between alcohol and acrylic acid or methyl acrylate has been proposed (Izvest
, Akad, Nauk, 5SSR,Ot,d,
KhimNauk, 187x (1962)). However, a simple heating reaction such as this method has a problem in that the yield of γ-alkyl-γ-lactone is extremely poor at about 20 to 30%. This low yield can be improved by using a large excess of raw material alcohol, at least 10 times the mole relative to acrylic acid or methyl acrylate, but in this case, recovery and regeneration of raw material alcohol are complicated. This results in poor productivity and is economically disadvantageous. Therefore,
As a method for improving yield and productivity without such problems, sulfonic acids are added to the reaction solution (Japanese Patent Publication No. 53-36466), sulfates and/or sulfates are added ( Methods such as Japanese Patent Publication No. 5242794) are known.
［発明が解決しようとする課題］
しかし、これらの方法もその収率は未だ十分満足できる
ものではなく、より高い収率で効率良くγ−アルキル−
γ−ラクトンを製造できる方法の開発が望まれていた。[Problems to be Solved by the Invention] However, the yields of these methods are still not fully satisfactory, and γ-alkyl-
It has been desired to develop a method for producing γ-lactone.
［課題を解決するための手段］
かかる実情において、本発明者らは上記課題を解決すべ
く鋭意研究を重ねた結果、アクリル酸及び／又はアクリ
ル酸エステルとアルコールとの反応系に、ジ第三級ブチ
ルパーオキシドとノ１０ゲン化亜鉛を共存させることに
より収率が向上することを見いだし、本発明を完成した
。[Means for Solving the Problems] Under these circumstances, the present inventors have conducted intensive research to solve the above problems, and as a result, they have added di-tertiary to the reaction system of acrylic acid and/or acrylic acid ester and alcohol. The present invention was completed based on the discovery that the yield can be improved by coexisting dibutyl peroxide and zinc oxide.
すなわち本発明は、アクリル酸もしくはアクリル酸エス
テル又はそれらの混合物と、第一級アルコールもしくは
第二級アルコール又はそれらの混合物とを、ジ第三級ブ
チルパーオキシド及びハロゲン化亜鉛の存在下で加熱反
応させることを特徴とするγ−アルキル−γ−ラクトン
の製造方法を提供するものである。That is, the present invention involves a heating reaction of acrylic acid, an acrylic ester, or a mixture thereof, and a primary alcohol, a secondary alcohol, or a mixture thereof in the presence of ditertiary butyl peroxide and zinc halide. The present invention provides a method for producing a γ-alkyl-γ-lactone.
本発明方法に用いられる出発原料であるアクリル酸は含
水界及び無水晶のとちらでもよい。また、アクリル酸エ
ステルとしては炭素数１〜５の低級アルキルエステルが
挙げられ、その代表例としては、アクリル酸メチル、ア
クリル酸エチル等か挙げられる。The starting material acrylic acid used in the method of the present invention may be either hydrous or aquartz. Furthermore, examples of acrylic esters include lower alkyl esters having 1 to 5 carbon atoms, typical examples of which include methyl acrylate, ethyl acrylate, and the like.
本発明方法において出発原料として用いられる第一級ア
ルコールとしては、例えば炭素数２〜１０の第一級アル
コール、具体的にはエタノール、１−プロバノール、ｎ
（又はｉ）−ブタノール、ｎ（又はｉ）アミルアルコー
ル、ｎ（又はｉ）−ヘキサノール、ｎ（又はｉ）−ヘプ
タツール、ｎ（又はｉ）−オクタツール、ｎ（又はｉ）
−ノニルアルコール、ｎ（又はｉ）−デシルアルコール
等が挙げられる。第一級アルコールを用いた場合、得ら
れるラクトンはγ−モノアルキルーγ−ラクトンとなる
。また、第二級アルコールとしては、例えば炭素数３〜
１０の第２級アルコール、具体的には２−プロパツール
、２−ブタノール、５ｅｃ−アミルアルコール、２−ヘ
キサノール、２−ヘプタツール、２−オクタツール、５
ｅｅ−ノニルアルコール、５ｅｃ−デシルアルコール等
が挙げられる。第二級アルコールを用いた場合、得られ
るラクトンはγ−シアルキル〜γ−ラクトンとなる。こ
れらのアルコールの使用量は、アクリル酸又はアクリル
酸エステル１モルに対して３〜８モル、特に４〜７モル
の範囲が好ましい。Examples of the primary alcohol used as a starting material in the method of the present invention include primary alcohols having 2 to 10 carbon atoms, specifically ethanol, 1-probanol, n
(or i)-butanol, n (or i) amyl alcohol, n (or i)-hexanol, n (or i)-heptatool, n (or i)-octatool, n (or i)
-nonyl alcohol, n(or i)-decyl alcohol, and the like. When a primary alcohol is used, the resulting lactone is a γ-monoalkyl-γ-lactone. Further, as a secondary alcohol, for example, carbon number is 3 to
10 secondary alcohols, specifically 2-propatol, 2-butanol, 5ec-amyl alcohol, 2-hexanol, 2-heptatool, 2-octatool, 5
Examples include ee-nonyl alcohol and 5ec-decyl alcohol. When a secondary alcohol is used, the resulting lactone is γ-sialkyl to γ-lactone. The amount of these alcohols used is preferably in the range of 3 to 8 mol, particularly 4 to 7 mol, per 1 mol of acrylic acid or acrylic acid ester.
本発明に用いられるハロゲン化亜鉛としては、塩化亜鉛
、臭化亜鉛、ヨウ化亜鉛等が挙げられる。Examples of the zinc halide used in the present invention include zinc chloride, zinc bromide, zinc iodide, and the like.
これらのハロゲン化亜鉛の使用量は、アクリル酸又はア
クリル酸エステル１モルに対して１×１０−５〜Ｉ Ｘ
１０−”モル、特にＩ Ｘ １０−’〜Ｉ Ｘ １０
−”モルの範囲が好ましい。The amount of these zinc halides used is 1 x 10-5 to 1 x 1 mole of acrylic acid or acrylic ester.
10-" mol, especially I x 10-' to I x 10
-”molar range is preferred.
また、ジ第三級ブチルパーオキシドの使用量は、アクリ
ル酸又はアクリル酸エステル１モルに対して００１〜０
５モル、特に００４〜０．２モルが好ましい。In addition, the amount of ditertiary butyl peroxide used is 0.01 to 0.00 per mole of acrylic acid or acrylic acid ester.
5 mol, especially 0.004 to 0.2 mol is preferred.
本反応は１４０〜２００℃、好ましくは１５０〜１８０
℃の反応温度で、２〜１０時間行うのが効果的である。This reaction is carried out at 140-200°C, preferably 150-180°C.
It is effective to carry out the reaction at a reaction temperature of 2 to 10 hours.
また、反応混合物からγ〜アルキルーγ−ラクトンを精
製する方法としては、従来公知の方法、例えば蒸留法、
溶媒抽出法、再結晶法、カラムクロマト法等から適宜選
択することかできる。In addition, as a method for purifying γ-alkyl-γ-lactone from the reaction mixture, conventionally known methods such as distillation,
The method can be appropriately selected from solvent extraction, recrystallization, column chromatography, and the like.
本発明方法により好適に製造し得るγ−アルキル−γ−
ラクトンとしては、γ−メチルーγ−ブチロラクトン、
γ−エチルーγ−ブチロラクトン、γ−（ｎ−又はえ−
プロピル）−γ−ブチロラクトン、γ−（ロー又はｉ−
ブチル）−γ−ブチロラクトン、γ−（０−又は１ペン
チル）−γ−ブチロラクトン、γ−（ｎ−又はニーヘキ
シル）−γ−ブチロラクトン、γ−（ｎ−又はｉ−ヘフ
チル）−γ−ブチロラクトン、γ−（ｎ−又はｊ−オク
チル）−γ−ブチロラクトン、γ−（ｎ−又はｉ−ノニ
ル）−γ−ブチロラクトン、γ−ジメチルーγ−ブチロ
ラクトン等が挙げられる。γ-alkyl-γ- which can be suitably produced by the method of the present invention
Lactones include γ-methyl-γ-butyrolactone,
γ-ethyl-γ-butyrolactone, γ-(n- or er-
propyl)-γ-butyrolactone, γ-(rho or i-
butyl)-γ-butyrolactone, γ-(0- or 1 pentyl)-γ-butyrolactone, γ-(n- or nyhexyl)-γ-butyrolactone, γ-(n- or i-hephthyl)-γ-butyrolactone, γ -(n- or j-octyl)-γ-butyrolactone, γ-(n- or i-nonyl)-γ-butyrolactone, γ-dimethyl-γ-butyrolactone, and the like.
［実施例コ
以下、実施例を挙げて更に詳細に説明するが、本発明は
これらに限定されるものではない。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例１
１１のオートクレーブにｎ−オクタツール４７０ｇ（純
度９８％、 ３．５４ｍｏｌ）及び臭化亜鉛０．０７ｇ
（Ｏｊｍｍｏｌ）を入れ、１６５℃に加熱保持し、攪
拌しながら、この中にアクリル酸メチル６６ｇ （０、
７７８ｍｏｌ）とジ第三級プチルパーオキント１１．８
ｇ （０，０８ｍｏｌ）の混合液を６時間かけて圧入し
た。更に１時間同温度にて攪拌を続けた。反応終了後、
反応液から未反応のｎ−オクタツールを留去し、次いで
減圧蒸留してγ−（ｎ−ヘプチル）−γ−ブチロラクト
ンを１１５．３ｇ（ｏ、５４ｍｏｌ）得た（収率７０％
）。Example 1 470 g of n-octatool (purity 98%, 3.54 mol) and 0.07 g of zinc bromide were placed in a 11 autoclave.
(Ojmmol) was heated to 165°C, and while stirring, 66g of methyl acrylate (0,
778 mol) and ditertiary butylperoquinto 11.8
A mixture of g (0.08 mol) was injected over 6 hours. Stirring was continued at the same temperature for an additional hour. After the reaction is complete,
Unreacted n-octatool was distilled off from the reaction solution, and then distilled under reduced pressure to obtain 115.3 g (o, 54 mol) of γ-(n-heptyl)-γ-butyrolactone (yield 70%).
).
実施例２
１ｐのオートクレーブにｎ−オクタツール４７０ｇ（純
度９８％、 ３．５４ｍｏｌ）及び臭化亜鉛０．０７ｇ
（０，３ｍｍｏｌ）を入れ、１７５℃に加熱保持し、
攪拌しながら、この中にアクリル酸６９ｇ（純度８０％
、 ０．７７ｍｏｌ）とジ第三級ブチルバーオキシド１
１．８ｇ （０，０８ｍｏｌ）の混合液を６時間かけて
圧入した。更に１時間同温度にて攪拌を続けた。反応終
了後、反応液から未反応のｎ−オクタツールを留去し、
次いで減圧蒸留してγ−（ｎ−へブチル）−γ−ブチロ
ラクトンを１１９１ｇ （０，５７ｍｏｌ）得た（収率
７４％）。Example 2 470 g of n-octatool (purity 98%, 3.54 mol) and 0.07 g of zinc bromide were placed in a 1p autoclave.
(0.3 mmol) and heated and maintained at 175°C.
While stirring, add 69 g of acrylic acid (purity 80%) to this.
, 0.77 mol) and di-tert-butyl peroxide 1
1.8 g (0.08 mol) of the mixed solution was injected over 6 hours. Stirring was continued at the same temperature for an additional hour. After the reaction is completed, unreacted n-octatool is distilled off from the reaction solution,
The mixture was then distilled under reduced pressure to obtain 1191 g (0.57 mol) of γ-(n-hebutyl)-γ-butyrolactone (yield 74%).
実施例３及び４
臭化亜鉛の代わりに塩化亜鉛（実施例３）又はヨウ化亜
鉛（実施例４）を各０ 、３ｍｍ○１用いる以外は実施
例１と同様にして、γ−（ｎ−ヘプチル）−γ−ブチロ
ラクトンを得た。このときの収率を第１表に示す。Examples 3 and 4 γ-(n- Heptyl)-γ-butyrolactone was obtained. The yield at this time is shown in Table 1.
比較例１及び２
臭化亜鉛の代わりにｐ−ｔ−ルエンスルホン酸を０．０
３ｇ （比較例１）又はリン酸水素二カリウムを０．７
ｇ（比較例２）用いる以外は実施例１と同様にして、γ
−（ｎ−ヘプチル）−γ−ブチロラクトンを得た。この
ときの収率を第１表に示す。Comparative Examples 1 and 2 0.0 p-t-luenesulfonic acid instead of zinc bromide
3g (Comparative Example 1) or 0.7 dipotassium hydrogen phosphate
g (Comparative Example 2) Same as Example 1 except that γ
-(n-heptyl)-γ-butyrolactone was obtained. The yield at this time is shown in Table 1.
比較例３
臭化亜鉛を添加しない以外は実施例１と同様にしてγ−
（ｎ−ヘプチル）−γ−ブチロラクトンを得た。Comparative Example 3 γ-
(n-heptyl)-γ-butyrolactone was obtained.
このときの収率を第１表に示す。The yield at this time is shown in Table 1.
（以下余白）
第１表
［発明の効果］
以上のように、本発明によれば従来法に比べ、より高い
収率で効率良くγ−アルキル−γ−ラクトンを製造する
ことができる。(The following is a blank space) Table 1 [Effects of the Invention] As described above, according to the present invention, it is possible to efficiently produce γ-alkyl-γ-lactone with a higher yield than the conventional method.
以 上
実施例５〜７
ｎ−オクタツールの代わりにエタノールを１６６ｇ（実
施例５）、ｎ−デカノールを５６０ｇ （実施例６）又
はイソプロピルアルコールを２１５ｇ （実施例７）用
いた以外は実施例２と同様にしてγ−アルキルγ−ラク
トンを得た。この結果を第２表に示す。Examples 5 to 7 Example 2 except that 166 g of ethanol (Example 5), 560 g of n-decanol (Example 6), or 215 g of isopropyl alcohol (Example 7) was used instead of n-octatool. A γ-alkyl γ-lactone was obtained in the same manner as above. The results are shown in Table 2.
第２表Table 2
Claims (1)
らの混合物と、第一級アルコールもしくは第二級アルコ
ール又はそれらの混合物とを、ジ第三級ブチルパーオキ
シド及びハロゲン化亜鉛の存在下で加熱反応させること
を特徴とするγ−アルキル−γ−ラクトンの製造方法。(1) Heat reacting acrylic acid, acrylic ester, or a mixture thereof with a primary alcohol, a secondary alcohol, or a mixture thereof in the presence of ditertiary butyl peroxide and zinc halide. A method for producing a γ-alkyl-γ-lactone, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2161843A JPH0454177A (en) | 1990-06-20 | 1990-06-20 | Production of gamma-alkyl-gamma-lactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2161843A JPH0454177A (en) | 1990-06-20 | 1990-06-20 | Production of gamma-alkyl-gamma-lactone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0454177A true JPH0454177A (en) | 1992-02-21 |
Family
ID=15743000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2161843A Pending JPH0454177A (en) | 1990-06-20 | 1990-06-20 | Production of gamma-alkyl-gamma-lactone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0454177A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2000455A2 (en) | 2005-06-30 | 2008-12-10 | Asahi Kasei Chemicals Corporation | Process for production of substituted cyclopentanone |
| CN103030614A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Extracting method of synthetic peach aldehyde |
| CN107337656A (en) * | 2017-08-09 | 2017-11-10 | 上海化工研究院有限公司 | A kind of continuous reaction system and method for preparing γ undecalactones |
| CN108997270A (en) * | 2018-08-06 | 2018-12-14 | 安徽华业香料股份有限公司 | A kind of production method of reactive distillation synthesis gamma decalactone synthetic perfume |
-
1990
- 1990-06-20 JP JP2161843A patent/JPH0454177A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2000455A2 (en) | 2005-06-30 | 2008-12-10 | Asahi Kasei Chemicals Corporation | Process for production of substituted cyclopentanone |
| US7897802B2 (en) | 2005-06-30 | 2011-03-01 | Asahi Kasei Chemicals Corporation | Process for production of substituted cyclopentanone |
| CN103030614A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Extracting method of synthetic peach aldehyde |
| CN107337656A (en) * | 2017-08-09 | 2017-11-10 | 上海化工研究院有限公司 | A kind of continuous reaction system and method for preparing γ undecalactones |
| CN108997270A (en) * | 2018-08-06 | 2018-12-14 | 安徽华业香料股份有限公司 | A kind of production method of reactive distillation synthesis gamma decalactone synthetic perfume |
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