JPH01193242A - Production of propionylacetic acid ester - Google Patents
Production of propionylacetic acid esterInfo
- Publication number
- JPH01193242A JPH01193242A JP1724188A JP1724188A JPH01193242A JP H01193242 A JPH01193242 A JP H01193242A JP 1724188 A JP1724188 A JP 1724188A JP 1724188 A JP1724188 A JP 1724188A JP H01193242 A JPH01193242 A JP H01193242A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- methyl
- acid ester
- propionylacetoacetate
- acetoacetate
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- -1 propionylacetic acid ester Chemical class 0.000 title abstract description 33
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 5
- KLUDQUOLAFVLOL-UHFFFAOYSA-N acetyl propanoate Chemical compound CCC(=O)OC(C)=O KLUDQUOLAFVLOL-UHFFFAOYSA-N 0.000 claims description 12
- OSKSDTJRNSMQKC-UHFFFAOYSA-N 3,5-dioxoheptanoic acid Chemical compound CCC(=O)CC(=O)CC(O)=O OSKSDTJRNSMQKC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229920000642 polymer Chemical group 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 30
- BDCLDNALSPBWPQ-UHFFFAOYSA-M 3-oxohexanoate Chemical compound CCCC(=O)CC([O-])=O BDCLDNALSPBWPQ-UHFFFAOYSA-M 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 5
- CMGSHCJWRFSQBL-UHFFFAOYSA-N methyl 3,5-dioxoheptanoate Chemical compound CCC(=O)CC(=O)CC(=O)OC CMGSHCJWRFSQBL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 abstract description 3
- 239000004324 sodium propionate Substances 0.000 abstract description 3
- 235000010334 sodium propionate Nutrition 0.000 abstract description 3
- 229960003212 sodium propionate Drugs 0.000 abstract description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 230000006196 deacetylation Effects 0.000 abstract 1
- 239000003456 ion exchange resin Substances 0.000 abstract 1
- 229920003303 ion-exchange polymer Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- DPEYHNFHDIXMNV-UHFFFAOYSA-N (9-amino-3-bicyclo[3.3.1]nonanyl)-(4-benzyl-5-methyl-1,4-diazepan-1-yl)methanone dihydrochloride Chemical compound Cl.Cl.CC1CCN(CCN1Cc1ccccc1)C(=O)C1CC2CCCC(C1)C2N DPEYHNFHDIXMNV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- PCWFEIRYFVRNSR-UHFFFAOYSA-N ethyl 3,5-dioxoheptanoate Chemical compound CCOC(=O)CC(=O)CC(=O)CC PCWFEIRYFVRNSR-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical compound CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- BWILYWWHXDGKQA-UHFFFAOYSA-M potassium propanoate Chemical compound [K+].CCC([O-])=O BWILYWWHXDGKQA-UHFFFAOYSA-M 0.000 description 1
- 239000004331 potassium propionate Substances 0.000 description 1
- 235000010332 potassium propionate Nutrition 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- TWEGKFXBDXYJIU-UHFFFAOYSA-M sodium;2-methylpropanoate Chemical compound [Na+].CC(C)C([O-])=O TWEGKFXBDXYJIU-UHFFFAOYSA-M 0.000 description 1
- ABVTYDBFUDWAFT-UHFFFAOYSA-N tert-butyl 3,5-dioxoheptanoate Chemical compound CCC(=O)CC(=O)CC(=O)OC(C)(C)C ABVTYDBFUDWAFT-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は、医薬、農薬などの製造原料として有用なプロ
ピオニル酢酸エステルの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a method for producing propionyl acetate useful as a raw material for producing medicines, agricultural chemicals, and the like.
（従来の技術）
プロピオニルアセト酢酸エステルから脱アセチル化反応
により、プロピオニル酢酸エステルを製造する方法とし
ては、下記の方法が公知である。(Prior Art) The following method is known as a method for producing propionyl acetate from propionyl acetoacetate by deacetylation reaction.
■Ｇ、Ｗ、Ａｎｄｅｒｓｏｎらは、エーテル中でプロピ
オニルアセト酢酸エステルにアンモニアを反応させてプ
ロピオニル酢酸エステルを得る方法を提案しているＣＪ
、Ａａ、Ｃｈｅｍ、Ｓｏｃ、８７２１９７ （Ｉ８４
５）参照）。■CJ G, W, Anderson et al. have proposed a method to obtain propionyl acetoacetate by reacting propionyl acetoacetate with ammonia in ether.
, Aa, Chem, Soc, 872197 (I84
5)).
■Ｔ、Ｖｏｎｔｏｒらは、エタノール中１プロピオニル
アセト酢酸エステルに水酸化カリウムを反応させてプロ
ピオニル酢酸エステルを得る方法を提案している（Ｌｌ
：ｅｓｋｏｓｌｏｖ、Ｆａｒｍ、、 ３５１８２ （
Ｉ９８１１１）参照）。■T.Vontor et al. proposed a method to obtain propionyl acetate by reacting potassium hydroxide with 1-propionyl acetoacetate in ethanol (Ll
:eskoslov,Farm,, 35182 (
(See I98111).
■Ｍ、Ｖｉｓｃｏｎｔｉｎｉらは、アルコール中でナト
リウムメトキシドで処理することにより、プロピオニル
酢酸エステルを得る方法を提案している（Ｈｅｌｖｅｔ
ｉｃａ Ｃｈｉｍｉｃａ Ａｃｔａ、 ３５ ２
２８０ （Ｉ９５２） 参照）。M. Viscontini et al. proposed a method to obtain propionyl acetate by treatment with sodium methoxide in alcohol (Helvet
ica Chimica Acta, 35 2
280 (I952)).
しかしながら、いずれの方法も収率が４０〜７０％と低
いか、また、ある程度良好な収率であると報告されてい
る方法も、その一方で、大量に酢酸エステルが副生ずる
ため、この酢酸エステルを分離し、プロピオニル酢酸エ
ステルを精製する操作が煩雑になるという問題がある。However, all of these methods have low yields of 40 to 70%, and even methods that are reported to have somewhat good yields produce a large amount of acetate as a by-product. There is a problem in that the operations for separating and purifying propionyl acetate become complicated.
プロピオニル酢酸エステルの製造方法については、脱ア
セチル化反応を適用する方法以外に種々の方法が提案さ
れている。Various methods have been proposed for producing propionyl acetate in addition to the method of applying a deacetylation reaction.
■メルドラム酸を使用する方法（特開昭５４−１０８４
２１号公報及びＪ、Ｏｒｇ、Ｃｈｅｍ、、４３２０Ｂ？
（Ｉ９７８）参照）。■Method using Meldrum's acid (Japanese Patent Application Laid-Open No. 1084-1984)
No. 21 and J, Org, Chem, 4320B?
(See I978).
（シプロピオニトリル、アセト酢酸エステルに塩化第二
スズを作用させ加水分解する方法（特公昭４３−１７１
７０号公報及び５ｔｎｔｈｔｓｉｓ、 ８２Ｂ （Ｉ９
７８）参照）。(Method of hydrolyzing cypropionitrile and acetoacetate by acting on stannic chloride (Japanese Patent Publication No. 43-171)
No. 70 and 5tntthtsis, 82B (I9
78)).
ζ中マロン酸ハーフエステルを用いる方法（Ｊ、Ａｍ、
Ｃｈｅｍ、Ｓｏｃ、、 ８８１２８Ｂ （Ｉ９４４）
参照）。Method using malonic acid half ester in ζ (J, Am,
Chem, Soc, 88128B (I944)
reference).
■エチルグリニヤールとシアン酢酸エステルとの反応（
Ｃｈｅｍ、Ｂｅｒ、、 ４０７３ （Ｉ９８５）参照
）。■Reaction of ethyl Grignard and cyanacetic ester (
See Chem, Ber, 4073 (I985)).
（ロ）プロピオニルマロン酸エステルを有機酸で分解す
る方法（Ａｃｔａ Ｃｈｅｓ、５ｃａｎｄ、、 ５１４
１３ （Ｉ９５１）参照）。(b) Method of decomposing propionyl malonic acid ester with organic acid (Acta Ches, 5cand, 514
13 (I951)).
■アセト酢酸エステルのエナミンを、強塩基の存在下で
、メチルハライドと反応させる方法（Ｅ、Ｐ、、 １２
８９２３ （Ｉ９Ｂ４）参照）。■A method of reacting enamine of acetoacetate with methyl halide in the presence of a strong base (E, P, 12
8923 (I9B4)).
・［相］アセト酢酸エステルのジアニオンとメチルハラ
イドとの反応（Ｊ、＾ｍ、ｃｈｅｍ、ｓａｃ、、９２８
７０２（Ｉ９７０）参照）。・[Phase] Reaction of acetoacetate dianion and methyl halide (J, ^m, chem, sac,, 928
702 (I970)).
■α、β−不飽和エステルのパラジウムによる酸化（Ｃ
ｈｅｍｉｓｔｒｙ Ｌｅｔｔｅｒｓ ２５７ （Ｉ９
８０）参照）。■ Oxidation of α, β-unsaturated esters with palladium (C
hemistry Letters 257 (I9
80)).
＠アルキニルエステルの加水分解（ＬｉｅｂｉｇＡｎｎ
、、２８２ （Ｉ９７７）参照）。@Hydrolysis of alkynyl esters (LiebigAnn
, 282 (I977)).
しかしながら、■、■、■、■、■、［株］、■及び＠
の方法は、使用する原料が高価であり、とりわけ■及び
［株］の方法を工業的に実施することは困難であり、■
及び■の方法では、副生物の分離操作が極めて煩雑であ
るという問題点を有しており、いずれの方法も工業的に
有利ではない。However, ■, ■, ■, ■, ■, [stock], ■ and @
In method (2), the raw materials used are expensive, and in particular, it is difficult to implement methods (2) and [Co., Ltd.] industrially;
Methods (1) and (2) have the problem that the separation operation for by-products is extremely complicated, and neither method is industrially advantageous.
［発明の構成］
（発明が解決しようとする問題点）
本発明は、上記の問題点を解決し、簡便な方法により、
高い収率でプロピオニル酢酸エステルを得ることができ
るプロピオニル酢酸エステルの製造方法を提供すること
を目的とする。[Structure of the Invention] (Problems to be Solved by the Invention) The present invention solves the above-mentioned problems and solves the problems by a simple method.
An object of the present invention is to provide a method for producing propionyl acetate that can obtain propionyl acetate in high yield.
（問題点を解決するための手段及び作用）本発明のプロ
ピオニル酢酸エステルの製造方法は、一般式（Ｉ）；
Ｃ０Ｃ２Ｈｓ
■
ＣＨ，ＣＣＨＣＯ２Ｒ’ （Ｉ）口
（式中 ）１１は炭素数ｌＮ１０のアルキル基、アラル
キル基、シクロアルキル基又はアリール基を表す）
で示されるプロピオニルアセト酢酸エステルの脱アセチ
ル化反応により、一般式（■）；Ｃ２Ｈ，ＣＣＨ２Ｃｏ
２Ｒ’ （ｎ）薦
（式中、Ｒ１は前記と同じである）
で示されるプロピオニル酢酸エステルを製造する方法に
おいて、
前記一般式（Ｉ）で示される化合物と、一般式（■）：
Ｒ２Ｃ００Ｍ （ｍ）（式中、Ｒ
２は炭素数１〜１０のアルキル基、アリール基又は高分
子残基を表し、Ｍはアルカリ金属またはアルカリ土類金
属を表す）で示される有機酸塩をアルコール系溶媒中で
反応させることを特徴とする。(Means and effects for solving the problems) The method for producing propionyl acetate of the present invention is based on the general formula (I); group, aralkyl group, cycloalkyl group, or aryl group), the general formula (■); C2H, CCH2Co
2R' (n) (in the formula, R1 is the same as above) A method for producing propionyl acetate ester represented by the above general formula (I) and the general formula (■): R2C00M ( m) (wherein, R
2 represents an alkyl group, aryl group, or polymer residue having 1 to 10 carbon atoms, and M represents an alkali metal or alkaline earth metal) is reacted in an alcoholic solvent. shall be.
本発明で用いる一般式ＣＩ）で示されるプロピオニルア
セト酢酸エステルとしては、プロピオニルアセト酢酸メ
チル、プロピオニルアセト酢酸エチル、プロピオニルア
セト酢酸−ｎ−プロピル、プロピオニルアセト酢酸−ｉ
−プロピル、プロピオニルアセト酢酸−ｎ−ブチル、プ
ロピオニルアセト酢酸−１−ブチル、プロピオニルアセ
ト酢酸−Ｓ−ブチル、プロピオニルアセト酢酸−ｔ−ブ
チル、プロピオニルアセト酢酸−ｎ−アミル、プロピオ
ニルアセト酢酸シクロペンチル、プロピオニルアセト酢
酸シクロヘキシル、プロピオニルアセト酢酸−ｎ−ヘキ
シルなどを例示することができる。The propionylacetoacetate represented by the general formula CI) used in the present invention includes methyl propionylacetoacetate, ethyl propionylacetoacetate, n-propyl propionylacetoacetate, and propionylacetoacetate-i.
-propyl, n-butyl propionylacetoacetate, 1-butyl propionylacetoacetate, S-butyl propionylacetoacetate, t-butyl propionylacetoacetate, n-amyl propionylacetoacetate, cyclopentyl propionylacetoacetate, propionylacetoacetate Examples include cyclohexyl acetate and n-hexyl propionylacetoacetate.
本発明で用いる一般式（ｍ）で示される有機酸塩として
は、酢酸、プロピオン酸、イソプロピオン酸、ブタン酸
、イソブタン酸、ペンタン酸、インペンタン酸、カプロ
ン酸、安息香酸などのアルカリ金属塩（例えば、ナトリ
ウム塩、カリウム塩など）又はアルカリ土類金属塩（例
えば、カルシウム塩、マグネシウム塩など）を例示する
ことができ、また、カルボキシル基を有する高分子化合
物、例えばイオン交換樹脂のアルカリ金属塩をも例示す
ることができる。かかる有機酸塩としては、プロピオン
酸の塩が好ましい。Examples of the organic acid salts represented by the general formula (m) used in the present invention include alkali metal salts such as acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, impentanoic acid, caproic acid, and benzoic acid. (e.g., sodium salts, potassium salts, etc.) or alkaline earth metal salts (e.g., calcium salts, magnesium salts, etc.); Salt can also be exemplified. As such organic acid salts, propionic acid salts are preferred.
本発明における有機酸塩の使用量は、プロピオニルアセ
ト酢酸エステルに対して０．０１ Ｎ１０当量であり、
好ましくは０．０５〜２当量である。The amount of organic acid salt used in the present invention is 0.01 N10 equivalent relative to propionyl acetoacetate,
Preferably it is 0.05 to 2 equivalents.
本発明で用いられるアルコール系溶媒は、アルコール又
はアルコールを含有する溶媒であり、メタノール、エタ
ノールなどのアルコール又はこれらの水溶液を例示する
ことができる。アルコール系溶媒としてアルコールを含
有する溶媒を用いる場合には、アルコールの含有量が５
０容量％以上であることが好ましい。The alcoholic solvent used in the present invention is alcohol or a solvent containing alcohol, and examples thereof include alcohols such as methanol and ethanol, and aqueous solutions thereof. When using a solvent containing alcohol as the alcoholic solvent, the alcohol content is 5.
It is preferable that it is 0% by volume or more.
かかるアルコール系溶媒の使用量は、プロピオニルアセ
ト酢酸エステル１００重量部に対して２０〜１００．０
００重量部であり、好ましくは５０〜４，０００重量部
である。The amount of alcoholic solvent used is 20 to 100.0 parts by weight per 100 parts by weight of propionyl acetoacetate.
00 parts by weight, preferably 50 to 4,000 parts by weight.
反応温度は０〜１００℃であり、好ましくは２０〜６０
℃である。The reaction temperature is 0 to 100°C, preferably 20 to 60°C.
It is ℃.
反応時間は、有機酸塩の使用量、アルコール系溶媒の使
用量及び反応温度などにより異なるが、通常は２〜７０
時間で充分である。The reaction time varies depending on the amount of organic acid salt used, the amount of alcoholic solvent used, the reaction temperature, etc., but is usually 2 to 70 minutes.
Time is enough.
反応により副生じたアセト酢酸エステルは、蒸留操作な
どにより分離除去することができる。The acetoacetate produced as a by-product of the reaction can be separated and removed by distillation or the like.
（実施例） 以下、本発明を実施例によりさらに詳しく説明する。(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
プロピオニルアセト酢酸メチル１．５１ｋｇをメタノー
ル２．３ｆＬに溶解させ、さらにプロピオン酸ナトリウ
ム８６．４ｇを添加した０次いで。Example 1 1.51 kg of methyl propionylacetoacetate was dissolved in 2.3 fL of methanol, and then 86.4 g of sodium propionate was added.
この溶液を４０℃で４時間、加熱攪拌した。冷却後、硫
酸で中和し、メタノールを減圧下で除去した。その後、
残液にジクロロメタン１．３Ｊ１及び水０．８Ｊ１を添
加し静置したのち、生じた有機層を分液した０次いで、
該有機層からジクロロメタンを留去し、残部を精密蒸留
して、アセト酢酸メチルの含有量が２モル％以下である
プロピオニル酢酸メチル０．８２ｋｇを得た（収率７２
％）。This solution was heated and stirred at 40° C. for 4 hours. After cooling, it was neutralized with sulfuric acid and methanol was removed under reduced pressure. after that,
After adding 1.3 J1 of dichloromethane and 0.8 J1 of water to the residual liquid and leaving it to stand, the resulting organic layer was separated.
Dichloromethane was distilled off from the organic layer, and the residue was precision distilled to obtain 0.82 kg of methyl propionyl acetate with a methyl acetoacetate content of 2 mol% or less (yield: 72
%).
精密蒸留前のプロピオニル酢酸メチルの収量はガスクロ
マトグラムによる分析の結果、０．９１３ｋｇであった
。The yield of methyl propionyl acetate before precision distillation was 0.913 kg as a result of analysis by gas chromatography.
実施例２
プロピオニルアセト酢酸メチルを３．２５ｇをメタノー
ル５−に溶解させ、陽イオン交換樹脂（アンバーライト
ＩＲＣ−５０）を常法でナトリウム型にしたものを０
．８ｇ添加した０次いで、この溶液を室温で２日間攪拌
し、反応を行わせた。その結果、プロピオニル酢酸メチ
ル１．９７ｇを得た（収率８０％）、アセト酢酸メチル
は０．３７ｇ生成した。この測定値は高速液体クロマト
グラフィーにより求めた。以下、測定法は同様である。Example 2 3.25 g of methyl propionyl acetoacetate was dissolved in methanol 5-, and cation exchange resin (Amberlite IRC-50) was made into sodium form using a conventional method.
．． Then, this solution was stirred at room temperature for 2 days to allow the reaction to occur. As a result, 1.97 g of methyl propionyl acetate was obtained (yield 80%), and 0.37 g of methyl acetoacetate was produced. This measured value was determined by high performance liquid chromatography. The measurement method is the same below.
実施例３
プロピオニルアセト酢酸メチル２．０ｇをメタノール１
２−に溶解させ、さらにプロピオン酸カリ°ウム０．１
３ｇを添加した０次いで、この溶液を室温で８時間攪拌
し、反応を行わせた。その結果、プロピオニル酢酸メチ
ル１．２６ｇを得た（収率８４％）、アセト酢酸メチル
は０．２０ｇ生成した。Example 3 2.0 g of methyl propionyl acetoacetate was added to 1 part of methanol.
2- and further potassium propionate 0.1
Then, the solution was stirred at room temperature for 8 hours to allow the reaction to take place. As a result, 1.26 g of methyl propionyl acetate was obtained (yield 84%), and 0.20 g of methyl acetoacetate was produced.
実施例４
プロピオニルアセト酢酸メチル１．０ｇをメタノール１
０−に溶解させ、さらに酢酸ナトリウム０．４８ｇを添
加した０次いで、この溶液を室温で８時間攪拌し１反応
を行わせた。その結果、プロピオニル酢酸メチル０．６
０ｇを得た（収率７９％）、アセト酢酸メチルは０．１
３ｇ生成した。Example 4 1.0 g of methyl propionyl acetoacetate was added to 1 part of methanol.
0.0- was dissolved in O, and 0.48 g of sodium acetate was added thereto.Then, this solution was stirred at room temperature for 8 hours to carry out one reaction. As a result, 0.6 methyl propionyl acetate
0g (yield 79%), methyl acetoacetate was 0.1
3g was produced.
実施例５
プロピオニルアセト酢酸メチル１．７ｇをメタノール１
０−に溶解させ、さらにイソブタン酸ナトリウム１．１
ｇを添加した０次いで、この溶液を室温で８時間攪拌し
１反応を行わせた。その結果、プロピオニル酢酸メチル
１．０５ｇを得た（収率８２％）、アセト酢酸メチルは
０．２０ｇ生成した。Example 5 1.7 g of methyl propionyl acetoacetate was added to 1 part of methanol.
0- and further sodium isobutanoate 1.1
Then, this solution was stirred at room temperature for 8 hours to carry out one reaction. As a result, 1.05 g of methyl propionyl acetate was obtained (yield 82%), and 0.20 g of methyl acetoacetate was produced.
実施例６
プロピオニルアセト酢酸メチル１．７ｇをメタノールに
１０ｗＪに溶解させ、さらにインペンタン酸ナトリウム
１．２３ｇを添加した０次いで、この溶液を室温で８時
間攪拌し１反応を行わせた。Example 6 1.7 g of methyl propionylacetoacetate was dissolved in methanol to 10 wJ, and 1.23 g of sodium impentanoate was added thereto.Then, this solution was stirred at room temperature for 8 hours to carry out a reaction.
その結果、プロピオニル酢酸メチル１．０４ｇを得た（
収率８１％）、アセト酢酸メチルは０．２１ｇ生成した
。As a result, 1.04 g of methyl propionyl acetate was obtained (
Yield: 81%), 0.21 g of methyl acetoacetate was produced.
実施例７
プロピオニルアセト酢酸メチル１．７ｇを７０％メタノ
ール水溶液ｌＯ−に溶解させ、さらにプロピオン酸ナト
リウム０．１ｇを添加した０次いで、この溶液を室温で
３日間攪拌し１反応を行わせた。その結果、プロピオニ
ル酢酸メチル１．１０ｇを得た（収率８６％）、アセト
酢酸メチルはＯ，１４ｇ生成した。Example 7 1.7 g of methyl propionylacetoacetate was dissolved in a 70% methanol aqueous solution lO-, and 0.1 g of sodium propionate was added thereto.Then, this solution was stirred at room temperature for 3 days to carry out one reaction. As a result, 1.10 g of methyl propionyl acetate was obtained (yield 86%), and 14 g of methyl acetoacetate was produced.
［発明の効果］
本発明の製造方法によれば、高い収率でプロピオニル酢
酸エステルを得ることができる。また、副生物も少量で
あり、その除去も容易である。[Effects of the Invention] According to the production method of the present invention, propionyl acetate can be obtained in high yield. Furthermore, the amount of by-products is small and their removal is easy.
Claims (1)
キル基、シクロアルキル基又はアリール基を表す） で示されるプロピオニルアセト酢酸エステルの脱アセチ
ル化反応により、一般式（II）； ▲数式、化学式、表等があります▼（II） （式中、Ｒ＾１は前記と同じである） で示されるプロピオニル酢酸エステルを製造する方法に
おいて、 前記一般式（ I ）で示される化合物と、一般式（III）
； Ｒ＾２ＣＯＯＭ（III） （式中、Ｒ＾２は炭素数１〜１０のアルキル基、アリー
ル基又は高分子残基を表し、Ｍはアルカリ金属またはア
ルカリ土類金属を表す）で示される有機酸塩をアルコー
ル系溶媒中で反応させることを特徴とするプロピオニル
酢酸エステルの製造方法。[Claims] General formula (I); ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is an alkyl group having 1 to 10 carbon atoms, an aralkyl group, a cycloalkyl group, or an aryl group. By the deacetylation reaction of propionylacetoacetate represented by (representing a group), the general formula (II); ) A method for producing propionyl acetate represented by the above formula (I) and a compound represented by the general formula (III)
; R^2COOM(III) (wherein R^2 represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a polymer residue, and M represents an alkali metal or an alkaline earth metal); A method for producing propionyl acetate, which comprises reacting an acid salt in an alcoholic solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1724188A JPH0643371B2 (en) | 1988-01-29 | 1988-01-29 | Method for producing propionyl acetate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1724188A JPH0643371B2 (en) | 1988-01-29 | 1988-01-29 | Method for producing propionyl acetate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01193242A true JPH01193242A (en) | 1989-08-03 |
| JPH0643371B2 JPH0643371B2 (en) | 1994-06-08 |
Family
ID=11938450
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1724188A Expired - Fee Related JPH0643371B2 (en) | 1988-01-29 | 1988-01-29 | Method for producing propionyl acetate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643371B2 (en) |
-
1988
- 1988-01-29 JP JP1724188A patent/JPH0643371B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0643371B2 (en) | 1994-06-08 |
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