JPS62111977A - Production of 2,2-dimethyl-delta-valerolactone - Google Patents

Production of 2,2-dimethyl-delta-valerolactone

Info

Publication number
JPS62111977A
JPS62111977A JP23000585A JP23000585A JPS62111977A JP S62111977 A JPS62111977 A JP S62111977A JP 23000585 A JP23000585 A JP 23000585A JP 23000585 A JP23000585 A JP 23000585A JP S62111977 A JPS62111977 A JP S62111977A
Authority
JP
Japan
Prior art keywords
dimethyl
compound
alkali
benzoyl peroxide
formula
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
Application number
JP23000585A
Other languages
Japanese (ja)
Other versions
JPH0643414B2 (en
Inventor
Denji Sato
佐藤 傳治
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Chemical Industry Co Ltd
Original Assignee
Nitto Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nitto Chemical Industry Co Ltd filed Critical Nitto Chemical Industry Co Ltd
Priority to JP60230005A priority Critical patent/JPH0643414B2/en
Priority to ES86114272T priority patent/ES2016553B3/en
Priority to DE8686114272T priority patent/DE3673492D1/en
Priority to EP86114272A priority patent/EP0219117B1/en
Priority to US06/919,641 priority patent/US4734511A/en
Publication of JPS62111977A publication Critical patent/JPS62111977A/en
Publication of JPH0643414B2 publication Critical patent/JPH0643414B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Abstract

PURPOSE:To obtain the titled compound easily in high yield, from an easily available raw material, by adding hydrogen bromide to 2,2-dimethyl-4-pentenoic acid using benzoyl peroxide as a catalyst and treating the product with an alkali. CONSTITUTION:The objective compound of formula III can be produced by adding hydrogen bromide to the compound of formula II at -10-+70 deg.C, preferably -10-+40 deg.C using benzoyl peroxide as a catalyst and treating the resultant 2,2-dimethyl-5-bromovaleric acid of formula II with an alkali (e.g. in a 5-50% aqueous solution containing 1-3 times mol of an alkali at 0-50 deg.C). The amount of benzoyl peroxide is preferably 0.05-5wt%, especially 0.1-2wt% based on the starting compound. The compound of formula III is useful as a raw material of the compound of formula IV useful as a remedy for lipogenous hyperproteinemia, etc.

Description

【発明の詳細な説明】 産業上の利用分野 本発明は2.2ジメチルδバレロラクトンの製造方法に
関する。2.2ジメチルδバレロラクトンは、化合物中
−(CH2)s O(C+H5)2000H基を持つ化
合物例えば抗脂性蛋白過剰症薬として有効なヒス社製L
Op1d)等の原料として有用なものである。
DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a process for producing 2.2 dimethyl δ valerolactone. 2.2 Dimethyl δ valerolactone is a compound having a -(CH2)sO(C+H5)2000H group in the compound, such as L manufactured by His Company, which is effective as an antilipidemia drug.
It is useful as a raw material for products such as Op1d).

従来技術 従来、2.2ジメチルδバレロラクトンの製造方法とし
ては、次のような方法が知られている。
Prior Art Conventionally, the following method is known as a method for producing 2.2 dimethyl δ valerolactone.

1)2.2ジメチルゲルタール酸の無水物を無水アルコ
ール中で金属ソーダで還元する方法。
1) A method in which 2.2 dimethylgeltal acid anhydride is reduced with metallic soda in absolute alcohol.

(J、 QC,vol、 as l j410 (19
70)第3574〜3576頁)。
(J, QC, vol, as l j410 (19
70) pp. 3574-3576).

2)2,2ジメチルビニール酪酸エステルとC0(00
)4を反応させる方法(ベルギー特許第6161141
号)。
2) 2,2 dimethyl vinyl butyrate and C0(00
) 4 (Belgian Patent No. 6161141)
issue).

3)ブチルリチウムとイソプロピルアミンよりリチウム
イソプロピルアマイドを作り、これをイソ酪酸ソーダと
反応させ、次にジブロムプロパンと反応させてアルカリ
処理する方法(USP3674+836号)。
3) A method of preparing lithium isopropylamide from butyllithium and isopropylamine, reacting it with sodium isobutyrate, and then reacting it with dibromopropane for alkali treatment (USP No. 3674+836).

4)イソブチルアルデヒドのアリルアルコールのアセタ
ールの転移をする方法(5ynth、  Oommnl
o(4) 273 (1980)。
4) Method for transferring the acetal of allyl alcohol of isobutyraldehyde (5ynth, Oommnl
o(4) 273 (1980).

5)アクロレイシ・のエチレングリコールのアセタール
をf[す、HB rを附加しグリニヤ試薬を作り、2−
ブロムイソ醋酸と反応させた後、加水分解ラクトン化さ
せる方法。
5) Add f[su, HBr] to the acetal of ethylene glycol of acroreish to make a Grignard reagent,
A method of reacting with bromoisoacetic acid and then hydrolyzing and lactonizing it.

(−2妙・17.1)のh法相分子内の立体障害のため
、ラクトンのIItziが悪い。2)の方法はコバルl
−J)ルボニルのような訪異な試薬を用いるので、取扱
いも峻しく高価となる。3)の方法はブチルリチウムの
ような高価な薬剤を使用するので、コスト高となる。(
4)のJJ“法V1ア+タールの転移におけろ反応時間
が長く収率も悪いのでコスト高となる。(5)の方法は
原料費が高くコスト高となる勢、それぞれ欠点を有する
The IItzi of the lactone is poor due to steric hindrance within the h-law phase molecule of (-2-2-17.1). Method 2) is Kobal l
-J) Since a foreign reagent such as rubonyl is used, handling is difficult and expensive. Method 3) uses expensive chemicals such as butyllithium, resulting in high costs. (
In the case of the JJ "method V1 a+tar transformation of 4), the reaction time is long and the yield is poor, resulting in high costs. The method (5) has its own drawbacks, such as high raw material costs and high costs.

発明の目的 本発明は位来法における欠点を解消すべくなされたもの
で、その目的は特異な薬剤または高価な薬剤を使用する
ことなく、容易に入手できる原料を使用し、容易にふつ
好収率で安価に2,2ジメチルδバレロラクトンを製造
する方法を提供するにある。
OBJECT OF THE INVENTION The present invention has been made to overcome the drawbacks of conventional methods.The purpose of the present invention is to use readily available raw materials without using special or expensive drugs, and to easily produce a product with good yields. The object of the present invention is to provide a method for producing 2,2 dimethyl δ valerolactone at a low cost and at a high rate.

発明の構成 本発明者し1前111目的を達成すべり紛哲研究の結果
、2,2ジメチルベンデノイツク酸を原料とし、これに
過酸化ベンゾイルを触四としてHBrを附加して、2,
2ジメチル5ブロム青草酸な作り、これをアルカリ処理
すると、容易に好収率で2+2ジメチルδバレロラクト
ンが得られることを究明■2得た。
Structure of the Invention The inventor of the present invention has achieved the following objectives: As a result of theoretical research, 2,2 dimethylbendenoxic acid was used as a raw material, HBr was added to it using benzoyl peroxide, and 2,
It was discovered that 2+2 dimethyl δ valerolactone could be easily obtained in good yield by preparing 2 dimethyl 5 bromozoic acid and treating it with an alkali. 2 was obtained.

その反応式を示すと次の通りである。The reaction formula is as follows.

この知見に邦いて本発明を完bνL5た。Based on this knowledge, we completed the present invention bνL5.

本発明の要旨は 2.2ジメチルペンテノイツク酸を過酸化ベンゾイルを
触媒としてHBrを附加して、2,2ジメチル5ブロム
吉草酸を作り、アルカリ処理することを特徴とする2、
2ジメチルδバレロラクトンの製造方法にある。
The gist of the present invention is to add HBr to 2.2 dimethylpentenoic acid using benzoyl peroxide as a catalyst to produce 2,2 dimethyl 5-bromovaleric acid, which is then treated with an alkali.
A method for producing 2-dimethyl δ valerolactone.

本発明の方法で使用する2、2ジメチルペンテノイツク
酸は、例えばイソ醋酸アリルエステルをソジウムハイド
ライドな用いて転移させることによって容易に?()ら
れる。その反応式は次の通ねである。
The 2,2-dimethylpentenoic acid used in the method of the present invention can be easily prepared, for example, by rearranging isoacetic acid allyl ester using sodium hydride. () to be. The reaction formula is as follows.

aH (OH3)2041(iooOH2・01にGH2−一
頌0H2=OH−0■12G(O1’b) 2000H
L7ふしこの方法に限定されるものではない2.2ジメ
チル5グロム吉草酸をアルカリ処理するアルカリとして
けNaOHr Na2CO3等何んでもよいが、NaO
Hの場合は反応後中和する必要があるが、Na2(]0
5の場合はこれを必要としないので、Na2005であ
ることが好ましい。
aH (OH3) 2041 (iooOH2・01 GH2-one 0H2=OH-0■12G(O1'b) 2000H
L7 Fushi is not limited to this method.2.2 Dimethyl 5-glomovaleric acid can be treated with an alkali. Any alkali such as NaOHr, Na2CO3, etc. may be used, but NaO
In the case of H, it is necessary to neutralize after the reaction, but Na2(]0
5 does not require this, so Na2005 is preferable.

実施例1 攪拌機1分液漏斗、濡度計、コンデンサーを具備した4
¥j4フラスコに、2,2ジメチル4ペンテノイツク酸
64v、溶媒の0014300 ccを仕込んで攪拌溶
解させた。これに無水のNaBr 567を粉末として
加えて懸濁させた。次に過酸化ベンゾイルを(1,5r
加え、攪拌しながら常温でH2SO427,5Vを徐々
に滴下し、滴下終了後2時間反応を続けた。水に分散す
る、Na2SO4け水層に浴けて、反応生成物は溶聾層
に朴るので、溶媒層を分液し、水洗・脱水し、犬部勿の
(’j Q l 4 ’f回収し冷却するこノーにより
ブロム仕合物を(j) 7”’−0これをt1過水洗1
=、10%ソーダ灰液を絵加した。次いでベンゼンで抽
出し抽出液よりベンゼンを除き、減圧分留した。
Example 1 4 units equipped with a stirrer 1 separatory funnel, wetness meter, and condenser
A ¥j4 flask was charged with 64 v of 2,2 dimethyl 4-pentenoic acid and 0014300 cc of a solvent, and the mixture was stirred and dissolved. To this was added anhydrous NaBr 567 as a powder and suspended. Next, add benzoyl peroxide (1,5r
In addition, 27.5V of H2SO4 was gradually added dropwise at room temperature while stirring, and the reaction was continued for 2 hours after completion of the dropwise addition. The reaction product is soaked in the aqueous layer of Na2SO4 dispersed in water, and the reaction product is deposited in the aqueous layer, so the solvent layer is separated, washed with water and dehydrated, and then By collecting and cooling the bromine product (j) 7'''-0, it was washed with water at
=, 10% soda ash solution was added. Next, the extract was extracted with benzene to remove benzene from the extract, which was then fractionated under reduced pressure.

初留 〜108/19關   7V 本留 108〜113/19闘 43.7 r収率け6
7.9%(純度97.1%)であった。
Hatsutome ~108/19 7V Hondome 108~113/19 43.7 r yield 6
It was 7.9% (purity 97.1%).

更施例2 実施例1のフラスコに、2.2ジメチル4ペンテノイツ
ク1d64rと溶媒ベンゼン300ccを仕込んで攪拌
溶解させた。
Additional Example 2 The flask of Example 1 was charged with 2.2 dimethyl 4-pentenoic 1d64r and 300 cc of benzene as a solvent, and dissolved with stirring.

こねに過酸化ベンゾイル0.51i’を加え、攪拌しな
がら常温でHBrガスを2〜3時間吹込んだ。吹込終了
後2時間攪拌を続け、その後反応生成液を水洗し、溶媒
を回収した。ベンゼンの回収量204ノ、残液は106
vであった。
0.51 i' of benzoyl peroxide was added to the dough, and HBr gas was blown into the dough at room temperature for 2 to 3 hours while stirring. After the blowing was completed, stirring was continued for 2 hours, and then the reaction product liquid was washed with water and the solvent was recovered. The amount of benzene recovered was 204, and the remaining liquid was 106.
It was v.

この残液に10%NaOHを添加し弱アルカリ性となし
、これにベンゼン100(!(!を加えて抽出した。
10% NaOH was added to this residual liquid to make it slightly alkaline, and benzene 100 (!(!) was added thereto for extraction.

水層に活1f1炭ム・加え、1過後、HClを加えてp
H4,0にして更にベンゼンで抽出し7た。このベンゼ
ン液よりベンゼンを除き、減圧で分留した。
Add 1f1 charcoal to the aqueous layer, and after 1 filtration, add HCl and p
The mixture was adjusted to 4.0 H and further extracted with benzene. Benzene was removed from this benzene liquid, and fractional distillation was performed under reduced pressure.

初留 〜108/20闘   9v 本留 108〜113/20mm  42.9 r4v
率i 66.7%(純度97.2 % )であった。
Hatsutome ~108/20 fight 9v Hondome 108~113/20mm 42.9 r4v
The percentage i was 66.7% (purity 97.2%).

発明の効果 本発明の方法によると、特異な薬剤オたけ高価な薬剤を
使用することなく、容易に入手でへる原料を使用し1、
容易に好収率で得られるので、安価に2+2ジメチルδ
バレロラクトンが得られる優れた効果を有する。
Effects of the Invention According to the method of the present invention, easily available raw materials are used without using specific or expensive drugs.1.
Since it is easily obtained in good yield, 2+2 dimethyl δ can be obtained at low cost.
Valerolactone has excellent effects.

Claims (1)

【特許請求の範囲】[Claims] 2,2ジメチルペンテノイツク酸を過酸化ベンゾイルを
触媒としてHBrを附加して、2,2ジメチル5ブロム
吉草酸を作り、アルカリ処理することを特徴とする2,
2ジメチルδバレロラクトンの製造方法。
2, characterized by adding HBr to 2,2 dimethylpentenoic acid using benzoyl peroxide as a catalyst to produce 2,2 dimethyl 5-bromovaleric acid, and treating it with an alkali.
A method for producing 2-dimethyl δ valerolactone.
JP60230005A 1985-10-17 1985-10-17 Method for producing 2,2 dimethyl delta valerolactone Expired - Lifetime JPH0643414B2 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP60230005A JPH0643414B2 (en) 1985-10-17 1985-10-17 Method for producing 2,2 dimethyl delta valerolactone
ES86114272T ES2016553B3 (en) 1985-10-17 1986-10-15 A METHOD TO PRODUCE ALPHA, ALPHA-DIMETHYL-DELTA-VALEROLACTONE.
DE8686114272T DE3673492D1 (en) 1985-10-17 1986-10-15 METHOD FOR PRODUCING ALPHA, ALPHA-DIMETHYL-DELTA-VALEROLACTONE.
EP86114272A EP0219117B1 (en) 1985-10-17 1986-10-15 A method for producing alpha,alpha-dimethyl-delta-valerolactone
US06/919,641 US4734511A (en) 1985-10-17 1986-10-16 Method for producing α,α-dimethyl-Δ-valerolactone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60230005A JPH0643414B2 (en) 1985-10-17 1985-10-17 Method for producing 2,2 dimethyl delta valerolactone

Publications (2)

Publication Number Publication Date
JPS62111977A true JPS62111977A (en) 1987-05-22
JPH0643414B2 JPH0643414B2 (en) 1994-06-08

Family

ID=16901103

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60230005A Expired - Lifetime JPH0643414B2 (en) 1985-10-17 1985-10-17 Method for producing 2,2 dimethyl delta valerolactone

Country Status (1)

Country Link
JP (1) JPH0643414B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4524554B2 (en) 2003-09-25 2010-08-18 信越化学工業株式会社 Method for producing γ, δ-unsaturated carboxylic acid and silyl ester thereof, organosilicon compound having carboxyl group and method for producing the same

Also Published As

Publication number Publication date
JPH0643414B2 (en) 1994-06-08

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