JPS59141538A - Production of halogenated propionic acid ester - Google Patents
Production of halogenated propionic acid esterInfo
- Publication number
- JPS59141538A JPS59141538A JP58014816A JP1481683A JPS59141538A JP S59141538 A JPS59141538 A JP S59141538A JP 58014816 A JP58014816 A JP 58014816A JP 1481683 A JP1481683 A JP 1481683A JP S59141538 A JPS59141538 A JP S59141538A
- Authority
- JP
- Japan
- Prior art keywords
- halogenated
- propionic acid
- acid ester
- mixture
- halogenated 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.)
- Granted
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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は一般式
％式％
Ｘ、 ７Ｃ−Ｃ−Ｃ−ＯＨ（式中ｔｙ） Ｒ，、Ｒ２は
水素原子１ １ １
ＨＸ４Ｒ２−’Ｊ＊ハアｙｖキｙｖ基、Ｘ＋ 、 Ｘ２
、ｘ３およびＸ４はハロゲン原子である）のハロゲン化
アルコールのプロピオン酸エステルの製法の改良方法で
、さらに詳しく言えば、ハロゲン化アルコールよりプロ
ピオン酸エステルを製造する際に不飽和ア）Ｖコールお
よび不飽和アルコールのプロピオン酸エステルの生成を
極力おさえて、目的のハロゲン化プロピオン酸エステル
の収率を向上させる方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula: X+, X2
, x3 and X4 are halogen atoms. The present invention relates to a method for suppressing the production of propionate esters of saturated alcohols as much as possible to improve the yield of the target halogenated propionate esters.
本発明者は先に、ハロゲン化アルコールの酢酸エステル
を、塩素含有不飽和アルコールと無水酢酸の混合液中に
リン酸を滴下することによって、塩素含有アルコールの
酢酸エステルの製造方法を提案した。（日本特許第７ｇ
３１０３号）しかし、この方法をプロピオン酸エステル
の製造に適要した場合に、前記のようにハロゲン化不飽
和アルコールおよびハロゲン化不飽和エステルを副生ず
る欠点がある。このため、本発明者は、副生ずるハロゲ
ン化不飽和アルコール
生成を極力おさえて、目的のプロピオン酸エステルの収
率を向上させる努力を行なった結果、本発明をなすに至
った。The present inventor previously proposed a method for producing an acetate ester of a chlorine-containing alcohol by dropping phosphoric acid into a mixed solution of a chlorine-containing unsaturated alcohol and acetic anhydride. (Japanese Patent No. 7g
(No. 3103) However, when this method is applied to the production of propionic acid esters, it has the disadvantage that halogenated unsaturated alcohols and halogenated unsaturated esters are produced as by-products as described above. Therefore, the present inventor has made efforts to improve the yield of the target propionic acid ester by suppressing the production of a by-product halogenated unsaturated alcohol as much as possible, and as a result has achieved the present invention.
本発明に従うと、一般式
％式％
（式中のＲ＋ 、Ｒ２ 、Ｘ４ 、Ｘ２ 、Ｘ３ ’ｉ
；？ ｊ Ｕ Ｘ４ （ｄ 前記ト同じ意味を持つ）で
表わされるハロゲン化アルコールを無水プロピオン酸と
リン酸の混合液中に滴下後加熱反応せしめることを特徴
とする。According to the invention, the general formula % formula % (in which R+ , R2 , X4 , X2 , X3 'i
;? The method is characterized in that a halogenated alcohol represented by j U
一般式
％式％
（１）
（式中のＲ＋ 、Ｒ２ 、Ｘ＋ 、Ｘ２ 、Ｘ３および
Ｘ４は前記Ｚと同じ意味を持つ）で示されるハロゲン化
プロピオン酸エステルの製法である。This is a method for producing a halogenated propionate ester represented by the general formula % (1) (R+, R2, X+, X2, X3 and X4 have the same meaning as Z above).
本発明方法において原料として用いられるハロゲン化ア
ルコールは直鎖状または枝分かれ状のいスレでもよいが
、ハロゲン化アルコールの炭素数は３〜１０までが適当
である。The halogenated alcohol used as a raw material in the method of the present invention may be linear or branched, but it is appropriate that the halogenated alcohol has 3 to 10 carbon atoms.
ハロゲンとしてはフッ素原子、塩素原子、臭素原子など
が用いられる。無水プロピオン酸と混合するリン酸は乙
００Ｂｅを用い、場合によってはメタリン酸、ポリリン
酸を併用して用いることができる。As the halogen, a fluorine atom, a chlorine atom, a bromine atom, etc. are used. Otsu00Be is used as the phosphoric acid to be mixed with propionic anhydride, and metaphosphoric acid and polyphosphoric acid may be used in combination depending on the case.
しかし、リン酸の濃度が高い場合などは次式で示す反応
により不飽和結合を有する化合物（１）、（ｎ）が生成
する。However, when the concentration of phosphoric acid is high, compounds (1) and (n) having unsaturated bonds are produced by the reaction shown by the following formula.
？Ｈ３ Ｈ３’ＰＯ４
ＣＨＣＩ２−ＣＣ上，−ＣＨＯＨ半（’ＣＨ．ＣＨ２Ｃ
ｏｈ Ｏ −一→Ｈ３
ＣＣ工２二ＣＣ上−〇ＨＯＨー１ーＨＣ］−（１）
このため、無水プロピオン酸とリン酸を混合したのち、
ハロゲン化アルコール全滴下反応させることによって（
Ｉｔ）、（ＩＩ）への反応が極力おさえられることがわ
かった。? H3 H3'PO4 CHCI2-CC, -CHOH half ('CH.CH2C
oh O -1→H3 CC engineering 22 CC top -〇HOH-1-HC]-(1) Therefore, after mixing propionic anhydride and phosphoric acid,
By reacting by dropping all of the halogenated alcohol (
It was found that the reactions to It) and (II) were suppressed as much as possible.
無水プロピオン酸はハロゲン化ア）Ｖ Ｖ． − ）Ｖ
／に対して／〜１０が適当で、ｌ〜乙が最も好ましい
。Propionic anhydride is halogenated a) V V. -)V
/~10 is appropriate for /, and l~B is most preferable.
この割合が少ないと副生物の生成が増加する。リン酸は
乙０°ＣＢｅのものであれば充分で、原料ハロゲン化ア
ルコール、に対して３０−りＯモル％程度が適当である
。反応時間は７〜３時間で温度は９０〜１００°Ｃで充
分である。If this ratio is low, the formation of by-products will increase. It is sufficient that the phosphoric acid has a concentration of 0°CBe, and is suitably about 30% by mole based on the raw material halogenated alcohol. A reaction time of 7 to 3 hours and a temperature of 90 to 100°C are sufficient.
本発明のハロゲン化プロピオン酸エステルは、昆虫の誘
引物質としてまた臭素化して難燃処理剤製造などに用い
られる。！．た脱ハロゲン化を行なってアセチレン化合
物となし、光エネルギーを蓄えることのできる有機蓄熱
剤の合成原料として有用なものである。The halogenated propionic acid ester of the present invention can be used as an insect attractant, and can also be brominated and used in the production of flame retardant treatment agents. ! ．． It undergoes dehalogenation to form an acetylene compound, which is useful as a raw material for the synthesis of organic heat storage agents that can store light energy.
次に本発明を実施例によって、さらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例／″
２、２，、３．３−テトラクロロプロパン〜／ーオー／
Ｌ’ ／ ２．乙？９ＣＯＯ３モｔｖ）ｆ無水７” ａ
ヒｙｌーン酸３９０３ｊｉ’ （ ０．３．０モｗ）
とＡｏｏＢｅｌ）ン酸λ．２乙Ｆ （ ０． ０ ２モ
ル）の混合液中にθ〜ータ°Ｃで３０分かかつて滴下す
る。滴下後反応液を７０〜９！；′Ｃの温度に徐々に上
昇させたのち、その温度で３時間加熱反応させた。反応
復水水中に投入分解し、四塩化炭素で抽出する。抽出液
は酸性水素ナトリウム水溶液および塩化す） ＩＪウム
の飽和水溶液で洗ったのち亡硝で乾燥した。抽出液より
四塩化炭素および未反応無水プロピオン酸を留去し、粗
油／９． ｇ ０９を得た。粗油を蒸留して沸慨り乙０
〜１０．ｆＯ°Ｃ／１０ｍｍＨｇの留分／７乙３Ｚを得
た。これを分留して沸点９汐０ ’Ｃ／ ７ ｙｎｍ
Ｈｌ （ ｄ：’ ｉ ４１ 、２／ ３、？Ｌ−，
ｉ ４１．！ 、２４１ ）の留分／２．１０グ（収
率９夕３％）を得た。この留分の元素分析値は、Ｈ’．
３０９．Ｃ：、２ｇ３ｇ。Example/''2,2,,3.3-tetrachloropropane~/-o/
L'/2. Otsu? 9COO3mo tv) f anhydrous 7” a
Hylic acid 3903ji' (0.3.0 mow)
and AooBel) acid λ. It was added dropwise into a mixed solution of 2 F (0.02 mol) at θ to 30 °C for 30 minutes. After dropping the reaction solution is 70-9! ; After the temperature was gradually raised to 'C, the reaction was carried out by heating at that temperature for 3 hours. The reaction condensate is decomposed in water and extracted with carbon tetrachloride. The extract was washed with an aqueous acidic sodium hydrogen solution and a saturated aqueous solution of IJium chloride, and then dried over cold nitrogen. Carbon tetrachloride and unreacted propionic anhydride were distilled off from the extract to obtain a crude oil/9. g09 was obtained. Crude oil is distilled and boiling
~10. A fraction of fO°C/10 mmHg/7 Otsu 3Z was obtained. This is fractionated to a boiling point of 9 0'C/7 ynm
Hl (d:' i 41, 2/3, ?L-,
i41. ! , 241)/2.10 g (yield: 9, 3%) was obtained. The elemental analysis value of this fraction was H'.
309. C:, 2g3g.
Ｃ工：ｊ左７３で分子式Ｃ６ Ｈ８ ０２ Ｃ工４の元
素分析値Ｈ’．３．７７、Ｃ”、２ｇ３７．Ｃ工：ｓｓ
ｇ４１ｔｖ値とよく一致する。また赤外線吸収スペクト
ルは、波数／７５３ｃｍ に強いエステルのカルボニル
のｄ＝ｏの伸縮振動を示し、目的の／−プロピオールオ
キシ−，２，２，３，３−テトラクロロプロパンである
。C engineering: j 73 on the left, molecular formula C6 H8 02 Elemental analysis value H' of C engineering 4. 3.77, C”, 2g37.C engineering: ss
It agrees well with the g41tv value. In addition, the infrared absorption spectrum shows a strong stretching vibration of d=o of the carbonyl of the ester at a wave number of 753 cm, indicating that it is the desired /-propioloxy-,2,2,3,3-tetrachloropropane.
実施例２
３．３．グ、４１−テトラクロロブタン−２−オー）ｖ
１３．３９！（００！；−Ｆ＝ル）を無水フロピオン酸
３９．０３！（０３０−ｅ−／ｖ）と乙００Ｂｅリン酸
λ１．２乙ｆＺ（００，２モ／Ｌ／）の混合液中にθ〜
＝夕°Ｃで３０分かかつて滴下する。滴下後反応液ヲ９
０〜り５ ’Ｃの温度に徐々に上昇させたのち、その温
度で３時間反応させた。反応後、実施例／と同様に処理
して粗油２４１／乙ｇｔヲ得た。粗油全蒸留して沸屯り
ＳＯ〜／／２．０°Ｃ／１０朋Ｈｇの留分／７０乙ｙを
得た。これをさらに分留して沸転１０１０°Ｃ／７糖Ｈ
ｇＣｄ−ｔ１３ｇクタ、９ｔγ／りｇ２ｇ、Ｃ１３２，
９３％）の２−プロピオールオキシ−３，３，４１，４
１−テトラクロロブタン／／、７７ Ｐ （収率ｇ７ｇ
％）を得た。Example 2 3.3. 41-tetrachlorobutan-2-o)v
13.39! (00!;-F=L) to fropionic anhydride 39.03! (030-e-/v) and θ~
Drop once for 30 minutes at = evening °C. After dropping reaction solution 9
The temperature was gradually raised to 0 to 5'C, and the reaction was continued at that temperature for 3 hours. After the reaction, the crude oil was treated in the same manner as in Example 2 to obtain 241 gt of crude oil. The crude oil was completely distilled to obtain a boiling SO~/2.0°C/10 Hg fraction/70 Oty. This is further fractionated and boiled at 1010°C/7 sugar H
gCd-t13gcta, 9tγ/g2g, C132,
93%) of 2-propioloxy-3,3,41,4
1-tetrachlorobutane //, 77 P (yield g7g
%) was obtained.
実施例３
ｙ、ｑ、ｓ、ｓ−テトラクロロベンクン−３−オー）Ｌ
”／４１．０りｙ＜ｏｏｓモル）を無水フロピオン酸３
’？ＩＯ！９ＣＯ３０モｔｖ）と乙００Ｂｅｌ）ン酸、
２．．２乙ｆ！ （０，０２モｙ’ｖ）（Ｄ混合液中に
ｏ〜−ｔ’ｃで３０分かかつて滴下する。滴下後、反応
液は９０〜９３”Ｑの温度で３時間反応させた。反応後
、実施例／と同様に処理して粗油／７９り２を得た。Example 3 y, q, s, s-tetrachlorobencune-3-o)L
”/41.0 y<oos mol) to 3 ml of fropionic anhydride
'? IO! 9CO30motv) and 00Bel) acid,
2. ．． 2 o f! (0,02 moy'v) (Dropped into the D mixture at o~-t'c for 30 minutes. After the dropwise addition, the reaction mixture was reacted for 3 hours at a temperature of 90~93''Q. Reaction Thereafter, it was treated in the same manner as in Example to obtain crude oil/79ri 2.
粗油全分留して沸ｇ、 ／ ／ ００ °Ｃ／ ７ ａ
ｍ Ｈｇ （ｔｌ：／３クタざ、飛／グざグア、ｃエタ
ｏｏり％）の３−プロピオニルオキシーク、り、５．！
；−テトラクロロベンクン／／： ２９ Ｓ’ （収率
ｇ００％）を得た。Total distillation of crude oil to boiling g, / / 00 °C / 7 a
m Hg (tl:/3ktaza, fly/guzagua, cetaooori%), 3-propionyloxy, ri, 5. !
;-Tetrachlorobencune//: 29S' (yield: 00%) was obtained.
実施例り 。Examples.
２−メチルー３．３，４１．４７−チトラクロロブタン
ー２−オール／グｏ９ノ（０，０３モル）を無水プロピ
オン酸３９０３９ （０３０モル）と乙。。2-Methyl-3.3,41.47-titrachlorobutan-2-ol/guo9 (0.03 mol) and propionic anhydride 39039 (0.30 mol). .
Ｂｅリン酸２．２乙９ＣＯＯ２モ／ｌ／ ）の混合液中
に０〜−夕°Ｃで３０分かがって滴下する。滴下後、反
応液を９０〜９３℃で３時間反応させた。反応後、実施
例／と同様に処理して粗油３７乙９７を得た。これを分
留して沸点／−？り〜／２乙０ ’Ｃ／／ ＯｙｎｍＪ
（Ｃ１３０，／ ３％）の−一プロピオニルオキシー
２−メチ／Ｉ／−３，３，４１，ゲーテ１−ラクロロブ
クン／グＯタン（収率１００％）を得た。The mixture was added dropwise to a mixture of 2.2% Be and 9COO2 mo/l/) at 0°C to -12°C over 30 minutes. After the dropwise addition, the reaction solution was reacted at 90 to 93°C for 3 hours. After the reaction, the crude oil 37 Otsu 97 was obtained by processing in the same manner as in Example. Fractionally distill this and boiling point /-? Ri~/2 Otsu0 'C// OynmJ
(C130,/3%) -1-propionyloxy-2-methy/I/-3,3,41, Goethe 1-lachlorobucne/gOtan (yield 100%) was obtained.
実施例Ｓ
タウ５．乙、乙−テトヲクロロヘキサンーグーオー／Ｌ
／ ／グｇ０９（００３モル）を無水プロピオン酸３９
０３ ｙ、（？）３０モル）と乙。。Ｂｅ ｌ） ン酸
２．２乙Ｆ （０，０，２モル）の混合液にＱ〜−ｓ
’ｃで３０分かかつて滴下する。滴下後、反応液′ｆ！
：９０〜？ｊ°Ｃで３時間反応させた。反応後、実施例
／と同様に処理して粗油２／乙２２を得た。これを分留
して沸慨／ 、２ ｏ ｏ°ｃ／７ｍｙｇＨｇ （、ｔ
ｌ：／３０７／、入Ｄ／りｇ、２グ、Ｃニゲ７ｇｇ％）
のグープロピオニルオキシ−５，、ｆｆ、乙、乙−テト
ラクロロヘキサン／１１．ｇ０９ （収率１００％）を
得た。Example S Tau5. Otsu, Otsu-tetowochlorohexane-goo/L
/ /g09 (003 mol) to propionic anhydride 39
03 y, (?) 30 mole) and Otsu. . Be l) Add Q~-s to a mixture of 2.2 F (0,0,2 mol) of phosphoric acid.
Drip for 30 minutes at 'C. After dropping, the reaction solution 'f!
:90～? The reaction was carried out at 1°C for 3 hours. After the reaction, crude oil 2/Otsu 22 was obtained by processing in the same manner as in Example. This was fractionated and boiled / , 2 o o ° C / 7 mygHg (, t
l: /307/, entering D/rig, 2, C 7gg%)
Gopropionyloxy-5,, ff, Otsu, Otsu-tetrachlorohexane/11. g09 (yield 100%) was obtained.
Claims (1)
１１ ＨＸ４Ｒ２またはアルキル基、Ｘｌ、Ｘ２Ｘ３およびＸ
４はハロゲン原子である）のハロゲン化アルコールを無
水プロピオン酸とリン酸の混合液中で反応させ 一般式 ％式％ ｘ４は前記と同じ意味を持つ）で表わされるハロゲン化
プロピオン酸エステ／Ｌ／の製法。[Claims] General formula Xl-C-C-C-OH (in the formula, R1 and R2 are hydrogen atoms 11 HX4R2 or alkyl groups,
4 is a halogen atom) is reacted in a mixture of propionic anhydride and phosphoric acid to produce a halogenated propionic acid ester /L/ manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58014816A JPS59141538A (en) | 1983-02-01 | 1983-02-01 | Production of halogenated propionic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58014816A JPS59141538A (en) | 1983-02-01 | 1983-02-01 | Production of halogenated propionic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59141538A true JPS59141538A (en) | 1984-08-14 |
| JPH0138776B2 JPH0138776B2 (en) | 1989-08-16 |
Family
ID=11871560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58014816A Granted JPS59141538A (en) | 1983-02-01 | 1983-02-01 | Production of halogenated propionic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59141538A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61286351A (en) * | 1985-06-10 | 1986-12-16 | チバ−ガイギ− アクチエンゲゼルシヤフト | Manufacture of cyclopropylamine |
| US4791223A (en) * | 1986-12-22 | 1988-12-13 | Societe Atochem | Process for the preparation of 1,1,2,2-tetrahydroperfluoroalkanols and their esters |
-
1983
- 1983-02-01 JP JP58014816A patent/JPS59141538A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61286351A (en) * | 1985-06-10 | 1986-12-16 | チバ−ガイギ− アクチエンゲゼルシヤフト | Manufacture of cyclopropylamine |
| JPH0529214B2 (en) * | 1985-06-10 | 1993-04-28 | Ciba Geigy | |
| US4791223A (en) * | 1986-12-22 | 1988-12-13 | Societe Atochem | Process for the preparation of 1,1,2,2-tetrahydroperfluoroalkanols and their esters |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0138776B2 (en) | 1989-08-16 |
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