JPH0314816B2 - - Google Patents
Info
- Publication number
- JPH0314816B2 JPH0314816B2 JP60270428A JP27042885A JPH0314816B2 JP H0314816 B2 JPH0314816 B2 JP H0314816B2 JP 60270428 A JP60270428 A JP 60270428A JP 27042885 A JP27042885 A JP 27042885A JP H0314816 B2 JPH0314816 B2 JP H0314816B2
- Authority
- JP
- Japan
- Prior art keywords
- cppa
- acrylic acid
- mol
- yield
- sodium chloride
- 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
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 40
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 239000011780 sodium chloride Substances 0.000 claims description 20
- 239000008346 aqueous phase Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 7
- LIDRHDRWTSPELB-UHFFFAOYSA-N 2-chloro-3-phenylpropanoic acid Chemical compound OC(=O)C(Cl)CC1=CC=CC=C1 LIDRHDRWTSPELB-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- CIZVQWNPBGYCGK-UHFFFAOYSA-N benzenediazonium Chemical class N#[N+]C1=CC=CC=C1 CIZVQWNPBGYCGK-UHFFFAOYSA-N 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- -1 copper halide Chemical class 0.000 description 7
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 6
- 239000010949 copper Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 3
- 235000010288 sodium nitrite Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- ZUPBNBYEVVGQKK-UHFFFAOYSA-N 2-chloro-3-phenylpropanenitrile Chemical compound N#CC(Cl)CC1=CC=CC=C1 ZUPBNBYEVVGQKK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000007192 Meerwein reaction reaction Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007039 two-step reaction Methods 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
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はベンゼンジアゾニウム塩（以下BDS
と称する）とアクリル酸とをハロゲン化銅存在下
に反応させて、２−クロロ−３−フエニルプロピ
オン酸（以下CPPAと称する）を製造する方法に
関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to benzene diazonium salt (hereinafter referred to as BDS)
The present invention relates to a method for producing 2-chloro-3-phenylpropionic acid (hereinafter referred to as CPPA) by reacting 2-chloro-3-phenylpropionic acid (hereinafter referred to as CPPA) with acrylic acid in the presence of copper halide.
CPPAは、アンモニアでアミノ化することによ
つてフエニルアラニンに誘導できるから、フエニ
ルアラニン製造の中間体として有用な化合物であ
る。 CPPA is a useful compound as an intermediate for the production of phenylalanine because it can be derived into phenylalanine by amination with ammonia.
（従来の技術）
CPPAを製造する方法としては、アニリンをジ
アゾ化して得られるBDSとアクリル酸とをハロ
ゲン化銅の存在下に反応させる方法がメールワイ
ン（Meerwein）反応として知られている。(Prior Art) As a method for producing CPPA, a method in which BDS obtained by diazotizing aniline and acrylic acid are reacted in the presence of copper halide is known as the Meerwein reaction.
ケミストリー・アンド、インダストリー
（Chemistry and Industry）468（1960）には、PH
が２〜６の条件でBDSとアクリル酸を反応させ
てCPPAを合成してからアミノ化してフエニルア
ラニンが収率10％で得られることが示されてい
る。 Chemistry and Industry 468 (1960) includes PH
It has been shown that phenylalanine can be obtained in a yield of 10% by reacting BDS and acrylic acid under conditions of 2 to 6 to synthesize CPPA and then aminating it.
プロシーデイングス・オブ・ザ・ケミカル・ソ
サエテイー（Proc.Chem.Soc）117（1962）には、
PHが１近くでアクリル酸をBDSの３倍モル用い
て反応を行なつて、CPPAが０〜40％の収率で得
られることが記れている。 Proceedings of the Chemical Society (Proc.Chem.Soc) 117 (1962),
It is described that CPPA can be obtained in a yield of 0 to 40% by carrying out the reaction at a pH close to 1 using 3 times the molar amount of acrylic acid as BDS.
Proc.Chem.Sos.，117（1962）や特開昭60−
81144号公報には、アクリロニトリルやアクリル
酸エステルを用いて２−クロロ−３−フエニルプ
ロピオニトリルや２−クロロ−３−フエニルプロ
ピオン酸エステルを合成し、これらを加水分解し
てCPPAを得る方法が記載されている。 Proc.Chem.Sos., 117 (1962) and JP-A-60-
Publication No. 81144 describes the synthesis of 2-chloro-3-phenylpropionitrile and 2-chloro-3-phenylpropionic acid ester using acrylonitrile and acrylic acid ester, and the hydrolysis of these to obtain CPPA. The method is described.
（発明が解決しようとする問題点）
しかし、これらいずれの方法においてもCPPA
の収率が低く、満足すべきものはない。(Problem to be solved by the invention) However, in any of these methods, CPPA
The yield is low and unsatisfactory.
アクリル酸を用いた時の収率は０〜40％に過ぎ
ず、アクリロニトリルやアクリル酸エステルを用
いた時の収率はせいぜい60％どまりである。 The yield when using acrylic acid is only 0 to 40%, and the yield when using acrylonitrile or acrylic ester is only 60% at most.
BDSとアクリロニトリルやアクリル酸エステ
ルとを塩化銅の存在下に反応させる場合は２−ク
ロロ−３−フエニルプロピオニトリルや２−クロ
ロ−３−フエニルプロピオン酸エステルを製造
後、加水分解を行なう２段階反応であるため工程
が長くなる問題もある。 When reacting BDS with acrylonitrile or acrylic acid ester in the presence of copper chloride, hydrolysis is performed after producing 2-chloro-3-phenylpropionitrile or 2-chloro-3-phenylpropionic acid ester. Since it is a two-step reaction, there is also the problem that the process is long.
本発明の目的は簡単で収率の良いCPPAの製造
方法を見い出すことにある。 The purpose of the present invention is to find a simple and high-yield method for producing CPPA.
（問題点を解決するための手段）
本発明者らは、CPPAの工業的に有利な製造方
法について鋭意検討したところ１段階反応で収率
よく得る方法を見い出し本発明を完成するに至つ
た。(Means for Solving the Problems) The present inventors have conducted intensive studies on industrially advantageous production methods for CPPA, and have found a method for obtaining CPPA in a high yield through a one-step reaction, thereby completing the present invention.
即ち本発明は、アニリンをジアゾ化して得られ
るBDSとアクリル酸とを塩化銅の存在下に反応
させるに当り、BDSに対してアクリル酸を1.2〜
３倍モル使用し、塩化ナトリウムの濃度を溶液に
対し３〜10wt％にし、かつ水相のPHを１以下に
することを特徴とする２−クロロ−３−フエニル
プロピオン酸の製造方法である。 That is, in the present invention, when reacting BDS obtained by diazotizing aniline with acrylic acid in the presence of copper chloride, the ratio of acrylic acid to BDS is 1.2 to 1.
A method for producing 2-chloro-3-phenylpropionic acid, characterized in that 3 times the molar amount is used, the concentration of sodium chloride is 3 to 10 wt% with respect to the solution, and the pH of the aqueous phase is 1 or less. .
本発明において用いられる触媒としてはメール
ワイン反応に用いられる公知の触媒が使用され、
特に限定されないが塩化（又は臭化）第一銅、塩
化（又は臭化）第二銅等が例示される。 As the catalyst used in the present invention, a known catalyst used in the Mehrwein reaction is used,
Examples include, but are not limited to, cuprous chloride (or bromide), cupric chloride (or bromide), and the like.
本発明の方法で原料として使用するBDSは、
鉱酸の存在下アニリンを亜硝酸塩あるいはN2O3
にてジアゾ化すれば容易に製造することができ
る。 BDS used as a raw material in the method of the present invention is
Nitrite or N 2 O 3 of aniline in the presence of mineral acids
It can be easily produced by diazotization.
本発明における塩化ナトリウムの量は、溶液に
対して３〜10wt％にすることが必要であり、４
〜8wt％が好適である。 The amount of sodium chloride in the present invention needs to be 3 to 10 wt% with respect to the solution;
~8wt% is suitable.
塩化ナトリウムの量がこの範囲より少ない場
合、フエノールの副生等によりCPPAの収率が低
下する。またこの範囲より大きい場合、反応上何
ら支障はないが塩化ナトリウムのスラリーが生成
する問題がある。 If the amount of sodium chloride is less than this range, the yield of CPPA will decrease due to the by-product of phenol. If it is larger than this range, there will be no problem with the reaction, but there will be a problem that a slurry of sodium chloride will be produced.
BDSを製造する際に鉱酸として塩酸を用いた
場合には、塩酸と亜硝酸ソーダとから塩化ナトリ
ウムが生成するが、溶媒の使用量によつては３〜
10wt％の範囲を外れる時がある。この時には希
釈あるいは塩化ナトリウムを添加して所定の濃度
になるようにする。 When hydrochloric acid is used as a mineral acid when producing BDS, sodium chloride is produced from hydrochloric acid and sodium nitrite, but depending on the amount of solvent used,
Sometimes it falls outside the 10wt% range. At this time, it is diluted or sodium chloride is added to achieve a predetermined concentration.
本発明において用いられるアクリル酸の使用量
は、BDSに対して1.2〜３倍モル用いる必要があ
り、好ましくは1.4〜2.5倍モルの範囲で用いられ
る。 The amount of acrylic acid used in the present invention needs to be 1.2 to 3 times the mole of BDS, preferably 1.4 to 2.5 times the mole.
アクリル酸の使用量がこの範囲より少ない場合
はクロロベンゼンの副生等によりCPPAの収率が
低下する。また使用量がこの範囲より多い場合は
反応上何ら支障はないが、使用量に見合つた効果
は得られず、経済的に好ましくない。 If the amount of acrylic acid used is less than this range, the yield of CPPA will decrease due to the by-product of chlorobenzene. If the amount used is more than this range, there will be no problem with the reaction, but the effect commensurate with the amount used will not be obtained, which is economically unfavorable.
本発明におけるPHは、１以下に保つ必要があ
る。PHを１以上にした場合はタールの副生等によ
りCPPAの収率が低下する。 The PH in the present invention must be kept at 1 or less. When the pH is set to 1 or more, the yield of CPPA decreases due to by-products such as tar.
本発明の反応温度は、BDSの分解温度以下で
あれば特に制限されないが、好ましくは−20〜40
℃の範囲が良い。 The reaction temperature of the present invention is not particularly limited as long as it is below the decomposition temperature of BDS, but preferably -20 to -40
Good range of °C.
本発明の反応圧力については特に制限はない。 There is no particular restriction on the reaction pressure in the present invention.
本発明における溶媒には、通常メールワイン反
応に用いられるアセトン−水系が好ましい。 The solvent used in the present invention is preferably an acetone-water system that is usually used in the Mehlwein reaction.
また本発明はBDSとアクリル酸とをハロゲン
化銅の存在下にメールワイン反応が行なわれれば
よいのであつて、BDS、アクリル酸およびハロ
ゲン化銅の添加方法や添加順序は何ら制限されな
い。 Further, in the present invention, the Meherwein reaction between BDS and acrylic acid in the presence of copper halide is sufficient, and the method and order of addition of BDS, acrylic acid, and copper halide are not limited at all.
反応時間は反応温度、撹拌速度等により変わり
うるが、一般的には１時間ないし10時間程度であ
る。反応終了後オイル層を分液しアセトンや未反
応のアクリル酸を留去した後、蒸留にてCPPAを
容易に得ることができる。 The reaction time may vary depending on the reaction temperature, stirring speed, etc., but is generally about 1 to 10 hours. After the reaction is completed, the oil layer is separated, acetone and unreacted acrylic acid are distilled off, and CPPA can be easily obtained by distillation.
（発明の効果）
本発明によれば、従来の方法に比べて極めて収
率よく、また１段階反応で２−クロロ−３−フエ
ニルプロピオン酸を製造することができる。(Effects of the Invention) According to the present invention, 2-chloro-3-phenylpropionic acid can be produced in extremely high yield compared to conventional methods, and in a one-step reaction.
（実施例） 以下実施例により本発明を詳細に説明する。(Example) The present invention will be explained in detail below with reference to Examples.
実施例 １
撹拌機、温度計、滴下ロート及び吹き込み管を
備えた１の反応器中に、アニリンを37.2ｇ
（0.4モル）加えた。Example 1 In one reactor equipped with a stirrer, thermometer, addition funnel and blow tube, 37.2 g of aniline
(0.4 mol) was added.
次いで撹拌下に、35％の濃塩酸88ｇ（0.844モ
ル）を滴下した。反応混合物を−５℃まで冷却し
た。 Then, 88 g (0.844 mol) of 35% concentrated hydrochloric acid was added dropwise while stirring. The reaction mixture was cooled to -5°C.
次に、これに33％の亜硝酸ソーダ85ｇ（0.406
モル）を内温−５〜０℃に保ちつつ滴下してジア
ゾ化反応を行なつた。窒息ガスで充分に装置内の
空気を置換した後、アセトン240ml、水10.8ｇと
アクリル酸43.2ｇ（0.6モル）を加えた。 Next, add 85 g of 33% sodium nitrite (0.406
mol) was added dropwise while maintaining the internal temperature at -5 to 0°C to carry out a diazotization reaction. After the air in the apparatus was sufficiently replaced with suffocating gas, 240 ml of acetone, 10.8 g of water, and 43.2 g (0.6 mol) of acrylic acid were added.
塩化第一銅２ｇ（0.02モル）を35％塩酸８ｇ
（0.077モル）に溶解した触媒液を内温10〜15℃に
保ちつつ２時間にわたり加えた。窒素ガスの発生
が全く止んだ点を反応終了点とし撹拌を停めた。
なお、水相のPHは０以下であり、塩化ナトリウム
は亜硝酸ソーダと塩酸より生成し、溶液に対して
5.1wt％であつた。 2g (0.02mol) of cuprous chloride and 8g of 35% hydrochloric acid
(0.077 mol) was added over 2 hours while maintaining the internal temperature at 10 to 15°C. The point at which the generation of nitrogen gas completely stopped was defined as the end point of the reaction, and stirring was stopped.
Note that the pH of the aqueous phase is 0 or less, and sodium chloride is produced from sodium nitrite and hydrochloric acid.
It was 5.1wt%.
反応液を静置し、生じた水層とオイル層を分液
した。上層のオイル層をエバポレーターにてアセ
トン、水、アクリル酸を留去後、液体クロマトグ
ラフイーで分析した。 The reaction solution was allowed to stand, and the resulting water layer and oil layer were separated. After acetone, water, and acrylic acid were distilled off from the upper oil layer using an evaporator, it was analyzed using liquid chromatography.
CPPAは55.4ｇ得られ、収率はアニリンベース
で75モル％であつた。 55.4 g of CPPA was obtained, with a yield of 75 mol% based on aniline.
実施例 ２
アセトン240mlと水10.8ｇの代わりにアセトン
300mlと水47.8ｇ用いた以外は実施例１と同様に
行なつた。なお、水相のPHは０以下であり、塩化
ナトリウムは溶液に対して4.3wt％であつた。Example 2 Acetone instead of 240ml of acetone and 10.8g of water
The same procedure as in Example 1 was carried out except that 300 ml and 47.8 g of water were used. Note that the pH of the aqueous phase was 0 or less, and sodium chloride was 4.3 wt% with respect to the solution.
CPPAは、53.2ｇ得られ、収率はアニリンベー
スで72モル％であつた。 53.2 g of CPPA was obtained, with a yield of 72 mol% based on aniline.
実施例 ３
アセトン240mlと水10.8ｇの代わりにアセトン
420mlと水128.8ｇ用いた以外は実施例１と同様に
行なつた。なお、水相のPHは０以下であり、塩化
ナトリウムは溶液に対して3.3wt％であつた。Example 3 Acetone instead of 240ml of acetone and 10.8g of water
The same procedure as in Example 1 was carried out except that 420 ml and 128.8 g of water were used. Note that the pH of the aqueous phase was 0 or less, and sodium chloride was 3.3 wt% with respect to the solution.
CPPAは、45.0ｇ得られ、収率はアニリンベー
スで61モル％であつた。 45.0 g of CPPA was obtained, with a yield of 61 mol% based on aniline.
比較例 １
アセトン240mlと水10.8ｇの代わりにアセトン
600mlと水239.1ｇ用いた以外は実施例１と同様に
行なつた。なお、水相のPHは０以下であり、塩化
ナトリウムは溶液に対して2.4wt％であつた。Comparative example 1 Acetone instead of 240ml of acetone and 10.8g of water
The same procedure as in Example 1 was carried out except that 600 ml and 239.1 g of water were used. Note that the pH of the aqueous phase was 0 or less, and sodium chloride was 2.4 wt% with respect to the solution.
CPPAは、29.5ｇ得られ、収率はアニリンベー
スで40モル％であつた。 29.5 g of CPPA was obtained, with a yield of 40 mol% based on aniline.
実施例 ４
アセトン240mlと水10.8ｇの代わりにアセトン
240mlと水10.8ｇと塩化ナトリウム22ｇ用いた以
外は実施例１と同様に行なつた。なお、水相のPH
は０以下であり、塩化ナトリウムは溶液に対して
9.4wt％であつた。Example 4 Acetone instead of 240ml of acetone and 10.8g of water
The same procedure as in Example 1 was carried out except that 240 ml, 10.8 g of water, and 22 g of sodium chloride were used. In addition, the pH of the aqueous phase
is less than 0, and sodium chloride is
It was 9.4wt%.
CPPAは、54.6ｇ得られ、収率はアニリンベー
スで74モル％であつた。 54.6 g of CPPA was obtained, with a yield of 74 mol% based on aniline.
実施例 ５
アセトン240mlと水10.8ｇの代わりにアセトン
240mlと水10.8ｇと酢酸ナトリウム13.6ｇ用いた
以外は実施例１と同様に行なつた。なお、水相の
PHは0.8であり、塩化ナトリウムは溶液に対して
7.0wt％であつた。Example 5 Acetone instead of 240ml of acetone and 10.8g of water
The same procedure as in Example 1 was carried out except that 240 ml, 10.8 g of water, and 13.6 g of sodium acetate were used. In addition, the aqueous phase
PH is 0.8 and sodium chloride is relative to the solution
It was 7.0wt%.
CPPAは、44.3ｇ得られ、収率はアニリンベー
スで60モル％であつた。 44.3 g of CPPA was obtained, with a yield of 60 mol% based on aniline.
比較例 ２
アセトン240mlと水10.8ｇの代わりにアセトン
240mlと水10.8ｇと酢酸ナトリウム27.2ｇ用いた
以外は実施例１と同様に行なつた。なお、水相の
PHは3.1であり、塩化ナトリウムは溶液に対して
8.1wt％であつた。Comparative example 2 Acetone instead of 240ml of acetone and 10.8g of water
The same procedure as in Example 1 was carried out except that 240 ml, 10.8 g of water, and 27.2 g of sodium acetate were used. In addition, the aqueous phase
PH is 3.1 and sodium chloride is for solution
It was 8.1wt%.
CPPAは、22.1ｇ得られ、収率はアニリンベー
スで30モル％であつた。 22.1 g of CPPA was obtained, with a yield of 30 mol% based on aniline.
実施例 ６
アクリル酸43.2ｇ（0.6モル）の代わりにアク
リル酸34.6ｇ（0.48モル）用いた以外は実施例１
と同様に行なつた。なお、水相のPHは０以下であ
り、塩化ナトリウムは溶液に対して5.2wt％であ
つた。Example 6 Example 1 except that 34.6 g (0.48 mol) of acrylic acid was used instead of 43.2 g (0.6 mol) of acrylic acid.
I did the same thing. Note that the pH of the aqueous phase was 0 or less, and sodium chloride was 5.2 wt% with respect to the solution.
CPPAは、45.8ｇ得られ、収率はアニリンベー
スで62モル％であつた。 45.8 g of CPPA was obtained, with a yield of 62 mol% based on aniline.
実施例 ７
アクリル酸43.2ｇ（0.6モル）の代わりにアク
リル酸40.3ｇ（0.56モル）用いた以外は実施例１
と同様に行なつた。なお、水相のPHは０以下であ
り、塩化ナトリウムは溶液に対して5.1wt％であ
つた。Example 7 Example 1 except that 40.3 g (0.56 mol) of acrylic acid was used instead of 43.2 g (0.6 mol) of acrylic acid.
I did the same thing. Note that the pH of the aqueous phase was 0 or less, and sodium chloride was 5.1 wt% with respect to the solution.
CPPAは、50.2ｇ得られ、収率はアニリンベー
スで68モル％であつた。 50.2 g of CPPA was obtained, with a yield of 68 mol% based on aniline.
比較例 ３
アクリル酸43.2ｇ（0.6モル）の代わりにアク
リル酸28.8ｇ（0.40モル）用いた以外は実施例１
と同様に行なつた。なお、水相のPHは０以下であ
り、塩化ナトリウムは溶液に対して5.3wt％であ
つた。Comparative Example 3 Example 1 except that 28.8 g (0.40 mol) of acrylic acid was used instead of 43.2 g (0.6 mol) of acrylic acid.
I did the same thing. Note that the pH of the aqueous phase was 0 or less, and sodium chloride was 5.3 wt% with respect to the solution.
CPPAは、40.6ｇ得られ、収率はアニリンベー
スで55モル％であつた。 40.6 g of CPPA was obtained, with a yield of 55 mol% based on aniline.
実施例 ８
アクリル酸43.2ｇ（0.6モル）の代わりにアク
リル酸72.0ｇ（1.00モル）用いた以外は実施例１
と同様に行なつた。なお、水相のPHは０以下であ
り、塩化ナトリウムは溶液に対して4.8wt％であ
つた。Example 8 Example 1 except that 72.0 g (1.00 mol) of acrylic acid was used instead of 43.2 g (0.6 mol) of acrylic acid.
I did the same thing. Note that the pH of the aqueous phase was 0 or less, and sodium chloride was 4.8 wt% with respect to the solution.
CPPAは、55.3ｇ得られ、収率はアニリンベー
スで75モル％であつた。 55.3 g of CPPA was obtained, with a yield of 75 mol% based on aniline.
実施例 ９
アクリル酸43.2ｇ（0.6モル）の代わりにアク
リル酸86.4ｇ（1.20モル）用いた以外は実施例１
と同様に行なつた。なお、水相のPHは０以下であ
り、塩化ナトリウムは溶液に対して4.7wt％であ
つた。Example 9 Example 1 except that 86.4 g (1.20 mol) of acrylic acid was used instead of 43.2 g (0.6 mol) of acrylic acid.
I did the same thing. Note that the pH of the aqueous phase was 0 or less, and the sodium chloride content was 4.7 wt% based on the solution.
CPPAは、55.4ｇ得られ、収率はアニリンベー
スで75モル％であつた。 55.4 g of CPPA was obtained, with a yield of 75 mol% based on aniline.
Claims (1)
化銅の存在下に反応させるに当り、ベンゼンジア
ゾニウム塩に対してアクリル酸を1.2〜３倍モル
用い、塩化ナトリウムの濃度を溶液に対し３〜
10wt％にし、かつ水相のPHを１以下にすること
を特徴とする２−クロロ−３−フエニルプロピオ
ン酸の製造方法。1. When reacting benzenediazonium salt and acrylic acid in the presence of copper chloride, use 1.2 to 3 times the mole of acrylic acid to the benzenediazonium salt, and adjust the concentration of sodium chloride to 3 to 3 times the mole of the solution.
A method for producing 2-chloro-3-phenylpropionic acid, characterized in that the concentration is 10 wt% and the pH of the aqueous phase is 1 or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60270428A JPS62129244A (en) | 1985-11-29 | 1985-11-29 | Production of 2-chloro-4-phenylpropionic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60270428A JPS62129244A (en) | 1985-11-29 | 1985-11-29 | Production of 2-chloro-4-phenylpropionic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62129244A JPS62129244A (en) | 1987-06-11 |
| JPH0314816B2 true JPH0314816B2 (en) | 1991-02-27 |
Family
ID=17486138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60270428A Granted JPS62129244A (en) | 1985-11-29 | 1985-11-29 | Production of 2-chloro-4-phenylpropionic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62129244A (en) |
-
1985
- 1985-11-29 JP JP60270428A patent/JPS62129244A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62129244A (en) | 1987-06-11 |
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