JPS649306B2 - - Google Patents
Info
- Publication number
- JPS649306B2 JPS649306B2 JP10658081A JP10658081A JPS649306B2 JP S649306 B2 JPS649306 B2 JP S649306B2 JP 10658081 A JP10658081 A JP 10658081A JP 10658081 A JP10658081 A JP 10658081A JP S649306 B2 JPS649306 B2 JP S649306B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- methyl
- chlorosulfonyloxypropionate
- benzene
- 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
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- -1 α-chlorosulfonyloxypropionate ester Chemical class 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 11
- 150000003903 lactic acid esters Chemical class 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- YPGCWEMNNLXISK-UHFFFAOYSA-N hydratropic acid Chemical class OC(=O)C(C)C1=CC=CC=C1 YPGCWEMNNLXISK-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 4
- 239000002841 Lewis acid Substances 0.000 description 4
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 229940057867 methyl lactate Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- RFZDJFAEEDDFCX-UHFFFAOYSA-N 2-chlorosulfonyloxypropanoic acid Chemical compound OC(=O)C(C)OS(Cl)(=O)=O RFZDJFAEEDDFCX-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000005910 alkyl carbonate group Chemical group 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical class CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QXYOROBKCZWFKK-UHFFFAOYSA-N 2-(4-methylphenyl)sulfonyloxypropanoic acid Chemical compound OC(=O)C(C)OS(=O)(=O)C1=CC=C(C)C=C1 QXYOROBKCZWFKK-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-M chlorosulfate Chemical compound [O-]S(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- KPONZKAWZSMLQR-UHFFFAOYSA-N ethyl 2-chlorosulfonyloxypropanoate Chemical compound CCOC(=O)C(C)OS(Cl)(=O)=O KPONZKAWZSMLQR-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、医薬,農薬,染料中間体として有用
なα―フエニルプロピオン酸エステル類およびこ
れを必要に応じて加水分解に付して得られるα―
フエニルプロピオン酸の製造方法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to α-phenylpropionate esters useful as intermediates for pharmaceuticals, agricultural chemicals, and dyes, and α-phenylpropionic acid esters obtained by subjecting the same to hydrolysis as necessary.
The present invention relates to a method for producing phenylpropionic acid.
従来、α―フエニルプロピオン酸およびそのエ
ステルの製造方法には種々の方法が提案されてい
る。これらは、全て多工程を経る欠点や、原料が
高価である欠点を有し、経済的な方法とはいえな
い。例えば特公昭40―7491号にはアルキルフエニ
ル酢酸エステル類に炭酸アルキル,金属アルコラ
ートを反応させてロマン酸エステルとなし、次い
で活性メチレン基をヨウ化メチルでメチル化した
後、加水分解,脱炭酸を行なつて製造する方法が
提案されている。この方法は多工程を要する上に
高価な炭酸アルキル,ヨウ化メチルを用いる欠点
がある。 Conventionally, various methods have been proposed for producing α-phenylpropionic acid and its esters. All of these methods have disadvantages of requiring multiple steps and expensive raw materials, and cannot be said to be economical methods. For example, in Japanese Patent Publication No. 40-7491, alkyl phenyl acetates are reacted with alkyl carbonates and metal alcoholates to form romanic acid esters, the active methylene group is then methylated with methyl iodide, and then hydrolyzed and decarboxylated. A manufacturing method has been proposed. This method requires multiple steps and has the disadvantage of using expensive alkyl carbonate and methyl iodide.
特開昭51―95035号にはアルキルアセトフエノ
ンにシアン化ナトリウムまたはシアン化カリウム
と塩酸を作用させ、次いで苛性アルカリで加水分
解した後、還元を行なう方法が提案されている。
この方法は多工程を要する上に取扱い上危険性の
多いシアン化ナトリウムまたはシアン化カリウム
を用いる等の欠点がある。 JP-A-51-95035 proposes a method in which alkyl acetophenone is treated with sodium cyanide or potassium cyanide and hydrochloric acid, then hydrolyzed with caustic alkali, and then reduced.
This method has drawbacks such as requiring multiple steps and using sodium cyanide or potassium cyanide, which are often dangerous to handle.
また、特開昭54―27533号には、ベンゼンに乳
酸のトシレートまたは乳酸エステルのトシレート
を作用させて、α―フエニルプロピオン酸および
そのエステルを製造する方法が提案されている。
この方法は、種々の方法の中では比較的工程が短
かく、経済的な方法と考えられるが、それでもP
―トルエンスルホニルクロライドが比較的高価で
ある上、容易に入手し難く、さらに全く不要なP
―トルエンスルホン酸を副生するという欠点を有
する。 Furthermore, JP-A-54-27533 proposes a method for producing α-phenylpropionic acid and its ester by reacting benzene with tosylate of lactic acid or tosylate of lactic acid ester.
This method has relatively short steps among various methods and is considered to be an economical method, but still
-Toluenesulfonyl chloride is relatively expensive, difficult to obtain, and completely unnecessary P.
-It has the disadvantage of producing toluenesulfonic acid as a by-product.
本発明者らは、従来方法の諸欠点を解決すべく
α―フエニルプロピオン酸およびそのエステルの
経済的な工業的製造方法について鋭意研究した結
果、式(1)のようにベンゼンとα―クロルスルホニ
ルオキシプロピオン酸エステルを好ましくはルイ
ス酸の存在下、反応させるとα―フエニルプロピ
オン酸エステルが生成することを見出し本発明に
到達した。 The present inventors have conducted intensive research on an economical industrial production method for α-phenylpropionic acid and its ester in order to solve the various drawbacks of conventional methods. As a result, as shown in formula (1), benzene and The present invention was achieved by discovering that α-phenylpropionate is produced when sulfonyloxypropionate is reacted, preferably in the presence of a Lewis acid.
ここで、式(1)のRはアルキル基を示す。 Here, R in formula (1) represents an alkyl group.
本発明の目的は、容易に且つ安価に、従つて経
済的なα―フエニルプロピオン酸エステルを製造
する方法を提供するものであり、その要旨はベン
ゼンとα―クロルスルホニルオキシプロピオン酸
エステル類とを反応させることを特徴とするα―
フエニルプロピオン酸エステル類の製造方法であ
る。さらに具体的には、安価で且つ入手が容易な
原料を用い、簡単な工程で収率よく高純度のα―
フエニルプロピオン酸エステル類を得る方法を提
供するものである。 The purpose of the present invention is to provide a method for easily and inexpensively producing α-phenylpropionic acid ester, and the gist thereof is to provide a method for producing α-phenylpropionic acid ester easily and inexpensively. α-, which is characterized by reacting with
This is a method for producing phenylpropionate esters. More specifically, we use inexpensive and easily available raw materials to produce high-yield α-
A method for obtaining phenylpropionate esters is provided.
本発明のα―クロルスルホニルオキシプロピオ
ン酸エステルは一般には乳酸エステルと塩化スル
フリルとから公知の方法によつて合成される。こ
のα―クロルスルホニルオキシプロピオン酸エス
テルは蒸留などの方法により単離できるが、本発
明の実施に当つては、必ずしも単離精製されたα
―クロルスルニルオキシプロピオン酸エステルは
必要でなく、乳酸エステルと塩化スルフリルとの
反応生成物をそのまま用いることができる。例え
ば、室温下で乳酸エステルに塩化スルフリルを加
えて得た反応混合物、或はさらに過剰の塩化スル
フリルを加えた場合には過剰の塩化スルフリルを
減圧下に留去せしめた残液をそのまま、本発明に
用いることができる。乳酸エステルとしては、メ
チル,エチル,プロピル等の低級アルキルエステ
ルの他、高級アルキルエステルも使用される。 The α-chlorosulfonyloxypropionic ester of the present invention is generally synthesized from a lactic acid ester and sulfuryl chloride by a known method. This α-chlorosulfonyloxypropionate ester can be isolated by methods such as distillation, but in carrying out the present invention, it is not necessary to use isolated and purified α-chlorosulfonyloxypropionate.
-Chlorsulnyloxypropionate is not necessary, and the reaction product of lactic acid ester and sulfuryl chloride can be used as is. For example, a reaction mixture obtained by adding sulfuryl chloride to a lactic acid ester at room temperature, or when an excess of sulfuryl chloride is further added, the residual liquid obtained by distilling off the excess sulfuryl chloride under reduced pressure can be directly used in the present invention. It can be used for. As the lactic acid ester, in addition to lower alkyl esters such as methyl, ethyl, and propyl, higher alkyl esters are also used.
本発明の反応は好ましくは、ルイス酸の存在下
に行なわれる。ルイス酸としては、例えば塩化ア
ルミニウム,塩化亜鉛,塩化鉄,塩化錫,三弗化
硼素等が用いられるが、とくに塩化アルミニウム
が入手しやすい点、比較的安価である点などから
も使用されることが多い。 The reaction of the invention is preferably carried out in the presence of a Lewis acid. As the Lewis acid, aluminum chloride, zinc chloride, iron chloride, tin chloride, boron trifluoride, etc. are used, and aluminum chloride is especially used because it is easily available and relatively inexpensive. There are many.
本反応には必ずしも溶媒を必要としないが、本
反応に不活性な溶媒であればいずれも使用でき
る。特に反応試剤であるベンゼンを多少過剰に用
いてこれを溶媒とする方法が本発明を有利に逐行
できる。 Although a solvent is not necessarily required for this reaction, any solvent can be used as long as it is inert to this reaction. In particular, the present invention can be carried out advantageously by using benzene, which is a reaction reagent, in a slight excess and using this as a solvent.
本発明の方法を円滑に行なうには、例えば塩化
アルミニウムをベンゼンに懸濁させ、−10〜50℃,
好ましくは0〜30℃の温度でα―クロルスルホニ
ルオキシプロピオン酸エステルを撹拌下徐々に加
えた後、さらにこの温度に0.5〜3時間保つこと
によつて行なわれる。 In order to carry out the method of the present invention smoothly, for example, aluminum chloride is suspended in benzene,
Preferably, this is carried out by gradually adding α-chlorosulfonyloxypropionic acid ester at a temperature of 0 to 30° C. under stirring, and then maintaining this temperature for an additional 0.5 to 3 hours.
また、このα―クロルスルホニルオキシプロピ
オン酸エステルに対するルイス酸のモル比は0.2
〜10の範囲が適当であるが、さらに好ましくは1
〜5の範囲にした場合に好結果が得られる。 In addition, the molar ratio of Lewis acid to this α-chlorosulfonyloxypropionate is 0.2
A range of 10 to 10 is appropriate, but more preferably 1
Good results can be obtained when the value is in the range of 5 to 5.
反応終了後、適当量の氷水に反応生成物を注入
して有機層を水層から分離した後、水洗を繰返
し、有機層からベンゼンを留去した後、減圧下に
精留して、高純度のα―フエニルプロピオン酸エ
ステルを85%以上の収率で得ることができる。水
層には、塩酸,硫酸,塩化アルミニウムが含ま
れ、中和処理のみによつて無害化できる。 After the reaction is complete, the reaction product is poured into an appropriate amount of ice water to separate the organic layer from the aqueous layer, which is then repeatedly washed with water. After distilling off benzene from the organic layer, it is rectified under reduced pressure to obtain high purity. α-phenylpropionate can be obtained with a yield of over 85%. The aqueous layer contains hydrochloric acid, sulfuric acid, and aluminum chloride, and can be rendered harmless only by neutralization.
従来の特開昭54―27533号に記載されたベンゼ
ンと乳酸エステル―P―トシレートを用いる方法
が、触媒ならびに溶媒としてピリジンを用いるた
め後処理が困難であり、かつ反応時間が長くかか
るため原料のα―トシルオキシプロピオン酸エス
テルの合成が困難であること、反応時間が長く、
かつ反応温度が高いこと、副生するP―トルエン
スルホン酸の処理が困難である等の欠点を有する
のに反し、本発明に用いる原料は乳酸エステル,
塩化スルフリル,塩化アルミニウム,ベンゼン等
の安価、かつ取扱い容易な原料である。これは溶
媒を必要としないこと、後処理を必要としないこ
と等によるものである。また、α―クロルスルホ
ニルオキシプロピオン酸エステルとしては、乳酸
エステルと塩化スルフリルとの反応混合物をその
まま用いることができること、クロル硫酸エステ
ルとベンゼンとの反応は、ベンゼンそのものを溶
媒とすることができ、その上、特殊な反応条件を
必要としないこと、反応温度は常温で、かつ反応
時間が短いこと、目的物の分離精製が容易である
こと、廃水処理等の公害面に関してもP―トルエ
ンスルホン酸等の不要な物質がないので処理は簡
単であること等、数々の利点を有し、本発明は工
業的に有利な方法といえる。 The conventional method using benzene and lactic acid ester-P-tosylate described in JP-A-54-27533 uses pyridine as a catalyst and solvent, making post-treatment difficult and requiring a long reaction time. The synthesis of α-tosyloxypropionate is difficult, the reaction time is long,
However, the raw materials used in the present invention are lactic acid ester,
It is a cheap and easy-to-handle raw material such as sulfuryl chloride, aluminum chloride, and benzene. This is due to the fact that no solvent is required, no post-treatment is required, etc. Furthermore, as α-chlorosulfonyloxypropionate, a reaction mixture of lactic acid ester and sulfuryl chloride can be used as it is, and for the reaction between chlorosulfate and benzene, benzene itself can be used as a solvent; In addition, it does not require special reaction conditions, the reaction temperature is room temperature, the reaction time is short, the separation and purification of the target product is easy, and P-toluenesulfonic acid etc. The present invention can be said to be an industrially advantageous method, as it has many advantages such as simple processing since there are no unnecessary substances.
次に実施例をあげて本発明を具体的に説明す
る。ただし、本発明はこの実施例によつて限定さ
れるものではない。 Next, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to this example.
実施例 1
α―フエニルプロピオン酸メチルの製造
かきまぜ機,温度計および滴下ロートを付けた
フラスコ中に乳酸メチル52.1g(0.5モル)を入れ
て、液温を0〜5℃に保ちつつ滴下ロートから塩
化スルフリル101.2g(0.75モル)を1時間要して
加えた。さらに10〜20℃で2時間かきまぜたの
ち、減圧下で副生の塩化水素および過剰の塩化ス
ルフリルを留去し、減圧蒸留を行ない、沸点70〜
71℃/2mmHgのα―クロルスルホニルオキシプ
ロピオン酸メチルを得た。収量60.1g収率59.4%
(対乳酸メチル)であつた。Example 1 Production of methyl α-phenylpropionate 52.1 g (0.5 mol) of methyl lactate was placed in a flask equipped with a stirrer, a thermometer, and a dropping funnel, and the temperature was maintained at 0 to 5°C. 101.2 g (0.75 mol) of sulfuryl chloride was added over a period of 1 hour. After further stirring at 10 to 20°C for 2 hours, by-product hydrogen chloride and excess sulfuryl chloride were distilled off under reduced pressure.
Methyl α-chlorosulfonyloxypropionate was obtained at 71°C/2mmHg. Yield 60.1g Yield 59.4%
(vs. methyl lactate).
次いで、上記と同じフラスコにベンゼン93.7g
(1.2モル)および無水塩化アルミニウム80.0g(0.6
モル)を入れてかきまぜ、この中に上記精製α―
クロルスルホニルオキシプロピオン酸メチル
40.5g(0.2モル)を液温10〜15℃にて1時間要し
て加えた。 Then add 93.7g of benzene to the same flask as above.
(1.2 mol) and anhydrous aluminum chloride 80.0 g (0.6
mol), stir, and add the purified α-
Methyl chlorsulfonyloxypropionate
40.5 g (0.2 mol) was added over 1 hour at a liquid temperature of 10 to 15°C.
さらに10〜25℃で2時間かきまぜて反応を終了
した。 The reaction was further stirred at 10 to 25°C for 2 hours to complete the reaction.
反応物を氷水200g中に排出してよくかきまぜ
静置して有機層を分け取り、水で十分洗浄した。
無水ボウ硝を加えて乾燥したのち蒸留し、まず過
剰のベンゼンを回収し、次いで沸点55〜56℃/
11.5mmHgの留分としてα―フエニルプロピオン
酸メチルを得た。収量28.1g,収率85.6%であつ
た。(対α―クロルスルホニルオキシプロピオン
酸メチル)。 The reaction product was discharged into 200 g of ice water, stirred well and allowed to stand. The organic layer was separated and thoroughly washed with water.
After adding anhydrous sulfur salt and drying, distillation is performed to first recover excess benzene, then reduce the boiling point to 55-56℃/
Methyl α-phenylpropionate was obtained as a fraction at 11.5 mmHg. The yield was 28.1g, and the yield was 85.6%. (vs. methyl α-chlorosulfonyloxypropionate).
実施例 2
実施例1と同様にして、乳酸メチル52.1g(0.5
モル)と塩化スルフリル74.2g(0.55モル)とを反
応させ、α―クロルスルホニルオキシプロピオン
酸メチル約80%を含む反応生成物101.0gを得た。Example 2 In the same manner as in Example 1, 52.1 g (0.5
mol) and 74.2 g (0.55 mol) of sulfuryl chloride were reacted to obtain 101.0 g of a reaction product containing about 80% of methyl α-chlorosulfonyloxypropionate.
次いで、実施例1において精製α―クロルスル
ホニルオキシプロピオン酸メチル40.5g(0.2モル)
を用いる代りに、上記α―クロルスルホニルオキ
シプロピオン酸メチルを含む反応生成物40.6gを
用いた以外は実施例1と同様に反応および処理し
た。 Next, in Example 1, purified methyl α-chlorosulfonyloxypropionate 40.5 g (0.2 mol)
The reaction and treatment were carried out in the same manner as in Example 1, except that 40.6 g of the reaction product containing methyl α-chlorosulfonyloxypropionate was used instead of using methyl α-chlorosulfonyloxypropionate.
収量19.8g,収率60.1%(対乳酸メチル)であ
つた。 The yield was 19.8g, 60.1% (based on methyl lactate).
実施例 3
α―フエニルプロピオン酸エチルの製造
実施例1において乳酸メチル52.1gを用いる代
わりに乳酸エチル59.1g(0.5モル)を用いた以外
は実施例2と同じ要領で反応および後処理を行な
い、沸点90〜92℃/2mmHgのα―クロルスルホ
ニルオキシプロピオン酸エチルを得た。Example 3 Production of ethyl α-phenylpropionate The reaction and post-treatment were carried out in the same manner as in Example 2, except that 59.1 g (0.5 mol) of ethyl lactate was used instead of 52.1 g of methyl lactate in Example 1. , ethyl α-chlorosulfonyloxypropionate having a boiling point of 90-92°C/2 mmHg was obtained.
収量62.3g,収率57.5%(対乳酸エチル)。次い
で、実施例1においてα―クロルスルホニルオキ
シプロピオン酸メチル40.5gを用いる代わりにα
―クロルスルホニルオキシプロピオン酸エチル
43.3g(0.2モル)を用いた以外は実施例2と同じ
要領で反応および後処理を行ない、沸点69〜70
℃/2mmHgのα―フエニルプロピオン酸エチル
を得た。収量30.7g、収率86.0%(対α―クロル
スルホニルオキシプロピオン酸エチル)であつ
た。 Yield 62.3g, yield 57.5% (based on ethyl lactate). Next, instead of using 40.5 g of methyl α-chlorosulfonyloxypropionate in Example 1, α
-Ethyl chlorsulfonyloxypropionate
The reaction and post-treatment were carried out in the same manner as in Example 2, except that 43.3 g (0.2 mol) was used, and the boiling point was 69-70.
℃/2mmHg ethyl α-phenylpropionate was obtained. The yield was 30.7 g, yield 86.0% (based on ethyl α-chlorosulfonyloxypropionate).
Claims (1)
ピオン酸エステル類とを反応させることを特徴と
するα―フエニルプロピオン酸エステル類の製造
方法。 2 α―クロルスルホニルオキシプロピオン酸エ
ステル類として乳酸エステルと塩化スルフリルと
の反応生成物を単離することなく用いる特許請求
範囲1記載の方法。[Scope of Claims] 1. A method for producing α-phenylpropionic esters, which comprises reacting benzene with α-chlorosulfonyloxypropionic esters. 2. The method according to claim 1, in which a reaction product of a lactic acid ester and sulfuryl chloride is used as the α-chlorosulfonyloxypropionate ester without isolation.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10658081A JPS588045A (en) | 1981-07-07 | 1981-07-07 | Preparation of alpha-phenylpropionic ester |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10658081A JPS588045A (en) | 1981-07-07 | 1981-07-07 | Preparation of alpha-phenylpropionic ester |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS588045A JPS588045A (en) | 1983-01-18 |
JPS649306B2 true JPS649306B2 (en) | 1989-02-16 |
Family
ID=14437150
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10658081A Granted JPS588045A (en) | 1981-07-07 | 1981-07-07 | Preparation of alpha-phenylpropionic ester |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS588045A (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3404336A1 (en) * | 1984-02-08 | 1985-08-08 | Basf Ag, 6700 Ludwigshafen | METHOD FOR THE PRODUCTION OF ESTERS OPTICALLY ACTIVE 2-ARYLALKANIC ACIDS |
US6028824A (en) * | 1986-07-08 | 2000-02-22 | Canon Kabushiki Kaisha | Magnetooptical recording medium allowing overwriting with two or more magnetic layers |
ATE216528T1 (en) * | 1986-07-08 | 2002-05-15 | Canon Kk | APPARATUS AND SYSTEM FOR RECORDING ON A MAGNETOPTICAL RECORDING MEDIUM |
KR960003420B1 (en) * | 1986-07-08 | 1996-03-13 | 캐논 가부시끼가이샤 | Magneto optical recording medium |
-
1981
- 1981-07-07 JP JP10658081A patent/JPS588045A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS588045A (en) | 1983-01-18 |
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