JPH0267249A - Production of 2-chloro-3,3,3-trifluoropropyl ester - Google Patents
Production of 2-chloro-3,3,3-trifluoropropyl esterInfo
- Publication number
- JPH0267249A JPH0267249A JP21614488A JP21614488A JPH0267249A JP H0267249 A JPH0267249 A JP H0267249A JP 21614488 A JP21614488 A JP 21614488A JP 21614488 A JP21614488 A JP 21614488A JP H0267249 A JPH0267249 A JP H0267249A
- Authority
- JP
- Japan
- Prior art keywords
- chlorine
- fatty acid
- metal salt
- chloro
- reaction
- 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.)
- Pending
Links
- -1 2-chloro-3,3,3-trifluoropropyl ester Chemical class 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 14
- 239000000460 chlorine Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 10
- 229930195729 fatty acid Natural products 0.000 claims abstract description 10
- 239000000194 fatty acid Substances 0.000 claims abstract description 10
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 150000002148 esters Chemical class 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 3
- RQBSYMINZKITIR-UHFFFAOYSA-N 2-chloro-3,3,3-trifluoropropan-1-ol Chemical compound OCC(Cl)C(F)(F)F RQBSYMINZKITIR-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 150000002730 mercury Chemical class 0.000 abstract description 2
- KDWQLICBSFIDRM-UHFFFAOYSA-N 1,1,1-trifluoropropane Chemical compound CCC(F)(F)F KDWQLICBSFIDRM-UHFFFAOYSA-N 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229940079593 drug Drugs 0.000 abstract 2
- 239000000575 pesticide Substances 0.000 abstract 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- CXGICDWOZWWNAY-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoropropan-1-ol Chemical compound OC(Cl)CC(F)(F)F CXGICDWOZWWNAY-UHFFFAOYSA-N 0.000 description 1
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 1
- HDBGBTNNPRCVND-UHFFFAOYSA-N 3,3,3-trifluoropropan-1-ol Chemical compound OCCC(F)(F)F HDBGBTNNPRCVND-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 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
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は医農薬合成の中間体等として有用な２−クロロ
−３，３，３−トリフルオロプロパツールの合成等に使
用する２−クロロ−３，３，３−）リフルオロプロピル
エステルの製造法に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to 2-chloro-3,3,3-trifluoropropatol, which is useful as an intermediate for the synthesis of pharmaceuticals and agricultural chemicals. The present invention relates to a method for producing -3,3,3-)rifluoropropyl ester.
［従来技術］
１ｚｖｅｓｔ、Ａｋａｄ、Ｎａｕｋ Ｓ、Ｓ、Ｓ、Ｒ，
，０ｔｄｅ１．Ｋｈｉｓ、Ｎａｕｋ。[Prior art] 1zvest, Akad, Nauk S, S, S, R,
,0tde1. Khis, Nauk.
８４３（１９５６）および８８（１９６１）によれば硝
酸第二水銀あるいは酢酸第二水銀の酢酸溶液にハロゲン
の存在下に３．３．３−トリフルオロプロペンを通じる
ことにより２−ハロゲノ−３，３，３）リフルオロプロ
ピルアセテートを得ているが、毒性の強い水銀を等モル
使用する反応であって工業的実施には問題のあるもので
ある。また、このエステルを加水分解して得られる２−
ハロゲノ−３，３，３−）リフルオロプロパツールの合
成法として米国特許第２７００６８６号明細書において
は酸化水銀を用いて得られる２５％濃度の次亜塩素酸水
溶液に３．３．３−トリフルオロプロペンを通じること
により得ているが、この場合にも同様に水銀塩を用いる
ものであり、工業的な方法とはいえないものである。843 (1956) and 88 (1961), 2-halogeno-3,3 is prepared by passing 3.3.3-trifluoropropene into an acetic acid solution of mercuric nitrate or mercuric acetate in the presence of a halogen. , 3) Lifluoropropyl acetate has been obtained, but the reaction uses equimolar amounts of highly toxic mercury, which is problematic for industrial implementation. In addition, 2- obtained by hydrolyzing this ester
In U.S. Pat. No. 2,700,686, as a method for synthesizing halogeno-3,3,3-)lifluoropropanol, 3,3,3-trifluoropropanol is added to a 25% aqueous hypochlorous acid solution obtained using mercury oxide. It has been obtained by passing fluoropropene, but in this case as well, a mercury salt is used, so it cannot be called an industrial method.
［問題点を解決するための具体的手段］本発明者らはか
かる従来技術の問題点に鑑み鋭意検討の結果、塩素と脂
肪酸金属塩との反応により得られるアルカノイルハイポ
クロライドを３．３゜３−トリフルオロプロペンに付加
させることにより２−クロロ−３，３，３−トリフルオ
ロプロピルエステルが得られることを見いだし本発明に
到達したものである。[Specific Means for Solving the Problems] In view of the problems of the prior art, the present inventors have conducted intensive studies and found that alkanoyl hypochloride obtained by the reaction of chlorine and a fatty acid metal salt is 3.3°3 The present invention was achieved by discovering that 2-chloro-3,3,3-trifluoropropyl ester can be obtained by addition to -trifluoropropene.
すなわち本発明は３，３．３−トリフルオロプロペンを
塩素の存在下に一般式
％式％（１）
（Ｒは炭素数１〜５のアルキル基、Ｍはアルカリ金属を
表わす）で示される脂肪酸金属塩と反応させることを特
徴とする一般式
％式％（）
（Ｒは前記と同じ）
で示される２−クロロ−３，３，３−）リフルオロプロ
ピルエステルの製造法である。That is, the present invention provides 3,3,3-trifluoropropene in the presence of chlorine to form a fatty acid represented by the general formula % (1) (R is an alkyl group having 1 to 5 carbon atoms, and M is an alkali metal). This is a method for producing 2-chloro-3,3,3-)lifluoropropyl ester represented by the general formula % (R is the same as above), which is characterized by reacting with a metal salt.
本発明においては脂肪酸金属塩と塩素との反応によりア
ルカノイルハイポクロライドが生成し、３．３．３−ト
リフルオロプロペンに付加するものであるが、このアル
カノイルハイポクロライドの生成は完全なものではなく
、塩素の３．３．３−トリフルオロプロペンへの付加反
応が競争的に進行するものであり、遷移金属塩例えば塩
化パラジウムや塩化第二銅、あるいは塩化リチウム、酢
酸リチウム等を触媒量添加することで塩素の付加反応を
抑えることができ、目的とするエステルを満足すべき収
率で得ることができるものである。In the present invention, alkanoyl hypochloride is produced by the reaction of fatty acid metal salt and chlorine, and is added to 3.3.3-trifluoropropene, but the production of this alkanoyl hypochloride is not complete; The addition reaction of chlorine to 3.3.3-trifluoropropene proceeds competitively, and a catalytic amount of a transition metal salt such as palladium chloride, cupric chloride, lithium chloride, lithium acetate, etc. is added. The addition reaction of chlorine can be suppressed and the desired ester can be obtained in a satisfactory yield.
本発明において用いる脂肪酸金属塩としては一般式（１
）においてＲが炭素数１〜５のアルキル基のものを用い
ることができ、金属としてはナトリウム、カリウム等の
アルカリ金属が好ましく、他の条件が同一であれば、カ
リウムの方が目的エステルの選択率を高くすることがで
きる。 ３，３．３−トリフルオロプロペンに対する塩
素のモル比は１〜３の範囲が選ばれる。また、塩素に対
する脂肪酸金属塩のモル比は１〜３、好ましくは１〜１
．５の範囲である。The fatty acid metal salt used in the present invention has the general formula (1
), R can be used as an alkyl group having 1 to 5 carbon atoms, and the metal is preferably an alkali metal such as sodium or potassium.If other conditions are the same, potassium is preferred for selection of the target ester. rate can be increased. The molar ratio of chlorine to 3,3.3-trifluoropropene is selected in the range of 1 to 3. Further, the molar ratio of fatty acid metal salt to chlorine is 1 to 3, preferably 1 to 1.
．． The range is 5.
本発明においては反応を溶媒中でおこなうことが好まし
く、酢酸が最も好ましく、その量は原料の脂肪酸金属塩
に対して２〜１０倍量の範囲が選ばれる。また、溶媒と
してさらに水を添加した系での反応においては、生成エ
ステルが加水分解され２−クロロ−３，３，３−トリフ
ルオロプロパツールが生成するものであり、このものを
直接得たい場合には水を添加した系で反応をおこなえば
よい。In the present invention, it is preferable to carry out the reaction in a solvent, and acetic acid is most preferable, and the amount thereof is selected to be 2 to 10 times the amount of the fatty acid metal salt as the raw material. In addition, in the reaction in a system in which water is further added as a solvent, the produced ester is hydrolyzed to produce 2-chloro-3,3,3-trifluoropropanol, and if you want to directly obtain this product, The reaction may be carried out in a system to which water is added.
本発明における反応温度としては、反応温度が高いほど
反応速度は大となるが、選択率が低下するため、常温で
の反応が好ましい０反応圧力は特に限定されず、原料ガ
スの装入圧力でおこなわれる。Regarding the reaction temperature in the present invention, the higher the reaction temperature, the higher the reaction rate, but since the selectivity decreases, the reaction pressure is not particularly limited to 0, where the reaction is preferably at room temperature, and the charging pressure of the raw material gas is It is carried out.
反応形式は特に限定されないが、酢酸等の有機溶媒およ
び脂肪酸金属塩を仕込んだ反応容器に塩素、３．３．３
− ）リフルオロプロペンを装入し、反応をおこなう。The reaction format is not particularly limited, but chlorine, 3.3.3.
−) Charge refluoropropene and carry out the reaction.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
１００ｍ ｌ耐圧ガラス反応器に酢酸５０■１、酢酸ナ
トリウム８．６ ｇ （０，１モル）を仕込み、塩素７
．１ｇを圧入し、３０分間室温で加温したのち、３．３
．３−トリフルオロプロペン９．７ ｇ （０，１０１
モル）を圧入し、１０時間室温で撹拌した。水冷下に未
反応ガスを放出し、反応液をガスクロ分析したところ３
゜３．３−トリフルオロプロペンの転化率は８４．９モ
ル％、２−クロロ−３，３，３−トリフルオロプロピル
アセテートの選択率は２０゜５モル％であった。Example 1 A 100 ml pressure glass reactor was charged with 50 ml of acetic acid and 8.6 g (0.1 mol) of sodium acetate, and 7 ml of chlorine was charged.
．． After press-fitting 1 g and warming at room temperature for 30 minutes, 3.3
．． 3-trifluoropropene 9.7 g (0,101
mol) was injected under pressure, and the mixture was stirred at room temperature for 10 hours. Unreacted gas was released under water cooling, and the reaction solution was analyzed by gas chromatography.3
The conversion rate of 3.3-trifluoropropene was 84.9 mol%, and the selectivity of 2-chloro-3,3,3-trifluoropropyl acetate was 20.5 mol%.
実施Ｎ２〜８
実施例１と同様にして各条件をかえ、室温にて反応をお
こなった。この結果を第１表に示した。Examples N2 to 8 The reaction was carried out in the same manner as in Example 1, with different conditions, and at room temperature. The results are shown in Table 1.
［発明の効果］
本発明によれば医ａ東合成の中間体等として有用な２−
クロロ−３，３，３−トリフルオロプロパツールの合成
原料等として使用できる２−クロロ−３，３，３−トリ
フルオロプロピルエステルを毒性の強い試剤を用いるこ
となく、工業的容易に得ることができるものである。[Effect of the invention] According to the present invention, 2-
2-chloro-3,3,3-trifluoropropyl ester, which can be used as a raw material for the synthesis of chloro-3,3,3-trifluoropropanol, can be easily obtained industrially without using highly toxic reagents. It is possible.
Claims (1)
般式 ＲＣＯ＿２Ｍ（ I ） （Ｒは炭素数１〜５のアルキル基、Ｍはアルカリ金属を
表わす）で示される脂肪酸金属塩と反応させることを特
徴とする一般式 ＣＦ＿３ＣＨＣｌＣＨ＿２ＯＣＯＲ（II） （Ｒは前記と同じ） で示される２−クロロ−３，３，３−トリフルオロプロ
ピルエステルの製造法。[Claims] 3,3,3-trifluoropropene is prepared in the presence of chlorine into a fatty acid represented by the general formula RCO_2M(I) (R is an alkyl group having 1 to 5 carbon atoms, and M is an alkali metal). A method for producing 2-chloro-3,3,3-trifluoropropyl ester represented by the general formula CF_3CHClCH_2OCOR(II) (R is the same as above), which comprises reacting with a metal salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21614488A JPH0267249A (en) | 1988-08-30 | 1988-08-30 | Production of 2-chloro-3,3,3-trifluoropropyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21614488A JPH0267249A (en) | 1988-08-30 | 1988-08-30 | Production of 2-chloro-3,3,3-trifluoropropyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0267249A true JPH0267249A (en) | 1990-03-07 |
Family
ID=16683965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21614488A Pending JPH0267249A (en) | 1988-08-30 | 1988-08-30 | Production of 2-chloro-3,3,3-trifluoropropyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0267249A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007143154A1 (en) * | 2006-06-02 | 2007-12-13 | Purdue Research Foundation | Methods for preparing halohydrins and methods for preparing epoxides |
-
1988
- 1988-08-30 JP JP21614488A patent/JPH0267249A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007143154A1 (en) * | 2006-06-02 | 2007-12-13 | Purdue Research Foundation | Methods for preparing halohydrins and methods for preparing epoxides |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0267249A (en) | Production of 2-chloro-3,3,3-trifluoropropyl ester | |
| JPH04253934A (en) | Production of retinoic acid and isomer thereof | |
| JPH0613472B2 (en) | Method for producing 2-methoxy-6-methylaminopyridine | |
| JPS6232188B2 (en) | ||
| JP4099630B2 (en) | Method for producing perfluoroalkyl compound | |
| KR910003635B1 (en) | Process for the preparation of 2-(2-naphthyloxy)propion anilide derivatives | |
| JPH0285232A (en) | Production of long-chain dibasic monoester salt | |
| KR930003756B1 (en) | The producing method of substituted beta phenyl acrylic acid | |
| JPH0558953A (en) | Production of 2-hydroxyisobutyric acid ester | |
| JPH0768185B2 (en) | Process for producing nitro-substituted 4-trifluoromethylbenzoic acid | |
| JPS60501709A (en) | Cyanohydrin production method | |
| JPH0753507A (en) | Production of p-aminothiophenol | |
| KR100245015B1 (en) | Process for preparation of o-(carboxy)phenylmethanesulfonyl chloride derivatives | |
| JPS62228041A (en) | Production of carboxylic acid derivative | |
| JP2000086610A (en) | Production of cyanobenzamide | |
| JPH02268134A (en) | Preparation of optically active 2-(4-hydroxyphenoxy) propionic acid | |
| JPS591435A (en) | Preparation of orthoformic acid trimethyl or triethyl ester | |
| JPS5933570B2 (en) | Method for producing O-alkoxy-p-allylphenol | |
| JPH072690B2 (en) | Method for producing 3-methyl-4-nitrophenol | |
| JPS63135340A (en) | Production of organic compound | |
| JPS5821641A (en) | Preparation of beta-chloropropionic acid | |
| JPS59122455A (en) | Preparation of p-toluenesulfonic acid (meth)allyl ester | |
| JPS637192B2 (en) | ||
| JPS6318924B2 (en) | ||
| JPS6141907B2 (en) |