JPS6212784B2 - - Google Patents
Info
- Publication number
- JPS6212784B2 JPS6212784B2 JP4976080A JP4976080A JPS6212784B2 JP S6212784 B2 JPS6212784 B2 JP S6212784B2 JP 4976080 A JP4976080 A JP 4976080A JP 4976080 A JP4976080 A JP 4976080A JP S6212784 B2 JPS6212784 B2 JP S6212784B2
- Authority
- JP
- Japan
- Prior art keywords
- oxyphenyl
- formula
- general formula
- group
- alkyl group
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 235000019439 ethyl acetate Nutrition 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- -1 alkali metal salt Chemical class 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000003916 acid precipitation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 125000004344 phenylpropyl group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- PBVZQAXFSQKDKK-UHFFFAOYSA-N 3-Methoxy-3-oxopropanoic acid Chemical compound COC(=O)CC(O)=O PBVZQAXFSQKDKK-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 229930186147 Cephalosporin Natural products 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- HGINADPHJQTSKN-UHFFFAOYSA-N Monoethyl malonic acid Chemical compound CCOC(=O)CC(O)=O HGINADPHJQTSKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229940124587 cephalosporin Drugs 0.000 description 1
- 150000001780 cephalosporins Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
【発明の詳細な説明】
本発明はオキシフエニルマロン酸半エステルの
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing oxyphenyl malonic acid half ester.
本発明の目的とするオキシフエニルマロン酸半
エステルは強い抗菌力を有するセフアロスポリン
系抗生物質の合成原料として有用であり、本発明
の目的は該化合物を安価にしてかつ工業的に極め
て有利に製造する方法を提供することにある。 Oxyphenyl malonic acid half ester, which is the object of the present invention, is useful as a raw material for the synthesis of cephalosporin antibiotics that have strong antibacterial activity, and the object of the present invention is to produce this compound at a low cost and with great industrial advantage. The goal is to provide a way to do so.
オキシフエニルマロン酸半エステルの製造法に
ついては、オキシフエニル酢酸エステル類にヘキ
サアルキルジシラザンのアルカリ金属塩を作用さ
せたのち、二酸化炭素を作用させる方法（特開昭
54−106447号公報）が知られているが、この方法
では極めて特殊な試剤を使用しなければならない
ため、必ずしも工業的に有利な製法とはいえなか
つた。 Regarding the production method of oxyphenyl malonic acid half ester, a method of reacting oxyphenyl acetate with an alkali metal salt of hexaalkyldisilazane and then reacting with carbon dioxide (JP-A-Sho)
No. 54-106447) is known, but this method requires the use of very special reagents, so it cannot necessarily be said to be an industrially advantageous manufacturing method.
本発明者らは、オキシフエニルマロン酸半エス
テルを工業的有利に製造すべく、特にオキシフエ
ニル酢酸エステル類のカルボキシ化について検討
を行なつた結果、炭酸ジアルキルと共に、数多く
ある金属アルコラートのなかでもカリウムターシ
ヤリーブトキシドを用いた場合にのみ極めて高収
率で、容易にオキシフエニルマロン酸ジエステル
が得られ、これを部分加水分解することにより容
易に目的とするオキシフエニルマロン酸半エステ
ルが得られることを見出し、本発明を完成するに
至つた。 In order to industrially advantageously produce oxyphenyl malonic acid half ester, the present inventors have particularly investigated the carboxylation of oxyphenyl acetic acid esters, and found that, along with dialkyl carbonate, among many metal alcoholates, potassium Only when tertiary butoxide is used, oxyphenyl malonic acid diester can be easily obtained in extremely high yield, and by partial hydrolysis of this, the desired oxyphenyl malonic acid half ester can be easily obtained. This discovery led to the completion of the present invention.
すなわち本発明は、一般式（）
（式中、R1はC1〜5のアルキル基を、Ｘは水素原
子、C1〜5のアルキル基、アラルキル基、C1〜5の
アルコキシ基またはアラルコキシ基を示す。）で
示されるオキシフエニル酢酸エステル類に、カリ
ウムターシヤリーブトキシドと一般式（）
（R2）2CO2 （）
（式中、R2はC1〜5のアルキル基を示す。）
で示される炭酸ジアルキルを作用させて、一般式
（）
（式中、R1、R2およびＸは前記と同意義であ
る。）
で示されるオキシフエニルマロン酸ジエステルを
得、次いでこれを部分加水分解することを特徴と
する一般式（）
（式中、R3はR1またはR2を示し、R1、R2およびＸ
は前記と同意義である。）
で示されるオキシフエニルマロン酸半エステルの
製造方法である。 That is, the present invention is based on the general formula () (In the formula, R 1 represents a C 1-5 alkyl group, and X represents a hydrogen atom, a C 1-5 alkyl group, an aralkyl group, a C 1-5 alkoxy group, or an aralkoxy group.) Acetic esters are reacted with potassium tertiary butoxide and dialkyl carbonate represented by the general formula () (R 2 ) 2 CO 2 () (in the formula, R 2 represents a C 1-5 alkyl group). , general expression () (In the formula, R 1 , R 2 and X have the same meanings as above) (In the formula, R 3 represents R 1 or R 2 , R 1 , R 2 and
has the same meaning as above. ) This is a method for producing oxyphenyl malonic acid half ester.
上記式中におけるＸ、R1、R2の定義を更に詳
細に述べればアルキルとは炭素数１〜５の低級ア
ルキルを意味し、例えばメチル、エチル、プロピ
ル、イソプロピル、ブチル、イソブチル、ｓ−ブ
チル、ｔ−ブチル、ペンチル、イソペンチル、ネ
オペンチル、ｔ−ペンチルなどがあげられる。ア
ラルキルとはベンジル、フエネチル、フエニルプ
ロピルなどがあげられ、これらはメチル、エチ
ル、メトキシ、エトキシ、ニトロなどの置換基を
有していてもよい。アルコキシとは炭素数１〜５
の低級アルコキシを意味し、例えばメトキシ、エ
トキシ、プロポキシ、イソプロポキシ、ブトキ
シ、イソブトキシ、ｓ−ブトキシ、ｔ−ブトキ
シ、ペンチルオキシ、イソペンチルオキシ、ネオ
ペンチルオキシ、ｔ−ペンチルオキシなどがあげ
られる。アラルコキシとしては、メトキシ、エト
キシ、ニトロなどの置換基を有してもよいベンジ
ル、フエネチル、フエニルプロピルなどがあげら
れる。 To explain in more detail the definitions of X, R 1 and R 2 in the above formula, alkyl means lower alkyl having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl. , t-butyl, pentyl, isopentyl, neopentyl, t-pentyl, and the like. Examples of aralkyl include benzyl, phenethyl, and phenylpropyl, which may have a substituent such as methyl, ethyl, methoxy, ethoxy, and nitro. Alkoxy has 1 to 5 carbon atoms.
Examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, isopentyloxy, neopentyloxy, t-pentyloxy, and the like. Examples of aralkoxy include benzyl, phenethyl, and phenylpropyl, which may have substituents such as methoxy, ethoxy, and nitro.
一般式（）で示されるオキシフエニルマロン
酸ジエステルの製造は通常溶媒の存在下もしくは
非存在下に行なわれるが、溶媒を使用する場合は
非プロトン性有機溶媒として一般に使用されてい
る溶媒、例えばベンゼン、トルエン、キシレン、
エーテル、テトラヒドロフラン、ジオキサン、ア
セトニトリル、ｎ−ヘキサン等の単独又は混合物
が用いられる。原料である一般式（）の化合物
が常温で固体である場合にはそれを溶解する溶媒
を選ぶのが操作的により好適である。カリウムタ
ーシヤリーブトキシドの使用量は通常一般式
（）化合物１モルに対して２モルから10モルの
範囲で任意であるが、好ましくは２〜６モルの範
囲である。炭酸ジアルキルの使用モル数は一般式
（）化合物１モルに対し２モルから50モルの範
囲で任意であるが、好ましくは３〜30モルの範囲
である。10モル以下の範囲では反応によつて生成
するアルコールを留去しながら反応を行わしめる
のが望ましい。 The production of oxyphenyl malonic acid diester represented by the general formula () is usually carried out in the presence or absence of a solvent, but when a solvent is used, a solvent commonly used as an aprotic organic solvent, e.g. benzene, toluene, xylene,
Ether, tetrahydrofuran, dioxane, acetonitrile, n-hexane, etc. may be used alone or in mixtures. When the starting compound of the general formula () is solid at room temperature, it is more convenient to select a solvent that dissolves it. The amount of potassium tertiary butoxide to be used is generally arbitrary in the range of 2 to 10 moles, but preferably in the range of 2 to 6 moles, per 1 mole of the compound of general formula (). The number of moles of dialkyl carbonate used is arbitrary in the range of 2 to 50 moles, but preferably in the range of 3 to 30 moles, per mole of the compound of general formula (). In the range of 10 moles or less, it is desirable to carry out the reaction while distilling off the alcohol produced by the reaction.
反応温度は通常−20℃から200℃の範囲で任意
であるが、好ましくは０℃〜150℃が採用され
る。 The reaction temperature is generally arbitrary within the range of -20°C to 200°C, but preferably 0°C to 150°C.
反応圧力については特に制限なく、常圧、加圧
いずれでもよい。反応形式は回分法、連続法いず
れでもよい。 The reaction pressure is not particularly limited and may be either normal pressure or increased pressure. The reaction format may be either a batch method or a continuous method.
このような反応により得られた反応混合物を塩
酸水或いは硫酸水に投入して酸析を行つた後抽
出、濃縮等の一般的な操作を行なう事により高純
度の一般式（）化合物が極めて高収率で得られ
る。 The reaction mixture obtained by such a reaction is poured into aqueous hydrochloric acid or sulfuric acid to perform acid precipitation, followed by general operations such as extraction and concentration, resulting in a highly pure compound of general formula (). obtained in high yield.
次いで一般式（）化合物をアルカリ水溶液中
で、必要ならば加熱し、部分加水分解を行なうこ
とにより一般式（）で示される目的化合物を得
ることができる。又上記化合物（）の製造にお
いて、酸析を行なうかわりに水を加えて、必要な
らば加熱して部分加水分解を行なわせしめること
により中間体である化合物（）を単離すること
なく、直接目的化合物（）を得ることができ
る。 Next, the target compound represented by the general formula () can be obtained by partially hydrolyzing the compound of the general formula () in an alkaline aqueous solution by heating if necessary. In addition, in the production of the above compound (), instead of performing acid precipitation, water is added, and if necessary, heating is performed to cause partial hydrolysis, thereby directly producing the desired product without isolating the intermediate compound (). Compound () can be obtained.
以下に本発明を実施例により説明する。 The present invention will be explained below using examples.
本発明がこれらの実施例のみに制約されるもの
でないことは言うまでもない。 It goes without saying that the present invention is not limited only to these examples.
実施例 １
ｐ−オキシフエニル酢酸メチル99.7ｇを炭酸ジ
メチル810ｇに溶解し、５℃に冷却する。常に液
温が20℃以下になるように冷却しながらカリウム
ターシヤリーブトキシド299.2ｇを徐々に加え
る。ブトキシド添加終了後、45〜50℃に昇温し１
時間撹拌を続ける。反応液に水を600ｇ加え15〜
20℃で20時間撹拌後、35％塩酸水330ｇを加え酸
析し、メチルイソブチルケトン500ｇで抽出す
る。油層を濃縮し濃縮物をトルエン溶媒で再結晶
を行なうとｐ−オキシフエニルマロン酸モノメチ
ルエステルが98.3ｇ（収率ｐ−オキシフエニル酢
酸メチルに対して78.0％）得られる。Example 1 99.7 g of methyl p-oxyphenylacetate is dissolved in 810 g of dimethyl carbonate and cooled to 5°C. Gradually add 299.2 g of potassium tertiary butoxide while cooling the liquid so that the temperature is always below 20°C. After the addition of butoxide, the temperature was raised to 45-50℃ and
Continue stirring for an hour. Add 600g of water to the reaction solution and
After stirring at 20°C for 20 hours, 330 g of 35% hydrochloric acid solution was added to precipitate the mixture, followed by extraction with 500 g of methyl isobutyl ketone. The oil layer was concentrated and the concentrate was recrystallized from a toluene solvent to obtain 98.3 g of p-oxyphenyl malonic acid monomethyl ester (yield: 78.0% based on methyl p-oxyphenyl acetate).
実施例 ２
炭酸ジエチル283.2ｇとカリウムターシヤリー
ブトキシド119.7ｇをトルエン360ｇに溶解する。
これにｐ−オキシフエニル酢酸エチル72.0ｇを加
え、110℃まで徐々に昇温し、1.5時間から２時間
で生成するエタノールを完全に留去せしめる。反
応液を15％塩酸水390ｇに投入しエーテルで抽出
する。エーテル層を濃縮し濃縮物に15％苛性水溶
液320ｇを加え15〜20℃で24時間撹拌後15％塩酸
水350ｇで酸析する。メチルイソブチルケトン300
ｇで抽出し油層を濃縮するとｐ−オキシフエニル
マロン酸モノエチルエステルが163.4ｇ（収率ｐ
−オキシフエニル酢酸エチルに対して72.8％）得
られる。Example 2 283.2 g of diethyl carbonate and 119.7 g of potassium tertiary butoxide are dissolved in 360 g of toluene.
72.0 g of ethyl p-oxyphenylacetate is added to this, and the temperature is gradually raised to 110°C, and the ethanol produced is completely distilled off in 1.5 to 2 hours. The reaction solution was poured into 390 g of 15% hydrochloric acid and extracted with ether. The ether layer was concentrated, 320 g of a 15% caustic aqueous solution was added to the concentrate, and the mixture was stirred at 15-20°C for 24 hours, followed by acid precipitation with 350 g of 15% aqueous hydrochloric acid. Methyl isobutyl ketone 300
g and concentrated the oil layer to obtain 163.4 g of p-oxyphenylmalonic acid monoethyl ester (yield: p
-72.8% based on ethyl oxyphenyl acetate).
比較例 １
カリウムターシヤリーブトキシドのかわりにナ
トリウムメチラートを用いたほかは実施例１と同
じとした。ｐ−オキシフエニル酢酸メチルより収
率2.8％でｐ−オキシマロン酸モノメチルエステ
ルが得られる。Comparative Example 1 The same procedure as Example 1 was carried out except that sodium methylate was used instead of potassium tertiary butoxide. p-oxymalonic acid monomethyl ester is obtained from methyl p-oxyphenylacetate in a yield of 2.8%.
比較例 ２
カリウムターシヤリーブトキシドのかわりにナ
トリウムエチラートを用いたほかは実施例２と同
じとした。ｐ−オキシフエニル酢酸エチルより収
率８％でｐ−オキシフエニルマロン酸モノエチル
エステルが得られる。Comparative Example 2 The same procedure as Example 2 was carried out except that sodium ethylate was used instead of potassium tertiary butoxide. p-oxyphenyl malonic acid monoethyl ester is obtained from ethyl p-oxyphenyl acetate in a yield of 8%.
Claims (1)
子、C1〜5のアルキル基、アラルキル基、C1〜5の
アルコキシ基またはアラルコキシ基を示す。）で
示されるオキシフエニル酢酸エステル類に、カリ
ウムターシヤリーブトキシドと一般式 （R2）2CO2 （式中、R2はC1〜5のアルキル基を示す。） で示される炭酸ジアルキルを作用させて、一般式 （式中、R1、R2およびＸは前記と同意義であ
る。） で示されるオキシフエニルマロン酸ジエステルを
得、次いでこれを部分加水分解することを特徴と
する一般式 （式中、R3はR1またはR2を示し、R1、R2およびＸ
は前記と同意義である。） で示されるオキシフエニルマロン酸半エステルの
製造方法。[Claims] 1. General formula (In the formula, R 1 represents a C 1-5 alkyl group, and X represents a hydrogen atom, a C 1-5 alkyl group, an aralkyl group, a C 1-5 alkoxy group, or an aralkoxy group.) Acetic esters are reacted with potassium tertiary butoxide and dialkyl carbonate represented by the general formula (R 2 ) 2 CO 2 (wherein, R 2 represents a C 1-5 alkyl group) to form the general formula (In the formula, R 1 , R 2 and X have the same meanings as above) (In the formula, R 3 represents R 1 or R 2 , R 1 , R 2 and
has the same meaning as above. ) A method for producing oxyphenyl malonic acid half ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4976080A JPS56147747A (en) | 1980-04-15 | 1980-04-15 | Preparation of oxyphenylmlonic half ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4976080A JPS56147747A (en) | 1980-04-15 | 1980-04-15 | Preparation of oxyphenylmlonic half ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56147747A JPS56147747A (en) | 1981-11-16 |
| JPS6212784B2 true JPS6212784B2 (en) | 1987-03-20 |
Family
ID=12840132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4976080A Granted JPS56147747A (en) | 1980-04-15 | 1980-04-15 | Preparation of oxyphenylmlonic half ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56147747A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01313682A (en) * | 1988-06-09 | 1989-12-19 | Daikin Ind Ltd | Refrigeration unit |
| WO2020149664A1 (en) * | 2019-01-18 | 2020-07-23 | 삼성전자 주식회사 | Method for providing service on basis of genetic information on user group, and electronic device therefor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229531B (en) * | 2011-05-09 | 2013-04-17 | 山东睿鹰先锋制药有限公司 | Preparation method of p-hydroxy benzal propane diacid derivative |
-
1980
- 1980-04-15 JP JP4976080A patent/JPS56147747A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01313682A (en) * | 1988-06-09 | 1989-12-19 | Daikin Ind Ltd | Refrigeration unit |
| WO2020149664A1 (en) * | 2019-01-18 | 2020-07-23 | 삼성전자 주식회사 | Method for providing service on basis of genetic information on user group, and electronic device therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56147747A (en) | 1981-11-16 |
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