DE1274127B - Process for the preparation of ª ‡ -Alkoxyarylessigsaeurealkylestern - Google Patents
Process for the preparation of ª ‡ -AlkoxyarylessigsaeurealkylesternInfo
- Publication number
- DE1274127B DE1274127B DED48510A DED0048510A DE1274127B DE 1274127 B DE1274127 B DE 1274127B DE D48510 A DED48510 A DE D48510A DE D0048510 A DED0048510 A DE D0048510A DE 1274127 B DE1274127 B DE 1274127B
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- Prior art keywords
- methyl
- optionally
- substituted
- alkyl
- methoxy
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 5
- -1 alkyl radicals Chemical class 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000002390 heteroarenes Chemical class 0.000 claims description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims description 2
- 150000005840 aryl radicals Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- DCOWHZYIFORKFC-UHFFFAOYSA-N methyl 2-chloro-2-methoxyacetate Chemical compound COC(Cl)C(=O)OC DCOWHZYIFORKFC-UHFFFAOYSA-N 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 125000005907 alkyl ester group Chemical group 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- BNQRSYFOIRGRKV-UHFFFAOYSA-N methyl 2-(2-methoxyphenyl)acetate Chemical compound COC(=O)CC1=CC=CC=C1OC BNQRSYFOIRGRKV-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- RMIODHQZRUFFFF-UHFFFAOYSA-M methoxyacetate Chemical compound COCC([O-])=O RMIODHQZRUFFFF-UHFFFAOYSA-M 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- HQDBRHNBKCRLNH-UHFFFAOYSA-N 2-hydroxy-2-methoxy-2-phenylacetic acid Chemical compound COC(O)(C(O)=O)C1=CC=CC=C1 HQDBRHNBKCRLNH-UHFFFAOYSA-N 0.000 description 1
- DIWVBIXQCNRCFE-UHFFFAOYSA-N DL-alpha-Methoxyphenylacetic acid Chemical compound COC(C(O)=O)C1=CC=CC=C1 DIWVBIXQCNRCFE-UHFFFAOYSA-N 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
- QRMHDGWGLNLHMN-UHFFFAOYSA-N Methyl methoxyacetate Chemical compound COCC(=O)OC QRMHDGWGLNLHMN-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 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 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940089960 chloroacetate Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- XOIOYHPJZJLTGK-UHFFFAOYSA-N methyl 2-chloro-2-phenylacetate Chemical compound COC(=O)C(Cl)C1=CC=CC=C1 XOIOYHPJZJLTGK-UHFFFAOYSA-N 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/10—Indoles; Hydrogenated indoles with substituted hydrocarbon radicals attached to carbon atoms of the hetero ring
- C07D209/18—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/02—Alkylation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von a-Alkoxyarylessigsäurealkylestern Die Erfindung betrifft ein Verfahren zur Herstellung von a-Alkoxyarylessigsäurealkylestern der allgemeinen Formel in der R, R' und Ar die weiter unten genannte Bedeutung haben.Process for the preparation of α-alkoxyarylacetic acid alkyl esters The invention relates to a process for the preparation of α-alkoxyarylacetic acid alkyl esters of the general formula in which R, R 'and Ar have the meaning given below.
Die freien a-Alkoxyarylessigsäuren finden als Fällungs- und Nachweisreagenz für Natrium und als Mittel zur Beeinflussung des Pflanzenwachstums Anwendung. The free α-alkoxyarylacetic acids are used as precipitation and detection reagents for sodium and as a means of influencing plant growth.
Es ist bekannt, zur Herstellung von a-Alkoxyphenylessigsäuremethylestern Benzaldehyd und Chloroform in Gegenwart von Alkalien umzusetzen (USA.-Patentschrift 3 082 002 und J. Amer. Chem. It is known to produce methyl α-alkoxyphenylacetates Reacting benzaldehyde and chloroform in the presence of alkalis (USA.Patent 3,082,002 and J. Amer. Chem.
Soc., 82 [1960], S. 4062 bis 4066). Die Umsetzung erfolgt gemäß der Gleichung Dieses Verfahren ist auch für andere Aldehyde anwendbar, liefert aber schlechte Ausbeuten. Darüber hinaus fallen in erheblichen Mengen Nebenprodukte an.Soc., 82 [1960], pp. 4062 to 4066). The implementation takes place according to the equation This process can also be used for other aldehydes, but gives poor yields. In addition, by-products are produced in considerable quantities.
In J. Amer. Chem. Soc., 79 (1957), S. 1932 bis 1934 ist die Umsetzung von Benzaldehyd mit Natriumcyanid nach folgender Gleichung beschrieben: Dieses Verfahren ist nur auf die Herstellung von a-Methoxymandelsäure anwendbar, außerdem sind die Ausgangsprodukte schwer zugänglich und teuer.In J. Amer. Chem. Soc., 79 (1957), pp. 1932 to 1934, the reaction of benzaldehyde with sodium cyanide is described according to the following equation: This process can only be used for the production of α-methoxymandelic acid; in addition, the starting materials are difficult to access and expensive.
Das trifft auch auf das folgende Verfahren zu.This also applies to the following procedure.
Danach wird a-Methoxyphenylessigsäuremethylester durch die Umsetzung von Phenylchloressigsäuremethylester mit methylalkoholischer Natriummethylatlösung nach der Gleichung erhalten (J. Chem. Soc. [London], 93, S. 824).Thereafter, methyl a-methoxyphenylacetate is obtained by reacting methyl phenylchloroacetate with methyl alcoholic sodium methylate solution according to the equation (J. Chem. Soc. [London], 93, p. 824).
Beide Verfahren finden deshalb in der Technik keine Anwendung.Both methods are therefore not used in technology.
Zweck der Erfindung ist die Entwicklung eines Verfahrens zur technischen Herstellung unterschiedlich substituierter a-Alkoxyarylessigsäurealkylester, ausgehend von leicht zugänglichen Ausgangsprodukten. The purpose of the invention is to develop a method for technical Preparation of variously substituted alkyl α-alkoxyarylacetates, starting of easily accessible starting products.
Erfindungsgemäß werden a-Alkoxyarylessigsäure alkylester der allgemeinen Formel in der R und R' Alkylreste bedeuten und Ar einen Arylrest, der gegebenenfalls im Kern substituiert oder Teil eines gegebenenfalls vernetzten Polystyrols sein kann, oder einen Heteroarylrest darstellt, erhalten, in dem man a-Alkoxy-a-chlor- bzw. a-Alkoxya-bromessigsäurealkylester mit Aromaten, die gegebenenfalls im Kern substituiert oder Teil eines gegebenenfalls vernetzten Polystyrols sein können, oder Heteroaromaten in Gegenwart eines Friedel-Crafts-Katalysators umsetzt. a-Alkoxy-a-chlor- bzw. a-Alkoxy-a-bromessigsäurealkylester erhält man beispielsweise durch Umsetzung von Dialkoxyessigsäurealkylestern mit Phosphorpentachlorid.According to the invention, α-alkoxyarylacetic acid are alkyl esters of the general formula in which R and R 'are alkyl radicals and Ar is an aryl radical which can optionally be substituted in the nucleus or part of an optionally crosslinked polystyrene, or a heteroaryl radical, obtained by α-alkoxy-α-chloro- or α-alkoxy alkyl bromoacetate with aromatics, which may optionally be substituted in the nucleus or may be part of an optionally crosslinked polystyrene, or converts heteroaromatics in the presence of a Friedel-Crafts catalyst. α-Alkoxy-α-chloro- or α-alkoxy-α-bromoacetic acid alkyl esters are obtained, for example, by reacting dialkoxyacetic acid alkyl esters with phosphorus pentachloride.
So reagiert z. B. Benzol mit a-Methoxy-a-chloressigsäuremethylester in Gegenwart von Zinntetrachlorid unter Bildung von a-Methoxyphenylessigsäuremethylester: Analog können auch andere aromatische Verbindungen, wie z. B. Toluol, Mesitylen, Anisol, weitere Aromaten mit O-funktionellenund N-funktionellen Resten, Chlorbenzol, Naphthalin oder Heteroaromaten in die entsprechenden a-Alkoxyarylessigsäurealkylester übergeführt werden.This is how z. B. Benzene with methyl a-methoxy-a-chloroacetate in the presence of tin tetrachloride to form methyl a-methoxyphenylacetate: Similarly, other aromatic compounds, such as. B. toluene, mesitylene, anisole, other aromatics with O-functional and N-functional radicals, chlorobenzene, naphthalene or heteroaromatics can be converted into the corresponding alkyl α-alkoxyarylacetate.
Bei der Reaktion mit Polystyrol erhält man je nach Reaktionsbedingungen bis zu 900/0 substituierte Derivate, die in der Kette noch unsubstituierte Phenylkerne enthalten, wie z. B. In the reaction with polystyrene, depending on the reaction conditions, up to 900/0 substituted derivatives which still contain unsubstituted phenyl nuclei in the chain, such as e.g. B.
Die erhaltenen a-Alkoxyarylessigsäurealkylester lassen sich alkalisch oder sauer in bekannter Weise zu den entsprechenden freien a-Alkoxyarylessigsäuren hydrolysieren. The alkyl α-alkoxyarylacetates obtained can be alkaline or acidic in a known manner to give the corresponding free α-alkoxyarylacetic acids hydrolyze.
Beispiel 1 Ein Gemisch aus 300 cm3 wasserfreiem Benzol und 156 g Zinn(IV)-chlorid wird bei 60 bis 800C tropfenweise unter Rühren mit 68,3 g a-Methoxychloressigsäuremethylester versetzt. Nach Beendigung der lebhaften HC1-Entwicklung wird noch etwa 1 Stunde auf 60 bis 800 C unter Rühren erwärmt und nach Abkühlung auf Eis gegossen. Die organische Schicht wird abgetrennt, die wäßrige Schicht nochmals mit äther extrahiert, die vereinigten organischen Phasen werden mit Wasser, verdünnter Natronlauge und nochmals mit Wasser gewaschen und nach dem Trocknen und Abdestillieren des Lösungsmittels im Vakuum destilliert. Example 1 A mixture of 300 cm3 of anhydrous benzene and 156 g Tin (IV) chloride is added dropwise at 60 to 80 ° C. with 68.3 g of methyl α-methoxychloroacetate while stirring offset. After the vigorous development of HC1 has ended, about 1 hour is left heated to 60 to 800 ° C. with stirring and, after cooling, poured onto ice. The organic Layer is separated off, the aqueous layer is extracted again with ether combined organic phases with water, dilute sodium hydroxide solution and again washed with water and after drying and distilling off the solvent distilled in vacuo.
Ausbeute: 70 g a-Methoxyphenylessigsäuremethylester (78010 der Theorie), Kp.lo = 120 bis 121"C. Yield: 70 g of methyl a-methoxyphenylacetate (78010 of theory), Kp.lo = 120 to 121 "C.
Beispiel 2 300 cm3 Benzol und 156 g Zinntetrachlorid werden, wie im Beispiels beschrieben, mit 91 g a-Methoxya-bromessigsäuremethylester umgesetzt und aufgearbeitet. Example 2 300 cm3 of benzene and 156 g of tin tetrachloride are, as described in the example, reacted with 91 g of methyl a-methoxy-bromoacetate and worked up.
Ausbeute: 62 g a-Methoxyphenylessigsäuremethylf ester (69°lo der Theorie), Kp.lo =- 121 bis 123"C. Yield: 62 g of a-methoxyphenylacetic acid methyl ester (69 ° lo der Theory), Kp.lo = - 121 to 123 "C.
Beispiel 3 Ein Gemisch aus 80 g Aluminiumchlorid, 60,5 cm3 (68 g) a-Methoxy-a-chloressigsäuremethylester und 250 cm3 Methylenchlorid wird unter Außenkühlung mit Eiswasser bei einer Innentemperatur von 5 bis 10°C mit 46 g Toluol versetzt, 1 Stunde bei 5 bis 10"C, 2 Stunden bei Raumtemperatur gerührt und, wie im Beispiel 1 beschrieben, aufgearbeitet. Example 3 A mixture of 80 g aluminum chloride, 60.5 cm3 (68 g) Methyl α-methoxy-α-chloroacetate and 250 cm3 methylene chloride are cooled with external cooling 46 g of toluene are added with ice water at an internal temperature of 5 to 10 ° C, Stirred for 1 hour at 5 to 10 ° C., 2 hours at room temperature and, as in the example 1 described, worked up.
Ausbeute: 76 g a-Methoxy-p-toluylessigsäureme thylester (780/oder Theorie), Kp.ll = 130 bis 131,5"C. Yield: 76 g of methyl a-methoxy-p-toluylacetate (780 / or Theory), Kp.II = 130 to 131.5 "C.
Beispiel 4 300 cm3 Chlorbenzol, 80 g Aluminiumchlorid und 68 g a-Methoxy-a-chloressigsäuremethylester werden, wie im Beispiel 1 beschrieben, umgesetzt und aufgearbeitet. Example 4 300 cm3 of chlorobenzene, 80 g of aluminum chloride and 68 g of methyl α-methoxy-α-chloroacetate are, as described in Example 1, implemented and worked up.
Ausbeute: 64,5 g a-Methoxy-(p-chlorphenyl)-essigsäuremethylester (600/6 der Theorie), Kp.lo = 138"C. Yield: 64.5 g of methyl a-methoxy- (p-chlorophenyl) -acetate (600/6 of theory), Kp.lo = 138 "C.
Beispiel 5 60 g Mesitylen, 80 g AluminiumchIorid und 60,5 cm3 Methoxychloressigsäuremethylester werden in 250 cm3 Methylenchlorid, wie im Beispiel 1 beschrieben, umgesetzt und aufgearbeitet. Example 5 60 g of mesitylene, 80 g of aluminum chloride and 60.5 cm 3 of methyl methoxychloroacetate are in 250 cm3 of methylene chloride, as described in Example 1, reacted and worked up.
Ausbeute: 82 g a-Methoxy-2,4,6-trimethylphenylessigsäuremethylester (73°/o der Theorie), Kp.lo = 1500C. Yield: 82 g of methyl α-methoxy-2,4,6-trimethylphenylacetate (73% of theory), Kp.lo = 1500C.
Beispiel 6 76,5g p-Nitroanisol, 156 g Zinntetrachlorid und 60,5 cm3 Methoxychloressigsäuremethylester werden in 300 cm3 Methylenchlorid bei 42"C innerhalb 3 Stunden umgesetzt. Example 6 76.5 g of p-nitroanisole, 156 g of tin tetrachloride and 60.5 cm3 Methoxychloroacetic acid methyl ester in 300 cm3 of methylene chloride at 42 "C within 3 hours implemented.
Ausbeute: 105 g O-Methyl-[2-methoxy-5-nitro]-mandelsäuremethylester (820/oder Theorie), F. = 60° C. Yield: 105 g of O-methyl- [2-methoxy-5-nitro] -mandelic acid methyl ester (820 / or theory), F. = 60 ° C.
Beispiel 7 64 g Naphthalin, 156 g Zinntetrachlorid und 60,5 g Methoxychloressigsäuremethylester werden in 250 cm3 Methylenchlorid, wie im Beispiel 1 beschrieben, umgesetzt und aufgearbeitet. Example 7 64 g of naphthalene, 156 g of tin tetrachloride and 60.5 g of methyl methoxychloroacetate are in 250 cm3 of methylene chloride, as described in Example 1, reacted and worked up.
Ausbeute: 95,8 g a-Methoxynaphthyl- 1-essigsäuremethylester (830/0 der Theorie), Kp.2 = 1510 C. Yield: 95.8 g of methyl a-methoxynaphthyl-1-acetic acid (830/0 of theory), Kp.2 = 1510 C.
Beispiel 8 60 g Polystyrolharz (60/0 Divinylbenzol, vernetzt) werden 1 Stunde in Methylenchlorid vorgequollen und dann mit einer Mischung von 80 g Aluminiumchlorid und 55,5 cm3 a-Methoxy-a-chloressigsäuremethylester in insgesamt 350cm3 Methylenchlorid bei 5 bis 10°C umgesetzt. Nach 14 Stunden Stehenlassen bei Zimmertemperatur wird auf Eis gegossen, das Reaktionsprodukt abgesaugt, 1 Stunde in destilliertem Wasser gerührt und anschließend je 10 Minuten mit Methanol und Äther gewaschen. pas Reaktionsprodukt wird im Vakuumexsikkator über Paraffin bei 100"C getrocknet. Man erhält ein Polystyrolharz, dessen Benzolkerne nach Ausweis der Methoxylbestimmung zu etwa 300/0 durch den a-Methoxyessigsäuremethylesterrest substituiert sind. Example 8 60 g of polystyrene resin (60/0 divinylbenzene, crosslinked) are used Preswollen for 1 hour in methylene chloride and then with a mixture of 80 g of aluminum chloride and 55.5 cm3 of methyl α-methoxy-α-chloroacetate in a total of 350 cm3 of methylene chloride reacted at 5 to 10 ° C. After standing at room temperature for 14 hours Poured onto ice, the reaction product filtered off with suction, in distilled water for 1 hour stirred and then washed for 10 minutes each with methanol and ether. pas reaction product is dried in a vacuum desiccator over paraffin at 100 ° C. A polystyrene resin is obtained, its benzene nuclei according to the methoxyl determination to about 300/0 through the a-methoxyacetic acid methyl ester residue are substituted.
Beispiel 9 52 g Polystyrolharz (4,50/o Divinylbenzol, vernetzt, porös) werden 1 Stunde in Methylenchlorid vorgequollen und dann mit einer Mischung von 156 g Zinntetrachlorid in 350 cm3 Methylenchlorid und 60,5 cm3 a - Methoxy - a - chloressigsäuremethylester 8 Stunden bei 42"C umgesetzt. Anschließend gießt miii itif Eis, saugt das Reaktionsprodukt ab, rührt 1 Stunde mit destilliertem Wasser und anschließend je lO PvEmuten mit Methanol und Ather. Nach Trocknen im Vakuum über Paraffin erhält man ein Polystyrolharz, dessen Benzolkerne zu 9()O/ durch den cl-hiIethoxyessigsäuremethylesterrest substituiert sind. Example 9 52 g polystyrene resin (4.50 / o divinylbenzene, crosslinked, porous) are preswollen for 1 hour in methylene chloride and then with a mixture of 156 g tin tetrachloride in 350 cm3 methylene chloride and 60.5 cm3 a - methoxy - a - methyl chloroacetate reacted for 8 hours at 42 ° C. Then pour miii itif ice, sucks the reaction product off, stirs with distilled water for 1 hour and then 10 PvEmuten each with methanol and ether. After drying in vacuo A polystyrene resin is obtained via paraffin, the benzene nuclei of which are 9 () O / by the Cl-hiIethoxyessigsäuremethylesterrest are substituted.
Beispiel 10 70 g Brenzschleimsäureäthylester, 156 g Zinntetrachlorid und 60,5 cm³ Methoxychloressigsäuremethyl ester werden in 250 cm3 Methylenchlorid, wie im Beispiel 6 beschrieben, umgesetzt und aufgearbeitet. Example 10 70 g of ethyl pyrogenate, 156 g of tin tetrachloride and 60.5 cm³ methoxychloroacetic acid methyl ester in 250 cm3 methylene chloride, as described in Example 6, implemented and worked up.
Ausbeute: 75 g [2-Äthoxycarbonylfuranyl-(5)]-methoxyessigsäuremethylester (620/0 der Theorie), Kp.10-2 = 110°C, F. = 70 bis 72°C. Yield: 75 g of [2-ethoxycarbonylfuranyl- (5)] methoxyacetic acid methyl ester (620/0 of theory), bp 10-2 = 110 ° C, m.p. = 70 to 72 ° C.
Beispiel 11 42 g Thiophen, 156 g Zinntetrachlorid und 60,5 cm³ Methoxychloressigsäuremethylester werden in 250 cm3 Methylenchlorid bei einer Innentemperatur von - 10°C innerhalb von 10 Minuten umgesetzt und wie üblich aufgearbeitet. Example 11 42 g of thiophene, 156 g of tin tetrachloride and 60.5 cm 3 of methyl methoxychloroacetate are in 250 cm3 of methylene chloride at an internal temperature of -10 ° C within implemented by 10 minutes and worked up as usual.
Ausbeute: 19,5 g Thienyl-(2)-methoxyessigsäuremethylester (21 0/o der Theorie), Kp.lo = 124 bis 125°C. Yield: 19.5 g of methyl thienyl (2) methoxyacetate (21% theory), Kp.lo = 124 to 125 ° C.
B e i s p i e l 12 59 g Indol und 56cm3 Methoxychloressigsäuremethylester werden unter Zugabe katalytischer Mengen (etwa 1 g) Bortrifluoridätherat in 300 cm³ Ather gelöst und 24 Stunden im Dunkeln bei Raumtemperatur belassen. Die abgeschiedenen k: rlstalle werden abgesaugt und mit 100 cm³ Äther nachgewaschen. For example, 12 59 g indole and 56 cm3 methyl methoxychloroacetate are added with the addition of catalytic amounts (about 1 g) boron trifluoride etherate in 300 cm³ Dissolved ether and left for 24 hours in the dark at room temperature. The departed K: rlstalle are sucked off and washed with 100 cm³ of ether.
Ausbeute: 40 g Indolyl-(3)-methoxyessigsäuremethylester (37% der Theorie), F. = 168 bis 169 C. Yield: 40 g of methyl indolyl (3) methoxyacetate (37% of Theory), F. = 168 to 169 C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED48510A DE1274127B (en) | 1965-10-26 | 1965-10-26 | Process for the preparation of ª ‡ -Alkoxyarylessigsaeurealkylestern |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED48510A DE1274127B (en) | 1965-10-26 | 1965-10-26 | Process for the preparation of ª ‡ -Alkoxyarylessigsaeurealkylestern |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1274127B true DE1274127B (en) | 1968-08-01 |
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ID=7051226
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DED48510A Pending DE1274127B (en) | 1965-10-26 | 1965-10-26 | Process for the preparation of ª ‡ -Alkoxyarylessigsaeurealkylestern |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1274127B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996007633A1 (en) * | 1994-09-10 | 1996-03-14 | Basf Aktiengesellschaft | Phenylacetic acid alkyl esters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3038002A (en) * | 1957-08-19 | 1962-06-05 | Fundamental Res Inc | Syntheses of alpha-methoxyphenylacetates |
| US3086990A (en) * | 1959-07-10 | 1963-04-23 | Fundamental Res Inc | Halogenated alpha-methoxyphenyl acetic acids |
-
1965
- 1965-10-26 DE DED48510A patent/DE1274127B/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3038002A (en) * | 1957-08-19 | 1962-06-05 | Fundamental Res Inc | Syntheses of alpha-methoxyphenylacetates |
| US3086990A (en) * | 1959-07-10 | 1963-04-23 | Fundamental Res Inc | Halogenated alpha-methoxyphenyl acetic acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996007633A1 (en) * | 1994-09-10 | 1996-03-14 | Basf Aktiengesellschaft | Phenylacetic acid alkyl esters |
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