DE1930328A1 - 3-nitro-2,6-dihydroxybenzoic acid esters and process for their preparation - Google Patents
3-nitro-2,6-dihydroxybenzoic acid esters and process for their preparationInfo
- Publication number
- DE1930328A1 DE1930328A1 DE19691930328 DE1930328A DE1930328A1 DE 1930328 A1 DE1930328 A1 DE 1930328A1 DE 19691930328 DE19691930328 DE 19691930328 DE 1930328 A DE1930328 A DE 1930328A DE 1930328 A1 DE1930328 A1 DE 1930328A1
- Authority
- DE
- Germany
- Prior art keywords
- nitro
- dihydroxybenzoic acid
- phenyl
- preparation
- acid esters
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
- C07C205/57—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C205/59—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
- C07C205/60—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms in ortho-position to the carboxyl group, e.g. nitro-salicylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
FARBWERKE HOECHST AG. vormals Meister Lucius & Brüning Aktenzeichen: P - Fw 6107FARBWERKE HOECHST AG. formerly Meister Lucius & Brüning file number: P - Fw 6107
Datum: 10. Juni 1969
Dr.Ot/brDate: June 10, 1969
Dr.Ot / br
3-Nitro-2,6-dihydroxybenzoesäureester und Verfahren zu ihrer Herstellung3-nitro-2,6-dihydroxybenzoic acid ester and method too their manufacture
Gegenstand der Erfindung sind 3-Nitro-286-dihydroxybenzoesäureester der allgemeinen Formel IThe invention relates to 3-nitro-2 8 6-dihydroxybenzoic acid esters of the general formula I
(D(D
HO j OH COORHO j OH COOR
in der X Wasserstoff, Chlor, Brom und Jod und R ein niederes Alkyl mit 1 bis h C-Atomen, oder Phenyl, Halogenphenyl, Alkylphenyl oder Nitrophenyl bedeutet, und Verfahren zu ihrer Herstellung, dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formel IIin which X is hydrogen, chlorine, bromine and iodine and R is a lower alkyl with 1 to h carbon atoms, or phenyl, halophenyl, alkylphenyl or nitrophenyl, and a process for their preparation, characterized in that compounds of the general formula II
(H)(H)
wobei X und R obige Bedeutung haben9 nitriert, oder Verbindungen der allgemeinen Formel IIIwhere X and R have the above meaning 9 nitrated, or compounds of the general formula III
009883/2199009883/2199
•a P mm • a P mm
(III)(III)
wobei R die obige Bedeutung hat, in der 5-Steilung halogeniert,where R has the above meaning, halogenated in the 5-position,
Als Ausgangsstoffe der Formel II werden erfindungsgemäß 2, 6-Dihydroxybenzoesäureester verwendet, in denen X Wasser·» stoff, Chlor, Brom und Jod und R ein niederes Alkyl mit 1 bis 4 C-Atomen, oder Phenyl, Halogenphenyl, Alkylphenyl oder Nitrophenyl bedeutet.According to the invention, the starting materials of the formula II are 2, 6-dihydroxybenzoic acid ester used, in which X water · » substance, chlorine, bromine and iodine and R is a lower alkyl with 1 to 4 carbon atoms, or phenyl, halophenyl, alkylphenyl or Means nitrophenyl.
Als Ausgangsstoffe der Formel III werden erfindungsgemäß 3-Nitro-2,6-dihydroxybenzoesäureester verwendet, in denen R ein niederes Alkyl mit T bis h C-Atomen oder Phenyl, Halogenphenyl, Alkylphenyl oder Nitrophenyl bedeutet.According to the invention, 3-nitro-2,6-dihydroxybenzoic acid esters in which R is a lower alkyl with T to h carbon atoms or phenyl, halophenyl, alkylphenyl or nitrophenyl are used as starting materials of the formula III.
Diese Ester werden nach ddm erfindungsgemäßen Verfahren dadurch hergestellt, daß man 2,6-Dihydroxybenzoesäureester der Formel II, gegebenenfalls nach erfolgter Halogenierung, nitriert, oder 3-Nitro-2,6-dihydroxybenzoesäureester der Formel III halogeniert.These esters are produced by the process according to the invention prepared by adding 2,6-dihydroxybenzoic acid ester of the formula II, optionally after halogenation has taken place, nitrated, or 3-nitro-2,6-dihydroxybenzoic acid ester of Formula III halogenated.
Die Umsetzung wird derart durchgeführt, daß man die 2,6-Dihydroxybenzoesäureester der Formel II mit Nitrierungsmitteln in einem unter den Reaktionsbedingungen inerten Lösungsmittel bei Temperaturen zwischen O und 40 C umsetzt, oder daß man 3-Nitro-2,6-dihydroxybenzoesäureester der Formel III mit Halogenierungsmitteln in inerten Lösungsmitteln bei Temperaturen zwischen -20 bis + l60 C reagieren läßt. Als Nitrierungsmittel verwendet man vorzugsweiseThe reaction is carried out in such a way that the 2,6-dihydroxybenzoic acid ester of formula II with nitrating agents in an inert under the reaction conditions Reacts solvents at temperatures between 0 and 40 C, or that 3-nitro-2,6-dihydroxybenzoic acid ester of Formula III react with halogenating agents in inert solvents at temperatures between -20 to + 160 C. leaves. The nitrating agent used is preferably
009883/2199009883/2199
65 - 1OO$i(ye Salpetersäure, als Lösungsmittel konirtien insbesondere Eisessig und Schwefelsäure in Betracht. Die Reaktion wird bei Temperaturen zwischen 0° und 40°C, vorzugsweise 10° bis 20°C, durchgeführt. Als Halogonierungsmittel kommen vorzugsweise Chlor, Sulfurylchlorid, Brom, Jod und Jodmonochlorid, als inerte Lösungsmittel insbesondere Chloroform, Tetrachlorkohlenstoff, Benzol und Eisessig in Betracht. Die Reaktion wird bei -20° bis +16O C, vorzugsweise 0 bis 120°C, durchgeführt. 65-100 $ i (ye nitric acid, especially glacial acetic acid and sulfuric acid as solvents. The reaction is carried out at temperatures between 0 ° and 40 ° C., preferably 10 ° to 20 ° C. The halogenating agents are preferably chlorine, sulfuryl chloride, Bromine, iodine and iodine monochloride, especially chloroform, carbon tetrachloride, benzene and glacial acetic acid as inert solvents .
Aus "Monatshefte für Chemie" 3*4, Seite 818 (1913) war bekannt, daß die Nitrierung von ^^esorcylsäure unter Abspaltung einer Hydroxylgruppe zur Trinitrosalicylsäure führt. Es war daher überraschend und nicht vorhersehbar, daß die Nitrierung von ^-Resorcylsäureestern so glatt und in guter Ausbeute die Mononitrierungsprodukte liefern würde.From "MONTHS FOR CHEMISTRY" 3 * 4, page 818 (1913) it was known that the nitration of ^^ esorcylic acid with cleavage a hydroxyl group leads to trinitrosalicylic acid. It was therefore surprising and not predictable that the nitration of ^ -resorcyläureestern so smoothly and in good Yield which would provide mononitration products.
Die Verfahrensprodiakte dienen zur Herstellung der 3-Nitro-2,6-dihydroxybenzoesäureanilide, welche wertvolle Antihelminthika darstellen.The process products are used to produce the 3-nitro-2,6-dihydroxybenzoic acid anilides, which are valuable antihelminthics.
3-Nitro-2,6-dihydroxybenzoesäuremethylester3-nitro-2,6-dihydroxybenzoic acid methyl ester
Zu einer Lösung von 88 g 2,6-'Dihydroxybenzoesäuremethylester in 420 ml Eisessig läßt man unter Rühren und Kühlung innerhalb einer Stunde 16O ml 65#ige Salpetersäure so zutropfen, daß die Innentemperatür sich bei 10 bis 15 C hält. Während der Nitrierung fällt der 3-Nitro-2,6-dihydroxybenzoesüuremethylester kristallin aus. Man rührt noch eine Stunde bei 10°C nach, saugt die Kristalle ab und wäscht sie mit 320 ml Methanol. Ausbeute: 70 g. F = 153° - 155°C.To a solution of 88 g of methyl 2,6-dihydroxybenzoate in 420 ml of glacial acetic acid, 16O ml of 65 # strength nitric acid are added dropwise over the course of one hour while stirring and cooling, that the internal temperature is kept at 10 to 15 C. While the nitration precipitates the 3-nitro-2,6-dihydroxybenzoic acid methyl ester in crystalline form. The mixture is stirred for another hour 10 ° C, sucks off the crystals and washes them with 320 ml Methanol. Yield: 70 g. F = 153 ° - 155 ° C.
009883/21.99009883 / 21.99
3-Nitro-2,6-dihydroxybenzoesäurephenylester3-nitro-2,6-dihydroxybenzoic acid phenyl ester
Zu k6 g 2,6-Dihydroxybenzoesäurephenyl'ester in 16O ml Eisessig läßt man unter Rühren und Kühlung 62 ml 65/^ige Salpetersäure innerhalb einer Stunde so zutropfen, daß die Innentemperatur sich unter 10 Cpäl^t· Man rührt 20 Minuten bei 10 C nach, saugt die ausgefallenen Kristalle ab, wäscht sie mit 50 ml Eisessig, I80 ml Wasser und trocknet sie bei Raumtemperatir. Ausbeute: 40 g. F = 119° - 121°C. Der reine 3-Nitro-2,6-dihydroxybenzoesäurephenylester schmilzt nach dem Umkristallisieren aus CCl. bei 121° - 123°C.To k6 g of 2,6-Dihydroxybenzoesäurephenyl'ester in 16O ml of glacial acetic acid is allowed under stirring and cooling, 62 ml of 65 / ^ nitric acid is added dropwise within one hour so that the internal temperature below 10 Cpäl ^ t · M at stirred for 20 minutes at 10 C., sucks off the precipitated crystals, washes them with 50 ml of glacial acetic acid, 180 ml of water and dries them at room temperature. Yield: 40 g. F = 119 ° - 121 ° C. The pure phenyl 3-nitro-2,6-dihydroxybenzoate melts after recrystallization from CCl. at 121 ° - 123 ° C.
5-Chlor-3-nitro-2, 6-dihyd'röxybenzoe säurephenyle s ter5-chloro-3-nitro-2,6-dihydroxybenzoic acid phenyl ester
a) k6 g 2,6-Dihydroxybenzoesäurephenylester, 230 ml Benzol und 27 g Sulfurylchlorid werden zusammen 2 Stunden unter Rückfluß erhitzt. Anschließend wird die Lösung im Vakuum eingeengt und der Rückstand aus Diisopropyläther-Benzol (2:1) umkristallisiert. Man erhält 35 g 3-Chlor-2,6-dihydroxybenzoesäurephenylester. F = 125° - 126°C,a) k6 g of phenyl 2,6-dihydroxybenzoate, 230 ml of benzene and 27 g of sulfuryl chloride are refluxed together for 2 hours. The solution is then concentrated in vacuo and the residue is recrystallized from diisopropyl ether-benzene (2: 1). 35 g of phenyl 3-chloro-2,6-dihydroxybenzoate are obtained. F = 125 ° - 126 ° C,
b) Zu 19 e 3-Chlor-2,6-dihydroxybenzoesäurephenylester inb) To 19 e 3-chloro-2,6-dihydroxybenzoic acid phenyl ester in
75 n>l Eisessig läßt man innerhalb 20 Minuten unter Rühren 22 ml 65#ige Salpetersäure bei 15°C bis 20°C zutropfen. Man rührt eine Stunde bei 15°C nach, saugt den kristallinen Niederschlag ab, wäscht ihn mit 25 ml Eisessig und kristallisiert aus Benzol um. Man erhält Ik g 5-Chlor-3-nitro-2,6-dihydroxybenzoesäurephenylester. F = °75 n> l glacial acetic acid is allowed to drop in 22 ml of 65 # nitric acid at 15 ° C to 20 ° C within 20 minutes with stirring. The mixture is stirred for one hour at 15 ° C., the crystalline precipitate is filtered off with suction, washed with 25 ml of glacial acetic acid and recrystallized from benzene. Ik g of 5-chloro-3-nitro-2,6-dihydroxybenzoic acid phenyl ester is obtained. F = °
009883/2199009883/2199
5-Chlor-3-nitro-2f 6-dihydroxybenzoesäurephenylester5-Chloro-3-nitro-2 f 6-dihydroxybenzoic acid phenyl ester
14 g 3-Nitro-2,6-dihydroxybenzoesäurephenylester werden in 25 ml Eisessig mit 7»5 ml Sulfurylchlorid 5 Minuten auf 700C erhitzt. Danach läßt man bei Raumtemperatur 15 Stunden stehen, saugt die Kristalle ab und wäscht sie mit 15 ml Benzol. Aus Benzol umkristallisiert erhält man 10,7 g 5-Chlor-3-nitro-2,6-dihydroxybenzoesäurephenylester. F = 145°C.14 g of phenyl 3-nitro-2,6-dihydroxybenzoate are heated in 25 ml of glacial acetic acid with 7.5 ml of sulfuryl chloride to 70 ° C. for 5 minutes. The mixture is then left to stand at room temperature for 15 hours, and the crystals are filtered off with suction and washed with 15 ml of benzene. Recrystallized from benzene, 10.7 g of 5-chloro-3-nitro-2,6-dihydroxybenzoic acid phenyl ester are obtained. F = 145 ° C.
5-Brom-3-nitro-2,6-dihydroxybenzoesäurephenylester 5-bromo-3-n itro-2,6-dihydroxybenzoesäurephenylester
Zu 11,5 S 3-Nitro-2,6-dihydroxybenzoesäurephenylester in 30 ml Eisessig läßt man innerhalb 5 Minuten 7»0 & Brom bei Raumtemperatur zutropfen und steigert dann die Temperatur des Gemisches innerhalb JO Minuten auf 70 C. Die Lösung wird abgekühlt, die ausgeschiedenen Kristalle werden abgesaugt r mit 5 ral Eisessig gewaschen und aus Eisessig umkristallisiert. Man erhält 8,2 g 5~Brom-3-nitro-2,6-dihydroxybenzoesäurephenylester. F = 147 C.To 11.5 S 3-nitro-2,6-dihydroxybenzoesäurephenylester in 30 ml of glacial acetic acid is allowed to over 5 minutes 7 »0 & bromine are added dropwise at room temperature and then the temperature increases of the mixture within JO minutes at 70 C. The solution is cooled, the precipitated crystals are filtered off with suction r washed with 5 ral glacial acetic acid and recrystallized from glacial acetic acid. 8.2 g of phenyl 5-bromo-3-nitro-2,6-dihydroxybenzoate are obtained. F = 147 C.
009883/2199009883/2199
Claims (1)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691930328 DE1930328A1 (en) | 1969-06-14 | 1969-06-14 | 3-nitro-2,6-dihydroxybenzoic acid esters and process for their preparation |
| JP4839170A JPS4823434B1 (en) | 1969-06-14 | 1970-06-04 | |
| GB2836270A GB1294298A (en) | 1969-06-14 | 1970-06-11 | 3-nitro-2,6-dihydroxy benzoic acid esters and process for their manufactrue |
| CH881670A CH540879A (en) | 1969-06-14 | 1970-06-11 | Process for the preparation of 3-nitro-2,6-dihydroxy-benzoic acid esters |
| AT532070A AT305259B (en) | 1969-06-14 | 1970-06-12 | Process for the preparation of new 3-nitro-2,6-dihydroxybenzoic acid esters |
| NL7008611A NL7008611A (en) | 1969-06-14 | 1970-06-12 | |
| BE751979D BE751979A (en) | 1969-06-14 | 1970-06-15 | 3-NITRO-2,6-DIHYDROXY-BENZOIC ACID ESTERS AND THEIR PREPARATION |
| FR7021863A FR2052567A5 (en) | 1969-06-14 | 1970-06-15 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19691930328 DE1930328A1 (en) | 1969-06-14 | 1969-06-14 | 3-nitro-2,6-dihydroxybenzoic acid esters and process for their preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1930328A1 true DE1930328A1 (en) | 1971-01-14 |
Family
ID=5737043
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19691930328 Pending DE1930328A1 (en) | 1969-06-14 | 1969-06-14 | 3-nitro-2,6-dihydroxybenzoic acid esters and process for their preparation |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS4823434B1 (en) |
| AT (1) | AT305259B (en) |
| BE (1) | BE751979A (en) |
| CH (1) | CH540879A (en) |
| DE (1) | DE1930328A1 (en) |
| FR (1) | FR2052567A5 (en) |
| GB (1) | GB1294298A (en) |
| NL (1) | NL7008611A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0489670A1 (en) * | 1990-12-06 | 1992-06-10 | Rhone-Poulenc Agrochimie | 2,6 Alkoxyphenyl alkylketone and herbicidal derivatives |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5580441U (en) * | 1978-11-30 | 1980-06-03 |
-
1969
- 1969-06-14 DE DE19691930328 patent/DE1930328A1/en active Pending
-
1970
- 1970-06-04 JP JP4839170A patent/JPS4823434B1/ja active Pending
- 1970-06-11 CH CH881670A patent/CH540879A/en not_active IP Right Cessation
- 1970-06-11 GB GB2836270A patent/GB1294298A/en not_active Expired
- 1970-06-12 AT AT532070A patent/AT305259B/en not_active IP Right Cessation
- 1970-06-12 NL NL7008611A patent/NL7008611A/xx unknown
- 1970-06-15 FR FR7021863A patent/FR2052567A5/fr not_active Expired
- 1970-06-15 BE BE751979D patent/BE751979A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0489670A1 (en) * | 1990-12-06 | 1992-06-10 | Rhone-Poulenc Agrochimie | 2,6 Alkoxyphenyl alkylketone and herbicidal derivatives |
| FR2670205A1 (en) * | 1990-12-06 | 1992-06-12 | Rhone Poulenc Agrochimie | 2,6-ALKOXYPENYL ALKYLCETONE AND DERIVATIVES HERBICIDES. |
Also Published As
| Publication number | Publication date |
|---|---|
| NL7008611A (en) | 1970-12-16 |
| JPS4823434B1 (en) | 1973-07-13 |
| BE751979A (en) | 1970-12-15 |
| GB1294298A (en) | 1972-10-25 |
| FR2052567A5 (en) | 1971-04-09 |
| AT305259B (en) | 1973-02-26 |
| CH540879A (en) | 1973-08-31 |
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