DE213593C - - Google Patents
Info
- Publication number
- DE213593C DE213593C DENDAT213593D DE213593DA DE213593C DE 213593 C DE213593 C DE 213593C DE NDAT213593 D DENDAT213593 D DE NDAT213593D DE 213593D A DE213593D A DE 213593DA DE 213593 C DE213593 C DE 213593C
- Authority
- DE
- Germany
- Prior art keywords
- acids
- acid
- parts
- aromatic series
- bromoethyl
- 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.)
- Active
Links
- 239000002253 acid Substances 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 5
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- -1 haloalkyl ethers Chemical class 0.000 claims description 3
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 150000001896 cresols Chemical class 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N Manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VCYNKCKSPFGUSA-UHFFFAOYSA-N 1-(2-bromoethoxy)-4-methylbenzene Chemical compound CC1=CC=C(OCCBr)C=C1 VCYNKCKSPFGUSA-UHFFFAOYSA-N 0.000 description 2
- VZJVWSHVAAUDKD-UHFFFAOYSA-N Potassium permanganate Chemical compound [K+].[O-][Mn](=O)(=O)=O VZJVWSHVAAUDKD-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N O-Cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drugs Drugs 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000004438 haloalkoxy group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- NPDODHDPVPPRDJ-UHFFFAOYSA-N permanganate Chemical compound [O-][Mn](=O)(=O)=O NPDODHDPVPPRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
;t ν.'ί!<ΐ(·: fficijöc/; t ν.'ί! <ΐ (: fficijöc /
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
^F PATENTSCHRIFT^ F PATENT LETTERING
KLASSE 12 #. GRUPPECLASS 12 #. GROUP
Bromalkyloxycarbonsäuren in Form ihrer Ester, Amide usw., erhält man durch Behandeln
von Oxycarbonsäuren mit großem Überschuß von DihalogenkohlenWasserstoffen.
Unmittelbar, ohne den Umweg über die Ester, Amide usw. erhält man diese Säuren,
soweit sie der aromatischen Reihe angehören, wie nunmehr gefunden wurde, dadurch, daß
man Halogenalkyloxykohlenwasserstoffe der ίο aromatischen Reihe mit Kohlenwasserstoffseitenkette
— am einfachsten die Halogenalkyläther der Kresole, ζ. B. ■ .Bromoalkyloxycarboxylic acids in the form of their esters, amides, etc., are obtained by treating oxycarboxylic acids with a large excess of dihalocarbons.
Immediately, without going through the esters, amides, etc., these acids, insofar as they belong to the aromatic series, as has now been found, are obtained by using haloalkyloxy hydrocarbons of the ίο aromatic series with hydrocarbon side chains - the simplest way is the haloalkyl ethers of the cresols, ζ. B. ■.
Br-C2H1-OC6H^CH3,Br-C 2 H 1 -OC 6 H ^ CH 3 ,
mit solchen Oxydationsmitteln, welche Toluol zu Benzoesäure oxydieren, wie Permanganat, Bichromat und Schwefelsäure oder Braunstein und Schwefelsäure, behandelt. Die Halogenalkyloxyseitenkette bleibt dabei unversehrt; lediglich die Kohlenwasserstoffseitenkette wird zur Carbonsäuregruppe oxydiert.with oxidizing agents that oxidize toluene to benzoic acid, such as permanganate, Bichromate and sulfuric acid or manganese dioxide and sulfuric acid. The haloalkyloxy side chain remains intact; only the hydrocarbon side chain is oxidized to the carboxylic acid group.
30 Teile p-Kresolbromäthyläther
CH3 30 parts of p-cresol bromoethyl ether
CH 3
0-CH2-CH2-Br0-CH 2 -CH 2 -Br
(vgl. Ber. 24 [1891] S. 190) werden mit 750 Teilen Wasser zusammengerührt und in der !5 Hitze langsam mit 45 Teilen Kaliumpermanganat versetzt. Nachdem das letztere aufgebraucht ist, wird vom Braunstein abfiltriert, das Filtrat durch Ausäthern von etwa unverbrauchtem Ausgangsprodukt befreit und dann angesäuert. Die so erhaltene Bromätliyl-p-oxybenzoesäure (cf. Ber. 24 [1891] p. 190) with 750 parts Stirring water together and slowly adding 45 parts of potassium permanganate in the heat offset. After the latter is used up, the brownstone is filtered off, the filtrate is freed from any unused starting product by etherification and then acidified. The bromoethyl-p-oxybenzoic acid thus obtained
COOHCOOH
4545
0-CH2-CH2-Br0-CH 2 -CH 2 -Br
besitzt nach dem Umkristallisieren aus Aikohol einen Schmelzpunkt von ungefähr 178 ° C. Sie besteht aus weißen, glänzenden Blättchen, ist leicht löslich in verdünntem Alkohol, Äther, schwerer in Wasser; ihr Äthylester schmilzt bei ungefähr 760C. Die auf gleiche Weise aus dem Bromäthyläther des o-Kresols (vgl. Ann. 357 [1907], S. 356) hergestellte BromäthylsalicylsäureAfter recrystallization from alcohol, it has a melting point of about 178 ° C. It consists of white, shiny flakes, is easily soluble in dilute alcohol, ether, more difficult in water; The ethyl ester melting at about 76 0 C. The Bromäthylsalicylsäure prepared in the same manner from the Bromäthyläther of o-cresol (see FIG. Ann. 357 [1907], p 356)
COOHCOOH
6060
^0-CH2-CH2-Br^ 0-CH 2 -CH 2 -Br
schmilzt bei ungefähr 164 ° C, ist in Alkohol, Äther leicht, schwerer in heißem Wasser, sehr schwer in kaltem Wasser löslich.melts at about 164 ° C, is light in alcohol, ether, heavier in hot water, very difficult to dissolve in cold water.
20 Teile p-Kresolbromäthyläther werden in einem verbleiten Kessel mit 300 Teilen 25 pro-20 parts of p-cresol bromoethyl ether are placed in a leaded kettle with 300 parts of 25 pro
zentiger Schwefelsäure und unter starkem Umrühren nach und nach mit 35 Teilen Braunstein von etwa 70 Prozent Gehalt an Mn O2 versetzt, wobei man zuletzt durch Wärmezufuhr auf ungefähr 85 ° erhitzt. Nachdem man neutralisiert und unverändertes Ausgangsprodukt mit Wasserdampf abgetrieben hat, wird von ungelösten Anteilen abfiltriert und das Filtrat angesäuert, wobei rohe Bromäthyl p-oxybenzoesäure ausfällt. Aus der Mutterlauge kann durch Ausäthern noch Bromäthylp-oxybenzoesäure gewonnen werden. Durch Umlösen mittels Bicarbonat und Wiederausfällen mit Mineralsäure und Umkristallisieren aus verdünntem Alkohol gewinnt man die Säure rein.percent sulfuric acid and, with vigorous stirring, gradually added 35 parts of manganese dioxide with about 70 percent Mn O 2 content, finally heating to about 85 ° by adding heat. After neutralization and unchanged starting material has been driven off with steam, undissolved components are filtered off and the filtrate is acidified, crude bromoethyl-p-oxybenzoic acid precipitating out. Bromoethylp-oxybenzoic acid can also be obtained from the mother liquor by etherification. The acid is obtained in pure form by redissolving with bicarbonate and reprecipitation with mineral acid and recrystallization from dilute alcohol.
Die Halogenalkyloxymonocarbonsäuren der aromatischen Reihe dienen zur Herstellung von Arzneistoffen.The haloalkyloxymonocarboxylic acids of the aromatic series are used for production of drugs.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE213593C true DE213593C (en) |
Family
ID=475228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT213593D Active DE213593C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE213593C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2696498A (en) * | 1951-02-07 | 1954-12-07 | Gen Aniline & Film Corp | Process of preparing (beta halo alkoxy) benzoic acid |
-
0
- DE DENDAT213593D patent/DE213593C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2696498A (en) * | 1951-02-07 | 1954-12-07 | Gen Aniline & Film Corp | Process of preparing (beta halo alkoxy) benzoic acid |
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