DE722338C - Process for the preparation of p-nitrobenzoic acid esters - Google Patents
Process for the preparation of p-nitrobenzoic acid estersInfo
- Publication number
- DE722338C DE722338C DEI64658D DEI0064658D DE722338C DE 722338 C DE722338 C DE 722338C DE I64658 D DEI64658 D DE I64658D DE I0064658 D DEI0064658 D DE I0064658D DE 722338 C DE722338 C DE 722338C
- Authority
- DE
- Germany
- Prior art keywords
- nitrobenzoic acid
- preparation
- acid
- acid esters
- heptyl
- 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
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical class OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- FPRSKHDBFYFDHU-UHFFFAOYSA-N 4-nitrobenzenecarbothioic s-acid Chemical compound [O-][N+](=O)C1=CC=C(C(S)=O)C=C1 FPRSKHDBFYFDHU-UHFFFAOYSA-N 0.000 claims description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- -1 heptyl halide Chemical class 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- LCFKURIJYIJNRU-UHFFFAOYSA-N 2-methylhexan-1-ol Chemical compound CCCCC(C)CO LCFKURIJYIJNRU-UHFFFAOYSA-N 0.000 description 2
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 208000022362 bacterial infectious disease Diseases 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- CETWDUZRCINIHU-UHFFFAOYSA-N methyl-n-amyl-carbinol Natural products CCCCCC(C)O CETWDUZRCINIHU-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DGHALKQQEBRFBQ-UHFFFAOYSA-N CC(C)CCCCOC(C(C=C1)=CC=C1[N+]([O-])=O)=O Chemical compound CC(C)CCCCOC(C(C=C1)=CC=C1[N+]([O-])=O)=O DGHALKQQEBRFBQ-UHFFFAOYSA-N 0.000 description 1
- YTQUPTOSKQVXRA-UHFFFAOYSA-N CCCCCCC[Mg].[O] Chemical compound CCCCCCC[Mg].[O] YTQUPTOSKQVXRA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VPIAKHNXCOTPAY-UHFFFAOYSA-N Heptane-1-thiol Chemical compound CCCCCCCS VPIAKHNXCOTPAY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- WMUVYRILEXKYQK-UHFFFAOYSA-N heptyl 4-nitrobenzoate Chemical compound CCCCCCCOC(=O)C1=CC=C([N+]([O-])=O)C=C1 WMUVYRILEXKYQK-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Darstellung von p-Nitrobenzoesäureestern Es ist bekannt, daß Ester der p-Nitrobenzoesä.ure mit Cyclohexanol und Guajakol gegen Erreger bakterieller Infektionskrankheiten, wie Streptokokken und Pneumokokken, wirksam sind.Process for the preparation of p-nitrobenzoic acid esters It is known that esters of p-nitrobenzoesä.ure with cyclohexanol and guaiacol against pathogens bacterial Infectious diseases such as streptococci and pneumococci are effective.
Es wurde nun gefunden, daß man zu Verbindungen, die gegen bakterielle Infektionskrankheiten, im besonderen gegen die durch Pneumokokken verursachten Erkrankungen, hoch wirksam sind, auch dann gelangt, wenn man die Ester der p-Nitrobenzoesäure oder der p-Nitrothiobenzoesäure bzw. ihrer Substitutionsprodukte mit einem eine gerade oder verzweigte, jedoch offene Kohlenstoffkette enthaltenden aliphatischen Alkohol oder Mercaptan mit 7 Kohlenstoffatomen darstellt. Der gerade oder verzweigte Heptylalkohol oder das Heptylmercaptan können primär, sekundär oder tertiär sein; es können auch Gemische der Alkohole oder der Mercaptane verwendet werden.It has now been found that compounds which are highly effective against bacterial infectious diseases, in particular against diseases caused by pneumococci, can also be obtained if the esters of p-nitrobenzoic acid or p-nitrothiobenzoic acid or their substitution products are used represents a straight or branched but open carbon chain containing aliphatic alcohol or mercaptan with 7 carbon atoms. The straight or branched heptyl alcohol or the heptyl mercaptan can be primary, secondary or tertiary; mixtures of the alcohols or the mercaptans can also be used.
Die newcn Ester sind meist flüssig und in hoher Konzentration in vl löslich. Die Darstellung der neuen Ester ezfolgt unter Anwendung üblicher Esterifizierungsweisen, z. B. in der Weise, daß man p-Nitrobenzoesäure mit einem Heptylalkohol vermittels einer Säure, wie Schwefelsäure oder Halogenwasserstoffsäuren, verestert oder daß man ein Halogenid der p-Nitxobenzoesäure mit einem Heptylalkohol, gegebenenfalls in Gegenwart eines säurebindenden Mittels, wie organische Basen von der Art des Pyridins, Chinolins und Dimethylanilins, oder Alkalien von der Art der Alkali- oder Erdalkalihydroxyde in einem indifferenten oder wäßrigen Mittel umsetzt; das Säurehalogenid kann. man auch in der Reaktionsmischung intermediär entstehen lassen, indem man zu der Mischurig von p-Nitrobenzoesäure und einem Heptylalkohol Thionylchlorid .oder ein anderes Halogenierungsmittel zugibt, wobei zweckmäßig ein säurebindendes Mittel, wie z. B. Pyridin, in der Reaktionsmischung vorhanden ist. Man kann ferner Hcptylalkolnolate mit einem Halogenid cler p-Nitrobenzoesiiure oder umgekehrt Salze der p-Nitrobenzoes-,iure mit cinein reaktionsfähigen Ester eines Hep.tylalkohols, z. B. mit Heptylhalogenid oder -sulfat, umsetzen. Weiterhin läßt sich p - Nitrobenzoesäu @rcanhydrid mit Heptylalkoholen zu den zugehörigen Estern iLLunsetzen. Man erhält die -Ester auch, wenn man auf eine Heptyl- -magnesiumsauerstoifv.erbindung, wie man sie durch Einwirken von Sauerstoff auf Heptylmagnesiumhalogenid erhält, ein Halogenid der p-Nitrobenzoesäure einwirken läßt. Ferner können Ester der p-Nitrobenzoesäure mit anderen Alkoholen durch Umestern mit einem Heptylalkohol in die gewünschten neuen Ester verwandelt werden. In analoger Weise erhält man die Thioester.The new esters are mostly liquid and in high concentrations in vl soluble. The preparation of the new esters follows using the usual esterification methods, z. B. in such a way that p-nitrobenzoic acid is mediated with a heptyl alcohol an acid, such as sulfuric acid or hydrohalic acids, or that a halide of p-nitxobenzoic acid with a heptyl alcohol, optionally in the presence of an acid-binding agent, such as organic bases of the type Pyridine, quinoline and dimethylaniline, or alkalis of the type of alkali or Alkaline earth hydroxides in an inert or aqueous agent; the acid halide can. can also be formed as an intermediate in the reaction mixture by to the mixture of p-nitrobenzoic acid and a heptyl alcohol thionyl chloride. or another halogenating agent is added, advantageously an acid-binding agent, such as B. pyridine, is present in the reaction mixture. One can also use Hcptylalkolnolate with a halide of p-nitrobenzoic acid or vice versa Salts the p-nitrobenzoic acid with a reactive ester of a hepyl alcohol, z. B. with heptyl halide or sulfate, implement. In addition, p-nitrobenzoic acid can be used @rcanhydrid with heptyl alcohols to form the associated esters. You get the -Ester also, if you look at a heptyl-magnesium oxygen compound, like they are obtained by the action of oxygen on heptyl magnesium halide Let the halide of p-nitrobenzoic acid act. Esters of p-nitrobenzoic acid can also be used with other alcohols by transesterification with a heptyl alcohol into the desired transformed into new esters. The thioesters are obtained in an analogous manner.
Die neuen Ester sind in Wasser unlöslich, hingegen- leicht löslich in indifferenten organischen Lösungsmitteln. Beispiel i 92,5 g p-Nitrobenzoylchlorid werden mit 58 g n-Heptylalkohol mehrere Stunden auf 12o bis 13o° bis zur Beendigung der Chlorwasserstoffentwicklung erhitzt. Nach dem Erkalten der Mischung werden Wasser und Äther hinzugegeben, die ätherische Lösung wird mit n-Natronlauge und Wasser ausgezogen und dann mit Chlorcalcium getrocknet. Nach Abdestillieren des Äthers und Rektifizieren erhält man den p-Nitrobenzoesäuren-heptylester als gelbliches öl vom Siedepunkt 175° unter i mm Druck. Beispiel 2 Eüie `Mischung von 925g p-Nitrobenzoylchlorid, 580- 2-Metliylliexanol- i und 7 5o ccm Xylol wird allmählich mit .115g Pyridin versetzt. Nach Abklingen der heftigen Reaktion wird die Mischung i Stunde auf i2o bis i3o' erhitzt. Das Xylol wird danach unter vermindertem Druck abdestilliert und der Rückstand mit Wasser und Äther versetzt. Die ätherische Lösung wird mit n-Natronlauge und Wasser geschüttelt und dann mit Chlorcalcium getrocknet. Der Äther wird dann abdestilliert und der Rückstand rektifiziert. Man erhält den p-Nitrobenzoesäureisoheptylester als gelbliches öl vom Siedepunkt 165 bis 167° unter 0,7 mm Druck.The new esters are insoluble in water, but easily soluble in inert organic solvents. Example i 92.5 g of p-nitrobenzoyl chloride are heated with 58 g of n-heptyl alcohol for several hours at 120 ° to 130 ° until the evolution of hydrogen chloride has ended. After the mixture has cooled down, water and ether are added, the ethereal solution is extracted with sodium hydroxide solution and water and then dried with calcium chloride. After the ether has been distilled off and rectified, the p-nitrobenzoic acid heptyl ester is obtained as a yellowish oil with a boiling point of 175 ° under 1 mm pressure. EXAMPLE 2 A mixture of 925 g of p-nitrobenzoyl chloride, 580-2 -methylethylanol and 75o ccm of xylene is gradually mixed with 115 g of pyridine. After the vigorous reaction has subsided, the mixture is heated to between 120 and 130 'for 1 hour. The xylene is then distilled off under reduced pressure and water and ether are added to the residue. The ethereal solution is shaken with sodium hydroxide solution and water and then dried with calcium chloride. The ether is then distilled off and the residue is rectified. The isoheptyl p-nitrobenzoate is obtained as a yellowish oil with a boiling point of 165 ° to 167 ° under 0.7 mm pressure.
In genau derselben Weise erhält man den p -Nitrobenzoesäure - i - methylhexanol- i --ester vom Siedepunkt 161° bei o,6 mm Druck, Schmelzpunkt 65°, wenn man anstatt des 2 - Methylhexanol - i das i - Methylhexanol - i unter sonst gleichen Bedingungen venvendet.The p -nitrobenzoic acid - i - is obtained in exactly the same way methylhexanol i - ester with a boiling point of 161 ° at 0.6 mm pressure, melting point 65 °, if instead of the 2 - methylhexanol - i the i - methylhexanol - i is used under otherwise used under the same conditions.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI64658D DE722338C (en) | 1939-05-24 | 1939-05-24 | Process for the preparation of p-nitrobenzoic acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI64658D DE722338C (en) | 1939-05-24 | 1939-05-24 | Process for the preparation of p-nitrobenzoic acid esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE722338C true DE722338C (en) | 1942-07-09 |
Family
ID=7196169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI64658D Expired DE722338C (en) | 1939-05-24 | 1939-05-24 | Process for the preparation of p-nitrobenzoic acid esters |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE722338C (en) |
-
1939
- 1939-05-24 DE DEI64658D patent/DE722338C/en not_active Expired
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