DE1068712B - Process for the preparation of nitro-substituted aromatic phosphoric acid chlorides - Google Patents
Process for the preparation of nitro-substituted aromatic phosphoric acid chloridesInfo
- Publication number
- DE1068712B DE1068712B DENDAT1068712D DE1068712DA DE1068712B DE 1068712 B DE1068712 B DE 1068712B DE NDAT1068712 D DENDAT1068712 D DE NDAT1068712D DE 1068712D A DE1068712D A DE 1068712DA DE 1068712 B DE1068712 B DE 1068712B
- Authority
- DE
- Germany
- Prior art keywords
- phosphoric acid
- nitro
- acid chlorides
- aromatic phosphoric
- acid
- 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
- -1 aromatic phosphoric acid chlorides Chemical class 0.000 title claims description 13
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- 239000000203 mixture Substances 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000006396 nitration reaction Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OBXCIBSDYYUTFK-UHFFFAOYSA-N OP(NC1=CC=CC=C1)(O)=O.Cl.Cl Chemical compound OP(NC1=CC=CC=C1)(O)=O.Cl.Cl OBXCIBSDYYUTFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZWWCURLKEXEFQT-UHFFFAOYSA-N dinitrogen pentoxide Inorganic materials [O-][N+](=O)O[N+]([O-])=O ZWWCURLKEXEFQT-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- YUPUMTKNEQZQFR-UHFFFAOYSA-N CN(C1=CC=CC=C1)P(O)(O)=O.Cl.Cl Chemical compound CN(C1=CC=CC=C1)P(O)(O)=O.Cl.Cl YUPUMTKNEQZQFR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- NJAQRIIIIZLWAC-UHFFFAOYSA-N OP(O)(O)=O.ClP(Cl)(Cl)=O Chemical compound OP(O)(O)=O.ClP(Cl)(Cl)=O NJAQRIIIIZLWAC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical class [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical class ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/26—Amides of acids of phosphorus containing P-halide groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von nitrosubstituierten aromatischen Phosphorsäurechloriden Es ist bekannt, daß die Nitraniline bei der Umsetzung mit Phosphoroxychlorid das Phosphorsäure-nitraniliddichlorid, Phosphorsäure-dinitranilid-chlorid und Phosphorsäure-trinitranilid bilden (Michaelis, Annalen, 326, S.236 [1903]).Process for the preparation of nitro-substituted aromatic phosphoric acid chlorides It is known that the nitroanilines when reacted with phosphorus oxychloride Phosphoric acid nitranilide dichloride, phosphoric acid dinitranilide chloride and phosphoric acid trinitranilide form (Michaelis, Annalen, 326, p.236 [1903]).
Die Trennung dieser Gemische macht große Schwierigkeiten.The separation of these mixtures presents great difficulties.
Es wurde nun gefunden, daß man nitrosubstituierte aromatische Phosphorsäurechloride erhält, wenn man aromatische Phosphorsäurechloride von der folgenden allgemeinen Formel worin X Chlor und mindestens ein X die Gruppe Y-R bedeutet, in der Y für > NH oder >N-Alkyl steht und R einen Phenyl-, Naphthyl- oder Diphenylrest darstellt, der durch Halogen, Alkyl- und/oder Alkoxygruppen substituiert sein kann, mit üblichen wasserfreien Salpetersäure-Schwefelsäure-Mischungen behandelt und die entstandenen Nitroverbindungen mit niedrigsiedenden chlorierten aliphatischen Kohlenwasserstoffen aus der Reaktionsmischung extrahiert. In jeden aromatischen Rest wird jeweils nur eine Nitrogruppe eingeführt.It has now been found that nitro-substituted aromatic phosphoric acid chlorides are obtained when aromatic phosphoric acid chlorides of the following general formula are used where X is chlorine and at least one X is the group YR, in which Y is> NH or> N-alkyl and R is a phenyl, naphthyl or diphenyl radical which can be substituted by halogen, alkyl and / or alkoxy groups, treated with customary anhydrous nitric acid-sulfuric acid mixtures and extracted the resulting nitro compounds with low-boiling chlorinated aliphatic hydrocarbons from the reaction mixture. Only one nitro group is introduced into each aromatic radical.
Es ist überraschend, daß bei der Nitrierung die leicht verseifbare Säurechloridgruppe erhalten bleibt.It is surprising that in the case of nitration the easily saponifiable Acid chloride group is retained.
Als Ausgangsprodukte für die Umsetzung kommen z. B. folgende Verbindungen in Frage: Phosphorsäure-anilid-dichlorid, Phosphorsäure-N-methyl-1 oder -2-naphthylamid-dichlorid, Phosphorsäure-bis-(N-methylanilid)-chlorid. Die Nitrierung wird so ausgeführt, daß man die Verbindungen als solche oder in Schwefelsäuremonohydrat bzw. in niedrigsiedenden chlorierten Kohlenwasserstoffen gelöst, mit wasserfreien Salpetersäure-Schwefelsäure-Mischungen unter Kühlung behandelt. Bei träge reagierenden Säurechloriden muß die Umsetzungstemperatur erhöht werden, es istvorteilhaft,50° C nicht zu übersteigen.As starting products for the implementation come z. B. the following connections in question: phosphoric acid anilide dichloride, phosphoric acid N-methyl-1 or -2-naphthylamide dichloride, Phosphoric acid bis (N-methylanilide) chloride. The nitration is carried out so that the compounds as such or in sulfuric acid monohydrate or in low boiling points chlorinated hydrocarbons dissolved with anhydrous nitric acid-sulfuric acid mixtures treated under cooling. In the case of sluggishly reacting acid chlorides, the reaction temperature be increased, it is advantageous not to exceed 50 ° C.
Als Nitrierungsmischsäure wird die in der Technik übliche Mischung aus 30 Gewichtsprozent wasserfreier Salpetersäure und 70 Gewichtsprozent Schwefelsäuremonohydrat verwendet, die Nitrierung kann aber auch mit anders zusammengesetzten Mischsäuren durchgeführt werden. Je nach Reaktionsfähigkeit des Ausgangsmaterials kann man die Schwefelsäuremenge variieren, bei schwer zu nitrierenden Säurechloriden wird die Monohydratmenge vergrößert.The mixture customary in technology is used as the mixed nitration acid from 30 percent by weight anhydrous nitric acid and 70 percent by weight sulfuric acid monohydrate used, but nitration can also be carried out with mixed acids of different compositions be performed. Depending on the reactivity of the starting material, one can use the Varying the amount of sulfuric acid, in the case of acid chlorides that are difficult to nitrate, the Amount of monohydrate increased.
Nach Beendigung der Reaktion werden die nitrierten Säurechloride aus der Reaktionsmischung mit niedrigsiedenden chlorierten aliphatischen Kohlenwasserstoffen, wie z. B. Methylenchlorid, extrahiert. Die Extrakte werden entsäuert und vom Lösungsmittel durch Abdampfen befreit. Als Rückstände erhält man nitrosubstituierte aromatische Phosphorsäurechloride, die in öliger oder kristalliner Form anfallen.After the reaction has ended, the nitrated acid chlorides are out the reaction mixture with low-boiling chlorinated aliphatic hydrocarbons, such as B. methylene chloride extracted. The extracts are deacidified and removed from the solvent freed by evaporation. Nitro-substituted aromatic residues are obtained as residues Phosphoric acid chlorides, which occur in oily or crystalline form.
Die nitrierten aromatischen Phosphorsäurechloride stellen wertvolle Zwischenprodukte für Farbstoffe, Schädlingsbekämpfungsmittel und Flammfestausrüstungen dar.The nitrated aromatic phosphoric acid chlorides are valuable Intermediates for dyes, pesticides and flame retardants represent.
Die in den folgenden Beispielen erwähnte Mischsäure bezieht sich, wenn nicht anders vermerkt, auf eine Nitriersäure aus 30 Gewichtsprozent wasserfreier Salpetersäure und 70 Gewichtsprozent Monohydrat.The mixed acid mentioned in the following examples refers to unless otherwise noted, to a nitrating acid of 30 percent by weight anhydrous Nitric acid and 70 weight percent monohydrate.
Beispiel 1 21 Gewichtsteile Phosphorsäure-anilid-dichlorid werden mit 50 Volumteilen Methylenchlorid versetzt und zwischen 0 und 10° C mit 12 Volumteilen Mischsäure nitriert. Nach der Extraktion mit Methylenchlorid und Abdampfen des Lösungsmittels erhält man 19 Gewichtsteile eines Phosphorsäure-nitranilid-dichlorids vom Fp. 143° C.Example 1 21 parts by weight of phosphoric acid anilide dichloride mixed with 50 parts by volume of methylene chloride and between 0 and 10 ° C with 12 parts by volume Mixed acid nitrated. After extraction with methylene chloride and evaporation of the solvent 19 parts by weight of a phosphoric acid nitranilide dichloride with a melting point of 143 ° are obtained C.
Beispiel 2 22,4 Gewichtsteile Phosphorsäure-N-methylanilid-dichlorid werden zwischen 5 und 15° C mit 12 Volumteilen Mischsäure versetzt. Nach Beendigung der exothermen Reaktion werden 50 Volumteile Methylenchlorid zugegeben, und das Gemisch wird 1 Stunde nachgerührt. Nach der Aufarbeitung erhält man 23 Gewichtsteile eines Phosphorsäure-(nitro-N-methylanilid)-dichlorids alsFlüssigkeit, nö = 1,5755.Example 2 22.4 parts by weight of phosphoric acid N-methylanilide dichloride 12 parts by volume of mixed acid are added between 5 and 15 ° C. After completion 50 parts by volume of methylene chloride are added to the exothermic reaction, and that The mixture is stirred for 1 hour. After working up, 23 parts by weight are obtained of a phosphoric acid (nitro-N-methylanilide) dichloride as a liquid, no = 1.5755.
Beispiel 3 27,4 Gewichtsteile Phosphorsäure-(N-methyl-l-naphthylamid)-dichlorid werden mit 50 Volumteilen Methylenchlorid versetzt und bei Temperaturen zwischen 15 und 25° C mit 12 Volumteilen Mischsäure nitriert. Nach der Extraktion und dem Abdampfen des Lösungsmittels werden 30 Gewichtsteile eines Phosphorsäure-(nitro-N-methyl-l-naphthylamid)-dichlorids als sehr zähe Paste erhalten.Example 3 27.4 parts by weight of phosphoric acid (N-methyl-1-naphthylamide) dichloride are mixed with 50 parts by volume of methylene chloride and at temperatures between 15 and 25 ° C with 12 parts by volume of mixed acid nitrated. After extraction and evaporation of the solvent, 30 parts by weight of a phosphoric acid (nitro-N-methyl-1-naphthylamide) dichloride obtained as a very viscous paste.
Beispiel 4 29,5 Gewichtsteile Phosphorsäure-bis-(N-methylanilid)-chlorid werden mit 100 Volumteilen Tetrachlorkohlenstoff versetzt und unterhalb 20° C mit 24 Volumteilen Mischsäure nitriert. Nach der Aufarbeitung werden 25 GewichtsteileeinesPhosphorsäure-bis-(nitro-N-methylanilid)-chlorids als zähe Paste erhalten.Example 4 29.5 parts by weight of phosphoric acid bis (N-methylanilide) chloride 100 parts by volume of carbon tetrachloride are added and below 20 ° C with 24 parts by volume of mixed acid nitrated. After working up, 25 parts by weight of a phosphoric acid bis (nitro-N-methylanilide) chloride are used obtained as a tough paste.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1068712B true DE1068712B (en) | 1959-11-12 |
Family
ID=594001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1068712D Pending DE1068712B (en) | Process for the preparation of nitro-substituted aromatic phosphoric acid chlorides |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1068712B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6384261B1 (en) * | 1996-03-26 | 2002-05-07 | Texas Biotechnology Corporation | Phosphoramidates, phosphinic amides and related compounds and the use thereof to modulate the activity of endothelin |
-
0
- DE DENDAT1068712D patent/DE1068712B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6384261B1 (en) * | 1996-03-26 | 2002-05-07 | Texas Biotechnology Corporation | Phosphoramidates, phosphinic amides and related compounds and the use thereof to modulate the activity of endothelin |
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