CH432499A - Process for the preparation of 2,6-dichlorobenzaldoxime - Google Patents
Process for the preparation of 2,6-dichlorobenzaldoximeInfo
- Publication number
- CH432499A CH432499A CH869966A CH869966A CH432499A CH 432499 A CH432499 A CH 432499A CH 869966 A CH869966 A CH 869966A CH 869966 A CH869966 A CH 869966A CH 432499 A CH432499 A CH 432499A
- Authority
- CH
- Switzerland
- Prior art keywords
- dichlorobenzaldoxime
- chloride
- preparation
- temperature
- sulfuric acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 7
- YBSXDWIAUZOFFV-ONNFQVAWSA-N (ne)-n-[(2,6-dichlorophenyl)methylidene]hydroxylamine Chemical compound O\N=C\C1=C(Cl)C=CC=C1Cl YBSXDWIAUZOFFV-ONNFQVAWSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- QQPXXHAEIGVZKQ-UHFFFAOYSA-N 1,3-dichloro-2-(dichloromethyl)benzene Chemical compound ClC(Cl)C1=C(Cl)C=CC=C1Cl QQPXXHAEIGVZKQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 238000006146 oximation reaction Methods 0.000 claims 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XCSNRORTQRKCHB-UHFFFAOYSA-N 2-chloro-6-nitrotoluene Chemical compound CC1=C(Cl)C=CC=C1[N+]([O-])=O XCSNRORTQRKCHB-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 2
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- VTWKXBJHBHYJBI-SOFGYWHQSA-N (ne)-n-benzylidenehydroxylamine Chemical compound O\N=C\C1=CC=CC=C1 VTWKXBJHBHYJBI-SOFGYWHQSA-N 0.000 description 1
- LBOBESSDSGODDD-UHFFFAOYSA-N 1,3-dichloro-2-(chloromethyl)benzene Chemical compound ClCC1=C(Cl)C=CC=C1Cl LBOBESSDSGODDD-UHFFFAOYSA-N 0.000 description 1
- MULRGOOZFNLPFF-UHFFFAOYSA-N 2,6-dichloro-n'-hydroxybenzenecarboximidamide Chemical compound ON=C(N)C1=C(Cl)C=CC=C1Cl MULRGOOZFNLPFF-UHFFFAOYSA-N 0.000 description 1
- XACGZMBUDCYGPB-UHFFFAOYSA-N 2,6-dichlorobenzonitrile oxide Chemical compound [O-][N+]#CC1=C(Cl)C=CC=C1Cl XACGZMBUDCYGPB-UHFFFAOYSA-N 0.000 description 1
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- -1 α-substituted benzaldoximes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/55—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/62—Preparation of carboxylic acid halides by reactions not involving the carboxylic acid halide group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 2,6-Dichlorbenzaldoxim
Die vorliegende Erfindung bezieht sich auf ein Verfahren zur Herstellung von 2, 6-Dichlorbenzaldoxim, welches dadurch gekennzeichnet ist, dass man 2,6-Dibenzalchlorid mit Hydroxylamin in einem sauren Medium umsetzt.
Es konnte gefunden werden, dass durch Erhitzen von 2, 6-Dinitrotoluol oder 2-Nitro-6-chlortoluol unter bestimmten Reaktionsbedingungen die Nitrogruppe(n) durch Chlor ersetzt wird, während gleichzeitig ein oder zwei Wasserstoffatome der Methylkette ebenfalls durch ein oder zwei Chloratome ersetzt werden. Hiebei werden 2, 6-Dichlorbenzalchlorid und 2, 6-Dichlorbenzylchlorid in hoher Ausbeute erhalten.
Weiterhin konnte gefunden werden, dass beispielsweise gute Ausbeuten an 2,6-Dichlorbenzalchlorid durch Chlorierung von 2-Nitro-6-chlortoluol oder 2,6-Dinitrotoluol bei einer Temperatur zwischen 175 und 1850 C, hauptsächlich bei ungefähr 1800 C während ungefähr 10 bis 20 Stunden, z. B. während 15 Stunden, bei einer Chlorzufuhrgeschwindigkeit von beispielsweise zwischen 0,5 und 0,8 Mol pro Stunde und pro Mol 2-Nitro6-chlortoluol erhalten werden können. Unter diesen Bedingungen kann 2,6-Dichlorbenzalchlorid in einer Ausbeute von mindestens 70 Ges. % erhalten werden.
Das so erhaltene 2,6-Dichlorbenzalchlorid kann erfindungsgemäss direkt in das entsprechende Benzaldoxim durch Reaktion mit Hydroxylamin in einem sauren Medium umgewandelt werden.
Als saures Medium für die Oximbildung wird vorzugsweise eine konzentrierte Mineralsäure verwendet, insbesondere konzentrierte Schwefelsäure, deren Konzentration zwischen 75 und 100 Ges. %, vorzugsweise zwischen 90 und 100 Ges. % variieren kann. Das Gewicht der verwendeten Schwefelsäure stellt keinen kritischen Faktor dar. Es können Mengen bis zu dem zwanzigfachen, vorzugsweise jedoch bis zum doppelten Gewicht des Benzalchlorids verwendet werden. Obwohl die Reaktionskomponenten in variablen Verhältnissen zur Anwendung kommen können, so werden doch im allgemeinen äquimolekulare Mengen derselben bevorzugt. Auch die Reaktionstemperatur kann bedeutend variieren. Sie wird vorzugsweise zwischen 30 und 700 C, im besonderen zwischen 45 und 600 C, z. B. zwischen 50 und 550 C gehalten.
Im allgemeinen dauert die Reaktion mindestens eine Stunde.
Das entstandene 2,6-Dichlorbenzaldoxim besitzt unkrautvertilgende Eigenschaften und eignet sich ebenfalls als Zwischenprodukt für die Herstellung von Verbindungen mit sehr hohen unkrautvertilgenden Eigenschaften, z. B. für die Herstellung von 2,6-Dichlorbenzonitril, 2, 6-Dichlorbenzonitriloxyd und a-substituierten Benzaldoximen, wie 2, 6-Dichlor-a-aminobenzaldoxim.
Beispiel 1
Zu einer Mischung aus 290 g 98 gew.% iger konzentrierter Schwefelsäure und 23 g (0,1 Mol) 2,6-Dichlorbenzalchlorid wurden unter Rühren bei Zimmertemperatur 14,0 g oder 0,2 Mol Hydroxylaminhydrochlorid in getrennten Anteilen zugegeben. Die Mischung wurde anschliessend während drei Stunden bei einer Temperatur von 50 bis 550 C gerührt und dann langsam unter weiterem Rühren in Eiswasser gegeben. Das Oxim wurde abgetrennt, getrocknet und aus Benzol umkristallisiert. Die Ausbeute betrug 87 %, der Schmelzpunkt nach viermaliger Umkristallisation 133-1370 C.
Beispiel 2
Ein Gemisch aus 23 g 2,6-Dichlorbenzalchlorid, 29 g konzentrierter Schwefelsäure und 7,0 g Hydroxylaminhydrochlorid wurde während drei Stunden bei einer Temperatur von 50 bis 550 C gerührt. Dann wurde das Gemisch unter Rühren in 0,5 1 Eiswasser gegossen, abfiltriert, gewaschen und im Vakuum getrocknet. Das gebildete 2,6-Dichlorbenzaldoxim wurde in einer Menge von 18,5 g oder einer theoretischen Ausbeute von 97 % erhalten.
Unter Verwendung von Essigsäureannydrid kann dieses Oxim ohne vorherige Reinigung in einer Ausbeute von 92% in 2,6-Dichlorbenzonitril umgewandelt werden.
Process for the preparation of 2,6-dichlorobenzaldoxime
The present invention relates to a process for the preparation of 2,6-dichlorobenzaldoxime, which is characterized in that 2,6-dibenzal chloride is reacted with hydroxylamine in an acidic medium.
It has been found that by heating 2,6-dinitrotoluene or 2-nitro-6-chlorotoluene under certain reaction conditions the nitro group (s) is replaced by chlorine, while at the same time one or two hydrogen atoms of the methyl chain are also replaced by one or two chlorine atoms will. Here, 2,6-dichlorobenzal chloride and 2,6-dichlorobenzyl chloride are obtained in high yield.
Furthermore, it was found that, for example, good yields of 2,6-dichlorobenzal chloride can be achieved by chlorinating 2-nitro-6-chlorotoluene or 2,6-dinitrotoluene at a temperature between 175 and 1850 ° C., mainly at about 1800 ° C. for about 10 to 20 Hours, e.g. B. during 15 hours, at a chlorine feed rate of, for example, between 0.5 and 0.8 moles per hour and per mole of 2-nitro6-chlorotoluene can be obtained. Under these conditions, 2,6-dichlorobenzal chloride can be obtained in a yield of at least 70% by weight.
The 2,6-dichlorobenzal chloride thus obtained can, according to the invention, be converted directly into the corresponding benzaldoxime by reaction with hydroxylamine in an acidic medium.
A concentrated mineral acid is preferably used as the acidic medium for the formation of the oxime, in particular concentrated sulfuric acid, the concentration of which can vary between 75 and 100% by weight, preferably between 90 and 100% by weight. The weight of the sulfuric acid used is not a critical factor. Amounts up to twenty times, but preferably up to twice the weight of the benzal chloride can be used. Although the reaction components can be used in variable proportions, equimolecular amounts thereof are generally preferred. The reaction temperature can also vary significantly. It is preferably between 30 and 700 ° C., in particular between 45 and 600 ° C., e.g. B. held between 50 and 550 C.
Generally the reaction lasts at least one hour.
The resulting 2,6-dichlorobenzaldoxime has weed-killing properties and is also suitable as an intermediate for the production of compounds with very high weed-killing properties, e.g. B. for the preparation of 2,6-dichlorobenzonitrile, 2,6-dichlorobenzonitrile oxide and α-substituted benzaldoximes, such as 2,6-dichloro-α-aminobenzaldoxime.
example 1
To a mixture of 290 g of 98% strength by weight concentrated sulfuric acid and 23 g (0.1 mol) of 2,6-dichlorobenzal chloride, 14.0 g or 0.2 mol of hydroxylamine hydrochloride were added in separate portions with stirring at room temperature. The mixture was then stirred for three hours at a temperature of 50 to 550 ° C. and then slowly poured into ice water with continued stirring. The oxime was separated, dried and recrystallized from benzene. The yield was 87%, the melting point after four recrystallizations was 133-1370 C.
Example 2
A mixture of 23 g of 2,6-dichlorobenzal chloride, 29 g of concentrated sulfuric acid and 7.0 g of hydroxylamine hydrochloride was stirred at a temperature of 50 to 550 ° C. for three hours. The mixture was then poured into 0.5 l of ice water with stirring, filtered off, washed and dried in vacuo. The 2,6-dichlorobenzaldoxime formed was obtained in an amount of 18.5 g or a theoretical yield of 97%.
Using acetic anhydride, this oxime can be converted to 2,6-dichlorobenzonitrile in 92% yield without prior purification.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB4154360A GB953554A (en) | 1960-12-02 | 1960-12-02 | Improvements in or relating to a process for the manufacture of halogenated aromaticcompounds |
| GB343461 | 1961-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH432499A true CH432499A (en) | 1967-03-31 |
Family
ID=26238299
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1392161A CH421920A (en) | 1960-12-02 | 1961-11-30 | Production of chlorinated toluene derivatives |
| CH870066A CH424758A (en) | 1960-12-02 | 1961-11-30 | Process for the preparation of 2,6-dichlorobenzaldoxime |
| CH869966A CH432499A (en) | 1960-12-02 | 1961-11-30 | Process for the preparation of 2,6-dichlorobenzaldoxime |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1392161A CH421920A (en) | 1960-12-02 | 1961-11-30 | Production of chlorinated toluene derivatives |
| CH870066A CH424758A (en) | 1960-12-02 | 1961-11-30 | Process for the preparation of 2,6-dichlorobenzaldoxime |
Country Status (9)
| Country | Link |
|---|---|
| AT (1) | AT233555B (en) |
| BE (1) | BE610998A (en) |
| BR (1) | BR6134599D0 (en) |
| CA (1) | CA693199A (en) |
| CH (3) | CH421920A (en) |
| DE (1) | DE1237552B (en) |
| DK (1) | DK112306B (en) |
| GB (1) | GB953554A (en) |
| NL (2) | NL110918C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1101779A (en) * | 1966-12-12 | 1968-01-31 | Shell Int Research | Process for the preparation of halogenated aromatic compounds |
| DE3431826A1 (en) * | 1984-08-30 | 1986-03-13 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING AROMATIC BROMIC CONNECTIONS |
| CN107473973A (en) * | 2017-07-31 | 2017-12-15 | 山东福尔有限公司 | A kind of nitrotoleune preparation method of 6 chlorine 2 |
-
0
- NL NL271984D patent/NL271984A/xx unknown
- CA CA693199D patent/CA693199A/en not_active Expired
- BE BE610998D patent/BE610998A/xx unknown
- NL NL110918D patent/NL110918C/xx active
-
1960
- 1960-12-02 GB GB4154360A patent/GB953554A/en not_active Expired
-
1961
- 1961-11-30 AT AT910361A patent/AT233555B/en active
- 1961-11-30 BR BR13459961A patent/BR6134599D0/en unknown
- 1961-11-30 DK DK479361A patent/DK112306B/en unknown
- 1961-11-30 CH CH1392161A patent/CH421920A/en unknown
- 1961-11-30 CH CH870066A patent/CH424758A/en unknown
- 1961-11-30 CH CH869966A patent/CH432499A/en unknown
- 1961-11-30 DE DE1961S0076925 patent/DE1237552B/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NL271984A (en) | |
| CH421920A (en) | 1966-10-15 |
| CH424758A (en) | 1966-11-30 |
| NL110918C (en) | |
| GB953554A (en) | 1964-03-25 |
| CA693199A (en) | 1964-08-25 |
| AT233555B (en) | 1964-05-11 |
| DK112306B (en) | 1968-12-02 |
| BE610998A (en) | |
| BR6134599D0 (en) | 1973-05-17 |
| DE1237552B (en) | 1967-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2512614C2 (en) | Process for the preparation of 4-hydroxy-3,5-dibromobenzaldehyde | |
| EP0026291B1 (en) | Process for the preparation of terephthalaldehyde or isophthalaldehyde | |
| DE1129153B (en) | Process for the preparation of ª‡-cyano-ª‰-alkyl-ª‰-phenylacrylic acid esters | |
| DE1965782A1 (en) | Improved process for the preparation of aromatic trifluoromethyl compounds of the benzene series | |
| CH432499A (en) | Process for the preparation of 2,6-dichlorobenzaldoxime | |
| DE1618207C (en) | ||
| DD239591A5 (en) | PROCESS FOR THE PREPARATION OF 2,4-DICHLOR-5-FLUORO BENZOESAEURE | |
| DE2708185A1 (en) | PROCESS FOR THE PRODUCTION OF ALPHA-KETOCARBONIC ACIDS (B) | |
| DE2947475C2 (en) | Process for the preparation of 3-cyanopropionic acid amide | |
| DE1543869B1 (en) | Process for the preparation of hydroxybenzonitriles | |
| DE1543869C (en) | Process for the production of hydroxy benzonite oils | |
| DE2060329C3 (en) | Process for the preparation of substituted benzamides | |
| AT203495B (en) | Process for the preparation of new tertiary amines | |
| DE2708184A1 (en) | PROCESS FOR THE PRODUCTION OF ALPHA-KETOCARBONIC ACID AMIDES (A) | |
| DE533129C (en) | Process for the production of chloranil and bromanil | |
| DE2250550A1 (en) | METHOD FOR PRODUCING TETRABROMPHTHALIC ANHYDRIDE | |
| AT303004B (en) | Process for the preparation of sulfamylanthranilic acids | |
| AT227254B (en) | Process for the preparation of 2, 3, 6-trichlorobenzonitrile and 2, 3, 6-trichlorobenzoic acid | |
| AT234105B (en) | Process for the preparation of 4-methyl-6-isobutenyl-pyrone- (2) | |
| AT219616B (en) | Process for the production of dibenzyltin dichloride or dibenzyltin dichlorides substituted in the benzene nucleus | |
| DE929191C (en) | Process for the production of aminocarboxylic acids | |
| DE1240520B (en) | Process for the preparation of 2,6-dichlorobenzaldoxime | |
| DE2244652C3 (en) | Process for the preparation of 2,3-dicyano-1,4-dithiaanthrahydroquinone and anthraquinone | |
| DE929192C (en) | Process for the preparation of aliphatic aminocarboxamides which are acylated or sulfonylated on the nitrogen atom | |
| DE2648944C3 (en) | Process for the preparation of N-phenyl-5-chloro-2-nitroaniline |