DE949946C - Process for the preparation of chlorinated acetamides which are trichloroalkyl-substituted on the nitrogen - Google Patents

Process for the preparation of chlorinated acetamides which are trichloroalkyl-substituted on the nitrogen

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Publication number
DE949946C
DE949946C DEL13804A DEL0013804A DE949946C DE 949946 C DE949946 C DE 949946C DE L13804 A DEL13804 A DE L13804A DE L0013804 A DEL0013804 A DE L0013804A DE 949946 C DE949946 C DE 949946C
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Germany
Prior art keywords
acetamides
chlorinated
substituted
trichloroalkyl
preparation
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
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DEL13804A
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German (de)
Inventor
Dr Heinz Schubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
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Hoechst AG
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Publication date
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Priority to DEL13804A priority Critical patent/DE949946C/en
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Publication of DE949946C publication Critical patent/DE949946C/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C11/00—Other nitrogenous fertilisers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur -Herstellung von am Stickstoff trichloralkylsubstituierten, chlorierten Acetamiden Es ist bereits bekannt, Chloralhydrat durch einfachesZusammenschmelzen mit Carbonsäureamiden zu N-(i-Oxy-2, 2, 2-trichloräthyl)-carbonsäureamiden zu kondensieren. Es ist weiter bekannt, daß auf diese Weise auch Butyralhydrat und Carbonsäureamide zu N-(i-Oxy-2, 3, 3-trichlorbutyl)-carbonsäureamiden kondensiert werden können (vgl. J. P. Larocca, J. M. Leonard und W. E. Weaver, Journal of Organic Chemistry, Bd. 16, Jg. 1951, S. 47 bis 50). Es läßt sich nach dieser Methode auch Monochloracetamid mit Butyralhydrat zum N-(i-Oxy-2, 2, 3-trichlorbutyl)-chloracetamid kondensieren (a. a. O., S. 48, Tabelle 2).Process for the preparation of chlorinated acetamides trichloroalkyl-substituted on the nitrogen It is already known to condense chloral hydrate by simply melting it together with carboxamides to give N- (i-oxy-2,2,2-trichloroethyl) carboxamides. It is also known that butyral hydrate and carboxamides can also be condensed to form N- (i-oxy-2, 3, 3-trichlorobutyl) carboxamides (cf. JP Larocca, JM Leonard and WE Weaver, Journal of Organic Chemistry , Vol. 16, vol. 1951, pp. 47 to 50). This method can also be used to condense monochloroacetamide with butyral hydrate to give N- (i-oxy-2, 2, 3-trichlorobutyl) chloroacetamide (loc. Cit., P. 48, table 2).

Es gelingt jedoch nach dieser Arbeitsweise nicht, aus Mono-, Di- oder Trichloracetamid mit Chloralhydrat die entsprechenden N-(i-oxy-2, 2, 2-trichloräthyl)-substituierten chlorierten Acetamide herzustellen. Es findet entweder keine Umsetzung statt, oder man erhält z. B. im Falle des Monochloracetamids in ganz geringer Menge ein Kondensationsprodukt, das durch Zusammentritt zweier Moleküle Monochloracetamid mit einem Molekül Chloralhydrat nach folgender Reaktion entstanden ist 2 CH2Cl-CO-NHz + (OH)2HC-CCls (CH2C1-CONH)2HC-CCls Es wurde nun gefunden, daß sich Mono-, Di- und Trichloracetamid mit Chloralhydrat in der Schmelze zu den entsprechenden N-(i-oxy-2, 2, 2-trichloräthyl)-substituierten chlorierten Acetamiden umsetzen lassen, wenn man die Kondensation in Gegenwart katalytischer Mengen starker Säuren, besonders Schwefelsäure, vornimmt. Dabei findet folgende Reaktion statt: CLH(3-") C-CO-NH2+(HO)ZHC-CC13 -> C1.H (3_") C-CO-NH-CHOH-CCi3 n bedeutet in den obigen Formeln die ganze Zahl i, 2 oder 3.However, this procedure does not succeed in preparing the corresponding N- (i-oxy-2,2,2-trichloroethyl) -substituted chlorinated acetamides from mono-, di- or trichloroacetamide with chloral hydrate. There is either no implementation, or you get z. B. in the case of monochloroacetamide in a very small amount a condensation product that was formed by the coming together of two molecules of monochloroacetamide with one molecule of chloral hydrate after the following reaction 2 CH2Cl-CO-NHz + (OH) 2HC-CCls (CH2C1-CONH) 2HC-CCls It has now been found that mono-, di- and trichloroacetamide can be reacted with chloral hydrate in the melt to give the corresponding N- (i-oxy-2, 2, 2-trichloroethyl) -substituted chlorinated acetamides if the condensation is carried out in the presence catalytic amounts of strong acids, especially sulfuric acid. The following reaction takes place: CLH (3- ") C-CO-NH2 + (HO) ZHC-CC13 -> C1.H (3_ ") C-CO-NH-CHOH-CCi3 In the above formulas, n denotes the integer i, 2 or 3.

Es ist vorteilhaft, mit einem großen Überschuß an Chloralhydrat (bis ioo °/o) zu arbeiten, da. dann die Kondensationsprodukte von einer verhältnismäßig kleinen Menge nicht umgesetzter Amide getrennt werden müssen. Insbesondere gilt dies für die Kondensationsprodukte von Mono- und Trichloracetamid, die bei längerem Erwärmen in Lösungsmitteln zum Zerfall in ihre Komponenten neigen.It is advantageous to use a large excess of chloral hydrate (up to ioo ° / o) to work there. then the condensation products of a proportionate small amount of unreacted amides must be separated. In particular, this for the condensation products of mono- and trichloroacetamide, which for a long time Heating in solvents tend to break down into their components.

Die erfindungsgemäß dargestellten Kondensationsprodukte haben bemerkenswerte fungicide und Wuchsstoffwirkung.The condensation products prepared according to the invention have remarkable ones fungicide and growth substance effect.

Beispiel i 661 g Chloralhydrat, 187 g Chloracetamid und 8,5 g konzentrierte Schwefelsäure werden verschmolzen und die Schmelze 9 Stunden im Ölbad auf 115° gehalten. Nach dem Erkalten löst man in der notwendigen Menge Methanol und versetzt die Lösung.so lange mit Wasser, bis bei weiterem Wasserzusatz keine Kristalle mehr abgeschieden werden. Man saugt ab und wäscht mit Wasser. Nach dem Trocknen über Schwefelsäure im Vakuum erhält man 29o g (6o °/o) N-(2, 2, 2-Trichlor-i-oxyäthyl)-chloracetamid ClH,C-CO-NH-CH(OH) -CC13 Nach Umkristallisation aus Äther schmilzt das Produkt bei 139 bis 1q.0°.Example i 661 g chloral hydrate, 187 g chloroacetamide and 8.5 g concentrated Sulfuric acid are fused and the melt is kept at 115 ° in an oil bath for 9 hours. After cooling, the necessary amount of methanol is dissolved and the solution is added with water for a long time, until no more crystals are deposited with further addition of water will. It is suctioned off and washed with water. After drying over sulfuric acid 29o g (60%) of N- (2,2,2-trichloro-i-oxyethyl) chloroacetamide are obtained in vacuo ClH, C-CO-NH-CH (OH) -CC13 After recrystallization from ether, the product melts 139 to 1q.0 °.

A_ rbeitet man jedoch ohne Schwefelsäurezusatz, so erhält man nach gleicher Aufarbeitung kein N-(2, 2, 2-Trichlor-i-oxyäthyl)-chloracetamid, sondern in ganz geringer Menge 2, 2, 2-Trichloräthyliden-bis-N, N'-(chloracetamid), (Cl H2C CONH)2CHCC13 (farblose Kristalle aus Benzol oder Alkohol, F. 211°). Beispiel 2 33o,8 g Chloralhydrat und 255,9 g Dichloracetamid und 6 g konzentrierte Schwefelsäure werden durch Schmelzen vermischt und die Schmelze g Stunden auf 1q.o bis i5o° gehalten. Man löst nach dem Erkalten in etwa 3oo ccm Methanol und gießt die Lösung in goo ccm Wasser. Das auskristallisierte Produkt wird abgesaugt und durch zweimaliges Umkristallisieren aus Benzol und schließlich aus wäßrigem Methanol (i : x) gereinigt; man erhält go g (i6,3 °/o) N-(2, 2, 2-Trichlor-i-oxyäthyl)-dichloracetamid C12HC - CO -NH -CH(OH) -CCl3 farblose Kristalle vom F. 122 bis i23°. Ein 2,5 °/o des Produktes enthaltender Talkumstaub wirkt bei einem zu 76 °/o fusariumbefallenen Winterroggen voll fungistatisch.However, if you work without the addition of sulfuric acid, you get after same work-up no N- (2, 2, 2-trichloro-i-oxyethyl) chloroacetamide, but in a very small amount 2, 2, 2-trichloroethylidene-bis-N, N '- (chloroacetamide), (Cl H2C CONH) 2CHCC13 (colorless crystals from benzene or alcohol, mp 211 °). example 2,330.8 g chloral hydrate and 255.9 g dichloroacetamide and 6 g concentrated sulfuric acid are mixed by melting and the melt is kept at 1q.o to 150 ° for g hours. After cooling, it is dissolved in about 300 cc of methanol and the solution is poured into goo cc of water. The product that has crystallized out is filtered off with suction and washed twice Recrystallization from benzene and finally purified from aqueous methanol (i: x); one receives g (16.3%) N- (2,2,2-trichloro-i-oxyethyl) dichloroacetamide C12HC - CO -NH-CH (OH) -CCl3 colorless crystals with a temperature of 122 ° to 233 °. A 2.5% of the product Talc dust containing it acts on winter rye that is 76% fusarium-infested fully fungistatic.

Beispiel 3 Eine Schmelze aus 661 g Chloralhydrat, 324 g Trichlöracetamid und 9,8 g konzentrierter Schwefelsäure wird 9 Stunden auf i2o° gehalten. Nach dem Erkalten löst man den Schmelzkuchen in der notwendigen Menge Methanol und fällt die Lösung mit Wasser. Nach dem Trocknen im Vakuum über Schwefelsäure werden Zoo g (32,2 °%) N-(2, 2, 2-Trichlor-i-oxyäthyl)-trichioracetamid Cl, C-CO-NH-CH(OH)-CC13 erhalten, das nach Umkristallisieren aus Chloroform bei 115 bis 116° schmilzt.Example 3 A melt of 661 g of chloral hydrate, 324 g of trichloacetamide and 9.8 g of concentrated sulfuric acid is kept at i20 ° for 9 hours. After this When cooling down, the melt cake is dissolved in the necessary amount of methanol and precipitated the solution with water. After drying in a vacuum over sulfuric acid become zoo g (32.2%) N- (2,2,2-trichloro-i-oxyethyl) -trichioracetamide Cl, C-CO-NH-CH (OH) -CC13 obtained, which melts after recrystallization from chloroform at 115 to 116 °.

Die wuchsfördernde Wirkung der in Beispiel i und 3 beschriebenen Substanzen geht aus der unten angegebenen Tabelle hervor. Die Samen wurden mit einem Beizstaub aus Talkum, der die angegebenen Mengen der nach Beispiel i und 3 erfindungsgemäß dargestellten Kondensationsprodukte enthielt, behandelt, wobei jeweils eine Aufwandmenge von ioo g Beizstaub auf ioo kg Samen zur Anwendung kam. Daneben wurden unbehandelte Kontrollen beobachtet. Konzen- Zunahme derWurzel- Keimzahl Zunahme der Keimlänge trTaon % gegenüber Kontrolle in % länge gegenüber im Talkum Kontrolle in /o in % Weizen f Kresse Weizen Kresse Weizen (2, z, 2-Trichlor-i-oxyäthyl)- chloracetamid . ... ...... 0,005 86 100 25 23 33 Kontrolle ............. - 86 72 - - (2, 2, 2-Trichlor-i-oxyäthyl)- trichloracetamid ... . . ... o,oi 10o 96 65 33 66 Kontrolle ...... ..... . .. - 75 89 - - .. The growth-promoting effect of the substances described in Examples i and 3 can be seen from the table given below. The seeds were treated with a dressing dust made from talc which contained the specified amounts of the condensation products according to the invention according to Examples 1 and 3, an application rate of 100 g dressing dust per 100 kg seeds being used in each case. Untreated controls were also observed. Concentration increase in root Germ count Increase in germ length trTaon% versus control in% length versus in talc control in / o in% wheat f cress wheat cress wheat (2, z, 2-trichloro-i-oxyethyl) - chloracetamide. ... ...... 0.005 86 100 25 23 33 Control ............. - 86 72 - - (2, 2, 2-trichloro-i-oxyethyl) - trichloroacetamide .... . ... o, oi 10o 96 65 33 66 Control ...... ...... .. - 75 89 - - ..

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von am Stickstoff trichloralkylsubstituierten, chlorierten Acetamiden der allgemeinen Formel Cl"H(3-") C-CO-NH-CHOH-CCls in der n 1, 2 oder 3 bedeutet, durch Kondensation von Chloralhydrat mit chlorierten Acetamiden der allgemeinen Formel C1"1 ("_$) CONH2, in der n die gleiche Bedeutung wie oben hat, dadurch gekennzeichnet, daß man die Umsetzung in Gegenwart einer starken Säure sich vollziehen läßt und die Reaktionsprodukte von den nicht umgesetzten Reaktionspartnern durch ihre verschiedene Löslichkeit in Lösungsmitteln oder Lösungsmittelgemischen trennt. PATENT CLAIM: Process for the preparation of chlorinated acetamides of the general formula Cl "H (3-") C-CO-NH-CHOH-CCls in which n is 1, 2 or 3, by condensation of chloral hydrate with chlorinated acetamides, which are trichloroalkyl-substituted on nitrogen general formula C1 "1 (" _ $) CONH2, in which n has the same meaning as above, characterized in that the reaction can be carried out in the presence of a strong acid and the reaction products of the unreacted reactants by their different solubility in Solvents or solvent mixtures separates.
DEL13804A 1952-11-07 1952-11-07 Process for the preparation of chlorinated acetamides which are trichloroalkyl-substituted on the nitrogen Expired DE949946C (en)

Priority Applications (1)

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DEL13804A DE949946C (en) 1952-11-07 1952-11-07 Process for the preparation of chlorinated acetamides which are trichloroalkyl-substituted on the nitrogen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEL13804A DE949946C (en) 1952-11-07 1952-11-07 Process for the preparation of chlorinated acetamides which are trichloroalkyl-substituted on the nitrogen

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DE949946C true DE949946C (en) 1956-09-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1151975B (en) * 1960-08-17 1963-07-25 Hoechst Ag Selective means of destroying undesirable plant species

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1151975B (en) * 1960-08-17 1963-07-25 Hoechst Ag Selective means of destroying undesirable plant species

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