US2644003A - Quaternary ammonium compounds and their manufacture - Google Patents

Quaternary ammonium compounds and their manufacture Download PDF

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Publication number
US2644003A
US2644003A US209210A US20921051A US2644003A US 2644003 A US2644003 A US 2644003A US 209210 A US209210 A US 209210A US 20921051 A US20921051 A US 20921051A US 2644003 A US2644003 A US 2644003A
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quaternary ammonium
manufacture
ammonium compounds
compounds
ammonium chloride
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US209210A
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Gysin Hans
Hagenbach Rudolf Edward
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Novartis AG
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JR Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • 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
    • A01N37/44—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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • C07C233/45—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 carboxyl groups
    • C07C233/46—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 carboxyl groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/06—Protein or carboxylic compound containing

Definitions

  • R represents an alkyl radical with 7--15 C atoms
  • Hal represents chlorine or bromine
  • R represents a low alkyl radical
  • R.” represents hydrogen, chlorine, bromine, an
  • alkyl or alkoxy radical or more of these substituents.
  • the compounds according to the present invention also have the advantage that they are mostly solid crystallised bodies and therefore come into consideration for a greater number of intended uses.
  • the new compounds can be produced by various related processes.
  • RCON CHa-CHzN cfls can be reacted with halogen acetanilides of the general formula:
  • the above reactions may take place in the wesence or absence'of suitable solvents such as benzene, toluene, xylene, acetone, ethyl and butyl acetate and also water, and may be simplified if required by the addition of small amounts of potassium iodide.
  • suitable solvents such as benzene, toluene, xylene, acetone, ethyl and butyl acetate and also water, and may be simplified if required by the addition of small amounts of potassium iodide.
  • the basic amides used in the first above reaction can be obtained for example by heating higher fatty acids, in particular lauric acid or myristic acid, or also palmitic acid, with low dimethylamino ethyl alkylamines for a fairly long period.
  • higher fatty acids in particular lauric acid or myristic acid, or also palmitic acid
  • low dimethylamino ethyl alkylamines for a fairly long period.
  • Derivatives of the free fatty acids in particular acid halides or esters, may also be used.
  • the alkyl radical of the fatty acid should have a homogenous chain.
  • Mixtures of higher fatty acids may be used with advantage, as they result from the saponification of vegetable and animal fats and oils.
  • Such mixtures of fatty acids e. g. from palm kernal fats, apart from fatty acids with an average alkyl chain length of 11-13 carbon atoms, also contain small portions of lower and higher fatty acids. By distilling once, these portions can be separated and then a fatty acid mixture is obtained with an alkyl chain length of substantially 11-13 carbon atoms.
  • the radical of this fatty acid mixture is referred to in the examples as Lauroyl radical.
  • dichloranilide, -2.4-dimethylanilide and -2.5-dimethylanilide can be named as examples of halogen acetanilides of the general formula:
  • Hal-OHz-CO-NHQ medical instruments patients personal and bed linen.
  • the solutions for use may be prepared in the usual way, e. g. by diluting concentrated solutions or also by direct dissolution of the solid compounds in water.
  • the new compounds may also be prepared in tablet form.
  • they can also be adapted for various intended uses by the addition of other materials with a disinfectant action, such as phenols, or of rust-proofing agents such as sodium nitrite or sodium salt of octyloxyacetic acid. They can also be combined with pulverulent substances or with organic solvents and also incorporated in ointments and pastes.
  • the disinfectant action is excellent both against gram positive and gram negative germs such as staphylococci, and bacterium coli, typhus, paratyphus B', bacterium pyocyaneum, enteritis-Gartner, etc. respectively.
  • Example 2 298 parts of dodecanoyl-N.N-dimethylaminoethyl-N-ethy1amide and 183.5 parts of chloraceto-p-toluidide are heated for 8 hours under reflux with 700 parts of benzene.
  • the benzene is distilled oiT and the solid residue is recrystalethy1-N-propylamide (B. P. 130150 at 0.3 mm. pressure), prepared for example from lauric acid methylester and N.N-dimethyl'-N-propyl-ethyl@- enediamine, are heated for 12 hours in a boiling Water bath While stirring with 169.5 parts of chloracetanilide. After cooling, the solid mass is recrystallized from ethyl acetate/acetone.
  • R represents an alkyl chain of from 9 to 15 carbon'atoms
  • R.” represents an alkyl radical of from 1 to 3 carbon atoms
  • R represents a substituent selected. from the group consisting of hydrogen, chlorine, methyl and methoxy.

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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

Patented June 30, 1953 QUATERNARY AMMONIUM COMPOUNDS AND THEIR MANUFACTURE Hans Gysin and Rudolf Edward Hagenbach, Basel, Switzerland, assignors to J. R. Geigy A. G., Basel, Switzerland, a Swiss firm No Drawing. Application February 2, 1951, Serial No. 209,210. In Switzerland February 24, 1950 Claims. (01. 260-4045) According to the present invention, new quaternary ammonium compounds are provided having the general formula:
wherein R represents an alkyl radical with 7--15 C atoms,
Hal represents chlorine or bromine,
R represents a low alkyl radical, and
R." represents hydrogen, chlorine, bromine, an
alkyl or alkoxy radical, or more of these substituents.
It has been found that these compounds are distinguished from the previously known quaternary ammonium compounds by a very strong bactericidal activity and at the same time in contrast to the greater part of thelatter compounds,
the compounds according to the present invention also have the advantage that they are mostly solid crystallised bodies and therefore come into consideration for a greater number of intended uses.
The new compounds can be produced by various related processes.
The basic amides of the general formula:
RCON CHa-CHzN cfls can be reacted with halogen acetanilides of the general formula:
In these and all following formulae, R, Hal, R, and R." always have the meanings given above.
Also, compoundsof the general formula:
can be reacted in the autoclave with methyl chloride or methyl bromide.
The above reactions may take place in the wesence or absence'of suitable solvents such as benzene, toluene, xylene, acetone, ethyl and butyl acetate and also water, and may be simplified if required by the addition of small amounts of potassium iodide.
The basic amides used in the first above reaction can be obtained for example by heating higher fatty acids, in particular lauric acid or myristic acid, or also palmitic acid, with low dimethylamino ethyl alkylamines for a fairly long period. Derivatives of the free fatty acids, in particular acid halides or esters, may also be used.
In this reaction it is not necessary that the alkyl radical of the fatty acid should have a homogenous chain. Mixtures of higher fatty acids may be used with advantage, as they result from the saponification of vegetable and animal fats and oils. Such mixtures of fatty acids, e. g. from palm kernal fats, apart from fatty acids with an average alkyl chain length of 11-13 carbon atoms, also contain small portions of lower and higher fatty acids. By distilling once, these portions can be separated and then a fatty acid mixture is obtained with an alkyl chain length of substantially 11-13 carbon atoms. The radical of this fatty acid mixture is referred to in the examples as Lauroyl radical.
Chloracetoand bromaceto anilide, -o-tolu"- dide, -mtoluidide, -p-toluidide, -o-anisidide, -manisidide, -p-anisidide, -'o-chloranilide, -in-chloranilide, -p-chloranilide, -p-bromanilide, -3.4-
dichloranilide, -2.4-dimethylanilide and -2.5-dimethylanilide can be named as examples of halogen acetanilides of the general formula:
Hal-OHz-CO-NHQ medical instruments, patients personal and bed linen. The solutions for use may be prepared in the usual way, e. g. by diluting concentrated solutions or also by direct dissolution of the solid compounds in water. For this latter purpose the new compounds may also be prepared in tablet form. Further, they can also be adapted for various intended uses by the addition of other materials with a disinfectant action, such as phenols, or of rust-proofing agents such as sodium nitrite or sodium salt of octyloxyacetic acid. They can also be combined with pulverulent substances or with organic solvents and also incorporated in ointments and pastes. The disinfectant action is excellent both against gram positive and gram negative germs such as staphylococci, and bacterium coli, typhus, paratyphus B', bacterium pyocyaneum, enteritis-Gartner, etc. respectively.
As result of the capillary ante pro erties of the new compounds, they also come into consideration as Wetting and dispersing agents for. various technical purposes, for example in the leather, paper and textile industries.
The following examples serve to illustrate the invention. Parts are always given as parts by.
weight and temperaturesare in' degreescenti grade. 7 I 3 Examplel 28 parts of dodecanoyl N.N dimethylamino ethyl-N-methyl amide (boiling point 1510-160? at 0.3 mm. pressure) produced, for example from lauric acid. and trimethyl ethylenecliamine, are
"boiled for 6. hours underreflux with 169.5 parts of chloracetanilide-in 800 parts of ethyl acetate. The precipitate which forms on standing is drawn off by suction. (Dodecanoyl-N-methyl-aminoethyl). (phenylcarbamyl-methyl) -dimethyl ammonium chloride is obtained'on recrystallization from acetone'as 'a White substance. It melts at 124 and is completely soluble inwater.
is produced inlan I i The corresponding bromide analogous manner." V
7 Example 2 298 parts of dodecanoyl-N.N-dimethylaminoethyl-N-ethy1amide and 183.5 parts of chloraceto-p-toluidide are heated for 8 hours under reflux with 700 parts of benzene. The benzene ,is distilled oiT and the solid residue is recrystalethy1-N-propylamide (B. P. 130150 at 0.3 mm. pressure), prepared for example from lauric acid methylester and N.N-dimethyl'-N-propyl-ethyl@- enediamine, are heated for 12 hours in a boiling Water bath While stirring with 169.5 parts of chloracetanilide. After cooling, the solid mass is recrystallized from ethyl acetate/acetone.
(Dodecanoyl N-propylamino ethyD-(phenylcarbamylmethyD-dimethyl ammonium chloride is obtained as 'a White crystalline substance. It melts at 135 and is completely'soluble in water.
The corresponding bromide is produced in an analogous manner.
The following compounds may pared inthe above described manner:
( Dodecanoyl-N' -methylamino ethyl) (pechloroalso be pre L phenylcarbamylmethyl) dimethyl ammonium chloride, M. P. 116. (Dodecanoyl N-ethy1amino ethyl) -(phenylcar'- bamylmethyl)'-dimethyl ammonium chloride.
M. P. 164. A (Dodecanoyl-N'-propylamino ethyl) -(p-toly1carbamylmethyl) dirnethyl ammonium chloride.
(Lauroy1-N-methylamino ethyl) (phenylcarbamylmethyl) -dimethyl ammonium chloride. M. P. about 110.
(Dodecanoyl N methylaminoethyl) -(p-methoxyphenylcarbamylmethyl) dimethyl ammomum.
Whatweclaimis: v,
mula
l. A quaternary ammonium'chloride of the for r mula:
wherein R represents an alkyl chain of from 9 to 15 carbon'atoms,
R." represents an alkyl radical of from 1 to 3 carbon atoms,
R represents a substituent selected. from the group consisting of hydrogen, chlorine, methyl and methoxy. r
2. A quaternary ammonium chloride of the formula:
C11H23C OI?'--CHQQHQN A quaternary ammonium chloride of the for- C2115 CH3 41A quaternary ammonium chloride ofthefor- CH3 CH3 wherein R represents an alkyl chain of from 11 to 13 carbon atoms.
5. A quaternary ammonium chloride of the formula:
HANS GYSIN. I RUDOLF EDWARD HAGENBACH.
References Cited in the file of this patent UNITED STATES PATENTS Number Name 'Date 1,737,458 Hartmann et a1. Nov. 26, 1929 2,345,570 Bley Apr. 4, 1944 2,459,062
Cook Jan. 11, 1 949
US209210A 1950-02-24 1951-02-02 Quaternary ammonium compounds and their manufacture Expired - Lifetime US2644003A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2851466A (en) * 1955-02-04 1958-09-09 Miles Lab Substituted polyamines
US2935474A (en) * 1955-11-28 1960-05-03 Visco Products Co Process of inhibiting corrosion and corrosion inhibiting compositions
US3028402A (en) * 1952-12-12 1962-04-03 Ciba Ltd High molecular nitrogen condensation products
US4855497A (en) * 1985-04-02 1989-08-08 Chugai Seiyaku Kabushiki Kaisha Novel diamine derivatives

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1737458A (en) * 1927-07-26 1929-11-26 Chem Ind Basel Quaternary ammonium compound and process of making same
US2345570A (en) * 1938-10-07 1944-04-04 North American Rayon Corp Coagulating bath containing cationactive inhibitors
US2459062A (en) * 1944-02-08 1949-01-11 American Cyanamid Co Quaternary ammonium compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1737458A (en) * 1927-07-26 1929-11-26 Chem Ind Basel Quaternary ammonium compound and process of making same
US2345570A (en) * 1938-10-07 1944-04-04 North American Rayon Corp Coagulating bath containing cationactive inhibitors
US2459062A (en) * 1944-02-08 1949-01-11 American Cyanamid Co Quaternary ammonium compounds

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3028402A (en) * 1952-12-12 1962-04-03 Ciba Ltd High molecular nitrogen condensation products
US2851466A (en) * 1955-02-04 1958-09-09 Miles Lab Substituted polyamines
US2935474A (en) * 1955-11-28 1960-05-03 Visco Products Co Process of inhibiting corrosion and corrosion inhibiting compositions
US4855497A (en) * 1985-04-02 1989-08-08 Chugai Seiyaku Kabushiki Kaisha Novel diamine derivatives

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