US3674811A - Heterocyclic compounds - Google Patents

Heterocyclic compounds Download PDF

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Publication number
US3674811A
US3674811A US868590A US3674811DA US3674811A US 3674811 A US3674811 A US 3674811A US 868590 A US868590 A US 868590A US 3674811D A US3674811D A US 3674811DA US 3674811 A US3674811 A US 3674811A
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US
United States
Prior art keywords
compounds
formula
dimethylol
acid
carbamic acid
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Expired - Lifetime
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US868590A
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English (en)
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Joerg Kern
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Novartis Corp
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Ciba Geigy Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/08—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and more than one oxygen atom
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/41—Amides derived from unsaturated carboxylic acids, e.g. acrylamide
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins

Definitions

  • cyclooctanes are provided These compounds are manufac- 260/561 260/561 260/553 tured by eliminating water from the N,N-dimethylol com- 260/553 D,260/559 6 5 pounds or the mixtures for the formation of these N,N- 8/1 16.2, 252/l39.4, 252/136 dimethylol compounds from formaldehyde and the cor- [51] Int. Cl. ..C07d 87/54 responding amides or carbamic acid esters.
  • heterocyclic [58] Field of Search ..260/338 compounds are suitable as finishing agents for cellulose-containing materials, e.g., for creaseproofing, softening, [56' m- Cited hydrophobizing or oleophobizing textiles. Furthermore they may be useful as flameproofing or antImIcrobIcal agents, or as UNITED STATES PATENTS intermediates in the manufacture of various products.
  • heterocyclic compounds contain a hetero-ring with eight ring members and correspond to the formula wherein R denotes an optionally further-substituted alkyl, alkenyl, aryl, heterocyclic, alkoxy or aryloxy residue.
  • R denotes an optionally further-substituted alkyl, alkenyl, aryl, heterocyclic, alkoxy or aryloxy residue.
  • These eight-membered heterocyclic structures are thus N,N'-substituted l,5-dioxa 3,7-diazacyclooctanes.
  • R denotes an alkyl or aryl residue or a heterocyclic residue, then these residues are bonded to the CO group by a carbon atom.
  • An alkyl residue can be branched or, preferably, unbranched. It can furthermore be free of further substitutents or contain substituents, especially halogen atoms such as fluorine or chlorine. It can for example be low molecular and contain one to three carbon atoms. Higher molecular alkyl residues for example contain 1 l to 21 carbon atoms.
  • the benzene residues above all those with a single benzene ring, should primarily be mentioned.
  • the aromatic rings can also carry substituents, for example alkyl groups such as methyl or ethyl, halogen atoms such as bromine or chlorine, alkoxy groups such as methoxy, trifluoromethyl groups, or carboxylic acid alkyl ester groups.
  • R denotes an alkoxy group
  • this group can again be branched or unbranched, and for example contains one to 22 carbon atoms. It can, like an alkyl group R, contain further substituents and its carbon chain can also be interrupted by hetero-atoms, for example sulphur or oxygen bridges.
  • R denotes an aryloxy residue
  • this is again mainly a residue of the benzene series, for example a monocyclic benzene residue which is not substituted further or is substituted further in the usual manner like an aryl group R.
  • heterocyclic compounds of formula l those of composition (2) CHr-O-HgC are preferred, wherein R denotes an alkyl residue with at most 21 carbon atoms, a halogenalkyl residue with preferably at most 14 carbon atoms, an optionally substituted benzene residue, a pyridine residue, an alkoxy group with at most 22 carbon atoms or a benzene residue bonded to the -CO- group via an oxygen atom.
  • n represents an integer having a value of at most 22 are particularly valuable.
  • the heterocyclic compounds of formula (1) are appropriately manufactured by eliminating water from dimethylol compounds of formula or the mixtures for the formation of these dimethylol compounds which contain anhydrous formaldehyde and a compound of formula RJLM wherein R has the significance indicated and X denotes a hydrogen atom or a methylol group.
  • the compounds of formula (5) which here serve as starting substances are either carboxylic acid dimethylolamides or N,N-dimethylol-carbamic acid esters.
  • dimethylol compounds can be used: dimethylol compounds of amides of aliphatic carboxylic acids such as acetic acid, propionic acid, butyric acid, laun'c acid, stearic acid, oleic acid, behenic acid, monochloracetic, dichloracetic or trichloracetic acid and pivalic acid; dimethylol compounds of amides of aromatic carboxylic acids such as benzoic acid, methylbenzoic acids, chlorobenzoic acids, methoxybenzoic acids, trifluoromethylbenzoic acids, 1- or 2-naphthoic acid and salicylic acid; dimethylol compounds of amides of heterocyclic carboxylic acids such as pyridinecarboxylic acids, especially nicotinic acid; dimethylol compounds of alkyl esters of carbamic acid such as carbamic acid methyl ester, carbamic acid ethyl ester, carbamic acid-n-butylester,
  • the compounds of formula (6)used in the manufacture of the compounds of formula (1) are either carboxylic acid amides or carbamic acid esters or their monomethylol compounds, and in particular one is here dealing with the same compounds from which the corresponding dimethylol compounds of formula (5 are derived.
  • the anhydrous formaldehyde serving as a constituent of the formation mixtures for the manufacture of the compounds of formula l is preferably paraformaldehyde.
  • the course of the reaction depends on the chosen starting products and conditions, and especially on the solvent, in that in non-polar solvents such as benzene or toluene the reaction generally takes place via the dimethylol compound and in polar solvents such as alcohols, for example methanol or ethanol, the reaction as a rule leads directly to a compound of formula (1).
  • the course of the reaction can be easily followed by thin layer chromatography.
  • the preferred compounds of formula (3) are obtained by eliminating water from dimethylol compounds of formula /CH2OH CHzOH or from formation mixtures of these dimethylol compounds,
  • the compounds of formula (4) are obtained from dimethylol compounds offormula CHaOH or from formation mixtures of these dimethylol compounds containing paraformaldehyde and a compound of formula wherein n has the indicated significance.
  • the compounds of formulas (l) to (4) are preferably manufactured from the formation mixtures containing anhydrous formaldehyde and the appropriate carboxylic acid amide or carbamic acid ester.
  • the compounds of formula 1 are above all suitable for the finishing of materials containing cellulose. Here different effects can be achieved depending on the nature of the residue R. A large part of these compounds, but especially those which contain low molecular alkoxy groups as residues R, are suitable for the creaseproofing of textile materials containing cellulose.
  • the compounds of formula (1) contain higher molecular alkoxy groups as residues R, especially alkoxy groups with at least 16 carbon atoms, they can be used for rendering cellulose-containing textile materials water-repellent, whereby in some cases a soft handle of the treated material is simultaneously achieved.
  • the compounds of formula (1) can be used for combatting harmful micro-organisms, inter alia also for protecting materials containing cellulose.
  • the compounds of formula 1) can be applied onto the cellulose-containing fiber materials, preferably textile materials, in the usual manner and fixed thereon.
  • aqueous solutions or dispersions are used, with which cellulose fabrics, preferably cotton fabrics, are impregnated at room temperature or slightly elevated temperature, for example on a padder.
  • fixing can then be carried out at a higher temperature, for example between and C, and approximately in the presence of a curing catalyst having an acid action.
  • EXAMPLE 2 373.5 g (1 mol) of N,N-dimethylol-carbamic acid n-octadecyl ester of formula 0 CHz-OH CHz-OH are fused under nitrogen at 100 C. 185 g (2 mols) of epichlorhydrin are then added dropwise at this temperature over the course of 30 minutes whilst stirring, and the mixture is stirred for a further 12 hours at 100 C. Thereafter the reaction mixture is slowly poured into about 2,000 g of acetone at 20 C, which hereupon rises in temperature up to the boil. After cooling, the mixture is filtered and the filter residue is twice recrystallized from acetone. About 147 g (41 percent of theory) of the compound of formula H ⁇ CH2/m O C N CHr-O-H C of melting point 80 to 83 C are obtained.
  • This compound is especially suitable for rendering cellulose-containing textile material water-repellent.
  • N,N-dimethylol-carbamic acid n-octadecyl ester can be manufactured as follows:
  • EXAMPLE 3 62.7 g of carbamic acid octadecyl ester, 36.03 g of paraformaldehyde and 500 ml of toluene are introduced into a reaction vessel equipped with a stirrer, reflux condenser and thermometer.
  • the mixture is warmed to 60 C internal temperature whilst stirring and a pinch of p-toluenesulphonic acid is then added as the catalyst.
  • the course of the reaction is checked hourly by means of thin layer chromatography. After three hours the reaction has ended.
  • the mixture is filtered hot and is allowed to cool, and the product is twice recrystallized from isopropanol.
  • EXAMPLE 4 46.8 g of chloracetamide, 33 g of paraformaldehyde and 300 ml of methanol are introduced into a reaction vessel equipped with a stirrer, reflux condenser and thermometer.
  • the mixture is heated to the boiling point of the solvent, a little p-toluenesulphonic acid is then added as the catalyst, and the mixture left at this temperature until the reaction has ended after 6 hours, this being established by means of a thin layer chromatogram.
  • the mixture is filtered hot and the filtrate is then concentrated in stages. Hereupon the starting substance still present first precipitates. On further concentration the reaction product is obtained and is recrystallized from benzene until the melting point is constant.
  • the mixture is heated to the boil and a little p-toluenesulphonic acid is then added as the catalyst.
  • the reaction has ended after 7 hours.
  • the mixture is filtered hot and the mother liquor is concentrated to dryness in vacuo. A moderately viscous oil, which soon crystallizes, remains. This is purified by recrystallization from carbon tetrachloride until the melting point is constant.
  • HOH2CHzC-0 0 Cannot be distilled 82. 0 H 5C17- C M.P., 87-83 51. 5
  • EXAMPLE 6 A cotton fabric is impregnated on a padder with an aqueous liquor which per liter contains g of compound of formula 16) and 7.5 g of ammonium phosphate as well as 150 g of reactive emulsifier.
  • the fabric After squeezing out, the weight increase is about 68 percent.
  • the fabric is dried for 30 minutes at 80 C and thereafter subjected to a heat treatment for 4% minutes.
  • the fabric treated in this way is water-repellent.
  • the 50 percent strength aqueous solution of a trans-ethen'fication product of hexarnethylolmelamine-pentabutyl ether and a polyglycol of average molecular weight 4,000 is used as the reactive emulsifier.
  • n is an integer having a value of at most 22.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US868590A 1968-11-01 1969-10-22 Heterocyclic compounds Expired - Lifetime US3674811A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1633268A CH498858A (de) 1968-11-01 1968-11-01 Verfahren zur Herstellung von acht Ringglieder enthaltenden heterocyclischen Verbindungen

Publications (1)

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US3674811A true US3674811A (en) 1972-07-04

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US (1) US3674811A (enrdf_load_stackoverflow)
JP (2) JPS4820558B1 (enrdf_load_stackoverflow)
AT (1) AT292009B (enrdf_load_stackoverflow)
BE (1) BE741092A (enrdf_load_stackoverflow)
BR (1) BR6913810D0 (enrdf_load_stackoverflow)
CH (1) CH498858A (enrdf_load_stackoverflow)
CS (1) CS153533B2 (enrdf_load_stackoverflow)
DE (1) DE1953249A1 (enrdf_load_stackoverflow)
FR (1) FR2022359A1 (enrdf_load_stackoverflow)
GB (1) GB1257948A (enrdf_load_stackoverflow)
NL (1) NL6916452A (enrdf_load_stackoverflow)
NO (1) NO126020B (enrdf_load_stackoverflow)
PL (1) PL80406B1 (enrdf_load_stackoverflow)
SE (1) SE363335B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445762A (en) * 1991-08-21 1995-08-29 Hoechst Aktiengesellschaft Stabilized complex ligands and their use in liquid crystal displays
US6077319A (en) * 1996-09-13 2000-06-20 The Regents Of The University Of California Processes for preparing microbiocidal textiles
US6241783B1 (en) 1996-09-13 2001-06-05 The Regents Of The University Of California Formaldehyde scavenging in microbiocidal articles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3329368A1 (de) * 1983-08-13 1985-02-28 Richard Hirschmann Radiotechnisches Werk, 7300 Esslingen Hochfrequenz-rohrkernuebertrager mit in drucktechnik ausgefuehrten wicklungen

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5445762A (en) * 1991-08-21 1995-08-29 Hoechst Aktiengesellschaft Stabilized complex ligands and their use in liquid crystal displays
US6077319A (en) * 1996-09-13 2000-06-20 The Regents Of The University Of California Processes for preparing microbiocidal textiles
US6241783B1 (en) 1996-09-13 2001-06-05 The Regents Of The University Of California Formaldehyde scavenging in microbiocidal articles

Also Published As

Publication number Publication date
BR6913810D0 (pt) 1973-01-16
NL6916452A (enrdf_load_stackoverflow) 1970-05-06
SE363335B (enrdf_load_stackoverflow) 1974-01-14
CH1633268A4 (enrdf_load_stackoverflow) 1970-12-31
NO126020B (enrdf_load_stackoverflow) 1972-12-11
PL80406B1 (enrdf_load_stackoverflow) 1975-08-30
CH498858A (de) 1970-12-31
DE1953249A1 (de) 1970-05-27
CS153533B2 (enrdf_load_stackoverflow) 1974-02-25
FR2022359A1 (enrdf_load_stackoverflow) 1970-07-31
JPS4820558B1 (enrdf_load_stackoverflow) 1973-06-21
BE741092A (enrdf_load_stackoverflow) 1970-04-30
GB1257948A (enrdf_load_stackoverflow) 1971-12-22
JPS4821115B1 (enrdf_load_stackoverflow) 1973-06-26
AT292009B (de) 1971-08-10

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