US3674811A

US3674811A - Heterocyclic compounds

Info

Publication number: US3674811A
Application number: US868590A
Authority: US
Inventors: Joerg Kern
Original assignee: Ciba Geigy Corp
Current assignee: Novartis Corp
Priority date: 1968-11-01
Filing date: 1969-10-22
Publication date: 1972-07-04
Anticipated expiration: 1989-07-04
Also published as: CS153533B2; GB1257948A; JPS4821115B1; JPS4820558B1; FR2022359A1; NL6916452A; PL80406B1; DE1953249A1; BE741092A; SE363335B; CH498858A; NO126020B; AT292009B; CH1633268A4; BR6913810D0

Abstract

Heterocyclic compounds containing a hetero-ring with eight ring members, namely N,N''-substituted 2,5-dioxa-3,7-diazacyclooctanes are provided. These compounds are manufactured by eliminating water from the N,N-dimethylol compounds or the mixtures for the formation of these N,N-dimethylol compounds from formaldehyde and the corresponding amides or carbamic acid esters. The heterocyclic compounds are suitable as finishing agents for cellulose-containing materials, e.g., for creaseproofing, softening, hydrophobizing or oleophobizing textiles. Furthermore they may be useful as flameproofing or antimicrobical agents, or as intermediates in the manufacture of various products.

Description

0 United States Patent [151 3,674,81 1

Kern July 4, 1972 s41 HETEROCYCLIC COMPOUNDS FORElGN PATENTS OR APPLICATIONS [72] Inventor: Joerg Kern, Oberwil/Basel-land, Switzer- 1,49 9/ 1967 France I d I an OTHER PUBLlCATlONS [73] Asslgnee' CIBA-GEIGY Corporation Basel Swlt' Houben-Weyl, Methoden der Organischen Chemie Vl/4 zerland (1966), P. 692 [22] Filed: Oct. 22, 1969 4 Primary Examiner-Norma S. Milestone [21] PP N03 868,590 AnorneyHarry Goldsmith, Joseph G. Kolodny and Mario A.

Monaco [30] Foreign Appllcation Priority Data I 57] ABSTRACT Nov. 1, 1968 Switzerland ..16332/68 Heterocycfic compounds containing a hetero ring with eight ring members, namely N,N'-substituted 2,5-dioxa-3,7-diaza- US. Cl. 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. The 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.

2,468,722 4/1949 Wyler ..260/338 3Claims,No Drawings HETEROCYCLIC COMPOUNDS The subject of the invention are heterocyclic compounds. These 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. These eight-membered heterocyclic structures are thus N,N'-substituted l,5-dioxa 3,7-diazacyclooctanes.

If 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.

Amongst the aryl residues R, 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.

As heterocyclic residues, the residues of pyridine bases may be mentioned. If R denotes an alkoxy group, then 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.

If R denotes an aryloxy residue, then 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.

Accordingly, amongst the 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.

Compounds of particular interest are those corresponding to formula wherein 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.

For example, the following 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, carbamic acid n-dodecylester and carbamic acid n-octadecylester; dimethylol compounds of aryl esters of carbamic acid such as carbamic acid phenylester and carbamic acid pmethylphenyl ester.

Both carboxylic acid dimethylolamides and N,N- dirnethylol-carbamic acid esters are in themselves known, and otherwise these compounds can be manufactured according to methods which are in themselves known. Appropriately, corresponding H N-compounds are reacted with excess paraforrnaldehyde in an organic solvent, optionally with the addition of alkali hydroxide.

Water is now eliminated from the dimethylol compounds obtainable in this way, with the eight-membered hetero-ring forming from two molecules of dimethylol compound with the elimination of two molecules of water:

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 elimination of water from the formation mixtures, with the formation of an eight-membered hetero-ring, takes place directly, that is to say without significant intermediate formation of dimethylol compounds of formula (5), or indirectly,

that is to say via the dimethylol compound of formula 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.

In the manufacture from the formation mixtures the condensation also takes place with the elimination of two molecules of water.

Compounds of formula (2) are appropriately obtained by eliminating water from dimethylol compounds of formula CH2OH or from formation mixtures of these dimethylol compounds, containing anhydrous formaldehyde and a compound of formula wherein R has the indicated significance.

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,

wherein R has the indicated significance.

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.

Depending on the constitution of the starting substances, somewhat different working instructions can prove particularly advantageous for the elimination of water. It is generally advisable to carry out this elimination at elevated temperature, for example 30 to 130 C. In many cases the addition of reagent which eliminates water and is in itself known, for example H PO HCl H 80 trifluoroacetic acid and especially p-toluenesulphonic acids, is indicated. This is for example the case for the simplest urethane, N,N-dimethylol-carbamic acid ethyl ester. In other cases it proves advantageous to use an organic solvent instead of the agent which eliminates water or additionally thereto, for example when formation mixtures are used"; Ifstarting from urethanes with higher alkyl residues, for example N,N-dimethylolcarbamic acid octadecyl ester, the elimination of water in epichlorhydrin, for which no further additives are required, proves particularly advantageous.

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.

If 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.

Furthermore the compounds of formula (1), especially those of which the residues R possess halogen atoms, can be used for combatting harmful micro-organisms, inter alia also for protecting materials containing cellulose.

Finally, a flameproofing effect on cellulose-containing textile materials can also be achieved with these compounds. Compounds of formula (1) which possess perfluoralkyl residues, are suitable for rendering the most diverse substrates oleophobic, especially fiber materials such as textiles or paper.

The compounds of formula 1) can be applied onto the cellulose-containing fiber materials, preferably textile materials, in the usual manner and fixed thereon. Appropriately, 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. After a preliminary drying, for example at temperatures between 50 and C, 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 1 100 g (0.74 mol) of N,N-dimethylol-carbamic acid methyl ester of formula 13 CHz-OII CHg-Oll remains in the form of colorless prisms which are recrystallized from methanol. Melting point: 134 to 136 C.

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.

The N,N-dimethylol-carbamic acid n-octadecyl ester can be manufactured as follows:

200 g (0.64 mol) of octadecylcarbamate are initially introduced into 800 ml of toluene, and mixed with 126 g (4.2 mols) of paraformaldehyde and 1 g of powdered sodium hydroxide. The mixture is stirred for 20 hours at 60 C. It is then filtered hot. The product crystallizes out from the filtrate on cooling, and is filtered off and then washed with n-pentane. About 130 g (54 percent of theory) are thus obtained. The melting point of the dimethylol compound of formula (15) is 8 1 to 83 C.

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.

Melting point: 79 to 81 C. Yield 49.7 g (=70 percent of theory). The mass spectrum and infrared spectrum show that the reaction product corresponds to formula 16).

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.

Melting point 101 to 102 C, yield 59 percent of theory. The mass spectrum and infrared spectrum show that the reaction product corresponds to the formula EXAMPLE 5 41 g of trichloracetamide, 30 g of parafonnaldehyde and 500 ml of methanol are introduced into a reaction vessel equipped with a stirrer and reflux condenser and thermometer.

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.

Melting point 1 19 to C. Yield: 53.2 percent. The mass spectrum and infrared spectrum show that the reaction product corresponds to the formula ant-04sec Further compounds of formula (1) are listed in the table which follows. Column I gives the composition of the residue R. Column H relates to the manufacturing process. Herein A denotes: manufacture as in Example 1, with dimethylol compound as the starting substance; B denotes: manufacture as in Example 3, from H N-cornpound and paraformaldehyde in an inert organic solvent (toluene); C denotes: manufacture as in Example 4, from H N-compound and paraformaldehyde in a polar organic solvent (methanol). Column 111 indicates which melting points (m.p.) or boiling points (b.p.) were found for the compounds of formula (1) manufactured in the indicated manner. and column IV contains data as to the yield.

I II III IV Yield, Composition of R- Process M.P., b.p., 0.) percent H CO-- A M.P., 134-136 23. 4 H CO- C M.P., 135-131 41.8 H37018-0- B M.P., 79-81 69. 7

rltr livr B Cannot be distilled 95. 7 HzCHCH2C-O H2C=HCHzCO- A B.P., -150 at 6 57. 7

C M.P., 128138.5 85. 6

HOH2CHzC-0 0 Cannot be distilled 82. 0 H 5C17- C M.P., 87-83 51. 5

('31 C M.P., 101-102 59. 0 H2C- C1 C B M.P., 115-117 53.2 F3C(CF2)7 C 34.3

f j C 80.1

f j o 85.1

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.

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.

EXAMPLE 7 in which n is an integer having a value of at most 22.

2. The compound according to claim 1 which corresponds to the formula 3. The compound according to claim 1 which corresponds to the formula O H cm oJLN "H050. UNITED STATES PATENT OFFICE 69 CETTFTCATE F CORECTION Patent No. 3,67 hall Dated July 4, 197

Inventor(s) Joerg Kern It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, [73], after "CIBA-GEIGY" delete "Corporation" .and

substitute AG Signed and sealed this 23rd day of April 197M (SEAL) Attest:

EDWARD M.FLETCHER,JR. c. MARSHALL DANN Atte sting Officer Commissioner of Patents

Claims

2. The compound according to claim 1 which corresponds to the formula
3. The compound according to claim 1 which corresponds to the formula