Antibacterial surface active agent containing azaalkenelactam

TECHNICAL FIELD
This invention relates to novel antibacterial surface active agents containing novel cyclic amides. More particularly, the antibacterial surface active agent of this invention comprises a compound which has in the same molecule a hydrophobic group comprising a chain of 8 to 22 carbon bonds and a hydrophilic group as shown below, comprising a 7- or 8--membered lactam group containing a basic nitrogen atom, ##STR2## wherein R', R" and R'" are hydrogen atoms or methyl groups, m=1 or 2 and n=2 or 3; said compound may assume a structure which allows the compound to combine at the position of said basic nitrogen atom with an organic acid radical by covalent bond or to add to an organic or inorganic acid.
DISCLOSURE OF THE INVENTION
As a result of extensive studies, the present inventors confirmed by IR, NMR and mass spectral analyses of the reaction products that on reacting an acetoacetic ester or formylpropionic ester of a lower alcohol with a polyamine having primary amino groups and secondary amino groups which are interposed therebetween with 2 or 3 methylene radicals there is formed at first a nitrile bond by the reaction between said primary amino group of the polyamine and the carbonyl group of the ketone or aldehyde, followed by the formation of a lactam group by the reaction between said secondary amino group and the carbonyl group of the ester in the same molecule; they further confirmed by neutralization titration using an organic and an inorganic acids that the nitrogen forming said nitrile bond has a basic property, and found that the reaction products including those having an organic acid radical obtained by the reaction of a monohalocarboxylic acid with said nitrogen have a surface activity at the liquid-water interfaces and have an antibacterial activity, too.
More particularly, the antibacterial surface active compound of this invention is a cyclic amide represented by the general formula ##STR3## (wherein, R is an alkyl group, alkenyl group, alkylaryl preferably monoalkylphenyl group, alkylarylalkyl preferably monoalkylbenzyl group, hydroxyalkyl group, acyl preferably alkylcarbonyl or alkenylcarbonyl group, or hydroxyl-substituted acyl preferably hydroxyl-substituted alkycarbonyl or alkenylcarbonyl group having 8 to 22 total carbon atoms, R', R" and R'" are hydrogen atoms or methyl groups, A is hydrogen atom or hydroxyl group, O.ltoreq.W.ltoreq.1, O.ltoreq.X+Z.ltoreq.3, O.ltoreq.Y.ltoreq.3, O.ltoreq.p+q+r.ltoreq.3, m=1 or 2, and n=2 or 3; said cyclic amide may have a structure which, if necessary, allows the nitrogen atoms, except for the amide group, to combine with an organic acid radical by covalent bond or to add to an organic or inorganic acid) which is formed by reacting an acetoacetic ester or formylpropionic ester of an alcohol having 4 or less carbon atoms with at least one compound represented by the general formula ##STR4## (wherein R is an alkyl group, alkenyl group, alkylaryl preferably monoalkylphenyl group, alkylarylalkyl preferably monoalkylbenzyl group, hydroxyalkyl group, acyl preferably alkyl- or alkenylcarbonyl group, or hydroxyl-substituted acyl preferably hydroxy-substituted alkyl- or alkenylcarbonyl group having 8 to 22 total carbon atoms, A is hydrogen atom or hydroxyl group, O.ltoreq.W.ltoreq.1, O.ltoreq.X+Z.ltoreq.3, O.ltoreq.V.ltoreq.3, 1.ltoreq.a+b+c.ltoreq.4) composed of a terminally monoalkylated polyalkylenepolyamine (the hydrocarbon radicals include alkyl groups, alkenyl groups, alkylaryl preferably monoalkylbenzyl groups, alkylarylalkyl preferably monoalkylbenzyl groups, hydroxyalkyl groups, alkoxyalkyl groups, alkoxyhydroxyalkyl groups, etc.), said polyalkylenepolyamine being obtained by the addition of 1 to 3 moles of ethyleneimine to 1 mole of ethylenediamine or 1,3-propylenediamine or by the addition of acrylonitrile to said diamine followed by hydrogenation, said addition and hydrogenation being repeated 1 to 3 times (in each reaction cycle, 1 mole of acrylonitrile and 2 moles of hydrogen are used for 1 mole of the amine used as starting material) or by carrying out the above both reactions; a polyalkylenepolyamine (the hydrocarbon groups thereof include alkyl groups, alkenyl groups, hydroxyalkyl groups, hydroxyalkenyl groups, etc.); and a monoalkylated (the hydrocarbon groups thereof include alkyl groups, alkenyl groups, alkylaryl preferably monoalkylphenyl groups, alkylarylalkyl preferably monoalkylbenzyl groups, hydroxyalkyl groups, alkoxyalkyl groups, alkoxyhydroxyalkyl groups, etc.) ethylenediamine and 1,3-propylenediamine; or formed by reacting an acetoacetic ester or formylpropionic ester of an alcohol having 4 or less carbon atoms with 1, 2, or more polyalkylenepolyamines obtained by the addition of 1 to 3 moles of ethyleneimine to 1 mole of ethylenediamine or 1,3-propylenediamine, or by 1 to 3 cycles of the addition of acrylonitrile followed by hydrogenation (the molar ratio in each reaction cycle is 1 mole of acrylonitrile and 2 moles of hydrogen for 1 mole of the amine used as starting material), or by carrying out the above both reactions, and then, further reacting with a carboxylic acid having an alkyl, alkenyl or hydroxyalkenyl group of 7 to 21 carbon atoms; or formed by reacting an acetoacetic ester or formylpropionic ester of an alcohol having 4 or less carbon atoms with hydroxyethylated ethylenediamine, hydroxypropylated ethylenediamine, hydroxyethylated 1,3-propylenediamine and hydroxypropylated 1,3-propylenediamine and then further reacting with a carboxylic acid having an alkyl group, alkenyl group, hydroxyalkyl group or hydroxyalkenyl group and/or reacting with a monochlorinated or monobrominated carboxylic acid or a salt thereof.
As for the polyalkylenepolyamines used as starting materials for the above-said amines, mention may be made of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, adduct of 1,3-propylenediamine with 1 mole ethyleneimine, adduct of 1,3-propylene diamine with 2 moles ethyleneimine, adduct of 1,3-propylenediamine with 3 moles ethyleneimine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, and polyethylenepolypropylenepolyamine having 5 or less nitrogen atoms in total. As for the monoalkylated products of these amines, there may be cited monooctylated product, monononylated product, monodecylated product, monoundecylated product, monododecylated product, monotridecylated product, monotetradecylated product, monopentadecylated product, monohexadecylated product, monooctadecylated product, mono(9-octdecenyl)ated product, monoeicosylated product, monodocosylated product, mono(2-hydroxy)dodecylated product, mono(2-hydroxy)hexadecylated product, mono(2-hydroxy)tetradecylated product, mono(2-hydroxy)docosylated product, monooctoxy(2-hydroxy)propylated product, monononylphenoxy(2-hydroxy)propylated product, monododecoxy(2-hydroxy)propylated product, monooctylpoly(1-3 moles)oxyethylated product, monononylpoly(1-3 moles)oxyethylated product, monodecylpoly(1-3 moles)oxyethylated product, monoundecylpoly(1-3 moles)oxyethylated product, monododecylpoly(1-3 moles)oxyethylated product, monotridecylpoly(1-3 moles)oxyethylated product, monotetradecylpoly(1-3 moles)oxyethylated product, monopentadecylpoly(1-3 moles)oxyethylated product, monohexadecylpoly(1-3 moles)oxyethylated product, monooctadecylpoly(1-3 moles)oxyethylated product, mono(9-octadecenyl)poly(1-3 moles)oxyethylated product, monoeicosylpoly(1-3 moles)oxyethylated product, monodocosylpoly(1-3 moles)oxyethylated product, monobutylphenylpoly(1-3 moles)oxyethylated product, monooctylphenylpoly(1-3 moles)oxyethylated product, monononylphenylpoly(1-3 moles)oxyethylated product, monooctylpoly(1-3)oxypropylated product, monononylpoly(1-3 moles)oxypropylated product, monodecylpoly(1-3 moles)oxypropylated product, monododecylpoly(1-3 moles)oxypropylated product, monotridecylpoly(1-3 moles)oxypropylated product, monotetradecylpoly(1-3 moles)oxypropylated product, monopentadecylpoly(1-3 moles)oxypropylated product, monohexadecylpoly(1-3 moles)oxypropylated product, monooctadecylpoly(1-3 moles)oxypropylated product, mono(9-octadecenyl)poly(1-3 moles)oxypropylated product, monoeicosylpoly(1-3 moles)oxypropylated product, monodocosylpoly(1-3 moles)oxypropylated product, monobutylphenyl(1-3 moles)oxypropylated product, monooctylphenyl(1-3 moles)oxypropylated product, monononylphenyl(1-3 moles)oxypropylated product, monooctylpoly(2-3 moles in total)oxyethyloxypropylated product, monononylpoly(2-3 moles in total)oxyethyloxypropylated product, monodecylpoly(2-3 moles in total)oxyethyloxypropylated product, monoundecylpoly(2-3 moles in total)oxyethyloxypropylated product, monododecylpoly(2-3 moles in total)oxyethyloxypropylated product, monotridecylpoly(2-3 moles in total)oxyethyloxypropylated product, monotetradecylpoly(2-3 moles in total)oxyethyloxypropylated product, monopentadecylpoly(2-3 moles in total)oxyethyloxypropylated product, monohexadecylpoly(2-3 moles in total)oxyethyloxypropylated product, monooctadecylpoly(2-3 moles in total)oxyethyloxypropylated product, mono(9-octadecenyl)poly(2-3 moles in total)oxyethyloxypropylated product, monoeicosylpoly(2-3 moles in total)oxyethyloxypropylated product, monodocosylpoly(2-3 moles)oxyethyloxypropylated product, monobutylphenylpoly(2-3 moles in total)oxyethyloxypropylated product, monooctylphenylpoly(2-3 moles in total)oxyethyloxypropylated product, and monononylphenylpoly(2-3 moles in total)oxyethyloxypropylated product. Among monohydroxyalkylalkylenediamines, there may be cited monohydroxyethylethylenediamine, monohydroxyethyl1,3-propylenediamine, monohydroxypropylethylenediamine and monohydroxypropyl-1,3-propylenediamine. As for the acetoacetic esters, on the other hand, mention may be made of methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, isopropyl acetoacetate and butyl acetoacetate. As for the formylpropionic esters, there may be cited methyl, ethyl, propyl and butyl esters of 2-formylpropionic acid, 3-formylpropionic acid, 2-formyl-2-methylpropionic acid and 3-formyl-2-methylpropionic acid. Among carboxylic acids, mention may be made of octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linolic acid, 12-hydroxystearic acid, ricinolic acid and behenic acid. As for the monohalogenated carboxylic acids, there may be cited monochloroacetic acid, monobromoacetic acid, and monochloropropionic acid.
In producing the antibacterial surface active compound of this invention, the reaction between an acetoacetic ester or formylpropionic ester and a monoamide prepared from a carboxylic acid and a polyalkylenepolyamine, N-alkylpolyalkylenepolyamine, N-alkoxyalkylpolyalkylenepolyamine, monohydroxyalkylalkylenediamine or polyalkylenepolyamine is allowed to proceed by removing water or an alcohol under reduced pressure or atmospheric pressure at 50.degree. to 250.degree. C., preferably 100.degree. to 180.degree. C., thus leading to the N-alkylazaalkenylactam of this invention. In this case, neither a catalyst nor a solvent is particularly needed, while bubbling of an inert gas such as nitrogen or carbon dioxide is effective in accelerating the reaction. The reaction between an N-alkylazaalkenelactam and a monohalogenated carboxylic acid is allowed to proceed by bringing both into contact with each other at 30.degree. to 100.degree. C., preferably 50.degree. to 80.degree. C. in a polar solvent such as water, an alcohol, dioxane or tetrahydrofuran in the presence of a water-soluble inorganic alkali such as sodium hydroxide or potassium hydroxide. On the other hand, the reaction between an N-alkylazaalkenelactam and a salt of monohalogenated carboxylic acid proceeds simply on being contacted with each other at 30.degree. to 100.degree. C., preferably 50.degree. to 80.degree. C. in the presence of the above-noted polar solvent, leading to the compound of this invention. Further, the reaction between a carboxylic acid and a polyalkylenepolyamine or a reaction product of a polyalkylenepolyamine and an acetoacetic ester or formylpropionic ester, and the reaction between a carboxylic acid and a reaction product of a monohydroxyalkylalkylenediamine and an acetoacetic ester or formylpropionic ester proceed, similarly to wellknown amide formations and esterifications, by the dehydration under a reduced pressure or atmospheric pressure at 50.degree. to 250.degree. C., preferably 120.degree. to 200.degree. C. In these cases also neither a catalyst nor a reaction solvent is particularly needed, while the bubbling of an inert gas such as nitrogen or carbon dioxide makes easier the completion of the reaction.

BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a diagrams of IR spectra of 4-dodecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one (solid line) and its starting material ethyl acetoacetate (dotted line), respectively. (1) represents the absorption band of .nu..sub.C.dbd.O (ester), (2) that of .nu..sub.C.dbd.O (ketone), (3) that of .nu..sub.C.dbd.O (amide) and (4) that of .nu..sub.C.dbd.N.
FIG. 2 is the diagram of IR spectrum of 4-dodecyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate which is the final product in Example 1. (5) represents the absorption band of ##STR5## and (6) represents that of .nu..sub.C.dbd.N.sup.+.
FIG. 3* and 4** are diagrams of 1H-NMR spectra of 4-dodecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one and 4-dodecyl-7-methyl-1-azonia-4-azacylohept-7-en-5-one-1-acetate, respectively.
(*TMS stands for tetramethylsilane and **DSS stands for sodium 2,2-dimethyl-2-silapentanesulfonate.)
FIG. 5 is the diagram of mass spectrum of 4-dodecyl-7-methyl-3-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Further, since the N-alkylazaalkenelactams and their derivatives having an organic acid radical, e.g. a carboxylate, which are the antibacterial surface active compounds containing a cyclic amide according to this invention, exhibit, even in a small amount, antibacterial activity against aerobic bacteria, anaerobic bacteria, gram-positive bacteria and gram-negative bacteria, they act as bactericides on man, animals, and environment. Even more, they act as an inhibitor for the bacterial corrosion of metals. Also, they themselves form a coating film on various metals to inhibit corrosion. Thus, these compounds are used as bactericides by themselves or, if necessary, in admixtures with various diluents.

BEST MODES FOR CARRYING OUT THE INVENTION
Examples are described below.
EXAMPLE 1
Into a four-necked flask provided with a stirrer, thermometer, gas inlet tube, and water measuring tube connected with a reflux condenser, were charged 228.1 g (1 mole) of N-dodecylethylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. While bubbling nitrogen gas, the flask was heated at 150.degree. to 160.degree. C. to distill off 18 g of water and 46 g of ethanol, and then 4-dodecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one in slight yellow liquid was obtained.
Elementary analysis: C.sub.18 H.sub.34 ON.sub.2 ; Calculated (%)--C 73.48, H 11.64, N 9.52, Found (%)--C 73.50, H 11.65, N 9.55.
Amine value--192.0 (theoretical 190.8).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1. (.nu..sub.C.dbd.O, amide).
NMR spectrum-- ##STR6## proton 1.76 ppm (.delta., TMS standard, 50 MHz).
Mass spectrum--(M+1) peak 295.
Subsequently, to a four-necked flask provided with a stirrer, thermometer, dropping funnel and an adapter for connecting with a reflux condenser, were charged 116.5 g (1 mole) of sodium monochloroacetate and 600 g of water to form a homogeneous solution. To the solution at 60.degree. to 70.degree. C., was added dropwise 294.2 g (1 mole) of 4-dodecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one to perform acetate radical formation at the same temperature and to synthesize water-soluble 4-dodecyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-on-1-acetate.
Elementary analysis: C.sub.20 H.sub.36 O.sub.3 N.sub.2 ; Calculated (%)--C 68.20, H 10.30, N 7.95, Found (%)--C 68.18, H 10.32, N 7.96.
IR spectrum--1640 cm.sup.-1 ##STR7##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.06 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 2
Into an apparatus similar to that in Example 1, were charged 271.1 g (1 mole) of N-dodecyldiethylenetriamine and 116.1 g (1 mole) of methyl acetoacetate. After 18 g of water and 32 g of methanol had been distilled off at 140.degree. to 150.degree. C., there was obtained 4-dodecylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one in slight red liquid.
Elementary analysis: C.sub.20 H.sub.39 ON.sub.3 ; Calculated (%)--C 71.23, H 11.66, N 12.45, Found (%)--C 71.26, H 11.69, N 12.44.
Amine value--333.1 (theoretical 332.8).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
NMR spectrum-- ##STR8## proton 1.78 ppm (.delta., TMS standard, 50 MHz).
Mass spectrum (M+1) peak 338.
Subsequently, into a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 675 g of water, was added dropwise 337.2 g (1 mole) of 4-dodecylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one to perform acetate radical formation at 50.degree. to 60.degree. C. and to synthesize 4-dodecylaminoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.22 H.sub.41 O.sub.3 N.sub.3 ; Calculated (%)--C 66.86, H 10.46, N 10.63, Found (%)--C 66.83, H 10.45, N 10.67.
IR spectrum--1635 cm.sup.-1 ##STR9##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 3
Into an apparatus similar to that in Example 1, were charged 242.1 g (1 mole) of N-dodecyl-1,3-propylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 1-dodecyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.19 H.sub.36 ON.sub.2 ; Calculated (%)--C 74.04; H 11.77, N 9.09, Found (%)--C 74.04, H 11.79, N 9.08.
Amine value--181.9 (theoretical 182.1)
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
NMR spectrum-- ##STR10## proton, 1.80 ppm (.delta., TMS standard, 50 MHz).
Mass spectrum--(M+1) peak 309.
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 620 g of water, was added dropwise 308.2 g (1 mole) of 1-dodecyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one to perform acetate radical formation as 60.degree. to 70.degree. C. and to synthesize 1-dodecyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.21 H.sub.38 O.sub.3 N.sub.2 ; Calculated (%)--C 68.67, H 10.46, N 7.65, Found (%)--C 68.66, H 10.48, N 7.64.
IR spectrum--1635 cm.sup.-1 ##STR11##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 4
Into an apparatus similar to that in Example 1, were charged 324.1 g (1 mole) of N-(9-octadecenyl)-1,3-propylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. At 110.degree. to 120.degree. C. and under a reduced pressure of 50 mmHg, 18 g of water and 46 g of ethanol had been distilled off to obtain 1-(9-octadecenyl)-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.25 H.sub.46 ON.sub.2 ; Calculated (%)--C 76.95, H 11.88, N 7.18, Found (%)--C 76.93, H 11.89, N 7.17.
Amine value--145.0 (theoretical 143.8)
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 700 g of water, was added dropwise 390.2 g (1 mole) of 1-(9-octadecenyl)-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 70.degree. to 80.degree. C. to synthesize 1-(9-octadecenyl)-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.27 H.sub.48 O.sub.3 N.sub.2 ; Calculated (%)--C 72.35, H 10.80, N 6.25, Found (%)--C 72.34, H 10.79, N 6.26.
IR spectrum--1635 cm.sup.-1 ##STR12##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.07 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 5
Into an apparatus similar to that in Example 1, were charged 284.1 g (1 mole) of N-hexadecylethylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. At 160.degree. to 170.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-hexadecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.22 H.sub.42 ON.sub.2 ; Calculated (%)--C 75.45, H 12.09, N 8.00, Found (%)--C 75.48, H 12.11, N 7.99.
Amine value--161.1 (theoretical 160.3).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, into a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 350.2 g (1 mole) of 4-hexadecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 350 g of dioxane. The acetate radical formation was effected at 80.degree. to 85.degree. C. to synthesize 4-hexadecyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.24 H.sub.44 O.sub.3 N.sub.2 ; Calculated (%)--C 70.61, H 10.86, N 6.86, Found (%)--C 70.64, H 10.86, N 6.88.
IR spectrum--1640 cm.sup.-1 ##STR13##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 6
Into an apparatus similar to that in Example 1, were charged 315.1 g (1 mole) of N-dodecoxyethyldiethylenetriamine and 130.1 g (1 mole) of ethyl acetoacetate at 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-dodecoxyethylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.22 H.sub.43 O.sub.2 N.sub.3 ; Calculated (%)--C 69.31, H 11.37, N 11.02, Found (%)--C 69.29, H 11.39, N 10.98.
Amine value--296.1 (theoretical 294.4).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, into a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 700 g of water, was added dropwise 381.2 g (1 mole) of 4-dodecoxyethylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 60.degree. to 70.degree. C. to synthesize 4-dodecoxyaminoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.24 H.sub.45 O.sub.4 N.sub.3 ; Calculated (%)--C 65.63, H 10.33, N 9.56, Found (%)--C 65.68, H 10.30, N 9.58.
IR spectrum--1640 cm.sup.-1 ##STR14##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 7
Into an apparatus similar to that in Example 1, were charged 364.2 g (1 mole) of N-nonylphenylpoly(2 moles)oxyethyleneoxyethyl-1,3-propylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. At 110.degree. to 120.degree. C. and under a reduced pressure of 50 mmHg, 18 g of water and 46 g of ethanol were distilled off to obtain 1-nonylphenylpoly(2 moles)oxyethyleneoxyethyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.26 H.sub.42 O.sub.3 N.sub.2 ; Calculated (%)--C 72.57, H 9.84, N 6.51, Found (%)--C 72.55, H 9.87, N 6.48.
Amine value--128.2 (theoretical 130.4).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, into a solution of 161.0 g (1 mole) of sodium monobromoacetate dissolved in 500 g of water, was added dropwise 430.3 g (1 mole) of 1-nonylphenylpoly(2 moles)oxyethyleneoxyethyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one dissolved in 300 g of tetrahydrofuran. The acetate radical formation was effected at 80.degree. to 85.degree. C. to synthesize 1-nonylphenylpoly(2 moles)oxyethyleneoxyethyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.28 H.sub.44 O.sub.5 N.sub.2 ; Calculated (%)--C 68.87, H 9.08, N 5.73, Found (%)--C 68.85, H 9.09, N 5.77.
IR spectrum--1635 cm.sup.-1 ##STR15##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 8
Into an apparatus similar to that in Example 1, were charged 230.1 g (1 mole) of N-octoxypropylethylenediamine and 116.1 g (1 mole) of methyl acetoacetate. At 140.degree. to 145.degree. C., 18 g of water and 32 g of ethanol were distilled off to obtain 4-octoxypropyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.17 H.sub.32 O.sub.2 N.sub.2 ; Calculated (%)--C 68.93, H 10.89, N 9.45, Found (%)--C 68.91, H 10.90, N 9.45.
Amine value--190.0 (theoretical 189.4).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 132.6 g (1 mole) of potassium monochloroacetate dissolved in 600 g of water, was added dropwise 296.2 g (1 mole) of 4-octoxypropyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to synthesize 4-octoxypropyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.19 H.sub.34 O.sub.4 N.sub.2 ; Calculated (%)--C 64.42, H 9.68, N 7.91, Found (%)--C 64.46, H 9.66, N 7.89.
IR spectrum--1635 cm.sup.-1 ##STR16##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.17 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 9
Into an apparatus similar to that in Example 1, were charged 103.1 g (1 mole) of diethylenetriamine and 116.1 g (1 mole) of methyl acetoacetate. At 140.degree. to 150.degree. C., 18 g of water and 32 g of methanol were distilled off. Then, with the addition of 200.3 g (1 mole) of lauric acid, the amide formation was effected at 200.degree. to 210.degree. C. and 18 g of water was distilled off, leaving behind 4-lauramidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.20 H.sub.37 O.sub.2 N.sub.3 ; Calculated (%)--C 68.37, H 10.62, N 11.96, Found (%)--C 68.37, H 10.60, N 11.95.
Amine value--161.3 (theoretical 159.7).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 400 g of water, was added dropwise 351.3 g (1 mole) of 4-lauramidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 350 g of methanol. The acetate radical formation was effected at 55.degree. to 60.degree. C. to synthesize 4-lauramidoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.22 H.sub.39 O.sub.4 N.sub.3 ; Calculated (%)--C 64.55, H 9.60, N 10.26, Found (%)--C 64.58, H 9.58, N 10.23.
IR spectrum--1640 cm.sup.-1 ##STR17##
NMR spectrum N.sup.+ -CH.sub.2 COO.sup.- proton 2.03 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 10
Into an apparatus similar to that in Example 1, were charged 103.1 g (1 mole) of diethylenetriamine and 116.1 g (1 mole) of methyl acetoacetate. At 110.degree. to 120.degree. C. and under a reduced pressure of 70 mmHg, 18 g of water and 32 g of methanol were distilled off. Then, with the addition of 282.5 g (1 mole) of oleic acid, the amide formation was effected at 210.degree. to 215.degree. C. to distil off 18 g of water and to obtain 4-oleamidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.26 H.sub.47 O.sub.2 N.sub.3 ; Calculated (%)--C 72.07, H 10.93, N 9.69, Found (%)--C 72.04, H 10.97, N 9.66.
Amine value--131.0 (theoretical 129.6).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 161.0 g (1 mole) of sodium monobromoacetate dissolved in 800 g of water, was added dropwise 433.3 g (1 mole) of 4-oleamidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 70.degree. to 80.degree. C. to synthesize 4-oleamidoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.28 H.sub.49 O.sub.4 N.sub.3 ; Calculated (%)--C 68.45, H 10.05, N 8.55, Found (%)--C 68.44, H 10.01, N 8.58.
IR spectrum--1635 cm.sup.-1 ##STR18##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.11 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 11
Into an apparatus similar to that in Example 1, were charged 103.1 g (1 mole) of diethylenetriamine and 284.5 g (1 mole) of isostearic acid. At 200.degree. to 210.degree. C., 18 g of water was distilled off to effect the monoamide formation. Then, after the addition of 130.1 g (1 mole) of ethyl acetoacetate, 18 g of water and 46 g of ethanol were distilled off at 150.degree. to 160.degree. C. to obtain 4-isostearamidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.26 H.sub.49 O.sub.2 N.sub.3 ; Calculated (%)--C 71.73, H 11.35, N 9.65, Found (%)--C 71.75, H 11.33, N 9.65.
Amine value--127.1 (theoretical 128.9).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g of sodium monochloroacetate dissolved in 800 g of water, was added dropwise 435.3 g (1 mole) of 4-isostearamidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 70.degree. to 80.degree. C. to synthesize 4-isostearamidoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.28 H.sub.51 O.sub.4 N.sub.3 ; Calculated (%)--C 68.17, H 10.42, N 8.51, Found (%)--C 68.20, H 10.42, N 8.49.
IR spectrum--1630 cm.sup.-1 ##STR19##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.05 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 12
Into an apparatus similar to that in Example 1, were charged 104.2 g (1 mole) of N-hydroxyethylethylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off. Then, after addition of 200.3 g (1 mole) of lauric acid, the esterification was effected at 200.degree. to 210.degree. C. to distil off 18 g of water and to obtain 4-lauroyloxyethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.20 H.sub.36 O.sub.3 N.sub.2 ; Calculated (%)--C 68.12, H 10.29, N 7.94, Found (%)--C 68.15, H 10.27, N 7.96.
Amine value--161.2 (theoretical 159.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1740 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, into a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 800 g of water, was added dropwise 352.6 g (1 mole) of 4-lauroyloxyethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 55.degree. to 65.degree. C. to synthesize 4-lauroyloxyethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.22 H.sub.38 O.sub.5 N.sub.2 ; Calculated (%)--C 64.35, H 9.33, N 6.82, Found (%)--C 64.31, H 9.35, N 6.79.
IR spectrum--1635 cm.sup.-1 ##STR20##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 13
Into an apparatus similar to that in Example 1, were charged 104.2 g (1 mole) of N-hydroxyethylethylenediamine and 130.1 g (1 mole) of ethylacetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off. Then, after addition of 282.5 g (1 mole) of oleic acid, the esterification was effected at 210.degree. to 215.degree. C. to distil off 18 g of water and to obtain 4-oleoyloxyethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.26 H.sub.46 O.sub.3 N.sub.2 ; Calculated (%)--C 71.83, H 10.67, N 6.44, Found (%)--C 71.85, H 10.69, N 6.44.
Amine value--130.6 (theoretical 129.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide) 1740 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, to a solution of 434.7 g (1 mole) of 4-oleoyloxyethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 400 g of isopropyl alcohol, was added dropwise an aqueous solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 500 g of water. The acetate radical formation was effected at 60.degree. to 70.degree. C. to synthesize 4-oleoyloxyethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.28 H.sub.48 O.sub.5 N.sub.2 ; Calculated (%)--C 68.25, H 9.82, N 5.68, Found (%)--C 68.21, H 9.80, N 5.69.
IR spectrum--1630 cm.sup.-1 ##STR21##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 14
Into an apparatus similar to that in Example 1, were charged 118.2 g (1 mole) of N-hydroxyethyl-1,3-propylenediamine and 116.1 g (1 mole) of methyl acetoacetate. At 115.degree. to 120.degree. C. and under a reduced pressure of 100 mmHg, 18 g of water and 32 g of methanol were distilled off. Then, after addition of 200.3 g (1 mole) of lauric acid, the esterification was effected at 190.degree. to 200.degree. C. to distil off 18 g of water and to obtain 1-lauroyloxyethyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.21 H.sub.38 O.sub.3 N.sub.2 ; Calculated (%)--C 68.82, H 10.45, N 7.64, Found (%)--C 68.79, H 10.47, N 7.66.
Amine value--153.0 (theoretical 153.1).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1735 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, to a solution of 177.0 g (1 mole) of potassium monobromoacetate dissolved in 800 g of water, was added dropwise 366.5 g (1 mole) of 1-lauroyloxyethyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 55.degree. to 65.degree. C. to synthesize 1-lauroyloxyethyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.23 H.sub.40 O.sub.5 N.sub.2 ; Calculated (%)--C 65.07, H 9.50, N 6.60, Found (%)--C 65.10, H 9.49, N 6.60.
IR spectrum--1635 cm.sup.-1 ##STR22##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.07 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 15
Into an apparatus similar to that in Example 1, were charged 256.1 g (1 mole) of N-coconutalkyl-1,3-propylenediamine (wherein, the carbon number composition is 5% C.sub.8, 10% C.sub.10, 50% C.sub.12, 20% C.sub.14, 10% C.sub.16 and 5% C.sub.18) and 116.1 g (1 mole) of methyl acetoacetate. At 145.degree. to 155.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 1-coconutalkyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.20 H.sub.38 ON.sub.2 ; Calculated (%)--C 74.48, H 11.88, N 8.68, Found (%)--C 74.51, H 11.90, N 8.65.
Amine value--175.1 (theoretical 174.0).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 850 g of water, was added dropwise 322.5 g (1 mole) of 1-coconutalkyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 70.degree. to 80.degree. C. to synthesize 1-coconutalkyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.22 H.sub.40 O.sub.3 N.sub.2 ; Calculated (%)--C 69.44, H 10.60, N 7.36, Found (%)--C 69.40, H 10.59, N 7.39.
IR spectrum--1635 cm.sup.-1 ##STR23##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 16
Into an apparatus similar to that in Example 1, were charged 301.5 g (1 mole) of monooctylated 1,3-propylenediamine-poly(3 moles on the average)ethyleneimine adduct and 158.1 g (1 mole) of butyl acetoacetate. At 150.degree. to 160.degree. C. and under a reduced pressure of 50 mmHg, 18 g of water and 74 g of butanol were distilled off to synthesize N-alkylalkenelactam.
Elementary analysis: C.sub.21 H.sub.42 ON.sub.5 ; Calculated (%)--C 66.23, H 11.12, N 18.38, Found (%)--C 66.23, H 11.10, N 18.41.
Amine value--592.1 (theoretical 589.4).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 94.5 g (1 mole) of monochloroacetic acid dissolved in 450 g of water, was added dropwise 380.8 g of N-alkylalkenelactam obtained above. After mixing at 60.degree. to 70.degree. C. and further adding 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed at the same temperature to synthesize the compound having anacetate radical.
Elementary analysis: C.sub.23 H.sub.44 O.sub.3 N.sub.5 ; Calculated (%)--C 62.95, H 10.11, N 15.95, Found (%)--C 62.96, H 10.01, N 15.97.
IR spectrum--1640 cm.sup.-1 ##STR24##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.03 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 17
Into an apparatus similar to that in Example 1, were charged 203.3 g (1 mole) of 1,3-propylenediamine-poly(3 moles on the average)ethyleneimine adduct and 300.5 g (1 mole) of 12-hydroxystearic acid. At 220.degree. to 225.degree. C., 18 g of water was distilled off to effect the monoamide formation. Then, 116.1 g (1 mole) of methyl acetoacetate was charged. At 110.degree. to 115.degree. C. and under a reduced pressure of 70 mm Hg, 18 g of water and 32 g of methanol were distilled off to synthesize N-alkylazaalkenelactam.
Elementary analysis: C.sub.31 H.sub.61 O.sub.3 N.sub.5 ; Calculated (%)--C 67.47, H 11.14, N 12.69, Found (%)--C 67.46, H 11.12, N 12.71.
Amine value--306.1 (theoretical 305.0).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide). Subsequently, a solution of 139.0 g (1 mole) of monobromoacetic acid dissolved in 800 g of water and a solution of 551.8 g (1 mole) of N-alkylazaalkenelactam dissolved in 500 g of tetrahydrofuran were mixed at 50.degree. to 60.degree. C. After addition of 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed to form the compound having an acetate radical.
Elementary analysis: C.sub.33 H.sub.63 O.sub.5 N.sub.5 ; Calculated (%)--C 64.99, H 10.42, N 11.48, Found (%)--C 64.96, H 10.42, N 11.45.
IR spectrum--1640 cm.sup.-1 ##STR25##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.12 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 18
Into an apparatus similar to that in Example 1, were charged 528.8 g of N-dodecylpoly(2 moles on the average)oxypropyleneoxypropylethylenediamine and 116.5 g (1 mole) of methyl acetoacetate. At 170.degree. to 175.degree. C., 18 g of water and 32 g of methanol were distilled off to synthesize N-alkylazaalkenelactam.
Elementary analysis: C.sub.37 H.sub.72 O.sub.4 N.sub.2 ; Calculated (%)--C 72.97, H 11.92, N 4.60, Found (%)--C 73.00, H 11.88, N 4.62.
Amine value--92.0 (theoretical 92.1).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, a solution of 94.5 g (1 mole) of monochloroacetic acid in 500 g of water and a solution of 609.0 g (1 mole) of the N-alkylazaalkenelactam in 600 g of dioxane were mixed at 70.degree. to 80.degree. C. After further addition of 56.1 g (1 mole) of potassium hydroxide, the reaction was allowed to proceed to form the compound having an acetate radical
Elementary analysis: C.sub.39 H.sub.74 O.sub.6 N.sub.2 ; Calculated (%)--C 70.22, H 11.18, N 4.20, Found (%)--C 72.20, H 11.22, N 4.17.
IR spectrum--1640 cm.sup.-1 ##STR26##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.07 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 19
Into an apparatus similar to that in Example 1, were charged 408.5 g (1 mole) of N-octylphenoxyethyleneoxypropyleneoxypropylethylenediamine and 116.5 g (1 mole) of methyl acetoacetate. At 170.degree. to 175.degree. C., 18 g of water and 32 g of methanol were distilled off to synthesize N-alkylazaalkenelactam.
Elementary analysis: C.sub.28 H.sub.46 O.sub.4 N.sub.2 ; Calculated (%)--C 70.84, H 9.77, N 5.90, Found (%) C 70.80, H 9.75, N 5.90.
Amine value--117.7 (theoretical 118.2).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide). Subsequently, a solution of 94.5 g (1 mole) of monochloroacetic acid dissolved in 500 g of water and a solution of 474.7 g (1 mole) of the formed N-alkylazaalkenelactam dissolved in 500 g of isopropyl alcohol were mixed at 65.degree. to 75.degree. C. After further addition of 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed to form the compound having an acetate radical.
Elementary analysis: C.sub.30 H.sub.48 O.sub.6 N.sub.2 ; Calculated (%)--C 67.63, H 9.08, N 5.26, Found (%)--C 67.60, H 9.08, N 5.23.
IR spectrum--1630 cm.sup.-1 ##STR27##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 20
Into an apparatus similar to that in Example 1, were charged 429.6 g (1 mole) of a monotridecoxyethyl derivative of 1,3-propylenediamine-poly(3 moles on the average)ethyleneimine adduct and 130.1 g (1 mole) of ethyl acetoacetate. At 165.degree. to 170.degree. C., 18 g of water and 46 g of ethanol were distilled off to synthesize N-alkylazaalkenelactam.
Elementary analysis: C.sub.28 H.sub.57 O.sub.2 N.sub.5 ; Calculated (%)--C 67.83, H 11.59, N 14.12, Found (%)--C 67.86, H 11.60, N 14.10.
Amine value--454.0 (theoretical 452.7).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 1,000 g of water, was added dropwise 495.8 (1 mole) of the formed N-alkylazaalkenelactam. The reaction was allowed to proceed at 60.degree. to 70.degree. C. to obtain the compound having an acetate radical.
Elementary analysis: C.sub.30 H.sub.59 O.sub.4 N.sub.5 ; Calculated (%)--C 65.07, H 10.74, N 12.64, Found (%)--C 65.11, H 10.75, N 12.60.
IR spectrum--1635 cm.sup.-1 ##STR28##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 21
Into an apparatus similar to that in Example 1, were charged 132.2 g (1 mole) of N-hydroxypropyl-1,3-propylenediamine and 116.1 g (1 mole) of methyl acetoacetate. At 140.degree. to 150.degree. C., 18 g of water and 32 g of methanol were distilled off. After addition of 298.5 g (1 mole) of ricinolic acid, the esterification was effect at 220.degree. to 225.degree. C. to distil off 18 g of water and to synthesize N-alkylazaalkenelactam.
Elementary analysis: C.sub.28 H.sub.50 O.sub.4 N.sub.2 ; Calculated (%)--C 70.25, H 10.53, N 5.85, Found (%)--C 70.30, H 10.55, N 5.86.
Amine value--117.1 (theoretical 117.2).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1740 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 1,000 g of water, was added dropwise 478.7 g (1 mole) of the formed N-alkylazaalkenelactam. The reaction was allowed to proceed at 60.degree. to 70.degree. C. to obtain the compound having an acetate radical.
Elementary analysis: C.sub.30 H.sub.52 O.sub.6 N.sub.2 ; Calculated (%)--C 67.14, H 9.77, N 5.22, Found (%)--C 67.12, H 9.76, N 5.23.
IR spectrum--1640 cm.sup.-1 ##STR29##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 22
In a manner similar to that in Example 1, at first 4-docosylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one was synthesized using as starting materials 411.7 g (1 mole) of N-docosyldiethylenetriamine and 130.1 g (1 mole) of ethyl acetoacetate.
Elementary analysis: C.sub.30 H.sub.59 ON.sub.3 ; Calculated (%)--C 75.40, H 12.45, N 8.79, Found (%)--C 75.38, H 12.46, N 8.82.
Amine value--234.0 (theoretical 234.9).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Then, 477.8 g (1 mole) of the formed 4-docosylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one and 116.5 g (1 mole) of sodium monochloroacetate were allowed to react in the presence of 1,200 g of water to synthesize 4-docosylaminoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.32 H.sub.61 O.sub.3 N.sub.3 ; Calculated (%)--C 71.73, H 11.48, N 7.84, Found (%)--C 71.73, H 11.45, N 7.83.
IR spectrum--1635 cm.sup.-1 ##STR30##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 23
In a manner similar to that in Example 9, using 103.1 g (1 mole) of diethylenetriamine 116.1 g (1 mole) of methyl acetoacetate, and 144.2 g (1 mole) of octylic acid as starting materials, at first 4-octamidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one was synthesized.
Elementary analysis: C.sub.16 H.sub.29 O.sub.2 N.sub.3 ; Calculated (%)--C 65.09, H 9.90, N 14.23, Found (%)--C 65.11, H 9.88, N 14.20.
Amine value--192.2 (theoretical 190.1).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.O), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Then, 295.2 g (1 mole) of the formed 4-octamidoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one and 116.5 g (1 mole) of sodium monochloroacetate were allowed to react in the presence of 600 g of water to synthesize 4-octamidoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.18 H.sub.31 O.sub.4 N.sub.3 ; Calculated (%)--C 61.21, H 8.85, N 11.89, Found (%)--C 61.18, H 8.83, N 11.90.
IR spectrum--1635 cm.sup.-1 ##STR31##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 24
In a manner similar to that in Example 12, using 104.2 g (1 mole) of N-hydroxyethylethylenediamine, 130.1 g (1 mole) of ethyl acetoacetate and 144.2 g (1 mole) of octylic acid as starting materials, at first 4-octoyloxyethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.16 H.sub.28 O.sub.3 N.sub.2 ; Calculated (%)--C 64.83, H 9.52, N 9.45, Found (%)--C 64.80, H 9.49, N 9.43.
Amine value--190.8 (theoretical 189.3).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1740 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Then, 296.4 g (1 mole) of the formed 4-octoyloxyethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one and 116.5 g (1 mole) of sodium monochloroacetate were allowed to react in the presence of 750 g of water to synthesize 4-octoyloxyethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.18 H.sub.30 O.sub.5 N.sub.2 ; Calculated (%)--C 61.00, H 8.53, N 7.90, Found (%)--C 60.95, H 8.50, N 7.93.
IR spectrum--1635 cm.sup.-1 ##STR32##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 25
In a manner similar to that in Example 12, using 132.2 g (1 mole) of N-hydroxypropyl-1,3-propylenediamine, 116.1 g (1 mole) of methyl acetoacetate, and 340.5 g (1 mole) of behenic acid as starting materials, at first 1-behenoyloxypropyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one was synthesized.
Elementary analysis: C.sub.32 H.sub.58 O.sub.3 N.sub.2 ; Calculated (%)--C 74.08, H 11.27, N 53.97, Found (%)--C 74.11, H 11.27, N 54.00.
Amine value--108.2 (theoretical 108.1).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1735 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Then, 518.8 g (1 mole) of 1-behenoyloxypropyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one and 116.5 g (1 mole) of sodium monochloroacetate were allowed to react in the presence of 600 g of water and 600 g of isopropyl alcohol to synthesize 1-behenoyloxypropyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.34 H.sub.60 O.sub.5 N.sub.2 ; Calculated (%)--C 70.79, H 10.49, N 4.85, Found (%)--C 70.81, H 10.51, N 4.84.
IR spectrum--1640 cm.sup.-1 ##STR33##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.04 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 26
Into an apparatus similar to that in Example 1, were charged 244.8 g (1 mole) of N-(2-hydroxy)dodecylethylenediamine and 116.1 g (1 mole) of methyl acetoacetate. At 140.degree. to 150.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain white wax-like 4-(2-hydroxy)dodecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.18 H.sub.34 O.sub.2 N.sub.2 ; Calculated (%)--C 69.56, H 11.03, N 9.01, Found (%)--C 69.39, H 11.06, N 9.07.
Amine value--180.6 (theoretical 180.5).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide). Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added a solution of 310.8 g (1 mole) of 4-(2-hydroxy)dodecyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 150 g of dioxane. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-(2-hydroxy)dodecyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.20 H.sub.36 O.sub.4 N.sub.2 ; Calculated (%)--C 65.13, H 9.84, N 7.59, Found (%)--C 65.17, H 9.80, N 7.57.
IR spectrum--1635 cm.sup.-1 ##STR34##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 27
Into an apparatus similar to that in Example 1, were charged 284.5 g (1 mole) of N-(2-hydroxy)tetradecylpropylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain white waxy 1-(2-hydroxy)tetradecyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.21 H.sub.38 O.sub.2 N.sub.2 ; Calculated (%)--C 71.96, H 10.93, N 7.99, Found (%)--C 71.96, H 10.97, N 8.03.
Amine value--160.3 (theoretical 160.1).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added a solution of 350.5 g (1 mole) of 1-(2-hydroxy)tetradecyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one dissolved in 200 g of ethanol. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 1-(2-hydroxy)tetradecyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.23 H.sub.40 O.sub.4 N.sub.2 ; Calculated (%)--C 67.62, H 9.87, N 6.85, Found (%)--C 67.60, H 9.91, N 6.89.
IR spectrum--1640 cm.sup.-1 ##STR35##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.11 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 28
Into an apparatus similar to that in Example 1, were charged 313.5 g (1 mole) of N-(2-hydroxy)tetradecyldiethylenetriamine and 158.1 g (1 mole) of butyl acetoacetate. At 150.degree. to 160.degree. C. and under a reduced pressure of 50 mmHg, 18 g of water and 74 g of butanol were distilled off to obtain 4-(2-hydroxytetradecyl)aminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.22 H.sub.41 O.sub.2 N.sub.3 ; Calculated (%)--C 69.62, H 10.89, N 11.07, Found (%)--C 69.65, H 10.85, N 11.10.
Amine value--296.0 (theoretical 295.7).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 94.5 g (1 mole) of monochloroacetic acid dissolved in 450 g of water, was added dropwise 379.5 g (1 mole) of the formed 4-(2-hydroxytetradecyl)aminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. After mixing at 60.degree. to 70.degree. C. and further addition of 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 4-(2-hydroxytetradecyl)aminoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.24 H.sub.43 O.sub.4 N.sub.3 ; Calculated (%)--C 65.88, H 9.91, N 9.60, Found (%)--C 65.86, H 9.90, N 9.58.
IR spectrum--1645 cm.sup.-1 ##STR36##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 29
Into an apparatus similar to that in Example 1, were charged 339.5 g (1 mole) of N-(2-hydroxy)hexadecyldiethylenetriamine and 116.1 g (1 mole) of methyl acetoacetate. At 140.degree. to 150.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-(2-hydroxyhexadecyl)aminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.24 H.sub.43 O.sub.2 N.sub.3 ; Calculated (%)--C 71.08, H 10.69, N 10.36, Found (%)--C 71.03, H 10.70, N 10.36.
Amine value--276.2 (theoretical 276.7).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 405.5 g (1 mole) of 4-(2-hydroxyhexadecyl)aminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 200 g of isopropyl alcohol, was added 132.6 g (1 mole) of potassium monochloroacetate dissolved in 600 g of water. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 4-(2-hydroxyhexadecyl)aminoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.26 H.sub.45 O.sub.4 N.sub.3 ; Calculated (%)--C 67.37, H 9.79, N 9.06, Found (%)--C 67.40, H 9.82, N 9.07.
IR spectrum--1645 cm.sup.-1 ##STR37##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 30
Into an apparatus similar to that in Example 1, were charged 484.8 g (1 mole) of a mono(2-hydroxy)docosyl derivative of a 1,3-propylenediamine-poly-(2 moles on the average)ethyleneimine adduct and 116.1 g (1 mole) of methyl acetoacetate. At 160.degree. to 170.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 1-(2-hydroxy)aminoethylaminoethyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.33 H.sub.66 O.sub.2 N.sub.4 ; Calculated (%)--C 71.96, H 12.08, N 10.17, Found (%)--C 71.80, H 12.06, N 10.18.
Amine value--308.8 (theoretical 305.6).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 161.0 g (1 mole) of sodium monochloroacetate dissolved in 900 g of water, was added dropwise 550.8 g (1 mole) of 1-(2-hydroxy)docosylaminoethylaminoethyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 70.degree. to 80.degree. C. to obtain 1-(2-hydroxy)docosylaminoethylaminoethyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.35 H.sub.68 O.sub.4 N.sub.4 ; Calculated (%)--C 69.04, H 11.26, N 9.20, Found (%)--C 69.00 H 11.30, N 9.19.
IR spectrum--1640 cm.sup.-1 ##STR38##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.13 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 31
Into an apparatus similar to that in Example 1, were charged 218.3 g (1 mole) of N-octoxy(2-hydroxy)propylethylenediamine and 130.1 g (1 mole) of ethyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-octoxy(2-hydroxy)propyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.15 H.sub.28 O.sub.3 N.sub.2 ; Calculated (%)--C 63.36, H 9.93, N 9.85, Found (%)--C 63.35, H 9.92, N 9.88.
Amine value--197.3 (theoretical 197.3).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 284.3 g (1 mole) of 4-octoxy(2-hydroxy)propyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-octoxy(2-hydroxy)propyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.17 H.sub.30 O.sub.5 N.sub.2 ; Calculated (%)--C 59.64, H 8.83, N 8.18, Found (%)--C 59.60, H 8.83, N 8.21.
IR spectrum--1650 cm.sup.-1 ##STR39##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.11 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 32
Into an apparatus similar to that in Example 1, were charged 465.7 g (1 mole) of N-nonylphenoxy(2-hydroxy)propyltetraethylenepentamine and 130.1 g (1 mole) of ethyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.30 H.sub.53 O.sub.3 N.sub.5 ; Calculated (%)--C 67.77, H 10.05, N 13.17, Found (%)--C 67.80, H 10.06, N 13.16.
Amine value--424.0 (theoretical 422.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 177.0 g (1 mole) of potassium monobromoacetate dissolved in 1,000 g of water, was added 531.7 g (1 mole) of 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 55.degree. C. to obtain 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.32 H.sub.55 O.sub.5 N.sub.5 ; Calculated (%)--C 65.18, H 9.40, N 11.87, Found (%)--C 65.15, H 9.41, N 11.90.
IR spectrum--1655 cm.sup.-1 ##STR40##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.11 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 33
Into an apparatus similar to that in Example 1, were charged 316.5 g (1 mole) of N-docoxy(2-hydroxy)propylpropylenediamine and 116.1 g (1 mole) of methyl acetoacetate. At 145.degree. to 155.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 1-docoxy(2-hydroxy)propyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.22 H.sub.42 O.sub.3 N.sub.2 ; Calculated (%)--C 69.08, H 11.07, N 7.32, Found (%)--C 69.08, H 11.09, N 7.35.
Amine value--146.7 (theoretical 146.7).
IR spectrum--1617 cm.sup.-1 (.nu..sub.C.dbd.O), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 107.6 g (1 mole) of monochloropropionic acid dissolved in 450 g of water, was added dropwise 382.5 g (1 mole) of 1-docoxy(2-hydroxy)propyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. After mixing at 50.degree. to 60.degree. C. and adding a solution of 56.1 g (1 mole) of potassium hydroxide dissolved in 200 g of water, the reaction was allowed to proceed at the same temperature to obtain 1-docoxy(2-hydroxy)propyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-propionate.
Elementary analysis: C.sub.25 H.sub.46 O.sub.5 N.sub.2 ; Calculated (%)--C 66.06, H 10.20, N 6.16, Found (%)--C 66.10, H 10.18, N 6.18.
IR spectrum--1645 cm.sup.-1 ##STR41##
NMR spectrum-- ##STR42## methyne proton 2.40 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 34
Into an apparatus similar to that in Example 1, were charged 314.5 g (1 mole) of N-dodecyltriethylenetetramine and 116.1 g (1 mole) of methyl acetoacetate. At 140.degree. to 150.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-dodecylaminoethylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.22 H.sub.44 ON.sub.4 ; Calculated (%)--C 69.42, H 11.65, N 14.71, Found (%)--C 69.48, H 11.68, N 14.72.
Amine value--444.2 (theoretical 442.2).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 700 g of water, was added dropwise 380.6 g (1 mole) of 4-dodecylaminoethylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to synthesize 4-dodecylaminoethylaminoethyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.24 H.sub.46 O.sub.3 N.sub.4 ; Calculated (%)--C 65.72, H 10.57, N 12.77, Found (%)--C 65.75, H 10.55, N 12.79.
IR spectrum--1640 cm.sup.-1 ##STR43##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHZ).
EXAMPLE 35
Into an apparatus similar to that in Example 1, were charged 299.5 g (1 mole) of N-tetradecyldiethylenetriamine and 116.1 g (1 mole) of methyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-tetradecylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.22 H.sub.43 ON.sub.3 ; Calculated (%)--C 72.27, H 11.86, N 11.49, Found (%)--C 72.26, H 11.88, N 11.52.
Amine value--306.8 (theoretical 306.9).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 700 g of water, was added dropwise 365.6 g (1 mole) of 4-tetradecylaminoethyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 4-tetradecylaminoethyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.24 H.sub.45 O.sub.3 N.sub.3 ; Calculated (%)--C 68.05, H 10.71, N 9.92; Found (%)--C 68.06, H 10.73, N 9.91.
IR spectrum--1635 cm.sup.-1 ##STR44##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 36
Into an apparatus similar to that in Example 1, were charged 299.5 g (1 mole) of N-dodecyldipropylenetriamine and 130.1 g (1 mole) of ethyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 1-dodecylaminopropyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.22 H.sub.43 ON.sub.3 ; Calculated (%)--C 72.29, H 11.86, N 11.49, Found (%)--C 72.33, H 11.88, N 11.46.
Amine value--308.1 (theoretical 307.0).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 132.6 g (1 mole) of potassium monochloroacetate dissolved in 800 g of water, was added dropwise 365.5 g (1 mole) of 1-dodecylaminopropyl-4methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 1-dodecylaminopropyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.24 H.sub.45 O.sub.3 N.sub.3 ; Calculated (%)--C 68.06, H 10.71, N 9.92, Found (%)--C 68.09, H 10.72, N 9.95.
IR spectrum--1635 cm.sup.-1 ##STR45##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.06 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 37
Into an apparatus similar to that in Example 1, were charged 381.7 g (1 mole) of N-octadecyldipropylenetriamine and 130.1 g (1 mole) of ethyl acetoacetate. At 150.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 1-octadecylaminopropyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.28 H.sub.53 ON.sub.3 ; Calculated (%)--C 75.11, H 11.93, N 9.38, Found (%)--C 75.14, H 11.93, N 9.40.
Amine value--250.9 (theoretical 250.6).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 107.6 g (1 mole) of monochloropropionic acid dissolved in 600 g of water, was added dropwise 447.7 g (1 mole) of 1-octadecylaminopropyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. After mixing at 70.degree. to 80.degree. C. and adding 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 1-octadecylaminopropyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-propionate.
Elementary analysis: C.sub.31 H.sub.57 O.sub.3 N.sub.3 ; Calculated (%)--C 71.63, H 11.05, N 8.08, Found (%)--C 71.60, H 11.08, N 8.09.
IR spectrum--1640 cm.sup.-1 ##STR46##
NMR spectrum-- ##STR47## methyne proton 2.36 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 38
Into an apparatus similar to that in Example 1, were charged 385.6 g (1 mole) of a monododecyl-derivative of an adduct of dipropylenetriamine with 2 moles of ethyleneimine and 158.1 g of butyl acetoacetate. At 155.degree. to 160.degree. C. and under a reduced pressure of 40 mmHg, 18 g of water and 74 g of butanol were distilled off to obtain 1-dodecylaminoethylaminoethylaminopropyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.26 H.sub.53 ON.sub.5 ; Calculated (%)--C 69.15, H 11.83, N 15.50, Found (%)--C 69.20, H 11.87, N 15.53.
Amine value--500.0 (theoretical 496.9).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C= O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 800 g of water, was added dropwise 451.6 g (1 mole) of 1-dodecylaminoethylaminoethylaminopropyl-4-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 1-dodecylaminoethylaminoethylaminopropyl-4-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.28 H.sub.55 O.sub.3 N.sub.5 ; Calculated (%)--C 65.99, H 10.88, N 13.74, Found (%)--C 66.03, H 10.85, N 13.80.
IR spectrum--1640 cm.sup.-1 ##STR48##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 39
Into an apparatus similar to that in Example 1, were charged 338.5 g (1 mole) of N-methylbenzylpoly(2 moles)oxypropyleneoxypropylethylenediamine and 116.1 g (1 mole) of methyl acetoacetate. At 140.degree. to 150.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-methylbenzylpoly(2moles)oxypropyleneoxypropyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.23 H.sub.36 O.sub.4 N.sub.2 ; Calculated (%)--C 68.29, H 8.97, N 6.92, Found (%)--C 68.32, H 8.95, N 6.93.
Amine value--139.5 (theoretical 138.7).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium chloroacetate dissolved in 600 g of water, was added dropwise 404.5 g (1 mole) of 4-methylbenzylpoly(2moles)oxypropyleneoxypropyl-7-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-methylbenzylpoly(2 moles)oxypropyleneoxypropyl-7-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.25 H.sub.38 O.sub.6 N.sub.2 ; Calculated (%)--C 64.92, H 8.28, N 6.05, Found (%)--C 64.96, H 8.26, N 6.06.
IR spectrum--1640 cm.sup.-1 ##STR49##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 40
Into an apparatus similar to that in Example 1, were charged 299.5 g (1 mole) of N-tetradecyldiethylenetriamine and 116.1 g (1 mole) of methyl 2-formylpropionate. At 130.degree. to 135.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-tetradecylaminoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.22 H.sub.43 ON.sub.3 ; Calculated (%)--C 72.27, H 11.86, N 11.49, Found (%)--C 72.30, H 11.88, N 11.46.
Amine value--306.8 (theoretical 306.9).
IR spectrum--1618 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 365.6 g (1 mole) of 4-tetradecylaminoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-tetradecylaminoethyl-6-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.24 H.sub.45 O.sub.3 N.sub.3 ; Calculated (%)--C 68.05, H 10.71, N 9.92, Found (%)--C 68.03, H 10.73, N 9.94.
IR spectrum--1635 cm.sup.-1 ##STR50##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 41
Into an apparatus similar to that in Example 1, were charged 339.5 g (1 mole) of N-(2-hydroxy)hexadecyldiethylenetriamine and 130.1 g of ethyl 2-formylpropionate. At 140.degree. to 150.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-(2-hydroxyhexadecyl)aminoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.24 H.sub.43 O.sub.2 N.sub.3 ; Calculated (%)--C 71.08, H 10.69, N 10.36, Found (%)--C 71.10, H 10.71, N 10.36.
Amine value--276.5 (theoretical 276.7).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 405.5 g (1 mole) of 4-(2-hydroxyhexadecyl)aminoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 200 g of dioxane, was added a solution of 132.6 g (1 mole) of potassium monochloroacetate dissolved in 600 g of water. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 4-(2-hydroxyhexadecyl)aminoethyl-6-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.26 H.sub.45 O.sub.4 N.sub.3 ; Calculated (%)--C 67.37, H 9.79, N 9.06, Found (%)--C 67.41, H 9.78, N 9.06.
IR spectrum--1645 cm.sup.-1 ##STR51##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 42
Into an apparatus similar to that in Example 1, were charged 228.1 g (1 mole) of N-dodecylethylenediamine and 130.1 g (1 mole) of ethyl 2-formylpropionate. At 140.degree. to 145.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-dodecyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.18 H.sub.34 ON.sub.2 ; Calculated (%)--C 73.48, H 11.64, N 9.52, Found (%)--C 73.51, H 11.68, N 9.54.
Amine value--192.1 (theoretical 190.8).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 294.2 g (1 mole) of 4-dodecyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-dodecyl-6-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.20 H.sub.36 O.sub.3 N.sub.2 ; Calculated (%)--C 68.20, H 10.30, N 7.95, Found (%)--C 68.25, H 10.31, N 7.98.
IR spectrum--1640 cm.sup.-1 ##STR52##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.05 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 43
Into an apparatus similar to that in Example 1, were charged 244.8 g (1 mole) of N-(2-hydroxy)dodecylethylenediamine and 144.2 g (1 mole) of isopropyl 2-formylpropionate. At 150.degree. to 155.degree. C., 18 g of water and 60 g of isopropyl alcohol were distilled off to obtain 4-(2-hydroxy)dodecyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.18 H.sub.34 O.sub.2 N.sub.2 ; Calculated (%)--C 69.56, H 11.03, N 9.01, Found (%)--C 69.39, H 11.05, N 9.05.
Amine value--180.5 (theoretical 180.5).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added a solution of 310.8 g (1 mole) of 4-(2-hydroxy)dodecyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 150 g of ethanol. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-(2-hydroxy)dodecyl-6-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.20 H.sub.36 O.sub.4 N.sub.2 ; Calculated (%)--C 65.13, H 9.84, N 7.59, Found (%)--C 65.15, H 9.80, N 7.60.
IR spectrum--1635 cm.sup.-1 ##STR53##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 44
Into an apparatus similar to that in Example 1, were charged 242.1 g (1 mole) of N-dodecylpropylenediamine and 130.1 g (1 mole) of ethyl 2-formylpropionate. At 145.degree. to 150.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 1-dodecyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.19 H.sub.36 ON.sub.2 ; Calculated (%)--C 74.04, H 11.77, N 9.09, Found (%)--C 74.03, H 11.76, N 9.09.
Amine value--181.9 (theoretical 182.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 308.2 g (1 mole) of 1-dodecyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 1-dodecyl-3-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.21 H.sub.38 O.sub.3 N.sub.2 ; Calculated (%)--C 68.67, H 10.46, N 7.65, Found (%)--C 68.68, H 10.49, N 7.65.
IR spectrum--1635 cm.sup.-1 ##STR54##
NMR spectrum--N.sup.+ -CH.sub.2 -COO.sup.- proton 2.09 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 45
Into an apparatus similar to that in Example 1, were charged 256.5 g (1 mole) of N-(2-hydroxy)dodecylpropylenediamine and 116.1 g (1 mole) of methyl 2-formylpropionate. At 130.degree. to 135.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 1-(2-hydroxy)dodecyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.19 H.sub.34 O.sub.2 N.sub.2 ; Calculated (%)--C 75.97, H 10.63, N 8.68, Found (%)--C 76.00, H 10.62, N 8.71.
Amine value--174.1 (theoretical 173.9).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, into a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 322.5 g (1 mole) of 1-(2-hydroxy)dodecyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 1-(2-hydroxy)dodecyl-3-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.21 H.sub.36 O.sub.4 N.sub.2 ; Calculated (%)--C 66.28, H 9.54, N 7.36, Found (%)--C 66.30, H 9.50, N 7.38.
IR spectrum--1635 cm.sup.-1 ##STR55##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 46
Into an apparatus similar to that in Example 1, were charged 103.1 g (1 mole) of diethylenetriamine and 116.1 g (1 mole) of methyl 2-formylpropionate. At 130.degree. to 135.degree. C., 18 g of water and 32 g of methanol were distilled off. Then, after addition of 200.3 g (1 mole) of lauric acid, the amide formation was effected at 200.degree. to 210.degree. C. to distil off 18 g of water, leaving behind 4-lauramidoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.20 H.sub.37 O.sub.2 N.sub.3 ; Calculated (%)--C 68.37, H 10.62, N 11.96, Found (%)--C 68.38, H 10.62, N 11.99.
Amine value--161.2 (theoretical 159.7).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 400 g of water, was added dropwise a solution of 351.3 g (1 mole) of 4-lauramidoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one dissolved in 400 g of methanol. The acetate radical formation was effected at 55.degree. to 60.degree. C. to obtain 4-lauramidoethyl-6-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.22 H.sub.39 O.sub.4 N.sub.3 ; Calculated (%)--C 64.55, H 9.60, N 10.26, Found (%)--C 64.58, H 9.61, N 10.23.
IR spectrum--1640 cm.sup.-1 ##STR56##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.06 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 47
Into an apparatus similar to that in Example 1, were charged 104.2 g (1 mole) of N-hydroxyethylenediamine and 130.1 g (1 mole) of ethyl 2-formylpropionate. At 145.degree. to 150.degree. C., 18 g of water and 46 g of ethanol were distilled off. Then, after addition of 200.3 g (1 mole) of lauric acid, esterification was carried out while distilling off 18 g of water to obtain 4-lauroyloxyethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.20 H.sub.36 O.sub.3 N.sub.2 ; Calculated (%)--C 68.12, H 10.29, N 7.94, Found (%)--C 68.15, H 10.28, N 7.96.
Amine value--159.5 (theoretical 159.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1740 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, to 116.5 g (1 mole) of sodium monochloroacetate dissolved in 800 g of water, was added dropwise 352.6 g (1 mole) of 4-lauroyloxyethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was carried out at 60.degree. to 70.degree. C. to obtain.4-lauroyloxyethyl-6-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.22 H.sub.38 O.sub.5 N.sub.2 ; Calculated (%)--C 64.35, H 9.33, N 6.82, Found (%)--C 64.36, H 9.36, N 6.78.
IR spectrum--1635 cm.sup.-1 ##STR57##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 48
Into an apparatus similar to that in Example 1, were charged 313.5 g (1 mole) of N-monotetradecylaminoethylpropylenediamine and 116.1 g (1 mole) of methyl-2-formylpropionate. At 130.degree. to 135.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 1-tetradecylaminoethyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.23 H.sub.45 ON.sub.3 ; Calculated (%)--C 72.76, H 11.96, N 11.06, Found (%)--C 72.77, H 11.99, N 11.08.
Amine value--295.4 (theoretical 295.6).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 107.6 g (1 mole) of monochloropropionic acid dissolved in 600 g of water, was added dropwise 379.6 g (1 mole) of 1-tetradecylaminoethyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one. After mixing at 70.degree. to 80.degree. C. and addition of 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 1 -tetradecylaminoethyl-3-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-propionate.
Elementary analysis: C.sub.26 H.sub.49 O.sub.3 N.sub.3 ; Calculated (%)--C 69.14, H 10.94, N 9.30, Found (%)--C 69.15, H 10.95, N 9.32.
IR spectrum--1645 cm.sup.-1 ##STR58##
NMR spectrum-- ##STR59## methyne proton 2.40 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 49
Into an apparatus similar to that in Example 1, were charged 353.5 g (1 mole) of N-mono(2-hydroxy)hexadecylaminoethylpropylenediamine and 158.2 g (1 mole) of butyl 2-formyl propionate. At 155.degree. C. and under a reduced pressure of 50 mmHg, 18 g of water and 74 g of butanol were distilled off to obtain 1-(2-hydroxyhexadecyl)aminoethyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.25 H.sub.45 O.sub.2 N.sub.3 ; Calculated (%)--C 71.55, H 10.82, N 10.01, Found (%)--C 71.59, H 10.81, N 10.00.
Amine value--268.0 (theoretical 267.3)
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 419.7 g (1 mole) of 1-(2-hydroxyhexadecyl)aminoethyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one dissolved in 250 g of isopropyl alcohol, was added a solution of 132.6 g (1 mole) of potassium monochloroacetate dissolved in 600 g of water. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 1-(2-hydroxyhexadecyl)aminoethyl-3-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.27 H.sub.47 O.sub.4 N.sub.3 ; Calculated (%)--C 67.89, H 9.92, N 8.79, Found (%)--C 67.92, H 9.89, N 8.81.
IR spectrum--1645 cm.sup.-1 ##STR60##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 50
Into an apparatus similar to that in Example 1, were charged 301.5 g (1 mole) of a monooctyl derivative of a 1,3-propylenediamine-poly(3moles on the average)ethyleneimine adduct and 130.1 g (1 mole) of ethyl 2-formylpropionate. At 130.degree. to 140.degree. C. and under a reduced pressure of 50 mmHg, 18 g of water and 46 g of ethanol were distilled off to synthesize N-alkylalkenelactam.
Elementary analysis: C.sub.21 H.sub.42 ON.sub.5 ; Calculated (%)--C 66.23, H 11.12, N 18.38, Found (%)--C 66.28, H 11.14, N 18.33.
Amine value--590.1 (theoretical 589.4).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 94.5 g (1 mole) of monochloroacetic acid dissolved in 500 g of water, was added dropwise 380.8 g (1 mole) of the formed N-alkylalkenelactam. After mixing at 60.degree. to 70.degree. C. and addition of 56.1 g (1 mole) of potassium hydroxide, the reaction was allowed to proceed at the same temperature to obtain the compound having an acetate radical.
Elementary analysis: C.sub.23 H.sub.44 O.sub.3 N.sub.5 ; Calculated (%)--C 62.95, H 10.11, N 15.95, Found (%)--C 62.99, H 10.98, N 15.95.
IR spectrum--1640 cm.sup.-1 ##STR61##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.05 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 51
Into an apparatus similar to that in Example 1, were charged 132.2 g (1 mole) of N-hydroxypropyl-1,3-propylenediamine and 116.1 g (1 mole) of methyl 2-formylpropionate. At 130.degree. to 135.degree. C., 18 g of water and 32 g of methanol were distilled off. Then, after adding 340.5 g (1 mole) of behenic acid, esterification was carried out at 180.degree. to 190.degree. C. under a reduced pressure of 70 mmHg, while distilling off 18 g of water, to obtain 1-behenoyloxypropyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one.
Elementary analysis: C.sub.32 H.sub.58 O.sub.3 N.sub.2 ; Calculated (%)--C 74.08, H 11.27, N 53.98, Found (%)--C 74.10, H 11.27, N 53.98.
Amine value--108.3 (theoretical 108.1).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1735 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, to a solution of 518.8 g (1 mole) of 1-behenoyloxypropyl-3-methyl-3,6,7,8-tetrahydro-1,5-diazocin-2-one dissolved in 600 g of isopropyl alcohol, was added dropwise a solution of 177.0 g (1 mole) of potassium monobromoacetate dissolved in 600 g of water. The acetate radical formation was effected at 70.degree. to 80.degree. C. to obtain 1-behenoyloxypropyl-3-methyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.34 H.sub.60 O.sub.5 N.sub.2 ; Calculated (%)--C 70.79, H 10.49, N 4.85, Found (%)--C 70.82, H 10.51, N 4.85.
IR spectrum--1640 cm.sup.-1 ##STR62##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.05 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 52
Into an apparatus similar to that in Example 1, were charged 465.7 g (1 mole) of N-nonylphenoxy(2-hydroxy)propyltetraethylenepentamine and 130.1 g (1 mole) of ethyl 2-formylpropionate. At 140.degree. to 145.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.30 H.sub.53 O.sub.3 N.sub.5 ; Calculated (%)--C 67.77, H 10.05, N 13.17, Found (%)--C 67.81, H 10.05, N 13.19.
Amine value--423.5 (theoretical 422.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.O), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 177.0 g (1 mole) of potassium monobromoacetate dissolved in 1,000 g of water, was added 531.7 g (1 mole) of 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-6-methyl-3,6-dihydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-6-methyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.32 H.sub.55 O.sub.5 N.sub.5 ; Calculated (%)--C 65.18, H 9.40, N 11.87, Found (%)--C 65.18, H 9.39, N 11.88.
IR spectrum--1650 cm.sup.-1 ##STR63##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 53
Into an apparatus similar to that in Example 1, were charged 299.5 g (1 mole) of N-tetradodecyldiethylenetriamine and 116.1 g (1 mole) of methyl 3-formylpropionate. At 125.degree. to 130.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-tetradecylaminoethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.22 H.sub.43 ON.sub.3 ; Calculated (%)--C 72.27, H 11.86, N 11.49, Found (%)--C 72.31, H 11.87, N 11.48.
Amine value--306.8 (theoretical 306.9)
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 700 g of water, was added dropwise 365.6 g (1 mole) of 4-tetradecylaminoethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one. The acetate radical formation was effected at 60.degree. to 65.degree. C. to obtain 4-tetradecylaminoethyl-4-aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.24 H.sub.45 O.sub.3 N.sub.3 ; Calculated (%)--C 68.05, H 10.71, N 9.92, Found (%)--C 68.09, H 10.74, N 9.90.
IR spectrum--1635 cm.sup.-1 ##STR64##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 54
Into an apparatus similar to that in Example 1, were charged 339.5 g (1 mole) of N-(2-hydroxy)hexadecyldiethylenetriamine and 130.1 g (1 mole) of ethyl 3-formylpropionate. At 135.degree. to 140.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-(2-hydroxyhexadecyl)aminoethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.24 H.sub.43 O.sub.2 N.sub.3 ; Calculated (%)--C 71.08, H 10.69, N 10.36, Found (%)--C 71.11, H 10.70, N 10.34.
Amine Value: 276.6 (theoretical 276.7).
IR spectrum: 1618 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 405.5 g (1 mole) of 4-(2-hydroxyhexadecyl)aminoethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one dissolved in 300 g of isopropyl alcohol, was added a solution of 132.6 g (1 mole) of potassium monochloroacetate dissolved in 600 g of water. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-(2-hydroxyhexadecyl)aminoethyl-4-aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.26 H.sub.45 O.sub.4 N.sub.3 ; Calculated (%)--C 67.37, H 9.79, N 9.06, Found (%)--C 67.36, H 9.78, N 9.06.
IR spectrum--1640 cm.sup.-1 ##STR65##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.08 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 55
Into an apparatus similar to that in Example 1, were charged 310.1 g (1 mole) of N-(9-octadecenyl)ethylenediamine and 158.2 g (1 mole) of butyl 3-formylpropionate. At 150.degree. C. and under a reduced pressure of 50 mmHg, 18 g of water and 74 g of butanol were distilled off to obtain 4-(9-octadecenyl)-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.24 H.sub.44 ON.sub.2 ; Calculated (%)--C 76.53, H 11.79, N 7.43, Found (%)--C 76.55, H 11.80, N 7.45.
Amine value--149.0 (theoretical 149.0).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 94.5 g (1 mole) of monochloroacetic acid dissolved in 500 g of water, was added dropwise 376.6 g (1 mole) of the formed 4-(9-octadecenyl)-2,3,6,7-tetrahydro-1,4-diazocin-5-one. After mixing at 65.degree. to 75.degree. C. and further addition of 56.1 g (1 mole) of potassium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 4-(9-octadecenyl)-4-aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.26 H.sub.46 O.sub.3 N.sub.2 ; Calculated (%)--C 71.84, H 10.67, N 6.44, Found (%)--C 71.80, H 10.65, N 6.46.
IR spectrum--1635 cm.sup.-1 ##STR66##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 56
Into an apparatus similar to that in Example 1, were charged 103.1 g (1 mole) of diethylenetriamine and 144.2 g (1 mole) of propyl 3-formylpropionate. At 140.degree. to 145.degree. C., 18 g of water and 60 g of propyl alcohol were distilled off. Then, after adding 144.2 g (1 mole) of octylic acid, the reaction was allowed to proceed at 150.degree. to 155.degree. C. to distil off 18 g of water, obtaining 4-octamidoethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.16 H.sub.29 O.sub.2 N.sub.3 ; Calculated (%)--C 65.09, H 9.90, N 14.23, Found (%)--C 65.08, H 9.89, N 14.24.
Amine value--192.2 (theoretical 190.1).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 107.6 g (1 mole) of monochloropropionic acid dissolved in 600 g of water, was added dropwise 295.2 g (1 mole) of 4-octamidoethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one. After mixing at 70.degree. to 80.degree. C. and adding 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 4-octamidoethyl-4-aza-1-azoniacyclooct-8-en-5-one-1-propionate.
Elementary analysis: C.sub.19 H.sub.33 O.sub.4 N.sub.3 ; Calculated (%)--C 62.09, H 9.06, N 11.43, Found (%)--C 62.05, H 9.04, N 11.43.
IR spectrum--1635 cm.sup.-1 ##STR67##
NMR spectrum-- ##STR68## methyne proton 2.25 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 57
Into an apparatus similar to that in Example 1, were charged 104.2 g (1 mole) of N-hydroxyethylethylenediamine and 116.1 g (1 mole) of methyl 3-formylpropionate. At 130.degree. C., 18 g of water and 32 g of methanol were distilled off. After adding 340.5 g (1 mole) of behenic acid, esterification was carried out at 210.degree. to 220.degree. C. to obtain 4-behenoyloxyethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.30 H.sub.54 O.sub.3 N.sub.2 ; Calculated (%)--C 73.43, H 11.09, N 5.71, Found (%)--C 73.41, H 11.09, N 5.74.
Amine value--115.0 (theoretical 114.3).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1735 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, 490.7 g (1 mole) of 4-behenoyloxyethyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one and 116.5 g (1 mole) of sodium monochloroacetate were allowed to react in the presence of 600 g of water and 600 g of ethanol to obtain 4-behenoyloxyethyl-4-aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.32 H.sub.56 O.sub.5 N.sub.2 ; Calculated (%)--C 70.04, H 10.28, N 5.10, Found (%)--C 70.08, H 10.31, N 5.08.
IR spectrum--1635 cm.sup.-1 ##STR69##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.13 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 58
Into an apparatus similar to that in Example 1, were charged 299.5 g (1 mole) of N-tetradecyldiethylenetriamine and 130.1 g (1 mole) of methyl 2-formyl-2-methylpropionate. At 140.degree. to 145.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-tetradecylaminoethyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.23 H.sub.45 ON.sub.3 ; Calculated (%)--C 72.76, H 11.96, N 11.06, Found (%)--C 72.74, H 11.98, N 11.06.
Amine value--296.0 (theoretical 295.6).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 107.6 g (1 mole) of monochloropropionic acid dissolved in 600 g of water, was added dropwise 379.6 g (1 mole) of 4-tetradecylaminoethyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one. After mixing at 70.degree. to 75.degree. C. and adding 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 4-tetradecylaminoethyl-6,6-dimethyl-1-azonia-4-azacyclohept-7-en-5-one-1-propionate.
Elementary analysis: C.sub.26 H.sub.49 O.sub.3 N.sub.3 ; Calculated (%)--C 69.14, H 10.94, N 9.30, Found (%)--C 69.16, H 10.96, N 9.33.
IR spectrum--1645 cm.sup.-1 ##STR70##
NMR spectrum-- ##STR71## methyne proton 2.42 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 59
Into an apparatus similar to that in Example 1, were charged 339.5 g (1 mole) of N-(2-hydroxy)hexadecyldiethylenetriamine and 144.2 g (1 mole) of ethyl 2-formyl-2-methylpropionate. At 140.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-(2-hydroxyhexadecyl)aminoethyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.25 H.sub.45 O.sub.2 N.sub.3 ; Calculated (%)--C 71.55, H 10.82, N 10.01, Found (%)--C 71.59, H 10.83, N 10.00.
Amine value--267.5 (theoretical 267.3)
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 419.7 g (1 mole) of 4-(2-hydroxyhexadecyl)aminoethyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one dissolved in 300 g of tetrahydrofuran, was added a solution of 177.0 g (1 mole) of potassium monobromoacetate dissolved in 800 g of water. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 4-(2-hydroxyhexadecyl)aminoethyl-6,6-dimethyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.27 H.sub.47 O.sub.4 N.sub.3 ; Calculated (%)--C 67.89, H 9.92, N 8.79, Found (%)--C 67.91, H 9.90, N 8.81.
IR spectrum--1645 cm.sup.-1 ##STR72##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.12 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 60
Into an apparatus similar to that in Example 1, were charged 313.5 g (1 mole) of N-monotetradecylaminoethylpropylenediamine and 158.2 g (1 mole) of isopropyl 2-formyl-2-methylpropionate. At 150.degree. to 155.degree. C., 18 g of water and 60 g of isopropyl alcohol were distilled off to obtain 1-tetradecylaminoethyl-3,3-dimethyl-6,7,8-trihydro-1,5-diazocin-5-one.
Elementary analysis: C.sub.24 H.sub.47 ON.sub.3 ; Calculated (%)--C 73.32, H 12.04, N 10.67, Found (%)--C 73.30, H 12.00, N 10.69.
Amine value--285.1 (theoretical 285.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 107.6 g (1 mole) of monochloropropionic acid dissolved in 700 g of water, was added dropwise 393.6 g (1 mole) of 1-tetradecylaminoethyl-3,3-dimethyl-6,7,8-trihydro-1,5-diazocin-5-one. After mixing at 70.degree. to 80.degree. C. and adding 56.1 g (1 mole) of potassium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 1-tetradecylaminoethyl-3,3-dimethyl-1-aza-5-azoniacyclooct-4-en-2-one-5-propionate.
Elementary analysis: C.sub.27 H.sub.51 O.sub.3 N.sub.3 ; Calculated (%)--C 69.64, H 11.04, N 9.02, Found (%)--C 69.60, H 11.03, N 9.04.
IR spectrum--1630 cm.sup.-1 ##STR73##
NMR spectrum-- ##STR74## metyne proton 2.38 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 61
Into an apparatus similar to that in Example 1, were charged 353.5 g (1 mole) of N-mono(2-hydroxy)hexadecylaminoethylpropylenediamine and 172.2 g (1 mole) of butyl 2-formyl-2-methylpropionate. At 160.degree. to 165.degree. C. and under a reduced pressure of 70 mmHg, 18 g of water and 74 g of butanol were distilled off to obtain 1-(2-hydroxyhexadecyl)aminoethyl-3,3-dimethyl-6,7,8-trihydro-1,5-diazocin-5-one.
Elementary analysis: C.sub.26 H.sub.47 O.sub.2 N.sub.3 ; Calculated (%)--C 72.01, H 10.93, N 9.68, Found (%)--C 71.98, H 10.90, N 9.68.
Amine value--258.9 (theoretical 258.7).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 433.7 g (1 mole) of 1-(2-hydroxyhexadecyl)aminoethyl-3,3-dimethyl-6,7,8-trihydro-1,5-diazocin-5-one dissolved in 300 g of ethanol, was added a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 1-(2-hydroxyhexadecyl)aminoethyl-3,3-dimethyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.28 H.sub.49 O.sub.4 N.sub.3 ; Calculated (%)--C 68.40, H 10.05, N 8.54, Found (%)--C 68.40, H 10.08, N 8.55.
IR spectrum--1640 cm.sup.-1 ##STR75##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.11 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 62
Into an apparatus similar to that in Example 1, were charged 364.2 g (1 mole) of N-nonylphenylpoly(2 moles) oxyethyleneoxyethyl-1,3-propylene diamine and 130.1 g (1 mole) of methyl 2-formyl-2-methylpropionate. At 100.degree. C. and under a reduced pressure of 100 mmHg, 18 g of water and 32 g of methanol were distilled off to obtain 1-nonylphenylpoly(2 moles)oxyethyleneoxyethyl-3,3-dimethyl-6,7,8-trihydro-1,5-diazocin-5-one.
Elementary analysis: C.sub.27 H.sub.44 O.sub.3 N.sub.2 ; Calculated (%)--C 72.93, H 9.98, N 6.30, Found (%)--C 72.90, H 9.97, N 6.34.
Amine value--125.0 (theoretical 126.2).
IR spectrum--1620 cm.sup.-1 (.nu..sub.C.dbd.N), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 161.0 g (1 mole) of sodium monobromoacetate dissolved in 500 g of water, was added dropwise 444.7 g (1 mole) of 1-nonylphenylpoly(2 moles)oxyethyleneoxyethyl-3,3-dimethyl-6,7,8-trihydro-1,5-diazocin-5-one. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 1-nonylphenylpoly(2 moles)oxyethyleneoxyethyl-3,3-dimethyl-1-aza-5-azoniacyclooct-4-en-2-one-5-acetate.
Elementary analysis: C.sub.28 H.sub.46 O.sub.5 N.sub.2 ; Calculated (%)--C 68.53, H 9.46, N 5.71, Found (%)--C 68.57, H 9.48, N 5.71.
IR spectrum--1635 cm.sup.-1 ##STR76##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 63
Into an apparatus similar to that in Example 1, were charged 230.1 g (1 mole) of N-octoxypropylethylenediamine and 130.1 g (1 mole) of methyl 2-formyl-2-methylpropionate. At 130.degree. to 135.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-octoxypropyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.18 H.sub.34 O.sub.2 N.sub.2 ; Calculated (%)--C 69.63, H 11.05, N 9.02, Found (%)--C 69.60, H 11.04, N 9.05.
Amine value--180.7 (theoretical 180.7).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 310.5 g (1 mole) of 4-octoxypropyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-oxtoxypropyl-6,6-dimethyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.20 H.sub.36 O.sub.4 N.sub.2 ; Calculated (%)--C 65.18, H 9.85, N 7.60, Found (%)--C 65.20, H 9.85, N 7.61.
IR spectrum--1635 cm.sup.-1 ##STR77##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.18 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 64
Into an apparatus similar to that in Example 1, were charged 103.1 g (1 mole) of diethylenetriamine and 144.2 g (1 mole) of ethyl 2-formyl-2-methylpropionate. At 140.degree. C., 18 g of water and 46 g of methanol were distilled off. Then, after addition of 312.5 g (1 mole) of methyl ricinoleate, amide formation was carried out at 170.degree. to 180.degree. C. under a reduced pressure of 70 mmHg to distil off 32 g of methanol, yielding 4-ricinolamidoethyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one.
Elementary analysis: C.sub.27 H.sub.49 O.sub.3 N.sub.3 ; Calculated (%)--C 69.94, H 10.65, N 9.06, Found (%)--C 69.98, H 10.66, N 9.05.
Amine value--120.6 (theoretical 121.0).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 94.5 g (1 mole) of monochloroacetic acid dissolved in 500 g of water, was added dropwise 463.7 g (1 mole) of 4-ricinolamidoethyl-6,6-dimethyl-3-hydro-2H-1,4-diazepin-5-one. After mixing at 50.degree. to 60.degree. C. and adding 40.0 g (1 mole) of sodium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 4-ricinolamidoethyl-6,6-dimethyl-1-azonia-4-azacyclohept-7-en-5-one-1-acetate.
Elementary analysis: C.sub.29 H.sub.51 O.sub.5 N.sub.3 ; Calculated (%)--C 66.76, H 9.85, N 8.05, Found (%)--C 66.78, H, 9.85, N 8.05.
IR spectrum--1630 cm.sup.-1 ##STR78##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 65
Into an apparatus similar to that in Example 1, where charged 299.5 g (1 mole) of N-tetradecyldiethylenetriamine and 130.1 g (1 mole) of methyl 3-formyl-2-methylpropionate. At 145.degree. to 150.degree. C., 18 g of water and 32 g of methanol were distilled off to obtain 4-tetradecylaminoethyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.23 H.sub.45 ON.sub.3 ; Calculated (%)--C 72.76, H 11.96, N 11.06, Found (%)--C 72.73, H 11.94, N 11.08.
Amine value--295.9 (theoretical 295.6).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 107.6 g (1 mole) of monochloropropionic acid dissolved in 600 g of water, was added dropwise 379.6 g (1 mole) of 4-tetradecylaminoethyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one. After mixing at 70.degree. C. to 80.degree. C. and adding 56.1 g (1 mole) of potassium hydroxide, the reaction was allowed to proceed at the same temperature to obtain 4-tetradecylaminoethyl-6-methyl-4-aza-1-azoniacyclooct-8-en-5-one-1-propionate.
Elementary analysis: C.sub.26 H.sub.49 O.sub.3 N.sub.3 ; Calculated (%)--C 69.14, H 10.94, N 9.30, Found (%)--C 69.14, H 10.95, N 9.32.
IR spectrum--1640 cm.sup.-1 ##STR79##
NMR spectrum-- ##STR80## methyne proton 2.40 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 66
Into an apparatus similar to that in Example 1, were charged 339.5 g (1 mole) of N-(2-hydroxy)hexadecyldiethylenetriamine and 144.2 g (1 mole) of ethyl 3-formyl-2-methylpropionate. At 140.degree. to 160.degree. C., 18 g of water and 46 g of ethanol were distilled off to obtain 4-(2-hydroxyhexadecyl)aminoethyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.25 H.sub.45 O.sub.2 N.sub.3 ; Calculated (%)--C 71.55, H 10.82, N 10.01, Found (%)--C 71.51, H 10.80, N 10.04.
Amine value--267.7 (theoretical 267.3).
IR spectrum--1615 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 419.7 g (1 mole) of 4-(2-hydroxyhexadecyl)aminoethyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one dissolved in 200 g of dioxane, was added a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 800 g of water. The acetate radical formation was effected at 60.degree. to 70.degree. C. to obtain 4-(2-hydroxyhexadecyl)aminoethyl-6-methyl-4-aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.27 H.sub.47 O.sub.4 N.sub.3 ; Calculated (%)--C 67.89, H 9.92, N 8.79, Found (%)--C 67.92, H 9.94, N 8.80.
IR spectrum--1645 cm.sup.-1 ##STR81##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.10 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 67
Into an apparatus similar to that in Example 1, were charged 338.5 g (1 mole) of N-methylbenzylpoly(2 moles)oxypropyleneoxypropylethylenediamine and 172.2 g (1 mole) of butyl 3-formyl-2-methylpropionate. At 150.degree. to 160.degree. C., 18 g of water and 74 g of butanol to obtain 4-methylbenzylpoly(2 moles)oxypropyleneoxypropyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.24 H.sub.38 O.sub.4 N.sub.2 ; Calculated (%)--C 68.86, H 9.15, N 6.69, Found (%)--C 68.80, H 9.14, N 6.71.
Amine value--135.0 (theoretical 134.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water, was added dropwise 418.5 g (1 mole) of 4-methylbenzylpoly(2moles)oxypropyleneoxypropyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one. The acetate radical formation was effected at 50.degree. to 60.degree. C. to obtain 4-methylbenzylpoly(2 moles)oxypropyleneoxypropyl-6-methyl-4-aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.26 H.sub.40 O.sub.6 N.sub.2 ; Calculated (%)--C 65.53, H 8.46, N 5.87, Found (%)--C 65.58, H 8.46, N 5.86.
IR spectrum--1630 cm.sup.-1 ##STR82##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.07 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 68
Into an apparatus similar to that in Example 1, were charged 118.2 g (1 mole) of N-hydroxypropylethylenediamine and 158.2 g (1 mole) of isopropyl 3-formyl-2-methylpropionate. From the apparatus, 18 g of water and 60 g of isopropyl alcohol were distilled off. Then, 340.5 g (1 mole) of behenic acid was charged and 18 g of water was distilled off at 180.degree. C. and under a reduced pressure of 70 mmHg to obtain 4-behenoyloxypropyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.32 H.sub.58 O.sub.3 N.sub.2 ; Calculated (%)--C 74.08, H 11.27, N 53.97, Found (%)--C 74.10, H 11.27, N 54.01.
Amine value--108.5 (theoretical 108.1).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1660 cm.sup.-1 (.nu..sub.C.dbd.O, amide), 1735 cm.sup.-1 (.nu..sub.C.dbd.O, ester).
Subsequently, to a solution of 518.1 g (1 mole) of 4-behenoyloxypropyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one dissolved in 600 g of tetrahydrofuran, was added dropwise a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 600 g of water. The acetate radical formation was effected at 70.degree. to 80.degree. C. to obtain 4-behenoyloxypropyl-6-methyl-4aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.34 H.sub.60 O.sub.5 N.sub.2 ; Calculated (%)--C 70.79, H 10.49, N 4.85, Found (%)--C 70.78, H 10.47, N 4.85.
IR spectrum--1640 cm.sup.-1 ##STR83##
NMR spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.06 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 69
Into an apparatus similar to that in Example 1, were charged 465.7 g (1 mole) of N-nonylphenoxy(2-hydroxy)propyltetraethylenepentamine and 144.2 g (1 mole) of ethyl 3-formyl-2-methylpropionate. At 120.degree. to 130.degree. C. and under a reduced pressure of 100 mmHg, 18 g of water and 46 g of ethanol were distilled off to obtain 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one.
Elementary analysis: C.sub.31 H.sub.55 O.sub.3 N.sub.5 ; Calculated (%)--C 68.22, H 10.15, N 12.83, Found (%)--C 68.20, H 10.15, N 12.80.
Amine value--410.0 (theoretical 411.2).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.N), 1655 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 177.0 g (1 mole) of potassium monobromoacetate dissolved in 1,000 g of water, was added dropwise 545.7 g (1 mole) of 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-6-methyl-2,3,6,7-tetrahydro-1,4-diazocin-5-one. The acetate radical formation was effected at 55.degree. to 60.degree. C. to obtain 4-nonylphenoxy(2-hydroxy)propylaminoethylaminoethylaminoethyl-6-methyl-4-aza-1-azoniacyclooct-8-en-5-one-1-acetate.
Elementary analysis: C.sub.33 H.sub.57 O.sub.5 N.sub.5 ; Calculated (%)--C 65.63, H 9.52, N 11.59, Found (%)--C 65.50, H 9.49, N 11.59.
IR spectrum--1645 cm.sup.-1 ##STR84##
NMRS spectrum--N.sup.+ -CH.sub.2 COO.sup.- proton 2.11 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 70
Into an apparatus similar to that in Example 1, were charged 429.6 g (1 mole) of a monotridecoxyethyl derivative of a 1,3-propanediaminepoly(3 moles on the average)ethyleneimine adduct and 130.1 g (1 mole) of methyl 3-formyl-2-methylpropionate. At 150.degree. to 155.degree. C., 18 g of water and 32 g of methanol were distilled off to synthesize an N-alkylazaalkenelactam.
Elementary analysis: C.sub.29 H.sub.59 O.sub.2 N.sub.5 ; Calculated (%)--C 68.32, H 11.67, N 13.73, Found (%)--C 68.36, H 11.69, N 13.70.
Amine value--439.1 (theoretical 440.2).
IR spectrum--1610 cm.sup.-1 (.nu..sub.C.dbd.O), 1650 cm.sup.-1 (.nu..sub.C.dbd.O, amide).
Subsequently, to a solution of 116.5 g (1 mole) of sodium monochloroacetate dissolved in 1,000 g of water, was added dropwise 509.8 g (1 mole) of the formed N-alkylazaalkenelactam. The reaction was allowed to proceed at 60.degree. to 70.degree. C. to obtain the compound having an acetate radical.
Elementary analysis: C.sub.31 H.sub.61 O.sub.4 N.sub.5 ; Calculated (%)--C 65.57, H 10.83, N 12.33, Found (%)--C 65.57, H 10.80, N 12.33.
IR spectrum--1635 cm.sup.-1 ##STR85##
NMR spectrum--N.sup.+ -CH.sub.2 COO proton 2.11 ppm (.delta., DSS standard, 50 MHz).
EXAMPLE 71
Below are described the antibacterial activities of the compounds in the compositions according to this invention. The results of antibacterial activity tests on the N-alkyl-substituted azaalkenelactams and their derivatives having a carboxylate radical of Examples 1 to 70 were as shown in Tables 1 to 3.
The testing method complied with the standard method of Japan Sociaty of Chemotherapy. Aqueous solutions of each compound in distilled water in various concentrations were added to the following bacteria cultivated in heart infusion agar media at 37.degree. C. and the minimum concentration of the compound to inhibit completely the growth of test bacteria in 24 hours (hereinafter referred to as MIC) was examined: Escherichia coli NIHJ, Staphylococcus aureus FDA 209P, Desulfovibrio desulfuricans IFO 3699, Pseudomonas aeruginosa IFO 3445, Bacillus subtilis ATCC 6633, Pasteurella multocida, almonella typhimurium, Staphylococcus epidermidis, and Streptococcus faecalis, wherein Desulfovibrio desulfuricans is a bacterium which generates hydrogen sulfide and, for this reason, acts to cause corrosion of metals.
EXAMPLE 72
In Tables 4 and 5, are further shown the results of tests for the metal corrosion inhibiting performance of the systems comprising an automobile brake fluid A of the following composition and, incorporated therein, each 0.25% by weight of N-alkyl-substituted azaalkenelactams or their derivatives having a carboxylate radical obtained in Examples 1 to 70.
Brake fluid composition A;
Trioxyethylene glycol monomethyl ether--35 parts
Trioxyethylene glycol monoethyl ether--20 parts
Trioxyethylene glycol monobutyl ether--20 parts
Poly(20 moles on the average)oxyethylene glycol monomethyl ether--15 parts
Poly(10 moles on the average)oxyethylene-poly(10 moles on the average)oxypropylene glycol monoethyl ether--10 parts
The testing method conformed to Japanese Industrial Standards JIS K 2233: a series of metal plates of tin-plate, steel, aluminum, cast iron, brass and copper connected to each other in the order indicated was immersed in the brake fluid system being tested, then left standing at 100.degree..+-.2.degree. C. for 120.+-.2 hours and the weight difference per unit area before and after the test was examined.
As for the reference substances, laurylbutylamine and oleylaminopropyloleamide were selected for the N-alkyl-substituted azaalkenelactam, and lauryldimethylbetaine and 1-hydroxyethyl-2-undecylimidazolineumbetaine were selected for the derivatives having an organic acid, e.g. a carboxylate radical of said lactam. These were subjected to the antibacterial activity test and the metal corrosion test in a similar manner to that described above.
TABLE 1__________________________________________________________________________Antibacterial Activity of Azaalkenelactamswith Long chain hydrocarbon radical MIC (.mu.g/ml)Sample Esherichia coli Staphylococcus aureus Desulfovibrio desul-(Azaalkenelactam) HIHJ FDA209P furicans IFO 13699__________________________________________________________________________Example 1 1600 50 6.25Example 2 25 12.5 12.5Example 3 1600 50 6.25Example 4 800 25 12.5Example 5 3200 12.5 6.25Example 6 50 12.5 25Example 7 200 12.5 12.5Example 8 800 50 50Example 9 25 12.5 6.25Example 10 1600 50 6.25Example 11 1600 100 6.25Example 12 1600 100 12.5Example 13 1600 100 12.5Example 14 1600 100 12.5Example 15 1600 50 6.25Example 16 50 100 25Example 17 1600 50 25Example 18 1600 100 12.5Example 19 400 50 25Example 20 800 50 12.5Example 21 800 50 25Example 22 800 25 12.5Example 23 25 25 50Example 24 800 200 25Example 25 1600 200 50Example 26 50 50 12.5Example 27 25 12.5 6.25Example 28 25 25 12.5Example 29 25 6.25 3.12Example 30 25 12.5 3.12Example 31 400 50 50Example 32 800 200 25Example 33 400 25 25Example 34 25 3.12 3.12Example 35 6.25 1.56 1.56Example 36 50 12.5 25Example 37 25 6.25 6.25Example 38 50 12.5 25Example 39 200 25 50Example 40 6.25 1.56 1.56Example 41 25 3.12 3.12Example 42 400 12.5 6.25Example 43 400 12.5 12.5Example 44 800 50 25Example 45 800 100 50Example 46 25 6.25 6.25Example 47 200 50 50Example 48 12.5 3.12 3.12Example 49 25 3.12 3.12Example 50 50 25 50Example 51 100 25 12.5Example 52 100 100 50Example 53 6.25 1.56 3.12Example 54 6.25 6.25 6.25Example 55 200 100 50Example 56 100 200 50Example 57 100 100 12.5Example 58 6.25 3.12 3.12Example 59 25 6.25 3.12Example 60 12.5 6.25 6.25Example 61 25 6.25 6.25Example 62 200 100 50Example 63 400 100 50Example 64 400 200 25Example 65 12.5 3.12 6.25Example 66 25 12.5 12.5Example 67 400 200 50Example 68 200 100 25Example 69 200 200 50Example 70 200 100 25Laurylbutylamide 10000 or more 10000 or more 400Oleylaminopropyl 10000 or more 10000 or more 100oleamide__________________________________________________________________________
TABLE 2__________________________________________________________________________Antibacterial Activity of Derivatives having a carboxylateradical of Azaalkenelactams with long chain hydrocarbon radical MIC (.mu.g/ml) Desulfovibrio Esherichia coli Staphylococcus desulfuricansSample NIHJ aureus FDA 209P IFO 13699__________________________________________________________________________Example 1, Compound having an 3200 50 12.5 acetate radicalExample 2, Compound having an 100 50 12.5 acetate radicalExample 3, Compound having an 3200 100 12.5 acetate radicalExample 4, Compound having an 800 12.5 12.5 acetate radicalExample 5, Compound having an 3200 100 12.5 acetate radicalExample 6, Compound having an 200 25 25 acetate radicalExample 7, Compound having an 200 12.5 25 acetate radicalExample 8, Compound having an 1600 50 50 acetate radicalExample 9, Compound having an 100 50 12.5 acetate radicalExample 10, Compound having an 3200 25 12.5 acetate radicalExample 11, Compound having an 3200 50 25 acetate radicalExample 12, Compound having an 3200 400 25 acetate radicalExample 13, Compound having an 3200 200 25 acetate radicalExample 14, Compound having an 3200 400 25 acetate radicalExample 15, Compound having an 3200 200 12.5 acetate radicalExample 16, Compound having an 100 400 50 acetate radicalExample 17, Compound having an 3200 100 50 acetate radicalExample 18, Compound having an 3200 100 25 acetate radicalExample 19, Compound having an 800 50 50 acetate radicalExample 20, Compound having an 1600 50 25 acetate radicalExample 21, Compound having an 1600 50 25 acetate radicalExample 22, Compound having an 3200 12.5 12.5 acetate radicalExample 23, Compound having an 100 800 50 acetate radicalExample 24, Compound having an 3200 800 50 acetate radicalExample 25, Compound having an 3200 100 50 acetate radicalExample 26, Compound having an 200 100 6.25 acetate radicalExample 27, Compound having an 100 25 6.25 acetate radicalExample 28, Compound having an 100 50 12.5 acetate radicalExample 29, Compound having an 50 25 3.12 acetate radicalExample 30, Compound having an 50 25 6.25 acetate radicalExample 31, Compound having an 800 100 25 acetate radicalExample 32, Compound having an 800 100 50 acetate radicalExample 33, Compound having a 800 25 12.5 propionate radicalExample 34, Compound having an 100 12.5 6.25 acetate radicalExample 35, Compound having an 100 3.12 3.12 acetate radicalExample 36, Compound having an 100 12.5 50 acetate radicalExample 37, Compound having a 100 6.25 6.25 propionate radicalExample 38, Compound having an 100 12.5 25 acetate radicalExample 39, Compound having an 400 50 50 acetate radicalExample 40, Compound having an 100 6.25 6.25 acetate radicalExample 41, Compound having an 100 12.5 3.12 acetate radicalExample 42, Compound having an 800 25 25 acetate radicalExample 43, Compound having an 800 25 25 acetate radicalExample 44, Compound having an 1600 50 25 acetate radicalExample 45, Compound having an 1600 100 50 acetate radicalExample 46, Compound having an 50 12.5 6.25 acetate radicalExample 47, Compound having an 200 50 50 acetate radicalExample 48, Compound having a 100 6.25 6.25 propionate radicalExample 49, Compound having an 100 12.5 6.25 acetate radicalExample 50, Compound having an 100 50 50 acetate radicalExample 51, Compound having an 100 50 25 acetate radicalExample 52, Compound having an 400 200 50 acetate radicalExample 53, Compound having an 100 3.12 6.25 acetate radicalExample 54, Compound having an 100 12.5 6.25 acetate radicalExample 55, Compound having an 400 200 50 acetate radicalExample 56, Compound having a 200 400 50 propionate radicalExample 57, Compound having an 200 100 12.5 acetate radicalExample 58, Compound having a 100 6.25 6.25 propionate radicalExample 59, Compound having an 200 12.5 6.25 acetate radicalExample 60, Compound having a 100 12.5 6.25 propionate radicalExample 61, Compound having an 100 12.5 12.5 acetate radicalExample 62, Compound having an 400 100 50 acetate radicalExample 63, Compound having an 800 200 50 acetate radicalExample 64, Compound having an 1600 400 50 acetate radicalExample 65, Compound having a 100 6.25 6.25 propionate radicalExample 66, Compound having an 100 25 25 acetate radicalExample 67, Compound having an 800 400 25 acetate radicalExample 68, Compound having an 800 200 25 - acetate radicalExample 69, Compound having an 400 200 50 acetate radicalExample 70, Compound having an 400 200 25 acetate radicalLauryldimethylbetaine 10000 or more 10000 or more 16001-hydroxyethyl-2-undecylimi- 10000 or more 3600 400dazoliniumbetaine__________________________________________________________________________
TABLE 3__________________________________________________________________________Antibacterial activity of Azaalkenelactams with long chain hydrocarbonradical and their derivatives having an organic acid radical MIC (.mu.g/ml) Paste- Salmo- Staphylo- Pseudomonas Bacillus urella nella coccus Strepto-aruginosa subtilis multo- typhi- epider- coccusSample IFO 3443 ATCC 6633 cida nurium midis faecalis__________________________________________________________________________Example 2, Azaalkene- 100 12.5 <1.56 3.12 1.56 12.5 lactamExample 9, Azaalkene- 100 25 3.12 6.25 6.25 12.5 lactamExample 9, Compound having 200 50 <1.56 6.25 12.5 12.5 an acetate radicalExample 29, Azaalkene- 100 3.12 <1.56 3.12 1.56 6.25 lactamExample 34, Azaalkene- 100 3.12 <1.56 3.12 <1.56 6.25 lactamExample 35, Azaalkene- 54 3.12 <1.56 1.56 <1.56 3.12 lactamExample 35, Compound having 100 12.5 3.12 6.25 3.12 6.25 an acetate radicalExample 40, Azaalkene- 50 3.12 <1.56 3.12 < 1.56 3.12 lactamExample 41, Azaalkene- 100 3.12 <1.56 3.12 1.56 6.25 lactamExample 48, Azaalkene- 50 6.25 <1.56 3.12 1.56 6.25 lactamExample 49, Azaalkene- 200 3.12 <1.56 3.12 1.56 6.25 lactamExample 53, Azaalkene- 100 3.12 <1.56 3.12 1.56 6.25 lactamExample 54, Azaalkene- 200 3.12 <1.56 3.12 1.56 6.25 lactamExample 58, Azaalkene- 50 3.12 <1.56 1.56 <1.56 3.12 lactamExample 59, Azaalkene- 100 3.12 <1.56 3.12 1.56 6.25 lactamExample 60, Azaalkene- 100 3.12 <1.56 3.12 1.56 6.25 lactamExample 61, Azaalkene- 200 3.12 <1.56 3.12 1.56 6.25 lactamExample 65, Azaalkene- 100 3.12 <1.56 3.12 1.56 6.25 lactamExample 66, Azaalkene- 200 6.25 <1.56 3.12 1.56 6.25 lactam__________________________________________________________________________
TABLE 4__________________________________________________________________________Metal corrosion inhibiting performance of azaalkenelactamswith long chain hydrocarbon radical in brake fluid A Test metal Tin- Alumi- Cast plate Steel num iron Brass Copper Weight Weight Weight Weight Weight Weight -Sample added change change change chang e change changeBlanc (Brake fluid -0.15 -0.20 +0.07 -0.14 -0.20 +0.18composition A) mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2__________________________________________________________________________Example 1, N-Alkyl sub- 0 -0.01 +0.02 -0.02 0 +0.02 stituted aza- alkenelactamExample 2, N-Alkyl sub- 0 -0.01 0 0 -0.01 0 stituted aza- alkenelactamExample 3, N-Alkyl sub- 0 0 +0.01 -0.02 -0.01 +0.01 stituted aza- alkenelactamExample 4, N-Alkyl sub- -0.01 0 0 -0.01 -0.01 +0.02 stituted aza- alkenelactamExample 5, N-Alkyl sub- -0.01 -0.01 0 0 -0.02 +0.02 stituted aza- alkenelactamExample 6, N-Alkyl sub- 0 -0.01 +0.02 -0.01 0 +0.03 stituted aza- alkenelactamExample 7, N-Alkyl sub- 0 0 +0.03 -0.01 -0.02 +0.01 stituted aza- alkenelactamExample 8, N-Alkyl sub- -0.01 -0.02 +0.01 -0.02 -0.01 +0.01 stituted aza- alkenelactamExample 9, N-Alkyl sub- 0 0 0 -0.01 -0.02 +0.03 stituted aza- alkenelactamExample 10, N-Alkyl sub- -0.02 -0.01 0 0 -0.02 +0.01 stituted aza- alkenelactamExample 11, N-Alkyl sub- 0 -0.01 +0.01 -0.02 -0.03 +0.02 stituted aza- alkenelactamExample 12, N-Alkyl sub- 0 -0.01 0 0 -0.02 +0.02 stituted aza- alkenelactamExample 13, N-Alkyl sub- 0 -0.02 +0.03 -0.03 -0.02 +0.01 stituted aza- alkenelactamExample 14, N-Alkyl sub- -0.01 0 -0.01 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 15, N-Alkyl sub- 0 0 0 -0.01 0 +0.01 stituted aza- alkenelactamExample 16, N-Alkyl sub- -0.02 -0.01 +0.01 0 -0.01 +0.01 stituted aza- alkenelactamExample 17, N-Alkyl sub- 0 -0.01 +0.01 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 18, N-Alkyl sub- -0.01 0 0 -0.01 -0.03 +0.03 stituted aza- alkenelactamExample 19, N-Alkyl sub- -0.02 -0.02 +0.01 -0.02 0 +0.01 stituted aza- alkenelactamExample 20, N-Alkyl sub- -0.01 -0.02 +0.02 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 21, N-Alkyl sub- 0 -0.02 +0.01 0 -0.01 +0.02 stituted aza- alkenelactamExample 22, N-Alkyl sub- 0 0 +0.01 -0.03 -0.01 +0.01 stituted aza- alkenelactamExample 23, N-Alkyl sub- 0 -0.01 0 -0.01 -0.03 +0.03 stituted aza- alkenelactamExample 24, N-Alkyl sub- -0.01 -0.01 +0.01 0 -0.02 +0.01 stituted aza- alkenelactamExample 25, N-Alkyl sub- 0 -0.01 0 -0.01 -0.03 +0.03 stituted aza- alkenelactamExample 26, N-Alkyl sub- 0 -0.01 +0.01 -0.02 -0.01 +0.03 stituted aza- alkenelactamExample 27, N-Alkyl sub- -0.01 -0.01 +0.02 0 -0.03 +0.01 stituted aza- alkenelactamExample 28, N-Alkyl sub- -0.01 -0.01 0 -0.01 -0.03 +0.02 stituted aza- alkenelactamExample 29, N-Alkyl sub- -0.01 0 +0.01 -0.01 -0.01 0 stituted aza- alkenelactamExample 30, N-Alkyl sub- 0 -0.01 +0.01 -0.02 -0.02 +0.02 stituted aza- alkenelactamExample 31, N-Alkyl sub- -0.01 -0.02 +0.01 -0.01 -0.03 +0.01 stituted aza- alkenelactamExample 32, N-Alkyl sub- -0.02 -0.02 +0.03 0 -0.03 +0.02 stituted aza- alkenelactamExample 33, N-Alkyl sub- -0.01 0 +0.01 -0.01 -0.02 +0.02 stituted aza- alkenelactamExample 34, N-Alkyl sub- 0 -0.01 0 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 35, N-Alkyl sub- 0 -0.01 0 -0.01 0 +0.01 stituted aza- alkenelactamExample 36, N-Alkyl sub- -0.01 -0.02 +0.02 -0.01 -0.02 +0.02 stituted aza- alkenelactamExample 37, N-Alkyl sub- -0.01 0 +0.01 -0.01 -0.03 +0.03 stituted aza- alkenelactamExample 38, N-Alkyl sub- -0.01 0 +0.02 -0.02 -0.02 +0.01 stituted aza- alkenelactamExample 39, N-Alkyl sub- 0 -0.01 +0.02 -0.01 -0.02 +0.02 stituted aza- alkenelactamExample 40, N-Alkyl sub- -0.01 -0.01 +0.01 -0.01 0 0 stituted aza- alkenelactamExample 41, N-Alkyl sub- -0.01 -0.01 0 -0.01 0 +0.01 stituted aza- alkenelactamExample 42, N-Alkyl sub- -0.02 -0.01 +0.01 0 -0.02 +0.01 stituted aza- alkenelactamExample 43, N-Alkyl sub- -0.01 0 +0.01 -0.02 -0.02 +0.01 stituted aza- alkenelactamExample 44, N-Alkyl sub- 0 -0.01 +0.02 -0.01 -0.02 +0.03 stituted aza- alkenelactamExample 45, N-Alkyl sub- -0.02 -0.02 +0.01 -0.02 -0.02 +0.03 stituted aza- alkenelactamExample 46, N-Alkyl sub- 0 -0.01 +0.01 -0.02 -0.01 +0.01 stituted aza- alkenelactamExample 47, N-Alkyl sub- -0.01 0 +0.01 -0.02 -0.02 +0.02 stituted aza- alkenelactamExample 48, N-Alkyl sub- 0 -0.01 +0.01 -0.01 -0.01 0 stituted aza- alkenelactamExample 49, N-Alkyl sub- 0 -0.01 0 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 50, N-Alkyl sub- -0.02 -0.02 +0.01 0 -0.02 +0.02 stituted aza- alkenelactamExample 51, N-Alkyl sub- -0.02 -0.02 0 -0.01 -0.03 +0.02 stituted aza- alkenelactamExample 52, N-Alkyl sub- 0 -0.01 +0.01 -0.02 -0.02 +0.02 stituted aza- alkenelactamExample 53, N-Alkyl sub- -0.01 0 +0.01 -0.01 -0.01 0 stituted aza- alkenelactamExample 54, N-Alkyl sub- -0.01 0 0 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 55, N-Alkyl sub- 0 -0.01 +0.02 -0.02 -0.01 +0.01 stituted aza- alkenelactamExample 56, N-Alkyl sub- -0.02 -0.01 +0.02 -0.02 -0.02 +0.01 stituted aza- alkenelactamExample 57, N-Alkyl sub- -0.01 -0.01 +0.01 -0.02 -0.03 +0.02 stituted aza- alkenelactamExample 58, N-Alkyl sub- 0 -0.01 0 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 59, N-Alkyl sub- -0.01 0 +0.01 0 -0.01 +0.01 stituted aza- alkenelactamExample 60, N-Alkyl sub- -0.01 0 0 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 61, N-Alkyl sub- 0 -0.01 +0.01 -0.01 0 +0.01 stituted aza- alkenelactamExample 62, N-Alkyl sub- -0.01 -0.02 +0.02 -0.02 -0.02 +0.02 stituted aza- alkenelactamExample 63, N-Alkyl sub- -0.02 -0.01 +0.03 -0.02 -0.01 +0.02 stituted aza- alkenelactamExample 64, N-Alkyl sub- -0.01 -0.01 +0.02 -0.02 -0.02 +0.02 stituted aza- alkenelactamExample 65, N-Alkyl sub- 0 -0.01 0 -0.01 -0.01 -0.01 stituted aza- alkenelactamExample 66, N-Alkyl sub- 0 0 +0.01 -0.01 -0.01 +0.01 stituted aza- alkenelactamExample 67, N-Alkyl sub- -0.01 -0.01 +0.01 -0.02 -0.02 +0.02 stituted aza- alkenelactamExample 68, N-Alkyl sub- -0.01 -0.02 +0.01 -0.02 -0.01 +0.02 stituted aza- alkenelactamExample 69, N-Alkyl sub- -0.02 -0.02 +0.01 -0.02 -0.02 +0.03 stituted aza- alkenelactamExample 70, N-Alkyl sub- -0.01 -0.01 +0.02 -0.01 -0.01 +0.02 stituted aza- alkenelactamLaurylbutyramide -0.06 -0.09 +0.06 -0.08 -0.12 +0.07Oleylaminopropylamide -0.04 -0.07 +0.05 -0.04 -0.10 +0.11__________________________________________________________________________
TABLE 5__________________________________________________________________________Metal corrosion inhibiting performance of derivatives havinga carboxylate radical of azaalkenelactams with long chainhydrocarbon radical in brake fluid composition A Test metal Tin Alumi- Cast plate Steel num iron Brass Copper Weight Weight Weight Weight Weight WeightSample added change change change change change changeBlanc (Brake fluid -0.15 -0.20 +0.07 -0.14 -0.20 +0.18composition A) mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2 mg/cm.sup.2__________________________________________________________________________Example 1, Compound having -0.03 -0.01 0 -0.04 +0.01 0 an acetate radicalExample 2, Compound having -0.02 -0.02 +0.01 -0.01 -0.03 -0.04 an acetate radicalExample 3, Compound having -0.01 -0.01 +0.01 0 0 0 an acetate radicalExample 4, Compound having -0.01 -0.03 +0.01 -0.03 0 0 an acetate radicalExample 5, Compound having -0.01 -0.02 0 -0.01 0 0 an acetate radicalExample 6, Compound having -0.02 -0.01 0 0 -0.01 -0.01 an acetate radicalExample 7, Compound having -0.02 -0.03 +0.01 -0.02 -0.01 0 an acetate radicalExample 8, Compound having -0.02 -0.03 +0.01 0 -0.01 +0.01 an acetate radicalExample 9, Compound having -0.03 -0.03 +0.01 -0.02 -0.01 0 an acetate radicalExample 10, Compound having -0.01 -0.01 0 -0.01 0 0 an acetate radicalExample 11, Compound having -0.02 -0.02 +0.01 -0.02 0 -0.01 an acetate radicalExample 12, Compound having -0.02 -0.01 0 -0.01 -0.01 0 an acetate radicalExample 13, Compound having -0.01 -0.02 0 0 -0.01 +0.02 an acetate radicalExample 14, Compound having -0.03 -0.02 +0.02 -0.02 0 0 an acetate radicalExample 15, Compound having -0.02 -0.03 +0.02 -0.01 -0.02 +0.01 an acetate radicalExample 16, Compound having -0.02 -0.02 +0.02 -0.02 0 0 an acetate radicalExample 17, Compound having -0.01 -0.02 0 -0.02 -0.01 0 an acetate radicalExample 18, Compound having -0.02 -0.03 +0.01 -0.01 0 -0.01 an acetate radicalExample 19, Compound having -0.02 -0.01 0 -0.01 0 0 an acetate radicalExample 20, Compound having -0.02 -0.03 +0.01 -0.02 -0.01 0 an acetate radicalExample 21, Compound having -0.03 -0.01 0 -0.01 -0.01 -0.01 an acetate radicalExample 22, Compound having -0.03 -0.02 +0.02 0 -0.01 0 an acetate radicalExample 23, Compound having -0.03 -0.02 0 -0.01 0 0 an acetate radicalExample 24, Compound having -0.02 -0.03 +0.01 -0.02 0 +0.01 an acetate radicalExample 25, Compound having -0.02 -0.03 +0.01 -0.02 0 0 an acetate radicalExample 26, Compound having -0.01 -0.03 +0.01 -0.02 -0.01 -0.02 an acetate radicalExample 27, Compound having -0.02 -0.03 +0.02 -0.02 -0.02 -0.02 an acetate radicalExample 28, Compound having -0.02 -0.03 +0.01 -0.01 0 -0.01 an acetate radicalExample 29, Compound having -0.01 -0.02 0 -0.02 +0.01 -0.01 an acetate radicalExample 30, Compound having -0.03 -0.03 +0.01 -0.02 -0.02 -0.01 an acetate radicalExample 31, Compound having -0.03 -0.03 +0.02 -0.04 -0.01 0 an acetate radicalExample 32, Compound having -0.03 -0.02 +0.02 -0.02 -0.01 +0.01 an acetate radicalExample 33, Compound having -0.02 -0.02 0 -0.01 -0.02 -0.01 a propionate radicalExample 34, Compound having -0.02 -0.03 +0.02 -0.03 -0.01 0 an acetate radicalExample 35, Compound having -0.01 -0.02 0 -0.01 0 0 an acetate radicalExample 36, Compound having - 0.02 -0.03 +0.02 -0.02 -0.02 -0.01 an acetate radicalExample 37, Compound having -0.02 -0.02 +0.02 -0.02 -0.01 0 a propionate radicalExample 38, Compound having -0.01 -0.02 +0.02 -0.01 0 -0.01 an acetate radicalExample 39, Compound having -0.01 -0.03 +0.02 -0.01 -0.01 0 an acetate radicalExample 40, Compound having -0.02 -0.01 +0.02 0 -0.02 -0.01 an acetate radicalExample 41, Compound having -0.02 -0.02 +0.01 0 -0.01 0 an acetate radicalExample 42, Compound having -0.02 -0.03 +0.01 -0.02 0 0 an acetate radicalExample 43, Compound having -0.03 -0.02 +0.02 -0.03 -0.01 -0.02 an acetate radicalExample 44, Compound having -0.03 -0.01 0 -0.03 -0.01 -0.01 an acetate radicalExample 45, Compound having -0.01 -0.03 +0.01 -0.02 -0.01 -0.01 an acetate radicalExample 46, Compound having -0.03 -0.03 +0.02 -0.02 0 -0.01 an acetate radicalExample 47, Compound having -0.03 -0.03 +0.02 -0.04 -0.02 -0.02 an acetate radicalExample 48, Compound having -0.01 -0.02 0 -0.02 -0.01 -0.01 a propionate radicalExample 49, Compound having -0.02 -0.02 +0.01 0 -0.01 -0.01 an acetate radicalExample 50, Compound having -0.02 -0.03 +0.02 -0.03 -0.01 0 an acetate radicalExample 51, Compound having -0.03 -0.03 +0.02 -0.03 -0.01 0 an acetate radicalExample 52, Compound having -0.02 -0.03 +0.02 0 -0.01 -0.01 an acetate radicalExample 53, Compound having -0.02 -0.02 +0.01 -0.01 0 -0.01 an acetate radicalExample 54, Compound having -0.02 -0.02 +0.02 -0.02 -0.02 -0.02 an acetate radicalExample 55, Compound having -0.03 -0.02 +0.02 -0.02 -0.01 0 an acetate radicalExample 56, Compound having -0.02 -0.03 +0.02 -0.03 -0.01 -0.02 a propionate radicalExample 57, Compound having -0.01 -0.02 +0.01 -0.02 0 -0.01 an acetate radicalExample 58, Compound having -0.03 -0.01 +0.01 0 -0.02 -0.02 a propionate radicalExample 59, Compound having -0.02 -0.02 0 -0.01 -0.02 -0.02 an acetate radicalExample 60, Compound having -0.02 -0.02 +0.02 -0.02 -0.01 0 a propionate radicalExample 61, Compound having -0.01 -0.03 +0.01 -0.02 0 -0.01 an acetate radicalExample 62, Compound having -0.02 -0.01 +0.01 -0.02 -0.01 0 an acetate radicalExample 63, Compound having -0.02 -0.02 +0.01 -0.03 -0.01 0 an acetate radicalExample 64, Compound having -0.02 -0.01 +0.02 -0.03 -0.02 -0.02 an acetate radicalExample 65, Compound having -0.02 -0.02 0 -0.02 -0.02 -0.02 a propionate radicalExample 66, Compound having -0.01 -0.02 +0.02 -0.01 0 -0.01 an acetate radicalExample 67, Compound having -0.02 -0.02 +0.02 -0.01 -0.01 0 an acetate radicalExample 68, Compound having -0.03 -0.03 +0.01 -0.01 0 -0.01 an acetate radicalExample 69, Compound having -0.02 -0.02 +0.02 -0.02 -0.01 0 an acetate radicalExample 70, Compound having -0.02 -0.02 +0.01 -0.03 -0.02 -0.02 an acetate radicalLauryldimethylbetaine -0.10 -0.19 +0.09 -0.15 -0.23 -0.151-Hydroxyethyl-2-unde- -0.12 -0.16 +0.10 -0.12 -0.24 -0.12cylimidazolium betaine__________________________________________________________________________
INDUSTRIAL APPLICABILITY
Since the bactericidal surface active agents of this invention exhibit excellent bactericidal action against any of the aerobic, anaerobic, gram-positive and gram-negative bacteria, they are of high industrial applicability.

Number	Date	Country
39-29848	Dec 1964	JPX
43-26176	Nov 1968	JPX

Antibacterial surface active agent containing azaalkenelactam

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