CA1057654A - Germicidal agent - Google Patents
Germicidal agentInfo
- Publication number
- CA1057654A CA1057654A CA248,062A CA248062A CA1057654A CA 1057654 A CA1057654 A CA 1057654A CA 248062 A CA248062 A CA 248062A CA 1057654 A CA1057654 A CA 1057654A
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- Canada
- Prior art keywords
- carbon atoms
- agent according
- germicidal agent
- alkyl
- formula
- Prior art date
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Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/02—Acyclic compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
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- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract of the Disclosure:
The invention concerns a germicidal agent comprising a ger-micidally active quaternary ammonium salt, sulfonium salt, phosphonium salt, pnenol, phenol ester, amphotenside, aldahyde, polyvinyl pyrrolidone-I2-complex, amine oxide, or amine imide, to which has been added a compound of the general formula:
(I) in which n is 0, 1 or 2, R1 is alkyl of 6 to 18 carbon atoms, and R2 is alkyl of 1 to 18 carbon atoms, aralkyl, hydroxyalkyl having 2 to 4 carbon atoms, -(-CH2-CH2-O-)? or
The invention concerns a germicidal agent comprising a ger-micidally active quaternary ammonium salt, sulfonium salt, phosphonium salt, pnenol, phenol ester, amphotenside, aldahyde, polyvinyl pyrrolidone-I2-complex, amine oxide, or amine imide, to which has been added a compound of the general formula:
(I) in which n is 0, 1 or 2, R1 is alkyl of 6 to 18 carbon atoms, and R2 is alkyl of 1 to 18 carbon atoms, aralkyl, hydroxyalkyl having 2 to 4 carbon atoms, -(-CH2-CH2-O-)? or
Description
~576~ -: .
.,`:
GERMICIDAL AGENT .~ ~
Disinfectants and antiseptics comprlsing quaternary ~ :
ammonium or sulfonuim salts are known and find wide application. :
The compounds known as "quats" wh.ich are added include -:~
a large variety of compound types, in which -the common characteristic is a quaternary ni-trogen or sulfur a-tom.
The best known is alkyldimethyl benzyl ammonium chloride.
Other than this there is also a series bactericidal quats, .
which belong to the groups of alkyl pyridinium salts or cetyl trimethyl ammonium salts. Alkyl imidazoleum salts and benzo triazoleum salts also possess a good bacteriostatic activity. ~ :
Other quats, which are derived ~rom isoquinoline, such as - : .
lauryl isoquinoline, in addition to bactericidal activity, also possess a good fungistatic activity.
It is also known that in the presence of non-ionic tensides, the bactericidal and fungicidal activity of quats is signlficantly reduced.
.. ~...
I o , ':
.. , ,,. , -. . , . - . . ., . , ... . .. . . , .. . . -:, 57~4 :
Furthermore, it is known that phosphonium saltS, phenols r phenol esters, amphotensides, aldehydes, polyvinylpyrrolidone- ;
I - complexes, amine oxides and/or amine imides possess a germicidal activity.
The invention concerns the surprising finding that the biological activity of the abovem~ntioned known germicidal agents can be synergistically increased by the addition of compounds described in more detail below. :. :
,,. ~; . ~ :
Thus, in accordance with the present teachings, a germicidal .... ~
:;, agent is provided which has a germicidally active quaternary ~ -j ammonium salt, sulfonium salt, phosphonium salt, phenol, phenol ester, amphotenside, aldehyde, polyvinyl pyrrolidone~
I2-complex, amine oxide, or amine imide, to which has been added a compound of the general formula~
Rl - S R2 ()n ~` in which n is 0, 1 or 2, ~ :
:I Rl is an alkyl of 6 to 18 carbon atoms, and - .~ `
j R2 lS an alkyl of 1 to 18 carbon atoms, aralkyl, ;
,' 20 hydroxyalkyl having 2 to 4 carbon atoms, -(-CE12-CH2-O-)m or -(-CH-CH2-O)m in which m is a whole 3 .:~:: ?
~ number of from 1 to 12, and R3 is CH3, -CH2Cl :: :
.~ .
1 or C2E~5 .i ':,' :.
~1 .;'. .. .
:i! ~, . ~ .
i 30 . ' :
1 ~2-.-, ~ ' ,``' :
The compounds of formula I addecl in accordance with the invention can be produced in known manner. The compounds are neutral substances which in general possess the properties of non-ionic tensides. They posses a low biological activity so that it can be regarded as most surprising that a mixture of the said germicidally active 1 , :
compounds with substances of the general formula I .
exhibit a synergistic increase in activi~y. One would much rather expect a decrease in biological activlty ;
i on the basis of the known lowering of bactericidal 1, and fungicidal activity by non-ionic ~ensides.
~'.fl .
The quats which come into question in accordance with the invention are similarly produced by known processes.
~, The germicidal agents in accordance with the invention ` .
3~ ~ particularly possess a significantly increased activity .
.1 against skin pathogenic fungi as against the known compounds, which is of particular importance in the I cllnical area.
1 .
;I The phosphonium salts which come into question in. ~. .
. , .
. accordance with the invention correspond to the formula:
PRlR2R3R~ ~) X ~3 ~
:" 1 .:
.-,. ::
.~ i . , . . -.: I .
`'- 3 :~ - 3 _ ~ ~
. ... ,, .. . , . : ., ~2~576S4 ` .
in which preferably one of the radica]s Rl to R~ is straight-chained alkyl of 10 to 16,particularly 12 to 14, carbon atoms, whilst the other radicals are alkyl ~-o~ 1 to 4 carbon atoms, whereby one o these can also be benzyl, particularly methyl, and X ~ is the usual anion for this known germicidally active phosphonium salt, perferably chlorine- Particularly, the phosphonium salts consist of dodecyltrimethyl-phosphoniumchloride or dodecylc~imethylbenzylphosphoniumchloride.
The germicidally active phenols which may be employed in the germ;cidal agent o the invention are preferably chloro phenols, particularly mono-chlcro phenols, di-chloro phenols, tri-chloro phenols or penta-chloro phenol, or phenols having a lower alkyl of 1 to 4 carbon atom substituent, particularly cresols.
~1) ' ' , ' .' ~! The germicldal phenol ester which is preferably employed in accordance with the invention, consist of phenols, such as defined above, in particular pentachloro phenol, ! and ~ranched or straight-chained fatty acids with up to :~
18 carbon atoms, preferably up to 6 carbon atoms, especially 3 butyric acid.
; :~
:; I ,'. ~:
1 - 4 ~
.j :
.. .
, .! ' . ,:
., . . ~ . . . 1 '.'. ' ' `' ' '' ,~
The amphoten$ides, in which the known germicidal activity ~.
can be synergistically increased by the addition of compounds of formula I, are tensides with several functional groups which can ionise in aqueous solution : .
and thus, dependent on the nature of the medium, lend .
to the compound an anionic or cationic character.
The amphotensides preferably consist of compounds of the following formula:
.''', ~
~, ' . `, ~
: ,2 R1 ~ co~r ~ (CE~2)X - N2~ (CH2)y COO ;~
:l ~2 - :
,1 , .
l R1 - CO~ ~ (CH2)x- N0~ ~CH2)~ S03 :........................................ 3 , . . ', R1 ~ N _ (CH2)~ S3 .
~ 3 .-", . : :
R2 '' '' l, R1 ~ N~ - (CH2~y COO
:~ . 3 ~ . . . .
~` . R4 - NH - ~CH2)xcooMe .~ ~
j R~ - NH(CH2)xNH(CH2jxCOOMe or ~ ; :
Rl-NH-~cH2)~-NH-(cH2)x-NH-cH2-cooH
;'~ . ' ~.:
'. , `
~L~5~6~4 in which Rl is a long chain saturated or unsaturated alkyl ~roup preferably having lO to 14 carbon atoms, R2 and R3 are lower alkyl having 1 to 4 carbon atoms, : ~:
particularly methyl or e~hyl, x is a whole number from 1 to 3, y is a whole number from 2 to 3, Y is -NH-or-O-, R4 is a saturated or unsaturated alkyl group having :j ~
. 8 to 18 carbon atoms, particularly an oleic group, and Me is an alkali metal, particularly Na. ;~
; :~
The germicidal aldehydes which are preferably employed in the germicidal agent of the in~ention, consist of ~.
saturated aliphatic mono- and di-aldehydes havin~ up to ~
i lO carbon atoms, in particular formaldehyde, acetaldehyde, ~.
.:l glyoxal glutaraldehyde, succinic dialdehyde, 2-ethyl ~
I hexanal, or substances which release aldehydes, in ~ :
. :i, .
~, particular in acetylated form. .;.;.~
~. : : -: .
., The amino oxides correspond to the formula : :
~::3 R - N ~
! R2 . ~ . ' `, ':
wherein R ls preferably a straight or branched long ~ :
chain alkyl radical with 10 to 18, particularly 12 to 14, ., ... ,~; , .
'1 , :~ , '.: 1 ~ , ' ',' - - 6 - - :
;,, ' . , : ., . ~
5 715~4 carbon atoms and Rl and R2 is lower alkyl or oxalkyl with 1 to 4 carbon atoms, particularly methyl or
.,`:
GERMICIDAL AGENT .~ ~
Disinfectants and antiseptics comprlsing quaternary ~ :
ammonium or sulfonuim salts are known and find wide application. :
The compounds known as "quats" wh.ich are added include -:~
a large variety of compound types, in which -the common characteristic is a quaternary ni-trogen or sulfur a-tom.
The best known is alkyldimethyl benzyl ammonium chloride.
Other than this there is also a series bactericidal quats, .
which belong to the groups of alkyl pyridinium salts or cetyl trimethyl ammonium salts. Alkyl imidazoleum salts and benzo triazoleum salts also possess a good bacteriostatic activity. ~ :
Other quats, which are derived ~rom isoquinoline, such as - : .
lauryl isoquinoline, in addition to bactericidal activity, also possess a good fungistatic activity.
It is also known that in the presence of non-ionic tensides, the bactericidal and fungicidal activity of quats is signlficantly reduced.
.. ~...
I o , ':
.. , ,,. , -. . , . - . . ., . , ... . .. . . , .. . . -:, 57~4 :
Furthermore, it is known that phosphonium saltS, phenols r phenol esters, amphotensides, aldehydes, polyvinylpyrrolidone- ;
I - complexes, amine oxides and/or amine imides possess a germicidal activity.
The invention concerns the surprising finding that the biological activity of the abovem~ntioned known germicidal agents can be synergistically increased by the addition of compounds described in more detail below. :. :
,,. ~; . ~ :
Thus, in accordance with the present teachings, a germicidal .... ~
:;, agent is provided which has a germicidally active quaternary ~ -j ammonium salt, sulfonium salt, phosphonium salt, phenol, phenol ester, amphotenside, aldehyde, polyvinyl pyrrolidone~
I2-complex, amine oxide, or amine imide, to which has been added a compound of the general formula~
Rl - S R2 ()n ~` in which n is 0, 1 or 2, ~ :
:I Rl is an alkyl of 6 to 18 carbon atoms, and - .~ `
j R2 lS an alkyl of 1 to 18 carbon atoms, aralkyl, ;
,' 20 hydroxyalkyl having 2 to 4 carbon atoms, -(-CE12-CH2-O-)m or -(-CH-CH2-O)m in which m is a whole 3 .:~:: ?
~ number of from 1 to 12, and R3 is CH3, -CH2Cl :: :
.~ .
1 or C2E~5 .i ':,' :.
~1 .;'. .. .
:i! ~, . ~ .
i 30 . ' :
1 ~2-.-, ~ ' ,``' :
The compounds of formula I addecl in accordance with the invention can be produced in known manner. The compounds are neutral substances which in general possess the properties of non-ionic tensides. They posses a low biological activity so that it can be regarded as most surprising that a mixture of the said germicidally active 1 , :
compounds with substances of the general formula I .
exhibit a synergistic increase in activi~y. One would much rather expect a decrease in biological activlty ;
i on the basis of the known lowering of bactericidal 1, and fungicidal activity by non-ionic ~ensides.
~'.fl .
The quats which come into question in accordance with the invention are similarly produced by known processes.
~, The germicidal agents in accordance with the invention ` .
3~ ~ particularly possess a significantly increased activity .
.1 against skin pathogenic fungi as against the known compounds, which is of particular importance in the I cllnical area.
1 .
;I The phosphonium salts which come into question in. ~. .
. , .
. accordance with the invention correspond to the formula:
PRlR2R3R~ ~) X ~3 ~
:" 1 .:
.-,. ::
.~ i . , . . -.: I .
`'- 3 :~ - 3 _ ~ ~
. ... ,, .. . , . : ., ~2~576S4 ` .
in which preferably one of the radica]s Rl to R~ is straight-chained alkyl of 10 to 16,particularly 12 to 14, carbon atoms, whilst the other radicals are alkyl ~-o~ 1 to 4 carbon atoms, whereby one o these can also be benzyl, particularly methyl, and X ~ is the usual anion for this known germicidally active phosphonium salt, perferably chlorine- Particularly, the phosphonium salts consist of dodecyltrimethyl-phosphoniumchloride or dodecylc~imethylbenzylphosphoniumchloride.
The germicidally active phenols which may be employed in the germ;cidal agent o the invention are preferably chloro phenols, particularly mono-chlcro phenols, di-chloro phenols, tri-chloro phenols or penta-chloro phenol, or phenols having a lower alkyl of 1 to 4 carbon atom substituent, particularly cresols.
~1) ' ' , ' .' ~! The germicldal phenol ester which is preferably employed in accordance with the invention, consist of phenols, such as defined above, in particular pentachloro phenol, ! and ~ranched or straight-chained fatty acids with up to :~
18 carbon atoms, preferably up to 6 carbon atoms, especially 3 butyric acid.
; :~
:; I ,'. ~:
1 - 4 ~
.j :
.. .
, .! ' . ,:
., . . ~ . . . 1 '.'. ' ' `' ' '' ,~
The amphoten$ides, in which the known germicidal activity ~.
can be synergistically increased by the addition of compounds of formula I, are tensides with several functional groups which can ionise in aqueous solution : .
and thus, dependent on the nature of the medium, lend .
to the compound an anionic or cationic character.
The amphotensides preferably consist of compounds of the following formula:
.''', ~
~, ' . `, ~
: ,2 R1 ~ co~r ~ (CE~2)X - N2~ (CH2)y COO ;~
:l ~2 - :
,1 , .
l R1 - CO~ ~ (CH2)x- N0~ ~CH2)~ S03 :........................................ 3 , . . ', R1 ~ N _ (CH2)~ S3 .
~ 3 .-", . : :
R2 '' '' l, R1 ~ N~ - (CH2~y COO
:~ . 3 ~ . . . .
~` . R4 - NH - ~CH2)xcooMe .~ ~
j R~ - NH(CH2)xNH(CH2jxCOOMe or ~ ; :
Rl-NH-~cH2)~-NH-(cH2)x-NH-cH2-cooH
;'~ . ' ~.:
'. , `
~L~5~6~4 in which Rl is a long chain saturated or unsaturated alkyl ~roup preferably having lO to 14 carbon atoms, R2 and R3 are lower alkyl having 1 to 4 carbon atoms, : ~:
particularly methyl or e~hyl, x is a whole number from 1 to 3, y is a whole number from 2 to 3, Y is -NH-or-O-, R4 is a saturated or unsaturated alkyl group having :j ~
. 8 to 18 carbon atoms, particularly an oleic group, and Me is an alkali metal, particularly Na. ;~
; :~
The germicidal aldehydes which are preferably employed in the germicidal agent of the in~ention, consist of ~.
saturated aliphatic mono- and di-aldehydes havin~ up to ~
i lO carbon atoms, in particular formaldehyde, acetaldehyde, ~.
.:l glyoxal glutaraldehyde, succinic dialdehyde, 2-ethyl ~
I hexanal, or substances which release aldehydes, in ~ :
. :i, .
~, particular in acetylated form. .;.;.~
~. : : -: .
., The amino oxides correspond to the formula : :
~::3 R - N ~
! R2 . ~ . ' `, ':
wherein R ls preferably a straight or branched long ~ :
chain alkyl radical with 10 to 18, particularly 12 to 14, ., ... ,~; , .
'1 , :~ , '.: 1 ~ , ' ',' - - 6 - - :
;,, ' . , : ., . ~
5 715~4 carbon atoms and Rl and R2 is lower alkyl or oxalkyl with 1 to 4 carbon atoms, particularly methyl or
2-hydroxy ethyl.
. ; .
The amine imides which may be employed may be of the formula~
` . 1 ' ~ R - CO ~ ~ N ~ - R2 ,, \ .
.
.
wherein, preferably, R is a straight or branched long chain alkyl radical having 10 to 18, particularly '~ 12 to 14, carbon atoms and Rl, R2 and R3 are lower alkyl or oxalkyl radicals with 1 to 4 carbon atoms, particularly methyl or methoxy radicals.
:-~
:~
The polyvinylpyrrolidone - I2 ~ complexes which ~
~1 may be incorporated in accordànce with the invention -.,~
! are similarly known as germicides.
~ , ~ ... .. .
;~ Preferably, the compounds of formula I which are added . : ::
in accordance with the invention are those in which Rl ~
: , ~., ,- .
~ is an alkyl radical having 8 to 14 carbon atoms. R~ is ~ .
.. , .; . , ~ .
~~ - 7 ~`
. ' . .
l~S ~s554 ., preferably an alkyl radical having 1 to 7 carbon atoms and in the case of an aralkyl radical is preferably a phenyl alkyl or benzyl radical. Preferably n signifies a whole number from 1 to 6.
, . . . .
:, :
In the germicidal agents in accordance with the invention, any desired ratio of the quaternary ammonium salts, . .
sulfonium salts, phosphonium salts, phenols, phenol esters, amphotensides, aldehydes, polyvinylpyrrolidone~
.`'! I~ - complexes, amine oxides and/or amine imides to .`! ;:;
the compounds of the general formula I can be maintained.
Preferably however the weight ratio of the said compounds to the compounds of the genera~ formula I varies between 95:5 and 5:95, and most preferably stoichiometric ratios are maintained. With regard to the disinfectant activity, the cross-linking activity,as well as the detergent activity, the respective ratios can be determined. This ~ .
i determination may be made by simple preliminary experments.
The germicidal agents in accordanoe with the invention may, dependent on its use, be employed as such or in mixture with an inert carrier or diluent and/or in combination , ::' :,:.
i with other structuring, washing, cleaning and water :', '; ' ~ .':`.' ~ ~ ~ softening agents.
~.-1 : . . , ~., .
~ ~ - 8 -; ~ . ' . . ;~
.. :; -, . . .
5~54 Examples of inert carriers or diluents are the ~ollowing:
' , ;:.:
propellants, such as carbon dioxide, fluorine carbohydrates, fluortne-chlorine carkohydrates, ethanol, isopropanol, dimethylsulfoxide, water, talcum, silica gel, carbohydrates, such as lower paraffins, and salts, such as sodium sulfate.
Preferably, the agents of the invention are employed in the form of f]uids, solutions, emulsions, suspenslons, sprays, powders, salts etc.
,.;,.
Examples of additional components of a combined cleaning and i disinfectant agent are silicates, such as sodium meta-silicate carbonates, such as sodium carbonate, as well as polymeric phosphates, such as ~etra-sodium triphosphate.
The germicidal agents of the invention are of particular importance in the clinical area.
j ..
.. . ..
' With the addltion of compounds of formula I to higher `i1 chlorinated phenols, such as for example pentachloro ! phenol, which until now it has only been possible to keep and use in alkaline solution, whilst it precipitates out in aqueous acid medium, the advantage is obtàined , :
in a surprising manner~that such chlorinated phenols can also be added to aqueous acid medi~s~
''',~ ' ~' :'`
., . ` .
~ ~ .
. q . .
: ~ _ 9 _ :.:
.. . .
- . - . ... .. . ... . ~ , ......
1~5~ 4 A further advantage of the germici.dal agents of the invention consists in that on the one hand the biological decomposition of the compounds of formula I is practically complete, whereas in addition the synergistic increase in activity requires less active agent to be employed, whereby the pollution effect remains the same or is even significantly reduced.
Mixtures of quats with compounds of formula I with .
particularly significant synergism are for example ' stoichiometric mixtures of the fol].owing qua.ternary ammonium and sulfonium salts:
: .
J
'' : , "~, . ' ,', . "~ ' ` '~ '`
' ' '`," ;.:
'"I ' . , .
., , ,',, ,,' ~, ~ 10. r , ,,~
: ' , ' ' - ~
'~ ' : , ' '~, ' .
,'; ' . ' `" `' ' ' ; '' "-', ~ ' ''~
'`'~''.`: ` '' ' . ' . ' '. .' .'. . . .. '''.. . ~ ``' ' ~ '' s~;s~ : ~
[~12 25 IS CH2~CH2~OH~ CH3-o-so a [ n 2n + 1 -N-CE~2 ~ ~ Cle ~ .
[ CH2-CH2O~3 ~ Cle CH2-cM2oH
¦C12H25-NI C 2 ~~ ] Cl L 1 3 3 1 -~ -O- (CE~2) 2-- (CH2) 2 ~l -CH2--~ ~ Cl . CH3 H3C` CH3 :
~',", ~
,'1' [e=~N~)-C16E~33~1,C1;3 `.`~'~
....
'`"1 `~
,'~', ' ' ~
.~ ~ .
~.
', .:
! . , ~
':~ .~ . ' .
``'`1' ~: ~-:' , - -il ` , ,, :~ . `:' "''~ `'' '`
. .~, '' ' ~'~;
.-i 30 :~ ~
.:, ::
.,"~
~5'~6~q~
[cH3-c-cH2-c ~ o-(cEl2)2-o-(cH2)2 N CH2 ~ ] Cl~
CH
[ ~ -0rCH2-cH2-~-cl2H25 ~ Br LC2 2 ~ Cl~H33 ~ 3r ~CH3)3N-Cl6H33 ¦
. ! ' , '' i ' ~ ~
L ~ ] Hr~ ~
. ' ~,',' ,: . , L , C}12-C}12-CH~ -(CH2)6-N-CH-CH -CH ~ 1 2 Cl~
; . .
.,~ ;
. ~ , ' .
.~,,~ . .
:"~
1 3 0 : :
.'-~ , ; - 1 2 ,; ~ - .
., ~ .
., .
. j . . i ~
.. :~ , .. . . . .. . ` . .... : . " - .. , .. . :
11~5765~
with sulfoxides of the formula:
` CnH2n ~ 1 -I-cl~I C 2 O R
wherein n = 8 to 14 and R = -CH3, -C2H5 and CH2Cl :;~
Preferably the following compounds o formula I are added:
CnH2n + 1 ~ S - C~2 CH2 n = 6 - 8 CnH2n ~ S - C~H CH2 n = 8 - 14 O R R = -CH3, -C2H5, `. 10 -OEI2Cl "
CnH2n + 1 -~S~- CIH CH2 n = 8 - 14 ;i O O R R = -CH3cl C2 5, . j ; .
.' The germicidal activity of the germicidal agents of the :~ invention is provided by determining the minimum inhibition .
:~ concentration (MIC) in accordance with the procedure :~ described for example in "Richtlinien zur Prufung chemischer Desinfektionsmittel - Gustav Fischer Verlag, Stuttgart ~'~ ;. .. .
~3 ~L959)" or in accordance with the inhibition test with -:
2 : graded growth of microorganisms.
` ~ ' ' ;' : ~ .
'1~ : . ;': '' ;.3 : ~
~l 30 : ~-.`. ! ~ 13 -: ',', :
The following Examples illustrate the invention, without ; limiting the invention.
::
The Examples 1 to 6 illustrate the addition of quaternary ammonium and sulfonium salts.
~.', ,; ;~
For carrying out the Exarnples 1 to 4, the agents in`
accordance with the invention are employed in pure form, ;
i.e. without carriers or diluents. The procedure employed !, follows precisely the aforesaid method of testing chemical disinfectant agents. The concentrations, which the agents of the invention are in general employed, correspond to those ~ of the quaternary ammonium compound, i.e. they are employed i in an amount of from 100 to 200 p.p.m., calculated on the 100% substance. `~
12H25 N - C~12 ~ C1 I ` 3 `
1 ` `` - , ~ : `
' B = Mixture of 28 parts CnH2n ~ ~ CH2 C~2 ' and o ¦ 35 parts of compound A ~;
'' ' 1 . :, :'1 ~ ' `. :
"~
... , .
.,, ~ . . . ~ :
".':-~, - ;
7~i5~
Test organism Growth inhibition:
Minimum inhibition concentxation tMIC) in ~ by weight of agent A B :~
. Proteus vulgaris 0,00025 0,0005 : Escherichia coli 0,0025 0,0050 Pseudomonas Fluorescens 0,0100 0,0250 Pseudomonas aeruginos 0,0125 0,0250 Staphylococcus aureus 0,0005 0,00025 ~., Bacillus subtilis 0,0005 0,00025 Aspexgillus niger 0,005 0,0025 Trichoderma sp. 0,0006 0,0005 Saccharomyces vini 0,001 0,001 Candida albicans 0,0025 0,0025 :
Trichophyton mentagrophytes 0,001 0,0005 Trichophyton rubrum 0,0025 0,0005 ; Microsporum gypseum 0,0005 0,00025 Microsporum canis 0,00025 0,0001 :~ :
: Oidium sp. 0,001 0,00025 .
Epidermophyton :~.l.occosum 0,001 0,00025 Saccaromyces cerevisiae 0,001 0,0005 :~ Example 2 3 ;~ ~ .
12 25 f 2 B = Mixture of ;
25 parts C12H25 - ~S CH2 2 :'' . ' ~
and .
35 parts of compound A ~:
., I , ~
~.~ 30 ~ ~
:'' ". .,~
:`, - 15 - :
:: :
7fi~4 Test organism Growth inhibition:
Minimum inhibi.tion concentration (MIC) in ~ by weight of agent A B
Escherichia coli 0,0125 0,0125 ~ .
Staphylococcus aureus 0,0010 0,0010 Proteus vulgaris 0,00125. 0,00125 Microsporum canis 0,001 0,00050 ~. :
Aspergillus niger 0,0025 0,00125 :
Saccharomyces cerevisiae 0,0010 0,0005 ~ ::
.pidermophyton floccosum 0,0010 0,00050 ~:
A - Cn~2n + 1 1 CH2 ~ ] n = 12 - 14 B = Mixture of -P n 2n ~ 1 S - CH2 - CH2 - OH n = 10 - 14 O
;~
n 2n + 1 / \ CH2 ~ CH2 - OH n = 10 - 14 O O "
and 35 parts of compound A
~ Test organism Growth inhibition:
:.' Minimum inhibition conce~tration ' (MIC) in % by weight of agent ; ~`
A B :
Staphylococcus aureus 0,0005 0,00025 Escherichia COlI ` O, 0025 0,0050 , Aspergillus niger 0,005 0,0025 'J ~richodérma `sp. 0,0005 0,00025 "; Trichophyton mentagrophytes 0,001 0,0005 `.
.~ Trichophyton rubrum 0,0025 0,00125 Oidium sp. 0,001 0,0005 ~-~`', Epidermophyton floccosum 0,001 0,00025 .~ ~
:1~ 30 :
~'.
. - 16 -:
`~' , S7~j5~
Example 4 CH
A C12H25 1 2 ~ Cl~
B = Mixture of . . ~:
20 parts CnH2n ~ S CH2 2 n = ll - 14 :
O
8 parts C6Hl3 - S CH2 C 2 and 35 parts of compound A
Test organism Growth inhibition ~
Minimum inhibition eoncentration ~ :
(MIC) in ~ weight of a~ent A B -Staphylococcus aureus 0,0005 0,00025 :
Baeillus subtilis 0,0005 0,00025 Aspergillus niger 0,005 0,0025 Trichoderma mentagrophytes 0,001 0,0005 :-Trichophyton rubrum 0.0025 0,0005 ~ :
Microsporum gypseum 0,OOOS 0,0001 Microsporum canis 0,00025 0,0001 `
Saccharomyees eerevisiae 0,001 0,0005 .:
.; ~ ~ . :
, - - ~
1`~57~jS~
~: `
The surpris~ng synergistic activlt~ of the germicidal ~ :
agents of the invention are shown by these examples.
,'-~ "'' ','' The following Examples S and 6 illustrate the addition of the combination of cleanin~ and disinfectant agents in accordance with the invention. ::
Example.5 :;
Powder from cleaning and disinfectant agent for the oodstuff industry Active agent mixture according to Example 1 B S parts ` ~ :
Anti foaming agent 2 parts Stearyl alcohol-Polyglycol ether 1 part Tripolyphosphate 36 parts ;
Sodium carbonate 40 parts Sodium meta-silicate (nonahydrate~ 16 parts Example 6 ~:, Liquid disinfectant agent for the foodstuff industry Aative ayent mixture of Example 3 B 8 parts :~
NTA (Nitrilo triacetic acid Na salt) 2 parts Potassium hydroxide 50~ 4 parts water 86 parts The following Examples 7 to 13 illustrate the addition of :~
further known germicidally active substances .: , ' ' , ~ ~ ~:' ~ ~ - 18 ~
- ' ' . ' ~ .
, : ; :
EXa~ple 7 ActiYe agent Amount of active agent in the nutrient solution in parts of active agent per million parts of solution 100 7S 50 25 10 5 1 .
pentachloro phenol O O O 1 2 3 5 mixture of A) 50 parts pentachloro phenol :~
and B) 50 parts CnH2n ~ CH2CH2H 2 3 ~ : O '~
n = 11 to 14 .: .
'' Example 8 Active agent ~mount of active agent in the nutrient solution in parts o - .
active agent per milli.on parts of solution Mixture of A)50 parts pentachlorphenol, ` :`
10 parts glutaraldehyde and . ;
B)40 parts CnH2n -~ 1 S CH2CH2H o 3 2 Q ~
n= 11 to 14 .
In the Table .
:,. ... ..
O = no fungus growth . i~
graded to 5 = uninhibited growth - `;~
.. . ~ . .
" ~ ' - 19 ~ ~`":
.: ' ~5~
E~ample 9 A = [CI2 H25 - P~ - CH3 ] Cl~ ~
. ; .
The amine imides which may be employed may be of the formula~
` . 1 ' ~ R - CO ~ ~ N ~ - R2 ,, \ .
.
.
wherein, preferably, R is a straight or branched long chain alkyl radical having 10 to 18, particularly '~ 12 to 14, carbon atoms and Rl, R2 and R3 are lower alkyl or oxalkyl radicals with 1 to 4 carbon atoms, particularly methyl or methoxy radicals.
:-~
:~
The polyvinylpyrrolidone - I2 ~ complexes which ~
~1 may be incorporated in accordànce with the invention -.,~
! are similarly known as germicides.
~ , ~ ... .. .
;~ Preferably, the compounds of formula I which are added . : ::
in accordance with the invention are those in which Rl ~
: , ~., ,- .
~ is an alkyl radical having 8 to 14 carbon atoms. R~ is ~ .
.. , .; . , ~ .
~~ - 7 ~`
. ' . .
l~S ~s554 ., preferably an alkyl radical having 1 to 7 carbon atoms and in the case of an aralkyl radical is preferably a phenyl alkyl or benzyl radical. Preferably n signifies a whole number from 1 to 6.
, . . . .
:, :
In the germicidal agents in accordance with the invention, any desired ratio of the quaternary ammonium salts, . .
sulfonium salts, phosphonium salts, phenols, phenol esters, amphotensides, aldehydes, polyvinylpyrrolidone~
.`'! I~ - complexes, amine oxides and/or amine imides to .`! ;:;
the compounds of the general formula I can be maintained.
Preferably however the weight ratio of the said compounds to the compounds of the genera~ formula I varies between 95:5 and 5:95, and most preferably stoichiometric ratios are maintained. With regard to the disinfectant activity, the cross-linking activity,as well as the detergent activity, the respective ratios can be determined. This ~ .
i determination may be made by simple preliminary experments.
The germicidal agents in accordanoe with the invention may, dependent on its use, be employed as such or in mixture with an inert carrier or diluent and/or in combination , ::' :,:.
i with other structuring, washing, cleaning and water :', '; ' ~ .':`.' ~ ~ ~ softening agents.
~.-1 : . . , ~., .
~ ~ - 8 -; ~ . ' . . ;~
.. :; -, . . .
5~54 Examples of inert carriers or diluents are the ~ollowing:
' , ;:.:
propellants, such as carbon dioxide, fluorine carbohydrates, fluortne-chlorine carkohydrates, ethanol, isopropanol, dimethylsulfoxide, water, talcum, silica gel, carbohydrates, such as lower paraffins, and salts, such as sodium sulfate.
Preferably, the agents of the invention are employed in the form of f]uids, solutions, emulsions, suspenslons, sprays, powders, salts etc.
,.;,.
Examples of additional components of a combined cleaning and i disinfectant agent are silicates, such as sodium meta-silicate carbonates, such as sodium carbonate, as well as polymeric phosphates, such as ~etra-sodium triphosphate.
The germicidal agents of the invention are of particular importance in the clinical area.
j ..
.. . ..
' With the addltion of compounds of formula I to higher `i1 chlorinated phenols, such as for example pentachloro ! phenol, which until now it has only been possible to keep and use in alkaline solution, whilst it precipitates out in aqueous acid medium, the advantage is obtàined , :
in a surprising manner~that such chlorinated phenols can also be added to aqueous acid medi~s~
''',~ ' ~' :'`
., . ` .
~ ~ .
. q . .
: ~ _ 9 _ :.:
.. . .
- . - . ... .. . ... . ~ , ......
1~5~ 4 A further advantage of the germici.dal agents of the invention consists in that on the one hand the biological decomposition of the compounds of formula I is practically complete, whereas in addition the synergistic increase in activity requires less active agent to be employed, whereby the pollution effect remains the same or is even significantly reduced.
Mixtures of quats with compounds of formula I with .
particularly significant synergism are for example ' stoichiometric mixtures of the fol].owing qua.ternary ammonium and sulfonium salts:
: .
J
'' : , "~, . ' ,', . "~ ' ` '~ '`
' ' '`," ;.:
'"I ' . , .
., , ,',, ,,' ~, ~ 10. r , ,,~
: ' , ' ' - ~
'~ ' : , ' '~, ' .
,'; ' . ' `" `' ' ' ; '' "-', ~ ' ''~
'`'~''.`: ` '' ' . ' . ' '. .' .'. . . .. '''.. . ~ ``' ' ~ '' s~;s~ : ~
[~12 25 IS CH2~CH2~OH~ CH3-o-so a [ n 2n + 1 -N-CE~2 ~ ~ Cle ~ .
[ CH2-CH2O~3 ~ Cle CH2-cM2oH
¦C12H25-NI C 2 ~~ ] Cl L 1 3 3 1 -~ -O- (CE~2) 2-- (CH2) 2 ~l -CH2--~ ~ Cl . CH3 H3C` CH3 :
~',", ~
,'1' [e=~N~)-C16E~33~1,C1;3 `.`~'~
....
'`"1 `~
,'~', ' ' ~
.~ ~ .
~.
', .:
! . , ~
':~ .~ . ' .
``'`1' ~: ~-:' , - -il ` , ,, :~ . `:' "''~ `'' '`
. .~, '' ' ~'~;
.-i 30 :~ ~
.:, ::
.,"~
~5'~6~q~
[cH3-c-cH2-c ~ o-(cEl2)2-o-(cH2)2 N CH2 ~ ] Cl~
CH
[ ~ -0rCH2-cH2-~-cl2H25 ~ Br LC2 2 ~ Cl~H33 ~ 3r ~CH3)3N-Cl6H33 ¦
. ! ' , '' i ' ~ ~
L ~ ] Hr~ ~
. ' ~,',' ,: . , L , C}12-C}12-CH~ -(CH2)6-N-CH-CH -CH ~ 1 2 Cl~
; . .
.,~ ;
. ~ , ' .
.~,,~ . .
:"~
1 3 0 : :
.'-~ , ; - 1 2 ,; ~ - .
., ~ .
., .
. j . . i ~
.. :~ , .. . . . .. . ` . .... : . " - .. , .. . :
11~5765~
with sulfoxides of the formula:
` CnH2n ~ 1 -I-cl~I C 2 O R
wherein n = 8 to 14 and R = -CH3, -C2H5 and CH2Cl :;~
Preferably the following compounds o formula I are added:
CnH2n + 1 ~ S - C~2 CH2 n = 6 - 8 CnH2n ~ S - C~H CH2 n = 8 - 14 O R R = -CH3, -C2H5, `. 10 -OEI2Cl "
CnH2n + 1 -~S~- CIH CH2 n = 8 - 14 ;i O O R R = -CH3cl C2 5, . j ; .
.' The germicidal activity of the germicidal agents of the :~ invention is provided by determining the minimum inhibition .
:~ concentration (MIC) in accordance with the procedure :~ described for example in "Richtlinien zur Prufung chemischer Desinfektionsmittel - Gustav Fischer Verlag, Stuttgart ~'~ ;. .. .
~3 ~L959)" or in accordance with the inhibition test with -:
2 : graded growth of microorganisms.
` ~ ' ' ;' : ~ .
'1~ : . ;': '' ;.3 : ~
~l 30 : ~-.`. ! ~ 13 -: ',', :
The following Examples illustrate the invention, without ; limiting the invention.
::
The Examples 1 to 6 illustrate the addition of quaternary ammonium and sulfonium salts.
~.', ,; ;~
For carrying out the Exarnples 1 to 4, the agents in`
accordance with the invention are employed in pure form, ;
i.e. without carriers or diluents. The procedure employed !, follows precisely the aforesaid method of testing chemical disinfectant agents. The concentrations, which the agents of the invention are in general employed, correspond to those ~ of the quaternary ammonium compound, i.e. they are employed i in an amount of from 100 to 200 p.p.m., calculated on the 100% substance. `~
12H25 N - C~12 ~ C1 I ` 3 `
1 ` `` - , ~ : `
' B = Mixture of 28 parts CnH2n ~ ~ CH2 C~2 ' and o ¦ 35 parts of compound A ~;
'' ' 1 . :, :'1 ~ ' `. :
"~
... , .
.,, ~ . . . ~ :
".':-~, - ;
7~i5~
Test organism Growth inhibition:
Minimum inhibition concentxation tMIC) in ~ by weight of agent A B :~
. Proteus vulgaris 0,00025 0,0005 : Escherichia coli 0,0025 0,0050 Pseudomonas Fluorescens 0,0100 0,0250 Pseudomonas aeruginos 0,0125 0,0250 Staphylococcus aureus 0,0005 0,00025 ~., Bacillus subtilis 0,0005 0,00025 Aspexgillus niger 0,005 0,0025 Trichoderma sp. 0,0006 0,0005 Saccharomyces vini 0,001 0,001 Candida albicans 0,0025 0,0025 :
Trichophyton mentagrophytes 0,001 0,0005 Trichophyton rubrum 0,0025 0,0005 ; Microsporum gypseum 0,0005 0,00025 Microsporum canis 0,00025 0,0001 :~ :
: Oidium sp. 0,001 0,00025 .
Epidermophyton :~.l.occosum 0,001 0,00025 Saccaromyces cerevisiae 0,001 0,0005 :~ Example 2 3 ;~ ~ .
12 25 f 2 B = Mixture of ;
25 parts C12H25 - ~S CH2 2 :'' . ' ~
and .
35 parts of compound A ~:
., I , ~
~.~ 30 ~ ~
:'' ". .,~
:`, - 15 - :
:: :
7fi~4 Test organism Growth inhibition:
Minimum inhibi.tion concentration (MIC) in ~ by weight of agent A B
Escherichia coli 0,0125 0,0125 ~ .
Staphylococcus aureus 0,0010 0,0010 Proteus vulgaris 0,00125. 0,00125 Microsporum canis 0,001 0,00050 ~. :
Aspergillus niger 0,0025 0,00125 :
Saccharomyces cerevisiae 0,0010 0,0005 ~ ::
.pidermophyton floccosum 0,0010 0,00050 ~:
A - Cn~2n + 1 1 CH2 ~ ] n = 12 - 14 B = Mixture of -P n 2n ~ 1 S - CH2 - CH2 - OH n = 10 - 14 O
;~
n 2n + 1 / \ CH2 ~ CH2 - OH n = 10 - 14 O O "
and 35 parts of compound A
~ Test organism Growth inhibition:
:.' Minimum inhibition conce~tration ' (MIC) in % by weight of agent ; ~`
A B :
Staphylococcus aureus 0,0005 0,00025 Escherichia COlI ` O, 0025 0,0050 , Aspergillus niger 0,005 0,0025 'J ~richodérma `sp. 0,0005 0,00025 "; Trichophyton mentagrophytes 0,001 0,0005 `.
.~ Trichophyton rubrum 0,0025 0,00125 Oidium sp. 0,001 0,0005 ~-~`', Epidermophyton floccosum 0,001 0,00025 .~ ~
:1~ 30 :
~'.
. - 16 -:
`~' , S7~j5~
Example 4 CH
A C12H25 1 2 ~ Cl~
B = Mixture of . . ~:
20 parts CnH2n ~ S CH2 2 n = ll - 14 :
O
8 parts C6Hl3 - S CH2 C 2 and 35 parts of compound A
Test organism Growth inhibition ~
Minimum inhibition eoncentration ~ :
(MIC) in ~ weight of a~ent A B -Staphylococcus aureus 0,0005 0,00025 :
Baeillus subtilis 0,0005 0,00025 Aspergillus niger 0,005 0,0025 Trichoderma mentagrophytes 0,001 0,0005 :-Trichophyton rubrum 0.0025 0,0005 ~ :
Microsporum gypseum 0,OOOS 0,0001 Microsporum canis 0,00025 0,0001 `
Saccharomyees eerevisiae 0,001 0,0005 .:
.; ~ ~ . :
, - - ~
1`~57~jS~
~: `
The surpris~ng synergistic activlt~ of the germicidal ~ :
agents of the invention are shown by these examples.
,'-~ "'' ','' The following Examples S and 6 illustrate the addition of the combination of cleanin~ and disinfectant agents in accordance with the invention. ::
Example.5 :;
Powder from cleaning and disinfectant agent for the oodstuff industry Active agent mixture according to Example 1 B S parts ` ~ :
Anti foaming agent 2 parts Stearyl alcohol-Polyglycol ether 1 part Tripolyphosphate 36 parts ;
Sodium carbonate 40 parts Sodium meta-silicate (nonahydrate~ 16 parts Example 6 ~:, Liquid disinfectant agent for the foodstuff industry Aative ayent mixture of Example 3 B 8 parts :~
NTA (Nitrilo triacetic acid Na salt) 2 parts Potassium hydroxide 50~ 4 parts water 86 parts The following Examples 7 to 13 illustrate the addition of :~
further known germicidally active substances .: , ' ' , ~ ~ ~:' ~ ~ - 18 ~
- ' ' . ' ~ .
, : ; :
EXa~ple 7 ActiYe agent Amount of active agent in the nutrient solution in parts of active agent per million parts of solution 100 7S 50 25 10 5 1 .
pentachloro phenol O O O 1 2 3 5 mixture of A) 50 parts pentachloro phenol :~
and B) 50 parts CnH2n ~ CH2CH2H 2 3 ~ : O '~
n = 11 to 14 .: .
'' Example 8 Active agent ~mount of active agent in the nutrient solution in parts o - .
active agent per milli.on parts of solution Mixture of A)50 parts pentachlorphenol, ` :`
10 parts glutaraldehyde and . ;
B)40 parts CnH2n -~ 1 S CH2CH2H o 3 2 Q ~
n= 11 to 14 .
In the Table .
:,. ... ..
O = no fungus growth . i~
graded to 5 = uninhibited growth - `;~
.. . ~ . .
" ~ ' - 19 ~ ~`":
.: ' ~5~
E~ample 9 A = [CI2 H25 - P~ - CH3 ] Cl~ ~
3 :
B = Mixture of 50 parts CnH2n + 1 ~ I CH2C~2 n = C11-14 AlkYl O ~:
and .
50 parts of compound A : -Test Organism Growth inhibition: ~
Minimum inhibition concentration ~ :
(MIC) in ~ by weight of active agent A B
Aspergillus niger 0,005 0,0025 Candida albicans 0,0025 0,0025 ~ ~.
Microsporum canis 0,00025 0,0001 .
Epidermophyton floccosum 0,001 0,00025 Saccaromyces cerevisiae 0,001 0,0005 ~ .
. : ~
Example 10 H CH
A = C11 H23 CO N - CH2 CH2 CH2 ~ ~ CH2 ;~
.
, :
.;: , ' ~'" .
.
~ ' : - 20 - .
:~
. . , , ~ , ~.~35 ~
B = Mixture of 50 parts Cn H2n + 1 ~ S ~ CH2 CH2 n = 11 to 14 d ~ :
50 parts of cornpound A
~ ~ .
Test organism Growth inhibition: ~ :
Minimum inhibition concentra-, tion (MIC) in ~ by weight ~ . .
of active agent - :
A B
Trichoderma sp. 0,010 0,005 . .
Staphylococcus aureus 0,001 0,0025 Epidermophyton ~loccosum 0,005 0,001 ~ ~
Example ll ., A = Polyvinylpyyrolidone I2 ~ Complex B = Mixture of 50 parts C H2n + l - I - CH2 C 2 n = ll to 14 O : :
and 50 parts of compo.und A
Test organism Growth inhibition ~ ~
Minimum inhibition concentration ~ ~:
(MIC) in ~ by weight of active :
agent A B
Trichophyton rubrum O,OQl 0,0025 Microsporum gypseum 0,001 0,0005 ~
~ ~ .
:~
~;-- 21 - .
Example 12 / C~13 .
CH~ , and B = Mixture of 50 parts Cn H2n ~ l ~ SO CH2 CH2 n = ll to 14 ,~
and 50 parts of compound A
Test organism Minimum inhibition concentration ;~ :
(MIC) in ~g/ml A B
Aspergillus niger l00 l00 :~
Candida albicans l00 50 : Example 13 , ~
' " ,. H3 . ~:
A C13 H27 CO ~ N CE3 . : t~ournal of the A~lerican Oil Chemist t S Socie-~y, : 5~, 316-317 (1975)) . . ::
;
.
~ ! ~ 22 ~
.. . ... . . . . . . . ..
~5~54 : `
:
B = Mixture of 50 parts Cn H2n + 1 ~ SO C~l2 CH2 OH n = 11 to 14 ;~
and ~ ;
50 parts of compound A
Test organ.ism Minimum inhibition concentration (MIC) in ~g/ml A B ~:~
Candida albicans 100 50 Staphylococcus aureus 10 10 Saccharomyces cerevisiae10 10 :
~:,,.,; ., `.~
~ .
., ,.................................... ' ~ .
B = Mixture of 50 parts CnH2n + 1 ~ I CH2C~2 n = C11-14 AlkYl O ~:
and .
50 parts of compound A : -Test Organism Growth inhibition: ~
Minimum inhibition concentration ~ :
(MIC) in ~ by weight of active agent A B
Aspergillus niger 0,005 0,0025 Candida albicans 0,0025 0,0025 ~ ~.
Microsporum canis 0,00025 0,0001 .
Epidermophyton floccosum 0,001 0,00025 Saccaromyces cerevisiae 0,001 0,0005 ~ .
. : ~
Example 10 H CH
A = C11 H23 CO N - CH2 CH2 CH2 ~ ~ CH2 ;~
.
, :
.;: , ' ~'" .
.
~ ' : - 20 - .
:~
. . , , ~ , ~.~35 ~
B = Mixture of 50 parts Cn H2n + 1 ~ S ~ CH2 CH2 n = 11 to 14 d ~ :
50 parts of cornpound A
~ ~ .
Test organism Growth inhibition: ~ :
Minimum inhibition concentra-, tion (MIC) in ~ by weight ~ . .
of active agent - :
A B
Trichoderma sp. 0,010 0,005 . .
Staphylococcus aureus 0,001 0,0025 Epidermophyton ~loccosum 0,005 0,001 ~ ~
Example ll ., A = Polyvinylpyyrolidone I2 ~ Complex B = Mixture of 50 parts C H2n + l - I - CH2 C 2 n = ll to 14 O : :
and 50 parts of compo.und A
Test organism Growth inhibition ~ ~
Minimum inhibition concentration ~ ~:
(MIC) in ~ by weight of active :
agent A B
Trichophyton rubrum O,OQl 0,0025 Microsporum gypseum 0,001 0,0005 ~
~ ~ .
:~
~;-- 21 - .
Example 12 / C~13 .
CH~ , and B = Mixture of 50 parts Cn H2n ~ l ~ SO CH2 CH2 n = ll to 14 ,~
and 50 parts of compound A
Test organism Minimum inhibition concentration ;~ :
(MIC) in ~g/ml A B
Aspergillus niger l00 l00 :~
Candida albicans l00 50 : Example 13 , ~
' " ,. H3 . ~:
A C13 H27 CO ~ N CE3 . : t~ournal of the A~lerican Oil Chemist t S Socie-~y, : 5~, 316-317 (1975)) . . ::
;
.
~ ! ~ 22 ~
.. . ... . . . . . . . ..
~5~54 : `
:
B = Mixture of 50 parts Cn H2n + 1 ~ SO C~l2 CH2 OH n = 11 to 14 ;~
and ~ ;
50 parts of compound A
Test organ.ism Minimum inhibition concentration (MIC) in ~g/ml A B ~:~
Candida albicans 100 50 Staphylococcus aureus 10 10 Saccharomyces cerevisiae10 10 :
~:,,.,; ., `.~
~ .
., ,.................................... ' ~ .
Claims (20)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A germicidal agent comprising a germi-cidally active quaternary ammonium salt, sulfonium salt, phosphonium salt, phenol, phenol ester, amphotenside, aldehyde, polyvinyl pyrrolidone-I2-complex, amine oxide, or amine imide, to which has been added a compound of the general formula:
(I) in which n is 0, 1 or 2, R1 is alkyl of 6 to 18 carbon atoms, and R2 is alkyl of l to 18 carbon atoms, aralkyl, hydroxyalkyl having 2 to 4 carbon atoms, -(-CH2-CH2-0-)? or in which m is a whole number of from 1 to 12, and R3 is -CE3, -CH2C1 or C2H5
(I) in which n is 0, 1 or 2, R1 is alkyl of 6 to 18 carbon atoms, and R2 is alkyl of l to 18 carbon atoms, aralkyl, hydroxyalkyl having 2 to 4 carbon atoms, -(-CH2-CH2-0-)? or in which m is a whole number of from 1 to 12, and R3 is -CE3, -CH2C1 or C2H5
2. A germicidal agent according to Claim 1, in which R1 is alkyl of 8 to 14 carbon atoms.
3. A germicidal agent according to Claim 1 or Claim 2, in which R2 is alkyl of 1 to 7 carbon atoms.
4. A germicidal agent according to Claim 1, in which R2 is phenylethyl or benzyl.
5. A germicidal agent according to Claims 1 or 2, in which m is a whole number of from 1 to 6.
6. A germicidal agent according to Claim 1, in which the compound of formula I consists of CnH2n + 1 - S - CH2 - CH2OH (n = 6 - 8) CnH2n + 1 - ? - CH - ?H2OH (n = 8 - 14) R = -CH3, -C2H5, -CH2C1) or (n = 8 - 14 R = -CH3, -C2H5, -CH2C1).
7. A germicidal agent according to Claim 1, comprising a phosphonium salt of the formula:
[PR1R2R3R4] ? X ?
in which R1 to R4 signify a straight chained alkyl group having 10 to 16 carbon atoms, whilst one of R1 to R4 may be benzyl or lower alkyl of 1 to 4 carbon atoms, and X? is a cation.
[PR1R2R3R4] ? X ?
in which R1 to R4 signify a straight chained alkyl group having 10 to 16 carbon atoms, whilst one of R1 to R4 may be benzyl or lower alkyl of 1 to 4 carbon atoms, and X? is a cation.
8. A germicidal agent according to Claim 7, in which the phosphonium salt is dodecyl trimethyl phosphonium chloride or dodceyl dimethyl benzyl phosphonium chloride.
9. A germicidal agent according to Claim 1, in which the phenol is a chloro phenol, or an alkyl of 1 to 4 carbon atoms substituted phenol.
10. A germicidal agent according to Claim 1, in which the phenol ester is an ester of phenols in accordance with Claim 9 with a branched or straight chain carbonic acid having up ta 18 carbon atoms, or an ester of o-phenyl phenol.
11. A germicidal agent according to Claim 1, in which the amphotenside is a compound of the formula:
R4 - NH - (CH2)y COO?
R4 - NH (CH2)x NH~CH2~CooMe or R -NH-(CH2) ~NH-(CH2~x-NH CH2 C
wherein Rl is a long chain saturated or.unsaturated alkyl grou~, ~
' :
R2~and R3 are lower alkyl of 1 to 4 carbon atoms, : x is a whol~ number of from 1 to 3, y is a whole number of from 2 to 3, Y is -NH or 0, R4 is a saturated or unsaturated alkyl group having 8 to 18 carbon at-oms, and Me is an alkall metal~
R4 - NH - (CH2)y COO?
R4 - NH (CH2)x NH~CH2~CooMe or R -NH-(CH2) ~NH-(CH2~x-NH CH2 C
wherein Rl is a long chain saturated or.unsaturated alkyl grou~, ~
' :
R2~and R3 are lower alkyl of 1 to 4 carbon atoms, : x is a whol~ number of from 1 to 3, y is a whole number of from 2 to 3, Y is -NH or 0, R4 is a saturated or unsaturated alkyl group having 8 to 18 carbon at-oms, and Me is an alkall metal~
12. A germicldal agent accordlng to Claim 1, in~which the aldehyde is a staurated allphatic mono- or :~ :
.
` - ;! 7 -di-aldehyde having up to 10 carbon atoms,, or an aldehyde-releasing substance.
.
` - ;! 7 -di-aldehyde having up to 10 carbon atoms,, or an aldehyde-releasing substance.
13. A germicidal agent according to Claim 1, in which the amino oxide is of the formula:
in which R is a long straight or branched chain alkyl group having 10 to 18 carbon atoms, and R1 and R2 are lower alkyl or oxalkyl of 1 to 4 carbon atoms,
in which R is a long straight or branched chain alkyl group having 10 to 18 carbon atoms, and R1 and R2 are lower alkyl or oxalkyl of 1 to 4 carbon atoms,
14. A germicidal agent according to Claim 1, in which the amine amine is of the formula:
in which R is a long straight or branched chain alkyl group having 10 to 18 carbon atoms, and R1, R2 and R3 are lower alkyl or oxalkyl of 1 to 4 carbon atoms.
in which R is a long straight or branched chain alkyl group having 10 to 18 carbon atoms, and R1, R2 and R3 are lower alkyl or oxalkyl of 1 to 4 carbon atoms.
15. A germicidal agent according to Claim 1, in which the ratio by weight of the germicidally active agent to the compound of the formula I lies between 95 : 5 and 5 : 95.
16. A germicidal agent according to Claim 15, in which the germicidally active agent and the compound of formula I are present in stoichiometric amounts.
17. A germicidal agent according to Claim 1, which includes an inert carrier or diluent.
18. A germicidal agent according to Claim 17, in which the inert carrier or diluent consists of a propellant, an alcohol, dimethyl sulfoxide, water, talcum, silica gel, a carbohydrate or a salt.
19. A germicidal agent according to Claim 1, which is formulated in the form of a fluid, solution, emulsion, suspension, spray, powder or ointment.
20. A germicidal agent according to Claim 1, which additionally comprises one or more structure-forming, washing, cleaning and water-softening agents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752511830 DE2511830B2 (en) | 1975-03-18 | 1975-03-18 | Germicidal agent |
| DE19762609019 DE2609019A1 (en) | 1976-03-04 | 1976-03-04 | Potentiated germicidal compns - contg dialkyl sulphides, sulphoxides or sulphones as synergist |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1057654A true CA1057654A (en) | 1979-07-03 |
Family
ID=25768646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA248,062A Expired CA1057654A (en) | 1975-03-18 | 1976-03-17 | Germicidal agent |
Country Status (6)
| Country | Link |
|---|---|
| AT (1) | AT352295B (en) |
| CA (1) | CA1057654A (en) |
| CH (1) | CH609246A5 (en) |
| FR (1) | FR2304356A1 (en) |
| GB (1) | GB1525178A (en) |
| NL (1) | NL7602816A (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE496622A (en) * | ||||
| GB461614A (en) * | 1935-07-15 | 1937-02-15 | Ig Farbenindustrie Ag | Improvements in the treatment of textile and other fibrous materials |
| GB743984A (en) * | 1952-09-03 | 1956-01-25 | Monsanto Chemicals | Improvements relating to germicides |
| DE1074189B (en) * | 1955-01-26 | 1960-01-28 | Monsanto Chemicals Limited, London | Germicidal detergents and cleaning agents |
| US2787595A (en) * | 1955-07-11 | 1957-04-02 | Union Oil Co | Sulfoxide containing detergent compositions |
| US3064048A (en) * | 1958-07-10 | 1962-11-13 | Lever Brothers Ltd | Process for preparing 3, 4', 5-tribromosalicylanilide in the presence of a wetting agent |
| DE1145292B (en) * | 1961-10-21 | 1963-03-14 | Hoechst Ag | Disinfecting mild detergents |
| CA810625A (en) * | 1965-07-30 | 1969-04-15 | The Procter & Gamble Company | Antimicrobial detergent compositions |
| US3507796A (en) * | 1967-05-11 | 1970-04-21 | Procter & Gamble | Antibacterial compositions |
| DE1767683A1 (en) * | 1968-06-04 | 1971-09-30 | Henkel & Cie Gmbh | Detergents, washing auxiliaries and cleaning agents containing antimicrobial agents |
| LU60407A1 (en) * | 1970-02-25 | 1970-09-24 |
-
1976
- 1976-03-17 CA CA248,062A patent/CA1057654A/en not_active Expired
- 1976-03-17 AT AT199176A patent/AT352295B/en not_active IP Right Cessation
- 1976-03-17 FR FR7607629A patent/FR2304356A1/en not_active Withdrawn
- 1976-03-17 NL NL7602816A patent/NL7602816A/en not_active Application Discontinuation
- 1976-03-18 GB GB1099776A patent/GB1525178A/en not_active Expired
- 1976-03-18 CH CH342576A patent/CH609246A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| GB1525178A (en) | 1978-09-20 |
| AT352295B (en) | 1979-09-10 |
| CH609246A5 (en) | 1979-02-28 |
| ATA199176A (en) | 1979-02-15 |
| FR2304356A1 (en) | 1976-10-15 |
| NL7602816A (en) | 1976-09-21 |
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