JPH01233264A - Novel quaternary ammonium salt derived from halogenated glycerol and germicide containing said salt as active ingredient - Google Patents
Novel quaternary ammonium salt derived from halogenated glycerol and germicide containing said salt as active ingredientInfo
- Publication number
- JPH01233264A JPH01233264A JP6139888A JP6139888A JPH01233264A JP H01233264 A JPH01233264 A JP H01233264A JP 6139888 A JP6139888 A JP 6139888A JP 6139888 A JP6139888 A JP 6139888A JP H01233264 A JPH01233264 A JP H01233264A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- expressed
- quaternary ammonium
- glycerol
- ammonium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 title claims abstract description 13
- 239000004480 active ingredient Substances 0.000 title claims description 4
- 150000002314 glycerols Chemical class 0.000 title abstract description 7
- 230000002070 germicidal effect Effects 0.000 title abstract 2
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 239000003899 bactericide agent Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 13
- 150000003512 tertiary amines Chemical class 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 244000144972 livestock Species 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000000249 desinfective effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- WQHOLQNBJWMURG-UHFFFAOYSA-L decyl-[3-[decyl(dimethyl)azaniumyl]-2-hydroxypropyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCC[N+](C)(C)CC(O)C[N+](C)(C)CCCCCCCCCC WQHOLQNBJWMURG-UHFFFAOYSA-L 0.000 abstract 1
- 150000002367 halogens Chemical group 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 241000894006 Bacteria Species 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 12
- 239000002609 medium Substances 0.000 description 11
- 230000000844 anti-bacterial effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 235000017557 sodium bicarbonate Nutrition 0.000 description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 229920001817 Agar Polymers 0.000 description 5
- 239000008272 agar Substances 0.000 description 5
- 238000007405 data analysis Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- -1 methylammonium Didecylmethylamine Chemical compound 0.000 description 3
- 239000008213 purified water Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SIBFQOUHOCRXDL-UHFFFAOYSA-N 3-bromopropane-1,2-diol Chemical compound OCC(O)CBr SIBFQOUHOCRXDL-UHFFFAOYSA-N 0.000 description 2
- GLJRUXJFSCIQFV-UHFFFAOYSA-N 3-iodopropane-1,2-diol Chemical compound OCC(O)CI GLJRUXJFSCIQFV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000001888 Peptone Substances 0.000 description 2
- 108010080698 Peptones Proteins 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YWWNNLPSZSEZNZ-UHFFFAOYSA-N n,n-dimethyldecan-1-amine Chemical compound CCCCCCCCCCN(C)C YWWNNLPSZSEZNZ-UHFFFAOYSA-N 0.000 description 2
- ATBNMWWDBWBAHM-UHFFFAOYSA-N n-decyl-n-methyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCCCC ATBNMWWDBWBAHM-UHFFFAOYSA-N 0.000 description 2
- 235000019319 peptone Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000006150 trypticase soy agar Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- RUPBZQFQVRMKDG-UHFFFAOYSA-M Didecyldimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCC[N+](C)(C)CCCCCCCCCC RUPBZQFQVRMKDG-UHFFFAOYSA-M 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- ZJBLBMWIJVBKMA-UHFFFAOYSA-N N,N-dimethyldecan-1-amine Chemical compound C(CCCCCCCCC)N(C)C.C(CCCCCCCCC)N(C)C ZJBLBMWIJVBKMA-UHFFFAOYSA-N 0.000 description 1
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 229960004670 didecyldimethylammonium chloride Drugs 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- MEKULSCNDYBJBL-UHFFFAOYSA-N n-decyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCC MEKULSCNDYBJBL-UHFFFAOYSA-N 0.000 description 1
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 1
- CQFRPHDWUIZNOK-UHFFFAOYSA-N n-methyl-n-octyldecan-1-amine Chemical compound CCCCCCCCCCN(C)CCCCCCCC CQFRPHDWUIZNOK-UHFFFAOYSA-N 0.000 description 1
- KUFYUMSBZMUWAN-UHFFFAOYSA-N n-methyl-n-tetradecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCC KUFYUMSBZMUWAN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
［技術分野］
本発明は、ハロゲン化グリセリンから誘導されるモノア
ンモニウム塩型又はジアンモニウム塩型の新規第四級ア
ンモニウム塩とそれを有効成分とする殺菌剤に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel monoammonium salt type or diammonium salt type quaternary ammonium salt derived from halogenated glycerin, and a disinfectant containing the same as an active ingredient.
［従来技術］
従来、第四級アンモニウム塩はカチオン性界面活性剤と
して多くの目的に使用されており。[Prior Art] Conventionally, quaternary ammonium salts have been used as cationic surfactants for many purposes.
或種のものには強い抗菌性があることが知られている。Some species are known to have strong antibacterial properties.
それらの抗菌力は、Ｒ置換基の疎水性とアンモニウムカ
チオンの親水性とのバランスにより支配されると考えら
れており、より強い殺菌力を求めて多数の化合物が合成
されて来た。Their antibacterial activity is thought to be controlled by the balance between the hydrophobicity of the R substituent and the hydrophilicity of the ammonium cation, and a large number of compounds have been synthesized in search of stronger bactericidal activity.
それらのうち、ジアルキル型第四級アンモニウム塩は最
も殺菌力の強いものの１つであり、そのアルキル炭素鎖
長が８〜１０の場合が最適であると言われている（Ｂｒ
ｉｔ、 Ｐａｔｅｎｔ １，２２１，２２４、ＵＳ Ｐ
ａｔｅｎｔ ４，４４４，７９０）。例えば、下記の
塩化ジデシルジメチルアンモニウムは殺菌
本発明者等は、ハロゲン化グリセリンを原料として、さ
らに遊離の水酸基を含む新規なモノおよびジアンモニウ
ム塩を合成し、前者では炭素数８〜１２、後者では炭素
数１０〜１２の化合物が上側に匹敵する強い殺菌力を示
すことをみいだした。Among them, dialkyl type quaternary ammonium salts are one of the most antibacterial, and it is said that the optimal case is when the alkyl carbon chain length is 8 to 10 (Br
it, Patent 1,221,224, USP
4,444,790). For example, the following didecyldimethylammonium chloride is a sterilizing agent.The present inventors used halogenated glycerin as a raw material to synthesize new mono- and diammonium salts containing free hydroxyl groups. It was discovered that compounds with 10 to 12 carbon atoms exhibited strong bactericidal activity comparable to the above.
［目 的］
本発明の目的は、新規かつ有用な第四級アンモニウム塩
およびそれを主成分とする殺菌剤を提供する点にある。[Objective] An object of the present invention is to provide a novel and useful quaternary ammonium salt and a fungicide containing the same as a main component.
［構 成］ 本発明は、下記の一般式 で示されるモノアンモニウム塩型（式中、Ｒｏ。[composition] The present invention is based on the following general formula A monoammonium salt type represented by (wherein, Ro.
Ｒ２は炭素数８〜１８、好ましくは８〜１２のアルキル
基、Ｘはハロゲンを示す。）および下記の一般式
（式中、Ｒ１は炭素数８〜１８、好ましくは１０〜１２
のアルキル基、Ｘはハロゲンを示す。）で示されるジア
ンモニウム塩型よりなる群から選らばれた新規第四級ア
ンモニウム塩およびそれを有効成分とする殺菌剤に関す
る。R2 represents an alkyl group having 8 to 18 carbon atoms, preferably 8 to 12 carbon atoms, and X represents a halogen. ) and the following general formula (wherein R1 has 8 to 18 carbon atoms, preferably 10 to 12 carbon atoms)
an alkyl group, X represents a halogen. The present invention relates to a novel quaternary ammonium salt selected from the group consisting of the diammonium salt types shown in ) and a disinfectant containing the same as an active ingredient.
前記、アニオンとしては、ハロゲンとくにＣＱ。The anion mentioned above is halogen, especially CQ.
Ｂｒが好ましい。Br is preferred.
式ＣＩ）で示される第４級アンモニウム塩は例えば、第
３級アミンとモノハロゲン化グリセリンである３−ハロ
ー１，２−プロパンジオールとを反応させることにより
得ることができる。反応式％式％
また、式（ｎ）で示される第４級アンモニウム塩は例え
ば、第３級アミンとジハロゲン化グリセリンである１、
３−ジハロ−２−プロパツールとを反応させることによ
り得ることができる。反応式は次の如くである。The quaternary ammonium salt represented by formula CI) can be obtained, for example, by reacting a tertiary amine with 3-halo-1,2-propanediol, which is monohalogenated glycerin. Reaction formula % formula % In addition, the quaternary ammonium salt represented by formula (n) is, for example, tertiary amine and dihalogenated glycerin 1,
It can be obtained by reacting with 3-dihalo-2-propatol. The reaction formula is as follows.
ＣＨ。CH.
／
本発明において使用されるハロゲン化合物として式（Ｉ
ｌｌ）においては、３−クロロ−１，２−プロパンジオ
ール、３−ブロモ−１，２−プロパンジオール。/ The halogen compound used in the present invention has the formula (I
In ll), 3-chloro-1,2-propanediol, 3-bromo-1,2-propanediol.
３−ヨード−１，２−プロパンジオール、式（ｒＶ）に
おいては、１，３−ジクロロ−２−プロパツール、 １
．３−ジブロモ−２−プロパツール、１，３−ショート
−２−プロパツールがあるが、価格１反応性、生成物の
有用性などの点から、式（Ｉ［Ｉ）においては、３−ク
ロロ−１，２−プロパンジオール及び式（ＩＶ）におい
いては５１，３−ジクロロ−２−プロパツールが好まし
い。また第３級アミンは炭素数８〜１８の直鎖アルキル
基１個または２個有するアミンで、たとえば式（ＩＩＩ
）においては、ジオクチルメチルアミン、オクチルデシ
ルメチルアミン、ジデシルメチルアミン、デシルドデシ
ルメチルアミン、ジドデシルメチルアミン等のジアルキ
ルメチルアミン及び式（ＩＶ）においては、オクチルジ
メチルアミン、デシルジメチルアミン、ドデシルジメチ
ルアミン等のアルキルジメチルアミンが挙げられる。3-iodo-1,2-propanediol, in formula (rV), 1,3-dichloro-2-propanedol, 1
．． There are 3-dibromo-2-propatol and 1,3-short-2-propatol, but from the viewpoint of price, reactivity, and usefulness of the product, in formula (I[I), 3-chloro In -1,2-propanediol and formula (IV), 51,3-dichloro-2-propatol is preferred. Further, the tertiary amine is an amine having one or two straight chain alkyl groups having 8 to 18 carbon atoms, for example, the formula (III
), dialkylmethylamines such as dioctylmethylamine, octyldecylmethylamine, didecylmethylamine, decyldodecylmethylamine, didodecylmethylamine; and in formula (IV), octyldimethylamine, decyldimethylamine, dodecyldimethyl Examples include alkyldimethylamines such as amines.
このような第３級アミンとハロゲン化合物を反応させて
第４級アンモニウム塩を得るのであ、るが、触媒として
重炭酸ナトリウムを原料アミンの５重量％を用い、反応
溶媒としてイソプロパツールを反応原料の５０〜１００
重量％程度用いる。また、反応温度は１４０〜１５０℃
で行なうのが良く、反応時間は一般に約１０〜４０時間
で、好適には２４時間程度で十分である。反応終了後シ
リカゲルカラムを用いてヘキサン−酢酸エチル系および
クロロホルム−メタノール系溶出溶媒で分離精製し、凍
結乾燥すると第４級アンモニウム塩の白色結晶を得る。A quaternary ammonium salt is obtained by reacting such a tertiary amine with a halogen compound. In this case, sodium bicarbonate is used as a catalyst in an amount of 5% by weight of the raw amine, and isopropanol is used as a reaction solvent. 50-100 of raw materials
Approximately % by weight is used. In addition, the reaction temperature is 140-150℃
The reaction time is generally about 10 to 40 hours, preferably about 24 hours. After the reaction is completed, the product is separated and purified using a silica gel column with hexane-ethyl acetate and chloroform-methanol elution solvents, and freeze-dried to obtain white crystals of the quaternary ammonium salt.
本発明化合物は、水酸基を含有するためか水溶性が高く
、使用に便利である。The compounds of the present invention have high water solubility, possibly because they contain hydroxyl groups, and are convenient to use.
本発明の殺菌剤は食器洗用、家畜台の消毒用などとして
有用である。The disinfectant of the present invention is useful for washing dishes, disinfecting livestock stands, etc.
得られた化合物の分子式および収率を第１表、第２表に
示す。The molecular formula and yield of the obtained compound are shown in Tables 1 and 2.
第１表モノアンモニウム塩（１）の収率等第２表ジアン
モニウム塩（ＩＩ）の収率等これらの化合物は水に溶性
で１石油エーテル系以外の有機溶媒にも可溶性であり、
その強い吸湿性のために正しい融点の測定は困難である
。Table 1: Yield of monoammonium salt (1) Table 2: Yield of diammonium salt (II) These compounds are soluble in water and 1. Soluble in organic solvents other than petroleum ether.
Due to its strong hygroscopicity, determining the correct melting point is difficult.
それらの構造は、第３表および第４表に示した”Ｈ−Ｎ
ＭＲデータおよび元素分析により確認した。Their structures are shown in Tables 3 and 4.
Confirmed by MR data and elemental analysis.
（以下余白）
本発明化合物の殺菌力はつぎのようにして測 □定した
。(The following is a blank space) The bactericidal activity of the compound of the present invention was measured as follows.
試験方法
１、被験菌
被験菌としては家畜感染症の起因菌あるいは環境衛生上
問題となる菌種からダラム陰性菌３種、ダラム陽性菌１
種を選択し、第５表に示した６菌株を供試した。Test method 1, test bacteria The test bacteria include 3 types of Durham-negative bacteria and 1 Durham-positive bacteria from bacteria that cause livestock infectious diseases or bacterial species that pose environmental hygiene problems.
Species were selected and six strains shown in Table 5 were tested.
第５表被験菌
ｌ）社団法人孔型研究所
２）農林水産省動物医薬品検査所
３）東京大学応用微生物研究所
２、操作
殺菌力試験は厚生省線さん消毒薬検査指針の石炭酸係数
試験法に準じて行なった。即ち、試料液（注１）５ｍｌ
を滅菌試験管に取り、２０℃に保った。これに被験菌の
培養液（注２）０．５ｍｌを接種し、試料薬剤と作用さ
せた。１０分間作用させた後、この液５μｍを後培養培
地（普通ブイヨン培地）５ｍｌに加え、これを３７℃で
２日間培養後、肉眼で観察を行なって培地が混濁してい
るものは菌の生存、澄明なものは死滅と判定した。Table 5 Test Bacteria l) Mold Research Institute 2) Ministry of Agriculture, Forestry and Fisheries Animal Drug Inspection Center 3) Applied Microbiology Research Institute, University of Tokyo 2, Operation Bactericidal power test is based on the carbolic acid coefficient test method of the Ministry of Health and Welfare's Line-san Disinfectant Testing Guidelines I followed the instructions. That is, 5 ml of sample solution (Note 1)
was placed in a sterile test tube and kept at 20°C. This was inoculated with 0.5 ml of culture solution (Note 2) of the test bacteria, and allowed to interact with the sample drug. After allowing it to act for 10 minutes, add 5 μm of this solution to 5 ml of the post-culture medium (ordinary bouillon medium) and culture it at 37°C for 2 days. Observe with the naked eye. If the medium is cloudy, it indicates the survival of bacteria. , clear ones were determined to be dead.
菌が死滅した試料液のうち、最も低い濃度をその物質の
最小殺菌濃度とした。Among the sample liquids in which bacteria were killed, the lowest concentration was taken as the minimum bactericidal concentration of that substance.
注１）試料液の調整
試料は乾燥後精密に秤量し、１０００μｇ／ｍｌ水溶液
を調整した。これを孔径０．２μｍのメンブランフィル
タ−で濾過滅菌した後に滅菌精製水で８００．４００，
２００．１００．５０．２５．１３．６．３．３．１．
１．６および０．８ μｇ／ｍｌの濃度に希釈して使用
した。Note 1) Preparation of sample solution The sample was accurately weighed after drying, and a 1000 μg/ml aqueous solution was prepared. After filtering and sterilizing this with a membrane filter with a pore size of 0.2 μm,
200.100.50.25.13.6.3.3.1.
It was used after being diluted to concentrations of 1.6 and 0.8 μg/ml.
注２）被験菌の培養液の調整
被験菌は各々１〜３か月ごとに継代し、４℃で保存して
いる斜面培地からチフス菌はハートインフュージョン寒
天培地、他の菌株はトリプチケースソイ寒天培地の斜面
に接種し、３７℃で２４時間培養した。Note 2) Preparation of culture solution for test bacteria Each test bacteria was subcultured every 1 to 3 months, and cultured on slant culture medium stored at 4°C. It was inoculated onto a slant of Case Soy agar medium and cultured at 37°C for 24 hours.
斜面に生育した菌１白金耳を取り、普通ブイヨン培地１
０ｍ１を分注した試験管に接種して３７℃で２４時間培
養した。この培養液１白金耳を取り、同培地に接種し、
３７℃で２４時間培養した後、２０℃に保って試験に用
いた。Take 1 platinum loop of bacteria grown on the slope and add 1 piece of ordinary bouillon medium.
0ml was inoculated into test tubes and cultured at 37°C for 24 hours. Take a loopful of this culture solution and inoculate it into the same medium,
After culturing at 37°C for 24 hours, the cells were kept at 20°C and used in the test.
注３）使用培地
普通ブイヨン培地
肉エキス ３ｇ
ペプトン Ｌｏｇ
塩化ナトリウム ５ｇ
精製水 １０００耐（ｐＨ７，０）ハートイ
ンフュージョン寒天培地
ウシ心臓浸出液 ５００ｇ
ペプトン ｔｏｇ
塩化ナトリウム ５ｇ
寒天 １５ｇ
精製水 １０００ｍ１００Ｏ７，４）ト
リプチケースソイ寒天培地
Ｐａｎｃｒｅａｔｉｃ Ｄｉｇｅｓｔ ｏｆ Ｃａ５ｅ
ｉｎ １５ｇＰａｐａｉｃ Ｄｉｇｅｓｔ ｏｆ ５
ｏｙｂｅａｎ Ｍｅａｌ ５ｇ塩化ナトリウム
５ｇ
寒天 １５ｇ
精製水 １０００ｍｌ（１００Ｏ，：Ｉ
ｔ）試験には普通ブイヨンおよびハートインフュージョ
ン寒天培地は栄研製を、トリプチケースソイ寒天培地は
Ｂｅｃｔｏｎ Ｄｉｃｋｉｎｓｏｎ ａｎｄ Ｃｏ、製
を用い、常法通り調製して使用した。Note 3) Medium used Regular bouillon medium Meat extract 3g Peptone Log Sodium chloride 5g Purified water 1000 resistant (pH 7,0) heart infusion agar medium Bovine heart infusion 500g Peptone tog Sodium chloride 5g Agar 15g Purified water 1000ml 100O7,4) Trypticase Soy agar medium Pancreatic Digest of Ca5e
in 15gPapaic Digest of 5
oybean Meal 5g Sodium Chloride
5g agar 15g purified water 1000ml (100O,:I
t) For the test, ordinary broth and heart infusion agar medium were manufactured by Eiken, and trypticase soy agar medium was manufactured by Becton Dickinson and Co. They were prepared and used in a conventional manner.
試験結果 試験の結果は第６，７表に示した。Test results The test results are shown in Tables 6 and 7.
七ノアンモニウム塩（［）ではアルキル鎖長が８〜１２
（化合物番号１〜５）の化合物、ジアンモニウム塩では
アルキル鎖長が１０〜１８（化合物番号２〜６）の化合
物に殺菌性がみられた。In heptanoammonium salt ([), the alkyl chain length is 8 to 12
Among the compounds (compound numbers 1 to 5) and diammonium salts, bactericidal properties were observed in compounds with alkyl chain lengths of 10 to 18 (compound numbers 2 to 6).
特に前者の鎖長８〜１２（化合物番号２〜４）の化合物
および後者の鎖長が１０〜１２（化合物番号２．３）は
すぐれた殺菌力を示し、十分に実用に供し得ることが明
らかである。以下実施例をもって本発明を説明する。In particular, it is clear that the former compounds with a chain length of 8 to 12 (compound numbers 2 to 4) and the latter compounds with a chain length of 10 to 12 (compound number 2.3) exhibit excellent bactericidal activity and can be sufficiently put to practical use. It is. The present invention will be explained below with reference to Examples.
ジデシルメチルアミン４．６７ｇ（１５ｍｍｏｌ）、３
−クロロ−１，２−プロパンジオールＬ８２ｇ（１６，
５ｍｍｏｌ）をイソプロパツール６．５ｇに溶かした溶
液に重炭酸ナトリウム０．２３ｇを加え、１４０〜１５
０℃で２４時間加熱攪拌する。反応混合物をシリカゲル
カラムを用いて分離精製した後、凍結乾燥すると白色結
晶５．７４ｇ（収率９０．７％）が得られた。第３表に
示したＮＭＲデータおよび
元素分析の結果から式（Ｖ）の構造であることがわかる
。Didecylmethylamine 4.67g (15mmol), 3
-Chloro-1,2-propanediol L82g (16,
Add 0.23 g of sodium bicarbonate to a solution of 5 mmol) dissolved in 6.5 g of isopropanol,
Heat and stir at 0°C for 24 hours. The reaction mixture was separated and purified using a silica gel column, and then freeze-dried to obtain 5.74 g of white crystals (yield: 90.7%). It can be seen from the NMR data and elemental analysis results shown in Table 3 that it has the structure of formula (V).
〈元素分析＞ Ｃｚ４ＨｓｚＮＯ□ＣＱ（分子量４２
２．１３）トラデシルメチルアンモニウムの合成
ジテトラデシルメチルアミン６．３６ｇ（１５ｍｍｏｌ
）、３−クロロ−１，２−プロパンジオール１．８２ｇ
（１６，５ｍｍ。<Elemental analysis> Cz4HszNO□CQ (molecular weight 42
2.13) Synthesis of tradecylmethylammonium ditetradecylmethylamine 6.36g (15mmol
), 3-chloro-1,2-propanediol 1.82g
(16.5mm.
１）をイソプロパツール４．５ｇに溶かした溶液に重炭
酸ナトリウム０．３２ｇを加え、１４０〜１５０℃で２
４時間加熱攪拌する。反応混合物をシリカゲルカラムを
用いて分離精製した後、凍結乾燥すると白色結晶７．３
５ｇ（収率９１．７％）が得られた。この化合物のＮＭ
Ｒデータを第３表中に示す。元素分析の結果も計算値と
一致した。Add 0.32 g of sodium bicarbonate to a solution of 1) dissolved in 4.5 g of isopropanol, and heat at 140 to 150°C for 2 hours.
Heat and stir for 4 hours. The reaction mixture was separated and purified using a silica gel column and then lyophilized to give white crystals 7.3
5 g (yield 91.7%) was obtained. NM of this compound
R data is shown in Table 3. The results of elemental analysis also agreed with the calculated values.
〈元素分析＞ Ｃ，□Ｈ，，ＮＯ，ＣＱ （分子量５
３４．３４）デシルジメチルアミン５．５６ｇ（３０ｍ
ｍｏｌ）、１，３−ジクロロ−２−プロパツール１．９
３ｇ（１５ｍｍｏｌ）をイソプロパツール７．５ｇに溶
かした溶液に重炭酸ナトリウム０．２８ｇを加え、１４
０〜１５０℃で２４時間加熱攪拌する。反応混合物をシ
リカゲルカラムを用いて分離精製した後、凍結乾燥する
と白色結晶６．３９ｇ（収率８５．２％）が得られた。<Elemental analysis> C, □H,, NO, CQ (molecular weight 5
34.34) Decyldimethylamine 5.56g (30m
mol), 1,3-dichloro-2-propatol 1.9
Add 0.28 g of sodium bicarbonate to a solution of 3 g (15 mmol) dissolved in 7.5 g of isopropanol,
Heat and stir at 0 to 150°C for 24 hours. The reaction mixture was separated and purified using a silica gel column, and then freeze-dried to obtain 6.39 g of white crystals (yield: 85.2%).
第４表に示したＮＭＲデータおよび
元素分析の結果から式（ＶＩ）の構造であることがわか
る。It can be seen from the NMR data and elemental analysis results shown in Table 4 that it has the structure of formula (VI).
〈元素分析＞ Ｃ２，ＨＧ、Ｎ２０Ｃ１２２（分子量
４９９．６８）ドデシルジメチルアミン４．２７ｇ（２
０ｍｍｏｌ）、■、３−ジクロロー２−プロパツール１
．２９ｇ（１０ｍｍｏｌ）をイソプロパツール６．０ｇ
に溶がした溶液に重炭酸ナトリウム０．２１ｇを加え、
１４０〜１５０℃で２４時間加熱攪拌する。反応混合物
をシリカゲルカラムを用いて分離精製した後、凍結乾燥
すると白色結晶５．０２ｇ（収率９０．４％）が得られ
た。この化合物のＮＭＲデータを第４表中に示す。元素
分析の結果も計算値と一致した。<Elemental analysis> C2, HG, N20C122 (molecular weight 499.68) dodecyldimethylamine 4.27g (2
0 mmol), ■, 3-dichloro 2-propatool 1
．． 29g (10mmol) and 6.0g of isopropanol
Add 0.21 g of sodium bicarbonate to the solution dissolved in
Heat and stir at 140-150°C for 24 hours. The reaction mixture was separated and purified using a silica gel column, and then freeze-dried to obtain 5.02 g of white crystals (yield: 90.4%). NMR data for this compound is shown in Table 4. The results of elemental analysis also agreed with the calculated values.
〈元素分析＞ Ｃ３□Ｈ，、Ｎ２ＱＣＱ ２ （分子
量５５５．７９）ルメチルアンモニウムの合成
ジデシルメチルアミン４．６７ｇ（１５ｍｍｏｌ）、３
−ブロモ−１，２−プロパンジオール２．５６ｇ（１６
，５ｍｍｏｌ）をインプロパツール５．０ｇに溶かした
溶液に重炭酸ナトリウム０．２３ｇを加え、１４０〜１
５０℃で２４時間加熱攪拌する。反応混合物をシリカゲ
ルカラムを用いて分離精製した後、凍結乾燥すると白色
結晶６．４７ｇ（収率９２．４％）が得られた。第３表
に示すＮＭＲデータおよび元素分析の結果からこの化合
物が臭化（２，３−ジヒドロキシプロピル）ジデシルメ
チルアンモニウムであることが分かる。<Elemental analysis> Synthesis of C3□H,, N2QCQ 2 (molecular weight 555.79) methylammonium Didecylmethylamine 4.67 g (15 mmol), 3
-bromo-1,2-propanediol 2.56 g (16
, 5 mmol) was dissolved in 5.0 g of Improper Tool, 0.23 g of sodium bicarbonate was added, and 140-1
Heat and stir at 50°C for 24 hours. The reaction mixture was separated and purified using a silica gel column and then freeze-dried to obtain 6.47 g of white crystals (yield: 92.4%). The NMR data and elemental analysis results shown in Table 3 show that this compound is (2,3-dihydroxypropyl)didecylmethylammonium bromide.
〈元素分析） Ｃ２，Ｈ，２Ｎｏ２Ｂｒ（分子量４６
６．５９）（デシルジメチルアンモニウム）の合成デシ
ルジメチルアミン５．５６ｇ（３０ｍｍｏｌ）、 １，
３−ジブロモ−２−プロパツール３．２７ｇ（１５ｍｍ
ｏｌ）をイソプロパツール９．０ｇに溶かした溶液に重
炭酸ナトリウム０．２８ｇを加え、１４０−１５０℃で
２４時間加熱攪拌する。反応混合物をシリカゲルカラム
を用いて分離精製した後、凍結乾燥すると白色結晶８．
０８ｇ（収率９１．５％）が得られた。第４表に示すＮ
ＭＲデータおよび元素分析の結果からこの化合物が臭化
（２−ヒドロキシトリメチレン）ビス（デシルジメチル
アンモニウム）であることが分かる。<Elemental analysis) C2, H, 2No2Br (molecular weight 46
6.59) Synthesis of (decyldimethylammonium) Decyldimethylamine 5.56g (30mmol), 1,
3-dibromo-2-propatool 3.27g (15mm
0.28 g of sodium bicarbonate is added to a solution of ol) dissolved in 9.0 g of isopropanol, and the mixture is heated and stirred at 140-150°C for 24 hours. The reaction mixture was separated and purified using a silica gel column and then lyophilized to give white crystals8.
08g (yield 91.5%) was obtained. N shown in Table 4
MR data and elemental analysis indicate that this compound is (2-hydroxytrimethylene)bis(decyldimethylammonium) bromide.
Claims (1)
２は炭素数８〜１８のアルキル基、Ｘはハロゲンを示す
。）および下記の一般式 ▲数式、化学式、表等があります▼（II） （式中、Ｒ＿３は炭素数８〜１８のアルキル基、Ｘはハ
ロゲンを示す。） で示されるジアンモニウム塩型よりなる群から選らばれ
た新規第四級アンモニウム塩。 ２、特許請求の範囲第１項記載の第四アンモニウム塩を
有効成分とする殺菌剤。[Claims] 1. Monoammonium salt type represented by the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (in the formula, R_1, R_
2 represents an alkyl group having 8 to 18 carbon atoms, and X represents a halogen. ) and the following general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) (In the formula, R_3 is an alkyl group having 8 to 18 carbon atoms, and X represents a halogen.) A novel quaternary ammonium salt selected from the group. 2. A bactericidal agent containing the quaternary ammonium salt according to claim 1 as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6139888A JPH01233264A (en) | 1988-03-14 | 1988-03-14 | Novel quaternary ammonium salt derived from halogenated glycerol and germicide containing said salt as active ingredient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6139888A JPH01233264A (en) | 1988-03-14 | 1988-03-14 | Novel quaternary ammonium salt derived from halogenated glycerol and germicide containing said salt as active ingredient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01233264A true JPH01233264A (en) | 1989-09-19 |
| JPH0257537B2 JPH0257537B2 (en) | 1990-12-05 |
Family
ID=13170006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6139888A Granted JPH01233264A (en) | 1988-03-14 | 1988-03-14 | Novel quaternary ammonium salt derived from halogenated glycerol and germicide containing said salt as active ingredient |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01233264A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6172117B1 (en) | 1998-02-27 | 2001-01-09 | Akzo Nobel N.V. | Biocidal preservatives |
| WO2007094806A1 (en) * | 2006-02-15 | 2007-08-23 | Dow Global Technologies Inc. | Process for preparing dihydroxytrialkylammonium halides and products thereof |
| WO2012007412A1 (en) * | 2010-07-12 | 2012-01-19 | Unilever Plc | Preservative system and composition based on glycinate and dihydroxypropyl quaternary ammonium salt combination |
| US8470883B2 (en) | 2010-07-12 | 2013-06-25 | Conopco, Inc. | Preservative system and composition based on glycinate and hydroxyethyl sulfonate salt combination |
| US8501808B2 (en) | 2010-07-12 | 2013-08-06 | Conopco, Inc. | Foam enhancement of fatty acyl glycinate surfactants |
| US8999315B2 (en) * | 2004-07-15 | 2015-04-07 | Nalco Company | Bis-quaternary ammonium salt corrosion inhibitors |
| EP2881122A4 (en) * | 2012-08-01 | 2016-05-18 | Nms Technologies Co Ltd | Physical antimicrobial method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4734277A (en) * | 1984-12-03 | 1988-03-29 | Jordan Chemical Company | Bis-quaternary ammonium compounds |
-
1988
- 1988-03-14 JP JP6139888A patent/JPH01233264A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4734277A (en) * | 1984-12-03 | 1988-03-29 | Jordan Chemical Company | Bis-quaternary ammonium compounds |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6172117B1 (en) | 1998-02-27 | 2001-01-09 | Akzo Nobel N.V. | Biocidal preservatives |
| US8999315B2 (en) * | 2004-07-15 | 2015-04-07 | Nalco Company | Bis-quaternary ammonium salt corrosion inhibitors |
| WO2007094806A1 (en) * | 2006-02-15 | 2007-08-23 | Dow Global Technologies Inc. | Process for preparing dihydroxytrialkylammonium halides and products thereof |
| CN101370770A (en) * | 2006-02-15 | 2009-02-18 | 陶氏环球技术公司 | Process for preparing dihydroxytrialkylammonium halides and products thereof |
| US7541496B2 (en) | 2006-02-15 | 2009-06-02 | Dow Global Technologies Inc. | Process for preparing dihydroxytrialkylammonium halides and products thereof |
| JP2009526842A (en) * | 2006-02-15 | 2009-07-23 | ダウ グローバル テクノロジーズ インコーポレイティド | Process for the preparation of dihydroxytrialkylammonium halides and products thereof |
| WO2012007412A1 (en) * | 2010-07-12 | 2012-01-19 | Unilever Plc | Preservative system and composition based on glycinate and dihydroxypropyl quaternary ammonium salt combination |
| US8470883B2 (en) | 2010-07-12 | 2013-06-25 | Conopco, Inc. | Preservative system and composition based on glycinate and hydroxyethyl sulfonate salt combination |
| US8501808B2 (en) | 2010-07-12 | 2013-08-06 | Conopco, Inc. | Foam enhancement of fatty acyl glycinate surfactants |
| EP2881122A4 (en) * | 2012-08-01 | 2016-05-18 | Nms Technologies Co Ltd | Physical antimicrobial method |
| US9504255B2 (en) | 2012-08-01 | 2016-11-29 | Nms Technologies Co., Ltd. | Physical antimicrobial method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0257537B2 (en) | 1990-12-05 |
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