CN1066170A - 用作生物杀伤剂和防腐剂的二羟甲基2，5-哌嗪二酮 - Google Patents
用作生物杀伤剂和防腐剂的二羟甲基2，5-哌嗪二酮 Download PDFInfo
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- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
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- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
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- A23B2/00—Preservation of foods or foodstuffs, in general
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- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/495—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with two or more nitrogen atoms as the only ring heteroatoms, e.g. piperazine or tetrazines
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Abstract
如文后所示的1，4-二(羟甲基)-2，5-哌嗪二酮
可用于杀灭宿主物质内部或表面的微生物和用于使
易受各种微生物污染的产品防腐。
Description
本发明是关于二羟甲基2，5-哌嗪二酮的应用，即作为生物杀伤剂和灭菌剂来杀灭存在于物质内部或表面的微生物和使各种易受微生物污染的物质保持防腐。
二羟甲基2，5-哌嗪二酮（Glycine anhydride dimethylol）又称为1，4-二羟甲基-2，5-哌嗪二酮是一个已知化合物，它是使2，5-哌嗪二酮与甲醛按如下反应式反应而制备的（例如参见Cherbuliez等，Helv.Chim.Octa，5 678，688（1923））。
本发明的目的是提供向宿主物质施加杀灭有效量的二羟甲基2，5-哌嗪二酮来杀死存在于宿主物质内部或表面的微生物的方法。
本发明的另一目的是提供向产品中掺入灭菌有效量的二羟甲基2，5-哌嗪二酮来使易受微生物污染的产品防腐的方法。
本发明的再一目的是提供一种防腐产品，这是一种含有防止产品受微生物污染有效量的二羟甲基2，5-哌嗪二酮的产品，它已经受到保护可免受微生物的污染。
本领域的技术人员在详细阅读下面的描述后会明显地看出本发明的其它目的和优点。
本发明是根据如下式所代表的1，4-二（羟甲基）-2，5-哌嗪二酮，具有抵抗包括细菌、酵母和霉菌的广谱微生物的生物活性功能的发现。
因此，此化合物是有效的生物杀伤剂。它可以杀灭存在于宿主物质体内或表面的微生物和可以抑制各种物质和产品（无论是固体、液体或乳剂）的内部或表面的微生物生长。这样的产品包括但不限于：化妆品、食品、药品、油漆、切削油或切削液、农产品、油井钻探浆液、润滑u剂、造纸业产品、尸体防腐液、医学和牙医的冷消毒装置、冷却水塔、纤维浸渍、胶乳、泳池、油墨、家用消毒剂、蜡制剂及抛光剂、洗脸间面盆及浴缸清洁剂、洗衣剂、肥皂、木材防腐剂、医院和医学防腐剂和胶粘剂。其中食品、药品、化妆品和个人卫生用品（如洗发精）是特别关注的。
根据本发明的二羟甲基2，5-哌嗪二酮的其它应用，还包括用此化合物控制微生物生长的工业应用，如造纸厂流出液的泥浆控制。
依靠二羟甲基2，5-哌嗪二酮的生物活性，它可用于杀灭已沾污宿主物质的微生物或可用作防腐剂来抑制和防止对微生物生长敏感的物质内部的微生物生长。这化合物对易受微生物污染的表面的消毒和/或灭菌也是有效的。所需的二羟甲基2，5-哌嗪二酮的有效量当然是变化的，视应用的类型而定，例如应用类型可作为杀灭微生物菌落的生物杀伤剂或作为抑制微生物生长的防腐剂。但本领域的技术人员是不难确定某个具体应用所需的有效量的。
当处理宿主物质时，二羟甲基2，5-哌嗪二酮的给药方式，可以是固体粉末、水溶液或乳液形式，可以单独投药，也可以与其它成分一起投药，其它成分包括别的生物杀伤剂和/或药剂。掺入防腐产品中所需的二羟甲基2，5-哌嗪二酮的量也是变化的，视所保护的产品和使用的环境而定。一般说来，产品含有低于约1.0%（重量）的二羟甲基2，5-哌嗪二酮可有效地防止在大多数环境下的微生物污染。主要是从经济考虑，推荐浓度低于约0.5%（重量）。根据本发明书提供的情报特别是实施例，本领域技术人员对于具体应用选择所需的具体用量是不会有什么困难的。
除了二羟甲基2，5-哌嗪二酮以外，其它常规的成分也可以加入需要防腐的产品中，这些其它成分包括其它灭菌剂、悬浮剂、润滑剂、防垢剂、腐蚀抑制剂和pH控制剂。如果需要的话，这些添加成分的选择也视需要防腐的具体产品而定。
当与要防腐剂产品一起拌合时，二羟甲基2，5-哌嗪二酮可以以固体粉末或水溶液的形式加入。因为粉末比液体易于操作，因而推荐用粉末。如果应用是液体配方，粉末易于溶解水性介质中。向产品拌合的二羟甲基2，5-哌嗪二酮，可以作为单独的灭菌剂加入，也可以作为灭菌体系的一部分与其它灭菌剂一起加入。在产品需要对广谱微生物都有防腐作用时，这样的体系是特别需要的。通过对此体系中灭菌剂的仔细选择，对某一产品对某一组微生物的灭菌活性可以得到最优化。使用灭菌体系时把灭菌剂加入普通溶剂如丙二醇中更加有利，因为此溶剂也有灭菌活性，因此可兼具溶剂和灭菌剂的双重功能。
本发明因此提供一种有效的防腐方法，通过抑制细菌、酵母和霉菌的生长使易受微生物污染的物质防腐。本发明化合物易于加入到各种形式包括液体、固体和乳液的物质中。
为进一步以实例说明本发明的各个方面，提供如下的实例。但是应理解这些实例的目的完全是例示性的，绝无限制本发明范围之意。实例中除另有说明都是以重量百分数表示的。
实例1
二羟甲基2，5-哌嗪二酮的制备
向41.0毫升水中11.4克（0.1摩尔）2，5-哌嗪二酮的搅拌着的浆液中加入16.2克（0.2摩尔）37%甲醛水溶液。加入0.10克10%氢氧化钠水溶液使悬浮固体溶解，然后生成大量白色沉淀。混合物加热到70℃，所有固体就溶解了。再冷却至室温，白色结晶析出。分出结晶，用冷水洗涤和在100℃下真空干燥1小时。二羟甲基2，5-哌嗪二酮的白色结晶产物重12.6克（产率72.4%），熔点185-188℃，对于C6H10N2O4（174.16）中N的计算值为16.09和N的测定值为16.17。
实例2
微生物学活性
A 最小抑制浓度（MIC）
1%二羟甲基2，5-哌嗪二酮的水溶液用无菌蒸馏水进行系列稀释，不同浓度的每份用等体积特接种的培养基混合。AOAC肉汤用作细菌培养基，和Sabourand液体培养基用作酵母和霉菌的培养基。二羟甲基2，5-哌嗪二酮水溶液与培养基的混合物在35℃接种细菌和酵母48小时，和在26℃接种霉菌7天。靠目测混浊（cloudiness）来确定有无微生物生长。对给定微生物的MIC值是在接种期过后仍保持清亮的灭菌剂最低浓度。
结果如下：
细菌 MIC
革兰氏阴性菌 Pseudomonas aeruginosa ATCC 9027 310ppm
革兰氏阳性菌 Staphylococcus aureus ATCC 6538 310ppm
酵母 Candida albicans ATCC 10231 310ppm
霉菌 Aspergillus niger ATCC 16404 2500ppm
B.化妆品乳液的激惹（challenge）试验
制备用于微生物学激惹试验的典型化妆品乳液。制得的乳液为四种情况：不加防腐剂、含有0.05%二羟甲基2，5-哌嗪二酮、含有0.10%二羟甲基2，5-哌嗪二酮和含有0.20%二羟甲基2，5-哌嗪二酮。供激惹试验使用的配方如下：
A相 %重/重
软化水 67.90 67.85 67.80 67.70
三乙醇胺 99% 1.00 1.00 1.00 1.00
B相
Laneth-5（和）Ceteth-5（和）
Oleth-5（和）Steareth-5 0.50 0.50 0.50 0.50
矿物油 2.50 2.50 2.50 2.50
硬脂酸XXX 5.00 5.00 5.00 5.00
十六烷醇 1.00 1.00 1.00 1.00
甘油硬脂酸脂（和）
PEG-100硬脂酸脂 1.50 1.50 1.50 1.50
C相 %重/重
柠檬酸（30%水溶液） 0.60 0.60 0.60 0.60
D相
软化水 20.00 20.00 20.00 20.00
二羟甲基2，5-哌嗪二酮（GAD） - 0.05 0.10 0.20
100.00 100.00 100.00 100.00
使用四种不同微生物进行激惹试验，在接种24、48和72小时后进行微生物计数。基本上按照USP灭菌防腐有效性试验（UPS XXII方法）进行。
24小时的微生物计数
无防腐剂 0.05%GAD 0.10%GAD 0.20%GAD
P.aeruginosa 9×105＜10 50 100
S.aureus 2×1064×1045×1042×103
C.albicans 215×1041×10450 ＜10
A.niger 5×104500 ＜10 ＜10
48小时的微生物计数
无防腐剂 0.05%GAD 0.10%GAD 0.20%GAD
P.aeruginosa 1×106＜10 15 60
S.aureus 6×106100 15 200
C.albicans 2×1041×104＜10 ＜10
A.niger 4×104＜10 ＜10 ＜10
72小时的微生物计数
无防腐剂 0.05%GAD 0.10%GAD 0.20%GAD
P.aeruginosa 1×106＜10 ＜10 ＜10
S.aureus 5×106＜10 ＜10 ＜10
C.albicans 2×1041×103＜10 ＜10
A.niger 3×104＜10 ＜10 ＜10
C.洗发精的激惹试验
制备了含有和不含有二羟甲基2，5-哌嗪二酮的典型洗发精，然后对几种微生物进行激惹试验，基本上采用USP灭菌防腐有效性试验（USP XXII方法）进行，在24、48和72小时后进行微生物计数。使用上述的相同微生物（ATCC保藏号相同）。
洗发精配方如下
A相 %重/重
软化水
十二烷基硫酸铵 25.00 25.00
椰子酰胺DEA 6.50 6.50
椰子酰胺丙基甜菜碱 5.00 5.00
B相
柠檬酸，30%溶液 ＊ ＊
C相
去离子水 20.00 20.00
二羟甲基2，5-哌嗪二酮 - 0.20
100.00 100.00
＊适量，至pH6
微生物激惹试验结果如下：
24小时微生物计数
无防腐剂 0.2%GAD
P.aeruginosa 5×10550
S.aureus ＜10 ＜10
C.albicans 2×104＜10
A.niger 5×104＜10
48小时微生物计数
无防腐剂 0.2%GAD
P.aeruginosa 1×104＜10
S.aureus ＜10 ＜10
C.albicans 2×104＜10
A.niger 1×105＜10
72小时微生物计数
无防腐剂 0.2%GAD
P.aeruginosa 50 ＜10
S.aureus ＜10 ＜10
C.albicans 2×104＜10
A.niger 5×103＜10
D.牛奶的防腐
加入0.16%二羟甲基2，5-哌嗪二酮可防止全奶在室温下的微生物坏损。如下一系列试验的期间是59天。
向全奶中加入的防腐剂 变质时间
（即出现臭味、结块等）
无 10天
0.16% 59+天
0.16% 59+天
0.32% 59+天
0.32% 59+天
本发明已通过一些较好的实例予以描述，但本领域技术人员容易了解：不偏离本发明的精神仍可作出各种修正、变化、取舍和代替。因此本发明仅以权利要求书的范围来限定。
Claims (24)
1、杀灭宿主物质内部或表面的微生物的方法，包括将下式所示的杀灭有效量的二羟甲基2，5-哌嗪二酮投药给宿主物质
2、。根据权利要求1的方法，其中二羟甲基2，5-哌嗪二酮是以水溶液形式投药。
3、根据权利要求1的方法，其中二羟甲基2，5-哌嗪二酮是以乳液形式投药。
4、根据权利要求1的方法，其中二羟甲基2，5-哌嗪二酮是以粉末形式投药。
5、根据权利要求1的方法，其中二羟甲基2，5-哌嗪二酮是与其它生物杀伤剂一起投药的。
6、保护物质免受微生物污染的方法，包括在该物质中加入灭菌有效量的如下式所示的二羟甲基2，5-哌嗪二酮
7、根据权利要求6的方法，其中加入所述物质中的二羟甲基2，5-哌嗪二酮的量约低于1.0%（重量）。
8、根据权利要求6的方法，其中加入所述物质中的二羟甲基2，5-哌嗪二酮的量约低于0.5%（重量）。
9、根据权利要求6的方法，其中二羟甲基2，5-哌嗪二酮是以固体形式加入所述物质中。
10、根据权利要求6的方法，其中二羟甲基2，5-哌嗪二酮是以水溶液形式加入所述物质中。
11、根据权利要求6的方法，其中所述的物质是化妆品。
12、根据权利要求6的方法，其中所述的物质是个卫生用品。
13、根据权利要求12的方法，其中所述的个人卫生用品是洗发精。
14、根据权利要求6的方法，其中所述的物质是药品。
15、根据权利要求6的方法，其中所述的物质是食品。
16、根据权利要求6的方法，其中所述的物质是造纸厂的流出液。
17、一种防腐产品，包括一种易受微生物污染的物质和如下式所式的抑制微生物生长有效量的二羟甲基2，5-哌嗪二酮
18、根据权利要求17的产品，其中二羟甲基2，5-哌嗪二酮的含量约低于1.0%（重量）。
19、根据权利要求18的产品，其中二羟甲基2，5-哌嗪二酮的含量约低于0.5%（重量）。
20、根据权利要求17的产品，其中所述的物质是化妆品。
21、根据权利要求17的产品，其中所述的物质是个人卫生用品。
22、根据权利要求21的产品，其中所述的物质是洗发精。
23、根据权利要求17的产品，其中所述的物质药品。
24、根据权利要求17的产品，其中所述的物质是食品。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/694,252 US5244653A (en) | 1991-05-01 | 1991-05-01 | Glycine anhydride dimethylol as a biocide and preservative |
| US694,252 | 1991-05-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1066170A true CN1066170A (zh) | 1992-11-18 |
Family
ID=24788047
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92103219A Pending CN1066170A (zh) | 1991-05-01 | 1992-04-30 | 用作生物杀伤剂和防腐剂的二羟甲基2，5-哌嗪二酮 |
Country Status (12)
| Country | Link |
|---|---|
| US (3) | US5244653A (zh) |
| EP (1) | EP0583357A4 (zh) |
| JP (1) | JPH06507403A (zh) |
| CN (1) | CN1066170A (zh) |
| AU (1) | AU654192B2 (zh) |
| BR (1) | BR9205953A (zh) |
| CA (1) | CA2109418A1 (zh) |
| CZ (1) | CZ230193A3 (zh) |
| MX (1) | MX9201988A (zh) |
| NO (1) | NO933894L (zh) |
| WO (1) | WO1992019212A2 (zh) |
| ZA (1) | ZA923063B (zh) |
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-
1991
- 1991-05-01 US US07/694,252 patent/US5244653A/en not_active Expired - Fee Related
-
1992
- 1992-04-28 ZA ZA923063A patent/ZA923063B/xx unknown
- 1992-04-29 MX MX9201988A patent/MX9201988A/es unknown
- 1992-04-30 CZ CS932301A patent/CZ230193A3/cs unknown
- 1992-04-30 JP JP4511432A patent/JPH06507403A/ja active Pending
- 1992-04-30 EP EP19920911282 patent/EP0583357A4/en not_active Withdrawn
- 1992-04-30 WO PCT/US1992/003442 patent/WO1992019212A2/en not_active Application Discontinuation
- 1992-04-30 CN CN92103219A patent/CN1066170A/zh active Pending
- 1992-04-30 CA CA002109418A patent/CA2109418A1/en not_active Abandoned
- 1992-04-30 BR BR9205953A patent/BR9205953A/pt not_active Application Discontinuation
- 1992-04-30 AU AU19169/92A patent/AU654192B2/en not_active Ceased
-
1993
- 1993-05-10 US US08/058,238 patent/US5707993A/en not_active Expired - Fee Related
- 1993-10-28 NO NO933894A patent/NO933894L/no unknown
-
1995
- 1995-04-24 US US08/427,267 patent/US5593681A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU654192B2 (en) | 1994-10-27 |
| WO1992019212A3 (en) | 1993-01-21 |
| NO933894D0 (no) | 1993-10-28 |
| JPH06507403A (ja) | 1994-08-25 |
| WO1992019212A2 (en) | 1992-11-12 |
| US5244653A (en) | 1993-09-14 |
| MX9201988A (es) | 1992-11-01 |
| ZA923063B (en) | 1993-04-28 |
| AU1916992A (en) | 1992-12-21 |
| CZ230193A3 (en) | 1994-07-13 |
| EP0583357A1 (en) | 1994-02-23 |
| CA2109418A1 (en) | 1992-11-02 |
| US5593681A (en) | 1997-01-14 |
| NO933894L (no) | 1993-10-28 |
| EP0583357A4 (en) | 1994-05-18 |
| BR9205953A (pt) | 1994-09-27 |
| US5707993A (en) | 1998-01-13 |
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