丁酮肟 | 96-29-7

• 物质功能分类: 化学试剂 - 有机试剂 - 肟
• 分子结构分类: 有机化合物 - 有机氮化合物
• 中文名称: 丁酮肟
• 中文别名: 甲乙酮肟；甲基乙基酮肟；乙基甲基酮肟；2-丁酮肟；甲乙酮肪；甲乙铜肟
• 英文名称: ethyl methyl ketone oxime
• 英文别名: butanone oxime；2-butanone oxime；N-butan-2-ylidenehydroxylamine
• CAS: 96-29-7
• 化学式: C₄H₉NO
• mdl: MFCD00013935
• 分子量: 87.1216
• InChiKey: WHIVNJATOVLWBW-UHFFFAOYSA-N

物化性质

• 熔点：
  -30 °C
• 沸点：
  59-60 °C15 mm Hg(lit.)
• 密度：
  0.924 g/mL at 25 °C(lit.)
• 蒸气密度：
  3 (vs air)
• 闪点：
  140 °F
• 溶解度：
  水: 25°C时可溶100g/L
• 介电常数：
  3.4（20℃）
• LogP：
  0.63 at 25℃
• 物理描述：
  Methyl ethyl ketoxime is a clear colorless liquid with a musty odor. (NTP, 1992)
• 颜色/状态：
  Liquid
• 蒸汽密度：
  3 (NTP, 1992) (Relative to Air)
• 蒸汽压力：
  1.06 mm Hg at 20 °C
• 分解：
  When heated to decomposition it emits toxic fumes of /oxides of nitrogen/.
• 折光率：
  Index of refraction = 1.4410 at 20 °C/D
• 解离常数：
  pKa = 12.45 at 25 °C
• 保留指数：
  793
• 稳定性/保质期：

  避免与酸或氧化物接触。

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  6
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  32.6
• 氢给体数：
  1
• 氢受体数：
  2

ADMET

代谢

物质/2-丁酮肟/可以在动物体内代谢为2-丁酮和羟基胺。

The substance /2-butanone oxime/ can be metabolized in vivo in animals to 2-butanone and hydroxylamine.

来源:Hazardous Substances Data Bank (HSDB)

代谢

甲基乙基酮肟在体内被广泛代谢，不会在组织中积累。给大鼠单次灌胃剂量的2.7、27或270毫克/千克后，主要转化为二氧化碳，大部分在给药后的前24小时内完成。静脉给药后，以百分比为基础排出的二氧化碳放射性低于灌胃研究，更多的给药剂量以尿液和挥发性物质的形式排出。经皮给药后，排出的挥发性物质量显著大于灌胃或静脉给药。270毫克/千克的灌胃剂量可能导致代谢途径（s）饱和。有一些证据表明酮肟被代谢为酮，推测还会产生羟基胺...

...Methyl ethyl ketoxime is extensively metabolized and does not accumulate in tissues. Single gavage doses of 2.7, 27, or 270 mg/kg administered to rats were primarily converted to carbon dioxide, mostly in the first 24 hours after dosing. After intravenous administration, less radioactivity on a percentage basis was excreted as carbon dioxide than in the gavage study, and more of the administered dose was excreted in urine and as volatiles. Following dermal administration, significantly greater amounts of volatiles were excreted than after gavage or intravenous administration. The 270 mg/kg gavage dose may result in saturation of a metabolic pathway(s). There is some evidence that the ketoxime is metabolized to the ketone and, presumably, hydroxylamine...

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 副作用

神经毒素 - 其他中枢神经系统神经毒素 高铁血红蛋白血症 - 血液中高铁血红蛋白含量增加；该化合物被归类为次要毒性效应 溶血性贫血 - 血红蛋白或红细胞数量减少 皮肤致敏剂 - 能诱导皮肤过敏反应的剂

Neurotoxin - Other CNS neurotoxin Methemoglobinemia - The presence of increased methemoglobin in the blood; the compound is classified as secondary toxic effect Hemolytic anemia - Decreased hemoglobin or number of red blood cells. Skin Sensitizer - An agent that can induce an allergic reaction in the skin.

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

毒理性

• 毒性数据

大鼠LC50 > 1350 ppm/4小时

LC50 (rat) > 1350 ppm/4hr

来源:Haz-Map, Information on Hazardous Chemicals and Occupational Diseases

毒理性

• 解毒与急救

/SRP:/ 立即急救：确保已经进行了充分的中和。如果患者停止呼吸，请开始人工呼吸，最好使用需求阀复苏器、球囊阀面罩设备或口袋面罩，按训练操作。如有必要，执行心肺复苏。立即用缓慢流动的水冲洗受污染的眼睛。不要催吐。如果患者呕吐，让患者向前倾或将其置于左侧（如果可能的话，头部向下）以保持呼吸道畅通，防止吸入。保持患者安静，维持正常体温。寻求医疗帮助。 /毒物A和B/

/SRP:/ Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR if necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on the left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 基本治疗：建立专利气道（如有需要，使用口咽或鼻咽气道）。如有必要，进行吸痰。观察呼吸不足的迹象，如有需要，辅助通气。通过非循环呼吸面罩以10至15升/分钟的速度给予氧气。监测肺水肿，如有必要，进行治疗……。监测休克，如有必要，进行治疗……。预防癫痫发作，如有必要，进行治疗……。对于眼睛污染，立即用水冲洗眼睛。在运输过程中，用0.9%的生理盐水（NS）持续冲洗每只眼睛……。不要使用催吐剂。对于摄入，如果患者能吞咽、有强烈的干呕反射且不流口水，则用温水冲洗口腔，并给予5毫升/千克，最多200毫升的水进行稀释……。在去污后，用干燥的无菌敷料覆盖皮肤烧伤……。/毒药A和B/

/SRP:/ Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Cover skin burns with dry sterile dressings after decontamination ... . /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 解毒与急救

/SRP:/ 高级治疗：对于无意识、严重肺水肿或严重呼吸困难的病人，考虑进行口咽或鼻咽气管插管以控制气道。使用气囊面罩装置的正压通气技术可能有益。考虑使用药物治疗肺水肿……。对于严重的支气管痉挛，考虑给予β激动剂，如沙丁胺醇……。监测心率和必要时治疗心律失常……。开始静脉输注D5W /SRP: "保持开放"，最低流量/。如果出现低血容量的迹象，使用0.9%生理盐水（NS）或乳酸钠林格氏液。对于伴有低血容量迹象的低血压，谨慎给予液体。注意液体过载的迹象……。使用地西泮或劳拉西泮治疗癫痫……。使用丙美卡因氢氯化物协助眼部冲洗……。 /毒物A和B/

/SRP:/ Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Poisons A and B/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在妊娠的第14天，给怀孕的小鼠单次口服14(C)-2丁酮肟。此外，一只雄性小鼠也被给予单次口服(14)C-2-丁酮肟。看来这种物质通过口服途径被迅速吸收，并且完整地通过身体分布。整个研究过程中尿液和胆汁中含有所测活性的显著量。肠道活性最小。这表明这种物质主要通过肾脏排泄。

Pregnant mice were administered a single oral dose of 14(C)-2 butanone oxime on day 14 of gestation. In addition, a male mouse was administered a single oral dose of (14)C-2-butanone oxime. It appears that the substance is rapidly absorbed via the oral route, and distributed intact through the body. Urine and bile contained significant activity throughout the study. Intestinal activity was minimal. This suggests that the substance is primarily excreted via the kidneys.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

14(C)-甲基乙基酮肟（MEKO）在F344雄性大鼠体内的处置情况通过口服、静脉注射和皮肤给药后进行了确定。口服剂量为2.7、27和270 mg/kg的主要排泄方式为CO2（71-49%），随着剂量的增加，排泄百分比逐渐降低。尿液中（13-26%）和挥发性物质（5-18%）的排泄随着剂量的增加而增加。72小时后，大约5-6%的剂量仍留在主要组织中。静脉注射2.7 mg/kg的剂量也主要作为 （48.8%）排泄，尿液和呼出挥发性物质的排泄分别占21.4%和11.4%。大约7%的放射性物质在72小时后仍留在组织中。皮肤给药后，2.7和270 mg/kg剂量分别吸收了13%和26%。在放入代谢笼之前，剂量部位的挥发可能解释了低吸收率。MEKO被生物转化为至少五种极性代谢物，这些代谢物只能通过阴离子交换色谱部分分离。与葡萄糖醛酸酶孵育，但不是与硫酸酯酶孵育，改变了尿液中代谢物的轮廓。甲基乙基酮是挥发性物质中的主要成分。

The disposition of 14(C)-methyl ethyl ketoxime (MEKO) was determined in the male F344 rat following oral, iv and dermal administration. Oral doses of 2.7, 27 and 270 mg/kg were primarily excreted as CO2 (71-49%) in decreasing percentage as the dose increased. Excretion in urine (13-26%) and as volatiles (5-18%) increased as the dose increased. Five to 6% of the dose remained in the major tissues after 72 hr. An iv dose of 2.7 mg/kg was also principally excreted as CO2 (48.8%) with excretion in urine and as expired volatiles accounting for 21.4 and 11.4%, respectively. About 7% of the administered radioactivity remained in the tissues after 72 hr. Following dermal administration, 13 and 26% of a 2.7 and 270 mg/kg dose, respectively, were absorbed. Volatilization from the dose site prior to placement in the metabolism cage may account for the low absorption. MEKO was biotransformed to at least five polar metabolites that could only be partially resolved by anion exchange chromatography. Incubation with glucuronidase, but not sulphatase, changed the urinary metabolic profile. Methyl ethyl ketone was a major component in the volatiles.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

甲基乙基酮肟在体内被广泛代谢，不会在组织中积累。给大鼠单次灌胃剂量的2.7、27或270毫克/千克后，主要转化为二氧化碳，大部分在给药后的前24小时内完成。静脉给药后，以百分比为基础排出的二氧化碳放射性低于灌胃研究，更多的给药剂量以尿液和挥发性物质的形式排出。经皮给药后，排出的挥发性物质量显著大于灌胃或静脉给药。270毫克/千克的灌胃剂量可能导致代谢途径（s）饱和。有一些证据表明酮肟被代谢为酮，推测还会生成羟基胺...

...Methyl ethyl ketoxime is extensively metabolized and does not accumulate in tissues. Single gavage doses of 2.7, 27, or 270 mg/kg administered to rats were primarily converted to carbon dioxide, mostly in the first 24 hours after dosing. After intravenous administration, less radioactivity on a percentage basis was excreted as carbon dioxide than in the gavage study, and more of the administered dose was excreted in urine and as volatiles. Following dermal administration, significantly greater amounts of volatiles were excreted than after gavage or intravenous administration. The 270 mg/kg gavage dose may result in saturation of a metabolic pathway(s). There is some evidence that the ketoxime is metabolized to the ketone and, presumably, hydroxylamine...

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• TSCA：
  Yes
• 危险等级：
  3
• 危险品标志：
  Xn
• 安全说明：
  S13,S23,S25,S26,S36/37,S36/37/39,S45,S61
• 危险类别码：
  R40,R41,R21,R43
• WGK Germany：
  1
• 海关编码：
  29280090
• 危险品运输编号：
  UN 1993 3/PG 3
• RTECS号：
  EL9275000
• 包装等级：
  III
• 危险类别：
  3
• 储存条件：
  1. 储存在阴凉、通风的仓库中，并远离火源和热源，确保容器密封。与氧化剂分开存放，禁止混存。 2. 配备适当的消防器材，并在储区准备泄漏应急处理设备及合适的吸收材料。

SDS

Name:	2-Butanone oxime 99% Material Safety Data Sheet
Synonym:	Ethyl methyl ketone oxime; Ethyl methyl ketoxime; 2-Butanone oxime; Methyl ethyl ketoxime; MEK-oxime
CAS:	96-29-7

Section 1 - Chemical Product MSDS Name:2-Butanone oxime 99% Material Safety Data Sheet
Synonym:Ethyl methyl ketone oxime; Ethyl methyl ketoxime; 2-Butanone oxime; Methyl ethyl ketoxime; MEK-oxime

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
96-29-7	Methyl ethyl ketoxime	99	202-496-6

Hazard Symbols: XN
Risk Phrases: 21 40 41 43

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Harmful in contact with skin. Limited evidence of a carcinogenic effect. Risk of serious damage to eyes. May cause sensitization by skin contact.
Potential Health Effects
Eye:
Causes severe eye irritation.
Skin:
Harmful if absorbed through the skin. May cause skin sensitization, an allergic reaction, which becomes evident upon re-exposure to this material.
Ingestion:
Methemoglobinemia is characterized by dizziness, drowsiness, headache, shortness of breath, cyanosis (bluish discoloration of skin due to deficient oxygenation of the blood), rapid heart rate and chocolate-brown colored blood. May be harmful if swallowed.
Overexposure may cause methemoglobinemia.
Inhalation:
Not available.
Chronic:
Chronic exposure may cause liver damage.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid immediately.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Remove contaminated clothing and shoes.
Ingestion:
If victim is conscious and alert, give 2-4 cupfuls of milk or water.
Get medical aid immediately.
Inhalation:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.
Notes to Physician:

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion. Flammable liquid and vapor. Vapors are heavier than air and may travel to a source of ignition and flash back. Vapors can spread along the ground and collect in low or confined areas.
Extinguishing Media:
Use extinguishing media most appropriate for the surrounding fire.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Clean up spills immediately, observing precautions in the Protective Equipment section. Remove all sources of ignition. Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Remove contaminated clothing and wash before reuse. Avoid contact with eyes, skin, and clothing. Avoid ingestion and inhalation. Use only with adequate ventilation. Keep away from heat, sparks and flame.
Storage:
Keep away from sources of ignition. Keep container closed when not in use. Store in a cool, dry, well-ventilated area away from incompatible substances.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use process enclosure, local exhaust ventilation, or other engineering controls to control airborne levels.
Exposure Limits CAS# 96-29-7: Personal Protective Equipment Eyes: Wear chemical splash goggles.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
A respiratory protection program that meets OSHA's 29 CFR 1910.134 and ANSI Z88.2 requirements or European Standard EN 149 must be followed whenever workplace conditions warrant respirator use.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Clear liquid
Color: clear colorless to pale yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: 0.904 mm Hg @ 25 deg C
Viscosity: Not available.
Boiling Point: 152.5 deg C @ 760 mm Hg
Freezing/Melting Point: -29.5 deg C
Autoignition Temperature: Not available.
Flash Point: 59 deg C ( 138.20 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Slightly soluble.
Specific Gravity/Density: .9200 g/cm3
Molecular Formula: C4H9NO
Molecular Weight: 87.12

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures.
Conditions to Avoid:
High temperatures, ignition sources.
Incompatibilities with Other Materials:
Strong oxidizing agents, strong acids.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, carbon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 96-29-7: EL9275000 LD50/LC50:
CAS# 96-29-7: Draize test, rabbit, eye: 100 uL Severe; Oral, mouse: LD50 = 1 gm/kg; Oral, rat: LD50 = 930 mg/kg; Skin, rabbit: LD50 = 200 uL/kg.
Skin, rabbit: LD50 = 200 uL/kg = 184 mg/kg.
Carcinogenicity:
Methyl ethyl ketoxime - Not listed by ACGIH, IARC, or NTP.
Other:
See actual entry in RTECS for complete information.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Shipping Name: FLAMMABLE LIQUIDS, N.O.S.
Hazard Class: 3
UN Number: 1993
Packing Group: III
IMO
Shipping Name: FLAMMABLE LIQUIDS, N.O.S.
Hazard Class: 3
UN Number: 1993
Packing Group: III
RID/ADR
Shipping Name: FLAMMABLE LIQUIDS, N.O.S.
Hazard Class: 3
UN Number: 1993
Packing group: III

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XN
Risk Phrases:
R 21 Harmful in contact with skin.
R 40 Limited evidence of a carcinogenic effect.
R 41 Risk of serious damage to eyes.
R 43 May cause sensitization by skin contact.
Safety Phrases:
S 13 Keep away from food, drink and animal feeding
stuffs.
S 23 Do not inhale gas/fumes/vapour/spray.
S 26 In case of contact with eyes, rinse immediately
with plenty of water and seek medical advice.
S 36/37/39 Wear suitable protective clothing, gloves
and eye/face protection.
WGK (Water Danger/Protection)
CAS# 96-29-7: 1
Canada
CAS# 96-29-7 is listed on Canada's DSL List.
CAS# 96-29-7 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 96-29-7 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

肟类除氧剂

肟类化合物（如二甲基酮肟、甲乙酮肟、乙醛肟）作为新型除氧剂，于1984年由美国Drew化学公司首次公开专利。这类化合物低毒、高效且速度快，并具有钝化保护作用，在欧美日等发达国家得到广泛应用。我国也在九十年代成功开发并推广了这一技术。

性能与应用 1. 除氧性能

肟类化合物是有机含肟基化合物，主要应用于锅炉除氧和停炉保护。常用的肟类化合物包括乙醛肟、二甲基酮肟（丙酮肟）及甲乙酮肟。这类化合物具有较强的还原性，易于与氧气反应。在较宽的温度（138～336℃）和压力范围（0.3～13.7Mpa）内表现出良好的除氧性能。实验表明，在相同条件下，肟类化合物的除氧速度及效率均优于联氨。

2. 缓蚀与钝化作用

肟类化合物能够将高价铁、铜氧化物还原为低价态，并在钢材表面形成良好的磁性氧化膜，从而提供优异的钝化和缓蚀效果。其中，二甲基酮肟的效果最佳且用量最少。实验数据显示，肟类化合物的钝化及缓蚀作用与联氨相似，在高温高压条件下，能显著减少溶液中铁含量并对钢材起到保护作用。

3. 挥发性

肟类化合物的挥发性高于联氨、DEHA、吗啉和环己胺等物质，接近于NH3。这类除氧剂在蒸汽凝结时，会有一部分药剂溶入凝结水中，有助于保护金属材料不受损害。

4. 分解性

高温高压条件下，肟类化合物分解生成NH3、N2、H2O及微量乙酸，并无甲酸产生，对水汽系统没有不良影响。

5. 低毒性

根据LD50的数据比较，联氨的毒性最强（290mg/kg），而肟类化合物如乙醛肟（1900mg/kg）、甲乙酮肟（2800mg/kg）和二甲基酮肟（5500mg/kg）的毒性较低。皮肤接触实验表明，肟类除氧剂无明显刺激作用，联氨则可能导致皮肤红肿、粘膜充血等损伤。

化学性质

肟类化合物为无色油状液体，熔点-29.5℃，沸点152-153℃（2kPa），相对密度0.9232（20/4℃），折光率1.4410。能与醇、醚混溶，并可溶解于水中的10份水中。

用途

主要用于醇酸树脂涂料防结皮剂和硅固化剂，作为防止结皮的抗氧剂使用效果更佳。此外，也用于有机合成及各种油基漆、醇酸漆、环氧酯漆等储运过程中的防结皮处理，并可用作硅固化剂。

生产方法

由丁酮与盐酸羟胺反应制得，也可通过丁酮与硫酸羟胺反应实现。

反应信息

• 作为反应物：
  描述：

  丁酮肟 在 三聚氯氰 作用下， 以 二甲基亚砜 、 乙腈 为溶剂， 反应 10.0h， 以47%的产率得到N-乙基乙酰胺
  参考文献：
  名称：

  氰尿酰氯和二甲基亚砜在温和条件下促进酮肟的贝克曼重排

  摘要：

  酰胺的合成通过在温和条件下DMSO已经报道/由氰尿酰氯（TCT）促进酮肟的贝克曼重排。使用二苯甲酮肟作为底物，研究贝克曼重排的条件，例如溶剂，TCT / DMSO的比例和温度。采用优化的条件得到十四种酰胺，收率范围为20％至99％。根据质谱分析，提出了一种涉及活性二甲基烷氧基s中间体的合理机理。据我们所知，这是第一个研究TCT / DMSO在温和条件下促进酮肟的贝克曼重排以有效提供酰胺的案例。

  DOI：

  10.1016/j.tetlet.2020.152707
• 作为产物：
  描述：

  丁酮 在 氨 、 双氧水 作用下， 反应 2.0h， 生成 丁酮肟
  参考文献：
  名称：

  Lewis acidic strength controlled highly selective synthesis of oxime via liquid-phase ammoximation over titanosilicates

  摘要：

  钛硅酸盐的Lewis酸性通过影响Ti-O-OH的反应活化能，决定了氨氧化中肟的选择性，从而高效形成NH₂OH。

  DOI：

  10.1039/c4ra08799b
• 作为试剂：
  描述：

  sodium monochloroacetic acid 在 丁酮肟 、 水 、 sodium hydroxide 作用下， 以 丙酮 为溶剂， 反应 2.0h， 以55%的产率得到羧甲基羟胺半盐酸盐
  参考文献：
  名称：

  α−（アミノオキシ）カルボン酸類の製造方法

  摘要：

  题目：提供一种高效的制备α-（烷基亚氨基氧）羧酸类化合物作为醛捕捉剂的原料的α-（烷基亚基氨基氧）羧酸类化合物的方法。 解决方法：通过在酮类溶剂中，在碱的存在下，使式（1）所示的肟和式（2）所示的α-卤代羧酸反应，制备式（3）所示的α-（烷基亚基氨基氧）羧酸或其碱金属盐。（其中，R1，R2是氢原子或烷基，R3是烷基或苯基，X表示卤素原子。）【选项图】无。

  公开号：

  JP2020158452A

文献信息

• Efficient Reductive Deoximation by Tungsten(VI) Chloride (WCl₆) or Molybdenum(V) Chloride (MoCl₅) in the Presence of Zn Powder in CH₃CN
  作者：Habib Firouzabadi、Arezu Jamalian、Babak Karimi

  DOI：10.1246/bcsj.75.1761

  日期：2002.8

  Tungsten(VI) chloride (WCl6) or molybdenum(V) chloride (MoCl5) in the presence of zinc powder in CH3CN provides an efficient and facile procedure for the deprotection of oximes to their corresponding aldehydes and ketones in high yields.

  在 CH3CN 中存在锌粉的情况下，氯化钨 (VI) (WCl6) 或氯化钼 (V) (MoCl5) 为将肟以高产率脱保护为其相应的醛和酮提供了一种有效且简便的方法。
• <i>m</i>-CPBA Mediated Metal Free, Rapid Oxidation of Aliphatic Amines to Oximes
  作者：Vilas V. Patil、Eknath M. Gayakwad、Ganapati S. Shankarling

  DOI：10.1021/acs.joc.5b01740

  日期：2016.2.5

  An efficient, rapid oxidation of various aliphatic amines to oximes using m-CPBA as an oxidant in ethyl acetate is described. High conversion (100%) with >90% oxime selectivity is achieved at room temperature under catalyst-free conditions. Mild reaction conditions along with an easy work up procedure offer lower byproduct formation and high selectivity for oximes in good yield and purity.

  一种高效，快速的各种脂族胺的使用肟氧化米-CPBA如乙酸乙酯中的氧化剂进行说明。在室温下在无催化剂条件下实现了高转化率（100％）和> 90％的肟选择性。温和的反应条件以及简便的后处理步骤可降低副产物的生成，并以较高的收率和纯度提供对肟的高选择性。
• 一种肟氧化制备硝基烷烃的绿色合成方法
  申请人：南京工业大学

  公开号：CN106631809B

  公开（公告）日：2019-02-22

  本发明属于有机化工领域，提供了一种肟氧化制备硝基烷烃的绿色合成方法。在55～120℃和0～1.0MPa压力下，肟、溶剂和双氧水在一定量的纳米孔骨架金属杂化催化剂和助催化剂存在下反应20～200min，反应液经膜分离，催化剂可重复使用7次以上，精馏得到硝基烷烃产品，产品纯度≥99％，收率≥95％。是一种硝基烷烃的绿色合成方法，适合大规模工业化生产。
• Deoximation of Oximes with 2-Iodylbenzoic Acid in Water in the Presence of β-Cyclodextrin
  作者：K. Rama Rao、N. Srilakshmi Krishnaveni、K. Surendra、Y. V. Nageswar

  DOI：10.1055/s-2003-41448

  日期：——

  Oximes of various aldehydes and ketones can be converted to the corresponding carbonyl compounds at room temperature in impressive yields with 2-iodylbenzoic acid in water in the presence of β-cyclodextrin.

  在β-环糊精存在下，各种醛和酮的肟可以在室温下，在水中用2-碘苯甲酸以令人瞩目的产率转化为相应的羰基化合物。
• Brønsted acid catalyzed transoximation reaction: synthesis of aldoximes and ketoximes without use of hydroxylamine salts
  作者：Kengo Hyodo、Kosuke Togashi、Naoki Oishi、Genna Hasegawa、Kingo Uchida

  DOI：10.1039/c6gc02156e

  日期：——

  The transoximation reaction enables the transfer of oxime to a carbonyl compound and is catalyzed by transoximase in the pupae of silkworm. Inspired by this bio-synthetic pathway, we achieved the...

  转肟化反应使肟能够转移到羰基化合物上，并被家蚕p中的转肟酶催化。受到这种生物合成途径的启发，我们实现了...

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