二甲基过氧化物 | 690-02-8

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 中文名称: 二甲基过氧化物
• 英文名称: dimethyl peroxide
• 英文别名: methyl peroxide；methoxy methyl ether；methylperoxymethane
• CAS: 690-02-8
• 化学式: C₂H₆O₂
• 分子量: 62.0684
• InChiKey: SRXOCFMDUSFFAK-UHFFFAOYSA-N

物化性质

• 熔点：
  -100°C
• 沸点：
  40.6°C (rough estimate)
• 密度：
  0.8360
• 物理描述：
  Liquid

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  4
• 可旋转键数：
  1
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 海关编码：
  2909600000

反应信息

• 作为反应物：
  描述：

  二甲基过氧化物 以 gas 为溶剂， 生成 methoxyl radical
  参考文献：
  名称：

  Photolysis of Dimethyl Peroxide

  摘要：

  Dimethyl peroxide has been photolyzed in vapor phase by 2537 A-light under various peroxide pressures at temperatures from 21 to 60°C, and for various light intensities at 30°C. The over-all rate was measured manometrically. The reaction is self-inhibiting and is also greatly inhibited by a small amount of formaldehyde. The initial rate is expressed by AI+BI½[CH3OOCH3]½ (A≪B and I is absorbed light intensity), and it tends to 3I when formaldehyde is added sufficiently. Carbon monoxide, methanol, and formaldehyde were found in the reaction product. The amount of hydrogen was quite small in the normal run and also in the run where much formaldehyde was added. Based on these results the following mechanism has been proposed: CH3OOCH3+hν→2(H+HCHO),H+CH3OOCH3→CH3OH+CH3O,{CH3O+CH3OOCH3→CH3OH+CH3OOCH2,CH3OOCH2→CH3O+HCHO,CH3OOCH2+CH3O→CH3OH+2HCHO. From the temperature coefficient of the rate, Ea+Eb—Ec= 5.8 kcal, the difference of activation heats, has been obtained; the numerical value is supposed to be the upper limit of Eb.

  DOI：

  10.1063/1.1742961
• 作为产物：
  描述：

  硫酸二甲酯 在 氢氧化钾 、 水 、 双氧水 作用下， 生成 二甲基过氧化物
  参考文献：
  名称：

  Rieche, Chemische Berichte, 1928, vol. 61, p. 952,953

  摘要：

  DOI：

文献信息

• The extraordinary selectivity of methoxyphenylcarbene; The case of the curious “olefin”
  作者：Robert A Moss、Joanna Wlostowska

  DOI：10.1016/s0040-4039(00)86111-0

  日期：1988.1

  The reaction of MeOCPh with Me2CCMe2 gives a low yield of the appropriate cyclopropane (3); however, aged olefin containing traces of the related hydroperoxide (8) or alcohol (9) impurities, selectively affords the formal O-H insertion products 7 or 4.

  MeOCPh与我的反应2 CCMe 2给出了适当的环丙烷（产率低3）; 但是，老化的烯烃中含有痕量的相关氢过氧化物（8）或醇（9）杂质，有选择地提供了正式的OH插入产物7或4。
• Insertion of Molecular Oxygen into a Palladium(II) Methyl Bond: A Radical Chain Mechanism Involving Palladium(III) Intermediates
  作者：Luc Boisvert、Melanie C. Denney、Susan Kloek Hanson、Karen I. Goldberg

  DOI：10.1021/ja9061932

  日期：2009.11.4

  oxygen results in the formation of the palladium(II) methylperoxide complex (bipy)PdMe(OOMe) (2). The identity of the product 2 has been confirmed by independent synthesis. Results of kinetic studies of this unprecedented oxygen insertion reaction into a palladium alkyl bond support the involvement of a radical chain mechanism. Reproducible rates, attained in the presence of the radical initiator 2,2'-a

  (bipy)PdMe(2) (1) (bipy = 2,2'-bipyridine) 与分子氧的反应导致钯 (II) 甲基过氧化物络合物 (bipy)PdMe(OOMe) (2) 的形成。产物2的身份已通过独立合成得到确认。这种前所未有的氧插入烷基钯键的动力学研究结果支持自由基链机制的参与。在自由基引发剂 2,2'-偶氮双 (2-甲基丙腈) (AIBN) 存在下获得的可重现速率表明反应总体上是一级反应（[1] 和 [AIBN] 中的半级反应） ，零阶 [O(2)])。不寻常的速率定律（[1] 中的半阶）意味着反应进行的机制与有机自动氧化和最近报道的将 O(2) 插入 Pd(II) 氢化物键的例子显着不同。1 的自氧化机制与主族和早期过渡金属烷基配合物的自氧化机制更密切相关。值得注意的是，链增长被提议通过 Pd 中心 1 处的逐步缔合均裂取代进行，形成五配位 Pd(III) 中间体。
• Low-Temperature Transformation of Methane to Methanol on Pd₁ O₄ Single Sites Anchored on the Internal Surface of Microporous Silicate
  作者：Weixin Huang、Shiran Zhang、Yu Tang、Yuting Li、Luan Nguyen、Yuanyuan Li、Junjun Shan、Dequan Xiao、Raphael Gagne、Anatoly I. Frenkel、Franklin Feng Tao

  DOI：10.1002/anie.201604708

  日期：2016.10.17

  Direct conversion of methane to chemical feedstocks such as methanol under mild conditions is a challenging but ideal solution for utilization of methane. Pd1O4 single‐sites anchored on the internal surface of micropores of a microporous silicate exhibit high selectivity and activity in transforming CH4 to CH3OH at 50–95 °C in aqueous phase through partial oxidation of CH4 with H2O2. The selectivity

  在温和的条件下将甲烷直接转化为化学原料（例如甲醇）是具有挑战性但理想的甲烷利用解决方案。的Pd 1 Ò 4在变换CH锚定微孔硅酸盐表现出高的选择性和活性的微孔的内表面上的单点4至CH 3在水相中OH在50-95℃下通过CH部分氧化4用H 2 ö 2。当使用2.0 wt％CuO作为Pd的助催化剂时，甲醇生产的选择性保持在86.4％，而在95°C下甲醇生产的活性为每Pd 1 O 4位点每秒约2.78分子。1 O 4 @ ZSM-5。热力学计算表明，与副产物过氧化甲基的形成相比，对甲醇生产的反应非常有利。
• Peroxides of elements other than carbon. Part XVII. The reaction of trialkylstibines and trialkylbismuthines with t-butyl hydroperoxide and with oxygen
  作者：Alwyn G. Davies、Simon C. W. Hook

  DOI：10.1039/j39710001660

  日期：——

  t-Butyl hydroperoxide reacts with trialkylstibines, R3M, to give the corresponding stibine oxides, R3MO, but with trialkylbismuthines to give products such as RO·OBut, ROH, and ROR. Both reactions are thought to involve the intermediate metallonium ion R3MOH, which undergoes nucleophilic attack on H when M = Sb, and on R when M = Bi.

  叔丁基氢过氧化物与三烷基stibines R 3 M反应，生成相应的氧化锑，R 3 MO，但与三烷基双变色氨酸生成RO·OBu t，ROH和ROR等产物。认为这两个反应都涉及中间体金属离子R 3 MOH，当M = Sb时，它对H发生亲核攻击，而当M = Bi时，对R发生亲核攻击。
• C−O Coupling of LPt^IVMe(OH)X Complexes in Water (X = ¹⁸OH, OH, OMe; L = di(2-pyridyl)methane sulfonate)
  作者：Julia R. Khusnutdinova、Peter Y. Zavalij、Andrei N. Vedernikov

  DOI：10.1021/om070165h

  日期：2007.7.1

  hydrolyzed in acidic H218O solution to produce Me16OH isotopologue exclusively. Kinetic studies established that C−O elimination from 1 was first order in 1; it was catalyzed by acids and by one of the reaction products, complex 3. In the latter case reversible formation of intermediates 6 occurred. A suggested reaction mechanism for the formation of Me16OH from 1 in H218O solutions involves a bimolecular

  从LPt IV Me（OH）2（1，Me = CH 3 ; 1- d 3，Me = CD 3 ; L =二（2-吡啶基）甲磺酸盐）中进行C-O还原消除，生成甲醇，二甲醚和在80°C的H 2 O和H 2 18 O中的酸性溶液（60和120 mM HBF 4）中研究了LPt II（OH 2）2 BF 4（3）。在18 O标记的水中，两种同位素甲醇Me 18 OH和Me 16的混合物OH，以1：1至5：1的比例形成。在给定的酸度和1- d 3的〜10％转化率下，Me 18 OH / Me 16 OH的比例与复合物1- d 3（29-120 mM）的浓度成反比。ESI-MS研究表明，配合物1和1- d 3的羟基配体中的18 O / 16 O交换缓慢，导致反应结束时Me 18 OH / Me 16 OH的比例更高。类似地，单- 18 O形标记的复合物，1- 18O在HBF 4存在下于H 2 16 O中反应形成Me

表征谱图