3-(acetoxyamino)-2-isopropylquinazolin-4-one | 160422-27-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 3-(acetoxyamino)-2-isopropylquinazolin-4-one
• 英文别名: [(4-Oxo-2-propan-2-ylquinazolin-3-yl)amino] acetate
• CAS: 160422-27-5
• 化学式: C₁₃H₁₅N₃O₃
• 分子量: 261.28
• InChiKey: LFAHIJQIBYTBPB-UHFFFAOYSA-N

物化性质

• 沸点：
  386.0±25.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  71
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  3-(acetoxyamino)-2-isopropylquinazolin-4-one 在 sodium hydride 、 六甲基二硅氮烷 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 3.25h， 生成 (3aR,7aS)-3-(4-oxo-2-propan-2-ylquinazolin-3-yl)-3a,4,5,7a-tetrahydro-1,3-benzoxazol-2-one
  参考文献：
  名称：

  Aziridination of cyclic dienes with enantiopure 3-acetoxyaminoquinazolin-4(3H)-ones

  摘要：

  环戊二烯和环七烯-1,3-二烯与(S)-3-乙酸氧氨基-2-(3-羟基-2,2-二甲基丙基)喹唑啉-4(3H)-酮6 (Q1NHOAc) 在四氧化钛和二氯甲烷的存在下发生了高的非对映选择性：X射线结构分析显示，两种情况下的非对映选择性偏好与之前发现的对丁二烯与6的非对映选择性一致。环己烯-1,3-二烯与6的环化反应在二氯甲烷溶液中表现出较低的非对映选择性，但在乙腈中则表现出高度的非对映选择性：在这种溶剂中还获得了两个非对映异构体的顺式-4-(Q1-氨基)环己烯-3-醇27和28作为副产物。这两个氨醇通过酸催化环戊烯开环也获得，并被转化为不含Q1的噁唑烷酮，且它们的光旋度在大小上相似但符号相反。

  DOI：

  10.1039/b102592a
• 作为产物：
  描述：

  邻氨基苯甲酸甲酯 在 一水合肼 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 18.5h， 生成 3-(acetoxyamino)-2-isopropylquinazolin-4-one
  参考文献：
  名称：

  Reaction of 3-(acetoxyamino)quinazolin-4(3H)-ones with enolic β-diketones: the N–N bond as a chiral axis in N-(3,4-dihydro-4-oxoquinazolin-3-yl)-N-acyl-α-aminoketones; reductive and base-catalysed cleavage of the N–N bond in N-acetyl-N-(3,4-dihydro-4-oxoquinazolin-3-yl)-α-amino acid esters

  摘要：

  Following the method of Foucaud and coworkers, reaction of pentane-2,4-dione with 3-(acetoxy-amino)quinazolin-4-one 8 gave the keto amide 9 (15%). 3-Methylpentane-2,4-dione reacts with compound 8 to give a relatively stable enol 11 (66%) which can be isolated in a crystalline form. Rotation around the N-N bonds in both compounds 9 and 11 is believed to be slow on the real time-scale and hence the N-N bonds can be considered as a chiral axes. As a result, protonation of the enol double bond in compound 11 and the creation of an additional chiral centre, gives rise to the separable keto amides 14 and 15; this protonation can be accomplished completely diastereoselectively. Lead tetraacetate acetoxylation of compound 11 to give compound 19 is also completely diastereoselective, Brief heating of the enol effects the elimination of the quinazolinone and the formation of the N-acetylimine 16 via an 8-membered transition state. Base-catalysed elimination of the quinazolinone ring from compound 22 is surprisingly easy: reductive cleavage of this N-N bond in compound 22 is facile by comparison with the 3-(alkylamino)quinazolin-4-ones.

  DOI：

  10.1039/p19940003209

文献信息

• Aziridination of alkenes using 3-acetoxyaminoquinazolin-4-(3H)ones in the presence of tertiary amines: evidence for an azaimide (N-nitrene) intermediate
  作者：Robert S. Atkinson、Emma Barker

  DOI：10.1039/c39950000819

  日期：——

  Solutions of the triethylammonium imide 8, formed from triethylamine and 3-acetoxyaminoquinazolinone 4, react with alkenes at –30 °C to give aziridines; the reactivity of the aziridinating intermediate is consistent with its formulation as an azaimide (N-nitrene).

  由三乙胺和3-乙酰氧基氨基喹唑啉酮4形成的三乙酰亚胺亚胺8的溶液在–30°C下与烯烃反应生成氮丙啶；叠氮基化中间体的反应性与其作为氮杂酰亚胺（N-氮化物）的配方一致。
• Diastereoselective aziridination of cyclic dienes with 3-acetoxyaminoquinazolin-4(3H)-ones: competitive formation of insertion products from cyclohexadienes
  作者：Robert S Atkinson、Christopher K Meades

  DOI：10.1016/s0040-4039(00)01328-9

  日期：2000.9

  highly diastereoselectively: the corresponding aziridination product of cyclohexa-1,3-diene is formed less diastereoselectively and is accompanied by a by-product 9 from formal insertion into an allylic CH bond, a previously unobserved reaction type for 3-acetoxyaminoquinazolinones.

  在叔丁醇钛（IV）存在下，将3-戊氧基氨基-2-[[（S）-1-羟基-2,2-二甲基丙基]喹唑啉-4（3 H）-one 1）环戊二烯和环庚二烯氮杂环化高度非对映选择性的相应乙烯基氮丙啶：环己-1,3-二烯的相应叠氮化产物的非对映选择性较小，并且伴随有从形式上插入烯丙基CH键的副产物9，这是以前观察不到的3-型反应类型乙酰氧基氨基喹唑啉酮。
• Preparation of cyclic α-(3,4-dihydro-2-isopropyl-4-oxoquinazolin-3-yl)amino-β-ketoesters: Further oxidation with lead tetra-acetate in dichloromethane and in methanol leading to ring-expansion and ring-cleavage products, respectively
  作者：Robert S. Atkinson、Emma Barker、Paul J. Edwards、Gordon A. Thomson

  DOI：10.1016/0040-4039(94)80138-x

  日期：1994.10

  Cyclic β-ketoesters e.g. 7 and the enol silyl ether 18 are converted to the corresponding α-(quinazolinonyl)amino (α-Q′NH) derivatives 10 and 19 respectively by reaction with the 3-acetoxyaminoquinazolinone 6: further oxidation of 10 and 19 with lead tetra-acetate in dichloromethane gave ring-expanded products 15 and 20 respectively but with methanol as solvent the corresponding ring-cleaved products

  通过与3-乙酰氧基氨基喹唑啉酮6反应，分别将环状β-酮酸酯（例如7）和烯醇甲硅烷基醚18分别转化为相应的α-（喹唑啉酮基）氨基（α-Q'NH）衍生物10和19：进一步氧化10和19用四乙酸铅在二氯甲烷中的溶液分别得到扩环产物15和20，但是用甲醇作为溶剂，得到相应的环裂解产物21和22：似乎不涉及自由基中间体。
• Carbon–hydrogen bond insertion reactions of 3-acetoxy-aminoquinazolin-4(3H)-ones with cyclic dienes: stereochemistry and mechanism
  作者：Robert S Atkinson、Christopher K Meades

  DOI：10.1016/s0040-4020(01)01246-7

  日期：2002.2

  cyclohexadienyl ring carbon has been correlated with that at the 6-position of the major aziridine diastereoisomer co-produced in the reaction. A mechanism involving concerted insertion into the C–H bond of the diene by QNHOAc is proposed with endo-overlap of both double bonds of the diene with the Q group in the transition state.

  2-取代的3-乙酰氧基氨基喹唑啉-4（3 H）-ones（QNHOAc）与环己-1,3-二烯或环己-1,4-二烯（2当量）的反应除了稳定的叠氮化产物外，还可以稳定通过将[QN̈：]插入双烯丙基CH键中而正式产生的二氢芳族副产物。发生类似的插入9,10-二氢蒽或v吨（1.5-2当量）的亚甲基CH键的过程。使用3- acetoxyamino -2 - [（小号）-2,2-二甲基-1-羟基丙基]喹唑啉-4（3 H ^） -酮2（Q 1在钛的存在下NHOAc）（IV）吨-丁氧基，完全非对映选择性地插入环己-1,3-二烯中，并且在环己二烯基环碳上的构型与反应中共同生成的主要氮丙啶非对映异构体的6位上的构型相关。提出了一种机制，该机制涉及通过QNHOAc一致地插入二烯的CH键中，二烯的两个双键均与Q基团处于过渡态时发生内重叠。
• N-(3,4-dihydro-4-oxoquinazolin-3-yl)pyridmium imides: aziridinating agents for alkenes: measurement of rotational barriers around each N–N bond in an N–N–N system
  作者：Robert S. Atkinson、Emma Barker、Paul J. Edwards、Gordon A. Thomson

  DOI：10.1039/c39950000727

  日期：——

  Pyridinium imides 3–5 and 8 are obtained as crystalline solids from the reaction of 3-acetoxyaminoquinazolinones 2 and 10 with the corresponding pyridines; barriers to rotation around each of the N–N bonds in 3 have been measured by NMR spectroscopy, and the imides 3–5 react both with styrene and with diethyl fumarate to give the corresponding aziridines.

  3-乙酰氧基氨基喹唑啉酮 2 和 10 与相应的吡啶反应得到结晶固体吡啶鎓亚胺 3â5 和 8；通过核磁共振光谱测定了 3 中每个 NâN 键周围的旋转障碍，亚胺 3â5 与苯乙烯和富马酸二乙酯反应得到相应的氮丙啶。