5-amino-N'-methoxy-1-methylimidazole-4-carboxamidine | 33174-57-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 5-amino-N'-methoxy-1-methylimidazole-4-carboxamidine
• 英文别名: 5-amino-N-methoxy-1-methyl-1H-imidazole-4-carboximidic acid amide；5-amino-N'-methoxy-1-methylimidazole-4-carboximidamide
• CAS: 33174-57-1
• 化学式: C₆H₁₁N₅O
• 分子量: 169.186
• InChiKey: SELMSKPCFUYMLI-UHFFFAOYSA-N

物化性质

• 沸点：
  352.9±52.0 °C(Predicted)
• 密度：
  1.42±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  91.4
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-amino-N'-methoxy-1-methylimidazole-4-carboxamidine 在 palladium on activated charcoal 盐酸 、 氨 、 氢气 、 双氧水 、 sodium carbonate 、 sodium iodide 、 sodium nitrite 作用下， 以 水 、 溶剂黄146 为溶剂， 25.0 ℃ 、101.33 kPa 条件下， 反应 5.0h， 生成 阿卡地新
  参考文献：
  名称：

  Saito, Tohru; Asahi, Yayoi; Nakajima, Satoshi, Heterocycles, 1990, vol. 30, # 1, p. 329 - 332

  摘要：

  DOI：
• 作为产物：
  描述：

  9-甲基腺嘌呤 在 sodium hydroxide 、 Amberlite IRA-402 (HCO₃(-1)) 、 间氯过氧苯甲酸 作用下， 以 甲醇 、 N,N-二甲基乙酰胺 为溶剂， 反应 13.75h， 生成 5-amino-N'-methoxy-1-methylimidazole-4-carboxamidine
  参考文献：
  名称：

  A New Synthetic Route to 2-Deuterioadenines Substituted or Unsabustituted at the 9-Position

  摘要：

  DOI：

  10.3987/r-1986-09-2449

文献信息

• Purines. XXIX. Syntheses of 9-alkyl-2-deuterio-N6-methoxyadenines and 2-deuterio-N6,9-dimethyladenine: Tautomerism in 9-substituted N6-alkoxyadenines.
  作者：TOZO FUJII、TOHRU SAITO、TAISUKE ITAYA、KYOKO KIZU、YUKINARI KUMAZAWA、SATOSHI NAKAJIMA

  DOI：10.1248/cpb.35.4482

  日期：——

  Cyclizations of the alkoxyamidines 7a, i with formic acid gave N6-methoxy-9-methyladenine (8a) and 9-benzyl-N6-methoxyadenine (8i). Replacement of formic acid by formic-d acid-d in these cyclizations afforded the 2-deuterated species 13a and 13i. A similar cyclization of 22, obtained from 21 by alkaline hydrolysis, with formic-d acid-d yielded 2-deuterio-N6-methoxy-1, 9-dimethyladenine (24). The N6-methyl isomer 19 was prepared from 13a by treatment with NaH and MeI. Comparison of the proton nuclear magnetic resonance (1H-NMR) spectrum of 8a in Me2SO-d6 with that of 13a revealed that 8a exists as an equilibrated 1 : 3.5 mixture of the amino (type 14 or 15) and the imino (type 16 or 17) forms. The deuterated species 19 and 24 were utilized for interpretation of the 1H-NMR spectra of the amino-form model 18 and the imino-form model 23. The existence of amino-imino tautomerism in 8a was also supported by ultraviolet and infrared spectroscopic evidence. Such tautomerism, with a preference for the imino form, in Me2SO-d6 was found to be common to 13 other 9-substituted N6-alkoxyadenines (type 8) including adenosine analogues. On the other hand, comparison of the 1H-NMR spectra of 11, N6, 9-dimethyladenine (12), and N6, N6, 9-trimethyladenine (36) indicated that 12 exists solely in the amino form in CDCl3 or Me2SO-d6.

  烷氧基脒7a、7i与甲酸的环化反应分别得到了N6-甲氧基-9-甲基腺嘌呤（8a）和9-苄基-N6-甲氧基腺嘌呤（8i）。在这些环化反应中，用重氢甲酸（formic-d酸-d）替代甲酸得到了2-氘化的物种13a和13i。类似地，从21通过碱水解获得的22与重氢甲酸的环化反应得到了2-氘代-N6-甲氧基-1,9-二甲基腺嘌呤（24）。N6-甲基异构体19是通过NaH和MeI处理13a制备的。8a在二甲亚砜-d6中的质子核磁共振（1H-NMR）谱与13a的谱图对比显示，8a以1:3.5的比例平衡存在氨基（类型14或15）和亚氨基（类型16或17）形式。氘代物种19和24用于解释氨基形式模型18和亚氨基形式模型23的1H-NMR谱图。8a中存在的氨基-亚氨基互变异构现象也得到了紫外和红外光谱证据的支持。这种在二甲亚砜-d6中偏好亚氨基形式的互变异构现象在其他13种9-取代的N6-烷氧基腺嘌呤（类型8）中普遍存在，包括腺苷类似物。另一方面，N6,9-二甲基腺嘌呤（12）和N6,N6,9-三甲基腺嘌呤（36）的1H-NMR谱图对比表明，12在CDCl3或二甲亚砜-d6中仅以氨基形式存在。
• Purines. XLVIII. Syntheses and proton nuclear magnetic resonance study of 2-deuterioadenines substituted or unsubstituted at the 9-position and of their N-oxygenated derivatives.
  作者：Tozo FUJII、Tohru SAITO、Kyoko KIZU、Hiromi HAYASHIBARA、Yukinari KUMAZAWA、Satoshi NAKAJIMA、Tetsunori FUJISAWA

  DOI：10.1248/cpb.39.301

  日期：——

  A detailed account is given of the syntheses of 9-alkyl-2-deuterioadenines (5b-d), adenosine-2-d (5e), and 2'-deoxyadenosine-2-d (5f) from the 9-substituted adenines 1b-f through cyclization of the aminoimidazolecarbox-amidine salts 9 or the corresponding free bases 8 with formic-d acid-d or 1-(formyl-d)-2(1H)-pyridone. Glycosidic hydrolysis of 5e with boiling 0.5N aqueous HCl afforded adenine-2-d (5a) in 77% yield. Peracid oxidation of 5a-e produced the corresponding 1-N-oxides (12a-e) in fair yields. Methylation of 9-methyl- (12b) and 9-benzyladenine-2-d 1-oxide (12d) and adenosine-2-d 1-oxide (12e) with MeI in AcNMe2 gave the corresponding 1-methoxy derivatives (13b, d, e) in good yields. Dimroth rearrangements of 13b, 13d, and 13e via the free bases 14b, 14d, and 14e furnished the N6-methoxy isomers 15b, 15d, and 15e, but their isotopic purities were unsatisfactory. Unambiguous assignments of the purine-ring proton signals in the proton nuclear magnetic resonance spectra of the unlabeled adenines (1a-f, 2a-e, 3b, d, and 10e) have been made by comparison with those of the labeled species (5a-f, 12a-e, 13b, d, and 14e).

  详细描述了通过对氨基咪唑羧氨盐9或相应游离碱8与氨基甲酸-氘或1-(甲酰氘)-2(1H)-吡啶酮的环化，从9-取代腺苷1b-f合成9-烷基-2-氘腺苷（5b-d）、腺苷-2-d（5e）和2'-脱氧腺苷-2-d（5f）。用沸腾的0.5N盐酸水解5e，得到腺苷-2-d（5a），产率为77%。对5a-e进行过氧酸氧化，得到了相应的1-N-氧化物（12a-e），产率较好。用甲基碘（MeI）在二甲基乙腈（AcNMe2）中对9-甲基（12b）、9-苄腺苷-2-d 1-氧化物（12d）和腺苷-2-d 1-氧化物（12e）进行甲基化，得到了相应的1-甲氧基衍生物（13b、d、e），产率良好。通过游离碱14b、14d和14e对13b、13d和13e进行Dimroth重排，得到了N6-甲氧基异构体15b、15d和15e，但其同位素纯度不尽如人意。通过与标记物种（5a-f、12a-e、13b、d和14e）进行比较，明确分配了未标记腺苷（1a-f、2a-e、3b、d和10e）在质子核磁共振谱中的嘌呤环质子信号。
• Purines. LXIV. Syntheses of 9-Methyl-2-azaadenine 1-Oxide, Its O-Methyl Derivative, and 1-Substituted 5-Azidoimidazole-4-carboxamides.
  作者：Tohru SAITO、Yayoi ASAHI、Satoshi NAKAJIMA、Tozo FUJII

  DOI：10.1248/cpb.42.2263

  日期：——

  Diazotization of 5-amino-N'-methoxy-1-methylimidazole-4-carboxamidine (4a) with NaNO2 in 1N aqueous HCl was found to give the 1-methoxy-2-azaadenine derivative 8a·HI, which produced 5-azido-1-methylimidazole-4-carbonitrile (5a) on treatment with aqueous Na2CO3. The ribosyl analogue 5b, obtained from the riboside 4b by similar diazotization, was utilized for the synthesis of 5-azido-1-β-D-ribofuranosylimidazole-4-carboxamide (9b), a novel AICA riboside analogue. On heating in HCONMe2 at 70°C for 10min, 8a·HI yielded the 1-N-oxide 7a. Several reactions to transform the functional groups in 5a were also investigated.

  5-氨基-N'-甲氧基-1-甲基咪唑啉-4-甲脒（4a）在1N水合HCl中用NaNO2进行重氮化反应，得到1-甲氧基-2-氮杂腺嘌呤衍生物8a·HI，该物质在处理后与水合Na2CO3反应生成5-叠氮-1-甲基咪唑啉-4-氰化物（5a）。通过类似的重氮化反应从核苷4b得到的核糖类似物5b，被用于合成5-叠氮-1-β-D-呋喃核糖基咪唑啉-4-羧酰胺（9b），这是一种新颖的AICA核苷类似物。在HCONMe2中加热至70°C并保持10分钟，8a·HI生成1-N-氧化物7a。还研究了几种转化5a中功能团的反应。
• SAITO, TOHRU;ASAHI, YAYOI;NAKAJIMA, SATOSHI;FUJII, TOSO, HETEROCYCLES, 30,(1990) N, C. 329-332
  作者：SAITO, TOHRU、ASAHI, YAYOI、NAKAJIMA, SATOSHI、FUJII, TOSO

  DOI：——

  日期：——
• FUJII, TOZO;SAITO, TOHRU;KIZU, KYOKO;HAYASHIBARA, HIROMI;KUMAZAWA, YUKINA+, CHEM. AND PHARM. BULL., 39,(1991) N, C. 301-308
  作者：FUJII, TOZO、SAITO, TOHRU、KIZU, KYOKO、HAYASHIBARA, HIROMI、KUMAZAWA, YUKINA+

  DOI：——

  日期：——