磷酸单丁酯 | 1623-15-0

• 物质功能分类: 化学试剂 - 有机试剂 - 酯类
• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 中文名称: 磷酸单丁酯
• 中文别名: 磷酸二氢丁酯
• 英文名称: n-butyl phosphoric acid
• 英文别名: Phosphorsaeure-monobutylester；n-Butylphosphat；Butylphosphat；monobutyl phosphate；Phosphorsaeure-mono-n-butylester；phosphoric acid monobutyl ester；Phosphorsaeure-n-butylester；n-Butyl-dihydrogenphosphat；monobutylphosphoric acid；NSC 41911；Butyl dihydrogen phosphate
• CAS: 1623-15-0
• 化学式: C₄H₁₁O₄P
• mdl: MFCD00013947
• 分子量: 154.103
• InChiKey: BNMJSBUIDQYHIN-UHFFFAOYSA-N

物化性质

• 沸点：
  272.5±23.0 °C(Predicted)
• 密度：
  1.283±0.06 g/cm3(Predicted)
• 溶解度：
  DMSO（微溶）、乙酸乙酯（微溶）、甲醇（微溶）
• 物理描述：
  Butyl acid phosphate appears as a colorless liquid. Insoluble in water. Corrosive to metals and tissues.

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.8
• 氢给体数：
  2
• 氢受体数：
  4

安全信息

• 危险等级：
  8
• 包装等级：
  III
• 危险类别：
  8
• 危险品运输编号：
  UN 1718

反应信息

• 作为反应物：
  描述：

  磷酸单丁酯 在 Methanothermobacter thermautotrophicus str. Delta H isopentenyl phosphate kinase 、 5’-三磷酸腺苷 、 2-巯基乙醇 、 magnesium chloride 、 bovine serum albumin 作用下， 生成 n-Butyldiphosphat
  参考文献：
  名称：

  Characterization of Thermophilic Archaeal Isopentenyl Phosphate Kinases

  摘要：

  Archaea synthesize isopentenyl diphosphate (IPP) and dimethylallyl diphosphate (DMAPP), the essential building blocks of isoprenoid compounds, from mevalonate (MVA). However, an analysis of the genomes of several members of the Archaea failed to identify genes for the enzymes required to convert phosphomevalonate (PM) to IPP In eukaryotes. The recent discovery of an isopentenyl kinase (IPK) in Methanocaldococcus jannaschii (MJ) Suggests a new variation of the MVA pathway where PM is decarboxylated to give isopentenyl phosphate (IP), which is phosphorylated to produce IPP. A blast search using the MJ protein as a probe revealed a subfamily of amino acid kinases that include the fosfomycin resistance protein fomA, which deactivates the antibiotic by phosphorylation of its phosphonate residue in a reaction similar to the conversion of IP to IPP. IPK genes were cloned from two organisms identified in the search, Methanothermobacter thermautotrophicus (MTH) and Thermoplasma acidophilum (THA), and the His-tagged recombinant proteins were purified by Ni-NTA chromatography. The enzymes catalyze the reversible phosphorylation of IP by ATP, K-cq = 6.3 +/- 1. The catalytic efficiencies (V/K) of the proteins were similar to 2 x 10(6) M-1 s(-1). In the reverse direction, ADP wits a substrate inhibitor for THA IPK, K-i(ADP) = 58 +/- 6 mu M, but not for MTH IPK. Both enzymes were active over a broad range of pH and temperature. Five compounds, dimethylallyl phosphate, isopentenyl thiolophosphate, 1-butyl phosphate, 3-buten-1-yl phosphate, and geranyl phosphate, were evaluated as alternative substrates for the MTH and THA IP kinases. All of the compounds were phosphorylated, although the catalytic efficiency was low for geranyl phosphate.

  DOI：

  10.1021/bi9017957
• 作为产物：
  描述：

  n-Butyl-dibenzyl-phosphat 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 20.0 ℃ 、344.74 kPa 条件下， 反应 8.0h， 以86%的产率得到磷酸单丁酯
  参考文献：
  名称：

  Fatty Alcohol Phosphates are Subtype-Selective Agonists and Antagonists of Lysophosphatidic Acid Receptors

  摘要：

  对溶血磷脂酸（LPA）的生理和病理作用进行更全面的理解，需要针对不同受体亚型的激动剂和拮抗剂。本文报道了含有4至22个碳的饱和碳氢链的脂肪醇磷酸盐（FAP）的合成和药理学特性。选择FAP作为主要结构是基于计算模型，该模型以满足先前为LPA与其受体相互作用而开发的两点药效团的最小结构为基础。癸基和十二烷基FAP（FAP-10和FAP-12）分别是LPA2的特异性激动剂（EC50分别为3.7±0.2μM和700±22nM），同时也是LPA3的选择性拮抗剂（FAP-12的K i为90nM），而FAP-12对LPA1是弱的拮抗剂。FAP既不能激活LPA1也不能激活LPA3受体；相反，LPA2被含10至14个碳链的FAP激活。通过计算模拟，将每个化合物对接在LPA结合位点，来评估单个FAP（8至18）与LPA2的相互作用。FAP-12显示最低的对接能，与其较低的观察EC50一致。FAP的抑制效应显示出强烈的碳氢链长度依赖性，在非洲爪蟾卵母细胞和表达LPA3的RH7777细胞中，C12是最适长度。FAP-12未激活或干扰包括S1P1,2,3,5受体介导的S1P反应在内的几个其他G蛋白偶联受体。这些数据表明FAP是LPA受体的配体，且FAP-10和FAP-12是首批针对LPA2受体亚型的特异性激动剂。

  DOI：

  10.1124/mol.63.5.1032
• 作为试剂：
  描述：

  苯胺 、 碳酸二甲酯 在 磷酸单丁酯 、 磷酸二丁酯 作用下， 以 二氯甲烷 为溶剂， 反应 96.0h， 以14%的产率得到N-苯基香豆甲酯
  参考文献：
  名称：

  氨基甲酸酯部分的仿生堆积：羧基磷酸酯类似物在由磷酸促进的芳基胺和有机碳酸酯合成N-芳基氨基甲酸酯的过程中的中介作用

  摘要：

  在有机磷酸[Ph 2 P（O）OH（1）;的存在下，芳族胺与碳酸二甲酯（DMC）或碳酸二苯酯（DPC）的反应。（PhO）2 P（O）OH（2）; （BuO）2 P（O）OH /（BuO）P（O）（OH）2等摩尔混合物（3）]产生具有高选择性的氨基甲酸酯ArNHC（O）OR（R = Me，Ph）。对P-酸所起的催化作用已进行了研究，并根据涉及中间形成碳-次膦酸（磷）酸酐X 2的反应机理进行了合理化研究。P（O）OC（O）OR（X = Ph，PhO; R = Me，Ph）。所提出的机制与通过氨基甲酰磷酸合成酶（CPS）酶在生物系统中形成氨基甲酸酯阴离子的机制具有相似的趣味。

  DOI：

  10.1016/0040-4020(95)00424-7

文献信息

• Regioselective Phosphorylation of Carbohydrates and Various Alcohols by Bacterial Acid Phosphatases; Probing the Substrate Specificity of the Enzyme fromShigella flexneri
  作者：Teunie van Herk、Aloysius F. Hartog、Alida M. van der Burg、Ron Wever

  DOI：10.1002/adsc.200505072

  日期：2005.6

  broad range of carbohydrates and alcohols. Many cyclic carbohydrates are phosphorylated in a regioselective manner. Non-cyclic carbohydrates are phosphorylated as well. Phosphorylation of linear alcohols, cyclic and aromatic alcohols is also possible. In all cases the acid phosphatase from Shigella prefers a primary alcohol function above a secondary one. We conclude that these enzymes are an attractive

  细菌非特异性酸性磷酸酶通常催化多种底物的去磷酸化。如前所述，来自弗氏志贺氏菌和肠炎沙门氏菌的酶也能够使用廉价的焦磷酸盐作为磷酸盐供体，催化将肌苷磷酸化为肌苷单磷酸和将D-葡萄糖磷酸化为D-葡萄糖6-磷酸（D-G6P）。经过优化后，在后一反应中可实现高收率（95％），我们在此表明​​可以以制备方式使用这些酶。这促使我们使用31P NMR和HPLC还可以使多种碳水化合物和醇类进行磷酸化。许多环状碳水化合物以区域选择性方式被磷酸化。非环状碳水化合物也被磷酸化。直链醇，环状和芳族醇的磷酸化也是可能的。在所有情况下，志贺氏菌的酸性磷酸酶都比伯醇更喜欢伯醇功能。我们得出结论，在广泛范围的化合物磷酸化中，这些酶是现有化学和酶促方法的一种有吸引力的替代物。
• SYNTHESIS OF MONO-AND DIALKYLPHOSPHATES BY THE REACTIONS OF HYDROXYCOMPOUNDS WITH THE PHOSPHORUS PENTAOXIDE UNDER MICROWAVE IRRADIATION
  作者：Abdelhamid Elias、M. Amine Didi、Didier Villemin、T. Semaoune、S. Ouattas

  DOI：10.1080/10426500490494705

  日期：2004.12.1

  The reactions of phosphorus pentoxide with two alcohols and one phenol were performed in different conditions under microwave irradiation. The products (alkylphosphates and dialkylphosphates) were identical to those formed by classic heating and were obtained with better yields. The speed of the reaction was increased by a factor from 100 to 4000.

  五氧化二磷与两种醇和一种酚的反应在不同条件下在微波辐射下进行。产物（烷基磷酸酯和二烷基磷酸酯）与通过经典加热形成的产物相同，并且以更高的产率获得。反应速度从 100 倍增加到 4000 倍。
• Determination of Phosphoric Acid Mono- and Diesters in Municipal Wastewater by Solid-Phase Extraction and Ion-Pair Liquid Chromatography−Tandem Mass Spectrometry
  作者：José Benito Quintana、Rosario Rodil、Thorsten Reemtsma

  DOI：10.1021/ac0517186

  日期：2006.3.1

  The first analytical method for the determination of 13 phosphoric acid mono- and diesters from aqueous samples is presented. The method consists of solid-phase extraction (SPE) and ion-pair liquid chromatographic separation with tri-n-butylamine coupled to electrospray ionization tandem mass spectrometry in the negative ion mode. Due to a lack of pure standards, only 3 of the 13 esters could be quantified. SPE recoveries ranged from 71 to 112% for di-n-butyl phosphate, diphenyl phosphate, and di-(2-ethylhexyl) phosphate (DEHP) with limits of quantification from 7 to 14 ng/L for 100-mL samples. At analyte concentrations ≥1 μg/L, aqueous samples can be analyzed by direct injection without extraction. In municipal wastewater, six diesters and one monoester were unambiguously identified by comparison with synthesized reference material. DEHP showed highest concentrations of 60 and 5 μg/L in raw and treated wastewater, respectively. The detection of monoethylhexyl phosphate was confirmed by LC−Q-TOF-MS analysis, and it was found at a concentration level comparable to DEHP. Laboratory degradation tests show that phosphoric acid diesters can be formed as intermediates in the microbial degradation of trialkyl phosphates that are being used as flame retardants and plasticizers.

  本文介绍了用于测定水样中13种磷酸单酯和双酯的首次分析方法。该方法包括固相萃取（SPE）和离子对液相色谱分离，配合三丁胺与电喷雾电离串联质谱（负离子模式）。由于缺乏纯标准品，仅能定量其中的3种酯。SPE回收率对于二丁基磷酸酯、二苯基磷酸酯和二（2-乙基己基）磷酸酯（DEHP）分别为71至112%，定量限为100毫升样品中的7至14纳克/升。当分析物浓度≥1微克/升时，水样可直接注入分析而不需萃取。通过与合成参考物质的比对，在市政污水中明确鉴定出了6种双酯和1种单酯。DEHP在原污水和处理后的污水中最高浓度分别为60和5微克/升。通过LC−Q-TOF-MS分析确认了单乙基己基磷酸酯的存在，其浓度水平与DEHP相当。实验室降解试验表明，磷酸双酯可作为三烷基磷酸盐微生物降解过程中的中间产物，这些三烷基磷酸盐被用作阻燃剂和增塑剂。
• Preparation and structure of n-alkyl ester derivatives of zirconium bis (monohydrogen orthophosphate) dihydrate with a layer structure
  作者：Shoji Yamanaka、Makoto Matsunaga、Makoto Hattori

  DOI：10.1016/0022-1902(81)80040-1

  日期：1981.1

  Zirconium bis (monohydrogen orthophosphate) dihydrate with a layer structure, called γ-zirconium phosphate, has been heated with phosphoric acid esters of n-alkyl alcohols [n-CnH2n+1OPO3H2 (n = 1 ∼ 18)] under reflux in a mixture of water and acetone. Half of the interlayer monohydrogen orthophosphate groups are exchanged with a phosphate esters. Only monoesters are involved in the exchange even though

  具有层状结构的双（正磷酸一氢）锆二水合物，称为γ-磷酸锆，已与正烷基醇[ n -C n H 2 n +1 OPO 3 H 2（n = 1〜18）的磷酸酯一起加热）]在水和丙酮的混合物中回流。一半的层间正磷酸单氢基团被磷酸酯交换。即使单酯和二酯的混合物用于回流，也只有单酯参与交换。X射线和电子显微镜检查表明，在反应过程中，γ-磷酸锆的层构架没有变化，而基间距（d001）随着磷酸酯烷基链中碳原子数（n）的增加而增加。的情节d 001 VS Ñ由两个线性关系的斜率，其中对于2.43和1.42埃/碳原子的Ñ ⩽4和Ñ分别⩾5。当所获得的化合物溶胀具有Ñ具有烷基链的那些交换磷酸酯类中的相同长度的烷基醇，所述基面间距的增加而线性与单斜率2.43埃/碳原子。斜率的变化归因于磷酸盐层之间烷基链的排列的变化，并且与聚乙烯晶体的结构进行了讨论。
• Zirconium Arene-Phosphonates:  Chemical and Structural Characterization of 2-Naphthyl- and 2-Anthracenylphosphonate Systems
  作者：Jay C. Amicangelo、Willem R. Leenstra

  DOI：10.1021/ic0400282

  日期：2005.3.21

  Several new zirconium phosphonates incorporating naphthalene and anthracene ring systems and having the general formula Zr(O3PR)1(O3PR')1 [R and R' = -C10H7, -C14H9, -OC4H9, and -OC2H5] have been synthesized. These compounds were chemically characterized using thermal gravimetric analysis (percentage of organic content), infrared spectroscopy (presence of the desired organic functional groups), and

  已经合成了几种新的引入萘和蒽环系统并具有通式Zr（O3PR）1（O3PR'）1 [R和R'= -C10H7，-C14H9，-OC4H9和-OC2H5]的膦酸锆。使用热重分析（有机物含量百分比），红外光谱法（存在所需的有机官能团）和固态31P NMR（磷环境）对这些化合物进行化学表征，而结构参数使用X射线粉末测定衍射（层间d间距）。双（膦酸酯）锆的d间距与基于有机官能团有效长度的简单预测模型相关性很好。