3,4-二氯苯甲酸酐 | 86866-14-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 3,4-二氯苯甲酸酐
• 中文别名: (2-溴乙氧基)-特丁基二甲基硅烷；3-溴乙氧基叔丁基二甲基硅烷
• 英文名称: 3,4-dichlorobenzoic anhydride
• 英文别名: (3,4-dichlorobenzoyl) 3,4-dichlorobenzoate
• CAS: 86866-14-0
• 化学式: C₁₄H₆Cl₄O₃
• 分子量: 364.012
• InChiKey: JKRVKAAJSJWYFT-UHFFFAOYSA-N

物化性质

• 熔点：
  148-150℃
• 沸点：
  499.0±45.0 °C(Predicted)
• 密度：
  1.551

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

安全信息

• 海关编码：
  2916399090

反应信息

• 作为反应物：
  描述：

  3,4-二氯苯甲酸酐 在 N-甲基吡咯烷酮 、 sodium hydroxide 、 三乙胺 作用下， 反应 9.0h， 生成 N^α-(4-amino-4-deoxypteroyl)-N^δ-(3,4-dichlorobenzoyl)-L-ornithine
  参考文献：
  名称：

  Methotrexate analogs. 33. N.delta.-Acyl-N.alpha.-(4-amino-4-deoxypteroyl)-L-ornithine derivatives. Synthesis and in vitro antitumor activity

  摘要：

  N delta-Acyl derivatives of the potent folylpolyglutamate synthetase (FPGS) inhibitor N alpha-(4-amino-4-deoxypteroyl)-L-ornithine (APA-L-Orn) were synthesized from N alpha-(4-amino-4-deoxy-N10-formylpteroyl)-L-ornithine by reaction with an N-(acyloxy)succinimide or acyl anhydride, followed by deformylation with base. The N delta-hemiphthaloyl derivative was also prepared from 4-amino-4-deoxy-N10-formylpteroic acid by reaction with persilylated N delta-phthaloyl-L-ornithine, followed by simultaneous deformylation and ring opening of the N delta-phthaloyl moiety with base. The products were potent inhibitors of purified dihydrofolate reductase (DHFR) from L1210 murine leukemia cells, with IC50's ranging from 0.027 and 0.052 microM as compared with 0.072 microM for APA-L-Orn. Several of the N delta-acyl-N10-formyl intermediates also proved to be good DHFR inhibitors. One of them, N alpha-(4-amino-4-deoxy-N10-formylpteroyl)-N delta-(4-chlorobenzoyl)-L- ornithine, had a 2-fold lower IC50 than its deformylated product, confirming that the N10-formyl group is well tolerated for DHFR binding. While N delta-acylation of APA-L-Orn did not significantly alter anti-DHFR activity, inhibition of FPGS was dramatically diminished, supporting the view that the basic NH2 on the end of the APA-L-Orn side chain is essential for the activity of this compound against FPGS. N delta-Acylation of APA-L-Orn markedly enhanced toxicity to cultured tumor cells. However, N delta-acyl derivatives also containing an N10-formyl substituent were less cytotoxic than the corresponding N10-unsubstituted analogues even though their anti-DHFR activity was the same, suggesting that N10-formylation may be unfavorable for transport. Two compounds, the N delta-benzoyl and N delta-hemiphthaloyl derivatives of APA-L-Orn, with IC50's against L1210 cells of 0.89 and 0.75 nM, respectively, were more potent than either methotrexate (MTX) or aminopterin (AMT) in this system. These compounds were also more potent than MTX against CEM human lymphoblasts and two human head and neck squamous cell carcinoma cell lines (SCC15, SCC25) in culture. Moreover, in assays against SCC15/R1 and SCC25/R1 sublines with 10-20-fold MTX resistance, the N delta-hemiphthaloyl derivative of APA-L-Orn showed potency exceeding that of MTX itself against the parental cells.(ABSTRACT TRUNCATED AT 400 WORDS)

  DOI：

  10.1021/jm00402a013
• 作为产物：
  描述：

  3,4-二氯苯甲酸 在 trichloroisocyanuric acid 、 三苯基膦 、 potassium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 2.17h， 生成 3,4-二氯苯甲酸酐
  参考文献：
  名称：

  使用新制备的功能强大且高效的混合试剂轻松直接合成对称酸酐

  摘要：

  已经制备了用于从羧酸直接合成对称羧酸酐的有效混合试剂。在室温下，在温和的反应条件下，使用三苯膦/三氯异氰尿酸将羧酸转化为酸酐。该方法的主要优点是反应时间短，产物收率高，成本低，试剂的可获得性，实验步骤简单和产物后处理容易。

  DOI：

  10.1515/chempap-2015-0042

文献信息

• Construction of Functionalized Carbocycles Having Contiguous Tertiary Carbinol and All-Carbon Stereogenic Centers
  作者：Chennakesava Reddy、Srinivasarao Arulananda Babu、Nayyar Ahmad Aslam、Vadla Rajkumar

  DOI：10.1002/ejoc.201201382

  日期：2013.4

  A highly stereoselective protocol is reported for customizing functionalized carbocyclic building blocks (β-hydroxy esters) and bicyclic lactones with a stereoarray that contains contiguous tertiary carbinol and all-carbon stereocenters. The efficient asymmetric induction and diastereofacial selective addition of allyl and propargyl indiums to hindered α,α-disubstituted cycloalkanones is presented

  报告了一种高度立体选择性的协议，用于定制功能化碳环结构单元（β-羟基酯）和双环内酯，其立体阵列包含连续的叔甲醇和全碳立体中心。介绍了烯丙基和炔丙基铟与受阻 α,α-二取代环烷酮的有效不对称诱导和非对映选择性加成。代表性产物的立体化学是从单晶 X 射线晶体结构分析中明确建立的，并提出了一种合理的反应途径来支持高非对映面选择性。
• P^III -Chelation-Assisted Indole C7-Arylation, Olefination, Methylation, and Acylation with Carboxylic Acids/Anhydrides by Rhodium Catalysis
  作者：Xiaodong Qiu、Panpan Wang、Dingyi Wang、Minyan Wang、Yu Yuan、Zhuangzhi Shi

  DOI：10.1002/anie.201813182

  日期：2019.1.28

  olefination, and methylation of indoles with carboxylic acids or anhydrides by C−H and C−C bond activation have been developed. Furthermore, C7‐acylation products can also be generated selectively at a lower reaction temperature in the developed system. The key to the high reactivity and regioselectivity of this transformation is the appropriate choice of an indole N‐PtBu2 chelation‐assisted group

  已开发出通过CH和C-C键活化铑催化的C7-选择性脱羰芳基化，吲哚与羧酸或酸酐的吲哚甲基化反应。此外，在开发的系统中，还可以在较低的反应温度下选择性生成C7酰化产物。这一转变的高反应性和区域选择性的关键是吲哚的适当选择Ñ -P吨卜2螯合辅助基团。该方法具有许多优点，包括易于接近和除去导向基团，使用便宜且可广泛获得的偶联剂，不需要外部配体或氧化剂，广泛的底物范围，高效率以及形成唯一的区域异构体。
• Heteroaryl substituted bis-trifluoromethyl carbinols as malonyl-CoA decarboxylase inhibitors
  作者：Jie-Fei Cheng、Chi Ching Mak、Yujin Huang、Richard Penuliar、Masahiro Nishimoto、Lin Zhang、Mi Chen、David Wallace、Thomas Arrhenius、Donald Chu、Guang Yang、Miguel Barbosa、Rick Barr、Jason R.B. Dyck、Gary D. Lopaschuk、Alex M. Nadzan

  DOI：10.1016/j.bmcl.2006.03.100

  日期：2006.7

  A series of heteroaryl-substituted bis-trifluoromethyl carbinols were prepared and evaluated as malonyl-CoA decarboxylase (MCD) inhibitors. Some thiazole-based derivatives showed potent in vitro MCD inhibitory activities and significantly increased glucose oxidation rates in isolated working rat hearts. (c) 2006 Elsevier Ltd. All rights reserved.
• Synthesis of 2,4-disubstituted thiazoles and selenazoles as potential antifilarial and antitumor agents. 2. 2-Arylamido and 2-alkylamido derivatives of 2-amino-4-(isothiocyanatomethyl)thiazole and 2-amino-4-(isothiocyanatomethyl)selenazole
  作者：Yatendra Kumar、Rachel Green、Dean S. Wise、Linda L. Wotring、Leroy B. Townsend

  DOI：10.1021/jm00076a013

  日期：1993.11

  The synthesis of a series of 2-arylamido and 2-alkylamido derivatives of 2-amino-4-(isothio-cyanatomethyl)thiazole and 2-amino-4-(isothiocyanatomethyl)selenazo is described. In vitro antiproliferative evaluations were carried out using L1210 cells. The 2-(alkylamido)thiazole derivatives were moderately antiproliferative, with IC50's of 4-8 mu M. A significant increase in activity was obtained for the arylamido derivatives, with IC50's of 0.2-1 mu M. The results obtained for the selenazoles were similar to those for the thiazoles. 2-Benzamido-4-(isothiocyanatomethyl)thiazole (19) was found to be a potent inhibitor of GMP synthetase. None of the compounds prepared in this study demonstrated antifilarial activity.
• ROSOWSKY, ANDRE;BADER, HENRY;CUCCHI, CAROL A.;MORAN, RICHARD G.;KOHLER, W+, J. MED. CHEM., 31,(1988) N 7, 1332-1337
  作者：ROSOWSKY, ANDRE、BADER, HENRY、CUCCHI, CAROL A.、MORAN, RICHARD G.、KOHLER, W+

  DOI：——

  日期：——