11-bromoundecanenitrile | 6948-45-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 11-bromoundecanenitrile
• 英文别名: 11-Bromundecannitril
• CAS: 6948-45-4
• 化学式: C₁₁H₂₀BrN
• 分子量: 246.19
• InChiKey: LPCZYFKPSJYXDA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  13
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  11-bromoundecanenitrile 在 氢氧化钾 、 sodium amide 、 乙二醇 作用下， 生成 2,2-diphenyl-tridecanedioic acid dimethyl ester
  参考文献：
  名称：

  Salmon-Legagneur et al., Bulletin de la Societe Chimique de France, 1957, p. 1463,1467

  摘要：

  DOI：
• 作为产物：
  描述：

  10-溴癸醛 在 氨 、 碘 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 水 、 乙腈 为溶剂， 反应 4.0h， 生成 11-bromoundecanenitrile
  参考文献：
  名称：

  在无金属氰化物条件下通过 Wittig 反应从醛中一锅法制备 C1-同系化脂肪腈

  摘要：

  通过用（甲氧基甲基）三苯基鏻叶立德处理芳香族和脂肪族醛，然后用 pTsOH（Ts = 对甲苯磺酰基）水解所得甲基乙烯基醚并用分子碘处理，实现了获得 C1 同系脂肪腈的一锅法和氨水在无金属氰化物条件下。使用本方法成功地获得了新戊基型腈，这些方法不能通过将新戊醇转化为甲苯磺酸盐并用金属氰化物处理的常规方法获得。

  DOI：

  10.1002/ejoc.201700277

文献信息

• Orthocarbonsäure-ester mit 2,4,10-Trioxaadamantanstruktur als Carboxylschutzgruppe; Verwendung zur Synthese von substituierten Carbonsäuren mit Hilfe von<i>Grignard</i>-Reagenzien
  作者：Gundula Voss、Hans Gerlach

  DOI：10.1002/hlca.19830660741

  日期：1983.11.2

  Ortho Esters with 2,4,10-Trioxaadamantane Structure as Carboxyl Protecting Group; Applications in the Synthesis of Substituted Carboxylic Acids by Means of Grignard Reagents

  具有2,4,10-三氧杂金刚烷结构作为羧基保护基的邻苯二甲酸酯; 格氏试剂在取代羧酸合成中的应用。
• Rearrangement of 3-Hydroxyazetidines into 2-Oxazolines
  作者：Michele Ruggeri、Amanda W. Dombrowski、Stevan W. Djuric、Ian R. Baxendale

  DOI：10.1021/acs.joc.0c00656

  日期：2020.6.5

  A novel rearrangement sequence of 3-hydroxyazetidines via a Ritter initiated cascade provides highly substituted 2-oxazolines in high yields. The reaction conditions and substrate scope of the transformation have been studied demonstrating the generality of the process. The derived products can also be functionalized in order to undergo further intramolecular cyclization leading to a new class of macrocycle

  通过Ritter引发的级联反应的3-羟基氮杂环丁烷的新颖重排序列以高产率提供了高度取代的2-恶唑啉。研究了转化的反应条件和底物范围，证明了该方法的一般性。衍生的产物也可以被官能化，以进行进一步的分子内环化，从而产生一类新的大环。最终的环化步骤显示为适合连续流处理的转化，可显着减少反应时间并简单地按比例放大。
• Synthesis and Biological Evaluation of Bivalent Ligands for the Cannabinoid 1 Receptor
  作者：Yanan Zhang、Anne Gilliam、Rangan Maitra、M. Imad Damaj、Julianne M. Tajuba、Herbert H. Seltzman、Brian F. Thomas

  DOI：10.1021/jm1006676

  日期：2010.10.14

  (GPCRs), including the cannabinoid 1 (CB1) receptor, is now widely accepted and may have significant implications for medications development targeting these receptor complexes. A library of bivalent ligands composed of two identical CB1 antagonist pharmacophores derived from SR141716 linked by spacers of various lengths were developed. The affinities of these bivalent ligands at CB1 and CB2 receptors

  许多 G 蛋白偶联受体 (GPCR) 的二聚化或寡聚化，包括大麻素 1 (CB1) 受体，现已被广泛接受，并且可能对针对这些受体复合物的药物开发产生重大影响。开发了由两个相同的 CB1 拮抗剂药效团组成的二价配体库，这些药效团源自 SR141716，通过不同长度的间隔物连接。这些二价配体对 CB1 和 CB2 受体的亲和力使用放射性标记的结合测定法确定。使用 GTP-γ-S 积累和细胞内钙动员测定法测量它们的功能活性。结果表明，接头的性质及其长度是这些配体在 CB1 受体结合位点的最佳相互作用的关键因素。最后，选择二价配体（图 5d和7b ) 能够在啮齿动物甩尾试验中减弱大麻素激动剂 CP55,940 ( 21 )的镇痛作用。这些新型化合物可作为探针，进一步表征 CB1 受体二聚化和寡聚化及其功能意义，并可能证明可用于开发 G 蛋白偶联受体介导的疾病的新治疗方法。
• Electrical conductivity and glass formation in nitrile-functionalized pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids: chain length and odd–even effects of the alkyl spacer between the pyrrolidinium ring and the nitrile group
  作者：Jan Leys、Chandra Shekhar Pati Tripathi、Christ Glorieux、Stefan Zahn、Barbara Kirchner、Stéphane Longuemart、Kallidanthiyil Chellappan Lethesh、Peter Nockemann、Wim Dehaen、Koen Binnemans

  DOI：10.1039/c4cp00259h

  日期：——

  The electrical conductivity of a series of pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquids, functionalized with a nitrile (cyano) group at the end of an alkyl chain attached to the cation, was studied in the temperature range between 173 K and 393 K. The glass formation of the ionic liquids is influenced by the length of the alkyl spacer separating the nitrile function from the pyrrolidinium ring. The electrical conductivity and the viscosity do not show a monotonic dependence on the alkyl spacer length, but rather an odd–even effect. An explanation for this behavior is given, including the potential energy landscape picture for the glass transition.

  在 173 K 至 393 K 的温度范围内研究了一系列吡咯烷鎓双（三氟甲基磺酰基）亚胺离子液体的电导率，这些离子液体在连接到阳离子的烷基链末端用腈（氰基）基团进行功能​​化。离子液体的玻璃形成受到将腈官能团与吡咯烷鎓环分开的烷基间隔基的长度的影响。电导率和粘度并不表现出对烷基间隔基长度的单调依赖性，而是表现出奇偶效应。给出了对此行为的解释，包括玻璃化转变的势能景观图。
• Amino-substituted phenyl and heteroaryl compounds, process for their preparation and pharmaceutical compositions containing them
  申请人：AMERICAN CYANAMID COMPANY

  公开号：EP0003663A2

  公开（公告）日：1979-08-22

  The invention provides novel amino-substituted phenyl and heteroaryl compounds which show pharmaceutically useful properties, particularly as hypolipidemic and antiatherosclerotic agents, and processes for the preparation of the novel compounds. The novel compounds have the formula: Q is wherein Y is loweralkyl, loweralkoxy, hydroxy, nitro, acyloxy or halo, and m is an integer of from 0 to 4 inclusive, or a 5- or 6-membered heteroaryl ring containing 1 or more nitrogen, sulfur or oxygen atoms and which may be optionally substituted with one fluorine atom; R is hydrogen or a group convertible in vivo thereinto; Z is: wherein J is selected from the group consisting of hydroxy, loweralkoxy, loweralkoxyloweralkyloxy, diloweralkylaminoloweralkoxy, hydrogen, loweralkyl, (mono-or polyhydroxy)loweralkoxy, (mono- or polycarboxy)loweralkoxy, (mono- or polycarboxy)hydroxyloweralkoxy, allyloxy, 2,3-epoxypropoxy, substituted or unsubstituted(phen- oxy, benzyloxy and 3-pyridyloxy), pyridylmethoxy, tetra- hydropyranyloxy, (mono- or polyhydroxyl)loweralkyl- amino, (mono- or polycarboxy)loweralkylamino, (mono-or polycarboalkoxy)loweralkylamino, allylamino, propargylamino, 2-sulfoethylamino. (substituted or unsubstituted aroyl)amino, loweralkanoylamino, loweralkanesulfonylamino, (substituted or unsubstituted arene)sulfonylamino, loweralkanoylhydrazino, hydroxylamino, polymethyleneimino, (4-carboxy- or 4-carboethoxy)thiazolidino, and loweralkyl bearing one or more carboxy, carboloweralkoxy, carbamoyl, acyl, sulfinyl or sulfonyl groups, or wherein B is a saturated or unsaturated loweralkylene group and K is selected from the group consisting of hydrogen, loweralkyl, loweralkoxyethyl, diloweralkyl aminoethyl, (mono- or polyhydroxy)loweralkyl, (mono- or polycarboxy)loweralkyl, (mono- or polycarb- oxy)hydroxyloweralkyl, allyl, 2,3-epoxypropyl, substituted or unsubstituted (phenyl, benzyl or 3-pyridyl) or pyridylmethyl and tetrahydropyranyl; and wherein Q, Y, m and X are defined as follows: Formula I-A) Q is m is O; X is Sa-Ta- wherein Sa is selected from the group consisting of C3-C16 cycloalkyl or C4-C17 cycloalkenyl and is either unsubstituted or substituted with at least one C1-C13 alkyl, C4-C8 cycloalkyl, decahydronaphthyl, methylene, ethylidene, or isopropylidene group; Ta is a bond or a divalent radical selected from the group consisting of unbranched or branched C,-C,3 alkylene or alkenylene and is either unsubstituted or substituted with at least one C1-C4 alkyl group; with the proviso that the total number of carbon atoms in Sa and Ta shall not exceed twenty; and with the further proviso that when Ta is not a bond, Sa is not an unsubstituted cyclopropyl nor a cyclopropyl substituted with at least one C1-C13 alkyl; Formula I-B) Q is m is O; X is Sb- wherein Sb is a branched or unbranched mono- or polyunsaturated or cyclopropylated C3-C22 alkyl group and can be represented by the formula: wherein R2 and R3 are the same or different and are hydrogen or a saturated or unsaturated C,-Cg alkyl group: R, is a: Formula I-Ba) C2 to C21 E- or Z-alkenyl group unsubstituted or substituted with at least one loweralkyl group; Formula I-Bb) C2 to C20 alkynyl group unsubstituted or substituted with at least one methyl or ethyl group; Formula I-Bc) C. to C20 alkyl group containing at least 2 non-cumulative double bonds, said group being unsubstituted or substituted with at least one methyl or ethyl group; Formula I-Bd) C3 to C,2 allenyl group unsubstituted or substituted with at least one methyl or ethyl group; Formula I-Be) vinyl or C3 to C8 E- or Z-alkenyl group said vinyl or alkenyl group being unsubstituted or substituted with at least one methyl group, and in this Formula I-Be, R2 is a vinyl or C3 to CB E- or Z-alkenyl group unsubstituted or substituted with at least one methyl group; Formula I-Bf) allyl or C. to C8 E- or Z-alkenyl group said allyl or alkenyl group being substituted with at least one exo-(methylene, ethylidene, or isopropylidene), and either further unsubstituted or substituted with at least one methyl group; Formula I-Bg) vinyl or C3 to C8 E- or Z-alkenyl group substituted between the nitrogen and the double bond with at least one loweralkenyl, said vinyl or alkenyl group being unsubstituted or substituted with at least one methyl group; Formula I-Bh) vinyl or C3 to Cs E- or Z-alkenyl group said vinyl or alkenyl group being unsubstituted or substituted with at least one methyl and in this case, R2 is a C2 to C9 alkynyl group unsubstituted or substituted with at least one methyl group; Formula I-B,) C. to C20 alkyl group containing at least one carbon-carbon double bond and at least one carbon-carbon triple bond said group being unsubstituted or substituted with at least one loweralkyl group; or wherein Sb is a; Formula I-Bj) group of the formula wherein R4 is hydrogen or a C, to C15 alkyl group unsubstituted or substituted with at least one methyl group, R5 is hydrogen or methyl and W is a bond or a C, to C15 branched or unbranched alkylene group unsubstituted or substituted with at least one methyl group; Formula I-C) Q is m is O; X is Sc-Tc- wherein Sc is selected from the group consisting of mercapto, lowerakylthio, aralkylthio, arylthio, loweralkylsulinyl, loweralkylsulfonyl, aralkylsulfinyl, aralkylsulfonyl, arylsulfinyl, arylsulfonyl, arylamino, acylamino, loweralkylsulfonylamino, arylsulfonylamino, azido, oxo. oximino, chloro, bromo, and iodo; wherein the substituent Sc may contain q carbon atoms with q being an integer from 0 to 8. inclusive: Te is an unbranched or branched alkylene group, optionally saturated or (mono- or poly-)unsaturated and containing or not containing a cycloalkyl group, represented by the formula CnH2(n-p) with n being an integer from 7 to 18, inclusive, and p being an integer from 0 to 5, inclusive, both being selected in a manner such that the sum of n and q is greater than 6 but less than 19; provided that when Sc is halogen Tc must be a saturated alkylene group; J may not be loweralkyl bearing one or more carboxy. carboloweralkoxy, carbamoyl, acyl, sulfinyl or sulfonyl groups, and Z may not be 0 II -B-C-OK; Formula I-D) Q is m is O; X is Sd-Td- wherein Sd is selected from the group consisting of substituted or unsubstituted aryl and heteroaryl groups; Td is a saturated or unsaturated alkylene group of 1-18 carbon atoms which may be branched or unbranched; such that the total number of carbon atoms in Sd and Td shall not exceed 24; provided that J may not be hydroxyl, loweralkoxy, loweralkoxyloweralkyloxy, diloweralkylaminoloweralkoxy, or substituted or unsubstituted benzyloxy; Formula I-E) Q is m is 1 to 4 inclusive; X is a saturated or unsaturated hydrocarbon radical of 7-19 carbon atoms which may be branched or unbranched and which may contain one or more radicals selected from the group consisting of saturated or unsaturated cycloalkyl, substituted or unsubstituted aryl and substituted or unsubstituted heteroaryl; Y is loweralkyl, loweralkoxy, hydroxy, nitro, acyloxy, or halo; Formula I-F) Q is a 5- or 6-membered heteroaryl ring containing one or more nitrogen, sulfur, or oxygen atoms and optionally unsubstituted or substituted with one fluoro; X is Sf-Tf- wherein Sf is selected from the group consisting of hydrogen, C3-C8 cycloalkyl, and substituted or unsubstituted aryl; Tf is a divalent radical selected from the group consisting of branched or unbranched C6-C,g alkylene, alkenylene, and alkynylene; Formula I-G) Q is m is O; X is Sg-Tg- wherein Sg is selected from the group consisting of carboxy, loweralkoxycarbonyl, aryloxycarbonyl, heteroaryloxycarbonyl, carbamyl, mono- or diloweralkyl- carbamyl, cyano, sulfo, monoalkyl- or monoarylsulfamyl; Tg is an unbranched or branched alkylene group, optionally saturated or mono- or polyunsaturated, and containing or not containing a cycloalkyl group, represented by the formula CrH2(r-p) with r being an integer from 1 to 18, inclusive, and p being an integer from 0 to 5, inclusive; with the proviso that when Sg is a carbamyl, cyano, or sulfo group, Sg and the nitrogen atom in Formula I may not be bonded to the same carbon atom of the group Tg; Formula I-H) Q is m is O; X is a saturated or unsaturated hydrocarbon radical of 7-19 carbon atoms which may be branched or unbranched and which may contain a saturated or unsaturated cycloalkyl group, said radical containing one or more perfluorinated (-CF2 or -CF3) carbon atoms excluding the carbon adjacent to the nitrogen atom; and the pharmacologically acceptable acid-addition and cationic salts thereof.

  本发明提供了一种新型氨基取代的苯基和杂环芳基化合物，这些化合物具有药学上的有用性质，特别是作为降血脂和抗动脉硬化的药物，并且提供了这些新型化合物的制备方法。新型化合物具有如下通式： Q是 其中，Y是低级烷基、低级烷氧基、羟基、硝基、酰氧基或卤素，m是0到4之间的整数(包括0和4)，或者是一个含有1个或多个氮、硫或氧原子的5-或6-元杂环芳基环，该环可能被一个氟原子取代。R是氢或在体内可转化为氢的基团；Z是： 其中，J选自羟基、低级烷氧基、低级烷氧基低级烷氧基、二低级烷基氨基低级烷氧基、氢、低级烷基、(单或多个羟基)低级烷氧基、(单或多个羧基)低级烷氧基、(单或多个羧基)羟基低级烷氧基、烯丙氧基、2,3-环氧丙氧基、取代或未取代的苯氧基、苄氧基和3-吡啶氧基、吡啶基甲氧基、四氢吡喃氧基、(单或多个羟基)低级烷基氨基、(单或多个羧基)低级烷基氨基、(单或多个羧基烷氧基)低级烷基氨基、烯丙基氨基、炔丙基氨基、2-磺乙基氨基、(取代或未取代的芳酰基)氨基、低级烷酰氨基、低级烷磺酰氨基、(取代或未取代的芳基)磺酰氨基、低级烷酰基肼基、羟胺基、多甲基亚氨基、(4-羧基或4-羧乙氧基)四氢噻唑烷基，以及一个或多个含有羧基、羧低级烷氧基、氨基甲酰基、酰基、亚砜基或砜基的低级烷基；或者 其中，B是饱和或不饱和的低级烷基亚甲基基团，K选自氢、低级烷氧基乙基、双低级烷基氨基乙基、(单或多个羟基)低级烷基、(单或多个羧基)低级烷基、(单或多个羧基烷氧基)低级烷基、烯丙基、2,3-环氧丙基、取代或未取代的(苯基、苄基或3-吡啶基)或吡啶基甲基和四氢吡喃基；并且其中Q、Y、m和X的定义如下： 通式I-A) Q是 m是0；X是Sa-Ta-，其中Sa选自C3-C16环烷基或C4-C17环烯基，并且Sa可以是未取代的或取代有一个或多个C1-C13烷基、C4-C8环烷基、十氢萘基、亚甲基、乙烯基或异丙烯基的环；Ta是一个键或选自直链或支链C1-C3烷基亚基或烯基亚基的二价基团，并且Ta可以是未取代的或取代有一个或多个C1-C4烷基的；并且，Sa和Ta中的碳原子总数不得超过20；并且进一步规定，当Ta不为键时，Sa不是未取代的环丙基，也不是取代有一个或多个C1-C13烷基的环丙基； 通式I-B) Q是 m是0；X是Sb-，其中Sb是直链或支链的单或多不饱和或环丙烷化的C3-C22烷基基团，并且可以用如下通式表示： 其中，R2和R3是相同的或不同的，它们是氢或饱和或不饱和的C1-C8烷基基团；R1是： 通式I-Ba) C2到C21 E或Z-烯基基团，未取代或取代有一个或多个低级烷基的； 通式I-Bb) C2到C20炔基基团，未取代或取代有一个或多个甲基或乙基的； 通式I-Bc) C1到C20烷基基团，含有至少2个非累积性双键，该基团未取代或取代有一个或多个甲基或乙基的； 通式I-Bd) C3到C12炔烯基基团，未取代或取代有一个或多个甲基或乙基的； 通式I-Be) 氯乙烯或C3到C8 E或Z-烯基基团，所述氯乙烯或烯基基团未取代或取代有一个或多个甲基，此时在通式I-Be中，R2是氯乙烯或C3到C8 E或Z-烯基基团，未取代或取代有一个或多个甲基的； 通式I-Bf) 烯丙基或C3到C8 E或Z-烯基基团，所述烯丙基或烯基基团在氮和双键之间被至少一个外位(甲基、乙烯基、或异丙烯基)取代，并且进一步未取代或取代有一个或多个甲基的； 通式I-Bg) 氯乙烯或C3到C8 E或Z-烯基基团，所述氯乙烯或烯基基团在氮和双键之间被至少一个低级烯基取代，所述氯乙烯或烯基基团未取代或取代有一个或多个甲基的； 通式I-Bh) 氯乙烯或C3到C8 E或Z-烯基基团，所述氯乙烯或烯基基团未取代或取代有一个或多个甲基，并且此时R2是C2到C9炔基基团，未取代或取代有一个或多个甲基的； 通式I-Bi) C1到C20烷基基团，含有至少一个碳-碳双键和至少一个碳-碳三键，所述基团未取代或取代有一个或多个低级烷基的； 或者，Sb是： 通式I-Bj) 其中，R4是氢或C1到C15烷基基团，未取代或取代有一个或多个甲基的；R5是氢或甲基；W是键或C1到C15直链或支链烷基亚甲基基团，未取代或取代有一个或多个甲基的； 通式I-C) Q是 m是0；X是Sc-Tc-，其中Sc选自巯基、低级烷基巯基、芳烷基巯基、芳基巯基、低级烷基亚砜基、低级烷基砜基、芳烷基亚砜基、芳烷基砜基、芳基亚砜基、芳基砜基、芳基氨基、酰基氨基、低级烷基砜基氨基、芳基砜基氨基、叠氮基、氧基、氧亚氨基、氯、溴和碘；其中，取代基Sc可能含有的碳原子数q是0到8之间的整数；Tc是直链或支链的烷基亚甲基基团，可以是饱和的或单或双不饱和的，并且可能含有或不含环烷基基团，用通式CnH2(n-p)表示，其中n是从7到18的整数，p是从0到5的整数，两个选择使得n和q的和大于6但小于19；并且规定，当Sc是卤素时，Tc必须是饱和的烷基亚甲基基团；并且J不能是含有一个或多个羧基、羧低级烷氧基、氨基甲酰基、酰基、亚砜基或砜基的低级烷基基团，Z不能是0—N—B—O—K； 通式I-D) Q是 m是0；X是Sd-Td-，其中Sd选自取代或未取代的芳基和杂环芳基基团；Td是含有1到18个碳原子的饱和或不饱和烷基亚甲基基团，可以是支链的或直链的；并且Sd和Td中的碳原子总数不得超过24；并且规定，J不能是羟基、低级烷氧基、低级烷氧基低级烷氧基、双低级烷基氨基低级烷氧基，或取代或未取代的苄氧基； 通式I-E) Q是 m是1到4之间的整数(包括1和4)；X是含有7到19个碳原子的饱和或不饱和的碳氢化合物基团，可以是支链的或直链的，并且可能含有一个或多个选自饱和或不饱和环烷基、取代或未取代的芳基和取代或未取代的杂环芳基的基团；Y是低级烷基、低级烷氧基、羟基、硝基、酰氧基或卤素； 通式I-F) Q是含有一个或多个氮、硫或氧原子的5-或6-元杂环芳基环，并且可能未取代或取代有一个氟原子；X是Sf-Tf-，其中Sf选自氢、C3-C8环烷基，以及取代或未取代的芳基；Tf是直链或支链C6-C8烷基亚基、烯基亚基或炔基亚基； 通式I-G) Q是 m是0；X是Sg-Tg-，其中Sg选自羧基、低级烷氧基羰基、芳氧基羰基、杂环芳氧基羰基、氨基甲酰基、单或双低级烷基氨基甲酰基、氰基、亚砜基、单烷基或单芳基磺酰氨基；Tg是直链或支链烷基亚甲基基团，可以是饱和的或单或双不饱和的，并且可能含有或不含环烷基基团，用通式CrH2(r-p)表示，其中r是从1到18的整数，p是从0到5的整数；并且规定，当Sg是氨基甲酰基、氰基或亚砜基时，Sg和通式I中的氮原子可能不与Tg上的同一碳原子键合； 通式I-H) Q是 m是0；X是含有7到19个碳原子的饱和或不饱和的碳氢化合物基团，可以是支链的或直链的，并且可能含有一个饱和或不饱和的环烷基基团，所述基团含有一个或多个全氟化的(-CF2或-CF3)碳原子，不包括与氮原子相邻的碳原子；以及其药理学上可接受的酸加成盐和阳离子盐。