CN111187185B - 一种合成烯丙基叠氮衍生物的方法 - Google Patents
一种合成烯丙基叠氮衍生物的方法 Download PDFInfo
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- VYZOFUACMOJPRL-UHFFFAOYSA-N 3-azidoprop-1-ene Chemical class C=CCN=[N+]=[N-] VYZOFUACMOJPRL-UHFFFAOYSA-N 0.000 title claims abstract description 23
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- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
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- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
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- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 claims abstract description 3
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- 238000006243 chemical reaction Methods 0.000 claims description 35
- 229960002089 ferrous chloride Drugs 0.000 claims description 23
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical group Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 23
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- 238000003786 synthesis reaction Methods 0.000 claims description 11
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
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- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 claims 4
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 3
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 claims 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 claims 1
- 125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims 1
- 125000006281 4-bromobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Br)C([H])([H])* 0.000 claims 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 claims 1
- 125000004176 4-fluorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1F)C([H])([H])* 0.000 claims 1
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- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 80
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- 239000000203 mixture Substances 0.000 description 21
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 20
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 239000003208 petroleum Substances 0.000 description 20
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- 239000012265 solid product Substances 0.000 description 16
- 238000004587 chromatography analysis Methods 0.000 description 9
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- 238000004440 column chromatography Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
- 150000001361 allenes Chemical group 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- 150000001540 azides Chemical class 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 238000005937 allylation reaction Methods 0.000 description 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
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- 229940046149 ferrous bromide Drugs 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- RZXMPPFPUUCRFN-UHFFFAOYSA-N para-methylaniline Natural products CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C247/00—Compounds containing azido groups
- C07C247/02—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton
- C07C247/08—Compounds containing azido groups with azido groups bound to acyclic carbon atoms of a carbon skeleton being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
Abstract
本发明公开了一种合成烯丙基叠氮衍生物的方法,在有机溶剂中,采用铁试剂诱导结构如式(Ⅰ)所示的联烯胺化合物与结构如式(Ⅱ)所示的叠氮基三甲基硅烷进行反应,合成得结构如式(Ⅲ)所示的烯丙基叠氮衍生物;其中,取代基R1为芳基、苄基、烷基;取代基R2为对甲苯磺酰基、乙酰基、甲磺酰基。
Description
技术领域
本发明涉及有机化学技术领域,具体涉及一种合成烯丙基叠氮衍生物的方法。
背景技术
有机叠氮衍生物作为含有叠氮官能团的一类化合物,被广泛应用于有机合成中,如通过click反应构建三唑类衍生物。另外,含有叠氮官能团的化合物表现出很好的生物活性,如抗HIV、抗炎、抗菌及抗骨髓瘤等活性。相对于一般的叠氮化合物,烯丙基叠氮化合物表现出更特殊的反应活性。例如,它被作为胺类、氰化物及烯丙基三唑等化合物的合成前体。由于其具有很好的应用价值,因此近年来发展了许多合成方法。
传统的合成烯丙基叠氮的方法是通过烯丙基取代化合物与叠氮类化合物,如烯丙基醇、烯丙基卤代烃、烯丙基酯、烯丙基硅醚等与叠氮化钠或三甲基硅基叠氮反应。但是该方法存在的缺陷是需要预合成一系列烯丙基化合物,增加了合成目标产物的步骤,无形中增加了反应的成本,不符合绿色化学的发展方向。Bugarin课题组最近报道了非金属诱导的末端联烯与叠氮的分子间串联反应构建烯丙基叠氮衍生物,该方法存在的不足是反应产率偏低,且底物为易爆的叠氮化钠,不利于大规模生产应用。Toast and Munoz课题组报道了利用金催化联烯与三甲基硅基叠氮的分子间串联反应构建烯丙基叠氮衍生物的反应,该反应作为构建烯丙基叠氮的新方法具有十分重要的意义,但是由于联烯具有不同的反应位点,导致该反应的区域选择性不好。
因此,发展一种经济适用、温和高效的制备烯丙基叠氮衍生物的方法具有十分重要的意义。
发明内容
为解决现有技术中存在的问题,本发明提供了一种合成烯丙基叠氮衍生物的方法,解决了上述背景技术中提到的问题。
为实现上述目的,本发明提供如下技术方案:一种合成烯丙基叠氮衍生物的方法,包括以下步骤:在有机溶剂中,采用铁试剂诱导结构如式(Ⅰ)所示的联烯胺化合物与结构如式(Ⅱ)所示的叠氮基三甲基硅烷进行反应,合成得结构如式(Ⅲ)所示的烯丙基叠氮衍生物;反应式如下所示:
其中,取代基R1为芳基、苄基、烷基;
取代基R2为对甲苯磺酰基、乙酰基、甲磺酰基。
在该反应中,铁试剂诱导联烯胺化合物与叠氮基三甲基硅烷的反应为选择性烯丙基化反应,以实现烯丙基叠氮衍生物的合成。
优选的,所述的联烯胺化合物为苯胺联烯、对氟苯胺联烯、对甲基苯胺联烯、对甲氧基苯胺联烯、对氯苯胺联烯、对溴苯胺联烯、间溴苯胺联烯、间甲氧基苯胺联烯、均三甲基苯胺联烯、3,5-二甲氧基苯胺联烯、苄胺联烯、对氯苄胺联烯、对氟苄胺联烯、对甲基苄胺联烯、对溴苄胺联烯、1-苯基丙胺联烯、苯酰胺联烯、甲磺酰胺联烯、恶唑烷-2-酮联烯或2-萘胺联烯。
优选的,所述的铁试剂是氯化亚铁、溴化亚铁、乙酰丙酮铁、1,1'-双(二苯基膦)二茂铁中的一种。
优选的,所述的铁试剂是氯化亚铁。
优选的,所述的有机溶剂是二氯甲烷、1,2-二氯乙烷、氯仿、甲苯、1,4二氧六环、乙腈中的一种。
优选的,所述的有机溶剂是二氯甲烷。
优选的,所述的联烯胺化合物、铁试剂、叠氮基三甲基硅烷的摩尔比为1:0.15-0.25:1.2-1.8。
优选的,所述的联烯胺化合物、铁试剂、叠氮基三甲基硅烷的摩尔比为1:0.2:1.5。
优选的,所述的反应温度为38-42℃,所述反应时间为22-48小时。
优选的,所述的反应温度为40℃,所述反应时间为35小时。
本发明的有益效果是:本发明的方法反应条件温和,所用原料廉价易得,反应速度快,底物适应性宽,合成步骤简单,使用本发明方法合成烯丙基叠氮衍生物,其产率可达到35%以上,最高达到99%,产率优异,适用于推广应用。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
在25mL的反应管中加入苯胺联烯(28.5mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流26小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得黄色固体产物(30.9mg,产率为95%)。
所制得化合物结构式如下所示:
m p 81.4-82.3℃;IR(neat)3610,2932,2108,1661,1587,1489,1409,743cm-1;1HNMR(400MHz,CDCl3)δ7.55(d,J=8.0Hz,2H),7.38–7.36(m,3H),7.31(d,J=12.4Hz,1H),7.27(d,J=2.6Hz,2H),6.96(d,J=6.3Hz,2H),4.40(dt,J=14.7,7.5Hz,1H),3.70(d,J=7.4Hz,2H),2.44(s,3H).13C NMR(100MHz,CDCl3)δ144.29,135.81,135.24,134.30,130.03,129.71,129.66,129.34,127.49,103.09,51.00,21.64.HRMS(ESI)m/z calcd forC16H17N4O2S+(M+H)+329.1066,found 329.1063.
实施例2
在25mL的反应管中加入对氟苯胺联烯(30.3mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流40小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(33.6mg,产率为97%)。所制得化合物结构式如下所示:
m p 92.7-93.8℃;IR(neat)3691,2935,2378,2110,1662,1549,1371,744cm-1,1HNMR(400MHz,CDCl3)δ7.52(d,J=8.0Hz,2H),7.28(s,2H),7.27(d,J=9.2Hz,1H),7.04(t,J=8.3Hz,2H),6.92(s,2H),4.38(dt,J=13.8,7.4Hz,1H),3.69(d,J=7.2Hz,2H),2.42(s,3H).13C NMR(100MHz,CDCl3)δ162.70(d,J=248.7Hz),144.52,134.90,134.21,131.93(d,J=8.9Hz),131.59(d,J=3.2Hz),129.81,127.47,116.76(d,J=22.7Hz),103.18,50.89,21.65.HRMS(ESI)m/z calcd for C16H16FN4O2S+(M+H)+347.0972,found 347.0970.
实施例3
在25mL的反应管中加入对甲基苯胺联烯(30mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流40小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得黄色固体产物(33.4mg,产率为98%)。所制得化合物结构式如下所示:
m p 83.4-84.8℃;IR(neat)3463,2935,2377,2112,1661,1370,1172,744cm-1,1HNMR(400MHz,CDCl3)δ7.61(d,J=7.4Hz,2H),7.35(d,J=17.2Hz,1H),7.32(s,2H),7.21(d,J=7.5Hz,2H),6.88(d,J=7.5Hz,2H),4.46(dt,J=13.6,7.3Hz,1H),3.75(d,J=7.2Hz,2H),2.49(s,3H),2.41(s,3H).13C NMR(100MHz,CDCl3)δ144.19,139.46,135.35,134.41,133.04,130.32,129.68,127.49,122.38,102.93,51.01,21.63,21.24.HRMS(ESI)m/zcalcd for C17H19N4O2S+(M+H)+343.1223,found343.1222.
实施例4
在25mL的反应管中加入对甲氧基苯胺联烯(31.5mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流26小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(31.9mg,产率为90%)。所制得化合物结构式如下所示:
m p 80.3-81.6℃;IR(neat)3477,2936,2112,1661,1513,1271,1171,744cm-1,1HNMR(400MHz,CDCl3)δ7.60(d,J=7.6Hz,2H),7.36(d,J=13.4Hz,1H),7.33(d,J=8.4Hz,2H),6.91(s,4H),4.47(dt,J=13.6,7.3Hz,1H),3.87(s,3H),3.75(d,J=7.1Hz,2H),2.49(s,3H).13C NMR(100MHz,CDCl3)δ159.95,144.20,135.24,134.56,131.11,129.68,127.49,125.55,114.81,102.77,55.44,51.00,21.63.HRMS(ESI)m/z calcd for C17H19N4O3S+(M+H)+359.1172,found 359.1173.
实施例5
在25mL的反应管中加入对氯苯胺联烯(31.9mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流48小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(34.2mg,产率为95%)。所制得化合物结构式如下所示:
m p 107.6-108.2℃;IR(neat)3451,2931,2113,1661,1496,1273,719,589cm-1,1HNMR(400MHz,CDCl3)δ7.60(d,J=7.7Hz,2H),7.40(d,J=8.0Hz,2H),7.35(d,J=6.1Hz,2H),7.34(d,J=16.8Hz,1H),6.95(d,J=8.0Hz,2H),4.47(dt,J=13.8,7.2Hz,1H),3.76(d,J=7.1Hz,2H),2.50(s,3H).13C NMR(100MHz,CDCl3)δ144.56,135.41,134.92,134.33,133.98,131.39,129.99,129.83,127.47,103.40,50.87,21.64.HRMS(ESI)m/z calcd forC16H16ClN4O2S+(M+H)+363.0677,found363.0676.
实施例6
在25mL的反应管中加入对溴苯胺联烯(36.3mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流48小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(36.6mg,产率为90%)。所制得化合物结构式如下所示:
m p 89.4-90.7℃;IR(neat)3461,2937,2376,2110,1659,1489,1171,744cm-1,1HNMR(400MHz,CDCl3)δ7.60(d,J=7.8Hz,2H),7.56(d,J=8.1Hz,2H),7.35(d,J=7.7Hz,2H),7.32(d,J=13.6Hz,1H),6.89(d,J=8.0Hz,2H),4.47(dt,J=13.8,7.3Hz,1H),3.76(d,J=7.2Hz,2H),2.50(s,3H).13C NMR(100MHz,CDCl3)δ144.56,134.92,134.90,133.92,133.00,131.70,129.83,127.47,123.58,103.45,50.87,21.63.HRMS(ESI)m/z calcd forC16H16BrN4O2S+(M+H)+407.0172,found 407.0174.
实施例7
在25mL的反应管中加入间溴苯胺联烯(36.3mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流48小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(34.5mg,产率为85%)。所制得化合物结构式如下所示:
m p 90.7-91.2℃;IR(neat)3482,2939,2376,2112,1661,1475,1173,699cm-1,1HNMR(400MHz,CDCl3)δ7.59(t,J=6.9Hz,3H),7.35(d,J=7.8Hz,2H),7.32(d,J=14.2Hz1H),7.29(s,1H),7.17(s,1H),6.94(d,J=7.8Hz,1H),4.47(dt,J=13.8,7.4Hz,1H),3.75(d,J=7.3Hz,2H),2.49(s,3H).13C NMR(100MHz,CDCl3)δ144.66,137.16,134.87,133.78,133.24,132.59,130.83,129.84,128.74,127.49,122.72,103.77,50.86,21.65.HRMS(ESI)m/z calcd for C16H16BrN4O2S+(M+H)+407.0172,found 407.0178.
实施例8
在25mL的反应管中加入间甲氧基苯胺联烯(31.5mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流46小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得黄色固体产物(30.1mg,产率为84%)。所制得化合物结构式如下所示:
m p 70.8-71.3℃;IR(neat)3467,2943,2112,1660,1495,1293,1173,744cm-1 1HNMR(400MHz,CDCl3)δ7.58(d,J=7.7Hz,2H),7.29(d,J=7.5Hz,3H),7.25(d,J=14.5Hz,1H),6.93(d,J=8.3Hz,1H),6.50(d,J=7.9Hz,2H),4.46(dt,J=13.6,7.4Hz,1H),3.71(s,3H),2.44(s,3H).13C NMR(100MHz,CDCl3)δ160.37,144.28,136.89,135.31,134.18,130.14,129.68,127.55,121.92,115.44,115.25,103.26,55.31,50.98,21.61.HRMS(ESI)m/z calcd for C17H19N4O3S+(M+H)+359.1172,found 359.1170.
实施例9
在25mL的反应管中加入均三甲苯胺联烯(32.7mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流22小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(35.8mg,产率为97%)。所制得化合物结构式如下所示:
m p 135.9-136.7℃;IR(neat)3481,2935,2114,1662,1549,1122,744,711cm-1 1HNMR(400MHz,CDCl3)δ7.65(d,J=7.9Hz,2H),7.30(d,J=7.8Hz,2H),7.24(d,J=13.4Hz,1H),6.89(s,2H),4.25(dt,J=14.5,7.4Hz,1H),3.69(d,J=7.4Hz,2H),2.43(s,3H),2.28(s,3H),1.83(s,6H).13C NMR(100MHz,CDCl3)δ144.16,139.11,138.43,136.93,132.17,130.30,129.96,129.85,127.37,100.79,50.87,22.21,20.52,18.12.HRMS(ESI)m/z calcdfor C18H21N4O4S+(M+H)+389.1278,found 389.1276.
实施例10
在25mL的反应管中加入3,5-二甲氧基苯胺联烯(34.5mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流29小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(36.5mg,产率为94%)。所制得化合物结构式如下所示:
m p 102.9-103.7℃;IR(neat)3471,2946,2112,1662,1271,1170,744cm-1 1H NMR(400MHz,CDCl3)δ7.63(d,J=7.6Hz,2H),7.32(d,J=7.7Hz,2H),7.27(d,J=12.4Hz,1H),6.48(s,1H),6.10(s,2H),4.54(dt,J=13.8,7.5Hz,1H),3.73(s,2H),3.69(s,6H),2.45(s,3H).13C NMR(100MHz,CDCl3)δ161.13,144.29,137.47,135.37,134.03,129.66,127.60,107.79,103.41,101.75,55.40,50.96,21.61.HRMS(ESI)m/z calcd for C19H23N4O2S+(M+H)+371.1536,found 371.1530.
实施例11
在25mL的反应管中加入苄胺联烯(30mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流25小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(31.0mg,产率为91%)。所制得化合物结构式如下所示:
m p 69.5-70.8℃;IR(neat)3471,2110,1661,1364,1271,1169,746,706cm-1;1HNMR(400MHz,CDCl3)δ7.70(d,J=7.7Hz,2H),7.33(d,J=6.8Hz,2H),7.30(d,J=7.1Hz,2H),7.27(s,1H),7.26–7.22(m,2H),7.04(d,J=14.0Hz,1H),4.70(dt,J=14.4,7.4Hz,1H),4.52(s,2H),3.63(d,J=7.2Hz,2H),2.44(s,3H).13C NMR(100MHz,CDCl3)δ144.16,139.10,138.43,136.93,132.17,129.96,129.85,127.37,100.94,50.87,21.60,21.01,18.04.HRMS(ESI)m/z calcd for C17H19N4O2S+(M+H)+343.1223,found 343.1217.
实施例12
在25mL的反应管中加入对氯苄胺联烯(33.3mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流40小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(34mg,产率为90%)。所制得化合物结构式如下所示:
m p 59.5-60.8℃;IR(neat)3467,2114,1643,1261,1172,744cm-1.1H NMR(400MHz,CDCl3)δ7.69(d,J=7.8Hz,2H),7.33(d,J=7.8Hz,2H),7.29(s,1H),7.20(d,J=8.0Hz,2H),7.03(d,J=14.2Hz,1H),4.66(dt,J=14.2,7.2Hz,1H),4.49(s,2H),3.65(d,J=7.1Hz,2H),2.44(s,3H).13C NMR(100MHz,CDCl3)δ144.44,135.40,133.43,133.25,131.35,130.04,128.86,128.15,126.93,103.62,51.09,48.82,21.58.HRMS(ESI)m/zcalcd for C17H18ClN4O2S+(M+H)+377.0833,found 377.0828.
实施例13
在25mL的反应管中加入对氟苄胺联烯(31.7mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流48小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得无色油状产物(33.7mg,产率为94%)。所制得化合物结构式如下所示:
IR(neat)3480,2378,2110,1662,1272,1170,752cm-1.1H NMR(400MHz,CDCl3)δ7.69(d,J=7.8Hz,2H),7.33(d,J=7.8Hz,2H),7.23(d,J=6.3Hz,2H),7.03(d,J=13.1Hz,2H),6.98(d,J=8.2Hz,1H),4.68(dt,J=14.3,7.2Hz,1H),4.48(s,2H),3.64(d,J=7.1Hz,2H),2.44(s,3H).13C NMR(100MHz,CDCl3)δ162.30(d,J=247.0Hz),144.56,135.91,131.39,130.40(d,J=3.0Hz),130.02,128.48(d,J=7.7Hz),126.96,115.53(d,J=37.1Hz),103.61,51.08,48.84,21.51.HRMS(ESI)m/z calcd for C17H18FN4O2S+(M+H)+361.1129,found 361.1126.
实施例14
在25mL的反应管中加入对甲基苄胺联烯(31.3mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流40小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩溶剂,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得黄色固体产物(32.0mg,产率为90%)。所制得化合物结构式如下所示:
m p 77.4-78.1℃;IR(neat)3473,2112,1662,1524,1272,1170,745,584cm-1.1HNMR(400MHz,CDCl3)δ7.70(d,J=7.8Hz,2H),7.32(d,J=7.7Hz,2H),7.15(d,J=7.6Hz,2H),7.10(d,J=7.7Hz,2H),7.03(d,J=14.1Hz,1H),4.71(dt,J=14.2,7.2Hz,1H),4.48(s,2H),3.63(d,J=7.2Hz,2H),2.43(s,3H),2.32(s,3H).13C NMR(100MHz,CDCl3)δ143.35,136.42,134.68,130.77,130.72,129.10,128.42,126.13,125.78,102.32,50.32,47.92,20.71,19.65.HRMS(ESI)m/z calcd for C18H21N4O2S+(M+H)+357.1379,found 357.1376.
实施例15
在25mL的反应管中加入对溴苄胺联烯(37.7mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流47小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(37.5mg,产率为89%)。所制得化合物结构式如下所示:
m p 70.3-71.2℃;IR(neat)3446,2380,2112,1662,1364,1170,745cm-1;1H NMR(400MHz,CDCl3)δ7.69(d,J=8.1Hz,2H),7.43(d,J=8.2Hz,2H),7.33(d,J=7.9Hz,2H),7.13(d,J=8.0Hz,2H),7.03(d,J=14.1Hz,1H),4.65(dt,J=14.4,7.3Hz,1H),4.47(s,2H),3.65(d,J=7.2Hz,2H),2.44(s,3H).13C NMR(100MHz,CDCl3)δ144.45,135.38,133.79,131.84,131.40,130.05,128.53,126.93,121.51,103.92,50.88,49.08,21.18.HRMS(ESI)m/z calcd for C17H18BrN4O2S+(M+H)+421.0328,found421.0325.
实施例16
在25mL的反应管中加入1-苯基丙胺联烯(31.3mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流36小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(35.3mg,产率为99%)。所制得化合物结构式如下所示:
m p 60.6-61.4℃;IR(neat)3435,2925,2103,1650,1495,1186,1161,580cm-1;1HNMR(400MHz,CDCl3)δ7.69–7.64(m,2H),7.29(d,J=7.8Hz,4H),7.25–7.21(m,1H),7.17(d,J=7.7Hz,2H),7.01(d,J=14.0Hz,1H),4.90(dt,J=14.5Hz,1H),3.79(d,J=7.2Hz,2H),3.52(dd,J=8.9,7.4Hz,2H),2.91–2.86(m,2H),2.40(s,3H).13C NMR(100MHz,CDCl3)δ144.14,137.86,135.81,131.55,129.94,128.68,126.87,126.75,101.66,51.45,47.06,33.34,29.30,21.52.HRMS(ESI)m/z calcd for C18H21N4O2S+(M+H)+357.13780,found357.1379.
实施例17
在25mL的反应管中加入苯酰胺联烯(17.3mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流50小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得黄色油状产物(7.56mg,产率为35%)。所制得化合物结构式如下所示:
IR(neat)3435,2920,2099,1683,1653,1304,1279,700cm-1;1H NMR(400MHz,CDCl3)δ7.76(d,J=14.2Hz,1H),7.51(t,J=7.6Hz,2H),7.46(d,J=7.0Hz,1H),7.20(d,J=7.8Hz,2H),4.46(dt,J=14.4,7.4Hz,1H),3.73(d,J=7.4Hz,2H),1.88(s,3H).13C NMR(100MHz,CDCl3)δ168.86,133.08,130.23,128.99,128.63,105.73,51.18,29.65,23.14.HRMS(ESI)m/z calcd for C11H13N4O+(M+H)+217.1084,found 217.1082.
实施例18
在25mL的反应管中加入甲磺酰胺联烯(20.9mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流48小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩溶剂,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得黄色固体产物(32mg,产率为89%)。所制得化合物结构式如下所示:
m p 77.6-78.1℃;IR(neat)3434,2928,2104,1649,1351,1162,741,551cm-1;1HNMR(400MHz,CDCl3)δ7.49(dt,J=7.6,6.0Hz,3H),7.34(d,J=7.1Hz,2H),7.15(d,J=13.9Hz,1H),4.52(dt,J=14.6,7.4Hz,1H),3.72(d,J=7.4Hz,2H),3.04(s,3H).13C NMR(100MHz,CDCl3)δ135.89,133.70,130.15,129.80,129.61,103.26,50.88,39.05.HRMS(ESI)m/z calcd for C10H13N4O2S+(M+H)+253.0754,found 253.0752.
实施例19
在25mL的反应管中加入恶唑烷-2-酮联烯(12.5mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流48小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩溶剂,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得白色固体产物(15.0mg,产率为89%)。所制得化合物结构式如下所示:
m p 55.4-57.1℃;IR(neat)3429,2103,1667,1480,1196,1109,1070,740,702cm-1;1H NMR(400MHz,CDCl3)δ6.95(d,J=14.2Hz,1H),4.90(dt,J=14.4,7.3Hz,1H),4.49(dd,J=8.8,7.3Hz,2H),3.82(d,J=7.3Hz,2H),3.78–3.73(m,2H).13C NMR(100MHz,CDCl3)δ155.37,128.22,102.98,62.27,50.89,42.33.HRMS(ESI)m/z calcd for C6H9N4O2 +(M+H)+169.0720,found 169.0720.
实施例20
在25mL的反应管中加入2-萘胺联烯(35.0mg,0.1mmol),氯化亚铁(2.5mg,0.02mmol),叠氮基三甲基硅烷(17.3mg,0.15mmol),加入2mL二氯甲烷,40℃下搅拌回流35小时直到原料联烯胺消耗完毕,然后将混合物减压浓缩溶剂,色谱柱纯化(石油醚/乙酸乙酯=20/1)制得黄色油状产物(34.3mg,产率为89%)。所制得化合物结构式如下所示:
IR(neat)3434,2922,2103,1648,1596,1164,774,705cm-1;1H NMR(400MHz,CDCl3)δ7.91–7.84(m,2H),7.80(d,J=8.2Hz,1H),7.62(d,J=7.6Hz,2H),7.48(dd,J=12.3,6.8Hz,2H),7.44(d,J=10.1Hz,1H),7.37(t,J=7.7Hz,1H),7.27(d,J=7.8Hz,2H),6.88(d,J=7.3Hz,1H),4.22(dt,J=14.4,7.4Hz,1H),3.63(t,J=6.9Hz,2H),2.43(s,3H).13CNMR(100MHz,CDCl3)δ144.55,135.61,134.80,134.02,132.37,131.24,130.04,129.78,128.20,127.86,127.63,127.20,126.72,125.24,123.40,103.33,50.83,21.60.HRMS(ESI)m/z calcd for C20H19N4O2S+(M+H)+379.1223,found 379.1220.
尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (8)
2.根据权利要求1所述的合成烯丙基叠氮衍生物的方法,其特征在于:所述的联烯胺化合物为4-甲基-N-苯基-N-丙二烯基苯磺酰胺、N-(4-氟苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(4-甲基苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(4-甲氧基苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(4-氯苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(4-溴苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(3-溴苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(3-甲氧基苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(1,3,5-三甲基苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-(3,5-二甲氧基苯基)-4-甲基-N-丙二烯基苯磺酰胺、N-苄基-4-甲基-N-丙二烯基苯磺酰胺、N-(4-氯苄基)-4-甲基-N-丙二烯基苯磺酰胺、N-(4-氟苄基)-4-甲基-N-丙二烯基苯磺酰胺、N-(4-甲基苄基)-4-甲基-N-丙二烯基苯磺酰胺、N-(4-溴苄基)-4-甲基-N-丙二烯基苯磺酰胺、4-甲基-N-苯乙基-N-丙二烯基苯磺酰胺、N-苯基-N-丙二烯基乙酰胺、N-苯基-N-丙二烯基甲磺酰胺、3-丙二烯基恶唑烷-2-酮或4-甲基-N-(2-萘基)-N-丙二烯基苯磺酰胺。
3.根据权利要求1所述的合成烯丙基叠氮衍生物的方法,其特征在于:所述的有机溶剂是二氯甲烷、1,2-二氯乙烷、氯仿、甲苯、1,4二氧六环、乙腈中的一种。
4.根据权利要求3所述的合成烯丙基叠氮衍生物的方法,其特征在于:所述的有机溶剂是二氯甲烷。
5.根据权利要求1所述的合成烯丙基叠氮衍生物的方法,其特征在于:所述的联烯胺化合物、铁试剂、叠氮基三甲基硅烷的摩尔比为1:0.15-0.25:1.2-1.8。
6.根据权利要求5所述的合成烯丙基叠氮衍生物的方法,其特征在于:所述的联烯胺化合物、铁试剂、叠氮基三甲基硅烷的摩尔比为1:0.2:1.5。
7.根据权利要求1所述的合成烯丙基叠氮衍生物的方法,其特征在于:所述的反应温度为38-42℃,所述反应时间为22-48小时。
8.根据权利要求7所述的合成烯丙基叠氮衍生物的方法,其特征在于:所述的反应温度为40℃,所述反应时间为35小时。
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