張愛(ài)清,區(qū)文彩

(中南民族大學(xué)化學(xué)與材料科學(xué)學(xué)院催化材料科學(xué)湖北省暨國(guó)家民委-教育部共建重點(diǎn)實(shí)驗(yàn)室,武漢430074)

1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的合成

張愛(ài)清,區(qū)文彩

(中南民族大學(xué)化學(xué)與材料科學(xué)學(xué)院催化材料科學(xué)湖北省暨國(guó)家民委-教育部共建重點(diǎn)實(shí)驗(yàn)室,武漢430074)

以對(duì)乙酰氨基酚、氯丙烯為原料合成了4-烯丙氧基乙酰苯胺,4-烯丙氧基乙酰苯胺經(jīng)鹽酸水解得到4-烯丙氧基苯胺,2步反應(yīng)的總產(chǎn)率為66.5%.4-烯丙氧基苯胺與甲醛水溶液反應(yīng)得到1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪,產(chǎn)率為70.9%.采用傅里葉紅外光譜(FT-IR)和核磁共振(1H-NM R)對(duì)目標(biāo)產(chǎn)物及其中間體進(jìn)行了表征.

4-烯丙氧基苯胺;三嗪;苯并嗪

圖1 1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的合成路線Fig.1 Synthetic route of 1,3,5-tri-(4-(allyloxy)phenyl)-1,3,5-triazine

1 實(shí)驗(yàn)部分

1.1 主要試劑和儀器

對(duì)乙酰氨基酚、氯丙烯、氫氧化鈉、二甲基亞砜、鹽酸溶液、37%甲醛水溶液,以上試劑均為分析純.

N EXU S 470 FT-IR傅立葉紅外光譜儀(KBr壓片);Varian Mercury 400核磁共振儀:以TM S為內(nèi)標(biāo),CDCl3為溶劑.

1.2 實(shí)驗(yàn)步驟

1.2.1 4-烯丙氧基乙酰苯胺的合成

于100 mL三頸瓶中加入2.83 g(0.019 mol)對(duì)乙酰氨基酚,0.82 g(0.02mol)N aOH,7 mLDM SO,裝上回流冷凝管,常溫下磁力攪拌1 h.加入1.4 mL(0.017 mol)氯丙烯,攪拌1 h后水浴升溫至60℃,反應(yīng)8 h.待反應(yīng)結(jié)束冷卻至室溫,加足量乙酸乙酯溶解,經(jīng)1 mol/L N aOH溶液反復(fù)洗滌,再蒸餾水洗至中性,無(wú)水硫酸鎂干燥.過(guò)濾,旋蒸,干燥后得4-烯丙氧基乙酰苯胺粗產(chǎn)物.用石油醚和乙酸乙酯重結(jié)晶,得到產(chǎn)物2.54 g,產(chǎn)率78.2%[12-14].

1.2.2 4-烯丙氧基苯胺的合成

將2.5 g(0.013 mol)4-烯丙氧基乙酰苯胺加入質(zhì)量分?jǐn)?shù)為12%的45 mL鹽酸水溶液中,升溫至80℃,反應(yīng)3 h,然后靜置冷卻,固體析出,抽濾得到固體鹽酸鹽產(chǎn)物.1 mol/L N aOH溶液中和抽濾所得胺鹽,乙酸乙酯萃取,水洗至中性,無(wú)水硫酸鎂干燥,過(guò)濾,旋蒸抽去乙酸乙酯后得淺棕色液體1.65 g,產(chǎn)率85.1%[7].

1.2.3 1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的合成

將4.11 g(0.05 mol)甲醛水溶液和6 mL乙醇加入至100 mL的圓底燒瓶中,常溫下攪拌混合均勻.于冰水浴下(溫度控制10℃以下)滴加3.73 g(0.025 mol)4-烯丙氧基苯胺,滴加完畢后開始計(jì)時(shí),冰水浴下攪拌30 m in.反應(yīng)畢將產(chǎn)物溶于氯仿中,依次用1 mol/L N aOH溶液、蒸餾水洗滌,無(wú)水硫酸鎂干燥.過(guò)濾、旋蒸除去氯仿得產(chǎn)物2.85 g,產(chǎn)率70.9%[7,15,16].

2 結(jié)果與討論

2.1 4-烯丙氧基苯胺的合成

文獻(xiàn)[7]采用硝基還原法制備4-烯丙氧基苯胺.以對(duì)硝基酚為原料,經(jīng)過(guò)醚化、氯化亞錫還原、中和反應(yīng),總產(chǎn)率僅為37.3%,且操作繁瑣.本文以對(duì)乙酰氨基酚為原料,經(jīng)醚化、鹽酸水解脫乙?；⒅泻头磻?yīng),總產(chǎn)率可達(dá)66.5%,相比下產(chǎn)率提高較大,且操作簡(jiǎn)便、生成雜質(zhì)少.

圖2 4-烯丙氧基苯胺的FT-IR譜圖Fig.2 Infrared spectrum of 4-(allyloxy)aniline

圖2為4-烯丙氧基苯胺的IR譜圖.圖中3 428,3 358,3 222 cm-1為芳香族伯胺 ν(—NH2)特征吸收峰,1 365,1 231 cm-1為ν(C—N)特征吸收峰,1 119,1 022 cm-1分別為醚鍵 νas(C—O—C)、νs(C—O—C)吸收峰,3 082,3 036,3 015 cm-1為苯環(huán)ν(=C—H)吸收峰,1 510,1 459 cm-1為苯環(huán)ν(C=C)吸收峰,820 cm-1為苯環(huán)δ(=C—H)吸收峰,725 cm-1為苯環(huán)對(duì)位取代吸收峰,2 917,2 863 cm-1分別為亞甲基 νas(—CH2—)、νs(—CH2—)吸收峰,1 625 cm-1為烯丙基ν(C=C)吸收峰,996,928 cm-1為烯丙基δ(=C—H)吸收峰[7-11].

圖3為4-烯丙氧基苯胺的1H-NM R譜圖.由圖可見,化學(xué)位移(δ)6.65～6.80為苯環(huán)上氫的共振峰,3.29為苯環(huán)上氨基氫的共振峰,5.27～5.43,6.02～ 6.12,4.48～ 4.49分別為烯丙基醚=CH2、—CH=、—CH2—中氫的共振峰[7-11].

由圖2和圖3分析,可確認(rèn)合成了4-烯丙氧基苯胺.

圖3 4-烯丙氧基苯胺的1H-NMR譜圖Fig.31H-NMR spectrum of 4-(allyloxy)aniline

2.2 1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的合成

由于4-烯丙氧基苯胺較易氧化,故在較低溫度下制備三嗪較之較高溫下反應(yīng)[7],其操作簡(jiǎn)便、產(chǎn)生的雜質(zhì)較少.

圖4為1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的IR譜圖.圖中1 243,1 023 cm-1分別為醚鍵νas(C—O—C)、νs(C—O—C)吸收峰,1 362,1 185 cm-1為ν(C—N)吸收峰,3 020,1 511,1 456,821 cm-1分別為苯環(huán)ν(=C—H)、ν(C=C)、δ(C=C)、δ(=C—H)吸收峰,1 644 cm-1為烯丙基ν(C=C)吸收峰,997,926 cm-1為烯丙基 δ(=C—H)吸收峰[4,7].

圖5為1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的1H-NM R譜圖.由圖5可見,化學(xué)位移(δ)6.77～7.00處為苯環(huán)上氫的共振峰,4.68為氮雜環(huán)上—N—CH2—N—中氫的共振峰,5.24～5.40,5.99～6.06,4.45～ 4.46分別為烯丙基醚=CH2、—CH=、—CH2—中氫的共振峰[4,7].IR譜圖(圖4)和1HNM R譜圖(圖5)結(jié)果均與目標(biāo)產(chǎn)物的結(jié)構(gòu)完全符合.

3 結(jié)論

圖4 1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的FT-IR譜圖Fig.4 Infrared spectrum of 1,3,5-tri-(4-(allyloxy)phenyl)-1,3,5-triazine

圖5 1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪的1H-NMR譜圖Fig.5 1H-NMR spectrum of 1,3,5-tri-(4-(allyloxy)phenyl)-1,3,5-triazine

以對(duì)乙酰氨基酚,氯丙烯為原料,于60℃下反應(yīng)7 h,合成4-烯丙氧基乙酰苯胺,產(chǎn)率可達(dá)78.2%;在4-烯丙氧基乙酰苯胺水解反應(yīng)中,用質(zhì)量分?jǐn)?shù)為12%的鹽酸水溶液進(jìn)行水解,反應(yīng)時(shí)間短,副反應(yīng)少,水解產(chǎn)率達(dá)85.1%.以乙醇為溶劑,冰浴下制備1,3,5-三(4-(烯丙氧基)苯基)-1,3,5-三嗪,產(chǎn)率為70.9%,操作方便,反應(yīng)時(shí)間短.經(jīng)過(guò)3步反應(yīng)合成目標(biāo)產(chǎn)物,總產(chǎn)率為47.1%,較文獻(xiàn)[7]提高了14.4%.

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Synthesis of 1,3,5-Tri-(4-(Allyloxy)Phenyl)-1,3,5-Triazine

Zhang Aiqing,Ou Wencai
(Key Laboratory of Catalysis and Materials Science of the State Ethnic Affair Comm ission&Ministry of Education,Hubei Provinc,South-CentralU niversity for Nationalities,Wuhan 430074,China)

N-[4-(allyloxy)phenyl]acetam ide was prepared by the reaction of paracetamol with 3-chloropropylene,and 4-(allyloxy)aniline was produced from N-[4-(allyloxy)phenyl]acetam ide by acid hydrolysis,the total yield of two-step reaction is 66.5%.Then 1,3,5-tri-(4-(allyloxy)phenyl)-1,3,5-triazine was synthesized from 4-(allyloxy)aniline and aqueous solution of formaldehyde in 70.9%yield.These compounds have been characterized by FT-IR and 1H-NM R.

4-(allyloxy)aniline;triazine;benzoxazine

TQ 031.2

A

1672-4321(2010)01-0010-04

2010-03-05

張愛(ài)清(1963-),男,教授,研究方向:功能高分子,E-mail:aiqingzhang-2000@sina.com

國(guó)家中小企業(yè)創(chuàng)新基金資助項(xiàng)目