纽甜及其衍生物的合成、工业设计及硝基蒽醌废渣的综合利用
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摘要
本论文分为两部分。
第一部分N-烷基化阿斯巴甜衍生物的合成
近年来,伴随着饮食生活质量的提高,特别是过多摄取糖分所导致的肥胖以及由肥胖引起的各种疾病已越来越受到人们的关注。因此,迫切需要开发出一种新型替代蔗糖的高甜度低热量甜味剂。以氨基酸为原料生产的二肽甜味剂具有口感好甜度高和热量低的优点,是蔗糖的替代品之一,正越来越受消费者青睐。
本文以简单化合物为原料合成了N-[N-(3,3-二甲基丁基)-L-α-天冬氨酰]-L-苯丙氨酸1-甲酯和N-[N-(3,3-二甲基戊基)-L-α-天冬氨酰]-L-苯丙氨酸1-甲酯。合成方法大体是:3,3-二甲基丁(戊)基氯与乙烯在低温催化条件下,制备3,3-二甲基丁(戊)基氯乙烷,DMSO氧化3,3-二甲基丁(戊)基氯乙烷制备3,3-二甲基丁(戊)基乙醛,最后3,3-二甲基丁(戊)基乙醛与阿斯巴甜经催化氢化生成相应的N-烷基化阿斯巴甜衍生物,总产率较高。
本文的创新之处:1.以3,3-二甲基丁(戊)醇为原料经过数步合成了两个N-烷基化阿斯巴甜衍生物;2.结合工业化生产实际,为N-烷基化阿斯巴甜衍生物的合成合理设计并完善了的中试方案,可直接应用于工业化生产。
第二部分硝基蒽醌废渣的综合利用
蒽醌型染料是染料界除了偶氮类之外的第二大系列的染料,具有颜色鲜艳,牢固度高,不易褪色等优良性质。蒽醌衍生物(特别是氨基蒽醌(简写为AAQ))是染料工业中的重要中间体,所制染料主要用于棉、毛、丝织品的染色和印花,在生产中占有很大的比重;同样它也是重要的医药中间体。
在生产染料过程中,特别是蒽醌硝化的过程,会副产大量的硝基蒽醌衍生物,其中含大量未反应的蒽醌及其异构体,若直接排放至环境或者燃烧处理,不仅会造成资源的浪费,也会对环境造成很大的污染,对粗硝基蒽醌进行分离精制,可以对它们综合利用,因此对这个课题的研究有很大的实际意义。
1-硝基蒽醌提纯部分:
在硝基蒽醌废渣中,1-硝基蒽含量35-42%,本篇文章研究了两种1-硝基蒽醌的提纯分离方法:有机溶剂萃取分离,亚硝酸钠分离精制法,取得了较好的分离效果。其中,有机溶剂萃取分离中进行了详细的研究,在溶剂种类、溶剂废渣比例、引发剂的种类及用量和冷却时间分别进行了研究,并开发了一种混合引发剂进行分离精制,并成功应用于工业化。
利用精制物进行进一步的反应,其中还原制得氨基蒽醌和甲胺基化来制造一种优良的染料——溶剂红111。讨论了两种氨基蒽醌的制备方法,硫化钠还原法和氨解法,并进行了试验论证,证实硫化钠还原法是80%纯度的1-硝基蒽醌还原的主要方法,而氨解法得到的氨基蒽醌颜色发灰。对此本文做出了详细解释。本文还利用80%纯度的1-硝基蒽醌经甲胺化得到了溶剂红111,其用途广泛,是一种非常成熟的红色溶剂染料、分散染料。本文第一次使用80%纯度的1-硝基蒽醌在甲胺水溶液中于无机碱的催化作用下得到暗红色的染料,经提纯后得到艳红色的染料,经液相色谱检测,含量可达到80%。
废渣二硝化部分:
许多十分重要的蓝、绿、棕色等深色蒽醌染料是以1,5位、1,8位蒽醌二取代物为原料合成的。1,5(1,8).二硝基蒽醌的生产在染料制备工艺中起到非常重要的作用。本文重点研究了通过硝基蒽醌废渣硝化制备二硝基蒽醌的方法。其中主要有硫酸介质中硝化法、纯硝酸硝化法、混酸介质中硝化、溶剂硝化法,并对每种硝化方法的优缺点进行了对比。而且使用了硝化生成的二硝基蒽醌制备了一种紫色分散染料,该分散染料可以对聚丙烯纤维、醋酸纤维等染色,有很好的洗涤牢度和升华牢度,但耐晒牢度稍差。
The content of this thesis consist two parts.
1.The synthesis of N-alkyl derivatives aspartame
In recent years,it has received more and more people's attention to the enhancement of life quality.Especially excessively ingesting the sugar could cause adiposity which would lead to various diseases.A sweeter with high sweetness and low heat should urgently be developed.Dipeptide sweeters with good sweetness feeling and low heat were the substitute of sucrose,which have received more and more favour by consumers.
In this paper,N-[N-(3,3-dimethylbutyl)-L-aspartyl]-L-phenylalanine 1-methyl ester and N-[N-(3,3-dimethylamyl)-L-aspartyl]-L-phenylalanine 1-methyl ester were simply synthesized by the hydrogenation of aspartame and alkyl aldehyde.Generally, the synthetic method was showed as follows:3,3-dimethylbutyl(amyl)chloride was produced by tert-butyl(amyl)chloride and ethylene with the catalyst of aluminium chloride at ice-bath.3,3-dimethylbutyl(amyl)aldehyde was preparaed by the oxidation reaction of 3,3-dimethylbutyl(amyl)chloride.N-alkyl aspartame derivatives were produced by the hydrogenation reaction of aspartame and 3,3-dimethylbutyl (amyl)aldehyde with the catalyst of Pd/C to give high yields.
Main innovations of the paper:
1)Two N-alkyl aspartame derivatives were synthesized by a few steps with the original material——tert-butyl(amyl)alcohol.
2)Combined with the practical production,a reasonable pilot programme of N-alkyl aspartame derivatives was designed and successfully applied into industrialized production.
2.Comprehensive utilization of nitroanthraquinone waste residue
Anthraquinone dyestuff is the second largest series beside the azo dyes.It has the good property of bright colour,high fastness,no fading and so on.Nitroanthraquinone is an important material in the dyestuff industry.During the dyestuff production,there are a lot of nitroanthraquinone derivatives in the waste residue.
During the dyestuff production,there are a lot of nitroanthraquinone derivatives in the waste residue,including 1-Nitroanthraquinone,2-Nitroanthraquinone,1,5-,1,8-, 1,6- and 1,7-Dinitroanthraquinone and Anthraquinone.If they are discarded in the environment,or burnt,they will cause serious pollution.
Procession of Purification of 1-nitroanthraquinone:
The waste residue contains 35-42%1-nitroanthraquinone.This work puts emphasis upon the purification and separation of the waste residue.In the study,the treatment including two methods such as extracting and separating with organic solvent as well as sodium nitrates solution.After treated by the organic solvent,we gained a preferable effect.After we studied of one or two kinds of organic solvent,dichloride ethanes and chlorobenzene,various proportion of solvent,various proportion of initiators and the time of cooling,we found a perfect way of purification 1-nitroanthraquinone and put into industrialization successfully.
This article contains preparation 80%1-aminoanthraquinone and 1-methylamino-anthraquinone from 80%1-nitroanthraquinone purified by waste residue.The reduction by Na_2S solution could give a better result than the directly substitution by NH_3.We prepared 1-methylaminoanthraquinone,which is an important disperse dye and solvent dye,by the reaction between 1-nitroanthraquinone and methylamine catalyzed by inorganic base.After recrystallization,we could get bright red dye, containing 80%1-methylaminoanthraquinone by HPLC.
Process of nitration of the waste residue:
Lots of important dark anthraquinone dyestuff such as blue,green and brown et al are prepared by 1,5- and/or 1,8-dinitroanthraquinone which are very important in the dye industry.This article puts emphasis upon the nitration of the waste residue.The nitration includes four methods:nitration in sulfate,nitration by pure nitrate,nitration by mixed acid and nitration in organic solvent.We prepared a purple disperse dye, which could dye Polypropylene and Cellulose acetate,by dinitroanthraquinone.It has perfect Wash fastness and Sublimation fastness,but bad light fastness.
第一部分N-烷基化阿斯巴甜衍生物的合成
近年来,伴随着饮食生活质量的提高,特别是过多摄取糖分所导致的肥胖以及由肥胖引起的各种疾病已越来越受到人们的关注。因此,迫切需要开发出一种新型替代蔗糖的高甜度低热量甜味剂。以氨基酸为原料生产的二肽甜味剂具有口感好甜度高和热量低的优点,是蔗糖的替代品之一,正越来越受消费者青睐。
本文以简单化合物为原料合成了N-[N-(3,3-二甲基丁基)-L-α-天冬氨酰]-L-苯丙氨酸1-甲酯和N-[N-(3,3-二甲基戊基)-L-α-天冬氨酰]-L-苯丙氨酸1-甲酯。合成方法大体是:3,3-二甲基丁(戊)基氯与乙烯在低温催化条件下,制备3,3-二甲基丁(戊)基氯乙烷,DMSO氧化3,3-二甲基丁(戊)基氯乙烷制备3,3-二甲基丁(戊)基乙醛,最后3,3-二甲基丁(戊)基乙醛与阿斯巴甜经催化氢化生成相应的N-烷基化阿斯巴甜衍生物,总产率较高。
本文的创新之处:1.以3,3-二甲基丁(戊)醇为原料经过数步合成了两个N-烷基化阿斯巴甜衍生物;2.结合工业化生产实际,为N-烷基化阿斯巴甜衍生物的合成合理设计并完善了的中试方案,可直接应用于工业化生产。
第二部分硝基蒽醌废渣的综合利用
蒽醌型染料是染料界除了偶氮类之外的第二大系列的染料,具有颜色鲜艳,牢固度高,不易褪色等优良性质。蒽醌衍生物(特别是氨基蒽醌(简写为AAQ))是染料工业中的重要中间体,所制染料主要用于棉、毛、丝织品的染色和印花,在生产中占有很大的比重;同样它也是重要的医药中间体。
在生产染料过程中,特别是蒽醌硝化的过程,会副产大量的硝基蒽醌衍生物,其中含大量未反应的蒽醌及其异构体,若直接排放至环境或者燃烧处理,不仅会造成资源的浪费,也会对环境造成很大的污染,对粗硝基蒽醌进行分离精制,可以对它们综合利用,因此对这个课题的研究有很大的实际意义。
1-硝基蒽醌提纯部分:
在硝基蒽醌废渣中,1-硝基蒽含量35-42%,本篇文章研究了两种1-硝基蒽醌的提纯分离方法:有机溶剂萃取分离,亚硝酸钠分离精制法,取得了较好的分离效果。其中,有机溶剂萃取分离中进行了详细的研究,在溶剂种类、溶剂废渣比例、引发剂的种类及用量和冷却时间分别进行了研究,并开发了一种混合引发剂进行分离精制,并成功应用于工业化。
利用精制物进行进一步的反应,其中还原制得氨基蒽醌和甲胺基化来制造一种优良的染料——溶剂红111。讨论了两种氨基蒽醌的制备方法,硫化钠还原法和氨解法,并进行了试验论证,证实硫化钠还原法是80%纯度的1-硝基蒽醌还原的主要方法,而氨解法得到的氨基蒽醌颜色发灰。对此本文做出了详细解释。本文还利用80%纯度的1-硝基蒽醌经甲胺化得到了溶剂红111,其用途广泛,是一种非常成熟的红色溶剂染料、分散染料。本文第一次使用80%纯度的1-硝基蒽醌在甲胺水溶液中于无机碱的催化作用下得到暗红色的染料,经提纯后得到艳红色的染料,经液相色谱检测,含量可达到80%。
废渣二硝化部分:
许多十分重要的蓝、绿、棕色等深色蒽醌染料是以1,5位、1,8位蒽醌二取代物为原料合成的。1,5(1,8).二硝基蒽醌的生产在染料制备工艺中起到非常重要的作用。本文重点研究了通过硝基蒽醌废渣硝化制备二硝基蒽醌的方法。其中主要有硫酸介质中硝化法、纯硝酸硝化法、混酸介质中硝化、溶剂硝化法,并对每种硝化方法的优缺点进行了对比。而且使用了硝化生成的二硝基蒽醌制备了一种紫色分散染料,该分散染料可以对聚丙烯纤维、醋酸纤维等染色,有很好的洗涤牢度和升华牢度,但耐晒牢度稍差。
The content of this thesis consist two parts.
1.The synthesis of N-alkyl derivatives aspartame
In recent years,it has received more and more people's attention to the enhancement of life quality.Especially excessively ingesting the sugar could cause adiposity which would lead to various diseases.A sweeter with high sweetness and low heat should urgently be developed.Dipeptide sweeters with good sweetness feeling and low heat were the substitute of sucrose,which have received more and more favour by consumers.
In this paper,N-[N-(3,3-dimethylbutyl)-L-aspartyl]-L-phenylalanine 1-methyl ester and N-[N-(3,3-dimethylamyl)-L-aspartyl]-L-phenylalanine 1-methyl ester were simply synthesized by the hydrogenation of aspartame and alkyl aldehyde.Generally, the synthetic method was showed as follows:3,3-dimethylbutyl(amyl)chloride was produced by tert-butyl(amyl)chloride and ethylene with the catalyst of aluminium chloride at ice-bath.3,3-dimethylbutyl(amyl)aldehyde was preparaed by the oxidation reaction of 3,3-dimethylbutyl(amyl)chloride.N-alkyl aspartame derivatives were produced by the hydrogenation reaction of aspartame and 3,3-dimethylbutyl (amyl)aldehyde with the catalyst of Pd/C to give high yields.
Main innovations of the paper:
1)Two N-alkyl aspartame derivatives were synthesized by a few steps with the original material——tert-butyl(amyl)alcohol.
2)Combined with the practical production,a reasonable pilot programme of N-alkyl aspartame derivatives was designed and successfully applied into industrialized production.
2.Comprehensive utilization of nitroanthraquinone waste residue
Anthraquinone dyestuff is the second largest series beside the azo dyes.It has the good property of bright colour,high fastness,no fading and so on.Nitroanthraquinone is an important material in the dyestuff industry.During the dyestuff production,there are a lot of nitroanthraquinone derivatives in the waste residue.
During the dyestuff production,there are a lot of nitroanthraquinone derivatives in the waste residue,including 1-Nitroanthraquinone,2-Nitroanthraquinone,1,5-,1,8-, 1,6- and 1,7-Dinitroanthraquinone and Anthraquinone.If they are discarded in the environment,or burnt,they will cause serious pollution.
Procession of Purification of 1-nitroanthraquinone:
The waste residue contains 35-42%1-nitroanthraquinone.This work puts emphasis upon the purification and separation of the waste residue.In the study,the treatment including two methods such as extracting and separating with organic solvent as well as sodium nitrates solution.After treated by the organic solvent,we gained a preferable effect.After we studied of one or two kinds of organic solvent,dichloride ethanes and chlorobenzene,various proportion of solvent,various proportion of initiators and the time of cooling,we found a perfect way of purification 1-nitroanthraquinone and put into industrialization successfully.
This article contains preparation 80%1-aminoanthraquinone and 1-methylamino-anthraquinone from 80%1-nitroanthraquinone purified by waste residue.The reduction by Na_2S solution could give a better result than the directly substitution by NH_3.We prepared 1-methylaminoanthraquinone,which is an important disperse dye and solvent dye,by the reaction between 1-nitroanthraquinone and methylamine catalyzed by inorganic base.After recrystallization,we could get bright red dye, containing 80%1-methylaminoanthraquinone by HPLC.
Process of nitration of the waste residue:
Lots of important dark anthraquinone dyestuff such as blue,green and brown et al are prepared by 1,5- and/or 1,8-dinitroanthraquinone which are very important in the dye industry.This article puts emphasis upon the nitration of the waste residue.The nitration includes four methods:nitration in sulfate,nitration by pure nitrate,nitration by mixed acid and nitration in organic solvent.We prepared a purple disperse dye, which could dye Polypropylene and Cellulose acetate,by dinitroanthraquinone.It has perfect Wash fastness and Sublimation fastness,but bad light fastness.
引文
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[42] Prakash, Indra., Method for preparing and purifying an N-alkylated aspartame derivative [p]. US5728862, Mar. 17,1998
[43] Nofre et al, N-substituted derivatives of aspartame useful as sweetening agents [p]. US5480668, Jan. 2,1996
[44] Prakash, et al, Method for the purification of N-[N-(3,3-dimethylbutyl)-L-.alpha.-aspartyl]-L -phenylalanine 1-methyl ester [p]. US6784309, Aug. 31,2004
[45] H. Nace, Reactions of sulfoxides with organic halides, J. Org. Chem. 1959,24(11): pp. 6562
[1]Hohmann et al,Process for the isolation of 1,6- and 1,7-dinitroanthraquinone[p].USP 4155921(1979)
[2]Hartwig Ernst DR et al,Verfahren zur Herstellung von 1-Nitroanthrachinon[p].Get Offen 2039822(1972)
[3]Frey,Walter et al,Verfahren zur trermen yon Anthrachinon nitrienrungs producten yon der mutterlauge[p].Ger Often 2142100(1974)
[4]Bantel et al,Recovery of purified 1-nitroanthraquinone[p].USP 3923845.(1975)
[5]Auge et al,Process for the preparation of 1,5- and 1,8-dinitroanthraquinone[p].USP 3906011.(1975)
[6]Hohmann et al,Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8- dinitroanthraquinone[p].USP 4259248.(1981)
[7]Hohmann et al,Process for the preparation of pure 1-nitroanthranthraquinone[p].GB 1465739,(1977)
[8]Takeda,Yo shiyuki et al,Purification of 1-nitroanthraquinone[p].日本公开特许1974-81358(1974)
[9]Kaya,S.et al,Process for the preparation of pure 1-nitroanthranthraquinone[p].日本公开特许1975-114438(1975)
[10]Schaefeer et al,Process for separating solid 1,5- and/or 1,8-dinitroanthraquinone and liquid nitrobenzene[p].USP 4389344(1983)
[11]Schroeder et al,Process for the preparation of pure 1,8-dinitroanthranthraquinone[p].GBP 1490318(1977)
[12]Toth,Purification of 1-nitroanthraquinone[p].USP 4012426(1977)
[13]Hohmann et al,Process for the separation of dinitroanthranthraquinone mixtures[p].GBP 1564373(1980)
[14]Bruenemann Hilmar et al,Separation of 1,5-dinitroanthranthraquinone and 1,8-dinitroanthranthraquinone,[p].GBP 1553099(1979)
[15]Schroeder et al,Process for the preparation of pure 1,8-dinitroanthranthraquinone[p].GBP 1490318(1977)
[16]Toth,Purification of 1-nitroanthraquinone[p].USP 4012426(1977)
[17]Bantel et al,Production of pure 1-nitroanthranthraquinone[p].USP 3868395(1975)
[18]王庆均,陈立平et al,Method of making dye using master slag of 1-aminoanthraquinone production[p].CN 1513921.2004-07-21
[19]尹云,李少文 et al,Method for refining 1-nitroanthraquinone by using mixed nitroanthraquinone[p].CN 1594440.2005-03-16
[20]杨希川,1-氨基葱醒的工艺改进(内部资料)(1996)
[21]F.W.Evans,W Frey,"Industrial and Laboratory Nitration"(1975)American Chemical Society,P243
[22]Hohrnann,H et al,Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8- dinitroanthraquinone[p].Ger Often 2637732(1978)
[23]Takeda,Y.;Kaya,S.Process for the separation of dinitroanthranthraquinone mixtures[p].JP 日本公开特许75-04056(1975)
[24]翁绍琳,染料工业生产中的技术问题(内部资料)(1986)
[25]Hohmann,W et al,Verfahren zur Herstellung von 1,5-Dinitroanthrachinon und 1,8-Dinitroanthrachinon[p].Ger Offen 2351590(1975)
[26]Yamada,E.et al,Verfahren zur Herstellung von dinitroanthrachinon[p].Ger Offen 2248704(1973)
[27]李嘉禾,分散蓝2BLN合成工艺的研究(内部资料)(1992)
[28]Winkler,Rudolf,Process for recovery waste nitrate[p].Swiss 592,044(1978)
[29]Takeda,Yo shiyuki,Process for preparation of mixtures of dinitroanthraquinones[p].日本公开特许78-132,552(1978)
[30]Takeda,Y;Kaya,S.Process for preparation of mixtures of dinitroanthraquinones[p].日本公开特许78-95,955(1978)
[31]Takeda,Y et al,Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8一dinitroanthraquinone[p].日本公开特许80-39,536(1980)
[32]Takeda,Y;Kaya,S.Process for the preparation of pure 1,5-dinitroanthranthraquinone [p].GBP 1564054(1980)
[33]Takeda,Y;Kaya,S.Verfahren zur Herstellung von 1,5-Dinitroanthrachinon[p].Ger Offen 2740403(1978)
[34]Kaya,s.Process for the preparation of pure 1,5-dinitroanthranthraquinone[p].日本公开特许62-09,102(1987)
[35]Kaya,s.Process for the preparation of pure dinitmanthranthraquinone[p].日本公开特许54-100,362(1979)
[36]Takeda,Y Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8-dinitroanthraquinone[p].日本公开特许78-34 765(1978)
[37]Vogel,Axel(Bayer A.G)VERFAHREN ZUR HERSTELLUNG VON DINITROANTHRACHINONEN Ger Offen 2,346,317(1979)04.10.1979
[38]CA 88:22469 Dinitroanthraquinone.Yoshiura,Koichi;Kawakami,Michio;Iwamura,Akio;Sakai,Tsunehiro(Mitsui Toatsu Chemicals,Inc.,Japan).Japan.Kokai JP 52111550 19 Sep 1977 Showa,3 pp.(Japanese).(Japan).Dinitroanthraquinone(Ⅰ)was prepd.by nitration of anthraquinone(Ⅱ)with mixed acid in chlorodinitrobenzene(solvent).Thus,11.3 g 98%HNO3 was added to 10.4 g Ⅱ in 1,2,4-Cl(O2N)2C6H3 at 50°,ll.1 g 20%fuming H2SO4 added over 1 h at 30-40°,and the mixt.stirred 3 h at 35° and 12 h at 54°,and treated with MeOH to give 13.8 g Ⅰ contg.42%1,5-Ⅰ,33%1,8-Ⅰ,and other isomers.
[39]CA 89:90146 Separation of 1,5-dinitroanthraquinone from 1,8-dinitroanthraquinone.Yoshiura,Koichi;Kawakami,Michio;Iwamura,Akio;Sakai,Tsunehiro(Mitsui Toatsu Chemicals,Inc.,Japan).Japan.Kokai JP 53044551 21 Apr 1978 Showa,3 pp.(Japanese).(Japan).Sepn.of 1,5-dinitroanthraquinone(I)from 1,8-dinitroanthraquinone(II)was eftected by heating nitroanthraquinone mixt.contg,mainly Ⅰ and Ⅱ in cyclohexane or MeCN,filtering at ~360° to sep.Ⅰ,and pptg.Ⅱ from the filtrate.Thus,100 g dinitroanthraquinone mixt.(Ⅰ:Ⅱ:-isomer=2:2:1)in cyclohexane was heated 1 h at 150-5°,cooled to 100° over 1 h,kept 30 min at 100°,and filtered to give 39.6 g Ⅰ(purity 95%).The filtrate was cooled to 25° to ppt.20.1 g Ⅱ(purity 98%).
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[13]Chao Y P et al.Selective production of L-aspartic acid and L-phenylalanine by coupling reactions of aspartame and aminottans-ferase in Escherichia coli.Enzyrne & Microbial Tcch,2000(27):19-25
[14]张红缨等.a-天冬氨酰胺酶的高表达和产物回收.生物工程学报,1998,14(2):208-213
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[16]许激扬等.新型甜味剂天-N-肽制备与分析.中国药科大学学报,1997,28(1):114-115
[17]Hendrick,M.E.,Alitame,chapter 3 in Alternative Sweeteners,2nd edition,Marcel Dekker.New York.1991.pp.29-33.
[18]Toshime Yanazakietal.Conformation Requirements for Sweet tasging Peptide and Pelptidomimetics.Angew Chem.Ed,1996(33):1437
[19] Van der Heijden A., In Flavor Science Sensible Principles and Techniques (Acree T. E. and Teranishi R. eds.) pp. 67, J. Am. Chem. Soc, 1993
[20] Walters D. E., Orthoefer F. T. and DuBois G E., Sweeteners, Discovery, molecular design and chemoreception, ACS, 1991
[21] Tinti J. M. and Nofre C, In Sweeteners, Discovery, Molecular Design and Chemoreception (Walters D. E., Orthoefer F. T. and DuBois G, E., eds.)ACS Symposium Series 450, pp. 206, Washington, DC, 1991
[22] Windawi, Preparation of aldehydes [p]. US 4421938, December 20,1983
[23] Gulkova et al. Dehydrogenation of Substituted Alcohols to Aldehydes on Zinc Oxide-Chromium Oxide Catalysts. Collect. Czech. Chem. Commun., 1992(57): pp. 2215-2226
[24] Prakash, et al. Synthesis and purification of 3,3-dimethylbutyraldehyde via hydrolysis of 1,1-dichloro-3,3-dimethylbutane or 1-bromo-1-chloro-3,3-dimethylbutane [p]. US5994593, Nov. 30,1999
[25] Prakash, et al., Preparation of 3,3-dimethylbutyraldehyde from a tert-butyl cation precursor, vinyl chloride and an acidic catalyst [p]. US5977415, Nov. 2,1999
[26] Anderson et al, Azetidines III. A Convenient sysnthesis of 1-Alkyl-3,3-Dimethylazetidines, J. Org. Chem., 1968, 33(5): pp. 2123-2136.
[27] Guo, er al, Synthesis and purification of 3,3-dimethylbutyraldehyde via oxidation of 1-chloro-3,3-dimethylbutane with dimethy sulfoxide [p]. US5905175, May 18,1999
[28] Zhi Guo, Rachal Sawyer, and Indra Prakash, A convenient synthesis of 3,3-dimethylbutyraldehyde, Synth. Commun, 2001, 31(21): pp. 3395-3399
[29] Brandstrom, A., A method for the preparation of trialkylacetaldehydes, Acta. Chem. Scand. 1959(13)NO.3
[30] Schmerling, L. J. Am. Chem. Soc. 1945(67): pp. 1152
[31] Paritosh Dave, Hop-Sup Byun, and Robert Engel, An improved direct oxidation of alkyl halides to alkdehydes, Synth. Commun, 1986,16 (11): pp. 1343-1346
[32] N. Kornblum, A New and Selective Method of Oxidation, J. Am. Chem. Soc, 1957, 79(24): pp. 6562.
[33] R. Major, Reactions of Organic Halides with Dimethyl Sulfoxide, J. Org. Chem., 1958, 23 (10): pp. 1563-1564.
[34] P. Dave, An Improved Direct Oxidation of Alkyl Halides to Aldehydes, Syn. Comm., 1986, 16(11): pp. 1343-1346.
[35] B. Ganem, Silver-Assisted Dimethylsulfoxide Oxidations, Tetrahedron Letter, 1974(11): pp. 917-920.
[36] C. Cheung, Effect of Pressure on the Rate of Methylation of a Buttressed Pyridine, J. Org. Chem., vol. 54,1989(3): pp. 570-573.
[37] N. Wilson, A Desilylation and a One-Pot Desilylation-Oxidation of Aliphatic ter-Butyl- dimethylsilyl Ethers J. Org. Chem., 1996, 61(9): pp. 2918-2919.
[38] K. Wiberg, Thermochemical Studies of Carbonyl Reactions, Journal of America Chemistry Society. 1981, 103(13): pp. 4473-4478.
[39] T. Fujii, Synthesis of 3-tert-Butylpyridine, Chem. and Pharm. Bull, 1978, 26(10): pp. 3233-3237.
[40] H. Mager, Activation and Transfer of Oxygen-IX, Tetrahedron, 1974(30): pp. 917-927.
[41] Nofre, et al. N-substituted derivatives of aspartame useful as sweetening agents [p]. US5480668, Jan. 2, 1996
[42] Prakash, Indra., Method for preparing and purifying an N-alkylated aspartame derivative [p]. US5728862, Mar. 17,1998
[43] Nofre et al, N-substituted derivatives of aspartame useful as sweetening agents [p]. US5480668, Jan. 2,1996
[44] Prakash, et al, Method for the purification of N-[N-(3,3-dimethylbutyl)-L-.alpha.-aspartyl]-L -phenylalanine 1-methyl ester [p]. US6784309, Aug. 31,2004
[45] H. Nace, Reactions of sulfoxides with organic halides, J. Org. Chem. 1959,24(11): pp. 6562
[1]Hohmann et al,Process for the isolation of 1,6- and 1,7-dinitroanthraquinone[p].USP 4155921(1979)
[2]Hartwig Ernst DR et al,Verfahren zur Herstellung von 1-Nitroanthrachinon[p].Get Offen 2039822(1972)
[3]Frey,Walter et al,Verfahren zur trermen yon Anthrachinon nitrienrungs producten yon der mutterlauge[p].Ger Often 2142100(1974)
[4]Bantel et al,Recovery of purified 1-nitroanthraquinone[p].USP 3923845.(1975)
[5]Auge et al,Process for the preparation of 1,5- and 1,8-dinitroanthraquinone[p].USP 3906011.(1975)
[6]Hohmann et al,Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8- dinitroanthraquinone[p].USP 4259248.(1981)
[7]Hohmann et al,Process for the preparation of pure 1-nitroanthranthraquinone[p].GB 1465739,(1977)
[8]Takeda,Yo shiyuki et al,Purification of 1-nitroanthraquinone[p].日本公开特许1974-81358(1974)
[9]Kaya,S.et al,Process for the preparation of pure 1-nitroanthranthraquinone[p].日本公开特许1975-114438(1975)
[10]Schaefeer et al,Process for separating solid 1,5- and/or 1,8-dinitroanthraquinone and liquid nitrobenzene[p].USP 4389344(1983)
[11]Schroeder et al,Process for the preparation of pure 1,8-dinitroanthranthraquinone[p].GBP 1490318(1977)
[12]Toth,Purification of 1-nitroanthraquinone[p].USP 4012426(1977)
[13]Hohmann et al,Process for the separation of dinitroanthranthraquinone mixtures[p].GBP 1564373(1980)
[14]Bruenemann Hilmar et al,Separation of 1,5-dinitroanthranthraquinone and 1,8-dinitroanthranthraquinone,[p].GBP 1553099(1979)
[15]Schroeder et al,Process for the preparation of pure 1,8-dinitroanthranthraquinone[p].GBP 1490318(1977)
[16]Toth,Purification of 1-nitroanthraquinone[p].USP 4012426(1977)
[17]Bantel et al,Production of pure 1-nitroanthranthraquinone[p].USP 3868395(1975)
[18]王庆均,陈立平et al,Method of making dye using master slag of 1-aminoanthraquinone production[p].CN 1513921.2004-07-21
[19]尹云,李少文 et al,Method for refining 1-nitroanthraquinone by using mixed nitroanthraquinone[p].CN 1594440.2005-03-16
[20]杨希川,1-氨基葱醒的工艺改进(内部资料)(1996)
[21]F.W.Evans,W Frey,"Industrial and Laboratory Nitration"(1975)American Chemical Society,P243
[22]Hohrnann,H et al,Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8- dinitroanthraquinone[p].Ger Often 2637732(1978)
[23]Takeda,Y.;Kaya,S.Process for the separation of dinitroanthranthraquinone mixtures[p].JP 日本公开特许75-04056(1975)
[24]翁绍琳,染料工业生产中的技术问题(内部资料)(1986)
[25]Hohmann,W et al,Verfahren zur Herstellung von 1,5-Dinitroanthrachinon und 1,8-Dinitroanthrachinon[p].Ger Offen 2351590(1975)
[26]Yamada,E.et al,Verfahren zur Herstellung von dinitroanthrachinon[p].Ger Offen 2248704(1973)
[27]李嘉禾,分散蓝2BLN合成工艺的研究(内部资料)(1992)
[28]Winkler,Rudolf,Process for recovery waste nitrate[p].Swiss 592,044(1978)
[29]Takeda,Yo shiyuki,Process for preparation of mixtures of dinitroanthraquinones[p].日本公开特许78-132,552(1978)
[30]Takeda,Y;Kaya,S.Process for preparation of mixtures of dinitroanthraquinones[p].日本公开特许78-95,955(1978)
[31]Takeda,Y et al,Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8一dinitroanthraquinone[p].日本公开特许80-39,536(1980)
[32]Takeda,Y;Kaya,S.Process for the preparation of pure 1,5-dinitroanthranthraquinone [p].GBP 1564054(1980)
[33]Takeda,Y;Kaya,S.Verfahren zur Herstellung von 1,5-Dinitroanthrachinon[p].Ger Offen 2740403(1978)
[34]Kaya,s.Process for the preparation of pure 1,5-dinitroanthranthraquinone[p].日本公开特许62-09,102(1987)
[35]Kaya,s.Process for the preparation of pure dinitmanthranthraquinone[p].日本公开特许54-100,362(1979)
[36]Takeda,Y Process for the preparation of mixtures of dinitroanthraquinones with a high content of 1,5- and 1,8-dinitroanthraquinone[p].日本公开特许78-34 765(1978)
[37]Vogel,Axel(Bayer A.G)VERFAHREN ZUR HERSTELLUNG VON DINITROANTHRACHINONEN Ger Offen 2,346,317(1979)04.10.1979
[38]CA 88:22469 Dinitroanthraquinone.Yoshiura,Koichi;Kawakami,Michio;Iwamura,Akio;Sakai,Tsunehiro(Mitsui Toatsu Chemicals,Inc.,Japan).Japan.Kokai JP 52111550 19 Sep 1977 Showa,3 pp.(Japanese).(Japan).Dinitroanthraquinone(Ⅰ)was prepd.by nitration of anthraquinone(Ⅱ)with mixed acid in chlorodinitrobenzene(solvent).Thus,11.3 g 98%HNO3 was added to 10.4 g Ⅱ in 1,2,4-Cl(O2N)2C6H3 at 50°,ll.1 g 20%fuming H2SO4 added over 1 h at 30-40°,and the mixt.stirred 3 h at 35° and 12 h at 54°,and treated with MeOH to give 13.8 g Ⅰ contg.42%1,5-Ⅰ,33%1,8-Ⅰ,and other isomers.
[39]CA 89:90146 Separation of 1,5-dinitroanthraquinone from 1,8-dinitroanthraquinone.Yoshiura,Koichi;Kawakami,Michio;Iwamura,Akio;Sakai,Tsunehiro(Mitsui Toatsu Chemicals,Inc.,Japan).Japan.Kokai JP 53044551 21 Apr 1978 Showa,3 pp.(Japanese).(Japan).Sepn.of 1,5-dinitroanthraquinone(I)from 1,8-dinitroanthraquinone(II)was eftected by heating nitroanthraquinone mixt.contg,mainly Ⅰ and Ⅱ in cyclohexane or MeCN,filtering at ~360° to sep.Ⅰ,and pptg.Ⅱ from the filtrate.Thus,100 g dinitroanthraquinone mixt.(Ⅰ:Ⅱ:-isomer=2:2:1)in cyclohexane was heated 1 h at 150-5°,cooled to 100° over 1 h,kept 30 min at 100°,and filtered to give 39.6 g Ⅰ(purity 95%).The filtrate was cooled to 25° to ppt.20.1 g Ⅱ(purity 98%).