CN117384116A - 一种氨基酸呋喃酮酯类潜香化合物及其合成方法与应用 - Google Patents
一种氨基酸呋喃酮酯类潜香化合物及其合成方法与应用 Download PDFInfo
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- furanone
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- -1 Amino acid furanone ester Chemical class 0.000 title claims abstract description 58
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 25
- 238000010189 synthetic method Methods 0.000 title abstract description 3
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- 235000019504 cigarettes Nutrition 0.000 claims abstract description 19
- 150000001413 amino acids Chemical class 0.000 claims abstract description 17
- 238000001308 synthesis method Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 34
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 16
- 241000208125 Nicotiana Species 0.000 claims description 15
- 235000002637 Nicotiana tabacum Nutrition 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 8
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- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004066 1-hydroxyethyl group Chemical group [H]OC([H])([*])C([H])([H])[H] 0.000 claims description 2
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- XPCTZQVDEJYUGT-UHFFFAOYSA-N 3-hydroxy-2-methyl-4-pyrone Chemical compound CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 description 4
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- ZYJPUMXJBDHSIF-NSHDSACASA-N (2s)-2-[(2-methylpropan-2-yl)oxycarbonylamino]-3-phenylpropanoic acid Chemical compound CC(C)(C)OC(=O)N[C@H](C(O)=O)CC1=CC=CC=C1 ZYJPUMXJBDHSIF-NSHDSACASA-N 0.000 description 1
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- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical class O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
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- 108090000790 Enzymes Proteins 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- SUKKTJPEBBDSNS-UHFFFAOYSA-N O1C(=CC=C1)O.O1C(CC=C1)=O Chemical compound O1C(=CC=C1)O.O1C(CC=C1)=O SUKKTJPEBBDSNS-UHFFFAOYSA-N 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/12—Steaming, curing, or flavouring tobacco
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24B—MANUFACTURE OR PREPARATION OF TOBACCO FOR SMOKING OR CHEWING; TOBACCO; SNUFF
- A24B3/00—Preparing tobacco in the factory
- A24B3/18—Other treatment of leaves, e.g. puffing, crimpling, cleaning
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/0076—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing less than six atoms
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0092—Heterocyclic compounds containing only N as heteroatom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Indole Compounds (AREA)
Abstract
本发明公开了一种氨基酸呋喃酮酯类潜香化合物及其合成方法与应用,化学结构通式为
Description
技术领域
本发明属于新型潜香香料制备领域,具体涉及一种氨基酸呋喃酮酯类潜香化合物及其合成方法与应用。
背景技术
焦甜香型化合物是一类可以减少苦味与酸刺激味,增加甜味与烤香味的香料化合物。1971年,Elmenhorst首次从卷烟冷凝物中发现了带有焦甜香的麦芽酚(Acta ChemicaScandinavica,1990,44:916-926)。此后,日本、瑞典等烟草公司对卷烟焦甜香进行了深入的研究,相继发现了呋喃类、呋喃酮、环戊烯酮类和吡喃酮类等带有焦甜香特征的化合物,其中最为重要的是甲基环戊烯醇酮(cyclotene)、呋喃酮(furaneol)和麦芽酚。这些具有焦甜香的香原料在甜味香精(饮料、糖果、巧克力、奶制品等)、咸味香精(肉制品等)及烟用香精中已得到了广泛的应用。这些化合物以糖苷类、酯类等结构作为潜香物存在于烟草中。
氨基酸是烟草中一类重要的含氮化合物,其含量影响着烟草的品质,也是重要的致香前体化合物(分析测试技术与仪器,2019,25:48-52.)。烟草中常见的氨基酸有20余种,在烟草的燃烧过程中,与还原糖可以发生美拉德反应,生成多种具有蒸煮、烤香、爆米花香味特征的吡喃、吡嗪、吡咯、吡啶等杂环化合物,某些氨基酸如苯丙氨酸还可以自身分解成香味化合物,如苯甲醇、苯乙醇等。
潜香化合物,是一类本身没有香味或香味不明显、但当用酶或者加热等方法促使其分解或裂解后才能释放出香味成分的化合物(Recent advances in tobacco science,1981,7,107-153;Australian Journal ofChemistry,1989,42:2071-2084)。潜香化合物在自然条件下具有挥发性弱、化学性质稳定等特点,将其添加至卷烟后,当卷烟未燃吸时其处于无味的稳定结构状态,当卷烟燃吸时其发生裂解、释放出期望的香味物质,并且预期香味的释放量在卷烟燃吸过程中始终保持一致,从而达到稳定的香味补偿效果。因此利用潜香化合物在卷烟加香加料中的应用,不仅解决了常规香精香料存在的缺点,而且可以使卷烟的香精配方具有一定保密效果。这是传统的加香加料技术所无法达到的,符合低焦油卷烟产品发展的需求。
发明内容
本发明的目的是提供一种氨基酸呋喃酮酯类潜香化合物,该类化合物挥发性弱、热解后释放出焦甜香物质呋喃酮,应用于卷烟产品中可赋予卷烟焦甜香香韵,提升卷烟感官品质。
本发明的另一目的是提供一种氨基酸呋喃酮酯类潜香化合物的合成方法,该方法是将氨基酸与呋喃酮通过缩合反应,合成得到新型的氨基酸呋喃酮酯类潜香化合物。
本发明为实现目的,采用如下技术方案:
本发明提供了一种氨基酸呋喃酮酯类潜香化合物,该化合物结构通式如下:
其中:R为氢、甲基、异丙基、仲丁基、羟甲基、1-羟基乙基、巯甲基、(甲硫基)乙基、羧甲基、羧乙基、氨基甲酰甲基、氨基甲酰乙基、咪唑基甲基、胍基丙基、苄基或4-羟基苄基、(3-吲哚基)甲基;R’为氢、烷基、芳基或烷氧基羰基。
本发明中氨基酸呋喃酮酯类潜香化合物典型的结构式1-3如下:
上述氨基酸呋喃酮酯类潜香化合物的合成方法是:以取代的氨基酸和呋喃酮为起始原料,在缩合剂和催化剂的作用下,氨基酸的羧基和呋喃酮的羟基发生缩合,生成氨基酸呋喃酮酯类潜香化合物。所述取代的氨基酸的结构式为所述呋喃酮的结构式为具体包括如下步骤:
步骤1、将取代的氨基酸、呋喃酮溶于有机溶剂中,加入缩合剂和催化剂,在25~100℃下反应1~24小时,通过薄层色谱监测反应原料转化情况;
步骤2、反应结束后,抽滤,用有机溶剂冲洗滤层,滤液使用旋转蒸发仪蒸干,再通过柱层析分离纯化,获得目标产物。
进一步地,步骤1中,每5~7mmol取代的氨基酸与5mmol的呋喃酮反应,使用5~10mmol的缩合剂、0.05~0.5mmol的催化剂和25~50mL的有机溶剂。
进一步地,步骤1中,所述缩合剂为二环己基碳二亚胺、二异丙基碳二亚胺和1-(3-二甲胺基丙基)-3-乙基碳二亚胺中的至少一种,更优选为二环己基碳二亚胺。
进一步地,步骤1中,所述催化剂为4-二甲氨基吡啶和4-吡咯烷基吡啶中的至少一种,更优选为4-二甲氨基吡啶。
进一步地,步骤1中,所述有机溶剂为乙酸乙酯、乙腈、二氯甲烷、1,2-二氯乙烷、氯苯、四氢呋喃、2-甲基四氢呋喃、乙醚和甲基叔丁基醚中的至少一种,更优选为二氯甲烷。
进一步地,步骤2中,所述柱层析分离是指在空气加压下进行柱层析,硅胶为200~300目,洗脱液为石油醚与乙酸乙酯体积比100~1:1的混合物或二氯甲烷与甲醇体积比为100~10:1的混合物。
例如,当采用二氯甲烷作为有机溶剂、采用二环己基碳二亚胺(DCC)和4-二甲氨基吡啶(DMAP)作为缩合剂和催化剂时,反应式如下:
本发明的氨基酸呋喃酮酯类潜香化合物在使用时,可以溶解在醇或醇水混合溶剂中,然后均匀喷洒到烟丝或造纸法薄片上,所述潜香化合物的添加量占烟丝或造纸法薄片重量的0.0001%-0.1%,更优选为0.001%。
本发明的有益效果体现在:
1、本发明首次设计合成了氨基酸呋喃酮酯类潜香化合物,通过将氨基酸与呋喃酮有机结合,大大提高了呋喃酮香料的稳定性,在燃烧热解时能够释放出焦甜香物质呋喃酮,添加至卷烟中可以赋予卷烟焦甜香韵,提升卷烟感官品质。
2、本发明涉及的合成方法工艺操作简单、环境污染小、生产成本低,便于工业化生产,是一种极具工业应用前景的生产工艺。
3、与呋喃酮相比,氨基酸呋喃酮酯热稳定性大大提高,其中:Boc-L-苯丙氨酸呋喃酮酯热分解温度由原来的127℃提高到158℃,且最大热失重温度由187℃提升至247℃;Boc-L-脯氨酸呋喃酮酯热分解温度由原来的127℃提高到174℃,且最大热失重温度由187℃提升至235℃;N-Boc-N’-Boc-L-色氨酸呋喃酮酯热分解温度由原来的127℃提高到139℃,且最大热失重温度由187℃提升至217℃。由此可知,氨基酸呋喃酮酯结构更加稳定,不易氧化变质,在燃烧热解时能够释放出焦甜香物质甲基环戊烯醇酮,明显提高卷烟感官品质。
附图说明
图1为Boc-L-苯丙氨酸呋喃酮酯的1H NMR谱图。
图2为Boc-L-苯丙氨酸呋喃酮酯的13C NMR谱图。
图3为Boc-L-脯氨酸呋喃酮酯的1H NMR谱图。
图4为Boc-L-脯氨酸呋喃酮酯的13C NMR谱图。
图5为N-Boc-N’-Boc-L-色氨酸呋喃酮酯的1H NMR谱图。
图6为N-Boc-N’-Boc-L-色氨酸呋喃酮酯的13C NMR谱图。
图7为呋喃酮、Boc-L-苯丙氨酸呋喃酮酯、Boc-L-脯氨酸呋喃酮酯和N-Boc-N’-Boc-L-色氨酸呋喃酮酯的TG-DTG图,其中(a)为TG曲线,(b)为DTG曲线。
图8为Boc-L-苯丙氨酸呋喃酮酯在300℃下的热裂解产物GC谱图。
图9为Boc-L-脯氨酸呋喃酮酯在300℃下的热裂解产物GC谱图。
图10为N-Boc-N’-Boc-L-色氨酸呋喃酮酯在300℃下的热裂解产物GC谱图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂,下面结合附图和实施例对本发明的具体实施方式做详细的说明。以下内容仅仅是对本发明的构思所做的举例和说明,所属本技术领域的技术人员对所描述的具体实施案例做各种各样的修改或补充或采用类似的方式代替,只要不偏离发明的构思或者超越本权利要求书所定义的范围,均应属于本发明的保护范围。
实施例1:Boc-L-苯丙氨酸呋喃酮酯的制备
在圆底烧瓶中依次加入Boc-L-苯丙氨酸(1.2915g,6mmol,1.2equiv)和呋喃酮(0.5607g,5mmol,1equiv)和二氯甲烷(25mL),再加入二环己基碳二亚胺(1.2380g,6mmol,1.2equiv),4-二甲氨基吡啶(0.0244g,0.2mmol,0.04equiv),室温反应3h。反应结束后,抽滤,二氯甲烷冲洗滤饼,滤液使用旋转蒸发仪旋除溶剂,使用柱层析法分离产物(PE:EA=10:1)。得到1.5569g化合物,收率为83%。1H NMR(600MHz,Chloroform-d)δ7.29(dt,J=30.7,7.5Hz,5H),4.99–4.95(m,1H),4.72(q,J=7.2Hz,1H,4.58(q,J=7.5Hz,1H),3.21(ddd,J=49.5,14.1,6.3Hz,2H),2.12(d,J=8.2Hz,2H),1.50(d,J=7.2Hz,3H),1.40(s,9H);13C NMR(151MHz,Chloroform-d)δ195.89(195.86),181.24(181.20),169.84(169.78),155.73,136.04(135.97),130.09,130.04,129.27,127.78,82.11(82.09),80.81,54.90(54.79),38.44(38.40),28.81,16.89(16.86),14.62(14.61)。HRMS(ESI)m/z[M+H]+Calcdfor C20H26NO6:376.1755;Found:376.1756。
实施例2:Boc-L-脯氨酸呋喃酮酯的制备
在圆底烧瓶中依次加入Boc-L-脯氨酸(2.1525g,10mmol,1.25equiv)和呋喃酮(1.025g,8mmol,1equiv),加入二氯甲烷(25mL),再加入二环己基碳二亚胺(2.0633g,10mmol,1.25equiv),4-二甲氨基吡啶(0.04g,0.32mmol,0.04equiv),室温反应3h。反应结束后,抽滤,二氯甲烷冲洗滤饼,收集滤液。滤液使用旋转蒸发仪旋除溶剂,使用柱层析法分离(PE/EA=6:1)。得到1.5087g化合物,收率为58%。1HNMR(600MHz,Chloroform-d)δ4.54–4.46(m,1H),4.40(dt,J=8.6,4.4Hz,1H),3.58–3.31(m,2H),2.36–2.18(m,1H),2.16–2.10(m,3H),2.06–1.91(m,1H),1.92–1.81(m,2H),1.45–1.40(m,3H),1.40(d,J=2.2Hz,9H);13CNMR(150MHz,Chloroform-d)δ198.82,178.30(175.82),155.87(154.04),134.09,81.11(80.51),80.33,58.93,46.87(46.32),30.78(29.01),28.36(28.22),24.26(23.63),20.74(20.16),16.43(13.63)。HRMS(ESI)m/z[M+H]+Calcd for C16H24NO6:326.1598;Found:326.1598。
实施例3:N-Boc-N’-Boc-L-色氨酸呋喃酮酯的制备
在圆底烧瓶中依次加入N-Boc-N’-Boc-L-色氨酸(4.0446g,10mmol,1.25equiv)和呋喃酮(1.0250g,8mmol,1equiv),加入二氯甲烷(25mL),再加入二环己基碳二亚胺(2.0633g,10mmol,1.25equiv),4-二甲氨基吡啶(0.04g,0.32mmol 0.04equiv),室温反应8h。反应结束后,抽滤,二氯甲烷冲洗滤饼,收集滤液。滤液使用旋转蒸发仪旋除溶剂,使用柱层析法分离(PE:EA=25:1)。得到1.4810g化合物,收率为36%。1H NMR(600MHz,Chloroform-d)δ8.13(s,1H),7.59(dd,J=29.5,12.3Hz,2H),7.31(t,J=7.8Hz,1H),7.24(t,J=7.5Hz,1H),5.12(d,J=7.9Hz,1H),4.80(t,J=6.2Hz,1H),4.58(dt,J=14.6,7.2Hz,1H),3.40(d,J=13.0Hz,1H),3.26(dd,J=14.7,6.2Hz,1H),2.08(s,3H),1.66(s,9H),1.50(d,J=2.4Hz,3H),1.41(s,9H);13C NMR(150MHz,Chloroform-d)δ176.41,156.00,150.25,135.96,131.17,125.04,124.76,123.15,119.55,119.33,115.76,84.28,81.99,80.79,61.09,54.07(55.18),32.46(30.25),28.74(28.85),28.31(28.08),21.59(14.72)。HRMS(ESI)m/z[M+H]+Calcd for C27H35N2O8:515.2388;Found:515.2390。
实施例4:热稳定性比较
由图7可知,呋喃酮在127℃时开始分解,在127-395℃温度区间出现明显的失重现象,且在187℃时失重速率最大,总失重率达99.5%。Boc-L-苯丙氨酸呋喃酮酯在158℃时开始分解,在148-433℃温度区间出现明显的失重现象,且在247℃时失重速率最大,总失重率达92.7%;Boc-L-脯氨酸呋喃酮酯在174℃时开始分解,在174-428℃温度区间出现明显的失重现象,且在235℃时失重速率最大,总失重率达98.3%;N-Boc-N’-Boc-L-色氨酸呋喃酮酯在139℃时开始分解,在139-431℃温度区间出现明显的失重现象,且在217℃时失重速率最大,总失重率达95.6%。从数据上可知,与呋喃酮相比,Boc-L-苯丙氨酸呋喃酮酯、Boc-L-脯氨酸呋喃酮酯、N-Boc-N’-Boc-L-色氨酸呋喃酮酯热分解温度由127℃分别提高至158℃、174℃、139℃,热稳定性提高,且最大热失重温度由187℃分别提升至247℃、235℃、217℃。
实施例5:目标产物的热裂解产物
准确称取2mg的Boc-L-苯丙氨酸呋喃酮酯,置于热裂解仪中,在氦气氛围下以20℃/ms的升温速率快速升温至300℃,对裂解产物进行分析;将样品分别换成Boc-L-脯氨酸呋喃酮酯和N-Boc-N’-Boc-L-色氨酸呋喃酮酯,重复上述操作。三种氨基酸呋喃酮酯类化合物热裂解产物总离子流图见图8、图9、图10,分析结果表明,三种化合物在300℃下均可有效释放出呋喃酮(图中箭头标出),带有焦甜香香气。
实施例5:目标产物在烟草中的加香评价
将上述3种氨基酸呋喃酮酯类潜香化合物溶于95%乙醇中,配制成质量浓度为0.1%的溶液,取1.0g上述浓度溶液均匀喷洒至100g空白烟丝中,放置2小时后卷制成样品卷烟。将样品卷烟放置在温度22℃±1℃,60%±2%的恒温恒湿箱中平衡48小时后,与在相同条件下放置的未加香样品对照评吸。感官评价结果如下表:
以上仅为本发明的示例性实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所做的任何修改,等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (12)
1.一种氨基酸呋喃酮酯类潜香化合物,其特征在于,其结构通式为:
其中:R为氢、甲基、异丙基、仲丁基、羟甲基、1-羟基乙基、巯甲基、(甲硫基)乙基、羧甲基、羧乙基、氨基甲酰甲基、氨基甲酰乙基、咪唑基甲基、胍基丙基、苄基或4-羟基苄基或(3-吲哚基)甲基;R’为氢、烷基、芳基或烷氧基羰基。
2.一种权利要求1所述的氨基酸呋喃酮酯类潜香化合物的合成方法,其特征在于:
以取代的氨基酸和呋喃酮为起始原料,在缩合剂和催化剂的作用下,氨基酸的羧基和呋喃酮的羟基发生缩合,生成氨基酸呋喃酮酯类潜香化合物。
3.根据权利要求2所述的合成方法,其特征在于:所述取代的氨基酸的结构式为:
其中,R与R’与权利要求1相同。
4.根据权利要求2所述的合成方法,其特征在于:所述呋喃酮的结构式为:
5.根据权利要求2所述的合成方法,其特征在于,包括如下步骤:
将取代的氨基酸、呋喃酮、缩合剂、催化剂和有机溶剂进行混合,在25~100℃下反应1~24小时,反应结束后通过柱层析分离纯化获得目标产物。
6.根据权利要求2或5所述的合成方法,其特征在于:每5~7mmol取代的氨基酸与5mmol的呋喃酮反应,使用5~10mmol的缩合剂、0.05~0.5mmol的催化剂和25~50mL的有机溶剂。
7.根据权利要求2或5所述的合成方法,其特征在于:所述缩合剂为二环己基碳二亚胺、二异丙基碳二亚胺和1-(3-二甲胺基丙基)-3-乙基碳二亚胺中的至少一种。
8.根据权利要求2或5所述的合成方法,其特征在于:所述催化剂为4-二甲氨基吡啶和4-吡咯烷基吡啶中的至少一种。
9.根据权利要求2或5所述的合成方法,其特征在于:所述有机溶剂为乙酸乙酯、乙腈、二氯甲烷、1,2-二氯乙烷、氯苯、四氢呋喃、2-甲基四氢呋喃、乙醚和甲基叔丁基醚中的至少一种。
10.根据权利要求5所述的合成方法,其特征在于:所述柱层析分离是指在空气加压下进行柱层析,硅胶为200~300目,洗脱液为石油醚与乙酸乙酯体积比为100~1:1的混合物或二氯甲烷与甲醇体积比为100~10:1的混合物。
11.一种权利要求1所述氨基酸呋喃酮酯类潜香化合物在卷烟中的应用。
12.根据权利要求11所述的应用,其特征在于:将所述氨基酸呋喃酮酯类潜香化合物溶解在醇或醇水混合溶剂中,然后均匀喷洒到烟丝或造纸法薄片上,所述潜香化合物的添加量占烟丝或造纸法薄片重量的0.0001%-0.1%。
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