CN117384123A - Amino acid phenol ester type latent aromatic compound and synthetic method and application thereof - Google Patents
Amino acid phenol ester type latent aromatic compound and synthetic method and application thereof Download PDFInfo
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- CN117384123A CN117384123A CN202311320251.3A CN202311320251A CN117384123A CN 117384123 A CN117384123 A CN 117384123A CN 202311320251 A CN202311320251 A CN 202311320251A CN 117384123 A CN117384123 A CN 117384123A
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- Prior art keywords
- amino acid
- maltol
- compound
- aromatic compound
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- -1 Amino acid phenol ester Chemical class 0.000 title claims abstract description 76
- 150000001491 aromatic compounds Chemical class 0.000 title claims abstract description 25
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- XPCTZQVDEJYUGT-UHFFFAOYSA-N allomaltol Natural products CC=1OC=CC(=O)C=1O XPCTZQVDEJYUGT-UHFFFAOYSA-N 0.000 claims abstract description 40
- HYMLWHLQFGRFIY-UHFFFAOYSA-N Maltol Natural products CC1OC=CC(=O)C1=O HYMLWHLQFGRFIY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229940043353 maltol Drugs 0.000 claims abstract description 31
- 150000001413 amino acids Chemical class 0.000 claims abstract description 18
- 235000019504 cigarettes Nutrition 0.000 claims abstract description 17
- 238000001308 synthesis method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 230000009471 action Effects 0.000 claims abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 52
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 20
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 11
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- 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
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 claims description 2
- RGUKYNXWOWSRET-UHFFFAOYSA-N 4-pyrrolidin-1-ylpyridine Chemical compound C1CCCN1C1=CC=NC=C1 RGUKYNXWOWSRET-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 15
- 235000009508 confectionery Nutrition 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 9
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 230000000391 smoking effect Effects 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract 1
- 229940093503 ethyl maltol Drugs 0.000 description 42
- 229940024606 amino acid Drugs 0.000 description 28
- YIKYNHJUKRTCJL-UHFFFAOYSA-N Ethyl maltol Chemical compound CCC=1OC=CC(=O)C=1O YIKYNHJUKRTCJL-UHFFFAOYSA-N 0.000 description 24
- 239000000047 product Substances 0.000 description 16
- 230000004580 weight loss Effects 0.000 description 16
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000000796 flavoring agent Substances 0.000 description 10
- 235000019634 flavors Nutrition 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 6
- ZQEBQGAAWMOMAI-ZETCQYMHSA-N (2s)-1-[(2-methylpropan-2-yl)oxycarbonyl]pyrrolidine-2-carboxylic acid Chemical compound CC(C)(C)OC(=O)N1CCC[C@H]1C(O)=O ZQEBQGAAWMOMAI-ZETCQYMHSA-N 0.000 description 5
- 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 5
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000003776 cleavage reaction Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 230000007017 scission Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000001953 sensory effect Effects 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- CFAKWWQIUFSQFU-UHFFFAOYSA-N 2-hydroxy-3-methylcyclopent-2-en-1-one Chemical compound CC1=C(O)C(=O)CC1 CFAKWWQIUFSQFU-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 230000009189 diving Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002304 perfume Substances 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- 239000001837 2-hydroxy-3-methylcyclopent-2-en-1-one Substances 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- BZKFMUIJRXWWQK-UHFFFAOYSA-N Cyclopentenone Chemical class O=C1CCC=C1 BZKFMUIJRXWWQK-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 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
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 241000482268 Zea mays subsp. mays Species 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000002241 furanones Chemical class 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000013622 meat product Nutrition 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229960005190 phenylalanine Drugs 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- A24B3/14—Forming reconstituted tobacco products, e.g. wrapper materials, sheets, imitation leaves, rods, cakes; Forms of such products
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
- C07D309/40—Oxygen atoms attached in positions 3 and 4, e.g. maltol
-
- 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
- C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing 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
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an amino acid phenol ester type latent aromatic compound, a synthetic method and application thereof, and the chemical structural general formula is
Description
Technical Field
The invention belongs to the field of preparation of novel diving perfume, and particularly relates to an amino acid phenol ester diving perfume compound, a synthesis method and application thereof.
Background
Sweet flavor compounds are a class of flavor compounds that reduce bitter and sour-stimulating flavors and increase sweetness and roasted flavor. In 1971, elmendorst first discovered a sweet and fragrant maltol from cigarette condensate (Acta Chemica Scandinavica,1990, 44:916-926). After that, tobacco companies such as japan and sweden have conducted intensive studies on the burnt sweet flavor of cigarettes, and compounds having the characteristic of burnt sweet flavor such as furans, furanones, cyclopentenones and pyrones, among which methylcyclopentenolone (cyclotene), furanone (furaneol) and ethyl maltol are the most important, have been successively found. These fragrant materials having a burnt sweet fragrance have been widely used in sweet flavors (beverages, candies, chocolate, milk products, etc.), salty flavors (meat products, etc.), and tobacco flavors. These compounds exist in tobacco as a latent aromatic substance in the form of glycosides, esters and the like.
Amino acids are an important class of nitrogen-containing compounds in tobacco, whose content affects the quality of tobacco, and are also important aroma precursor compounds (analytical testing techniques and instruments, 2019, 25:48-52.). More than 20 common amino acids in tobacco can react with reducing sugar in the combustion process of tobacco to generate various heterocyclic compounds with the characteristics of cooking, baking and popcorn fragrance, such as pyran, pyrazine, pyrrole, pyridine and the like, and certain amino acids such as phenylalanine can be decomposed into fragrant compounds such as benzyl alcohol, phenethyl alcohol and the like.
The latent aromatic compound is a compound which has no fragrance or insignificant fragrance, but can release fragrance components after being decomposed or decomposed by enzyme or heating method (Recent advances in tobacco science,1981,7,107-153;Australian Journal ofChemistry,1989,42:2071-2084). The latent aromatic compound has the characteristics of weak volatility, stable chemical property and the like under natural conditions, is in a tasteless stable structure state when the cigarette is not burnt and smoked, is cracked and releases expected aromatic substances when the cigarette is burnt and smoked, and the expected release amount of the aromatic substances is always consistent in the smoking process of the cigarette, so that a stable aromatic compensation effect is achieved. Therefore, the application of the latent aromatic compound in the flavoring of cigarettes not only solves the defects of the conventional essence and spice, but also ensures that the essence formula of the cigarettes has a certain confidentiality effect. This is not achieved by conventional flavoring and charging technology, and meets the development requirement of low-tar cigarette products.
Disclosure of Invention
The invention aims to provide an amino acid phenolic ester type latent aromatic compound which is weak in volatility and releases maltol substances after pyrolysis, and can be applied to cigarette products to endow the cigarettes with sweet aroma and improve the sensory quality of the cigarettes.
The invention also aims to provide a synthesis method of the amino acid phenolic ester latent aromatic compound, which is to synthesize the novel amino acid phenolic ester latent aromatic compound through a condensation reaction of amino acid and malt phenolic compound.
The invention adopts the following technical scheme for realizing the purpose:
the invention provides an amino acid phenol ester type latent aromatic compound, which has the following structural general formula:
wherein: r is hydrogen, methyl, isopropyl, sec-butyl, hydroxymethyl, 1-hydroxyethyl, mercaptomethyl, (methylthio) ethyl, carboxymethyl, carboxyethyl, carbamoylmethyl, carbamoylethyl, imidazolylmethyl, guanidinopropyl, benzyl or 4-hydroxybenzyl, (3-indolyl) methyl; r' is hydrogen, alkyl, aryl or alkoxycarbonyl; r' is hydrogen or methyl.
Typical structural formulas 1-5 of the amino acid phenol ester type latent aromatic compound in the invention are as follows:
the synthesis method of the amino acid phenolic ester type latent aromatic compound comprises the following steps: the amino acid phenolic ester type latent aromatic compound is produced by using substituted amino acid and maltol compound as initial material and through condensation of carboxyl of amino acid and hydroxyl of maltol compound under the action of condensing agent and catalyst. The structural formula of the substituted amino acid isThe maltol compound is maltol or ethyl maltol, and has a structural formula of +.>The method specifically comprises the following steps:
step 1, dissolving substituted amino acid and maltol compound in an organic solvent, adding a condensing agent and a catalyst, reacting for 1-24 hours at 25-100 ℃, and monitoring the conversion condition of the reaction raw materials through thin layer chromatography;
and step 2, after the reaction is finished, carrying out suction filtration, flushing a filter layer by using an organic solvent, evaporating filtrate by using a rotary evaporator, and separating and purifying by using column chromatography to obtain a target product.
Further, in step 1, 5 to 10mmol of condensing agent, 0.05 to 0.5mmol of catalyst and 25 to 50mL of organic solvent are used per 5 to 7mmol of substituted amino acid to react with 5mmol of maltol compound.
Further, in the step 1, the condensing agent is at least one of dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, more preferably dicyclohexylcarbodiimide.
Further, in step 1, the catalyst is at least one of 4-dimethylaminopyridine and 4-pyrrolidinylpyridine, more preferably 4-dimethylaminopyridine.
Further, in step 1, the organic solvent is at least one of ethyl acetate, acetonitrile, dichloromethane, 1, 2-dichloroethane, chlorobenzene, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether and methyl tert-butyl ether, more preferably dichloromethane.
In step 2, the column chromatography separation refers to column chromatography under air pressurization, silica gel is 200-300 meshes, and eluent is a mixture of petroleum ether and ethyl acetate in a volume ratio of 100-1:1 or a mixture of dichloromethane and methanol in a volume ratio of 100-10:1.
For example, when methylene chloride is used as an organic solvent, dicyclohexylcarbodiimide (DCC) and 4-Dimethylaminopyridine (DMAP) are used as condensing agents and catalysts, the reaction formula is as follows:
when the amino acid phenol ester type latent aromatic compound is used, the amino acid phenol ester type latent aromatic compound can be dissolved in alcohol or alcohol-water mixed solvent and then uniformly sprayed on tobacco shreds or paper-making sheets, and the addition amount of the latent aromatic compound is 0.0001-0.1% of the weight of the tobacco shreds or paper-making sheets, and more preferably 0.001%.
The beneficial effects of the invention are as follows:
1. the invention designs and synthesizes the amino acid phenol ester type latent aromatic compound for the first time, and by organically combining the amino acid and the maltol compound, the stability of the maltol spice is greatly improved, and maltol burnt sweet aromatic substances can be released during combustion pyrolysis, so that the burnt sweet aromatic flavor can be enriched, and the sensory quality of the cigarette is remarkably improved.
2. The synthesis method has the advantages of simple process operation, small environmental pollution, low production cost and convenience for industrial production, and is a production process with great industrial application prospect.
3. Taking the amino acid ethyl maltol ester as an example, the amino acid ethyl maltol ester has greatly improved thermal stability compared with ethyl maltol, wherein: the thermal decomposition temperature of Boc-L-phenylalanine ethyl maltol ester is increased from 117 ℃ to 154 ℃, and the maximum thermal weight loss temperature is increased from 192 ℃ to 226 ℃; the thermal decomposition temperature of Boc-L-proline ethyl maltol ester is increased from 117 ℃ to 212 ℃, and the maximum thermal weight loss temperature is increased from 192 ℃ to 257 ℃; the thermal decomposition temperature of the N-Boc-N' -Boc-L-tryptophan ethyl maltol ester is increased from 117 ℃ to 255 ℃, and the maximum thermal weight loss temperature is increased from 192 ℃ to 259 ℃. Therefore, the amino acid ethyl maltol ester has a more stable structure, is not easy to oxidize and deteriorate, can release the sweet and fragrant substance ethyl maltol during combustion and pyrolysis, and obviously improves the sensory quality of cigarettes.
Drawings
FIG. 1 shows Boc-L-phenylalanine maltol ester 1 H NMR spectrum.
FIG. 2 shows Boc-L-phenylalanine maltol ester 13 C NMR spectrum.
FIG. 3 shows Boc-L-phenylalanine ethyl maltol ester 1 H NMR spectrum.
FIG. 4 shows Boc-L-phenylalanine ethyl maltol ester 13 C NMR spectrum.
FIG. 5 shows Boc-L-proline maltol ester 1 H NMR spectrum.
FIG. 6 shows Boc-L-proline maltol ester 13 C NMR spectrum.
FIG. 7 shows Boc-L-proline ethyl maltol ester 1 H NMR spectrum.
FIG. 8 shows Boc-L-proline ethyl maltol ester 13 C NMR spectrum.
FIG. 9 is a diagram of N-Boc-N' -Boc-L-tryptophan ethyl maltol 1 H NMR spectrum.
FIG. 10 is a diagram of N-Boc-N' -Boc-L-tryptophan ethyl maltol 13 C NMR spectrum.
FIG. 11 is a thermogravimetric analysis (TG-DTG) plot of ethyl maltol, boc-L-phenylalanine ethyl maltol, boc-L-proline ethyl maltol and N-Boc-N' -Boc-L-tryptophan ethyl maltol, wherein (a) is a TG curve and (b) is a DTG curve.
FIG. 12 is a GC spectrum of the thermal cleavage product of Boc-L-phenylalanine maltol ester at 300 ℃.
FIG. 13 is a GC spectrum of the thermal cleavage product of Boc-L-phenylalanine ethyl maltol at 300 ℃.
FIG. 14 is a GC spectrum of the thermal cleavage product of Boc-L-proline maltol ester at 300 ℃.
FIG. 15 is a GC spectrum of the thermal cleavage product of Boc-L-proline ethyl maltol at 300 ℃.
FIG. 16 is a GC spectrum of the cleavage product of N-Boc-N' -Boc-L-tryptophan ethyl maltol at 300 ℃.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. The following is merely illustrative and explanatory of the principles of the invention, as it would be apparent to those skilled in this art that various modifications or additions may be made to the specific embodiments described or in a similar manner without departing from the principles of the invention or beyond the scope of the claims.
Example 1: preparation of Boc-L-phenylalanine maltol ester
Boc-L-phenylalanine (1.2915 g,6mmol,1.2 equiv) and maltol (0.6306 g,6mmol,1 equiv) were added sequentially to a round bottom flask, dichloromethane (25 mL) was added, dicyclohexylcarbodiimide (1.2380 g,6mmol,1.2 equiv) and 4-dimethylaminopyridine (0.0244 g,0.2mmol,0.04 equiv) were added and reacted at room temperature for 3h. After the reaction was completed, suction filtration, washing of the filter cake with dichloromethane, spin-removal of the solvent from the filtrate using a rotary evaporator and isolation of the product using column chromatography (DCM: meoh=125:1). 1.8583g of the compound was obtained in a yield of 83%. 1 HNMR(600MHz,Chloroform-d)δ7.33(d,J＝4.4Hz,3H),7.28–7.25(m,2H),6.41(d,J＝5.7Hz,1H),4.96(d,J＝7.9Hz,1H),4.74(dt,J＝7.8,5.4Hz,1H),3.41(dd,J＝14.3,5.5Hz,1H),3.20(dd,J＝14.3,7.9Hz,1H),2.24(s,3H),1.39(s,9H)； 13 C NMR(151MHz,Chloroform-d)δ176.18,173.83,155.83,154.88,151.07,143.81,136.63,130.01,129.04,127.48,113.88,80.54,54.77,38.50,28.85,14.96。HRMS(ESI)m/z[M+H] + Calcd for C 20 H 24 NO 6 :374.1598；Found:374.1600。
Example 2: preparation of Boc-L-phenylalanine ethyl maltol ester
Boc-L-phenylalanine (2.6513 g,10mmol,1.25 equiv) and ethyl maltol (1.428 g,8mmol,1 equiv) were added sequentially to a round bottom flask, dichloromethane (25 mL) was added, dicyclohexylcarbodiimide (2.0600 g,10mmol,1.25 equiv) and 4-dimethylaminopyridine (0.0400 g,0.32mmol,0.04 equiv) were added and reacted at room temperature for 3h. After the reaction was completed, the filter cake was washed with DCM and the filtrate was collected. The filtrate was spun off the solvent using a rotary evaporator and the product was isolated using column chromatography (DCM: meoh=100:1). 2.0133g of the compound was obtained in a yield of 65%. 1 H NMR(600MHz,Chloroform-d)δ7.70(d,J＝5.7Hz,1H),7.34–7.22(m,5H),6.40(d,J＝5.7Hz,1H),5.01(d,J＝8.1Hz,1H),4.73(td,J＝7.9,5.5Hz,1H),3.40(dd,J＝14.3,5.6Hz,1H),3.19(dd,J＝14.3,7.9Hz,1H),2.56(qd,J＝7.4,2.8Hz,2H),1.38(s,9H),1.18(t,J＝7.6Hz,3H)； 13 C NMR(151MHz,Chloroform-d)δ175.52,173.49,155.27,154.82,154.42,142.49,136.07,129.44,128.47,126.91,113.19,79.97,54.20,37.94,28.28,21.74,10.77。HRMS(ESI)m/z[M+H] + Calcd for C 21 H 26 NO 6 :388.1755；Found:388.1756。
Example 3: preparation of Boc-L-proline maltol ester
Boc-L-proline (2.1525 g,10mmol,1.25 equiv) and maltol (1.0089 g,8mmol,1 equiv) were added sequentially to a round bottom flask, dichloromethane (25 mL) was added, dicyclohexylcarbodiimide (2.0633 g,10mmol,1.25 equiv) and 4-dimethylaminopyridine (0.04 g,0.32mmol,0.04 equiv) were added and reacted at room temperature for 3h. After the reaction is finished, suction filtration is carried out, a filter cake is washed by methylene dichloride, and filtrate is collected. The filtrate was spin-removed from the solvent using a rotary evaporator and separated using column chromatography (DCM: meoh=100:1). 1.9905g of the compound was obtained in 77% yield. 1 H NMR(600MHz,Chloroform-d)δ7.68–7.62(m,1H),6.36(ddd,J＝9.2,5.9,2.2Hz,1H),4.57–4.44(m,1H),3.68–3.28(m,2H),2.61–2.40(m,1H),2.39–2.31(m,1H),2.28(dd,J＝18.0,2.5Hz,3H),2.22–2.02(m,1H),1.94(ddt,J＝12.8,8.8,4.6Hz,1H),1.46(d,J＝2.6Hz,9H)； 13 C NMR(150MHz,Chloroform-d)δ172.02(171.68),170.06(169.80),159.97(158.88),154.48(153.75),154.20,138.48(138.23),116.78(116.70),80.18(79.86),58.82,46.74(46.47),31.27(30.28),28.39,24.42(23.37),14.92。HRMS(ESI)m/z[M+H] + Calcd for C 16 H 22 NO 6 :324.1442；Found:324.1444。
Example 4: preparation of Boc-L-proline ethyl maltol ester
Boc-L-proline (2.1525 g,10mmol,1.25 equiv) and ethyl maltol (1.428 g,8mmol,1 equiv) were added sequentially to a round bottom flask, dichloromethane (25 mL) was added, dicyclohexylcarbodiimide (2.0633 g,10mmol,1.25 equiv) and 4-dimethylaminopyridine (0.05 g,0.4mmol,0.04 equiv) were added and reacted at room temperature for 3h. After the reaction is finished, suction filtration is carried out, a filter cake is washed by methylene dichloride, and filtrate is collected. The filtrate was spin-removed from the solvent using a rotary evaporator and separated using column chromatography (DCM: meoh=100:1). 1.8801g of the compound was obtained in a yield of 70%. 1 H NMR(600MHz,Chloroform-d)δ7.66(dd,J＝8.4,5.7Hz,1H),6.29(p,J＝4.0Hz,1H),4.43(ddd,J＝16.7,8.6,3.5Hz,1H),3.56–3.45(m,1H),3.43–3.30(m,1H),2.65–2.49(m,2H),2.49–2.33(m,1H),2.31–2.17(m,1H),2.13–1.96(m,1H),1.86(tt,J＝8.0,4.0Hz,1H),1.39(d,J＝3.0Hz,9H),1.15(dtd,J＝23.0,7.6,2.7Hz,3H)； 13 C NMR(150MHz,Chloroform-d)δ178.28,175.79,173.99,154.93,154.89,143.05,113.71,81.47(80.70),59.51,47.42(46.86),31.40(29.46),28.94(28.80),24.85(24.20),22.26,11.34。HRMS(ESI)m/z[M+H] + Calcd for C 17 H 24 NO 6 :338.1601；Found:338.1604。
Example 5: preparation of N-Boc-N' -Boc-L-tryptophan ethyl maltol
N-Boc-N' -Boc-L-tryptophan (4.0446 g,10mmol,1.25 equiv) and ethyl maltol (1.1211 g,8mmol,1 equiv) were added sequentially to a round bottom flask, dichloromethane (25 mL) was added, dicyclohexylcarbodiimide (2.0633 g,10mmol,1.25 equiv) and 4-dimethylaminopyridine (0.04 g,0.32mmol,0.04 equiv) were added, and the reaction was carried out at room temperature for 8h. After the reaction is finished, suction filtration is carried out, a filter cake is washed by methylene dichloride, and filtrate is collected. The filtrate was freed from the solvent by rotary evaporation and separated using column chromatography (PE: ea=20:1). 1.4734g of the compound was obtained in a yield of 35%. 1 HNMR(600MHz,Chloroform-d)δ8.11(s,1H),7.66(d,J＝8.4Hz,1H)7.50(d,J＝7.7Hz,1H),7.39(s,1H),7.30(t,J＝7.5Hz,1H),7.22(t,J＝7.2Hz,1H),6.29(d,J＝8.4Hz,1H)5.13(d,J＝7.0Hz,1H),4.62(d,J＝5.8Hz,1H),4.14(dd,J＝13.7,6.7Hz,2H),3.22(ddd,J＝45.6,14.5,4.9Hz,2H),1.65(s,9H),1.43(s,9H),1.21(t,J＝7.1Hz,3H)； 13 C NMR(150MHz,Chloroform-d)δ199.66,198.61,176.72,176.51,155.84,150.21,135.46,133.80,131.24,124.97,124.76,123.09,119.59,115.72,85.43,84.16,80.76(80.60),54.04,28.85(28.73),28.38(28.15),25.12(21.71),17.10,14.10(10.29),9.11(9.09)。HRMS(ESI)m/z[M+H] + Calcd for C 28 H 35 N 2 O 8 :527.2388；Found:527.2383。
Example 6: comparison of thermal stability (taking amino acid ethyl maltol as an example)
As shown in FIG. 11, ethyl maltol starts to decompose at 117℃and has a significant weight loss phenomenon in the temperature range of 117-205℃and a maximum weight loss rate at 192℃with a total weight loss rate of 90.1%. The Boc-L-phenylalanine ethyl maltol ester starts to decompose at 154 ℃, obvious weight loss phenomenon occurs in the temperature range of 154-415 ℃, the weight loss rate is maximum at 226 ℃, and the total weight loss rate reaches 98.5%; the Boc-L-proline ethyl maltol ester starts to decompose at 212 ℃, obvious weight loss phenomenon occurs in the temperature range of 212-296 ℃, the weight loss rate is maximum at 257 ℃, and the total weight loss rate reaches 93.4%; N-Boc-N' -Boc-L-tryptophan ethyl maltol ester starts to decompose at 177 ℃, obvious weight loss occurs in the temperature range of 177-287 ℃, the weight loss rate is maximum at 255 ℃, and the total weight loss rate reaches 91.1%. From the data, it is seen that the thermal decomposition temperatures of Boc-L-phenylalanine ethyl maltol ester, boc-L-proline ethyl maltol ester and N-Boc-N' -Boc-L-tryptophan ethyl maltol ester are increased from 117 ℃ to 154 ℃, 212 ℃, 255 ℃ respectively, the thermal stability is greatly improved, and the maximum thermal weight loss temperatures are increased from 192 ℃ to 226 ℃, 257 ℃ and 259 ℃ respectively, as compared with ethyl maltol.
Example 7: thermal cracking products of target products
Accurately weighing 2mg of Boc-L-phenylalanine maltol ester, placing in a thermal cracking instrument, rapidly heating to 300 ℃ at a heating rate of 20 ℃/ms under helium atmosphere, and analyzing a cracking product; the samples were changed to Boc-L-phenylalanine ethyl maltol, boc-L-proline ethyl maltol, N-Boc-N' -Boc-L-tryptophan ethyl maltol, and the above procedure was repeated. The total ion flow diagrams of the thermal cracking products of the five amino acid phenolic ester compounds are shown in fig. 12, 13, 14, 15 and 16, and analysis results show that the five compounds can effectively release maltol or ethyl maltol (marked by arrows in the figure) at 300 ℃ and have sweet aroma.
Example 8: evaluation of flavoring of target products in tobacco
The 5 amino acid phenolic ester type potential aromatic compounds synthesized in the examples 1-5 are dissolved in 95% ethanol to prepare a solution with the mass concentration of 0.1%, 1.0g of the solution with the mass concentration is evenly sprayed into 100g of blank tobacco shreds, and the blank tobacco shreds are placed for 2 hours and then rolled into sample cigarettes. The sample cigarettes were equilibrated in a constant temperature and humidity cabinet at a temperature of 22+ -1deg.C and a humidity of 60% + -2% for 48 hours, and then compared with the non-flavored samples placed under the same conditions for smoking. The sensory evaluation results are shown in the following table:
the foregoing is illustrative only and is not intended to limit the present invention, and any modifications, equivalents, improvements and modifications falling within the spirit and principles of the invention are intended to be included within the scope of the present invention.
Claims (12)
1. An amino acid phenol ester type latent aromatic compound is characterized by having a structural general formula:
wherein: r is hydrogen, methyl, isopropyl, sec-butyl, hydroxymethyl, 1-hydroxyethyl, mercaptomethyl, (methylthio) ethyl, carboxymethyl, carboxyethyl, carbamoylmethyl, carbamoylethyl, imidazolylmethyl, guanidinopropyl, benzyl or 4-hydroxybenzyl or (3-indolyl) methyl; r' is hydrogen, alkyl, aryl or alkoxycarbonyl; r' is hydrogen or methyl.
2. A method for synthesizing an amino acid phenolic ester latent aromatic compound according to claim 1, which is characterized in that:
the amino acid phenolic ester type latent aromatic compound is produced by using substituted amino acid and maltol compound as initial material and through condensation of carboxyl of amino acid and hydroxyl of maltol compound under the action of condensing agent and catalyst.
3. The synthesis method according to claim 2, characterized in that: the structural formula of the substituted amino acid is as follows:
wherein R and R' are the same as in claim 1.
4. The synthesis method according to claim 2, characterized in that: the structural formula of the maltol compound is as follows:
wherein R' is the same as in claim 1.
5. The synthesis method according to claim 2, comprising the steps of:
mixing the substituted amino acid, the maltol compound, the condensing agent, the catalyst and the organic solvent, reacting for 1-24 hours at 25-100 ℃, and separating and purifying by column chromatography after the reaction is finished to obtain the target product.
6. The synthesis method according to claim 2 or 5, wherein: every 5-7 mmol substituted amino acid reacts with 5mmol maltol compound, 5-10 mmol condensing agent, 0.05-0.5 mmol catalyst and 25-50 mL organic solvent are used.
7. The synthesis method according to claim 2 or 5, wherein: the condensing agent is at least one of dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide.
8. The synthesis method according to claim 2 or 5, wherein: the catalyst is at least one of 4-dimethylaminopyridine and 4-pyrrolidinylpyridine.
9. The method of synthesis according to claim 5, wherein: the organic solvent is at least one of ethyl acetate, acetonitrile, dichloromethane, 1, 2-dichloroethane, chlorobenzene, tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether and methyl tertiary butyl ether.
10. The method of synthesis according to claim 5, wherein: the column chromatography separation is to perform column chromatography under air pressurization, silica gel is 200-300 meshes, and eluent is a mixture of petroleum ether and ethyl acetate with the volume ratio of 100-1:1 or a mixture of dichloromethane and methanol with the volume ratio of 100-10:1.
11. Use of the amino acid phenolic ester latent aromatic compound according to claim 1 in cigarettes.
12. The use according to claim 11, characterized in that: the amino acid phenol ester type latent aromatic compound is dissolved in alcohol or alcohol-water mixed solvent and then evenly sprayed on cut tobacco or paper-making sheet, and the addition amount of the latent aromatic compound accounts for 0.0001% -0.1% of the weight of the cut tobacco or paper-making sheet.
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