CN106243167A - A kind of glucoside compounds of Flos Caryophylli fragrance and preparation method thereof - Google Patents

A kind of glucoside compounds of Flos Caryophylli fragrance and preparation method thereof Download PDF

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Publication number
CN106243167A
CN106243167A CN201610548757.3A CN201610548757A CN106243167A CN 106243167 A CN106243167 A CN 106243167A CN 201610548757 A CN201610548757 A CN 201610548757A CN 106243167 A CN106243167 A CN 106243167A
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glucoside
flos caryophylli
fragrance
preparation
compounds
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潘仙华
陈宇
史尧
陆欢
常路
陈丹婷
何先喆
丁黎亚
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Shanghai Institute of Technology
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Shanghai Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/18—Acyclic radicals, substituted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

The invention provides a kind of glucoside compounds with Flos Caryophylli fragrance, its general structure is: Or

Description

A kind of glucoside compounds of Flos Caryophylli fragrance and preparation method thereof
Technical field
The invention belongs to chemical field, relate to a kind of glucoside compounds, one has the Flos Caryophylli fragrance of a flower specifically Glucoside compounds of taste and preparation method thereof.
Background technology
Flos Caryophylli fragrance has pneumostatic of allaying excitement, allaying tiredness, promotes the effects such as respiratory system is unobstructed.But from Flos Caryophylli Purify the most loaded down with trivial details yield of these perfume compounds low, and the mixture obtained often is mixed with a large amount of impurity thus reduces fragrance Quality.The compound then with Flos Caryophylli fragrance is developed, and the most representational is some alcohol compound.
But, these alcohol compounds have stronger volatility and case of thermal instability, As time goes on, fragrant Taste and medicinal efficacy can die down.Additionally, this type of alcohol compound poorly water-soluble, need bigger organic molten of cooperation toxicity Agent uses after dissolving.Therefore raising heat stability and water solublity are the keys that this type of alcohol compound maximum plays effect and effect.
And alcohol molecule and glucose combination are prepared as glucoside compounds is a kind of very effective method.Known There are menthol glucoside (J Agric Food Chem 2,001 49 5888), phenethanol glucoside (Biosci Biotech Biochem1994 58 (8) 1532) etc. report.These glucoside compounds in placement process by pyrolysis, The process slow release such as photodissociation, hydrolysis goes out fragrance alcohol molecule, thus is greatly improved the stability of alcohol molecule so that these alcohol molecules Performance effect that energy is lasting.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of glucoside with Flos Caryophylli fragrance Compound and preparation method thereof, described this glucoside compounds with Flos Caryophylli fragrance and preparation method thereof knack is existing There are the alcohol compound heat stability in technology and the technical problem of water solublity deficiency.
The invention provides a kind of glucoside compounds with Flos Caryophylli fragrance, its general structure is:
OrP be H or Person's acetyl group.
Further, its structural formula is the tetra-acetylated glucoside of a-terpineol (II a) or a-terpineol glucoside (I A):
P is H or acetyl group.
Further, requiring a kind of glucoside compounds with Flos Caryophylli fragrance described in 1 according to profit, its feature exists In, its structural formula is 3-methyl isophthalic acid-tetra-acetylated glucoside of phenyl-3-amylalcohol (II b) or 3-methyl isophthalic acid-phenyl-3-amylalcohol Glucoside (I b):
P is H or acetyl group.
Further, its structural formula is the tetra-acetylated glucoside of dimethyl benzyl carbinol (II c) or dimethylbenzyl base Alcohol glucoside (I c):
P is H or acetyl group.
Further, its structural formula is 2-methyl isophthalic acid-tetra-acetylated glucoside of p-methylphenyl-2-propanol (II d) or 2- Methyl isophthalic acid-p-methylphenyl-2-propanol glucoside (I d):
P is H or acetyl group.
Present invention also offers the preparation method of above-mentioned a kind of glucoside compounds with Flos Caryophylli fragrance, including Following steps:
(1) tetra-acetylated replacement glucose bromo-derivative (IV) is reacted with alcohol (III) and is obtained tetra-acetylated replacement glucoside (II),
Wherein, ROH is
Or
(2) tetra-acetylated replacement glucoside (II) deacetylation obtains glucoside (I),
Further, the reaction preparing compound (II) is carried out under carbonate effect, and carbonate used is selected from Any one in Disilver carbonate, chromium carbonate or potassium carbonate.
Further, the reaction preparing compound (II) is carried out under organic solvent effect, organic solvent used Any one in N,N-dimethylformamide, dichloromethane, chloroform, oxolane, acetonitrile, toluene or acetone Kind.
Further, the reaction preparing compound (I) is carried out under Feldalat NM and methanol effect.
Above-mentioned reaction with alcohol (III) from tetra-acetylated replacement glucose bromo-derivative (IV) obtains tetra-acetylated replacement glucose The operating process of the reaction of glycosides (II) approximately as: in reaction bulb, add compound (IV), alcohol (III), carbonate and molten Agent, reacts 1-72h at appropriate temperatures.After removal of solvent under reduced pressure, column chromatography for separation, obtain compound (II).
The operating process of the above-mentioned reaction obtaining glucoside (I) from tetra-acetylated replacement glucoside (II) deacetylation Approximately as: in reaction bulb, add compound (II), Feldalat NM and methanol, react 1-24h at appropriate temperatures.Neutralize After, after removal of solvent under reduced pressure, column chromatography for separation, obtain compound (I).
The present invention utilize glucose be combined with alcohol be prepared for having Flos Caryophylli fragrance glucoside compounds, it has The feature such as stability height, water solublity height, pure fragrance.
The advantage of the method for the present invention is by brief step, the compound being prepared for easily.
Detailed description of the invention
Further illustrate technical scheme with specific embodiment below, but protection scope of the present invention is not limited to This:
The synthesis of the tetra-acetylated glucoside of embodiment 1 alpha-terpineol (II a)
2g compound (IV), 0.38g alpha-terpineol (III a), 0.73g Disilver carbonate and 10mL bis-is added in reaction bulb Chloromethanes, reacts 24 hours under room temperature.Removal of solvent under reduced pressure, by column chromatography for separation, eluant (petrol ether/ethyl acetate= 5/1) 0.77g white solid is swept away, for compound (II a).
The synthesis of embodiment 2 alpha-terpineol glucoside (I a)
0.5g compound (II a), 0.23g Feldalat NM, 5mL methanol, room temperature reaction 24 hours is added in reaction bulb.Add Hydrogen chloride methanol solution neutralizes, removal of solvent under reduced pressure, and by column chromatography for separation, eluant (methylene chloride/methanol=10/1) rushes The lower colourless mucus of 0.31g, for compound (I a).
The synthesis of embodiment 3 3-methyl isophthalic acid-tetra-acetylated glucoside of phenyl-3-amylalcohol (II b)
2g compound (IV), 0.43g 3-methyl isophthalic acid-phenyl-3-amylalcohol (III b), 0.73g carbonic acid is added in reaction bulb Silver and 10mL dichloromethane, react 24 hours under room temperature.Removal of solvent under reduced pressure, by column chromatography for separation, eluant (oil Ether/ethyl acetate=5/1) sweep away 0.89g white solid, for compound (II b):
1H NMR(400MHz,CDCl3) δ: 0.89 (q, J=7.6Hz, 3H), 1.23 (d, J=1.6Hz, 3H), 1.50- 1.60(m,1H),1.65-1.88(m,3H),1.96-2.03(4s,12H),2.51-2.73(m,2H),3.66-3.70(m,1H), 4.05-4.11 (m, 1H), 4.16-4.22 (m, 1H), 4.71 (dd, J=2.4,7.6Hz, 1H), 5.00-5.07 (m, 2H), 5.23 (t, J=9.6Hz, 1H), 7.16-7.28 (m, 5H)
The synthesis of embodiment 4 3-methyl isophthalic acid-phenyl-3-amylalcohol glucoside (I b)
0.5g compound (II b), 0.21g Feldalat NM, 5mL methanol, room temperature reaction 24 hours is added in reaction bulb.Add Entering hydrogen chloride methanol solution to neutralize, removal of solvent under reduced pressure, by column chromatography for separation, eluant (methylene chloride/methanol=10/1) Sweep away the faint yellow mucus of 0.31g, for compound (I b):
1H NMR (400MHz, MeOD) δ: 0.95 (t, J=7.6Hz, 3H), 1.28 (d, J=1.6Hz, 3H), 1.62- 1.72 (m, 2H), 1.78-1.88 (m, 2H), 2.61-2.78 (m, 2H), 3.18 (t, J=8.8Hz, 1H), 3.22-3.26 (m, 1H), 3.37 (q, J=8.8Hz, 2H), 3.62-3.68 (m, 1H), 3.77-3.83 (m, 1H), 4.50 (d, J=8.0Hz, 1H), 4.85(br,4H),7.08-7.25(m,5H)
The synthesis of the tetra-acetylated glucoside of embodiment 5 dimethyl benzyl carbinol (II c)
In reaction bulb add 2g compound (IV), 0.37g dimethyl benzyl carbinol (III b), 0.73g Disilver carbonate and 10mL dichloromethane, reacts 24 hours under room temperature.Removal of solvent under reduced pressure, by column chromatography for separation, eluant (petroleum ether/acetic acid Ethyl ester=5/1) sweep away 0.80g white solid, for compound (II c):
1H NMR(400MHz,CDCl3)δ:1.10(s,3H),1.28(s,3H),1.80-2.06(4s,12H),2.65(d,J =13.2Hz, 1H), 2.94 (d, J=13.2Hz, 1H), 3.68-3.72 (m, 1H), 4.10 (dd, J=2.4,12.0Hz, 1H), 4.23 (dd, J=5.6,12.0Hz, 1H), 4.69 (d, J=8.4Hz, 1H), 4.98 (dd, J=8.0,9.6Hz, 1H), 5.06 (d, J=10.4Hz, 1H), 5.19 (t, J=9.6Hz, 1H), 7.16-7.27 (m, 5H)
The synthesis of embodiment 6 dimethyl benzyl carbinol glucoside (I c)
0.5g compound (II c), 0.23g Feldalat NM, 5mL methanol, room temperature reaction 24 hours is added in reaction bulb.Add Hydrogen chloride methanol solution neutralizes, removal of solvent under reduced pressure, and by column chromatography for separation, eluant (methylene chloride/methanol=10/1) rushes Lower 0.29g faint yellow solid, for compound (I c):
1H NMR (400MHz, MeOD) δ: 1.19 (s, 3H), 1.23 (s, 3H), 2.84 (d, J=12.8Hz, 1H), 2.92 (d, J=12.8Hz, 1H), 3.19 (dd, J=8.0,8.8Hz, 1H), 3.25-3.38 (m, 3H), 3.64 (dd, J=5.2, 12.0Hz, 1H), 3.82 (dd, J=2.4,12.0Hz, 1H), 4.56 (d, J=7.6Hz, 1H), 4.85 (br, 4H), 7.15- 7.28(m,5H)
The synthesis of embodiment 7 2-methyl isophthalic acid-tetra-acetylated glucoside of p-methylphenyl-2-propanol (II d)
2g compound (IV), 0.40g 2-methyl isophthalic acid-p-methylphenyl-2-propanol (III d), 0.73g is added in reaction bulb Disilver carbonate and 10mL dichloromethane, react 24 hours under room temperature.Removal of solvent under reduced pressure, by column chromatography for separation, eluant (stone Oil ether/ethyl acetate=5/1) sweep away 0.82g white solid, for compound (II d):
1H NMR(400MHz,CDCl3)δ:1.10(s,3H),1.26(s,3H),1.82-2.05(4s,12H),2.31(s, 3H), 2.62 (d, J=13.2Hz, 1H), 2.89 (d, J=13.2Hz, 1H), 3.68-3.72 (m, 1H), 4.10 (dd, J=2.4, 12.0Hz, 1H), 4.23 (dd, J=5.6,12.0Hz, 1H), 4.70 (d, J=8.0Hz, 1H), 4.97 (dd, J=8.0, 9.6Hz, 1H), 5.05 (t, J=10.0Hz, 1H), 5.19 (d, J=10.0Hz, 1H), 7.00-7.20 (m, 4H)
The synthesis of embodiment 8 2-methyl isophthalic acid-p-methylphenyl-2-propanol glucoside (I d)
0.5g compound (II d), 0.2g Feldalat NM, 5mL methanol, room temperature reaction 24 hours is added in reaction bulb.Add Hydrogen chloride methanol solution neutralizes, removal of solvent under reduced pressure, and by column chromatography for separation, eluant (methylene chloride/methanol=10/1) rushes Lower 0.30g white solid, for compound (I d):
1H NMR (400MHz, MeOD) δ: 1.18 (s, 3H), 1.21 (s, 3H), 2.28 (s, 3H), 2.79 (d, J= 13.2Hz, 1H), 2.87 (d, J=13.2Hz, 1H), 3.17 (t, J=8.4Hz, 1H), 3.27-3.30 (m, 2H), 3.35-3.38 (m, 1H), 3.64 (dd, J=4.4,11.2Hz, 1H), 3.82 (d, J=12.0Hz, 1H), 4.55 (d, J=7.6Hz, 1H), 4.85 (br, 4H), 7.05 (d, J=7.2Hz, 2H), 7.13 (d, J=7.2Hz, 2H).

Claims (5)

1. a glucoside compounds with Flos Caryophylli fragrance, it is characterised in that its general structure is:
OrP is H or acetyl group.
2. the preparation method of a kind of glucoside compounds with Flos Caryophylli fragrance described in claim 1, it is characterised in that Comprise the steps:
(1) tetra-acetylated replacement glucose bromo-derivative (IV) and alcohol (III) react and obtain tetra-acetylated replacement glucoside (II),
Wherein, ROH is
Or
(2) tetra-acetylated replacement glucoside (II) deacetylation obtains glucoside (I),
The preparation method of a kind of glucoside compounds with Flos Caryophylli fragrance the most according to claim 2, its feature Being: the reaction preparing compound (II) is carried out under carbonate effect, carbonate used is selected from Disilver carbonate, carbonic acid Any one in chromium or potassium carbonate.
The preparation method of a kind of glucoside compounds with Flos Caryophylli fragrance the most according to claim 2, its feature Being: the reaction preparing compound (II) is carried out under organic solvent effect, organic solvent used is selected from N, N-diformazan Any one in base Methanamide, dichloromethane, chloroform, oxolane, acetonitrile, toluene or acetone.
The preparation method of a kind of glucoside compounds with Flos Caryophylli fragrance the most according to claim 2, its feature It is: the reaction preparing compound (I) is carried out under Feldalat NM and methanol effect.
CN201610548757.3A 2016-07-13 2016-07-13 A kind of glucoside compounds of Flos Caryophylli fragrance and preparation method thereof Pending CN106243167A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369743A (en) * 2018-10-31 2019-02-22 华宝香精股份有限公司 A kind of method of easy synthesis cedar wood alcohol glucoside
CN109970826A (en) * 2019-04-22 2019-07-05 上海应用技术大学 Glucoside compounds and preparation method thereof containing tertiary base carbon atom

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06336401A (en) * 1991-05-23 1994-12-06 T Hasegawa Co Ltd Plant aroma enhancer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06336401A (en) * 1991-05-23 1994-12-06 T Hasegawa Co Ltd Plant aroma enhancer

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOHJI YAMAHARA，ET AL.: ""Cholagogic Action and Characteristics of (±)-α-Terpineol-β-D-O-glucopyranoside, a New Monoterpenoid Glucoside"", 《CHEM. PHARM. BULL.》 *
PATRICK J.WILLIAMS，ET AL.: ""NOVEL MONOTERPENE DISACCHARIDE GLYCOSIDES OF VITIS VINIFERA GRAPES AND WINES"", 《PHYTOCHEMISTRY》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369743A (en) * 2018-10-31 2019-02-22 华宝香精股份有限公司 A kind of method of easy synthesis cedar wood alcohol glucoside
CN109970826A (en) * 2019-04-22 2019-07-05 上海应用技术大学 Glucoside compounds and preparation method thereof containing tertiary base carbon atom

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Application publication date: 20161221