CN105884618A - Converting method for cis and trans isomers of cinnamic acid compound - Google Patents
Converting method for cis and trans isomers of cinnamic acid compound Download PDFInfo
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- CN105884618A CN105884618A CN201610362724.XA CN201610362724A CN105884618A CN 105884618 A CN105884618 A CN 105884618A CN 201610362724 A CN201610362724 A CN 201610362724A CN 105884618 A CN105884618 A CN 105884618A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
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- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
- C07H17/06—Benzopyran radicals
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- C07J—STEROIDS
- C07J63/00—Steroids in which the cyclopenta(a)hydrophenanthrene skeleton has been modified by expansion of only one ring by one or two atoms
- C07J63/008—Expansion of ring D by one atom, e.g. D homo steroids
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Abstract
The invention relates to a converting method for cis and trans isomers of a cinnamic acid compound, and belongs to the field of organic chemical synthesis technology and analysis chemical technology. According to the method, a trace amount of iodine is used as a reaction reagent, and then a cis phenyl acrylate (conjunction) type compound is completely converted into a trans isomer in a solution; under sunlight irradiation, the trans phenyl acrylate compound can be converted into a cis isomer, and the conversion rate is 25-55%. The converting method has the advantages that reaction conditions are mild, the converting rate is high, environmental protection is achieved, and amplification is easy. The converting method not only can be used for separation analysis and organic synthesis research of phenyl acrylate compounds, but also can be applied to industrial production.
Description
Technical field:
The present invention relates to mutually turning of a kind of cis-trans-isomer containing derived from phenyl acrylic acid construction unit compound
Become, belong to organic chemical synthesis technology and separate the field of technique of analytical chemistry.Use trace the most exactly
Cis compounds derived from phenyl acrylic acid is converted into transisomer by iodine, can be turned by transisomer again under sunlight
Turn to cis.
Background technology:
Derived from phenyl acrylic acid construction unit is frequently present of, in medicine, chemical industry and material in organic synthesis the most often
It is applied to.And in nature, the chemical composition containing derived from phenyl acrylic acid construction unit is widely present also especially
Being reported in a large number, its type includes cinnamic acid triterpene esters, cinnamic acid flavone esters, cinnamic acid phenolic acid
Esters and freely derived from phenyl acrylic acid, such as caffeic acid, cinnamic acid and p-Coumaric Acid etc. exist in a large number
Native compound.Research confirms that this compounds generally exists cis-double bonds and two kinds of isomers of trans double bond, one
As transisomer exist in a large number, and syn-isomerism body burden is relatively low.Literature research is had to report, derived from phenyl acrylic acid
The transisomer of compound can be transformed into cis different under the ultra violet lamp of 254nm and 365nm
Structure body, until the two balance.And there is not yet from the cis-isomer of compounds derived from phenyl acrylic acid to transisomer
The report thoroughly converted.
Summary of the invention:
The present invention provides mutually turning of a kind of cis-trans-isomer containing derived from phenyl acrylic acid construction unit compound
The method changed.
One compounds derived from phenyl acrylic acid of the present invention is by following side along anti-two kinds of mutual method for transformation of isomer
Formula completes: the syn-isomerism physical ability of conjunction type compounds derived from phenyl acrylic acid (cinnamic acid esters) is at trace iodine
Under the conditions of heating-up temperature 48 DEG C-52 DEG C, in 1-3 minutes, it is fully converted to its transisomer,
The cis compounds derived from phenyl acrylic acid of free type is converted into the conversion ratio of its transisomer and reaches 50-70%；
The trans-isomerism physical ability of derived from phenyl acrylic acid chemical composition is under sunlight effect, through 2-48 hour, with
The conversion ratio of 20-55% produces its cis-isomer.
Cis-isomer with the reaction equation of transisomer phase co-conversion is:
In formula: R=hydroxyl, methoxyl group, fluorine, chlorine, bromine, iodine；R '=methyl, triterpene, flavone, phenolic acid.
Described compounds derived from phenyl acrylic acid chemical composition structure is that chemical composition contains cinnamic acid construction unit, then
The ester formed with other chemical composition including compounds derived from phenyl acrylic acid freely and compounds derived from phenyl acrylic acid.
The condition flag that described cis-isomer changes to transisomer is: trace iodine and temperature are 50 DEG C,
1-3 minute heat time heating time.
Described transisomer to syn-isomerism concrete conditions in the establishment of a specific crime is: common sunlight, and 2 hours response time arrived
48 hours.
Described compounds derived from phenyl acrylic acid freely and compounds derived from phenyl acrylic acid are formed with other chemical composition
Ester refer to Caffeic acids, cinnamic acid flavone esters, cinnamic acid triterpene esters, cinnamic acid phenolic acid esters
And cinnamic acid quininic acid esters.
A kind of compounds derived from phenyl acrylic acid along the method that anti-two kinds of isomers mutually convert be applied to medicine, chemical industry,
Material, the analysis detection of Lab Organic and field of industrial production.
During natural product chemistry composition Study, it is frequently encountered the suitable anti-of cinnamic acid ester type compound
Two kinds of isomers exist simultaneously, and syn-isomerism body burden is little, it is extremely difficult to isolated and purified, are typically necessary employing
Preparation or semi-preparative liquid chromatography, if can the artificial amount increasing cis-compound, by for cis-isomer
Separate and identify the convenience providing bigger.Additionally, cinnamic acid mode isomer is the most often mixed with the most cis
Isomer, the NMR spectra causing compound is complicated, and interference is identified, if it is cis different to realize cinnamic acid
Structure body is changed into transisomer thoroughly, will be greatly simplified the Structural Identification of this compounds.Meanwhile, industry
Produce and be also subjected to during organic synthesis the interference of both cis-trans-isomers, it is achieved both isomers
Controllability converts also great meaning for commercial production.
More than based on, we have invented utilize the iodine of trace as reaction reagent, in a heated condition, Ji Ke
In solution, the efficient cis compounds derived from phenyl acrylic acid of Quantitative yield is its transisomer.And in sunlight
Under, trans-cinnamic acid compounds can be converted into its cis-isomer again, conversion ratio is up to 20-65%.
It is an advantage of the invention that reaction condition gentleness, conversion ratio height, environmental protection and easily amplify, both can use
In separation analysis and the organic synthesis research of compounds derived from phenyl acrylic acid, it is equally applicable in commercial production.
Accompanying drawing illustrates:
Fig. 1 is that the compounds of this invention 7 is changed into 8 in the sun and reaches along during back balance1H H NMR spectroscopy.
Fig. 2 is that the compounds of this invention 9 is changed into 10 in the sun and reaches along during back balance1H H NMR spectroscopy.
Fig. 3 is that the compounds of this invention 15 is changed into 16 in the sun and reaches along during back balance1H H NMR spectroscopy.
Fig. 4 compound 21 be changed in the sun 22 and reach along back balance time1H H NMR spectroscopy.
Fig. 5 compound 27 be changed in the sun 28 and reach along back balance time1H H NMR spectroscopy.
The mixture of Fig. 6 compound 21 and 22 is changed into 21 after trace iodine reacts1H H NMR spectroscopy.
The mixture of Fig. 7 compound 15 and 16 is changed into 15 after trace iodine reacts1H H NMR spectroscopy.
The mixture of Fig. 8 compound 27 and 28 is reacted through trace iodine1H H NMR spectroscopy.
Fig. 9 contains the compound 15 of trace iodine after sunlight irradiates1H H NMR spectroscopy.
Figure 10 trans caffeic acid quininic acid methyl ester is main compound1H H NMR spectroscopy (before reaction).
Figure 11 trans caffeic acid quininic acid methyl ester cis-product ratio after sunlight irradiates improves1H H NMR spectroscopy.
Detailed description of the invention:
The present invention is expanded on further below in conjunction with embodiment, but the present invention is not limited to this specific embodiment, ability
Field technique personnel it should be appreciated that present invention encompasses in right all possible alternative,
Improvement project and equivalents.
Use trace iodine under conditions of heating (50 DEG C), through 1-3 minute, make derived from phenyl acrylic acid chemical combination
What the suitable isomer of thing was the most quantitative is converted into its transisomer.And under the effect of sunlight, through 2-48
Hour, the trans isomer of compounds derived from phenyl acrylic acid can produce its cis-isomer with the conversion ratio of 20-60%.
1. transisomer is the most trans right to the conversion of cis-isomer derived from phenyl acrylic acid chemical composition freely
Hydroxyl cinnamic acid, trans caffeic acid and the chemical composition containing derived from phenyl acrylic acid construction unit are exposed under sunlight
Several minutes, to 48 hours, can change into corresponding cis-isomer.
Cis-trans-isomer mutual transformation reaction reaction equation is:
R=hydroxyl, methoxyl group, fluorine, chlorine, bromine, iodine；R '=methyl, triterpene, flavone, phenolic acid.
2. cis-isomer to transisomer convert solution to cis-isomer (conventional organic solvent,
Such as methanol, acetone, pyridine or their deuterated reagent) in, add trace iodine, and 50 DEG C of heating,
The transisomer of correspondence can be thoroughly changed in 1-10 minute；
3. used by the conversion situation of magnetic resonance detection cis-trans-isomer1H NMR tests, according to suitable
(one of characteristic signal chemical shift range is 5.0～6.7ppm to the characteristic signal of trans isomer；Cis-isomer
Coupling constant be about 12.8Hz, the coupling constant of transisomer is 15.8Hz) judge that it belongs to,
Its relative amount is may determine that by the integral area of its double bond hydrogen.
4., in laboratory research, precise Identification is not required to use preparation or half along the structure of anti-two kinds of isomers
Preparative high-performance liquid chromatographic technology, can utilize NMR spectra to identify the structure of the two respectively exactly.Particularly
For transisomer, pure compound can be obtained the most in post-conversion, can be with precise Identification by nuclear magnetic data.
5. the reaction of the cis-trans-isomer expanding the reaction application present invention in the industrial production is expanding to gram
Still can realize after Ji, be expected to obtain in the industrial production application.
Embodiment:
1.1 transisomers are the most trans right to the conversion of cis-isomer derived from phenyl acrylic acid chemical composition freely
Hydroxyl cinnamic acid, trans caffeic acid and the chemical composition containing derived from phenyl acrylic acid construction unit are exposed under sunlight
Or several minutes tens hours, can change into corresponding cis-isomer.
1.1 free type trans-cinnamic acid compounds to the conversion of free type cis cinnamic acid compound with coffee
As a example by acid, first do the hydrogen spectrum of trans caffeic acid (7), then nuclear magnetic tube is placed under the sun, respectively 4
Hour, within 8 hours, 16 hours, 24 hours and 48 hours, do nuclear-magnetism test.Carefully analyze this 5 time points
Hydrogen spectrum key signal (hydrogen signal of cis-isomer double bond is δH5.74, d, J=13.2Hz；Trans
One hydrogen signal of isomer is δH6.21, d, J=16.0Hz), it has been found that the phase of cis caffeic acid (8)
To content at 16 hours and 24 hours almost without difference.Above result of study shows, cis caffeic acid is with anti-
Formula caffeic acid was to reach inversion equilibrium at the 16th hour.Now, cis caffeic acid and trans caffeinic ratio
It is 47:53 (Fig. 1).
1.2 trans-phenylacrylic acid quininic acid ester compounds are to the conversion of cis cinnamic acid quininic acid ester compounds
As a example by caffeic acid quininic acid methyl ester, utilizing similar method, result shows cis caffeic acid quininic acid first
Ester (10) and trans caffeic acid quininic acid methyl ester (9) were to reach inversion equilibrium at the 16th hour.Now,
The ratio of cis caffeic acid quininic acid methyl ester and trans caffeic acid quininic acid methyl ester is 38:62 (Fig. 2).
1.3 trans-phenylacrylic acid phenols acids to the conversion of cis cinnamic acid phenols acids with
4-hydroxy-cis-cinnamomic acid 4-β-D-glucopyranosyloxybenzyl ester (16) and
As a example by 4-hydroxy-trans-cinnamomic acid 4-β-D-glucopyranosyloxybenzyl ester (15), adopt
With with similar method, result is: cis-structure and transconfiguration reached to convert flat at the 16th hour
Weighing apparatus, during balance, the relative ratios of cis-trans-isomer is 46:54 (Fig. 3).
1.4 trans-phenylacrylic acid flavone esters to the conversion of cis cinnamic acid flavone ester with kaempferol
(6 '-O-are trans for-3-O-β-D-(the cis coumaric acyl of 6 '-O-) pyranglucoside (22) and kaempferol-3-O-β-D-
Coumaric acyl) as a example by pyranglucoside (21), use and be similar to aforesaid method, result is: cis knot
Structure and transconfiguration reached inversion equilibrium at the 16th hour, and during balance, the relative ratios of cis-trans-isomer is
37:63 (Fig. 4).
1.5 trans-cinnamic triterpene esters are fragrant with cis termentic acid-3-O-to the conversion of cis cinnamic acid triterpene ester
As a example by bean acid fat (28) and trans termentic acid-3-O-coumaric acid fat (27), use similar aforesaid method,
Result is: cis-structure and transconfiguration reached inversion equilibrium at the 4th hour, the phase of cis-trans-isomer during balance
Contrast ratio is 56:44 (Fig. 5).
2. cis-isomer to transisomer convert cis-isomer easy in, add trace iodine,
And heat, can within the extremely short time the most quantitative transisomer changing into correspondence.
2.1 cis cinnamic acid flavone esters to the conversion of trans-phenylacrylic acid flavone ester with kaempferol
-3-O-β-D-(the cis coumaric acyl of 6 '-O-) pyranglucoside (22) and kaempferol-3-O-β-D-(the trans perfume (or spice) of 6 '-O-
Bean acyl) as a example by pyranglucoside (21), in the nuclear magnetic tube equipped with the compound of the two, add the iodine of trace,
During suitably shaking is placed in the water-bath of 50 DEG C 1 minute, wipe the water on nuclear magnetic tube outer wall, carry out NMR
Test, analyzes hydrogen spectrum, finds the characteristic signal (δ of cis-isomerH5.51, d, J=12.8Hz) disappear.
This information alert we, cis-isomer converts (Fig. 6) completely to transisomer.
2.2 cis cinnamic acid phenols acids are similar to aforesaid to the conversion employing of trans-phenylacrylic acid phenols acids
Method, with 4-hydroxy-cis-cinnamomic acid 4-β-D-glucopyranosyloxybenzyl ester (16) and
As a example by 4-hydroxy-trans-cinnamomic acid 4-β-D-glucopyranosyloxybenzyl ester (15), cis
Isomer converts (Fig. 7) completely to transisomer.
Employing is similar to aforesaid method, cis termentic acid-3-O-coumaric acid fat (28) also can to trans committee
Mound dish acid-3-O-coumaric acid fat (27) converts (Fig. 8) completely.
3. the cis-trans-isomer reversible conversion of compounds derived from phenyl acrylic acid contains the transisomer of trace iodine, puts
Under sunlight, transisomer can convert to cis-isomer again, until the two balances again.With
As a example by 4-hydroxy-trans-cinnamomic acid 4-β-D-glucopyranosyloxybenzyl ester (15), will contain
The sample of trace iodine, is placed in sunlight lower 12 hours, and transisomer converts 64.0% to cis-isomer, during balance
The ratio of cis and trans isomer is 64:36 (Fig. 9).
4. 1 gram of trans caffeic acid is dissolved in 30mL AG by derived from phenyl acrylic acid cis-trans-isomer scale-up
In methanol (0.185mM), it is placed under sunlight, and stirs 48 hours, take appropriate reactant liquor, evaporated under reduced pressure,
Doing NMR test with deuterated methanol for solvent, analyze its hydrogen spectrum, trans different caffeic acid is to cis caffeinic turn
Rate is 32.8%.In reaction system, add the iodine of 10mg, add reflux, be placed in 50 DEG C of water-baths
In, to react 30 minutes, take appropriate reactant liquor, evaporated under reduced pressure, do NMR experiment, result shows cis
Caffeic acid convert to trans caffeic acid.
5. the Preliminary Applications of this patent is as a example by caffeic acid quininic acid methyl ester, the cis caffeic acid that relative amount is less
Quininic acid methyl ester is it is considered to be impurity in the research in past, and its structure fails to identify.Utilize the present invention, suitable
The nuclear magnetic signal that formula is one is strengthened, and we successfully identify chemical constitution (Figure 10 and Figure 11).
Table 1 cis-isomer under the effect of the iodine of trace to the conversion (reaction temperature: 50 DEG C) of transisomer
Table 2 transisomer under sunlight to the conversion of cis-isomer
The compound structure containing cinnamic acid construction unit related in table 3 present invention.
Claims (7)
1. the method that a compounds derived from phenyl acrylic acid mutually converts along anti-two kinds of isomers, it is characterised in that knot
The syn-isomerism physical ability of mould assembly compounds derived from phenyl acrylic acid (cinnamic acid esters) is in trace iodine and heating-up temperature
Under the conditions of 48 DEG C-52 DEG C, in 1-3 minutes, being fully converted to its transisomer, free type is suitable
Formula compounds derived from phenyl acrylic acid is converted into the conversion ratio of its transisomer and reaches 50-70%；
The trans-isomerism physical ability of derived from phenyl acrylic acid chemical composition is under sunlight effect, through 2-48 hour, with
The conversion ratio of 20-55% produces its cis-isomer.
2. according to the method described in claim 1 and 2, it is characterised in that cis-isomer and transisomer
The reaction equation of phase co-conversion is:
In formula: R=hydroxyl, methoxyl group, fluorine, chlorine, bromine, iodine；R '=methyl, triterpene, flavone, phenolic acid.
3. according to the method described in claim 1 and 2, it is characterised in that described compounds derived from phenyl acrylic acid chemistry
Constituent structure is that chemical composition contains cinnamic acid construction unit, then include freely compounds derived from phenyl acrylic acid and
The ester that compounds derived from phenyl acrylic acid and other chemical composition are formed.
Method the most according to claim 1, it is characterised in that described cis-isomer is to trans-isomerism
The condition flag that body changes is: trace iodine and temperature are 50 DEG C, 1-3 minute heat time heating time.
Method the most according to claim 2, it is characterised in that described transisomer is to cis-isomer
Condition is: common sunlight, 2 hours to 48 hours response time.
6. according to the method described in claim 1 and 2, it is characterised in that described derived from phenyl acrylic acid chemical combination freely
The ester that thing and compounds derived from phenyl acrylic acid and other chemical composition are formed refers to Caffeic acids, cinnamic acid flavone
Esters, cinnamic acid triterpene esters, cinnamic acid phenolic acid esters and cinnamic acid quininic acid esters.
7. the method that a compounds derived from phenyl acrylic acid mutually converts along anti-two kinds of isomers is applied to medicine, change
Work, material, the analysis detection of Lab Organic and field of industrial production.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964538A (en) * | 2019-12-18 | 2020-04-07 | 江苏创拓新材料有限公司 | The method of transposition of 1-cyclohexyl-2,3-difluorobenzene |
| CN115490740A (en) * | 2022-07-14 | 2022-12-20 | 广西壮族自治区中国科学院广西植物研究所 | Phenolic components having lipase inhibitory activity, preparation method thereof, salt, lipidated derivative, medicine and application |
-
2016
- 2016-05-28 CN CN201610362724.XA patent/CN105884618A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| ZHEN-JIE LI，ET AL: "A highly efficient transformation of cis- to trans-cinnamic acid derivatives by iodine", 《TETRAHEDRON LETTERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964538A (en) * | 2019-12-18 | 2020-04-07 | 江苏创拓新材料有限公司 | The method of transposition of 1-cyclohexyl-2,3-difluorobenzene |
| CN110964538B (en) * | 2019-12-18 | 2022-01-04 | 江苏创拓新材料有限公司 | The method of transposition of 1-cyclohexyl-2,3-difluorobenzene |
| CN115490740A (en) * | 2022-07-14 | 2022-12-20 | 广西壮族自治区中国科学院广西植物研究所 | Phenolic components having lipase inhibitory activity, preparation method thereof, salt, lipidated derivative, medicine and application |
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