JP6315560B2 - Method for producing cis-isomer-containing lycopene and lycopene isomerization method - Google Patents

Description

  The present invention relates to a process for producing cis isomer-containing lycopene by isomerizing trans isomer lycopene to cis isomer lycopene using an electrophile as a catalyst.

  Lycopene is a red pigment contained in tomato and is a kind of naturally occurring carotenoid compound. It has been reported that lycopene has a greater antioxidant effect than other carotenoid compounds such as β-carotene (see Non-Patent Document 1, for example). In addition, since lycopene has 11 conjugated π bonds, various cis isomers exist, and cis isomer lycopene is also known to have better intestinal absorption than trans isomer lycopene ( For example, refer nonpatent literature 2.).

  Most carotenoid compounds such as β-carotene and lycopene exist as trans isomers in nature. For this reason, a carotenoid compound-containing composition extracted and purified from a plant or the like usually contains many trans isomers. Therefore, a method for increasing the content (cis content) of a cis isomer of a carotenoid compound is desired. For example, Patent Document 1 discloses that the cis-isomer content can be increased by subjecting a carotenoid compound such as lycopene to heat treatment, electromagnetic wave irradiation treatment, or radical reaction, and further, the cis-isomer content of lycopene. To about 40% by thermal reaction at 100 ° C., to about 65% by electromagnetic wave irradiation treatment using a microwave oven, and to about 77% by photoisomerization using iodine as a catalyst (radical reaction) in dichloromethane solution. It is described that it was raised.

JP 2012-2111169 A

Bohm, 3 others, Journal of Agricultural and Food Chemistry, 2002, 50, 221-226. Failla, two others, Journal of Nutrition, 2008, 138, 482-486.

  Among the methods described in Patent Document 1, in the heat treatment, the cis-body content remains at most about 40%, and the electromagnetic wave treatment requires an electromagnetic wave device. In the radical reaction, iodine that cannot be used for food processing is used, so that there is a problem that the use of lycopene after isomerization is limited.

  The present invention provides a method for producing lysine-containing lycopene by efficiently cis-isomerizing lycopene while suppressing decomposition of lycopene using iron (III) chloride, which is an edible electrophile, as a catalyst. For the purpose.

  As a result of intensive studies to solve the above problems, the present inventors have conducted lysopine cis isomerization reaction in ethyl acetate, acetone or dichloromethane using iron (III) chloride as a catalyst. The present invention was completed by finding that cis isomerization can be carried out efficiently while inhibiting the decomposition of.

That is, the manufacturing method of the cis isomer containing lycopene concerning this invention, the manufacturing method of food-drinks, the manufacturing method of cosmetics, and the isomerization method of lycopene are the following [1]-[20].
[1] A method for producing a cis-isomer-containing lycopene, comprising cis-isomerizing lycopene in a solvent comprising ethyl acetate, acetone or dichloromethane in the presence of iron (III) chloride.
[2] The cis-isomer-containing lycopene according to the above [1], wherein the cis-isomer content of lycopene after the cis-isomerization reaction of lycopene is 50% or more and the residual ratio of lycopene is 70% or more. Manufacturing method.
[3] Content ratio of iron (III) chloride to lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) at the time of starting the cis isomerization reaction of lycopene is 0 The method for producing lycopene containing the cis isomer of [1] or [2], which is 0.005 to 0.04.
[4] Content ratio of iron (III) chloride to lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) at the start of the cis isomerization reaction of lycopene is 0 The method for producing lycopene containing cis isomer according to [1] or [2], which is 0.01 to 0.04.
[5] The method for producing lycopene containing cis isomer according to any one of the above [1] to [4], wherein the reaction temperature of the cis isomerization reaction of lycopene is 20 to 75 ° C.
[6] The method for producing a lycopene-containing lycopene according to any one of the above [1] to [5], wherein the reaction time of the cis-isomerization reaction of lycopene is 1 to 48 hours.
[7] The process for producing lycopene containing cis isomer according to any one of [1] to [5] above, wherein the reaction time of the cis isomerization reaction of lycopene is 3 to 48 hours.
[8] The method for producing lycopene containing cis isomer according to any one of the above [1] to [7], wherein the lycopene used in the cis isomerization reaction of lycopene is derived from fruits and vegetables.
[9] The method for producing cis-isomer-containing lycopene according to [8], wherein the fruits and vegetables include tomatoes.
[10] A method for producing a food or drink, characterized by using as a raw material the cis isomer-containing lycopene produced by the method for producing a cis isomer-containing lycopene according to any one of [1] to [9].
[11] A method for producing a cosmetic, characterized in that the cis isomer-containing lycopene produced by the method for producing a cis isomer-containing lycopene according to any one of [1] to [9] is used as a raw material.
[12] A method for isomerizing lycopene, comprising cis-isomerizing lycopene in a solvent consisting of ethyl acetate, acetone or dichloromethane in the presence of iron (III) chloride.
[13] The method for isomerizing lycopene according to [12], wherein the cis-isomer content of lycopene after the cis-isomerization reaction of lycopene is 50% or more, and the residual ratio of lycopene is 70% or more.
[14] The content ratio of iron (III) chloride and lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) at the start of the cis isomerization reaction of lycopene is 0. The lycopene isomerization method according to the above [12] or [13], which is 0.005 to 0.04.
[15] Content ratio of iron (III) chloride and lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) at the time of starting the cis isomerization reaction of lycopene is 0 The isomerization method of lycopene according to the above [12] or [13], which is 0.01 to 0.04.
[16] The lycopene isomerization method according to any one of the above [12] to [15], wherein the reaction temperature of lycopene cis isomerization reaction is 20 to 75 ° C.
[17] The lycopene isomerization method according to any one of [12] to [16] above, wherein the reaction time of the cis-isomerization reaction of lycopene is 1 to 48 hours.
[18] The method for isomerizing lycopene according to any one of the above [12] to [16], wherein the reaction time of the cis-isomerization reaction of lycopene is 3 to 48 hours.
[19] The lycopene isomerization method according to any one of the above [12] to [18], wherein the lycopene used in the cis-isomerization reaction of lycopene is derived from fruits and vegetables.
[20] The method for isomerizing lycopene according to [19], wherein the fruits and vegetables contain tomatoes.

  According to the present invention, it is possible to efficiently obtain lycopene having a higher content ratio of cis isomer having better bioabsorbability than trans isomer.

In Example 1, it is the figure which showed the measurement result of the cis-isomer content rate (%) of each reaction solution which used ethyl acetate, acetone, or a dichloromethane as a solvent. In Example 1, it is the figure which showed the measurement result of the lycopene residual rate (%) of each reaction solution which used ethyl acetate, acetone, or a dichloromethane as a solvent. In Example 2, it is the figure which showed the measurement result of the cis-isomer content rate (%) of each reaction solution from which ethyl acetate is used as a solvent and the concentration of iron (III) chloride is different. In Example 2, it is the figure which showed the measurement result of the lycopene residual rate (%) of each reaction solution from which ethyl acetate is used as a solvent and in which the concentration of iron (III) chloride is different. In Example 3, it is the figure which showed the measurement result of the cis-isomer content rate (%) of each reaction solution which uses acetone as a solvent and differs in the concentration of iron (III) chloride. In Example 3, it is the figure which showed the measurement result of the lycopene residual rate (%) of each reaction solution which uses acetone as a solvent and differs in the density | concentration of iron (III) chloride. In Example 4, it is the figure which showed the measurement result of cis-isomer content rate (%) of each reaction solution which uses dichloromethane as a solvent and differs in the concentration of iron (III) chloride. In Example 4, it is the figure which showed the measurement result of the lycopene residual rate (%) of each reaction solution which uses dichloromethane as a solvent and differs in the concentration of iron (III) chloride. In Example 5, it is the figure which showed the measurement result of the cis-isomer content rate (%) of each reaction solution which uses ethyl acetate as a solvent and reaction temperature differs. In Example 5, it is the figure which showed the measurement result of the lycopene residual rate (%) of each reaction solution which uses ethyl acetate as a solvent and differs in reaction temperature. In Example 6, it is the figure which showed the measurement result of the cis-isomer content rate (%) of each reaction solution which uses acetone as a solvent and differs in reaction temperature. In Example 6, it is the figure which showed the measurement result of the lycopene residual rate (%) of each reaction solution which uses acetone as a solvent and differs in reaction temperature. In Example 7, it is the figure which showed the measurement result of the cis-isomer content rate (%) of each reaction solution which uses dichloromethane as a solvent and differs in reaction temperature. In Example 7, it is the figure which showed the measurement result of the lycopene residual rate (%) of each reaction solution which uses dichloromethane as a solvent and differs in reaction temperature.

In the present invention and the present specification, the cis-isomer content (%) means the ratio (%) of the total cis-isomer lycopene amount to the total lycopene amount. The lycopene residual rate means the ratio of the amount of lycopene after the isomerization treatment to the amount of lycopene before the isomerization treatment (in the present invention, the isomerization reaction with an iron (III) chloride catalyst). Furthermore, the cis isomer content (%) means the cis isomer lycopene content (%) in the reaction solution after the isomerization reaction, and is specifically calculated by the following formula.
[Cis isomer content (%)] = [cis isomer content (%)] × [lycopene residual rate (%)] / 100

  In addition, in this invention and this-application specification, content of lycopene can be measured by HPLC (high performance liquid chromatography) method using a reverse phase column or a normal phase column. The quantification is calculated based on the peak area of each lycopene isomer peak in the chromatogram. More specifically, the cis-isomer content (%) and the lycopene residual rate (%) can be calculated by the following equations.

[Cis isomer content (%)] = [total value of peak areas of all cis isomers] / [total value of peak areas of all lycopene peaks] × 100
[Lycopene residual ratio (%)] = [total value of peak areas of all lycopene peaks after isomerization] / [total value of peak areas of all lycopene peaks before isomerization] × 100

  The method for producing lysopine containing cis isomer according to the present invention (hereinafter sometimes referred to as “the production method according to the present invention”) catalyzes iron (III) chloride in a solvent comprising ethyl acetate, acetone or dichloromethane. The lycopene is characterized by cis isomerization. The production method according to the present invention can efficiently cis-isomerize lycopene while suppressing decomposition of lycopene by reacting with a specific electrophile in a specific solvent. The cis isomer contained in the cis isomer-containing lycopene obtained by the production method according to the present invention is not particularly limited as long as it is a cis isomer, and contains one kind of cis isomer. Or may contain two or more cis isomers. The cis isomer of lycopene includes various isomers such as a 5-cis isomer, a 9-cis isomer, and a 13-cis isomer.

  Lycopene is soluble in various organic solvents such as tetrahydrofuran, chloroform, benzene, hexane, petroleum ether, etc., but in the production method according to the present invention, among the organic solvents capable of dissolving lycopene, particularly ethyl acetate, acetone. Alternatively, dichloromethane is used as a solvent. By using ethyl acetate, acetone, or dichloromethane as a solvent, cis isomerization reaction of lycopene catalyzed by iron (III) chloride can be efficiently performed while suppressing decomposition of lycopene. In the present invention, it is particularly preferable to use ethyl acetate or acetone as a solvent. By using ethyl acetate or acetone as a solvent, the decomposition rate of lycopene during the isomerization reaction can be sufficiently reduced (that is, the lycopene residual rate is remarkably improved). The cis isomer can be obtained efficiently. In particular, in ethyl acetate or acetone, the lycopene residual rate is high even under relatively high temperature conditions of about 60 ° C., so that the produced cis isomer is hardly decomposed even when the solvent is distilled off after the cis isomerization reaction. There are also advantages. In addition, since ethyl acetate and acetone are edible solvents, lysopine containing cis isomers obtained using these solvents is highly safe and suitable as a raw material for foods, drinks, pharmaceuticals, cosmetics, etc. .

  In the production method according to the present invention, the balance between lycopene cis-isomer content and residual rate is important. If the decomposition of lycopene progresses and the residual lycopene ratio decreases, the lycopene-derived decomposition products and the like increase, and the purity as lycopene may decrease. For this reason, from the point of obtaining cis isomer-containing lycopene obtained by efficiently cis-isomerizing lycopene while suppressing decomposition of lycopene, in the production method according to the present invention, after isomerization reaction, the cis-isomer content of lycopene is It is preferably 50% or more and the lycopene residual rate is preferably 70% or more, the ciscopper content of lycopene is 50% or more, and the lycopene residual rate is more preferably 80% or more. More preferably, the cis-isomer content is 50% or more and the lycopene residual rate is 90% or more.

  In the production method according to the present invention, iron (III) chloride, which is an electrophile, is used as a catalyst. The content of iron (III) chloride in the reaction solution of the cis isomerization reaction is not particularly limited. However, since cis isomerization of lycopene can be performed more efficiently, iron (III) chloride at the start of the reaction The content ratio of lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) is preferably 0.005 or more, and more preferably 0.01 or more. On the other hand, as the content of iron (III) chloride in the reaction system increases, lycopene may be easily decomposed. For this reason, from the viewpoint of inhibiting decomposition of lycopene, the content ratio (mass ratio) of iron (III) chloride and lycopene at the start of the reaction is preferably 0.08 or less, more preferably 0.04 or less. preferable. The content ratio (mass ratio) of iron (III) chloride and lycopene at the start of the reaction is 0.005 to 0.04 in view of the balance between the cis-isomer content after the isomerization reaction and the suppression of decomposition of lycopene. Is preferable, it is more preferable that it is 0.01-0.04, and it is further more preferable that it is 0.02-0.04. The “lycopene content” means the total content of all lycopene including all isomers.

  The lycopene provided in the production method according to the present invention may be a synthetic product, but is preferably a natural product derived from plants, animals, microorganisms and the like. Especially, the thing derived from fruits and vegetables with much lycopene content is preferable. Examples of fruits and vegetables with a high lycopene content include tomato, eggplant, paprika, pepper, carrot, watermelon, melon, grapefruit, oyster, cherry, apricot, plum, papaya, and red guava, with tomato being particularly preferred.

  The lycopene provided in the production method according to the present invention preferably does not contain water or an organic solvent or has a very low content thereof. When the amount of the solvent brought along with lycopene is small, the cis-isomerization effect of lycopene by a specific solvent such as ethyl acetate can be sufficiently exerted. For example, when lycopene derived from fruits and vegetables is cis-formed, a concentrate or oleoresin (extracted with an organic solvent and then the organic solvent is removed by fully concentrating the juice of the fruits and vegetables in a solvent such as ethyl acetate. A lycopene solution can be prepared by mixing the obtained lipid fractions) and dissolving the lycopene contained therein. In the production method according to the present invention, the lycopene derived from fruits and vegetables includes lycopene extracted from fruits and vegetables.

  In addition, the squeezed juice of fruit and vegetables can be prepared by squeezing the fruit and vegetables used as a raw material by a conventional method. As the squeezer, those commonly used for squeezing and squeezing in the field of food and drink such as a pulper, screw press, ginner, decanter, uniaxial or biaxial (same direction or different direction rotation type) extruder are used in combination. be able to. Squeezing can also be performed in an inert gas atmosphere such as nitrogen gas. It is also preferable that the fruits and vegetables are shredded or crushed to an appropriate size before squeezing. For shredding and the like, those usually used for shredding or crushing vegetables and fruits such as dicers, cutters, slicers and hammer crushers can be used. Moreover, before squeezing fruit and vegetables or its shredded material etc., you may heat-process as needed. The concentration treatment of the squeezed liquid can be performed by a conventional method using a commonly used concentrator such as a vacuum concentrator, a stirring type thin film concentrator, or a plate concentrator.

  The oleoresin of fruits and vegetables can be prepared by a conventional method. For example, the insoluble fraction is recovered from the juice of fruits and vegetables, and the insoluble fraction is mixed with an organic solvent such as acetone, ethyl acetate, hexane, dichloromethane, dichloroethane, lower aliphatic alcohols, and the lipid fraction is extracted. Thereafter, the oleoresin is obtained by removing the organic solvent by a distillation method or the like. In the present invention, commercially available oleoresin may be used.

  In the production method according to the present invention, first, a reaction solution in which lycopene and iron (III) are dissolved is prepared using ethyl acetate, acetone or dichloromethane as a solvent. The reaction solution may be prepared by adding iron (III) chloride to a solution in which lycopene is dissolved in a solvent, or by dissolving lycopene in a solvent containing iron (III) chloride. Good.

  The concentration of lycopene in the reaction solution is not particularly limited. In the present invention, for example, the total lycopene concentration is preferably 0.001 to 10 mg / mL, more preferably 0.01 to 10 mg / mL, and further preferably 0.01 to 1 mg / mL. preferable.

  An isomerization reaction is performed by holding the reaction solution for a predetermined time. The higher the reaction temperature, the easier the isomerization reaction proceeds, but the lycopene tends to decompose. In the production method according to the present invention, the reaction temperature of the isomerization reaction is preferably within a range of 0 to 80 ° C, and more preferably within a range of 20 to 75 ° C. Moreover, as reaction time, it is preferable that it is 1 to 48 hours, and it is more preferable that it is 3 to 48 hours.

  The reaction conditions for the isomerization reaction are preferably adjusted so that the cis-isomer content of lycopene and the lycopene residual rate after the reaction are within a desired range. In the production method according to the present invention, the cis-isomer content of lycopene after the isomerization reaction is 50% or more, and the lycopene residual rate is 70% or more, preferably 80% or more, more preferably 90% or more. Thus, it is preferable to adjust the lycopene concentration in the isomerization reaction, the content ratio of lycopene and iron (III) chloride, the reaction temperature, the reaction conditions, and the like.

  The cis isomer-containing lycopene obtained by the production method according to the present invention can be used for various applications in the same manner as lycopene used as a raw material. In particular, the cis isomer-containing lycopene obtained by the production method according to the present invention performed using ethyl acetate or acetone as a solvent has a high content of cis isomers excellent in intestinal absorption and is safe. It is suitable as a raw material for foods, drinks, cosmetics, pharmaceuticals and the like. Although it does not specifically limit as the said food-drinks, Various drinks, jelly, jelly, jam, sherbet, a supplement (dietary supplement) etc. are preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to a following example. The HPLC for quantifying each isomer of lycopene was performed under the following conditions.

<Normal phase HPLC conditions for lycopene>
Apparatus: Hitachi high-performance liquid chromatograph Chromamaster (manufactured by Hitachi High-Technologies Corporation),
Column: Nucleosil 300-5 [stationary phase: silica gel, inner diameter: 4.6 mm × 250 mm, GL Sciences, Inc.]
Column temperature: 30 ° C.
Sample injection volume: 10 μL,
Mobile phase: hexane (containing 0.1% N, N-diisopropylethylamine),
Mobile phase flow rate: 1.0 mL / min,
Detector: Photodiode array detector,
Detection wavelength: 460 nm.

[Example 1]
The cis isomerization reaction of lycopene was performed using iron acetate (III) as a catalyst using ethyl acetate, acetone or dichloromethane as a solvent. The raw material lycopene used for the reaction was lycopene extracted from tomato paste with a purity of 95% or more and an all-trans isomer ratio of 99% or more (all-trans isomer lycopene content: 99.2%, cis lycopene content: 0.0. 8%) was used.
First, a solution in which lycopene as a raw material was dissolved in each solvent so as to be 0.1 mg / mL was adjusted to 20 ° C., and then iron (III) chloride was further added to a final concentration of 0.001 mg / mL (in the reaction solution). A reaction solution was added and dissolved so that the content ratio (mass ratio) of iron (III) and lycopene was 0.01), and cis isomerization reaction was performed. The liquid temperature of the reaction solution was maintained at 20 ° C. during the cis isomerization reaction. A portion of each reaction solution is sampled over time before the start of the isomerization reaction (before the addition of iron (III) chloride) and after the start of the isomerization reaction. Based on the area, the cis-isomer content (%), lycopene residual rate (%), and cis-isomer content (%) of lycopene were determined. The cis-isomer content (%) was calculated from the following formula.
[Cis isomer content (%)] = [cis isomer content (%)] × [lycopene residual rate (%)] / 100

  The measurement result of cis isomer content (%) is shown in FIG. 1, the measurement result of lycopene residual rate (%) is shown in FIG. 2, and the calculation result of cis isomer content (%) is shown in Table 1. As a result, the cis isomerization reaction proceeded in all the solvents, and the cis isomer content reached a plateau after a sufficient reaction time. When reacted in dichloromethane, the cis-isomer content was the highest, but lycopene decomposed over time, and the lycopene residual rate was 24.2% at 24 hours after the start of the reaction (reaction time 24 hours). there were. On the other hand, in ethyl acetate or acetone, although the cis-isomer content was lower than in dichloromethane, the cis-isomer content was as high as 50% or more when the reaction time was 6 hours. Further, in ethyl acetate or acetone, the lycopene residual rate was as high as 90% or more even when the reaction time was 24 hours. As shown in Table 1, the cis-isomer content was highest at 59.8 to 63.8% when dichloromethane was used when the reaction time was 1 to 6 hours, but the reaction time was 12 hours later. In the following, when ethyl acetate or acetone was used, it was higher than 50%, and the cis isomer was efficiently and stably obtained.

[Example 2]
The effect of iron (III) chloride concentration on the cis isomerization reaction of lycopene when ethyl acetate was used as a solvent was investigated. The raw material lycopene used in the cis isomerization reaction was the same as in Example 1.
Specifically, after adjusting the solution of raw material lycopene in ethyl acetate so as to be 0.1 mg / mL to 20 ° C., iron (III) chloride is further added at final concentrations of 0.0005, 0.001. , 0.002, 0.004, 0.008, or 0.016 mg / mL (content ratio of iron (III) chloride and lycopene in the reaction solution (mass ratio): 0.005, 0.01,. 02, 0.04, 0.08, or 0.16) were added and dissolved to prepare cis isomerization reaction. The liquid temperature of the reaction solution was maintained at 20 ° C. during the cis isomerization reaction. In the same manner as in Example 1, the reaction solution was sampled over time, and lycopene cis-isomer content (%), lycopene residual rate (%), and cis-isomer content (%) were determined.

  The measurement result of cis isomer content (%) is shown in FIG. 3, the measurement result of lycopene residual rate (%) is shown in FIG. 4, and the calculation result of cis isomer content (%) is shown in Table 2. As a result, the higher the concentration of iron (III) chloride, the higher the cis-body content of lycopene and the faster the decomposition rate. Further, when the concentration of iron (III) chloride was 0.0005 to 0.002 mg / mL, lycopene was hardly decomposed and cis isomerization proceeded efficiently. From the balance between the cis-isomer content and the residual rate, as shown in Table 2, when the concentration of iron (III) chloride is 0.001 to 0.004 mg / mL, the reaction time is 3 hours or more and the cis-isomer content is 50. The cis isomer-containing lycopene having a high cis isomer content and a high cis isomer content could be efficiently produced.

[Example 3]
The effect of iron (III) chloride concentration on the cis isomerization reaction of lycopene when acetone was used as a solvent was investigated. Specifically, a cis isomerization reaction was performed in the same manner as in Example 2 except that acetone was used instead of ethyl acetate as a solvent, sampled over time from the reaction solution, and ciscopper content of lycopene (%) The lycopene residual rate (%) and the cis-isomer content (%) were determined.

  The measurement result of cis isomer content (%) is shown in FIG. 5, the measurement result of lycopene residual rate (%) is shown in FIG. 6, and the calculation result of cis isomer content (%) is shown in Table 3. As a result, as in Example 2, the higher the concentration of iron (III) chloride, the higher the cis-body content of lycopene, the faster the decomposition rate, and the concentration of iron (III) chloride was 0.0005-0. Almost no degradation of lycopene was observed at 0.002 mg / mL. From the balance of cis-isomer content and residual rate, as shown in Table 3, when the concentration of iron (III) chloride is 0.001 to 0.004 mg / mL, the cis-isomer content is 6 to 12 hours. A cis isomer-containing lycopene having a high cis isomer content rate of 50% or more was efficiently produced.

[Example 4]
The effect of iron (III) chloride concentration on the cis isomerization reaction of lycopene when dichloromethane was used as a solvent was investigated. Specifically, a cis isomerization reaction was performed in the same manner as in Example 2 except that dichloromethane was used in place of ethyl acetate as a solvent, sampled from the reaction solution over time, and the cis isomer content (%) of lycopene The lycopene residual rate (%) and the cis-isomer content (%) were determined.

  The measurement result of cis isomer content (%) is shown in FIG. 7, the measurement result of lycopene residual rate (%) is shown in FIG. 8, and the calculation result of cis isomer content (%) is shown in Table 4. As a result, the higher the iron (III) chloride concentration, the faster the lycopene cisification rate and decomposition rate. Unlike the case of using ethyl acetate or acetone, lycopene was decomposed over time even when the concentration of iron (III) chloride was 0.0005 to 0.002 mg / mL, and the cis-isomer content rate was as high as 80% or more. However, the cis content was as low as less than 50% at a reaction time of 12 hours or longer. Since the decomposition tendency of lycopene continues until the dichloromethane is distilled off, when dichloromethane is used as a solvent, the reaction time of the cis isomerization reaction is shortened (for example, 1 hour or more and less than 3 hours), and the solvent is used immediately after the reaction is completed. It is preferable to carry out a distillation treatment.

[Example 5]
The effect of reaction temperature on the cis-isomerization reaction of lycopene when using ethyl acetate as a solvent was investigated. Specifically, the cis isomerization reaction was performed in the same manner as in Example 2 except that the iron (III) chloride concentration was 0.001 mg / mL and the reaction temperature was 0, 20, 40, or 60 ° C. Sampling was performed from the solution with time, and the cis-body content (%), lycopene residual rate (%), and cis-body content (%) of lycopene were determined.

  The measurement result of cis isomer content (%) is shown in FIG. 9, the measurement result of lycopene residual rate (%) is shown in FIG. 10, and the calculation result of cis isomer content (%) is shown in Table 5. As a result, the higher the reaction temperature, the higher the cis-isomer content of lycopene and the higher the cis-isomer content. The lycopene residual rate was about 80% when the reaction time was 24 hours at 60 ° C., but the others were as high as 90% or more, and lycopene was hardly decomposed.

[Example 6]
The influence of reaction temperature on the cis-isomerization reaction of lycopene when acetone was used as a solvent was investigated. Specifically, a cis isomerization reaction was performed in the same manner as in Example 5 except that acetone was used instead of ethyl acetate as a solvent, sampled over time from the reaction solution, and the cis-body content (%) of lycopene The lycopene residual rate (%) and the cis-isomer content (%) were determined.

  The measurement result of the cis isomer content (%) is shown in FIG. 11, the measurement result of the lycopene residual rate (%) is shown in FIG. 12, and the calculation result of the cis isomer content (%) is shown in Table 6. As a result, the higher the reaction temperature, the higher the cis-isomer content of lycopene and the higher the cis-isomer content. The lycopene residual rate was about 80% when the reaction time was 24 hours at 40 to 60 ° C., but the others were as high as 90% or more, and almost no lycopene was decomposed.

[Example 7]
The effect of reaction temperature on the cis isomerization reaction of lycopene when dichloromethane was used as a solvent was investigated. Specifically, a cis isomerization reaction was performed in the same manner as in Example 5 except that dichloromethane was used in place of ethyl acetate as a solvent, sampled over time from the reaction solution, and ciscopper content of lycopene (%) The lycopene residual rate (%) and the cis-isomer content (%) were determined.

  The measurement result of cis isomer content (%) is shown in FIG. 13, the measurement result of lycopene residual rate (%) is shown in FIG. 14, and the calculation result of cis isomer content (%) is shown in Table 7. As a result, the higher the reaction temperature, the faster the ciscopping rate and decomposition rate of lycopene. Unlike the case of using ethyl acetate or acetone, lycopene was decomposed over time even when the reaction temperature was 0 to 20 ° C., and the cis isomer content was as high as 80% or more. The reaction time was as low as less than 50% over 12 hours.

Claims (20)

  A process for producing a lysine containing cis isomer, characterized in that lycopene is cis-isomerized in the presence of iron (III) chloride in a solvent comprising ethyl acetate, acetone or dichloromethane. The method for producing lysopine containing cis isomer according to claim 1, wherein the cis isomer content of lycopene after the cis isomerization reaction of lycopene is 50% or more and the residual ratio of lycopene is 70% or more. The content ratio of iron (III) chloride to lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) at the time of initiation of the cis isomerization reaction of lycopene is 0.005. The method for producing lysopine containing cis isomer according to claim 1 or 2, which is 0.04. Content ratio of iron (III) chloride and lycopene ( [ content of iron (III) chloride] / [content of lycopene] ) (mass ratio) at the start of the cis isomerization reaction of lycopene is 0.01 to The method for producing lysopine containing cis isomer according to claim 1 or 2, which is 0.04. The method for producing a cis-isomer-containing lycopene according to any one of claims 1 to 4, wherein the reaction temperature of the cis-isomerization reaction of lycopene is 20 to 75 ° C. The method for producing a cis-isomer-containing lycopene according to any one of claims 1 to 5, wherein the reaction time of the cis-isomerization reaction of lycopene is 1 to 48 hours. The method for producing lysopine containing cis isomer according to any one of claims 1 to 5, wherein the reaction time of the cis isomerization reaction of lycopene is 3 to 48 hours. The method for producing a cis isomer-containing lycopene according to any one of claims 1 to 7, wherein the lycopene used in the cis isomerization reaction of lycopene is derived from fruits and vegetables.   The method for producing cis-isomer-containing lycopene according to claim 8, wherein the fruits and vegetables contain tomatoes.   The manufacturing method of food-drinks characterized by using the cis isomer containing lycopene manufactured by the manufacturing method of the cis isomer containing lycopene as described in any one of Claims 1-9 as a raw material.   A method for producing a cosmetic, characterized in that the cis-isomer-containing lycopene produced by the method for producing a cis-isomer-containing lycopene according to any one of claims 1 to 9 is used as a raw material. A method for isomerizing lycopene, comprising cis-isomerizing lycopene in a solvent comprising ethyl acetate, acetone or dichloromethane in the presence of iron (III) chloride . The method for isomerizing lycopene according to claim 12, wherein the cis-isomer content of lycopene after the cis-isomerization reaction of lycopene is 50% or more and the residual ratio of lycopene is 70% or more . The content ratio of iron (III) chloride to lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) at the time of initiation of the cis isomerization reaction of lycopene is 0.005. The method for isomerizing lycopene according to claim 12 or 13, which is 0.04. The content ratio of iron (III) chloride and lycopene ([content of iron (III) chloride] / [content of lycopene]) (mass ratio) at the time of initiation of the cis isomerization reaction of lycopene is 0.01 to The method for isomerizing lycopene according to claim 12 or 13, which is 0.04 . The method for isomerizing lycopene according to any one of claims 12 to 15, wherein the reaction temperature of the cis-isomerization reaction of lycopene is 20 to 75 ° C. The method for isomerizing lycopene according to any one of claims 12 to 16, wherein the reaction time of the cis-isomerization reaction of lycopene is 1 to 48 hours . The method for isomerizing lycopene according to any one of claims 12 to 16, wherein the reaction time of the cis-isomerization reaction of lycopene is 3 to 48 hours . The lycopene isomerization method according to any one of claims 12 to 18, wherein the lycopene used in the cis-isomerization reaction of lycopene is derived from fruits and vegetables . The method for isomerizing lycopene according to claim 19, wherein the fruits and vegetables contain tomatoes .

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