JPS6028950A - Cis-3-alkenoic acid, its preparation and use - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R is 1-6C alkyl; R1 is H, or 1-3C alkyl; when R is 1C alkyl, R1 is 2-4C alkyl, and when R is 2C alkyl or 4-6C alkyl, R1 is 1-3C alkyl). EXAMPLE:2-Ethyl-cis-3-pentenoic acid. USE:An imparter for providing fragrance and flavor having durability or a modifier. Having a main tone of fragrance and flavor like fruit or grass, showing a tone of fruit, green flower, etc. which may have fatty fragrance and flavor. PREPARATION:A trans-2-alkenoic acid shown by the formula II is isomerized in an organic solvent in the presence of both hexamethylphosphoric acid triamide and a basic organic alkali metal compound (e.g., methyllithium, etc.) at about -70-about -50 deg.C, to give a compound shown by the formula I easily.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cis-3-alkenoic acids that have not been previously described in any known literature, their production method, and a method for producing cis-3-alkenoic acids that have not been previously described in any known literature.
1yA to its use as ml.

More specifically, the present invention is represented by the following formula +11, where R is Cr and represents an alkyl group, and R4 represents a hydrogen atom or C, -, C, or an alkyl group.

Here, if R is C or an alkyl group, RIBcffi
-c is an alkyl group, R is C, an alkyl group or C,
-, C, in the case of an alkyl group, R2 is c,, c;'
, is an alkyl group.

This applies to cis-3-alkenoic acids represented by

The present invention also includes: The present invention also relates to a method for producing the above-mentioned compound of formula (1), and also to a long-lasting aroma and flavor imparting or modulating agent containing the compound of formula (1) as an active ingredient.

The present inventors have conducted extensive research on 3-alkenoic acids. As a result, we discovered that a compound represented by the above formula (1), which had not been previously described in any known literature, existed and succeeded in its synthesis.

Historically, the new compound of formula (1) has been used as a synthetic intermediate in the fields of F materials, prefectures, etc., in addition to M pillars.

It has been discovered that the compound itself is useful as a sweet and mild flavor imparting or modulating agent with a principal fruit-like to grass-like aroma and flavor, and that it exhibits excellent flavor properties.

According to the 41F death of people with disabilities, the cis-3-alkenes of formula (1) in 11 have a fruit-like or acrid aroma as the main tone, and may be accompanied by a fat-like aroma. It is a new compound that exhibits tones such as , green, flower, citrus, and woody, and has ambiguous persistence. It has been discovered that it is an extremely useful and unique 977 ingredient as a long-lasting Aiki flavor imparter or *ai4x+ in a wide range of fields of use, such as health, 11# fresh, and medical products.

Therefore, the object of the present invention is to solve the above formula (1) which has not been described in the literature.
The present invention provides a compound and a method for producing the same. Another object of the present invention is to provide a long-lasting aroma and flavor preparation f containing the compound qjIJ of formula 11) as an active ingredient.

The above objects and many other objects and advantages of the present invention will be apparent from the following description.

The cis-3-alkenoic acids of the formula (1) of the present invention are, for example, the following formula (2), where R represents CI-1::, an alkyl group.

R1 represents a hydrogen atom, Hc, c, or an alkyl group.

Here, when R is a CI alkyl group, RlHc R,
c is an alkyl group, R is C, an alkyl group or C,
In the case of -C-alkyl, R1 is a C1-C alkyl group.

The trans-2-alkenoic acid represented by I can do that.

The trans-2-alkenoic acid phase of the raw material formula (2) is a known compound, for example, Organic Rgacti
ona.

The so-called Khos is a condensation/decarboxylation reaction of malon 2 and an aldehyde or ketone in the presence of a base catalyst such as pyridine according to the method described in Voj, 15, p. 204.
It can be easily synthesized using the tv#nαge1 reaction, or by a known method of converting commercially available trans-2-alkenoic acid into a curing agent such as silver chloride, chromic acid, etc. can.

According to the embodiment of the present invention, the filtration compound'f is produced.

For example, the compound of formula (2) above is subjected to an isomerization reaction in the presence of hexamethylphosphoric acid triamide and a basic organic alkali metal compound in a bathing medium. This exception.

Basic organic alkali metal compound used Q'a 1111
Depending on the type of solvent used, the temperature can be adjusted accordingly, for example, under temperature conditions of about -70°C to about 50°C.

For example, a compound of formula (2) can be combined with the formula (1) by subjecting it to reaction conditions for about 2 minutes to about 4 hours! Can be easily converted to heat. The above reaction is preferably carried out in an inert gas such as argon, N, gas and the like.

In the above reaction, the amount of hexamethylphosphorus cetriamide to be used can be selected as appropriate, and may be, for example, about 1 to about 5 times the molar amount of the compound of formula (2) above. In addition, the 1118 sensitivity of the basic alkali pine compound catalyst can be selected as appropriate.

For example, it may be about 2 to about 4 times the molar amount of the compound of formula (2) above. Examples of the basic organic alkali metal compound include 1 lithium diisopropylamine and methyl lithium.

Examples include butyllithium and triphenylmethyllithium. The liquid used in the above reaction may be selected as appropriate, for example, an ether-based or hydrogen ash-based organic solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane, hexane, toluene, etc. I can show you something. There are no particular restrictions on the amount of these organic solvents used, and they can be used in a wide variety of ways.

For example, about 0.5 to about 10 to 9 of the above formula (2) compound
The range of use can be about twice that of planting.

In the above formulas (1) and (2) compounds, specific examples of H include CF cores such as methyl, ethyl, propyl, inpropyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and the like. Examples include alkyl groups. Also, R
Specific examples of 戈 include hydrogen atoms and C, , C, alkyl groups such as methyl, ethyl, propyl, impropyl, and the like.

The production method of the present invention comprises the above formula (1) compound ea VCMu
No.

It can also be used in the production of various cis-3-alkene acids.

The cis isomerization rate to the new compound of formula (1), which has not been previously described in the literature, is almost 100%, and the yield is as high as about 85% or more, and the purity of the cis isomer is extremely high. For example, a reaction product that can be easily obtained industrially with a high yield of the desired product can be purified by, for example, a method of 〃≦〉ゐyrod.

The above formula (11 compound 9/, J
As a concrete example of 1, iyt + e is as follows - 1 = li
I can raise and lower things.

to C111 to prisoner to rN to prisoner to prisoner
To Nsanba Village! Deaf Bas Mi Bas Bas Anzu g
HO Lo O-Kyou O-Ko Ro-ro-ro Friend Ro 〇-------
−−− −Φ ψ − ＼ ＼ ＼ ＼ ＼ ＼ ＼ ＼ ＼ ＼ ＼ ＼−Ro LQ u'+ t−cq ロ cQeJ , -1cI
'103eQ 44--4 no.4- +m -+-1m +-1+m +-4m m +m
+-+ +-1? ? ? ? ? ? ? ? ? ? ? ? b ■ CVIo! Rumors Ro Ro − Ro ■ ■ Ro Nori moan--Pus-11 inch Zer to Se Gin bone Roku ＼ So and Ko book's n se
F
il to so no 1 to he he I 1 he he -
~ To) Heat ~ Juku I Roku 11-1 Iso
ro 1 1 be mouth )()l also [s l-1h
Ma 1 H also χ ri 1111111111 ink -- Contains: Kotoreidan Emperor; B g M m To 8
h Na Saku Left: 3 9 (It has been discovered that the cis-3-alkenoic acids of formula (1) which can be produced as described above are useful as long-lasting aroma imparting or flavor modulating agents. fl) The compound has a persistent aroma flavor such as green, fatty, fruity, and has a mild and rich naturalness,
In particular, it has a long-lasting and unique aroma that is excellent as a flavor imparting or modulating ingredient for various foods and beverages, cosmetics, health/hygiene/medicines, etc.

Specifically, when blended with synthetic essential oils such as bergamont oil, lemon oil-geranium oil, lavender oil, mandarin oil, etc., the cis-3-alkene of formula (1) has the mild properties inherent in natural essential oils. A rich and persistent aroma and flavor imparting or modulation 111j can be adjusted. It blends well with citrus essential oils such as orange, lime, lemon, grapefruit, etc.
It can emphasize the 4F characteristics and provide a long-lasting aroma and flavor imparting or modulating effect that has a fresh, supple and natural appearance. Further examples are strawberries and lemons.

When incorporated into flavor compositions such as orange, grapefruit, apple, pineapple, etc.

It has a mild, full-bodied, natural flavor, and has a long-lasting, emphasized aroma that can be used as a flavor imparting or modulating agent.

Furthermore, the cis-3-alkenoic acids of the above formula (1) blend well with various synthetic and natural fragrances, and can provide unique, long-lasting, aroma-imparting or flavor-imparting agents. . Although it depends on the purpose and the compound of formula (1) to be blended.

For example, a general range of about 0.001 to about 102 pieces can be exemplified.

Thus, according to the present invention, the cis-3-alkenoic acids of the formula (1) can be prepared by using the cis-3-alkenoic acids of the formula (1) as an active ingredient and a flavor imparting or modulating agent or reinforcing agent. 3-
Foods and beverages characterized by containing alkeno acids as a flavor component 1 Cosmetics characterized by containing the cis-3-alkenes of formula (1) as a flavor component fl
The purpose of the present invention is to provide health, sanitary, and medical textile products that specifically contain 1 of cis-3-alkenoic acids as an aiki flavor component.

For example, fruit juice drinks, alcoholic beverages, milk drinks, charcoal drinks, ice creams, sherbet fields, frozen desserts such as popsicles #, It, Japanese and Western sweets such as A+Japanese and Western Goji-, Duyamchi, and chewing gum. , coffee, cocoa, black tea, tea-like luxury goods; pressed soup soup, soup-flavored ingredients such as Western-style soups, instant beverages and foods.

It is possible to provide beverages distributed with Gekiga M, which can impart unique aroma and flavor, to Tanigoku snack foods and the like. For example, shampoos, hair creams, pomades, and other hair cosmetic sedatives; cosmetics, lipsticks, and other cosmetics, and cosmetic detergent bases, etc. Cosmetic products containing Tobin can be provided. Again in history.

Laundry detergents, disinfectant detergents, deodorizing fluids, and other health and hygiene detergents! Various health and rain materials such as toothpaste, tissues, and toilet paper; flavor masking to make it easier to take medicines.

It is possible to provide health, hygiene, and pharmaceutical products, such as flavoring agents, in which a suitable substance that can impart a unique flavor is blended or applied.

Below, several embodiments of the production and usage examples of the compound of formula (1) of the present invention will be explained in more detail with reference to Examples.

Example 1 2-ethyl-cis-3-pentenoic acid 1s% HuLi-hexane 1201I under alpine atmosphere
120 ml of tetrahydrofuran, 0.17 mol of diisozorobylamine 17JN)'f at 20°C or below.
JIJ D. Prepare lithium diisopropylamine bath solution. Next, hexamethyl phosphate triamide 35,6.9
(0.2 mol) f at 50° C., 2-ethyl-trans-2-pentenoic acid 10.2. After reacting for 30 minutes, 1 reaction solution was added to 0 to 1
The mixture was added at 0°C, extracted with ether, and then distilled.

Boiling point 108 (109℃/12 filtration for 1111 boxes, 2
-Ethyl-cis-3-pentenoic acid c+, 41 (QM
, car person 92). *4J structure was confirmed by nuclear energy resonance spectrum.

NMRCDCl, δIO,95(3H, t, J(
-, e=5.4Hz):,1.13~1.55 (2
H, m).

1.72(3)i*d*J4-1=5°6#g).

3, 26 ~ & 75 (1 horn, υz g J @ −
@ = 1 1 Hg 1&28~&84 (fllI
, m, J, -, = 6.0 ng) Example 2 2-Methyl-cis-3-hexene under nitrogen atmosphere, 15% 1JuLi-hexane 120 ml, diethyl ether 120 m, diisopropylamine 17
g (0.17 mol) is added at below 20°C. Next, hexamethylphosphorus L' and triamide 35.6I were added to give %2-methyl-trans-2-hexenoic acid 10.211%.
0.08 mol) was reacted with IJLI for 2 minutes, and the reaction solution was added to an oxalic acid aqueous solution at 0 to 10°C.

After extraction with ether, boiling point 108'-110'C, /
1 (1+*Hg fraction 2-methyl-cis-3-hexene I ¥114!9.?,? (yield 95%) ft was obtained.

NMRCDCl, ml O,90(3H,t,J,-
.

=5.6#g), 1.70 (3H, d, J*-,
/=5.8ffg), L13~1.55 (2B, ηL)
, 3-24 to 3.74 (I H*n'L*'
*-s"i 1-211 g), 5.26~Fh
, 82 (2H1tyL, J, == 6.0 Hg
) Example 3 Cis-3-heptenoic acid 120 g of 15% 1hbLi i-hexane under nitrogen atmosphere
To IE was added 120 N ft of dimethoxyethane and 35.6 N ft of hexamethylphosphoric acid triamide, and after stirring for 30 minutes, 10.2 N ft of trans-2-heptenoic acid, V(
Add 7JO of 0.08 mol) and react for 30 minutes.Then, add 1 reaction solution to dried salt water solution and extract with ether, then distill. Cis-3-heptene #i9.3.9 (yield 91%) was obtained.

NMRC: DC13δ 10.90 (3 horns, t, J
,-.

=5.60), 1.15-1.57 (211,1n).

3.18 (2H+ds'*-s=””), 5
．． 55-5.79 (2H, m), 1.84-')-
38 (2H, m ) Example 4 2-Methyl-cis-3-octene was added to 69@l of toluene under an argon atmosphere with 201 triphenylmethane! (0.08 mol) was added, then 6 Qml of 15T BuLi-hexane was added, and the mixture was diluted with triphenylmethyllithium.
8. L2-methyl-trans-2-octenoic acid 6.2
I! (0.04 mol) and reacted at 40-50°C for 4 hours, treated in the same manner as in Example 1, boiling point 127'-130
710 mB, 2-methyl- as a fraction with 9
Cis-3-octenoic acid 5.3. V (yield 85%)'fI
:Obtained.

NMRCDC1, δ=0.9 1 (3H t +
Jv-m=5.60), 1.13-1.59 (4B, m
), 1.30 (3H, d, 7.0 1J g ), 1.
82-21B (2B, m), 3.24-344 (IB.

m, δ2-a=xoHg), 5.55-5.80C21
Example 5 2-Methyl-cis-nonenoic acid under argon atmosphere, 5% MaLi-ether 36
Hexamethylphosphorus triamide 18.9% 2
-Methyl-trans-2-nonene 6.81 (0,0
4 mol) f: addition% 10'-20°C for 0.5 hours reaction 1
(.

Central h+'J 9! 1 and walk, 19μ points 14
2 (145℃/12 ?+!) 2- as a fraction of il
6.3 g of methyl-cis-3-nonenoic acid (Imx-〇:i
blood)?・It's 1q.

NM ノ < CI) C1, δ 10.92 (a) Bt
, J s-.

=5.62), LIO~1.62(6)l,m).

1, 3 2 (3R* d t J @-t = 6
．． 8 horn z).

1.80~Z 34 (211, n+), 3.22~:
(,74(1)!, Gat), 5.52-5.78
(2 horns, ηL) Example 6 2-Methyl-cis-3-decenoic acid alkone atmosphere, 15% thbLi-hexane 12
Hexamethylphosphorus triamide aO,V at 0mj.

2-Methyl-trans-2-decene [7,411C0,
04 mol) was added and the reaction was carried out for 1 hour at 12°C to 30°C.

Treated in the same manner as in Example 1, boiling point 1519-153°C 71
2-methyl-cis-3 as the fraction with 0 tuHi
-decenoic acid 6.8.9 (yield 92%) was obtained.

N M RCDC1, δ wealth 0.90 (3H, t,
J,-,.

=5.60), 1.32 (3H+ ct + Jt-
t/:6.9Hg), 1.12~1.62 (8H
+m).

i, 78~Z 33 (2Hern) -δ22~
3.72 (IH*rn) -5-50 to 5-76
(2He m) Example 7 2.5-Dimethyl-cis-3-hexenoic acid 120 m+ of 15% BuLi-hexane under argon atmosphere! ! 120 ml, 120 ml, 120 ml, 120 ml, 120 ml, Add 53.4 Iie of 7-acid triamide, and add 10.5 Iie of 2,5-dimethyl-trans-3-hexenoic acid at -6OL--qo°C.
After adding 2.9 (0.08 mol) and reacting at the same temperature for 1 hour, the reaction solution was added to an aqueous oxalic acid solution, extracted with ether, and then distilled.
Boiling point 110'-112℃/ 10 Dragon Hiwosuru 2,
9.8 # of 5-dimethyl-cis-3-hexenoic acid (96 yen) was obtained.

N M E C1) Cl δ10.92 (611, d,
J=5.82Eg), 1.11-1.53 (IM, m)
.

δ22~&71 (2B, fi), 5.23~5.
80 (211am*Jm-4=6.2RZ)
Example 8 The reaction was carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 10 A lira type fragrance composition was produced by mixing the following components (parts by weight).

Phenylethyl acetate l.

Cinnamic alcohol 4゜ Tarpine All 13G Cyclamenaldehyde i.

Heliotrobin 5゜Cinnamyl acetate 1゜Carnation 2゜Linalool゛ 3゜Indole 2 Stylacxreso/ ()'' 30 Ylang Ylang 1゜Hydroxycitronellal 290 Pendyl acetate 20 Anisaldehyde 2゜Absolute neat jasmine 20 Enyl ethyl alcohol 278% Varnish alcohol 30 000 5 g of 2-ethyl-cis J3-pentenoic acid was mixed with the above composition m1ooy to leave 4 q of the aroma composition.

As for the aroma of this product, a new aroma composition was obtained that emphasized the "greenness" and had good persistence.Although the nuances were slightly different, almost the same results were obtained.2-propyl-cis-3-pentenoic acid -isopropyl-cis-3-pentenoic acid,
Obtained by using 2-methyl-cis-3-hexenoic acid, cis-3-heptenoic acid, 2-ethyl-cis-3-hexenoic acid.

Example 11 A bouquet type fragrance composition was prepared by adding the following ingredients
It was prepared by mixing at

Phenylethyl alcohol 180 Linalyl acetate 3° Per I Motcin 7 tick 40 Geranium 5° Benzyl acetate) 60 Heliothrobin 8° Geraniol 110 Lavender 2° β-ionone 100 Amyl salicylate 45 Turbinyl acetate 135 Cedar oil 100 Citronellol 5° 1000 The above composition A fragrance composition was prepared by mixing 2-propyl-cis-3-hexenoic acid 3II with 100 g of the product.

The aroma of this product had a strong soft grass-like aroma and excellent aroma persistence. Although the nuances are slightly different, almost similar results were obtained for 2-isopropyl-cis-3-hexenoic acid, 2-methyl-cis-3-heptenoic acid, 2-methyl-cis-3-octenoic acid, and 2,5-methyl -cis-3-hexenoic acid, 2-propyl-5-methyl-cis-
3-hexenoic acid, 2-ethyl-5-methyl-cis-3-
Hexenoic acid, 2-isopropyl-5-methyl-cis-3
-obtained by using hexenoic acid. However, in this case, it was a noble composition with an emphasis on green.

Example 12 A Narcissus type fragrance composition was prepared using the following components (parts by weight).
It was manufactured by mixing with

Narcissus mixed fragrance composition bergamot oil 15 ylang ylang oil 5 linalool 20 benzyl acetate 5 benzyl alcohol 24 terpineol 15 balacresol acetate 1 cinnamic alcohol 5 eugenol 4 heliotropin 4 absolute jasmine 2 00 2-methyl in Yotobi composition 99I -cis-3-nonene a1
g to produce a fragrance composition. The aroma of this product had a strong characteristic of a natural narcissus-like aroma with a fresh green-like aroma, and excellent aroma persistence. Although the nuances are slightly different, similar results were obtained for 2-ethyl-cis-3-nonenoic acid and 2-iso-propyl-cis-
3-octenoic acid, 2-propyl-cis-3-nonenoic acid,
Obtained by using 2-methyl-cis-3-decenoic acid, 2-propyl-cis-3-decenoic acid. However, 2-methyl-cis-3-decenoic acid and 2-propyl-
In the case of cis-3-decenoic acid, the fat-like aroma was stronger than that of the others.

Example 13 The following components (weight 1) were mixed as an aroma and flavor composition for plums.

Amyl butyrate 20 Benzaldehyde 175 Butylphomate 10 Citronellol 1 Ethyl butyrate 50 Ethyl valerate 15 Isoamyl propionate 10 r-nonalactone 5 Melene essential oil 15 2-phenyl-1-propyl fluoride) 100r-
Usodecalactone 3 Vanillin 1O Ethanol 586 Total 1000 By adding 20.9% of 2-ethyl-cis-3-pentenoic acid to 1ooy of the above composition, a very excellent new composition having a lasting plum aroma and flavor component was obtained. Although the nuances are slightly different, similar results were obtained for 2-propyl-cis-3-pentenoic acid, 2-inzolopyl-cis-3-pentenoic acid, 2-methyl-cis-3-hexenoic acid, 2- It was also obtained using ethyl-cis-3-hexenoic acid, 2-isopropyl-cis-3-hexenoic acid.

Example 14 The following ingredients (Jyuden) are used as aroma and flavor components for apples.
were mixed.

Ethyl acetate 50 Ethyl propionate 20 Ethyl butyrate 30 Ethyl isovalerate 60 Isoamyl acetate 30 Butyl alcohol 150 Amyl alcohol 50 Butyl propionate 70 Butyl butyrate 10 2-hexenol 100 2-hexenyl acetate 180 Iso connecting wire.

Vanillin 20 Hexyl butyrate 10 Ethyl alcohol 180 Total 1000 By adding 15.9 oz of 2-methyl-cis-3-octenoic acid to 100 oz. A new composition with excellent properties was obtained. Similar results were obtained for 2-glopyrucis-octene, 2-methyl-cis-3-nonenoic acid, 2-isozorobyl-3-nonenoic acid, and 2-methyl-cis-3-decene a.
It was also obtained using t. However, 2-methyl-cis-3-
In the case of decenoic acid, the composition had an accentuated fat-like appearance.

Example 15 Each of the following ingredients (
weight) were mixed.

Ethyl acetate 300 Ethyl butyrate 250 Isoamyl acetate 100 Isoamylpa V rate 55 Isobutyric a 70 Isovaleric acid 30 Orirulucaderoate 35 Ethyl caproate 20 Ethyl caprylate (5 Isomir alcohol 35 Soethyl malonate 30 Citral 15 Linalool 5 -q nt ) -A/ 20 Total 1000 The above composition 1000IiVc2-I is Copyrusis-3
- 10 g of octenoic acid and 2-isozolopyrcis-3-
By adding 1O1 of nonenoic acid, a very good new composition was obtained which has persistence as an aroma and flavor component of Kuri-no-inatsudel.

Patent applicant: Hasegawa Fragrance Co., Ltd.

Claims (1)

[Claims] 1. The following formula (1), where R represents a C3-C0 alkyl group. Itl represents a hydrogen atom or a C8-C, alkyl group. Here, when R is C, an alkyl group, R3 is CR-,
C, alkyl group, and R is C, alkyl group or C4~
It for bonding to Cs alkyl group. is C1□<, an alkyl group. cis-3-alkene W 6j. 2. The following formula (2) However, in the formula, R represents a C, C6 alkyl group. R1 represents a hydrogen atom or a C, -, C, alkyl group. Here, if %R is Ci alkyl group, Noah I is C,C
S is an alkyl group, and R is C, an alkyl group, or a C4-C
6 In the case of an alkyl group, R1 is C(-C, an alkyl group, trans-2-alkene W + represented by A method for cis-3-alkenoic acids represented by the following formula (11, in which R and R8 are as described above), characterized by carrying out a 4-functionalization reaction in the presence of In the formula, %R represents C, -C, or an alkyl group. R8 represents a hydrogen atom or a C, -, C, or alkyl group; Here, when R is C, an alkyl group, Rlr, hcl
-, c, is an alkyl group, and when Novi is C, alkyl group spanning c,, C, alkyl group, R3 is c l-, c
,' is an alkyl group. 1. A long-lasting Aiki flavor imparting or modulating agent characterized by containing a cis-3-alkene expressed as an active ingredient.