CA1121813A - Asymmetric synthesis of chrysanthemate - Google Patents
Asymmetric synthesis of chrysanthemateInfo
- Publication number
- CA1121813A CA1121813A CA000258220A CA258220A CA1121813A CA 1121813 A CA1121813 A CA 1121813A CA 000258220 A CA000258220 A CA 000258220A CA 258220 A CA258220 A CA 258220A CA 1121813 A CA1121813 A CA 1121813A
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- Prior art keywords
- phenyl
- amino
- group
- propanol
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/12—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
- C07C245/14—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom having diazo groups bound to acyclic carbon atoms of a carbon skeleton
- C07C245/18—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom having diazo groups bound to acyclic carbon atoms of a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
Abstract
ABSTRACT OF THE DISCLOSURE
A process for the production of an optically active alkyl chrysanthemate which comprises the reaction of 2,5-dimethyl-2,4-hexadiene with an alkyl diazoacetate of the formula:
wherein R is selected from the group consisting of (a) cyclo-alkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 - 20, (b) tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substituent(s) whose total carbon atom number is 4 - 20, in the presence of a copper complex coordi-natod with a chiral Schiff base of the formula:
A process for the production of an optically active alkyl chrysanthemate which comprises the reaction of 2,5-dimethyl-2,4-hexadiene with an alkyl diazoacetate of the formula:
wherein R is selected from the group consisting of (a) cyclo-alkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 - 20, (b) tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substituent(s) whose total carbon atom number is 4 - 20, in the presence of a copper complex coordi-natod with a chiral Schiff base of the formula:
Description
llZ18 13 The present invention relates to a process for producing an optically active chrysanthemate wherein
2,5-dimethyl-2,4-hexadiene is reacted with a alkyl diazo-acetate in the presence of a copper complex coordinated with a novel kind of Schiff base.
Chrysanthemic acid is an important material for the production of synthetic pyrethroids which are effective as insecticides. There are four stereoisomers of chrysanthemic acid: two kinds of geometric isomers, i.e. cis and trans, each having d and 1 optical isomers. The pyrethroids derived from d-trans and d-cis chrysanthemic acids are known to be particularly effective in insecticidal activity. In this connection, naturally occurring chrysanthemic acid is known to have _-trans structure.
Two industrial methods are possible to prepare optically active chrysanthemic acid. In one method, the racemic mixture is synthesized first,and is subsequently subjected to optical resolution. The other method is direct asymmetric synthesis of the desired optical isomer.
One of the synthetic processes for preparing chrysan-themic acid is to react an alkyl diazoacetate with 2,5-dimethyl-2,4-hexadiene in the presence of a copper catalyst (see British Patent No. 74Q,014) and then to hydrolyze the resulting alkyl chrysanthemate.
This invention is concerned with the asymmetric synthesis of chrysanthemates. In our Belgian Patent No. 787,473, a process is described and claimed for producing an optically active alkyl chrysanthemate by reaction an alkyl 11;~1~113 diazoacetate with 2,5-dimethyl-2,4-hexadiene in the presence of a copper catalyst coorainated with a chiral ligand according to the following equation:
COOR
,5/ N2CHCOOR * ) *
Cu(L*) ~ ~ + ~ I ICOOR
n * ~ *
wherein L* is a chiral ligand.
We have found, as described in our Belgian Patent ~o. 810,959, that it is advantageous to catalyse the asymmetric synthesis of alkyl chrysanthemates with copper complex coordinated with chiral Schiff base having the following formula:
1 H R * R2 X ~ ~ C~ - C - OH
~ / R2 (I) X2 ~ o~
wherein C* is an asymmetric carbon atom, Rl is selected from the group consisting of (a) alkyl groups whose carbon atom number is 1 - 10, and (b) aralkyl groups with or without alkoxy substituent(s), whose total carbon atom number is 7 - 20, R2 is selected from aryl groups with alkoxy substituent(s), whose total carbon atom number is 7 - 30, each of ~ and x2 is selected from the group consisting of (a) hydrogen atom, (b) alkyl groups having 1 - 10 carbon atoms, (c) phenyl group, (d) alkoxy groups having l - 10 carbon atoms, (e) halogen atoms and (f) nitro group, or (g) Xl and x2 together form a benzo group.
In the following a further explanation will be given or the novel Xind of chiral copper complexes used as catalysts 11~1813 in our Belgian Patent No. 810,959.
When the Schiff base of the formula (Il forms a metal complex with divalent copper ion, three kinds of chelates are possible. (For the chemistry of metal complexes of Schiff bases, see R.H. Holm, G.W. Everett, Jr., and A. Chakravorty "Progress in Inorganic Chemistry" 7, 83-214, (1966), Interscience Publishers, New York).
One has the following dimeric structure (II) wherein the Schiff base behaves as tridentate ligand:
H Rl H R2 (II) X C ~R2 wherein Rl, R2, Xl and X are as defined above. The other has the following monomeric structure (III) or (IV) wherein the Schiff base behaves as bidentate or tridentate ligand, respectively, x2 Hl R R
xl ~ - C*H - C - OH (III) H R
,~ ~ \L o R ~IV) wherein Rl, R2, Xl and x2 are as defined above, and L is a neutral monodentate ligand. (for the copper complexes of N-salicylidene-2-aminoethanol, see R.P. Houghton and D.J. Pointer, J. Chem. Soc. 4214 (1965)) ,~,'i ~
,~
We further made a study on the alkyl diazoacetate used as the substrate in this asymmetric synthesis. As a result, we found that the diazoacetate represented by the general formula:
N2CHCOOR (V) wherein R is selected from the group consisting of (a) mono-or poly-cyclic cycloalkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 2Q, (b) tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substitu-ent(s~ whose total carbon atom number is 4 - 20, is particularly effective for obtaining the resulting chrysanthemate with excellent optical purity as well as high trans isomer content.
This fact is quite unexpected from reaction results using primary diazoacetate of lower aliphatic alcohol having 1 - 8 carbon atom(s) such as ethyl ester.
The present invention has been accomplished on the basis of this new knowledge. That is to say, the present invention is a process for producing optically active chrysan-themate characterized by the reaction of a alkyl diazoacetaterepresented by the general formula (V) with 2,5-dimethyl-2,4-hexadiene in the catalytic use of a chiral copper complex derived from the optically active Schiff base, for example those having monomeric structure as shown by the general formula (III~ or (IV), or those having dimeric structure as shown by the general formula (II).
The invention comprises a process for the production of an optically active alkyl chrysanthemate which comprises the reaction of 2,5-dimethyl-2,4-hexadiene with a diazoacetate of ..............................
~ .
8i3 the formula:
wherein R is selected from the group consisting of (a) cyclo-alkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 20, ~bl tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substituent(s) whose total carbon atom number is 4 to 20, in the presence of a copper complex coordinated with a chiral Schiff base of the formula:
Xl H R R2 x2 ~ ~C*H - C - OH
wherein C* is an asymmetric carbon atom, Rl is selected from the group consisting of (a) alkyl groups whose carbon atom number is 1 to 10, and (b) aralkyl groups with or without alkoxy substituent(s), whose total carbon atom number is 7 to 20, R is selected from aryl groups with alkoxy substituent(s), whose total carbon atom number is 7 to 30, each of X and X is selected from the group consisting of (a) hydrogen atom, (b) alkyl groups having 1 to 10 carbon atoms, (c) phenyl group, (d) alkoxy groups having 1 to 10 carbon atoms, (e) halogen atoms and (f) nitro group, or (g) Xl and X together form a benzo group.
The substituent group R of the diazoacetate represented by the general formula (V) is previously mentioned, but is exemplified by the following:
(a) The mono- or poly-cyclic cycloalkyl groups are exemplified by cvclopentyl, 2-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,2-, 2,5- or 2,6-dimethylcyclohexyl, ..~`.i.
11;Z1813 2,2,6-trimethylcyclohexyl, cyclo-octyl, cyclododecyl, etc.
Mono- or poly-cyclic cycloalkyl groups of naturally or non-naturally occurring alicyclic alcohols are also effective.
For example, menthyl, isomenthyl, neomenthyl, neoisomenthyl, carbomenthyl, bornyl, isobornyl, 2-norbornyl, 1- and 2-ada-mantyl, etc. may be mentioned.
(b~ Tertiary aralkyl groups are exemplified by a,a-dimethylbenzyl, triphenylmethyl, a,a-diphenylethyl, 2-phenyl-2-butyl, etc.
(c) Tertiary alkyl groups are exemplified by t-butyl, t-amyl, 2,3-dimethyl-2-butyl, 2,3,4-trimethyl-3-pentyl, al a-dimethyl-~-menthoxyethyl, etc.
The diazoacetates of the general formula (V) can have either achiral or chiral structure. In the latter case, either form of enantiomers or racemic modification can be used for the present reaction. When chrysanthemate formed by the present reaction shows some insecticidal power, it may be used as insecticide by itself.
Although there is no limitation on the processes for synthesizing the diazoacetate of the formula (V), the following processes are examples:
(i) The method of diazotizing the corresponding ester of glycine with nitrous acid or a nitrous acid ester. Refer for example to Organic Syntheses, Coll. Vol.4, 424 and N. Takamura, T. Mizoguchi, K. Koga and S. Yamada, Tetrahedron 31, 227 (1975~.
The ester of glycine can be synthesized by the reaction of glycine with the corresponding alcohol or the corresponding olefin.
. .
L..~,'~: ``;
li;~l813 (ii) The method of Regitz: P-toluenesulfonylazide is reacted with the corresponding acetoacetate, and the resulting 2-diazoacetoacetate is deacetylated with a base to give diazoacetate. Refer, for example, to Organic Syntheses, Coll. Vol. 5, p. 179.
(iii) The method of House: Acid of the p-toluene-sulfonylhydrazone of glyoxylic acid chloride is reacted with the corresponding alcohol in the presence of a base. Refer, for example, to Organic Syntheses, Coll. Vol. 5, p. 258.
The chiral Schiff base of the formula (I) is synthesized by the reaction of a chiral amino alcohol having the formula (VI) with a salicylaldehyde derivative having the formula ~VII):
Rl _ C*H - C - OH (VI) ~H 2 R2 X H
~ (VII) wherein Rl, R2, Xl and x2 are as defined above.
Specific examples of the substituent Rl in the amino alcohol (VI) are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-butyl, t-butyl, hexyl~ octyl, benzyl, benzhydryl and 2,2-diphenylethyl. Among these examples, preferred substituents or Rl are methyl, isopropyl, isobutyl, benzyl, and a benzyl group having a substituent at the 4-position of the aromatic neucleus, of which the substituent is, for example, methoxy, ethoxy, propoxy, isopropoxy, ~.~
1.813 butoxy, or hexyloxy, etc. As R in the amino alcohol, a phenyl group having a substituent at the 2-position or having substituents at the 2,5-positions is preferred.
Specific examples of 2-substituted phenyl groups are 2-methoxyphenyl, 2-ethoxyphenyl, 2-propoxyphenyl, 2-isopro-poxyphenyl, 2-butoxyphenyl, 2-t-butoxyphenyl, 2-hexyloxyphenyl, 2-octyloxyphenyl, etc. Specific examples of 2,5-substituted phenyl groups are 2-methoxy-5-methylphenyl, 2-butoxy-5-methyl-phenyl, 5-methyl-2-octyloxyphenyl, 5-t-butyl-2-methoxyphenyl, 2-butoxy-5-t-butylphenyl, 5-t-butyl-2-octyloxyphenyl, 4-methoxybiphenyl-3-yl, 4-butoxybiphenyl-3-yl, 4-octyloxy-biphenyl-3-yl, 2,5-dimethoxyphenyl, 2,5-butoxyphenyl, 2,5-dioctyloxyphenyl, etc.
The optically active amino alcohols of the formula (:VI) to be used in this invention may be prepared in any of the following two ways, one is by resolving a racemic mixture of the corresponding amino alcohol with an appropriate resolving agent, and the other by preparing the amino alcohol from the reaction of optically active precursor. Thus, for example, an optically active amino ester of the following formula (VIII) with a Grignard reagent of the following formula (IX) gives the optically active amino alcohol (:VI) with retention of configuration.
Rl _ C*H - coOR3 + R MgZ > R - IC*H - C - OH
(VIII) (IX~ (VI) ~lZ11~13 wherein Rl is alkyl or aralkyl, R2 is aryl, R3 is alkyl of 1 - 10 carbon atoms or benzyl and z is chlorine, bromine or iodine. As for the addition reaction of phenyl magnesium bromide to (L)-alanine ethyl ester, see for example A. McKenzie, R. Roger, GØ Willis, J. Chem. Soc., 779 (1926) and B.M. Benjamin, H.J. Schaefer, C.J. Collins, J. Am. Chem.
Soc., 79 6160 (1957).
Specific examples of the salicylaldehyde derivatives (VII) are salicylaldehyde, 3-ethoxysalicylaldehyde, o-vanillin 3,5-dibromosalicylaldehyde, 5-chlorosalicylaldehyde,
Chrysanthemic acid is an important material for the production of synthetic pyrethroids which are effective as insecticides. There are four stereoisomers of chrysanthemic acid: two kinds of geometric isomers, i.e. cis and trans, each having d and 1 optical isomers. The pyrethroids derived from d-trans and d-cis chrysanthemic acids are known to be particularly effective in insecticidal activity. In this connection, naturally occurring chrysanthemic acid is known to have _-trans structure.
Two industrial methods are possible to prepare optically active chrysanthemic acid. In one method, the racemic mixture is synthesized first,and is subsequently subjected to optical resolution. The other method is direct asymmetric synthesis of the desired optical isomer.
One of the synthetic processes for preparing chrysan-themic acid is to react an alkyl diazoacetate with 2,5-dimethyl-2,4-hexadiene in the presence of a copper catalyst (see British Patent No. 74Q,014) and then to hydrolyze the resulting alkyl chrysanthemate.
This invention is concerned with the asymmetric synthesis of chrysanthemates. In our Belgian Patent No. 787,473, a process is described and claimed for producing an optically active alkyl chrysanthemate by reaction an alkyl 11;~1~113 diazoacetate with 2,5-dimethyl-2,4-hexadiene in the presence of a copper catalyst coorainated with a chiral ligand according to the following equation:
COOR
,5/ N2CHCOOR * ) *
Cu(L*) ~ ~ + ~ I ICOOR
n * ~ *
wherein L* is a chiral ligand.
We have found, as described in our Belgian Patent ~o. 810,959, that it is advantageous to catalyse the asymmetric synthesis of alkyl chrysanthemates with copper complex coordinated with chiral Schiff base having the following formula:
1 H R * R2 X ~ ~ C~ - C - OH
~ / R2 (I) X2 ~ o~
wherein C* is an asymmetric carbon atom, Rl is selected from the group consisting of (a) alkyl groups whose carbon atom number is 1 - 10, and (b) aralkyl groups with or without alkoxy substituent(s), whose total carbon atom number is 7 - 20, R2 is selected from aryl groups with alkoxy substituent(s), whose total carbon atom number is 7 - 30, each of ~ and x2 is selected from the group consisting of (a) hydrogen atom, (b) alkyl groups having 1 - 10 carbon atoms, (c) phenyl group, (d) alkoxy groups having l - 10 carbon atoms, (e) halogen atoms and (f) nitro group, or (g) Xl and x2 together form a benzo group.
In the following a further explanation will be given or the novel Xind of chiral copper complexes used as catalysts 11~1813 in our Belgian Patent No. 810,959.
When the Schiff base of the formula (Il forms a metal complex with divalent copper ion, three kinds of chelates are possible. (For the chemistry of metal complexes of Schiff bases, see R.H. Holm, G.W. Everett, Jr., and A. Chakravorty "Progress in Inorganic Chemistry" 7, 83-214, (1966), Interscience Publishers, New York).
One has the following dimeric structure (II) wherein the Schiff base behaves as tridentate ligand:
H Rl H R2 (II) X C ~R2 wherein Rl, R2, Xl and X are as defined above. The other has the following monomeric structure (III) or (IV) wherein the Schiff base behaves as bidentate or tridentate ligand, respectively, x2 Hl R R
xl ~ - C*H - C - OH (III) H R
,~ ~ \L o R ~IV) wherein Rl, R2, Xl and x2 are as defined above, and L is a neutral monodentate ligand. (for the copper complexes of N-salicylidene-2-aminoethanol, see R.P. Houghton and D.J. Pointer, J. Chem. Soc. 4214 (1965)) ,~,'i ~
,~
We further made a study on the alkyl diazoacetate used as the substrate in this asymmetric synthesis. As a result, we found that the diazoacetate represented by the general formula:
N2CHCOOR (V) wherein R is selected from the group consisting of (a) mono-or poly-cyclic cycloalkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 2Q, (b) tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substitu-ent(s~ whose total carbon atom number is 4 - 20, is particularly effective for obtaining the resulting chrysanthemate with excellent optical purity as well as high trans isomer content.
This fact is quite unexpected from reaction results using primary diazoacetate of lower aliphatic alcohol having 1 - 8 carbon atom(s) such as ethyl ester.
The present invention has been accomplished on the basis of this new knowledge. That is to say, the present invention is a process for producing optically active chrysan-themate characterized by the reaction of a alkyl diazoacetaterepresented by the general formula (V) with 2,5-dimethyl-2,4-hexadiene in the catalytic use of a chiral copper complex derived from the optically active Schiff base, for example those having monomeric structure as shown by the general formula (III~ or (IV), or those having dimeric structure as shown by the general formula (II).
The invention comprises a process for the production of an optically active alkyl chrysanthemate which comprises the reaction of 2,5-dimethyl-2,4-hexadiene with a diazoacetate of ..............................
~ .
8i3 the formula:
wherein R is selected from the group consisting of (a) cyclo-alkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 20, ~bl tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substituent(s) whose total carbon atom number is 4 to 20, in the presence of a copper complex coordinated with a chiral Schiff base of the formula:
Xl H R R2 x2 ~ ~C*H - C - OH
wherein C* is an asymmetric carbon atom, Rl is selected from the group consisting of (a) alkyl groups whose carbon atom number is 1 to 10, and (b) aralkyl groups with or without alkoxy substituent(s), whose total carbon atom number is 7 to 20, R is selected from aryl groups with alkoxy substituent(s), whose total carbon atom number is 7 to 30, each of X and X is selected from the group consisting of (a) hydrogen atom, (b) alkyl groups having 1 to 10 carbon atoms, (c) phenyl group, (d) alkoxy groups having 1 to 10 carbon atoms, (e) halogen atoms and (f) nitro group, or (g) Xl and X together form a benzo group.
The substituent group R of the diazoacetate represented by the general formula (V) is previously mentioned, but is exemplified by the following:
(a) The mono- or poly-cyclic cycloalkyl groups are exemplified by cvclopentyl, 2-methylcyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,2-, 2,5- or 2,6-dimethylcyclohexyl, ..~`.i.
11;Z1813 2,2,6-trimethylcyclohexyl, cyclo-octyl, cyclododecyl, etc.
Mono- or poly-cyclic cycloalkyl groups of naturally or non-naturally occurring alicyclic alcohols are also effective.
For example, menthyl, isomenthyl, neomenthyl, neoisomenthyl, carbomenthyl, bornyl, isobornyl, 2-norbornyl, 1- and 2-ada-mantyl, etc. may be mentioned.
(b~ Tertiary aralkyl groups are exemplified by a,a-dimethylbenzyl, triphenylmethyl, a,a-diphenylethyl, 2-phenyl-2-butyl, etc.
(c) Tertiary alkyl groups are exemplified by t-butyl, t-amyl, 2,3-dimethyl-2-butyl, 2,3,4-trimethyl-3-pentyl, al a-dimethyl-~-menthoxyethyl, etc.
The diazoacetates of the general formula (V) can have either achiral or chiral structure. In the latter case, either form of enantiomers or racemic modification can be used for the present reaction. When chrysanthemate formed by the present reaction shows some insecticidal power, it may be used as insecticide by itself.
Although there is no limitation on the processes for synthesizing the diazoacetate of the formula (V), the following processes are examples:
(i) The method of diazotizing the corresponding ester of glycine with nitrous acid or a nitrous acid ester. Refer for example to Organic Syntheses, Coll. Vol.4, 424 and N. Takamura, T. Mizoguchi, K. Koga and S. Yamada, Tetrahedron 31, 227 (1975~.
The ester of glycine can be synthesized by the reaction of glycine with the corresponding alcohol or the corresponding olefin.
. .
L..~,'~: ``;
li;~l813 (ii) The method of Regitz: P-toluenesulfonylazide is reacted with the corresponding acetoacetate, and the resulting 2-diazoacetoacetate is deacetylated with a base to give diazoacetate. Refer, for example, to Organic Syntheses, Coll. Vol. 5, p. 179.
(iii) The method of House: Acid of the p-toluene-sulfonylhydrazone of glyoxylic acid chloride is reacted with the corresponding alcohol in the presence of a base. Refer, for example, to Organic Syntheses, Coll. Vol. 5, p. 258.
The chiral Schiff base of the formula (I) is synthesized by the reaction of a chiral amino alcohol having the formula (VI) with a salicylaldehyde derivative having the formula ~VII):
Rl _ C*H - C - OH (VI) ~H 2 R2 X H
~ (VII) wherein Rl, R2, Xl and x2 are as defined above.
Specific examples of the substituent Rl in the amino alcohol (VI) are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-butyl, t-butyl, hexyl~ octyl, benzyl, benzhydryl and 2,2-diphenylethyl. Among these examples, preferred substituents or Rl are methyl, isopropyl, isobutyl, benzyl, and a benzyl group having a substituent at the 4-position of the aromatic neucleus, of which the substituent is, for example, methoxy, ethoxy, propoxy, isopropoxy, ~.~
1.813 butoxy, or hexyloxy, etc. As R in the amino alcohol, a phenyl group having a substituent at the 2-position or having substituents at the 2,5-positions is preferred.
Specific examples of 2-substituted phenyl groups are 2-methoxyphenyl, 2-ethoxyphenyl, 2-propoxyphenyl, 2-isopro-poxyphenyl, 2-butoxyphenyl, 2-t-butoxyphenyl, 2-hexyloxyphenyl, 2-octyloxyphenyl, etc. Specific examples of 2,5-substituted phenyl groups are 2-methoxy-5-methylphenyl, 2-butoxy-5-methyl-phenyl, 5-methyl-2-octyloxyphenyl, 5-t-butyl-2-methoxyphenyl, 2-butoxy-5-t-butylphenyl, 5-t-butyl-2-octyloxyphenyl, 4-methoxybiphenyl-3-yl, 4-butoxybiphenyl-3-yl, 4-octyloxy-biphenyl-3-yl, 2,5-dimethoxyphenyl, 2,5-butoxyphenyl, 2,5-dioctyloxyphenyl, etc.
The optically active amino alcohols of the formula (:VI) to be used in this invention may be prepared in any of the following two ways, one is by resolving a racemic mixture of the corresponding amino alcohol with an appropriate resolving agent, and the other by preparing the amino alcohol from the reaction of optically active precursor. Thus, for example, an optically active amino ester of the following formula (VIII) with a Grignard reagent of the following formula (IX) gives the optically active amino alcohol (:VI) with retention of configuration.
Rl _ C*H - coOR3 + R MgZ > R - IC*H - C - OH
(VIII) (IX~ (VI) ~lZ11~13 wherein Rl is alkyl or aralkyl, R2 is aryl, R3 is alkyl of 1 - 10 carbon atoms or benzyl and z is chlorine, bromine or iodine. As for the addition reaction of phenyl magnesium bromide to (L)-alanine ethyl ester, see for example A. McKenzie, R. Roger, GØ Willis, J. Chem. Soc., 779 (1926) and B.M. Benjamin, H.J. Schaefer, C.J. Collins, J. Am. Chem.
Soc., 79 6160 (1957).
Specific examples of the salicylaldehyde derivatives (VII) are salicylaldehyde, 3-ethoxysalicylaldehyde, o-vanillin 3,5-dibromosalicylaldehyde, 5-chlorosalicylaldehyde,
3-nitrosalicylaldehyde, 3-isopropyl-6-methylsalicylaldehyde, 2-hydroxy-1-naphthaldehyde,l-hydroxy-2-naphthaldehyde and the like.
Among the chiral copper complexes employed as catalysts in the present invention, specific examples of the copper complexes (II~, (III) and (IV) are those that are derived from the following chiral Schiff bases:
(a) ~-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-3-phenyl -l-propanol.
(b) N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl -l-propanol, (c) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxyphenyl) -3-phenyl-1-propanol, (d) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl) -3-phenyl-1-propanol, (e) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-heptyloxyphenyl) -3-(phenyl)-1-propanol, (f) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxyphenyl) -l-propanol, _ 9 _ 11;~18 ~3 (g) ~-salicylidene-2-amino-1,1-di(2-butoxy-S-t-butylphenyl) -l-propanol, (h) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxyphenyl) -l-propanol, (i) N-(3-methoxysalicylidene)-2-amino-1,1-di(5-t-butyl -2-octyloxyphenyl)-1-propanol, (j) ~-(3,5-dibromosalicylidene)-2-amino-1,1-di(2-isopropoxy-phenyl)-3-phenyl-1-propanol, (k) ~-(3ethoxysalicylidene)-2-amino-1,1-di(2-isopropoxyphenyl) -3-phenyl-1-propanol, (1) N-(2-hydroxy-1-naphthylmethylene)-2-amino-1,1-di(2-isopro-poxyphenyl)-3-phenyl-1-propanol, (m) ~-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl) -3-phenyl-1-propanol, (n) N-salicylidene-2-amino-1,1-di(2,5-dibutoxyphenyl)-3-phenyl -l-propanol, (o) N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-methyl -l-butanol, or (p) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)
Among the chiral copper complexes employed as catalysts in the present invention, specific examples of the copper complexes (II~, (III) and (IV) are those that are derived from the following chiral Schiff bases:
(a) ~-salicylidene-2-amino-1,1-di(2-methoxyphenyl)-3-phenyl -l-propanol.
(b) N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl)-3-phenyl -l-propanol, (c) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxyphenyl) -3-phenyl-1-propanol, (d) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl) -3-phenyl-1-propanol, (e) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-heptyloxyphenyl) -3-(phenyl)-1-propanol, (f) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxyphenyl) -l-propanol, _ 9 _ 11;~18 ~3 (g) ~-salicylidene-2-amino-1,1-di(2-butoxy-S-t-butylphenyl) -l-propanol, (h) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxyphenyl) -l-propanol, (i) N-(3-methoxysalicylidene)-2-amino-1,1-di(5-t-butyl -2-octyloxyphenyl)-1-propanol, (j) ~-(3,5-dibromosalicylidene)-2-amino-1,1-di(2-isopropoxy-phenyl)-3-phenyl-1-propanol, (k) ~-(3ethoxysalicylidene)-2-amino-1,1-di(2-isopropoxyphenyl) -3-phenyl-1-propanol, (1) N-(2-hydroxy-1-naphthylmethylene)-2-amino-1,1-di(2-isopro-poxyphenyl)-3-phenyl-1-propanol, (m) ~-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl) -3-phenyl-1-propanol, (n) N-salicylidene-2-amino-1,1-di(2,5-dibutoxyphenyl)-3-phenyl -l-propanol, (o) N-salicylidene-2-amino-1,1-di(2-butoxyphenyl)-3-methyl -l-butanol, or (p) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butylphenyl)
-4-methyl-1-pentanol.
As copper complexes of the optically active Schiff base of the formula (I), copper complexes of the previously mentioned general formulae (II), (III) and (IV) are effective, but the complex having dimeric structure of the formula (II) is used particularly advantageously. The complex of the general formula (II) is synthesized by the reaction of the Schiff base of the general formula (I) with a cupric salt such as cupric acetate.
I ,,~j .....
ll'~li~i3 The complex having monomeric structure of the formula ~IV) is synthesized by the reaction of the dimeric complex of the general formula (II) with a neutral monodentate ligand, for example pyridine, picoline, lutidine, etc. The cornplex having monomeric structure of the formula (III) is synthesized by reacting a copper complex of the salicylaldehyde derivative of the formula (VII) with the amino alcohol of the formula (VI).
In the actual practice of the present invention, the reaction can be carried out regardless of whether the chiral copper catalyst is soluble or insoluble in the reacting system.
The catalyst may be recovered and purified for repeated use by some appropriate method.
Preferably, the molar ratio of the copper complex to alkyl diazoacetate (V) is in a range of 0.001 - 0.1.
Although t`he reaction temperature is not particularly limited, usually a temperature between -50C. and 150C. is suitable. In those cases where the reaction is carried out at a temperature below the melting point of 2,5-dimetnyl-2, 4-hexadiene (15C.), a suitable solvent may be desirably added to the reaction system. Aromatic hydrocarbons such as benzene, toluene and xylene are suitable as the solvent in such cases.
The present invention is explained in further detail by the examples set forth below. They are not, however, to be taken as being limita-tive thereof.
In general, an unequivocal correlation exists between the absolute configuration of the substance which induces asymmetry and the absolute configuration of the substance to which asymmetry is induced. Therefore, in this invention~ too~
i3 it i5 needless to say that when the copper complex of enantiomeric structure opposite to the one described in the follow~ng examp~es is used as the catalyst, the resulting alkyl chrysanthemate and the corresponding chrysanthemic acid will also have the opposite enantiomeric structure.
Example 1 0.3 g. (0.2 m mol) of the dimeric copper complex of (R)-~-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxy)-pro-panol (corresponding to the formula (II) wherein Rl = methyl, R2 = 5-t-butyl-2-octyloxyphenyl, and Xl = x2 = hydrogen) was dissolved in 17.6 g. (160 m mols) of 2,5-dimethyl-2,4-hexadiene.
To this solution was added dropwise a mixture of 4.4 g.
(40 m mols) of the above mentioned diene and 4.5 g. ~20 m mols) of l-menthyl diazoacetate with stirring over a period of 7 hours.
At the beginning of the addition the solution of catalyst was once heated to 75C. to initiate the decomposition of diazo-acetate and thereafter the mixture was maintained at 40C. At the end o~ the addition a nearly quantitative amount of nitrogen gas was evolved.
The reaction mixture was distilled to recover the unreacted excess diene (boiling point 45C./20 mm Hg) under reduced pressure, and 4.7 g. of l-menthyl chrysanthemate was obtained as an oil having a boiling point o~ 123C.jO.2 mm Hg.
The yield was 76% based on the diazo compound.
The l-menthyl ester was analyzed on gas chromatography equipped with a glass capillary column (liquid phase QF-l) to determine the composition of optical isomers of the chrysanthemate.
llZ1~313 d-trans form 89.9 %; l-trans form 2.7 %;
total of d-cls and l-cis forms tseparation was impossible) 7.4 %
It is calculated that the percentage of the trans isomer in the ester is 93 ~,and the optical purity of the trans isomers is 94 %.
A mixture of 4.2 g. of l-menthyl ester, 1.8 g. of potassium hydroxide, 1.5 ml. of water and 11 ml. of ethanol was heated at 100C. with stirring for 7.5 hours. After distillation of ethanol from the reaction mixture, the residue was diluted with water and was extracted with ether. The alkaline aqueous solution was acidified with dilute sulfuric acid, and was extracted with toluene. After the organic layer was washed with water and dried, toluene was distilled off under reduced pressure to give chrysanthemic acid (2.4 g., yield 90 %).
Chrysanthemic acid was reacted with d-2-octanol and the resulting diasteromers were analyzed by gas chromatography to determine the composition of optical isomers of chrysanthemic acid.
_-trans form 90.4 %; _-trans form 4.7 %;
d-cis form 3.6 %; _-cls form 1.3 %
It is calculated that the optical purity of the trans isomers is 90 % and that of the cis isomer is 47 %.
For the analysis of chrysanthemic acid, refer to A. Murano, Agr. Biol. Chem., 36, 2203 ~1972) Examples 2 - 6 Experiments similar to Example 1 were performed, 11'~1~313 using dimeric chiral copper complexes shown in Table 1 and l-menthyl diazoacetate. The results are summarized in Table 1.
The content of the trans isomer of l-menthyl chrysanthemate was determined by gas chromatography. The optical purity of chrysanthemic acid obtained after hydrolysis was determined by gas chromatographic analysis of the corresponding (S)-1-methyl-1-heptyl ester.
It should be noted that when a catalyst of (R) configuration is used, dextrotatory-chrysanthemic acid is the favoured product, and when a catalyst of (S)configuration is used, laevorotatory-chrysanthemic acid is the favoured one.
Referential ExamPle 1 In place of chiral copper complex, copper powder was used as catalyst in the reaction between l-menthyl diazoacetate and 2~5-dimethyl-2,4-hexadiene. The results are shown in Table 1.
~' ~ ~ ul I ~ o u~ C\J In o .,, .~ .,., Ul ~o CU CU
.~ u Q~ U
~n . . . ,U ~ ~ ' O
a) co oo ~ o o ~
l O
d ~ ~ r~
,, .,, a~~ . .
U ~ C~ ~ ~ o o o a~
.,, .1: ~ . N a)N Q~CU ~ C~
~ H . I ,C
t~ H C~l ~ $ O ~ o X~: ~ o~ o ~ R ~ I R X R :~ R
~ ~ ~1~41 41 ~ 41 ~ 41 ~ ~
Q U u~ ou)~ Q u) S U) S 3 E~ O I ~ a C~ :
o q~ ~ ^ U~
~ ~ _ _ _ _ _ .
8 ~
,, X ~ CU ~
~ ~ W
Examples 7 - 16 Experiments similar to Example 1 were performed, using the diazoacetates shown in Table 2 and a chiral copper complex (the formula (II) wherein the configuration is (R~ , R1 = methyl, R2 = 5-t-butyl-2-octyloxyphenyl and Xl = x2 =
hydrogen). The results are summarized in Table 2. The content of trans isomer in the alkyl chrysanthemates was determined by gas chromatography. The optical purity of chrysanthemic acid obtained after hydrolysis of the esters was determined by gas chromatographic analysis of corresponding (Sl-l-methyl-1-heptyl ester.
The diazoacetates used in the examples were synthesized either by the following ~A) method of (B~ method.
In (A) method, a corresponding glycine ester is diazotized with isoamyl nitrite. The process is shown as follows:
ROH ~ H2NcH2cooR > N2CHCOOR
As a typical example, the preparation of l-menthyl diazo-acetate is shown in Example 17.
In (Bl method, the reaction proceeds as follows:
diketene ~ toluenesulfonylazide ROH ~CH3 CCH2COOR -corresponding acetoacetate alcohol 1l Na methoxide CH3CCOOR ~ N2CHCOOR
~2 diazoacetate ~-diazoacetoacetate ~i As a typical example, the preparation of 2,3,4-trimethyl -3-pentyl diazoacetate is shown in Example 18.
Referential Example 2 In the use of the same copper catalyst as in Examples 7 - 16, the reaction between ethyl diazoacetate and 2,5-dimethyl-2,4-hexadiene was carried out.
The results are shown in Table 2.
ll;~l~i3 o .
to Ul U~ , ~ ~ , U~ ~ ~ , , a~ ,~ r~ I~ ~ U~
~ ~ U
.,, ~
.. ~
R~
~ ~ ~n o ta ~ o t~ o In o ~ ~ ~ ~ ~ OD
~1 ~ ~ ~ CO 1` CO ~ 0 1 o U
U~ U~
00 ~ u~
~ ~o ~ ~ a) w co u~ I` I~ I` a~ n In U~
a~
. ~ l ~ o ~ ~ ~ o C~ ~
~rl _~ O u~ O ~ O O O O O O O
U ~ ~ ~ ~ d' ~ ~ d' ~O ~ d' ~ ~
td ~ o .Y P~ ~
~ ~n o o ~
tn ~ aJ
,, o ~ ~ m ma~
Q~
U~ Q~ ~
~ ~ ~ ~I
~ Id ~ ~1 -U~ ~ .
. ~ R -C\J N I ~ I ~ I
a ~
~D . ~ ~ 0 ~} P~ ,r~ aX) ~
E~
. . C~ O O ~ O ~ ~' u ~
CU
aJ
~1 a~ ~1 P~ ' S~
~ O t`CO ~ O ~ C~
X ~ X
P~
~ 8 11'~1813 Example 17 A mixture of l-men~hyl glycine (19.7 g.; 0.092 mol), isoamyl nitrite (12.0 g.; 0.10 mol) and acetic acid (1.6 g.;
0.027 mol) in chloroform (400 ml) was heated with stirring for 25 minutes under reflux. The reaction mixture was washed with l-N sulfuric acid followed by a saturated aqueous solution of sodium bicarbonate and then water. After the organic phase was dried, the xesidue (21 g.) obtained by condensation was purified by column chromatography (silica gel 160 g., methylene chloride) to give l-menthyl diazoacetate (15.0 g., 73%j.
Yellow crystal, [a]D - 86.8 (chloroform, c 1.0), -IR (film) ~ 2125 cm NMR (chloroform, TMS) ~ 5.29 ppm For l-menthyl glycine, refer to K. Harada, T. Hayakawa, Buil. Chem. Soc. Japan, 37, 191 (i964).
Example 18 To a mixture of 2,3,4-trimethyl-3-pentanol (24.3 g.;
0.18 mol) and triethylamine (0.1 g.) was added diketene (15.7 g ;
0.186 mol) dropwise at 70C. After the reaction mixture was stirred at 110C. for 1.5 hours, it was distilled under reduced pressure to give the corresponding acetoacetate (boiling point 84C./0.6 mm; 35.3 g.; 88 %).
To a mixture of the above mentioned ester (35.3 g., 0.164 mol), triethylamine tl7 g., 0.168 mol) and acetonitrile (200 ml) was added p-toluenesulfonylazide (38 g., 0.164 mol) dropwise at room temperature. After the reaction mixture was stirred for 1.5 hours, it was concentrated under reduced pressure. The residue was extracted with ether (200 ml) and the organic phase was washed twice with an aqueous solution of potassium hydroxide (12.6 g.). The organic phase was dried and concentrated to give the corresponding ~-diazoacetoaceta~e O g.).
To a solution of the above ester (40 g.) in methanol (65 ml) was added a sodium methoxide solution prepared from sodium (4.2 g.) and methanol (65 ml) at 0C. After the reaction mixture was further stirred for one hour at 0C., ice water (300 ml) was poured into it, sodium chloride was added and the mixture was extracted with-ether (400 ml in total).
After the organic phase was washed with water and dried, it was concentrated and distilled to give 2,3,4-trimethyl-3-pentyl diaæoacetate (b.p. 59C./0.2 mm; 20 g.; 64%).
Yellow oil, IR (fiLm) J 2125 cm 1 NMR (chloroform, TMS) ~ 5.40 ppm
As copper complexes of the optically active Schiff base of the formula (I), copper complexes of the previously mentioned general formulae (II), (III) and (IV) are effective, but the complex having dimeric structure of the formula (II) is used particularly advantageously. The complex of the general formula (II) is synthesized by the reaction of the Schiff base of the general formula (I) with a cupric salt such as cupric acetate.
I ,,~j .....
ll'~li~i3 The complex having monomeric structure of the formula ~IV) is synthesized by the reaction of the dimeric complex of the general formula (II) with a neutral monodentate ligand, for example pyridine, picoline, lutidine, etc. The cornplex having monomeric structure of the formula (III) is synthesized by reacting a copper complex of the salicylaldehyde derivative of the formula (VII) with the amino alcohol of the formula (VI).
In the actual practice of the present invention, the reaction can be carried out regardless of whether the chiral copper catalyst is soluble or insoluble in the reacting system.
The catalyst may be recovered and purified for repeated use by some appropriate method.
Preferably, the molar ratio of the copper complex to alkyl diazoacetate (V) is in a range of 0.001 - 0.1.
Although t`he reaction temperature is not particularly limited, usually a temperature between -50C. and 150C. is suitable. In those cases where the reaction is carried out at a temperature below the melting point of 2,5-dimetnyl-2, 4-hexadiene (15C.), a suitable solvent may be desirably added to the reaction system. Aromatic hydrocarbons such as benzene, toluene and xylene are suitable as the solvent in such cases.
The present invention is explained in further detail by the examples set forth below. They are not, however, to be taken as being limita-tive thereof.
In general, an unequivocal correlation exists between the absolute configuration of the substance which induces asymmetry and the absolute configuration of the substance to which asymmetry is induced. Therefore, in this invention~ too~
i3 it i5 needless to say that when the copper complex of enantiomeric structure opposite to the one described in the follow~ng examp~es is used as the catalyst, the resulting alkyl chrysanthemate and the corresponding chrysanthemic acid will also have the opposite enantiomeric structure.
Example 1 0.3 g. (0.2 m mol) of the dimeric copper complex of (R)-~-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxy)-pro-panol (corresponding to the formula (II) wherein Rl = methyl, R2 = 5-t-butyl-2-octyloxyphenyl, and Xl = x2 = hydrogen) was dissolved in 17.6 g. (160 m mols) of 2,5-dimethyl-2,4-hexadiene.
To this solution was added dropwise a mixture of 4.4 g.
(40 m mols) of the above mentioned diene and 4.5 g. ~20 m mols) of l-menthyl diazoacetate with stirring over a period of 7 hours.
At the beginning of the addition the solution of catalyst was once heated to 75C. to initiate the decomposition of diazo-acetate and thereafter the mixture was maintained at 40C. At the end o~ the addition a nearly quantitative amount of nitrogen gas was evolved.
The reaction mixture was distilled to recover the unreacted excess diene (boiling point 45C./20 mm Hg) under reduced pressure, and 4.7 g. of l-menthyl chrysanthemate was obtained as an oil having a boiling point o~ 123C.jO.2 mm Hg.
The yield was 76% based on the diazo compound.
The l-menthyl ester was analyzed on gas chromatography equipped with a glass capillary column (liquid phase QF-l) to determine the composition of optical isomers of the chrysanthemate.
llZ1~313 d-trans form 89.9 %; l-trans form 2.7 %;
total of d-cls and l-cis forms tseparation was impossible) 7.4 %
It is calculated that the percentage of the trans isomer in the ester is 93 ~,and the optical purity of the trans isomers is 94 %.
A mixture of 4.2 g. of l-menthyl ester, 1.8 g. of potassium hydroxide, 1.5 ml. of water and 11 ml. of ethanol was heated at 100C. with stirring for 7.5 hours. After distillation of ethanol from the reaction mixture, the residue was diluted with water and was extracted with ether. The alkaline aqueous solution was acidified with dilute sulfuric acid, and was extracted with toluene. After the organic layer was washed with water and dried, toluene was distilled off under reduced pressure to give chrysanthemic acid (2.4 g., yield 90 %).
Chrysanthemic acid was reacted with d-2-octanol and the resulting diasteromers were analyzed by gas chromatography to determine the composition of optical isomers of chrysanthemic acid.
_-trans form 90.4 %; _-trans form 4.7 %;
d-cis form 3.6 %; _-cls form 1.3 %
It is calculated that the optical purity of the trans isomers is 90 % and that of the cis isomer is 47 %.
For the analysis of chrysanthemic acid, refer to A. Murano, Agr. Biol. Chem., 36, 2203 ~1972) Examples 2 - 6 Experiments similar to Example 1 were performed, 11'~1~313 using dimeric chiral copper complexes shown in Table 1 and l-menthyl diazoacetate. The results are summarized in Table 1.
The content of the trans isomer of l-menthyl chrysanthemate was determined by gas chromatography. The optical purity of chrysanthemic acid obtained after hydrolysis was determined by gas chromatographic analysis of the corresponding (S)-1-methyl-1-heptyl ester.
It should be noted that when a catalyst of (R) configuration is used, dextrotatory-chrysanthemic acid is the favoured product, and when a catalyst of (S)configuration is used, laevorotatory-chrysanthemic acid is the favoured one.
Referential ExamPle 1 In place of chiral copper complex, copper powder was used as catalyst in the reaction between l-menthyl diazoacetate and 2~5-dimethyl-2,4-hexadiene. The results are shown in Table 1.
~' ~ ~ ul I ~ o u~ C\J In o .,, .~ .,., Ul ~o CU CU
.~ u Q~ U
~n . . . ,U ~ ~ ' O
a) co oo ~ o o ~
l O
d ~ ~ r~
,, .,, a~~ . .
U ~ C~ ~ ~ o o o a~
.,, .1: ~ . N a)N Q~CU ~ C~
~ H . I ,C
t~ H C~l ~ $ O ~ o X~: ~ o~ o ~ R ~ I R X R :~ R
~ ~ ~1~41 41 ~ 41 ~ 41 ~ ~
Q U u~ ou)~ Q u) S U) S 3 E~ O I ~ a C~ :
o q~ ~ ^ U~
~ ~ _ _ _ _ _ .
8 ~
,, X ~ CU ~
~ ~ W
Examples 7 - 16 Experiments similar to Example 1 were performed, using the diazoacetates shown in Table 2 and a chiral copper complex (the formula (II) wherein the configuration is (R~ , R1 = methyl, R2 = 5-t-butyl-2-octyloxyphenyl and Xl = x2 =
hydrogen). The results are summarized in Table 2. The content of trans isomer in the alkyl chrysanthemates was determined by gas chromatography. The optical purity of chrysanthemic acid obtained after hydrolysis of the esters was determined by gas chromatographic analysis of corresponding (Sl-l-methyl-1-heptyl ester.
The diazoacetates used in the examples were synthesized either by the following ~A) method of (B~ method.
In (A) method, a corresponding glycine ester is diazotized with isoamyl nitrite. The process is shown as follows:
ROH ~ H2NcH2cooR > N2CHCOOR
As a typical example, the preparation of l-menthyl diazo-acetate is shown in Example 17.
In (Bl method, the reaction proceeds as follows:
diketene ~ toluenesulfonylazide ROH ~CH3 CCH2COOR -corresponding acetoacetate alcohol 1l Na methoxide CH3CCOOR ~ N2CHCOOR
~2 diazoacetate ~-diazoacetoacetate ~i As a typical example, the preparation of 2,3,4-trimethyl -3-pentyl diazoacetate is shown in Example 18.
Referential Example 2 In the use of the same copper catalyst as in Examples 7 - 16, the reaction between ethyl diazoacetate and 2,5-dimethyl-2,4-hexadiene was carried out.
The results are shown in Table 2.
ll;~l~i3 o .
to Ul U~ , ~ ~ , U~ ~ ~ , , a~ ,~ r~ I~ ~ U~
~ ~ U
.,, ~
.. ~
R~
~ ~ ~n o ta ~ o t~ o In o ~ ~ ~ ~ ~ OD
~1 ~ ~ ~ CO 1` CO ~ 0 1 o U
U~ U~
00 ~ u~
~ ~o ~ ~ a) w co u~ I` I~ I` a~ n In U~
a~
. ~ l ~ o ~ ~ ~ o C~ ~
~rl _~ O u~ O ~ O O O O O O O
U ~ ~ ~ ~ d' ~ ~ d' ~O ~ d' ~ ~
td ~ o .Y P~ ~
~ ~n o o ~
tn ~ aJ
,, o ~ ~ m ma~
Q~
U~ Q~ ~
~ ~ ~ ~I
~ Id ~ ~1 -U~ ~ .
. ~ R -C\J N I ~ I ~ I
a ~
~D . ~ ~ 0 ~} P~ ,r~ aX) ~
E~
. . C~ O O ~ O ~ ~' u ~
CU
aJ
~1 a~ ~1 P~ ' S~
~ O t`CO ~ O ~ C~
X ~ X
P~
~ 8 11'~1813 Example 17 A mixture of l-men~hyl glycine (19.7 g.; 0.092 mol), isoamyl nitrite (12.0 g.; 0.10 mol) and acetic acid (1.6 g.;
0.027 mol) in chloroform (400 ml) was heated with stirring for 25 minutes under reflux. The reaction mixture was washed with l-N sulfuric acid followed by a saturated aqueous solution of sodium bicarbonate and then water. After the organic phase was dried, the xesidue (21 g.) obtained by condensation was purified by column chromatography (silica gel 160 g., methylene chloride) to give l-menthyl diazoacetate (15.0 g., 73%j.
Yellow crystal, [a]D - 86.8 (chloroform, c 1.0), -IR (film) ~ 2125 cm NMR (chloroform, TMS) ~ 5.29 ppm For l-menthyl glycine, refer to K. Harada, T. Hayakawa, Buil. Chem. Soc. Japan, 37, 191 (i964).
Example 18 To a mixture of 2,3,4-trimethyl-3-pentanol (24.3 g.;
0.18 mol) and triethylamine (0.1 g.) was added diketene (15.7 g ;
0.186 mol) dropwise at 70C. After the reaction mixture was stirred at 110C. for 1.5 hours, it was distilled under reduced pressure to give the corresponding acetoacetate (boiling point 84C./0.6 mm; 35.3 g.; 88 %).
To a mixture of the above mentioned ester (35.3 g., 0.164 mol), triethylamine tl7 g., 0.168 mol) and acetonitrile (200 ml) was added p-toluenesulfonylazide (38 g., 0.164 mol) dropwise at room temperature. After the reaction mixture was stirred for 1.5 hours, it was concentrated under reduced pressure. The residue was extracted with ether (200 ml) and the organic phase was washed twice with an aqueous solution of potassium hydroxide (12.6 g.). The organic phase was dried and concentrated to give the corresponding ~-diazoacetoaceta~e O g.).
To a solution of the above ester (40 g.) in methanol (65 ml) was added a sodium methoxide solution prepared from sodium (4.2 g.) and methanol (65 ml) at 0C. After the reaction mixture was further stirred for one hour at 0C., ice water (300 ml) was poured into it, sodium chloride was added and the mixture was extracted with-ether (400 ml in total).
After the organic phase was washed with water and dried, it was concentrated and distilled to give 2,3,4-trimethyl-3-pentyl diaæoacetate (b.p. 59C./0.2 mm; 20 g.; 64%).
Yellow oil, IR (fiLm) J 2125 cm 1 NMR (chloroform, TMS) ~ 5.40 ppm
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of an optically active chrysanthemate which comprises the reaction of 2,5-dimethyl-2,4-hexadiene with a diazoacetate of the formula:
wherein R is selected from the group consisting of (a) mono-or poly-cyclic cycloalkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 20, (b) tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substituent(s) whose total carbon atom number is 4 to 20, in the presence of a copper complex coordinated with a chiral Schiff base of the formula:
wherein C* is an asymmetric carbon atom, R1 is selected from the group consisting of (a) alkyl groups whose carbon atom number is 1 to 10, and (b) aralkyl groups with or without alkoxy substituent(s), whose total carbon atom number is 7 to 20, R2 is selected from aryl groups with alkoxy substituent(s), whose total carbon atom number is 7 to 30, each of X1 and X2 is selected from the group consisting of (a) hydrogen atom, (b) alkyl groups having 1 to 10 carbon atoms, (c) phenyl group, (d) alkoxy groups having 1 to 10 carbon atoms, (e) halogen atoms and (f) nitro group, or (g) X1 and X2 together form a benzo group.
wherein R is selected from the group consisting of (a) mono-or poly-cyclic cycloalkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 20, (b) tertiary aralkyl group whose carbon atom number is 9 to 20, and (c) tertiary alkyl group with or without alkoxy substituent(s) whose total carbon atom number is 4 to 20, in the presence of a copper complex coordinated with a chiral Schiff base of the formula:
wherein C* is an asymmetric carbon atom, R1 is selected from the group consisting of (a) alkyl groups whose carbon atom number is 1 to 10, and (b) aralkyl groups with or without alkoxy substituent(s), whose total carbon atom number is 7 to 20, R2 is selected from aryl groups with alkoxy substituent(s), whose total carbon atom number is 7 to 30, each of X1 and X2 is selected from the group consisting of (a) hydrogen atom, (b) alkyl groups having 1 to 10 carbon atoms, (c) phenyl group, (d) alkoxy groups having 1 to 10 carbon atoms, (e) halogen atoms and (f) nitro group, or (g) X1 and X2 together form a benzo group.
2. The process of claim 1 in which said copper complex has the following structure:
wherein R1, R2, X1 and X2 are defined as in Claim 1.
wherein R1, R2, X1 and X2 are defined as in Claim 1.
3. The process of Claim 1 in which said chiral Schiff base is prepared by the reaction of a chiral amino alcohol of the formula:
wherein C*, R1 and R2 are defined as in Claim 1, and a salicylaldehyde derivative of the formula:
wherein X1 and X2 are defined as in Claim 1.
wherein C*, R1 and R2 are defined as in Claim 1, and a salicylaldehyde derivative of the formula:
wherein X1 and X2 are defined as in Claim 1.
4. The process of Claim 2 in which said copper complex is prepared by the reaction of a chiral Schiff base of Claim 3 with a cupric salt.
5. The process of Claim 1 in which R is (a) menthyl, (b) neomenthyl, (c) 1-adamantyl, (d) a,.alpha.-dimethyl-.beta.(menthoxy)-ethyl, (e) 2,3-dimethyl-2-butyl, (f) 2,3,4-trimethyl-3-pentyl, (g) bornyl, (h) cyclohexyl, (i) t-butyl, or (j) .alpha.,.alpha.-dimethyl-benzyl.
6. The process of Claim 1 in which said diazoacetate is prepared by the diazotization of the glycine ester of the formula:
wherein R is cycloalkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 20.
wherein R is cycloalkyl group with or without alkyl substituent(s) whose total carbon atom number is 5 to 20.
7. The process of Claim 1 in which R1 is (a) benzyl, (b) methyl, (c) isopropyl, or (d) isobutyl.
8. The process of Claim 1 in which R2 is (a) 2-methoxyphenyl, (b) 2-ethoxyphenyl, (c) 2-isopropoxyphenyl, (d) 5-t-butyl-2-isopropoxyphenyl, (e) 5-t-butyl-2-heptyloxyphenyl, (f) 2-butoxy-5-t-butylphenyl, (g) 5-t-butyl-2-octyloxyphenyl, (h) 4-butoxybiphenyl-3-yl, or (i) 2,5-dibutoxyphenyl.
9. The process of Claim 3 in which said salicylaldehyde derivative is (a) salicylaldehyde (b) o-vanillin (c) 3-ethoxysalicylaldehyde, (d) 3,5-dibromosalicylaldehyde, (e) 5-chlorosalicylaldehyde, (f) 3-nitrosalicylaldehyde, (g) 3-isopropyl-6-methylsalicylaldehyde, (h) 2-hydroxy-1-naphthaldehyde, or (i) 1-hydroxy-2-naphthaldehyde.
10. The process of Claim 2 in which said chiral Schiff base is either an (R)- or an (S)-enantiomer of the following:
(a) N-salicylidene-2-amino-1,1-di(2-methoxyphenyl) -3-phenyl-1-propanol, (b) N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl) -3-phenyl-1-propanol, (c) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxy-phenyl)-3-phenyl-1-propanol, (d) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butyl-phenyl)-3-phenyl-1-propanol, (e) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-heptyloxy-phenyl)-3-phenyl-1-propanol, (f) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxy-phenyl)-1-propanol, (g) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butyl-phenyl)-1-propanol, (h) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxy-phenyl)-1-propanol, (i) N-(3-methoxysalicylidene)-2-amino-1,1-di(5-t-butyl-2-octyloxyphenyl)-1-propanol, (j) N-(3,5-dibromosalicylidene)-2-amino-1,1-di(2-isopro-poxyphenyl)-3-phenyl-1-propanol, (k) N-(3-ethoxysalicylidene)-2-amino-1,1-di(2-isopropoxy-phenyl)-3-phenyl-1-propanol, (l) N-(2-hydroxy-1-naphthylmethylene)-2-amino-1,1-di (2-isopropoxyphenyl)-3-phenyl-1-propanol, (m) N-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl) -3-phenyl-1-propanol, (n) N-salicylidene-2-amino-1,1-di(2,5-dibutoxyphenyl) -3-phenyl-1-propanol, (o) N-salicylidene-2-amino-1,1-di(2-butoxyphenyl) -3-methyl-1-butanol, or (p) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butyl-phenyl)-4-methyl-1-pentanol.
(a) N-salicylidene-2-amino-1,1-di(2-methoxyphenyl) -3-phenyl-1-propanol, (b) N-salicylidene-2-amino-1,1-di(2-isopropoxyphenyl) -3-phenyl-1-propanol, (c) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxy-phenyl)-3-phenyl-1-propanol, (d) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butyl-phenyl)-3-phenyl-1-propanol, (e) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-heptyloxy-phenyl)-3-phenyl-1-propanol, (f) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-isopropoxy-phenyl)-1-propanol, (g) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butyl-phenyl)-1-propanol, (h) N-salicylidene-2-amino-1,1-di(5-t-butyl-2-octyloxy-phenyl)-1-propanol, (i) N-(3-methoxysalicylidene)-2-amino-1,1-di(5-t-butyl-2-octyloxyphenyl)-1-propanol, (j) N-(3,5-dibromosalicylidene)-2-amino-1,1-di(2-isopro-poxyphenyl)-3-phenyl-1-propanol, (k) N-(3-ethoxysalicylidene)-2-amino-1,1-di(2-isopropoxy-phenyl)-3-phenyl-1-propanol, (l) N-(2-hydroxy-1-naphthylmethylene)-2-amino-1,1-di (2-isopropoxyphenyl)-3-phenyl-1-propanol, (m) N-salicylidene-2-amino-1,1-di(4-butoxybiphenyl-3-yl) -3-phenyl-1-propanol, (n) N-salicylidene-2-amino-1,1-di(2,5-dibutoxyphenyl) -3-phenyl-1-propanol, (o) N-salicylidene-2-amino-1,1-di(2-butoxyphenyl) -3-methyl-1-butanol, or (p) N-salicylidene-2-amino-1,1-di(2-butoxy-5-t-butyl-phenyl)-4-methyl-1-pentanol.
11. The process according to Claim 1, wherein the reaction is conducted in the absence of a solvent.
12. The process according to Claim 1, wherein the reaction is conducted in the presence of a solvent.
13. The process according to Claim 12, wherein said solvent is an aromatic hydrocarbon.
14. The process according to claim 1, wherein the reaction temperature is in a range of from - 50°C. to 150°C.
15. The process according to Claim 1, wherein the molar ratio of the said copper complex to alkyl diazoacetate is in a range of 0.001 to 0.1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50094349A JPS5910336B2 (en) | 1975-08-01 | 1975-08-01 | Asymmetric synthesis method of primary chrysanthemum acid ester |
| JP94349/75 | 1975-08-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1121813A true CA1121813A (en) | 1982-04-13 |
Family
ID=14107796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000258220A Expired CA1121813A (en) | 1975-08-01 | 1976-07-30 | Asymmetric synthesis of chrysanthemate |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS5910336B2 (en) |
| BE (1) | BE844631A (en) |
| CA (1) | CA1121813A (en) |
| CH (1) | CH621767A5 (en) |
| DE (1) | DE2634663C3 (en) |
| DK (1) | DK142765B (en) |
| FR (1) | FR2319623A1 (en) |
| GB (1) | GB1499094A (en) |
| IL (1) | IL50100A (en) |
| IT (1) | IT1070323B (en) |
| NL (1) | NL7608508A (en) |
| SU (1) | SU719491A3 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2919820A1 (en) * | 1979-05-16 | 1980-11-20 | Bayer Ag | FLUOR-SUBSTITUTED OXYALKENYL-CYCLOPROPANCARBONIC ACID ESTERS, METHODS FOR THE PRODUCTION THEREOF AND THEIR USE AS INSECTICIDES AND ACARICIDES |
| DE3064018D1 (en) * | 1979-07-13 | 1983-08-11 | Ici Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| EP0024796A1 (en) * | 1979-07-13 | 1981-03-11 | Imperial Chemical Industries Plc | Chiral amino-alcohol complexes and process for their preparation |
| EP0024797A1 (en) | 1979-07-13 | 1981-03-11 | Imperial Chemical Industries Plc | Chiral sugar complexes and process for their preparation |
| EP0024795A1 (en) * | 1979-07-13 | 1981-03-11 | Imperial Chemical Industries Plc | Chiral compounds and process for their preparation |
| EP0023075A1 (en) * | 1979-07-13 | 1981-01-28 | Imperial Chemical Industries Plc | Process for the preparation of cyclopropane carboxylic acid esters |
| JPS59158260A (en) * | 1983-02-28 | 1984-09-07 | Seikei Giken:Kk | Vacuum transfer apparatus |
| JPS59158261A (en) * | 1983-07-19 | 1984-09-07 | Seikei Giken:Kk | Transfer apparatus |
| JPH01232619A (en) * | 1988-03-11 | 1989-09-18 | Toska Co Ltd | Printing method for key top |
| JPH0671852A (en) * | 1992-08-31 | 1994-03-15 | Shizuoka Giken Sanki Kk | Method and device for subjecting curved surface to heat transfer by vacuum press |
| JP4576642B2 (en) * | 1998-01-29 | 2010-11-10 | 住友化学株式会社 | Process for producing optically active chrysanthemic acid |
| ITMI20041211A1 (en) * | 2004-06-16 | 2004-09-16 | Endura Spa | METAL COMPLEX-BASED CATALYSTS FOR THE SYNTHESIS OF OPTICALLY ACTIVE CHRYSANTHEMIC ACID |
| CN103789789B (en) * | 2014-02-11 | 2016-06-29 | 华东师范大学 | Electrochemical synthesis has the method for optically active Styrene carbonate |
| CN103789791B (en) * | 2014-02-12 | 2016-08-17 | 华东师范大学 | A kind of electrochemical synthesis has optically active 2-benzenpropanoic acid method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL44167A (en) * | 1973-02-14 | 1979-09-30 | Sumitomo Chemical Co | Chiral copper-complex catalyst |
-
1975
- 1975-08-01 JP JP50094349A patent/JPS5910336B2/en not_active Expired
-
1976
- 1976-07-22 IL IL50100A patent/IL50100A/en unknown
- 1976-07-28 BE BE6045627A patent/BE844631A/en not_active IP Right Cessation
- 1976-07-30 SU SU762387252A patent/SU719491A3/en active
- 1976-07-30 CH CH977576A patent/CH621767A5/en not_active IP Right Cessation
- 1976-07-30 IT IT68927/76A patent/IT1070323B/en active
- 1976-07-30 GB GB31985/76A patent/GB1499094A/en not_active Expired
- 1976-07-30 NL NL7608508A patent/NL7608508A/en not_active Application Discontinuation
- 1976-07-30 DK DK345276AA patent/DK142765B/en not_active IP Right Cessation
- 1976-07-30 CA CA000258220A patent/CA1121813A/en not_active Expired
- 1976-07-30 FR FR7623388A patent/FR2319623A1/en active Granted
- 1976-08-02 DE DE2634663A patent/DE2634663C3/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5910336B2 (en) | 1984-03-08 |
| FR2319623B1 (en) | 1979-09-28 |
| FR2319623A1 (en) | 1977-02-25 |
| BE844631A (en) | 1976-11-16 |
| DK142765B (en) | 1981-01-19 |
| DE2634663C3 (en) | 1980-01-17 |
| IL50100A0 (en) | 1976-09-30 |
| GB1499094A (en) | 1978-01-25 |
| DK142765C (en) | 1981-08-17 |
| IT1070323B (en) | 1985-03-29 |
| IL50100A (en) | 1982-02-28 |
| DE2634663A1 (en) | 1977-03-17 |
| DE2634663B2 (en) | 1979-05-31 |
| CH621767A5 (en) | 1981-02-27 |
| SU719491A3 (en) | 1980-02-29 |
| NL7608508A (en) | 1977-02-03 |
| JPS5217448A (en) | 1977-02-09 |
| DK345276A (en) | 1977-02-02 |
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