CA1067505A - Process for the oxidation of primary allylic and benzylic alcohols - Google Patents
Process for the oxidation of primary allylic and benzylic alcoholsInfo
- Publication number
- CA1067505A CA1067505A CA239,165A CA239165A CA1067505A CA 1067505 A CA1067505 A CA 1067505A CA 239165 A CA239165 A CA 239165A CA 1067505 A CA1067505 A CA 1067505A
- Authority
- CA
- Canada
- Prior art keywords
- alcohol
- primary
- oxidation
- alcohols
- oppenauer
- 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.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
Abstract
ABSTRACT OF THE DISCLOSURE
Improved conversions of primary allylic and benzylic alcohols are obtained in an Oppenauer oxidation process, under Oppenauer oxidation conditions, by carrying out the oxidation employing furfural as the hydrogen acceptor. Primary alcohols to which the present invention relates are: allylic alcohols substituted in at least the 2-position with a hydrocarbon radical; and benzylic alcohols.
Improved conversions of primary allylic and benzylic alcohols are obtained in an Oppenauer oxidation process, under Oppenauer oxidation conditions, by carrying out the oxidation employing furfural as the hydrogen acceptor. Primary alcohols to which the present invention relates are: allylic alcohols substituted in at least the 2-position with a hydrocarbon radical; and benzylic alcohols.
Description
1()67505 The present invention relates to the Oppenauer oxida-tion of primary alcohols to their corresponding aldehydes. The invention is particularly applicable to the oxidation of:
primary allylic alcohols substituted in at least the 2-position with a hydrocarbon radical; and primary benzylic alcohols. The allylic double bond may be acyclic, exocyclic or endocyclic.
An example of a cyclic allylic alcohol to which the present invention relates is perilly alcohol (l-hydroxymethyl-4-isopropenylcyclohexene). An example of a benzylic alcohol to which the present invention relates is benzyl alcohol.
The present application is related to Canadian application Serial No. 239,164 filed November 7, 1975, being assigned to the Assignee of the present application. The inventions of said application resides in the Oppenauer oxidation of 3-substituted and 3,3-disubstituted alcohols, such as geraniol and nerol (3,7-dimethyl-2,6-octadien-1-ol). to the corresponding aldehydes, such as citral.
The Oppenauer oxidation of secondary alcohols to ketones is a useful and well-known textbook reaction. The oxidation is carried out generally in the presence of an aluminum catalyst such as aluminum tert-butoxide or aluminum isopropoxide employing a large excess of acetone as a hydrogen -acceptor. The general application of this reaction is, however, for secondary alcohols. It is reported in Organic :
Rffactions, Vol. VI, chapter 5, on "The Oppenauer Oxidation", (pages 222-223) by Carl Djerassi, John Wiley and Sons Inc., 1951: "Until very ~ I ~
~ ~ .
.~ :
~i B
. .. .
........ ... .. . . . ... . ... . - . . . . .
.. .. ... .. .. . .. ... ..
., ... . - . . . : .. ~ - . .- . .
~o67505 recently the O~penauer reaction, except in isolated instances, has not been used as a preparative method for the oxidation of primary alcohols to aldehydes because the aldehydes condensed with the hydrogen acceptor." As indicated by Djerassi, experi-mental modifications in the usual Oppenauer procedure are necessary. These include the use of expensive or difficult to ; come by hydrogen acceptors, use of stoichiometric amounts of catalyst and careful distillation of the product as it is formed. The methods are expensive, difficult to carry out on lQ a large scale and are employed only when no other method is availaBle. ~ ~
. .
Previous observations of the oxidation of primary alcohols such as geraniol and nerol with acetone as a hydrogen -~
acceptor show that the aldehydes produced undergo a subsequent .: , aldol condensation reaction with the acetone and little aldehyde (citral~ is actually recoverable. Although the end product of `r~ the aldol condensation of citral is pseudoionone, two major problems have kept this reaction from being employed in the production of pseudoionone commercially. One problem is that 2a the aldol condensation reaction produces water as a by-product which hydrolyzes and consumes the aluminum catalyst. This requires nearly stoichiometric quantities tas compared to i catalytic quantities) of the aluminum catalyst (notice page 224 of D~erassi, supra). In addition, the hydrolyzed catalyst is in the form of a gel-like precipitate which is difficult to dispose of and which also presents mechanical problems in carry-ing out the oxidation reaction. Still further, large amounts of solvent are required to dissolve the correspondingly large amount o~ catalyst employed for the oxidation reaction. A second :~.
3Q disad~antage is that if the reaction is carried to high ,j -j ., ` 10~7S05 conversion, the yield tends to fall off, Substituting hydrogen acceptors such as cyclohexanone, which are less likely to undergo an aldol condensation, for the acetone may improve the aldehyde yield. Still, relatively high reaction temperatures are required when using ketones as hydrogen acceptors to carry out the oxidation to high conversion in a reasonable time. High temperatures would be a disadvantage with heat-sensitive aldehydes such as citral, as these are capable of self-condensation at high temperatures. In addition, other ketonic hydrogen acceptors present problems of avail-: ability or low equilibrium constants, the latter necessitating a large excess of hydrogen acceptor which causes difficulty in subsequent isolation of products.
Djerassi on page 230 points out: "Until recently . 15 aldehydes have been used only infrequently as hydrogen .. acceptors." Aldehydes are traditionally difficult products to .
make, being unstable and subject to side reactions. Use of an ` aldeh.yde as a reactant or hydrogen acceptor is subject to the ` same problems, being equally unstable and subject to side reactions. In the Oppenauer oxidation process, it is likely to : undergo both aldol and Tischenko condensation reactions, with . both. itself and with the Oppenauer oxidation product.
., A number of studies have been conducted by Adkins and others (for instance, Adkins et al, J. Am. Ch.em. Soc., Vol. 71, ; 25 pages 3622-3629) to determine the apparent oxidation potentials .
of various compounds (primarily ketones). Although it can be concluded that a high oxidation potential is desirable, a :~ :
relatively low one (as pointed out by Djerassi on page 228) can . be offset by using a large excess of hydrogen acceptor, and .
other factors such as rate of reaction and potential for side ' reactions may be more controlling. For instance, acetone h.as a relatively low oxidation potential but is inexpensive and can -3- :-: -. ~ .
,., : .. , : . : - : ~ :- i .............. . .............. .
. . . - . . . :. : : . . : .
` i~67505 be used in large excess. Cyclohexanone on the other hand has a higher oxidation potential, but in comparative tests cQnducted with this compound, the oxidation o geraniol resulted in only 15~ conversion to citral.
According to the present invention there is provided, an Oppenauer oxidation of primary alcohols selected from the group consisting of: primary allylic alcohols substituted in at least the 2-position with a hydrocarbon radical, in which the allylic double bond is acyclic, exo-cyclic or endocyclic; and primary benzylic alcohols; to the corresponding aldehyde, in the presence of an Oppenauer oxidation catalyst and hydrogen acceptor under Oppenauer oxidation conditions, the improvement for obtaining increased conversion and yield of aldehyde which comprises utilizing furfural as said hydrogen acceptor and forming a reaction product mixture containing the aldehyde corresponding to the primary alcohol, and a byproduct, furfuryl alcohol.
The present invention resides in the discovery that furfural unexpectedly constitutes a superior oxidizing agent or hydrogen acceptor for the conversion of primary allylic and benzylic alcohols to their corresponding aldehydes. Primary allylic alcohols to which the present invention relates are: allylic alcohols substituted in at least the 2-position with a hydrocarbon radical; the allylic double bond may be acyclic, , exocyclic or endocyclic and the 3-position may be unsubstituted, mono-'!
substituted or disubstituted. The reaction of the present invention is carried out under mild Oppenauer oxidation conditions in the presence of `l an aluminum catalyst. By way of example, the reaction can be represented by the following equation, employing perillyl alcohol as a substrate:
., . -~
-, ~
' :.
~1) CH OH
primary allylic alcohols substituted in at least the 2-position with a hydrocarbon radical; and primary benzylic alcohols. The allylic double bond may be acyclic, exocyclic or endocyclic.
An example of a cyclic allylic alcohol to which the present invention relates is perilly alcohol (l-hydroxymethyl-4-isopropenylcyclohexene). An example of a benzylic alcohol to which the present invention relates is benzyl alcohol.
The present application is related to Canadian application Serial No. 239,164 filed November 7, 1975, being assigned to the Assignee of the present application. The inventions of said application resides in the Oppenauer oxidation of 3-substituted and 3,3-disubstituted alcohols, such as geraniol and nerol (3,7-dimethyl-2,6-octadien-1-ol). to the corresponding aldehydes, such as citral.
The Oppenauer oxidation of secondary alcohols to ketones is a useful and well-known textbook reaction. The oxidation is carried out generally in the presence of an aluminum catalyst such as aluminum tert-butoxide or aluminum isopropoxide employing a large excess of acetone as a hydrogen -acceptor. The general application of this reaction is, however, for secondary alcohols. It is reported in Organic :
Rffactions, Vol. VI, chapter 5, on "The Oppenauer Oxidation", (pages 222-223) by Carl Djerassi, John Wiley and Sons Inc., 1951: "Until very ~ I ~
~ ~ .
.~ :
~i B
. .. .
........ ... .. . . . ... . ... . - . . . . .
.. .. ... .. .. . .. ... ..
., ... . - . . . : .. ~ - . .- . .
~o67505 recently the O~penauer reaction, except in isolated instances, has not been used as a preparative method for the oxidation of primary alcohols to aldehydes because the aldehydes condensed with the hydrogen acceptor." As indicated by Djerassi, experi-mental modifications in the usual Oppenauer procedure are necessary. These include the use of expensive or difficult to ; come by hydrogen acceptors, use of stoichiometric amounts of catalyst and careful distillation of the product as it is formed. The methods are expensive, difficult to carry out on lQ a large scale and are employed only when no other method is availaBle. ~ ~
. .
Previous observations of the oxidation of primary alcohols such as geraniol and nerol with acetone as a hydrogen -~
acceptor show that the aldehydes produced undergo a subsequent .: , aldol condensation reaction with the acetone and little aldehyde (citral~ is actually recoverable. Although the end product of `r~ the aldol condensation of citral is pseudoionone, two major problems have kept this reaction from being employed in the production of pseudoionone commercially. One problem is that 2a the aldol condensation reaction produces water as a by-product which hydrolyzes and consumes the aluminum catalyst. This requires nearly stoichiometric quantities tas compared to i catalytic quantities) of the aluminum catalyst (notice page 224 of D~erassi, supra). In addition, the hydrolyzed catalyst is in the form of a gel-like precipitate which is difficult to dispose of and which also presents mechanical problems in carry-ing out the oxidation reaction. Still further, large amounts of solvent are required to dissolve the correspondingly large amount o~ catalyst employed for the oxidation reaction. A second :~.
3Q disad~antage is that if the reaction is carried to high ,j -j ., ` 10~7S05 conversion, the yield tends to fall off, Substituting hydrogen acceptors such as cyclohexanone, which are less likely to undergo an aldol condensation, for the acetone may improve the aldehyde yield. Still, relatively high reaction temperatures are required when using ketones as hydrogen acceptors to carry out the oxidation to high conversion in a reasonable time. High temperatures would be a disadvantage with heat-sensitive aldehydes such as citral, as these are capable of self-condensation at high temperatures. In addition, other ketonic hydrogen acceptors present problems of avail-: ability or low equilibrium constants, the latter necessitating a large excess of hydrogen acceptor which causes difficulty in subsequent isolation of products.
Djerassi on page 230 points out: "Until recently . 15 aldehydes have been used only infrequently as hydrogen .. acceptors." Aldehydes are traditionally difficult products to .
make, being unstable and subject to side reactions. Use of an ` aldeh.yde as a reactant or hydrogen acceptor is subject to the ` same problems, being equally unstable and subject to side reactions. In the Oppenauer oxidation process, it is likely to : undergo both aldol and Tischenko condensation reactions, with . both. itself and with the Oppenauer oxidation product.
., A number of studies have been conducted by Adkins and others (for instance, Adkins et al, J. Am. Ch.em. Soc., Vol. 71, ; 25 pages 3622-3629) to determine the apparent oxidation potentials .
of various compounds (primarily ketones). Although it can be concluded that a high oxidation potential is desirable, a :~ :
relatively low one (as pointed out by Djerassi on page 228) can . be offset by using a large excess of hydrogen acceptor, and .
other factors such as rate of reaction and potential for side ' reactions may be more controlling. For instance, acetone h.as a relatively low oxidation potential but is inexpensive and can -3- :-: -. ~ .
,., : .. , : . : - : ~ :- i .............. . .............. .
. . . - . . . :. : : . . : .
` i~67505 be used in large excess. Cyclohexanone on the other hand has a higher oxidation potential, but in comparative tests cQnducted with this compound, the oxidation o geraniol resulted in only 15~ conversion to citral.
According to the present invention there is provided, an Oppenauer oxidation of primary alcohols selected from the group consisting of: primary allylic alcohols substituted in at least the 2-position with a hydrocarbon radical, in which the allylic double bond is acyclic, exo-cyclic or endocyclic; and primary benzylic alcohols; to the corresponding aldehyde, in the presence of an Oppenauer oxidation catalyst and hydrogen acceptor under Oppenauer oxidation conditions, the improvement for obtaining increased conversion and yield of aldehyde which comprises utilizing furfural as said hydrogen acceptor and forming a reaction product mixture containing the aldehyde corresponding to the primary alcohol, and a byproduct, furfuryl alcohol.
The present invention resides in the discovery that furfural unexpectedly constitutes a superior oxidizing agent or hydrogen acceptor for the conversion of primary allylic and benzylic alcohols to their corresponding aldehydes. Primary allylic alcohols to which the present invention relates are: allylic alcohols substituted in at least the 2-position with a hydrocarbon radical; the allylic double bond may be acyclic, , exocyclic or endocyclic and the 3-position may be unsubstituted, mono-'!
substituted or disubstituted. The reaction of the present invention is carried out under mild Oppenauer oxidation conditions in the presence of `l an aluminum catalyst. By way of example, the reaction can be represented by the following equation, employing perillyl alcohol as a substrate:
., . -~
-, ~
' :.
~1) CH OH
2 CHO
aluminum J \ / catalyst ~ \ O / CHO > \ J
- Perillyl Furfural Perillyl alcohol aldehyde \ o/ CH20H
- Furfuryl alcohol ' Under the mild reaction conditions, it was discovered that furfural does not undergo a Tischenko reaction as is common with ma~y aldehydes. Moreover, furfural, having no alphaprotons, does not undergo an aldol condensation with the ' ' ' .~' ., .
., - 4a -~, . -,.. . . . . . . .. . . . . . . . .... ..
` 106i750S
aldehyde product, for instance perillyl aldehyde, as does acetone. Hence, the amount of aluminum catalyst required for the reaction is greatly reduced to catalytic quantities, eliminating the attendant mechanical and pollution problems, and reducing catalyst cost.
Surprisingly, the reaction of furfural with primary allylic alcohols such as perillyl alcohol, and also with primary benzylic alcohols, has a high rate of reaction which permits it to be carried out under very mild conditions. This is important for heat-sensitive or highly reactive compounds. Specifically, at the mild conditions of the reaction of the present invention, perillyl aldehyde, itself, undergoes no aldol self-condensation.
Also, at the mild conditions of the present invention, no appreciable side reactions occur.
The reaction of the present invention also has a fortuitous high equilibrium constant so that it results in high conversion and yields of the aldehyde without employing a large excess of furfural.
Preferably, the reaction of furfural and alcohol is carried out with a molar ratio of furfural to alcohol of about 10 to about 10:1. A preferred range is about 1:2 to about
aluminum J \ / catalyst ~ \ O / CHO > \ J
- Perillyl Furfural Perillyl alcohol aldehyde \ o/ CH20H
- Furfuryl alcohol ' Under the mild reaction conditions, it was discovered that furfural does not undergo a Tischenko reaction as is common with ma~y aldehydes. Moreover, furfural, having no alphaprotons, does not undergo an aldol condensation with the ' ' ' .~' ., .
., - 4a -~, . -,.. . . . . . . .. . . . . . . . .... ..
` 106i750S
aldehyde product, for instance perillyl aldehyde, as does acetone. Hence, the amount of aluminum catalyst required for the reaction is greatly reduced to catalytic quantities, eliminating the attendant mechanical and pollution problems, and reducing catalyst cost.
Surprisingly, the reaction of furfural with primary allylic alcohols such as perillyl alcohol, and also with primary benzylic alcohols, has a high rate of reaction which permits it to be carried out under very mild conditions. This is important for heat-sensitive or highly reactive compounds. Specifically, at the mild conditions of the reaction of the present invention, perillyl aldehyde, itself, undergoes no aldol self-condensation.
Also, at the mild conditions of the present invention, no appreciable side reactions occur.
The reaction of the present invention also has a fortuitous high equilibrium constant so that it results in high conversion and yields of the aldehyde without employing a large excess of furfural.
Preferably, the reaction of furfural and alcohol is carried out with a molar ratio of furfural to alcohol of about 10 to about 10:1. A preferred range is about 1:2 to about
3:1 which results in high yields of the desired products without excessive amounts of unreacted starting materials. The specific ratio selected, however, depends on the end products desired.
Preferably, a catalytic amount of about 1-15 mol %
(based on the weight of primary allylic alcohol charged) of an aluminum catalyst such as aluminum isopropoxide is employed, although this depends in part on the amount of water present in the reaction mixture.
The use of less than 2 mol % catalyst is possible if extreme care is taken with regard to the water content. Other factors dictating tha amount of catalyst employed include rate ,A
, ~ ` ', ' ~ . : . . . .
~' ' ' , ; ' . ~'` .
10675~5 of reaction desired, amount of coincidental acid present in the reaction mixture, and the amount of water or acid produced in the course of the reaction.
Any aluminum alkoxide or aluminum aryloxide catalyst useful in an Oppenauer reaction, such as aluminum tert-butoxide L Al~t-OC4H9)3_7, may be used. Aluminum isopropoxide is preferred as it offers a cost advantage and an advantage in availability, although some furfural is consumed by oxidation of the isopropoxide to acetone. In this regard, it is reported in the aforementioned Or~anic Reactions, Vol. VI, page 209 (Djerassi) and also in PhYsical Or~nic Chemistry, by Hine, that the true active catalyst in the oxidation is an aluminum alkoxide which is generated in situ, and thus is dependent upon the reactants and conditions. It is normally generated by the addition of aluminum isopropoxide, aluminum t-butoxide or aluminum phenoxide. It may also be generated in situ by addition of an alkyl aluminum compound such as triisobutyl-aluminum (Djerassi also lists a number of other suitable compounds). These compounds, although they are normally referred to as the catalyst, are merely the source of the aluminum alkoxide. Hence the choice of aluminum source is largely one of convenience. For the purposes of this application, the term "Oppenauer Oxidation Catalyst" shall be deemed to ; embrace all of the above compounds.
Representative alcohols to which the present applica-tion is directed are set forth in the following Table 1:
.. . .
.,~
Table l CH2=C-CH2OH Methallyl alcohol CH2OH Perillyl alcohol CH OH
Benzyl alcohol ~ i ' ' It is apparent that the above alcohols have in common a hydrocarbon substitution at the 2-position beta to the carbinol hydroxyl radical. They may or may not be substituted in the 3-position, and the substitution can be by any aliphatic :- or aromatic radical. Other representative benzylic alcohols .,, within the scope of the present invention are such polyhydroxyl ~'!' compounds as saligenin r o-HOC6H4CH2OH_~, para hydroxy benzyl alcohol r p-HOC6H4CH2OHJ , and vanillyl alcohol La, 4-dih.ydroxy-.~ 3-meth.oxytoluene J . For purposes of the present application, ., the term "benzylic alcohol" h.as th.e common meaning that it A' 15 defines hydroxy methyl aromatic compounds.
~` An example of another cyclic allylic alcohol in which. .
the allylic double bond is endocyclic is myrtenol:
' l 2 W
i i, Other primary alcohols within the scope of the present invention will be apparent to those skilled in the art.
The following examples illustrate the present invention : and its practice, but should not be considered as limiting it.
', .
:~ -7-, !
~3067~5 In this specification, all percentages are by weight, all parts are parts by weight, and all temperatures are in degrees Centigrade unless otherwise specified.
This example illustrates the oxidation of perillyl alcohol to perillyl aldehyde. A flask was charged with 100 ml.
of toluene and 160 grams of furfural and heated to reflux to remove any water present by azeotropic distillation. The solution was then cooled to room temperature and 50 grams of perillyl alcohol and 2~5 grams of aluminum isopropoxide were added. The solution was then heated to 75C~ for three hours.
Analysis by glpc showed over 90% conversion to perillyl aldehyde.
~; EXAMPLE 2 This example illustrates the principles of the invention in the Oppenauer oxidation of benzyl alcohol to benzaldehyde. A flask equipped with a Dean-Stark trap was charged with 32~5 grams (0~3 mol) of benzyl alcohol and 30 ml.
of toluene and heated to reflux to remove any water present by azeotropic distillation. The solution was cooled to room temperature and 28~8 grams (0.3 mol) of furfural and 2.0 grams (0.01 mol) of aluminum isopropoxide were added. The mixture was stirred at ambient temperature and sampled periodically for analysis by glpc. After 5 hours 61. 5% of the benzyl alcohol `~ 25 was converted to benzaldehyde and 68~3~/o of furfural was converted to furfuryl alcohol.
After 72 hours, conversion to benzaldehyde increased to 63~9% and conversion to furfuryl alcohol increased to 74.5%.
; No by-products derived from either benzyl alcohol or furfural were detected by glpc. ~
' ~ :
~. . .. .. , . -. .
10~7SOS
A flask was charged with 3.1 grams (20 m~ol) of 2,6-dimethyl-2,7-octadien-1-ol, 0.3 grams (1.5 mmol) of aluminum isopropoxide, and 2.0 grams (21 mmol) of furfural, and stirred 16 hours at ambient temperature. Analysis of the product by vapor phase chromatography showed 95~/O conversion of the starting alcohol to 2,6-dimethyl-2,7-octadienal.
:.
.~
.,, ..
: ~ -.' .
, ' ., .
_ g_
Preferably, a catalytic amount of about 1-15 mol %
(based on the weight of primary allylic alcohol charged) of an aluminum catalyst such as aluminum isopropoxide is employed, although this depends in part on the amount of water present in the reaction mixture.
The use of less than 2 mol % catalyst is possible if extreme care is taken with regard to the water content. Other factors dictating tha amount of catalyst employed include rate ,A
, ~ ` ', ' ~ . : . . . .
~' ' ' , ; ' . ~'` .
10675~5 of reaction desired, amount of coincidental acid present in the reaction mixture, and the amount of water or acid produced in the course of the reaction.
Any aluminum alkoxide or aluminum aryloxide catalyst useful in an Oppenauer reaction, such as aluminum tert-butoxide L Al~t-OC4H9)3_7, may be used. Aluminum isopropoxide is preferred as it offers a cost advantage and an advantage in availability, although some furfural is consumed by oxidation of the isopropoxide to acetone. In this regard, it is reported in the aforementioned Or~anic Reactions, Vol. VI, page 209 (Djerassi) and also in PhYsical Or~nic Chemistry, by Hine, that the true active catalyst in the oxidation is an aluminum alkoxide which is generated in situ, and thus is dependent upon the reactants and conditions. It is normally generated by the addition of aluminum isopropoxide, aluminum t-butoxide or aluminum phenoxide. It may also be generated in situ by addition of an alkyl aluminum compound such as triisobutyl-aluminum (Djerassi also lists a number of other suitable compounds). These compounds, although they are normally referred to as the catalyst, are merely the source of the aluminum alkoxide. Hence the choice of aluminum source is largely one of convenience. For the purposes of this application, the term "Oppenauer Oxidation Catalyst" shall be deemed to ; embrace all of the above compounds.
Representative alcohols to which the present applica-tion is directed are set forth in the following Table 1:
.. . .
.,~
Table l CH2=C-CH2OH Methallyl alcohol CH2OH Perillyl alcohol CH OH
Benzyl alcohol ~ i ' ' It is apparent that the above alcohols have in common a hydrocarbon substitution at the 2-position beta to the carbinol hydroxyl radical. They may or may not be substituted in the 3-position, and the substitution can be by any aliphatic :- or aromatic radical. Other representative benzylic alcohols .,, within the scope of the present invention are such polyhydroxyl ~'!' compounds as saligenin r o-HOC6H4CH2OH_~, para hydroxy benzyl alcohol r p-HOC6H4CH2OHJ , and vanillyl alcohol La, 4-dih.ydroxy-.~ 3-meth.oxytoluene J . For purposes of the present application, ., the term "benzylic alcohol" h.as th.e common meaning that it A' 15 defines hydroxy methyl aromatic compounds.
~` An example of another cyclic allylic alcohol in which. .
the allylic double bond is endocyclic is myrtenol:
' l 2 W
i i, Other primary alcohols within the scope of the present invention will be apparent to those skilled in the art.
The following examples illustrate the present invention : and its practice, but should not be considered as limiting it.
', .
:~ -7-, !
~3067~5 In this specification, all percentages are by weight, all parts are parts by weight, and all temperatures are in degrees Centigrade unless otherwise specified.
This example illustrates the oxidation of perillyl alcohol to perillyl aldehyde. A flask was charged with 100 ml.
of toluene and 160 grams of furfural and heated to reflux to remove any water present by azeotropic distillation. The solution was then cooled to room temperature and 50 grams of perillyl alcohol and 2~5 grams of aluminum isopropoxide were added. The solution was then heated to 75C~ for three hours.
Analysis by glpc showed over 90% conversion to perillyl aldehyde.
~; EXAMPLE 2 This example illustrates the principles of the invention in the Oppenauer oxidation of benzyl alcohol to benzaldehyde. A flask equipped with a Dean-Stark trap was charged with 32~5 grams (0~3 mol) of benzyl alcohol and 30 ml.
of toluene and heated to reflux to remove any water present by azeotropic distillation. The solution was cooled to room temperature and 28~8 grams (0.3 mol) of furfural and 2.0 grams (0.01 mol) of aluminum isopropoxide were added. The mixture was stirred at ambient temperature and sampled periodically for analysis by glpc. After 5 hours 61. 5% of the benzyl alcohol `~ 25 was converted to benzaldehyde and 68~3~/o of furfural was converted to furfuryl alcohol.
After 72 hours, conversion to benzaldehyde increased to 63~9% and conversion to furfuryl alcohol increased to 74.5%.
; No by-products derived from either benzyl alcohol or furfural were detected by glpc. ~
' ~ :
~. . .. .. , . -. .
10~7SOS
A flask was charged with 3.1 grams (20 m~ol) of 2,6-dimethyl-2,7-octadien-1-ol, 0.3 grams (1.5 mmol) of aluminum isopropoxide, and 2.0 grams (21 mmol) of furfural, and stirred 16 hours at ambient temperature. Analysis of the product by vapor phase chromatography showed 95~/O conversion of the starting alcohol to 2,6-dimethyl-2,7-octadienal.
:.
.~
.,, ..
: ~ -.' .
, ' ., .
_ g_
Claims (8)
1. In an Oppenauer oxidation of primary alcohols selected from the group consisting of: primary allylic alcohols substituted in at least the 2-position with a hydrocarbon radical, in which the allylic double bond is acyclic, exocyclic or endocyclic; and primary benzylic alcohols; to the correspond-ing aldehyde, in the presence of an Oppenauer oxidation catalyst and hydrogen acceptor under Oppenauer oxidation conditions, the improvement for obtaining increased conversion and yield of aldehyde which comprises utilizing furfural as said hydrogen acceptor and forming a reaction product mixture containing the aldehyde corresponding to the primary alcohol. and as a by-product, furfuryl alcohol.
2. The oxidation process of claim 1 wherein said Oppenauer reaction is carried out with a molar ratio of furfural to primary alcohol in the range of 10:1 to 1:10.
3. The oxidation process of claim 1 wherein said Oppenauer reaction is carried out with a molar ratio of furfural to primary alcohol in the range of 2:1 to 1:2.
4. The oxidation process of claim 1 wherein the primary alcohol is perillyl alcohol (1-hydroxymethyl-4-isopropen-ylcyclohexene).
5. The oxidation process of claim 1 wherein said primary alcohol is benzyl alcohol.
6. The oxidation process of claim 1 wherein said alcohol is methallyl alcohol.
7. The oxidation process of claim 1 wherein said alcohol is 2,6-dimethyl-2,7-octadien-1-o1.
8. The oxidation process of claim 1 wherein said alcohol is myrtenol.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US58211375A | 1975-05-30 | 1975-05-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1067505A true CA1067505A (en) | 1979-12-04 |
Family
ID=24327903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA239,165A Expired CA1067505A (en) | 1975-05-30 | 1975-11-07 | Process for the oxidation of primary allylic and benzylic alcohols |
Country Status (2)
| Country | Link |
|---|---|
| CA (1) | CA1067505A (en) |
| GB (1) | GB1496378A (en) |
-
1975
- 1975-11-07 CA CA239,165A patent/CA1067505A/en not_active Expired
- 1975-11-18 GB GB4751975A patent/GB1496378A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1496378A (en) | 1977-12-30 |
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