JP2002524435A - Method for producing γ, δ-unsaturated ketone by Carroll reaction - Google Patents

Abstract

(57) The present invention relates to an acetoacetic acid alkyl ester and an allyl alcohol or propargyl alcohol of the formula II wherein R ¹ is H or even substituted with a saturated or unsaturated, branched, methoxy group. A hydrocarbon group having from 1 to 33 carbon atoms, and the dotted line indicates that there may be another bond between the carbon atoms connected by the dotted line). The present invention relates to a method for producing an unsaturated ketone. The reaction is carried out by a modified or unmodified Carroll reaction in the presence of an aluminum catalyst at a temperature in the range of 150 to 220 ° C., while distilling off the alkanol formed during the reaction. The process according to the invention is characterized in that, as alkyl acetoacetate, an acetoacetate ester of formula III wherein R ² is an alkyl group having 1 to 4 carbon atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

FIELD OF THE INVENTION The present invention relates to the use of γ, δ-unsaturated ketones, in particular methylheptenone, geranylacetone and farnesylacetone or their dihydro derivatives, or geranylgeranylacetone, in the presence of an aluminum catalyst in the Carroll reactant.
ion).

BACKGROUND OF THE INVENTION The Carroll reaction is a chain extension reaction in which allyl or propargyl alcohol is extended with acetoacetate or diketene to produce a γ, δ-unsaturated ketone. This reaction proceeds, for example, according to the following reaction scheme:

[0003] Thus, the central process is the formation of β-keto acids by Claisen rearrangement of acetoacetic esters of novel unsaturated alcohols formed mainly from allyl alcohol or propargyl alcohol and acetoacetic esters or diketene;
Subsequent spontaneous decarboxylation. Early work on the Carroll reaction was described by J. Am. Che
m. Soc. 65 (1943) 1992-1998.

[0004] Since the early 1950's, this reaction has been used in various ways in the preparation of terpenes. For example, terpenes required as essential precursors of vitamin A and vitamin E, 2-methyl-2-hepten-6-one, 6,10-dimethyl-5,9-undecadien-2-one (geranylacetone ) And 6,1
0,14-trimethyl-5,9,13-pentadecatrien-2-one (farnesylacetone) is produced on an industrial scale by this Carroll reaction.

[0005] For example, GB 695 313 discloses a Carroll reaction carried out in the gas phase at 300 ° C. to 600 ° C. using allyl acetoacetate or crotyl acetoacetate.

[0006] US 2,628,250 discloses 2-methyl-2-hepten-6-one with 2-methyl-3-
A process for making from buten-2-ol and diketene is disclosed.

US Pat. No. 2,660,608 discloses a process for producing tetrahydrofarnesylacetone from tetrahydronerolidol and diketene.

As catalysts for the Carroll reaction, according to the method of US Pat. No. 2,795,617, aluminum alkoxides, in particular aluminum isopropoxide having the formula: Al (O—CH (CH ₃ ) ₂ ) ₃ , are used as starting materials 0.8 to 2.5 for alcohol to be used
Used in mol%.

In the method of GB 886 353, an aluminum complex containing acetylacetone or acetoacetate such as aluminum tri (acetylacetonate), aluminum tri (methyl acetoacetate) or aluminum tri (ethyl acetoacetate) is used as a catalyst for the Carol reaction. It is used.

In the case of the previously known Carroll reaction of an acetoacetate with tert-vinylcarbinol or propargyl alcohol, methyl or ethyl esters have generally been used as alkyl acetoacetates. The low-boiling primary alcohols (methanol or ethanol) released in the acetoacetylation reaction of the unsaturated alcohols were separated by distillation during the reaction together with the carbon dioxide produced during the decarboxylation reaction.

The yields obtained by the Carroll reaction using methyl acetoacetate or ethyl acetoacetate are still not sufficiently satisfactory for use on an industrial scale. Firstly, the required reaction time is relatively long, and secondly, under the reaction conditions, the unsaturated ketone produced is slightly hydrogenated to give the alcohol, which is difficult to remove, and the yield is low. Due to the fact that it decreases.

[0012] SUMMARY OF THE INVENTION Accordingly, an object of the present invention, in Carroll reaction with aluminum catalyst, by reacting allyl alcohol or propargyl alcohol with acetoacetic ester, gamma, for producing a δ- unsaturated ketone Reduce the required reaction time,
It is to increase the possibility of a continuous manufacturing method. It is also an object of the present invention to further improve the yield.

The present inventors have found that this object is achieved by the method described at the outset. More surprisingly, tert-butanol, tert-pentyl alcohol (2-
When a tertiary alcohol acetoacetate such as methylbutan-2-ol) or dimethylpropylcarbinol (2-methylpentan-2-ol) is used in place of methyl acetoacetate (AME) or ethyl acetoacetate, the Carol reaction occurs. Progresses more rapidly to γ, δ-unsaturated ketones and the yield is increased, that is, the amount of by-products is reduced. The implications of these improvements are particularly significant when using higher and therefore more expensive unsaturated alcohols as starting materials. This is especially true for 3,7-dimethyl-1,6-octadiene-3-.
All (linalool), 3,7,11-trimethyl-1,6,10-dodecatrien-3-ol (nerolidol), 3,7,10-trimethyl-1,6-dodecadien-3-ol (dihydrolinalool) ) And especially E, E-9,7
, 11,15-Tetramethyl-1,6,10,14-hexatetraen-3-ol (E, E-geranyl linalool).

In EP 376 859 B1, acetoacetylation of a nucleophile such as an alkanol, an alkylamine or an alkylthiol with an acetoacetate or a derivative thereof is used as a acetoacetate such as tert-butanol or tert-amyl alcohol. It has already been disclosed that the use of esters of tertiary alcohols gives good yields, but this is not related to the Carroll reaction and is ultimately used as a coating to improve dyeing techniques It relates to the functionalization of low or high molecular weight nucleophiles by acetoacetylation.

DETAILED DESCRIPTION The present invention provides compounds of formula I:

Embedded image Comprising preparing a γ, δ-unsaturated ketone of the formula II:

Embedded image [Wherein, R ¹ is H or a saturated or unsaturated, branched, hydrocarbon group having 1 to 33 carbon atoms which may be substituted with a methoxy group. Indicating that there may be further bonds between the carbons.] Allyl alcohol or propargyl alcohol
Reacting in an unmodified or modified Carroll reaction in the presence of an aluminum catalyst at a temperature of from 0 to 220 ° C., while simultaneously separating the resulting alkanol by distillation, wherein the alkyl acetoacetate has the formula III:

Embedded image [Wherein R ² is alkyl having 1 to 4 carbon atoms].

Surprisingly, using the process according to the invention, the higher γ, δ-unsaturated ketones can be prepared in a simple manner and in a continuous process which is particularly desirable when carried out on an industrial scale, without the use of excess reactants. Alternatively, by using only a slight excess of one of the reaction components, a yield of 92-96% of theory can be obtained. It is also a great advantage that the process of the invention can improve the space-time yield of the previously known processes.

The process of the present invention relates to a method of formula II wherein R ¹ is of formula IV:

Embedded image [Wherein, n is an integer of 1 to 5, x and y are both H, x is methoxy and y is H, or x and y together have x and y Which is a bond further formed between carbons], for example, 3,7-dimethyl-1,6-octadien-3-ol (linalool) 3,7-dimethyl-1-octen-3-ol, 3,7,11-trimethyl-1,6-10-dodecatrien-3-ol (nerolidol), 3,7,11-trimethyl-1-dodecene-3-ol, 3,7,11-trimethyl-1 , 6-Dodecadien-3-ol (dihydronerolidol) and 3,7,11,15-tetramethyl-1,6,10,14- (E, E) hexadecatetraen-3-ol (E, E-geranyl linalool) Is particularly important in

The use of tert-butyl acetoacetate or tert-amyl acetoacetate has the advantage that the reaction can be carried out more quickly and the formation of by-products can be avoided. The amounts of reactants used are selected such that the molar ratio between the alcohol of the formula II and the alkyl acetoacetate of the formula III is between 0.8 and 1.2, preferably between 0.95 and 1.10.

Organoaluminum compounds suitable for the process of the invention are essentially of the formula V:

Embedded image [Wherein, R ⁴ is an optionally branched alkyl or alkoxy having 1 to 4 carbon atoms, preferably methyl or ethyl, and R ⁵ and R ^{6 each} have 1 to 5 carbon atoms.
Optionally branched alkyl or alkoxy, preferably methyl or 2
-Butyl, R ⁷ is an optionally branched alkyl having 1 to 4 carbon atoms, m and n are integers of 0 to 3, and n + m is 3 or less.] And aluminum Triaryloxylates. Particular preference is given to liquid aluminum compounds, especially aluminum compounds in which R ⁵ is methyl, R ⁶ is butyl and the sum of n + m is 3, and n / m is> 0.3.

The catalysts mentioned at the outset are, therefore, lower aluminum trialkoxides such as aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide, aluminum tri-butoxide and stoichiometric amounts of acetylacetate with said aluminum trialkoxide. It is a compound formed by reacting an ester, an alkyl acetoacetate or an alkyl malonate, removing an alcohol, and performing a transesterification reaction. For example, aluminum triacetoacetate,
There are aluminum triacetylacetonate, aluminum monoacetoacetate diethoxide, aluminum monoacetoacetate diisopropoxide, and aluminum diacetoacetate monoisopropoxide.

Preferably, aluminum trialkoxides, especially aluminum triisopropoxide and aluminum tri-butoxide are used. It is very particularly preferable to react aluminum sec-butoxide or aluminum triisopropoxide with methyl acetoacetate, remove 2-butanol or isopropanol, and carry out transesterification of methoxy groups with the released 2-butanol or isopropanol. The use of a mixture of aluminum triacetoacetates (where the transesterification rate is 30% or more) obtained by the method described above.

For the purposes of the present invention, aluminum triaryloxylates are those in which the aryl group is a lower alkyl or alkyloxy group such as an alkyl or alkyloxy group having 1 to 4 carbon atoms, a hydroxyl group or a phenyl group. It is an aluminum salt of an aromatic hydroxy compound which may be substituted, and examples thereof include aluminum triphenolate, aluminum tricresoleate, aluminum trixylenolate and aluminum trinaphtholate. Among these, aluminum triphenolate, which is relatively easily available, is particularly advantageously used.

Advantageously, a solution of a liquid catalyst or a solid catalyst is used and these are supplied in liquid form to the reaction vessel. Thus, for example, an aluminum trialkoxide dissolved in an alkyl acetoacetate or a mixture of an alkyl acetoacetate and an alcohol of the formula II can be used.

The amount of aluminum compound is generally such that the concentration in the reaction mixture is 0.0
It is not less than 5% by weight and does not exceed 6% by weight of aluminum at the start of the reaction. 0.5 to 5 m of the reaction amount of alkyl acetoacetate
ol% of the aluminum compound is generally required. In the case of the aluminum triisopropoxide and the aluminum triacetoacetate mixture preferably prepared from aluminum sec-butoxide and methyl acetoacetate, which are preferably used, the amount used is, for example, about 1 to 3 mol% of the alkyl acetoacetate reacted. is there.

Allyl alcohols of the formula II having a boiling point below 120 ° C., for example 2-methyl-3-
When butene-2-ol or the like is used, the reaction is carried out using a solvent as a solvent, such as a cyclic carbonate of formula VI or a γ-lactone of formula VII:

Embedded image Wherein the radicals R ¹ , R ² and R ³ are H, methyl or ethyl, preferably H
Or R ⁴ is H, methyl, ethyl, isopropyl, phenyl or methoxymethyl, preferably H or methyl] and it is particularly advantageous to carry out the Carroll reaction in said solvent.

Suitable cyclic 5-membered cyclic carbonates of formula VI include ethylene carbonate, 1
, 2-propylene carbonate, isobutylene carbonate, 1,2-butylene carbonate and the like, ie, in Formula VI, R ¹ -R ⁴ are H or methyl, or R ¹ -R ³ are H or methyl and R ⁴ is ethyl. In addition to certain conventional alkylene carbonates, those wherein R ¹ -R ³ are further ethyl and R ⁴ is H, methyl, ethyl, isopropyl, phenyl or methoxymethyl.

The cyclic carbonates used can also be produced industrially at very low cost by reacting the corresponding alkylene oxides with CO ₂ . Since they generally have a very high boiling point, temperatures of 170 ° C. at atmospheric pressure can be reached without problems.

Particularly suitable 5-membered lactones of the formula VII include γ-butyrolactone and 3-methyl-γ-butyrolactone, with γ-butyrolactone being particularly suitable.

The γ-butyrolactones of the formula VII used according to the invention can also be produced industrially advantageously by dehydrogenating the corresponding butanediols.

Since the alkanols formed in this reaction attack the cyclic carbonate or lactone surprisingly little under the reaction conditions, for example, when propylene carbonate is used, the solvent can be removed up to 10 times without cleanup. It can be reused up to the reaction cycle (compare with comparative example 1b). The cyclic carbonate or lactone separated after isolating the γ, δ-unsaturated ketone can be fed to a new reaction cycle without replenishing the catalyst. Unreacted acetoacetic ester remains in the solvent and does not disappear.

The amount of the 5-membered ring carbonate and 5-membered lactone used is generally 50 to 1000% by weight, preferably 100 to 500% by weight, based on the amount of γ, δ-unsaturated ketone produced.

When alcohols of the formula II having a boiling point higher than 140 ° C. are used, the Carroll reaction can be advantageously carried out without adding a large amount of solvent. Thereby, the after-treatment of the reaction mixture can be advantageously performed.

The process according to the invention can be carried out batchwise or continuously. If carried out continuously, the starting compound and the catalyst are advantageously pumped into a reaction vessel having a heating bath and equipped with an attached cooling device, the alcohol is removed with an attached cooling device and the product formed The carbon dioxide is discharged and the reaction product is obtained using overflow.

Using the process according to the invention, the required γ, δ-unsaturated ketones of the formula I can be obtained in a simple manner in surprisingly high yields. Te removed from acetoacetate
The rt-alcohols can be recovered virtually completely.

[0035] carried out at 180 ° C. In Example Example 1a propylene carbonate in 2-methyl-3-butene-2-O
Reaction with tert-butyl acetoacetate 25.7 g of 92% pure 2-methyl-3-buten-2-ol and 39.
8 g of tert-butyl acetoacetate were separately prepared (according to GB 886 353) with 50 ml (45 g) of 1,2-propylene carbonate over 2 hours at 170 ° C.
g of trimethylaluminum acetoacetate catalyst mixture. During the dropwise addition, CO ₂ and low-boiling compounds were violently generated, which were continuously separated by distillation (
b. p. = 80-85 ° C). After the addition was complete, the mixture was stirred and cooled for another 10 minutes until gas evolution was complete. At about 100 mbar, 2.5 g were initially distilled off, giving 30.9 g of a main fraction of 2-methyl-2-hepten-6-one with a purity of 96 to 98%. The yield (including the residue of the lower phase) is 92% of theory
Met.

Example 1b (Comparative Example) 2-Methyl-3-buten-2-O in 1,2-propylene carbonate
A ) 29.03 g (0.25 mol) of methyl acetoacetate (AME; purity 98%)
) And 23.68 g (0.275 mol) of 2-methyl-3-buten-2-ol (MBE: 94% pure) at 45 ° C. for 2 hours at 180 ° C. with 45 g of 1,2-propylene carbonate. To 2.8 g of a separately prepared mixture of trimethylaluminum acetoacetate catalyst (according to 886 353) was pumped in with stirring. During this time,
CO ₂ was eluted and 8 g of low boiling compounds were separated by distillation, the low boiling compounds being about 2/3 methanol and about 1/3 unreacted 2-methyl-3-butene-2-.
It was oar. The mixture was further stirred at 180 ° C. for 30 minutes, cooled and the desired 2-methyl-2-hepten-6-one was separated from the reaction mixture by distillation under a reduced pressure of 100 mbar.

B) The distillation residue formed in this case and the aforementioned amounts of AME and MBE are brought to 180 ° C.
For 2 hours, the reaction mixture was stirred at 180 ° C. for 30 minutes, and the resulting 2-methyl-2-hepten-6-one was cooled and separated therefrom by distillation.

C) Procedure b) was repeated eight more times. The average yield of 2-methyl-2-hepten-6-one for all 10 runs was 88% of theory based on reacted MBE (determined by gas chromatography using an internal standard).

Example 2a 3,7 for the production of 6,10-dimethyl-5,9-undecadien-2-one
-Dimethyl-1,6-octadien-3-ol (linalool) and acetoacetic acid
Carol reaction with rt-butyl 5.6 g of trimethylaluminum acetoacetate (prepared from aluminum triisopropoxide as in GB 886 353) was charged, heated to 180 ° C. and 115.7 g of this at room temperature over 2 hours. A homogeneous mixture of linalool and 128 g of tert-butyl acetoacetate was pumped into the reaction vessel. CO ₂ and tert- butanol was condensed since naturally produced during this time. 51 g of tert-butanol were isolated. After the feed was complete, the mixture was stirred for an additional 20 minutes at an internal temperature of 180-190 ° C. and then cooled. The reaction effluent was distilled under a reduced pressure of 0.1 mbar. This gives, in the two fractions, a total of 139.7 g of 6,10-dimethyl-5,9-undecadien-2-one (geranylacetone), which equates to a yield of 96% of theory.

Example 2b (Comparative Example) Carol reaction of linalool with methyl acetoacetate 5.6 g of the aluminum catalyst described in Example 2a) were charged as in Example 2a), 115.4 g of linalool and 94 g of acetoacetic acid The mixture with methyl was pumped in at an internal temperature of 180 ° C. During this time, CO ₂ and methanol were spontaneously formed and were condensed. The reaction solution was stirred for another 20 minutes until the evolution of CO ₂ ceased, as in Example 2a), and then cooled. Distillation was performed under reduced pressure to obtain 133 g of geranylacetone. The yield was 91.5% of theory. Example 2 as a by-product
6,10-dimethyl-5,9-undecadiene-2- not detected in a)
1.6 g of oar was produced.

Example 3a 6,10,14,18-tetramethyl-5,9,13,17-nonadecatetrate
3,7,11,15 for the production of 2-n-one (geranylgeranylacetone)
-Tetramethyl-1,6,10,14 (E, E) hexadecatetraen-3-o
(E, E-geranyl linalool) and tert-butyl acetoacetate
Acetoacetate tri -tert- butyl aluminum response 2.5g dissolved at 40 ° C. to acetoacetate tert- butyl 42.1 g, was added at 20 ° C. 72.5 g of E, the E- geranyl linalool thereto. The resulting mixture was pumped uniformly into a horizontally heated reaction vessel equipped with an overflow with a distillation bridge. The feed rate was set so that the average residence time was 10 minutes. The internal temperature was 190-200 ° C. During the reaction, 15 g of tert-butanol was separated by distillation.

After the completion of the supply, the reaction effluent was distilled. As a result, 75.9 g of geranylgeranylacetone having a purity of 98.8% was obtained. This equates to a yield of 92% of theory.

Example 3b (Comparative Example) E, E-geranyl linalool and aceto
Carol Reaction of Methyl Acetate 2.2 g of trimethylaluminum acetoacetate was dissolved in 37.6 g of methyl acetoacetate at 60 ° C., and the solution was mixed with 87 g of E, E-geranyl linalool. This solution was pumped uniformly into the horizontal reaction vessel described in Example 3a). The feed rate was adapted to the reaction volume such that the average residence time was 10 ± 0.5 minutes.
The mixture was continuously reacted at an internal temperature of 190-200 ° C. to produce geranylgeranylacetone. After the end of the supply, the contents of the reaction vessel were heated for another 10 minutes and sent to the cooled reaction outlet. The distillation was carried out at 0.3 mbar, giving 84.2 g of a main fraction geranylgeranylacetone having a purity of 97.1%. This equates to a yield of 85% of theory.

Example 4a Carol reaction of nerolidol with 2-methylbut-2-yl acetoacetate 5.6 g of trimethylaluminum acetoacetate were charged into the same reaction vessel as described in Example 4a and heated to 190.degree. A mixture of 166 g of nerolidol and 139 g of isopentyl acetoacetate (purity> 98%) prepared from isopentanol and diketene in a known manner was added dropwise dropwise over 2 hours. During this time, the reaction temperature was maintained at 190 to 200 ° C. by heating. After the feed was complete, the mixture was stirred for an additional 15 minutes and cooled. This gave 212 g of crude product, which was distilled at 0.1 mbar. 178.7 g of farnesylacetone were obtained from the two fractions.
This equates to a yield of 91% of theory.

Example 4b (comparative example) Reaction of nerolidol with methyl acetoacetate 5.6 g of trimethylaluminum acetoacetate 500 ml reactor equipped with a 10 cm column equipped with a measuring device, paddle stirrer, reflux condenser and distillation bridge Was charged. The contents were heated to 180-190C. 166.5 over 2 hours
A homogeneous mixture of g (0.75 mol) of nerolidol and 94 g (0.81 mol) of methyl acetoacetate was pumped in uniformly. The reaction temperature was maintained at 180 to 190 ° C. by external heating. The produced methanol condensed. After the feed was complete, the mixture was stirred for a further 15 minutes and then cooled. This gave 208 g of a crude product, which was distilled under high vacuum. A total of 167 g of farnesylacetone was isolated from the two fractions. This equates to a yield of 85% of theory.

Example 5 Nerolidol and 2-methyl-2-pentyl acetoacetate (isohexyl acetoacetate)
They were charged to the reaction vessel described in Example 4a acetoacetate trimethylaluminum Carroll reaction 2.8g with). A mixture of 75 g of isohexyl acetoacetate (purity> 98%) prepared from 83 g of nerolidol, isohexanol and diketene was added by pump over a period of 1 hour at a reaction temperature of 190-200 ° C. After the feed was complete, the reaction mixture was stirred at 200 ° C. for another 10 minutes and cooled after gas evolution was complete. This gave 108 g of a crude product, which was distilled under high vacuum. In this way, 88 g of farnesylacetone of high purity was isolated. This is 90 theoretical
% Yield.

Example 6 a) Reaction of the invention with E, E-geranyl linalool and tert-butyl acetoacetate 145 g (0.5 mol) of E, E-geranyl linalool, 5 g of tri-tert-butyl aluminum acetoacetate And 263 ml of a reaction solution consisting of 83 g (0.525 mol) of tert-butyl acetoacetate were stirred with a magnetic stirrer and heated to 190-200 ° C. with a heating mantle, and a 100 ml three-necked body with overflow in the center was used. It was introduced into the reaction vessel consisting of a flask (corresponding to a usable volume of the flask of 45 ml) by a pump at a rate of 5.6 ml / min.

This resulted in 185 g of crude product and 30.5 g of low boilers. The crude product contained 13% unreacted E, E-geranyl linalool and 79% of the desired geranylgeranylacetone.

B) Reaction of E, E, -geranyl linalool with methyl acetoacetate (Comparative Example) 145 g (0.5 mol) of E, E-geranyl linalool, 5 g of tri-tert-butyl aluminum acetoacetate, and 61 g ( 234 ml of a reaction solution consisting of 0.525 mol) of methyl acetoacetate was pumped into the reaction vessel heated to 190 to 200 ° C. at a rate of 5.0 ml / min. This makes 199
. 9 g of crude product and 5.7 g of low boiling material resulted. The crude product contained 53% unreacted E, E-geranyl linalool and only 34% of the desired geranylgeranylacetone.

Comparison of Example 6a with Comparative Example 6b clearly shows that the reaction using tert-butyl acetoacetate is much faster than the reaction using methyl acetoacetate which has hitherto been customarily used for the Carroll reaction ( (3 to 10 times faster).

[Procedure amendment]

[Submission date] April 6, 2001 (2001.4.6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image Comprising preparing a γ, δ-unsaturated ketone of the formula II:

Embedded image [In the formula, R ¹ is H or a saturated or unsaturated, branched, hydrocarbon group having 1 to 33 carbon atoms which may be substituted by a methoxy group, and the dotted line has the same. Indicating that there may be further bonds between the carbons.] Allyl alcohol or propargyl alcohol
Reacting in the presence of an aluminum catalyst at a temperature of from 0 to 220 ° C., while separating the resulting alkanol by distillation, wherein the alkyl acetoacetate has the formula III:

Embedded image [Wherein R ² is alkyl having 1 to 4 carbon atoms].

Embedded image The method according to claim 1, wherein the Carroll reaction is carried out using an acetoacetic ester of the formula: wherein R ² is methyl.

Embedded image [Wherein, n is an integer of 1 to 5, x and y are both H, x is methoxy and y is H, or x and y together have x and y Wherein the alcohol is a bond formed between carbons.

Embedded image Wherein the groups R ³ , R ⁴ and R ⁵ are H, methyl or ethyl, and R ⁶ is H,
Is methyl, ethyl, isopropyl, phenyl or methoxymethyl].

Embedded image The method of claim 4, wherein the reaction is performed in which the groups R ³ , R ⁴ , R ⁵ and R ⁶ are H or methyl.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AU, BG, BR, BY, CA, CN, CZ, GE, HR, HU, ID, IL, IN , JP, KR, KZ, LT, LV, MK, MX, NO, NZ, PL, RO, RU, SG, SI, SK, TR, UA, US, ZAF terms (reference) 4H006 AA02 AC26 AC44 AC09 BA45 BB17 BD20 4H039 CA21 CA42 CG40 CJ90

Claims (7)

[Claims] 1. Formula I: ## STR1 ## Of a γ, δ-unsaturated ketone of the formula II comprising: [Wherein, R ¹ is H or a saturated or unsaturated, branched, hydrocarbon group having 1 to 33 carbon atoms which may be substituted with a methoxy group. Indicating that there may be further bonds between the carbons.] Allyl alcohol or propargyl alcohol
Reacting at a temperature of 0 to 220 ° C. in the presence of an aluminum catalyst, while separating the resulting alkanol by distillation, wherein the alkyl acetoacetate has the formula III: [Wherein R ² is alkyl having 1 to 4 carbon atoms]. 2. A compound of formula III: Performing the reaction using an acetoacetic ester of the formula: wherein R ² is methyl.
The method of claim 1. 3. As an allyl alcohol of the formula II, R ¹ has the formula IV: [Wherein, n is an integer of 1 to 5, x and y are both H, x is methoxy and y is H, or x and y together have x and y Wherein the alcohol is a bond formed between carbons. 4. Allyl alcohols of the formula II include 2-methyl-3-buten-2-ol, linalool, 6,7-dihydrolinalool, nerolidol, 10
The method according to claim 1, wherein, 11-dihydronerolidol or geranyl linalool is used. 5. An allylic alcohol of the formula II comprising 2-methyl-3-butene-
When using 2-ols, the cyclic carbonate of the formula VI or the formula V
Γ-lactone of II: Wherein the groups R ³ , R ⁴ and R ⁵ are H, methyl or ethyl, and R ⁶ is
H, methyl, ethyl, isopropyl, phenyl or methoxymethyl]. 6. An allylic alcohol of the formula II comprising 2-methyl-3-butene-
When using 2-ols, the cyclic carbonate of formula VI or the γ-lactone of formula VII: Performing the reaction in [wherein the groups ^{R 3,} R 4, ^{R 5} and ^{R 6} is H or methyl, A method according to claim 4. 7. The process according to claim 1, wherein when using an alcohol of the formula II having a boiling point above 140 ° C., the reaction is carried out without adding a large amount of solvent.