GB2063877A - Preparation of substituted ketones - Google Patents

Preparation of substituted ketones Download PDF

Info

Publication number
GB2063877A
GB2063877A GB8036309A GB8036309A GB2063877A GB 2063877 A GB2063877 A GB 2063877A GB 8036309 A GB8036309 A GB 8036309A GB 8036309 A GB8036309 A GB 8036309A GB 2063877 A GB2063877 A GB 2063877A
Authority
GB
United Kingdom
Prior art keywords
methyl
compound
carbonyl compound
carbonyl
buten
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.)
Granted
Application number
GB8036309A
Other versions
GB2063877B (en
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anic SpA
Original Assignee
Anic SpA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Anic SpA filed Critical Anic SpA
Publication of GB2063877A publication Critical patent/GB2063877A/en
Application granted granted Critical
Publication of GB2063877B publication Critical patent/GB2063877B/en
Expired legal-status Critical Current

Links

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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/175—Saturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/78—Benzoic acid esters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Compounds containing one or more other functional groups in addition to a carbonyl group are prepared by reacting a carbonyl compound with a compound containing at least one unsaturated bond and one or more functional groups in the presence of a peroxide as a catalyst. Examples of the carbonyl compound are acetone and methylethylketone, and examples of the unsaturated compound are 2- methyl-3-buten-2-ol, 2-methyl-3-buten- 2-yl acetate, hydroxylinalol, 2-methyl-2- ethoxy-3-butene and 2-methyl-3-buten- 2-yl benzoate. An example of the product obtained by the reaction is 6- methylheptan-6-ol-2-one, which is useful as a starting material for producing terpene derivatives.

Description

SPECIFICATION Preparation of carbonyl compounds This invention relates to a process for preparing carbonyl compounds containing one or more functional groups besides the carbonyl group.
The process of the invention comprises reacting a carbonyl compound with a compound containing at least one unsaturated bond (double or triple) and one or more functional groups, the reaction being carried out in the presence of a catalytic quantity of a peroxide.
The carbonyl compound is preferably an aliphatic, aromatic or alicyclic ketone or aldehyde having a methyl or methylene group in the alpha position with respect to the carbonyl group and in particular is an alphamethylketone. The unsaturated compound contains one or more olefinic bonds and/or one or more actylenic bonds, an unsaturated bond in a terminal position being preferable, and also contains one or more functional groups such as, for example, -OH,-OOCCH3, -Cl, -OCH3, -OC2H5, -CN, -COOH, and -COOR (wherein R is hydrocarbyl such as alkyl).
The radical addition reaction of ketones to alpha-olefins or to cyclohexane has been known for some time, and is promoted by transition metal salts and oxides. In this case, low yields of final useful product are obtained. Organic peroxides or peroxyesters as radical sources have also been used in stoichiometric quantities with respect to the initial carbonyl compound. In this case, the final products are obtained at unsatisfactory conversion and selectivity values, and the presence of an excessive quantity of peroxide is not desirable. No mention has ever been made of the possibility of preparing compounds containing widely differing functional groups, since the possibility of carrying out the reaction directly between the carbonyl compound and the unsaturated compound containing one or more functional groups has not been foreseen.
We have now found that it is possible to react a carbonyl compound with a compound containing at least one unsaturated bond and one or more functional groups in the presence of catalytic quantities of peroxides.
In this manner, high conversion and selectivity values of final useful product are obtained, these products being compounds containing, in addition to the carbonyl group, one or more functional groups. These compounds include the ethers and esters of 6-methylheptan-6-ol-2-one.
The reaction is carried out in the presence of a peroxide in a quantity such that the molar ratio of it to the unsaturated compound is preferably from 1:1 to 0.055:1. Peroxides useful for this purpose include diacetylperoxide, dibenzoyl peroxide, t-butyl hydroperoxide and dicyclohexylperoxydicarbonate. The use of di-t-butylperoxide has proved to be particularly advantageous.
The reaction can be carried out using only the reactants and the catalyst. Alternatively, it can be carried out in the presence of a solvent such as water in such a quantity as to constitute either a single liquid phase or two liquid phases with the mixture of the unsaturated compound and carbonyl compound brought into reaction.
The molar ratio of the carbonyl compound to the unsaturated compound is preferably from 500:1 to 3:1, more preferably from 300:1 to 5:1.
The compounds obtained according to the process of the present invention have various applications. For example the product obtained from acetone and 2-methyl-3-buten-2-ol, namely 6-methylheptan-6-ol-2-one, can be used as a starting material for producing numerous terpene derivatives (e.g. hydroxylinalol, citral, hydroxycitral, hydroxycitronellal, geranonitrile and ionones) used in the aroma, perfume, vitamin, drug and surface active fields. Derivatives of 6-methylheptan-6-ol-2-one possessing specially valuable odour characteristics can be obtained from acetone and ethers or esters of 2-methyl-3-buten-2-ol by direct etherification or esterification of 6-methylheptan-6-ol-2-one.
The following Examples illustrate the invention.
Example I There was used a stainless steel autoclave of one litre capacity fitted with a pressure gauge, a tube for withdrawal purposes, a magnetically driven stirrer and electrical heating resistors. To the autoclave, there was fed 9.55 g of pure anhydrous 2-methyl-3-buten-2-ol(MBE), 386.80 g of acetone and 1.63 g of di-t-butylperoxide (DTBP). Thus, the acetone: MBE: catalyst molar ratio was about 60:1 :0.1. The mixture was heated with stirring to 1 250C. After 1 hour and 45 minutes of reaction the MBE conversion was 66%, and the selectivity with respect to the 1:1 addition product formed was 86%. After 5 hours the conversion was 98% and the selectivity was about 82%.The 1:1 addition product formed was 6-hydroxy-6-methyl heptan-2-one (also known as 6-methylheptan-6-ol-2-one), which has the structure:
The above structure was confirmed by the mass spectrum, the IR spectrum and the NMR spectrum of the product.
The numerical conversion and selectivity values given above are obtained from the relationships: Conversion = initial molar amount of MBE final molar amount of MBE x 100 initial molar amount of MBE molar = molar amount of product Selectivity = x 100 molar = molar amount of MBE reacted x100 Example 2 The procedure of Example 1 was repeated, using an acetone:MBE: DTBP molar ratio of 60:1:0.025. After 8 hours of reaction at 1 25 C, the conversion was 63% and the selectivity was 88%.
Example 3 The apparatus of Example 1 was fed with 19.13 g of hydroxylinalol (I), 387.09 of acetone and 1.62 g of DTBP. Thus, the acetone:l:DTBP molar ratio was 60:1:0.1. The structure of hydroxylinalol is as follows:
After 6 hours at 1 250C, the conversion of I was 88% and the sensitivity in terms of the following 1:1 addition product was 57%:
Example 4 The apparatus of Example 1 was fed with 116.0 g of pure acetone, 3.800 g of 2-methyl-2-ethoxy-3-butene (II) and 0.50 g of DTBP. Thus, the acetone: II:DTBP molar ratio was approximately 60:1:0.1.After 3 hours at 125"C, a 1:1 radical addition product had formed, this product being 6-methylheptane-6-ethoxy-2-one, which has the structure:
The conversion of Il was 90% and the selectivity was about 88%. The structure of the product was confirmed by GLC-mass analysis.
Example 5 The procedure of Example 4 was repeated, but using 6.33 g of 2-methyl-3-buten-2-yl benzoate (III) instead of the 2-methyl-2-ethoxy-3-butene. Thus, the acetone Ill: DTBP molar ratio was approximately 60:1 :0.1. After 3 hours at 125 C, there had formed 6-methylheptan-2-one-6-yl benzoate, which has the structure:
The conversion of Ill was 88% and the selectivity was about 86%. The structure of the product was confirmed by GLC-mass analysis.
Example 6 There was used a stainless steel autoclave of 5 litres capacity fitted with a pressure gauge, a pipe for feeding the reagents by means of a metering pump, a magnetically driven stirrer and electrical heating resistors. The autoclave was fed with 2978.35 g (51.208mol) of acetone and 75.97 g (0.8834mol) of 2-methyl-3-buten-2-ol (MBE). The mixture was heated with stirring. At 1300C, a mixture of 12.91 g (0883 mol) of di-t-butylperoxide (DTBP) and 100 g (1.816 mol) of acetone was fed to the autoclave by means of the pump. The pump output was adjusted such that the solution of the peroxide in acetone was fed over a period of 2 hours and 15 minutes.The acetone:MBE:DTBP molar ratio was 60:1:0.1. After 5 hours of reaction (calculated from the beginning of the peroxide feed) the MBE conversion was 82.5% and the selectivity in terms of 6-methylheptan-6-ol-2-one was 85.1 mol % with respect to the MBE. The conversion and selectivity values were determined by gas chromatograph analysis using the internal standard method.
Example 7 The procedure of the previous Example was repeated, but using an acetone:MBE:DTBP molar ratio of 60:1:0.05. The solution of DTBP in actone was pumped in over a period of 1.5 hours. After 5 hours of reaction (calculated from the beginning of the peroxide feed) the MBE conversion was 73% and the selectivity in terms of 6-methylheptan-6-ol-2-one was 89.8 mol % with respect to the MBE. The DTBP conversion was 59.1%.
Example 8 The 5 litre autoclave described in Example 6 was fed with 3078 g (52.996 mol) of acetone and 74.825 g (0.870 mol) of MBE. The mixture was heated with stirring. At 1300C, a feed of DTBP was commenced, the autoclave being fed over a period of one hour with 6.946 g (0.0475 mol) of DTBP. 30 minutes after beginning the DTBP feed, a feed of MBE was commenced, 40.320 g (0.469 mol) of MBE being fed over the course of 3 hours. After 6.5 hours of reaction (calculated from the beginning of the peroxide feed) the MBE conversion was 88.2% and the selectivity was 75.9 mol %. The final acetone: MBE: DTBP molar ratio was 39.6:1 :0.35.
Example 9 A stainless steel autoclave of 22 litres capacity and equipped in a similar manner to those described in the previous Examples was fed with 12.342 kg (212.1 mol) of acetone and 0.609 kg (7.083 mol) of MBE. The mixture was heated with stirring. At 130"C, 0.1036 kg (0.7083 mol) of DTBP were fed in during the course of two hours. After five hours of reaction (calculated from the beginning of the DTBP feed) the autoclave was cooled. The reaction mixture was distilled in an Oldenshaw perforated plate column to give 495 g of pure 6-methylheptan-6-ol-2-one. The molar yield with respect to the MBE fed to the reaction was48.5 At the end of the feeding of the DTBP, the acetone:MBE:DTBP molar ratio was 30:1:0.1.

Claims (17)

1. A process for preparing a carbonyl compound which also contains one or more other functional groups, which process comprises reacting a carbonyl compound with an unsaturated compound containing one or more functional groups in the presence of, as a catalyst, a peroxide.
2. A process as claimed in claim 1, wherein the carbonyl compound is an aliphatic, alicyclic or aromatic ketone or aldehyde having a methyl or methylene group in the alpha position with respect to the carbonyl group.
3. A process as claimed in claim 1, wherein the carbonyl compound is an alpha-methylketone.
4. A process as claimed in claim 3, wherein the carbonyl compound is acetone or methylethylketone.
5. A process as claimed in any of the preceding claims, wherein the unsaturated compound contains, in addition to one or more functional groups, at least one ethylenic or acetylenic bond in a terminal position.
6. A process as claimed in any of the preceding claims, wherein the unsaturated compound contains, in addition to the unsaturated bond, at least one functional group chosen from -OH, -OOCCH3, -Cl, -OCH3, -OC2H5, -CN, -COOH and ester groups.
7. A process as claimed in any of the preceding claims, wherein the unsaturated compound is 2-methyl-3-buten-2-ol, 2-methyl-3-buten-2-yl acetate, hydroxylinalol, 2-methyl-2-ethoxy-3-butene or 2methyl-3-buten-2-yl benzoate.
8. A process as claimed in any of the preceding claims, wherein the peroxide is di-t-butylperoxide, diacetylperoxide, dibenzoyl peroxide, t-butylhydroperoxide or dicyclohexylperoxydicarbonate.
9. A process as claimed in any of the preceding claims, wherein the molar ratio of the carbonyl compound to the unsaturated compound is from 500:1 to 3:1.
10. A process as claimed in claim 9, wherein the molar ratio of the carbonyl compound to the unsaturated compound is from 300:1 to 5:1.
11. A process as claimed in any of the preceding claims, wherein the molar ratio of the peroxide to the unsaturated compound is from 1:1 to 0.005:1.
12. A process according to claim 1, substantially as described in any of the foregoing Examples.
13. A carbonyl compound prepared by a process as claimed in any preceding claim.
14. 6-Methyl hepta n-6-ethoxy-2-one.
15. 6-Methylheptan-2-one-6-yl benzoate.
16. An ester of 6-methyl heptan-6-ol-2-one.
17. An ester of 6-methylheptan-6-ol-2-one.
GB8036309A 1979-11-29 1980-11-12 Preparation of substituted ketones Expired GB2063877B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
IT27688/79A IT1126417B (en) 1979-11-29 1979-11-29 PROCEDURE FOR THE PREPARATION OF CARBONYL COMPOUNDS CONTAINING AT LEAST A FUNCTIONAL GROUP IN ADDITION TO THE CARBONYL, AND COMPOUNDS SO OBTAINED

Publications (2)

Publication Number Publication Date
GB2063877A true GB2063877A (en) 1981-06-10
GB2063877B GB2063877B (en) 1984-06-27

Family

ID=11222133

Family Applications (1)

Application Number Title Priority Date Filing Date
GB8036309A Expired GB2063877B (en) 1979-11-29 1980-11-12 Preparation of substituted ketones

Country Status (11)

Country Link
BE (1) BE886411A (en)
DE (1) DE3044927A1 (en)
DK (1) DK473980A (en)
FR (1) FR2473505A1 (en)
GB (1) GB2063877B (en)
IE (1) IE50540B1 (en)
IT (1) IT1126417B (en)
LU (1) LU82959A1 (en)
NL (1) NL8006467A (en)
NO (2) NO803562L (en)
SE (1) SE8008191L (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB999251A (en) * 1962-05-31 1965-07-21 Hoffmann La Roche The manufacture of spirilloxanthin
GB1416501A (en) * 1972-04-21 1975-12-03 Hoffmann La Roche Phenyl derivatives
GB2004277A (en) * 1977-09-14 1979-03-28 Anic Spa Process for producing carbonyl compounds

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3957730A (en) * 1973-10-17 1976-05-18 Basf Aktiengesellschaft Recovery of pure 2-methyl-2-hydroxy-heptanone-6
IT1078799B (en) * 1976-09-16 1985-05-08 Snam Progetti PROCEDURE FOR THE PREPARATION OF CARBONYL COMPOUNDS CONTAINING AT LEAST ONE FUNCTIONAL GROUP IN ADDITION TO THE CARBONYL

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB999251A (en) * 1962-05-31 1965-07-21 Hoffmann La Roche The manufacture of spirilloxanthin
GB1416501A (en) * 1972-04-21 1975-12-03 Hoffmann La Roche Phenyl derivatives
GB2004277A (en) * 1977-09-14 1979-03-28 Anic Spa Process for producing carbonyl compounds

Also Published As

Publication number Publication date
IE50540B1 (en) 1986-05-14
FR2473505B1 (en) 1984-10-12
IT1126417B (en) 1986-05-21
NO812314L (en) 1981-06-01
FR2473505A1 (en) 1981-07-17
NL8006467A (en) 1981-07-01
NO803562L (en) 1981-06-01
SE8008191L (en) 1981-05-30
LU82959A1 (en) 1981-06-04
GB2063877B (en) 1984-06-27
DK473980A (en) 1981-05-30
IE802327L (en) 1981-05-29
IT7927688A0 (en) 1979-11-29
DE3044927A1 (en) 1981-09-17
BE886411A (en) 1981-06-01

Similar Documents

Publication Publication Date Title
Revis et al. Novel synthesis of β-siloxy esters by condensation of carbonyls and trimethylsilane with α, β-unsaturated esters catalyzed by RhCl3
US3932462A (en) Manufacture of unsaturated ketones
US4582648A (en) α-Cyanoacrylate compound, method of preparing same and adhesive comprising same
US4062898A (en) Conversion of acetals
SU586834A3 (en) Method of preparing a,b-unsaturated aldehydes
US5015760A (en) Process for the preparation of glyoxylic acid and glyoxylic acid derivatives
Kataoka et al. Palladium (II)-gatalyzed oxidative rearrangement of propargyl esters
US3487102A (en) Process for preparing alpha,3,3 - trimethyl cyclohexane methyl alkanoates
US2866813A (en) Aldehyde diacylates and process for producing the same
CA2343521A1 (en) Method for producing .gamma.,.delta.-unsaturated ketones by carroll-reaction
GB2063877A (en) Preparation of substituted ketones
De Klein The manganese (III) acetate initiated synthesis of carboxylic acids from α‐olefins and acid anhydrides
EP0411460A1 (en) Perfumery composition comprising 2-cyclohexylpropionic acid or its derivative
US6307106B1 (en) Process for preparing unsaturated ketones
US3739032A (en) Process for the preparation of unsaturated ethers
US4233464A (en) Cyclohexene carotinoid intermediates
US4246182A (en) Process for the preparation of omega-hydroxy fatty acids from omega-hydroxy (or acyloxy)-alkyl-γ-butyrolactones
Hirano et al. Oxidation by cobalt (III) acetate. Part 7. Regioselective synthesis of substituted cyclohexenyl acetates
US5981792A (en) Process for the production of 1-functional allylalcohol carboxylic esters
US3210408A (en) Processes for the production of unsaturated esters
US3962341A (en) Production of piperitenone
US4322561A (en) Method for the preparation of carbonyl compounds
US3567766A (en) Preparation of methyl acetate
US2478989A (en) Chemical process for the production of acrolein
RU2058309C1 (en) Method for production of 2-methyl-2-(4′-methylpent-3′-enyl)dihydrofuran

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee