IE50540B1 - Preparation of 6-methylheptan-6-01-2-one - Google Patents

Preparation of 6-methylheptan-6-01-2-one

Info

Publication number
IE50540B1
IE50540B1 IE2327/80A IE232780A IE50540B1 IE 50540 B1 IE50540 B1 IE 50540B1 IE 2327/80 A IE2327/80 A IE 2327/80A IE 232780 A IE232780 A IE 232780A IE 50540 B1 IE50540 B1 IE 50540B1
Authority
IE
Ireland
Prior art keywords
methyl
acetone
mbe
methylheptan
buten
Prior art date
Application number
IE2327/80A
Other versions
IE802327L (en
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 IE802327L publication Critical patent/IE802327L/en
Publication of IE50540B1 publication Critical patent/IE50540B1/en

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

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  • 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

This invention relates to a process for preparing 6-methylheptan-6-ol-2-one.
According to the present invention, there is provided a process for the preparation of 6-methylheptan-6-ol-2-one, which comprises reacting 2-methyl-3-butan-2-ol with acetone in the presence of a peroxide, the molar ratio of the acetone to the 2-methyl-3-buten-2-ol being from 300:1 to 5:1, and the molar ratio of the perpoxide to the 2-methy-3-butan-2-ol being from 1:1 to 0.005:1.
The radical addition reaction of ketones to alpha-olefins or to cyclohexene has been known for some time, and is promoted by transistion 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.
We have now found that it is possible to react 2-methyl-3-buten20 2-ol with acetone in the presence of, as a catalyst, a peroxide, to attain high conversion and selectivity values of final useful product namely 6-methylheptan-6-ol-2-one.
Examples of suitable peroxides are diacetylperoxide, di benzoylperoxide, t-butylhydroperoxide 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 2-methyl-3-buten-2-ol and acetone brought into reaction.
The 6-methylheptan-6-ol-2-one obtained according to the process of the present invention 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.
Esters and ethers of 6-methylheptan-6-ol-2-one possessing specially valuable odour characteristics can be obtained by direct etherification or esterification of 6-methylheptan-6-ol-2-one.
The following Examples illustrate the invention.
EXAMPLE 1 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), 386.80g 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 125°C. 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-methylheptan-2-one (also known as 6-methylheptan-6-ol2-one), which has the structure: OH I CH3- co - ch2 - ch2- ch2- c - ch3 ch3 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: initial molar amount of MBE Conversion = fi-na1· mo1ar amo.u.nt-°.f-MB_E. x 100 initial molar amount of MBE Selectivity molar amount of product molar amount of MBE reacted x TOO 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 125°C, the conversion was 63% and the selectivity was 88%.
EXAMPLE 3 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 (51.208 mol) of acetone and 75.97g (0.8834 mol) of 2-methyl-3-buten-2-ol (MBE).
The mixture was heated with stirring. At 130°, a mixture of 12.91g (0.0883 mol) of di-t-butylperoxide (DTBP) and lOOg (1.816 mol) of 9Ό540 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 4 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 acetone 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-methylheptan6-ol-2-one was 89.8 mol % with respect to the MBE. The DTBP conversion was 59.1%.
EXAMPLE 5 The 5 litre autoclave described in Example 3 was fed with 3078g (52,996 mol) of acetone and 74.825 g (0.870 mol) of MBE. The mixture was heated with stirring. At 130°C, 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 39.6:1:0.035.
EXAMPLE 6 A stainless steel autoclave of 22 litres capacity and equipped in a similar manner to those described in the previous Example 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-nethylhentan-6-ol-2-one. The molar yield with respect to the MBE fed to the reaction was 48.5%. At the end of the feeding of the DTBP, the acetone:MBE:DTBP molar ratio was 30:1:0.1.

Claims (4)

C LA I M S
1. A process for the preparation of 6-methylheptan-6-oI-2-one, which comprises reacting 2. -methyl-3-buten-2-oI with acetone in the presence of a peroxide, 5 the molar ratio of the acetone to the 2-methyl-3-buten-2-ol being from 300:1 to 5:1, and the molar ratio of the peroxide to the 2-methyl-3-buten-2-ol being from 1:1 to 0.005:1.
2. A process according to claim 1, wherein the peroxide is di-t-butylperoxide, diacetyl peroxide, di benzoylperoxide, 10 t-butylhydroperoxide or di cyclohexylperoxydicarbonate.
3. A process according to claim 1, substantially as described in any of the foregoing Examples.
4. 6-Methylheptan-6-ol-2-one, when prepared by a process according to any of claims 1 to 3.
IE2327/80A 1979-11-29 1980-11-10 Preparation of 6-methylheptan-6-01-2-one IE50540B1 (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
IE802327L IE802327L (en) 1981-05-29
IE50540B1 true IE50540B1 (en) 1986-05-14

Family

ID=11222133

Family Applications (1)

Application Number Title Priority Date Filing Date
IE2327/80A IE50540B1 (en) 1979-11-29 1980-11-10 Preparation of 6-methylheptan-6-01-2-one

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)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3156714A (en) * 1962-05-31 1964-11-10 Hoffmann La Roche Syntheses of spirilloxanthin and intermediates
ZA731683B (en) * 1972-04-21 1973-12-19 Hoffmann La Roche Phenyl derivatives
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
IT1087514B (en) * 1977-09-14 1985-06-04 Snam Progetti PROCEDURE FOR THE PREPARATION OF CARBONYL COMPOUNDS

Also Published As

Publication number Publication date
DE3044927A1 (en) 1981-09-17
GB2063877B (en) 1984-06-27
FR2473505A1 (en) 1981-07-17
IE802327L (en) 1981-05-29
IT7927688A0 (en) 1979-11-29
IT1126417B (en) 1986-05-21
NO803562L (en) 1981-06-01
SE8008191L (en) 1981-05-30
GB2063877A (en) 1981-06-10
NL8006467A (en) 1981-07-01
LU82959A1 (en) 1981-06-04
NO812314L (en) 1981-06-01
BE886411A (en) 1981-06-01
DK473980A (en) 1981-05-30
FR2473505B1 (en) 1984-10-12

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