NO803562L - PROCEDURE FOR SYNTHESIS OF CARBONYL COMPOUNDS - Google Patents
PROCEDURE FOR SYNTHESIS OF CARBONYL COMPOUNDSInfo
- Publication number
- NO803562L NO803562L NO803562A NO803562A NO803562L NO 803562 L NO803562 L NO 803562L NO 803562 A NO803562 A NO 803562A NO 803562 A NO803562 A NO 803562A NO 803562 L NO803562 L NO 803562L
- Authority
- NO
- Norway
- Prior art keywords
- stated
- peroxide
- methyl
- compound
- carbonyl
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 18
- 150000001728 carbonyl compounds Chemical class 0.000 title claims description 15
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 230000015572 biosynthetic process Effects 0.000 title description 2
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 claims description 54
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 43
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 claims description 27
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- 150000002978 peroxides Chemical class 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- BDKJAPPUGXLAHC-UHFFFAOYSA-N 6-hydroxy-6-methylheptan-2-one Chemical class CC(=O)CCCC(C)(C)O BDKJAPPUGXLAHC-UHFFFAOYSA-N 0.000 claims description 6
- -1 hydroxylinalbl Chemical compound 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 claims description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 4
- ZZKVKKJYPYTFHL-UHFFFAOYSA-N 3-ethoxy-3-methylbut-1-ene Chemical compound CCOC(C)(C)C=C ZZKVKKJYPYTFHL-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Chemical group C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 3
- ZJVWGOLNVKJRDF-UHFFFAOYSA-N 2-methylbut-3-en-2-yl acetate Chemical compound CC(=O)OC(C)(C)C=C ZJVWGOLNVKJRDF-UHFFFAOYSA-N 0.000 claims 2
- BOBGBONEXUVEAQ-UHFFFAOYSA-N (2-methyl-6-oxoheptan-2-yl) benzoate Chemical compound C(C1=CC=CC=C1)(=O)OC(CCCC(C)=O)(C)C BOBGBONEXUVEAQ-UHFFFAOYSA-N 0.000 claims 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 150000008365 aromatic ketones Chemical class 0.000 claims 1
- FPXFMRRAVFDHMN-UHFFFAOYSA-N carboxy hydrogen carbonate;cyclohexylperoxycyclohexane Chemical compound OC(=O)OC(O)=O.C1CCCCC1OOC1CCCCC1 FPXFMRRAVFDHMN-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 4
- NRPYXKQIFQXMQZ-UHFFFAOYSA-N 2-methylbut-3-en-2-yl benzoate Chemical compound C=CC(C)(C)OC(=O)C1=CC=CC=C1 NRPYXKQIFQXMQZ-UHFFFAOYSA-N 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000007342 radical addition reaction Methods 0.000 description 2
- HLCSDJLATUNSSI-JXMROGBWSA-N (2e)-3,7-dimethylocta-2,6-dienenitrile Chemical compound CC(C)=CCC\C(C)=C\C#N HLCSDJLATUNSSI-JXMROGBWSA-N 0.000 description 1
- WTWGQWLNUNSMGM-UHFFFAOYSA-N 8-hydroxy-3,7-dimethylocta-2,6-dienal Chemical compound OCC(C)=CCCC(C)=CC=O WTWGQWLNUNSMGM-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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)
Description
Foreliggende oppfinnesle vedrører en fremgangsmåte for syn-tese av karbonylforbindelser inneholdende en eller flere funksjonelle grupper utover karbonylgruppen i deres struktur. The present invention relates to a method for the synthesis of carbonyl compounds containing one or more functional groups in addition to the carbonyl group in their structure.
Fremgangsmåten i henhold til oppfinnelsen består i at en karbonylforbindélse omsettes med en forbindelse inneholdene ic.det:^minste en umettetrbinding :(dobbeltbinding eller trippel-binding) og en eller flere funksjonelle grupper, idet reaksjonen gjennomføres i nærvær av katalytiske mengder peroksyder. The method according to the invention consists in reacting a carbonyl compound with a compound containing at least one unsaturated bond (double bond or triple bond) and one or more functional groups, the reaction being carried out in the presence of catalytic amounts of peroxides.
Karbonylforbindelsen kan være et alifatisk, aromatisk eller alisykliske keton eller aldehyd, med en metyl- eller metylengruppe CÅ -stillingen i forhold til karbonylgruppen, og kan spesielt være et <X -metylketon. The carbonyl compound may be an aliphatic, aromatic or alicyclic ketone or aldehyde, with a methyl or methylene group in the CÅ position relative to the carbonyl group, and may in particular be a <X methyl ketone.
Den umettede forbindelse kan som nevnt inneholde én ellerAs mentioned, the unsaturated compound may contain one or
flere olefinbindinger og/eller en eller flere acetylenbind-inger, idet en umettet binding i en endestilling foretrekkes, og kan også innehold én eller flere funksjonelle grupper som kan velges f. eks. fra-OH, -OOCCH3, -Cl, -OCH3, -OC2Hj- , -CN, several olefin bonds and/or one or more acetylene bonds, with an unsaturated bond in an end position being preferred, and may also contain one or more functional groups which can be chosen, e.g. from-OH, -OOCCH3, -Cl, -OCH3, -OC2Hj- , -CN,
-COOH, -COOR.-COOH, -COOR.
Radikal-addisjonsreaksjonen av ketoner til :ok -olefiner eller cykloheksen har vært kjent i noen tid og fremmes f.eks. ved overgangsmétallsalter eller oksyder. I dette tilfellet oppnås lave utbytter av brukbart sluttprodukt. Organiske peroksyder eller; peroksyéstere som radikalkilder har også vært anvendt i støkiométriske mengder i forhold til den initiale karbonylforbindélse. ILtillegg til å oppnå sluttprodukter med abso-lutt utilfredstillende omdannelse og selektivitet, pluss nærvær av en uforholdsmessig stor mengde av peroksyd, er det aldri tidligere nevnt muligheten av å fremstille forbindelser inneholdende svært forskjellige funksjonelle grupper, slik at muligheten av gjennomføringen av reaksjonen direkte mellom karbonylforbindelsen og den umettede forbindelse inneholdende en eller flere funksjonelle grupper ikke var påtenkt. The radical addition reaction of ketones to :ok -olefins or cyclohexene has been known for some time and is promoted e.g. by transition metal salts or oxides. In this case, low yields of usable final product are obtained. Organic peroxides or; peroxyesters as radical sources have also been used in stoichiometric amounts in relation to the initial carbonyl compound. In addition to obtaining final products with absolutely unsatisfactory conversion and selectivity, plus the presence of a disproportionately large amount of peroxide, the possibility of preparing compounds containing very different functional groups, so that the possibility of carrying out the reaction directly between the carbonyl compound, has never before been mentioned and the unsaturated compound containing one or more functional groups was not contemplated.
Den erkjennelse som ligger til grunn for den foreliggende oppfinnelse er at det er funnet mulig å reagere en karbonylforbindelse med en forbindelse inneholdende i det minste en umettet binding samtidig med en eller flere funksjonelle grupper i nærvær av bare katalytiske peroksydmengder. På denne måte oppnås høy omdannelse og selektivitet til brukbare sluttprodukter idet de sistnevnte også omfatter forbindelser inneholdende karbonylgruppen samtid med en eller flere funksjonelle grupper hvor nærværet av disse aldri var; postulert eller påtenkt sammen med karbonylgruppen. Disse inkluderer eterne og esterne av 6-metylheptan-6 -ol-2-én .... Reaksjonen gjennomføres derfor i nærvær 'av et peroksyd i en mengde slik at dets molforhold til den umettede forbindelse varierer fra 1/1 til 0,005/1. Peroksyder anvendbare for dette formål er diacetylperoksyd, dibenzoylperoksyd, tért-butylhydroperoksyd, dicykloheksylperoksydekarbonat, etc. idet bruken av d-tert-butylperoksyd har vist seg spesielt fordelaktig.. Reaksjonen kan gjennomføres ved å gå ut fra substratene alene, eller alene, eller kan gjennomføres i nærvær av vann i en slik mengde at det utgjør enten en enkelLvæskefase eller to væske-faser med blandingen av den umettede "forbindelse og karbonylforbindelsen som bringes til reaksjon. The recognition that underlies the present invention is that it has been found possible to react a carbonyl compound with a compound containing at least one unsaturated bond simultaneously with one or more functional groups in the presence of only catalytic amounts of peroxide. In this way, high conversion and selectivity to usable end products is achieved, as the latter also include compounds containing the carbonyl group together with one or more functional groups where the presence of these was never; postulated or contemplated together with the carbonyl group. These include the ethers and esters of 6-methylheptan-6-ol-2-ene.... The reaction is therefore carried out in the presence of a peroxide in an amount such that its molar ratio to the unsaturated compound varies from 1/1 to 0.005/1 . Peroxides useful for this purpose are diacetyl peroxide, dibenzoyl peroxide, tert-butyl hydroperoxide, dicyclohexylperoxydecarbonate, etc., the use of d-tert-butyl peroxide having proved particularly advantageous.. The reaction can be carried out by starting from the substrates alone, or alone, or can be carried out in the presence of water in such an amount as to form either a single liquid phase or two liquid phases with the mixture of the unsaturated compound and the carbonyl compound being reacted.
Tilførselen av disse er slik at molforholdet mellom karbonylforbindélse og umettet forbindelse varierer fra 500/1 til 3/1, og spesielt fra 300/1 til 5/1. Det bemerkes til slutt at de forbindelser som oppnås ved fremgangsmåten i henhold til j oppfinnelsen har forskjellige anvendelser. F.eks. kan det produkt som oppnås ved å gå ut fra aceton og 2-metyl-3-buten-2-ol, nemlig 6-metylheptan-6-ol-2-6n , utgjøre utgangsforbindélse for fremstilling av tallrike terpen dérivater som f.eks. hydroksylinanol, citral, hydroksycitral, hydroksycitronellal, geranonitril, iononer etc. anvendt innenfor områdene aroma, parfyme, vitaminer, medisiner og overflateaktive forbindelser. The supply of these is such that the molar ratio between carbonyl compound and unsaturated compound varies from 500/1 to 3/1, and especially from 300/1 to 5/1. It is finally noted that the compounds obtained by the method according to the invention have different applications. E.g. can the product obtained by starting from acetone and 2-methyl-3-buten-2-ol, namely 6-methylheptan-6-ol-2-6n, constitute the starting compound for the production of numerous terpene derivatives such as e.g. hydroxylinanol, citral, hydroxycitral, hydroxycitronellal, geranonitrile, ionones etc. used in the areas of aroma, perfume, vitamins, medicines and surface-active compounds.
Derivater av det nevnte metylheptanolon, som har spesielt verdifulle luktegenskaper, kan oppnås fra aceton og etere eller estere av 2-metyl-3-buten-2-ol ved direkte foretring eller forestring av metyl-heptanolonet. De følgende eksempler illustrerer syntesene for fremstilling av de angjeldende forbindelser. Derivatives of the aforementioned methylheptanolone, which have particularly valuable odor properties, can be obtained from acetone and ethers or esters of 2-methyl-3-buten-2-ol by direct etherification or esterification of the methylheptanolone. The following examples illustrate the syntheses for the preparation of the compounds in question.
EKSEMPEL 1EXAMPLE 1
De følgende bestanddeler innføres i en rustfristålautoklav med romfang 1 liter utstyrt med manometer, et rør for tapping, et magnetisk drevet rørverk og utstyrt med elektriske mot-stands-varmeelementer: The following ingredients are introduced into a stainless steel autoclave with a capacity of 1 liter equipped with a manometer, a pipe for tapping, a magnetically driven pipework and equipped with electric resistance heating elements:
9,55 g ren vannfri 2-metyl-3-buten-2-ol (MBE),9.55 g pure anhydrous 2-methyl-3-buten-2-ol (MBE),
386,80 g aceton,386.80 g acetone,
1,63 g di-tert-butylperoksyd (DTBP).1.63 g di-tert-butyl peroxide (DTBP).
Molforholdet aceton /MBE/ katalysator er således omtrent 60/1/ 01 . The mole ratio acetone /MBE/catalyst is thus approximately 60/1/01.
Blandingen blir så oppvarmet under omrøring til 125°C og etter 1;. time og 45 minutters reaksjon er MBE-omdannelsen (initiale mol MBE minus endelige mol av MBE)x100/initiale mol MBE) 66% og selektiviteten med hensyn til 4:1 addisjons-préduktet (mol av produkt x 100/mol av reagert MBRE) er 86%. The mixture is then heated with stirring to 125°C and after 1;. hour and 45 minutes of reaction, the MBE conversion (initial moles of MBE minus final moles of MBE)x100/initial moles of MBE) is 66% and the selectivity with respect to the 4:1 addition product (moles of product x 100/mol of reacted MBRE) is 86%.
Etter 5 timer er omdannelsen 98% og selektiviteten er omtrent 82%. After 5 hours the conversion is 98% and the selectivity is about 82%.
Det 1:1 addisjonsprodukt som dannes på denne måte er 6-hydro-ksy-6-metylheptan-2-on (eller 6-metylheptan-6-ol-2son): The 1:1 addition product formed in this way is 6-hydroxy-6-methylheptan-2-one (or 6-methylheptan-6-ol-2-one):
og strukturen derav ble bekreftet ved hjelp av masse-, IR og ■ "F MNR-analyse. and its structure was confirmed by mass, IR and ■ "F NMR analysis.
EKSEMPEL 2EXAMPLE 2
Fremgangsmåten i eksempel 1 ble fulgt med et aceton/MBE/DTBP molforhold på 60/1/0.025. The procedure in Example 1 was followed with an acetone/MBE/DTBP molar ratio of 60/1/0.025.
o o
Etter 8 timers reaksjon ved 125 C ble det oppnådd en omdannelse på 63% og en selektivitet på 88%. After 8 hours of reaction at 125 C, a conversion of 63% and a selectivity of 88% was achieved.
EKSEMPEL 3EXAMPLE 3
Apparatet i eksempel 1 ble tilført:The apparatus in example 1 was supplied with:
19,13 g hydroksylinalol 19.13 g of hydroxylinalol
387,0 g aceton, 387.0 g acetone,
1,62 g DTBP,1.62 g DTBP,
tilsvarende et molforhold aceton/(I)/DTBP på 60/1/0,1. Etter 6 timer ved 125°C var omdannelsen av (I) 88% og selektiviteten med hensyn til 1:1 addisjonsproduktet. corresponding to an acetone/(I)/DTBP molar ratio of 60/1/0.1. After 6 hours at 125°C the conversion of (I) was 88% and the selectivity with respect to the 1:1 addition product.
målt til 57%. measured at 57%.
EKSEMPEL 4EXAMPLE 4
Apparatet^.i eksempel 1 tilføres:The apparatus in example 1 is supplied with:
116,0 g rent aceton,116.0 g pure acetone,
3,800 g 2-metyl-2-etoksy-3-buten (II),3,800 g of 2-methyl-2-ethoxy-3-butene (II),
0,50 g DTBP,0.50 g DTBP,
som gir et aceton/(II)/DTBP molforhold på omtrent 60/1/0,1. giving an acetone/(II)/DTBP molar ratio of about 60/1/0.1.
Etter 3 timer ved 125°C dannes et 1:1 radikal-addisjonsprodukt som utgjøres av 6-metylheptan-6-etoksy-2-6n After 3 hours at 125°C, a 1:1 radical addition product is formed which consists of 6-methylheptane-6-ethoxy-2-6n
med en 90% omdannelse av (II) og en selektivitet til omtrent 88%, idet strukturen ble bekreftet ved hjelp av GLC-masseanalyse. with a 90% conversion of (II) and a selectivity of about 88%, the structure being confirmed by GLC mass analysis.
EKSEMPEL 5EXAMPLE 5
Fremgangsmåten i eksempel 4 følges men det tilføres 6,35 g 2-metyl-3-buten-2-yl benzoat (III) istédét:for 2-metyl—2-etoksy-3-byten, slik at aceton/(III)/DTBP molforholdet også her er omtrent 60/1/0,1. The procedure in example 4 is followed, but 6.35 g of 2-methyl-3-buten-2-yl benzoate (III) is added instead of 2-methyl-2-ethoxy-3-butene, so that acetone/(III)/ The DTBP molar ratio here too is approximately 60/1/0.1.
Etter 3 timer ved 125°C dannes 6-metylheptan-2-on-6-ylAfter 3 hours at 125°C, 6-methylheptan-2-on-6-yl is formed
benzoat benzoate
med en 88% omdannelse av (III) og en selektivitet på omtrent 86%, idet strukturen av produktet også her ble bekreftet ved hjelp av GLC-masseanalyse. with an 88% conversion of (III) and a selectivity of approximately 86%, the structure of the product being confirmed here as well by means of GLC mass analysis.
EKSEMPEL 6 -,EXAMPLE 6 -,
En rustfri stålautoklav med 5 liters romfang utstyrt med r manometer, et rør for tilførsel av reagensene ved hjelp av en doseringspumpe, et magnetisk vevet røreverk og utstyrt med elektriéke motstandsvarmeelementer tilføres: 2978,35 g aceton (51,208 mol), A stainless steel autoclave with a volume of 5 liters equipped with r manometers, a tube for supplying the reagents by means of a dosing pump, a magnetically woven stirrer and equipped with electric resistance heating elements are fed: 2978.35 g of acetone (51.208 mol),
75,97 g 2-metyl-3-buten-2-ol (0,8834 mol) (MBE), blandingén oppvarmes under omrøring. Ved 130°C tilføres en blanding av 12,91 g di-tert-butylperoksyd (0,0883 mol) (DTBP) og 100 g aceton (1,816 mol) ved hjelp av pumpen. 75.97 g of 2-methyl-3-buten-2-ol (0.8834 mol) (MBE), the mixture is heated with stirring. At 130°C, a mixture of 12.91 g of di-tert-butyl peroxide (0.0883 mol) (DTBP) and 100 g of acetone (1.816 mol) is added using the pump.
Pumpeleveringen reguleres slik at oppløsningen av peroksydThe pump delivery is regulated so that the dissolution of peroxide
i aceton tilføres i løpet av 2 timer og 15 minutter. in acetone is added over 2 hours and 15 minutes.
Aceton/MBE/DTBP molforholdet er 60/1/0,1.The acetone/MBE/DTBP molar ratio is 60/1/0.1.
Etter 5 timers reaksjonstid (regnet fra begynnelsen av per-oksydtilførselen) var MBE-omdannelsen 82,5% og selektiviteten med hensyn til 6-metylheptan-6-ol-2-on 85,1 mol% i forhold til MBE. After 5 hours of reaction time (calculated from the beginning of the peroxide feed) the MBE conversion was 82.5% and the selectivity with respect to 6-methylheptan-6-ol-2-one 85.1 mol% in relation to MBE.
Omdannelsen og selektiviteten bestemmes ved hjelp av gass-kromatografisk analyse under anvendelse av en standard metode. The conversion and selectivity are determined by gas chromatographic analysis using a standard method.
EKSEMPEL 7EXAMPLE 7
Fremgangsmåten i det foregående eksempel følges, men med et aceton/MBE/DTBP molforhold på 60/1/0,05. The procedure in the previous example is followed, but with an acetone/MBE/DTBP molar ratio of 60/1/0.05.
DTBP-oppløsningen i aceton pumpes inn i løpet av et tidsrom på 1,5 time. The DTBP solution in acetone is pumped in over a period of 1.5 hours.
Etter 5 timers reaksjon (regnet fra begynnelsen av peroksyd-tilførsélen) er MBE-omdannelsen 73% og selektiviteten med hensyn til 6-metylheptan-6-ol-2-on er 89,8 mol% i forhold til MBE. After 5 hours of reaction (calculated from the beginning of the peroxide feed), the MBE conversion is 73% and the selectivity with respect to 6-methylheptan-6-ol-2-one is 89.8 mol% relative to MBE.
DTBP-omdånnelsen er 59,1%.The DTBP conversion is 59.1%.
EKSEMPEL 8EXAMPLE 8
Den 5 liters autoklav beskrevet ovenfor tilføres:The 5 liter autoclave described above is supplied with:
3078 g aceton (52,996■mol),3078 g of acetone (52.996 mol),
74,825 g MBE ( 0,870 mol). 74.825 g MBE (0.870 mol).
Blandingen oppvarmes under omrøring. Ved 130°C begynnes til-førselen av de-tert-peroksyd. Reaksjonen tilføres i løpet av et tidsrom på 1 time 6,946 g DTBP (0,0475 mol). 30 minutter etterlat DTBP-ti-lførselen er begynt igangsettes tilførselen av MBE og 40,320 g MBE (0,469 mol) tilføres i løpet av 3 timer. The mixture is heated while stirring. At 130°C, the addition of tert-peroxide begins. 6.946 g of DTBP (0.0475 mol) are added to the reaction over a period of 1 hour. 30 minutes after the DTBP supply has begun, the supply of MBE is started and 40.320 g of MBE (0.469 mol) are added over the course of 3 hours.
Etter 6,5 timers reaksjon (regnet fra begynnelsen av perok-sydtilførselen) er MBE-omdånnelsen 88,2% og selektiviteten er 75,9 mol%. After 6.5 hours of reaction (calculated from the beginning of the peroxy feed), the MBE conversion is 88.2% and the selectivity is 75.9 mol%.
Det endelige aceton/MBE/DTBP molforhold ér 39,6/1/0,035. The final acetone/MBE/DTBP mole ratio is 39.6/1/0.035.
EKSEMPEL 9EXAMPLE 9
En rustfri stålautoklav med 22 liters romfang og med samme egenskaper som beskrevet i de foregående eksempler tilføres: 12,34 2 kg aceton (212,1 mol) og A stainless steel autoclave with a volume of 22 liters and with the same properties as described in the previous examples is fed: 12.34 2 kg of acetone (212.1 mol) and
0,609 gk MBE :(7 , 083' mol) .0.609 gk MBE :(7 , 083' mol) .
Blandingen oppvarmes under omrøring. Ved 130°C tilføres 0,1036 kg DTBP (0,7083 mol) i løpet av 2 timer. Etter 5 timers reaksjon (beregnet fra begynnelsen av DTBP-tilførselen) avkjøles autoklaven. The mixture is heated while stirring. At 130°C, 0.1036 kg of DTBP (0.7083 mol) are added over the course of 2 hours. After 5 hours of reaction (calculated from the beginning of the DTBP supply), the autoclave is cooled.
Reaksjonsblandingen defineres i en perforert platekolonne av Oldenshaw-typen til å gi 495 g rent 6-metylheptan-6-ol-2-on. Det molare utbyttet med hensyn til tilført MBE til reaksjonen er 48,5%. The reaction mixture is defined in an Oldenshaw type perforated plate column to give 495 g of pure 6-methylheptan-6-ol-2-one. The molar yield with respect to added MBE to the reaction is 48.5%.
Ved avsluttet tilførsel er aceton/MBE/DTBP molforholdet 30/1/ 0,1 . At the end of the supply, the acetone/MBE/DTBP molar ratio is 30/1/0.1.
Claims (14)
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 (1)
| Publication Number | Publication Date |
|---|---|
| NO803562L true NO803562L (en) | 1981-06-01 |
Family
ID=11222133
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO803562A NO803562L (en) | 1979-11-29 | 1980-11-26 | PROCEDURE FOR SYNTHESIS OF CARBONYL COMPOUNDS |
| NO812314A NO812314L (en) | 1979-11-29 | 1981-07-07 | 6-METHYLHEPTAN-6-OL-2-ON AND ESTER AND ESTER DERIVATIVES OF THE HYDROXYL GROUP |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO812314A NO812314L (en) | 1979-11-29 | 1981-07-07 | 6-METHYLHEPTAN-6-OL-2-ON AND ESTER AND ESTER DERIVATIVES OF THE HYDROXYL GROUP |
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)
| 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 |
-
1979
- 1979-11-29 IT IT27688/79A patent/IT1126417B/en active
-
1980
- 1980-11-07 DK DK473980A patent/DK473980A/en not_active Application Discontinuation
- 1980-11-10 IE IE2327/80A patent/IE50540B1/en unknown
- 1980-11-12 GB GB8036309A patent/GB2063877B/en not_active Expired
- 1980-11-21 SE SE8008191A patent/SE8008191L/en not_active Application Discontinuation
- 1980-11-26 NO NO803562A patent/NO803562L/en unknown
- 1980-11-26 LU LU82959A patent/LU82959A1/en unknown
- 1980-11-27 NL NL8006467A patent/NL8006467A/en not_active Application Discontinuation
- 1980-11-27 FR FR8025207A patent/FR2473505A1/en active Granted
- 1980-11-28 BE BE0/202982A patent/BE886411A/en not_active IP Right Cessation
- 1980-11-28 DE DE19803044927 patent/DE3044927A1/en not_active Ceased
-
1981
- 1981-07-07 NO NO812314A patent/NO812314L/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2473505B1 (en) | 1984-10-12 |
| BE886411A (en) | 1981-06-01 |
| GB2063877B (en) | 1984-06-27 |
| LU82959A1 (en) | 1981-06-04 |
| NL8006467A (en) | 1981-07-01 |
| DE3044927A1 (en) | 1981-09-17 |
| SE8008191L (en) | 1981-05-30 |
| IT1126417B (en) | 1986-05-21 |
| IE50540B1 (en) | 1986-05-14 |
| IE802327L (en) | 1981-05-29 |
| IT7927688A0 (en) | 1979-11-29 |
| FR2473505A1 (en) | 1981-07-17 |
| DK473980A (en) | 1981-05-30 |
| GB2063877A (en) | 1981-06-10 |
| NO812314L (en) | 1981-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bittler et al. | Carbonylation of olefins under mild temperature conditions in the presence of palladium complexes | |
| JPH01146840A (en) | Production of ehther carboxylic acid | |
| US3718689A (en) | Preparation of trisubstituted-hydroxyalkyl alkanoates | |
| JPS6215536B2 (en) | ||
| CZ289859B6 (en) | Process for preparing primary amines and apparatus for making the same | |
| NO803562L (en) | PROCEDURE FOR SYNTHESIS OF CARBONYL COMPOUNDS | |
| JPH05201900A (en) | Production of alcohol having primary and secondary fluorines | |
| CN110407680A (en) | A method of preparing isoamyl olefine aldehydr | |
| US3952020A (en) | Lactone production | |
| JPH0157102B2 (en) | ||
| US5811588A (en) | Process for the preparation of 3-phenylpropanal | |
| US6307106B1 (en) | Process for preparing unsaturated ketones | |
| JPS6348855B2 (en) | ||
| US10259766B1 (en) | Preparation method for 2,3-pentanedione | |
| SU589906A3 (en) | Method of preparing acetoxybutanal | |
| KR20010049591A (en) | CONTINUOUS PROCESS FOR THE MANUFACTURE OF 3,5,5-TRIMETHYLCYCLOHEXA-3-EN-1-ONE (β-ISOPHORONE) | |
| JPS5826890B2 (en) | Method for producing methyl-nonyl-acetaldehyde | |
| US3786083A (en) | Process for the preparation of acyl succinic acid dialkyl esters | |
| WO2000046174A1 (en) | A method of preparing cyclohexanecaraboxylic acid using [2+4] diels-alder reaction | |
| SU813903A1 (en) | Method of producing c5 and c7 dialkylketones | |
| Ito et al. | A new synthesis of N-tert-butylvinylketenimines and their cycloaddition reactions | |
| JPH0131496B2 (en) | ||
| JPH0316928B2 (en) | ||
| US5786507A (en) | Process for the preparation of 3-phenylpropionic acid | |
| JPS6245855B2 (en) |