WO2019020466A1 - Process for the hydrolysis or alcoholysis of cyclic ketal or acetal groups with carbon dioxide or an alcohol - Google Patents
Process for the hydrolysis or alcoholysis of cyclic ketal or acetal groups with carbon dioxide or an alcohol Download PDFInfo
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- WO2019020466A1 WO2019020466A1 PCT/EP2018/069543 EP2018069543W WO2019020466A1 WO 2019020466 A1 WO2019020466 A1 WO 2019020466A1 EP 2018069543 W EP2018069543 W EP 2018069543W WO 2019020466 A1 WO2019020466 A1 WO 2019020466A1
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- Prior art keywords
- ketal
- acetal
- group
- compound
- formula
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 27
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 22
- 125000004036 acetal group Chemical group 0.000 title claims abstract description 20
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 20
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 125000004122 cyclic group Chemical group 0.000 title claims description 11
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 acetal compound Chemical class 0.000 claims abstract description 34
- 125000003277 amino group Chemical group 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 30
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 15
- 125000000962 organic group Chemical group 0.000 claims description 14
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- ADLFBRNPQMLXTQ-UHFFFAOYSA-N 2,2-dimethyl-1,3-dioxan-5-amine Chemical compound CC1(C)OCC(N)CO1 ADLFBRNPQMLXTQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 101100178983 Caenorhabditis elegans hyl-1 gene Proteins 0.000 claims 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- 150000001241 acetals Chemical group 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 150000002440 hydroxy compounds Chemical class 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001728 carbonyl compounds Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- HXOYWCSTHVTLOW-UHFFFAOYSA-N (2,2-dimethyl-1,3-dioxolan-4-yl)methanamine Chemical compound CC1(C)OCC(CN)O1 HXOYWCSTHVTLOW-UHFFFAOYSA-N 0.000 description 4
- KQIGMPWTAHJUMN-VKHMYHEASA-N 3-aminopropane-1,2-diol Chemical compound NC[C@H](O)CO KQIGMPWTAHJUMN-VKHMYHEASA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WOMTYMDHLQTCHY-UHFFFAOYSA-N 3-methylamino-1,2-propanediol Chemical compound CNCC(O)CO WOMTYMDHLQTCHY-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960005419 nitrogen Drugs 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
Definitions
- the present invention relates to a process for the hydrolysis or alcoholysis of a ketal or acetal compound wherein a ketal or acetal compound comprising at least one ketal or acetal group and at least one amino group is reacted with carbon dioxide and water or an alcohol.
- Ketals or acetals are used as protecting groups. Ketals or acetals are formed by reacting compounds with carbonyl groups (shortly carbonyl compound) and compounds with hydroxy groups (shortly hydroxy compound) under acidic conditions. An acetal is formed with an aldehyde group and a ketal is formed with a keto group as carbonyl group. Cyclic ketal and cyclic acetal groups are obtained using compounds with at least two hydroxyl groups.
- the ketal or acetal group protects the original carbonyl group respectively hydroxyl groups thus avoiding any undesired reactions of the original carbonyl respectively hydroxyl groups in critical steps of chemical synthesis.
- the protecting group will be removed by hydrolysis or alcoholysis thus setting free again the carbonyl compound or, in case of an alcoholysis, the acetal or ketal thereof and the hydroxyl compound.
- acids are used as catalysts in the hydrolysis or alcoholysis.
- the compound comprising at least one ketal or acetal group and at least one amino group herein is referred to as the ketal or acetal compound.
- Acetals or ketals are formed by reacting a carbonyl compound with at least one carbonyl group and a hydroxy compound with at least one hydroxy group. If the carbonyl group is an aldehyde, an acetal is formed. If the carbonyl group is a keto group, a ketal is formed. In both cases two mols of hydroxy groups are required for each mol of carbonyl groups.
- the hydroxy compound may be a mono hydroxy compound. In this case two mols of the mono hydroxy compound are required.
- the hydroxy compound may be a compound with two hydroxy groups which are positioned either at neighbored carbon atoms (so called 1 ,2 or a-position) or which are positioned at two carbon atoms which are linked by one further carbon atom in between (so called 1 ,3 or ⁇ - position) or which are positioned at two carbon atoms which are linked by two further carbon atoms in between (so called 1 ,4 or ⁇ -position).
- 1 ,2 or a-position two hydroxy groups which are positioned either at neighbored carbon atoms
- 1 ,3 or ⁇ - position or which are positioned at two carbon atoms which are linked by one further carbon atom in between
- 1 ,4 or ⁇ -position the reaction with the carbonyl group results in a cyclic acetal or ketal compound.
- the ketal or acetal compound is a compound with one to three, more preferably with one or two ketal or acetal groups.
- the ketal or acetal compound is a compound with one ketal or acetal group.
- the at least one amino group of the ketal or acetal compound is preferably a primary or secondary amino group.
- the ketal or acetal compound is a compound with one to three, notably one or two amino groups.
- the ketal or acetal compound is a compound with one amino group.
- the ketal or acetal compound comprises one ketal or acetal group and one amino group which is a primary or secondary amino group; in a specifically preferred embodiment, this one amino group is a primary amino group.
- the ketal or acetal compound does not comprise any other functional groups than ketal, acetal and amino groups.
- the ketal or acetal compound has a molecular weight of at maximum 10OOg/mol.
- the ketal or acetal group is a cyclic ketal or acetal group and the ketal or acetal compound is a compound with at least one cyclic ketal or cyclic acetal group.
- the preferred embodiments above apply to compounds with at least one cyclic ketal or acetal group.
- a preferred compound with at least one cyclic ketal or acetal group is the compound of formula I
- R 1 and R 2 independently from one another represent a hydrogen atom or an organic group and X represents an ethylene group CR 3 R 4 - CR 5 R 6 ,
- R 3 to R 20 independently from one another representing a hydrogen atom, an organic group or a primary amino group with the provision that the compound of formula I comprises at least one amino group.
- X represents an ethylene group CR 3 R 4 - CR 5 R 6 ,
- groups R 1 to R 20 represent an organic group or a primary amino group, all other groups R 1 to R 20 are hydrogen.
- groups R 1 to R 20 represent an organic group or a primary amino group, all other groups R 1 to R 20 are hydrogen.
- the organic groups are groups with 1 to 30, notably 1 to 10 carbon atoms and may comprise functional groups such as amino groups, further ketal or acetal groups, hydroxy groups or ether groups.
- the organic group may be a secondary amino group -NHR 21 with R 21 being an aliphatic group, notably an alkyl group, preferably an alkyl group with 1 to 10 carbon atoms.
- the organic groups are hydrocarbon groups which may comprise amino groups, ketal or acetal groups but no further functional groups.
- the organic groups are hydrocarbon groups which may comprise amino groups but no further functional groups.
- At least one of R 1 to R 20 is a primary amino group or an organic group comprising an amino group, notably a primary or secondary amino group.
- R 1 to R 20 are a primary amino group or an organic group comprising an amino group, notably a primary or secondary amino group. More preferably, the compound of formula I comprises only one amino group, which means that only one of R 1 to R 20 is a primary amino group or an organic group comprising an amino group, notably a primary or secondary amino group.
- both R 1 and R 2 are an aliphatic hydrocarbon group, notably an alkyl group with 1 to 10 carbon atoms, preferably a methyl group; in this preferred embodiment R 3 to R 20 may be a primary amino group or comprise organic groups with amino groups, only.
- the process is a hydrolysis or alcoholysis of the ketal or acetal compound by reacting the ketal or acetal compound with carbon dioxide and water or an alcohol.
- R 1 ⁇ R 2 or, in case of an alcoholysis, the ketal respectively acetal thereof
- the process is performed with an alcohol.
- the alcohol is preferably an alkanol with 1 to 4 carbon atoms, notably methanol or ethanol.
- the compound of formula III is obtained and the ketal or acetal of the compound of formula II which is easily transferred into the carbonyl compound under aqueous acid conditions, if desired.
- the process is a hydrolysis.
- the reaction with carbon dioxide may be performed in a batch process, semi-continuously or continuously.
- the ketal or acetal compound, water, respectively alcohol are filled into a reactor.
- Carbon dioxide may be fed as gas, liquid or in solid form (as dry ice). Preferably it is fed as gas.
- Carbon dioxide may be used as such or in combination with inert gases, such as nitro- gen or noble gases.
- Carbon dioxide may be used in less than stoichiometric amounts, for example, carbon dioxide may be used in amounts of 0.1 to 0.9 mol carbon dioxide per mol of the amino groups of the ketal or acetal compound.
- a semi-continuous process at least one of the starting materials is supplied continuously.
- the ketal or acetal compound is filled completely into the reactor whereas gaseous carbon dioxide or a mixture of gaseous carbon dioxide and an inert gas and water (in case of a hydrolysis) or alcohol (in case of an alcoholysis) are fed continuously to the reactor; gaseous products, such as acetone are continuously withdrawn from the reactor.
- Water, respectively the alcohol is preferably used in an amount of 10 to 1000 parts by weight, in particular of 100 to 500 parts by weight and most preferably in an amount of 200 to 400 parts by weight per 100 parts by weight of the ketal or acetal compound.
- the reaction with carbon dioxide is preferably performed at a pressure above normal pressure.
- the pressure is at least 1.5 bar, in particular at least 5 bar, more preferably at least 10 bars and most preferred at least 20 bars.
- the pressure is at maximum 500 bars, respectively at maximum 200 bars, as higher pressures are not required.
- the temperature is preferably kept at 50 to 200, in particular at 90 to 170°C.
- the product mixture may be removed from the reactor.
- the product mixture comprises the products of the hydrolysis or alcoholysis which are a car- bonyl compound or, alternatively the acetal or ketal of the carbonyl compound in case of an alcoholysis, and a hydroxy compound.
- the addition of a basic compound for neutralization is not necessary and any precipitates resulting from such addition are avoided.
- the products of the hydrolysis of the compound of formula I are compounds of formula II and III.
- the products of the hydrolysis or alcoholysis are obtained in high yields and selectivity.
- the product mixture may optionally be further worked up or purified by distillation or rectification.
- the process of this invention is an easy and effective hydrolysis or alcoholysis of ketal or acetal compounds which comprise at least one amino group.
- the product of the hydrolysis or alcoholysis is obtained in high yield.
- the process is easy to perform and requires less work-up than a prior art process. No precipitates have to be removed by filtration as an additional step of neutralization with a basic compound is not necessary.
- Example 1 hydrolysis of solketalamine with carbon dioxide
- methylmethanamine (/V-methylsolketalamine) and 40 g of H2O.
- the autoclave was pressurized with 30 bar CO2 and the mixture was heated to 140 °C for 12 h. After depressurization, the composition of the mixture was analyzed by GC.
- the mixture contained 83% (area % deter- mined from gas chromatography) of 3-(methylamino) propane-1 ,2-diol (MAPD) (Conversion: >99%, Selectivity: 83%).
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Abstract
Process for the hydrolysis or alcoholysis of a ketal or acetal compound wherein a ketal or acetal compound comprising at least one ketal or acetal group and at least one amino group is reacted with carbon dioxide and water oran alcohol.
Description
PROCESS FOR THE HYDROLYSIS OR ALCOHOLYSIS OF CYCLIC KETAL OR ACETAL GROUPS
WITH CARBON DIOXIDE OR AN ALCOHOL
The present invention relates to a process for the hydrolysis or alcoholysis of a ketal or acetal compound wherein a ketal or acetal compound comprising at least one ketal or acetal group and at least one amino group is reacted with carbon dioxide and water or an alcohol.
In chemical synthesis ketal or acetal groups are used as protecting groups. Ketals or acetals are formed by reacting compounds with carbonyl groups (shortly carbonyl compound) and compounds with hydroxy groups (shortly hydroxy compound) under acidic conditions. An acetal is formed with an aldehyde group and a ketal is formed with a keto group as carbonyl group. Cyclic ketal and cyclic acetal groups are obtained using compounds with at least two hydroxyl groups.
The ketal or acetal group protects the original carbonyl group respectively hydroxyl groups thus avoiding any undesired reactions of the original carbonyl respectively hydroxyl groups in critical steps of chemical synthesis.
Finally, the protecting group will be removed by hydrolysis or alcoholysis thus setting free again the carbonyl compound or, in case of an alcoholysis, the acetal or ketal thereof and the hydroxyl compound. Usually acids are used as catalysts in the hydrolysis or alcoholysis.
In case of compounds comprising amino groups the addition of acid leads to protonation of the amino groups. Hence the acid must be added in a molar excess compared to the amino groups to have some remaining acid that can act as catalyst in the hydrolysis or alcoholysis. After the hydrolysis/alcoholysis of the acetal or ketal the amino groups remain protonated and an additional process step of neutralization, for example with a basic compound such as sodium hydroxide, is required.
Organic Process Research & Development 2007, 1 1 , 121 -132 discloses in scheme 14, page 131 the hydrolysis of the cyclic ketal of cyclohexanone with carbon dioxide at 20 bar and 65°C. Cyclohexanone and ethylene glycol are the products of the hydrolysis. A further use of carbon dioxide in the hydrolysis of acetals or ketals is not discussed or suggested.
It is the object of the present invention to provide an easy and effective process for the hydroly- sis of acetals or ketals which further comprise an amino group.
Accordingly, the process as defined above has been found.
To the ketal or acetal compound
The compound comprising at least one ketal or acetal group and at least one amino group herein is referred to as the ketal or acetal compound.
Acetals or ketals are formed by reacting a carbonyl compound with at least one carbonyl group and a hydroxy compound with at least one hydroxy group. If the carbonyl group is an aldehyde, an acetal is formed. If the carbonyl group is a keto group, a ketal is formed. In both cases two mols of hydroxy groups are required for each mol of carbonyl groups. The hydroxy compound may be a mono hydroxy compound. In this case two mols of the mono hydroxy compound are required. The hydroxy compound may be a compound with two hydroxy groups which are positioned either at neighbored carbon atoms (so called 1 ,2 or a-position) or which are positioned at two carbon atoms which are linked by one further carbon atom in between (so called 1 ,3 or β- position) or which are positioned at two carbon atoms which are linked by two further carbon atoms in between (so called 1 ,4 or γ-position). In case of a hydroxy compound with two hydroxy groups in 1 ,2 or 1 ,3 or 1 ,4 position the reaction with the carbonyl group results in a cyclic acetal or ketal compound.
Preferably, the ketal or acetal compound is a compound with one to three, more preferably with one or two ketal or acetal groups. In a most preferred embodiment the ketal or acetal compound is a compound with one ketal or acetal group.
The at least one amino group of the ketal or acetal compound is preferably a primary or secondary amino group.
Preferably, the ketal or acetal compound is a compound with one to three, notably one or two amino groups. In a most preferred embodiment the ketal or acetal compound is a compound with one amino group. In a most preferred embodiment, the ketal or acetal compound comprises one ketal or acetal group and one amino group which is a primary or secondary amino group; in a specifically preferred embodiment, this one amino group is a primary amino group.
Preferably, the ketal or acetal compound does not comprise any other functional groups than ketal, acetal and amino groups.
Preferably, the ketal or acetal compound has a molecular weight of at maximum 10OOg/mol.
In a preferred embodiment of the invention the ketal or acetal group is a cyclic ketal or acetal group and the ketal or acetal compound is a compound with at least one cyclic ketal or cyclic acetal group. The preferred embodiments above apply to compounds with at least one cyclic ketal or acetal group.
A preferred compound with at least one cyclic ketal or acetal group is the compound of formula I
0-X
R+O
wherein R1 and R2 independently from one another represent a hydrogen atom or an organic group and X represents an ethylene group CR3R4- CR5R6,
a propylene group CR7R8 -CR9R10 - CR11R12 or
a butylene group CR13R14- CR15R16- CR17R18 - CR19R20
with R3 to R20 independently from one another representing a hydrogen atom, an organic group or a primary amino group with the provision that the compound of formula I comprises at least one amino group.
Preferably, X represents an ethylene group CR3R4- CR5R6,
or a propylene group CR7R8 -CR9R10 - CR11R12.
In a preferred embodiment at maximum four of groups R1 to R20 represent an organic group or a primary amino group, all other groups R1 to R20 are hydrogen.
In a more preferred embodiment at maximum three of groups R1 to R20 represent an organic group or a primary amino group, all other groups R1 to R20 are hydrogen.
Preferably, the organic groups are groups with 1 to 30, notably 1 to 10 carbon atoms and may comprise functional groups such as amino groups, further ketal or acetal groups, hydroxy groups or ether groups. The organic group may be a secondary amino group -NHR21 with R21 being an aliphatic group, notably an alkyl group, preferably an alkyl group with 1 to 10 carbon atoms.
More preferably, the organic groups are hydrocarbon groups which may comprise amino groups, ketal or acetal groups but no further functional groups.
Most preferably, the organic groups are hydrocarbon groups which may comprise amino groups but no further functional groups.
At least one of R1 to R20 is a primary amino group or an organic group comprising an amino group, notably a primary or secondary amino group.
Preferably, one or two of R1 to R20 are a primary amino group or an organic group comprising an amino group, notably a primary or secondary amino group. More preferably, the compound of formula I comprises only one amino group, which means that only one of R1 to R20 is a primary amino group or an organic group comprising an amino group, notably a primary or secondary amino group.
In one preferred embodiment of the invention both R1 and R2 are an aliphatic hydrocarbon group, notably an alkyl group with 1 to 10 carbon atoms, preferably a methyl group; in this preferred embodiment R3 to R20 may be a primary amino group or comprise organic groups with amino groups, only.
Compounds of formula I are, for example:
(2,2-dimethyl-1 ,3-dioxolan-4-yl) methanamine (solketalamine ) of formula
or a dimeric solketalamine derivative of formula
or (/V,2,2-trimethyl-1 ,3-dioxolane-4-yl)-methanamine of formula
or 5-amino-2,2-dimethyl-1 ,3-dioxane of formula
To the process The process is a hydrolysis or alcoholysis of the ketal or acetal compound by reacting the ketal or acetal compound with carbon dioxide and water or an alcohol.
In case of the compound of formula I the product of the hydrolysis are compounds of formula II
O
R1^R2
or, in case of an alcoholysis, the ketal respectively acetal thereof
and compounds of formula III
ΗΟ' Χ~ΌΗ wherein R1, R2 and X have the above meaning.
In case of a hydrolysis the process is performed with water. With the compound of formula I as starting material, compounds of formula II and III are obtained.
In case of an alcoholysis the process is performed with an alcohol. The alcohol is preferably an alkanol with 1 to 4 carbon atoms, notably methanol or ethanol. With the compound of formula I as starting material, the compound of formula III is obtained and the ketal or acetal of the compound of formula II which is easily transferred into the carbonyl compound under aqueous acid conditions, if desired.
Preferably, the process is a hydrolysis.
The reaction with carbon dioxide may be performed in a batch process, semi-continuously or continuously.
In a batch process, the ketal or acetal compound, water, respectively alcohol, are filled into a reactor. Carbon dioxide may be fed as gas, liquid or in solid form (as dry ice). Preferably it is fed as gas. Carbon dioxide may be used as such or in combination with inert gases, such as nitro- gen or noble gases. Carbon dioxide may be used in less than stoichiometric amounts, for example, carbon dioxide may be used in amounts of 0.1 to 0.9 mol carbon dioxide per mol of the amino groups of the ketal or acetal compound.
In a semi-continuous process, at least one of the starting materials is supplied continuously. In one embodiment of a semi-continuous operation of the process, the ketal or acetal compound is filled completely into the reactor whereas gaseous carbon dioxide or a mixture of gaseous carbon dioxide and an inert gas and water (in case of a hydrolysis) or alcohol (in case of an alcoholysis) are fed continuously to the reactor; gaseous products, such as acetone are continuously withdrawn from the reactor.
Water, respectively the alcohol, is preferably used in an amount of 10 to 1000 parts by weight, in particular of 100 to 500 parts by weight and most preferably in an amount of 200 to 400 parts by weight per 100 parts by weight of the ketal or acetal compound. The reaction with carbon dioxide is preferably performed at a pressure above normal pressure. Preferably, the pressure is at least 1.5 bar, in particular at least 5 bar, more preferably at least 10 bars and most preferred at least 20 bars. Usually the pressure is at maximum 500 bars, respectively at maximum 200 bars, as higher pressures are not required. The temperature is preferably kept at 50 to 200, in particular at 90 to 170°C.
When the reaction is completed (in case of a batch or semi-continuous process) the product mixture may be removed from the reactor.
The product mixture comprises the products of the hydrolysis or alcoholysis which are a car- bonyl compound or, alternatively the acetal or ketal of the carbonyl compound in case of an alcoholysis, and a hydroxy compound. The addition of a basic compound for neutralization is not necessary and any precipitates resulting from such addition are avoided. The products of the hydrolysis of the compound of formula I are compounds of formula II and III. The products of the hydrolysis or alcoholysis are obtained in high yields and selectivity.
The product mixture may optionally be further worked up or purified by distillation or rectification. The process of this invention is an easy and effective hydrolysis or alcoholysis of ketal or acetal compounds which comprise at least one amino group. The product of the hydrolysis or alcoholysis is obtained in high yield. The process is easy to perform and requires less work-up than a prior art process. No precipitates have to be removed by filtration as an additional step of neutralization with a basic compound is not necessary.
Comparison example: hydrolysis of solketalamine with sulfuric acid
Chemical Formula: C6H 3NC>2 Chemical Formula: C3HgN02
Molecular Weight: 131 ,18 Molecular Weight: 91 ,1 1
A flask was charged with 539 g of a 50% aqueous solution of H2SO4 and 655.5 g (2,2-dimethyl- 1 ,3-dioxolan-4-yl) methanamine obtained in example 1 were added dropwise within 2 h at 70 °C. After complete addition, stirring was continued at 70 °C for 1 h. During addition and stirring, acetone was removed continuously by distillation. Acetone removal was completed under reduced pressure and the solution was then treated at ambient temperature with 444.4 g of a 50% aqueous solution of NaOH. The precipitate was removed by filtration and the filter cake was washed with ca. 300 ml. of ethanol. The combined filtrates were concentrated under reduced pressure and the residue was distilled. 406 g (89% yield) of 3-aminopropane-1 ,2-diol (APD) were collected.
Example 1 : hydrolysis of solketalamine with carbon dioxide
Chemical Formula: C6H 3N02 Chemical Formula: C3HgN02
Molecular Weight: 131 ,18 Molecular Weight: 91 ,1 1
An autoclave was charged with 13.1 g of (2,2-dimethyl-1 ,3-dioxolan-4-yl) methanamine (solketalamine) obtained according to example 1 and 39.3 g of H2O. The autoclave was pressurized with 30 bar CO2 and the mixture was heated to 130 °C for 12 h. After depressurization, the composition of the mixture was analyzed by GC. The mixture contained 95% (area % determined from gas chromatography) of 3-aminopropane-1 ,2-diol (APD) (Conversion: >99%, Selectivity: 95%). Example 2: hydrolysis of /V-methylsolketalamine with carbon dioxide
Chemical Formula: C7H15N02 Chemical Formula: C H1 1 N02
Molecular Weight: 145,20 Molecular Weight: 105,14
An autoclave was charged with 4,0 g of 1 -(2,2-dimethyl-1 ,3-dioxolan-4-yl)-N
methylmethanamine (/V-methylsolketalamine) and 40 g of H2O. The autoclave was pressurized with 30 bar CO2 and the mixture was heated to 140 °C for 12 h. After depressurization, the composition of the mixture was analyzed by GC. The mixture contained 83% (area % deter- mined from gas chromatography) of 3-(methylamino) propane-1 ,2-diol (MAPD) (Conversion: >99%, Selectivity: 83%).
Claims
1 . Process for the hydrolysis or alcoholysis of a ketal or acetal compound wherein a ketal or acetal compound comprising at least one ketal or acetal group and at least one amino group is reacted with carbon dioxide and water or an alcohol.
2. Process according to claim 1 wherein the ketal or acetal compound is a compound with at least one cyclic ketal or cyclic acetal group.
3. Process according to any of claims 1 or 2 wherein the amino group is a primary or secondary amino group
4. Process according to any of claims 1 to 3 wherein the ketal or acetal compound comprises one ketal or acetal group and one amino group
5. Process according to claim 1 or 4 wherein the ketal or acetal compound comprises no other functional groups than ketal, acetal and amino groups.
6. Process according to any of claims 1 to 5 wherein the ketal or acetal compound has a molecular weight of at maximum 10OOg/mol.
7. Process according to any of claims 1 to 6 wherein the ketal or acetal compound is a compound of formula I
wherein R1 and R2 independently from one another represent a hydrogen atom or an organic group and
X represents an ethylene group CR3R4- CR5R6,
a propylene group CR7R8 -CR9R10 - CR11R12 or
a butylene group CR13R14- CR15R16- CR17R18 - CR19R20
with R3 to R20 independently from one another representing a hydrogen atom, an organic group or a primary amino group
with the provision that the compound of formula I comprises at least one amino group.
8. Process according to any of claims 1 to 7, wherein the ketal or acetal compound is (2,2- hyl-1 ,3-dioxolan-4-yl) methanamine (solketalamine) of formula
or a dimeric solketalamine derivative of formula
or (/V,2,2-trimethyl-1 ,3-dioxolane-4-yl)-methanamine of formula
or 5-amino-2,2-dimethyl-1 ,3-dioxane of formula
Process according to any of claims 1 to 8, wherein the process is a hydrolysis and the ketal or acetal compound is reacted with carbon dioxide and water.
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| EP17183300.7 | 2017-07-26 | ||
| EP17183300 | 2017-07-26 |
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Non-Patent Citations (3)
| Title |
|---|
| "Greene's Protective Groups in Organic Synthesis, Fourth Edition", 1 January 2007, article PETER G M WUTS ET AL: "PROTECTION FOR THE HYDROXYL GROUP, INCLUDING 1,2-AND 1,3-DIOLS", pages: 16 - 366, XP055406157 * |
| CHRISTOPHER M. RAYNER: "The Potential of Carbon Dioxide in Synthetic Organic Chemistry", ORGANIC PROCESS RESEARCH AND DEVELOPMENT, vol. 11, no. 1, 1 January 2007 (2007-01-01), US, pages 121 - 132, XP055505606, ISSN: 1083-6160, DOI: 10.1021/op060165d * |
| ORGANIC PROCESS RESEARCH & DEVELOPMENT, vol. 11, 2007, pages 121 - 132 |
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