Method for making end compounds from internal ketones issued from the decarboxylative ketonization of fatty acids or fatty acid derivatives

Abstract

Method (M) for the preparation of an end compound from an internal ketone, said method comprising: —synthesizing the internal ketone by a process (P) for the decarboxylative ketonization of a fatty acid, a fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst in the substantial absence of added solvent, wherein the fatty acid, fatty acid derivative or mixture thereof is added in sequential steps, the first step taking place at a temperature sequentially at a temperature from 100° C. to 270° C., —causing the internal ketone to react in accordance with a single or multiple chemical reaction scheme involving at least one reagent other than the internal ketone, wherein at least one product of the chemical reaction scheme is the end compound that is not further caused to be chemically converted into another compound.

Claims

1. A method M for the preparation of at least one end compound from at least one internal ketone, said method M comprising: synthesizing the internal ketone by a process P for the decarboxylative ketonization of at least one fatty acid, at least one fatty acid derivative or a mixture thereof in a liquid phase with a metal compound as catalyst, wherein a) in a first step, elementary metal or a metal compound and the fatty acid, fatty acid derivative or mixture thereof comprising at least 10 mol %, based on the entire amount of fatty acid or fatty acid derivative, of fatty acid having 12 carbon atoms or less or derivative of fatty acid having 12 carbon atoms or less, are mixed in a molar ratio of from 1:0.8 to 1:3.5 (molar ratio metal:carboxyl group equivalent) and reacted for a period P.sub.1 of from 5 min to 24 h at a temperature T.sub.1 of from 100° C. to 270° C. in the substantial absence of added solvent, and b) thereafter the temperature is raised to a temperature T.sub.2 which is strictly above 270° C. and up to 400° C., and additional fatty acid, fatty acid derivative or a mixture thereof comprising at least 10 mol %, based on the entire amount of fatty acid or fatty acid derivative, of fatty acid having 12 carbon atoms or less or derivative of such fatty acid, is added over a period of time P.sub.2 of from 5 min to 24 h in the substantial absence of added solvent until the molar ratio of fatty acid, fatty acid derivative or mixture thereof to metal is in the range of from 6:1 to 99:1, and causing the internal ketone to react in accordance with a single or multiple chemical reaction scheme involving at least one reagent other than the internal ketone, wherein at least one product of the chemical reaction scheme is the end compound that is not further caused to be chemically converted into another compound, with the proviso that when the internal ketone is caused to react by being subjected to a hydrogenation reaction to obtain a secondary alcohol, the so-obtained secondary alcohol is an intermediate that is in turn caused to react in accordance with a single or multiple reaction scheme that does not include a dehydration reaction that would convert said internal secondary alcohol into an internal olefin as an other intermediate or as the end compound, and the end compound differs from an α-sulfocarbonyl compound C1* of formula (1) ##STR00054## from an α-sulfocarbonyl compound C2* of formula (2) ##STR00055## and from a mixture thereof, wherein in above formulae (1) and (2) R.sub.1, R.sub.3 and R.sub.5, which may be the same or different at each occurrence, are hydrogen or a linear or branched alkyl chain having 1 to 20 carbon atoms, R.sub.2 and R.sub.4, which may be the same or different at each occurrence, are a linear or branched alkyl group having 4 to 24 carbon atoms and in which the alkyl chain may comprise one or more cycloaliphatic groups, and X is H or a cation forming a salt with the sulfonate group, and the end compound further differs from a surfactant C3* of formula (3) ##STR00056## from a diamine C4* of formula (4) ##STR00057## and from a mixture thereof, wherein in above formulae (3) and (4) each of R.sup.a and R.sup.b, which are identical or different, is a linear or branched, saturated or unsaturated, hydrocarbon chain that may be interrupted and/or substituted by at least a monocyclic or polycyclic group each of R.sup.c and R.sup.d, which are identical or different, is a linear or branched, alkyl chain having 1 to 10 carbon atoms each of (E.sup.1) and (E.sup.2) is a divalent hydrocarbon radical linear or branched, not substituted or substituted, A is: a carboxylate group —COO.sup.−, optionally in all or part in its protonated form —COOH; or a sulfonate group —SO.sub.3.sup.−, optionally in all or part in its protonated form —SO.sub.3H.

2. The process according to claim 1 wherein temperature T.sub.1 is from 230° C. to 270° C.

3. The process according to claim 1 wherein temperature T.sub.2 is from 280° C. to 320° C.

4. The method according to claim 1 wherein step a) is carried out at a temperature T.sub.1 of from 190° C. to 260° C. for a duration of from 15 min to 120 min and the fatty acid, fatty acid derivative or mixture thereof in step b) is added over a period P.sub.2 of from 2 hours to 12 hours.

5. The method according to claim 1 wherein, after the temperature has been raised to T.sub.2 and before the additional fatty acid, fatty acid derivative or mixture thereof is added over period of time P.sub.2, said temperature is maintained at temperature T.sub.2 during a period of time P.sub.12 of from 30 min to 300 min.

6. The method according to claim 1 wherein, after the additional fatty acid, fatty acid derivative or mixture thereof has been added over period of time P.sub.2, the temperature is maintained at temperature T.sub.2 during a period of time P.sub.23 of from 30 min to 300 min.

7. The method according to claim 1 wherein the internal ketone is caused to react directly with at least one reagent selected from the group consisting of ammonia, primary or secondary amines, mixtures of at least one aldehyde with ammonia or with at least one primary or secondary amine, and alkylating agents; and wherein the end compound is selected from the group consisting of twin tail primary, secondary or tertiary amines, twin-tail tertiary amines themselves substituted by one or two primary, secondary or tertiary amino groups, internal ketone monoamines, internal ketone diamines, (poly)aminocarboxylates twin-tail amines, twin tail quaternary ammonium salts, internal ketone mono-quaternary ammonium salts, internal ketone di-quaternary ammonium salts, aminoxide twin-tail amines, aminoxide Gemini compounds, dibetaine or disultaine twin-tail amines and betaine or sultaine Gemini compounds.

8. The method according to claim 1 wherein the internal ketone is caused to react directly with at least one reagent selected from the group consisting of diesters derived from tartaric acid, phenol and other aromatic mono- or polyalcohols, formaldehyde, pentareythritol, acrylates derivatives and hydrogen; and wherein the end compound is selected from the group consisting of dicarboxylate salt derivatives, non-ionic surfactants having a Gemini structure and ethylenically unsaturated monomers.

9. The method according to claim 1 wherein the end compound has a twin-tail Gemini structure.

10. The method according to claim 1 wherein the end compound is a surfactant.

11. The method according to claim 1 wherein the at least one internal ketone synthesized by the process P is a compound of formula (I) ##STR00058## wherein R.sub.n and R.sub.m independently represent a C.sub.3-C.sub.27 aliphatic group.

12. The method according to claim 11, wherein the at least one internal ketone of formula (I) is reacted with at least one amine of formula (II) under reductive amination conditions to afford the at least one twin-tail amine of formula (III) ##STR00059## wherein in the above amine formula (II), R.sub.1 and R.sub.2 independently represent: hydrogen or a linear or branched hydrocarbon radical having 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups, ethylamine of formula —CH.sub.2—CH.sub.2—NR′R″ wherein R′ and R″ independently represent hydrogen or a short alkyl group having from 1 to 6 carbon atoms, [poly(ethylenimine)]ethylamine of formula -(—CH.sub.2—CH.sub.2—NH—).sub.m—CH.sub.2—CH.sub.2—NR′R″ wherein R′ and R″ independently represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and m is an integer from 1 to 20, hydroxyethyl of formula —CH.sub.2—CH.sub.2—OH, [poly(ethylenimine)]ethanol of formula -(—CH.sub.2—CH.sub.2—NH—).sub.m—CH.sub.2—CH.sub.2—OH wherein m is an integer from 1 to 20, a N,N-dialkylaminoalkyl radical of formula —(CH.sub.2).sub.m—NR′R″ wherein m is an integer from 3 to 20 and R′ and R″ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and wherein R.sub.1 and R.sub.2 can also form an alkanediyl radical, which can be optionally interrupted or substituted by one or more heteroatoms or heteroatom containing groups.

13. The method according to according to claim 1 wherein the at least one internal ketone synthesized by the process P is a compound of formula (I′) ##STR00060## wherein R′.sub.n and R′.sub.m independently represent a C.sub.2-C.sub.26 aliphatic group.

14. The method according to according to claim 13 wherein the at least one internal ketone (I′) is reacted with at least one aldehyde of formula (IV) and at least one amine of formula (II) under Mannich reaction conditions to afford at least one ketone (Va) having one and only one of its carbonyl-adjacent carbon atoms substituted by an amine-containing group and/or at least one ketone (Vb) having both of its carbonyl-adjacent carbon atoms substituted by an amine-containing group (Gemine amine) ##STR00061## wherein, in the amine of formula (II), R.sub.1 and R.sub.2 independently represent: hydrogen or a linear or branched hydrocarbon radical having 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups, ethylamine of formula —CH.sub.2—CH.sub.2—NR′R″ wherein R′ and R″ independently represent hydrogen or a short alkyl group having from 1 to 6 carbon atoms, [poly(ethylenimine)]ethylamine of formula -(—CH.sub.2—CH.sub.2—NH—).sub.m—CH.sub.2—CH.sub.2—NR′R″ wherein R′ and R″ independently represent hydrogen or an alkyl group having from 1 to 6 carbon atoms and m is an integer from 1 to 20, hydroxyethyl of formula —CH.sub.2—CH.sub.2—OH, [poly(ethylenimine)]ethanol of formula -(—CH.sub.2—CH.sub.2—NH—).sub.m—CH.sub.2—CH.sub.2—OH wherein m is an integer from 1 to 20, a N,N-dialkylaminoalkyl radical of formula —(CH.sub.2).sub.m—NR′R″ wherein m is an integer from 3 to 20 and R′ and R″ independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and wherein R.sub.1 and R.sub.2 can also form an alkanediyl radical, which can be optionally interrupted or substituted by one or more heteroatoms or heteroatom containing groups, and, regarding the aldehyde (IV), R.sub.3 represents: hydrogen or a linear or branched hydrocarbon radical having from 1 to 24 carbon atoms which can be optionally substituted and/or interrupted by one or more heteroatoms or heteroatom containing groups, or an aromatic or a heterocyclic aromatic radical which can be optionally substituted by one or more branched or linear hydrocarbon radical which can optionally contain one or more heteroatom.

15. The method according to claim 12, wherein the at least one tertiary amine (III) is further reacted with at least one alkylating agent (VI) of formula R.sub.4—X to obtain at least one twin-tail quaternary ammonium salt (VII), as schemed below: ##STR00062## wherein, in the alkylating agent (VI), X is a leaving group and R.sub.4 represents a linear or branched hydrocarbon radical having 1 to 10 carbon atoms which can be optionally substituted and/or interrupted by a substituted or unsubstituted aromatic group and/or a heteroatom or heteroatom containing group.

16. The method according to claim 14, wherein the at least one ketone (Va) and/or the at least one ketone (Vb) is reacted with at least one alkylating agent (VI) of formula R.sub.4—X to obtain respectively at least one quaternary ammonium salt (VIIIa) and/or at least one quaternary ammonium salt Gemini compound (VIIIb), as schemed below: ##STR00063## wherein X is a leaving group and R.sub.4 represents a linear or branched hydrocarbon radical having 1 to 10 carbon atoms which can be optionally substituted and/or interrupted by a substituted or unsubstituted aromatic group and/or a heteroatom or heteroatom containing group.

17. The method according to claim 14, wherein the ketone (Va) or (Vb) or a mixture thereof is reduced using H.sub.2 or a secondary alcohol respectively to the alcohol derivative (XVa) or (XVb) or a mixture thereof: ##STR00064##

18. The method according to claim 17, wherein the tertiary amine group of the compound of formula (XVa) and/or the compound of formula (XVb) is oxidized using H.sub.2O.sub.2 to form respectively the aminoxide derivative of formula (XVIa) and/or the aminoxide Gemini compound of formula (XVIb): ##STR00065##

19. The method according to claim 13, further comprising the following steps: in a first step, at least one ketone (I′) is condensed with formaldehyde (CH.sub.2O) ##STR00066## in a second step, at least one product (XXVIa) and/or (XXVIb) is/are condensed with m+n equivalents of alkylene oxide (m equivalents of propylene oxide and/or n equivalents of ethylene oxide) to afford the non-ionic surfactants (XXVIIa) and/or (XXVIIb) ##STR00067## wherein: m and n are integers ranging from 0 to 40 but m and n cannot be both equal to 0, o, p, o′, p′, o″ and p″ are integers ranging from 0 to 40 and the following equalities must be respected:
o+o′+o″=m
p+p′+p″=n.

20. The method according to claim 11, further comprising the following steps: in a first step, the at least one internal ketone (I) is condensed with pentaerythritol to afford at least one intermediate (XXVIII) ##STR00068## in a second step, the at least one intermediate (XXVIII) is condensed with m+n equivalents of alkylene oxide (m equivalents of propylene oxide and/or n equivalents of ethylene oxide) to afford the non-ionic surfactant (XXIX) ##STR00069## wherein m and n are integers ranging from 0 to 40 provided at least one of m and n is of at least 1, m′, m″, n′ and n″ are integers ranging from 0 to 40 and the following equalities must be respected:
m′+m″=m
n′+n″=n.

Description

EXAMPLES

(1) The following examples show the effectiveness of the process P and further explain the process P of the present invention.

(2) They also show the effectiveness of the method M and further explain the method M of the present invention.

Example 1—Synthesis of 12-tricosanone (Diketone of Lauric Acid)

(3) The reaction was carried under argon in a round bottom flask equipped with mechanical stirring, Dean Stark apparatus and an addition funnel. In the reactor, 700 mg of iron powder were dispensed and 20 g of lauric acid was introduced into the addition funnel.

(4) A first partial amount of 5 g of acid was added into the reactor and the temperature was brought to 250° C. The mixture was stirred at this temperature for 30 minutes during which the color of the media changed to black and H.sub.2 gas was released.

(5) Then the temperature was raised to 300° C., the mixture was stirred during 1 h30 and the remaining amount of lauric acid (15 grams) was slowly added into the reactor during 4 h30 min at a flow rate which allowed keeping concentration of lauric acid in the reaction media very low (no accumulation of free acid in solution).

(6) At the end of the reaction, the addition funnel was replaced by a distillation apparatus and the products were distilled off at 290° C.-340° C. under 5 kPa pressure.

(7) Then the distillation apparatus was replaced by the addition funnel containing a new batch of 20 g of fatty acids and the operations described above were repeated for another cycle. No additional amount of iron was needed. The residue in the flask remaining after distillation was efficient to convert the next batch of acids.

(8) Overall 4 cycles were carried out without any loss of performances reducing thereby the concentration of iron to less than 1 wt % relative to fatty acids amount converted.

(9) The conversion, selectivity and yield (measured by gas chromatography (GC) and isolated) are given in Table 1 below.

(10) TABLE-US-00001 TABLE 1 (all values in % of theory) Cycle no. Conversion Selectivity Raw yield Isolated yield 1 100 90 90 77 2 100 89 89 70 3 100 87 87 85 4 100 89 89 87

(11) The data show the superior selectivity and yield of the desired ketone.

Example 2—Cut of Coco Fatty Acids as Starting Material

(12) Conversion of 400 g of coco fatty acids having the following weight distribution: C.sub.12: 55%, C.sub.14: 21%, C.sub.16:13%, C.sub.18: 12%.

(13) The transformation was carried out using 6.4 g of iron powder (1.6 wt %) and through 2 cycles involving a total of 200 g of fatty acids for each cycle.

(14) The reaction was carried under argon in a 11 round bottom flask equipped with mechanical stirring, Dean-Stark apparatus and an addition funnel.

(15) Into the 250 mL addition funnel 200 g of coco fatty acids were introduced which were maintained in molten form by an external heater.

(16) 6.4 g of iron powder were dispensed into the reactor and a first portion of fatty acids (around 58 mL) were added into the reactor. The mixture was stirred (500 rpm) at 250° C. during 30 minutes in order to convert metallic iron to iron salts. During this period, the mixture color changed to black and hydrogen was released. Then the temperature was raised to 300° C.-320° C. to perform the transformation to fatty ketones. The mixture was stirred at this temperature during 1 h30 and the remaining part of fatty acids was slowly added in the reactor during 5 hours at a flow which allowed keeping a low concentration of fatty acids in solution (no accumulation of free acids in solution). At the end of the reaction, the addition funnel was replaced by a distillation apparatus and the fatty ketones were recovered by distillation (290° C.-340° C., 5 kPa).

(17) A first crop of 141 g of fatty ketone was recovered as a white wax.

(18) The residue left in the reactor flask and mainly constituted of iron salts was used to convert the remaining 200 g of fatty acids in a second cycle. To achieve this, the distillation apparatus was replaced by the addition funnel containing 200 g of molten fatty acids and the operational steps described above were repeated.

(19) The total yield of the reaction after these 2 cycles was: 79% isolated as a white wax.

Example 3—Conversion of Internal Ketones to Secondary Alcohols Intermediates

(20) This example describes the hydrogenation of the ketones obtained in accordance with the present invention to obtain the corresponding secondary fatty acid alcohols. The reaction was carried out without any solvent using heterogeneous Pd/C (3%) as a catalyst and in an autoclave equipped with a Rushton turbine.

(21) The hydrogenation was carried out on a cut of internal fatty ketones obtained by condensation reaction performed on a cut of C.sub.12-C.sub.18 coco fatty acids following the procedure described in Example 2.

(22) The reaction was carried out in a 750 mL autoclave equipped with a Rushton turbine. 28 g of Pd/C (3%) and 280 g of fatty ketones were introduced into the reactor which was sealed. Then the temperature was brought to 80° C. and the mixture was stirred at 1000 rpm. The reactor atmosphere was purged 3 times with 4 MPa of nitrogen then 3 times with 3 MPa of hydrogen. The temperature was then raised to 150° C. and the mixture was stirred at this temperature maintaining 3 MPa of hydrogen until completion of the reaction (monitored by GC analysis). At the end of the reaction, the mixture was allowed to cool down to 80° C. and the reactor was purged with nitrogen. A 1st crop of the product (180 g) was obtained through filtration and the remaining part was extracted using 400 mL of hot toluene. After evaporation of the solvent, a total amount of 247 g of white solid was obtained corresponding to an isolated yield of 88%.

Example 4—Conversion of Secondary Alcohols Intermediates to Alkoxylated (Meth)Acrylates Useful as Monomers

(23) The secondary fatty acid alcohols of the preceding example are condensed with m=5 equivalents of propylene oxide followed by n=5 equivalents of ethylene oxide using common alkoxylation conditions for secondary fatty alcohols, so as to obtain another intermediate of formula

(24) ##STR00052##
wherein R.sub.n and R.sub.m are identical to R.sub.n and R.sub.m of the starting internal ketone and wherein m and n are approximately equal to 5.

(25) This other intermediate is then reacted according to a transesterification reaction respectively with methyl acrylate or methyl methacrylate to obtain the alkoxylated acrylate vs. methacrylate of formula

(26) ##STR00053##
wherein R.sub.1 is respectively hydrogen or methyl and R.sub.n and R.sub.m are identical to R.sub.n and R.sub.m of the starting internal ketone.

(27) This last reaction is carried out by contacting the secondary alcohol with methyl acrylate or methyl methacrylate for example at about 100° C., in the presence of an acidic or basic transesterification catalyst. The methyl acrylate or methyl methacrylate is added progressively in the reaction medium in order to avoid side-polymerization to occur.

Example 5—Comparative Example

(28) Lauric acid was mixed with 12.5 mol % of iron powder and heated to 298° C. (boiling point of lauric acid) and kept at this temperature for 5 hours. Thereafter the composition of the reaction product was determined. The yield of 12-tricosanone was only 18% and a significant amount of undecane was formed (8%). Furthermore, substantial amounts of unreacted lauric acid were still present (total conversion of lauric acid is 46%).

(29) This comparative example shows that adding the entire amount of acid in one step and not sequentially does not yield the desired ketones in a satisfactory yield and in addition a large amount of undesired by-products is formed.

Example 6—Synthesis of nonadecan-10-one (Diketone of C.SUB.10 .Capric Acid)

(30) The reaction was carried under argon in a 250 mL round bottom flask equipped with mechanical stirring, Dean-Stark apparatus and an addition funnel. In the reactor, 2.0 g (35.8 mmol) of iron powder were dispensed and 50 g (290.4 mmol) of capric acid were introduced into the addition funnel.

(31) A first partial amount of 12.5 g of capric acid was added into the reactor and the temperature was brought to 250° C. The mixture was stirred at this temperature during 1 h45. During this time the color of the media changed to black and H.sub.2 gas was released. FTIR analysis of the crude mixture showed complete formation of intermediate iron carboxylate.

(32) The temperature was then raised to 315° C. and the mixture was stirred during 1 h30 in order to transform the iron carboxlyate complex to ketone, CO.sub.2 and iron oxide.

(33) The remaining amount of capric acid (37.5 g) was then slowly added into the reactor during 5 h00 at a flow rate which allowed keeping concentration of capric acid in the reaction media very low (no accumulation of free acid in solution). In practise this could be done by the successive slow additions of fractions of 12.5 g of capric acid every 1.5 h.

(34) After the addition of capric acid was completed, the mixture was allowed to stir at 315° C. until the intermediate iron complex was not detected anymore by FTIR.

(35) When the reaction was completed, the mixture was allowed to cool down at room temperature and 200 mL of CHCl.sub.3 were added to the crude media. The mixture was stirred at 40° C. in order to solubilize the product (nonadecan-10-one). The obtained suspension was filtered on a silica plug and eluted using 1.5 L of chloroform. Evaporation of the solvent afforded 39.7 g (140.5 mmol) of the product nonadecan-10-one as an analytically pure yellow powder (97% isolated yield).

Example 7—Synthesis of a C.SUB.15.-C.SUB.35 .Ketones Cut Starting from a C.SUB.8.-C.SUB.18 .Coco Saturated Fatty Acids Cut

(36) The reaction was carried under argon in a 750 mL reactor equipped with mechanical stirring, Dean-Stark apparatus and an addition funnel. In the reactor, 6.8 g (0.12 mol) of iron powder were dispensed and 200 g (0.97 mol) of the coco saturated fatty acids cut (with the following distribution: C.sub.8: 7 wt %, C.sub.10: 8 wt %, C.sub.12: 48 wt %, C.sub.14: 17 wt %, C.sub.16: 10 wt %, C.sub.18: 10 wt %) were introduced into the addition funnel.

(37) A first partial amount of 50 g of fatty acids was added into the reactor and the temperature was brought to 250° C. The mixture was stirred at this temperature during 4 h00. During this time the color of the media changed to black and H.sub.2 gas was released. FTIR analysis of the crude mixture showed complete formation of intermediate iron carboxylate complexes.

(38) The temperature was then raised to 330° C. and the mixture was stirred at this temperature during 2 h00. During this period of time, the intermediate iron carboxylate complexes were decomposed to fatty ketones, iron oxide and CO2.

(39) The remaining fatty acids (150 g) were slowly introduced into the reactor, at a flow rate such that the temperature of the reaction medium did not fall down below 320° C. and which allowed keeping the concentration of fatty acids in the reaction medium very low. An average addition flow rate of around 25 g fatty acids/hour proved to be satisfactory. Practically, this was achieved through the successive slow additions (1 hour per addition) of 3 portions of 50 g of melted fatty acids followed by 1 hour of stirring at 330° C. between each addition.

(40) At the end of the third and last addition, the crude medium was stirred at 330° C. during 2 h and the reaction progress was monitored through FTIR. When the reaction was completed (no more iron complex detected by FTIR), the mixture was allowed to cool down at room temperature and 400 mL of CHCl.sub.3 was added to the crude media. The mixture was stirred at 40° C. in order to solubilize the product (C.sub.15-C.sub.35 ketones). The obtained suspension was filtered on a silica plug (400 g) and eluted using 3 L of chloroform. Evaporation of the solvent afforded 161 g (0.46 mol) of the product C.sub.15-C.sub.35 ketones as an analytically pure white wax (95% isolated yield).

(41) Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.