CATALYTIC OXIDATION OF BUT-3-ENE-1,2-DIOL

Abstract

The invention concerns a synthesis process of a compound of the following formula (I) or one of the salts thereof,

##STR00001## wherein R represents a COOH, CH.sub.2OH or CHO group, comprising the step according to which the but-3-ene-1,2-diol (BDO) is subjected to an oxidation in the presence of a catalyst, said catalyst comprising an active phase based on at least one noble metal selected from palladium, gold, silver, platinum, rhodium, osmium, ruthenium and iridium, and a support containing alkaline sites.

The invention also concerns the application of this reaction to the preparation of bioavailable compounds of methionine used, in particular, in animal nutrition.

Claims

1. A synthesis process of at least one compound of the following formula (I) or one of the salts thereof, ##STR00011## wherein R represents a COOH, CH.sub.2OH or CHO group, and wherein the but-3-ene-1,2-diol (BDO) is subjected to an oxidation in the presence of a catalyst, said catalyst comprising an active phase based on at least one noble metal selected from palladium, gold, silver, platinum, rhodium, osmium, ruthenium and iridium, and a support containing alkaline sites.

2. The process according to claim 1, wherein the active phase consists of palladium or of a mixture of palladium and at least one noble metal selected from platinum and gold.

3. The process according to claim 1, wherein the active phase consists of a noble metal or a mixture of noble metals in a content ranging from 0.005 to 50% by weight relative to the weight of the support in the oxide form.

4. The process according to claim 1, wherein the support comprises at least one of hydrotalcites (HT), brucites, hydroxyapatite Ca.sub.10(PO.sub.4).sub.6(OH).sub.2, tricalcium phosphate Ca.sub.3(PO.sub.4).sub.2, calcium hydrogenphosphate CaHPO.sub.4(0-2)H.sub.2O, calcium diphosphate Ca.sub.2P.sub.2O.sub.7, octacalcium phosphate Ca.sub.8H.sub.2(PO.sub.4).sub.6.5H.sub.2O, tetracalcium phosphate Ca.sub.4(PO.sub.4).sub.2O, amorphous calcium phosphates Ca.sub.3(PO.sub.4).sub.2.nH.sub.2O, oxides, hydroxides, carbonates, bicarbonates, phosphates, diphosphates, and calcium hydrogenphosphates, cesium, lithium, rubidium, potassium, magnesium, barium, cerium, lanthanum, aluminum, zinc, copper, and mixtures thereof.

5. The process according to claim 4, wherein the support comprises compounds corresponding to the following formulas A, B and C, and mixtures thereof:
M.sub.α[Al.sub.(1-b)La.sub.b]A.sup.z−].sub.c  Formula (A) wherein M is selected from the group composed of Mg.sup.2+, Ca.sup.2+, Sr.sup.2+, Ba.sup.2+, Ra.sup.2+, and combinations thereof, A.sup.z− is a monovalent or divalent anion selected from the group composed of carbonate (CO.sub.3.sup.2−, wherein the charge <<z>> is given by z=2), oxide (O.sup.2−, wherein z=2), hydroxide (OH.sup.−, wherein z=1), and bicarbonate (HCO.sub.3.sup.−, wherein z=1) or a mixture (A.sup.z′−.sub.xA.sup.z″−.sub.y) of divalent and monovalent anions with A.sup.z′− and A.sup.z″− of different anions, with A.sup.z− is A.sup.z′−.sub.xA.sup.z″−.sub.y with a charge z given by z=x(z′)+y(z″) and x+y=1 α varies from 0.01 to 0.4 b varies from 0.0011 to 0.11
c=(2α/z)+[3(1−b)/z]+(3b/z)
(M.sub.dM′.sub.eM″.sub.fM′″.sub.g).sub.5(PO.sub.4).sub.3(OH)  Formula (B) wherein M is Mg.sup.2+; M′ is Ca.sup.2+; M″ is Sr.sup.2+; M′″ is Ba.sup.2+ d varies from 0 to 1 e varies from 0 to 0.5 f varies from 0 to 1 g varies from 0 to 1
d+e+f+g=1
(M.sub.dM′.sub.eM″.sub.fM′″.sub.g).sub.3(PO.sub.4).sub.2  Formula (C) wherein M is Mg.sup.2+; M′ is Ca.sup.2+; M″ is Sr.sup.2+; M′″ is Ba.sup.2+ d varies from 0 to 1 e varies from 0 to 1 f varies from 0 to 1 g varies from 0 to 1
d+e+f+g=1.

6. The process according to claim 1, wherein the catalyst comprises a promoter selected from bismuth, lead, antimony, tin, niobium, tellurium, indium, gallium, zinc, copper, nickel, cobalt, silver, tungsten, molybdenum, zirconium, vanadium, chromium, manganese, iron, cerium, praseodymium, samarium, titanium and mixtures thereof.

7. The process according to claim 1, wherein the content of the promoter of the catalyst ranges from 0.005% to 500%, by weight relative to the weight of the support in the oxide form.

8. The process according to claim 1, wherein the BDO is in aqueous solution, in a concentration ranging from 1 to 70% by weight relative to the weight of the solution.

9. The process according to claim 1, wherein oxidation is carried out in the presence of a catalyst whose active phase is selected from palladium and the mixtures of palladium and platinum and the alkaline site support is selected from hydroxyapatite and hydrotalcite, and the compound (I) is the vinyl keto alcohol (CALV).

10. A synthesis process of at least one compound of the following formula (II) or one of the salts thereof, ##STR00012## wherein R′ represents a COOR1 or CH.sub.2OR2 group for which R1 and R2, identical or different, represent a group selected from the alkyl groups, linear or branched, having from 1 to 12 carbon atoms, and the cycloalkyl groups having from 3 to 12 carbon atoms, wherein the but-3-ene-1,2-diol (BDO) is subjected to an oxidation in the presence of a catalyst, said catalyst comprising an active phase based on at least one noble metal selected from palladium, gold, silver, platinum, rhodium, osmium, ruthenium and iridium, and a support containing alkaline sites, in order to obtain a compound of the following formula (I), ##STR00013## wherein R represents a COOH, CH.sub.2OH or CHO group, according to claim 1, and and the esterification or the etherification of the compound of formula (I) is carried out in order to obtain the compound of formula (II).

11. A synthesis process of at least one compound of the following formula (III) or one of the salts thereof, ##STR00014## wherein R″ represents a COOH, COOR1, CH.sub.2OH, CH.sub.2OR2 or CHO group for which R1 and R2, identical or different, represent an alkyl group, linear or branched, having 1 to 12 carbon atoms, and the cycloalkyl groups having 3 to 12 carbon atoms, wherein the but-3-ene-1,2-diol (BDO) is subjected to an oxidation in the presence of a catalyst in order to obtain at least one compound of the following formula (I) or one of the salts thereof, ##STR00015## wherein R represents a COOH, CH.sub.2OH or CHO group, according to a process defined in claim 1, if R″ represents a COOR1 or CH.sub.2OR2 group, the esterification or the etherification of the compound of formula (I) is carried out in order to obtain the compound of the following formula (II) or one of the salts thereof, ##STR00016## wherein R′ represents a COOR1 or CH.sub.2OR2 group for which R1 and R2, identical or different, represent a group selected from the alkyl groups, linear or branched, having from 1 to 12 carbon atoms, and the cycloalkyl groups having from 3 to 12 carbon atoms, and, said compound (I) or said compound (II) or said one of the salts thereof is reacted with methyl mercaptan in order to obtain said compound (III) or one of the salts thereof, at least.

12. The process according to claim 11, wherein the oxidation is carried out and the compound (III) is 1-hydroxy-4-methylthiobutan-2-one.

Description

EXAMPLES

Example 1: Preparation of Oxidation Catalysts for Implementing a Process According to the Invention

[0100] In the preparations hereinafter, the active phase content is expressed by weight of the one or more metals consisting it relative to the weight of the support in the oxide form.

[0101] Preparation of 2% Pd/HAP (Catalyst 4)

[0102] To 4 mL of an aqueous solution of H.sub.2PdCl.sub.4 containing 20 mg of Pd was added at ambient temperature under vigorous stirring 0.98 g of hydroxyapatite (HAP, Ca.sub.10(PO.sub.4).sub.6(OH).sub.2), as described in the literature [K. Mori, T. Hara, T. Mizugaki, K. Ebitani, K. Kaneda, J. Am. Chem. Soc. (2004) 126 (34):10657-10666]).

[0103] Preparation of 2% PdPt/HAP 50-50 (Catalyst 5)

[0104] The procedure for the preparation of the catalyst 4 was used but starting with 4 mL of an aqueous solution of H.sub.2PdCl.sub.4 and H.sub.2PtCl.sub.6 containing 10 mg of Pd and 10 mg of Pt.

[0105] Preparation of 4% Pd 1% Pt/HAP (Catalyst 8)

[0106] To 10 mL of an aqueous solution of H.sub.2PtCl.sub.6 and H.sub.2PdCl.sub.4 containing 10 mg of Pt and 40 mg of Pd was added at ambient temperature 0.95 g of HAP. The solution was stirred at 40° C. for 2 h then evaporated to dryness. The resulting solid was crushed and calcined at 400° C. for 3 h.

[0107] Preparation of 5% Pd/HAP (Catalyst 9)

[0108] The procedure for the preparation of the catalyst 4 was used but starting from 10 mL of an aqueous solution of H.sub.2PdCl.sub.4 containing 50 mg of Pd and by using 0.95 g of HAP.

[0109] Preparation of 2% Pd/HAP (Catalyst 10)

[0110] The procedure for the preparation of the catalyst 8 was used but starting from 20 mL of an aqueous solution of H.sub.2PdCl.sub.4 containing 100 mg of Pd and by using 4.90 g of HAP.

[0111] Preparation of 4% Pd 1% Pt/HT (Catalyst 11)

[0112] The procedure for the preparation of the catalyst 8 was used but by using 0.95 g of Mg—Al hydrotalcite (HT, Mg/Al=5) prepared according to a procedure of the literature [N. K. Gupta, S. Nishimura, A. Takagaki, K. Ebitani, Green Chem. (2011) 13:824-827].

[0113] Preparation of 2% Pd/HAP without Calcination (Catalyst 12)

[0114] The procedure for the preparation of the catalyst 8 was used but after evaporation, instead of being calcined, the catalyst was dried in an oven at 70° C. for 3 days.

Example 2: Oxidation of but-3-Ene-1,2-Diol (BDO) with the Catalysts of the Example 1, According to the Invention

[0115] Oxidation of BDO with the Catalyst 4

[0116] The catalyst 4 (30 mg) has been introduced into a glass tube, placed under oxygen via 3 vacuum/oxygen cycles then a BDO solution (0.1 M, 3 mL) in water has been introduced. The mixture was stirred (600 rotations/minute) at 50° C. under O.sub.2 (1 atm) during 5 h. After returning to ambient temperature, the catalyst was separated by filtration and the solution was analyzed by HPLC (IR and UV detectors) and GC/GC-MS in order to determine the conversion and the selectivity of the products.

[0117] The conversion of BDO is of 73%. The selectivity for CALV is of 87%.

[0118] Oxidation of BDO with the Catalyst 5

[0119] The test procedure of the catalyst 4 was repeated but by using the catalyst 5 (30 mg).

[0120] The conversion of BDO is 55%. The selectivity for CALV is of 89%.

[0121] Oxidation of BDO with the Catalyst 5 (1 M BDO Solution)

[0122] The test procedure of the catalyst 1 was repeated but by using the catalyst 5 and a 0.1 M BDO solution (3 mL).

[0123] The conversion of BDO is of 28%. The selectivity for CALV is of 59%.

[0124] Oxidation of BDO with the Catalyst 8

[0125] The test procedure of the catalyst 4 was repeated but by using the catalyst 8 (30 mg).

[0126] The conversion of BDO is of 92%. The selectivity for CALV is of 85%.

[0127] Oxidation of BDO with the Catalyst 9

[0128] The test procedure of the catalyst 4 was repeated but by using the catalyst 9 (30 mg).

[0129] The conversion of BDO is of 88%. The selectivity for CALV is of 88%.

[0130] Oxidation of BDO with the Catalyst 10

[0131] The test procedure of the catalyst 4 was repeated but by using the catalyst 10 (30 mg).

[0132] The conversion of BDO is of 66%. The selectivity for CALV is of 87%.

[0133] Oxidation of BDO with the Catalyst 11

[0134] The test procedure of the catalyst 4 was repeated but by using the catalyst 11 (30 mg).

[0135] The conversion of BDO is of 83%. The selectivity for CALV.

[0136] Oxidation of BDO with the Catalyst 12

[0137] The test procedure of the catalyst 4 was repeated but by using the catalyst 12 (30 mg).

[0138] The conversion of BDO is of 83%. The selectivity for CALV is of 88%.

Example 3: Oxidation of but-3-Ene-1,2-Diol (BDO) with Recycled Catalysts of Example 1, According to the Invention

[0139] Oxidation of BDO with the Catalyst 4 (2% Pd/HAP)

[0140] It is carried out under the conditions described in the example 3, with the catalyst 4. At the end of the reaction, the catalyst is separated from the reaction medium by centrifugation, washed 5 times with demineralized water and dried overnight at 70° C.

[0141] The BDO conversion and the selectivity of the process for CALV are illustrated in FIG. 1, for each test, the first column representing the percent conversion of BDO, the second representing the selectivity for CALV.

[0142] Oxidation of BDO with the Catalyst 5 (2% PdPt/HAP)

[0143] It is carried out under the conditions described in the example 3, with the catalyst 5. At the end of the reaction, the catalyst is separated from the reaction medium by centrifugation, washed 5 times with demineralized water and dried overnight at 70° C.

[0144] The BDO conversion and the selectivity of the process for CALV are shown in FIG. 2, for each test, the first column representing the percent conversion of BDO, the second representing the selectivity for CALV.

[0145] It appears from this example that the catalysts of the invention are recyclable. Their recycling does not in any way affect the selectivity of the oxidation reaction and reduces only slightly the BDO conversion rate.