Adipate-type compounds and a process of preparing it

Abstract

The present invention regards new adipate-type compounds suitable as an intermediate in organic chemistry, a platform chemical for the production of other chemicals, and as a monomer and co-monomer useful for the preparation of polymers and copolymers. The invention also regards the process of preparing the new adipate-type compounds from bio-based raw materials such as sugars.

Claims

1. A compound of the formula I: ##STR00022## wherein either: R.sup.1 is selected from the group consisting of H and C.sub.1-C.sub.2 alkyl; and R.sup.2 is CH.sub.3, or R.sup.1 is CH.sub.3; and R.sup.2 is selected from the group consisting of H and CH.sub.3.

2. The compound according to claim 1, wherein R.sup.1 is CH.sub.3 and R.sup.2 is H.

3. The compound according to claim 1, wherein R.sup.1 is selected from the group consisting of H, CH.sub.3, and CH.sub.2CH.sub.3 and R.sup.2 is CH.sub.3.

4. The compound according to claim 1, wherein R.sup.1 and R.sup.2 each are CH.sub.3.

5. The compound according to claim 1, wherein the CC double bond of Compound (I) is in (E) configuration.

6. A composition comprising a compound of formula (I) according to claim 1.

7. The composition according to claim 6, further comprising a solvent.

8. The composition according to claim 6, wherein at least 80 wt % of the compound of formula (I) is in (E)-configuration.

9. A process comprising the steps of: i) providing a compound of the formula: ##STR00023## wherein R.sup.1 is selected from the group consisting of H and C.sub.1-C.sub.2 alkyl; and R.sup.2 is selected from the group consisting of H and CH.sub.3; ii) providing a catalyst material catalyzing a metathesis reaction; iii) converting the compound of i) in the presence of the catalytic material of ii); and iv) recovering a reaction product comprising a compound of formula (I): ##STR00024## wherein R.sup.1 and R.sup.2 are as defined in formula (II).

10. The process according to claim 9, wherein the conversion temperature of iii) is in the range of from 20 to 120 C.

11. The process according to claim 9, wherein step iii) is continued for a period of time in the range of from 5 minutes to 24 hours.

12. The process according to claim 9, wherein the conversion step of iii) is conducted at a pressure in the range of from 1 to 1000 kPa.

13. The process according to claim 9, wherein the conversion step of iii) is conducted without the addition of solvent.

14. The process according to claim 13, wherein the compound of the formula (II) is provided in a feed comprising at least 50 wt % of the compound (II).

15. The process according to claim 9, wherein the conversion step of iii) is conducted in the presence of an alkyl lactate.

16. The process according to claim 9 conducted under continuous conditions.

17. The process according to claim 9, wherein: R.sup.1 is H; and R.sup.2 is H.

18. The process according to claim 9, wherein: R.sup.1 is H; and R.sup.2 is CH.sub.3.

19. The process according to claim 9, wherein: R.sup.1 is CH.sub.3; and R.sup.2 is H.

20. The process according to claim 9, wherein: R.sup.1 is CH.sub.3; and R.sup.2 is CH.sub.3.

21. The process according to claim 9, wherein: R.sup.1 is CH.sub.2CH.sub.3; and R.sup.2 is H.

22. The process according to claim 9, wherein: R.sup.1 is CH.sub.2CH.sub.3; and R.sup.2 is CH.sub.3.

23. The compound according to claim 1, wherein R.sup.1 is H and R.sup.2 is CH.sub.3.

24. The compound according to claim 1, wherein R.sup.1 is CH.sub.2CH.sub.3 and R.sup.2 is CH.sub.3.

Description

EXAMPLE

Example 1: Preparation of 2,5-dihydroxy-hex-3-enedioic acid dimethyl ester

(1) In a clean dry glass flask equipped with a coldfinger condenser and a spigot suitable for connection to a vacuum outlet/gas inlet was placed a magnetic stirbar and the metathesis catalyst. The flask was evacuated and purged with dry nitrogen several times. Methyl Vinyl Glycolate (the substrate) and optionally solvent (examples 3, 4 and 5) was added to the reaction vessel by the use of a syringe to form a reaction mixture. The reaction mixture was heated in an oil bath at 80 C. for 18 hours under a nitrogen atmosphere. After cooling to room temperature the metathesis product was obtained (or recovered) as a colorless solid. The compound was purified by recrystallization from ethyl acetate. All of the Grubbs catalysts used are ruthenium based.

(2) TABLE-US-00001 TABLE 1 Yield of 2,5-dihydroxy-hex-3-enedioic acid dimethyl ester from MVG. Amount of Solvent/ Loading/ substrate/ relative Yield/ Catalyst mol % mmol volume mol % 1 Grubbs 1st gen. 5 10 8% 2 Grubbs 2nd gen. 0.3 5 74% 3 Grubbs 2nd gen. 0.3 2.5 Toluene 1:1 55% 4 Grubbs 2nd gen. 0.3 5 Toluene 2:1 63% 5 Grubbs 2nd gen. 2.2 2.5 EtOAc 4:1 46% 6 Grubbs 2nd gen. 0.4 10 75% 7 Grubbs 2nd gen. 0.4 19 85% 8 Grubbs 2nd gen. 0.4 39 88% 9 Hoveyda-Grubbs 0.4 2.5 73% 2nd gen. 10 Hoveyda-Grubbs 0.4 19 93% 2nd gen. 11 Hoveyda-Grubbs 0.2 19 90% 2nd gen. 12 Hoveyda-Grubbs 0.05 20 77% 2nd gen. 13 Hoveyda-Grubbs 0.045 39 80% 2nd gen.

(3) The resulting product has 2 stereocenters, corresponding to three different stereoisomers, of which one is a meso form. Taking into account the possibility of forming both the (E)- and the (Z)-isomer, the total number of different isomers amounts to six. Surprisingly, the reaction yields only one isomeric form of the product, which was determined by X-ray diffraction to be the meso form of the (E)-isomer. NMR spectra of the crude reaction mixture show no signals from a (Z)-double bond, and a GC of the crude reaction mixture show no presence of other diastereomeric forms.

(4) It appears from rows 3, 4 and 5 that the yields are lower, when a solvent is addet to the reaction mixture.

Example 2: Preparation of a Compound of Formula (VII) from MVG

(5) In a 50 ml round bottomed flask is put 5.0 g of MVG (43.1 mmol), 1.3 g of ethylene glycol (21.0 mmol) and 25 ml of anhydrous toluene. Finally, 500 mg of strongly acidic resin is added (Amberlyst 15) and the product mixture is refluxed gently for one hour. The flask is fitted with a distillation head and over the course of two hours, 15 ml of liquid is distilled from the flask. The residue is cooled to room temperature and filtered and then concentrated to obtain around 5 ml of liquid product which is purified by column chromatography to obtain the diester of ethylene glycol and vinyl glycolic acid (compound (VII).

Example 3: Preparation of 6,9-dihydroxy-2,3,6,9-tetrahydro-[1,4]dioxecine-5,10-dione (Compound (VIII))

(6) compound (VIII) is made according to this method:

(7) In a 25 ml round bottomed flask containing 10 ml toluene is added 2.26 g of 2-hydroxybut-3-enoic acid 2-(2-hydroxy-but-3-enoyloxy)-ethyl ester (compound VII) and 31.0 mg of Hoveyda Grubbs 2.sup.nd generation catalyst under argon atmosphere (0.5% loading). The flask is heated on an oil bath at 80 C. for 18 hours. Analysis of the reaction mixture by GCMS shows that the starting material is almost completely converted and a new peak with M/Z 198, corresponding to compound (VIII) appears.

Example 4: Preparation of 7,10-dihydroxy-1,5-dioxa-cycloundec-8-ene-6,11-dione (Compound (X))

(8) compound (X) is made according to this method:

(9) In a 25 ml round bottomed flask containing 10 ml toluene is added 2.40 g of 2-hydroxybut-3-enoic acid 3-(2-hydroxy-but-3-enoyloxy)-propyl ester (compound IX) and 31.0 mg of Hoveyda Grubbs 2.sup.nd generation catalyst under argon atmosphere (0.5% loading). The flask is heated on an oil bath at 80 C. for 18 hours. Analysis of the reaction mixture by GCMS shows that the starting material is almost completely converted and a new peak with M/Z 212, corresponding to compound (X) appears.

EMBODIMENTS

Embodiment 1

(10) A compound of the formula I:

(11) ##STR00015## wherein R.sup.1 is selected from the group consisting of H; and C.sub.1-C.sub.12 alkyl; optionally substituted with a heteroatom selected from N, O, F, P, S, Cl, Br, and I; R.sup.2 is selected from the group consisting of H; and CH.sub.3.

Embodiment 2

(12) The compound according to embodiment 1, wherein R.sup.2 is H.

Embodiment 3

(13) The compound according to any one of embodiments 1 or 2, wherein R.sup.1 is selected from the group consisting of H, CH.sub.3 or CH.sub.2CH.sub.3, C.sub.3H.sub.7 and C.sub.4H.sub.9.

Embodiment 4

(14) The compound according to embodiment 1, wherein R.sup.1 and R.sup.2 each are CH.sub.3.

Embodiment 5

(15) The compound according to any one of embodiments 1 to 4, wherein the double bond is (E) configuration.

Embodiment 6

(16) A process for preparing the compound according to any one of embodiments 1 to 5 comprising the steps of: a. providing a compound of the formula:

(17) ##STR00016##
wherein
R.sup.1 is selected from the group consisting of H; and C.sub.1-C.sub.12 alkyl; optionally substituted with a heteroatom selected from O, N, S, F, Cl, Br, and I;
R.sup.2 is selected from the group consisting of H; and CH.sub.3; b. providing a catalyst material catalysing a metathesis reaction; c. converting the compound of i) in the presence of the catalytic material of ii); and d. recovering the reaction product.

Embodiment 7

(18) The process according to embodiment 6, wherein the conversion temperature of iii) is in the range of from 20 to 120 C.

Embodiment 8

(19) The process according to any one of embodiments 6 or 7, wherein step iii) is continued for a period of time in the range of from 5 minutes to 24 hours.

Embodiment 9

(20) The process according to any one of embodiments 6 to 8, wherein the conversion step of iii) is conducted without the addition of solvent.

Embodiment 10

(21) The process according to any one of embodiments 6 to 8, wherein the conversion step of iii) is conducted in the presence of an alkyl lactate, such as methyl, ethyl lactate or a mixture thereof.

Embodiment 11

(22) The process according to any one of embodiments 6 to 10, wherein the catalytic material of step ii) comprises a compound of the formula:

(23) ##STR00017## wherein M is a transition metal, for example ruthenium, molybdenum, osmium, chromium, rhenium and tungsten, preferably a group 8 transition metal; L.sup.2 and L.sup.3 are neutral electron donor ligands; n is 0 or 1; m is 0, 1 or 2; X.sup.1 and X.sup.2 are anionic ligands; R.sup.1 and R.sup.2 are each selected independently from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom containing hydro-carbyl, substituted heteroatom containing hydro-carbyl, and functional groups; and L.sup.1 is a carbene of the formula:

(24) ##STR00018## Wherein Y and Z are heteroatoms, such as N, O, S or P, and if X and/or Y are O or S, then p and/or q are 0, respectively, Q1, Q2, Q3 and Q4 are linkers, such as hydrocarbylene (including substituted hydrocarbylene, heteroatom containing hydro-carbylene, substituted heteroatom containing hydro-carbylene) or (CO), and two or more substituents on adjacent atoms within Q1, Q2, Q3 and Q4 may be linked to form an additional cyclic group; s, t, u, v are each 0 or 1 R3, R4, R5 and R6 are each selected independently from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom containing hydrocarbyl, substituted heteroatom containing hydro-carbyl, and functional groups.

Embodiment 12

(25) The process according to embodiment 11, wherein the catalytic material of step ii) comprises a compound of the formula:

(26) ##STR00019## wherein M, L2, L3, n, X1, X2, R1, R2 are as defined previously, and Preferably at least one, and more preferably both, of the substituents R3 and R4 are alicyclic or aromatic and may or may not contain heteroatoms and/or substituents. Q is a linker selected from the group consisting of hydrocarbylenes, substituted hydrocarbylenes, heteroatom containing hydro-carbylenes, and substituted heteroatom containing hydrocarbylenes, where two or more adjacent substituents in Q may be linked to form a polycyclic structure of two or more fused rings, so that the entire ligand is an N-heterocyclic Carbene (NHC) ligand.

Embodiment 13

(27) The process according to any one of embodiments 6 to 10, wherein the catalytic material of step ii) comprises a compound of the formula:

(28) ##STR00020## Wherein M, L1, L2, L3, n, X1, X2, R1, R2 are as defined previously, and L2 and R2 are linked to form a bidentate ligand.

Embodiment 14

(29) The process according to embodiment 13, wherein the catalytic material of step ii) comprises a compound of the formula:

(30) ##STR00021## Wherein M, L1, L2, L3, n, X1, X2, R1, R2, R3, R4 and Q are as defined previously, and L2 and R2 are linked to form a bidentate ligand.

Embodiment 15

(31) The process according to any one of embodiments 6 to 14 conducted under continuous conditions.

Embodiment 16

(32) A process of preparing 2,5-dihydroxy-hex-3-enedioic acid or esters thereof comprising the steps of: i. Providing a feedstock solution of a sugar composition; ii. Converting the sugar in the presence of a metallo-silicate material and one or more metal ions, such as one or more of potassium ion, sodium ion, lithium ion, rubidium ion and caesium ion; iii. providing a catalyst material catalysing a metatesis reaction; iv. converting the compound of i) in the presence of the catalytic material of ii) iv) recovering the reaction product.