Production of xylene derivatives

Abstract

The present invention relates to the production of xylene derivatives from furfural and its derivatives. The invention describes new routes for converting furfural and its derivatives into xylene derivatives including novel intermediates.

Claims

1. A process for the preparation of a compound of the Formula (I) ##STR00040## wherein X and Y are O, or X and Y are S; R is a C.sub.1-4 alkylene group which may optionally be substituted with one or more R.sup.1; R.sup.1 is a linear, branched and/or cyclic, saturated or unsaturated hydrocarbon alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more functional nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups; R.sup.2 independently is H, alkyl, alkenyl or aryl; and R.sup.3 and R.sup.4 independently are H or CN, provided that at least one of R.sup.3 and R.sup.4 is CN; and R.sup.5 is R.sup.2, CH.sub.2OR.sup.2, CO.sub.2R.sup.2 or ##STR00041## the process comprising reacting a compound of the Formula (II) ##STR00042## wherein X, Y, R, R.sup.2 and R.sup.5 are defined as above; with a compound of the Formula (III) or (III) ##STR00043## wherein R.sup.3 and R.sup.4 are defined as above.

2. The process according to claim 1, wherein R is CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH(CH.sub.3)CH(CH.sub.3) or CH.sub.2C(CH.sub.3).sub.2CH.sub.2.

3. The process according to claim 1, wherein R.sup.2 is H.

4. A process for the preparation of a compound of Formula (IV) ##STR00044## wherein R.sup.2 independently is H, alkyl, alkenyl or aryl; R.sup.3 and R.sup.4 independently are H or CN, provided that at least one of R.sup.3 and R.sup.4 is CN; R.sup.5 is R.sup.2, CH.sub.2OR.sup.2, CO.sub.2R.sup.2 or ##STR00045## wherein X and Y are O, or X and Y are S; R is a C.sub.1-4 alkylene group which may optionally be substituted with one or more R.sup.1; and R.sup.1 is a linear, branched and/or cyclic, saturated or unsaturated alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups; the process comprising a) dehydration/aromatization of a compound of the Formula (I) ##STR00046## wherein X, Y, R, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are defined as above; to obtain a compound of the Formula (V) ##STR00047## wherein X, Y, R, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are defined as above; followed by deprotection of the compound of Formula (V); or comprising b) carrying out the dehydration/aromatization and the deprotection of the compound of Formula (I) in a single step.

5. The process according to claim 4, wherein R is CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH(CH.sub.3)CH(CH.sub.3) or CH.sub.2C(CH.sub.3).sub.2CH.sub.2.

6. The process according to claim 4, wherein R.sup.2 is H.

7. The process according to claim 4, wherein the compound of Formula (I) is obtained by reacting a compound of the Formula (II) ##STR00048## wherein X and Y are O, or X and Y are S; R is a C.sub.1-4 alkylene group which may optionally be substituted with one or more R.sup.1; R.sup.1 is a linear, branched and/or cyclic, saturated or unsaturated alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups; R.sup.2 independently is H, alkyl, alkenyl or aryl; and R.sup.5 is R.sup.2, CH.sub.2OR.sup.2, CO.sub.2R.sup.2 or ##STR00049## with a compound of the Formula (III) or (III) ##STR00050## wherein R.sup.3 and R.sup.4 independently are H or CN, provided that at least one of R.sup.3 and R.sup.4 is CN.

8. A compound of the Formula (I) ##STR00051## wherein X and Y are O, or X and Y are S; R is a C.sub.1-4 alkylene group which may optionally be substituted with one or more R.sup.1; R.sup.1 is a linear, branched and/or cyclic, saturated or unsaturated alkyl, alkenyl, alkynyl, or aromatic group which optionally bears one or more nitro, nitroso, sulfo, sulfonate, cyano, cyanato, thiocyanato, amino, hydroxyl, or carboxyl groups; R.sup.2 independently is H, alkyl, alkenyl or aryl; R.sup.3 and R.sup.4 independently are H or CN, provided that at least one of R.sup.3 and R.sup.4 is CN; and R.sup.5 is R.sup.2, CH.sub.2OR.sup.2, CO.sub.2R.sup.2 or ##STR00052## provided that X and Y are O; and/or R is a C.sub.1-4 alkylene group which is substituted with one or more R.sup.1.

9. The compound according to claim 8, wherein R is CH.sub.2CH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH(CH.sub.3)CH(CH.sub.3) or CH.sub.2C(CH.sub.3).sub.2CH.sub.2.

10. The compound according to claim 8, wherein R.sup.2 is H.

11. A method comprising obtaining 3- or 2-cyanobenzaldehyde or 2,3-dicyanobenzaldehyde from a compound of Formula (I) made according to the process of claim 1 and converting the 3- or 2-cyanobenzaldehyde or 2,3-dicyanobenzaldehyde into 3-cyanobenzoic acid, 2-cyanobenzoic acid or 2,3-dicyanobenzoic acid, respectively.

12. The method according to claim 11, further comprising converting 3-cyanobenzoic acid, 2-cyanobenzoic acid or 2,3-dicyanobenzoic acid into isophthalic acid, orthophthalic acid or hemimellitic acid.

13. The method according to claim 11, further comprising converting 3-cyanobenzoic acid, 2-cyanobenzoic acid or 2,3-dicyanobenzoic acid into 3-aminomethylbenzoic acid, 2-aminomethylbenzoic acid or 2,3-di(aminomethyl)benzoic acid.

14. The compound according to claim 8, wherein X and Y are O.

15. The compound according to claim 8, wherein R is a C.sub.1-4 alkylene group which is substituted with one or more R.sup.1.

Description

EXAMPLE 1

(1) 1.1 Furfuryl Dioxolane Synthesis

(2) ##STR00024##

(3) In a two-neck round bottom flask with Dean-Stark trap and magnetic stirring bar, furfural (10.0 g; 103 mmol), toluene (400 ml) and ethylene glycol (4.5 g; 72.5 mmol) were added. Then, camphorsulfonic acid (270 mg; 1.2 mmol) was added to the mixture. The reaction mixture was stirred under reflux during 5 h. The mixture was then cooled to room temperature and was washed with saturated aqueous solution of NaHCO.sub.3 (50 ml, 3 times) and then with water (50 ml, 3 times). After drying (MgSO.sub.4), the solvent was evaporated and the residue purified by flash chromatography (silica gel, EtOAc/cyclohexane), yielding 8.6 g (85%) of a slight yellow liquid.

(4) 1H-NMR (400 Mhz, DMSO):

(5) ##STR00025##

1.2 Diels-Alder Reaction of 2-(2-furyl)1,3-dioxolane and Acrylonitrile

(6) ##STR00026##

(7) In a 100 ml single-neck round-bottom flask with condenser and magnetic stirring bar, 2-(2-furyl)1,3-dioxolane (19.80 g; 138.5 mmol) was weighted. Then, acrylonitrile (40.0 g; 746 mmol) and ZnCl.sub.2 (2.0 g; 14.4 mmol) were added. The reaction mixture was stirred at 60 C. during 24 h. The conversion is 90% and selectivity in adducts is 93% 1-(1,3-dioxolan-2-yl)-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile and 4-(1,3-dioxolan-2-yl)-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitrile).

(8) The reaction mixture was concentrated in vacuo to give 27 g of a black thick oil. This crude product was purified by flash chromatography (silica gel, EtOAc/cyclohexane) to afford 11.7 g of expected endo adducts and 7 g of expected exo adducts as slight yellow oils, global isolated yield is 70%. In those conditions repartition of different isomers are ortho/meta 52/48% and endo/exo 66/33%.

(9) 1H-NMR (400 Mhz, DMSO):

(10) ##STR00027##

1.3 Conversion of Diels-Alder Adducts of Previous Example to 2-(1,3-dioxolan-2-yl)benzonitrile and 3-(1,3-dioxolan-2-yl)benzonitrile

(11) ##STR00028##

(12) In a carousel tube fitted with a PTFE septum screw cap, endo adducts (1.0 g; 5.2 mmol), dimethyl sulfoxide (7.5 ml) and sodium methoxide solution (25 wt. % in methanol; 225 mg; 1.0 mmol) were charged. The reaction mixture was stirred at 100 C. during 1 h. After cooling, the crude product was diluted with dichloromethane (20 ml). The mixture was washed with water (10 ml). The aqueous phase is extracted with dichloromethane (20 ml) and the organic phase was washed with water (10 ml, 3 times). After drying (MgSO4), the solvent was evaporated to afford 840 mg of an oily liquid (93%). A slight hydrolysis of the nitrile group in meta can be observed in those conditions)

(13) 1H-NMR (400 Mhz, DMSO):

(14) ##STR00029##

1.4 Deprotection of 2-(1,3-dioxolan-2-yl)benzonitrile and 3-(1,3-dioxolan-2-yl)benzonitrile to 2-formylbenzonitrile and 3-formylbenzonitrile

(15) To a stirred solution of 2- and 3-(1,3-dioxolan-2-yl)benzonitrile (200 mg; 1.14 mmol) in THF (10 ml) was added 1N HCl solution (10 ml) at room temperature. The mixture was heated at 80 C. for 1 h and cooled to room temperature. The reaction mixture was extracted with chloroforme (10 ml, 3 times). The combined chloroforme solution was dried (anhydrous MgSO4), filtered and evaporated under reduced pressure to give 147 mg (98%) of 2-formylbenzonitrile and 3-formylbenzonitrile.

(16) 1H-NMR (400 Mhz, DMSO):

(17) ##STR00030##

1.5 Conversion of 3-formylbenzonitrile to 1,3-phenylenedimethanamine

(18) Simultaneous hydrogenation and reductive amination was carried out in batch reactor, containing 113 g of NH3 in MeOH (7 mol/l; d=0.779), 0.7 g of Raney Co and 7 g of 3-formylbenzonitrile, ratio of NH3/aromatic is 19, at 100 C. and 50 bar of hydrogen during 5 h. Yield was quantitative in metaxylenediamine.

(19) 1H-NMR (400 Mhz, DMSO):

(20) ##STR00031##

1.6 Conversion of m-cyanobenzaldehyde (3-formylbenzonitrile) to m-cyanobenzoic Acid

(21) ##STR00032##

(22) 26.2 g of m-cyanobenzaldehyde, 40 g of dioxane, 17.6 g of sodium hydrogen carbonate, and 100 g of water will be mixed with stirring. 210 g of an aqueous 13.5% by weight sodium hypochlorite solution adjusted to a pH of 9 will be added dropwise over 1 hour while maintaining the internal temperature of the reaction system at 50 C. or less, and the resulting mixture will be stirred for 1 additional hour. Then, 3.6 g of urea will be added and the resulting mixture will be stirred for 20 minutes. Furthermore, 12 g of 98% by weight sulfuric acid and 300 g of water will be added. Precipitated crystals will be formed; they will be filtered, washed with water, and dried to obtain about 27 g (yield: about 92%) of m-cyanobenzoic acid. The purity will be 98% or more.

1.7 Conversion of m-Cyanobenzoic Acid to Isophthalic Acid

(23) ##STR00033##

(24) 5.0 g of 3-cyanobenzoic acid (m-cyanobenzoic acid) was added to a solution of NaOH (2.93 g) in water (26 g). The resulting solution was heated to reflux (115 C.) for 5 hours. After cooling, 70 ml of water was added and the solution was acidified to pH=1 by dropwise addition of 95% sulfuric acid. A white solid precipitate was formed. The white solid precipitate was filtrated and washed 3 times with 10 ml of water. After drying (60 C., 10 mbar, 2 h), 5.44 g of isophthalic acid (96% yield) were obtained.

1.8 Conversion of Isophthalic Acid to 3-Aminomethylbenzoic Acid

(25) ##STR00034##

(26) Raney Nickel (0.4 g) will be added at 0 C. to a solution of 3-cyanobenzoic acid (2 g, 13.59 millimoles) in methanol (20 ml), and will be kept under hydrogen atmosphere using H.sub.2 balloon at room temperature for 1 hour. After completion, the reaction mixture will be filtered through a prewashed Celite pad in methanol and will be washed with methanol. The solvent will be evaporated under vacuum to afford the title compound as colorless syrup. About 2 g of 3-aminomethylbenzoic acid will be obtained.

EXAMPLE 2

(27) Similar to example 1.2

(28) The Diels-Alder (DA) condensation with acrylonitrile was conducted using various furfural derivatives thereby determining the different isomers obtained. The results are summarized in the following Table 1.

(29) TABLE-US-00001 TABLE 1 Furfural derivative Global selectivity in Adduct isomers Furfural derivatives Conditions conversion DA adducts repartition 0.2 eq. ZnCl2, 24 h, 60 C. 90% 93% (rest is retro-DA, not degradation Meta: 48% (endo: 30%, exo: 18%) Ortho: 52% (endo: 36%, exo: 15%) 0.1 eq. ZnCl2, 24 h, 60 C. 87% 95% Meta: 54% (endo: 30%, exo: 24%) Ortho: 46% (endo: 32%, exo: 14%) 0.1 eq. ZnCl2, 24 h, RT 80% 100% Ortho: 100% (endo: 66%, exo: 33%) 0.1 eq. ZnCl2, 24 h, 60 C. 63% 93% ~Meta: 48% (endo: 70%) ~Ortho: 52% (endo: 70%)

Comparative Example 1

(30) The above example 1 was repeated using 1 eq. of furfural instead of the furfural ethylene glycol ketal. The results are summarized in the following Table 2.

(31) TABLE-US-00002 TABLE 2 Acrylonitrile Catalyst equivalents Temperature No 1 RT, then 60 C. and then 120 C. 10% mol AlCl.sub.3 1 RT 30% mol ZnCl.sub.2 1 RT then 60 C. No 0.2 RT then 60 C. and then 120 C. 10% mol ZnI.sub.2 0.2 RT then 60 C. 1 eq. LiCl in EtOH 1 60 C. 10% mol Zn(CN).sub.2 1 RT then 60 C.

(32) Under none of the conditions summarized in the above table any reaction between furfural and acrylonitrile was observed.

Comparative Example 2

(33) Example 1 was repeated using 1 eq. of the diethyl-ketal of furfural instead of furfural ethylene glycol ketal. The results are summarized in the following Table 3.

(34) TABLE-US-00003 TABLE 3 Acrylonitrile Catalyst equivalent Temperature No 1 RT then 60 C. 10% mol ZnI.sub.2 1 RT then 60 C.

(35) Under none of the reaction conditions summarized in the above Table, any reaction between the diethyl-ketal of furfural and acrylonitrile was observed.

Comparative Example 3

(36) ##STR00039##

(37) In a carousel tube fitted with a PTFE septum screw cap, 2-(2-furyl)1.3-dioxolane (0.5 g; 3.6 mmol) was weighted. Then, allylamine (1.02 g; 17.9 mmol) and ZnCl.sub.2 (195 mg; 0.7 mmol) were added. The reaction mixture was stirred at 60 C. during 18 h. The reaction was monitored by .sup.1H NMR spectroscopy.

(38) After stirring at 60 C. for 18 h, no reaction was observed.