Process for preparing (meth)acrylic esters of functionalized furyl alcohols

Abstract

The invention relates to a process for preparing a compound of the formula (I), ##STR00001## in which R is H or C.sub.1-C.sub.6 alkyl, by reaction of at least one compound of the formula (II) ##STR00002## in which R has the same definition as in the formula (I) and in which R.sup.1 is H, C.sub.1-C.sub.12 alkyl or C.sub.3-C.sub.12 cycloalkyl, with a compound of the formula (III) ##STR00003## in which R.sup.2 is H or C(O)R.sup.3, in which R.sup.3 is H or C.sub.1-C.sub.12 alkyl, in the presence of at least one enzyme suitable for transesterification.

Claims

1. A process for preparing a compound of the formula (I), ##STR00012## wherein R is H or C.sub.1-C.sub.6 alkyl, the process comprising: reacting at least one compound of the formula (II) ##STR00013## wherein R is H or C.sub.1-C.sub.6 alkyl, and R.sup.1 is H, C.sub.1-C.sub.12 alkyl or C.sub.3-C.sub.12 cycloalkyl, with a compound of the formula (III) ##STR00014## wherein R.sup.2 is H or C(O)R.sup.3, and R.sup.3 is H or C.sub.1-C.sub.12 alkyl, in the presence of at least one enzyme suitable for transesterification, and in the presence of at least one stabilizer.

2. The process according to claim 1, where R is H or CH.sub.3.

3. The process according to claim 1, where R is H.

4. The process according to claim 1, where R is CH.sub.3.

5. The process according to claim 1, where R.sup.1 is CH.sub.3 or CH.sub.2CH.sub.3.

6. The process according to claim 1, where R.sup.2 is H.

7. The process according to claim 1, wherein the at least one enzyme comprises a hydrolase (EC 3.-.-.-).

8. The process according to claim 1, wherein the at least one enzyme comprises a lipase(EC 3.1.1.-).

9. The process according to claim 1, wherein the at least one compound of the formula (II) and the compound of the formula (III) are reacted in a molar ratio of 5:1 to 15:1.

10. The process according to claim 1, wherein the process is carried out at a temperature of from 20 to 60 C.

11. The process according to claim 1, wherein R.sup.2 is C(O)R.sup.3 and/or R is C.sub.1-C.sub.6 alkyl.

Description

EXAMPLES

(1) The 5-(hydroxymethyl)furfural (HMF) used in the synthesis examples was acquired commercially from Aldrich (CAS: 67-47-0).

(2) The methyl acrylate and methyl methacrylate used in the synthesis examples were acquired from BASF.

(3) The BASF Novozym 435 enzyme used in the synthesis examples was acquired from BASF.

(4) The term HMF-acrylate used in the synthesis examples stands for the compound depicted below:

(5) ##STR00010##

(6) The term HMF-methacrylate used in the synthesis examples stands for the compound depicted below:

(7) ##STR00011##

(8) The term MEHQ used in the synthesis examples stands for monomethyl ether of hydroquinone or hydroquinone monomethyl ether. A synonym thereof is para-methoxyphenol (PMP).

(9) Gas chromatography:

(10) Gas-chromatic observation of the progress of reaction took place according to the following method:

(11) Instrument: Agilent 6890N

(12) Column: RTX-200-MS.sub.length=30 m, .sub.internal=0.32 mm, .sub.external=0.45 mm, film thickness 0.5 m; from Restec, order No.: 15639

(13) Flow rate: 1.0 mL/min at 5.7 PSI (measured at oven temp. of 80 C.)

(14) Split: 1:50, split flow: 50 mL/min, septum purge 3.0 mL/min (measured at oven temp. of 80 C.)

(15) Carrier gas: nitrogen

(16) Injector: split/splitless with siltec-deactivated liner (from Restec #20782-213.5)

(17) Injector temperature: 280 C.

(18) Injection volume: 1 L

(19) Detector: FID with 300 mL/min air, 30 mL/min hydrogen, and 30 mL/min make-up gas (nitrogen)

(20) Detector temperature: 320 C.

(21) Temperature program:

(22) Start: 60 C.

(23) Dwell time 1: 5 min

(24) Temperature ramp 1: 15 C./min

(25) End temperature 1: 310 C.

(26) Dwell time 2: 10 min

(27) Total run time: 31.7 min

(28) Measurements and results: diluted samples according to area % without solvent and acrylate

(29) Analysis: Empower 3 software Service Release 1 (from Waters)

Example 1

(30) In a 25 mL Schott flask, HMF (1 g, 0.0079 mol) was dissolved in methyl acrylate (6.83 g, 0.079 mol). Added to this batch were molecular sieve (2.5 g, 5 angstroms) and a spatula tip of MEHQ. The batch was admixed with the enzyme BASF Novozym 435 (0.075 g, 7.5 wt %) and shaken on a water bath at a reaction temperature of 40 C. The reaction progress was observed via gas chromatography:

(31) TABLE-US-00003 Time Reactant: HMF Product: HMF acrylate Entry [h] (retention time: 14.1 min) (retention time: 15.5 min) 1 2 91.26 8.74 2 4 88.28 11.72 3 24 64.4 35.6 4 48 23.4 76.6

(32) After 48 hours, a conversion (of HMF to HMF-acrylate) of 76.6% was shown. The reaction was extremely selective, with no formation of byproducts, and without coloration of the reaction batch. Following filtration to remove the molecular sieve, the batch was amenable to concentration under reduced pressure (removal of the volatile methyl acrylate). The reaction residue obtained was colorless.

(33) The identity of the product was verified via GC-MS (mass.sub.theoretical: 180.6 (C.sub.9H.sub.8O.sub.4); mass.sub.found: 180) and also by 1H NMR.

Example 2

(34) In a 25 mL Schott flask, HMF (1 g, 0.0079 mol) was dissolved in methyl methacrylate (7.9 g, 0.079 mol). Added to this batch were molecular sieve (2.5 g, 5 angstroms) and also a spatula tip of MEHQ. The batch was admixed with the enzyme BASF Novozym 435 (0.075 g, 7.5 wt %) and shaken on a water bath at a reaction temperature of 40 C. The reaction progress was observed via gas chromatography. After 48 hours a conversion (of HMF to HMF-methacrylate) of 6% was shown.