Process for preparing an acetal from an olefin using an iodine-alkyl compound

Abstract

Process for preparing an acetal from an olefin using an iodine-alkyl compound.

Claims

1. Process comprising the process steps of: a) initially charging an olefin; b) adding a compound of formula (I): ##STR00004## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are selected from: H, (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl; and, if R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are (C.sub.6-C.sub.20)-aryl, the aryl ring may have substituents selected from: (C.sub.1-C.sub.12)-alkyl, O(C.sub.1-C.sub.12)-alkyl; c) adding a Pt compound selected from: Pt(II)(COD)Me.sub.2, diphenyl(1,5-COD)Pt(II), Pt(II)(acac).sub.2, Pt(0)(PPh.sub.3).sub.4, Pt(0)(DVTS) solution (CAS: 68478-92-2), Pt(0)(ethylene)(PPh.sub.3).sub.2, tris(benzylideneacetone)Pt(0), Pt(II)(OAC).sub.2 solution, Pt(0)(t-Bu).sub.2, Pt(II)(hexafluoroacetylacetonate).sub.2; d) adding an iodine-alkyl compound; e) adding an alcohol selected from: methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, ethane-1,2-diol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol; f) feeding in CO and H.sub.2; g) heating the reaction mixture from steps a) to f), to convert the olefin to an acetal.

2. Process according to claim 1, where R.sup.2, R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8 are selected from: (C.sub.1-C.sub.12)-alkyl, (C.sub.6-C.sub.20)-aryl.

3. Process according to claim 1, where R.sup.5, R.sup.6, R.sup.7, R.sup.8 are (C.sub.6-C.sub.20)-aryl.

4. Process according to claim 1, where R.sup.2 and R.sup.3 are (C.sub.1-C.sub.12)-alkyl.

5. Process according to claim 1, where R and R.sup.4 are H.

6. Process according to claim 1, wherein the compound (I) has the structure (1): ##STR00005##

7. Process according to claim 1, wherein the Pt compound is Pt(II)(COD)Me.sub.2.

8. Process according to claim 1, wherein the iodine-alkyl compound is selected from: ICH.sub.2CH.sub.2I, CH.sub.3I, CH.sub.2I.sub.2, CHI.sub.3, CI.sub.4, I.sub.2CHCHI.sub.2, I.sub.3CCI.sub.3, ICH.sub.2CH.sub.2CH.sub.2I, ICH.sub.2CH.sub.2CH.sub.2CH.sub.2I, ICH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2I.

9. Process according to claim 1, wherein the iodine-alkyl compound is selected from: ICH.sub.2CH.sub.2I, CH.sub.3I.

10. Process according to claim 1, wherein the iodine-alkyl compound is ICH.sub.2CH.sub.2I.

11. Process according to claim 1, wherein the iodine-alkyl compound is CH.sub.3I.

12. Process according to claim 1, wherein the alcohol in process step e) is selected from: methanol, ethanol, 1-propanol, 1-butanol, ethane-1,2-diol, propane-1,2-diol.

13. Process according to claim 1, wherein the alcohol in process step e) is MeOH.

14. Process according to claim 1, wherein the olefin is selected from: ethene, propene, 1-butene, cis-and/or trans-2-butene, isobutene, 1,3-butadiene, 1,2-butadiene, 1-pentene, cis-and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, tri-n-butene, 1,7-octadiene, 1,9-decadiene, methyl 9-decenoate (9-Dame) or mixtures thereof.

Description

GENERAL EXPERIMENTAL DESCRIPTION

[0044] The olefin, an inert solvent, the alcohol, the Pt compound, the ligand and the halogen compound are placed in a stainless steel autoclave from Parr Instruments under argon. Synthesis gas CO/H.sub.2 (1:1) is injected and the reaction is conducted at the chosen reaction temperature while stirring. After the end of the reaction time, the autoclave is cooled down to room temperature, the residual pressure is released, and a GC sample for determination of the yield of target product is taken and analysed.

##STR00003##

[0045] 4.1 mmol of butadiene (3.2 ml of 8.3% stock solution in toluene), 80 mmol of MeOH (3.2 ml), 7 ml of toluene, 1.2 mol % of Pt(II)(COD)Me.sub.2 (16.7 mg), 1.2 mol % of Xantphos (1) (29 mg) and 1.2 mol % of XCH.sub.2CH.sub.2X or 2.4 mol % of CH.sub.3X are introduced into a 25 ml autoclave from Parr under argon. Synthesis gas CO: H.sub.2=1:1 is injected to 40 bar and heated. The reaction is conducted while stirring. After the reaction has ended, the autoclave is cooled down, the pressure is released and the reaction solution is transferred into a Schlenk vessel. 10 mml of CH.sub.2Cl.sub.2 (0.6 ml) is added, and a .sup.1H NMR analysis and a GC analysis are carried out.

Reaction Conditions

[0046] 4.1 mmol butadiene, 1.2 mol % Pt(II)(COD)Me.sub.2, 1.2 mol % Xantphos (1), solvent: toluene, alcohol: MeOH, p(CO/H.sub.2): 40 bar (4 MPa).

[0047] These experimental results are listed in the table below.

Variation of the Halogen

[0048]

TABLE-US-00001 Halogen compound Temp [? C.] t [h] Yield [%] BrCH.sub.2CH.sub.2Br* 120 24 <1 ICH.sub.2CH.sub.2I 120 16 36 ICH.sub.2CH.sub.2I 80 20 59 *noninventive comparative experiment

Variation of the Iodine-Alkyl Compound

[0049]

TABLE-US-00002 Halogen compound Temp [? C.] t [h] Yield [%] CH.sub.3I 120 24 48 ICH.sub.2CH.sub.2I 120 16 36

[0050] As shown by the experimental results, the object is achieved by the process according to the invention.