Method for preparing tricyclodecane dicarboxaldehyde

Abstract

The present invention relates to a method for preparing tricyclodecane dicarboxaldehyde (Dicidal), comprising the following steps: a) pre-introducing dicyclopentadiene; b) adding a compound according to formula (I): #imgabs0# wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Selected from: ‑H, ‑(C1‑C 12 )-alkyl, -Ph; c) adding a Pt compound capable of forming a complex; d) adding an iodine compound; e) supplying CO and H2; f) heating the reaction mixture from a)-e), wherein the dicyclopentadiene is converted into tricyclodecane dicarboxaldehyde.

Description

Technical Field

[0001] The present invention relates to a method for preparing tricyclodecane dicarboxaldehyde (Dicidal). Background Art

[0002] US 2009 / 0171125 A1 describes a process for the hydroformylation of cyclic olefins, using an Rh catalyst. Summary of the Invention

[0003] The object of the present invention was to provide a novel hydroformylation process which should provide increased yields compared to the processes known from the prior art.

[0004] This object is achieved by the method according to the following.

[0005] The method comprises the following steps:

[0006] a) pre-introducing dicyclopentadiene;

[0007] b) adding a compound according to formula (I):

[0008]

[0009] where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Selected from: -H, -(C1-C 12 )-alkyl, -Ph;

[0010] c) adding a Pt compound capable of forming a complex;

[0011] d) adding an iodine compound;

[0012] e) supply of CO and H2;

[0013] f) heating the reaction mixture from a) to e), wherein the dicyclopentadiene is converted into tricyclodecanedicarboxaldehyde.

[0014] Here, process steps a) to e) can be carried out in any order. However, the addition of CO and H2 is usually carried out after the reaction partners in steps a) to d) have been previously charged.

[0015] In this case, method steps c) and d) can also be carried out in one step, for example by adding PtI 2 .

[0016] In a variant of the process, the Pt compound and the iodine compound are added in one step by adding PtI2.

[0017] Terminology (C1-C 12 )-Alkyl includes straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl, particularly preferably (C1-C6)-alkyl, most preferably (C1-C4)-alkyl.

[0018] Suitable (C1-C 12 )-alkyl, in particular methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2- Dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, n-octyl, 2-ethylhexyl, 2-propylheptyl, nonyl, decyl.

[0019] In one variation of this approach, R 1 and R 4 Yes -H.

[0020] In one variation of this approach, R 5 、R 6 、R 7 、R 8 Yes - Ph.

[0021] In one variation of this approach, R 2 and R 3 Yes-(C1-C 12 )-alkyl.

[0022] In one variation of this approach, R 2 and R 3 It is -CH3.

[0023] In one variation of this method, compound (I) has structure (1):

[0024]

[0025] In one variation of the method, the Pt compound is selected from the group consisting of: Pt(II)I2, Pt(IV)I4, diphenyl(1,5-COD)Pt(II), Pt(II)(acac)2, Pt(0)(PPh3)4, Pt(0)(DVTS) solution (CAS: 68478-92-2), Pt(0)(ethylene)(PPh3)2, tri(benzylideneacetone)Pt(0), Pt(II)(OAC)2 solution, Pt(0)(t-Bu)2, Pt(II)(COD)Me2, Pt(II)(COD)I2, Pt(IV)IMe3, Pt(II)(hexafluoroacetylacetonate)2.

[0026] In one variant of the method, the Pt compound is selected from the group consisting of: Pt(II)I2, Pt(II)(acac)2.

[0027] In one variation of the method, the Pt compound is Pt(II)I2.

[0028] In one variation of the method, the iodine compound is selected from the group consisting of alkali metal halides, alkaline earth metal halides, NH4X, alkylammonium halides, dialkylhalogenides, trialkylhalogenides, tetraalkylhalogenides and cycloalkylammonium halides.

[0029] In one variant of the method, the iodine compound is selected from: Pt(II)I2, LiI.

[0030] In one variant of the process, PtI 2 is added in an amount measured in mol % relative to dicyclopentadiene such that the value is in the range from 0.1 mol % to 5 mol %.

[0031] In one variant of the process, PtI 2 is added in an amount measured in mol % relative to dicyclopentadiene such that the value ranges from 0.1 mol % to 3 mol %.

[0032] In one variant of the process, PtI 2 is added in an amount measured in mol % relative to dicyclopentadiene such that the value ranges from 0.1 mol % to 1 mol %.

[0033] In one variant of the method, the method comprises the additional method step e'):

[0034] e') Adding solvent.

[0035] In one variation of the process, the solvent is selected from the group consisting of: THF, DCM, ACN, heptane, DMF, toluene, Texanol, pentane, hexane, octane, isooctane, decane, dodecane, cyclohexane, benzene, xylene, Marlotherm, propylene carbonate, MTBE, diglyme, triglyme, ethyl ether, dioxane, isopropanol, tert-butanol, isononanol, isobutanol, isoamyl alcohol, ethyl acetate.

[0036] In one variation of the process, the solvent is selected from the group consisting of: THF, DCM, ACN, heptane, DMF, toluene, Texanol.

[0037] In one variant of the process, CO and H2 are introduced at a pressure of 1 MPa (10 bar) to 6 MPa (60 bar).

[0038] In one variant of the process, CO and H2 are introduced at a pressure of 1 MPa (20 bar) to 6 MPa (50 bar).

[0039] In one variant of the process, heating is to a temperature of 25°C to 150°C.

[0040] In one variant of the process, heating is to a temperature of 30°C to 130°C.

[0041] In one variant of the method, the method comprises the additional method step g):

[0042] g) converting tricyclodecane dicarboxaldehyde into tricyclodecane dimethanol.

[0043] In one variant of the process, "Shvos catalyst" (CAS 104439-77-2) is used to convert tricyclodecane dicarboxaldehyde into tricyclodecane dimethanol. DETAILED DESCRIPTION

[0044] The present invention will be explained in more detail below using exemplary embodiments.

[0045] Experimental Description

[0046] Conversion of dicyclopentadiene to tricyclodecane dicarboxaldehyde

[0047]

[0048] Under argon, 10 mmol of dicyclopentadiene (DCPD), 10 ml of anhydrous toluene, 0.5 mol% PtI2, and 2.2 equivalents of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) (1) (based on Pt) from Parr Instruments were added to a 25 ml steel autoclave. 40 bar of synthesis gas (CO / H2=1:1) was introduced and the reaction was started by heating to 80°C and stirring. The reaction was carried out at 40 bar / 80°C for 18.5 hours. The autoclave was then cooled, the pressure was released, and a GC sample was collected.

[0049] In the comparative experiment, Rh(acac)(CO)2 was added instead of PtI2.

[0050] Tricyclodecane dicarboxaldehyde yield:

[0051] PtI2: 89.5%

[0052] Rh(acac)(CO)2:<5%

[0053] Conversion of tricyclodecane dicarboxaldehyde into tricyclodecane dimethanol

[0054]

[0055] In a 100 ml Parr autoclave, under argon, 10 ml of toluene, 5 ml of ethanol, 5.5 g of tricyclodecanedicarboxaldehyde (28.6 mmol), and 62.16 mg of "Shvos catalyst" (CAS 104439-77-2) (0.2 mol % based on tricyclodecanedicarboxaldehyde) were heated to 100° C. with stirring and reacted for 20 hours under 40 bar of hydrogen. The reaction was then stopped, the pressure released, and the reaction mixture was distilled under high vacuum. A colorless oil of a mixture of tricyclodecane dimethanol isomers was obtained as a fraction at 140° C.

[0056] Tricyclodecane dimethanol yield: 85%

[0057] As shown by the experimental results, this object is achieved by the method of the present invention.

Claims

1. A method for preparing tricyclodecane dicarboxaldehyde, comprising the following steps: a) pre-introducing dicyclopentadiene; b) adding a compound according to formula (I): where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Selected from: -H, -(C1-C 12 )-alkyl, -Ph; c) adding a Pt compound capable of forming a complex; d) adding an iodine compound; e) supply of CO and H2; f) heating the reaction mixture from a) to e), wherein the dicyclopentadiene is converted into tricyclodecanedicarboxaldehyde.

2. The method according to claim 1, where R 1 and R 4 Yes -H.

3. The method according to any one of claims 1 or 2, where R 5 、R 6 、R 7 、R 8 Yes - Ph.

4. The method according to claim 1, where R 2 and R 3 Yes-(C1-C 12 )-alkyl.

5. The method according to claim 1, where R 2 and R 3 It is -CH3.

6. The method according to claim 1, Wherein compound (I) has structure (1):

7. The method according to claim 1, The Pt compound is selected from: Pt(II)I2, Pt(IV)I4, diphenyl(1,5-COD)Pt(II), Pt(II)(acac)2, Pt(0)(PPh3)4, Pt(0)(DVTS) solution, which has CAS: 68478-92-2, Pt(0)(ethylene)(PPh3)2, tri(benzylideneacetone)Pt(0), Pt(II)(OAC)2 solution, Pt(0)(t-Bu)2, Pt(II)(COD)Me2, Pt(II)(COD)I2, Pt(IV)IMe3, Pt(II)(hexafluoroacetylacetonate)2.

8. The method according to claim 1, The iodine compound is selected from the group consisting of Pt(II)I2 and LiI.

9. The method according to claim 1, Wherein PtI2 is added in an amount measured in mol% relative to dicyclopentadiene such that the value is in the range of 0.1 mol% to 5 mol%.

10. The method according to claim 1, comprising the additional method step e'): e') Adding solvent.

11. The method according to claim 1, CO and H2 are introduced at a pressure of 1 MPa (10 bar) to 6 MPa (60 bar).

12. The method according to claim 1, The heating is carried out to a temperature of 25°C to 150°C.

13. The method according to claim 1, The method comprises the additional method step g): g) converting tricyclodecane dicarboxaldehyde into tricyclodecane dimethanol.

14. The method according to claim 13, The Shvos catalyst, which has CAS number 104439-77-2, was used to convert tricyclodecane dicarboxaldehyde into tricyclodecane dimethanol.

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