Method for preparing dicydal

Abstract

To provide a novel process for hydroformylation that affords an increased yield.SOLUTION: A process comprises the steps of: a) initially charging dicyclopentadiene; b) adding a compound of formula (I); c) adding a Pt compound capable of forming a complex; d) adding an iodine compound; e) feeding in CO and H2; and f) heating the reaction mixture from the steps a) to e), to convert the dicyclopentadiene to dicidal (where R1-R8 are selected from H, alkyl, and Ph).SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a process for the preparation of dicidal. [Background technology]

[0002] US Patent Application Publication No. 2009 / 0171125 describes a process for the hydroformylation of cyclic olefins. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] US Patent Application Publication No. 2009 / 0171125 Summary of the Invention [Problem to be solved by the invention]

[0004] The object of the present invention is to provide a novel hydroformylation process which should result in an increased yield compared to the processes known from the prior art.

[0005] This object is achieved by the method according to claim 1. [Means for solving the problem]

[0006] a) Dicyclopentadiene is added first, b) Formula (I):

[0007] [ka]

[0008] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8-H, -(C1-C 12 )-alkyl, -Ph. Adding a compound of c) adding a Pt compound capable of forming a complex; d) adding an iodine compound; e) placing in CO and H2; f) heating the reaction mixture from steps a) through e) to convert the dicyclopentadiene to dicidal. The method includes:

[0009] In this method, steps a) through e) can be carried out in any order desired, although typically the co-reactant is charged first in steps a) through d), followed by the addition of CO and H2.

[0010] Steps c) and d) may be carried out in a single step, for example by adding PtI2. In one variation of this method, the Pt compound and the iodine compound are added in one step by adding PtI2.

[0011] The expression “(C1-C 12 "(C1-C8)-alkyl" encompasses straight-chain and branched alkyl groups having 1 to 12 carbon atoms. These are preferably (C1-C8)-alkyl groups, more preferably (C1-C6)-alkyl, most preferably (C1-C4)-alkyl.

[0012] Appropriate (C1-C 12)-Alkyl groups are 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.

[0013] In one variation of this method, R 1 and R 4 is -H.

[0014] In one variation of this method, R 5 , R 6 , R 7 , R 8 is -Ph.

[0015] In one variation of this method, R 2 and R 3 HA-(C1-C 12 )-alkyl.

[0016] In one variation of this method, R 2 and R 3 is -CH3.

[0017] In one variation of the method, compound (I) has the structure (1):

[0018] [ka]

[0019] has.

[0020] In one variation of the method, 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 (CAS:68478-92-2), Pt(0)(ethylene)(PPh3)2, tris(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.

[0021] In one variation of the method, the Pt compound is selected from Pt(II)I2, Pt(II)(acac)2.

[0022] In one variation of this method, the Pt compound is Pt(II)I2.

[0023] In one variation of the method, the iodine compound is selected from alkali metal halides, alkaline earth metal halides, NH4X, alkylammonium halides, dialkyl halides, trialkyl halides, tetraalkyl halides, cycloalkylammonium halides.

[0024] In one variation of the method, the iodine compound is selected from Pt(II)I2, LiI.

[0025] In one variation of the method, PtI2 is added in an amount ranging from 0.1 mol % to 5 mol %, measured in mol % based on dicyclopentadiene.

[0026] In one variation of the method, PtI2 is added in an amount ranging from 0.1 mol % to 3 mol %, measured in mol % based on dicyclopentadiene.

[0027] In one variation of the method, PtI2 is added in an amount ranging from 0.1 mol % to 1 mol %, measured in mol % based on dicyclopentadiene.

[0028] In one variation of the method, the method comprises the additional step of e') adding a solvent.

[0029] In one variation of the method, the solvent is selected from THF, DCM, ACN, heptane, DMF, toluene, texanol, pentane, hexane, octane, isooctane, decane, dodecane, cyclohexane, benzene, xylene, malotherm, propylene carbonate, MTBE, diglyme, triglyme, diethyl ether, dioxane, isopropanol, tert-butanol, isononanol, isobutanol, isopentanol, ethyl acetate.

[0030] In one variant of the process, the solvent is selected from THF, DCM, ACN, heptane, DMF, toluene, texanol.

[0031] In one variation of the method, CO and H2 are supplied at a pressure in the range of 1 MPa (10 bar) to 6 MPa (60 bar).

[0032] In one variation of the method, CO and H2 are supplied at a pressure in the range of 2 MPa (20 bar) to 5 MPa (50 bar).

[0033] In one variation of the process, the reaction mixture is heated to a temperature in the range of 25°C to 150°C.

[0034] In one variation of the process, the reaction mixture is heated to a temperature in the range of 30°C to 130°C.

[0035] In one variation of the process, the process includes the additional step of g) converting the dicidal to dicidol.

[0036] In one variation of the process, the conversion of dicidal to dicidol is carried out using "Shvo catalyst" (CAS: 104439-77-2).

[0037] The present invention will now be described in detail with reference to examples. EXAMPLES

[0038] Experiment Description Conversion of dicyclopentadiene to dicidal.

[0039] [ka]

[0040] 10 mmol of dicyclopentadiene (DCPD), 10 mL of anhydrous toluene, 0.5 mol% PtI2, and 2.2 equivalents of Xantphos (1) (based on Pt) are placed in a Parr Instruments 25 mL steel autoclave under argon. The autoclave is pressurized to 40 bar with syngas (CO:H2=1:1) and the reaction is started by heating to 80°C and stirring. The reaction is carried out at 40 bar and 80°C for 18.5 hours. The autoclave is then cooled, the pressure is released, and a GC sample is taken.

[0041] In the comparative example, Rh(acac)(CO)2 was added instead of PtI2. Yield of dicidal: PtI2: 89.5% Rh(acac)(CO)2: Less than 5%

[0042] Conversion of dicidal to dicidol

[0043] [ka]

[0044] 10 mL of toluene, 5 mL of ethanol, 5.5 g of dicydal (28.6 mmol) and 62.16 mg of "Shvo catalyst" (CAS: 104439-77-2) (0.2 mol % with respect to dicydal) are heated to 100 °C in a Parr 100 mL pressure autoclave under argon and 40 bar hydrogen pressure and reacted with stirring for 20 hours. The reaction is then stopped, the pressure is released and the reaction mixture is distilled in high vacuum. At 140 °C a colorless oil of the isomeric mixture of dicydal is obtained as the distillate. Yield of dicydol: 85%

[0045] As the experimental results show, the object of the present invention is achieved by the method of the present invention.

Claims

1. a) Dicyclopentadiene is added first, b) Formula (I): 【Chemistry 1】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 is -H, -(C 1 -C 12 ) -alkyl, -Ph. Adding a compound of c) adding a Pt compound capable of forming a complex; d) adding an iodine compound; e) CO and H 2 Put it in, f) heating the reaction mixture from steps a) through e) to convert the dicyclopentadiene to dicidal. The method includes:

2. a) Dicyclopentadiene is added first, b) Formula (I): 【Chemistry 1】 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 is -H, -(C 1 -C 12 ) -alkyl, -Ph. Adding a compound of c) and d) adding a Pt iodide compound capable of forming a complex; e) CO and H 2 Put it in, f) heating the reaction mixture from steps a) through e) to convert the dicyclopentadiene to dicidal. The method includes:

3. The R 1 and the R 4 The method of claim 1 or 2, wherein is -H.

4. The R 5 , the R 6 , the R 7 , the R 8 The method of claim 1 or 2, wherein is -Ph.

5. The R 2 and the R 3 But-(C 1 -C 12 3. The method of claim 1 or 2, wherein the aryl group is aryl.

6. The R 2 and the R 3 Ga-CH 3 The method according to claim 1 or 2,

7. The compound (I) has the structure (1): 【Chemistry 2】 3. The method of claim 1 or 2, comprising:

8. The Pt compound is diphenyl(1,5-COD)Pt(II), Pt(II)(acac). 2 , Pt(0)(PPh 3 ) 4 , Pt(0)(DVTS) solution (CAS: 68478-92-2), Pt(0)(ethylene)(PPh 3 ) 2 , tris(benzylideneacetone)Pt(0), Pt(II) (OAC) 2 Solution, Pt(0)(t-Bu) 2 , Pt(II)(COD)Me 2 , Pt(II)(hexafluoroacetylacetonate) 2 The method of claim 1 , wherein the compound is selected from the group consisting of

9. The method of claim 1 , wherein the iodine compound is LiI.

10. The Pt iodide compound capable of forming the complex is Pt(II)I 2 , Pt(IV)I 4 , Pt(II)(COD)I 2 , Pt(IV)IMe 3 The method of claim 2, wherein the compound is selected from the group consisting of

11. The Pt iodide compound capable of forming the complex is Pt(II)I 2 The method of claim 2, wherein

12. The Pt(II)I 2 is added in an amount ranging from 0.1 mol % to 5 mol %, measured in mol % based on the dicyclopentadiene.

13. As an additional step, e') adding a solvent The method of claim 1 or 2, comprising:

14. The CO and the H 2 The method of claim 1 or 2, wherein the is supplied at a pressure in the range of 1 MPa (10 bar) to 6 MPa (60 bar).

15. The process of claim 1 or 2, wherein the reaction mixture is heated to a temperature in the range of from 25°C to 150°C.

16. As an additional step, g) Converting dicidal to dicidol The method of claim 1 or 2, comprising:

17. 17. The process of claim 16, wherein the conversion of dicidal to dicidol is carried out using "Shvo catalyst" (CAS: 104439-77-2).

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