Process for the preparation of dicidal

Abstract

Process for the preparation of dicidal.

Claims

1. Process comprising the process steps of: a) initially charging dicyclopentadiene; b) adding a compound of formula (I): ##STR00005## 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, -Ph; c) adding a Pt compound capable of forming a complex; d) adding an iodine compound; e) feeding in CO and H.sub.2; f) heating the reaction mixture from steps a) to e), to convert the dicyclopentadiene to dicidal.

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

3. Process according to claim 1, where R.sup.5, R.sup.6, R.sup.7, R.sup.8 are -Ph.

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.sup.2 and R.sup.3 are CH.sub.3.

6. Process according to claim 1, wherein the compound (I) has the structure (1): ##STR00006##

7. Process according to claim 1, wherein the Pt compound is selected from: Pt(II)I.sub.2, Pt(IV)I.sub.4, 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)(COD)Me.sub.2, Pt(II)(COD)I.sub.2, Pt(IV)IMe.sub.3, Pt(II)(hexafluoroacetylacetonate).sub.2.

8. Process according to claim 1, wherein the iodine compound is selected from: Pt(II)I.sub.2, LiI.

9. Process according to claim 1, wherein PtI.sub.2 is added in an amount, measured in mol % based on dicyclopentadiene, such that the value is in the range from 0.1 mol % to 5 mol %.

10. Process according to claim 1, comprising the additional process step e): e) adding a solvent.

11. Process according to claim 1, wherein CO and H.sub.2 is fed in at a pressure in a range from 1 MPa (10 bar) to 6 MPa (60 bar).

12. Process according to claim 1, wherein the reaction mixture is heated to a temperature in the range from 25 C. to 150 C.

13. Process according to claim 1, wherein the process comprises the additional process step g): g) converting dicidal to dicidol.

14. Process according to claim 13, wherein the conversion of dicidal to dicidol is carried out using Shvo's catalyst (CAS 104439-77-2).

Description

EXPERIMENTAL DESCRIPTION

[0043] Conversion of Dicyclopentadiene to Dicidal

##STR00003##

[0044] 10 mmol of dicyclopentadiene (DCPD), 10 ml of absolute toluene, 0.5 mol % PtI.sub.2, 2.2 equivalents of xantphos (1) (based on Pt) are placed under argon in a 25 ml steel autoclave from Parr Instruments. The autoclave was pressurized to 40 bar with synthesis gas (CO/H.sub.2=1:1) and the reaction started by heating to 80 C. and stirring. This reaction is conducted at 40 bar/80 C. for 18.5 h. The autoclave is then cooled, the pressure released and a GC sample is taken.

[0045] In a comparative example, Rh(acac)(CO).sub.2 was added instead of PtI.sub.2.

[0046] Yield of Dicidal: [0047] PtI.sub.2: 89.5% [0048] Rh(acac)(CO).sub.2: <5%

[0049] Conversion of Dicidal to Dicidol

##STR00004##

[0050] 10 ml of toluene, 5 ml of ethanol, 5.5 g of dicidal (28.6 mmol) and 62.16 mg of Shvo's catalyst (CAS 104439-77-2) (0.2 mol % with respect to dicidal) are heated to 100 C. under argon in a 100 ml Parr pressure autoclave at 40 bar hydrogen and reacted while stirring for 20 hours. The reaction is then stopped, the pressure released and the reaction mixture distilled in a fine vacuum. A colourless oil of the isomeric mixture of dicidol is obtained as a fraction at 140 C.

[0051] Yield of dicidol: 85%

[0052] As the experimental results show, the object is achieved by the inventive process.