Amine Derivatives of The Beta-Farnesene

Abstract

The invention provides a process for preparing farnesylamines by reacting -farnesene with one or more amines in the presence of a transition metal catalyst from transition group 10 at a temperature in the range from 60 to 150 C.

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Claims

1. A process for preparing a farnesylamine by reacting -famesene with at least one amine in the presence of a transition metal catalyst from transition group 10 at a temperature in the range from 60 to 150 C. ##STR00020##

2. The process as claimed in claim 1, wherein the transition metal catalyst is selected from the group consisting of nickel, palladium and platinum precursors.

3. The process as claimed in claim 1, wherein the transition metal catalyst is completely dissolved in the reaction mixture and is modified by an organic ligand.

4. The process as claimed in claim 1, wherein the precursors are selected from the group consisting of Ni.sup.0(cod).sub.2, Ni.sup.II(acac).sub.2, Ni.sup.II(hfacac).sub.2, Ni.sup.IICl.sub.2, Pd.sup.0.sub.2dba.sub.3, Pd.sup.II(acac).sub.2, Pd.sup.II(hfacac).sub.2, Pd.sup.II(tfa).sub.2, Pd.sup.IICl.sub.2, Pt.sup.IICl.sub.2, Pt.sup.II(cod)Cl.sub.2, Pt.sup.II(acac).sub.2, and K.sub.2Pt.sup.IICl.sub.4.

5. The process as claimed in claim 1, wherein the reacting is carried out in at least one solvent.

6. The process as claimed in claim 4, wherein at least one solvent is selected the group consisting aliphatic or aromatic, polar or polar-aprotic hydrocarbons, and ionic liquids.

7. The process as claimed in claim 1, wherein an ammonium carbamate and no further solvent is used for the reacting.

8. The process as claimed in claim 1, wherein an amine of the formula HNR.sup.1R.sup.2 is used, in which R.sup.1 and R.sup.2 independently of one another are H or branched, cyclic, heterocyclic, linear, optionally substituted alkyl radicals which are in saturated or unsaturated form and have a chain length in the range of C.sub.1-C.sub.30 or independently of one another are an aromatic or heteroaromatic radical, or one of the radicals R.sup.1 and R.sup.2 is NR.sup.2R.sup.3, in which R.sup.2 and R.sup.3 independently of one another are H or branched, cyclic, linear, optionally substituted alkyl radicals or aromatic or heteroaromatic radicals which are in saturated or unsaturated form and have a chain length in the range of C.sub.1-C.sub.30.

9. The process as claimed in claim 1, wherein the process is carried out in the presence of a phosphorus ligand.

10. The process as claimed in claim 9, wherein the phosphorus ligand is selected from the group consisting of triphenylphosphine, triphenyl phosphite, tris(ortho-methoxyphenyl)phosphines, tricyclohexylphosphine, triethylphosphine, tri-tert-butylphosphine, bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane, bis(diphenylphosphino)butane, bis(diphenylphosphino)heptane, 1,1-bis(diphenylphosphino)ferrocene, (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine), 4,6-bis(diphenylphosphinyl)-10H-phenoxazine, and (oxybis(2,1-phenyl))bis(diphenylphosphane).

11. The process as claimed in claim 10, wherein the metal/ligand ratio is in the range from 1:1 to 1:50 mol/mol.

12. The process as claimed in claim 1, wherein the farnesene:amine ratio used is 1:1 to 1:10 mol/mol.

13. The process as claimed in claim 1, wherein the catalyst and the farnesene are used in a ratio of 1:10 to 1:1000.

14. The process as claimed in claim 1, wherein the reaction is carried out in the presence of an inert gas.

15. The process as claimed in claim 1, wherein the reaction is carried out under pressure in a range from 1 to 10 bar.

16. The process as claimed in claim 1, wherein the reacting of the -farnesene is carried out at a temperature in the range from 50 to 150 C.

17. The process as claimed claim 1, wherein the reaction time is 1 to 16 hours.

18. The process as claimed in claim 1, wherein the catalyst used is recycled after the reaction.

19. The process as claimed in claim 1, wherein a dimethylammonium carbamate is used as dimethylamine source and a TPPMS, TPPTS or DPPBTS is used as ligand.

Description

EXAMPLES

[0058] Key to abbreviations used:

TABLE-US-00002 Abbreviation Meaning acac acetylacetonate cod 1,5-cyclooctadiene dba dibenzylideneacetone DMF N,N-dimethylformamide g gram h hour hfacac 1,1,1,5,5,5,-hexafluoroacetylacetonate mg milligram mL milliliter mmol millimol mol % mole percent rpm revolutions per minute tfa trifluoroacetate Dimcarb dimethylammonium dimethylcarbamate

[0059] In a typical experiment in accordance with the invention, the reaction mixture is weighed into a 25 mL steel autoclave with magnetic stirring kernel. The precursor is introduced together with the ligand and is dissolved in the solvent. Then the -farnesene and the amine are added. The reactor is closed and subjected where appropriate to argon pressure. The reactor is heated to reaction temperature and stirred with a heating stirrer. The reaction is ended by cooling the reactor to room temperature and degassing it. The reaction mixture present may be analyzed by gas chromatography.

[0060] Following removal of the solvent under a high vacuum, the product mixture can be purified by column chromatography.

Example 1

[0061] In a 25 mL steel autoclave, 16.6 mg of Pd(hfacac).sub.2 and 109.3 mg of DPPB are weighed out and dissolved in 5 mL of DMF. Then 817.4 mg of -farnesene and 296.9 mg of diethylamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0062] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0063] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 863.2 mg (78%) of the hydroamination products.

Example 2

[0064] In a 25 mL steel autoclave, 10.6 mg of Pd(tfa).sub.2 and 137.8 mg of DPEphos are weighed out and dissolved in 5 mL of methanol. Then 817.7 mg of -farnesene and 297.1 mg of diethylamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0065] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0066] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 960.4 mg (89%) of the hydroamination products.

Example 3

[0067] In a 25 mL steel autoclave, 10.5 mg of Pd(tfa).sub.2 and 137.7 mg of DPEphos are weighed out and dissolved in 5 mL of anisole. Then 816.8 mg of -farnesene and 516.6 mg of dibutylamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0068] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0069] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 960.8 mg (72%) of the hydroamination products.

Example 4

[0070] In a 25 mL steel autoclave, 10.7 mg of Pd(tfa).sub.2 and 137.5 mg of DPEphos are weighed out and dissolved in 5 mL of DMF. Then 817.2 mg of -farnesene and 965.3 mg of dioctylamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0071] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0072] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 998.6 mg (56%) of the hydroamination products.

Example 5

[0073] In a 25 mL steel autoclave, 11 mg of Pd(tfa).sub.2 and 138.2 mg of DPEphos are weighed out and dissolved in 5 mL of acetonitrile. Then 818.2 mg of -farnesene and 388.9 mg of diallylamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0074] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0075] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 410 mg (34%) of the hydroamination products.

Example 6

[0076] In a 25 mL steel autoclave, 11 mg of Pd(tfa).sub.2 and 137.9 mg of DPEphos are weighed out and dissolved in 5 mL of DMF. Then 818.0 mg of -farnesene and 420.8 mg of diethanolamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0077] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0078] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 643 mg (52%) of the hydroamination products.

Example 7

[0079] In a 25 mL steel autoclave, 11 mg of Pd(tfa).sub.2 and 138.0 mg of DPEphos are weighed out and dissolved in 5 mL of acetonitrile. Then 817.5 mg of -farnesene and 536.9 mg of dimethylammonium dimethylcarbamate are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0080] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0081] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 978 mg (98%) of the hydroamination products.

Example 8

[0082] In a 25 mL steel autoclave, 11.0 mg of Pd(tfa).sub.2 and 137.9 mg of DPEphos are weighed out and dissolved in 5 mL of anisole. Then 818.2 mg of -farnesene and 845.0 mg of N-methylglucamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0083] The reactor is heated to 100 C. for 16 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0084] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 351 mg (22%) of the hydroamination products.

Example 9

[0085] In a 25 mL steel autoclave, 11.1 mg of Pd(tfa).sub.2 and 138.2 mg of DPEphos are weighed out without solvent. Then 1636.2 mg of -farnesene and 601.5 mg of diethylamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0086] The reactor is heated to 100 C. for 4 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0087] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 1258 mg (65%) of the hydroamination products.

Example 10

[0088] In a 25 mL steel autoclave, 10.6 mg of Pd(tfa).sub.2 and 137.7 mg of DPPB are weighed out without solvent. Then 1602.4 mg of -farnesene and 2016.2 mg of dimethylammonium dimethylcarbamate are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0089] The reactor is heated to 100 C. for 4 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0090] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 1621 mg (80%) of the hydroamination products.

Example 11

[0091] In a 25 mL steel autoclave, 11.3 mg of Pd(tfa).sub.2 and 137.7 mg of DPEphos are weighed out and dissolved in 5 mL of DMF. Then 818.8 mg of farnesene and 857.6 mg of benzylamine are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0092] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0093] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 199 mg (16%) of the monoalkylated product and 495 mg (48%) of the dialkylated product.

Example 12

[0094] In a 25 mL steel autoclave, 10.6 mg of Pd(tfa).sub.2 and 100.0 mg of DPPBTS and subsequently 3066.4 mg of farnesene and 6039.2 mg of Dimcarb (=dimethylammonium dimethylcarbamate) are added. The reactor is closed and heated to 100 C. for 3 h, stirred at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and the gas pressure which has arisen is discharged.

[0095] The reaction mixture is transferred under an argon countercurrent to a Schlenk vessel, where spontaneous phase separation takes place. The lower, polar phase is returned to the reactor. The apolar product phase is extracted with 1073.8 mg of Dimcarb. After further phase separation, the polar phase is transferred together with 3065.7 mg of farnesene into the reactor, and a new reaction run is commenced.

[0096] The product phase can be purified by column chromatography. Over a number of runs, between 2543 and 3366 mg of products are obtained.

Example 13

[0097] In a 25 mL steel autoclave, 12.6 mg of Pd(tfa).sub.2 and 137.8 mg of DPEphos are weighed out and dissolved in 5 mL of DMF. Then 818.0 mg of farnesene and 745.0 mg of aniline are added. The reactor is closed and subjected to an argon pressure of 5 bar.

[0098] The reactor is heated to 100 C. for 5 h with stirring at 500 rpm by magnetic stirrer. To end the reaction, the reactor is cooled to room temperature and then the argon is cautiously discharged.

[0099] The reaction solution obtained is freed from the solvent under reduced pressure and the product is purified by column chromatography. This gives 916.3 mg (77%) of the monoalkylated products. The dialkylated product was not observed.