ISOMER-ENRICHED 3-CARANLACTAMS AND POLYAMIDES BASED THEREON WITH HIGH OPTICAL PURITY AND ADJUSTABLE CRYSTALLINITY FOR HIGH-PERFORMANCE APPLICATIONS

Abstract

The present invention relates to a process for the preparation of an isomer-enriched mixture of 3S- and 3R-caranone from 3-carane epoxide, a 3S-caranone obtained therefrom, a process for the production of 3S-caranlactam from 3-carene, a process for the production of 3R-caranlactam from 3-carene, a 3S-caranoxime, a 3S-caranlactam, a 3S-polycaranamide, a 3R-polycaranamide, a 3S/3R-co-polycaranamide, a 3S-caranlactam-laurolactam co-polycaranamide, a 3R-caranlactam-laurolactam co-polycaranamide, a 3S-caranlactam-3R-caranlactam-laurolactam co-polycaranamide, a 3S-caranlactam-caprolactam co-polycaranamide, a 3R-caranlactam-caprolactam co-polycaranamide, as well as a 3S/3R-caranlactam-caprolactam co-polycaranamide.

Claims

1. A polycaranamide, wherein the polycaranamide is 3S-polycaranamide according to the formula (with n repeat units): ##STR00027## or 3R-polycaranamide of the formula (with n repeat units): ##STR00028##

2. A 3S/3R-co-polycaranamide according to the formula (with a, b and n repeat units): ##STR00029##

3. (canceled)

4. A process for the preparation of an isomer-enriched mixture of 3S-caranone and 3R-caranone from 3-carane epoxide, comprising the following process steps: a) providing a reaction mixture containing 3-carane epoxide and at least one acid catalyst, b) reacting the 3-carane epoxide in the reaction mixture at a temperature of 40 C. to 140 C., with rearrangement, and c) obtaining the isomer-enriched mixture with an isomer ratio of at least 80% 3S-caranone or 3R-caranone (based on the total material quantity of caranone).

5. The process according to claim 4, wherein the reaction mixture provided in process step a) additionally contains a first organic solvent.

6. The process according to claim 4, wherein the 3-carane epoxide 3S-carane epoxide used in process step a) and the isomer-enriched mixture obtained in process step c) is a 3S-caranone-enriched mixture with an isomer ratio of at least 80% 3S-caranone (based on the total material quantity of caranone, i.e. 3R- and 3S-caranone).

7. The process according to claim 4, wherein the 3S-carane epoxide 3R-carane epoxide used in process step a) and the isomer-enriched mixture obtained in process step c) is a 3R-caranone-enriched mixture with an isomer ratio of at least 80% 3R-caranone (based on the total material quantity of caranone).

8. The process according to claim 4, wherein the acid catalyst is used in the reaction mixture according to process steps a) and b) at a concentration of 0.01 to 2.0 mol % with respect to the 3-carane epoxide used.

9. The process according to claim 4, wherein the 3-carane epoxide used in process step a) is obtained in a process step a1) by epoxidation of 3-carene.

10. The process according to claim 5, wherein the 3S-caranone-enriched mixture obtained in process step c) is isomerized in at least one second solvent in the presence of a base or a Brnsted acid with a pKa of at most 0.7 in a process step d) to produce a 3R-caranone-enriched mixture with an isomer content of at least 50% 3R-caranone (based on the total material quantity of caranone), wherein the second organic solvent is an aprotic polar solvent with a relative polarity of at least 0.200, or a protic polar solvent with a relative polarity of at least 0.200.

11. The process according to claim 4, wherein the isomer-enriched mixture of 3S- and 3R-caranone obtained in process step c) or d) is reacted in a further process step e) in the presence of at least one third organic solvent, a base and hydroxylamine (HONH.sub.2.HCl) to produce a 3-caranoxime-enriched mixture with an isomer ratio of at least 80% 3S- or 3R-caranoxime (based on the total material quantity of caranoximei.e., 3R- and 3S-caranoxime).

12. The process according to claim 11, wherein the 3-caranoxime-enriched mixture obtained in process step e) is reacted in a further process step f) with rearrangement, to produce a 3-caranlactam-enriched mixture with an isomer ratio of at least 80% 3S- or 3R-caranlactam (based on the total material quantity of caranlactami.e. 3R- and 3S-caranlactam).

13. The process according to claim 12, wherein 3S-caranlactam is obtained in a process step g) by crystallization from the 3S-caranlactam-enriched mixture obtained in process step f).

14. The process according to claim 12, wherein 3R-caranlactam is obtained in a process step h) from the 3-caranlactam-enriched mixture obtained in process step f) after separation of 3S-caranlactam.

15. The process according to claim 12, wherein the 3S-caranlactam, 3R-caranlactam or a mixture of 3R- and 3S-caranlactam obtained in a process step i) is polymerized to 3S-polycaranamide, 3R-polycaranamide or 3S/3R-co-polycaranamide.

16. A process for the preparation of 3S-caranlactam from 3-carene, wherein the process comprises the process steps a) to c), e), f), and g), in particular a1) to c), e), f) and g) according to claim 13, and wherein in process step a) a 3S-carane epoxide is used which is preferably obtained by epoxidation of 3-carene, in process step c) a 3S-caranone-enriched mixture with an isomer ratio of at least 80% 3S-caranone (based on the total material quantity of caranone) obtained in process step e) is reacted to produce a 3S-caranoxime-enriched mixture with an isomer ratio of at least 80% 3S-caranoxime (based on the total material quantity of caranoxime), which in process step f) is reacted to produce a 3S-caranlactam mixture with an isomer ratio of at least 80% 3S-caranlactam (based on the total material quantity of caranlactam), and 3S-caranlactam is obtained by crystallization in process step g).

17. A process for the preparation of 3R-caranlactam from 3-carene, wherein the process comprises process steps a) to h), preferably a1) to h), according to claim 14 and wherein in process step a) a 3S-carane epoxide is used which is preferably obtained by epoxidation of 3-carene, in process step c) a 3S-caranone-enriched mixture with an isomer ratio of at least 80% 3S-caranone (based on the total material quantity of caranone) is obtained, and this is isomerized in process step d) to produce a 3R-caranone-enriched mixture with an isomer ratio of at least 50% 3R-caranone (based on the total material quantity of caranone), which is reacted in process step e) to produce a 3R-caranoxime-enriched mixture with an isomer ratio of at least 50% 3R-caranoxime (based on the total material quantity of caranoxime), which is reacted in process step f) to produce a 3R-caranlactam-enriched mixture with an isomer ratio of at least 50% 3R-caranlactam (based on the total material quantity of caranlactam), and 3R-caranlactam is obtained in process step h) after separation of 3S-caranlactam.

18. A 3S-caranoxime, in particular which is prepared or can be prepared by a process according to claim 11, according to the formula: ##STR00030##

19. A 3S-caranlactam, in particular which is prepared or can be prepared by a process according to claim 12, according to the formula: ##STR00031##

20. Polymers, in particular polyamides, which contain 3-caranlactams completely or as a copolymer or as part of a mixture of different polymers or monomers, in particular according to claim 19, or their opened amino acids, amino acid esters or amino acid derivatives.

21. A plastic product containing at least one of the polyamides according to claim 1, in particular 3S-polycaranamide, 3R-polycaranamide or co-polycaranamide, in particular comprising at least 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 95 or 99 wt. % of the polyamide, in particular consisting of at least one of these polyamides.

Description

EMBODIMENTS

Embodiment 1 (Process Steps a), b) and c))

Synthesis of 3S-Caranone (Over 85% Isomeric Purity)

[0251] 1.8 g 3S-carane epoxide (11.8 mmol) were dissolved in 6.7 mL hexane (c=1.5 M) and heated to 60 C. 7.0 mg Fe(ClO.sub.4).sub.2.H.sub.2O (0.03 mmol, 0.2 mol %) were added and stirred for 20 min. The reaction mixture was cooled to 25 C. and 2 ml of semi-saturated sodium acetate solution were added. The phases were separated and the solvent was removed by distillation.

[0252] GCMS analytics (uncorrected): Total selectivity 80% caranone, ratio: 3S-caranone 85%: 15% 3R-caranone.

Mass Spectrum:

[0253] MS (EI, 70 eV): m/z (%)=153.10 (2.77), 152.10 (27.38), 138.10 (1.16), 137.10 (12.12), 135.15 (0.47), 134.10 (2.59), 125.15 (0.48), 124.10 (4.38), 123.10 (4.10), 121.10 (0.54).

[0254] MS (EI, 70 eV):% (m/z)=100.00 (67.10), 83.36 (81.10), 69.63 (41.10), 45.24 (39.10), 44.25 (82.10), 33.71 (95.10), 32.68 (109.10), 30.74 (110.10), 27.40 (55.10), 27.38 (152.10).

[0255] FIG. 4 shows the GC chromatogram of a 3S-caranone isomer-enriched mixture. FIG. 5 shows the 1H-NMR of 3S-caranone (in pure form) and FIG. 6 shows the 13C-NMR of 3S-caranone (in pure form).

NMR Assignment

[0256] .sup.1H NMR (400 MHz, DMSO-d6): /ppm=2.56-2.47 (m, 1H, COCHCH, superposition from solvent signal), 2.10 (qdd, J=7.3, 5.0, 2.7 Hz, 1H, CHCH.sub.3), 2.03-1.90 (m, 2H, CHCH.sub.3CH.sub.2CH, COCHCH), 1.70-1.62 (m, 1H, CHCH.sub.3CH.sub.2CH), 1.13 (d, J=7.2 Hz, 3H, CHCH.sub.3), 1.04 (s, 3H, CCHCH.sub.3CH.sub.3), 1.03-0.97 (m, 1H, COCH.sub.2CH), 0.90 (s, 3H, CCHCH.sub.3CH.sub.3), 0.80 (td, J=8.9, 6.4 Hz, 1H, CHCH.sub.3CH.sub.2CH).

[0257] .sup.13C NMR (100 MHz, DMSO-d6): /ppm=216.1 (CO), 40.7 (CHCH.sub.3), 33.9 (COCH.sub.2CH), 27.8 (CCHCHCH.sub.3CH.sub.3, 26.3 (CHCH.sub.3CH.sub.2CH), 21.1 (COCH.sub.2CH), 19.0 (CCHCHCH.sub.3CH.sub.3), 16.7 (CHCH.sub.3), 16.4 (COCH.sub.2CH), 14.6 (CCHCHCH.sub.3CH.sub.3).

Embodiment 1.1: Suitable Solvents

[0258]

TABLE-US-00011 TABLE 6 Influence of solvent polarity on the rearrangement of 3S-carane epoxide to a 3S-caranone and 3R-caranone enriched mixture. All experiments were carried out with a concentration of 1M 3S- carane epoxide at 25 C. and 0.2 mol % Fe(ClO.sub.4).sub.2H.sub.2O for 8 h. The conversion of 3S-carane epoxide was 100%. Values refer to the TIC area of the GCMS spectrum (uncorrected values). Relative Caranone 3R- 3S- Solvent polarity * [%] caranone [%] caranone [%] 1 Cyclohexane 0.006 70 11 89 2 Hexane 0.009 64 13 87 3 Toluene 0.099 71 14 86 4 Heptane 0.012 64 13 87 *Source: Christian Reichardt, Solvents and Solvent Effects in Organic Chemistry, Wiley-VCH Publishers, 3rd Ed., 2003

Embodiment 1.2.1: Comparison of Zinc and Iron Lewis Acids

[0259]

TABLE-US-00012 TABLE 7 Comparison of Fe and Zn Lewis acids at 60 C. in cyclohexane with a concentration of 1M 3S-carane epoxide and 0.2% catalyst (mol %). Conver- 3R- 3S- sion Caranone caranone caranone Catalyst [0.2%] [%] [%] [%] [%] t [h] 1 Zn(OTf).sub.2 48 70 9 91 40 2 Fe(OTf).sub.2 91 73 15 85 0.5 3 Fe(ClO.sub.4).sub.2 .Math. H.sub.2O 100 82 15 85 0.5 4 Fe(ClO.sub.4).sub.3 .Math. H.sub.2O 100 81 16 84 0.5 Values refer to the TIC area of the GCMS spectrum (uncorrected values).

Embodiment 1.2.2: Comparison of Different Sulfonic Acids

[0260]

TABLE-US-00013 TABLE 8 Conversion with Meinwald rearrangement of 3S-carane epoxide to a 3S-caranone and 3R-caranone-enriched mixture with various sulfonic acids as acid catalyst. c Conversion Caranone Catalyst [%] Solvent [M] T [ C.] [%] [%] 3R-caranone [%] 3S-caranone [%] t [h] 1 CF.sub.3SO.sub.3H 0.1% Toluene 1 25 100 73 13 87 12 2 PTSA 1% Cyclohexane 1 60 100 69 17 83 12 The values in Table 4 refer to the TIC area of the GCMS spectrum (uncorrected values).

Embodiment 1.3: Suitable Concentrations of Lewis Acid

[0261]

TABLE-US-00014 TABLE 9 Influence of the amount of Fe(ClO.sub.4).sub.2H.sub.2O on the rearrangement to the 3R and 3S-caranone isomers. All experiments were carried out with a concentration of 1M 3S-carane epoxide at 25 C. for 5 h. Values refer to the TIC area of the GCMS spectrum (uncorrected values). All experiments were carried out in cyclohexane. Con- 3R- 3S- version Caranone caranone caranone Fe(ClO.sub.4).sub.2H.sub.2O[mol %] [%] [%] [%] [%] 1 0.1 90 71 20 80 2 0.25 95 69 14 86 3 0.5 98 67 15 85 4 1 100 63 15 85

Embodiment 1.4: Suitable Concentrations of 3S-Carane Epoxide

[0262]

TABLE-US-00015 TABLE 10 Influence of the concentration of 3S-carane epoxide on the rearrangement of 3S-carane epoxide to a 3S-caranone and 3R- caranone enriched mixture. All experiments were carried out at 25 C. and 0.2% Fe(ClO.sub.4).sub.2H.sub.2O for 7 h. Values refer to the TIC area of the GCMS spectrum (uncorrected values). All experiments were carried out in cyclohexane. 3S-carane Conversion Caranone 3R- 3S- epoxide [M] [%] [%] caranone [%] caranone [%] 1 0.25 8 56 20 80 2 0.5 78 74 13 87 3 1.0 100 70 10 90 4 2.0 100 67 10 90 5 3.0 100 66 10 90

Embodiment 1.5: Temperature Influence

[0263]

TABLE-US-00016 TABLE 11 Temperature influence of Lewis acids on the Meinwald rearrangement of 3S-carane epoxide. Conversion Caranone Catalyst [%] Solvent c [M] T [ C.] [%] [%] 3R-caranone [%] 3S-caranone [%] t 1 Fe(ClO.sub.4).sub.2 .Math. H.sub.2O 0.2% Cyclohexane 1 25 100 70 10 90 7 h 2 Fe(ClO.sub.4).sub.2 .Math. H.sub.2O 0.2% Cyclohexane 1 60 100 82 15 85 5 min Values refer to the TIC area of the GCMS spectrum (uncorrected values).

Embodiment 1.6: Non-Iron Based Lewis Acids

[0264] 15.2 mg 3S-carane epoxide (0.1 mmol) are dissolved in 1 mL toluene. Then 2 mol % of Ni(ClO.sub.4).sub.2 solution in ethyl acetate are added and the reaction mixture is heated to 60 C. for 20.5 h. GCMS analysis (uncorrected): Caranone total purity 88.9%, 3S-caranone 92.0%, and 3R-caranone 8.0%.

[0265] 15.2 mg 3S-carane epoxide (0.1 mmol) are dissolved in 1 mL toluene. Then 2 mol % of Co(ClO.sub.4).sub.2 solution in ethyl acetate are added and the reaction mixture is heated to 60 C. for 20.5 h. GCMS analysis (uncorrected): Caranone total purity 89.0%, 3S-caranone 93.3%, and 3R-caranone 6.7%.

[0266] 152 mg 3S-carane epoxide (0.1 mmol) are dissolved in 1 mL toluene. Then 2 mol % Cu(CO.sub.4).sub.2 solution in ethyl acetate are added and the reaction mixture is stirred for 20 h at room temperature. GCMS analysis (uncorrected): Caranone total purity 63.0%, 3S-caranone 85.0%, and 3R-caranone 15.0%.

Embodiment 2.1 (Process Step d)): Isomerization of 3S-Caranone to 3R-Caranone

[0267] 152 L of an approximately 80% solution of a 3S-caranone (87%) and 3R-caranone (13%) enriched mixture from embodiment 1 were dissolved in 845 L MeCN and 5 L sulfuric acid was added. The reaction mixture was stirred at 60 C. for 5 h. The solvent was removed by distillation.

[0268] GCMS analytics (uncorrected): Total selectivity 80% caranone, ratio: 3S-caranone 15%: 85% 3R-caranone. FIG. 4 shows the GC chromatogram of a 3R-caranone isomer-enriched mixture. FIG. 5 shows the 1H-NMR of 3S-caranone (in pure form) and FIG. 6 shows the 13C-NMR of 3S-caranone (in pure form).

Embodiment 2.2 (Process Step d)): Influence of Solvent on the Isomerization of 3S-Caranone to 3R-Caranone (III)

[0269]

TABLE-US-00017 TABLE 12 Influence of the solvent on the isomerization of a 3S-caranone-enriched mixture (purity 79%, 3S-caranone 89%, 3R-caranone 11%). Caranone [%] 3S-caranone [%] 3R-caranone [%] Solvent Relative polarity* (a) (b) (c) (a) (b) (c) (a) (b) (c) 1 Tetrahydrofuran 0.207 76 76 73 22 15 22 78 85 78 2 Ethyl acetate 0.228 77 77 73 45 15 22 55 85 78 3 Acetone 0.355 78 78 30 15 15 0 85 85 100 4 Acetonitrile 0.460 78 78 20 20 18 0 80 82 100 All experiments were carried out with a concentration of 1M 3S-caranone and 2M HCl solution as an isomerization catalyst. Samples were taken after 6 h at room temperature (a), another 15 h at room temperature (b) and another 48 h at 60 C. (c) stirring. Values refer to the TIC area of the GCMS spectrum (uncorrected values).

Embodiment 3.1 (Process Step a1a): Epoxidation of 3-Carene to 3S-Carane Epoxide Using the Enzyme Lipase Cal-B (Over 99%)

[0270] 10.87 g of 3-carene (80 mmol) were dissolved in 160 ml of ethyl acetate and transferred to a reactor with KPG stirring unit and nylon enzyme bag loaded with 2.5 g of Lipase Cal-B from Candida antarctica (immobilized). The mixture was heated to 60 C. and 9.35 g of H.sub.2O.sub.2 35% were added continuously (2 ml/h). After 4 h, the reaction mixture was cooled to room temperature and the enzyme pocket was removed and washed with 250 mL NaOH 2 M, 150 mL saturated Na.sub.2SO.sub.3 solution and 150 mL water. The solvent was removed under vacuum.

[0271] GCMS analysis (uncorrected): 3S-carane epoxide (2)>99%

Embodiment 3.2 (Process Step a1a)): Epoxidation of 3-Carene with Dilute Peracetic Acid to 3S-Carane Epoxide (Over 99%)

[0272] 1 eq. NaOAc is dissolved in 12% peracetic acid to c=1M (corresponds to 1.3 eq peracetic acid) and 1 eq at room temperature. 3-carene was added within an hour. The temperature is kept constantly below 40 C.

[0273] GCMS analysis (uncorrected): 3S-carane epoxide (2)>99%

Exemplary Embodiment 3.3 (Process Step a1b): Epoxidation of 3-Carene to 3R-Carane Epoxide (Purity Over 85%)

[0274] 50 g of 3-carene (367 mmol, 1.0 eq.) were dissolved in 200 mL acetone and 200 mL water and brought to 0 C. 72 g of N-bromosuccinimide (404 mmol, 1.1 eq.) were added in portions; the internal temperature was kept below 10 C. It was stirred for 0.5 h at a temperature below 10 C., then stirred at room temperature for a further 2 h. Subsequently, 250 ml of 5M NaOH were added dropwise (5.5 ml/min.) and the mixture was stirred until the 3R-carane epoxide was completely converted (0.5 h). The reaction mixture was mixed with 200 mL hexane and the phases were separated. The aqueous phase was extracted with 200 mL hexane. The combined organic phases were washed with 250 ml of saturated sodium sulfite solution and 250 ml of water. The solvent was then removed at 50 C. under vacuum. 50 g of 3R-carane epoxide (purity above 85%) were obtained (312 mmol, 85%).

Embodiment 4.1 (Process Step e)): Oximation of 3S-Caranone

[0275] A 3S-caranone and 3R-caranone-enriched mixture (80% purity, 85% 3S-caranone, 15% 3R-caranone) was dissolved in acetonitrile to c=2 M. Then 1.3 eq NaOAc in water were added in the same volume and stirred for 5 min. 1.1 eq HONH.sub.2.HCl are added and the mixture is stirred at 25 C. for one hour.

[0276] GCMS analysis (uncorrected): Total oximes 80%, of which 3S-caranoxime 85%, 3R-caranoxime 15%.

Mass Spectrum:

[0277] MS (EI, 70 eV): m/z (%)=168.05 (1.30), 167.00 (11.80), 166.05 (1.66), 153.10 (1.47), 152.05 (15.72), 151.05 (1.69), 150.05 (10.83), 149.05 (1.90), 148.10 (5.97), 139.10 (2.56).

[0278] MS (EI, 70 eV):% (m/z)=100.00 (41.05), 51.40 (39.10), 47.59 (67.05), 43.19 (112.10), 42.42 (79.05), 41.89 (107.10), 40.65 (55.10), 39.11 (106.05), 38.33 (43.05), 29.88 (81.05).

NMR Assignment

[0279] .sup.1H NMR (400 MHz, DMSO-d6): /ppm=10.07 (s, 1H, NOH), 2.56 (dd, J=18.6, 1.6 Hz, 1H, CNOHCH.sub.2CH), 2.32-2.17 (m, 2H, CHCH.sub.3, CNOHCH.sub.2CH), 1.90-1.78 (m, J=16.8, 8.1, 3.1 Hz, 1H, CHCH.sub.3CH.sub.2CH), 1.37 (dt, J=14.4, 4.9 Hz, 1H, CHCH.sub.3CH.sub.2CH), 1.05 (d, J=7.1 Hz, 3H, CH.sub.2CHCH.sub.3CNOH), 0.96 (s, 3H, CCHCHCH.sub.3CH.sub.3), 0.79 (td, J=8.9, 1.8 Hz, 1H, CNOHCH.sub.2CH) 0.71 (s, 3H, CCHCHCH.sub.3CH.sub.3), 0.69-0.62 (m, 1H, CHCH.sub.3CH.sub.2CH).

[0280] .sup.13C NMR (100 MHz, DMSO-d6): /ppm=161.5 (CNOH), 32.8 (CHCH.sub.3), 28.5 (CCHCHCH.sub.3CH.sub.3), 26.8 (CHCH.sub.3CH.sub.2CH), 19.3 (CH.sub.2CHCH.sub.3CNOH), 19.1 (CNOHCH.sub.2CH), 18.3 (CCHCHCH.sub.3CH.sub.3), 17.1 (CNOHCH.sub.2CH), 16.7 (CHCH.sub.3CH.sub.2CH), 14.9 (CCHCHCH.sub.3CH.sub.3).

[0281] FIG. 7 shows the 1H-NMR of 3S-caranoxime (in pure form) and FIG. 8 shows the 13C-NMR of 3S-caranoxime (in pure form).

Exemplary Embodiment 4.2 (Process Step e): Oximation of 3R-Caranone

[0282] 9.00 g of 3R-caranone (58 mmol) are dissolved in 60 mL acetonitrile. 50 ml of water with 10.6 g of sodium acetate trihydrate (75 mmol) and 4.6 g of hydroxylamine hydrochloride (64 mmol) are then added and the mixture is stirred at 60 C. for 20 h. The reaction mixture was washed with sodium hydrogen carbonate solution and water, dried with magnesium sulfate and concentrated under vacuum. 5 g of the crude product were purified via column chromatography (hexane/EtOAc). The yield was 3.6 g (72%) with a purity of 92%. The ratio of the oximes is 3R-caranoxime 85%, 3S-caranoxime 15%.

Embodiment 5.1.1 (Process Step f1)): Beckmann Rearrangement of 3S-Caranoxime

[0283] The reaction mixture from embodiment 4.1 (process step e)) is cooled to 15 C. and 4 eq NaOH as 10M NaOH are slowly added. After two hours of stirring at 15 C., 1 eq of para-toluenesulfonyl chloride is added in portions and the mixture is stirred for a further two hours at room temperature. The aqueous phase is separated off and extracted with ethyl acetate (twice equal in volume). The organic phases are washed with semi-saturated sodium bicarbonate solution (2) and then with saturated sodium chloride solution.

[0284] GCMS analysis (uncorrected): Caranlactams total purity 62%, 3S-caranlactam 94.9% and 3R-caranlactam 5.1%.

Mass Spectrum

[0285] MS (EI, 70 eV): m/z (%)=168.10 (1.05), 167.15 (8.33), 166.25 (0.70), 154.20 (0.30), 153.20 (4.44), 152.20 (44.99), 151.25 (0.22), 150.20 (0.23), 139.20 (1.42), 138.15 (1.09).

[0286] MS (EI, 70 eV):% (m/z)=100.00 (44.10), 60.39 (67.10), 44.99 (152.20), 44.18 (81.10), 42.43 (82.10), 37.54 (110.15), 35.25 (41.05), 28.11 (57.10), 19.97 (39.05), 19.46 (55.10).

[0287] FIG. 9 shows the 1H-NMR of 3S-caranlactam (in pure form) and FIG. 10 shows the 13C-NMR of 3S-caranlactam (in pure form).

NMR Assignment

[0288] .sup.1H NMR (400 MHz, DMSO-d6): /ppm=6.92 (s, 1H, CONH) 3.5-3.14 (m, 1H, NHCHCH.sub.3CH.sub.2), 2.31-2.15 (m, 2H, COCHCH), 1.71-1.49 (m, 2H, CHCH.sub.2CCHCH.sub.3), 1.05 (d, J=6.4 Hz, 3H, NHCHCH.sub.3), 1.01 (s, 3H, CCHCHCH.sub.3CH.sub.3), 0.97 (s, 3H, CCHCHCH.sub.3CH.sub.3), 0.85-0.76 (m, 1H, CCHCHCH.sub.3CH.sub.3), 0.57 (td, J=9.0, 2.1 Hz, 1H, CCHCHCH.sub.3CH.sub.3)

[0289] .sup.13C NMR (100 MHz, DMSO-d6): /ppm=173.8 (CO), 46.3 (NHCHCH.sub.3), 30.6 (COCH.sub.2CH), 30.4 (CHCH.sub.2CHCH.sub.3), 28.6 (CCHCHCH.sub.3CH.sub.3), 21.11 (NHCHCH.sub.3), 20.1 (COCH.sub.2CH), 20.1 (CHCH.sub.3CH.sub.2CH), 17.4 (CCHCHCH.sub.3CH.sub.3), 14.9 (CCHCHCH.sub.3CH.sub.3).

Embodiment 5.1.2 (Process Step f2): Catalytic Beckmann Rearrangement of 3S-Caranoxime

[0290] 167 mg of 3S-caranoxime (1.0 mmol) were dissolved in 2 mL MeCN and heated under reflux. Then 7.5 mol % of Zn(ClO.sub.4).sub.2. 6H.sub.2O was added and the mixture was stirred for 48 h. The solvent was removed under vacuum and the residue was dissolved in ethyl acetate and washed several times with semi-saturated sodium hydrogen carbonate solution and water. After crystallization from ethyl acetate, 120 mg of 3S-caranlactam were obtained (72%).

Embodiment 5.2 (Process Steps e) and f)): Oximation and Beckmann Rearrangement in One Step (One-Pot)

[0291] 35 g of a mixture of 3S-caranone (15%) and 3R-caranone (85%) were dissolved in 280 ml of acetonitrile (MeCN) and mixed with 280 ml of water and 50 g of sodium acetate. Then 19.5 g of hydroxylamine hydrochloride were added and the mixture was stirred at room temperature for 48 h. The phases were separated and 270 ml of 3M NaOH were added in portions to the organic phase while cooling in an ice bath. The reaction mixture was stirred in an ice bath for 2 h and then 53.2 g of tosyl chloride were added in portions. The reaction mixture was stirred for 4 h, then washed with 2M hydrochloric acid, sodium hydrogen carbonate solution and semi-saturated sodium chloride solution. The solvent was removed under vacuum and the obtained crude product was recrystallized several times from ethyl acetate. 7.90 g (20%) of pure 3R-caranlactam were obtained.

Embodiment 6.1 (Process Steps g) and h)): Obtaining Crystalline 3S-Caranlactam

[0292] The reaction mixture from embodiment 5 (process step f)) is fractionally distilled until the 3S-caranlactam is almost completely crystallized. The remaining portion of 3R-caranlactam cannot crystallize under the reaction conditions and is therefore removed by a further distillation step (process step h)), so that the 3S-caranlactam is obtained. The 3R-caranlactam can be obtained as the distillate from the distillation mentioned.

Exemplary Embodiment 6.2 (Process Steps g) and h)): Obtaining 3R-Caranlactam

[0293] The 3R-caranlactam was obtainable as a pure product from the mother liquor (remaining solution from embodiment 6.1) of the synthesis of 3S-caranlactam after distillation (bp: 350 C.) and multiple recrystallization (ethyl acetate).

Embodiment 6.3 (Process Steps g) and h)): Obtaining 3R-Caranlactam

[0294] 3.50 g of 3R-caranoxime (21 mmol) were dissolved in 25 mL acetonitrile and cooled in an ice bath. Then 33 mL NaOH 2M were added in portions and stirred for 2 h. Then 4.50 g of tosyl chloride (23 mmol) were added in portions and the mixture was stirred in an ice bath for 2.5 h.

[0295] The reaction mixture was washed with sodium hydrogen carbonate solution and water, dried with magnesium sulfate and concentrated under vacuum. The crude product was recrystallized from ethyl acetate at 20 C. and 2.61 g (75%) of pure 3R-caranlactam were obtained.

Embodiment 7.1 (Process Step i)): Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0296] 300 mg of 3S-caranlactam (1.8 mmol), 10 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.036 mmol) and 0.5 mg of NaH on paraffin (0.02 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 180 C. oil bath and stirred. The polymerization was complete after about 20 seconds, the polymer was slowly cooled to room temperature and a partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

Embodiment 7.1.1 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0297] 300 mg of 3S-caranlactam (1.80 mmol), 10 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.036 mmol) and 0.5 mg of NaH on paraffin (0.01 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 180 C. oil bath and stirred. The reaction mixture was kept at temperature for five minutes, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0298] DSC method (3.1)

[0299] Tg (center point): 115 C.

[0300] Tm (range): 260-290 C.

[0301] Mn: 10.5 kDa (GPC method 4.2)

[0302] Mw: 16.8 kDa (GPC method 4.2)

[0303] PD: 1.6

[0304] 1H (FIG. 11)

[0305] 13C (FIG. 12)

[0306] COSY: (FIG. 13)

[0307] HSQC: (FIG. 14)

[0308] DEPT: (FIG. 15)

[0309] DSC: (FIG. 25)

[0310] GPC: (FIG. 51)

[0311] Crystallinity: semi-crystalline

Embodiment 7.1.2 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0312] 300 mg of 3S-caranlactam (1.8 mmol), 5.4 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.02 mmol) and 3.5 mg of NaH on paraffin (0.09 mmol) were mixed in a vacuum glass vessel mixed and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 180 C. oil bath and stirred. The reaction mixture was kept at temperature for 1.5 hours, then was cooled in air to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0313] DSC method (3.1)

[0314] Tg (center point): 115 C.

[0315] Tm (range): 250-285 C.

[0316] Mn: 10.2 (GPC method 4.2)

[0317] Mw: 16.2 (GPC method 4.2)

[0318] PD: 1.6

[0319] DSC: (FIG. 26)

[0320] GPC: (FIG. 52)

[0321] Crystallinity: semi-crystalline

Embodiment 7.1.3 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0322] 302 mg 3S-caranlactam (1.81 mmol), 9.8 mg N-benzoyl-3S-caranlactam (Bz-5, 0.036 mmol) and 0.9 mg NaH on paraffin (0.02 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 180 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0323] DSC process 3.1

[0324] Tg (center point): 115 C.

[0325] Tm (range): 260-290 C.

[0326] Mn: 9.3 kDa (GPC method 4.2)

[0327] Mw: 14.5 kDa (GPC method 4.2)

[0328] PD: 1.6

[0329] DSC: (FIG. 27)

[0330] GPC: (FIG. 53)

[0331] Crystallinity: semi-crystalline

Embodiment 7.1.4 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0332] 305 mg of 3S-caranlactam (1.84 mmol), 10.7 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.039 mmol) and 1.6 mg of NaH on paraffin (0.04 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 180 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0333] DSC process 3.1

[0334] Tg (center point): 113 C.

[0335] Tm (range): 255-285 C.

[0336] Mn: 9.1 kDa (GPC method 4.2)

[0337] Mw: 14.1 kDa (GPC method 4.2)

[0338] PD: 1.3

[0339] DSC: (FIG. 28)

[0340] GPC: (FIG. 54)

[0341] Crystallinity: semi-crystalline

Embodiment 7.1.5 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0342] 308 mg of 3S-caranlactam (1.84 mmol), 20.7 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.076 mmol) and 4.0 mg of NaH on paraffin (0.1 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 180 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0343] DSC process 3.1

[0344] Tg (center point): 111 C.

[0345] Tm (range): 245-285 C.

[0346] Mn: 6.7 kDa (GPC method 4.2)

[0347] Mw: 9.5 kDa (GPC method 4.2)

[0348] PD: 1.4

[0349] DSC: (FIG. 29)

[0350] GPC: (FIG. 55)

[0351] Crystallinity: semi-crystalline

Embodiment 7.1.6 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0352] 300 mg of 3S-caranlactam (1.80 mmol), 30.0 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.11 mmol) and 3.9 mg of NaH on paraffin (0.10 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 180 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0353] DSC process 3.1

[0354] Tg (center point): 105

[0355] Tm (range): 240-280 C.

[0356] Mn: 5.9 kDa (GPC method 4.2)

[0357] Mw: 8.3 kDa (GPC method 4.2)

[0358] PD: 1.4

[0359] DSC: (FIG. 30)

[0360] GPC: (FIG. 56)

[0361] Crystallinity: semi-crystalline

Embodiment 7.1.7 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0362] 300 mg of 3S-caranlactam (1.8 mmol), 4.9 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.02 mmol) and 4.0 mg of NaH on paraffin (0.1 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 220 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0363] DSC process 3.1

[0364] Tg (center point): 112 C.

[0365] Tm (range): 240-275 C.

[0366] Mn: 7.5 kDa (GPC method 4.2)

[0367] Mw: 9.6 kDa (GPC method 4.2)

[0368] PD: 1.3

[0369] DSC: (FIG. 31)

[0370] GPC: (FIG. 57)

[0371] Crystallinity: semi-crystalline

Embodiment 7.1.8 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0372] 300 mg of 3S-caranlactam (1.8 mmol), 10.6 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.04 mmol) and 3.8 mg of NaH on paraffin (0.1 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 220 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0373] DSC process 3.1

[0374] Tg (center point): 112 C.

[0375] Tm (range): 230-270 C.

[0376] Mn: 7.1 kDa (GPC method 4.2)

[0377] Mw: 9.0 kDa (GPC method 4.2)

[0378] PD: 1.3

[0379] DSC: (FIG. 32)

[0380] GPC: (FIG. 58)

[0381] Crystallinity: semi-crystalline

Embodiment 7.1.9 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0382] 309 mg of 3S-caranlactam (1.85 mmol), 19.6 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 4.0 mg of NaH on paraffin (0.1 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 220 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0383] DSC process 3.1

[0384] Tg (center point): 110 C.

[0385] Tm (range): 240-280

[0386] Mn: 6.0 kDa (GPC method 4.2)

[0387] Mw: 7.5 kDa (GPC method 4.2)

[0388] PD: 1.3

[0389] DSC: (FIG. 33)

[0390] GPC: (FIG. 59)

[0391] Crystallinity: semi-crystalline

Embodiment 7.1.10 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0392] 300 mg of 3S-caranlactam (1.83 mmol), 30.0 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.11 mmol) and 3.8 mg of NaH on paraffin (0.1 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 220 C. oil bath and stirred. The reaction mixture was kept at temperature for one hour, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline 3S-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0393] DSC process 3.1

[0394] Tg (center point): 109 C.

[0395] Tm (range): 230-270

[0396] Mn: 5.6 kDa (GPC method 4.2)

[0397] Mw: 7.3 kDa (GPC method 4.2)

[0398] PD: 1.3

[0399] DSC: (FIG. 34)

[0400] GPC: (FIG. 60)

[0401] Crystallinity: semi-crystalline

Embodiment 7.1.11 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0402] 523 mg of 3S-caranlactam (3.1 mmol), 10.4 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.038 mmol) and 3.7 mg of NaH on paraffin (0.09 mmol) were polymerized under nitrogen in a heating block for one hour at 190 C. in a glass reaction. The polymer was dissolved directly in hexafluoroisopropanol (HFIP) and samples were taken for GPC and NMR analysis.

[0403] Mn: 8.6 kDa (GPC method 4.2)

[0404] Mw: 16.9 kDa (GPC method 4.2)

[0405] PD: 2.0

[0406] GPC: (FIG. 61)

Embodiment 7.1.12 (Process Step i))

Polymerization of 3S-Caranlactam to a 3S-Polycaranamide

[0407] 500 mg of 3R-caranlactam (3.0 mmol) were melted under an inert atmosphere at 190 C. in a flask with stirring. Then 5.0 mg NaH on paraffin (0.13 mmol) and 4.5 L acetic anhydride (0.048 mmol) were added. After the reaction mixture had solidified, it was slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0408] Mn: 1.4.Math.10.sup.4 g/mol (GPC method 4.1)

[0409] Mw: 65.2.Math.10.sup.5 g/mol (GPC method 4.1)

[0410] Tg: 110-120 C. (DSC process 3)

[0411] Tm: 260-290 C. (DSC process 3)

[0412] GPC: (FIG. 78)

[0413] DSC: (FIG. 81)

[0414] Crystallinity: semi-crystalline

Embodiment 7.2 (Process Step i)): Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0415] 300 mg of 3R-caranlactam (1.8 mmol), 10 mg of N-benzoyl-3R-caranlactam (0.036 mmol) and 0.5 mg of NaH on paraffin (0.02 mmol) were mixed in a vacuum vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 170 C. oil bath and stirred. After about 20 seconds, the polymerization was complete, the polymer was slowly cooled to room temperature and an amorphous 3R-polycaranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

Embodiment 7.2.1 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0416] 500 mg of 3R-caranlactam (3.0 mmol) were melted under an inert atmosphere at 170 C. in a flask with stirring. Then 3.0 mg NaH on paraffin (0.08 mmol) and 1.5 L acetic anhydride (0.016 mmol) were added. The reaction mixture was kept at temperature for 20 seconds, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0417] Tg (center point): 122 C. (DSC process 3.2)

[0418] Tm (range): not available (DSC process 3.2)

[0419] Tg: 110-120 C. (DSC process 3)

[0420] Tm (area): not available (DSC process 3)

[0421] Mn: 1.1.10.sup.5 g/mol (GPC method 4.1)

[0422] Mw: 3.0-10.sup.5 g/mol (GPC method 4.1)

[0423] Mn: 33.3 kDa (GPC method 4.2)

[0424] Mw: 64.7 kDa (GPC method 4.2)

[0425] PD: 1.9

[0426] 1H (FIG. 16)

[0427] 13C (FIG. 17)

[0428] COSY: (FIG. 18)

[0429] HSQC: (FIG. 19)

[0430] DEPT: (FIG. 20)

[0431] DSC: FIG. 82 (DSC process 3)

[0432] DSC: FIG. 35 (DSC process 3.2)

[0433] GPC: (FIG. 62)

[0434] GPC: (FIG. 79)

[0435] Crystallinity: amorphous

Embodiment 7.2.2 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0436] 500 mg of 3R-caranlactam (3.0 mmol) were melted under an inert atmosphere at 170 C. in a flask with stirring. Then 5.0 mg NaH on paraffin (0.13 mmol) and 4.5 L acetic anhydride (0.05 mmol) were added. The reaction mixture was kept at temperature for 30 minutes, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0437] Mn: 29.5 kDa (GPC method 4.2)

[0438] Mw: 55.2 kDa (GPC method 4.2)

[0439] PD: 1.9

[0440] GPC: (FIG. 63)

Embodiment 7.2.3 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0441] 1.0 g of 3R-caranlactam (6.0 mmol), 14.6 mg of potassium (0.37 mmol) and 20 L of benzoyl chloride (0.17 mmol) were polymerized under an inert atmosphere at 150 C. in a flask with stirring. The reaction mixture was kept at temperature for 6 hours, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0442] Mn: 22.4 kDa (GPC method 4.2)

[0443] Mw: 38.1 kDa (GPC method 4.2)

[0444] PD: 1.7

[0445] GPC: (FIG. 64)

Embodiment 7.2.4 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0446] 511 mg of 3R-caranlactam (3.1 mmol), 0.6 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.002 mmol) and 3.5 mg of NaH on paraffin (0.09 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190 C. The polymer was directly dissolved in hexafluoroisopropanol (HFIP) and samples were taken for GPC and NMR analysis. An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0447] DSC process 3.2

[0448] Tg (center point): 119 C.

[0449] Tm (range): not available

[0450] Mn: 19.9 kDa (GPC method 4.2)

[0451] Mw: 32.9 kDa (GPC method 4.2)

[0452] PD: 1.7

[0453] DSC: (FIG. 36)

[0454] GPC: (FIG. 65)

[0455] Crystallinity: amorphous

Embodiment 7.2.5 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0456] 506 mg of 3R-caranlactam (3.0 mmol), 1.03 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.004 mmol) and 3.3 mg of NaH on paraffin (0.08 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190 C. The polymer was directly dissolved in hexafluoroisopropanol (HFIP) and samples were taken for GPC and NMR analysis. An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0457] DSC process 3.2

[0458] Tg (center point): 120 C.

[0459] Tm (range): not available

[0460] Mn: 20.2 kDa (GPC method 4.2)

[0461] Mw: 43.8 kDa (GPC method 4.2)

[0462] PD: 2.2

[0463] DSC: (FIG. 37)

[0464] GPC: (FIG. 66)

[0465] Crystallinity: amorphous

Embodiment 7.2.6 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0466] 505 mg of 3R-caranlactam (3.0 mmol), 2.45 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.009 mmol) and 3.3 mg of NaH on paraffin (0.08 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190 C. The polymer was directly dissolved in hexafluoroisopropanol (HFIP) and samples were taken for GPC and NMR analysis. An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0467] DSC process 3.2

[0468] Tg (center point): 117 C.

[0469] Tm (range): not available

[0470] Mn: 19.6 kDa (GPC method 4.2)

[0471] Mw: 45.6 kDa (GPC method 4.2)

[0472] PD: 2.3

[0473] DSC: (FIG. 38)

[0474] GPC: (FIG. 67)

[0475] Crystallinity: amorphous

Embodiment 7.2.7 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0476] 508 mg of 3R-caranlactam (3.0 mmol), 5.13 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.02 mmol) and 3.2 mg of NaH on paraffin (0.08 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190 C. The polymer was directly dissolved in hexafluoroisopropanol (HFIP) and samples were taken for GPC and NMR analysis. An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0477] DSC process 3.2

[0478] Tg (center point): 116 C.

[0479] Tm (range): not available

[0480] Mn: 15.2 kDa (GPC method 4.2)

[0481] Mw: 36.3 kDa (GPC method 4.2)

[0482] PD: 2.4

[0483] DSC: (FIG. 39)

[0484] GPC: (FIG. 68)

[0485] Crystallinity: amorphous

Embodiment 7.2.8 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0486] 513 mg of 3R-caranlactam (3.1 mmol), 7.50 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.03 mmol) and 3.5 mg of NaH on paraffin (0.09 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190 C. The polymer was directly dissolved in hexafluoroisopropanol (HFIP) and samples were taken for GPC and NMR analysis. An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0487] DSC process 3.2

[0488] Tg (center point): 115 C.

[0489] Tm (range): not available

[0490] Mn: 13.5 kDa (GPC method 4.2)

[0491] Mw: 31.8 kDa (GPC method 4.2)

[0492] PD: 2.3

[0493] DSC: (FIG. 40)

[0494] GPC: (FIG. 69)

[0495] Crystallinity: amorphous

Embodiment 7.2.9 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0496] 512 mg of 3R-caranlactam (3.1 mmol), 10.2 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.04 mmol) and 3.4 mg of NaH on paraffin (0.09 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190 C. The polymer was directly dissolved in hexafluoroisopropanol (HFIP) and samples were taken for GPC and NMR analysis. An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0497] DSC process 3.2

[0498] Tg (center point): 117 C.

[0499] Tm (range): not available

[0500] Mn: 13.1 kDa (GPC method 4.2)

[0501] Mw: 29.7 kDa (GPC method 4.2)

[0502] PD: 2.3

[0503] DSC: (FIG. 41)

[0504] GPC: (FIG. 70)

[0505] Crystallinity: amorphous

Embodiment 7.2.10 (Process Step i))

Polymerization of 3R-Caranlactam to a 3R-Polycaranamide

[0506] 900 mg of 3R-caranlactam (5.39 mmol), 5.5 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.02 mmol) and 7.5 mg of NaH on paraffin (0.19 mmol) were mixed in a vacuum glass vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to a 170 C. oil bath and stirred. The reaction mixture was kept at temperature for 30 minutes, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous poly-3R-caranamide was obtained. According to NMR analysis, the homopolymers are isotactic.

[0507] DSC process 3.2

[0508] Tg (center point): 112 C.

[0509] Tm (range): not available

[0510] Mn: 24.6 kDa (GPC method 4.2)

[0511] Mw: 55.5 kDa (GPC method 4.2)

[0512] PD: 2.3

[0513] DSC: (FIG. 42)

[0514] GPC: (FIG. 71)

[0515] Crystallinity: amorphous

Embodiment 7.3 (Process Step i)): Polymerization of 3S-Caranlactam with 3R-Caranlactam to a 3S/3R-Co-Polycaranamide

[0516] 150 mg 3R-caranlactam (0.9 mmol), 150 mg 3S-caranlactam (0.9 mmol), 10 mg N-benzoyl-3S-caranlactam (0.036 mmol) and 0.5 mg NaH on paraffin (0.02 mmol) were mixed in a vacuum vessel and evacuated for 10 min. at 2 mbar. The reaction vessel was transferred to an oil bath at 180 C. and stirred. After about 20 seconds, the polymerization was complete, the polymer was slowly cooled to room temperature and an amorphous 3S/3R-polycaranamide was obtained.

Exemplary Embodiment 7.3.1 (Process Step i))

Polymerization of 3S-Caranlactam and 3R-Caranlactam to a 3S-Caranlactam-3R-Caranlactam Co-Polycaranamide

[0517] 250 mg of 3R-caranlactam (1.5 mmol) and 250 mg of 3S-caranlactam (1.5 mmol) were melted under an inert atmosphere at 190 C. in a flask with stirring. Then 5.0 mg NaH on paraffin (0.13 mmol) and 4.5 L acetic anhydride (0.048 mmol) were added. The reaction mixture was kept at temperature for 30 minutes, then slowly cooled to room temperature. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous 3S-caranlactam-3R-caranlactam-polycaranamide was obtained.

[0518] Tg (center): 112 C. (DSC process 3.2)

[0519] Tm (range): not available (DSC process 3.2)

[0520] Tg: 110-120 C. (DSC process 3)

[0521] Tm (area): not available (DSC process 3)

[0522] Mn: 3.2.Math.10.sup.4 (GPC method 4.1)

[0523] Mw: 1.1.Math.10.sup.5 (GPC method 4.1)

[0524] 1H (FIG. 21)

[0525] 13C (FIG. 22)

[0526] DSC: (FIG. 43)

[0527] DSC: (FIG. 83)

[0528] GPC: (FIG. 80)

[0529] Crystallinity: amorphous

Embodiment 7.3.2 (Process Step i))

Polymerization of 3S-Caranlactam and 3R-Caranlactam to a 3S-Caranlactam-3R-Caranlactam Co-Polycaranamide

[0530] 750 mg of 3S-caranlactam (5.5 mmol), 362 mg of caprolactam (0.9 mmol), 20.2 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 8.0 mg of NaH Paraffin (0.20 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block for one hour at 190 C. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). A partially crystalline poly-3S-caranlactam-3R-caranlactam co-polyamide was obtained.

[0531] DSC process 3.2

[0532] Mn: 10.4 kDa (GPC method 4.2)

[0533] Mw: 15.0 kDa (GPC method 4.2)

[0534] PD: 1.4

[0535] Tg (center): 109 C.

[0536] Tm (range): 210-250 C.

[0537] DSC: (FIG. 44)

[0538] GPC: (FIG. 72)

[0539] Crystallinity: semi-crystalline

Embodiment 8 (Process Step i2): Co-Polymerization of 3S-Caranlactam with Laurolactam

[0540] 5.00 g of laurolactam (26 mmol) were melted at 190 C. and 2.50 g of 3S-caranlactam (15 mmol) were dissolved therein. Then 75 mg of N-benzoyl-3S-caranlactam (JUPAC: (1R,5S,7S)-4-benzoyl-5,8,8-trimethyl-4-azabicyclo[5.1.0]octan-3-one) and 50 mg NaH 60% on paraffin wax were added. After the polymerization had taken place, the temperature was kept at 190 C. for 30 minutes, then the mixtures was cooled to room temperature without active cooling. The polymer obtained was milled and stirred in an ethanol-water mixture (1:1) for 24 h at reflux temperature. After filtration, the polymer obtained was dried at 120 C. for 16 h.

[0541] Glass transition point Tg range: 40-50 C.

[0542] Melting point Tm range: Not visible

[0543] Crystallinity: amorphous

Embodiment 8.1.1 (Process Step i2))

Polymerization of 3S-Caranlactam and Laurolactam to a 3S-Caranlactam-Laurolactam Co-Polycaranamide

[0544] 1.0 g laurolactam (5.0 mmol), 500 mg 3S-caranlactam (3.0 mmol), 50 mg N-benzoyl-3S-caranlactam (Bz-5, 0.18 mmol) and 18 mg NaH on paraffin (0.45 mmol) were polymerized in a glass reaction vessel under nitrogen in an oil bath for one hour at 190 C. The residual monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. An amorphous 3S-caranlactam-laurolactam co-polycaranamide was obtained.

[0545] DSC process 3.2

[0546] Tg (center): 46 C.

[0547] Tm (range): not available

[0548] 1H (FIG. 23)

[0549] Mn: 12.5 kDa (GPC method 4.2)

[0550] Mw: 24.5 kDa (GPC method 4.2)

[0551] PD: 2.0

[0552] DSC: (FIG. 45)

[0553] GPC: (FIG. 73)

[0554] Crystallinity: amorphous

Embodiment 8.1.2 (Process Step i2))

Polymerization of 3S-Caranlactam and Laurolactam to a 3S-Caranlactam-Laurolactam Co-Polycaranamide

[0555] 10 g laurolactam (50 mmol), 5 g 3S-caranlactam (30 mmol), 54 mg N-benzoyl-3S-caranlactam (Bz-5, 0.2 mmol) and 20 mg NaH on paraffin (0.50 mmol) were polymerized in a glass reaction vessel under nitrogen in an oil bath for one hour at 190 C. The residual monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. An amorphous 3S-caranlactam-laurolactam co-polycaranamide was obtained.

[0556] DSC process 3.2

[0557] Mn: 30.2 kDa (GPC method 4.2)

[0558] Mw: 60.1 kDa (GPC method 4.2)

[0559] PD: 2.0

[0560] Tg (center): 49 C.

[0561] Tm (range): not available

[0562] DSC: (FIG. 46)

[0563] GPC: (FIG. 74)

[0564] Crystallinity: amorphous

Embodiment 8.1.3 (Process Step i2))

Polymerization of 3S-Caranlactam and Laurolactam to a 3S-Caranlactam-Laurolactam Co-Polycaranamide

[0565] 411 mg of 3S-caranlactam (2.5 mmol), 486 mg of laurolactam (2.5 mmol), 20.0 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 8.0 mg of NaH Paraffin (0.20 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block at 190 C. for one hour. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous 3S-caranlactam-laurolactam co-polyamide was obtained.

[0566] DSC process 3.2

[0567] Mn: 10.0 kDa (GPC method 4.2)

[0568] Mw: 15.6 kDa (GPC method 4.2)

[0569] PD: 1.6

[0570] Tg (center point): 55 C.

[0571] Tm (range): not available

[0572] DSC: (FIG. 47)

[0573] GPC: (FIG. 75)

[0574] Crystallinity: amorphous

Exemplary Embodiment 8.2.1 (Process Step i2)

Polymerization of 3S-Caranlactam and Caprolactam to a 3S-Caranlactam-Caprolactam Co-Polycaranamide

[0575] 5.0 g caprolactam (44 mmol), 2.5 g 3S-caranlactam (15 mmol), 75 mg N-benzoyl-3S-caranlactam (Bz-5, 0.28 mmol) and 50 mg NaH on paraffin (1, 3 mmol) were polymerized in a glass reaction vessel under nitrogen in an oil bath at 190 C. for one hour. The residual monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. A partially crystalline 3S-caranlactam-caprolactam co-polycaranamide was obtained.

[0576] DSC process 3.2

[0577] Mn: 15.2 kDa (GPC method 4.2)

[0578] Mw: 31.1 kDa (GPC method 4.2)

[0579] PD: 2.0

[0580] Tg (center): 62 C.

[0581] Tm (range): 160-190 C.

[0582] 1H (FIG. 24)

[0583] DSC: (FIG. 48)

[0584] GPC: (FIG. 76)

[0585] Crystallinity: semi-crystalline

Exemplary Embodiment 8.2.2 (Process Step i2)

Polymerization of 3S-Caranlactam and Caprolactam to a 3S-Caranlactam-Caprolactam Co-Polycaranamide

[0586] 537 mg of 3S-caranlactam (3.2 mmol), 362 mg of caprolactam (3.2 mmol), 20.1 mg of N-benzoyl-3S-caranlactam (Bz-5, 0.07 mmol) and 7.9 mg of NaH on paraffin (0.20 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block at 190 C. for one hour. The obtained polymer was milled. The residual monomers and soluble oligomers were removed by refluxing in a mixture of water and ethanol (1:1). An amorphous 3S-caranlactam-caprolactam co-polycaranamide was obtained.

[0587] DSC process 3.2

[0588] Mn: 12.1 kDa (GPC method 4.2)

[0589] Mw: 17.3 kDa (GPC method 4.2)

[0590] PD: 1.4

[0591] Tg (center): 88 C.

[0592] Tm (range): not available

[0593] DSC: (FIG. 49)

[0594] GPC: (FIG. 77)

[0595] Crystallinity: amorphous

Exemplary Embodiment 8.2.3 (Process Step i2)

Polymerization of 3S-Caranlactam and Caprolactam to a 3S-Caranlactam-Caprolactam Co-Polycaranamide

[0596] 250 mg 3S-caranlactam (1.5 mmol), 57 mg caprolactam (0.5 mmol), 10 mg N-benzoyl-3S-caranlactam (Bz-5, 0.04 mmol) and 1.5 mg NaH on paraffin (0.04 mmol) were polymerized in a glass reaction vessel under nitrogen in a heating block at 175 C. for one hour. The obtained polymer was milled. The residual monomers and oligomers were separated by precipitation of the polymer from HFIP with ethanol. An amorphous poly-3S-caranlactam-caprolactam co-polycaranamide was obtained.

[0597] DSC process 3.2

[0598] Tg (center): 99 C.

[0599] Tm (range): not available

[0600] DSC: (FIG. 50)

[0601] Crystallinity: amorphous

Embodiment 9 (Process Step i2): Co-Polymerization of 3S-Caranlactam with Caprolactam

[0602] 5.00 g of caprolactam (44 mmol) were melted at 190 C. and 2.50 g of 3S-caranlactam (15 mmol) were dissolved therein. Then 75 mg of N-benzoyl-3S-caranlactam (JUPAC: (1R,5S,7S)-4-benzoyl-5,8,8-trimethyl-4-azabicyclo[5.1.0]octan-3-one) and 50 mg NaH 60% on paraffin wax were added. After the polymerization had taken place, the temperature was kept at 190 C. for 30 minutes, then the mixture was cooled to room temperature without active cooling. The polymer obtained was milled and stirred in an ethanol-water mixture (1:1) for 24 h at reflux temperature. After filtration, the polymer obtained was dried at 120 C. for 16 h.

[0603] Glass transition point Tg range: 50-60 C.

[0604] Melting point Tm range: 160-200 C.

[0605] Crystallinity: semi-crystalline

Embodiment 10: Water Absorption of a 3R-Polyamide

[0606] PA6 was prepared by anionic ring opening polymerization (2.8 mmol caprolactam, 0.1 mmol NaH 60% on paraffin wax, 0.05 mmol Ac.sub.2O, 180 C.). Residual monomer was removed by refluxing in water/ethanol. 30-42 mg of PA6 (three samples) and two samples of poly-3R-caranamide were annealed in the DSC (same device as described in DSC analytical method (3)) for three minutes at 230 C., resulting in the production of uniform polyamide blocks. The masses were determined on an OHAUS Discovery DV215CD balance with a maximum error of 0.01 mg. The samples were then each stirred in water at 25 C. for three days. The samples were then air dried and weighed after 30 minutes and four and a half hours. The samples were then dried at 80 C. for three hours and weighed. This time was sufficient for the poly-3R-caranamide samples to dry completely. The overall higher water absorption of PA6 and the longer drying time of PA6 indicate a generally lower water absorption of the aliphatic substituted poly-3R-caranamide compared to PA6.

TABLE-US-00018 TABLE 13 Water absorption. Pretreatments A B C. D Sample weight [mg] Entry Polyamide Water absorption [w %] 1 PA6-1 35.66 37.45 37.01 36.05 5.4 4.0 1.5 2 PA6-2 37.78 39.57 39.36 38.16 4.9 4.3 1.1 3 PA6-3 31.86 33.67 32.58 32.2 5.7 2.3 1.1 4 Poly-3R- 40.75 41.44 40.80 40.62 caranamide- 2.0 0.44 0 1 5 Poly-3R- 30.89 31.32 30.92 30.7 caranamide- 2.3 0.75 <0.1 2 Pretreatments: A = polyamide block from the DSC; B = water bath (3 days) and air drying (30 minutes); C = air drying (four and a half hours); D = drying at 80 C. (3.0 hours)

Embodiment 11.1: Qualitative Measurement of the Transparency of 3R-Polyamide Compared to PA6 and PA12

[0607] 3R-polyamide was dissolved in HFIP (25 mg/mL) and applied to a PTFE film by carefully dropping it on. After evaporation of the solvent and drying for three hours at 85 C., a transparent film with defects due to uneven evaporation and air inclusions was obtained, compared to PA6 and PA12.

Embodiment 11.2: Qualitative Measurement of the Transparency of Amorphous 3S-Caranlactam-Laurolactam Co-Polycaranamide in Comparison to PA6 and PA12

[0608] Amorphous 3S-caranlactam-laurolactam co-polycaranamide was dissolved in HFIP (25 mg/mL) and transferred to a crystallizing dish (diameter 9 cm). After evaporation of the solvent and drying for three hours at 85 C., a transparent (transparent) film with defects due to uneven evaporation and air inclusions was obtained, compared to PA6 and PA12.

Embodiment 11.3: Qualitative Measurement of the Transparency of Amorphous 3S-Caranlactam-Caprolactam Co-Polycaranamide in Comparison to PA6 and PA12

[0609] Amorphous 3S-caranlactam-caprolactam co-polycaranamide was dissolved in HFIP (25 mg/mL) and applied to a PTFE film by carefully dropping it on. After evaporation of the solvent and drying for three hours at 85 C., a transparent (transparent) film with defects due to uneven evaporation and air inclusions was obtained, compared to PA6 and PA12.