CS243565B1 - Tetracyclic hydrocarbons with 11 carbons and method of their preparation - Google Patents

Description

The present invention relates to novel tetracyclic hydrocarbons of 11 carbons and to a process for their preparation.

Polycyclic hydrocarbons, whether natural or artificially prepared, have long been the subject of systematic research. Essential for their use are their characteristic properties resulting from their number of cycles, substituents, spatial shape of the molecule and its symmetry.

The best-known polycyclic hydrocarbons are adamantane C10H16 (preparation from the cyclopentadiene dimer: eg Schneider A., Warren RW, Janoski EJ, J. Amer. Chem. Soc., 86, 5 366 (1964)) and diamantane C14H20 (preparation from cycloheptatriene according to (certificate No 212 821). Hydrocarbons having a C11 backbone are available only by sophisticated syntheses, eg Katsushima S., Yamaguchi R., Kawanishi M., Bull. Chem. Soc. Japan 55, 3245 (1982 J and not commercially available).

The present invention provides tetracyclic hydrocarbons having 11 carbons of the general formula

where Ri and R? are 2 H or a combination of H and Z is a single or double bond.

The present invention further provides a process for preparing 11-carbon tetracyclic hydrocarbons by treating a mixture of 1,3,5-cycloheptatriene and a diene selected from butadiene, isoprene or 1,3-pentadiene in a molar ratio of 1: 0.5 to 5. 50 to 1,000 times the molar amount of a compound of the formula AIR 1 R 2 R 3, wherein R 1 is ethyl, R 2 and R 3 is ethyl and / or chlorine, and at the same time a complex selected from TiCl 2, TiCl 2, AlCl 3.

. Dichlorθitanθ, dichlorotitanium diacetylacetonate (Cs 2 O 2 O 2 Z 2 TiCl 3) or an alkyl titanium (Ti) OR (4) wherein R is an alkyl of 2 to 6 carbons, maintaining an Al: Ti molar ratio of 2 to 50: 1 in an aromatic solvent at 20 to 80 ° C The reaction mixture is quenched with ethanol, shaken with water and the organic phase is heated at 175 to 240 ° C for 1 to 4 hours and the resulting unsaturated tetracyclic hydrocarbons of 11 carbons are isolated and optionally hydrogenated saturated tetracyclic hydrocarbons at 20 to 40 ° C and normal pressure using a platinum catalyst.

Unsaturated tetracyclic hydrocarbons are formed by catalyzed addition of butadiene, isoprene and 1,3-pentadiene to 1,3,5-cycloheptatriene and subsequent thermal intramolecular cyclization of the addition products. Intramolecular cyclization proceeds quantitatively and the isolation of unsaturated tetracyclic hydrocarbons from cycloheptatriene dimer admixtures and trimers and diene dimers is accomplished by vacuum distillation, optionally supplemented by column chromatography.

The 11-carbohydrate tetracyclic hydrocarbons of the invention find analogous uses to adamantane and its homologues and derivatives thereof, i.e., in medicine as antiviral agents, as bulky substituents retarding the hydrolytic or enzymatic cleavage of biologically active substances and drugs, or in polymer chemistry to prepare highly resistant polymers either as substituents or as additives.

Furthermore, they can be used in organic synthesis as intermediates for the preparation of more complex derivatives, for example by the Diels-Alder reaction with conjugated dienes or photochemical reactions with olefins. Technically the simplest is to prepare tetracyclo (5.4.0.0 ^{2 '6} .0 ^{4' 10]} undec-8-ene and its hydrogenated derivative.

The invention is further illustrated by the following examples without being limited thereto.

Example 1

To 8 ml of liquid butadiene was added 8 ml of 1,3,5-cycloheptatriene and 8 ml of benzene solution of diethylaluminum chloride (C 2 H 5 Z 2 AlCl (1 Nj), followed by 4 ml of benzene titanium tetrachloride solution TiCl 3 (0.1 Nj). The mixture was sealed in a glass vial and heated in a thermostat at 60 ° C for 6 hours, after which the vial was opened, 1 ml of ethanol was added, and after gas evolution was complete, the reaction mixture was poured into a water shaker and repeatedly shaken.

The organic phase was dried over anhydrous sodium sulfate, poured into a glass vial, partially concentrated under evacuation, and the vial was sealed and heated in a thermostat at 240 degrees C for 2 hours. After cooling to room temperature, 10 ml of hexane was added to the partially solid product and the resulting solution was subjected to silica gel column chromatography with n-hexane as eluent. The first portions containing pure tetracyclo [5.4.0.0 ^{3 ', 4} .0 ^lu] undec-8-ene, 8 g total.

Tetracyclo [5.4.0.0 ² ' ⁶ .0 ⁴ ' ¹⁰ ] undec-8-ene (R 1 = H, R 2 = H) has a mp of 149-151 ° C, a molecular weight of 146 and the following additional properties:

Infrared spectrum:

033, 1,311, 1,247,

937, 1,297, 1,225,

867, 1 293, 1180,

613, 1 280, 1137,

1453, 1,367, 1273, 1254, 1127, 1104,

073, 1,039, 1,017, 1,010, 1,000, 971, 960, 932, 919, 907, 865, 849, 830, 813, 781, 767, 747, 727, 714, 697, 680, 663, 590, 559, 530, 503 ^cm-first

'H-NMR (CDCl3, δ, ppm):

6.21 (Ηθ, m, J = ₈ o 8.3 Hz, J = 7.2 _{9 watts} Hz, J _{7, 9} = 1.2 HZJ, '

5.56 (He, m, J ₈ 9-8-3 Hz, J 7 _S = 6.3 Hz, J ₈ = 1.0 Hz), '

2.59 (Hio, m),

2.51 (Hz, m),

2.18. (H2, m)

2.07 (Ηθ, j,

1.96 (m, m),

1.48 (H3, m)

1.43 (Hu, et al.,

1.35 (Hs, ddd, J ₅₅ , = 10.0 Hz, J = 2.4 and 2.2 Hz),

1.19 (Hs *, ddd, J = 9.5 Hz, 1.6 and 1.6 Hz), 0.95 (Hu ', dm, J _d = 10.0 Hz),

0.91 (H ⁵ , dm, J _d = 10.0 Hz).

¹³ C-NMR (CDCl 3, δ, ppm):

136.72 d,

126.45 d,

47.95 d,

41.68 d,

40.80 d,

40.16 d,

36.82 d,

36.67 d,

36.67 t,

34.49 t,

34.28 t.

Example 2

The procedure was as in the example except that 9 ml of isoprene was added instead of butadiene. In the first chromatographic fractions for a total of 7.4 g of l-methyl-tetracyclo [5.4.0.0 _2, 6.0, _4, thio] undec-8-ene.

1-methyl-tetracyclo [5.4.0.0 _{2, 6} .0 _4J i _0] undec-8-ene (R = CH _3, R = H) having mp 99 to 101 degrees C, a molecular weight of 160 and the following additional features:

Infrared spectrum:

030, 2,924, 2,858, 1,614, 1473, 1,452,

363, 1 330, 1 303, 820, 756, 703, 675, 620

590, 518 cm ^-1 .

@ 1 H-NMR (CDCl3, .delta., ppm):

1.86 (m, m),

1.66 (H, DQP, J _d = 8.2 Hz, J = 2.0 Hz _qp). 1.43 (Hs-exo, et al.,

1.38 (H ₃ = one m),

1.16 ₍₅ H _END, ddd, J = 9.2, 1.2 and 1.2 Hz), 0.92 ₍₃ H _exo, ddm, J _d = 11.6 and 7.6 Hz), 0.77 (CH, d, J = 6.6 Hz 1st

6.16 (Hg, ddd, J ₈₉ = 8.2Hz, J ₁₀ = 6.9Hz,

J _{7, 9} = 1.1 Hz)

5.60 (Hb, ddd, J ₇₈ = 6.2 Hz, J = ₈ and 1.3 Hz ₀₎

2.06 (H7, dd, J _{6, 7} = 5.7 Hz)

2.48 (H10, m),

1.83 (2 H, m),

1.58 (1 H, m),

1.54 (1 H, m),

1.39 (Hn ‘, dd, J = 10.1 and 5.6 Hz),

1.33 (H3 ‘, ddd, J = 11.4, 1.8 and 1.6 Hz),

1.08 (Hn, ddd, J = 10.0, 2.0 and 1.6 Hz),

1.04 (CH 2, s),

0.93 (H5 ‘, d, J = 9,9 Hz),

0.92 (H 3, d, I = 10.0 Hz).

¹³ C-NMR (CDCl 3, δ, ppm):

136.10 d,

127.48 d,

52.41 d,

48.68 d,

46.30 s,

45.43 t,

38.69 d,

38.32 d,

37.16 d,

33.91 t,

31.71 t,

23.14 q.

Example 3

The procedure was as in Example 1 except that 8 ml of trans-1,3-pentadiene was used instead of butadiene and 1,3,5-cycloheptatriene was dosed in an amount of 6 ml. A total of 2 g of 11-exo-methyltetracyclo Γ 5.4.0.0 was obtained from the first chromatographic fractions? ₆ .O ₄ io] undec-8-ene.

11-Exo-methyl-tetracyclo [5.4.0.0 ₂ . ₆ .0 _4, and _0] undec-8-ene (R = H, R2 = CH3) is a liquid. has a molecular weight of 160 and has the following other characteristics:

Infrared spectrum:

030, 2,925, 2,866, 1,619, 1,466, 1,457, 1,450,

373, 1,306, 1297, 1,181, 875, 829, 765,

720, 696, 647 ^cm-first 1 H-NMR (CDCl 3, δ, ppm):

5.79 (Hb + Hg, m, 2H);

2.51 (H 10, m, J ₄ 10 = 7.2 Hz, J = 5.6 a

2.0 Hz),

2.42 (H7, m, J 1, ₇ = 8.4 Hz, J = 4.8 Hz),

2.19 (m, m),

2.14 (H4 m)

1.91 (H11, m), ¹³ C-NMR (CDCl 3, δ, ppm):

129.47 d,

128.49 d,

48.42 d,

47.61 d.

44.29 d,

39.69 d,

39.54 d,

38.07 d,

36.54 d,

34.31 t,

34.13 t,

14.85 q.

Example 4

To a solution containing 200 mg of tetracyclo [5.4.0.0 _2, <,. 04 io] undec-8-ene in 5 ml of ethanol-dioxane 1: 1 was added 10 mg of Adams catalyst (PtOa) and the solution was hydrogenated at 40 ° C at normal pressure. After adding 20 ml of ether, filtered off the catalyst, the solvent was evaporated and tetracyclo [5.4.0.0 _{3, 6} .04,10 jundekan was recrystallized from methanol. It was obtained in a yield of 170 mg.

Tetracyclo [5.4.0.0 _{2 6 4} 10 .0 jundekan (R = H, R ₂ = H) is t 't. 179 to 181 ° C, molecular weight of the 148th

Infrared spectrum:

920, 2,860, 1488, 1,470, 1431, 1,334,

314, 1,298, 1,283, 1,001, 973, 926, 886,

860, 786, 735 ^cm-first

Example 5

200 mg of 1-methyltetracyclo [5.4.0.0 _{2, 6} .0 ₄ io] undec-8-ene, were treated as described in Example 4 to give 170 mg of 1-methyltetracyclo [5.4.0.0 _{2, 6,} .04, io] undecane.

1-methyltetracyclo [5.4.0.0 _{2 6} .0 _{4 watts} jundekan (R = CH3, R = H) has mp '144 to 145 ° C and a molecular weight 162nd

Infrared spectrum:

920, 2 860, 1 491, 1 467, 1 45.1, 1 372

334, 1,294, 1,252, 1,166, 1,071, 988, 808,

748 cm ^-1 .

Example 6

The same procedure of Example 4 was transferred 200 mg of LL-exo-methyltetracyclo [5.4.0.02> 04 io] undec-8-ene 11-exo-methyltetra243565 cyclo [5.4.0.0 _{2 liters} O.0 ₄ io] undecane yield 170 milligrams.

11-exo-methyltetracyclo _[5.4.0.0 2ι6 .0 _{4 0} ι] undecane (Ri = H, R2 = CH3) is a liquid having a molecular weight of 162 giving:

Infrared spectrum:

925, 2866, 1490, 1469, 1456, 1376, 1337, 1300, 1134, 1020, 988, 961, 948, 850, 837, 587, 552 ^cm-first

Claims (2)

SUBJECT Tetracyclic hydrocarbons of 11 carbons of the general formula wherein R 1 and R 2 are 2 H or a combination of H and CH 3 and Z is a single or double bond. 2. A process for the preparation of tetracyclic hydrocarbons according to claim 1, characterized in that a mixture of 1,3,5-cycloheptatriene and one compound from the group of butadiene, isoprene or 1,3-pentadiene in a molar ratio of 1: 0.5 of YNAlEZ to 5 is treated. 50 to 1,000-fold less molar amounts of a compound of the formula AIR 1 R 21 R 3, wherein R 1 is ethyl, R 2 and R 3 is ethyl and / or chloro, and at the same time a complex selected from TiCl4, TiCl2.2 AlCl3. C6H6, dichlorotitanium diacetylacetonate (CsHrCUjaTiCh) or an alkyl titanate of Ti (OR) 4, where R is an alkyl of 2 to 6 carbons, maintaining an Al: Ti molar ratio of 2 to 50: 1 in an aromatic solvent at 20 to 80 ° C for 0.5 to 24 hours, after which the reaction is quenched with ethanol, shaken with water and the organic phase is heated at 175 to 240 ° C for 1 to 4 hours, and the resulting unsaturated tetracyclic hydrocarbons of 11 carbons are isolated and optionally hydrogenated to saturated 11-carbon tetracyclic hydrocarbons at 20-40 ° C and atmospheric pressure using a platinum catalyst.