WO2013006098A2 - 2,6-diisobornylphenol derivatives - Google Patents

2,6-diisobornylphenol derivatives Download PDF

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WO2013006098A2
WO2013006098A2 PCT/RU2012/000533 RU2012000533W WO2013006098A2 WO 2013006098 A2 WO2013006098 A2 WO 2013006098A2 RU 2012000533 W RU2012000533 W RU 2012000533W WO 2013006098 A2 WO2013006098 A2 WO 2013006098A2
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isobornyl
configuration
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formula
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WO2013006098A3 (en
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Александр Васильевич КУЧИН
Ирина Юрьевна ЧУКИЧЕВА
Ирина Витальевна ФЕДОРОВА
Евгений Владимирович БУРАВЛЕВ
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Федеральное Государственное Бюджетное Учреждение Науки Институт Химии Коми Научного Центра Уральского Отделения Российской Академии Наук
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
    • C07C215/52—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups linked by carbon chains having two carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
    • C07C215/54—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups linked by carbon chains having at least three carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

Definitions

  • the invention relates to space-hindered phenols, namely to terpenophenols, and more specifically, to functional derivatives of isobornylphenol.
  • the group of compounds represented by formula (I) isobornylphenol.
  • isobornyl moieties have the configuration (IS, 2R, 4R, VR, 2'S, 4'S) or (IS, 2R, 4R, l'S, TR, 4'R) and (IR, 2S, 4S VR, TS, 4'S).
  • Ri represents a group of the general formula II - (CH 2 ) n NX 2 , where X is the C1-C8 alkyl radical linear or branched, cyclohexyl, morpholine, piperidine, benzyl, salsolidine, salsoline, M-benzyl-1- phenylethylamine
  • n 1-30.
  • isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S) or (IS, 2R, 4R, 1 'S, TR, 4'R) and ( ⁇ R, 2S, 4S 1' D, 2'S, 4'S).
  • isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S) or (IS,
  • Ri is a formyl group
  • n l-30.
  • the aim of the invention is to obtain derivatives of 2,6-diisobornylphenol.
  • inventive compounds are synthesized by standard Mannich aminomethylation, bromomethylation, oxidation and reduction procedures.
  • Example 1 4-Hydroxy-3,5-bis (1, 7,7-trimethylbicyclo [2.2.1] hept-exo-2-yl) benzaldehyde, a colorless powder, so pl. 233-235 ° C.
  • the compound was obtained by a known method [V.V. Ershov, A. A. Volodkin, G. A. Nikiforov, K. M. Dyumaev. Sterically hindered phenols. Bromination of 2,6-dialkyl-p-cresols and 2,6-dialkyl-4- (bromomethyl) phenols // Russian Chemical Bulletin. 1962. Volume 11. No. 10. P. 1744-1747].
  • Example 2 4-Bromomethyl-2,6-bis (1, 7,7-trimethylbicyclo [2.2.1] hept-exo-2-yl) phenol, obtained by the known method [A.A. Volodkin, VV Ershov. Sterically hindered phenols. Phenol-dienone rearrangement in the bromination of 2,4,6-trialkylphenols // Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya. - 1962. - No. 6. - pp. 1108-1111; Galvin M. Coppinger, Tod W. Campbell. Reaction between 2,6-di-t-butyl-p-cresol and bromine. - 1952].
  • NMR spectrum I3 C (CDC1 3 , 75 MHz, ⁇ , ppm): 12.41 (C-10, C-10 '); 14.04 (C-24); 16.29 (C-17); 20.32 (C-9, C-9 '); 21.44 (C-8, C-8 '); 22.63 (C-23); July 27 (C-22); 27.57 (C-5, C-5 '); 30.00 (S-21); 31.79 (C-20); 34.23 (C-3, C-3 '); 30.08 (C-6, C-6 '); 45.60 (C-2, C-2 '); 45.83 (C-4, C-4 '); 48.07 (C-7, C-7 '); 49.29 (C-19); 49.72 (C-1, C-D); 53.98 (C-18); 122.74, 128.93, 131.19 (C-11, C-13, C-15); 125.81, 127.95 (C-14, C-16); 152.10 (C-12).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Cosmetics (AREA)
  • Hydrogenated Pyridines (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to sterically hindered phenols, and specifically to terpenophenols, and more precisely, to functional derivatives of isobornylphenol. The group of compounds is represented by formula (I):

Description

Производные 2,6-диизоборнилфенола  Derivatives of 2,6-diisobornylphenol
Изобретение относится к пространственно-затрудненным фенолам, а именно к терпенофенолам, и более точно, к функциональным производным изоборнилфенола. Группа соединений, представлена формулой (I) The invention relates to space-hindered phenols, namely to terpenophenols, and more specifically, to functional derivatives of isobornylphenol. The group of compounds represented by formula (I)
Figure imgf000002_0001
Figure imgf000002_0001
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, VR, 2'S, 4'S) или (IS, 2R, 4R, l 'S, TR, 4'R) и (IR, 2S, 4S VR, TS, 4'S).  where the isobornyl moieties have the configuration (IS, 2R, 4R, VR, 2'S, 4'S) or (IS, 2R, 4R, l'S, TR, 4'R) and (IR, 2S, 4S VR, TS, 4'S).
Ri представляет собой группу общей формулы II -(CH2)nNX2, где X - алкильный радикал С1-С8 линейный или разветвленный, циклогексил-, морфолин-, пиперидин-, бензил- , сальсолидина, сальсолина, М-бензил-1-фенилэтиламина, Ri represents a group of the general formula II - (CH 2 ) n NX 2 , where X is the C1-C8 alkyl radical linear or branched, cyclohexyl, morpholine, piperidine, benzyl, salsolidine, salsoline, M-benzyl-1- phenylethylamine
п=1-30.  n = 1-30.
Группа соединений, представлена формулой (I)  The group of compounds represented by formula (I)
Figure imgf000002_0002
Figure imgf000002_0002
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, VR, 2'S, 4'S) или (IS, 2R, 4R, 1 'S, TR, 4'R) и (\R, 2S, 4S 1 'Д, 2'S, 4'S).  where the isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S) or (IS, 2R, 4R, 1 'S, TR, 4'R) and (\ R, 2S, 4S 1' D, 2'S, 4'S).
R\ представляет собой группу общей формулы II— (СН2)ПНХ, где X - алкильный радикал С1-С8 линейный или разветвленный, циклогексил-, морфолин-, пиперидин-, бензил, п=1-30. R \ represents a group of general formula II— (CH 2 ) P HX, where X is an alkyl radical C1-C8 linear or branched, cyclohexyl, morpholine, piperidine, benzyl, n = 1-30.
Группа соединений, представлена формулой (I)  The group of compounds represented by formula (I)
Figure imgf000002_0003
Figure imgf000002_0003
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, VR, 2'S, 4'S) или (IS, 2R, 4R, 1 'S, TR, 4'R) и (IR, 2S, 4S 1 *R, TS, 4'S). Ri представляет собой группу общей формулы III— (CH2)„Y где Y - ОН-группа; Hal п=1-30. where the isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S) or (IS, 2R, 4R, 1'S, TR, 4'R) and (IR, 2S, 4S 1 * R, TS, 4'S ) Ri represents a group of the general formula III— (CH 2 ) “Y where Y is an OH group; Hal p = 1-30.
Группа соединений, представлена формулой (I)  The group of compounds represented by formula (I)
Figure imgf000003_0001
Figure imgf000003_0001
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, VR, 2'S, 4'S) или (IS, where the isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S) or (IS,
2R, 4R, VS, TR, 4' К) и (\R, 2S, 4S VR, 2'S, 4'S). 2R, 4R, VS, TR, 4'K) and (\ R, 2S, 4S VR, 2'S, 4'S).
Ri - формильная группа,  Ri is a formyl group,
n=l-30.  n = l-30.
Известно о получении 3,5-диизоборнил-4-оксибензальдегида [Казаринова Н.Ф., Новицкая Л.П. Определение стабилизаторов и некоторых продуктов их превращения методом хроматографии // Пластические массы. 1975. 3. 76-77]. Однако в качестве характеристик указанного производного авторы приводят только значение Rf. It is known about the receipt of 3,5-diisobornyl-4-hydroxybenzaldehyde [Kazarinova N.F., Novitskaya L.P. Determination of stabilizers and some products of their conversion by chromatography // Plastics. 1975. 3. 76-77]. However, the authors cite only the value of R f as characteristics of this derivative.
Иных прототипов для описываемых в изобретении функциональных производных 2,6- диизоборнилфенола нами не выявлено.  We have not identified other prototypes for the functional derivatives of 2,6-diisobornylphenol described in the invention.
Целью изобретения является получение производных 2,6-диизоборнилфенола.  The aim of the invention is to obtain derivatives of 2,6-diisobornylphenol.
Заявляемые соединения синтезированы по типовым методикам аминометилирования по Манниху, бромометилирования, окисления и восстановления.  The inventive compounds are synthesized by standard Mannich aminomethylation, bromomethylation, oxidation and reduction procedures.
Пример 1. 4-Гидрокси-3,5-бис(1 ,7,7-триметилбицикло[2.2.1 ]гепт-экзо-2-ил)бензаль- дегид, бесцветный порошок, т. пл. 233-235 °С. Соединение получено по известной методике [V.V. Ershov, A. A. Volodkin, G. A. Nikiforov, К. М. Dyumaev. Sterically hindered phenols. Bromination of 2,6-dialkyl-p-cresols and 2,6-dialkyl-4-(bromomethyl)phenols // Russian Chemical Bulletin. 1962. Volume 11. No. 10. P. 1744-1747].  Example 1. 4-Hydroxy-3,5-bis (1, 7,7-trimethylbicyclo [2.2.1] hept-exo-2-yl) benzaldehyde, a colorless powder, so pl. 233-235 ° C. The compound was obtained by a known method [V.V. Ershov, A. A. Volodkin, G. A. Nikiforov, K. M. Dyumaev. Sterically hindered phenols. Bromination of 2,6-dialkyl-p-cresols and 2,6-dialkyl-4- (bromomethyl) phenols // Russian Chemical Bulletin. 1962. Volume 11. No. 10. P. 1744-1747].
ИК спектр (табл. KBr), ν/см-1: 3595 (v OH), 2951, 2875, 1452, 1381, 1369 (Me, CH2), 1662 (C=0). Спектр ЯМР 1H (CDC13, 300 МГц, δ, м.д., J/Гц): 0.88 (с, 6Н, Ме-10, Ме-10*); 0.90 (с, 6Н, Ме-9, Ме-9'); 0.93 (с, 6Н, Ме-8, Ме-8'); 1.40-1.48, 1.63-1.71 (оба м, по 4Н, Н-З, Н-З', Н-4, Н-4', СН2-5, СН2-5'); 1.90-1.94 (м, 4Н, СН2-6, СН2-6'); 2.27-2.38 (м, 2Н, Н-З, Н-З*); 3.02 (т, 2Н, J = 9.0 Гц, Н-2, Н-2'); 5.49 (с, 1Н, ОН); 7.75 (с, 2Н, Н-14, Н-16); 9.87 (с, 1Н, СНО). Спектр ЯМР 13С (CDC13, 75 МГц, δ, м.д.): 12.63 (С-10, С-10'); 20. 23 (С-9, С-9'); 21.32 (С-8, С-8'); 27.50 (С-5, С-5'); 34.06 (С-3, С-3'); 40.04 (С-6, С-6'); 45.36 (С-4, С-4*); 46.06 (С-2, С-2'); 48.38 (C-l, C-l*); 50.10 (C-7, C-7'); 128.11 (C-14, C-16); 128.59 (C-15); 129.49 (C-l l, C-13); 159.86 (C-12); 191.67 (CHO). IR spectrum (Table KBr), ν / cm -1 : 3595 (v OH), 2951, 2875, 1452, 1381, 1369 (Me, CH 2 ), 1662 (C = 0). 1H NMR spectrum (CDC1 3 , 300 MHz, δ, ppm, J / Hz): 0.88 (s, 6H, Me-10, Me-10 * ); 0.90 (s, 6H, Me-9, Me-9 '); 0.93 (s, 6H, Me-8, Me-8 '); 1.40-1.48, 1.63-1.71 (both m, 4Н, Н-З, Н-З ', Н-4, Н-4', СН 2 -5, СН 2 -5 '); 1.90-1.94 (m, 4H, CH 2 -6, CH 2 -6 '); 2.27-2.38 (m, 2H, Н-З, Н-З * ); 3.02 (t, 2H, J = 9.0 Hz, H-2, H-2 '); 5.49 (s, 1H, OH); 7.75 (s, 2H, H-14, H-16); 9.87 (s, 1H, CHO). 13 C NMR spectrum (CDC1 3 , 75 MHz, δ, ppm): 12.63 (C-10, C-10 '); 20.23 (C-9, C-9 '); 21.32 (C-8, C-8 '); 27.50 (C-5, C-5 '); 34.06 (C-3, C-3 '); 40.04 (C-6, C-6 '); 45.36 (C-4, C-4 * ); 46.06 (C-2, C-2 '); 48.38 (Cl, Cl *); 50.10 (C-7, C-7 '); 128.11 (C-14, C-16); 128.59 (C-15); 129.49 (Cl l, C-13); 159.86 (C-12); 191.67 (CHO).
Пример 2. 4-Бромметил-2,6-бис(1 ,7,7-триметилбицикло[2.2.1]гепт-экзо-2-ил)фенол, получен по известной методике [А.А. Volodkin, V.V. Ershov. Sterically hindered phenols. Phenol-dienone rearrangement in the bromination of 2,4,6-trialkylphenols // Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya. - 1962. - No. 6. - pp. 1108-1111; Galvin M. Coppinger, Tod W. Campbell. Reaction between 2,6-di-t-butyl-p-cresol and bromine. - 1952]. Бесцветный порошок, т. пл. 161-164 °С. ИК спектр (табл. КВг), V/CM"1: 3595, 3440 (ОН), 2951, 2875, 1452, 1381, 1369 (Me, СН2), 1183 (=С-0). Спектр ЯМР 1H (CDC13, 300 МГц, δ, м.д., У/Гц): 0.81 (с, 6Н, Ме-10, Ме-10'); 0.85 (с, 6Н, Ме-9, Ме-9'); 0.89 (с, 6Н, Ме-8, Ме-8'); 1.31-1.51, 1.57-1.80 (оба м, по 4Н, Н-3, Н-3', Н-4, Н-4*, СН2-5, СН2-5'); 1.83-2.01 (м, 4Н, СН2-6, СН2-6'); 2.25-2.35 (м, 2Н, Н-3, Н-3'); 2.98 (т, 2Н, J= 9.0 Гц, Н-2, Н-2'); 4.52 (с, 2Н, СН2-17); 4.92 (с, 1Н, ОН); 7.19 (с, 2Н, Н-14, Н-16). Спектр ЯМР 13С (CDC13, 75 МГц, δ, м.д.): 12.55 (С-10, С-10'); 20.17 (С-9, С-9'); 21.39 (С-8, С-8'); 27.51 (С-5, С-5'); 34.02 (С-3, С-3'); 35.77 (С-17); 40.03 (С-6, С-6'); 45.42 (С-4, С-4'); 46.11 (С-2, С-2'); 48.23 (С-1, С-Г); 50.00 (C-7, С-7'); 126.55 (С-14, С-16); 128.09 (С- 15); 128.98 (C-l 1, С-13); 154.28 (С-12). Example 2. 4-Bromomethyl-2,6-bis (1, 7,7-trimethylbicyclo [2.2.1] hept-exo-2-yl) phenol, obtained by the known method [A.A. Volodkin, VV Ershov. Sterically hindered phenols. Phenol-dienone rearrangement in the bromination of 2,4,6-trialkylphenols // Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya. - 1962. - No. 6. - pp. 1108-1111; Galvin M. Coppinger, Tod W. Campbell. Reaction between 2,6-di-t-butyl-p-cresol and bromine. - 1952]. Colorless powder, mp 161-164 ° C. IR spectrum (Table KBr), V / CM "1 : 3595, 3440 (OH), 2951, 2875, 1452, 1381, 1369 (Me, CH 2 ), 1183 (= C-0). 1H NMR spectrum (CDC1 3 , 300 MHz, δ, ppm, V / Hz): 0.81 (s, 6H, Me-10, Me-10 '); 0.85 (s, 6H, Me-9, Me-9'); 0.89 (s, 6H, Me-8, Me-8 '); 1.31-1.51, 1.57-1.80 (both m, 4Н, Н-3, Н-3', Н-4, Н-4 * , СН 2 - 5, СН 2 -5 '); 1.83-2.01 (m, 4Н, СН 2 -6, СН 2 -6'); 2.25-2.35 (m, 2Н, Н-3, Н-3 '); 2.98 (t , 2H, J = 9.0 Hz, H-2, H-2 '); 4.52 (s, 2H, CH 2 -17); 4.92 (s, 1H, OH); 7.19 (s, 2H, H-14, H -16) 13 C NMR spectrum (CDC1 3 , 75 MHz, δ, ppm): 12.55 (С-10, С-10 '); 20.17 (С-9, С-9'); 21.39 (С -8, C-8 '); 27.51 (C-5, C-5'); 34.02 (C-3, C-3 '); 35.77 (C-17); 40.03 (C-6, C-6'); 45.42 (С-4, С-4 '); 46.11 (С-2, С-2'); 48.23 (С-1, С-Г); 50.00 (C-7, С-7 '); 126.55 (C-14, C-16); 128.09 (C-15); 128.98 (Cl 1, C-13); 154.28 (C-12).
Пример 3. 4-Гидроксиметил-2,6-бис(1 ,7,7-триметилбицикло[2.2.1]гепт-э зо-2-ил)фенол получен при восстановлении альдегида .  Example 3. 4-Hydroxymethyl-2,6-bis (1, 7,7-trimethylbicyclo [2.2.1] hept-e zo-2-yl) phenol was obtained by reduction of the aldehyde.
Раствор 4.3 г (10.90 ммоль) альдегида (1) в 60 мл абсолютного ТГФ добавляли по каплям к интенсивно перемешиваемой суспензии 0.83 г (21.79 ммоль) LiAlH4 в 50 мл абсолютного ТГФ. Перемешивали при комнатной температуре 3 ч. К реакционной смеси добавляли по каплям 0.8 мл этилацетата, 0.8 мл 10%-ного водного раствора NaOH, 2.5 мл воды и перемешивали при комнатной температуре 4 ч. Осадок отфильтровали, эфирный раствор высушивали К2СО3. Растворитель удаляли в вакууме, остаток разделяли методом колоночной хроматографии на SiO2 (элюент - петролейный эфир-СН2С12). Выделили 0.50 г побочного продукта реакции - диборнола (2) и 2.36 г (55 %) соединения (3) в виде порошка серого оттенка, Т пл.=96-98 °С. Спектр ЯМР 1H (CDC13, 300 МГц, 6, м.д., J/Гц): 0.85 (с, 6Н, Ме-10, Ме-10'); 0.88 (с, 6Н, Ме-9, Ме-9'); 0.93 (с, 6Н, Ме-8, Ме-8'); 1.40-1.55, 1.59-1.76 (оба м, по 4Н, Н-3, Н-3', Н-4, Н-4', СН2-5, СН2-5'); 1.91 (м, 4Н, СН2-6, СН2-6'); 2.29-2.35 (м, 2Н, Н- 3, Н-3'); 3.04 (т, 2Н, J = 9.0 Гц, Н-2, Н-2'); 4.63 (д, 2Н, J = 5.3 Гц, СН2-17); 4.89 (с, Ш, ОН); 7.20 (с, 2Н, Н-14, Н-16). Спектр ЯМР 13С (CDC13, 75 МГц, 6, м.д.): 12.56 (С-10, С-10'); 20.29 (С-9, С-9'); 21.44 (С-8, С-8'); 27.58 (С-5, С-5'); 34.01 (С-3, С-3'); 40.05 (С-6, С-6'); 45.47 (С-4, С-4*); 46.12 (С-2, С-2'); 48.24 (C-l, С-1'); 50.03 (C-7, С-7'); 66.19 (С-17); 124.78 (С-14, С-16); 128.74 (С-15); 131.30 (С-11, С-13); 153.82 (С-12). з Пример 4. Третичные аминометильные производные получены по реакции Манниха [Н. А. Ниязов, В. П. Тимофеев, В. Д. Сурков, Н. В. Любимов. Способ получения 2-(N,N- диметиламинометил)фенола. // Пат. док. RU2144529C1. заявл. 18.03.1998. опубл. 20.01.2000; Ki-Whan Chi, Yoon Soo Ahn, Kwang Taeg Shim, Tae Ho Park, Jeong Soo Ahn. One-pot synthesis of Mannich base using hydroxy aromatic rings and secondary amines. // Bull. Korean Chem. Soc. - 1999. -Vol.20. -No.8. -Р.973-976]. A solution of 4.3 g (10.90 mmol) of aldehyde (1) in 60 ml of absolute THF was added dropwise to an intensely stirred suspension of 0.83 g (21.79 mmol) of LiAlH 4 in 50 ml of absolute THF. Stirred at room temperature for 3 hours. 0.8 ml of ethyl acetate, 0.8 ml of 10% aqueous NaOH solution, 2.5 ml of water were added dropwise to the reaction mixture and stirred at room temperature for 4 hours. The precipitate was filtered off, the ethereal solution was dried with K 2 CO 3 . The solvent was removed in vacuo, the residue was separated by column chromatography on SiO 2 (eluent was petroleum ether-CH 2 Cl 2 ). 0.50 g of the reaction by-product dibornol (2) and 2.36 g (55%) of compound (3) were isolated in the form of a gray powder, T pl. = 96-98 ° С. 1H NMR spectrum (CDC1 3 , 300 MHz, 6, ppm, J / Hz): 0.85 (s, 6H, Me-10, Me-10 '); 0.88 (s, 6H, Me-9, Me-9 '); 0.93 (s, 6H, Me-8, Me-8 '); 1.40-1.55, 1.59-1.76 (both m, 4Н, Н-3, Н-3 ', Н-4, Н-4', СН 2 -5, СН 2 -5 '); 1.91 (m, 4H, CH 2 -6, CH 2 -6 '); 2.29-2.35 (m, 2H, H-3, H-3 '); 3.04 (t, 2H, J = 9.0 Hz, H-2, H-2 '); 4.63 (d, 2H, J = 5.3 Hz, CH 2 -17); 4.89 (s, W, OH); 7.20 (s, 2H, H-14, H-16). 13 C NMR spectrum (CDC1 3 , 75 MHz, 6, ppm): 12.56 (C-10, C-10 '); 20.29 (C-9, C-9 '); 21.44 (C-8, C-8 '); 27.58 (C-5, C-5 '); 34.01 (C-3, C-3 '); 40.05 (C-6, C-6 '); 45.47 (C-4, C-4 *); 46.12 (C-2, C-2 '); 48.24 (Cl, C-1 '); 50.03 (C-7, C-7 '); 66.19 (S-17); 124.78 (C-14, C-16); 128.74 (C-15); 131.30 (C-11, C-13); 153.82 (C-12). s Example 4. Tertiary aminomethyl derivatives obtained by the Mannich reaction [N. A. Niyazov, V.P. Timofeev, V.D. Surkov, N.V. Lyubimov. The method of obtaining 2- (N, N-dimethylaminomethyl) phenol. // Pat. doc RU2144529C1. declared 03/18/1998. publ. 01/20/2000; Ki-Whan Chi, Yoon Soo Ahn, Kwang Taeg Shim, Tae Ho Park, Jeong Soo Ahn. One-pot synthesis of Mannich base using hydroxy aromatic rings and secondary amines. // Bull. Korean Chem. Soc. 1999. Vol. 20. -No.8. -P. 973-976].
4-(диметиламино)метил-2,6-бис( 1 ,7,7-триметилбицикло[2.2.1 ]гепт-экзо-2-ил)фенола. Белый порошок. Т™ = 134-136 °С. ИК спектр (табл. с KBr), V/CM"1: 3620 (ОН), 2960, 2888, 1462, 1392, 1372 (Me, СН2), 1200 (C-N). 4- (dimethylamino) methyl-2,6-bis (1, 7,7-trimethylbicyclo [2.2.1] hept-exo-2-yl) phenol. White powder. T ™ = 134-136 ° C. IR spectrum (tab. With KBr), V / CM "1 : 3620 (OH), 2960, 2888, 1462, 1392, 1372 (Me, CH 2 ), 1200 (CN).
Спектр ЯМР 1H (CDC13, 300 МГц, δ, м.д., J/Гц): 0.80 (с, 6Н, Ме-10, Ме-10'); 0.84 (с, 6Н, Ме-9, Ме-9'); 0.89 (с, 6Н, Ме-8, Ме-8'); 1.33-1.45 (м, 4Н, Н-6, Н-6'); 1.55-1.67 (м, 4Н, Н-3, Н- 3'); 1.85-1.88 (м, 4Н, Н-5, Н-5'); 2.18 (с, 6Н, Ме-18, Ме-18'); 2.28-2.32 (м, 2Н, Н-4, Н-4'); 3.01 (т, 2Н, Н-2, Н-2', J = 9 Гц); 3.41 (с, 2Н, СН2-17); 7.05 (с, 2Н, Н-14 и Н-16). Спектр ЯМР 13С (CDC13, 75 МГц, 5, м.д.): 12.49 (С-10, С-10'); 20.13 (C-9, С-9'); 21.41 (C-8, С-8'); 27.55 (C-5, С- 5'); 33.93 (C-3, С-3'); 39.97 (C-6, С-6'); 44.55 (С-18, С-18'); 45.46 (С-2, С-2'); 46.05 (С-4, С-4'); 48.12 (C-7, С-7'); 49.94 (С-1, С-1 '); 64.31 (С-17); 126.75 (С-14, С-16); 127.31 (С-11, С-13); 128.21 (С-15). 1H NMR spectrum (CDC1 3 , 300 MHz, δ, ppm, J / Hz): 0.80 (s, 6H, Me-10, Me-10 '); 0.84 (s, 6H, Me-9, Me-9 '); 0.89 (s, 6H, Me-8, Me-8 '); 1.33-1.45 (m, 4H, H-6, H-6 '); 1.55-1.67 (m, 4H, H-3, H-3 '); 1.85-1.88 (m, 4H, H-5, H-5 '); 2.18 (s, 6H, Me-18, Me-18 '); 2.28-2.32 (m, 2H, H-4, H-4 '); 3.01 (t, 2H, H-2, H-2 ', J = 9 Hz); 3.41 (s, 2H, CH 2 -17); 7.05 (s, 2H, H-14 and H-16). 13 C NMR spectrum (CDC1 3 , 75 MHz, 5, ppm): 12.49 (C-10, C-10 '); 20.13 (C-9, C-9 '); 21.41 (C-8, C-8 '); 27.55 (C-5, C-5 '); 33.93 (C-3, C-3 '); 39.97 (C-6, C-6 '); 44.55 (C-18, C-18 '); 45.46 (C-2, C-2 '); 46.05 (C-4, C-4 '); 48.12 (C-7, C-7 '); 49.94 (C-1, C-1 '); 64.31 (C-17); 126.75 (C-14, C-16); 127.31 (C-11, C-13); 128.21 (C-15).
4-(диэтиламино)метил-2,6-бис( 1 ,7,7-триметилбицикло[2.2.1 ]гепт-экзо-2-ил)фенол.  4- (diethylamino) methyl-2,6-bis (1, 7,7-trimethylbicyclo [2.2.1] hept-exo-2-yl) phenol.
Порошок желтого цвета. Тпл = 128-130 °С. The powder is yellow. Mp = 128-130 ° C.
ИК спектр (табл. с KBr), V/CM-1: 3620 (ОН), 2964, 2880, 1468, 1392, 1380 (Me, СН2), 1200 (C-N). IR spectrum (tab. With KBr), V / CM -1 : 3620 (OH), 2964, 2880, 1468, 1392, 1380 (Me, CH 2 ), 1200 (CN).
Спектр ЯМР 1H (CDCI3, 300 МГц, δ, м.д., J/Гц): 0.84 (с, 6Н, Ме-10, Ме-10'); 0.88 (с, 6Н, Ме-9, Ме-9'); 0.93 (с, 6Н, Ме-8, Ме-8'); 1.05 (т, 6Н, Ме-19, Ме-19', J = 7 Гц); 1.38-1.50 (м, 4Н, Н-6, Н-6'); 1.58-1.74 (м, 4Н, Н-3, Н-3'); 1.91-1.98 (м, 4Н, Н-5, Н-5'); 2.28-2.35 (м, 2Н, Н-4, Н- 4'); 3.03 (т, 2Н, Н-2, Н-2', J = 9 Гц); 3.58 (с, 2Н, СН2-17); 4.78 (с, Ш, ОН); 7.13 (с, 2Н, Н-14 и Н-16). Спектр ЯМР 13С (CDC13, 75 МГц, δ, м.д.): 12.14 (С-19, С-19'); 12.57 (С-10, С-10'); 20.16 (C-9, С-9'); 21.50 (C-8, С-8'); 27.62 (C-5, С-5'); 34.08 (С-3, С-3'); 40.08 (C-6, С-6'); 45.49 (С-2, С-2'); 46.14 (С-4, С-4'); 46.44 (С-18, С-18'); 48.16 (C-7, С-7'); 49.93 (С-1, С-1'); 57.42 (С- 17); 126.07 (С-14, С-16); 127.93 (С-11, С-13). 1H NMR spectrum (CDCI3, 300 MHz, δ, ppm, J / Hz): 0.84 (s, 6H, Me-10, Me-10 '); 0.88 (s, 6H, Me-9, Me-9 '); 0.93 (s, 6H, Me-8, Me-8 '); 1.05 (t, 6H, Me-19, Me-19 ', J = 7 Hz); 1.38-1.50 (m, 4H, H-6, H-6 '); 1.58-1.74 (m, 4H, H-3, H-3 '); 1.91-1.98 (m, 4H, H-5, H-5 '); 2.28-2.35 (m, 2H, H-4, H-4 '); 3.03 (t, 2H, H-2, H-2 ', J = 9 Hz); 3.58 (s, 2H, CH 2 -17); 4.78 (s, W, OH); 7.13 (s, 2H, H-14 and H-16). 13 C NMR spectrum (CDC1 3 , 75 MHz, δ, ppm): 12.14 (C-19, C-19 '); 12.57 (C-10, C-10 '); 20.16 (C-9, C-9 '); 21.50 (C-8, C-8 '); 27.62 (C-5, C-5 '); 34.08 (C-3, C-3 '); 40.08 (C-6, C-6 '); 45.49 (C-2, C-2 '); 46.14 (C-4, C-4 '); 46.44 (C-18, C-18 '); 48.16 (C-7, C-7 '); 49.93 (C-1, C-1 '); 57.42 (C-17); 126.07 (C-14, C-16); 127.93 (C-11, C-13).
Пример 5. Вторичные аминометильные производные получены по реакции переаминирования.  Example 5. Secondary aminomethyl derivatives obtained by the transamination reaction.
Полученное ранее производное 2,6-диизоборнилфенола - 4-(диэтиламино)метил-2,6- бис(1,7,7-триметилбицикло[2.2.1]гепт-экзо-2-ил)фенол - (1 ммоль) кипятили с обратным холодильником в течение часа в пятикратном избытке соответствующего вторичного амина. За ходом реакции следили методом тонкослойной хроматографии. По окончании реакции реакционную смесь разделяли на колонке (Silica gel 70/230 μ, элюент - петролейный эфир:метил-итрея2-бутиловый эфир). The previously obtained 2,6-diisobornylphenol derivative - 4- (diethylamino) methyl-2,6-bis (1,7,7-trimethylbicyclo [2.2.1] hept-exo-2-yl) phenol - (1 mmol) was boiled with reflux for one hour in a five-fold excess of the corresponding secondary amine. The progress of the reaction was monitored by thin layer chromatography. At the end of the reaction the reaction mixture was separated on a column (Silica gel 70/230 μ, eluent - petroleum ether: methyl ytrea 2-butyl ether).
4-((гексиламино)метил)- 2,6-бис(1,7,7-триметилбицикло[2.2.1]гепт-эюо-2-ил)фенол Светло-желтое масло. Выход 57 %. Спектр ЯМР 1H (CDC13, 300 МГц, δ, м.д., J/Гц): 0.81 (с, 6Н, Ме-10, Ме-10'); 0.88 (с, 6Н, Ме-9, Ме-9'); 0.90 ( , ЗН, Ме-24); 0.93 (с, 6Н, Ме-8, Ме- 8'); 1.22-1.60 (м, 12Н, Н-6, Н-6', СН2-20, СН2-21, СН2-22, СН2-23); 1.62-1.70 (м, 4Н, Н-3, Н- 3'); 1.87-1.90 (м, 4Н, Н-5, Н-5'); 2.20 (м, 2Н, Н-4, Н-4'); 2.26 (с, 1Н, Ме-17); 2.62 (т, 2Н, СН2- 19, J = 7 Гц); 3.13 (т, 2Н, Н-2, Н-2', 3 = 9 Гц); 3.71-3.76 (м, 2Н, СН2-18); 6.94 и 7.11 (оба с. по Ш, Н-14 и Н-16). Спектр ЯМР I3C (CDC13, 75 МГц, δ, м.д.): 12.41 (С-10, С-10'); 14.04 (С-24); 16.29 (С-17); 20.32 (C-9, С-9'); 21.44 (C-8, С-8'); 22.63 (С-23); 27.07 (С-22); 27.57 (C-5, С-5'); 30.00 (С-21); 31.79 (С-20); 34.23 (C-3, С-3'); 30.08 (C-6, С-6'); 45.60 (C-2, С-2'); 45.83 (С-4, С- 4'); 48.07 (C-7, С-7'); 49.29 (С-19); 49.72 (С-1, С-Г); 53.98 (С-18); 122.74, 128.93, 131.19 (С- 11, С-13, С-15); 125.81, 127.95 (С-14, С-16); 152.10 (С-12). 4 - ((hexylamino) methyl) - 2,6-bis (1,7,7-trimethylbicyclo [2.2.1] hept-euo-2-yl) phenol Light yellow oil. Yield 57%. 1H NMR spectrum (CDC1 3 , 300 MHz, δ, ppm, J / Hz): 0.81 (s, 6H, Me-10, Me-10 '); 0.88 (s, 6H, Me-9, Me-9 '); 0.90 (, ZN, Me-24); 0.93 (s, 6H, Me-8, Me-8 '); 1.22-1.60 (m, 12H, H-6, H-6 ', CH 2 -20, CH 2 -21, CH 2 -22, CH 2 -23); 1.62-1.70 (m, 4H, H-3, H-3 '); 1.87-1.90 (m, 4H, H-5, H-5 '); 2.20 (m, 2H, H-4, H-4 '); 2.26 (s, 1H, Me-17); 2.62 (t, 2H, CH 2 - 19, J = 7 Hz); 3.13 (t, 2H, H-2, H-2 ', 3 = 9 Hz); 3.71-3.76 (m, 2H, CH 2 -18); 6.94 and 7.11 (both pp. W, H-14 and H-16). NMR spectrum I3 C (CDC1 3 , 75 MHz, δ, ppm): 12.41 (C-10, C-10 '); 14.04 (C-24); 16.29 (C-17); 20.32 (C-9, C-9 '); 21.44 (C-8, C-8 '); 22.63 (C-23); July 27 (C-22); 27.57 (C-5, C-5 '); 30.00 (S-21); 31.79 (C-20); 34.23 (C-3, C-3 '); 30.08 (C-6, C-6 '); 45.60 (C-2, C-2 '); 45.83 (C-4, C-4 '); 48.07 (C-7, C-7 '); 49.29 (C-19); 49.72 (C-1, C-D); 53.98 (C-18); 122.74, 128.93, 131.19 (C-11, C-13, C-15); 125.81, 127.95 (C-14, C-16); 152.10 (C-12).

Claims

Формула Formula
1. Г ппа соединений, представлена формулой (I) 1. G PPA compounds represented by formula (I)
Figure imgf000007_0001
Figure imgf000007_0001
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, VR, 2'S, 4'S).  where the isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S).
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, l 'S, 2'i?, 4'i?) и (IR, 2S, 4S l 'i?, 2'S, 4'S).  where the isobornyl fragments have the configuration (IS, 2R, 4R, l'S, 2'i ?, 4'i?) and (IR, 2S, 4S l'i ?, 2'S, 4'S).
Ri представляет собой группу общей формулы II -(CH2)„NX2, где X - алкильный радикал С1-С8 линейный или разветвленный, циклогексил-, морфолин-, пиперидин-, бензил- , сальсолидина, сальсолина, 1 -бензил-1-фенилэтиламина, Ri represents a group of the general formula II - (CH 2 ) N NX 2 , where X is the C1-C8 alkyl radical linear or branched, cyclohexyl, morpholine, piperidine, benzyl, salsolidine, salsoline, 1-benzyl-1- phenylethylamine
п=1-30.  n = 1-30.
2. Группа соединений, представлена формулой (I)  2. The group of compounds represented by formula (I)
Figure imgf000007_0002
Figure imgf000007_0002
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, VR, 2'S, 4'S).  where the isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S).
где изоборнильные фрагменты имеют конфигурацию (IS 2R, 4R, l 'S, 2'i?, 4'i?) и (li?, 2S, 4S l'i?, 2'S, 4'S).  where the isobornyl fragments have the configuration (IS 2R, 4R, l'S, 2'i ?, 4'i?) and (li ?, 2S, 4S l'i ?, 2'S, 4'S).
Ri представляет собой группу общей формулы II— (СН2)ПНХ, где X - алкильный радикал С1-С8 линейный или разветвленный, циклогексил-, морфолин-, пиперидин-, бензил; п=1-30. Ri represents a group of the general formula II— (CH 2 ) P HX, where X is an alkyl radical C1-C8 linear or branched, cyclohexyl-, morpholine-, piperidine-, benzyl; n = 1-30.
3. Группа соединений, представлена формулой (I)  3. The group of compounds represented by formula (I)
Figure imgf000007_0003
Figure imgf000007_0003
где изоборнильные фрагменты имеют конфигурацию (IS, 2i?, 4i?, VR, 2'S, 4'S). где изоборнильные фрагменты имеют конфигурацию (IS, 27?, 47?, l'S, 2'7?, 4'7?) и (17?, 2S,4S1'7?,2'S,4'S). where the isobornyl fragments have the configuration (IS, 2i ?, 4i ?, VR, 2'S, 4'S). where the isobornyl fragments have the configuration (IS, 27 ?, 47 ?, l'S, 2'7 ?, 4'7?) and (17 ?, 2S, 4S1'7?, 2'S, 4'S).
Ri представляет собой группу общей формулы III— (CH2)nY где Y - ОН-группа; Hal;Ri represents a group of the general formula III— (CH 2 ) n Y where Y is an OH group; Hal;
SH; SH;
n=l-30.  n = l-30.
4. Г ппа соединений, представлена формулой (I)  4. G PPA compounds represented by formula (I)
Figure imgf000008_0001
Figure imgf000008_0001
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, VR, 2'S, 4'S).  where the isobornyl fragments have the configuration (IS, 2R, 4R, VR, 2'S, 4'S).
где изоборнильные фрагменты имеют конфигурацию (IS, 2R, 4R, l'S, 2'7?, 4'i?) и (17?, 2S,4S1'7?,2'S,4'S).  where the isobornyl fragments have the configuration (IS, 2R, 4R, l'S, 2'7 ?, 4'i?) and (17 ?, 2S, 4S1'7?, 2'S, 4'S).
Ri - формильная группа.  Ri is a formyl group.
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CHUKICHEVA, IRINA YUREVNA ET AL.: 'Alkilirovanie fenola kamfenom v prisutstvii venolyata aliuminiya. Khimiya i kompyuternoe modelirovanie.' BUTLEROVSKIE SOOBSHCHENIIA no. 1, 2003, pages 9 - 13 *
I.YU. CHUKICHEVA ET AL.: 'Issledovanie alkilirovaniia p-krezola kamfenom v prisutstvii kislotnykh katalizatorov.' KHIMIYA RASTITELNOGO SYRYA vol. 3, 2009, pages 63 - 68 *

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