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5P,O-Macrocycles P,O-Макроциклы
Макрогэтероцмклы
http://macroheterocycles.isuct.ru
Paper Статья
DOI: 10.6060/mhc150458s
Phosphorylation of the 2,2'-Dihydroxy-1,1'-dinaphthylmethane and Synthesis of Phosphamacrocycles on its Basis
Pavel V. Slitikov,a@ and Elena N. Rasadkinab
aBauman Moscow State Technical University, 105005 Moscow, Russian Federation
bMoscow Pedagogical State University, Institute of Biology and Chemistry, 119021 Moscow, Russian Federation @Corresponding author E-mail: pavlasiy@mail.ru
Phosphorylation of 2,2'-dihydroxy-l,l'-dinaphthylmethane with diamidophosphites with different substituents at phosphorus atom was investigated. It was demonstrated that leaving of either two amide groups or phenyl group occurs upon formation of 1,3,2-dioxaphosphacine. Phosphamacrocyclic systems containing fragments of 2,2'-dihydroxy-1,1'-dinaphthylmethane and aromatic diols - resorcinol and 1,3-dihydroxynaphthalene - were synthesized, their low stability in solution is specified. Oxidation reactions of the synthesized compounds were studied.
Keywords: Phosphorylation, 2,2'-dihydroxy-1,1'-dinaphthylmethane, diamidophosphites, aromatic diols, molecular assembly, NMR spectroscopy, X-ray.
Фосфорилирование 2г2г-дигидрокси-1,Г-динафтилметана и синтез фосфомакроциклов на его основе
П. В. Слитиков,а@ Е. Н. Расадкинаь
Московский государственный технический университет им. Н.Э. Баумана, 105055 Москва, Россия ьМосковский педагогический государственный университет, Институт биологии и химии, 119021 Москва, Россия ®Е-шаИ: рау^1у@шаИ. ги
Проведено фосфорилирование 2,2'-дигидрокси-1,1'-динафтилметана диамидоэфирами фосфористой кислоты с различными заместителями у атома фосфора; показана принципиальная возможность ухода как двух амид-ных групп, так и фенильного заместителя при образовании 1,3,2-диоксафосфацина. Синтезированы фосфома-кроциклические системы, содержащие в своей структуре остатки 2,2'-дигидрокси-1,1'-динафтилметана и ароматических диолов - резорцина и 1,3-дигидроксинафталина, отмечена их низкая устойчивость в растворах. Рассмотрены окислительные реакции синтезированных систем.
Ключевые слова: Фосфорилирование, 2,2'-дигидрокси-1,1'-динафтилметан, диамидофосфиты, ароматические диолы, молекулярная сборка, спектроскопия ЯМР, рентгеноструктурный анализ.
Synthesis of Phosphamacrocycles Introduction
Active studies of phosphorylation of naphthalene derivatives with two distal hydroxy-groups with di- and tri-amides of phosphorus acid were performed over last decade. [1-6] As a result, there were synthesized macrocyclic compounds containing several fragments of macrocyclic diols and derivatives of phosphorous and phosphoric acids, which can be referred either as phosphacyclophanes or as benzo-crown ethers.[7] Such compounds can be used in synthesis of polynuclear complexes with transition metals for catalytic purposes, as well as supramolecular receptors which can capture ions and small molecules, and for structural tasks of modern organoelemental chemistry.
2,2'-Dihydroxy-1,1'-dinaphthylmethane 1 was investigated in reactions with derivatives of trivalent phosphorus together with other diatomic phenols. It was shown that application of alkyleneamidophosphites and other cyclic derivatives of Pffl has afforded open-chain molecules, which have been used as ligands for asymmetric catalysis.[8,9] Phos-phorylation of 1 with triamidophosphites and other acyclic derivatives have resulted in formation of cyclic products -1,3,2-dioxaphophacines.[10-12] At the same time, compound 1 has never been applied as a building block in synthesis of macrocyclic systems.
Therefore, the aim of the present investigation was to study applicability of 1 in synthesis of phosphamacrocycles.
Results and Discussion
At the first step, hexabutyltriamidophosphine (HBTA) 2a and trimorpholinophosphite (TMF) 2b were used as phos-phorylating agents due to their low rate of phosphorylation in 1,4-dioxane in comparison with other triamides of phosphorous acid.[13] However, even at reagent ratio 1:2a,b = 1:3 the formation of bisamidophosphites was not observed in 31P NMR spectra of reaction mixtures. Instead of them, in both cases 1,3,2-dioxaphosphacines 3a and 3b were obtained (5P = 140.1 and 134.3 ppm respectively) (Scheme 1). Therefore, even application of phosphorylating agents 2a,b with bulky substituents did not result in formation of bisphoso-phorylated derivatives.
At the next step, other phosphorylating agents were applied, namely, butyl and phenyl esters of phosphorous acid tetraethyldiamide 4a,b as well as phenyl ester of phospho-
rous acid tetrabutyldiamide 4c. Phosporylation of 1 with these reagents was performed in acetonitrile and 1,4-dioxane (Scheme 2).
In the case of 4a irrespectively on reagent ratio (1:1, 1:2 or 1:3) in 31P NMR spectra there was observed a singlet with c 5P = 147.6 ppm corresponding to 1,3,2-dioxaphosphacine 5a with ester substituent at P111 atom. Notably, neither phos-phacine 3 or bisphosphorylated system 5 were not formed. Therefore, it can be concluded that upon phosporylation of 1 by diamidophosphite containing aliphatic ester fragment, the leaving of amide groups is favourable. The rate of phospho-rylation increases when passing from 1,4-dioxane to acetonitrile, which is common for this type of reactions.
Again, irrespectively on reagent ratio the reaction of bisnaphthol 1 with tetraethyldiamidophenylphosphite 4b has yielded 1,3,2-dioxaphosphacines 3c and 5b together with bi-sphosporylated derivatives 6b (Scheme 2). The latter compounds were found to be unstable and they gradually have converted into mixture of 3c and 5b. Apparently, this process occurs via intramolecular dismutation,[1415] which leads to thermodynamically favourable 8-membered ring system (Scheme 3).
The rate of this cyclization is faster in acetonitrile, while in 1,4-dioxane bisphosphorylated derivatives 6b,c are more stable (up to 3 weeks).
Noteworthy, in contrast to diamidoester 4a, in the case of 4b leaving of amide or ester fragments upon phosphorylation is equiprobable independently on reagent ratio as evidenced by 31P NMR spectroscopy. Upon phosphorylation of bisnaphthol 1 with tetraethyldiamidophenylphosphite 4b in 1,4-dioxane or reaction mixture in one day after beginning in NMR spectrum there were observed resonance signals 5P = 133.8 (6b) and 132.9 ppm (4b), while in one week there were observed resonance signals 5P = 142.0 (3e), 140.6 (5b) and 132.9 ppm (4b) with integral ratios 1:1:2.
An application of acetonitrile instead of 1,4-dioxane has resulted in increase of reaction rate[16] - in two hours after beginning in 31P NMR spectrum of reaction mixture there was observed only 6b, however its signal has vanished in NMR spectrum afterwards.
In the case of tetrabutyldiamidophenylphosphite 4c phosphorylation of 1 was very slow. Even after 1 day in 31P NMR spectrum the most intensive signal was 5P = 132.5 ppm corresponded to starting diamide 4c, minor signal with 5P = 142.6 ppm corresponded to bisphosphorylated product 6c (Scheme 2). The latter have remained in reaction mix-
Scheme 1. Synthesis of 1,3,2-dioxaphosphacines 3a,b. 304
OH
+ R,OP(NR2)2 OH 4 a-c
4 a: R = Et; R' = n-Bu 4 b: R = Et; R' = Ph 4 c: R = n-Bu; R' = Ph
3 a,c
R = Bu (3 a); Et (3 c)
5 a,b
NR2 OPh NR2
6 b,c
R = Et (6b); Bu (6c)
7 a,c
8 a,b
9 b,c
Scheme 2.
S
6 b 3 c 5 b
Scheme 3.
ture even after 2 weeks after the beginning of reaction, together with 5b (5P = 141.8 ppm), 3a (5P = 140.5 ppm) and 4c (5P = 132.5 ppm). The integral ratios were 1.5:1:1:6. The slow reaction rate can be explained by lower reactivity of 4c.
With the aim to separate and identify phosphorylated products, the reaction mixtures were sulfurized and column chromatography was used to isolate 1,3,2-dioxaphosphaci-nes 7a,c and 8a,b and b/sphosphorylated thione derivatives 9b,c. Because of similarity of solubility and chromatographic
mobility, isolation of compounds in pure forms was tedious, so the yields of individual thiones were modest. Physical-chemical properties of 7c have coincided with the previously reported data.[17]
X-Ray diffraction analysis of crystalline 8a was performed (Figure 1, Table 1). It has evidenced that the macro-cyclic part of the molecule adopts bath-bath conformation. [17] Stability of this conformation can be tentatively explained by the presence of bulky butoxy-substituent.
Figure 1. Molecular structure of 2-thione-2-0-butyl-4,5,7,8-dinaphtho-1,3,2-dioxaphosphacine 8a (a) and fragment of molecules packing in crystal (b).
Table 1. Bond lengths (A) and angles for 2-thione-2-0-butyl-4,5,7,8-dinaphtho-1,3,2-dioxaphosphacine 8a.
Bond d, A Angle w, grad
P(1)-O(1) 1.5824(18) 0(3)-P(1)-0(1) 99.95(10)
P(1)-0(2) 1.5845(18) 0(3)-P(1)-0(2) 101.68(10)
P(1)-0(3) 1.5491(19) 0(1)-P(1)-0(2) 105.19(9)
P(1)-S(1) 1.8993(11) O(3)-P(1)-S(1) 118.82(9)
O(1)-C(2) 1.414(3) O(1)-P(1)-S(1) 112.23(8)
0(2)-C(13) 1.403(3) O(2)-P(1)-S(1) 116.79(7)
0(3)-C(22) 1.422(4) C(13)-O(2)-P(1) 128.02(14)
C(1)-C(2) 1.365(3) C(22)-O(3)-P(1) 124.12(18)
C(1)-C(11) 1.517(3) C(2)-C(1)-C(10) 117.8(2)
C(2)-C(3) 1.393(3) C(2)-C(1)-C(11) 119.5(2)
C(11)-C(12) 1.521(3) C(10)-C(1)-C(11) 122.7(2)
C(12)-C(13) 1.370(3) C(1)-C(2)-O(1) 118.3(2)
C(13)-C(14) 1.400(3) C(3)-C(2)-O(1) 117.6(2)
C(22)-C(23) 1.509(4) C(1)-C(11)-C(12) 114.39(17)
C(23)-C(24) 1.466(5) C(13)-C(12)-C(21) 117.02(18)
C(13)-C(12)-C(11) 121.49(18)
C(12)-C(13)-C(14) 123.7(2)
C(12)-C(13)-O(2) 122.08(18)
C(14)-C(13)-O(2) 114.10(19)
O(3)-C(22)-C(23) 108.3(2)
C(24)-C(23)-C(22) 114.3(3)
The observed formation of phosphacines upon phosphorylation of 1 with acyclic amidophosphites has precluded formation of macrocycles containing two fragments of bis-naphthol. Therefore, we have proposed two-step approach to 14-membered macrocyclic systems,[18] containing a fragment of bisnaphthol 1 and a fragment of resorcinol 10 or 1,3-di-hydroxynaphthalene 11. This approach implies synthesis of primary bisphosphorylation of diols 10 and 11 with hexaeth-yltriamidophosphite (HETA) 2c with subsequent cyclization of resulting bisphosphorylated derivatives 12 and 13 with bisnaphthol 1 (Scheme 4).
Reactions were performed in 1,4-dioxane. The completion of bisphosphorylation of diols 10 and 11 was confirmed by 31P NMR spectroscopy - there was observed a singlet at 5P = 132.8 ppm, which is characteristic for diamidoesters of phosphorous esters with aromatic radicals - 12 and 13. Then, bisphenol 1 was added to reaction mixture and the mixture was kept for 3 days. During this time the signal at 132.8 ppm gradually vanished and a new signal at 140.5 ppm became intensive. This signal corresponded to the target amidodies-ters.
Resulting macrocycles 14 and 15 were found to be unstable. In solution they have rearranged with the formation of 1,3,2-dioxaphosphacine 3c and uniform cyclophanes.[316]
However, we have tried to isolate target macrocycles. With this aim the reaction mixtures containing products with 5P = 140 ppm were evaporated to minimal volume and cooled resulting in formation of oily product. The solvent was decanted, the oil was washed with cold acetonitrile and dried in vacuo. Their NMR spectra corresponded to the target macrocycles 14 and 15, however, they also contained resonance signals of 1,3,2-dioxaphosphacine 3c impurity. Isolation of pure macrocycles was possible only after their conversion into thiones and phosphates.
Sulfurization of cyclophosphites 14 and 15 was performed with elemental sulfur in CH2Cl2 during 1 day. Result-
ing cyclo(bisthioneamidophosphates) 16 and 17 were isolated by column chromatography in 30 and 25 % yields respectively as viscous oils. Their 31P NMR spectra contained singlets in 68 ppm region, what corresponded to amidoesters of thionephosphoric acid.
Oxidation of cyclophosphites 14 and 15 was peformed with urea peroxide in CH2Cl2 for 1 day. Phosphates 18 and 19 were isolated by precipitation with hexane. They were isolated as low-melting powders in 79 and 65 % yields respectively. Their 31P NMR spectra contained singlets at 1 ppm which corresponded to monoamidophosphates. 'H NMR spectrum of compound 19 revealed some broadening of resonance signals.
Conclusions
1. We have investigated phosphorylation of 2,2'-di-hydroxy-1,1'-dinaphthylmetane with derivatives of Pffl -hexabutyltriamide, trimorpholinephosphite, tetraethyl- and tetrabutyldiamidophenylphosphites, as well as tetraethyldi-amidobutylphosphite.
2. The equiprobable leaving of amide or aromatic ester substituent was found upon formation of 1,3,2-dioxaphos-phacine.
3. We have synthesized phosphamacrocyclic systems, containing 2,2'-dihydroxy-1,1'-dinaphthylmethane as a building block, the oxidation reactions of these macrocycles were investigated.
Experimental
All syntheses were conducted in dry solvents under an argon atmosphere. 'H, 13C and 31P NMR spectra were recorded on a JEOL ECX-400 spectrometer operating at 400, 100.5 and 161.8 MHz
+ 2 P(NEt2)3
HO OH
10, 11
2 c
EtoN Ar NEt
1,4-dioxane V r-/ + 1, 1,4-dioxane
—'-p—o °-p -
- 2 HNEt2 _ ../ ° O P\.
Et2N
12, 13
NEt
2
- 2 HNEt2
NEt2
2
°X°'
NEt2
14, 15
\ + X, CH2 Cl2 Ar -
VNEt2
\
Ar
№ X NEt2
16 - 19
Ar =
(10, 12, 14, 16, 18);
(11, 13, 15, 17, 19)
X = S (16, 17); O (18, 19)
Scheme 4.
respectively; 1H and 13C NMR spectra were recorded in CDCl3; chemical shifts (5, ppm) were referenced to TMS (1H and 13C) or to 85 % H3PO4 (31P). Spin-spin coupling constants (J) are given in Hz. Mass spectra were measured on a Bruker Ultraflex MALDI-TOF spectrometer using a nitrogen laser (X = 337 nm) and trihydroxy-anthracene as a matrix. Crystals of compound 8a have obtained by crystallization from hexane. X-ray analysis was performed on an automatic CAD-4 Enraf-Nonius diffractometer (P-filter, 1(Mo-Ka) 9/29 data collection, 9 = 24.88°). Colorless triclinic crystal
' ' max ' ~>
(C25H23O3PS, M= 434.46), size 0.56x0.40x0.15 mm, a = 9.881(2) A, b =10.846(2) A, c = 11.482(2) A, a = 87.10(3)°, b = 74.82(3)°, g = 71.12(3)°. V= 1122.9(5) A3. Z=2. p = 1.258 mg/cm3. Number of reflections: 4433, independent reflections: 4172 (R(int)=0.0200). F(000)=456; R1(F)=0.0431, wR2(F2)=0.1307. Refinement method: full-matrix least squares on F2 for non-hydrogen atoms. All hydrogen atoms have included in the refinement with fixed parameters (placed in calculated positions) in the isotropic approximation. Crystallographic data reported in this paper have been deposited with Cambridge Crysrallographic Data Centre (№ CCDC 1052567). Column adsorption chromatography was operated on silica gel L 100/250; TLC was performed on Silufol plates (UV-254) using C6H14:dioxane, 5:1 (A), C6H6:dioxane, 3:1 (B). Detection was achieved using iodine vapor treatment and calcination.
2,2'-Dihydroxy-1,1'-dinaphthylmethane 1 was synthesized by the method,[19] HBTA 2a,[16] tetraethyl- and tetrabutyldiamidophe-nylphosphites (4b,c),[15] HETA 12. [20]
2-Dibutylamido-4,5,7,8-dinaphtho-1,3,2-dioxaphosphacine (3a). A solution of 1.25 g (3 mmol) HBTA (2a) in 5 ml of 1,4-di-oxane was added to a solution of 0.3 g (1 mmol) of bisnaphthol 1 in 4 ml of 1,4-dioxane. The reaction mixture was kept at room temperature for 2 h. The solvent was evaporated in vacuo (12 mm Hg), and the residue was chromatographed on a column, the resulting product was eluted by hexane:dioxane (10:1) system. The resulting material was dried in vacuo for 1.5 h (1 mm Hg, 60 °C). Yield 0.41 g (89 %). Rf 0.69 (A). 1H NMR 5H ppm: 0.97 (6H, t, 3JHH= 7.3, CH3), 1.40 (4H, m, CH2), 1.62 (4H, m, CH2), 3.19 (4H, m, 3JPH = 11.0, N-CH2), 4.58 (1H, dd, 2JHH = 16.0, Ar-CH2), 5.11 (1H, d, 2JHH = 16.0, Ar-CH2), 7.18 (2H, d, 3JHH= 8.7, CH3), 7.3 8 (2H, dd, 3JHH =(5.9; 7.8, CH7), "7.49 (2H, dd, 3JHH= 7.8, CH6), 7.68 (2H, d, 3JHH= 8.8, CH4), 7.80 (2H, d, 3JHH = 7.8, CH5), 8.22 (2H, d, 3JHH = 8.7, CH8). 13C NMR 5C ppm: 14.1 CCH3), 20.2 (CH2), 25.1 (Ar-CH2), 30.9 (CH2), 43.7 (d, 2JPC = 19.1, CH2-N), 121.9 (d, 3JPC = 5.8, C3H), 122.6 (d, 3JPC = 3.8, C1), 123.4 (C8H), 124.1 (C7H), 126.8 (C6H), 128.4 (C5H), 128.9 (C4H), 130.9 (C9), 133.0 (C10), 151.8 (C-O). 31P NMR (1,4-dioxane) 5P ppm: 140.1.
2-Morpholino-4,5,7,8-dinaphtho-1,3,2-dioxaphosphacine (3b). A solution of 1.86 g (3 mmol) TMF (2b) in 5 ml of 1,4-di-oxane was added to a solution of 0.3 g (1 mmol) of bisnaphthol 1 in 4 ml of 1,4-dioxane. The reaction mixture was kept at room temperature for 2 h. The solvent was evaporated in vacuo (12 mm Hg); the residue was added to the 5 ml of acetonitrile. After 12 h the crystals precipitated were filtered off, washed with hexane and ace-tonitrile. The resulting material was dried in vacuo for 1.5 h (1 mm Hg, 60 °C). Yield 0.37 g (90 %). Mp 189-190 °C. Rf 0.32 (A). 1H NMR 5H ppm: 3.33 (4H, m, 3J1H = 7.8, 3JHH = 4.6, N-CH2), 3.75 (4H, dd, 3JHH= 4.6, O-CH2), 4.56 (1H, dd, 2JHH= 16.1, Ar-CH2), 5.09 (1H, d, 2JHH = 16.1, Ar-CH2), 7.18 (2H, d, 3JHH = 8.7, CH3), 7.39 (2H, dd, 3JHH=7.0; 7.6, CH7), 7.50 (2H, dd, 3JHH=7.0; 8.3, CH6), 7.69 (2H, d, 3JHH = 8.7, CH4), 7.81 (2H, d, 3JHH = 8.2, CH5), 8.21 (2H, d, ^JHH = 8.7, CH8). 13C NMR 5C ppm: 25.1 (Ar-CH2), 44.2 (d, 2J1C = 17.2, CH2-N), 68.1 (CH2-O), 121.9 (d, 3J1C = 5.7, C3H), 123.4 (C8H), 124.4 (C1), 126.9 (C7H), 128.6 (C6H), 128.9 (C45H), 131.1 (C9), 132.9 (C10), 151.1 (C-O). 31P NMR (CH2Cl2) 5p ppm: 134.3.
Phosphorylation of 2,2'-dihydroxy-1,1'-dinaphthylmethane 1 with diamidoesters of phosphorous acid 4a-c (general procedure). Solution of diamidophosphite 4a-c in 4 ml of acetonitrile or 1,4-dioxane was mixed with solution of 1 mmol of bisnaphthol 1 in acetonitrile or dioxane respectively, at room temperature and
continuous stirring. Molar ratios of bisnaphthol 1 and diamidophosphite 4a-c were 1:1, 1:2 or 1:3. In two weeks sulfur was added to reaction mixtures, its amount corresponded to that of used diami-dophosphite. In two days the reaction mixtures were evaporated, the residues were dissolved in minimal volume of benzene and chromatographed eluting products with hexane:dioxane, 10:1 mixture. Resulting compounds were dried in vacuo (1 mm Hg, 70 °C) for 2 hours.
2-Thione-2-dibutylamido-4,5,7,8-dinaphtho-1,3,2-dioxa-phosphacine (7a). Yield 0.39 g (79 %). M.p. 112-113 °C. Rf 0.57 (A). 1H NMR 5H ppm: 0.97 (6H, t, 3JHH=7.8, CH3), 1.40 (4H, m, CH2), 1.70 (4H, m, CH2), 3.35 (4H, m, 3J1H = 7.3, N-CH2), 4.99 (1H, d, 2JHH = 16.0, Ar-CH2), 5.12 (1H, d, 2JHH= 15.6, Ar-CH2), 7.19 (2H, d, 3JHH = 9.2, CH3), 7.44 (2H, dd, 3JHH=7.3, CH7), 7.55 (2H, dd, ^JHH = 7.3; 8.3, CH6), 7.73 (2H, d, 3JHH= 8.7, CH4), 7.83 (2H, d, 3JHH = 7.3, CH5), 8.34 (2H, d, 3JHH = 8.7, CH8). 13C NMR 5C ppm: 14.1 (CH3), 20.2 (CH2), 25.1 (Ar-CH2), 30.7 (CH2), 46.7 (CH2-N), 121.9 (C3H), 123.8 (C1), 124.9 (C8H), 125.1 (C7H), 127.1 (C6H), 128.4 (C5H), 128.9 (C4H), 131.8 (C9), 132.9 (C10), 149.9 (d, 2J1C = 11.5, C-O). 31P NMR (1,4-dioxane) 5p ppm: 67.8.
2-Thione-2-0-butyl-4,5,7,8-dinaphtho-1,3,2-dioxaphos-phacine (8a). Yield 0.087 g (20 %). M.p. 142-143 °C. Rf 0.73 (A). 1H NMR 5H ppm: 0.98 (3H, t, 3JHH = 7.3, CH3), 1.50 (2H, m, CH2), 1.80 (2H, m, 3JHH=6.4; 7.8, CH2), 4.36 (2H, m, 3J1H = 12.8, O-CH2), 4.76 (1H, d, 2JHH= 16.0, Ar-CH2), 5.18 (1H, d, 2JHH= 16.0, Ar-CH2), 7.22 (2H, d, J^ = 8.9, 4J1H = 1.4, CH3), 7.47 (dd, 2H, 3JHH = 7.3, CH7), 7.57 (2H, dd, 3JHH=7. 8, CH6), 7.77 (2H, d, 3JHH = 8.8, CH4), 7.86 (2H, d, ^JHH = 8.2, CH5), 8.28 (2H, d, 3JHH = 8.3, CH8). 13C NMR 5C ppm: 13.8 (CH3), 24.4 (Ar-CH2), 32.2 (CH2), 69.5 (CH2-O), 120.9 (C3H), 123.6 (C8H), 124.6 (d, C1), 125.5 (C7H), 127.4 (C6H), 129.1 (C45H), 132.1 (C9), 132.8 (C10), 148.9 (d, C-O). 31P NMR (1,4-dioxane) 5P ppm: 59.5.
2-Thione-2-0-phenyl-4,5,7,8-dinaphtho-1,3,2-dioxaphos-phacine (8b). Yield 0.068 g (15 %). M.p. 158-159 °C. Rf 0.51 (A). 1H NMR 5H ppm: 4.80 (1H, d, 2JHH = 16.0, Ar-CH2), 5.24 (1H, d, 2JHH = 16.0, Ar-CH2), 7.20 (2H, d, ,Jml = 8.8, CH3), 7.27 (2H, d, 1h), 7.36-7.44 (3H, m, 1h), 7.49 (2H, dd, 3JHH=7.3; 7.8, CH7), 7.58 (2H, dd, 3JHH = 7.3; 7.8, CH6), 7.75 (2H, d, 3JHH = 9.0, CH4), 7.86 (2H, d, 3JHH= 8.3, CH5), 8.29 (2H, d, 3JHH = 8.7, CH8). 13C NMR 5C ppm: 24.4 (Ar-CH2), 120.8 (C3H), 121.2 Co-Fh), 123.6 (C8H), 124.5 (d, 3J1C=7.7, C1), 125.6 (C7H), 125.9 (p-1h), 127.5 (C6H), 129.2 (C45H), 129.9 (m-1h), 133.2 (C9), 132.8 (C10), 150.1 (d, C-O), 153.2 (d, 1h-O). 31P NMR (1,4-dioxane) 5P ppm: 53.5. Mass spectrum (MALDI) m/z: 455.48 [M+H]+.
2,2'-Bis(diethylamidophenylthionephosphatoxy)-1,1'-di-naphthylmethane (9b). Yield 0.06 g (8 %). M.p. 157-158 °C. Rf 0.63 (A). 1H NMR 5H ppm: 1.17 (6H, t, = 7.3, CH3), 1.32 (6H, t, = 7.0, CH3), 3.46 (8H, m, 3JPH = 14.3, CH2), 5.00 (1H, d, 2JHH = 15.7, Ar-CH2), 5.14 (1H, d, 2JHH= 15.7, Ar-CH2), 7.19 (4H, d, Hi), 7.24 (2H, d, CH3), 7.32 (4H, t, 3Jml = 8.0, 1h), 7.3 6 (2H, m, 1h), 7.49 (2H, dd, 3JHH = 8.0, CH7), 7.56 (2H, dd, 3JHH = 8.0, 4JHH = 1.1, CH6), 7.74 (2H, d, 3JHH = 8.8, CH4), 7.86 (2H, d, 3JHH = 7.7, CH5), 8.35 (2H, d, 3JHH = 8.H, CH8). 311 NMR (CH3CN) 5p ppm: 66.8. Found, %: 1 8.18. C41H44N2O4P2S2. Calculated, %: 1 8.21.
Cyclophosphorylation of 2,2'-dihydroxy-1,1 '-dinaphthyl-methane (general procedure). A solution 0.16 g (1 mmol) of di-hydroxynaphthalene 10 or 11 in 6 ml of 1,4-dioxane was added at stirring at room temperature to 0.5 g (2 mmol) HETA 2c. After 12 h (10) or 6 h (11) a solution of 0.3 g (1 mmol) of bisnaphthol 1 in 4 ml of 1,4-dioxane was added to the reaction mixture. The mixture was stirred for 5 h and left for 60 h. The solvent was evaporated in vacuo (12 mm Hg); the remaining oily precipitate was washed twice with cold acetonitrile and dried in vacuo for 2 h (1 mm Hg, 60 °C).
1,3(1,2)-Dinaphthalina-7(1,3)-benzena-4,6,8,10-tetra-oxa-5,9-di(diethylamidate)phosphacyclodeca-phane (14). Yield 0.14 g (25 %). Oily substance. Rf 0.80 (B). 1H NMR 5H ppm: 1.19 (6H, t, 3JHH = 7.0, CH3), 1.25 (6H, t, 3JHH = 7.0, CH3), 3.31 (8H, m, 3J = 11.0, N-CH2), 4.55 (1H, d, 2J = 16.2, Ar-CH2), 5.26 (1H, d,
2J„„ = 16.2, Ar-CH), 6.38 (2H, dd, 3J„„ = 7.9, 4J„„=2.3, o-CH), 6.79
HH ' 2' ■ J J HH ' HH ' '
(1H, s, o'-CH), 6.95 (1H, d, m-CH), 7.23 (2H, d, 3JHH = 8.9, CH3), 7.41 (2H, m, 3JHH = 7.5, 7.6, CH6), 7.53 (2H, m, 3JHH = "7.2, 7.8, CH7), 7.80 (2H, d, 3JHH= 8.9, CH4), 7.88 (2H, d, 3JHH = 7.6, CH5), 8.36 (2H, d, 3JHH = 8.2, CH8). 31P NMR (1,4-dioxane) Sp ppm: 140.8.
Thionephosphoramidates (16, 17) (general procedure). Sulfur 0.064 g (2 mmol) was added to cyclophosphite (14, 15) in 5 ml of dichloromethane. The mixture was stirred for 3 h at room temperature and left for 24 h. The solution was filtered, the solvent was evaporated in vacuo (12 mm Hg), and the residue was chro-matographed on a column, the resulting product was eluted by the benzene:dioxane (7 : 1) system. The resulting material was dried in vacuo for 2 h (1 mm Hg, 70 °C).
1,3(1,2)-Dinaphtholina-7(1,3)-benzena-4,6,8,10-tetraoxa-5,9-di(diethylamidate)thionphosphacyclodeca-phane (17). Yield 0.20 g (30 %). Oily substance. R 0.61 (A). 1H NMR SH ppm: 1.00 (9H, t, CH3), 1.02 (3H, t, 3JHH = 7.2, CH3), 3.32 (8H, m, 3JpH=13.9, N-CH2), 4.70 (1H, d, 2JHH = 16.1, Ar-CH2), 5.14 (1H, d, 2JHH = 16.8, Ar-CH2), 6.68 (2H, d, 3JHH = 8.0, o-CH), 6.79 (1H, d, 4JpH=4.0, o'-CH), 6.85 (1H, m, 3JHH= 8.0, m-CH), 7.12 (2H, dd, 3J^ = 8.8, 4JPH = 1.5, CH3), 7.38 (2H, dd, 3JHH = 7.3, 7.8, CH7), 7.48 (2H, dd, 3JHH=7.7,4JHH = 1.5, CH6), 7.66 (2H, d, 3JHH = 8.8, CH4), 7.76 (2H, dd, 3JHH = 8.0h 4JHH = 1.2, CH5), 8.19 (2H, d, JHH = 8.0, CH8). 31P NMR (1,4-dioxane) Sp ppm: 66.8. Found, %: C, 62.07; H, 5.69; N, 4.12; P, 9.24. C H N.ORS,. Calculated, %: C, 62.12; H, 5.66; N,
35 38 2 4 2 2
4.14; P, 9.15.
1,3(1,2),7(1,3)-Trinaphthalina-4,6,8,10-tetraoxa-5,9-di-(diethylamidate)thionphosphacyclodecaphane (18). Yield 0.18 g (25 %). Oily substance. Rf 0.58 (CHCl3). 1H NMR 5H ppm: 1.17 (12H, t, 3JHH = 6.9, CH3), 3.26 (8H, m, 3JpH = 12.4, N-CH2), 4.81 (1H, d, 2JHH = 16.1, Ar-CH2), 5.26 (1H, d, 2JHH= 15.4, Ar-CH2), 7.04 (1H, s, CH2'), 7.13 (2H, dd, 3JHH = 8.8, 4JHH=1.1, CH3), 7.22 (1H, s, CH4'), 7.25 (1H, dd, CH6'), 7.35 (1H, dd, CH7'), 7.48 (2H, dd, CH6), 7.59 (2H, dd, CH7), 7.67 (2H, d, 3JHH = 8.8, CH4), 7.74 (1H, d, 3JHH = 8.8, CH5'), 7.83 (2H, d, 3JHH = 8.4, CH5), 8.12 (1H, d, 3JHH = 8.0, CH8 ), 8.20 (2H, d, 3JHH = 8.4, CH8). 31P NMR (1,4-dioxane) Sp ppm: 66.4, 67.0. Found, %. C, 64.34; H, 5.74; N, 3.89. C39H40N2O4P2S2. Calculated, %: C, 64.45; H, 5.55; N, 3.85.
Phosphoramidates (18, 19) (general procedure). The urea peroxide (commercial hydroperite) 0.23 g was added to cyclophosphite (14, 15) in 6 ml of dichloromethane. The mixture was left for 24 h at room temperature. Then the solution was cooled to 0 °C and filtered, the solvent was removed in vacuo (12 mm Hg) down to a small volume, and 10 ml hexane was added; after 10 min the solution was decanted from precipitate. The procedure was repeated twice. The resulting material was dried in vacuo for 2 h (1 mm Hg, 60 °C).
1,3(1,2)-Dinaphtholina-7(1,3)-benzena-4,6,8,10-tetraoxa-5,9-di(diethylamidate)oxophosphacyclodeca-phane (18). Yield 0.51 g (79 %). M.p. 89-91 °C. R 0.63 (B). 1H NMR SH ppm: 1.03 (9H, t, CH3), 1.30 (3H, t, 3JHH=7.3, CH3), 3.18 (6H, m, 3JpH = 12.4, N-CH2), 3.33 (2H, m 3JpH = 12.8, N-CH2), 4.93 (1H, d, 2JHH = 16.2, Ar-CH2), 5.16 (1H, d, 2JHH = 16.2, Ar-CH2), 6.58 (2H, d, 3JHH = 7.7, o-CH), 6.90 (1H, s, o'-CH), 7.05 (1H, t, m-CH), 7.21 (2H, d, 3JHH = 8.5, CH3), 7.43 (2H, dd, 3JHH = 6.8, 8.1, CH6), 7.54 (2H, dd, 3J = 7.7, CH7), 7.73 (2H, d, 3J = 8.9, CH4), 7.82 (2H, d, 3J = 8.1,
CH5), 8.28 (2H, d, 3JHH = 8.5, CH8). 31P NMR (CH2Cl2) Sp ppm: 0.9. Mass spectrum (MALDI) m/z: 645.22 [M+H]+.
1,3(1,2),7(1,3)-Trinaphthalina-4,6,8,10-tetraoxa-5,9-di(diethylamidate)oxophosphacyclodecaphane (19). Yield 0.48 g (81 %). M.p. 98-100 °C. R7 0.68 (B). 31P NMR (CH2Cl2) 5p ppm: 1.1, 0.9.
Acknowledgements. This work was supported by the Ministry of Education and Science of Russian Federation in the framework of state task for Institution of Higher Education.
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Received 24.04.2015 Received revised 18.08.2015 Accepted 20.08.2015
