Cyclobisphosphorylation of 1,7-dihydroxynaphthalene with phosphorous triamides

Russian Journal of General Chemistry, Vol. 74, No. 1, 2004, pp. 48 57. Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 1, 2004,

pp. 55 64.

Original Russian Text Copyright

2004 by Rasadkina, Evdokimenkova, Stash, Bel’skii, Vasyanina, Nifant’ev.

Cyclobisphosphorylation of 1,7-Dihydroxynaphthalene

with Phosphorous Triamides

E. N. Rasadkina, Yu. B. Evdokimenkova, A. I. Stash,

V. K. Bel’skii, L. K. Vasyanina, and E. E. Nifant’ev

Moscow Pedagogical State University, Moscow, Russia

Received December 25, 2001

Abstract Cyclobisphosphorylation of dihydroxynaphthalenes was studied with the aim to prepare organo-

phosphorus aromatic compounds containing intramolecular cavities. The design and the structural and

chemical features of cyclobisphosphites prepared from unsymmetrical 1,7-dihydroxynaphthalene are con-

sidered. New data are reported on regioselective cyclophosphorylation of 1,7-dihydroxynaphthalene by dis-

proportionation of its bis(diamidophosphorylated) derivatives.

Previously we reported on synthesis of new repre-

sentatives of cyclobis(naphthylene dialkylphosphor-

amidites) by reaction of hexaalkylphosphorous tri-

amides with 1,5- and 2,7-dihydroxynaphthalenes [1].

Note that these diols are symmetrical, and in their

cyclobisphosphorylation there are no problems with

regioselectivity. In this work we studied cyclobis-

phosphorylation of unsymmetrical dihydric phenols

and examined the possibility of controlling the regio-

selectivity of the process.

One of them is molecular assembling. This proce-

dure is two-step and involves preparation of bisphos-

phorylated derivatives III followed by their reaction

with an equimolar amount of the starting diol to ob-

tain the desired compounds IV. The first step was

performed at room temperature with no special meas-

ures taken to remove the released amine. The reaction

can be performed in various solvents; the best results

were obtained in acetonitrile.

The intermediate compounds IIIa IIId are viscous

oils; their properties changed in storage (see below).

Their ³¹P NMR spectra consisted of two singlets of

equal integral intensity in the range characteristic of

phosphorodiamidites; the difference between the

chemical shifts was 3 ppm on the average. For addi-

The reaction system consisted of a hexaalkylphos-

phorous triamide I and 1,7-dihydroxynaphthalene II;

the molecules of II contain - and -hydroxy groups

located in different aromatic rings. To prepare the

cyclic systems, we used several methods.

S

OPX₂

S

X PO

₁OH

OPX2

8

HO ⁷

X PO

2

3

S

CH CN

3

PX +

3

6

Ia Id

5

4

II

IIIa IIId

Va Vd

II

P X

O

X

O

O P

O

+

P

O

P

X

O

IV a VI d

X = NMe (a), NEt (b), N(i-Pr) (c), N

IV a IV d

(d).

2

1

070-3632/04/7401-0048 2004 MAIK Nauka/Interperiodica

CYCLOBISPHOSPHORYLATION OF 1,7-DIHYDROXYNAPHTHALENE

49

_C3¹

C³⁰

C¹⁸

_C21

C³²

C²⁹

_C19

_C3⁴

_C3³

N⁴

_C20

_C5

C¹⁷

C²²

C⁶

_C4

C¹⁰

N²

P¹

_P2

_C₂7

O²

C⁷

N³

C⁹

C²⁶

_C8

S¹

_C2⁵

_C1

O¹

_S2

C²³

C¹³

C²⁸

_C11

N¹

_C1⁵

C²⁴

_C12

_C1⁴

_C1⁶

Fig. 1. Molecular structure of 1,7-bis(tetraisopropyldiaminothiophosphoryloxy)naphthalene Vc.

tional identification of the bisphosphorylated naph-

thols, they were converted to phosphorodiamidothio-

ates Va Vd, which were isolated by column chroma-

tography. These crystalline substances, in contrast to

intermediates IIIa IIId, were quite stable; therefore,

we studied their structural features. Their P NMR

spectra also consisted of two singlets, but the differ-

IV and oily isomer IV started to precipitate. The

isomers differ in the physicochemical and structural

characteristics. Crystalline compounds IV were iso-

lated in 48 50% yields and were fully characterized.

They were sparingly soluble in common organic sol-

3

1

vents. The ³¹P NMR spectra of compounds IV con-

tained signals in the range typical of phosphoromono-

amidites. Compound IV a with methyl groups at the

ence between their chemical shifts was smaller

1

(

1 ppm). The H NMR spectra contained a single set

N atom gave two singlets at 135.05 and 135.59 ppm,

P

of signals corresponding to aromatic ring protons and

a double set of signals corresponding to alkyl protons,

suggesting their nonequivalence. It is interesting that

the diisopropylamino derivative IV c gave a narrow

singlet, and the diethylamino (IV b) and piperidino

(

IV d) derivatives gave broadened signals, which is

8

7

the H proton showed coupling with the adjacent P

presumably due to structural changes in the molecule.

The H NMR spectra of compounds IV contained

2

1

atom, whereas the H and P atoms showed no such

coupling. This is one more evidence that the phos-

phorus-containing functional groups are similar but

not fully equivalent.

signals from all the groups of protons with consistent

ratio of the integral intensities. The signals of aromat-

ic protons were shifted downfield as compared to the

bisphosphorylated compounds. Increased multiplicity

of the proton signals in alkyl groups was observed

only for the methyl protons in the diethylamino deriv-

ative IV b.

A single crystal X-ray diffraction study of Vc

Fig. 1; Tables 1, 2) showed that the P atom lies

1

(

beyond the plane of the aromatic system, with the

2

1

1 1

C C O P angle equal to 40.8 ; this fact may be re-

1

sponsible for the zero value of the H P coupling

constant in the H NMR spectrum. The P atom lies

virtually in the naphthalene plane; the C C O P

dihedral angle is 162.4 , and the H P coupling

constant takes the maximal value [2].

A single crystal X-ray diffraction study of IV a

showed that it has a 1,7,1,7-cycloamidophosphite

structure (Fig. 2; Tables 3, 4). The molecule is virtu-

ally fully symmetrical and has a steplike structure.

It is an anti conformer with the bridging fragments in

1

2

6

7

2 2

8

2

1

2

the trans-chair conformation. The O PO angle is

3.7 , the angle between the aromatic planes in the

Since bisphosphites IIIa IIId are extremely labile

in solution, their cyclization with an equimolar

amount of the starting naphthol should be performed

immediately after completion of bisphosphorylation

9

molecule is 11 , and the distance between them is as

short as 1.45 . The distance between the two nearest

3

1

hydrogen atoms oriented inside the ring is 2.14

.

(

as monitored by P NMR spectroscopy). Within a

short time after adding 1,7-dihydroxynaphthalene to

the reaction solution, a mixture of crystalline isomer

Oily compounds IV a IV d were separated from

the crystalline products by repeated washing with

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

50

RASADKINA et al.

4

Table 1. Atomic coordinates ( 10 ) and isotropic tempera-

ture factors (

Table 2. Selected bond lengths (d, ) and bond angles

( , deg) in 1,7-bis(tetraisopropyldiaminothiophosphoryl-

oxy)naphthalene Vc

2

3

10 ) for 1,7-bis(tetraisopropyldiamino-

thiophosphoryloxy)naphthalene Vc

Atom

x

y

z

U_i_s_o

Bond

d

Bond

d

S¹

1159(1)

1472(1)

1093(1)

1413(1)

1246(1)

1416(1)

652(1)

1296(1)

1000(1)

1740(1)

1617(2)

1848(2)

2208(2)

2330(2)

2215(2)

1993(2)

1642(2)

1516(2)

1736(2)

2099(2)

424(2)

900(2)

7312(2)

850(2)

4954(2)

2485(5)

4028(5)

938(6)

539(1)

3785(1)

1219(1)

3812(1)

1540(1)

3297(1)

1309(2)

1544(2)

3891(2)

4218(2)

1639(2)

1309(2)

1441(2)

1884(2)

2719(2)

3068(2)

2954(2)

2497(2)

2126(2)

2245(2)

1172(2)

640(3)

1538(3)

1264(3)

1751(3)

839(3)

2081(2)

2404(2)

2215(3)

1368(3)

1216(3)

971(3)

66(1)

74(1)

41(1)

46(1)

42(1)

53(1)

43(1)

48(1)

54(1)

47(1)

38(2)

54(2)

59(2)

48(2)

53(2)

51(2)

40(1)

38(2)

35(1)

42(2)

58(2)

87(3)

84(2)

54(2)

92(3)

79(2)

54(2)

73(2)

75(2)

62(2)

77(2)

84(3)

74(2)

93(3)

101(3)

85(3)

129(4)

124(4)

59(2)

82(2)

88(3)

69(2)

81(2)

86(3)

1

9

S P

1.936(2)

1.926(3)

1.628(4)

1.633(5)

1.657(4)

1.608(4)

1.637(5)

1.657(5)

1.393(5)

1.380(5)

1.351(7)

C C

1.427(7)

1.397(8)

1.341(8)

1.419(7)

1.370(8)

1.403(8)

1.398(8)

1.354(8)

1.414(7)

1.427(7)

2

1

2

3

S

P

O

N

S P

C C

1

2

1

2

4

3

4

P O

C C

1

4

10

6

P N

C C

1

2

1

2

3

4

1

5

P N

C C

2

5

10

7

P O

C C

2

6

P N

C C

2

7

8

705(6)

P N

C C

1

7

8

9

4212(7)

4032(6)

3073(7)

3105(8)

3813(9)

4512(8)

5176(9)

5068(9)

4276(7)

3638(7)

3726(7)

4493(7)

579(8)

645(10)

915(10)

2474(8)

3424(11)

3577(9)

777(8)

O C

C C

2

9

10

O C

C C

1

2

3

4

5

6

7

8

9

1

2

3

C

1

2

C C

Angle

1 1

2

1

2 2 2

O P N

105.3(2)

96.6(2)

O P S

114.05(18)

114.2(2)

118.3(2)

126.4(2)

130.3(3)

113.6(3)

115.1(3)

124.0(3)

118.4(3)

1 1

4 2 2

O P N

N P S

2 1

3 2 2

N P N

106.9(2)

114.54(16)

114.82(18)

116.65(17)

105.1(2)

96.3(2)

N P S

1 1 1

O P S

C O P

2 1 1

7 2 2

N P S

C O P

0

1

2

3

4

5

6

7

8

9

0

1

2

3

4

5

6

7

8

9

0

1

2

3

4

1 1 1

11 1 14

N P S

C N C

2 2

4

11 1 1

O P N

C N P

207(2)

163(2)

422(2)

479(2)

2 2

3

14 1 1

O P N

C N P

4

2

17 2 1

N P N

106.8(2)

C N P

460(2)

1

39.1 and 139.4 ppm for IV a and at 140.00 and

1283(2)

1675(2)

1088(2)

1518(2)

1877(2)

1281(2)

676(2)

595(2)

699(2)

898(2)

712(2)

140.9 ppm for IV b; in the case of IV c and IV d,

a broadened signal was observed at 143.0 and

135.3 ppm, respectively. We believe that compounds

IV are 1,1,7,7 isomers; their molecules are unsym-

metrical, with nonequivalent phosphorus atoms. Un-

fortunately, in attempted separation of compounds IV

from IV , a minor amount of compounds IV also

passed to the benzene solution, as judged from the

603(9)

2310(9)

2064(9)

1472(10)

3103(9)

3866(12)

5137(12)

2168(14)

4594(13)

3157(16)

6102(15)

2179(8)

1519(10)

1401(10)

4806(10)

5719(10)

5648(11)

3483(3)

3079(3)

3277(3)

4371(2)

4569(3)

4359(4)

4206(2)

4015(3)

4694(3)

4599(2)

4995(2)

4419(3)

1

H NMR spectra; therefore, isomers IV were charac-

O

S

P

657(3)

O

1741(2)

2078(2)

1712(2)

2037(2)

1891(2)

2346(2)

X

O

S

IV a IV d + IV a IV d

P

X

S

O

S

VI a VI d

X

P

O P

O

X

+

S

O

benzene followed by evaporation of the solution and

vacuum drying of the residue. These were low-melting

amorphous compounds. Their P NMR spectra con-

sisted of two singlets of equal integral intensities at

3

1

VI a VI d

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

CYCLOBISPHOSPHORYLATION OF 1,7-DIHYDROXYNAPHTHALENE

thioates of this type is associated with increased rigid-

51

C⁴

terized only after their conversion to the correspond-

ing phosphoramidothioates VI and VI , with their

separation by column chromatography.

_C3

C²

_C1⁰

C⁵

C⁹

Compounds VI a VI d are high-melting crystalline

_C1

3

1

substances. Their P NMR spectra consist of narrow

singlets. We believe that such a difference in the spec-

tral characteristics of cyclophosphites and -phosphoro-

ity of the pentavalent phosphorus derivatives and

C⁶

O²

C⁷

C⁸

P

1

_C1

2

absence of conformeric transitions. The H NMR

N

spectra of VI a VI d are fully consistent with the sug-

gested structures. Furthermore, a single crystal X-ray

diffraction study of VI b showed (Fig. 3; Tables 5, 6)

that the molecule does not change its shape and con-

figuration as compared to IV b, although some struc-

O¹

C¹¹

1

2

tural changes do take place. For example, the O PO

angle increases by 4 and reaches 97.7 , whereas in

a diarylamidophosphorothioate it is as large as 100

[

3]. The distance between the planes in the molecule

Fig. 2. Molecular structure of cyclo[bis(1,7-naphtylene

dimethylphosphoramidite)] IV a.

increases by 0.5 , whereas the distance between the

two closest hydrogen atoms oriented inside the ring

decreases.

Compounds VI isolated by column chromatog-

raphy were amorphous powdered substances; their

melting points were considerably lower than those

of the respective isomers VI . Compounds VI were

lated the reaction products chromatographically. We

obtained a mixture of and isomers of monothio-

phosphoryl derivatives and a minor amount of bis-

(thiophosphoryl) derivative Vb. The and isomers

3

1

31

readily soluble in organic solvents. Their P NMR

spectra consisted of two singlets of equal integral

intensity in the range typical of phosphorothioates.

These data strongly suggest that the difference in the

chemical shifts is due to structural nonequivalence of

the phosphorus atoms, since the number of signals and

the ratio of their integral intensities did not change in

going from cyclophosphites IV to thiophosphates

are indiscernible in the P NMR spectra and are not

separated chromatographically, but they can be identi-

1

fied by H NMR spectroscopy owing to differences in

8

the multiplicity and chemical shift of the H proton in

4

Table 3. Atomic coordinates ( 10 ) and isotropic tempera-

2

3

ture factors (

10 ) for cyclo[bis(1,7-naphtylene di-

methylphosphoramidite)] IV a

1

VI . In the H NMR spectra of compounds VI , the

signals of all groups of protons are broadened. Con-

struction of molecular models shows that the molecule

of this isomer can exist in several conformations, and

transitions between them, in our opinion, are responsi-

Atom

x

y

z

U_i_s_o

P

5823(1)

4226(2)

7137(2)

5724(2)

7286(2)

8115(3)

9628(3)

10271(3)

10080(3)

9304(3)

7855(2)

7194(2)

7966(2)

9455(2)

5382(4)

5923(6)

2451(1)

3352(1)

3334(1)

1273(2)

6986(2)

8019(2)

8346(2)

7674(2)

5851(2)

4790(2)

4405(2)

5091(2)

6209(2)

6588(2)

1442(3)

14(3)

5947(1)

6144(1)

6691(1)

6767(1)

4375(2)

4077(2)

4613(2)

5455(2)

6644(2)

6921(2)

6334(2)

5499(2)

5211(2)

5775(2)

7836(2)

6433(3)

41(1)

42(1)

46(1)

53(1)

41(1)

54(1)

59(1)

56(1)

54(1)

51(1)

39(1)

37(1)

45(1)

68(1)

86(1)

1

2

O

N

1

ble for the signal broadening in the H NMR spectra.

The second synthesis procedure is direct cyclobis-

phosphorylation. It involves primary monophosphory-

lation yielding a mixture of - and -phosphorodiami-

dites VII, which subsequently undergo self-condensa-

tion with the release of the amine and formation of

cyclobisphosphites IV.

1

2

3

4

5

6

7

8

9

1

C

Note that, in monophosphorylation of naphthodiol

II, certain stereoselectivity is possible, since it is

known that - and -hydroxy groups in naphthalene

derivatives may differ in reactivity. To confirm or

disprove this suggestion, we performed sulfurization

of the reaction mixture formed by phosphorylation of

naphthodiol II with phosphorous triamide Ib and iso-

0

1

2

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

52

RASADKINA et al.

IV a IV d + IV a IV d

HNR₂

OH

OPX2

X PO

2

HO

or (and)

CH CN

3

Ia Id + II

HNR₂

VIIa VIId

S

OP(NEt₂)₂

OH

HO

(EtN)2PO

+

+ Vb

-

Isomer

-Isomer

the aromatic moiety. In the spectrum of the isomer,

The third synthetic procedure is based on the labil-

ity of the bisphosphorylated derivatives of the starting

naphthodiol, as revealed by NMR monitoring of the

bisphosphorylation progress. A signal in the range

typical of phosphoromonoamidites (139 141 ppm)

appeared in the P NMR spectrum 10 15 min after

the start of the reaction. Then, on standing of the re-

action solution, a precipitate formed, which consisted

8

the H proton gives a doublet of doublets (owing to

6

coupling with the P and H atoms) at 7.86 ppm,

8

whereas in the isomer the H signal is shifted up-

field by 1.5 ppm and is a doublet owing to coupling

6

2

31

with the H atom only. The H proton shows no cou-

pling with the P atom. Calculations show that the

and isomers are formed in virtually equal amounts.

C⁴C³

C²

C⁵

C⁹

C⁶

C¹⁰C¹

C⁷

C⁸

O¹

O²

_C1²

P

_C1¹

N

S

_C1³

_C1⁴

Fig. 3. Molecular structure of cyclo[bis(1,7-O,O -naphtylene diethylphosphoramidothioate)] VI b.

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

CYCLOBISPHOSPHORYLATION OF 1,7-DIHYDROXYNAPHTHALENE

53

Table 4. Selected bond lengths (d, ) and bond angles

, deg) in cyclo[bis(1,7-naphtylene dimethylphosphor-

amidite)] IV a

Table 6. Selected bond lengths (d, ) and bond angles

( , deg) in cyclo[bis(1,7-O,O -naphtylene diethylphos-

phoramidothioate)] VI b^a

(

a

Bond

d

Bond

d

Bond

d

Bond

d

1

10

3

P N

_P_O2

1.6443(17)

1.6505(15)

1.6677(15)

1.391(2)

C²C³

_C₃_C4

_C₄_C10

C⁵C⁶

1.399(4)

1.355(3)

1.414(3)

1.358(3)

1.415(3)

P N

P S

1.615(2)

1.9096(10)

1.5966(18)

1.6156(18)

1.405(3)

1.395(3)

1.462(4)

1.473(3)

1.360(4)

1.405(3)

C C

1.417(3)

1.409(4)

1.351(4)

1.414(4)

1.355(4)

1.405(4)

1.405(3)

1.360(3)

1.412(3)

1.416(3)

2

C C

2

3

4

_P_O1

P O

C C

1

4

9

P O

C C

1

1a

O C

1

1a

5

6

O C

C C

O C⁷

2

1.381(2)

C⁵C¹⁰

2

7

5

9

O C

C C

N C¹²

1.4403

C C

6

7

1.400(3)

1.362(3)

1.411(3)

N C

13

11

2

C C

6

7

1

7

8

7

8

N C

1.456(3)

1.366(3)

1.391(2)

1.421(3)

C C

N C

C C

1

2

8

9

1

8

10

C C

1

1a

9

10

1

1a

9

C O

C C

C O

C C

1

9

C C

Angle

NPO²

Angle

NPO²

Angle

2

1

101.70(11)

108.05(11)

116.88(8)

115.83(9)

114.52(7)

O PO

97.69(10)

126.89(15)

120.13(15)

121.1(2)

1a

1

7 2

97.29(9)

103.37(9)

93.77(8)

C O P

117.35(12)

121.14(19)

118.17(16)

NPO

C O P

1

2

1

1a

9

2

1a 1

NPO

C C O

O PS

C O P

2

1

1a

1

2 1 1a

O PO

O C C

NPS

C C O

7

2

1

1a 1 10

C O P

122.92(12)

O PS

O C C

117.0(2)

a

Symmetry transformation: x + 1, y + 1, z + 1.

Symmetry transformation: x + 1, y + 1, z.

4

Table 5. Atomic coordinates ( 10 ) and isotropic tempera-

ture factors (

to 80% of cyclophosphite IV a IV d, and a signal of

the starting phosphorous triamide (118 122 ppm)

2

3

10 ) for cyclo[bis(1,7-O,O -naphtylene

appeared in the ³¹P NMR spectrum of the solution.

We believe that the reaction involves disproportiona-

tion of bisphosphorylated naphthodiol II with the

release of phosphorous triamides. Apparently, in our

experiments, the initially formed naphthylene bis-

diethylphosphoramidothioate)] VI b

Atom

x

y

z

^Uiso

P

S

O

N

5758(1)

7144(1)

5813(2)

3739(2)

6073(3)

2614(3)

5500(1)

4407(1)

6131(1)

5349(1)

6174(2)

3573(2)

2457(1)

2624(1)

1408(1)

2179(1)

3512(2)

1246(2)

33(1)

53(1)

36(1)

38(1)

42(1)

36(1)

(

phosphorodiamidites) show efficient intermolecular

1

2

recognition, resulting in ready formation of com-

pounds containing intramolecular cavities. The regio-

selectivity is apparently determined in this case by

specific features of molecular recognition on the level

of reaction of two molecules of bisphosphorylated

unsymmetrical naphthalenes:

1

C

C²

_C3

C⁴

C⁵

C⁶

C⁷

_C8

_C9

1581(4)

2(4)

2987(2)

2723(2)

3031(2)

3958(2)

4520(2)

4760(2)

4452(2)

3618(2)

3887(2)

1966(2)

1779(2)

897(2)

807(2)

1544(2)

1383(2)

500(2)

122(2)

286(2)

50(1)

55(1)

48(1)

42(1)

40(1)

34(1)

33(1)

37(1)

32(1)

496(3)

121(3)

1164(3)

2767(3)

3284(3)

582(3)

2183(3)

CH CN

3

2

IIIa IIId

IV a IV d.

P(NR₂)₃

Disproportionation is a slow process and is fully

complete only in 1.5 2 months; the reaction rate

steadily decreases, irrespective of the substituent at

the N atom.

C¹⁰

C¹

1

5102(4)

4011(5)

7559(5)

7320(8)

7049(2)

7115(3)

6093(3)

5547(4)

3458(2)

4235(3)

4446(3)

5344(5)

54(1)

78(1)

73(1)

Along with phosphorous triamides, we performed

phosphocyclization with phenyl tetraethylphosphoro-

diamidite VIII. We failed to prepare the cyclic prod-

ucts using the method of molecular assembling and

direct synthesis. This is due to formation, in the

1

2

3

4

C

123(2)

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

54

RASADKINA et al.

course of phosphorylation, of diaryl phosphoramidites

in which the amide group is inactive under the reac-

tion conditions [4]. However, disproportionation of

tions with I > 2 (I) were included in the calculation.

The final divergence factors are R 0.031 and wR

0.09.

1

2

bisphosphorylated compound IX showing in the ³¹

P

Compound IV a: C H N O P ; monoclinic sys-

2

4

26

2

4 2

NMR spectrum two singlets with

41.49 ppm results in precipitation of a crystalline

compound identified as cycloamidophosphite IV b.

141.74 and

P

tem, M 468.41, crystal size 0.55 0.50 0.20 mm,

1

space group P2 /c; a 8.247(2), b 10.546(2), c

1

3

1

2.965(3)

;

96.74(3) , V 1119.8(4)

, d_c_a_l_c

3

PhOP(NEt ) + II

2

1.389 Mg m . A total of 1330 unique reflections with

VIII

I > 2 (I) were included in the calculation. The final

divergence factors are R 0.026 and wR 0.073.

NEt₂

1

2

NEt₂

OPOPh

Compound VI b: C H N O P S ; monoclinic

28 32 2 4 2 2

system, M 586.62, crystal size 0.55 0.28 0.22 mm,

OPOPh

CH CN

3

IV b

space group P2 /c; a 8.089(2), b 14.357(3), c

1

(

PhO) PNEt

2 2

3

1

2.634(3)

;

104.58(3) , V 1420.0(6)

, d_c_a_l_c

IX

3

1

.372 Mg m . A total of 1624 unique reflections with

_T_h_e31_P_N_M_R_s_p_e_c_t_r_u_m_o_f_t_h_e_r_e_a_c_t_i_o_n_s_o_l_u_t_i_o_n

I > 2 (I) were included in the calculation. The final

divergence factors are R 0.032 and wR 0.089.

1

2

contains a singlet of diphenyl diethylphosphoramidite,

which formed in the course of the reaction. The reac-

tion was 70% complete in 2.5 months. Thus, we

showed that, in this case, formation of the 1,7,1,7

isomer in disproportionation is advantageous. We ob-

served such disproportionation of bisphosphorylated

atomatic diols with formation of macrocyclic systems

in experiments with resorcinol [5], hydroquinone and

diphenol [6], and 1,5- and 2,7-dihydroxynaphthalenes

The structures were solved by the direct method

and refined by the full-matrix least-squares method in

the anisotropic approximation.

The mass spectrum of VI a was obtained on a

Kratos Compact Maldi IV spectrometer.

1,7-Bis(tetraalkyldiaminothiophosphoryloxy)-

naphthalenes Va Vd. A 3-mmol portion of hexaal-

kylphosphorous triamide was added to a solution of

1.5 mmol of 1,7-dihydroxynaphthalene in 10 ml of

acetonitrile. The mixture was stirred for 3 min with

Va and 20 min with Vb Vd, after which 3 mmol of

sulfur was added, and the mixture was stirred for an

additional 1.5 h at room temperature. The solution

was filtered and vacuum-evaporated, and the residue

was chromatographed on a column using the 10 : 1

hexane dioxane mixture as eluent. The products were

vacuum-dried (1 mm Hg, 60 C) for 2.5 h.

[

1]. We believe that this is a common feature of

related systems and that the disproportionation is

facilitated by mutual approach of the phosphorus-

containing moieties due to stacking interaction of the

aromatic cores.

EXPERIMENTAL

1

The H NMR spectra were taken on a Bruker WH-

3

1

2

50 spectrometer (250 MHz), and the P NMR spec-

tra, on a Bruker WP-80SY spectrometer at the work-

ing frequency of 32.4 MHz, relative to 85% H PO .

1

,7-Bis(tetramethyldiaminothiophosphoryloxy)-

3

4

naphthalene Va. Yield 52%, mp 104 105 C, R 0.66

(B), 0.4 (C). H NMR spectrum, , ppm (CDCl ):

2.75 d (12H, NCH , J

NCH , J 7.3 Hz), 7.28 d.d (1H, C H, J

f

1

Adsorption column chromatography was performed

on silica gel L 100/160. The TLC analysis was per-

formed on Silufol plates with the systems benzene

dioxane, 5 : 1 (A), 10 : 1 (B); hexane dioxane, 3 : 1

3

7.3 Hz), 2.80 d (12H,

3

HP

3

6

3

6

5

8.9,

3

HP

H H

4

3

J

6

8

2.1 Hz), 7.33 d.d (1H, C H, J

3

2

7.7, J

3 4

H H

(

C), 5 : 1 (D); and chloroform methanol, 5 : 1 (E).

2

3

8

.3 Hz), 7.37 d (1H, C H, J

C H, J

.85 d.d (1H, C H, J

0.37, 80.64 ppm (CH Cl ). Found, %: C 46.91;

2

3

7.7 Hz), 7.59 d (1H,

H H

The plates were developed by exposure to iodine

vapor, calcination, and treatment with 1% aqueous

AgNO₃.

4

3

5

3

4

3

8.3 Hz), 7.79 d (1H, C H, J

5

6

8.9 Hz),

H H

1.7 Hz).

8

4

7

8

6

2.1, J

H H

HP

P

2

Single crystal X-ray diffraction study of IIIc was

performed with an Enraf-Nonius CAD-4 automated

diffractometer, MoK radiation. C H N O P S ;

H 6.53; N 12.19; P 13.47. C H N O P S . Calcu-

18 30 4 2 2 2

lated, %: C 46.93; H 6.57; N 12.17; P 13.46.

,7-Bis(tetraethyldiaminothiophosphoryloxy)-

3

4

62

4

2 2 2

1

monoclinic system, M 684.94, crystal size 0.50

naphthalene Vb. Yield 59%, oily substance, R 0.72

0

8

.40 0.10 mm, space group C2/c; a 36.040(6), b

f

3

1

.106(2), c 27.560(6)

;

101.38(3) , V 7893(3)

,

(B), 0.56 (C). H NMR spectrum, , ppm (CDCl ):

3

d_c_a_l_c1.153 Mg m . A total of 1921 unique reflec-

1.13 t (12H, CH CH , J

7.3 Hz), 1.15 t (12H,

2

3

HH

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

CYCLOBISPHOSPHORYLATION OF 1,7-DIHYDROXYNAPHTHALENE

55

3

6

3

CH CH , J

7.3 Hz), 3.25 m (8H, NCH , J

7.26 d.d (2H, C H, J

6

8

2.2, J

6

5

8.3 Hz), 7.34

2

3

HH

2

HP

H H

2

3

1

(

1.9 Hz), 3.33 m (8H, NCH , J 11.9 Hz), 7.30 d.d

1H, C H, J

d.d (2H, C H, J

3

4

8.3, J

3

7.7 Hz), 7.58 d

2

HP

H H

6

3

4

3

5

3

H H⁵

6

8.9, J

7.7, J

H H

6

8

2.1 Hz), 7.34 d.d (1H,

8.1 Hz), 7.55 d (1H, C H,

8.1 Hz),

8.9 Hz), 7.86 d.d (1H, C H,

(2H, C H, J

2

3

8.3 Hz), 7.82 d (2H, C H, J

5 6

H H

3

2

8

4

C H, J

3

2

3

4

H H

8.3 Hz), 8.70 d (2H, C H, J 2.2 Hz).

135.05,

HH

P

3

4

3

J

2

3

7.7 Hz), 7.63 d (1H, C H, J

.76 d (1H, C H, J

4

3

H H

135.59 ppm (CH Cl ). Found, %: C 61.58; H 5.24;

2 2

5

3

8

7

J

5

6

P 13.18. C H N O P . Calculated, %: C 61.79;

24 24 2 4 2

H 5.18; P 13.28.

H H

4

8

6

2.1, J_H_P1.7 Hz).

75.53, 75.98 ppm

H H

P

(

5

CH Cl ); 75.05, 76.34 ppm (CH CN). Found, %: C

2

3

Cyclo[bis(1,7-naphthylene diethylphosphorami-

0.43; H 8.78; N 10.62; P 11.90. C H N O P S .

22 46 4 2 2 2

dite)] IV b. Yield 49%, mp 173 174 C, R 0.73 (A),

Calculated, %: C 50.36; H 8.84; N 10.68; P 11.81.

f

1

0

(

3

.61 (C). H NMR spectrum, , ppm (CDCl ): 1.23 t

3

1

,7-Bis(tetraisopropyldiaminothiophosphoryl-

3

12H, CH CH , J

7.3 Hz), 3.32 m (4H, NCH ,

2

3

HH

2

oxy)naphthalene Vc. Yield 62%, mp 212 213 C, R

0

(

1

CH(CH ) , J

1

8

f

3

^JHP 9.0 Hz), 3.39 m (4H, NCH , J 9.0 Hz), 7.10 d

1

2

HP

.72 (B), 0.56 (C). H NMR spectrum, , ppm

2

3

6

3

(2H, C H, J

3

2

7.7 Hz), 7.24 d.d (2H, C H, J

6 5

CDCl ): 1.18 d [12H, CH(CH ) , J

7.15 Hz],

H H

3

3 2

HH

4

3

8.5, J

6

8

2.6 Hz), 7.28 d.d (2H, C H, J

3

4

8.1,

.29 d [12H, CH(CH ) , J 6.6 Hz], 1.40 d [24H,

H H

8.1 Hz),

3

2

HH

3

4

3

J

2

3

7.7 Hz), 7.56 d (2H, C H, J

.80 d (2H, C H, J

4

3

6.6 Hz], 3.87 m (8H, NCH, J

H H

3

2

HH

HP

4

5

3

8

3

2

7.7,

J

3

7

5

6

8.5 Hz), 8.71 d.d (2H, C H,

3.2 Hz), 7.31 d.d (1H, C H,

J

H H

4

2

3

J

8

6

2.6, ^JHP 1.7 Hz).

137.35 (br.) ppm

P

.3 Hz), 7.54 d (1H, C H, J

2

3

7.7 Hz), 7.77 d (1H,

H H

5

3

6

3

(CH Cl ).

C H, J

5

6

8.8 Hz), 7.91 d.d (1H, C H, J

2.2 Hz), 8.07 d.d (1H, C H, J

.7 Hz), 8.80 d (1H, C H, J

6

5

8.8,

2

H H

4

8

4

J

6

8

6

2.2, J

H H

H H HP

Cyclo[bis(1,7-naphthylene diisopropylphos-

4

3

1

6

4

3

8.3 Hz).

67.46,

P

H H

phoramidite)] IV c. Yield 32%, mp 182 183 C, R

f

8.19 ppm (CH Cl ). Found, %: C 59.48; H 9.18;

2

1

0

[

.74 (D). H NMR spectrum, , ppm (CDCl ): 1.27 d

N 8.24; P 9.00. C H N O P S . Calculated, %: C

5

3

4

62

4

2 2 2

3

12H, CH(CH ) , ^JHH 7.15 Hz], 1.36 d [12H,

CH(CH ) , J 7.15 Hz], 3.93 m [2H, NCH(CH ) ,

9.62; H 9.12; N 8.18; P 9.04.

3 2

3

2

HH

3 2

1

,7-Bis(dipiperidinothiophosphoryloxy)naph-

3

^JHP 10.44 Hz], 3.99 m [2H, NCH(CH ) , J_H_P

3 2

thalene Vd. Yield 42%, mp 128 129 C, R 0.60

f

6

3

4

1

2

0.44 Hz], 7.15 d.d (2H, C H, J

6

5

8.8, J

6 8

H H

(

hexane dioxane, 3 : 1), 0.32 (hexane dioxane, 7 : 1).

3

2

.2 Hz), 7.27 d (2H, C H), 7.52 d (2H, C H), 7.56 d

1

H NMR spectrum, , ppm (CDCl ): 1.57 m (24H,

4

5

3

(2H, C H), 7.78 d (2H, C H, J

5

6

8.8 Hz), 8.70 d.d

3

H H

CH ), 3.17 m (8H, CH , J 6.4 Hz), 3.22 m (8H,

8

4

2

HP

(2H, C H, J

8

6

2.2, J 2.7 Hz).

141.6 ppm

P

H H

HP

3

6

3

CH , J 6.6 Hz), 7.30 d.d (1H, C H, J

4

6

5

8.8,

2

HP

H H

(CH Cl ).

2

3

J

6

8

2.2 Hz), 7.32 d.d (1H, C H, J

3

2

7.7, J

3 4

H H

2

3

Cyclo[bis(1,7-naphthylene phosphoropiperi-

8

.2 Hz), 7.56 d (1H, C H, J

2

3

7.7 Hz), 7.66 d (1H,

H H

4

3

5

3

dite)] IV d. Yield 39%, mp 175 176 C, R 0.84 (B),

C H,

8

J

4

3

8.2 Hz), 7.78 d (1H, C H,

J

5

6

f

H H

8

4

1

.8 Hz), 7.94 d.d (1H, C H, J

8

6

2.2, J 1.7 Hz).

0.63 (D). H NMR spectrum, , ppm (CDCl ): 1.62 m

H H

HP

3

7

4.27, 75.09 ppm (CH Cl ). Found, %: C 58.01; H

(12H, CH ), 3.25 m (4H, CH , J

13.2, ^JHP

P

2

HH

3

7

%

.50; N 9.06; P 9.95. C H N O P S . Calculated,

30 46 4 2 2 2

8.11 Hz), 3.36 m (4H, CH , J 13.2, J 6.4 Hz),

2

HH

HP

: C 58.04; H 7.47; N 9.03; P 9.98.

2

3

6

7

.15 d (2H, C H, J

2

3

7.3 Hz), 7.25 d.d (2H, C H,

H H

3

4

3

Cyclo[bis(1,7-naphthylene dialkylphosphorami-

J

6

5

9, J

6

8

2.1 Hz), 7.30 d.d (2H, C H, J

H H

3 2

H H

3

4

3

dites)] IV a IV d. A 4.5-mmol portion of phosphorous

triamide Ia Id was added to a solution of 4.5 mmol

of diol II in 20 ml of anhydrous acetonitrile. The

mixture was stirred for 4 h at room temperature. The

precipitate was washed with acetonitrile and then

several times with benzene. The residue was recrystal-

lized from methylene chloride.

7

.7, J

3

4

8.1 Hz), 7.56 d (2H, C H, J

4

3

8.1 Hz),

H H

5

3

8

7

.81 d (2H, C H, J

5

6

9.0 Hz), 8.68 d.d (2H, C H,

H H

4

J

8

6

2.1, J_H_P1.7 Hz).

131.99 (br.) ppm

P

H H

(

1

5

CH Cl ). Found, %: C 65.99; H 5.81; N 5.21; P

2

1.21. C H N O P . Calculated, %: C 65.93; H

30 32 2 4 2

.90; N 5.13; P 11.33.

Cyclo[bis(1,7-naphthylene dialkylphosphor-

Cyclo[bis(1,7-naphthylene dimethylphosphor-

amidothioates)] VI a VI d. A 2.4-mmol portion of

sulfur was added to a solution of 1.2 mmol of a mix-

ture of isomers of cyclo[bis(1,7-naphthylene dialkyl-

phosphoramidites)] IVa IVd in 50 ml of methylene

amidite)] IV a. Yield 48%, mp 191 192 C, R 0.69

f

1

(

A). H NMR spectrum, , ppm (CDCl ): 2.88 d (12H,

3

2

3

NCH , J 9.4 Hz), 7.01 d (2H, C H, J

2

3

7.7 Hz),

3

HP

H H

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

56

RASADKINA et al.

1

chloride. The mixture was continuously stirred for

.5 h at room temperature. The solution was filtered

R 0.77 (A), 0.35 (C). H NMR spectrum, , ppm

f

3

2

(

CDCl ): 1.69 m (12H, CH ), 3.53 m (8H, CH , J

3

2

HP

off and vacuum-evaporated to 20 ml; the crystals were

filtered off, washed with benzene, and recrystallized

from chloroform (in the case of VI a VI d). The filtrate

was vacuum-evaporated, and the residue was chro-

atographed on a colunm, eluents hexane dioxane,

6

3

4

9

2

.81 Hz), 7.31 d.d (2H, C H,

J

6

5

8.9,

7.6,

J

6

8

H H

3

.1 Hz), 7.39 d.d (2H, C H,

J

3

2

3

4

H H

2

3

7

.7 Hz), 7.46 d (2H, C H, J

2

3

7.6 Hz), 7.67 d

H H

4

3

5

3

(2H, C H, J

4

3

7.7 Hz), 7.86 d (2H, C H, J

5 6

H H

8

4

8

.9 Hz), 8.95 d.d (2H, C H, J

8

6

2.1, J 1.6 Hz).

1

0 : 1 (VI a VI d) and benzene dioxane, 10 : 1

H H HP

6

3.8 ppm (CH Cl ). Found, %: C 59.11; H 5.19;

(VI a VI d).

P

2 2

P 10.12. C H N O P S . Calculated, %: C 59.00;

3

0

32

2

4 2 2

Cyclo[bis(1,7-naphthylene dimethylphosphor-

H 5.28; P 10.14.

amidothioate)] VI a. Yield 44%, mp 297 298 C, R

f

1

Cyclo[bis(1,7-naphthylene dimethylphosphor-

0

.74 (A), 0.62 (B). H NMR spectrum, , ppm

3

amidothioate)] VI a. Yield 32%, mp 92 94 C, R

(

CDCl ): 3.10 d (12H, NCH , J 12.1 Hz), 7.28 d

f

3

HP

1

2

3

6

3

2

3

7.7 Hz), 7.32 d.d (2H, C H, J

2.1 Hz), 7.40 d.d (2H, C H, J

6

5

0

.69 (A). H NMR spectrum, , ppm (CDCl ): 2.85

3

(2H, C H, J

H H

4

3

br.d (12H, NCH ), 7.32 br.d, 7.50 br.m, 7.69 br.d,

8

.8, J

6

8

3

2

7.7,

3

H H

3

4

3

4

8.3 Hz), 7.68 d (2H, C H, J

.88 d (2H, C H, J

4

3

8.3 Hz),

7

.95 br.d (12H, CH).

67.06, 67.78 ppm (CH Cl ).

J

P 2 2

H H

5

3

8

Found, %: C 54.19; H 4.77; P 11.70. C H N O P

7

5

6

8.8 Hz), 8.97 d.d (2H, C H,

24 24 2 4 2

H H

4

S₂. Calculated, %: C 54.32; H 4.56; P 11.6.

Cyclo[bis(1,7-naphthylene diethylphosphor-

J

8

6

2.1, J

1.7 Hz).

67.7 ppm (CH Cl ).

H H

HP

P 2 2

Found, %: C 54.16; H 4.83; P 11.41. M 531.0.

C H N O P S . Calculated, %: C 54.32; H 4.56; P

2

4

24

2

4 2 2

amidothioate)] VI b. Yield 36%, mp 73 74 C, R

1

1.6. M 530.5.

f

1

0

1

.72 (A). H NMR spectrum, , ppm (CDCl₃):

Cyclo[bis(1,7-naphthylene diethylphosphorami-

.00 br.t (12H, CH CH ), 3.39 br.m (8H, NCH ),

2

3

2

dothioate)] VI b. Yield 41%, mp 281 282 C, R 0.78

f

7.31 br.d, 7.52 br.m, 7.63 br.d, 7.98 br.d (12H, CH).

66.49, 67.06 ppm (CH Cl ).

1

(

1

A), 0.66 (B). H NMR spectrum, , ppm (CDCl ):

3

P

2

3

.30 t (12H, CH CH , J

NCH , J 14.3 Hz), 7.28 d.d (2H, C H, J

7.1 Hz), 3.57 m (8H,

2

3

HH

3

6

3

6

5

8.8,

Cyclo[bis(1,7-naphthylene diisopropylphosphor-

2

HP

H H

4

3

J

6

8

2.2 Hz), 7.30 d.d (2H, C H, J

3

2

7.7, J

3

4

amidothioate)] VI c. Yield 31%, mp 104 105 C, R

H H

f

2

3

1

7

.2 Hz), 7.39 d (2H, C H, J

2

3

7.7 Hz), 7.65 d

0.79 (C H dioxane, 5 : 1). H NMR spectrum,

,

H H

6

4

3

5

3

(2H, C H, J

4

3

7.2 Hz), 7.84 d (2H, C H, J

5

6

ppm (CDCl ): 1.34 br.m (24H, CH ), 3.96 br.m (2H,

H H

3 3

8

4

NCH), 4.05 br.m (2H, NCH), 7.33 br.d, 7.52 br.d,

.64 br.m, 8.07 br.d (12H, CH). 64.15, 64.69 ppm

8

1

.8 Hz), 9.01 d.d (2H, C H, J

8

6

2.2 Hz, J

66.9 ppm (CH Cl ). Found, %: C 57.40;

H H

HP

7

.7 Hz).

P

2

(

CH Cl ). Found, %: C 59.89; H 6.18; N 4.32; P 9.68.

H 5.48; P 10.59. C H O N P S . Calculated, %:

2 2

2

8

32

4

2 2 2

C H N O P S . Calculated, %: C 59.80; H 6.27;

C 57.32; H 5.50; P 10.56.

32 40

2

4 2 2

N 4.36; P 9.64.

Cyclo[bis(1,7-naphthylene diisopropylphos-

phoramidothioate)] VI c. Yield 32%, mp 182 183 C,

Cyclo[bis(1,7-naphthylene phosphoropiperidido-

1

R 0.74 (hexane dioxane, 5 : 1). H NMR spectrum, ,

thioate)] VI d. Yield 28%, mp 112 115 C, R 0.84

f

3

1

ppm (CDCl ): 1.27 d [12H, CH(CH ) , J 7.15 Hz],

.36 d [12H, CH(CH ) , J

2H, NCH(CH ) , ^JHP 10.44 Hz], 3.99 m [2H,

NCH(CH ) , J 10.44 Hz], 7.15 d (2H, C H, J

(A). H NMR spectrum, , ppm (CDCl ): 1.39 br.m

3

3 2

HH

3

1

[

7.15 Hz], 3.93 m

3

2

HH

(12H, CH ), 3.40 br.m (8H, NCH ), 7.33 br.d, 7.52

2

3

3 2

br.d, 7.64 br.m, 8.03 br.d (12H, CH).

64.69 ppm (CH Cl ).

64.15,

P

3

6

3

6 5

3

2

HP

H H

2

4

3

8

.8, J

6

8

2.2 Hz), 7.27 d (2H, C H), 7.52 d (2H,

H H

2

4

5

3

C H), 7.56 d (2H, C H), 7.78 d (2H, C H, J

5

6

ACKNOWLEDGMENTS

H H

8

4

8

.8 Hz), 8.70 d.d (2H, C H, J

8

6

2.2, J 2.7 Hz).

H H HP

The study was performed within the framework of

the program Basic Research of Higher School in the

Field of Natural Science and Humanities. Russian

Universities (project no. 990986) and was financially

supported by the Russian Foundation for Basic Re-

search (project no. 00-03-32578).

1

41.6 ppm (CH Cl ). Found, %: C 66.40; H 6.89;

P

2 2

N 4.88; P 10.75. C H N O P . Calculated, %: C

3

2

40

2

4 2

6

6.42; H 6.97; N 4.84; P 10.71.

Cyclo[bis(1,7-naphthylene phosphoropiperidido-

thioate)] VI d. Yield 32%, decomposes at 296 300 C,

RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

CYCLOBISPHOSPHORYLATION OF 1,7-DIHYDROXYNAPHTHALENE

57

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2

. Nifant’ev, E.E., Rasadkina, E.N., Evdokimenko-

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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 1 2004

Article Doi

Cyclobisphosphorylation of 1,7-dihydroxynaphthalene with phosphorous triamides

DOI: 10.1023/B:RUGC.0000025169.12605.2e

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Article abstract of DOI:10.1023/B:RUGC.0000025169.12605.2e

Full text of DOI:10.1023/B:RUGC.0000025169.12605.2e

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