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Derivatives of NPC12(NS0C1)2 and (NPC12)2NS0C1, Part XX [1] Reactions of Some Inorganic Ring Systems with N,N' -Dimethylethylenediamine

Barteld de Ruiter, Geert Kuipers, Jan H. Bijlaart, and Johan C. van de Grampel* Laboratorium voor Anorganische Chemie, Rijksuniversiteit Groningen, Nijenborgh 16, 9747 AG Groningen, The Netherlands Z. Naturforsch. 87 b, 1425-1429 (1982); received June 18, 1982 Phosphorus-Sulfur-Nitrogen Heterocycles, Diazaphospholidines, NMR Spectra

Reactions of the ring systems (NPC12)3, (NPCl2)2NSOX, and NPC12(NS0X)2 (X = Cl, Ph) with N,N'-dimethylethylenediamine lead to mono-, bis-, and tris(spirocyclic) com-pounds as the only characterizable products. The XH and 31P NMR parameters are re-ported and briefly discussed.

Generally, di- and tetrasubstituted secondary amino derivatives of hexachlorocyclotriphospha-zene, (NPC12)3, possess non-geminal structures [2]. The very few examples of geminal compounds have either been isolated in low yield or are derivatives of aziridine, an amine with a rather deviating behaviour [3, 4]. Recently, Goldschmidt has re-ported an indirect preparation pathway for geminal secondary amino derivatives [5].

An interesting other route to geminal compounds are substitution reactions of the ring system with a difunctional secondary amine, leading to spirocyclic compounds. The mono- and bis(spirocyclic) N,N'-dimethylethylenediamino derivatives of (NPC12)3 have already been described [6]. As we were particularly interested in the NMR characteristics of geminal derivatives of the ring systems (NPC12)3, (NPC12)2NS0X. and NPC12(NS0X)2 (see Fig. 1;

Results and Biscussion

Preparation

Depending on the conditions used, reactions of (NPC12)3 with N,N'-dimethylethylenediamine in ether afford the mono- and bis(spirocyclic) com-pounds (NPCl2)2NP(NMeCH2)2 and NPCl2[NP(NMeCH2)2]2, containing the 1,3,2-diaza-phospholidine (N2PC2) ring [6]. The hitherto un-known tris(spirocyclic) derivative [NP(NMeCH2)2]3 can be obtained by reaction of (NPC12)3 with an excess of amine in boiling acetonitrile.

A similar straightforward reaction behaviour is observed for (NPCl2)2NSOPh; the compounds NPCl2NP(NMeCH2)2NSOPh and [NP(NMeCH2)2]2NSOPh are obtained after reac-tions in ether (1:2 molar ratio) and acetonitrile (1:4), respectively.

^ P N N

ClJ II /Cl ^P ^ P

I ^ N / I Cl N Cl

CL

Cl

.0

XI

Cl

Cl. Cl

(NPCl ) (NPCl )2NSOX NPC12(NSOX)

X = C1, Ph), we have conducted a number of reactions between these rings and N,N'-dimethyl-ethylenediamine; for the spirocyclic compounds thus obtained, the XH and 31P NMR parameters were determined.

* Reprint requests to Dr. J. C. van de Grampel. 0340-5087/82/1100-1425/$ 01.00/0

Reactions with (NPC12)2NS0C1 offer a signifi-cantly less simple picture. A 1:2 molar ratio reac-tion in ether affords the (air-sensitive) mono(spiro-cyclic) NPCl2NP(NMeCH2)2NSOCl, but all attempts to prepare the bis(spiro) compound under a variety of reaction conditions failed. Instead, an air-sensitive amorphous solid was obtained, the infrared spectrum of which indicates a polymer-like

1426 B. de Ruiter et al. • Derivatives of NPCl2(NSOCl)2 and (NPC12)

structure. Presumably, the electron release of the four amino substituents in the hypothetical bis-(spirocyclic) [NP(NMeCH2)2]2NSOCl leads to a cleavage of the sulfur-chlorine bond, thus initiating polymerization.

trans-N PCl2(NSOPh)2 readily affords trans-NP(NMeCH2)2(NSOPh)2, which is accompanied by a second product (5% relative yield) with NMR parameters (31P: 16.5 ppm; (5(Me) 2.24, 3J(PH) 11.7 Hz) very close to those of the main product (see Tables I and II). The side-product could neither be isolated nor identified.

Finally, cw-NPCl2(NSOCl)2 affords the expected spirocyclic derivative c*'s-NP(NMeCH2)2(NSOCl)2

after a reaction in ether. In acetonitrile, in which solvent the first chlorine substitution step of cis-NPC12(NS0C1)2 with secondary amines takes place

at one of the sulfur centres [7, 8], the reaction leads to a resinous mixture of products, in which traces of as-NP(NMeCH2)2(NSOCl)2 could be identified; no further oligomeric (e.g. bicyclic) products were observed.

NMR spectra

The m and 31P NMR data of the spirocyclic compounds are summarized in the Tables I and II, respectively. In the XH NMR spectra two groups of signals can be distinguished; one (2.2-2.8 ppm) arises from the methyl-, the other one (3.1-3.4 ppm) from the methylene protons. The methyl signals are sharp, whereas the methylene groups may give rise to complicated resonance patterns [9, 10] (see Fig. 2); this may be due to conformational effects within the N2PC2 ring(s). For compounds with two

Table I. XH-NMR para-meters of N,N'-dimethyl-ethylenediamino derivati-ves of inorganic ring sys-tems.

<5(CH3) 3J(PH) + 5J(PH)a <5(CH2) J( PH)*> (ppm) (Hz) (ppm) (Hz)

(NPCl9)9NP(NMeCH2)2 2.60 11.6° 3.23 10.0C

NPCl2[NP(NMeCH2)2]2 2.60 12.8C 3.20 12.0° [NP(NMeCH2)2]3 2.61 11.8 3.14 10.8 NPCl2NP(NMeCH2)2NSOPh 2.61 12.0 + 1.2 3.18 10.6

2.33 11.6 + 1.1 [NP(NMeCH2)2]2NSOPh 2.60 12.1 3.14 10.8

2.37 11.9 NPCl2NP(NMeCH2)2NSOCl 2.70 12.2 + 1.0 3.27 10.8

2.50 12.1 + 0.9 irans-NP(NMeCH2)o(NSOPh)2 2.26 11.9 3.10 10.7 cis-NP(NMeCH2)2(NSOCl)2 2.80 12.2 3.39 10.8

2.50 12.0

a Apparent coupling constant (where applicable); b apparent coupling constant ; c data from [6].

Table II. 3iP-NMR para-meters of relevant com-pounds.

d(PCl2) (ppm)

6[P(NMeCH2)2] (ppm)

2J(PP) (Hz)

(NPC12)3 19.9 (NPCl2)2NP(NMeCH2)2 23.8 20.4 41.8 NPClo[NP(NMeCH2)2]2 29.1 24.9 54.0 [NP(NMeCH2)2]3 29.4 (NPClo)2NSOPh 20.7 NPCl2NP(NMeCH2)2NSOPh 26.7 18.3 51.6 [NP(NMeCH2)2]2NSOPh 24.4 (NPC12)2NS0C1 26.3 NPCl2NP(NMeCH2)2NSOCl 30.3 18.4 65.9 trans-NPCl2(NSOPh)2 22.1 *rarcs-NP(NMeCHo)2(NSOPh)2 15.0 cis-NPCl2(NSOCl)2 27.6 eis-NP(NMeCH2)2(NSOCl)2 14.5 [NP(NMe2)2]3 25.7 [NP(NMe2)2]2NSOPh 21.7 } <5[P(NMe2)2] ira??s-NP(NMe2)2(NSOPh)2 15.1

1427 B. de Ruiter et al. • Derivatives of NPCl2(NSOCl)2 and (NPC12)

-CH,-

J w w

3.50 3.00 250 ppm

-CH2-

J

-CH,

k.

3.50 3.00 2.50 ppm

-CH2 -

J vj

Nl -Wi* -"PH

350 300 250 2.00 ppm

-CH 3

-CH2-

3.50 3.00 2.50 2.00 ppm

Fig. 2. iH-NMR spectra of a. [NP(NMeCH2)2]3, b. NPCl2NP(NMeCH2)2NSOPh, c. [NP(NMeCH2)2]2NSOPh, and d. *rans-NP(NMeCH2)2(NSOPh)2.

or three chemically equivalent phosphorus atoms the spectra show the second-order humps, already familiar from other derivatives of the ring systems [11, 12]. Typical spectra are shown in Fig. 2.

It is remarkable (cf. [7]), that the chemical shift of the methyl protons is hardly affected by sub-stitution of chlorine ligands of other phosphorus centres, as illustrated by the shift values for the three derivatives of (NPC12)3. A considerable upheld shift of the methyl signals is observed on replacing sulfur-bonded chlorine atoms by phenyl groups. By analogy with the dimethylamino derivatives [12] we assign the high-field signals in the spirocyclic derivatives of (NPCl2)2NSOPh to the methyl groups eis with respect to the phenyl group. The methylene signals show a relationship between chemical shift and electron-withdrawing capacity of the other ring units. The shielding effect of the different groupings decreases in the order SOPh > P(NMeCH2)2 > PC12 > SOC1.

The introduction of a spirocyclic centre affects the 31P NMR shift of the directly involved phospho-rus atom in a way strongly depending on the nature of the central ring. It varies from an upheld shift of 13.1 ppm for as-NP(NMeCH2)2(NSOCl)2 as com-pared with C?\S-NPC12(NSOC1)2, to a negligible down-field shift (about 1 ppm) for the three derivatives of (NPC12)3. The chemical shifts can be roughly compared with those of corresponding dimethyl-amino derivatives (if available; see Table II).

As expected [13], the chemical shifts of the phosphorus atoms, not directly involved in the substitution process, are also considerably affected; in general, a downfield shift of about 5 ppm for every introduced spirocyclic centre is noticed for both PC12 and P(NMeCH2)2 groupings.

Experimental

All reactions were carried out under dry nitrogen. (NPC12)3 was kindly provided by Otsuka Chemical Co., Ltd., Osaka, Japan; m-NPCl2(NSOCl)2, £rans-NPCl2(NSOPh)2, (NPC12)2NS0C1, and (NPCl2)2NSOPh were prepared as described else-where. N,N'-Dimethylethylenediamine (Aldrich) was distilled over KOH prior to use. Solvents were dried by conventional methods. Elemental analyses were carried out at the Microanalytical Department of this University under supervision of Mr. A. F. Hamminga. NMR spectra were taken of solutions in CDC13; chemical shifts are positive in the low field direction. XH NMR spectra were recorded with a Jeol C60-HL instrument using TMS as internal reference. The 31P NMR spectra (proton-noise de-coupled) were taken by or under supervision of Mr. C. Kruk at the Department of Organic Chemistry of the University of Amsterdam with a Varian XL-100 FT spectrometer, operating at 40.5 MHz; 85% H 3 P O 4 was used as external reference. Field frequency lock was achieved by using the 2H resonance line of the solvent.

Preparation of [NP(NMeCH2)i]z A solution of 9.70 g (0.11 mol) of N,N'-dimethyl-

ethylenediamine in 200 ml of acetonitrile is added

1428 B. do Ruiter et al. • Derivatives of NPC12(NS0C1)2 ancl (NPC12)

in 15 min to a well-stirred solution of 3.48 g (0.01 mol) of (NPC12)3 in 200 ml of the same solvent at room temperature. The mixture is boiled under reflux for 17 h. The solvent and excess of amine are thoroughly driven off in vacuo and the residue is extracted several times with boiling ether. Crystal-lization of the ether-soluble fraction from ether affords 26% of pure [NP(NMeCH2)2]3, m.p. 245 °C (dec.).

Analysis Calcd C 36.64 H 7.69 N 32.05. Found C 36.70 H 7.61 N 32.25.

Preparation of NPCl2NP(NMeCH2)2NSOPh A solution of 0.53 g (6.0 mmol) of N,N'-dimethyl-

ethylenediamine in 60 ml of ether is added in 30 min to a well-stirred solution of 1.11 g (3.0 mmol) of (NPCl2)2NSOPh in 60 ml of the same solvent, cooled at —30 °C. The mixture is allowed to warm up to room temperature and stirred for 17 h. The precipitated amine dihydrochloride is filtered off and washed thoroughly with boiling ether. Crystal-lization of the ether-soluble fractions from ether gives 62% of pure NPCl2NP(NMeCH2)2NSOPh, m.p. 107.5-108.5 °C.

Analysis Calcd C 31.10 H 3.92 N 18.14 S 8.30 Cl 18.36, Found C 31.10 H 3.86 N 18.14 S 8.23 Cl 18.42.

Preparation of [NP(NMeCH2)2]2NS()Ph A solution of 1.06 g (12.0 mmol) of the diamine in

60 ml of acetonitrile is added within 30 min to a well-stirred solution of 1.11 g (3.0 mmol) of (NPCl2)2NSOPh in an equal amount of the same solvent, cooled at —30 °C. The mixture is allowed to warm to room temperature and stirred for 17 h. The solvent is thoroughly driven off in vacuo and the residue is extracted several times with chloro-form. Crystallization of the chloroform-soluble fractions from ether affords 25% of pure [NP(NMeCH2)2]2NSOPh, m.p. 183.5-185.5 °C.

Analysis Calcd C 41.88 H 6.29 N 24.43 S 7.99, Found C 41.62 H 6.23 N 24.14 S 8.01.

Preparation of NPCl2NP(NMeCH2)2NSOCl A solution of 1.06 g (12.0 mmol) of diamine in

120 ml of ether is added in 1 h to a well-stirred

solution of 1.97 g (6.0 mmol) of (NPC12)2NS0C1 in 120 ml of the same solvent, cooled at — 30 °C. The mixture is allowed to warm to room temperature and stirred for 17 h. The precipitated amine di-hydrochloride is filtered off and washed thoroughly with ether. Crystallization of the ether-soluble fractions from ether affords 20% of pure (air-sensitive) NPCl2NP(NMeCH2)2NSOCl, m.p. 11 LÖ-HS °C.

Analysis

Calcd C 13.94 H 2.93 N 20.33 S 9.31 Cl 30.87. Found C 14.08 H 2.97 N 20.14 S 9.36 Cl 30.83.

Preparation of trans-NP(NMeCH2)2(NSOPh)2

A solution of 1.32 g (15.0 mmol) of diamine in 60 ml of acetonitrile is added in 30 min to a well-stirred solution of 1.18 g (3.0 mmol) of trans-NPCl2(NSOPh)2 in 60 ml of the same solvent at — 30 °C. The mixture is allowed to warm to room temperature and stirred for 17 h. The solvent and the excess of amine are thoroughly driven off in vacuo and the residue is washed with water. The water-insoluble material is dried at 40 °C and crystallized from a large quantity of ether. Yield 40% of pure £rarcs-NP(NMeCH2)2(NSOPh)2, m.p. 157-160 °C.

Analysis

Calcd C 46.92 H 4.93 N 1 7 . l l S 15.66. Found C 46.79 H 4.88 N 17.08 S 15.72.

Preparation of cis-NP(NMeCH2)2(NSOCl)2

A solution of 0.53 g (6.0 mmol) of diamine in 60 ml of ether is added in 30 min to a well-stirred solution of 0.93 g (3.0 mmol) of ci.s-NPCl2(NSOCl)2 in 60 ml of the same solvent at —30 °C. The mix-ture is allowed to warm to room temperature and stirred for 17 h. The precipitated material is filtered off and washed thoroughly with ether. Crystalliza-tion of the ether-soluble fractions from ether affords 65% of pure cw-NP(NMeCH2)2(NSOCl)2, m.p. 134.5-135.5 °C.

Analysis

Calcd C 14.73 H 3.10 N 21.48 S 19.66 Cl 21.74. Found C 14.96 H 3.25 N 21.26 S 19.81 Cl 21.52.

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[4] A. A. van der Huizen, A. P. Jekel, J. Rusch, and J. C. van de Grampel, Ree. Trav. Chim. Pays-Bas 100, 343(1981).

1429 B. de Ruiter et al. • Derivatives of NPCl2(NSOCl)2 and (NPC12)

[5] J. M. E. Goldschmidt, presented at the 3rd

International Symposium on Inorganic Ring Systems, Graz, Austria (1981).

[6] T. Chivers and R. Hedgeland, Can. J. Chem. 50, 1017(1972).

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