ChemInform Abstract: REACTION OF PHOSPHORUS PENTACHLORIDE WITH N‐CYANOARYLAMIDINES

Kornuta, P. P.; Kolotilo, N. V.; Markovskii, L. N.

doi:10.1002/chin.197724294

Cited by 5 publications

(6 citation statements)

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“…The chemistry of monocarbaphosphazenes has been explored with secondary amines − and Grignard reagents 24 and resulted in the formation of C-substituted (ring carbon substitution by amino or alkyl/aryl groups) or pentakis(amino)-substituted products. Reactions of II and C-alkyl/aryl- and C-amino-substituted monocarbaphosphazenes with alkoxides are also described, , and reactions of alkyl-substituted dicarbaphosphazenes are reported with nitrogen-, oxygen-, and sulfur-containing bifunctional nucleophiles …”

Section: Resultsmentioning

confidence: 99%

“…Both compounds are obtained as crystalline solids (∼80% yield) following recrystallization from a chloroform/hexane mixture. Substitution of the C−Cl bonds in N 3 PC 2 (C 6 H 5 )Cl 3 with C 6 H 5 SNa has been described, but the thiophenoxy-substituted chlorocarbaphosphazene could not be isolated . The EI mass spectral data for 16 does not show a parent ion peak as observed for 17 .…”

Section: Substitution Reactions Of Spirocyclic Chlorocarbaphosphazenesmentioning

confidence: 91%

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Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

et al. 1997

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Acyclic tertiary amines such as triethylamine and tri-n-propylamine used as HCl scavengers in nucleophilic substitution reactions of cyclic chlorocarbaphosphazenes [N(3)PC(2)Cl(4) (I) and N(3)P(2)CCl(5) (II)] with (CF(2))(n)()(CF(2)CH(2)OH)(2) [n = 0 (III) or 1 (IV)] are found to undergo a facile C-N bond cleavage with the regiospecific substitution of the dialkylamino groups on the ring carbon atoms of the carbaphosphazene. In the case of cyclic amines such as 1-methylpiperidine and 4-methylmorpholine, the cleavage was found to occur regiospecifically at the N-CH(3) bond, resulting in the ring substitution of the cyclic secondary amino group on the dicarbaphosphazene ring carbon atoms. The polyfluoro diol III forms a spirocyclic ring exclusively at the phosphorus site in compounds [CF(2)CH(2)O](2)PN(3)C(2)[N(C(2)H(5))(2)](2) (1), [CF(2)CH(2)O](2)PN(3)C(2)[N(C(3)H(7))(2)](2) (2), [CF(2)CH(2)O](2)PN(3)C(2)[NCH(2)(CH(2))(3)CH(2)](2) (3), and [CF(2)CH(2)O](2)PN(3)C(2)[N(CH(2))(2)O(CH(2))(2)](2) (5) along with the formation of carbon-substituted carbaphosphazenes, Cl(2)PN(3)C(2)[NCH(2)(CH(2))(3)CH(2)](2) (4) and Cl(2)PN(3)C(2)[N(CH(2))(2)O(CH(2))(2)](2) (6). Reaction of II with III in the presence of triethylamine affords the dispiro product [CF(2)CH(2)O)(2)](2)P(2)N(3)C[N(C(2)H(5))(2)] (7), which crystallizes in a polar orthorhombic space group, Cmc2(1). Upon refluxing of I or II with R(3)N (R = C(2)H(5), n-C(3)H(7)) in toluene, the amino-substituted carbaphosphazenes, Cl(2)PN(3)C(2)[N(C(2)H(5))(2)](2) (8), Cl(4)P(2)N(3)C[N(C(2)H(5))(2)] (9), and Cl(4)P(2)N(3)C[N(n-C(3)H(7))(2)] (10) are obtained in good yields. Hydrolysis of 8 leads to the formation of Cl(O)PN(H)N(2)C(2)[N(C(2)H(5))(2)](2) (11). When lithium salts of the fluoro diols III and IV are reacted with I or II in diethyl ether, the P-Cl bond is selectively substituted, yielding the spirocyclic [CF(2)CH(2)O](2)PN(3)C(2)Cl(2) (12), [CF(2)(CF(2)CH(2)O)(2)]PN(3)C(2)Cl(2) (13), [CF(2)CH(2)O](2)P(2)N(3)CCl(3) (14), and [(CF(2)CH(2)O)(2)](2)P(2)N(3)CCl (15). The C-Cl bonds in 12 and 14 were easily substituted by their reaction with 4-FC(6)H(4)XNa (X = O or S) to form [CF(2)CH(2)O](2)PN(3)C(2)[4-FC(6)H(4)O](2) (16) and [CF(2)CH(2)O](2)PN(3)C(2)[4-FC(6)H(4)S](2) (17). Reactions of 12 and 13 with (CH(3))(3)SiN(CH(3))(2) under mild conditions result in the elimination of (CH(3))(3)SiCl along with the formation of [CF(2)CH(2)O](2)PN(3)C(2)[N(CH(3))(2)](2) (18). The X-ray analyses of 13 and 18 represent the first examples of eight-membered spirocyclic phosphazenes. The thermal behavior of II, 9, 10, 14, and15 has also been investigated at 120 degrees C. Single-crystal X-ray diffraction studies were carried out for 1, 2, 7, 9-14, and 16-19, and these compounds are also characterized using IR, (1)H, (13)C, (19)F and (31)P NMR spectroscopy, MS, and elemental analysis.

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Section: Resultsmentioning

confidence: 99%

Section: Substitution Reactions Of Spirocyclic Chlorocarbaphosphazenesmentioning

confidence: 91%

Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

et al. 1997

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“…Most of these compounds were isolated from reactions between phosphorus halides PCl 5Ϫn Ph n (n ϭ 0Ϫ2) and dicyanamide or amidines, resulting in 1,3,5,2λ 5 -triazaphosphinines bearing halogen substituents at the ring carbon and phosphorus atoms. These halotriazaphosphinines react with various nucleophiles such as amines, [21,22] phenols, [23] alcohols [24] or sulfides [25] and yield the corresponding substituted heterocycles. It is worth noting that only a few 4,6-diamino-1,3,5,2λ 5 -triazaphosphinines have so far been synthesised.…”

Section: Reactivity Of the Sodium Phosphonium Diylidesmentioning

confidence: 99%

Synthesis of 1,3,5,2λ⁵‐Triazaphosphinines by Intramolecular Cyclisation of (N‐Cyanophosphorimidoyl)guanidines and Diguanidinophosphonium Chlorides

et al. 2004

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The sodium phosphonium diylide Na[Ph 2 P(NCN) 2 ] (3) − the first example of a stabilised phosphonium diylide − was synthesised by treatment of sodium diphenylphosphide with 2 equiv. of cyanic azide. Compound 3 reacted with alkyl-and arylammonium salts [RRЈNH 2 ]Cl {R = PhCH 2 , tBu, Ph; RЈ = H; RRЈ = −[(CH 2 ) 2 O(CH 2 ) 2 ]−}. Depending on the molar ratios (1:1 or 1:2), (N-cyano-P,P-diphenylphosphorimidoyl)guanidines Ph 2 P(NCN)N=C(NH 2 )NRRЈ (8)

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“…In bisher durchgeführten Studien der Reaktivität zeigte das 4,6-Bis(trifluormethyl)-substituierte Triazaphosphinin -N(CF 3 …”

Section: Introductionunclassified

Triazaphosphinine – Reaktionen, Zwitterionen, P–B-Austausch/ Triazaphosphinines – Reactions, Zwitter Ions, P – B-Exchange

Meyer

Kadel

Oberhammer

1988

Zeitschrift Für Naturforschung B

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Abstract2,2-Dichloro-triazaphosphinine (2) reacts with SbF3 in the molar ratio 3:1 to give the mixed halogenated triazaphosphinine (3). New addition compounds 5 and 6 can be formed in the reaction of the zwitter ion 4 and amines or in the reaction of 2.2-difluoro-triazaphosphinine (1) with KCN. Phosphorus-boron-exchange is observed in the reactions of 4 or 2 with BF3 · OEt2. The new C-B -N-heterocycles 8 and 9 are obtained. The gas-phase structure of 1 has been determined by electron diffraction. The scattering intensities are compatible with a planar ring conformation with C2v symmetry and with equivalent NC bond lengths (PN = 1.579(10) Å, NC = 1.299(7) Å, NPN = 109.2(7)°, PNC - 118.1(9)°, CNC - 119.6(7)° and NCN = 127.5(12)°).

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ChemInform Abstract: REACTION OF PHOSPHORUS PENTACHLORIDE WITH N‐CYANOARYLAMIDINES

Abstract: Die N‐Cyanarylamidine (I) reagieren mit Phosphorpentachlorid zu den Phosphatriazinderivaten (II).

Cited by 5 publications

References 0 publications

Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

Synthesis of 1,3,5,2λ⁵‐Triazaphosphinines by Intramolecular Cyclisation of (N‐Cyanophosphorimidoyl)guanidines and Diguanidinophosphonium Chlorides

Triazaphosphinine – Reaktionen, Zwitterionen, P–B-Austausch/ Triazaphosphinines – Reactions, Zwitter Ions, P – B-Exchange

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ChemInform Abstract: REACTION OF PHOSPHORUS PENTACHLORIDE WITH N‐CYANOARYLAMIDINES

Abstract: Die N‐Cyanarylamidine (I) reagieren mit Phosphorpentachlorid zu den Phosphatriazinderivaten (II).

Cited by 5 publications

References 0 publications

Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

Selective Reactivity of the Phosphorus−Chlorine and Carbon−Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon−Nitrogen Bond in Trialkylamines

Synthesis of 1,3,5,2λ5‐Triazaphosphinines by Intramolecular Cyclisation of (N‐Cyanophosphorimidoyl)guanidines and Diguanidinophosphonium Chlorides

Triazaphosphinine – Reaktionen, Zwitterionen, P–B-Austausch/ Triazaphosphinines – Reactions, Zwitter Ions, P – B-Exchange

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Synthesis of 1,3,5,2λ⁵‐Triazaphosphinines by Intramolecular Cyclisation of (N‐Cyanophosphorimidoyl)guanidines and Diguanidinophosphonium Chlorides