Derivatives of NPCl2(NSOCl) and (NPCl2)2 NSOCl. Part 19. Reactions of (NPCl2)2NSOCl with secondary amines

Deruiter, B; Baalmann, H. H.; Vandegrampel, Jc

doi:10.1039/dt9820002337

Cited by 6 publications

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“…After addition of the second equivalent, one major disubstituted product ( 5b ) can be seen by 31 P NMR with a singlet resonance at 18.1 ppm. This is most likely 5b c i s , c i s or 5b c i s , t r a n s as the trans -substituted product 5b t r a n s would possess two chemically inequivalent phosphorus environments which would give rise to two doublets . This revealed that substitution mainly occurs via a vicinal route and cis to the previously introduced aryloxy substituent.…”

Section: Resultsmentioning

confidence: 97%

Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl₂)₂] (X = Cl or F) with Oxygen-Based Nucleophiles

et al. 1996

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The reactions of the cyclic thionylphosphazenes [NSOX(NPCl(2))(2)] (1, X = Cl; 2, X = F) with three oxygen-based nucleophiles of increasing basicity, sodium phenoxide (NaOPh), sodium trifluoroethoxide (NaOCH(2)CF(3)), and sodium butoxide (NaOBu) have been studied. The reaction of 1 and 2 with 4 equiv of NaOPh at 25 degrees C yielded the regioselectively tetrasubstituted species [NSOX{NP(OPh)(2)}(2)] (5d, X = Cl; 6d, X = F). Further reaction of 5d with an additional 2 equiv of NaOPh over several days or at elevated temperatures gave the fully substituted compound [NSO(OPh){NP(OPh)(2)}(2)] (5e), whereas 6d did not react further. The reaction of 1 and 2 with 5 equiv of NaOCH(2)CF(3) yielded in both cases [NSO(OCH(2)CF(3)){NP(OCH(2)CF(3))(2)}(2)] (7e), and similarly reaction with 5 equiv of NaOBu yielded [NSO(OBu){NP(OBu)(2)}(2)] (9e). In all cases, the reactions were monitored by (31)P NMR and (where applicable) (19)F NMR and were found to involve complete substitution at phosphorus via a predominantly vicinal pathway, followed by substitution at sulfur. Substitutional control of the reactions of NaOPh, NaOBu, with 1 and 2 was found to conform to the following general order of reactivity, PCl(2) > PCl(OR) > SOX (X = Cl, F). Although the reaction with NaOCH(2)CF(3) followed the same order of reactivity, a significant enhancement of reaction rate was detected with each equivalent of trifluoroethoxide added. Reaction of 7e with excess NaOCH(2)CF(3) led to elimination of (CF(3)CH(2))(2)O and the formation of the salts Na[NSO(OCH(2)CF(3))NP(OCH(2)CF(3))(2)NP(OCH(2)CF(3))O] (11) and Na[NS(O)O{NP(OCH(2)CF(3))(2)}(2)] (12). Crystals of 6d are triclinic, space group P&onemacr;, with a = 9.789(3) Å, b = 11.393(4) Å, c = 12.079(5) Å, alpha = 107.40(3) degrees, beta = 91.23(3) degrees, gamma = 93.18(3), V = 1283.6(8) Å(3), and Z = 2. Crystals of 5e are monoclinic, space group C2/c, with a = 32.457(3) Å, b = 10.747(1) Å, c = 18.294(2) Å, beta = 110.37(1) degrees, V = 5982.4(9) Å(3), and Z = 8.

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Section: Resultsmentioning

confidence: 97%

Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl₂)₂] (X = Cl or F) with Oxygen-Based Nucleophiles

et al. 1996

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ChemInform Abstract: DERIVATIVES OF NPCL2(NSOCL)2 AND (NPCL2)2NSOCL. PART 19. REACTIONS OF (NPCL2)2NSOCL WITH SECONDARY AMINES

Ruiter¹,

Baalmann²,

Grampel³

1983

Chemischer Informationsdienst

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Mechanism of the controlled hydrolysis of (NPCl₂)₂NSOCl: Crystal and molecular structure of [KC₁₂H₂₄O₆]⁺[NHPO₂NPCl₂NSOCl]⁻

Winter

Meetsma

Vandegrampel

et al. 1994

Heteroatom Chemistry

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Derivatives of NPCl2(NSOCl) and (NPCl2)2 NSOCl. Part 19. Reactions of (NPCl2)2NSOCl with secondary amines

Cited by 6 publications

References 1 publication

Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl₂)₂] (X = Cl or F) with Oxygen-Based Nucleophiles

Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl₂)₂] (X = Cl or F) with Oxygen-Based Nucleophiles

ChemInform Abstract: DERIVATIVES OF NPCL2(NSOCL)2 AND (NPCL2)2NSOCL. PART 19. REACTIONS OF (NPCL2)2NSOCL WITH SECONDARY AMINES

Mechanism of the controlled hydrolysis of (NPCl₂)₂NSOCl: Crystal and molecular structure of [KC₁₂H₂₄O₆]⁺[NHPO₂NPCl₂NSOCl]⁻

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Derivatives of NPCl2(NSOCl) and (NPCl2)2 NSOCl. Part 19. Reactions of (NPCl2)2NSOCl with secondary amines

Cited by 6 publications

References 1 publication

Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl2)2] (X = Cl or F) with Oxygen-Based Nucleophiles

Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl2)2] (X = Cl or F) with Oxygen-Based Nucleophiles

ChemInform Abstract: DERIVATIVES OF NPCL2(NSOCL)2 AND (NPCL2)2NSOCL. PART 19. REACTIONS OF (NPCL2)2NSOCL WITH SECONDARY AMINES

Mechanism of the controlled hydrolysis of (NPCl2)2NSOCl: Crystal and molecular structure of [KC12H24O6]+[NHPO2NPCl2NSOCl]−

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Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl₂)₂] (X = Cl or F) with Oxygen-Based Nucleophiles

Regioselective Substitution Reactions of Sulfur(VI)−Nitrogen−Phosphorus Rings: Reactions of the Halogenated Cyclic Thionylphosphazenes [NSOX(NPCl₂)₂] (X = Cl or F) with Oxygen-Based Nucleophiles

Mechanism of the controlled hydrolysis of (NPCl₂)₂NSOCl: Crystal and molecular structure of [KC₁₂H₂₄O₆]⁺[NHPO₂NPCl₂NSOCl]⁻