Thiophosphonates

Detergent and dispersant additives sulfonates, thiophosphonates, phenates, salicylates more or less overbased, succinimides. 

Desmodur RF thiophosphonic acid tris(/t-isocyanatophenyl) ester 97... 

In 2003, Livinghouse et al. also reported that chelating bis(thiophosphonic amidates) complexes of lanthanide metals, such as yttrium or neodymium, were able to catalyse intramolecular alkene hydroaminations. These complexes were prepared by attachment of the appropriate ligands to the metals by direct metalation with Ln[N(TMS)2]3- When applied to the cyclisation of 2-amino-5-hexene, these catalysts led to the formation of the corresponding pyrrolidine as a mixture of two diastereomers in almost quantitative yields and diastereos-electivities of up to 88% de (Scheme 10.81). 

Scheme 10.82 Y-catalysed hydroamination of 1-amino-2,2-dimethyl-4-pentene with bis(thiophosphonic amidates) ligand.

The least studied of these two cycles are the tetra-chalcogen compounds [P(E)(EH)(/i-NR)]2 for which only the sulfur analogue (E = S) 37 has been reported. It can be prepared as its ammonium salt from reaction of di-thiophosphonic acid chloride betaine (py.PS2Cl py = pyridine) and one equivalent of primary amine in the presence of NEt3 (Equation 54).66,67... 

Ghosh, R. "New Basic Esters of Thiophosphonic Acids and Salts Thereof," Great Britain Patent 797603, July 12,1958. 

A series of /3-keto phosphonates have been hydrogenated with the Ru-BINAP system to give various chiral /3-hydroxyl phosphonates (Equation (75)).286 An Ru-MeO-BIPHEP catalyst is also effective for this transformation.287 /3-Keto thiophosphonates can also be smoothly transformed into /3-hydroxyl thiophosphonates with high ee.287... 

Enantioselective hydrogenation of / -keto phosphonates in the presence of an ( R)-BINAP-Ru complex under 1-4 atm H2 and at room temperature provides the (R)-yS-hydroxy phosphonates in up to 99% ee (Fig. 32.20) [69]. The sense of enantioface selection is the same as that observed in the reaction of / -keto carboxylic esters (see Fig. 32.14). A BDPP-Ru catalyst is also usable [70]. Similarly, / -keto thiophosphonates are hydrogenated with a MeO-BIPHEP-Ru catalyst with up to 94% optical yield [69 b]. 

Thiophosphonate phosphinate phosphinothioc amide phosphine oxide Figure 8-4. Some Wittig reagents. Fg = H, alkyl, aryl, or other functional groups. 

The addition of hypophosphites to alkenes under Et3B initiation is also reported [27]. Piettre described recently the addition of diethylthiophosphite to alkenes leading to the formation of thiophosphonates (Scheme 9, Eq. 9a) [28]. Interestingly, this reaction can be used for cyclization of dienes and ring opening of strained alkenes such as a-pinene (Eq. 9b). Parson prepared an... 

The alkynyl thiophosphonate 141 allowed an isomerization with sodium ethoxide [345] (Scheme 1.63). 

A convenient synthesis of half-derivatives of thiophosphonic acids starts from the corresponding phosphonic dichloride, with isolation of the trimeric thiophosphonic anhydride (53)44a and subsequent reaction of this with amines and alcohols.446... 

Reactions of Phosphonic and Phosphinic Acid Derivatives.—The reactions of phos-phonic and thiophosphonic amides and chlorides with carboxylic acid chlorides and amides have been discussed.101 Dialkyl alkylphosphonates and alkyl dialkylphos-phinates may be used for the iV-alkylation of imidazoles, triazoles, and pyrroles.105... 

Synonyms AI3-17798 BRN 2542580 Caswell No. 454 EINECS 218-276-8 ENT 17298 EPA pesticide chemical code 041801 EPN 300 ESA Ethoxy-4-nitrophenoxy phenylphosphine sulfide Ethyl p-nitrophenyl benzenethionophosphate Ethyl p-nitrophenyl benzenethio-phosphonate Ethyl p-nitrophenyl ester 0-Ethyl 0-4-nitrophenyl phenylphosphonothioate Ethyl jD-nitrophenyl phenylphosphonothioate 0-Ethyl 0-p-nitrophenyl phenylphosphonothioate Ethyl p-nitrophenyl thionobenzenephosphate Ethyl p-nitrophenyl thionobenzenephosphonate 0-Ethyl phenyl p-nitrophenyl phenylphosphorothioate Ethyl p-nitrophenyl thionobenzene phosphate 0-Ethyl phenyl p-nitrophenyl thiophosphonate MAPJ Meidon dust 15 NSC 8943 NSC 404840 OMS 219 Phenylphosphonothioic acid O ethyl O-p nitrophenyl ester Phosphonothioic acid, 0,0-diethyl 0-(3,5,6-trichloro-2-pyridinyl) ester PIN Santox. 

The use of thiophosphonic chloride reagent did not give clear results and more importantly, the stereoselectivity of the reaction is difficult to control. For instance, the reaction of C6H5P(S)Cl2 with the resorc[4]arene Ic afforded a mixture of isomers of 13, which have been only partially purified by col-... 

Reaction of 52 with benzyl chloride opens134 a new way to the deoxyhalo-genoisohexides (55). The oxidation of 52 with air or sulfur transforms the phosphinites into the phosphonates (56a) and thiophosphonates (56b), respectively (see Scheme 8). With 15% sodium hydroxide, the phosphonates... 

Two publications79,100 on thiophosphate and thiophosphonate triesters, which also dealt with their oxygen analogues, were referred to earlier. 

The next part of the present study concerns the oxidation of the phosphonate and thiophosphonate carbanions. Generally, this reaction was found to occur in two directions depending on the structure of the starting phosphonate and the reaction conditions. The lithium salts of thiophosphonate carbanions 5 give on treatment with oxygen the corresponding a-hydroxy thiophosphonates exclusi vely. 

Dimethylindole reacts with phosphorus trichloride in the presence of aluminum chloride at 100-120°C with the formation of 6-dichlorophosphinyl-l,3-dimethylindole, which is esterified without isolation from the reaction mixture to indolylphosphonite (33) and is converted into thiophosphonate (34) [33-35] ... 

Methylindoline and 1,3-dimethylindoline are phosphorylated by phosphorus trichloride at 100-120°C (3 h). Here 5-dichlorophosphinylindoline 36a,b is obtained from approximately half the indoline, while the other half is converted into the corresponding hydrochloride (indoline is regenerated from it by treatment with alkali) [34, 35]. With phosphorus trichloride 1,2,3,3-tetramethylindoline forms dichlorophosphine 36c with a quantitative yield [36]. The acid chlorides 36 undergo hydrolysis (37), amidation (38), and alcoholysis (39). Phosphonites 38 and 39 are converted into thiophosphonates and phosphonates 40, 41 and enter into the Arbuzov reaction (42) [160] ... 

The N-phosphorylated derivatives of pyrrolidine 134 [125, 126], 2-methoxymethylpyrrolidine 135 [127], and 2-ethoxycarbonylpyrrolidine 136 [128] are formed during the reaction of the corresponding heterocycles with mono- and dichlorides of phosphoric, phosphonic, thiophosphoric, and thiophosphonic acids ... 

N-(co-Hydroxyalkyl)pyrrolidines react at the mobile hydrogen atom of the hydroxy group with the formation of thiophosphonates 139 [130] and phosphates 140 [131, 132] and 141 [133] ... 

In the presence of alkylchloroformate esters, Ws(tributylstannyl)acetylene has been used in the 2-ethynylation of pyridines <94T(50)13089>. An unexpected regioselectivity has been observed in the rearrangement of 3-pyridyl thiophosphates to 2- and 4-pyridyl thiophosphonates <94ZOK(64)610>. A method for introduction of acyl carbon functional groups using trimethylstannyl pyridine (45) was explored and applied to making fusaric acid (46) (Scheme 34) <95H(41)817>. 

At this point it should be noted, that olefination involving reaction of PO-stabilized carbanions like those from phosphonates, phosphinates, phosphine oxides, phos-phonamides or thiophosphonates (Horner reaction 47), Horner-Wadsworth-Emmons reaction48 ) with carbonyl compounds almost exclusively yields ( )-olefins. This olefination is essentially restricted to PO-activated compounds carrying stabilizing groups on the carbanionic C-atom. However, these compounds are more reactive than the corresponding resonance-stabilized ylides. Therefore, this olefination method... 

Br or I by NMR, conductometric, stereochemical, and kinetic studies (256). In particular, it was demonstrated that silylation of optically active alkyl thiophosphonate with a stoichiometric amount of Me3SiBr leads to racemic silyl esters and the rate of optical rotation decay is equal to the rate of silyl ester formation (256) in spite of the fact that no bond to phosphorus was cleaved. Thus, the reaction must involve an achiral transient species [Eq. (58)]. This result is also proof of fast exchange of silyl groups between the complex and the silane, which occurs via the dissociation-recombination mechanism. 

Wahrcnd prim, und sek. Alkylbromide mit einem Komplex aus Phosphor(V)-sulfid und Aluminiumbromid zu Trithiophosphorsaure-bromid S,S-diestern reagieren, entsteht mit einem tert. Alkylbromid wie tert. Butylbromid z.B. 1,1 -Dimethyl-ethan-thiophosphon-sdure-dibromid (46°/0)714. 

Mit Chlorierungsmitteln sind Dithiophosphonsaure-O-monoester in Thiophosphon-saure-chlorid-O-ester iiberfiihrbar. Geeignete Chlorierungsmittel sind Chlor736,737 und Sulfurylchlorid731 ... 

Thiophosphorsaure-chlorid-O.O-diester reagieren mit Carbanionen zu Thiophosphon-saure-O.O-diestern. So erhalt man aus Thiophosphorsaure-chlorid-O,O-diethylester und 1-Alkinyl-lithium-Verbindungen in Diethylether bei 0° in Gegenwart katalytischer Mengen Pyridin 1-Alkin-l -thiophosphonsaure-O,O-diethylester (40-80%)781 ... 

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