Triphenylphosphine amine

Preparation. Sisler and co-workers developed a technique for obtaining chloramine by gas-phase reaction of chlorine with excess ammonia and showed that the reagent combines with tertiary amines to form the corresponding 1,1,1-trisubstituted hydrazinium chlorides (1) in good yield, and with tertiary phosphines to form aminophosphonium chlorides (2). The product of reaction (2) can be dehydrohalo-genated with magnesium hydride to triphenylphosphine amine. 

C5i,H3 1NO18P2RU6, Bis(triphenylphosphine)amine octadecacarbonylhydro-gen-octahedro-hexaruthenate, 46B, 1342 C5osNgSsTc, Tris(tetra-n-butylammonium) hexakis(isothiocyanato)-technetiumdll), 46B, 1137... 

Sulfonic acids are prone to reduction with iodine [7553-56-2] in the presence of triphenylphosphine [603-35-0] to produce the corresponding iodides. This type of reduction is also facile with alkyl sulfonates (16). Aromatic sulfonic acids may also be reduced electrochemicaHy to give the parent arene. However, sulfonic acids, when reduced with iodine and phosphoms [7723-14-0] produce thiols (qv). Amination of sulfonates has also been reported, in which the carbon—sulfur bond is cleaved (17). Ortho-Hthiation of sulfonic acid lithium salts has proven to be a useful technique for organic syntheses, but has Httie commercial importance. Optically active sulfonates have been used in asymmetric syntheses to selectively O-alkylate alcohols and phenols, typically on a laboratory scale. Aromatic sulfonates are cleaved, ie, desulfonated, by uv radiation to give the parent aromatic compound and a coupling product of the aromatic compound, as shown, where Ar represents an aryl group (18). 

Benzyl chloride undergoes self-condensation relatively easily at high temperatures or in the presence of trace metallic impurities. The risk of decomposition during distillation is reduced by the use of various additives including lactams (43) and amines (44,45). Lime, sodium carbonate, and triethylamine are used as stabilizers during storage and shipment. Other soluble organic compounds that are reported to function as stabilizers in low concentration include DMF (46), arylamines (47), and triphenylphosphine (48). 

In the chlorination of 2,4-dichlorophenol it has been found that traces of amine (23), onium salts (24), or triphenylphosphine oxide (25) are excellent catalysts to further chlorination by chlorine ia the ortho position with respect to the hydroxyl function. During chlorination (80°C, without solvent) these catalysts cause traces of 2,4,5-trichlorophenol ( 500 1000 ppm) to be transformed iato tetrachlorophenol. Thus these techniques leave no 2,4,5-trichlorophenol ia the final product, yielding a 2,4,6-trichlorophenol of outstanding quaUty. The possibiUty of chlorination usiag SO2CI2 ia the presence of Lewis catalysts has been discussed (26), but no mention is made of 2,4,5-trichlorophenol formation or content. 

Similarly the active oxygen of oxaziranes can be transferred to triphenylphosphine with the formation of ]ihosphine oxide and to tertiary amines yielding amine oxides. ... 

A variety of catalysts, solvents and amines as base can be employed for the Sonogashira reaction. Typical conditions are, e.g. tetrakis(triphenylphosphine)palladium(0)... 

The conversion of an alcohol to an amine can be achieved in a one-pot reaction the alcohol 1 is treated with hydrazoic azid (HN3), excess triphenylphosphine and diethyl azodicarboxylate (DEAD). The initial Mitsunobu product, the azide 14, further reacts with excess triphenylphosphine to give an iminophosphorane 15. Subsequent hydrolytic cleavage of 15 yields the amine—e.g. as hydrochloride 16 ... 

Tetrakis(tripheiiylphosphine)palladium(0) is often used for this reaction. However, Pd(II) complexes such as bis(triphenylphosphine)palladium dichloride or palladium acetate are also commonly employed for convenience, as they are stable in ah. The base is typically a secondary or tertiary amine such as triethy-lamine. Weak bases such as sodium (potassium) acetate, bicarbonate, or carbonate are also used. 

Phenol-epoxy reaction. See also Epoxy-phenolic reaction entries tertiary amine-catalyzed, 412 triphenylphosphine-catalyzed, 412 Phenol-formaldehyde novolac resin, preparation of, 429... 

Triphenylphosphine oxide, 297 Tris(4-aminophenyl) amine (TAPA), 308-309... 

The Suzuki reaction has been successfully used to introduce new C - C bonds into 2-pyridones [75,83,84]. The use of microwave irradiation in transition-metal-catalyzed transformations is reported to decrease reaction times [52]. Still, there is, to our knowledge, only one example where a microwave-assisted Suzuki reaction has been performed on a quinolin-2(lH)-one or any other 2-pyridone containing heterocycle. Glasnov et al. described a Suzuki reaction of 4-chloro-quinolin-2(lff)-one with phenylboronic acid in presence of a palladium-catalyst under microwave irradiation (Scheme 13) [53]. After screening different conditions to improve the conversion and isolated yield of the desired aryl substituted quinolin-2( lff)-one 47, they found that a combination of palladium acetate and triphenylphosphine as catalyst (0.5 mol %), a 3 1 mixture of 1,2-dimethoxyethane (DME) and water as solvent, triethyl-amine as base, and irradiation for 30 min at 150 °C gave the best result. Crucial for the reaction was the temperature and the amount of water in the... 

A great variety of suitable polymers is accessible by polymerization of vinylic monomers, or by reaction of alcohols or amines with functionalized polymers such as chloromethylat polystyrene or methacryloylchloride. The functionality in the polymer may also a ligand which can bind transition metal complexes. Examples are poly-4-vinylpyridine and triphenylphosphine modified polymers. In all cases of reactively functionalized polymers, the loading with redox active species may also occur after film formation on the electrode surface but it was recognized that such a procedure may lead to inhomogeneous distribution of redox centers in the film... 

Disubstituted-amino)triphenylphosphonium bromides (72) have been obtained from the reaction of triphenylphosphine dibromide and secondary amines in the presence of triethylamine. ... 

Bayer (1997) has claimed that in a water-CH2Cl2 system, using water soluble Pd(OAc)2 -triphenylphosphine trisulphonic acid catalyst, octa-2,7-dienyl-l-amine and octa 1,7-dienyl -3-amine can be obtained by telomerization of butadiene with ammonia. 

Ketones can also be reduced to alkenes via enol triflates. The use of Pd(OAc)2 and triphenylphosphine as the catalyst and tertiary amines as the hydrogen donors is effective.226... 

The majority of gold(I) carbene complexes are pure organometallic compounds and the are out of the scope of this work. Some halide or triphenylphosphine carbene complexes are known and they will be considered here. Nucleophilic addition of alcohols or amines to gold-coordinated isocyanides is one of the best-established methods to obtain gold carbene derivatives. The reaction of H[Au(CN)2] with propene oxide and estirene oxide yields (cyano)carbene complexes (380) avoiding the intermediate step.2257 A cyclic carbene compound is obtained by reaction of a dinuclear isocyanide with amine (Scheme 32).2258... 

The first asymmetric synthesis of (-l-)-abresoline was achieved from the chiral piperidine derivative 153, which upon treatment of its hydroxy side-chain substituent with carbon tetrabromide, triphenylphosphine, and triethyl-amine cyclized to the frarcr-quinazolidine 154. Deketalization and silyl protection of the phenolic group, followed by stereoselective reduction with lithium tri-t -butylborohydride (L-Selectride ), gave an alcohol, which after acylation and deprotection furnished (-l-)-abresoline 155 (Scheme 25) <2005TL2669>. 

Benzotriazole-related methodology publications appeared in 2006. Reaction of 1-formylbenzotriazole with triphenylphosphine/carbon tetrachloride afforded l-(2,2-dichlorovinyl)benzotriazole, where lithiation followed addition of electrophiles gave a variety of functionalized M-(ethynyl)benzotriazoles <06T3794>. Novel mono- and symmetrical di-/V-hydroxy- and IV-aminoguanidines were readily prepared from the reaction of diverse hydroxylamines or hydrazines with reagent classes di(benzotriazol-l-yl)methanimine, (bis-benzotriazol-1 -y 1-methy lene)amines, benzotriazole-1 -carboxamidines, benzotriazole-1 -... 

Hong et al. (2004) also found that modification of PAMAM dendrimers with a short PEG linker arm could act to reduce nonspecificity caused by the amines on the dendrimer-modified surface. An azido-PEGj-aininc spacer was activated with nitrophenyl carbamate to yield an activated intermediate that could be used to modify the amines on the dendrimer (Figure 7.24). Reaction at high molar ratio resulted in about 61 PEG-azido spacers on the dendrimer. Reduction of the azido group to an amine using triphenylphosphine in THF provided the dendrimer-PEG-amine derivative for surface modification. The added presence of the PEG spacer arm reduced... 

Early in the last century, the Nobel Prize winning chemist Hermann Staudinger discovered a reaction between phosphines and azides, which became known as the Staudinger reaction (Staudinger and Meyer, 1919). Triphenylphosphine reacts with azides to form an intermediate iminophosphorane with the release of nitrogen gas. This intermediate quickly breaks down in aqueous environments to yield triphenylphosphine oxide and a primary amine (Figure 17.17). 

Weik and Rademann have described the use of phosphoranes as polymer-bound acylation equivalents [65]. The authors chose a norstatine isostere as a synthetic target and employed classical polymer-bound triphenylphosphine in their studies (Scheme 7.54). Initial alkylation of the polymer-supported reagent was achieved with bromoacetonitrile under microwave irradiation. Simple treatment with triethyl-amine transformed the polymer-bound phosphonium salt into the corresponding stable phosphorane, which could be efficiently coupled with various protected amino acids. In this acylation step, the exclusion of water was crucial. 

The Sn2 reaction of triphenylphosphine with triethylbenzylammonium chloride (the tertiary amine is thus the leaving group) was studied under solvent-free microwave conditions. The reaction occurred only under the action of MW [83] irradiation (Eq. 53). 

---