Iridine

Suitable methods for linking a phosphoms—nitrogen bond to the ayiridine ring are the aminolysis of halogenated phosphoms compounds (2,280—282), the transamination of phosphoramines with excess a iridine (283), the reaction with phosphites (284) and phosphoramidites (285) which have a free OH group, or the reaction of phosphines with a iridines and carbon tetrachloride (286). 

A iridine traces in aqueous solution can be determined by reaction with 4-(p-nitroben25l)pyridine [1083-48-3] and potassium carbonate [584-08-7]. Quantitative determination is carried out by photometric measurement of the absorption of the blue dye formed (367,368). Alkylating reagents interfere in the determination. A iridine traces in the air can be detected discontinuously by absorption in Folin s reagent (l,2-naphthoquinone-4-sulfonate) [2066-93-5] (369,370) with subsequent chloroform extraction and hplc analysis of the red dye formed (371,372). The detection limit is ca 0.1 ppm. Nitrogen-specific thermal ionisation detectors can be used for continuous monitoring of the ambient air. 

Crosslinking the PSA will increase the solvent resistance of the material and it will also have a significant effect on the rubbery plateau modulus of the polymer. Fig. 8 shows the effect of increasing amounts of a multifunctional az.iridine crosslinker, such as CX-100 (available from Avecia, Blackley, Manchester, UK) on the rheology of an acrylic polymer containing 10% acrylic acid. The amounts of crosslinker are based by weight on the dry weight of the PSA polymer. 

Tanner et al. (58) investigated the asymmetric aziridination of styrene using bis(aziridines) such as 85. Low induction is observed with these ligands, Eq. 64. A significant electronic effect was noted with the p-fluoro-phenyl substituted bis(az-iridine) 85c (59). A binaphthyl-derived diamine was used as a ligand for the copper-catalyzed aziridination of dihydronaphthalene (81). The product was formed in 21% ee and 40% yield, Eq. 65. Other structurally related ligands proved to be less selective in this reaction. 

Iris aqyatuca Forskal I. buatatas (L.) Lamarck. I. dichotoma Pallas Rong Cai Gan Su She Gan (Iris) (root, whole plant) Tectoridin, iridin, flavone.48 Treat lung diseases, cough, pneumonia, uneasy breathing. 

Iris lactea Pall, subsp. chinensis (Fisch.) Kitag. Wu Gan (seed, flower, leaf, root) Iridin, irigenin, irisflorentin.60 Astringent, diuretic, hemostatic, remedy for hemorrhage, postpartum difficulties. 

N.A. Belamcanda chinensis (L.) DC Belamcandaquinones A and B, isoflavones, tectoridin, iridin, iridals, tectorigenin, irigenin, irisflorentin.318 319 320 Treat throat disorders, stimulate the mucous membrane of the throat. 

Iridin Iris aqyatuca, I. buatatas, I. dichotoma, I. lactea... 

Propane Hexafluoro-2-isocyanato-2-mcthyl- F.IObj, 249 [3,3-(CF,)2 - 2-OR — 3H-a/iridine,AJ... 

Butane Hexafluoro-3-isocyanato-2,2.3-tris-[lrifluoromethyl]-E10b2, 249 [3.3-(CF3)2 —1-1C. I, - 2-oxo-a7,iridin/A) isocyanate Pentadecafluoroheptyl-ElOb,. 715 (5-RF-2-oxo-1,3,4-dioxazole A)... 

Propannitrile 2-Amino-3-finoro-3-phenyl- ElOa, 120f. (A/iridine + HF)... 

Ethane 2-Beuzylamino-1,2-diphcnyl-I-fluoro- ElOb,. 259 (A/.iridin + HF)... 

CCI, - CF,) N-(Cliloro-diduoro-meihyl)-tetra-fluoro-N-tiiduoroaceiyl-4-trifluoromcthyl- E10b2. 250 ([3-CF,Cl-3-CF,-2-Arr — oxti/iridine/A] N-(Chloro-diduoro-tliioacctyl)-... 

The nitrogen atom of a/iridine 10 bears a tosyl group, whereas in 11 it is present as a free amine function. 

Another bisoxazoline ligand 31 was prepared from tartrate and applied to asymmetric aziridination. However, enantioselectivity observed was modest (Scheme 6B.33) [78], Bisaz-iridine ligand 32 was prepared, but its copper complex showed only modest enantioselectivity in the aziridination of styrene (Scheme 6B.34) [79],... 

The chemistry of ammonium ylides formed from the reaction of cyclic amines with carbenes was found to be dependent on the ring size of the amine.52 For example, treatment of 1-benzylazetidine (104) with ethyl diazoacetate in the presence of a copper (II) catalyst afforded pyrrolidine 106 in 96% yield. This result is consistent with ammonium ylide formation followed by ring expansion. In contrast, treatment of 1 -phenethylaz-iridine (107) under identical conditions gave the fragmentation product 109 in quantitative yield. Similar results were observed for the reaction of aziridine 107 with dichlorocarbene.53 On the other hand, reaction of 1-phenethylpyrrolidine with ethyl diazoacetate in the presence of a... 

To 70% HF/pyridine (10-l5mL) was added the a/iridine (5-10 mmol), pure or diluted in dry benzene or CHjCi, (2 mL), dropwisc at rt. The mixture was maintained under the conditions required for each starting material (see Table 12), then poured into H2O (10-20mL). washed with EljO or CHjClj (3 X 15mL), cautiously neutralized with 10-30% NH, or sat. aq NaHCO,. and extracted with EtjO or CH,CL (3 X 20 mL). The organic extracts were then dried (MgSOJ and evaporated in vacuo. Except for relatively volatile fluoro amines (for which the pyridine and the fluoro amine w ere separated by column chromatography or recrystallization), pure fluoro amines were obtained after evaporation of the pyridine in vacuo. 

Benzyl 3-Benzoylamino-4,6-0-benzylidene-2-fluoro-2,3-dideoxy- -D-aItropyranoside (22) Typical Procedure for Ring Opening of A/.iridines with Tetrabutylammonium Fluoride " ... 

A solution of cM-2-beiizoyl-1-methyl-3-(trif]uoromeihyl)a/iridine (2 500 mg, 2.18 mmol) and styrene (1.13 g. 10.9 mmol) in xylene (10 mL) was added to a 100-mL stainless steel cylinder. Then the sealed cylinder was kept at 140-150 C for 20 K. After removal of the solvent, the residue was chromatographed on silica gel (hexane. EtOAc, Et,0). then recrystallized yield 588 mg (81 %) mp 92-94 C (hexane, EtOAe/ Ei,0). 

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