3.4- dichloro phenyl analog

The 3,4-dichloro phenyl analog 6 can be reduced to the corresponding hydroxy alcohols with both configurations Mucor mihei affords the alcohol R-7 with good selectivity, while the chloro alcohol S-7 can be obtained with excellent yields and good e.e. (94%) at 2 g/L concentration with cultures of G. candidum. This compound is quantitatively converted into the epoxide 8 with the same absolute configuration. Partly regiose-... 

A study of the reactions of halogeno-phosphines with ketone derivatives has been extended to (44), which forms a heterocycle (45a) with dichloro(phenyl)phosphine38 under neutral conditions. The analogous oxide (45b) has already been isolated from... 

Ferrocene reacts with PC13/A1C13 with replacement of all three chlorine atoms, but the tertiary phosphine is sensitive to air and difficult to isolate. However, diferrocenylphenylpfiosphine [from dichloro(phenyl)phosphine] and ferrocenyldiphenylphosphine [from chloro(diphenyl)phosphine] are obtained analogously as stable compounds in 52% and 37% yield, respectively.156... 

A rationalization of the reactions between )8-keto-alcohols and halogenophosphines has been presented by a Russian group. In particular, the reaction between dichloro(phenyl)phosphine (26) and diacetone alcohol to give the oxide (27) has been shown to occur in stages (Scheme 9), and physical and chemical evidence has been presented for the initial formation of mesityl oxide (28) and the acid (29), followed by the addition product (30). A less detailed study of the analogous reaction of chlorodiphenyl-phosphine (5) with diacetone alcohol has also been published. ... 

The early development of aromatic phosphine chemistry took place during the last quarter of the nineteenth century mainly in Michaelis s school.He prepared dichloro(phenyl)phosphine by the passage of the mixed vapours of benzene and phosphorus trichloride through a red hot porcelain tube. This was quickly followed by the preparation of phenylphosphine, dialkylphenylphosphines, and triphenylphosphine. This latter phosphine was destined some 75 years later to become one of the most important phosphines in the development of homogeneous catalysis by phosphine metal complexes. Michaelis obtained it by the reaction of sodium with dichloro(phenyl)phosphine or phosphorus trichloride and bromobenzene in boiling ether.The development of aromatic phosphorus chemistry rapidly overtook that of their intractable aliphatic analogs. It was well established by the 1920s whereas the aliphatic had to await the... 

Dichloro-s-triazine and its 6-alkyl analogs are as easily hydrolyzed by water as trichloro-s-triazine and, on suspension in aqueous ammonia (25°, 16 hr), the first is diaminated in good yield. 2,4-Bistrichloromethyl-6-methyl- and -6-phenyl-s-triazines (321) require a special procedure for mono-alkoxylation (0-20°, 16 hr, alcoholic triethylamine) disubstitution occurs at reflux temperature (8 hr). Aqueous triethylamine (100°, 3 hr) causes complete hydroxy-lation of 2,4,6-tris-trichloromethyl-s-triazine which can be mono-substituted with ammonia, methylamine, or phenoxide ion at 20°. 

CHjAc, BuNHj, MeOH, 20°C, 12 h 83%), 2/.cr.zyi 2-benzyl-3-phenyl-quinoxahne 1,4-dioxide (469) [(PhCH2)2CO, NaNH2, Et20, °C, h 52%]. 5,6-Dichloro-2,l,3-benzoxadiazole 1-oxide (470) and a-(methylthio)acetone gave 6,7-dichloro-2-methyl-3-methylthioquinoxahne 1,4-dioxide (471) (NHa-MeOH, 20°C, 12 h 30%) many analogs likewise. ... 

In Grigg s approach to hippadine (37), he established the connection between the two phenyl rings via the Stille-Kelly reaction [45]. When diiodide 35 was submitted to the Pd(0)/ditin catalyst system, the intramolecular cyclization was realized to establish the C—C bond in lactam 36. Oxidation of the indoline moiety in 36 using 2,3-dichloro-5,6-dicyano-l,4-benzoquinone (DDQ) then delivered hippadine (37). Analogously, the intramolecular Stille coupling of dibromide 38 led directly to hippadine (37) [46]. 

Synthesis of a tetracyclic analog of 294 is also reported from the anhydride of pyrazine-2,3-dicarboxylic acid and a tetralin derivative under Friedel-Crafts conditions (85JCR(S)338). A representative of the o-quinonoid system (296) was prepared from 2,3-dichloro-1,4-naphthoquinone and o-phenyl-enediamine (63JOC1019). 

The insecticidal activity and structure-activity relationships of novel pyrethroids prepared by reacting methyl phenyl substituted pyrazole methanols with dichloro chrysanthemic acid chloride are reported. These pyrethroids are active on tobacco budworm, fall armyworm, southern corn rootworm, and aster leafhopper, generally in the concentration range of 1000-250 ppm. Although less active than the pyrethroid standard bifenthrin, the overall structure-activity of these pyrazole pyrethroids with regard to substitution patterns is similar to that previously observed with bifenthrin analogs. 

Conversion of norbornadiene to nortricyclenes can also be achieved with organomercurials. This reaction proceeds via transmetalation to form a c-bonded organopalladium system which inserts norbornadiene. Thus an enrfo-cw-addition is observed. Conversions of this type were observed in the phenylation of dichloro(t -norbornadiene)palladium either with diphenyl-mercury or, more conveniently, with sodium tetraphenylborate to give di-/r-chlorobis(2 5,6-t -c ffo-3-phenylbicyclo[2.2.1]hept-e /o-2-yl)palladium (30) via cis addition.By contrast, the analogous platinum complex did not give a phenylation product. The palladium complex 30 underwent reversible ring closure to a nortricyclenyl complex 31 with pyridine. ... 

---