P Hydroxy phenylation

The first stable derivative of methylene cyclopropene was the quinocyclopropene 108 reported in 1964 by Kende98 it was prepared from the cyclopropenium cation 106 which underwent pyrolysis and bromination with NBS to the p-hydroxy-phenyl substituted cation 107, which gave quinocyclopropene 108 by deprotonation ... 

This principle of formation proved to be general for quinocyclopropenes of type 61a ( phenylogous cyclopropenones )- The required p-hydroxy-phenyl cyclopropenium cations were available by electrophilic substitution of phenolic components (preferentially 2,6-disubstituted) and heterosubstituted cyclopropenium cations (75 and 109), as the representative examples 11099 11176 112and 113 show ... 

Surprisingly 6-(p-hydroxyphenyl)- and l,4-dimethyl-6-(p-hydroxy-phenyl)-dihydrodiazepinium salts react readily with bromine, giving 6-(3-bromo-4-hydroxyphenyl) and 6-(3,5-dibromo-4-hydroxyphenyl) derivatives (86LA1380). It is thought that in these cases the intermediate is a cyclohexadienone rather than a doubly charged species as shown above (86LA1380). 

If we apply this concept of samration to drug elimination we get a similar picture. The anticonvulsant phenytoin depends critically for its elimination on one enzyme reaction (to produce the p-hydroxy-phenyl metabolite) and this, like the turnstile, can exceed its capacity to metabolize the drug. Phenytoin is then eliminated at a constant amount (not a constant proportion) per unit time. If input then exceeds this elimination capacity (and volume of distribution does not change), plasma concentration will rise rapidly into the toxic range. 

An X-ray analysis128 of the clathrate129 formed by 4-(p-hydroxy-phenyl)-2,2,4-trimethylthiochroman has been reported. 

Bunnet und Marks (114) stellten ein optisch aktives Phenol-Formaldehydharz mit optisch aktiver / -(p-Hydroxy-phenyl)-butter-saure (LXXIV) sowie mit N-(p-Toluolsulfonyl)-L-tyrosin (LXXV) her. Es sollte zur Trennung von Antipoden dienen. ch3... 

The principal metabolic products of phenytoin are p-hydroxy-phenyl derivative (HPPH) and a conjugate of HPPH with glucuronic acid (13-21). 

Chang, S.-J. Fernando, D. P. King, S. Preparation of cyclopropyl p-hydroxyphenyl ketone and its precursor 3-chloropropyl p-hydroxy-phenyl ketone. Org. Process Res. Dev. 2001, 5, 141-143. 

Hydroxy 8 nonene 2.5 dione allethrin p.Hydroxy phenyl acetic acid cycloprothrin 3 Hydroxy 5 phenyl isoxazole isoxathion... 

It has been shown that nocardicin A (113) is formed from L-serine (112), from L-homoserine, and from two units of L-tyrosine with loss of C-l (cf. Vol. 9, p. 33). New results confirm these findings and extend them.97 The manner of utilization of tyrosine (L-phenylalanine was not a precursor) suggested that (p-hydroxy-phenyl)glycine [as (110)] would be a more immediate precursor than tyrosine. This was confirmed (110) and its D-isomer were incorporated without loss of a 14C label that was sited at C-l, and dl-[l-13C]-(/ -hydroxyphenyl)glycine las (110)1 gave nocardicin A (113) that was labelled at C-10 and at C-l. ... 

For the preparation of 4-(1.2.3.4-tetrahydroquinolino)-phenol 17 three different procedures were worked out [Eqs. (6)-(8)]. 17 was prepared by reacting N-p-methoxyphenyl-anthranilic acid with acetic anhydride and subsequent saponification to l-p-methoxyphenyl-4-hydroxy-2-quinolone, reaction withPOCl3 to form l-p-methoxyphenyl-4-chloro-2-quinolone, hydrogenation to l-(p-methoxy-phenyl)-3.4-dihydro-2-quinolone, splitting the ether with HBr to l-(p-hydroxy-phenyl)3.4-dihydro-2-quinolone, and reduction with LiAlH4 [Eq. (6)J. Another synthetic possibility was the reaction of p-anilinophenol with (3-propiolactone and subsequent cyclization to l-(p-acetoxyphenyl)2.3-dihydro-4-quinolone 18. The next step, the Wolff-Kishner reduction, led directly to the desired product [Eq. (7)]. The third way, the direct amination of p-iodoanisole with 1.2.3.4-tetrahydro-quinoline and the subsequent splitting of 4-(1.2.3.4-tetrahydro-quinolino)-anisol with HBr was the best one [Eq. (8)]. Saponification of l-(p-acetoxyphenyl>2.3-... 

Renilla (sea pansy) luciferin (and certain of its synthetic analogues) produces a brilliant blue chemiluminescence when dissolved in organic solvents such as dimethylformamide and involves the anion of 2-acetamido-3-benzyl-5-(p-hydroxy-phenyl)pyrazine (21) (1191). 5-Hydrazino-2-hydrazinocarbonylpyrazine is effective against mycobacterium tuberculosis and m. kansasii in vitro (1098). Aminonitro-pyrazines have been claimed as useful yellow dyes for wool (1180) and tetraamino-pyrazine (1180) and A -substituted amides of 2-carboxy-3,5-bismethylamino-6-(A -methylcarbamoyl)pyrazines (1192) as fluorescent brighteners (or optical bleaching agents) for textiles. 

Hordenine, p-Hydroxy phenyl-ethyl dimethyl amine. 

An alternative approach is to use the readily available P-hydroxy phenyl selenides as Ritter substrates. Amide formation occurs with retention of configuration, indicating that fission of the carbon-oxygen bond is assisted by the neighboring phenylseleno group (Scheme 61). Diphenyl diselenide and iodine react with 1,5-dienes to give carbocyclic products. Initial formation of the episelenonium ion is followed by intramolecular attack and subsequent Ritter reaction (Scheme 62). ... 

The influence of ascorbic acid on tyrosine metabolism in man and intact animals has been discussed under alkaptonuria and tyrosinosis q.v.). Ty-rosyluria, also called hydroxyphenyluria, i.e., the excretion of p-hydroxy-phenyl compounds in the urine, can be affected by factors other than ascor-... 

In a similar manner the other amino acids react tyrosine, j3-p-hydroxy-phenyl-a-amino-butyric acid yielding p-hydroxy-phenyl-ethyl alcohol, tyrosol while phenyl-alanine, a-amino-j8-phenyl-propionic acid, yields phenyl-ethyl alcohol. Succinic acid, for example, which is of usual occurrence in fermented liquors is probably formed by a similar reaction from glutamic acid with the additional step of oxidation in the process. 

The microbial biotechnology of amino acids production which was developed and industrialized in Japan have been summarized. The amino acids include L-glutamic acid, L-lysine, L-threonine, L-aspartic acid, L-alanine, L-cysteine, L-dihydroxyphenylalanine, D-p-hydroxy-phenyl-glycine, and hydroxy-L-proline. 

Reaction of p-hydroxy or p-acetoxy sulfones with Sml2 in the presence of HMPA caused effective reductive elimination to provide olefins [66]. In contrast, Kende recorded a poor result in the reductive elimination of the P-hydroxy phenyl sulfones with Sml2 without HMPA [67]. Finally, it has been reported that contrary to phenyl sulfones, 2-pyridyl sulfones are instantaneously reduced in the presence of Sml2 without additives [68]. 

Tyrosine. Tyr (lUPAC abbrev.) 0-(p-hydroxy-phenyl)alanine a-amino-p-hydroxyhydrocinnamic acid. C9H,N03 mol wt 181.19. C 59.66% H 6.12% N 7.73%, O 26-49%. A widely distributed amino acid, classified as non-essentia] in respect to the growth effect in rats Isoln from silk waste Abderhalen, Teruuchi Z Physiol Chem. 48, 528 (1906) see also Morrow in Biochemical Lab. Methods (New York, 1935) Stein, Moore. Biochem. Prepn. vol I (New York, 1949) p 11. From casein Marshall. J. Biol. Chem, 15 85 (1913) Cox, King, Qrg, Syn, toll, vol, U 612 (1943), From corn U.S pal. 2 178 210 (1940). 

Thus have been obtained, inter alia, dimethyl (82%), di-/ -tolyl (100%), bis-(p-hydroxy-phenyl) (27%), bis-(/Mnethoxyphenyl) (90%), bis-(j>-bromophenyl) (94%), and bis-Q -nitro-phenyl) sulfide (83 %). 

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