5-tert.-Butyl-2-hydroxy

Diphenylphosphinsdure-(5-tert.-butyl-2-hydroxy-3-methyl-anilid)789 79% Schmp. 207-209°... 

Diphenyl- -benzylamid E2, 233 Diphenyl- -bromid El, 210 Diphenyl- -tert.-butylester E2, 211 Diphenyl- -(5-tert.-butyl-2-hydroxy-3-methyI-anilid) E2, 236... 

Obtained by treatment of 3-amino-5-tert-butyl-2-hydroxy-benzophenone with 2 N hydrochloric acid [472],... 

Also obtained from 5-tert-butyl-2-hydroxy-3-methylpropiophenone by tert-butyl group elimination with aluminium chloride (2 equiv) at 190° for 15 min (77%) [6466],... 

Preparation by adding a solution of 5-tert-butyl-2-hydroxy-propiophenone in an acetic acid and hydrochloric acid (d = 1.19) mixture to an aqueous solution of 0.2 N potassium bromate and potassium bromide, then stirring 24 h after the addition of ketone (97%) [7560,7561]. 

Benzyl-(4-chlor-benzyliden)- 664 Bis-[fluoracetyl]- 239 Bis-[2-fluor-athyl]- 239 (Bis-[4-methoxy-phenyl]-methyl)- 377 Bis-[2-methyl-propyl]- 358 Bis-[2-phenyl-2-cyan-vinyl]- 58 tert.-Butyl-(hydroxy-tert.-butyl)-... 

H1 CH3O3C—Sl-CgHg 35 10 10 Bis- 3-(bzw. 4J-nitro-phenyl]-tert.-butyl-hydroxy-silan 65 (4 1) 2... 

Peroxid tert.-Butyl-(hydroxy-benzol-phosphoryl)- -Na-Salz E13/1, 942 (Cl -> O-OR)... 

The food presa-vative BHT (tert-butylated hydroxy toluene) has the stmcture shown here. Suggest a synthesis starting fiomd-methylphenol ( cresol). 

If a bromomethyl- or vinyl-substituted cyclopropane carbon atom bears a hydroxy group, the homoallyiic rearrangement leads preferentially to cyclobutanone derivatives (J. Sa-laun, 1974). Addition of amines to cydopropanone (N. J. Turro, 1966) yields S-lactams after successive treatment with tert-butyl hypochlorite and silver(I) salts (H.H. Wasserman, 1975). For intramolecular cyclopropane formation see section 1.16. 

The first practical method for asymmetric epoxidation of primary and secondary allylic alcohols was developed by K.B. Sharpless in 1980 (T. Katsuki, 1980 K.B. Sharpless, 1983 A, B, 1986 see also D. Hoppe, 1982). Tartaric esters, e.g., DET and DIPT" ( = diethyl and diisopropyl ( + )- or (— )-tartrates), are applied as chiral auxiliaries, titanium tetrakis(2-pro-panolate) as a catalyst and tert-butyl hydroperoxide (= TBHP, Bu OOH) as the oxidant. If the reaction mixture is kept absolutely dry, catalytic amounts of the dialkyl tartrate-titanium(IV) complex are suflicient, which largely facilitates work-up procedures (Y. Gao, 1987). Depending on the tartrate enantiomer used, either one of the 2,3-epoxy alcohols may be obtained with high enantioselectivity. The titanium probably binds to the diol grouping of one tartrate molecule and to the hydroxy groups of the bulky hydroperoxide and of the allylic alcohol... 

Triethylene glycol bis(3-tert-butyl-4-hydroxy-5-methylhydrocinnamate) [36443-68-2]... 

Tris(4-tert-butyl-3-hydroxy-2,6-dimethylben2yl)s-triazine-2,4,6-(lH,3H,5IT)trione [40601-76-1]... 

Table 15 shows that peroxyester stabiUty decreases for the alkyl groups in the following order tert — butyl > tert — amyl > tert — octyl > tert — cumyl > 3 — hydroxy — 1,1 dimethylbutyl. The order of activity of the R group in peroxyesters is also observed in other alkyl peroxides. Peroxyesters derived from benzoic acids and non-abranched carboxyUc acids are more stable than those derived from mono-a-branched acids which are more stable than those derived from di-a-branched acids (19,21,168). The size of the a-branch also is important, since steric acceleration of homolysis occurs with increasing branch size (236). Suitably substituted peroxyesters show rate enhancements because of anchimeric assistance (168,213,237). 

The parent indolo[2,3-fl]carbazole (1) has also been the subject of a study probing its reactivity toward oxidizing agents. One of the substrates involved, namely 85 (prepared from 1 and 2,5-dimethoxytetrahydrofuran in the presence of acid), was subjected to treatment with m-chloroperbenzoic acid, to give the dione 86 as the major product and a sensitive compound assigned the hydroxy structure 87. A cleaner reaction took place when 85 underwent oxidation with tert-butyl hydroperoxide assisted by VO(acac)2, to produce 86 exclusively in 86% yield. Likewise, A,N -dimethylindolo[2,3-fl]carbazole furnished the dione 88 on treatment with this combination of reagents (96J(X 413). 

A solution of 1.7 g of 2-hydroxymethyl-3-benzyloxy-(1-hydroxy-2-tert-butyl-aminoethyl)py-ridine in 30 ml of methanol containing 1.2 ml of water is shaken with 700 mg of 5% palladium-onatmospheric pressure. In 17 minutes the theoretical amount of hydrogen has been consumed and the catalyst is filtered. Concentration of the filtrate under reduced pressure provides 1.4 g of the crude product as an oil. Ethanol (5 ml) Is added to the residual oil followed by 6 ml of 1.75N ethanolic hydrogen chloride solution and, finally, by 5 ml of Isopropyl ether. The precipitated product is filtered and washed with isopropyl ether containing 20% ethanol, 1.35 g, melting point 182 (dec.). 

N-tert-Butyl-2-(5-benzyloxy-6-hydroxy-methyl-2-pyr idyl)-2-hydroxy acetamide Pirbuterol Butyl bromide Bufexamac Bupivacaine Fenipentol sec-Butyl bromide... 

R,5R)-2-tert-butyl-5-[(R)-hydroxy( phenyl)minhyl -3-oxa-7-thia-t-a abkydo 3.3.0 octan-4-(me yield ca. 50%... 

D. 2(S)-(fl-tert-Butoxycarbonyl-a-(R)-hydroxyethyl)-4-(R)-hydroxy-pyrrolidine- 1-carboxylic acid, tert-butyl ester. The identical procedure was followed, in this case using the (,S)-BINAP catalyst (5)-l. Hydrogenation is conducted for 64 hr, and the reaction mixture is then transferred to a 250-mL, round-bottomed flask and concentrated to dryness. The residue is dissolved in 17 mL of methanol and cooled to 15°C. After the slow addition of 7 mL of DI water, the solution is aged for 15 min gradually forming a thin slurry. More DI water (75 mL) is added over 1 hr and the mixture is allowed to stand for an additional 1 hr at 15°C. The resulting crystals (Note 19) are filtered at 15°C, washed with 10 mL of 1 4-MeOH water, and then dried overnight in a vacuum oven (35°C, 686 mm) to yield 7.0 g (70%) of (R)-hydroxy ester 4b (Note 20). 

S-4R)-2-tert-Butoxycarbonylacetyl-4-hydroxypyrrolidine-l-carboxylic acid, tert- butyl ester 2-Pyrrolidinepropanoic acid, l-[(l,l-dimethylethoxy)carbonyl]-4 hydroxy- P-oxo-, 1,1-dimethylethyl... 

Tab. 24 Hydrid-Rcduktion des ungehinderten 4-Oxo-l-tert.-butyl-cyclohexans untcr asymmetrischer Induktion zu trans- und cis-4-Hydroxy-l-tert.-butyl-cyclohexan...

R2 = CH(CHb2 R3 = C(CH3)-, (1 -Hydroxy-2-methyl-propyl)-tert.-butyl-diazen 52% d.Th. ... 

Bis- 3-(bzw.4)-[2,2-dimethyl-2-(2-hydroxy-propyl)-1 -dehydro-hydrazinocarbonyl]-phenyl - 687 Bis-[2-methy]-phenyl]- 538 -bis-phosphonsaure-diester 523 Bis-[trifluormethy]]- 538 tert.-Butyl-( 1-hydroperoxy-cyclopentyl)- 571 tert.-Butyl-( 1 -hydroxy-cyclopentyl)- 571 (4-Chlor-phenyl)-(2-nitro-phenyl)- 693 (4-Chlor-phenylthio)-(4-nitro-phenyl)- 700 [Cyclohexen-(l)-yl]-phenyl- 368 Diaryl- 550, 552, 558, 567 Diphenyl-... 

Hydroxy-2-phenyl-athyl)-benzyI- 633 (2-Hydroxy-2-phenyl-athyl)-phenyI- 667 [1-Hydroxy-l -phenyl-propyl-(2)J-phenyl- 633 Methyl-(2-tert.-butyl-phenyl)- 632 Methyl-(2-methyl-phenyl)- 632 Methyl-naphthyl- 663 Naphthyl-benzyl- 633 fi-Oxo- 634... 

Hydroxy-l-[3-methyl-buten-(l)-yl-(2)]- 520 4-Hydroxy-2-methyl-1 -tert.-butyl- 327... 

Brom-l-(2-chlor-athyl)- 623 4-Brom-l-(l-hydroxy-athyl)- 308, 607 4-Brom-l -jod- 624 Brommethyl- 505 4-Brom-l-methyl- 172 4-Brommethyl-l-tert.-butyl- 625 Brom-nitro- 621... 

The sole recent example in this category is the condensation (in hot aqueous ethanolic sodium hydrogen carbonate) of o-phenylenediamine (399) with tA-tert-butyl 2-hydroxy-3-oxo-l,2,6-piperidinetricarboxylate (400) to give tcrt-butyl 3-[3-(tcrt-butoxycarbonyl)-3-(tcrt-butoxycarbonylamino)propyl]-2-quinoxalinecarboxy-late (401) in 87% yield. ... 

This category is exemplified, albeit poorly, in the reaction of 3-methyl-1,2-benzenediamine (405) with tri-ferf-butyl 2-hydroxy-3-oxo-l,2,5-pyrrolidinetricar-boxylate (406) in aqueous ethanolic sodium hydrogen carbonate under reflux for 3 h. This gave, as minor products, an inseparable mixture (in 9% yield) of tert-butyl 3-[2-(ferf-butoxycarbonyl)-2-(ferf-butoxycarbonylamino)ethyl]-5-methyl-2-quinoxalmecarboxylate (407, Q = Me, R = H) and its 8-methyl isomer (407, Q = H, R = Me). ... 

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