Bromo-trimethyl

Bartlett and Long (1977) were able to synthesize a-diazophosphonates (as dianions, 2.143) by transesterification of the corresponding dimethyl a-diazophosphonates (2.141) with bromo-(trimethyl)silane, furnishing the extremely moisture-sensitive bis(trimethylsilyl) esters (2.142), which were hydrolyzed under very mild (pH 8-9) aqueous conditions. The half-life for decomposition of a-diazoben-zylphosphate dianion is less than 1 min in aqueous solution at pH 8.0, although it can be prolonged by appropriate choice of the buffer (2-60). 

Perfect 2,5-linked polypyrrole is prepared by using Stille chemistry [39]. t-BOC-protected pyrroles are converted into bromo-trimethyl stannyl monomers and subsequently polymerized using a Pd-catalyst. Although of relative low molecular weight (Af = 3400), the fully characterized protected polypyrrole can be converted to perfect polypyrrole by thermal deprotection, (Scheme 10.3). 

Dialkylphosphonopropionamides. CeUulosic derivatives that closely resemble those based on the dialkylphosphonopropionamides have been prepared (71). The fabric was treated with AJ-hydrox raethylhaloacetamides (chloro, bromo, or iodo) in DME solution by a pad-dry-cure technique with a 2inc nitrate [10196-18-6] catalyst. It was then allowed to react in solution with trimethyl phosphite [121 -45-9] at about 140—150°C the reaction rates decreased in the order iodo > bromo > chloro. With phosphoms contents above 1.5%, good flame resistance, durable to laundering, was obtained without noticeable loss in fabric strength. 

When methylene chloride was used as a solvent, it was found that 28 are obtained in minor amounts, while the dominating product is the -coordinated chloro-carbyne species [(> -Tp )Mo(CO)2(=CCl)], whose yield increases abruptly with substitution in the pyrazol-l-yl fragments (3-methyl-, 3,4,5-trimethyl-, and 3,5-dimethyl-4-chloro derivatives) [90AX(C)59,95JCS(D) 1709]. The tungsten analog can be prepared similarly. The chlorocarbyne molybdenum complex follows also from the reaction of the parent anion with triphenylsulfonium cation but conducted in dichloromethane. The bromo- and iodocarbyne derivatives are made similarly. 

Reaction of 10-bromo-iV,l,3-trimethyl-7-oxo-2,3-dihydro-7//-pyrido [ 1,2,3-i/e]quinoxaline-6-carboxamide with 2,6-dimethyl-4-(tributylstannyl)-pyridine in the presence of (Ph3P)2Pd(II)Cl in boiling toluene gave 10-(2,6-dimethyl-4-pyridyl) derivative (OOMIPIO). 

Reaction of ethyl 7-bromo-8-fluoro-l-(2-bromo-l-methylethyl)-4-oxo-l,4-dihydroquinoline-3-carboxylate with MeNH2 yielded 10-bromo-A, 1, 3-trimethyl-7-oxo-2,3-dihydro-7//-pyrido[l,2,3-<7e]quinoxaline-3-carboxamide (OOMIPIO). 

Caution This preparation should be conducted in a hood to avoid exposure to trimethyl-amine and to ct-bromo-p-xylene. 

Based on unrecovered starting material. b From 2-bromo-2, 4, 6 -trimethyl-4,6-dinitrodiphenyldiazene. c In refluxing xylene. 

Benzoic m-Toluic (Benzoic acid, 3-methyl-] p-Toluic [Benzoic acid, 4-methyl-J 3,5-Dimcthylbcnzoic [Benzoic acid, 3,5-dimcthyl-] p-Chlorobenzoic [Benzoic acid, 4-chloro-] p-Bromobenzoic [Benzoic acid, 4-bromo-J Phthalic [ 1,2-Bcnzcncdicarboxylic acid] Toluene [Benzene, methyl-] (78) m-Xylene [Benzene, 1,3-dimethyl-] (82) />-Xylene [Benzene, 1,4-dimethyl-] (74) Mesitylene [Benzene, 1,3,5-trimethyl-] (82) p-Chlorotolueno [Benzene, l-ehloro-4-methyl-] (94) p-Bromotolucnc [Benzene, l-bromo-4-methyl-] (94) o-Xylene [Benzene, 1,2-dimethyl-] (64)... 

B. l0-Bromo-ll-hydroxy-10,ll-dihydrofarnesyl Acetate [2,6-Dodeca-diene-1,11-diol, 10-bromo-3,7, -trimethyl-, 1-acetate, (E,E)-]. Farnesyl acetate (29 g., 0.11 mole) is dissolved in 1 1. of /erf-butyl alcohol (Note 4) contained in a 3-1. Erlenmeyer flask. Water is added (500 ml.), and the solution is cooled to about 12° using an external ice water bath. Maintaining this temperature, rapid magnetic stirring is begun, and more water is added until a saturated solution is obtained. The second addition of water may be rapid initially, but the saturation point must be approached carefully, like the end point of a titration. A total of about 1200 ml. of water is required for the above amounts of farnesyl acetate and ferf-butyl alcohol. The solution must remain clear and homogeneous at about 12°, and if the saturation point is accidentally passed by adding too much water, ferf-butyl alcohol should be added to remove the turbidity. 

Farnesyl, 10-bromo-10,l 1-dihydro-l 1-hydroxy-, acetate [2,6-Dodecadiene-1,11-diol, 10-bromo-3,7,11-trimethyl-, 1-acetate, ( , )-], 113 Ferrocene, 28... 

Bromo-Ar,Ar-dimethyl-3-(trifluoromethyl)aniline has been prepared by the methylation of 4-bromo-3-(trifhioromethvl)aniline with trimethyl phosphate in 70-80% yield.3 The present method, which effectively uses 3-(trifluoroinethyl)aniline as starting material, offers advantages in cost, yield, and ease of purification. 

Bromo-5,7,8-trichloroquinoxaline 6-Bromo-2,7,8-trimethyl-5-nitroquinoxaline 6-Bromo-3,7,8-trimethyl-5-nitroquinoxaline 6-Bromo-2,3,7-trimethylquinoxaline 6-Bromo-2,37-trimethylquinoxaline 1,4-dioxide 2-(But-1 -enyl)quinoxaline 2-Butoxy-3-chloroquinoxaline 2-sY r-BLiloxy-5-chloroc uinoxaline 2-Butoxy-3-hydrazinoquinoxaline... 

The reaction of potassium 3-amino-4-oxo-3,4-dihydroquinazoline-2-thiolate 62 with a-bromophenylacetic acid 63 resulted in the formation of (3-amino-4-oxo-3,4-dihydroquinazolin-2-ylsulfanyl)-phenyl-acetic acid methyl ester 64 which on alkali treatment and subsequent acidification resulted in the synthesis of 2-phenyl- 1-thia-4,4a,9-triaza-anthracene-3,10-dione 65 <1999JCR(S)86>. Similarly, the reaction of potassium 3-amino-5,6-dimethyl-4-oxo-3,4,4a,7a-tetrahydrothieno[2,3- pyrimidine-2-thiolate 66 with a-bromo-ester 67 resulted in the formation of 2-(3-amino-5,6-dimethyl-4-oxo-3,4,4a,7a-tetrahydrothieno[2,3- / pyrimidin-2-ylsulfanyl)-propionic acid ethyl ester 68. Subsequent treatment with alkali followed by acidification resulted in the formation of 2,3,7-trimethyl-3a,9a-dihydro-l,8-dithia-4a,5,9-triazacyclopenta[ ]naphthalene-4,6-dione 69 <2000JHC1161>... 

It is of course possible to name individual radialenes according to IUPAC rules [e.g. per(methylene)cycloalkanes 1-4]. However, the descriptiveness of the term radialene may some day pave its way into the official nomenclature. For substituted [ ]radialenes we have proposed1 a pragmatic numbering system, in which an inner ring is numbered first, followed by an outer ring . The numbering of substituents should follow IUPAC rules. Thus, the hydrocarbon 7 is 4,4-diethyl-5,5-dimethyl[3]radialene, the ester 8 should be called 7-methoxycarbonyl-5,5-dimethyl[4]radialene, the nitrile 9 which can exist in four diastereomeric forms is (6Z,7Z)-6-cyano-5,5,7-trimethyl[4]radialene and the difunctionalized [5]radialene 10 is (7 ,6Z)-7-bromo-6-formyl-6-methyl[5]radialene. 

Handy and coworkers [38] have also offered a very useful approach (Scheme 14) to lamellarin G trimethyl ether (36) and they have referred to this strategy as being modular in nature . The route starts with an N-protected 4-bromo-2-carboethoxypyrrole (72) and involves introduction of three different aryl groups via three sequential, regiospecific halogenations, which are... 

Sodium, with l-bromo-3-chloro-cyclobutane to give bicyclo [l.l.O]butane, 51, 55 Sodium amalgam, 50, 50, 51 Sodium amide, with 2,4-pentane-dione and diphenyliodonium chloride to give l-phenyl-2, 4-pentanedione, 51, 128 Sodium azide, 50, 107 with mixed carboxylic-carbonic anhydrides, 51, 49 Sodium borohydride, reduction of erythro-3-methanesulfony-loxy-2-butyl cyclobutanecar-boxylate, 51, 12 reduction of 2-(1-phenylcyclo-pentyl)-4,4,6-trimethyl-5,6-dihydro-1,3(4H)-oxazine to 2-(1-phenylcyclopentyl)-4,4, 6-trimethyltetrahydro-l,3-oxazine, 51, 25 Sodium cyanoborohydride, used... 

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