75366-14-2

Upstream product

• 824-53-3 2,6-dibromo-4-methylbenzyl alcohol 
• 553-94-6 4-bromo-m-xylene 
• 7697-27-0 2-bromo-4-methylbenzoic acid 
• 824-54-4 2-bromo-4-methylbenzaldehyde 
• 75366-05-1 3-methylbicyclo<4.1.0>hepta-1,3,5-triene 

Downstream Products

• 1069114-80-2 (2-bromo-4-methyl-phenyl)-acetonitrile 
• 1346964-52-0 1-(2-bromo-4-methylphenyl)pent-4-en-2-one 
• 1346964-68-8 (Z)-1-(2-bromo-4-methylphenyl)pent-3-en-2-one 
• 1346964-85-9 (E)-1-(2-bromo-4-methylphenyl)pent-3-en-2-one 
• 1069114-83-5 methyl 2-(2-bromo-4-methylphenyl)acetate 
• 31881-86-4 2-(2-bromo-4-methylphenyl)acetic acid 

Relevant academic research and scientific papers

Synthesis of Indolines by a Zn-Mediated Mannich Reaction/Pd-Catalyzed Amination Sequence

1,2-Disubstituted indolines have been prepared in fair to good yields by a Zn-mediated organometallic Mannich reaction, followed by an intramolecular Pd-catalyzed aromatic amination. The reactions are easy to set up and compatible with a large variety of simple or commercially available reagents. The method was further extended to the preparation of a 1,2,3-trisubstituted indoline.

A new protocol for the synthesis of 4,7,12,15-tetrachloro[2.2]paracyclophane

We report a green and convenient protocol to prepare 4,7,12,15-tetrachloro[2.2]paracyclophane, the precursor of parylene D, from 2,5-dichloro-p-xylene. In the first bromination step, with H2O2-HBr as a bromide source, this procedure becomes organic-waste-free and organic-solvent-free and can appropriately replace the existing bromination methods. The Winberg elimination-dimerization step, using aqueous sodium hydroxide solution instead of silver oxide for anion exchange, results in a significant improvement in product yield. Furthermore, four substituted [2.2]paracyclophanes were also prepared in this convenient way.

Hydrazone-palladium catalyzed annulation of 1-allyl-2-bromobenzene derivatives with internal alkynes

Annulation of 1-allyl-2-bromobenzene derivatives with internal alkynes using a hydrazone-palladium catalyst system proceeded smoothly and gave the corresponding polysubstituted naphthalene derivatives in good to high yields.

Diastereo- and enantioselective intramolecular C(sp3)-H arylation for the synthesis of fused cyclopentanes

All C-H bonds are not equal: The intramolecular arylation of unactivated C(sp3)-H bonds in the presence of a chiral Pd/binepine catalyst allows the synthesis of fused cyclopentanes efficiently and in an diastereo- and enantioselective manner (see scheme).

Synthesis of 2-naphthols via carbonylative stille coupling reaction of 2-bromobenzyl bromides with tributylallylstannane followed by the heck reaction

A method for the synthesis of 2-naphthols 4 is described. The carbonylative Stille coupling reactions of 2-bromobenzyl bromides with tributylallylstannane to produce 2-bromobenzyl β,γ-unsaturated ketones 2 in satisfactory to excellent yields has been achieved. The isomerization of 2-bromobenzyl β,γ-unsaturated ketones 2 can readily occur under basic conditions to generate 2-bromobenzyl α,β-unsaturated ketones 3. The 2-bromobenzyl α,β-unsaturated ketones 3 can be transformed into 2-naphthols 4 via intramolecular Heck reaction in satisfactory to good yields (Figure presented).

Synthesis of benzocyclobutenes by palladium-catalyzed C-H activation of methyl groups: Method and mechanistic study

An efficient catalytic system has been developed for the synthesis of benzocyclobutenes by C-H activation of methyl groups. The optimal conditions employed a combination of Pd(OAc)2 and PtBu3 as catalyst, K2CO3 as the base, and DMF as solvent. A variety of substituted BCB were obtained under these conditions with yields in the 44-92% range, including molecules that are hardly accessible by other methods. The reaction was found limited to substrates bearing a quaternary benzylic carbon, but benzocyclobutenes bearing a tertiary benzylic carbon could be obtained indirectly from diesters by decarboxylation. Reaction substrates bearing a small substituent para to bromine gave an unexpected regioisomer that likely arose from a 1,4-palladium migration process. The formation of this "abnormal" regioisomer could be suppressed by introducing a larger subsituent para to bromine. DFT(B3PW91) calculations on the reaction of 2-bromo-tert-butylbenzene with Pd(PtBu3) with different bases (acetate, bicarbonate, carbonate) showed the critical influence of the coordination mode of the base to induce both an easy C-H activation and to allow for a pathway for 1,4-palladium migration. Carbonate is shown to be more efficient than the two other bases because it can abstract the proton easily and at the same time maintain κ1-coordination without extensive electronic reorganization.

Regioselective Ring Opening in Substituted Benzocyclopropenes. An Alternative or Complementary Mechanism for Electrophilic Substitution Involving Attack at a ? Bond

2-Methylbenzocyclopropene (5) reacts with bromine, iodine, and HCl to give the m-xylenes 12a,c,d as the major products, whereas it reacts with silver nitrate in the presence of ethanol and aniline to give the o-xylenes 11e,f as the major products.Similarly, 3-methylbenzocyclopropene (10) gives mainly m-xylenes 14a,c,d with halogens and HCl and gives p-xylenes 13e,f with silver nitrate and ethanol or aniline.Cyclopropabenzocyclobutene (15) also gives different products with halogens and silver nitrate, but in this case HCl gives the same type of product as the silver ion.The difference in electrophilic behavior of 5, 10, and 15 toward the two types of reagents is suggested to arise from attack of the silver ion (and the proton in the case of 15) on the ? electrons of the cyclopropyl ring.

Amino-benzimidazole derivatives

Amino-benzimidazole derivatives of the structure STR1are provided which are useful as anti-inflammatory agents. In addition, a method for preparing such compounds, pharmaceutical compositions containing such compounds, and methods for using such pharmaceutical compositions in the treatment of inflammation are taught.