The pictures are actually hosted from my page, the only thing which is lacking at the moment is a nice HTML doc which links most pictures and shows the 3-4 most interesting ones, along the lines of the docs below:
https://www.thevespiary.org/rhodium/Rhodium/clandestine/nano/ (https://www.thevespiary.org/rhodium/Rhodium/clandestine/nano/)
https://www.thevespiary.org/rhodium/Rhodium/clandestine/nasa/ (https://www.thevespiary.org/rhodium/Rhodium/clandestine/nasa/)
Hi Xicori!
I red one of your earlier posts; it is impossible to reply to it, so I post the reply here, incredibly, there were no replies to it; Post 391039 (https://www.thevespiary.org/talk/index.php?topic=11308.msg39103900#msg39103900)
(Xicori: "New route to PCP´s?", Novel Discourse). You wanted to transform 1-Phenylcyclohexanol to (1-bromocyclohexyl)-benzene. (1-iodocyclohexyl)-benzene would work as well in the synthesis. It could be prepared using the notorious iodine/red phosphorous method. Aluminium and iodine might be adequate for this purpose as well. It works well with the simple alcohols (MeOH, EtOH…), giving generally lower (than rP/I2) but still excellent yields, see: Jones; Green; J.Chem.Soc.; 1926; 2760; J.Chem.Soc.; 1927; 928. Tosylation/mesylation of the 1-Phenylcyclohexanol is maybe yet another option?
Another more OTC and hence interesting approach would be to simply gas the alcohol with HCl in DCM, see: H.; Tsushima,T.; J.Amer.Chem.Soc.; 92; 1970; 3397-3403. and Arumugam,N. et al.; Indian J.Chem.Sect.B; 16; 1978; 917-920 - both describe the synthesis of (1-chloroyclohexyl)-benzene using conc. HCl (or gas?). Finally, there is a paper where they react (I) with various amines, amides...: Baiocchi,L. et al.; Gazz.Chim.Ital.; 103; 1973; 61-69.. Might be worth checking it out for the yields/chemistry as many different nucleophiles were used, unfortunately I can't get it...
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000451447-chlorocmpnd.gif)
2-Phenyl-2-bromopropane: A solution of 33 g of PBr3 (0.12 mol) in 55 mL of chloroform was added dropwise at 40 C to a stirred solution of 50 g of a,a-dimethylbenzyl alcohol (0.36 mol) in 700 mL of chloroform.The reaction mixture was stirred for 2 h at 40 C. The chloroform layer was separated from the viscous inorganic layer and poured into 500 mL of ice water. The organic layer was separated, washed twice with a saturated aqueous Na2CO3 solution and once with water, and dried over MgSO4. The chloroform was removed under reduced pressure. After distillation a colorless liquid was obtained; boiling region 57-80 C (0.05 mmHg). The product contained 31% of the elimination product a-methylstyrene. The product was used without further purification for the synthesis of lf. The yield of 2-phenyl-2-bromopropane was 57%
a,a-Dimethylbenzylamine: This amine was obtained by treatment of 2-phenyl-2-bromopropane with liquid ammonia.* After evaporation of the ammonia, the product was dissolved in 1 M aqueous HCl and the a-methylstyrene was extracted with diethyl ether. The water layer was brought to pH 14, and the free amine was extracted with ether. The ether layer was dried over MgSO4, and the ether removed under reduced pressure. The yield was 53%
*: Brander, M. M. Red. Trm. Chim. Puys-Bus Belg. 1918,37,76-87.
I agree, the yields are not the best..
Alcohols/Alkenes to chlorides:
A Convenient Procedure for the Quantitative Conversion of Reactive Alcohols and Olefins into the Corresponding Chlorides
Herbert C. Brown, Min-Hon Rei;
J. Org. Chem.; 1966; 31(4); 1090-1093.
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_imgs/pdf.gif)
..and refs in there.
Many thanks to Nicodem on the Ritter-type of reactions and their use for this purpose. At the espacenet a patent was found based on Ning's idea that tert. alcohols can be treated with urea and conc. H2SO4 to give condensation products, which upon hydrolysis give amines.
PCA intermediate is very interesting as simple reductive amination with various ketones/aldehydes can give a spectrum of extreamly potent analogues.
Tertiary Alkyl Urea and Process for Preparing Same: Patent US2247495 (http://l2.espacenet.com/dips/viewer?PN=US2247495&CY=gb&LG=en&DB=EPD)
(https://www.thevespiary.org/rhodium/Rhodium/hive/hiveboard/picproxie_docs/000451447-tert_urea.jpeg)