# Approaches to the Functionalization of Organosilicon Dendrones Based on Limonene
## 2 Experimental  
### Material and Methods  
All reactions were conducted under an inert atmosphere, and solvents were purified from the appropriate drying agents. D-Limonene, propoilic acid, n-butyllithium (solution 2.5 M in hexane) were purchased from Sigma-Aldrich; allychloride, dichloromethylsilane, sodium azide, meta-chloroperoxybenzoic acid, lithium aluminum hydride, and Karstedt's Pt catalyst (2% solution in o-xylene) Pt\({}_{2}\)(DVDS)\({}_{3}\) were obtained from ABCR commercial sources. Gel permeation chromatography (GPC) analysis was performed on a Shimadzu LC-10A series chromatograph (Tokyo, Japan) equipped with an RID-10A refractometer and SPD-M10A diode matrix detectors. For analytical separation, Phenomenex column (Torrance, USA) with a size of 7.8 mm \(\times\) 300 mm filled with the Phenogel sorbent with a pour size of 500 A was used. The GC analysis was performed on a \"Chromatech Analytic 5000\" chromatograph (Yoshkar-Ola, Russia) with a katharometer as detector, helium as carrier gas, with 2 m \(\times\) 3 mm column, and stationary phase SE-30 (5%) was applied to Chromat-H-AW. Registration and data collection was performed with the help of the program \"Chromatech Analyst\" (Yoshkar-Ola, Russia). \({}^{1}\)H, \({}^{13}\)C, \({}^{29}\)Si nuclear magnetic resonance (NMR) spectra and their nuclear correlations were recorded using a Bruker Avance II 300 spectrometer (Billerica, USA) at 300, 75 and 60 MHz, respectively. ### Material and Methods  
These compounds were synthesized according to [44]. Yield of the product (\(\phi\)) in all the cases is given. _Diallyl_(_2-(4-methylcyclohex-3-en-1-yl_)propyl_)_methylsilane (Lim-GOAll2)  
\(\phi=82\%\). For C\({}_{17}\)H\({}_{30}\)Si: C 77.71%; H 11.43%; Si 10.67%: C 77.39%; H 11.25%; Si 10.31%. _Triallyl_(_2-(4-methylcyclohex-3-en-1-yl_)propyl_)_silane (Lim-GOAll3)  
\(\phi=85\%\). For C\({}_{19}\)H\({}_{32}\)Si: C 79.02%; H 11.09%; Si 9.70%: C 75.57%; H 10.61%; Si 9.23%. _Dendrimer of the first generation (Lim-GAll4)_\(\phi\) = 7.5 g (66%). For C\({}_{31}\)H\({}_{88}\)Si\({}_{3}\): C 72.23%; H 11.26%; Si 16.31%: C 72.17%; H 11.16%; Si 16.24%. _1,1,1,3,5,5,5-heptamethyl-3-(2-(4-methylcyclohex-3-en-1-yl)propyl)trisiloxane (Lim-G\({}_{0.5}\)TMS\({}_{2}\))_  
\(\phi\) = 89%. For C\({}_{17}\)H\({}_{38}\)O\({}_{2}\)Si\({}_{3}\): C 56.87%; H 10.59%; O 8.92%; Si 23.42%: C 54.36%; H 10.01%; Si 21.00%. _Bis(heptamethylsilylpropyl)methylsilyllimonene (Lim-G1.5 TMS4)_  
\(\phi\) = 99%. For C\({}_{31}\)H\({}_{74}\)O\({}_{4}\)Si\({}_{7}\): C 52.58%; H 10.46%; O 9.05%; Si 27.70%: C 50.02%; H 9.84%; Si 26.56%. _Tris(heptamethylsilylpropyl)silyllimonene (Lim-G1.5 TMS6)_  
\(\phi\) = 99%. For C\({}_{40}\)H\({}_{98}\)O\({}_{6}\)Si\({}_{10}\): C 50.21%; H 10.25%; O 10.04%; Si 29.29%: C 48.96%; H 10.14%; Si 28.44%  
_Dendrimer of the 2.5 generation (Lim-G2.5 TMS8)_  
\(\phi\) = 99%. For C\({}_{59}\)H\({}_{146}\)O\({}_{8}\)Si\({}_{15}\): C 50.39%; H 10.39%; O 9.11%; Si 29.89%: C 48.91%; H 9.95%; Si 28.27%. _CD of the first generation (Lim-G1 Cl4)_  
To the stirred solution of _Lim-G\({}_{0}\)All\({}_{2}\)_ (5.0 g, 0.019 mol) and 50 \(\mu\)L of Pt\({}_{2}\)(DVDS)\({}_{3}\) in anhydrous toluene (100 mL), methyldichlorosilane (6.57 g, 0.057 mol) was added. RM was stirred at room temperature for 24 h. The completeness of the process was controlled by \({}^{1}\)H NMR spectroscopy from disappearance of proton signals at double bonds in allyl groups. The reaction mixture was evaporated to remove excess dimethylchlorosilane. _CD of the first generation (Lim-G1 Bu4)_  
To a stirred mixture of 37 mL (2.5 M) of \(n\)-BuLi in anhydrous hexane (50 mL), a solution of 9.38 g (0.019 mol) _Lim-G\({}_{1}\)Cl\({}_{4}\)_ in anhydrous hexane (50 mL) at \(-70\)\({}^{\circ}\)C was added. When addition of the mixture was finished, THF (70 mL) was added to the solution. RM was stirred at \(-70\)\({}^{\circ}\)C, and then at room temperature for 24 h. Excess \(n\)-BuLi was deactivated with ethanol. The precipitate of LiCl was filtered off and washed with \(n\)-hexane on the filter.