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\documentclass{report}
\usepackage{rotating}
\usepackage{german,times,multirow,array}
\usepackage[latin1]{inputenc}
\begin{document}

\newcommand{\headrotate}[1]
  {\makebox[5mm][c]{\begin{rotate}{60}#1\end{rotate}}}
\begin{table}
\caption{Anwendungsübersicht über verschiedene
  Derivatisierungsreagenzien II}
\setlength{\extrarowheight}{1pt}
\begin{tabular}{|ll|*6{c}|}\hline
& & \multicolumn{6}{c|}{\large\bfseries Substratklasse}\\
\rule{0mm}{25mm} & & % Freihalten in Höhe der Legende
\headrotate{Alkohole} &
\headrotate{Amine} &
\headrotate{Aminosäuren} &
\headrotate{Carbonsäuren} &
\headrotate{Hydroxylgruppen} &
\headrotate{Phenole}
\rule{2mm}{0mm} \\  % rechter Rand
\hline
\multirow{5}{5mm}{\begin{turn}{90}\large\bfseries Reagenz\end{turn}}
& Bortrifluorid-Methanol-Komplex & & & x & & & \\
& Chlortrimethylsilan & x & x & x & x & x & x \\
& Dichlordimethylsilan & & & x & & & \\
& Hexamethyldisiloxan & & & & & x & \\
& N-Methyl-bis(trifluoracetamid) & x & x & & & & x \\
\hline
\end{tabular}
\end{table}

\end{document}