清晰的计划

2024-5-22 • tag-icon

我正在使用 Lyx 写论文，快写完了，但是遇到了一个奇怪的问题。如果一些图形和方案不适合一页，它们会被移动到新页面，这没问题，但我不明白为什么它们上面或下面没有文本，因为有空间。我真的不知道问题是什么，因为有时甚至更大的浮动也会很好地放置在下方，下面有一些文本。

由于问题只涉及部分浮点数，我不知道如何构造最小工作示例，因此我附上了我的部分论文。方案 0.3 有问题，而类似大小的方案 0.5 没问题。

前言：

    \usepackage[labelfont=bf]{caption}
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班级：

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文档：

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\begin{document}
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\begin{onehalfspace}

\section{Procedures of syntheses}
\end{onehalfspace}

\begin{onehalfspace}
For each compound used as a functional monomer, a number was assigned.
If synthesis of a certain functional monomer required several steps,
the intermediates were labeled with a number of the final product
and a letter. For clarity, the NMR and MS spectra as well as crystallographic
data are given in Appendix.
\end{onehalfspace}

\begin{onehalfspace}

\subsection{Syntheses of new thiophene derivatives}
\end{onehalfspace}

\begin{onehalfspace}
Within the present research 16 new bis(2,2'-bithiophene) and 2 ten
{[}C60{]}fullerene derivatives were designed and synthesized to serve
as functional monomers (FMs) . Their recognition sites varied from
simple functional groups, such as hydroxyl, amino, nitro, carboxyl,
or amide groups, to bigger assemblies containing naturally occuring
recognizing moieties, such as biotin, thymine, cytosine, or guanine.
Other FMs contained succinimide, \mbox{4-tertbutylcalix{[}6{]}arene},
and pentaethyleneglycol as recognizing sites. Each of the newly prepared
FM contained one recognition site. \vspace{1em}

\end{onehalfspace}

\noindent \emph{4-Bis(2,2'-bithiophen-5-yl)methylphenol}\textbf{~1}
(Scheme~\ref{syn1}). First, 2,2\textasciiacute -bithiophene (2.045
g, 12.3 mmol) and 4-hydroxybenzaldehyde (500 mg, 4.1 mmol) were mixed
with ethylene glycol (80 mL) and the mixture was stirred for 30 min
under N\textsubscript{2}. Then, 70\% HClO\textsubscript{4} (12 mL,
184.5 mmol) was added and the resulting solution was stirred for 16
h at 60 \textdegree C. Next, the reaction mixture was cooled to room
temperature and excess of methylene chloride was added in order to
dissolve the desired product. Subsequently, the mixture was treated
with the saturated solution of Na\textsubscript{2}CO\textsubscript{3}
to neutralize excess acid. The collected organic liquid layer was
washed with water and dried with anhydrous Na\textsubscript{2}SO\textsubscript{4}.
After evaporation of the organic layer solvent, a crude product was
purified by liquid chromatography on a silica gel column using the
hexane : CHCl\textsubscript{3} (1 : 1 to 1 : 9, \emph{v}\inputencoding{latin2}\foreignlanguage{polish}{~}\inputencoding{latin9}:\inputencoding{latin2}\foreignlanguage{polish}{~}\inputencoding{latin9}\emph{v})
eluent. Yield: 1.13 g (63\%). \textsuperscript{1}H NMR (CHCl\textsubscript{3}-d),
Fig.~\ref{fig:NMR 1}: ($\delta$ in ppm) 7.22\textendash 7.18 (d,
2H, bithiophene H), 7.16\textendash 7.13 (dd, 2H, bithiophene H),
7.08-7.06 (dd, 2H, bithiophene H), 7.00\textendash 6.97 (d, 2H, phenyl
H), 6.96-6.93 (dd, 2H, phenyl H), 6.83\textendash 6.79 (d, 2H, bithiophene
H), 6.77\textendash 6.75 (dd, 2H, bithiophene H), 5.68 (s, 1H, \textendash CH\textendash ).
Product molecular mass calcd.: 436.6.

\vspace{1em}


\begin{Scheme}
\centering

\includegraphics[width=15cm]{\string"obrazki/ChemSketch/synteza 1\string".png}

\caption{ Synthesis of 4-bis(2,2'-bithiophen-5-yl)methylphenol \textbf{1}. \protect{\label{syn1}}}
\end{Scheme}

\noindent \textit{4-Bis(2,2'-bithien-5-yl)methylphenol biotin ester}\textbf{~2}
(Scheme~\ref{syn2}). First, d-biotin\linebreak{}
(366 mg, 1.5 mmol) was dissolved in DMF (40 mL) and cooled to 0 \textdegree C
by keeping in an ice bath. Then, EDCI (466 mg, 3 mmol) was added and
the mixture stirred for \includegraphics[scale=0.18]{obrazki/tylda2}30
min under N\textsubscript{2}. Next, \textbf{\textit{\emph{1}}} (655mg,
1.5 mmol) dissolved in 20 mL of DMF was added dropwise for 10 min.
After that, the reaction mixture was stirred in an ice bath for 1
h. The reaction was continued for another 45 h at room temperature.
Then, the reaction solvent was evaporated under reduced pressure.
The residue was purified by lyquid chromatography on a silica gel
column using first the\linebreak{}
hexane : CHCl\textsubscript{3} (1 : 1 to 0 : 1, \emph{v} : \emph{v}),
and then CHCl\textsubscript{3}: MeOH (9 : 1, \emph{v} : \emph{v})
eluent. Yield: 110 mg (11\%). \textsuperscript{1}H NMR (CHCl\textsubscript{3}-d),
Fig.~\ref{fig:NMR 2}: \emph{\textgreek{d}} (in ppm) 7.36-7.32 (d,
2H, bithiophene H), 7.16-7.14 (dd, 2H, bithiophene H), 7.08-7.02 (m,
4H, overlapped bitiophene and phenyl H), 7.00-6.97 (d, 2H, phenyl
H), 6.96-6.92 (dd, 2H, bithiophene H), 6.74-6.70 (dd, 2H, bithiophene
H), 6.24 (s, 1H, biotin -NH-), 5.74 (s, 1H, -CH-) 5.62 (s, 1H, biotin
-NH-), 4.42-4.38 (m, 1H, biotin), 4.25-4.21 (m, 1H, biotin), 3.12-3.08
(q, 1H, biotin), 2.84-2.80 (dd, 1H, biotin), 2.68-2.64 (d, 1H, biotin
H), 2.58-2.52 (t, 2H, biotin H), 1.80-1.60 (m, 4H, biotin H), 1.52-1.45
(m, 2H, biotin H). ESI-MS \emph{m/z} calcd. for C\textsubscript{32}H\textsubscript{28}N\textsubscript{2}O\textsubscript{3}S\textsubscript{5}+2H\textsubscript{2}O:
684.9, found: 685.1 (Fig. \ref{fig:MS 2}).\vspace{1em}


\begin{Scheme}
\centering

\includegraphics[width=14.5cm]{\string"obrazki/ChemSketch/synteza 2\string".png}

\caption{ Synthesis of 4-bis(2,2'-bithien-5-yl)methylphenol biotin ester \textbf{2}. \protect{\label{syn2}}}
\end{Scheme}

\noindent \textit{4-(2-Hydroxyethoxy)benzaldehyde}\textbf{~3a} (Scheme~\ref{syn3}).
First, 4-hydroxybenzaldehyde (3 g, 24.6 mmol) was dissolved in acetone.
Then, K\textsubscript{2}CO\textsubscript{3} (20 g, 144.6 mmol) was
added and the mixture stirred for 30 min under N\textsubscript{2}.
Next, bromoethanol\linebreak{}
(5.22 mL, 73.7 mmol) was added dropwise and the resulting mixture
stirred for 20 h at 80 \textdegree C. After cooling at room temperature,
the reaction mixture was filtered and the filtrate solvent evaporated.
A yellow oily residue left was diluted with dichloromethane, and then
washed with water. The organic layer was dried with anhydrous Na\textsubscript{2}SO\textsubscript{4},
and then the solvent evaporated. A crude product left was purified
by liquid chromatography on a silica gel column using the CHCl\textsubscript{2}
: MeOH\linebreak{}
(100 : 0 to 95 : 5, \emph{v} : \emph{v}) eluent. Yield: 1.96g (48\%).
\textsuperscript{1}H NMR (CHCl\textsubscript{3}-d), Fig.~\ref{fig:NMR 3a}:
\emph{\textgreek{d}} (in ppm) 9.82 (s, 1H, CHO), 7.81-7.79 (d, 2H,
phenyl H), 7.04\textendash 6.98 (d, 2H, phenyl H), 4.16-4.10 (t, 2H,
-CH2-), 4.00-3.96 (t, 2H, -CH2-). Product molecular mass calcd.: 166.2.
\vspace{1em}


\noindent \textit{4-Bis(2,2'-bithien-5-yl)methylphenol glycol ether}\textbf{~3}
(Scheme~\ref{syn3}). First,\linebreak{}
2,2\textasciiacute -bithiophene (3.6 g, 21.7 mmol) and 4-(2-hydroxyethoxy)benzaldehyde
(1.44 g, 8.7 mmol) were mixed with ethylene glycol (120 mL), and then
the mixture was stirred for 30 min under N\textsubscript{2}. Next,
70\% HClO\textsubscript{4} (12 mL, 184.5 mmol) was added and the
resulting solution was stirred for 16 h at 60 \textdegree C. Afterwards,
the reaction mixture was cooled to room temperature and excess of
methylene chloride was added in order to dissolve the desired compound.
Subsequently, the mixture was treated with the saturated solution
of Na\textsubscript{2}CO\textsubscript{3} to neutralize excess acid.
The collected organic liquid layer was washed with water, and then
dried with anhydrous Na\textsubscript{2}SO\textsubscript{4}. After
solvent evaporation out of the organic layer, the compound was purified
by liquid chromatography on a silica gel column using the hexane :
CHCl\textsubscript{3} (1 : 1 to 0 : 1, \emph{v} : \emph{v}) eluent.
Yield: 1.13g (1.714 g, 41\%). \textsuperscript{1}H NMR (CHCl\textsubscript{3}-d),
Fig.~\ref{fig:NMR 3}: \emph{\textgreek{d}} (in ppm) 7.30\textendash 7.25
(d, 2H, bithiophene H), 7.18\textendash 7.14 (dd, 2H, bithiophene
H), 7.10-7.07 (dd, 2H, bithiophene H), 7.03-7.00 (d, 2H, phenyl H),
6.98-6.95 (dd, 2H, phenyl H), 6.92\textendash 6.88 (d, 2H, bithiophene
H), 6.77\textendash 6.74 (dd, 2H, bithiophene H), 5.71 (s, 1H, \textendash CH\textendash ),
4.08-4.04 (t, 2H, -CH2-), 3.96-3.92 (t, 2H, -CH2-). Product molecular
mass calcd.: 480.7.\vspace{1em}


\begin{Scheme}
\centering\includegraphics{\string"obrazki/ChemSketch/synteza 3a i 3\string".png}

\caption{ Syntheses of 4-(2-hydroxyethoxy)benzaldehyde \textbf{3a} and 4-bis(2,2'-bithien-5-yl)methylphenol glycol ether \textbf{3}. \protect{\label{syn3}}}
\end{Scheme}

\noindent \textit{4-Bis(2,2'-bithienyl)-(4-{[}2-tosyl{]}ethoxy)methane}\textbf{~4a}
(Scheme~\ref{syn4}). First, \textbf{3} (1.5 g, 3.12 mmol), 4-dimethyloaminopyridine
(19 mg, 0.16 mmol) and triethylamine\linebreak{}
(435 \textmu L, 3.12 mmol) were dissolved in dichloromethane, and
then stirred under N\textsubscript{2} for 1 h. Next, 4-methylbenzenesulfonyl
chloride (595 mg, 3.12 mmol) dissolved in dichloromethane was added
dropwise for 10 min. After that, the reaction mixture was stirred
for 16 h. Subsequently, the solvent was evaporated, and then the residue
was dissolved in CHCl\textsubscript{3} followed by washing with water,
and then the NaHCO\textsubscript{3} solution. Subsequently the organic
layer was dried with anhydrous Na\textsubscript{2}SO\textsubscript{4},
and then the solvent evaporated. The residue was purified by liquid
chromatography on a silica gel column using the hexane : CHCl\textsubscript{3}
(1 : 1 to 8 : 2, \emph{v} : \emph{v}) eluent. Yield: 1.37g (69\%).
\textsuperscript{1}H NMR (CHCl\textsubscript{3}-d), Fig.~\ref{fig:NMR 4a}:
\emph{\textgreek{d}} (in ppm) 7.85\textendash 7.80 (d, 2H, tosylate
phenyl H), 7.34\textendash 7.29 (d, 2H, tosylate phenyl H), 7.28-7.24
(d, 2H, bithiophene H), 7.18-7.14 (dd, 2H, bithiophne H), 7.12-7.08
(dd, 2H, bithiophene H), 7.04-7.00 (d, 2H, phenyl H), 6.98-6.94 (dd,
2H, phenyl H), 6.78\textendash 6.74 (dd, 2H, bithiophene H), 5.71
(s, 1H, \textendash CH\textendash ), 4.38-4.32 (t, 2H, -CH2-), 4.12-4.08
(t, 2H, -CH2-), 2.41 (s, 3H, tosylate -CH3). Product molecular mass
calcd.: 634.9.\vspace{1em}


\noindent \textit{4-Bis(2,2'-bithien-5-yl)methylphenol 2-O-(4-tertbutylcalix{[}6{]}arene)
ethoxyl ether~}\textbf{4} (Scheme~\ref{syn4}). First, 4-terbutylcalix{[}6{]}arene
(1.91 g, 2 mmol) was dissolved in DMF (80 mL). Then, K\textsubscript{2}CO\textsubscript{3}
(667 mg, 4.9 mmol) was added, and then the mixture was stirred under
N\textsubscript{2} for 1 h. Next, \textbf{4a} (308 mg, 0.49 mmol)
dissolved in DMF was added dropwise. After that, the reaction mixture
was heated to 60 \textdegree C and stirred for 48 h. Then, K\textsubscript{2}CO\textsubscript{3}
was filtered out, and then the filtrate solvent was evaporated under
reduced pressure. The resulting solid was purified by liquid chromatography
on a silica gel column using the hexane : CHCl\textsubscript{3} (9
: 1 to 1 : 1, \emph{v} : \emph{v}) eluent. Yield: 150 mg (21\%). \textsuperscript{1}H
NMR (CHCl\textsubscript{3}-d), Fig.~\ref{fig:NMR 4}: \emph{\textgreek{d}}
(in ppm) 9.89 (s, 2H, calixarene OH), 9.34 (s, 1H, calixarene OH),
9.03 (s, 2H, calixarene OH), 7.34\textendash 7.30 (d, 2H, bithiophene
H), 7.20\textendash 7.14 (m, 4H, bithiophene H overlapped with calixarene
phenyl H), 7.20-7.02 (dd, 4H, overlapped with calixarene phenyl H
H), 7.09-7.02 (m, 8, bithiophene H overlapped with calixarene phenyl
H), 6.99-6.96 (dd, 2H, phenyl H), 6.95\textendash 6.92 (d, 2H, phenyl
H), 6.73\textendash 6.70 (dd, 2H, bithiophene H), 5.72 (s, 1H, \textendash CH\textendash ),
4.60-4.49 (m, 6H, calixarene -CH2- overlapped with \textendash CH2-),
3.60-3.42(d, 2H, calixarene \textendash CH2-) 3.50-3.36 (m, 4H, calixarene-CH2-overlapped
with \textendash CH2-). ESI(-)-MS \emph{m/z} calcd. for C\textsubscript{91}H\textsubscript{104}O\textsubscript{7}S\textsubscript{4}:
1436.0, found: 1433.6 (Fig.~\ref{fig:MS 4}).\vspace{1em}


\begin{Scheme}

\centerline{\includegraphics[scale=0.8]{\string"obrazki/ChemSketch/synteza 4a i 4\string".png}}

\caption{ Syntheses of 4-bis(2,2'-bithienyl)-(4-[2-tosyl]ethoxy)methane \textbf{4a} and 4-bis(2,2'-bithien-5-yl)methylphenol 2-O-(4-tertbutylcalix[6]arene) ethoxyl ether \textbf{4}. \protect{\label{syn4}}}
\end{Scheme}

\noindent \textit{4-(2-Bromoethoxy)benzaldehyde}\textbf{~5a} (Scheme~\ref{syn5}).
First, 4-hydroxy\-benzaldehyde\linebreak{}
(5 g, 40.9 mmol) was dissolved in acetone. Next, K\textsubscript{2}CO\textsubscript{3}
(28 g, 202.5 mmol) was added, and then the mixture was stirred for
30 min under N\textsubscript{2}. Subsequently, dibromoethane (10.6
mL, 122.7 mmol) was added dropwise and the resulting mixture was stirred
for 20 h at 80 \textdegree C. After that, K\textsubscript{2}CO\textsubscript{3}
was filtered out, and then the filtrate solvent was evaporated. A
yellow oily residue left was diluted with dichloromethane, and then
washed with water in order to remove the K\textsubscript{2}CO\textsubscript{3}
residue. The organic layer was dried with anhydrous Na\textsubscript{2}SO\textsubscript{4},
and then evaporated. Finally, a crude compound was purified by liquid
chromatography on a silica gel column using the hexane : CHCl\textsubscript{3}
(1 : 1 to 8 : 2, \emph{v} : \emph{v}) eluent. Yield: 4.09 g (44\%).
\textsuperscript{1}H NMR (CHCl\textsubscript{3}-d), Fig.~\ref{fig:NMR 5a}:
\emph{\textgreek{d}} (in ppm) 9.89 (s, 1H, CHO), 7.86-7.80 (d, 2H,
phenyl H), 7.04\textendash 6.98 (d, 2H, phenyl H), 4.38-4.32 (t, 2H,
-CH2-), 3.68-3.60 (t, 2H, -CH2-). Product molecular mass calcd.: 228.2.

\vspace{1em}


\noindent \textit{4-Bis(2,2'-bithien-5-yl)methylphenol 2-bromoethyl
ether~}\textbf{5} (Scheme~\ref{syn5}). First,\linebreak{}
2,2\textasciiacute -bithiophene (1.63 g, 9.8 mmol) and \textbf{5a}
(753 mg, 3.3 mmol) were mixed with ethylene glycol (120 mL), and then
the mixture was stirred for 30 min under N\textsubscript{2}. Then,
70\% HClO\textsubscript{4} (8.6 mL, 132 mmol) was added and the resulting
solution was stirred for 16 h at 60 \textdegree C. Next, the reaction
mixture was cooled to room temperature and excess of methylene chloride
was added in order to dissolve the desired compound. Subsequently,
the mixture was treated with the saturated solution of Na\textsubscript{2}CO\textsubscript{3}
to neutralize excess acid. The collected organic liquid layer was
washed with water, and then dried with anhydrous Na\textsubscript{2}SO\textsubscript{4}.
After evaporation of the organic layer, the compound was purified
by liquid chromatography on a silica gel column using the hexane :
CHCl\textsubscript{3} (100 : 100 to 95 : 5, \emph{v} : \emph{v})
eluent. Yield:\linebreak{}
1.08 g (1.714 g, 60\%). \textsuperscript{1}H NMR (CHCl\textsubscript{3}-d),
Fig.~\ref{fig:NMR 5}: \emph{\textgreek{d}} (in ppm) 7.30\textendash 7.26
(d, 2H, bithiophene H), 7.20\textendash 7.16 (dd, 2H, bithiophene
H), 7.10-7.07 (dd, 2H, bithiophene H), 7.02-7.00 (d, 2H, phenyl H),
6.98-6.96 (dd, 2H, phenyl H), 6.90\textendash 6.86 (d, 2H, bithiophene
H), 6.76\textendash 6.72 (dd, 2H, bithiophene H), 5.71 (s, 1H, \textendash CH\textendash ),
4.30-4.26 (t, 2H, -CH2-), 3.64-3.60 (t, 2H, -CH2-). Product molecular
mass calcd.: 543.6.\vspace{1em}


\begin{Scheme}
\centering\includegraphics{\string"obrazki/ChemSketch/synteza 5a i 5\string".png}

\caption{ Syntheses of 4-(2-bromoethoxy)benzaldehyde \textbf{5a} and 4-bis(2,2'-bithien-5-yl)methylphenol 2-bromoethyl ether \textbf{5}. \protect{\label{syn5}}}
\end{Scheme}\selectlanguage{english}%

\end{document}