Synthesis of γ-arylmethylene-aminopropyl-3,7,10-trimethyl-silatrane derivatives and their activities of regulating plant growth

Article abstract of DOI:10.1080/10426507.2010.496747

Chemical Equation Presented Five novel γ-arylmethylene-aminopropyl-3, 7,10-trimethyl-silatrane derivatives and three novel γ-arylmethylene- aminopropyl-silatrane derivatives were synthesized, and their activities of regulating the plant growth in culture dishes were tested. The compounds showed good activities of regulating the root/stem growth on turnips of amphibrya and corns of dicotyledon at a concentration of 40 ppm. Moreover, the activities of two were stronger than that of brassinolide, the positive control, while those of the remainder were not obvious. The activities of regulating plant growth of derivatives with a methyl group on the ring were stronger than those of derivatives with no methyl substituent. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426507.2010.496747

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Synthesis of γ-Arylmethylene-
aminopropyl-3,7,10-trimethyl-silatrane
Derivatives and Their Activities of
Regulating Plant Growth
Yukun Lin a , Bo Song a , Anyue Han a , Suwen Hu a , Faqing Ye a
Zixin Xie a
&
a School of Pharmacy, Wenzhou Medical College, Zhejiang, Wenzhou,
China
Published online: 19 Feb 2011.
To cite this article: Yukun Lin , Bo Song , Anyue Han , Suwen Hu , Faqing Ye & Zixin Xie (2011):
Synthesis of γ-Arylmethylene-aminopropyl-3,7,10-trimethyl-silatrane Derivatives and Their Activities
of Regulating Plant Growth, Phosphorus, Sulfur, and Silicon and the Related Elements, 186:2, 298-303
To link to this article: http://dx.doi.org/10.1080/10426507.2010.496747
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Phosphorus, Sulfur, and Silicon, 186:298–303, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.496747
SYNTHESIS OF γ -ARYLMETHYLENE-AMINOPROPYL-
3,7,10-TRIMETHYL-SILATRANE DERIVATIVES AND THEIR
ACTIVITIES OF REGULATING PLANT GROWTH
Yukun Lin, Bo Song, Anyue Han, Suwen Hu, Faqing Ye,
and Zixin Xie
School of Pharmacy, Wenzhou Medical College, Zhejiang, Wenzhou, China
GRAPHICAL ABSTRACT
Abstract Five novel γ -arylmethylene-aminopropyl-3,7,10-trimethyl-silatrane derivatives and
three novel γ -arylmethylene-aminopropyl-silatrane derivatives were synthesized, and their
activities of regulating the plant growth in culture dishes were tested. The compounds showed
good activities of regulating the root/stem growth on turnips of amphibrya and corns of
dicotyledon at a concentration of 40 ppm. Moreover, the activities of two were stronger than
that of brassinolide, the positive control, while those of the remainder were not obvious. The
activities of regulating plant growth of derivatives with a methyl group on the ring were stronger
than those of derivatives with no methyl substituent.
Supplemental materials are available for this article. Go to the publisher’s online edition of
Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.
Keywords Amino; plant growth; regulation; silatrane
INTRODUCTION
1-Substituted-2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3.01.5] undecanes, named sila-
tranes, a type of cage-like silicoorganic compound (Figure 1), are attractive because of
their structures and notable bioactivities.1–6 Optimizing the substituted groups on the
silicon atom is currently an important trend,7–13 because the bioactivities of silatranes are
correlated with those groups closely. The silatranes have shown bioactivities of regulating
plant growth7–9,14–17 when the substituent group on the silicon is an alkyl or alkyl.
Moreover, the bioactivity is stronger and the toxicity is lower when the substituted group
Received 6 April 2010; accepted 23 May 2010.
This work was supported by the Natural Science Foundation of Zhejiang Province in China (No. Y204089)
and Wenzhou Medical College for financial support. The NMR, elemental analysis, and MS spectra were recorded
by the Analysis and Test Center of Wenzhou Medical College.
Address correspondence to Faqing Ye, School of Pharmacy, Wenzhou Medical College, Zhejiang, Wenzhou
325035, China. E-mail: yfq664340@163.com
298

SYNTHESIS OF SILATRANE DERIVATIVES
299
R1
R1
R1
N
N
R1
R1
R1
R1
ii. R-CHO
i. (HOCHCH2)3N
O
O
O
O
O
H2N(CH2)3Si(OC2H5)3
O
Si
Si
CH2CH2CH2N
C R
H
CH2CH2CH2NH2
6
8
4
11
5
N
7
10
3
O
O
9
O
2
Si
1
X
Figure 1 Silatrane.
is an alkyl with nitrogen, and there are three carbons between the silicon and nitrogen
atoms.10 The bioactivities of regulating plant growth are used widely. For example,
broad-spectrum plant growth regulators with silatranes as a main component have been
produced in batches as agricultural chemicals (trade name MV),9,18 and are well known for
their characteristics of high performance resulting in increased production, low toxicity,
easy biodegradation, and environmental friendliness.
In our previous study, some derivatives with a methyl group on the ring of
silatranes9,12,19,20 were synthesized and tested for their activities of regulating the plant
growth. γ -(N-p-Methylphenylsulfonyl)aminopropyl-3,7,10-trimethyl-2,8,9-trioxa-5-aza-
1-silabicyclo[3.3.3.01.5]undecane9 and γ -(3,4-dichlorobenzoyl)aminopropyl-3,7,10-
trimethyl-2,8,9-trioxa-5-aza-1-silabicyclo[3.3.3.01.5]undecane20 showed good activities
of regulating plant growth. Nevertheless, the true necessity of the methyl on the ring of
silatranes for their activities still needs to be investigated.
RESULTS AND DISCUSSION
γ -Aminopropyl silatrane and γ -aminopropyl-3,7,10-trimethyl-silatrane were ob-
tained through silylation reaction using triethanolamine, triisopropanolamine, and γ -
aminopropyl triethoxysilane.9 Then, a nucleophilic addition reaction occurred between
them and benzaidehyde with different substitute groups, to obtain eight silatrane deriva-
tives (3a–3h) (Scheme 1). All the structures of the derivatives were determined by IR, 1H
NMR, ESI-MS, and elemental analysis.
In this study, five novel derivatives (3a–3e) with a methyl group on the ring of
silatranes and three derivatives (3f–3h) with no methyl were synthesized and tested for
their activities on regulating the plant growth. The results showed that the activities of
derivatives (3a–3e) were significant, while those of 3f–3h were not (see the Supplemental
Materials and Table S1, available online). So, drawing the methyl on the ring could enhance
the activities of silatranes to promote plant growth in certain concentrations.
EXPERIMENTAL
Instruments and Reagents
Melting points were measured using an XRC-1 micro-melting point apparatus
and were uncorrected. IR spectra were obtained on a Nicolet 670FT-IR spectrometer
1
(KBr tabletting). MS was conducted using a Zabspec instrument. H NMR data were

300
Y. LIN ET AL.
H2N(CH2)3Si(OC2H5)3
R1
1.
2.
i. (HOCHCH2)3N
R1
N
R1
R1
O
O
O
Si
CH2CH2CH2NH2
benzene.
reflex.
ii. R-CHO
3.
R1
N
R1
R1
O
O
O
Si
CH2CH2CH2N
C R
H
-
3a: R1=CH3, R=2,4-MeO-C6H3
-
3b: R1=CH3, R=3,4-MeO-C6H3
-
3c: R1=CH3, R=2,4- Cl - C6H3
3d: R1=CH3, R=4- NO2 - C6H4-
-
3e: R1=CH3, R=3- NO2 - C6H4
-
3f: R1= H, R=2,4-MeO-C6H3
3g: R1= H, R=3,4-MeO-C6H3
3h: R1= H, R=2,5-MeO-C6H3
-
-
Scheme 1
recorded on a JEOL-AL-300FT spectrometer, and TMS was used as internal stan-
dard.Triisopropanolamine was purchased from Tianjin Xinda Chemical Engineering Com-
merce Limited Company. γ -Aminopropyl triethoxysilane was purchased from Hangzhou
Guibao Chemical Engineering Limited Company. Analytical pure reagents were used else-
where. Turnip seeds were obtained from Beijing Shinong Seedling Limited Company, and
corn seeds were obtained from Shandong Defa Seedling Science & Technology Company.
Brassinolide (trade name Tiansufeng) was bought from Jiangmen Daguangming Agricul-
ture and Chemical Limited Company. γ -Aminopropyl silatrane and γ -aminopropyl-3,7,10-
trimethyl-silatrane were prepared by the method described in the literature.9 The activity
test of regulating the plant growth was assayed by the method described in the literature.7
γ -(2,4-Methoxyl-benzylideneamino)propyl-3,7,10-trimethyl-2,8,9-
trioxa-5-aza-1-silabicyclo[3.3.3.01.5]undecane (3a)
γ -Aminopropyl-3,7,10-trimethyl-silatrane 2.74 g (0.01mol) was added to a stirred
solution of benzene(20 mL) and was dissolved, and then 2,4-dimethoxybenzaldehyde 1.66 g

SYNTHESIS OF SILATRANE DERIVATIVES
301
(0.01 mol) was added. A water separator was installed, and the mixture was stirred and
refluxed for 2 h. The benzene and water were removed under reduced pressure, and the
residue was recrystallized from benzene and ether to give the pure product in 45.6% yield;
1
yellow solid, mp 99.6–101.5◦C; IR (KBr) υ/cm−1: 579(N→Si), 1633(C N). H NMR
(400 MHz, CDCl3): δ 0.47 (m, 2H, CH2Si), 1.82 (m, 2H, CH2CH2Si),1.27–1.16 (m, 9H,
3 × OCHCH3), 3.59–2.15 (m, 8H, 4 × NCH2), 3.88–3.71 (m, 9H, 3 × OCHCH3+2 ×
OCH3), 8.57 (s, 1H, CH N), 7.92 (d, 1H, J = 8.62 Hz, Ph-H), 6.52 (d, 1H, J = 8.36
Hz, Ph-H), 6.42 (s, 1H, Ph-H). ESI-MS [M+H]+: m/z 423.3, 216, 173.7. Anal. Calcd. For
C21H34N2O5Si (422.59): C, 59.69; N, 8.11; H, 6.63; Found C, 59.86; N, 8.31; H, 6.70.
γ -(3,4-Methoxyl-benzylidene amino)propyl-3,7,10-trimethyl-2,8,9-
trioxa-5-aza-1-silabicyclo[3.3.3.01.5]undecane (3b)
This compound was obtained as yellow solid and in 47.8% yield; mp 81.1–82.5◦C.
IR (KBr) υ/cm−1: 586 (N→Si), 1643 (C N). 1H NMR (400 MHz, CDCl3): δ 0.44 (m, 2H,
CH2Si), 1.82 (m, 2H, CH2CH2Si), 1.26–1.14 (m, 9H, 3 × OCHCH3), 3.58–2.19 (m, 8H,
4 × NCH2), 3.94–3.68 (m, 9H, 3 × OCHCH3+2 × OCH3), 8.16 (s, 1H, CH N), 7.42 (s,
1H, Ph-H), 7.10 (d, 1H, J = 1.56Hz, Ph-H), 6.86 (d, 1H, J = 14.19 Hz, Ph-H). ESI-MS
[M+H]+: m/z 423.2, 215.8, 173.7. Anal. Calcd. for C21H34N2O5Si (422.59): C, 59.69; N,
8.11; H, 6.63; Found C, 59.84; N, 8.13; H, 6.65.
γ -(2,4-Dichloro-benzylidene amino) propyl-3,7,10-trimethyl-2,8,9-trioxa-
5-aza-1-silabicyclo[3.3.3.01.5]undecane (3c)
This compound was obtained as a yellow solid and in 50.4% yield; mp 111.9–113.2◦C.
IR (KBr) υ/cm−1: 573(N→Si), 1640(C N). 1H NMR (400 MHz, CDCl3): δ 0.48 (m, 2H,
CH2Si), 1.87 (m, 2H, CH2CH2Si), 1.27–1.15 (m, 9H,3 × OCHCH3), 3.91–2.20 (m, 8H, 4
× NCH2), 4.11 (m, 3H, 3 × OCHCH3), 8.61 (s,1H,CH N), 8.00 (d, 1H, J = 46Hz, Ph-H),
7.37 (d, 1H, Ph-H), 7.27 (d, 1H, J = 11.96 Hz, Ph-H). ESI-MS [M+H]+: m/z 431.4, 215.8,
173.7. Anal. Calcd. for C19H28Cl2N2O3Si (431.43): C, 52.89; N, 6.54; H, 6.49; Found C,
52.61; N, 6.67; H, 6.56.
γ -(4-Nitro-benzylidene amino)propyl-3,7,10-trimethyl-2,8,9-trioxa-5-
aza-1-silabicyclo[3.3.3.01.5]undecane (3d)
This compound was obtained as yellow solid and in 60.3% yield; mp 109.6–110.2◦C.
IR(KBr) υ/cm−1: 553 (N→Si), 1642 (C N). 1H NMR (400 MHz, CDCl3): δ 0.46 (m 2H,
CH2Si), 1.87 (m, 2H, CH2CH2Si), 1.26–1.16 (m, 9H, 3 × OCHCH3), 3.69–2.21 (m, 8H, 4
× NCH2), 4.11–3.87 (m, 3H, 3 × OCHCH3), 8.34 (s, 1H, CH N), 8.12(d, 2H, J = 7.64Hz,
Ph-H),7.98 (d, 2H, J = 7.46 Hz, Ph-H). ESI-MS [M+H]+: m/z 408.2, 215.8, 173.7. Anal.
Calcd. for C19H29N3O5Si (407.54): C, 56.00; N, 7.17; H, 10.31; Found C, 56.23; N, 7.32;
H, 10.20.
γ -(3-Nitro-benzylidene amino)propyl-3,7,10-trimethyl-2,8,9-trioxa-5-
aza-1-silabicyclo[3.3.3.01.5]undecane (3e)
This compound was obtained as yellow solid and in 53.4% yield; mp 97.1–98.4◦C.
IR (KBr) υ/cm−1: 546 (N→Si), 1648 (C N). 1H NMR (400 MHz CDCl3): δ 0.47 (m, 2H,

302
Y. LIN ET AL.
CH2Si), 1.89 (m, 2H, CH2CH2Si), 1.27–1.16 (m, 9H, 3 × OCHCH3), 3.70–2.21 (m, 8H, 4
× NCH2), 4.12–3.88 (m, 3H, 3 × OCHCH3), 8.55 (s,1H,CH N), 8.33(s, 1H, Ph-H), 8.25
(d, 1H, J = 8.11Hz, Ph-H), 8.09 (d, 1H, J = 7.70Hz, Ph-H), 7.60 (t, 1H, J = 7.90Hz, Ph-H).
ESI-MS [M+H]+: m/z 408.6, 215.8, 173.7. Anal. Calcd. for C19H29N3O5Si (407.54): C,
56.00; N, 7.17; H, 10.31; Found C, 56.15; N, 7.22; H, 10.20.
γ -(2,4-Methoxyl-benzylidene amino) propyl-2,8,9-trioxa-5-aza-1-
silabicyclo[3.3.3.01.5]undecane (3f)
γ -Aminopropyl-silatrane (2.32 g, 0.01 mol) was added to a stirred solution of benzene
and dissolved, then 2,4–2-methoxybenzaldehyde (1.66 g, 0.01 mol) was added. The water
separator was installed, and the mixture was stirred and refluxed for 2 h. The benzene and
water were removed under reduced pressure, and residue was recrystallized from benzene
and ether to give yellow crystals in 46.7% yield; mp 124.8–125.7◦C; IR (KBr) υ/cm−1
:
583 (N→Si), 1636 (C N). 1H NMR (400 MHz CDCl3): δ 0.46 (m, 2H, CH2Si), 1.80 (m,
2H, CH2CH2Si), 3.59 (t, 2H, = NCH2), 2.81 (m, 6H, 3 × NCH2), 3.82–3.71 (m, 12H, 3 ×
OCH2+2 × OCH3), 8.56 (s, 1H, CH N), 7.90 (d, 1H, J = 8.69Hz, Ph-H), 6.50 (d, 1H, J
= 8.61Hz, Ph-H), 6.41 (d, 1H, Ph-H). ESI-MS [M+H]+ : m/z 381.2, 173.7, 129.7. Anal.
Calcd. for C18H28N2O5Si (380.51): C, 56.82; N, 7.42; H, 7.36; Found C, 56.94; N, 7.63;
H, 7.14.
γ -(3,4-Methoxyl-benzylidene amino) propyl-2,8,9-trioxa-5-aza-1-
silabicyclo[3.3.3.01.5]undecane (3g)
This compound was obtained as yellow crystals and in 64.3% yield; mp
1
135.0∼136.4◦C. IR (KBr) υ/cm−1: 578 (N→Si), 1638 (C N). H NMR (400 MHz
CDCl3): δ 0.47 (m, 2H, CH2Si), 1.75 (m, 2H, CH2CH2Si), 3.54 (t, 2H, = NCH2), 2.81 (m,
6H, 3 × NCH2), 3.82–3.74 (m, 12H, 3 × OCH+2 × OCH3), 8.19 (s,1H,CH N), 7.38 (s,
1H, Ph-H), 7.06 (d, 1H, J = 1.54Hz, Ph-H), 6.83 (d, 1H, J = 14.22Hz, Ph-H). ESI-MS
[M+H]+ : m/z 381.2, 173.7, 173.7. Anal. Calcd. for C18H28N2O5Si (380.51): C, 56.82; N,
7.42; H, 7.36; Found C, 56.94; N, 7.46; H, 7.29.
γ -(2,5-Methoxyl-benzylidene amino) propyl-2,8,9-trioxa-5-aza-1-
silabicyclo[3.3.3.01.5]undecane (3h)
This compound was obtained as yellow crystals and in 52.3% yield; mp
123.4∼124.7◦C. IR (KBr) υ/cm−1: 581(N→Si), 1639(C N). 1H NMR (400 MHz
CDCl3): δ 0.47 (m, 2H, CH2Si), 1.82 (m, 2H, CH2CH2Si), 3.64 (t, 2H, = NCH2), 2.81 (m,
6H, 3 × NCH2), 3.81–3.74 (m, 12H, 3 × OCH2+2 × OCH3), 8.63 (s, 1H, CH N), 7.50
(d, 1H, J = 2.90, Ph-H), 6.90 (d, 1H, J = 13.96Hz, Ph-H), 6.89 (d, 1H, J = 25.84Hz,Ph-H).
ESI-MS [M+H]+ : m/z 381.2, 173.7, 129.7. Anal. Calcd. for C18H28N2O5Si (380.51): C,
56.82; N, 7.42; H, 7.36; Found C, 56.98; N, 7.58; H, 7.21.
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