Jing Huang et al. / Chinese Journal of Catalysis 37 (2016) 1539–1548
1541
copolymer (PS‐PVPA)
Found:
C
69.16%,
H
5.45%,
N
7.26%; Calc. for
1‐Phenylvinyl phosphonic acid (PVPA) was synthesized ac‐
cording to the literature [35]. Its structure was confirmed by 1H
NMR, 31P NMR and FT‐IR. H NMR (CDCl3): δ = 6.06 (d, 1H),
C
176H169N16O11P3Na2Zn3: C 70.05%, H 5.61%, N 7.43%. 3d,
Found: 57.36%, 6.85%, 8.93%; Calc. for
C92H133N12O11P3Na2Zn3: C 57.58%, H 6.93%, N 9.01%. 3e,
C
H
N
1
6.23 (d, 1H), 7.26–7.33 (m, 3H), 7.48 (m, 2H). 31P NMR
(CD3OD): δ = 15.9. IR (KBr): ν = 2710, 2240, 1500, 1200, 1040,
950, 780, 720, 700 cm–1. Yield: 90%.
Found:
C
59.01%,
H
7.23%,
N
8.45%; Calc. for
C100H149N12O11P3Na2Zn3: C 59.12%, H 7.33%, N 8.52%. 3f,
Found:
C
60.27%,
H
7.58%,
N
7.95%; Calc. for
1‐Phenylvinyl phosphonic acid (4 g, 21.7 mmol), styrene (20
mL, 173.9 mmol), ethyl acetate (150 mL) and benzoyl peroxide
(BPO, 1.0 g, 4.7 mmol) were used for the preparation of
PS‐PVPA (7.52 g in 47% yield) as reported in the literature
[29]. GPC: Mn = 39700, m = 38.3, n = 8.2, Mw/Mn = 2.
C
108H165N12O11P3Na2Zn3: C 60.51%, H 7.69%, N 8.08%. 3g,
Found: 62.73%, 8.25%, 7.26%; Calc. for
124H197N12O11P3Na2Zn3: C 62.89%, H 8.32%, N 7.31%.
C
H
N
C
2.3. Synthesis of chiral salen Mn(III) catalyst anchored on
ZnAMPS‐PVPA (4)
2.2.2. Synthesis of zinc poly(styrenephenylvinylphosphonate)‐
phosphate (ZnPS‐PVPA, 1)
Chiral salen Mn(III) (4 mmol) in 10 mL of THF was added
dropwise to the solution of 3a (0.5 g) pre‐swelled in THF for 30
min and Et3N (5 mmol) with stirring. Then the mixture was
refluxed for 10 h, followed by neutralizing and evaporating. The
dark brown powder 4a was obtained by filtration and washing.
Samples 4(b–c) were obtained by the same process. For sam‐
ples 4(d–g), chiral salen Mn(III) (4 mmol) in 10 mL of THF was
added dropwise to the solution of 3a (0.5 g) pre‐swelled in THF
for 30 min and Et3N (5 mmol) with stirring. Then the mixture
was refluxed for 10 h. After cooling down, the solution was
neutralized and the solvent was evaporated. The dark brown
powder 4a was obtained by filtration and washed thoroughly
with CH2Cl2 and deionized water respectively until no Mn could
be detected by AAS. 4a, Found: C 70.16%, H 7.21%, N 3.05%;
Calc. for C416H545N32O27P3Na2Zn3Mn8: C 71.65%, H 7.82%, N
3.22%. 4b, Found: C 69.15%, H 7.01%, N 2.91%; Calc. for
PS‐PVPA (1.0 g, 1 mmol), sodium dihydrogen phosphate
(0.62 g, 4 mmol), zinc acetate (1.1 g, 5 mmol) and Et3N (0.68 g,
6.7 mmol) were used for the synthesis of ZnPS‐PVPA according
to the literature [30]. IR (KBr): ν = 3059, 3028, 2923 (CH),
1686, 1493, 1453, 756, 698 (–C6H5), 1027 (P=O) cm–1. Found: C
58.08%, H 4.97%; Calc. for C72H73O11P3 Na2Zn3: C 59.71%, H
5.04%.
2.2.3. Synthesis of chloromethyl‐zinc poly (styrene‐phenylvinyl‐
phosphonate)‐phosphate (ZnCMPS‐PVPA, 2)
Chloromethyl methyl ether (9.3 mL), anhydrous zinc chlo‐
ride (3.32 g, 24.34 mmol) and ZnPS‐PVPA (5.0 g, 3.4 mmol)
were mixed in 40 mL chloroform and stirred at 40 °C for 10 h.
Then, sodium carbonate saturated solution was added to neu‐
tralize the mixture. The solvent was evaporated under reduced
pressure, followed by filtering, washing and drying in vacuo to
obtain ZnCMPS‐PVPA (5.84 g, 90.1%). IR (KBr): ν = 3026, 2925
(CH), 2341(O=P–OH), 1650, 1542, 1510, 1493 (–C6H5), 1267
(P=O), 700 (C–Cl) cm−1. Found: C 51.16%, H 4.09%; Calc. for
C80H81O11P3Cl8Na2Zn3 : C 52.31%, H 4.41%.
C416H545N32O27P3Na2Zn3Mn8: C 71.65%, H 7.82%, N 3.22%. 4c,
Found: C 70.17%, H 7.25%, N 5.26%; Calc. for C464H577N32O27P3‐
Na2Zn3Mn8: C 71.39%, H 7.40%, N 5.74%. 4d, Found: C 67.91%,
H 7.93%, N 5.86%; C380H541N28O27P3Na2Zn3Mn8: C 68.03%, H
8.07%, N 5.93%. 4e, Found: C 68.26%, H 8.06%, N 5.74%; Calc.
for C388H557N28O27P3Na2Zn3 Mn8: C 68.32%, H 8.17%, N 5.83%.
2.2.4. Synthesis of aminomethyl‐zinc poly(styrene‐phenylvinyl‐
phosphonate)‐phosphate (ZnAMPS‐PVPA, 3)
4f, Found:
396H573N28O27P3Na2Zn3Mn8: C 68.60%, H 8.27%, N 5.73%. 4g,
Found: 69.02%, 8.37%, 5.48%; Calc. for
412H605N28O27P3Na2Zn3Mn8: C 69.14%, H 8.46%, N 5.55%.
C 68.52%, H 8.16%, N 5.62%; Calc. for
C
A proportional amount of m‐phenylenediamine was blend‐
ed with 2 (1 g), Na2CO3 (1.06 g, 0.01 mol), and alcohol 50 mL
(the molar ratio of alkyl diamine to chlorine element in 2 is
5:1). After the mixture was stirred and kept at 70 °C for 12 h,
the product 3a was filtered, washed, and dried in vacuo. The
product 3(b–g) was obtained by a similar course. The products
were abbreviated as 3(a–g). 3a, Found: C 62.16%, H 5.21%, N
9.16%; Calc. for C128H137N16O11P3Na2Zn3: C 63.81%, H 5.69%, N
9.31%. 3b, Found: C 61.15%, H 5.02%, N 9.05%; Calc. for
C
H
N
C
2.4. Synthesis of alkyldiamino‐modified chiral salen Mn(III)
(Scheme 2)
p‐phenylenediamine (20 mmol) and Na2CO3 (0.848 g, 8
mmol) were blended with benzyl bromide at 70 °C for 6 h to
gain compound 5a. The subsequent procedure was similar to
that used for the heterogeneous catalyst (in Section 2.3). 6a, IR
C128H137N16O11P3Na2Zn3: C 63.81%, H 5.69%, N 9.31%. 3c,
Br
salen Mn(III)
THF, Et3N
RH
N
O
N
O
CH3CH2OH
Mn
R
t-Bu
t-Bu
5
t-Bu
5a: R = p-NHPhNH-
5b: R = -NH(CH2)6NH-
t-Bu
6a: R = p-NHPhNH-
6b: R = -NH(CH2)6NH-
6
Scheme 2. Synthesis of the homogeneous catalysts.