有机化学 YOUJI H【 XuE 1 991,JJ,470~476,拜竟论支
冠醚化=苯甲酮的合成及其光物理行为
黄 枢‘、袁立半,田宝芝,蒋耀武 (四川大学化学系,四J1l,成都,910094)
擅要 本文报道采用在多聚磷酸中酰化的方法,台成了冠醚化二苯甲酮 1~8。它们与叔胺类共用可能被用作光
引发剂.为此.用紫外光谱详细研究了这些化台物及其络台后的光物理行为。还提及化台物5和4作为紫外吸收
剂的可能性
●一t二甲苯酮类,冠醚,合成,多聚磷酸.紫外光谱
Synthesis and hotophysical Belmv/our of Crowned Benzophenones
HUANG Shu*,YUAN Li-Hua, TIAN Bao-Zhi, JIANG Yao-W u
(Department 0J Chemi.~ry,Sichuan UriC'PerjUry,510054 C~ sdu.Sic,l“∞ )
AbstractI A series of crowned benzophenones (1~ 2 and 5~0) which may be applied as
co-photoinitiators together with tertiary amines.have been synthesized by acylation in PPA .
A detailed inveStigation On the photophysical behaviour of these con~rotJnLs and their cote-
plexation by means of UV spectra has be en carried out.The potential of 8 and 4 as UV
absorbers is al8o mentioned.
Descriptor: benzophenones,crown ether,synthesis.PPA·UV spectra
Introduction
It is well known tha t the incorpora-
tion of the structure of crown ethers into
some photoactivc molecules results in SOLB1~
new mesnin#ul characteristics[ ’ .Benzo-
phenone and its derivatives are photoactive
compounds,which ha ve been employed B矗
co--initiatots together with terttary m ines
for photopolymerization (e--s].A1K,.benzo-
phcnones with ortho ydroxyl Sron p6 are
applied a8 UV absorbe rs[”. The modified
be nzophenone with the crown structure is
expected to show unique photophysical and
photochemical he ha vtoues .Thus the
,
following crowned benzophenones and their
substituted derivatives l to 8 are designed.
Tlte acylation waS performed PPA
with prope.r acyl esrboxylic acid or 4t-ben-
1 R|=H,Rj=I-I; 2 RI=H.R =OCI.L,;
5 R|=OH,RI;OH;4 Rl=OH,R’ OCt;
5 Rt=H,RI:Cl;6 R‘=CI,R|=H
zocrdwn carboxylic acid and benzocrown
l990年10月24El收稿,1991年 1月20日修厕-
The project is supported by National Natural
Science Foundation of China.
f
一一一 ⋯~———]l盯 ⋯
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第5期 冠醚化二苯甲酮的合成及其光物理行为 47I
ether or meta—substituted phenol as starting
n~terials.But it was noted that 4 .(4 .
chlorobenzoy1) benzo-15-crown.5 (B)could
not be obtained in this way because of the
insolubility of p-chlorobenzuic acid in PPA.
~veil with the temperature over 120℃ at
which benzo-15-crown-5 bcgail to deeu m~
.
W Ith the improved method. where the
mixed anhydride of p-ohIorobenzoic acid
and PPA was formed at first from the
acyl chloride end then reacted with be n~o-15-
crown。5-the desired product 6 waS obtain-
ed.
The examination of photophysical be_
hayioues of these crowned benzopheDones
by UV spectra disclosed the relationship be-
1wecn their structures en d performances.
Experimental
PPA was prepared according to litera-
turet 7】.M elttng points were not corrected .
All of the samples for analysis Nvere sub-
jected to drying in vaccUm. UV spectra
w deretrained with Shimsdzu UV-240
spectro photometer .IR spectra were recorded
oll NICO ET FI'_IR 17O SX spectrometer.
with J【Br disks. H NM R were taken oil
JEOL-FX 90 Q spectrometer using TMS as
internal standard.M.s were obtained with
Finnigan--MAT 4510 oc/MS spectrometer.
Geneeal Procedures for the synthesis of
Crowned Benzophenonas
In a three=necked .round-bottomed flask
equipped with a mechanical stirrer and a
Cat12 drying tube we re mixed benzocrown
ether (or meta-substituted pheno1) and
a 5 excess of po wdered aryl carboxylic
acid or (4 -benzo-15-crown-5)carborylic
acid.5 to 10 times weight of PPA was ad-
ded and the mixture was sttrred to a homo-
geneous slurry.The flask was hllmcesed in
an oil bath.and the reaction proceeded with
batch asitatioil.W hen the mixture turn-
ed to a dark red or brOWUish red viscous
liquid.a drop of the reaetioll mixture was
taken to disso lve in water and extracted
with chlorofom .The disappe arance of the
benzocrown ether or its carboxylic d~ va-
tive by TLC aSSay [chloroform/ether/ace-
tone(1:1:1.v/v)as the eluent] sin~mais
the completion of the acylation. eoll-
tent WaS sl培htly cooled. and Water WaS
added to df。ct the hydrolysis of PpA.Af·
ter cooling.the mixture was extracted,3 to
4 times with an appropriste amount of chlo-
r0form. The combined extract was washed
with 5 aqueous solution of NaHCO~en d
deiontzed water successively until neutra1.
and dried over anhydrous Na2SO,.
The further treatment of the chiofram
extract is performed in either of the follow·
ing tWO ways;(A)Remove the chio~ro-
form and recrystallize from proper solvent
if the extract eontains only a few 。o1‘,rcd
impurities.And otherwise.(B)the extract
is concentrated en d chronmtosraphe d wi th
silica ge1. collected eluent was then re-
cryatallized.
Unless stated otherwise all crowned
benzophenones are prepared wit拄 the abovQ
general procedures.
4 Benzoylbenzo-I5-erown-5(I)
A mixture of benzoic acid. be nzo-15-
cro wn-5 and PPA was heated at 90℃ for
80 rain. chloroform extra ct was treated
in light of (A). Thc crude prO dUct wall
dissolved in a small amount of hot meth-
ailol and the sm utioIl waS allowed to staild
for a while to form a yellow sol1d.Reery—
stallization two times from methanol afford—
ed a white solid. yield 67%.m.P.103.5
~ l05℃ (103.5~ 104.5℃ 【 】).
4 一 (● -Meflmxyhen~oyi)benze-I|-crown-~
(2)
A mixture of 4-methorybenzoic acid,
benzo-15一crown-5 and PPA was heated at
90℃ for 1 h.The extract was treated ac~o-
rdin g t0 (B).The resulting orange yellow
crude product was reerystallized with me—
thanoI and the n with ether to give a white
powder yield 65 t m .P.98"C cl2H¨07t
Caled ~:Ct 65.66|H.6.51.Found:C.66,O7|
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472 有 机 化 学 1991楚
H,6.75. v⋯ :2929 2873, 1459(c ),
1629(C—o).1599,1512(ArH).1273,1134。
IO5 (C— —C)cm~. (CDC1 ): 3.82~
4.15(19 H-m,OCH2CH2O,OCHs),6.8O~
7.68(7 H,m,ArH)ppm.m/z:403(M +1.
20%),135(199).
4 -(2 .4 -Dihydroxybenzoy1)benzo-1 5-cro-
wn-5 (8)
A mixture of (4/-benzo-16-crown-5)
ea rboxylic aeid. resoreinol and P队 was
heated at 50℃ for 1h and treated accord-
ing to (B)with chloroform~ether/acetone
(1:1:1,v/v)as elucnt.Atier recrystalliza.
tion from ether or acetone a white po wder
was obtained,yield 43 。m .p.84℃ .C2l—
H:‘ .Calcd.;C.62.37;H,5
. 98.Found:
C, B2.O1; H 6. 10. v⋯ : 3442(oH)
2933,2872,1443(CH2)一1730,1883 (C— o),
1600,1518(ArH).1277。1255.1206(Ar— o—
C)·1129,1052(C一 0~ C)cm_。.6H(CDCI,):
1.4O (1H,s,2 -OH),2.43(1H, s,4#-
OH) 3.80~ 4.17(16 H,m, OCH2CH:o),
6.2O~ 6.9O一7.50 (6 H, m, ArH) ppm.
州 z:405(M +1,19 ) l80(109),
4t-(2 ·Hydroxy一4 -methoxybenzoy1) be~,to-
15~crown-~ (4)
A mixture of (4 - nzo-15-crown-j)
carboxylic acid m-methoxyphenol and
PPA waS heated at 70℃ for 2.5 Ii.FoHow—
ing (B) with chloroforrn/acetone/pctro-
leum ether(1:1:1.5 v/v)as eluent gave
the crude product. Rccrystallization fro m
ether/p~troleum ether twice afforded a white
crystal yield 26 一m . P. 1O2~ 1OCC.
c:: I .Calcd.:c,63
. 15j H,6.26.Found:
C, 63.28}H , 6
. 41.v⋯ :3435。9409(OH)
2925.2898,1428(CHz).1637(C=o),1589
1511(ArH),1274,1206(Ar_一。一C),l163,
1053(c一0_.c)锄 _。.6H(CDC13);1.88(1 H,
s,OH),3.8O~ 4.16(19 H,m , OCHzCH2O,
OCHs). 6. 0~ 7.53(6 H,m,Ar-H) ppm.
re~z:418(M ,109 ),151(28).
An alternative way,where the acyla-
tion proceed ed directly with 2-hydroxT--4--
mvthoxybenzoic acid and benzo-15-crown-5
only afforOxl the desired product in very
poor yield although much higher 蕾mperB—
ture had beeft exerted.This was considered
to be due to the existence of strong ~ydxo-
gen bonding in the ortho-hydroxy substl-
tuted benzo~ acid and side reactions stem-
reed from iotermolecular condensation of
phenolic acids.
The m onomethylation of compound 8
in the alcoh~ol salution of NaoH by fl~lc-
tion with dimethyl sulfate also provi~
.
co mpound 4 yield 18 . m . P. 1O2~
104℃ .
4 - ● -Chlorob~nzoy1)benzo-1 5-crown-e t5)
Here the acyl chloride is used instead
of ts-chl orol~enzoic aeid for the acylation
of ben zo-15-Cm wn-5. ,
A mixture of p-chlorobenzoyl chloride
(2.1 12mmo1) and PPA (40g) was
heated with stirring at 95℃ until the cvo-
lmion of hydrogen ch1oride ceased and the
solid dissolved . Then benzo-15-crowm-.~
(2.68 g, 10 mmo1)was added,followed by
stirring at 120℃ for an addidonal 2 h.Pu-
riflcation folin wing (B) and re~rystalltza-
rion twice from methanol gave a white so-
lid yield 10%.m.P.119~12O℃ CtIHzr
C lOs,Calcd. C 61.99}H,5.70. Fotmd~ -
C 62.24l H,5.53.Vmaz:2929,2879(CHt)
1642(C=ffiO),1592,1514(ArH),1276,1228
(Ar— o—C),1138,1955(C—o—C)a瞳『 - ,
6丑(cDc1 ):3.80~4.33(16H,m,oc a 0一
).6.8O~7.80(7 H,m,Ar-H)ppm.re~I;
496(M ,49 ), 163(190).
4 一(2 ·Chlorobenzoy1)beuzo-l&crown-~ ‘●)
A mixt u~ of 2-chlorohe nzoic icid.
be nzo.15.of.own~5 and PPA 'Was heated at
95℃ for 2 h.The salne work--up as that
of 5 gave a White solid.yield 59%.m·P.
儿 4~ 儿 5℃ .C2lH2 aCl ,Calcd-;C,01.99;
H.5.7O.Found:C,61.81; H ,5.79. Vm,x:
2941,2880,1431(CH2),1649(C— o).1590
1515(ArH),1281。1239(A —o—C),1132,
1052(C—o—C)cm_。.6H(CDCI3){ 3.16—一
4.23(16H,m,OCHzCHzO),6.70~ 7.50(TH,
m。Ar-H)ppm.m/2:496(M ,30 ),l63
(190).
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第 5期 冠醚化二苯甲酮的台成及其光物理行为 473
Bls(4t.benzo-1 5-crown一5)phenone (7)
A mixture of (4'-benzo-15-crown-5)
carboxylic acidt”。 benzo-16-crown-5 and
PPA waB heated at 9O~C for 80m fn.Trva-
tment after (B) and recrystallization twice
from acetone afforded a white crysta1.
Ticld 36 ,m.P.143~ 144℃ . C2日 $0ll。
Caled .c C,61. 91;H ,S.81.Found:C,61.73;
H , 6.7O.v⋯ : 2929,2869, 1432 (c ),
1644(C一 0),1596,1514(ArH), 1269,1206
(Ar一 0一 C),1 130,1931(C一 0一 C)cm_。.
6H(CDCl3):3.77~ 4.20(32 H,m,OCH2一
CH20), 6.8l~ 7.38(G H,m,Ar-H) ppm .
re~z:562(M ,lOO ),298(16),1 63(62).
4 ,4"-Dlbenzoyldibenzo-1 g-crown-6 (8)
A mixture of benzoic zeid,diben zo-16-
crown-6 and PPA was h~ ted at 90℃ for
1.5 h.Treating the extract following (B)
and rccrystallizing twice from acetone gave
a white cry stal,yield 92 , m. P. 182~
201℃ (184~ 186℃ f邶】, tr~/t typc; I78~
】84℃,ci导一type:197~ l98℃ ).C。‘ 2q ,
Calcd.:C,71.82;H ,5.67.Found:C,71.41;
H ,5.82.v⋯ :3084,2979,2929,1425(c ),
1651(C一0),1596,1512 (ArH), 1273,
1223(Az—o— C)。1132,1058(C— o )cm~.
m/新 569(M +1,63 ),105(100).
Results and Discussion
Sub~titutimt“feet on In,speetta
A systematic investigation of t如 UV
characteristics of crowned be nzopbe noncs
(CBPs,1 to 8) in four solvents with
a variety of polarities was ma出 .1 and
2【’ ,which H口 e previously I of似 l tObe
used in initiating po lymerization together
with bcnzophcnone (BP)Il 0, ‘1,were Chosen
for comparison.Thc resuhs are listed in
Tablc 1.
Table 1. IⅣ ab~orha nce of CBP in various solvents
Solvent Toluene 1,4-Dioxane 1,2-Dichlotoethane Methano1
Compounnd (^nm) Ig e (^nm)lg e k(nm) lg e (^nm)lg e
BP 287.0 3.35 256.0 4.14 251.8 4.28 251.4 4.25
345 2.14a 330b 2。26b
1 253.0 4.O5 238.2 4.47 237.0 4。21
286.8 3.89 280。0 4.O7 . 280.2 281.4 3.98
311.6 3.94 310。2 309.0 3.98 312.2 4。00
2 254.4 4.91 - 231.8 4.30 228.0 4.25
28 .2 4.22 283.0 4.26 285.6 4.27 290。8 4.26
335.0 4.20 332.4 334.4 4.14 332.8
5 247.4 3.96 230.4 4.17
288.2 284.8 4。08 283.0 4.07 291.2 4.05
334.2 331.4 4.05 332.4 4.02 333.8 4。08
4 247.0 4.05 238.2 4。15
288.6 4.12 285.O 4.16 287,8 4。07 287.4 4。12
335.0 4.2O 332.4 4。18 334.4 4.14 332。8 4.15
5 242.0 4.22 J 242.B 4.20 240.2 4.24
283.8 3.8 280.8 3.09 1 280.9 4.01 280.4 4.05
315.8 3.86 313.9 3.96 J 314,3 3.98 314.2 4.03
B 235.0 4.25 i 235.1 4.24 234.1 4.2B
281.8 4.06 282.5 4.O6 282.7 4.09
319.9 3.81 313.6 4.0l f 313.9 4.03 314.9 4.06
7 245.4 4.02 l 235.B 4.36 233.8 4.37 ·
283.2 279.6 4.13 J 280。6 4.08 280.0
312.4 4.19 312.2 4.22 l 3l3。0 4.18 315.2 4.21
8 285.0 280.0 4.27 l c
312.4 4.14 310.8 4.24 l
a.solventl benzene. b.solvent:ethano1. c. insoluble in l。2-dichlorocthane and methanol
As a typical photosensitizer, the lo-
west exited triplet (T) of BP belongs to
n— tYpe,which is characteristic of lower
value of e and the blue shift on goingflx)m
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‘ 有 机 化 学 1991燕
a nonpolar to a more polar solventt1 ”.
It is noteworthy for CBPs that the pres.
en∞ of crown ether inBP attenuatesth ein·
fluence of solvents upon the blue shift Of
n·丌‘ transitions. For instance. a change
from nonpoler to polat solvent brings ab.
out a Muc ahin l5 nm forBP but一0.6
nm for 1,2.2 nm for 2 and 0.4 nm for 8.
啦 trend is further embodied in biscrown
ed BlP 7,in which a red shift of 2.8蛐
in more poler solvents is obe erved (Table
1 & Fig 1).Obviously, the introduction
of Clown ether ring and/or subetituents
协 BP exerts Some effect on the mode of
clectron ttansiti0ns.This maY be reasona·
ble in view of the varied reletire energy
levels between the moleculer orbitale,i.e..
the transfer of n丌— 丌’in the case of CBP
occurs more efficiently. A com parison of
the UV spectra of 2。3 and 4 (with elcc·
tron-donating substituents on benzene ring)
with 1。7 and B (without sube titucm on
benzene ring) in the same solven t shows
that hydroxy and methoxy groups are in·
eltned to shift th en.丌‘bends t0longer wa-
velens~ .but have lnne effeet on ~-,Jr·.
More localized conjugation of these subeti-
tuents with be nzene ring may be responsi-
(^mn,
IⅣ Spectra of Crowned Ben-
Ⅻ he∞ m I
bls for the above d fcrence fn呵 red shi-
ft).It ca n be seen tha t in contrast with
BP.both polar solvents and elee tron-dona-
tins aubstituents in CBPs result in red shi-
fting of UV abe orption. For CBPs with
ch1Orinc as the substituent. p_chlor o sub-
stituted aBP 5 shows 8 smaller blue shift
(1.6 nm) than the o-substituted counterpe rt
0 (5.0rim).This may bc reaSonable 'm
terms of electronic effects indueed by the
sube tituen t.
Resesrches on aryl kctones demonstrate
tha t the electronic states of their lowest tri-
plet energy levels possess the feature of
mixing”.the character of which can be鼎·
timated by the formula:T=aT (n·丌‘)4-bT
n卜丌’).Fbr a molccule with 1arge conju.
gated system , the coefficient b is bigger
than a andT,ofthemolceuleha stheobvious
character of · 【 .St~ctly the judging
of T.cha racter shou埘 fol1Ow the rules pro-
posed by Yang et all .Here from the ab·
sorptlon c0e士ficicnt and structural faetOra
relatire to CBPs we obtained an approxi-
mate order in virtue of the decrease of
cha racter:7>8>1~ 4> 5> B> BP.
Complexing behaviour
Completing ability with alkali metal
Ca tions is the most fundamental feature of
crown ethers.It is em bodied in CBPs too
as shown in Table 2 where UV data in
their comple~ation tests w ith Na and K
in methanol are given .
As shown in Tablc 2, rather sj龃 越i-
Ca nt blue shift or red shift confirnIs the
occurrence of complexation between cBP
and the metal ions.W ith the exception of
2 and 3 with larger red shifts. mos t of
the a s show a blue shift(n ).In the
case of 7 and 8,12.1 nm and 11.7 nm
of the blue shifts were observed respective·
ly.This phenomenon can bc explained
from the contrtbution of the lone piar cle-
ctrons on the oxygen atoms of aryl ether
to complexing—which results in the wes-
kening of conjugative effect.1n comparison
一 旷一 一
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第6期 冠醚化二苯甲酮的合成及其光物理行为 5
Tab 2. UV absorbanca of CBP in methanol before and after complexing
No metal ions K Na coⅢ硎 nd
(nm) lg e (run) lg e (run) lg e
BP 251.5 4.2B 251.6 4.28 261.6 4.26
324.3 3.01 322.8 3.02 323.9 3.09
1 237.1 4.24 229.6 4.20 233.6 4.20
281.3 4.02 274.9 4.09 277.7 4.09
3l2.3 4.00 306.5 3.99
2 290.6 4.26 294.3 4.30 299.9 4.60
332.B 349.3
5 291.2 4.05 298.9 4.76
333.8 4.06 350.S 4.96
4 287.4 4.12 289.1 4.20 299.1 4.57
332.6 4.13 326.9 4.17
5 240.2 4.24 212.0 4.27 211.3 4.27
280.4 4.03 260.6 4.19 257.8 4.17
314.2 4.03 308.9 4.O2
B 234.1 4.26 228.5 4.29 230.8 4.27
282.7 4.09 276.4 4.16 278.9 4.13
314.9 4.06 303.3 4.02 309.1 4.04
7 280.0 280.9 4.40 280.9
315.2 4.21 311.1 4.44 303.1 4.60
8 281.4 3.98 279.3 4.04
312.2 303.1 3.99 300.5 4.66
with the case before complexing.the absorp-
rion in1【ensities of CBP are increased or
almost unchanged.Since Na is mole fit
for the cavity ot bcnzo--15--crown--5 than
K .shm of the wavelenSth in COlplexin8
Na could expect to be larger.
UV abe orbets
The BPs wi th ortho-hydroxy groups
were reported to be UV absorbe rs due to
enolization under UV irradiation and quick
reverse accmnpanied with heat release(z01.
Thus,8 and 4 are likely to be the poten-
tial alteeativ in this respect.One advan-
tase with CBP is high motar extinction
c鹋埔cient(ca. 100 times that of BP).
This applica tion of the substituted CBP
for initiating polymerization wi ll be l,e-
ported elsewhere.
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l76 有 机 化 学
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睾 睾 书 书 睾
有机化学 YOUJI HUAXUE,1 991,jI,476~481,研兜论文
双[(五甲二硅基)环戊二烯基]un羰基二铁的合成结构及性质
孙怀林 周秀中’ (南开大学化学系,天津,300071
毓 侃 王宏根 (南开大学中心实验室.天津,300071)
Synthesis.Structure and Properties of Bis一(pentamethyJ-disilanylcy-
clopentadieny1)Tetracarbon【yl Di-iron
SUN Huai-Lin ZHOU Xiu-Zhong’
(Depa~ment ol Chemistry,Nanka!Unt~ersity,Tlan]in 300072)
YAO Xia-Kai W ANG Hong--Gen
(Central Loborafory,Nanlca~Uni~rsity,3~0071 Tian]In)
Abstractl The title compound (1)was synthe sized by refluxing the xyle~e solution of cY-
clopemod ienyl pentamethyl disilane and pcntacarbonyl iron.1 reacts with iodine to yield
the iodinating product 2 with the Fe— Fe bond cleaved.1 was converted to the correspon’
ding mono~-imn anion by sodium-amalgam reduction.The iron anion resets “h mettIyl
iodide and benzyl chloride respectively lo give the corresl:er.di~g siloylaticn product 3 and
4.The crystal and molecular ctrnctnre of 1 were determined by X ray diffraction method.
The crystals are monoclinic,space group P 21/a witha=0.7885(1)J扫=1.1282(2),c=1.8255 .
(2)nm:B=102.85(1)。;V=1.5832 rim。,Z=2,D =1.289 g-cm--S.The R factor is 0.087,
R. is 0.085. ‘
I~ lptor} Sodium—amalgam reduction,X ray diffraction.cyelopentadienyl pentam ethyt dt- ’
silanc preparation·structure
五甲二硅基与环戍二烯基羰基过渡金属化
台物的金属直接配位的已有不少报道[1】,但五
甲二硅基取代环戊二烯基的羰基过渡金属化合
物中除铁、锰,铼的相应化合物在文献中有所
涉及外 ,其它尚未见报道。
环戊二烯基五甲基二硅烷和五羰基铁的二
甲苯溶液经回流 即生成双[(五 甲 基二硅基)
环戊二烯基]四羰 基二铁(I)。
1与计量或过量的碘在氯仿 或苯中反应,
均生成 Fe—Fe键断裂的相应[(五甲基二硅基)
环戊二烯基]--羰基碘化铁(2),而未观察到有
2
llae2SiMea
Me iMe2st
-i-2FeI C015 xY1ent
1990年 1】月 5日收稿。
南开大学元素有机化学研究所国家重点实验室部分资
助课题。
⋯⋯ _l r_一 一
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