MIT

5.301

Katherine J FranzKevin M Shea

Rich L DanheiserTimonthy M Swager
J Haseltine, Kevin M SheaSarah A Tabacco

IAP 2004


1
1.1.
1.2.
1.3.
1.4.
1.5.
1.6.
1.7.

3
4
5
6
7
8
9

2.
2.1. CC

14

2.2. EE

17

3.
3.1. CC

19

3.2. EE

21

4.
4.1. CC

24

4.2. EE?

26

5.
5.1. CC
5.2. EE

28
30

6.
6.1. CC
6.2. EE

32
35

7.
7.1. Mn(salen)

37

8.
8.1. FT-NMR
8.2 GC
8.3 TLC
8.4.
8.5.
8.6.
8.7.
8.8.
8.9.

44
46
47
50
53
55
57
59
63

9.
9.1 NMR
9.2 IR
9.3 GC
9.4 UV-Vis

68
73
74
75

1.
1.1.
5.301
5.301

UROPUROP

5.3015
CC(Competent Chemist)EE(Expert Experimentalist)
CC
CCEE
EE

5.301

1.2.
5.301
1James Zubrick
6 Zubrick2J. Leonard, B. Lygo G. Procter
2 LLP

Zubrick

Zubrick
5.301 LLP
J. Leonard, B. Lygo G. Procter Zubrick
Zubrick

LLP

1.3.
1 5

5.301
Zubrick

J. Leonard, B. Lygo G. Procter

5.301
Tabacco

IAP

1 5
Zubrick 6
1, 2, 4, 6, 9, 10
, 11, 15, 18, 19, 31
Leonard, Lygo Procter 2
12348

1.4.

5.301
UROP

UROP

CC

EE

CC EE

5.301 CC EE
EE

1.5.

5.301
2004 1

5 #1

6 #2

7 #3

8 #4

CC

CC

EE

CC

EE

11

12 #5

13 #6

14 #7

15 #8

16

CC

EE

CC

EE

CC

3
10

17

1
2

18

25

19

20 #9

21 #10

22 #11

23 #11

CC

EE

Salen

Mn

26 # 12

27 #13

28 #14

29

30

24

31

1.6.

5.301
2~6 5

2~6

NMRIRGCUV-Vis
7IAP

8
5.301

95.301
NMRGCIRUV-Vis

1.7.

Mircea GheorghiuScott Virgil

1.
:

1.
2.
3.
4.
5.

100

CO2

,
,

16

4-454
4-460

(4-450)

2.
()
:
1.
2.
3. (5.301)
4. 5.301

()

10

3.
2004130
$35.00

4.
a.

4-457
4-457
4-4544-460
b.

4-4544-460

4-454
c.

d.

LSLS=Lab Supplies

1
cm11cm
2

17mm 5

11

5.

Mircea Gheorghiu

Gheorghiu

ACGIHTLVs
40
ACGIHTLV

12

6.
1

9
:
a
b

10

11

13

2.
2.1. :

NMR

Zubrick15LLP10
Zubrick37
Zubrick87-92
NMRZubrick35LLP152

51
62

100mL
(125mL)
2250mL
150mL
100mL
NMR

14


1H NMR

100mg3-4
1H NMR3-

50~70mL
10HCl

1H NMR
NMR

15


CC90mg3-
1H NMR

36973

16

2.2.

pKa

CC

CC

100mL
(125mL)
4250mL
150mL
100mL
pH
NMR

17

pKa
4-100mgpKa
1

Na2CO3
6M HCl
1M NaOH

EE
90mg32

Gilbert J. C; Martin S F. Experimental Organic Chemistry: A Miniscale & Microscale

Approach; 3th ed.; Brooks/Cole: Pacific Grove, CA 93950; p. 141.

18

3.
3.1. :

Zubrick13LLP11.2

9.

(513100 mm)
(250-mL, 1125-mL)




/
(250mL)

19


2.00g
1

I.

Zubrick104-105

II.
50mL20mLI

CC 1.30g
3
7783

Fieser, L. F.; Williamson, K. L. Organic Experiments; 7th ed.; D. C. Heath and Company:
Lexington, MA, 1992; p. 40.
20

3.2.

X-

Cr(acac)3 2

50mL
2mL


D
250mL
34
2

Szafran, Z.; Pike, R. M.; Sing, M. M. Microscale Inorganic Chemistry: A Comprehensive

Laboratory Experience, Wiley: New York, 1991: synthesis of Metal Acetylacetonates p. 224-229.
21

CrCl36H2O

2,4-
Cr(acac)3

1.00mmol

1
17
8

50mLCrCl36H2O
2mL

2,4-

1
D

X-

pHNH3
NH3acac2,4-
2,4-
Cr(acac)3

22

EE50Cr(acac)3
X-

23

4.
4.1. ?

GC

Zubrick36LLP113
Zubrick20
GCZubrick32

125mL, 150mL

11.20g40

GC

GC

24

CC 7.00g
GC92

25

4.2. ?

25mL

-7.50g
VigreuxCC

26


EE
0.5torr4.00g -
93
_______________________________________________________________________________

27

5.
5.1.

TLC

Zubrick 27
TLC/Zubrick 28 LLP 9.3.1
Zubrick 29 LLP 11.6

T
100mL
18150 mm

3. TLC
10.

28


2mL (guaiazulene) 4- -2-
(benzylacetone)/
TLC 10%/ TLC
TLC
Rf
10%/ 50g 5

10mL
1mL

TLC
4--2-(benzylacetone)
GC
TLC

CC
0.95g 4--2- 95

29

5.2.
***

***

CC

20mL 0.2g (guaiazulene)0.2g (fluorenone) 0.2g

3-/
TLC TLC

30

 TLC

TLCRf

EE "TLC
Rf

31

6.
6.1.

-UV-Vis

100P1000P

8
Eppendorf
UV-Vis 5mL

C Pierce Coomassie Plus

Protein Assay

Eppendorf 3 50L C
pH 7 25mM MOPS

32

1.00g/mL
1L
Coomassie
Coomassie
465nm 595nm (A595)
(BSA) 595nm 595nm

+ G-250 Coomassie - 595nm

1 BSA
2.0mg/mL BSA
BSA 3

33

2Coomassie
Coomassie Plus Coomassie Plus

3
0.05mL Eppendorf 3
0.05mL 25mM MOPS pH 7,

1.5mL Coomassie Plus

595nm
595nm 595nm
595nm
g/mL

CC
R 0.930
0.048

34

6.2.

UV-Vis 1mL
20P100P1000P

Eppendorf


Eppendorf

CC
C

Ferrozine

(Fe )-
UV-Vis 562nmA562

Fe AA AA
25mM MOPSPH 7
HNO3 (5 M)
75 mM C
10 mM

1.
2mL Eppendorf
2 300L
35

 30L (5M)
Eppendorf Pyrex
30
12
300L

1020L
60L 75mM C
60L 10mM
60L
1015
1.5mL 562nm
A562
A562[Fe]
[Fe]

EE "
0.995
0.035

36

7.
7.1.

Mn(salen)

:
5.301

eq 1
Eric Jacobsen(
)1Mn(salen)eq 1
Mn(salen)Mn(salen)
Mn(salen)
Jacobsen

37


salen(eq 2)1H NMR
Mn(salen) (eq 3)

Jacobsen1,2-
1H NMR

1H NMR

1Salen(eq 2)
Mn(salen)
1)
+
2)
-12-+ 35---2-
3)
+
4)
+
1.00Mn(salen)70%

38

2. Mn(salen)(eq 3)
salenJacobsen

Mn(salen)

39

3. 1,2-eq 4
pHpH
pH
TLC

40

41

42

43

8.1. FT-NMR

1H NMR 10mg
NMRNMR

Zubrick 295

NMR
(CDCl3) (D2O) (C6D6)
(CD3C(O)CD3)(CD3CN)(C4D8O)
5.301 CDCl3CDCl3
CDCl3NMR
CDCl3TMS 4
K2CO3CDCl3
5.301 CDCl3TMS
K2CO3
NMR

1) NMR
2)
NMR
10mL

NMR
44

1)
2) NMR 10mL
3) NMR Kimwipe Kimwipe
Pasteur Pasteur

4) 10
5) NMR
6)
7) NMR NMR

8) NMR

NMR
1 1-3
2 10mg
3 1mL
4 NMR
5 6-8

NMR
1 NMR
2 NMR 1
3 NMR

45

8.2GC

GC

Zubrick 252

1)
2)
3)
4)
5)

Pasteur 10mg
1mL

1mL

1) 10mg 1mL
2) 3-5

46

8.3. TLC

TLC

5.301

Rf 01

LLP145-152

TLC
1)

2)

Rf 0.15~0.85

Rf 0.2~0.3
LLP

47

/ 0~30%
/ 0~40%
/ 5~30%
/5~30%
3) 1~2mL
4)
Pasteur UROP

5) 90%
6) Rf

7)
8)
5.301
UROP

48

9) 5.301

10) Rf
Rf

11) TLCRf

49

8.4.

Zubrick127-138

2125mL250mL1
10g500mL1L

3
50500mg25100mL
41/10~1/2
2~310HClNaHCO310NaOH

50

5
TLC

6NaCl

7
MgSO4MgSO4Na2SO4
Na2SO4

8Zubrick136-138

9)

10)

11)

51

12

30/

1315
30NMR

52

8.5.

LLP9.2

5.301
N2
1

2
3

41520

5.301

LLP6.4

53


Schlenk

1
!14/20Keck

3
!

54

8.6.

1
2

Zubrick114-117

1)
2) 50mL13.1
20mL

3)

4) 2mL
5) 15mL
6)
7) 2
22
22
1

55

8)
9)

10)
11)

56

8.7.

2
1
2
Pasture
Celite

57


CH2Cl2
/
CHCl3/

THF/
/

58

8.8.

5.301

Vigreux5.301

1
LLP196
2
2030C
200C
3
4
1/22/3

5.301UROP

59

7
8
7070C

10
11
1210

1312
145C
15

16
17

60


134
Perkin5.301

22~4
3
Zubrick 53-55

46~7
5
6

7
89~15
9

61

10

62

8.9.

(Flash Column Chromatography)

5.301 1g

LLP 205-214

1
2Rf 0.20.3

Rf 0.20.3
3

Rf 0

63

1.5mL
4 30~50
1 1201 LLP

5)
5.301

5.301

6)
4
200mL
64

 50mL
7)

8)

9
10)
1cm
11) 0.5 g/mL
100g200mL 1/3

12) 1.5

13)

14)

15)

65

16
2cm

17
18
19

2cm
20 1cm

21

22) TCL

66


23Rf

100mL
5

24

25

26 NMR

67

9.1. NMR
Varian Mercury 300 Plus FT (NMR)
()
(NMR) 5.301 ()
1H NMR
2~7 1 7
1H NMR
IAP
1H NMR 10
7 1H NMR
1)
5)
2)
6)
3)
7)
4) FID

1)
NMR
NMR
NMR
[eject]

NMR [insert]

[on]

68

2)
1H NMRppmFID

FID

1H NMR

69

3)

shim
()

20 / XY

( 4cm)/ NMR

70

4) FID()

5)

71

6)
NMR

7)

72

9.2. IR
5.301 FT-IR

XY Z

XY Z

IR Plot

73

9.3. GC

5.301 HP5890 Series II

HP 3365 HP 7673 HP 18765

5.301 GC

1) (
)

2) 1mL GC GC

3)

4)

74

9.4. -UV-Vis
HP 8542 UV-Vis

:
1) HP 89532A Kinetics
2) Time/Cell 2 6
Functions 596 562
3)

Scan Screen
Pre-Run Meas. Blank 5

4) Start
Run Begin
5) Return, Tabulate Time
Traces

3
6) Escape Scan
Screen
7) 4~6

75