c 5 h 12 o mw = 88.15. solve the structure with no further information

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C5H12O MW = 88.15OH

C5H12O MW = 88.15OH

OH

CH3H3C

+• OH

CH3H3C

+

m/z = 73m/z = 88

HH

C5H12O MW = 88.15OH

OH

CH3H3C

+• OH

CH3H3C

+

m/z = 73m/z = 88

HH

OH

CH3H3C

+•

m/z = 88

OH+

CH3

CH2H3C•

m/z = 45

HH

C5H12O MW = 88.15OH

OH

CH3H3C

+• OH

CH3H3C

+

m/z = 73m/z = 88

HH

OH

CH3H3C

+•+

• +•

m/z = 70 m/z = 70

OH

CH3H3C

+•

m/z = 88

OH+

CH3

CH2H3C•

m/z = 45

HH

Solve the structure with no further information

Solve the structure with no further information

Two equally sized peaksThat differ by 2 units:

Bromine

Solve the structure with no further information

Two equally sized peaksThat differ by 2 units:

Bromine

M–81

M–79

Solve the structure with no further information

Two equally sized peaksThat differ by 2 units:

Bromine

M–81

M–79

CH2

+

Solve the structure with no further information

Two equally sized peaksThat differ by 2 units:

Bromine

M–81

M–79

CH2

+

CH2

++•

Br Br•

C9H10O IHD=5

C9H10O IHD=5CH2

+

C9H10O IHD=5CH2

+

M–CH3

C9H10O IHD=5CH2

+

M–CH3

• The above fragments account for C8H10

C9H10O IHD=5CH2

+

M–CH3

• The above fragments account for C8H10

CH3

O+•

O+ O

+CH3•

m/z = 119

C9H10O IHD=5CH2

+

M–CH3

• The above fragments account for C8H10

CH3

O+•

O+ O

+CH3•

H2C+

m/z = 91

m/z = 119

C9H10O IHD=5CH2

+

M–CH3

• The above fragments account for C8H10

CH3

O +•

CH3

O+

CH3

O

+

m/z = 43

CH3

O+•

O+ O

+CH3•

H2C+

m/z = 91

m/z = 119

O O

OEt

O O

OEt

O O

OEt

+•

O +

O

OEt•

m/z = 105

O O

OEt

O O

OEt

+•

O +

O

OEt•

m/z = 105

O O

OEt

+•

OEt

O +O

m/z = 73

O O

OEt

O O

OEt

+•

O +

O

OEt•

m/z = 105

O O

OEt

+•

OEt

O +O

m/z = 73

+

CO

m/z = 77

142

113

85

7257

29

43

99

142

86

71

58

43O

O

match the compound toit's spectrum

A

B 1

2

142

113

85

7257

29

43

99

142

86

71

58

43A B

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 113m/z = 85

+

A B

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 113m/z = 85

+

O O+•

+

m/z = 57m/z = 29

+

A B

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 113m/z = 85

+

O O+•

+

m/z = 57m/z = 29

+

OH

OH+•

+•

m/z = 72

McLaffertyrearrangement

A B

OO+

+

m/z = 43

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 113m/z = 85

+

O O+•

+

m/z = 57m/z = 29

+

OH

OH+•

+•

m/z = 72

McLaffertyrearrangement

A B

OO+

+

m/z = 43

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 113m/z = 85

+

O O+•

+

m/z = 57m/z = 29

+

OH

OH+•

+•

m/z = 72

McLaffertyrearrangement

O A B1

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 99

m/z = 71

+

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 99

m/z = 71

+O O+

•+

m/z = 71

+

m/z = 43

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 99

m/z = 71

+O O+

•+

m/z = 71

+

m/z = 43

OH

OH+•

+•

m/z = 86

McLaffertyrearrangement

O OHH+•

+•

m/z = 114NOT OBSERVED

142

113

85

7257

29

43

99

142

86

71

58

43

OO+

+

m/z = 99

m/z = 71

+O O+

•+

m/z = 71

+

m/z = 43

OH

OH+•

+•

m/z = 86

McLaffertyrearrangement

O OHH+•

+•

m/z = 114NOT OBSERVED

OH OH+

•+•

m/z = 58

DoubleMcLaffertyrearrangement

142

113

85

7257

29

43

99

142

86

71

58

43O

OO+

+

m/z = 99

m/z = 71

+O O+

•+

m/z = 71

+

m/z = 43

OH

OH+•

+•

m/z = 86

McLaffertyrearrangement

O OHH+•

+•

m/z = 114NOT OBSERVED

OH OH+

•+•

m/z = 58

DoubleMcLaffertyrearrangement

O

O

OH

UV-Vis problems

-unsaturatedketoneTable 7.12

Base value: 202 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm-hydroxy group: 35 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm-hydroxy group: 35 nm-alkyl group: 12 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm-hydroxy group: 35 nm-alkyl group: 12 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

249 nm

O

Base value: 202 nm-hydroxy group: 35 nm-alkyl group: 12 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

249 nm

Base value: 215 nm

O

Base value: 202 nm-hydroxy group: 35 nm-alkyl group: 12 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

249 nm

Base value: 215 nm-alkyl group: 10 nm

O

Base value: 202 nm-hydroxy group: 35 nm-alkyl group: 12 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

249 nm

Base value: 215 nm-alkyl group: 10 nm-alkyl group: 12 nm

O

Base value: 202 nm-hydroxy group: 35 nm-alkyl group: 12 nm

O

OH

UV-Vis problems

-unsaturated ketoneTable 7.12

249 nm

Base value: 215 nm-alkyl group: 10 nm-alkyl group: 12 nm

237 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nmTwo exocyclic double bonds 10 nm

Me

O

Me

Me

O

Me

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nmTwo exocyclic double bonds 10 nm

259 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nmTwo exocyclic double bonds 10 nm

259 nm

OH

O

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nmTwo exocyclic double bonds 10 nm

259 nm

OH

O

Base value: 215 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nmTwo exocyclic double bonds 10 nm

259 nm

OH

O

Base value: 215 nm-hydroxy group: 30 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nmTwo exocyclic double bonds 10 nm

259 nm

OH

O

Base value: 215 nm-hydroxy group: 30 nm-alkyl group: 12 nm

UV-Vis problems

Me

O

Me-unsaturated ketoneTable 7.12

Base value: 215 nm-alkyl group: 10 nmTwo -alkyl groups 24 nmTwo exocyclic double bonds 10 nm

259 nm

OH

O

Base value: 215 nm-hydroxy group: 30 nm-alkyl group: 12 nm

257 nm

O

UV-Vis problems

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nmTwo exocyclic double bonds 10 nm

O O

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nmTwo exocyclic double bonds 10 nm

303 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nmTwo exocyclic double bonds 10 nm

303 nm

O

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nmTwo exocyclic double bonds 10 nm

303 nm

O

Base value: 215 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nmTwo exocyclic double bonds 10 nm

303 nm

O

Base value: 215 nm-alkyl group: 10 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nmTwo exocyclic double bonds 10 nm

303 nm

O

Base value: 215 nm-alkyl group: 10 nm-alkyl groups: 24 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nmDouble bondExtending conjug. 30 nm-alkyl group: 12 nm-alkyl group: 18 nm-alkyl group: 18 nmTwo exocyclic double bonds 10 nm

303 nm

O

Base value: 215 nm-alkyl group: 10 nm-alkyl groups: 24 nm

249 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm-alkyl group 10 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm-alkyl group 10 nmTwo -alkyl groups 24 nm

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm-alkyl group 10 nmTwo -alkyl groups 24 nmexocyclic double bond 5 nm O

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm-alkyl group 10 nmTwo -alkyl groups 24 nmexocyclic double bond 5 nm

241 nm

UV-Vis problems

O

O

O

CHO Br

O

OAc

UV-Vis problems

O

O

O

CHO Br

O

OAc

O

O

O

CHO Br

O

OAc

UV-Vis problems

O

O

O

CHO Br

O

OAc

O

O

O

CHO Br

O

OAc

-unsaturated ketoneTable 7.12

Base value: 215 nm

UV-Vis problems

O

O

O

CHO Br

O

OAc

O

O

O

CHO Br

O

OAc

-unsaturated ketoneTable 7.12

Base value: 215 nm-alkoxy (OMe) 35 nm

UV-Vis problems

O

O

O

CHO Br

O

OAc

O

O

O

CHO Br

O

OAc

-unsaturated ketoneTable 7.12

Base value: 215 nm-alkoxy (OMe) 35 nm-alkoxy (OMe) 30 nm

UV-Vis problems

O

O

O

CHO Br

O

OAc

O

O

O

CHO Br

O

OAc

-unsaturated ketoneTable 7.12

Base value: 215 nm-alkoxy (OMe) 35 nm-alkoxy (OMe) 30 nmDouble bond Extending conj 30 nm

UV-Vis problems

O

O

O

CHO Br

O

OAc

O

O

O

CHO Br

O

OAc

-unsaturated ketoneTable 7.12

Base value: 215 nm-alkoxy (OMe) 35 nm-alkoxy (OMe) 30 nmDouble bond Extending conj 30 nm> alkyl group 18 nm

O

O

O

CHO Br

O

OAc

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nm-alkoxy (OMe) 35 nm-alkoxy (OMe) 30 nmDouble bond extending conj 30 nm> alkyl group 18 nmHomodiene 39 nm

O

O

O

CHO Br

O

OAc

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 215 nm-alkoxy (OMe) 35 nm-alkoxy (OMe) 30 nmDouble bond extending conj 30 nm> alkyl group 18 nmHomodiene 39 nm

367 nm

UV-Vis problems

O

NH

Me

BrCOOCH3 triene

Table 7.5

UV-Vis problems

trieneTable 7.5

O

NH

Me

BrCOOCH3

Base value (heteroannular diene): 214 nm

UV-Vis problems

trieneTable 7.5

O

NH

Me

BrCOOCH3

Base value (heteroannular diene): 214 nmDouble bond extending conjugation 30 nm

UV-Vis problems

trieneTable 7.5

O

NH

Me

BrCOOCH3

Base value (heteroannular diene): 214 nmDouble bond extending conjugation 30 nmOalk group 6 nm

UV-Vis problems

trieneTable 7.5

O

NH

Me

BrCOOCH3

Base value (heteroannular diene): 214 nmDouble bond extending conjugation 30 nmOalk group 6 nmN(Alk)2 60 nm

UV-Vis problems

trieneTable 7.5

Base value (heteroannular diene): 214 nmDouble bond extending conjugation 30 nmOalk group 6 nmN(Alk)2 60 nm5 alkyl residues 25 nm

O

NH

Me

BrCOOCH3

O

NH

Me

BrCOOCH3

O

NH

Me

BrCOOCH3

O

NH

Me

BrCOOCH3

O

NH

Me

BrCOOCH3

UV-Vis problems

trieneTable 7.5

Base value (heteroannular diene): 214 nmDouble bond extending conjugation 30 nmOalk group 6 nmN(Alk)2 60 nm5 alkyl residues 25 nm4 exocyclic double bonds 20 nm

O

NH

Me

BrCOOCH3

UV-Vis problems

trieneTable 7.5

Base value (heteroannular diene): 214 nmDouble bond extending conjugation 30 nmOalk group 6 nmN(Alk)2 60 nm5 alkyl residues 25 nm4 exocyclic double bonds 20 nm

O

NH

Me

BrCOOCH3

355 nm

UV-Vis problems

N

O

O

AcO

O

UV-Vis problems

-unsaturated ketoneTable 7.12

Base value: 202 nm

N

O

O

AcO

O

UV-Vis problems

N

O

O

AcO

O

-unsaturated ketoneTable 7.12

Base value: 202 nmExtended conjugation 30 nm

N

O

O

AcO

O

UV-Vis problems

N

O

O

AcO

O

-unsaturated ketoneTable 7.12

Base value: 202 nmExtended conjugation 30 nm-NR2 95 nm

N

O

O

AcO

O

UV-Vis problems

N

O

O

AcO

O

-unsaturated ketoneTable 7.12

Base value: 202 nmExtended conjugation 30 nm-NR2 95 nm-OAc 6 nm

N

O

O

AcO

O

UV-Vis problems

N

O

O

AcO

O

-unsaturated ketoneTable 7.12

Base value: 202 nmExtended conjugation 30 nm-NR2 95 nm-OAc 6 nm2 and higher alkyls 36 nm

N

O

O

AcO

O

UV-Vis problems

N

O

O

AcO

O

-unsaturated ketoneTable 7.12

Base value: 202 nmExtended conjugation 30 nm-NR2 95 nm-OAc 6 nm2 and higher alkyls 36 nmTwo exocyclic olefins 10 nm

N

O

O

AcO

O N

O

O

AcO

O

N

O

O

AcO

O

UV-Vis problems

N

O

O

AcO

O

-unsaturated ketoneTable 7.12

Base value: 202 nmExtended conjugation 30 nm-NR2 95 nm-OAc 6 nm2 and higher alkyls 36 nmTwo exocyclic olefins 10 nm

N

O

O

AcO

O

379 nm

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