On the basicity of organic bases in different media

Ph3N

(2,6−Cl2−C6H3)3P

2,3,4,5,6−Cl5−Aniline

(2,6−F2−C6H3)2(Ph)P

(C6F5)(Ph)2P

Cl−Phenylfulvene

Thymine

2,3,5,6−Cl4−Aniline

H−Phenylfulvene

(2−F−C6H4)3P

5−Cl−2−NO2−Aniline

Uracil

Me−Phenylfulvene

2−Cl−4−NO2−Aniline

4−Cl−2−NO2−Aniline

BINAPH+

BIPHEPH+

(2−F−C6H4)2(Ph)P

MeO−Phenylfulvene

2−NO2−Aniline

6−NO2−Indazole

5−NO2−Indazole

2,6−Cl2−Aniline

(2,6−F2−C6H3)(Ph)2P

2−NO2−Imidazole

Ph2P−(CH2)2−PPh2−H+

Ph2NH

(2−F−C6H4)(Ph)2P

4−NO2−Aniline

2,5−Cl2−Aniline

4−NO2−Imidazole

4−NO2−N ,N−Dimethylaniline

MePh2N

(1−Napht)3P

2−Cl−Pyridine

Benzotriazole

TMPH+

Ph2P−(CH2)3−PPh2−H+

Quinoxaline

Caffeine

Indazole

Ph3P

2,6−(MeO)2−Pyridine

4−F−3−NO2−Aniline

3−NO2−Aniline

Pyrazine

OEPH+

BINAP

2−Cl−Aniline

1,2,3−triazole

BIPHEP

4−CF3−Aniline

9−O−1,5−(COOMe)2−N ,N'−Ph2−Bispidine

3−NO2−N ,N−Dimethylaniline

Ph2P−(CH2)4−PPh2−H+

2,4−F2−Aniline

4−(4−NO2−C6H4−N=N)−Aniline

TCPPH+

4−CF3−N ,N−Dimethylaniline

Pyrimidine

4−SCN−N ,N−Dimethylaniline

TPPH+

Pyrazole

Quinazoline

Ph2P−(CH2)2−PPh2

4−Br−Aniline

3−Cl−Pyridine

3−Br−N ,N−Dimethylaniline

1−NaphtNH2

Ph2P−(CH2)3−PPh2

2−MeO−Pyridine

MePh2P

TCPP

Pyridazine

(4−MeO−C6H4)3P

4−Br−N ,N−Dimethylaniline

TMP

Ph2P−(CH2)4−PPh2

dma−Phenylfulvene

5−NO2−Benzimidazole

TPP

2−Me−Aniline

Aniline

7,8−Benzoquinoline

N−Me−Aniline

9−Cl−Acridine

3−MeO−N ,N−Dimethylaniline

4−NO−N ,N−Dimethylaniline

2,2'−Biquinoline

N ,N−Dimethylaniline

8−NH2−2−Me−Quinoline

Phthalazine

4−MeO−Aniline

5,6−Benzoquinoline

Quinoline

4−Me−N ,N−Dimethylaniline

Carbendazim

2,2'−Bipyridine

OEP

Thiabendazole

Pyridine

Me2PhP

Acridine

Isoquinoline

4−MeO−N ,N−Dimethylaniline

2−Me−Pyridine

9−O−N ,N'−(CHPh2)2−Bispidine

Benzimidazole

2−NH2−Acridine

Phenanthroline

9−O−1,5−(COOMe)2−N ,N'−Bn2−Bispidine

4−CF3−7−N=P1(Ph)3−Coumarin

N ,N'−Ph2−Bispidine

2,6−Me2−Pyridine

2,6−(NO2)2−C6H3P1(pyrr)3

3−NH2−Pyridine

4−MeO−Pyridine

2,6−Cl2−4−NO2−C6H2P1(pyrr)3

2−NH2−Pyridine

2,6−(NH2)2−Pyridine

4−(4−NO2−C6H4−N=N)−C6H4P1(Ph)3

2,4−(NO2)2−C6H3P1(pyrr)3

2,4,6−Me3−Pyridine

Imidazole

4−CF3−7−N=P1(Ph)2pyrr−Coumarin

2,3−(NH2)2−Pyridine

Me3P

4−(Ph−N=N)−C6H4P1(Ph)3

Me2P−(CH2)2−PMe2

2−NH2−Benzimidazole

4−(4−dma−C6H4−N=N)−C6H4P1(Ph)3

4−(4−NO2−C6H4−N=N)−C6H4P1(Ph)2pyrr

2−NH2−1−Me−Benzimidazole

3−NH2−Acridine

2−NO2−4−CF3−C6H3P1(pyrr)3

4−CF3−7−N=P1(pyrr)2Ph−Coumarin

4−(Ph−N=N)−C6H4P1(Ph)2pyrr

BnNH2

9−O−N ,N'−Bn2−Bispidine

2−NO2−5−Cl−C6H3P1(pyrr)3

4−(4−dma−C6H4−N=N)−C6H4P1(Ph)2pyrr

N ,N'−Me2−Piperazine

9−O−1,5−Me2−N ,N'−Bn2−Bispidine

4−(Ph−N=N)−C6H4P1(dma)2Ph

4−NH2−Pyridine

2−NO2−4−Cl−C6H3P1(pyrr)3

4−(4−NO2−C6H4−N=N)−C6H4P1(pyrr)2Ph

N ,N'−(CHPh2)2−Bispidine

4−dma−Pyridine

N−Me−Piperazine

N−Me−Piperidine

Me2BuN

Pr3N

Me2EtN

4−pyrr−Pyridine

9−NH2−Acridine

Cyclohexylamine

4−(Ph−N=N)−C6H4P1(pyrr)2Ph

PrNH2

4−NO2−C6H4P1(pyrr)3

2,5−Cl2−C6H3P1(pyrr)3

[H][Ph]Triazine

2,6−Cl2−C6H3P1(pyrr)3

4−CF3−7−N=P1(pyrr)3−Coumarin

ProtonSp−dma

N ,N−Me2−Cyclohexylamine

Me2N−(CH2)2−NMe2

Piperazine

i−Pr2NH

Et3N

N−Me−Cyclohexylamine

MePrNH

Me2NH

4−(4−dma−C6H4−N=N)−C6H4P1(pyrr)2Ph

2−Cl−C6H4P1(dma)3

Homopiperazine

[Me][Ph]Triazine

Me2N−(CH2)3−NMe2

Piperidine

4−(4−NO2−C6H4−N=N)−C6H4P1(pyrr)3

Quino[7,8−h ]quinoline

Pyrrolidine

Me2N−(CH2)3−NH2

1−(o−Tolyl)biguanide

NH2−(CH2)3−NH2

Me2N−(CH2)4−NMe2

MeNH−(CH2)3−NMe2

MeNH−(CH2)3−NH2

Me2N−(CH2)2CHMe−NMe2

2−Cl−C6H4P1(pyrr)3

4−CF3−C6H4P1(pyrr)3

4−(Ph−N=N)−C6H4P1(pyrr)3

MeHN−(CH2)3−NHMe

1−NaphtP1(pyrr)3

PhTMG

4−(4−dma−C6H4−N=N)−C6H4P1(pyrr)3

PhP1(dma)2Me

4−Br−C6H4P1(pyrr)3

PhP1(dma)3

N ,N'−(CHMePh)2−Bispidine

N ,N'−Bn2−Bispidine

Bispidine

(−)−Sparteine

PhP1(pyrr)3

N ,N'−Me2−Bispidine

[Me][i−Pr]Triazine

4−MeO−C6H4P1(pyrr)3

[4−MeO−C6H4][i−Pr]IYA

TMG

4−dma−C6H4P1(pyrr)3

2−{hpp}C5H4N

2−Cl−C6H4P2(dma)5

DBU

[H][i−Pr]IYA

4−NO2−C6H4−CH=P(dma)3

PhP1(dma)2tmg

[OMe][OMe]Guanidine

[OMe][H]Guanidine

[H][OMe]Guanidine

[H][H]Guanidine

ProtonSp−tmg

4−CF3−C6H4P2(pyrr)5

Me2−IP

2−Cl−C6H4P2(pyrr)5

MTBD

4−NO2−C6H4−CH=P(pyrr)3

IP

2,6−{hpp}2C5H3N

[dma][H]Guanidine

HP1(dma)3

TBD

[CH2−t−Bu][i−Pr]IYA

4−Br−C6H4P2(pyrr)5

PhP2(dma)5

[H][dma]Guanidine

[(CH2)3OMe][(CH2)3OMe]TMAIMG

t−BuP1(pip)3

t−BuP1(dma)3

HP1(pyrr)3

[i−Pr][i−Pr]TMAIMG

[dma][dma]Guanidine

[Me][i−Pr]IYA

[ch][ch]TMAIMG

t−BuP1(TACD)

MeP1(dma)3

[Et][(CH2)3dma]TMAIMG

PhP2(pyrr)5

[(CH2)3dma][(CH2)3dma]TMAIMG

[i−Pr][i−Pr]IYA

4−MeO−C6H4P2(pyrr)5

t−BuP1(pyrr)3

EtP1(pyrr)3

H2C{hpp}2

PhP1(tmg)2dma

4−CF3−C6H4P3(dma)7

2,5−Cl2−C6H3P3(pyrr)6NEt2

HP1(pyrr−2−CH2−N−pyrr)3

[CMe2−t−Bu][i−Pr]IYA

[t−Bu][CH2−t−Bu]IYA

ProtonSp−N=P(dma)3

[CMe2CH2−t−Bu][i−Pr]IYA

2−Cl−C6H4P3(dma)6NEt2

[t−Bu][i−Pr]IYA

ProtonSp−N=P(i−Pr)3

ProtonSp−N=P(Me)3

4−CF3−C6H4P3(pyrr)7

ProtonSp−N=P(cp)3

4−NO2−C6H4−CH=P(tmp)3

ProtonSp−N=P(n−Bu)3

2−Cl−C6H4P3(pyrr)6NEt2

Ph−CH=P(dma)3

PhP1(tmg)3

PhP3(dma)7

4−MeO−C6H4P3(dma)7

ProtonSp−N=P(pyrr)3

Ph−CH=P(pyrr)3

PhP3(pyrr)7

t−BuP2(dma)5

Ph−CH=P(−NMe−CH2−CH2−)3N

Compound

0.03

1.120.78

0.48

0.610.51

0.98

0.150.08

0.70

0.10

1.28

0.66

0.32

0.14

1.22

1.05

0.50

0.81

0.08

0.64

0.610.17

0.64

0.60

0.69

1.21

0.550.25

0.95

1.03

1.04

1.70

0.81

1.050.61

0.25

1.56

0.28

1.111.23

1.77

0.63

1.20

0.03

0.63

1.09

0.100.35 0.42

0.440.05

0.50

1.59

0.46

0.58 0.77

1.89

1.44

1.26

0.68

0.01

0.60

1.691.69

0.04

0.08

1.07

0.21

0.25

0.70

1.20

0.08

0.98

0.47

1.17

0.401.14

1.60

0.210.09 0.30

0.37

0.65

1.33

0.27

0.10

0.74

0.44

0.45

0.51

0.22

0.75

0.73

0.52

0.06

0.900.98

1.60

1.05

0.630.65

0.180.18

0.590.61

0.77

0.56

0.41

0.25

1.07

0.49

0.04

0.310.28

1.01

0.770.65

0.88

1.10

0.43

0.570.37

0.95

0.56

0.850.48

0.19 0.370.40

0.13

0.03

0.38

0.33

0.14

0.12

1.77

0.73

0.99

0.85

0.20

0.17

0.35

0.25

0.44

0.17

0.44

0.20

0.05

0.01

0.05

1.43

0.04

0.86

0.86

0.23

0.67

0.85

0.240.27

0.24

1.28

0.25

−0.01

1.040.91

0.68

0.11

0.25

0.22

1.110.97

1.66

0.50

0.560.45

1.31

1.010.86

0.30

0.570.39

0.97

0.27

0.240.28

0.611.05

1.210.68

1.72

0.11

0.80

1.09

0.89

0.38

1.35

0.19

1.01

1.61

0.13

0.930.86

1.360.86

0.55

1.60

0.84 2.10

1.49

0.34

0.61

0.09

1.57

0.34

0.45

2.22

0.77

0.740.72

0.41

0.11

0.080.06

0.67

0.62

2.10

0.810.80

2.20

0.59

1.100.99

1.01

0.59

0.46

0.09

0.91

0.59

0.06

0.02

0.43

0.25

0.17

0.59

0.78

0.65

0.93

1.02

0.19

0.27

1.01

0.77

0.85

1.31

1.96

1.29

0.940.93

0.84

0.98

1.13

0.36

0.01 0.22

0.34

0.35

0.05

0.34

0.17

0.52

0.45

0.38

1.02

0.95

0.55

0.790.79

0.15

1.72

0.89

0.680.36

0.71

0.560.69

1.02

1.58

0.59

0.21

0.04

1.16

0.591.00

0.85

1.07

0.38

0.06

0.28

0.200.14

0.41

0.43

0.16

0.24

0.30

0.11

1.57

0.37

0.74

0.88

1.18

0.830.75

0.15

0.420.35

0.14

0.17

0.16

0.11

0.070.07

1.40

0.05

0.37

0.58

0.77

0.57 0.31

0.31

1.20

0.44

0.25

0.68

1.180.48

0.36

1.301.16

0.06

1.14

0.260.25

0.14

0.96

0.33

0.24

0.47

0.19

0.78

0.36

0.670.63

0.64

1.031.40

0.910.58

0.60

1.52

1.13

0.14

0.80

0.100.01

0.02

0.94

0.88

0.13

1.40

1.55

2.540.42

0.21

0.23

0.69

0.44

0.07

1.10

0.45

0.05

0.52

0.00

0.75

0.65

0.17

0.49

0.90

0.24

0.46

0.40

0.42

1.07

1.07

1.10

0.83

1.08

1.13

0.36

0.13

0.55

0.90

0.47

0.28

0.41

0.57

0.69

1.030.66

0.25

0.68

0.440.45

0.120.07

0.79

1.28

0.59

0.74

0.22

0.74

0.49

0.24

1.37

1.90

1.06

0.59

0.72

1.11

0.71

0.48 0.35

0.36

1.52

0.30

0.04

0.88

1.95

0.28

0.160.28

0.69

0.35 0.29

0.53

1.16

0.13

0.94

0.27

0.670.24

0.15

0.260.19

1.92

0.18

0.14

0.49

0.36

1.01

0.70

0.19

1.52

0.48

1.10

0.23

0.66

1.511.40

1.42

0.42

0.43

0.06

1.40

0.60

0.520.43

0.96

1.38

0.77

0.06

0.18

0.59

0.31

0.74

2.29

1.50

2.10

1.83

1.05

1.70

1.23

0.46

1.93

0.430.18

0.12

0.99

0.10

0.350.45

0.460.56

1.381.20

1.12

0.240.12

0.39

0.41

0.68

0.31

1.000.19

0.54

0.96

0.850.65

0.45

0.60

0.25

0.77

0.58

0.74

0.45

0.400.34

0.23

0.04

0.29

0.04

0.68

0.21

0.59

0.80

1.04

0.76

0.10

0.34

0.57

0.85

0.67 1.08

0.19

0.62

0.15

0.47

1.04

0.23

0.08

0.07

0.90

0.40

0.77

0.40

0.83

0.06

1.50

0.03

0.23

0.21

0.34

1.15

0.09

1.04

1.24

0.72

1.240.17

1.16

0.09

0.011.12

0.28

0.440.46

0.88

0.99

0.560.31

0.250.08

0.040.51

0.16

0.62

0.08

0.97

0.45

1.16

0.50

0.94

1.50

0.59

0.60

0.110.04

1.43

0.48

0.19

0.04

0.26

0.05

0.19

0.52

0.36

1.67

0.45

0.26

0.73

0.76

0.51

0.64

0.62

0.35

0.83

1.15

0.54

0.60

0.320.00

0.54

1.21

0.87

1.40

0.63

0.22

2.20

0.53

0.67

0.45

0.79

1.32

0.21

0.270.59

0.67

1.84

1.00

1.10

1.55

0.25

0.56

0.85

0.15

0.50

0.10

0.40

0.26

0.300.19

0.18

0.25

0.39

0.53

0.25

0.95

1.60

0.90

1.54

1.48

1.70

0.64

0.33

0.87

0.77

0.39

0.25

0.40

0.27

0.44

1.60

0.98

0.48

0.82

0.19

0.90

0.09

0.17

0.83

0.15

1.28

1.70

2.32

2.50

2.54

2.56

2.68

2.72

2.90

3.01

3.18

3.36

3.50

3.65

3.68

3.8

4.0

4.56

4.56

4.80

4.87

4.91

5.07

5.17

5.55

5.8

5.98

6.11

6.22

6.23

6.34

6.46

6.52

6.55

6.79

6.89

7.0

7.4

7.40

7.51

7.61

7.62

7.65

7.68

7.68

7.74

7.8

7.79

7.86

8.0

7.99

8.03

8.14

8.26

8.3

8.39

8.50

8.5

8.60

8.72

8.78

9.0

9.1

9.20

9.38

9.44

9.56

9.64

9.78

9.84

9.94

9.97

10.01

10.06

10.06

10.13

10.16

10.23

10.30

10.41

10.48

10.49

10.64

10.85

10.97

11.07

11.22

11.27

11.28

11.47

11.56

11.56

11.87

11.96

11.97

12.24

12.25

12.27

12.38

12.41

12.53

12.64

12.66

12.68

12.72

13.28

13.51

13.54

13.67

13.69

13.84

13.92

14.00

14.16

14.17

14.21

14.24

14.45

14.50

14.78

14.90

14.91

15.00

15.07

15.24

15.26

15.48

15.58

15.6

16.10

16.18

16.22

16.32

16.40

16.54

16.86

16.86

16.92

16.94

17.28

17.34

17.38

17.49

17.51

17.63

17.70

17.74

17.79

17.96

18.06

18.24

18.25

18.26

18.33

18.35

18.36

18.36

18.39

18.44

18.50

18.50

18.52

18.56

18.58

18.63

18.67

18.69

18.69

18.82

18.83

18.91

18.93

19.03

19.04

19.10

19.11

19.17

19.28

19.35

19.51

19.60

19.62

19.63

19.72

19.76

19.96

20.07

20.10

20.15

20.19

20.25

20.27

20.45

20.61

20.85

20.88

21.06

21.20

21.26

21.28

21.39

21.56

21.67

22.32

22.73

23.02

23.11

23.24

23.35

23.86

24.2

24.23

24.31

24.44

24.53

24.67

24.73

24.79

24.82

24.90

24.92

25.27

25.30

25.40

25.47

25.49

25.52

25.7

25.83

25.85

26.02

26.25

26.30

26.44

26.63

26.66

26.70

26.98

27.01

27.11

27.15

27.2

27.25

27.38

27.52

27.54

27.56

27.66

27.98

28.23

28.42

28.88

28.98

29.06

29.08

29.15

29.31

29.47

29.89

29.89

29.95

30.14

30.20

30.32

30.32

30.46

30.55

30.68

31.05

31.17

31.24

31.34

31.44

31.95

32.06

32.42

32.74

33.09

33.14

pKaH Directly measured ∆pK aH

Compound family:Phosphorylides

Phosphazenes

1,8−Naphtyl−Proton Sponges

Amidines

Aliphatic amines

Heterocycles

Porphyrines

Aromatic amines

Phosphanes

Phenylfulvenes

dma pyrr pip cp ch

tmg bn 1-Napht tmp

Ph-CH=P(-NMe-CH2-CH2-)3N

ProtonSp-R

XP1(R)3 XP2(R)5 XP3(R)7 XP3(R)6NEt2

t-BuP1(TACD) HP1(pyrr-2-CH2-N-pyrr)3 4-CF3-7-N=P1(R)3-Coumarin3

TBD MTBD DBU

[R1][R2]Guanidine TMG PhTMG

[R1][R2]TMAIMG [R1][R2]Triazine 1-(o-Tolyl)biguanide

[R1][R2]IYA IP Me2-IP

H2C{hpp}2 2,6-{hpp}2C5H3N 2-{hpp}C5H4N

Pyrrolidine Piperidine

Bispidine (-)-Sparteine

Piperazine Homopiperazine

9

1 5

1

2

3

45

6

7

8

6

7

8

5

91

4 10

2

3

4

7

5

61

2

3

4

7

5

61

3

2

1

2

34

5

4

5

6

3

2

1

Benzotriazole

2,2´-Bipyridine Phenanthroline

Isoquinoline

2,2´-Biquinoline

Quinoline

5,6-Benzoquinoline7,8-Benzoquinoline

Pyridazine

Pyrazole

Acridine

Pyrimidine

Pyrazine

Indazole

CaffeineUracil

Benzimidazole

Pyridine

Quinoxaline

Phthalazine 1,2,3-Triazole

Quino[7,8-h]quinoline

Imidazole

Carbendazim

Thymine

Thiabendazole

Quinazoline

OEP TPP

TMP TCPP

BIPHEP BINAP

Ph2 Ph2

Ph2Ph2

X-Phenylfulvene

* Protonation site

*