Migration of aminoalcohols on paper

JOURNAL

,WG~TION HOWARD, Departrae~zt

OF CHROMATOGRAPHY

OF AMINOALCOHOLS

I<. ZIMMERMAN of Chemistry,

*

l

AND

Agricdtzrral

College

Statiou,

(Received

77

ON PAPER*

ALEXANDROS and Mecha~~ical

Texas

April qth,

(U.S.A

COSMATOS College of Texas,

.)

1961)

Ekcegtfka~ number of.‘investigations associated with specific biochemical problemsl, t&ret aEEears; to 1be.little information about the paper chromatography of aminoalo~liokimgeneral~.Thusj although mono-, di- and tri-ethanolamines have been separated omamiomexchange colimx+; the most comprehensive reports of this type yet appearing iin &lie:literature. seem: to’ be those on aminoalcohols derived from amino acids?, on ~~~~ooBlie~y~~l~o~~ohols derived from amino acids3+, and on aminoalcohols mlkizedlto~adkenaline~i.Confronted with a continuing need for information about the r.ni&&iomproperkies-of! atwide variety of aminoalcohols on paper, we have determined B&~valhes ii11tliree.different solvent systems for the aminoalcohols given in Table I. Niierous; variations. in the migration properties are noted with changes in B&&I sol?ven~~ system: and aminoalcohol structure. For example, solvent I3 gives extiensi&tailiirgoofi‘thetspots in rnany.cases, sometimes-leading to a diffuseness of spot v&i~makes&s’-‘-‘-‘-‘-‘-‘-‘-‘-‘-‘-’_esence very diffknlt. to detect. On the other hand, solvent A has a ~~o~tOJgrOdCe~~ateral.di~ion of the spot, with similar though less pronounced effbat!s;omsensitiiti~ofi detection;: this tendency is compensated at least in part by a nelWkel.&- slow- rate’ ofi migration and a correspondingly good sensitivity to aminoaikohollst~~cture;. Solution: C- gives very good, coherent spots, but the migration is aorng~~~e~y-rapid~.leading to poorer separations than might be desired for certain miMiurest. Tit& e_xtxeme& rapid: migration of N-phenyl-ethanolamine derivatives, (comBo.~~g;,26;andi38)!is-especially noticeable in solvents A and C, and a similar behavior ~~o~B~se~lliFu~e.o-aminophenols (compounds 67, 68 and 69). A comparison of the &&4iies; off t&e N&substituted diethanolamines (compounds z-g) with those of the Bknonosubstitxtted ethanolamines (compounds 21-26) reveals a ..practically linear nelkt&~~j~imalllthreesolvent systems..This dependence of the migration rate on the rn&un~off tlie~nitxogensubstituent remains the most apparent feature.of all the data v&.iizkliax~beemobtainedl.It thus appears that the migration rates of aminoalcohols amq#inanil$-aontiolledbythe prevailing balance between the basicity of the amino~olkz.ndltha~ofthe:solvent system. “V&r& supported! by- U.S. Army Research Office (Durham), by the U.S. National Science, Etiund&ti&~;, andt by. the. Robert ,A. Welch Foundation. ““Rmsentaddtess::Dept. of Chemistry, University of the Pacific, Stockton, Calif., U.S.A. Chro-matog.,

7 (1962) 77-h

e 3

_.

-c-cc

-

f _.

PI,

_

t

ea.

_. u?_

U

s OS ;

0 e 0 $

5

$0

46 47 4s 49

45

.

.

3-Diethylamino-1-propanol q-Amino-1-butanol r-Methyl-4-diethylamino-r-butanol 5-Amino-r-pentanol (i-Amino-1-hexanol

.

,

I-Phenyl-2-methyl-ethanolamine I-Phenyl-2,2-dimethyl-ethanolamine i-Phenyl-+methyl-N-methylethanolamine I-Phenyl-2-methyl-N,N-dimethylethanolamine 2-Ethyl-ethanolamine

41 42 43

z,2-Dimethyl-ethanolamine 2-Pyridyl-methyl-phenyl-carbinol 2-Pyridvl-diphenyl-carbinol fl-(2-Py&lyl)-ethanol 3-Amino-I-propanol

p-(4-Methyl-1-piperazino)-ethanol @-(N-iVorpholino)-ethanol N:Ethyl-N-phenyl-ethanolamine N-(2-Aminoethyl)-ethanolamine 1,4~Bis-(n-hydroxyethyl)-piperazine

36 37 38 39 4o

44

fl-(2-Heptadkcenyl-I-imidazolino)-ethanol

35

H,N(CH&OH H&CH&OH

(C,H,),N(CH,),CH(CHdOH

H,N(CH,),OH

(C,H,)21\‘(CH,) ,OH

3.95

1.21

2.10

0.57 0.32 0.38

o-44 0.24

-

1.00

I.SI

2.22

0.88 0.58

0.71

3.00 I -68 2.00

2-75

o.s3 0.46

2.32 I .26

2.60 I.44

2.s2

0.70 0.90

I *33

1.2s 1.13 1.46 1.22

1.02

(contthrd on p. 80)

‘0.72

0.79 0.66

0.61

0.69

0.76

0.87

1130 1.61 1.41 -

1.32 0.71

2.38 0.76 1.sg

0.70

1.63

o.S8 2.68 0.56

2.18

I.65

2.90

1.67

o.sg 2.7s

o.sg

1.61

1.02

o.s7

I.24 -

I.Ij

3.00

4.95 0.72

2.75 2.68

I.34

0.47 o-55

1.00 I.25

2.88

0.62 0.67

1.76

I.Gj

1.26 I.33 1.50

I,J3 I,24 I.33 1.5’

3,

0.87 0.90

o-94

0.24

2.1s 2.10

0.95

g

0.88 0.86

0.40 o-43

0.70 0.67 0.92

2.90

o.sg

0.81

2.82 2.8s

0.72

0.66

o,6r 0~67 0.72 0.82

‘144 2.62

2.47 -

5

o,qr

2-79 3.10

0:6i

1.63 %

3.26

o-35

H2NCH(C,H,)CH20H

0.92

2.84

0.93

0.84 0.90

4-05

0.78

I ,63

“;I9

o;‘t3

2.10

0.40 0.62

o-55

(CH&NCH(CH,)CH(C,H,)OH

H,NC(CH,),CH,OH (C,H,N)C(CH,) (C,H,)OH (C,H,N)C(C,H,),OH (C,H,N)CH,CH,OH H2N(CH,),0H

o-53 o-59 o-57

0.91 0.13 0.13

H,NCH(CHJCti(C,HJOH H,NC(CH,),CH(C,H,)OH CH,NHCH(CH,)CH(C,HJOH

[(CH,)2NCH,CH,0Hl,

CH,N(CH&NCH&H,OH O(CH,),NCH,CH,OH C,HjN(CaH,)CH,Clj,OH H,N(CH2)2NHCH,CH,0H 0.23 0.31

o-77

LH, \ NH-CH-C,,H,, CH,-N-CH,CH,OH c/H, \ NH-CH&H,

0.31 0.40 0.54 0.75

(CH,),NCH,CH&)H (CH&,NCH&H,OH CH,CH(CH,),NCH,CH,OH CH,-N-CH,CH,OH

3.10

0.59

~-(N-P~rl70lidino)-ctbanol 32 /l-(N-Pipcridino)-ethanol 33 /?-(4-Mcthylhexamcthylenimino)-ethanol 34 fl-(a-Undecyl-I-imidazolino)-ethanol

31

I,63 I.79

28 N-Methyl-N-ethyl-cthanolaminc 29 N,N-Dicthyl-cthanolaminc 3Q N,N-Diallyl-cthanolaminc

1.42

a.27 Q,31 0.34

(CH,),NCH,CH,OH C,H,N(CH,)CH,CH,OH (C,H&NCH,CH,OH (CH,=CHCH,),NCH,CH,OH

27 N;NgUimotbyl-cthanalaminc

!?

2

x-Dicthylamino-3-amino-qropanol

r,3-Diamino-:!-propanol

IH - C&-l k-1

* R, refers to ethanolamine. **MOspot could be detected.

+Chloro-2-aminophenol 2

036

4.52

4$

0.87

q-Vitro-2-aminophcnol

O,N’A”NH,

3.42

0.37 2.26

I,11

1.11

0.6=j

0.43

0.07

(H,NCH,),CHOH [(CH,) $CH&(C&W’Hl~

O,?I

0.21

H,N(CH,)pMHCH,CHOHCH,

(C,H,),NCH,C~~~OH)CaH,I\‘H,

’ OH

2.42

I.37

o-Aminophenol

2,3-butancdiol

66 1,4-Bis-(dimcthylaminoj-q-diphcnyl-

65

64 N-(z-Aminoethyl)-isopropanolaminc

63

62

0.46

0.3?

(CH,),NCH,CHOHCH, CH,CHCH, \ CH,CHCH,N/ NCH,CHCH,

r,4-Bis+-hydrbxypropylj-2methyl-piperazinc

I.68

O.GG

C,H,,NHCH,CHOHCH,

KCyclohcxyl-isopropanolaminc

60

61

3.47

0.26

H,NCH,CHOHCH,

Isopropanolaminc

59

I.95

0.37

HN(CH,CHOHCHs),

Di-isopropanolamitlc

58

2.36

0.45

N(cHpcHoHcH3)~

0.90

0.17

Tri=isopropnnolaminc

I (~0tthttt~d)

57

56 Dihydroxymcthyl-cthylcncdiamino

*mm

o.s7

O.jS

o.so

o.s7

0.40

o*57

0.77

0.85

**

0.89

0.52

0.72

**

0.36

0.87

2.78

2.72

I.SI

2.ga

2.70

1.2j

1.7s

2.40

2.66

I .oo

1.00

1.00

0.85

0.39

0.52

0.50

0.78

Ohj

Oh0

1.G3

-

0.75

0.81

wi8

2.2j

-

1.12

-

-

-

I .58

0.72

0.96

0.93

I.?0

1.61

’ .39 1.11

’ *so

1.07

The solvent Solvent Solvent Solvent

systems ,emp;loyed :are iwe’llknos~ cones-MEidh lha_e l’bean u~5&ilk%xe:: A : .rtLButandl,;z.y*%:: :acetiicadid, 6(x:: \araltrer;, qcyO (@&. 7). B : ,tz-Butan~l:sa~ura~ed kitih (o.~~‘pj/~ zqne~us m ((k&f.“)>.. C: Pyridine, .q2’0/,:: :.etil@ :ac&a%e q’pi/O:: matier;,a<$$$:: aa&tiicti& 8@& (ref. ,‘). Whatman No. I .paper Iwas spotied kiI& meIiha~n&ic~dlultiimns&E t&e .SEAT~ aminoalcohols I :in. :from ithe ibottom &;a s’heet GJL_~S iin. ti& llxy~8351~ l.@@. YKken take spots were dry, ,theLsheet ~~was:sta.,lediinto:ac&lixu?ler;, zu&&ti.ixktr~~adliklhn&li&~ za glass plate and containing :the sdlvent. Xlhe \whde :assenBlywas co~~xex&iky:aand sealed at the base with kla8y. %Vit%sdltitiions 2k z&iiB,, ttIhenn&~attiimn~ ~I&DX&I to proceed 4 h. With solution C, ~~x+liidh rmo;r;red xnoxe n;a@i~y, nk&Miion JIB q after 3 h. Upon removal Iof rfhe pa.per q%in~er,, Whe &k&t fbn~mtasmxm&&i~ still wet. After air-drying, &he $heet was :qpr;rq\yed wsiitlIh NIL@‘?&&&r#h& iin ~f::lf pyridine-ethanol and :heated :s miin :a? IEQ~ O!kolbti~~gcati ttke &kxr cti ttlhe.q@k.

The mieation of ‘69 aminotilcdhdls con%Mha%manNa. IIpalper Ihaskeen && ‘- liniim three different develqping. sdlvent-s.‘Xhe:genel;a!l lb6hatim toffttihe ~~~~Q~~q@ksikm t&e .. three solvents .is indicated. ‘VaGa$ions iin xrii~ation n;atieskittlh~ndlmmIl e tics of the aniinoalcdho’ls:are Ibtii&Iy(discusse5,l.