|
|
|
24. Analytical aspects |
1051 |
|
TABLE 1. (continued) |
|
|
|
||
|
|
|
|
|
|
Compound and CAS registry |
|
|
Various |
||
number a |
Safetyb |
Spectrac |
protocolsd |
||
n-Propylamine [107-10-8] |
2961D |
I(3)364C, N(1)238D |
UH9100000, EPA |
||
L-Serine [56-45-1] |
3085C |
I(1)580B |
USP |
||
Tetraethylenepentamine |
3261B |
I(3)398D, N(1)268A |
KH8585000 |
||
[112-57-2]e,f |
|
|
|
||
D-Thyroxine [51-49-0] |
3349C |
I(2)254A |
USP |
||
L-Thyroxine [51-48-9] |
3349B |
I(2)254B |
YP2833500, USP |
||
Triethylenetetramine [112-24-3]e,f |
3431D |
I(3)498B, N(1)267C |
YE6650000 |
||
(+)-3,30 ,5-Triiodo-L-thyronine |
3467B |
I(2)253D |
USP |
||
sodium salt [55-06-1] |
|
|
|
||
L-Tyrosine [60-18-4] (46) |
3565B |
I(2)255D, N(2)254B |
YP2275600, USP |
||
Amino group attached to carbon |
|
carbon double bond |
|
|
|
|
|
|
|||
2-Amino-3-chloro-1, 4-naphtho- |
154C |
I(2)81A, N(2)87A |
QL7350000 |
||
quinone [2797-51-5]g |
|
|
|
||
Mitomycin C [50-07-7] |
2470B |
I(2)1068A |
CN0700000, USP |
||
Amino group attached to aromatic carbon |
|
|
|||
Aclonifen [74070-46-5]g |
|
|
|
||
Acrisorcin [7527-91-5] |
|
|
USP |
||
Amiloride hydrochloride |
|
|
USP |
||
[17440-83-4]e |
|
|
|
||
2-Aminobenzoic acid [119-92-3] |
282B |
I(2)189A, N(2)186B |
CB2450000 |
||
2-Aminobenzoic acid methyl ester |
2295A |
I(3)1371A, N(2)284A |
CB3325000 |
||
[134-20-3] (165) |
|
|
|
|
|
4-Aminobenzoic acid [150-13-0] |
138B |
I(2)198C, N(2)195B |
DG1400000, USP |
||
4-Aminobenzoic acid n-butyl ester |
|
|
DG1530000, USP |
||
[94-25-7] |
|
|
|
|
|
4-Aminobenzoic acid ethyl ester |
1571A |
I(3)1372B, N(2)287D |
DG2450000, USP |
||
[94-09-7] (165) |
|
|
|
|
|
4-Aminobiphenyl [92-67-1] |
143D |
I(3)1157B, |
DU8925000, EPA |
||
2-Amino-4-chlorophenol [95-85-2] |
789A |
I(1)1228A, |
SJ5700000 |
||
|
|
|
|
N(1)1038A |
|
DL-Aminoglutethimide [125-84-8] |
149B |
I(2)404A, |
MA4026950, USP |
||
4-Aminohippuric acid [61-78-9] |
|
I(2)378B, N(2)355A |
USP |
||
1-Aminonaphthalene [134-32-7] |
196D |
N(1)1058B |
QM1400000, EPA |
||
2-Aminonaphthalene [91-59-8] |
197A |
|
QM2100000, EPA |
||
2-Aminophenol [95-55-6] |
206C |
I(3)1115D, N(1)997B |
SJ4950000 |
||
4-Aminophenol [123-30-8] |
207A |
I(1)1210B, |
SJ5075000 |
||
|
|
|
|
N(1)1013A |
|
4-Aminosalicylic acid [65-49-6] |
225A |
I(2)219C, N(2)215C |
VO1225000, USP |
||
Amprolium |
|
|
USP |
||
Anileridine [144-14-9]f |
|
|
USP |
||
Aniline [62-53-3] |
270A |
I(3)1109A, N(1)987A |
BW6650000, EPA |
||
Asulam [2302-17-2]g |
|
|
|
||
Atrazine [1912-24-9] (1a)e,g |
|
|
|
||
Basic fuchsin [569-61-9; 632-99-5]e |
338C, |
I(2)963B, U126, 129 |
CX9850000, |
||
Benzidine [92-87-5] (32)e |
339A |
|
CX9850100, USP |
||
|
|
DC9625000, EPA |
|||
Chloramben [133-90-4]g |
|
|
|
||
2-Chloroaniline [107-47-8] |
732D |
I(3)1114C, N(1)995A |
BX0525000 |
||
(continued overleaf )
1052 |
Jacob Zabicky and Shmuel Bittner |
|
||
TABLE 1. |
(continued) |
|
|
|
|
|
|
|
|
Compound and CAS registry |
Safetyb |
Spectrac |
Various |
|
number a |
|
|
|
protocolsd |
4-Chloroaniline [107-47-8] |
733B |
I(3)1126C, |
BX0700000, EPA |
|
|
|
|
N(1)1010A |
|
3-Chloro-4-fluoroaniline [367-21-5] |
782A |
I(3)1137A, |
EPA |
|
|
|
|
N(1)1025D |
|
3-Chloro-4-methylaniline [95-74-9] |
797C |
I(3)1138C, |
XU5111000, EPA |
|
|
|
|
N(1)1026B |
|
2-Chloro-4-nitroaniline [121-87-9] |
815D |
I(3)1365D, |
BX1400000 |
|
|
|
|
N(1)1168D |
|
4-Chloro-2-nitroaniline [89-63-4] |
816B |
I(3)1211A, |
BX1575000 |
|
|
|
|
N(1)1169A |
|
Dapsone [80-08-0] |
212A |
I(2)490B, N(2)815C |
GA0875000, USP |
|
1,2-Diaminobenzene [95-54-5]e |
2773A |
I(1)1154A, |
SS7875000 |
|
1,3-Diaminobenzene [106-50-3]e |
|
N(1)1045C |
|
|
2773B |
I(1)1154D, |
SS7700000 |
||
1,4-Diaminobenzene [106-50-3]e |
|
N(1)1048A |
|
|
2773C |
I(1)1242B, |
SS8050000, EPA |
||
2,4-Diaminotoluene [95-80-7]e |
|
N(1)1051B |
|
|
1059C |
I(3)1155B, |
XS9625000, EPA |
||
|
|
|
N(1)1049A |
|
3,4-Dichloroaniline [95-76-1] |
1112C |
I(3)1139D, |
BX2625000 |
|
3,30 -Dichlorobenzidine [91-94-1]e |
|
N(1)1029A |
|
|
|
|
DD0525000, EPA |
||
2,6-Dichloro-4-nitroaniline |
|
|
|
|
[99-30-9]g |
|
|
|
|
2,6-Diethylaniline [579-66-8] |
1196C |
I(3)1131C, |
BX3500000, EPA |
|
|
|
|
N(1)1019A |
|
2,4-Dimethylaniline [95-68-1] |
1348C |
I(3)1135B |
ZE8925000 |
|
2,6-Dimethylaniline [87-62-7] |
1349A |
I(3)1131A, |
ZE9275000, EPA |
|
Dinitramine [29091-05-2]f,g |
|
N(1)1018C |
|
|
|
|
|
||
Fluroxypyr [69377-81-7]g |
|
|
|
|
Methotrexate [59-05-2]e,f |
129C |
I(2)896D |
MA1225000, USP |
|
2-Methoxy-5-methylaniline |
2252C |
I(3)1144A, |
BZ6720000 |
|
[120-71-8] |
|
|
N(1)1033B |
|
2-Methylaniline [95-53-4] |
3371C |
I(3)1112D, N(1)992D |
XU2975000, EPA |
|
4-Methylaniline [106-49-0] |
3372D |
I(3)1121B, |
XU3150000 |
|
|
|
|
N(1)1005B |
|
2-Methyl-5-nitroaniline [99-55-8] |
2388C |
I(1)1364B, |
XU8225000, EPA |
|
|
|
|
N(1)1167C |
|
2-Nitroaniline [88-74-4] |
2549C |
I(3)1185C, |
BY6650000, EPA |
|
|
|
|
N(1)1134D |
|
3-Nitroaniline [99-09-2] |
2550A |
I(3)1189B, |
BY6825000, EPA |
|
|
|
|
N(1)1139A |
|
4-Nitroaniline [100-01-6] |
2550C |
I(3)1193C, |
BY7000000, EPA |
|
|
|
|
N(1)1144C |
|
Procainamide hydrochloride |
2942D |
I(2)373B, N(2)350C |
CV2295000, USP |
|
[614-39-1]f |
|
|
|
|
Procaine hydrochloride [51-05-8]f |
2943B |
I(2)303D, N(2)349D |
DG2275000, USP |
|
Sulfadiazine [68-35-9] (111) |
3195A |
|
WP1925000, USP |
|
Sulfamethazine [57-68-1] |
|
I(2)836C |
WO9275000, USP |
|
Sulfathiazole [72-14-0] |
3322B |
|
WP2360000, USP |
|
Triamterene [396-01-0]e |
3389C |
|
UO3470000, USP |
|
|
24. Analytical aspects |
1053 |
|
TABLE 1. (continued) |
|
|
|
|
|
|
|
Compound and CAS registry |
Safetyb |
Spectrac |
Various |
number a |
|
|
protocolsd |
2,4,5-Trichloroaniline [636-30-6] |
3407A |
I(3)1152B, |
XU8225000, EPA |
|
|
N(1)1043A |
|
3-Trifluoromethylaniline [98-16-8] |
141A |
I(3)1114B, N(1)994B |
XU9210000, EPA |
a Nomenclature may vary from source to source. See also Reference 69. b Entry number in Reference 70.
c Codes beginning with I,N and U denote FTIR spectra in Reference 71, NMR spectra in Reference 72 and UVV spectra in Reference 73, respectively.
d A code of two letters followed by seven digits is a reference to Registry of Toxic Effects of Chemical Substances (RTECS) of National Institute for Occupational Safety and Health/Occupational Safety and Health Administration (NIOSH/OSHA). Standard samples are commercially available for most compounds with reference to protocols of the US Environmental Protection Agency (EPA) and the US Pharmacopea (USP)74.
e The compound has two or more amino groups of the same type. f The compound has several types of amino groups.
g A pesticide, see Reference 75.
TABLE 2. Examples of environmental, occupational and quality control protocols for industrial secondary amines
Compound and CAS registry |
|
|
Various |
number a |
Safetyb |
Spectrac |
protocolsd |
Amino group attached to two saturated aliphatic carbons |
|
||
2-(2-Aminoethylamino)ethanol |
168B |
I(3)466B, N(1)304C |
KJ6300000 |
[111-41-1]f |
|
|
|
1-(2-Aminoethyl)piperazine |
172B |
I(3)437D, N(1)330C |
TK8050000 |
[140-31-8]f |
|
|
|
Desipramine hydrochloride |
|
|
USP |
[58-28-6]f |
|
|
|
Dicyclohexylamine [101-83-7] |
1177C |
I(3)402D, N(1)272C |
HY4025000 |
Diethanolamine [111-42-2] |
1183D |
I(3)431B, N(1)297D |
KL2975000 |
Diethylenetriamine [111-40-0]f |
1207D |
I(1)396A, N(1)266B |
IE1225000 |
Dobutamine hydrochloride |
|
|
USP |
[49745-95-1] |
|
|
|
(1R,2S)-(-)-Ephedrine |
1513A |
I(1)1277C, |
KB0700000, USP |
[299-42-3] (30) |
|
N(1)1078C |
|
(R)-(-)-Epinephrine [51-43-4] (21b) |
1518C |
I(1)1296A, |
DO2625000, USP |
|
|
N(1)1099C |
|
Iminodiacetic acid [142-73-4] |
1976A |
I(1)564B, N(1)483B |
AI2975000 |
(š)-Isoproterenol hydrochloride |
2043D |
I(1)1296B, |
DO1930000, USP |
[949-36-0] (21c) |
|
N(1)1099D |
|
(š)-Ketamine hydrochloride |
|
|
GW1400000, USP |
[1867-66-9] |
|
|
|
Mitomycin C [50-07-7]f |
2470B |
I(2)1068A |
CN0700000, USP |
Morpholine [110-91-8] |
2477C |
I(3)472A, N(1)335C |
QD6475000 |
Oxamniquine [21738-42-1]f |
|
|
USP |
(R)-(-)-Phenylephrine hydrochloride |
2776D |
I(1)1286A, |
DO7525000, USP |
[61-76-7] (51) |
|
|
|
Piperazine [57-47-6]e |
2843D |
I(3)463B, N(1)326A |
TK7800000, USP |
Piperazine dihydrochloride |
2844C |
|
TL4025000 |
[142-64-3]e |
|
|
|
Piperazine hexahydrate [142-63-2]e |
2844A |
I(1)371B, N(1)326B |
TM0850000 |
(continued overleaf )
1054 |
Jacob Zabicky and Shmuel Bittner |
|
||||||
TABLE 2. |
(continued) |
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
|
Compound and CAS registry |
|
|
|
|
|
|
Various |
|
number a |
|
Safetyb |
|
Spectrac |
protocolsd |
|||
L-Proline [147-85-3] |
2946A |
I(1)583C |
TW3584000, USP |
|||||
(š)-Propranolol hydrochloride |
2961A |
I(1)1300D, |
UB7526000, USP |
|||||
[3506-09-0] |
|
|
N(1)1104B |
|
||||
(1S,2S)-(+)-Pseudoephedrine |
2983D |
|
|
|
|
|
UL5950000, USP |
|
hydrochloride [345-78-8] (180a) |
|
|
|
|
|
|
|
|
Sarcosine [107-97-1] |
3070A |
I(1)570A |
VQ2897000 |
|||||
Tetraethylenepentamine |
3261B |
I(3)398D, N(1)268A |
KH8585000 |
|||||
[112-57-2]e,f |
|
|
|
|
|
|
|
|
Triethylenetetramine [112-24-3]e,f |
3431D |
I(3)498B, N(1)267C |
YE6650000 |
|||||
Amino group attached to one saturated aliphatic carbon and one carbon |
|
carbon double bond |
||||||
|
||||||||
Flurtamone [96525-23-4]g |
|
|
|
|
|
|
|
|
Amino group attached to one saturated aliphatic carbon and one aromatic carbon |
|
|||||||
Benzonatate [104-31-4] |
|
|
|
|
|
|
USP |
|
Butralin [33629-47-9]g |
|
|
|
|
|
|
|
|
Chloroquine [54-05-7] |
|
|
|
|
|
|
VB2360000, USP |
|
Cyanazine [21725-46-2]e,g |
|
|
|
|
|
|
UG1490000 |
|
Desmetryn [1014-69-3]e,g |
|
|
|
|
|
|
|
|
Dinitramine [29091-05-2]f,g |
|
|
|
|
|
|
|
|
Ethoxyquin [91-53-2]g |
|
|
|
|
|
|
|
|
N-Ethyl-m-toluidine [102-27-2] |
1660B |
I(3)1117C, N(1)999D |
XU6400000 |
|||||
N-Ethyl-o-toluidine [94-68-8] |
|
I(3)1113A |
XU6440000 |
|||||
Hydroflumethazide [135-09-1] |
|
|
|
|
|
|
USP |
|
Oxamniquine [21738-42-1]f |
|
|
|
|
|
|
USP |
|
Pendimetalin [40487-42-1]g |
|
|
|
|
|
|
|
|
Primaquine phosphate [63-45-6] |
2942C |
I(2)864B, N(2)741A |
VA9660000, USP |
|||||
(148)f |
|
|
|
|
|
|
|
|
Quinacrine hydrochloride hydrate |
3020C |
I(2)877A, N(2)751D |
AR7875000, USP |
|||||
[6151-30-0]f |
|
|
|
|
|
|
|
|
Amino group attached to one aromatic carbon and one carbon |
|
carbon double bond |
|
|||||
|
|
|||||||
Bromocriptine mesylate |
|
|
|
|
|
|
KE8250000, USP |
|
[22260-51-1]f |
|
|
|
|
|
|
|
|
Reserpine [50-55-5]f |
3039C |
I(2)1069C, N(2)945A |
ZG0350000, USP |
|||||
Vinblastine sulfate |
3598B |
|
|
|
|
|
YY8400000, USP |
|
[143-67-9](102b)f |
|
|
|
|
|
|
|
|
Amino group attached to two aromatic carbons |
|
|
|
|
|
|
||
Amodiaquine [86-42-0] (146)f |
|
|
|
|
|
|
USP |
|
Carbazole [86-74-8] |
681B |
I(2)679C |
FE3150000, EPA |
|||||
Diphenylamine [122-39-4]g |
|
|
|
|
|
|
JJ7800000, EPA |
|
Fluazinam [79622-59-6]g |
|
|
|
|
|
|
|
|
a Nomenclature may vary from source to source. See also Reference 69. b Entry number in Reference 70.
c Codes beginning with I, N and U denote FTIR spectra in Reference 71, NMR spectra in Reference 72 and UVV spectra in Reference 73, respectively.
d A code of two letters followed by seven digits is a reference to RTECS of NIOSH/OSHA. Standard samples are commercially available for compounds with reference to protocols of EPA and USP74.
e The compound has two or more amino groups of the same type. f The compound has several types of amino groups.
g A pesticide, see Reference 75.
24. Analytical aspects |
1055 |
TABLE 3. Examples of environmental, occupational and quality control protocols for industrial tertiary amines
Compound and CAS registry |
Safetyb |
Spectrac |
Various |
number a |
|
|
protocolsd |
Amino group attached to three saturated aliphatic carbons |
|
||
Acetophenazine maleate |
|
|
OB4180000, USP |
[5714-00-1]e,f |
|
|
|
Alphaprodine hydrochloride |
|
|
TN7101000, USP |
[14405-05-1; 49638-24-6] |
|
|
|
1-(2-Aminoethyl)piperazine |
172B |
I(3)437D, N(1)330C |
TK8050000 |
[140-31-8] |
|
|
|
Aminotriptyline hydrochloride |
|
|
USP |
[549-18-8] |
|
|
|
Amodiaquine [86-42-0] (146)f |
|
|
USP |
Anileridine [144-14-9]f |
|
|
USP |
Apomorphine hydrochloride |
|
|
CE0700000, |
hemihydrate [41372-20-7] (54) |
|
|
HQ1750000, USP |
Atropine sulfate monohydrate |
320A |
I(2)286B, N(2)274B |
CK2455000, USP |
[5908-99-6] (159) |
|
|
|
Azatadine maleate [3978-86-7] |
|
|
DE8025500, USP |
Bensultap [17606-31-4]g |
|
|
|
Benztropine mesylate [132-17-2] |
277B |
I(1)381D |
YM3150000, USP |
Benzyldimethylamine [103-83-3] |
1357B |
I(3)1167D, |
DP4500000 |
|
|
N(1)1067D |
|
Bromocriptine mesylate |
|
|
KE8250000, USP |
[22260-51-1]f |
|
|
|
Bromodiphenhydramine hydrochlo- |
|
|
USP |
ride [1808-12-4] |
|
|
|
Bromopheniramine maleate |
|
|
US4025000, USP |
[980-71-2] |
|
|
|
Bupivacaine hydrochloride |
|
|
TK6060000, USP |
[18010-40-7] (11) |
|
|
|
Buspirone [33386-08-2; |
|
|
USP |
36505-88-7] (27)f |
|
|
|
Butorphanol tartrate [58786-99-5] |
|
|
USP |
Cartap [15263-53-3]g |
|
|
|
Chlorcyclizine hydrochloride |
|
|
TL2200000, USP |
[1620-21-9; 4362-31-3]e |
|
|
|
Chlorphenoxamine hydrochloride |
|
|
KR3155000, USP |
[562-09-4] |
|
|
|
Chlorpromazine hydrochloride |
871A |
|
SO1750000, USP |
[69-09-0]e |
|
|
|
Chlortetracycline hydrochloride |
871B |
|
QI7800000, USP |
[64-72-2]e |
|
|
|
Clindamycin hydrochloride |
|
|
GF2275000, USP |
[21462-39-5] |
|
|
|
Clomiphene citrate [50-41-9] |
|
|
YE0875000, USP |
Cocaine [50-36-2] (23a) |
|
|
YM2800000, USP |
Codein [76-57-3] |
|
|
QD0893000, USP |
Cyclizine [82-92-8]e |
|
|
USP |
Cyclomethycaine sulfate |
|
|
USP |
[50978-10-4] |
|
|
|
Cyproheptadine hydrochloride |
999C |
|
TM7050000, USP |
sesquihydrate [41354-29-4] |
|
|
|
Dibucaine hydrochloride [61-12-1] |
1095C |
|
GD3325000, USP |
(continued overleaf )
1056 |
Jacob Zabicky and Shmuel Bittner |
|
||
TABLE 3. (continued) |
|
|
|
|
|
|
|
|
|
Compound and CAS registry |
Safetyb |
Spectrac |
Various |
|
number a |
|
|
|
protocolsd |
2-(N,N-Diethylamino)ethanol |
1208D |
I(3)432B, N(1)299B |
KK5075000 |
|
[100-37-8] |
|
|
|
|
Diethylenetriaminepentaacetic acid |
1208A |
I(1)543C |
MB8205000 |
|
[67-43-6]e |
|
|
|
|
Diphenhydramine hydrochloride |
1450A |
|
KR7000000, USP |
|
[147-24-0] |
|
|
|
|
Diphenylpyraline hydrochloride |
1461A |
|
TM7823600, USP |
|
[132-18-3] |
|
|
|
|
Dodemorph [1593-77-7]g |
|
|
|
|
Erythromycin [114-07-8] |
|
|
I(1)703B |
KF4375000, USP |
Ethopropazine hydrochloride |
1551B |
|
SO5002000, USP |
|
[1094-08-2]f |
|
|
|
|
Ethylenediaminetetraacetic |
acid |
|
|
AH4025000, USP |
[60-00-4]e |
|
|
|
|
Ethylenediaminetetraacetic acid, |
1605D |
|
EV7700000, USP |
|
calcium disodium salt hydrate |
|
|
|
|
[23411-34-9]e |
|
|
|
|
Fenpropidin [67306-00-7]g |
|
|
|
|
Fenpropimorph [67564-91-4]g |
|
|
|
|
Flupropadin [81613-59-4]g |
|
|
|
|
Haloperidol [52-86-8] |
|
|
|
EU1575000, USP |
Hexamethylenetetramine |
|
1852B |
I(2)471D, N(2)332D |
MN4725000, USP |
[100-97-0]e |
|
|
|
|
D,L-Homatropine hydrobromide |
1882B |
I(2)286A, N(2)274C |
YM5602000, USP |
|
[51-56-9] |
|
|
|
|
Morphine sulfate [64-31-3] (55) |
|
|
QC8750000, USP |
|
Naloxone hydrochloride dihydrate |
|
|
QD2275000, USP |
|
[51481-60-8] |
|
|
|
|
(S)-(-)-Nicotine [54-11-5]g |
|
2541A |
I(3)1537B, N(2)647B |
QS5250000 |
Noscapine [128-62-1] |
|
|
|
RD2625000, USP |
Pargyline hydrochloride [306-07-0] |
2423C |
I(2)948C, N(2)964A |
DP6650000, USP |
|
Physostigmine [57-47-6]f |
|
1533B |
I(2)1065C, N(2)392D |
TJ2100000, USP |
Procainamide hydrochloride |
2942D |
I(2)373B, N(2)350C |
CV2295000, USP |
|
[614-39-1]f |
|
|
|
|
Procaine hydrochloride [51-05-8]f |
2943B |
I(2)303D, N(2)349D |
DG2275000, USP |
|
Promethazine hydrochloride |
2948C |
|
SO8225000, USP |
|
[58-33-3]f |
|
|
|
|
Propamocarb hydrochloride |
|
|
|
|
[25606-41-1]g |
|
|
|
|
Quinacrine hydrochloride hydrate |
3020C |
I(2)877A, N(2)751D |
AR7875000, USP |
|
[6151-30-0]f |
|
|
|
|
Quinidine sulfate [6591-63-5] |
3023A |
I(2)866A, |
VA6950000, USP |
|
Quinine sulfate [6119-70-6] (160) |
3023D |
I(2)865C, |
VA8440000, USP |
|
Reserpine [50-55-5] |
|
3039C |
I(2)1069C, N(2)945A |
ZG0350000, USP |
Scopolamine hydrobromide |
|
3073B |
I(2)286C, N(2)274D |
YM4550000, USP |
[114-49-8] |
|
|
|
|
Strychnine [57-29-9]g |
|
3180C |
I(2)1066B, N(2)942D |
WL2275000 |
Tetracycline hydrochloride [64-75-5] |
3252B |
I(2)421C |
QI9100000, USP |
|
Thioridazine hydrochloride |
|
3337C |
I(1)1316D |
SP2275000, USP |
[130-61-0]f |
|
|
|
|
|
|
24. Analytical aspects |
1057 |
|
TABLE 3. (continued) |
|
|
|
|
|
|
|
|
|
Compound and CAS registry |
|
Safetyb |
Spectrac |
Various |
number a |
|
|
|
protocolsd |
Tridemorph [81412-43-3]g |
|
|
|
|
Triethanolamine [102-71-6] |
|
3426B |
I(3)434C, N(1)301D |
KL9275000 |
Tubocurarine chloride pentahydrate |
|
3556D |
|
YO5100000, USP |
[41354-45-4] (205)f |
|
|
|
|
Vinblastine sulfate [143-67-9] |
|
3598B |
|
YY8400000, USP |
(102b)e,f |
|
|
|
|
Amino group attached to one carbon |
|
carbon double bond and two saturated aliphatic carbons |
||
|
||||
Mitomycin C [50-07-7]f |
|
2470B |
I(2)1068A |
CN0700000, USP |
Amino group attached to two carbon |
|
carbon double bonds and one saturated aliphatic carbon |
||
|
||||
Propyliodone [587-61-1] |
|
|
|
USP |
Amino group attached to one aromatic carbon, one carbon carbon double bond and one saturated aliphatic carbon
Nalidixic acid [389-08-2] |
2485D |
I(2)889B, N(2)763B |
QN2885000, USP |
||
Oxolinic acid [14698-29-4]g |
|
|
|
|
JI5075000 |
Amino group attached to one aromatic carbon and two carbon |
|
carbon double bonds |
|||
|
|||||
Pyrvinium pamoate [3546-41-6]f |
3018C |
I(2)873C |
VC3543500, USP |
||
Amino group attached to one aromatic carbon and two saturated aliphatic carbons |
|
||||
Ametrin [834-12-8]e,g |
|
|
|
|
EPA |
Benfluralin [1861-40-1]g |
|
|
|
|
EPA |
Buspirone [33386-08-2; |
|
|
|
|
USP |
36505-88-7] (27)f |
|
|
|
|
|
Crystal violet [548-62-9]e |
929B |
I(2)1029D, U239 |
BO9000000, USP |
||
N,N-Diethylaniline [91-66-7] |
1196B |
I(3)1111C, N(1)991B |
BX3400000 |
||
3-(Dimethylamino)phenol [99-07-0] |
1341D |
I(3)1120C, |
SL1050000, USP |
||
|
|
N(1)1004B |
|
||
N,N-Dimethylaniline [121-69-7] |
1347D |
I(3)1111A, N(1)990D |
BX4725000, EPA |
||
Dipyridamole [58-32-2]e |
1472B |
|
|
|
KK7450000, USP |
Ethalfluralin [55283-68-6]g |
|
|
|
|
EPA |
Isopropalin [33820-53-0]g |
|
|
|
|
EPA |
Methotrexate [59-05-2]f |
129C |
I(2)896D |
MA1225000, USP |
||
Methylene blue [7220-79-3]e |
2344C |
I(2)887D, U448 |
SO5600000, USP |
||
Methyl yellow [60-11-7] |
2464D |
U472 |
BX7350000, USP |
||
Oryzalin [19044-88-3]g |
|
|
|
|
|
Physostigmine [57-47-6]f |
1533B |
I(2)1065C, N(2)392D |
TJ2100000, USP |
||
Profluralin [26399-36-0]g |
|
|
|
|
EPA |
Propachlor [1918-16-7]g |
|
|
|
|
|
Pyrvinium pamoate [3546-41-6]f |
3018C |
I(2)873C |
VC3543500, USP |
||
Vinblastine sulfate [143-67-9] |
3598B |
|
|
|
YY8400000, USP |
(102b)f |
|
|
|
|
|
Amino group attached to two aromatic carbons and one saturated aliphatic carbon |
|
||||
Acetophenazine maleate |
|
|
|
|
OB4180000, USP |
[5714-00-1]f |
|
|
|
|
|
Antazoline phosphate |
|
|
|
|
USP |
Bromethaline [63333-35-7]g |
|
|
|
|
|
Desipramine hydrochloride |
|
|
|
|
USP |
[58-28-6]f |
|
|
|
|
|
Ethopropazine hydrochloride |
1551B |
|
|
|
SO5002000, USP |
[1094-08-2]f |
|
|
|
|
|
(continued overleaf )
1058 |
Jacob Zabicky and Shmuel Bittner |
|
|
TABLE 3. (continued) |
|
|
|
|
|
|
|
Compound and CAS registry |
Safetyb |
Spectrac |
Various |
number a |
|
|
protocolsd |
Promethazine hydrochloride |
2948C |
|
SO8225000, USP |
[58-33-3]f |
|
|
|
Thioridazine hydrochloride |
3337C |
I(1)1316D |
SP2275000, USP |
[130-61-0]f |
|
|
|
a Nomenclature may vary from source to source. See also Reference 69. b Entry number in Reference 70.
c Codes beginning with I, N and U denote FTIR spectra in Reference 71, NMR spectra in Reference 72 and UVV spectra in Reference 73, respectively.
d A code of two letters followed by seven digits is a reference to RTECS of NIOSH/OSHA. Standard samples are commercially available for compounds with reference to protocols of EPA and USP74.
e The compound has two or more amino groups of the same type. f The compound has several types of amino groups.
g A pesticide, see Reference 75.
containing the amino group are important intermediates in the manufacture of organic chemicals. Many of the pharmaceuticals listed in these tables stem from biological systems, possibly with some minor chemical modification. Some amines, including amino acids, are also traced in environmental samples to assess ecologic interaction of living organisms and pollution by industrial chemicals.
Nanomolar concentrations of low molecular weight amines and organic acids dissolved in seawater can be preconcentrated up to 1000-fold by diffusion across hydrophobic membranes and collecting in HCl or NaOH solutions, respectively. Of a set of 25 amines investigated, excepting pyrrole, all showed practically quantitative trapping efficiency76.
A comparative study was carried out between diffusive (passive) and pumping (active) sampling of airborne contaminants, including factors such as retention volumes, uptake rate, concentration, recovery by thermal desorption and sampling efficiency. Diffusive sampling gave precise and accurate results according to NIOSH standards (š25% accuracy), and the method is sensitive enough to measure benzene, aniline and nitrobenzene at concentrations as low as 0.1 mg/m3. Diffusive sampling has practical advantages and is cost effective77.
Interlaboratory studies were carried out on the precision characteristics of the analytical methods used for determination of certain biogenic amines in fish and fish products, as required by German law. These included putrescine (4a), cadaverine (4b), tyramine (5) and histamine (6)78.
CH2 CH2 NH2
|
CH2 CH2 NH2 |
N |
|
NH2 (CH2 )nNH2 |
|
N |
|
(a) n = 4, (b) n = 5, (c) n = 6 |
HO |
||
H |
|||
(4) |
(5) |
(6) |
24. Analytical aspects |
1059 |
B. Isotope Analysis
In Section III.D various methods were mentioned for determination of the 15N to 14N isotope ratio. Some applications to amines that appeared in the recent literature are presented here. Isotope dilution with a known aliquot of labelled compound allows solving some of the problems related to nonquantitative recovery yields of analyte in the analytical processing of a sample. However, the possibility of isotopic fractionation has to be taken into consideration.
Isotopic analysis of amino acids containing natural abundance levels of 15N was performed by derivatization, GC separation, on-line combustion and direct analysis of the combustion products by isotope-ratio MS. The N2 gas showed RSD better than 0.1‰ for samples larger than 400 pmol and better than 0.5‰ for samples larger than 25 pmol. After on-column injection of 2 nmol of each amino acid and delivery of 20% of the combustion products to the mass spectrometer, accuracy was 0.04‰ and RSD 0.23‰79.
Nitrogen uptake studies in plants can be made based on 15N labelling, taking advantage of developments in MS and automated on-line separation. 15N can be precisely analyzed in samples of plant extract containing as little as 5 50 mg of N, with isotope enrichment close to the natural abundance level, and then be ascribed to N pools in the plant, such as nitrate, amino acids and soluble protein80. Individual amino acids can be determined out of mixtures in the natural 13C abundance range by addition of 13C-labelled amino acid, derivatization to the N-acetyl propyl ester, GC separation, combustion and determination of 13C. Up to nine amino acids could be determined in 200 mg of a mixture. The global13C of casein calculated from individual amino acids differed by less than 1.5‰ from the directly determined value81.
Characteristic line pairs of the following isotopically enriched amino acids were investigated by MS-SIM: [˛-15N] and [ε-15N]lysine, [1-13C] and [15N]alanine and leucine, and [1-13C], [2-13C], [3-13C] and [4-13C]aspartic acid. Enrichments from 0.14 to 36% were determined with high precision82. A method of high precision and accuracy for determining 15N enrichment of eighteen common plasma amino acids and urea was proposed, based on derivatization with t-butyldimethylsilyl chloride (7) followed by a single GC analysis combined with electron impact (EI) MS-SIM detection. The monitored ions contained all the N atoms of the original compounds, except for arginine (8) that lost one of the guanidino nitrogens. The method was applied to human metabolism studies83.
|
|
Me |
|
|||
|
|
|
|
|
HN |
CO2 H |
t-Bu |
|
Si |
|
Cl |
CNH(CH2 )3 CH |
|
|
|
|||||
|
|
|
|
|
H2 N |
NH2 |
|
|
Me |
|
|||
(7) |
|
(8) |
||||
A sensitive method for determination of branched-chain L-amino acids is based on labelling individual species with 13C or 2H, isolating the amino acid by IEC and applying the derivatization scheme depicted in reaction 1. The L-amino acid is converted
1060 |
Jacob Zabicky and Shmuel Bittner |
enzymatically to the corresponding ˛-keto acid which, on reaction with o-phenylenedi- amine, yields a branched chain quinoxalinol. After SPE and O-trimethylsilylation the isotope enrichment is determined by GC using chemical ionization (CI) MS-SIM with ammonia and monitoring the [MH](C) and [MH C 1] C ions84.
H3 N+
CHR
O R
L-leucine
dehydrogenase
O O O OH
|
NH2 |
|
(1) |
|
NH2 |
|
|
N |
R |
N |
R |
|
Me3 SiCl |
|
|
N |
HO |
N |
OSiMe3 |
Determination of the 15NH4C :(15NH4C C 14NH4C ) ratio in samples enriched with 15NH4C can be performed by IEC with post-column derivatization according to reaction 7 (Section IV.D.3.a) and fluorescence measurement. The working principle is based on the slightly longer (1.2%) retention time of 15NH4C . This is insufficient for peak resolution, but causes a slight retardation to the emergence of the peak maximum, that can be correlated with the concentration of the heavier isotope in the 25 75% range85.
The problem of indigeneity assessment of organic matter in fossils can be solved by determining 13C and 15N for the enantiomers of each amino acid. These values should be the same for all amino acids in the fossil sample in indigenous organic matter, while a divergence points to contamination of the sample. The technique involves LC-MS for15N, combustion of the eluted amino acids and determination of the 13C content86. See also Section IV.D.5.
GC-MS analysis of the organic matter in hot water extracts from the Murchinson meteorite showed substantial enrichment of the heavier isotopes of the ‘organic’ elements over the terrestrial values: 2H C1221‰, 13C C22‰ and 15N C93‰. However, a lower value was found for ammonia 15N C69‰. The total amino acids separated from the extracts had 15N C94‰. The 15N values of the soluble organic compounds found in the meteorite are consistent with their formation, or formation of their precursors, by interstellar chemistry87,88.
C. Gas Chromatography
Innumerable applications of chromatographic methods to the analysis of amines appeared in the recent literature concerning biogenic amines, drugs and their metabolites, pesticides and industrial intermediates; however, due to the nonvolatile nature of many amines, application of the LC methods in Section IV.D became preponderant.
In Section III.C various detectors were mentioned that respond selectively to nitrogencontaining compounds; some applications to amines follow. A nonlinear calibration curve