JPS6391559A - Esterification of very small amount of specimen - Google Patents
Esterification of very small amount of specimenInfo
- Publication number
- JPS6391559A JPS6391559A JP23828486A JP23828486A JPS6391559A JP S6391559 A JPS6391559 A JP S6391559A JP 23828486 A JP23828486 A JP 23828486A JP 23828486 A JP23828486 A JP 23828486A JP S6391559 A JPS6391559 A JP S6391559A
- Authority
- JP
- Japan
- Prior art keywords
- diazomethane
- acid
- tank
- sample
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005886 esterification reaction Methods 0.000 title abstract description 17
- 230000032050 esterification Effects 0.000 title abstract description 13
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 claims abstract description 46
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 20
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000002832 nitroso derivatives Chemical class 0.000 claims abstract description 7
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims abstract description 5
- 239000000523 sample Substances 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 23
- 238000004817 gas chromatography Methods 0.000 claims description 10
- 150000007513 acids Chemical class 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000012470 diluted sample Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000000243 solution Substances 0.000 abstract description 12
- 238000004458 analytical method Methods 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 229910001854 alkali hydroxide Inorganic materials 0.000 abstract 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 8
- 238000007664 blowing Methods 0.000 description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000002360 explosive Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 2
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229960002446 octanoic acid Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229940005605 valeric acid Drugs 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KBRSJPHSCOAFDR-UHFFFAOYSA-N 3-chloro-6-methyl-5,5-dioxo-11h-benzo[c][2,1]benzothiazepin-11-ol Chemical compound O=S1(=O)N(C)C2=CC=CC=C2C(O)C2=CC=C(Cl)C=C21 KBRSJPHSCOAFDR-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZRKWMRDKSOPRRS-UHFFFAOYSA-N N-Methyl-N-nitrosourea Chemical compound O=NN(C)C(N)=O ZRKWMRDKSOPRRS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- -1 aromatic carboxylic acids Chemical class 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- CCNWZGXOWHXIJE-UHFFFAOYSA-N ethoxyethane;oxane Chemical compound CCOCC.C1CCOCC1 CCNWZGXOWHXIJE-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 238000003987 high-resolution gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000003533 narcotic effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本願発明は、酸性化合物を含む微量試料をジアゾメタン
によりエステル化する方法に関する、更に詳しくは、ジ
アゾメタン発生試薬としてのニトロソ化合物のジオキサ
ンおよび／またはジメチルホルムアミド溶液を、ジエチ
レングリコールおよび／またはそのモノアルキルエーテ
ル（アルキル基の炭素数＝１〜４）と、触媒としての少
量の苛性アルカリ水溶液の混合溶液の過剰量に滴下させ
て、ジアゾメタンを発生させ、それを不活性ガスにより
希釈し最大３０体積％とした後、試料、または揮発性溶
媒による希釈試料に吹込むことを特徴とする、回分式に
酸性化合物を含む微量試料を、安定的に再現性良く安全
かつ実質上完全にエステル化する方法に関する。特にガ
スクロマトグラフ分析試料の前処理法として有用な方法
である。Detailed Description of the Invention <Industrial Application Field> The present invention relates to a method for esterifying a trace amount of a sample containing an acidic compound with diazomethane. Formamide solution is added dropwise to an excess amount of a mixed solution of diethylene glycol and/or its monoalkyl ether (alkyl group carbon number = 1 to 4) and a small amount of caustic aqueous solution as a catalyst to generate diazomethane. A trace amount sample containing an acidic compound can be prepared in a batch manner stably and reproducibly by diluting it with an inert gas to a maximum of 30% by volume and then blowing it into the sample or the diluted sample with a volatile solvent. The present invention relates to a safe and substantially complete esterification process. This method is particularly useful as a pretreatment method for gas chromatography analysis samples.
〈従来の技術〉
ガスクロマトグラフ法は、−膜性のある高感度、高精度
かつ高速の分離分析法として、特に有機物の分析に、他
に例を見ないほど、重用されて来た。近年では実験室だ
けではなく、工場の工程管理や品質管理にも不可欠の分
析方法となっている。キャピラリーカラムの採用、検出
器の多様化と複合化、昇温法や熱分解法の応用、電子機
器の採用による運転とデータ処理の自動化や、更には人
工知能によるフールプルーフ方式化などが、この傾向を
助長してきた。これらの事情については、例えば、松隈
、薬木、王国らの著書に詳しい（松隈昭、ガスクロマト
グラフィーの実際（第２版）、東京化学同人、東京（１
９７８）：薬木峻、ガスクロマトグラフィー（第３版）
、東京化学同人、東京（１９８１）：王国芳部、小島次
雄、高分解能ガスクロマトグラフィー、化学同人１京都
（１９８３））、シかしガスクロマトグラフ法は、熱分
解法を除いて、測定対象物質の揮発性を前提に−する、
酸性物質は低分子量でも蒸気圧が極めて低いのが通常で
あり、それへの応用は、高分子量物質への応用と共に、
このガスクロマトグラフ法の大きな欠点であった。<Prior Art> Gas chromatography has been used as a membrane-based, highly sensitive, highly accurate, and high-speed separation and analysis method, especially in the analysis of organic substances, to a degree that is unprecedented. In recent years, it has become an indispensable analytical method not only for laboratories but also for process control and quality control in factories. This trend includes the adoption of capillary columns, the diversification and compounding of detectors, the application of heating methods and thermal decomposition methods, the automation of operation and data processing through the adoption of electronic equipment, and even fool-proof methods using artificial intelligence. has encouraged These circumstances are detailed, for example, in the books of Matsukuma, Yakugi, Koku et al.
978): Shun Yakugi, Gas Chromatography (3rd edition)
, Tokyo Kagaku Doujin, Tokyo (1981): Yoshibe Kingdom, Tsuguo Kojima, High-Resolution Gas Chromatography, Kagaku Doujin 1 Kyoto (1983)), Shikashi Gas chromatography methods, except for the thermal decomposition method, Assuming the volatility of the substance,
Acidic substances usually have extremely low vapor pressure even if they have a low molecular weight.
This gas chromatography method had a major drawback.
酸性物質への対策として古くより実験室的に活用された
方法は、試料中の活性水素をアルキル化し、揮発性を付
与する方法である。塩敢メタノール法、三弗化はう素メ
タノール法、ジアゾメタン法、Ｎ、Ｎ−ジメチルホルム
アミドジアルキルアセタール法、１−アルキル−３−ｐ
−トリルトリアゼン法などがそれである。前二者とジア
ゾメタン法の比較は、実験化学講座（統）９（日本化学
会編、ガスクロマトグラフィー、先着、東京（１９６５
）ｐｐ、３３９−３４２）で行なわれた。定量性におい
てジアゾメタン法が最も優れていることが示されている
。A method that has long been used in laboratories as a countermeasure against acidic substances is to alkylate active hydrogen in a sample to impart volatility. Shiogen methanol method, borotrifluoride methanol method, diazomethane method, N,N-dimethylformamide dialkyl acetal method, 1-alkyl-3-p
-Tolyltriazene method etc. A comparison of the former two methods and the diazomethane method can be found in Experimental Chemistry Course (Tokyo) 9 (edited by the Chemical Society of Japan, Gas Chromatography, First Arrival, Tokyo (1965).
) pp. 339-342). The diazomethane method has been shown to be the most superior in terms of quantitative performance.
本発明者の経験でも、一般にジアゾメタン法は、その他
の方法に較べて、定量性に優れ、エステル化またはアル
キル化の条件が簡単で、かつ応用可能の酸性物質の範囲
が広いのが特徴と言える。In the experience of the present inventor, the diazomethane method is characterized by superior quantitative performance, simpler esterification or alkylation conditions, and a wider range of applicable acidic substances than other methods. .
しかし、ジアゾメタンはそれ自体が有毒でかつ爆発性を
有する。この欠点はジアゾメタンがガス体であるため、
始末が一層慈い、ざらにジアゾメタンは炭化水素を副生
ずるが、これは分析上不純物となって、定量定性を妨げ
る。ジアゾメタン法の実験室的方法の詳細は、先述の実
験化学講座の外１例えば舟橋らの著書（全橋渡、池用信
夫、臼井浩、吉富和彦、最新ガスクロマトグラフィー、
■応用編、広用書店、東京（１９７７）ｐｐ、６４７〜
６５１）や試薬会社のカタログ（和光紬薬、新しいジア
ゾメタン発生用試薬）に詳しい、いくつもの方法が記載
されているが、ジアゾメタン発生試薬の溶媒にジエチル
エーテルを用いる点は共通である。これはジアゾメタン
発生試薬の溶解性、ジアゾメタン溶媒エステル化試料用
溶媒との共通性、およびエステル化反応完結後の溶媒分
離の容易さを考えると、当然ではあるが、その高い蒸気
圧は、ベーパーロック等の問題により遠隔操作による安
全衛生上の対策を妨げ、また設備を引火燃焼の危険に曝
している。エーテルの麻酔性も安全衛生上好ましくない
、これらの理由により、上述の長所にもかかわらず、最
近では、ジアゾメタン法自体が敬遠される風潮がでてい
た。However, diazomethane itself is toxic and explosive. This drawback is that diazomethane is a gas, so
In addition, diazomethane produces hydrocarbons as by-products, which become analytical impurities and impede quantitative determination. For details on the laboratory method of the diazomethane method, please refer to the above-mentioned experimental chemistry course.For example, see the works of Funahashi et al.
■Applied edition, Kouyo Shoten, Tokyo (1977) pp, 647~
651) and a reagent company's catalog (Wako Tsumugi, New Diazomethane Generating Reagent), a number of detailed methods are described, but the common point is that diethyl ether is used as the solvent for the diazomethane generating reagent. This is natural considering the solubility of the diazomethane generating reagent, the commonality with the diazomethane solvent esterification sample solvent, and the ease of solvent separation after the completion of the esterification reaction. These problems impede safety and health measures through remote control and expose equipment to the risk of ignition and combustion. The anesthetic properties of ether are also unfavorable in terms of safety and health.For these reasons, despite the above-mentioned advantages, there has recently been a trend to avoid the diazomethane method itself.
〈発明が解決すべき問題点〉 ジアゾメタンはそれ自体が有毒でかつ爆発性を宥する。<Problems to be solved by the invention> Diazomethane itself is toxic and explosive.
毒性は裸眼、むきだしの皮膚の炎症、呼吸による気管支
炎、ぜんそくなどの形で表れる。爆発性は、通常の可燃
性ガスと酸素の混合ガスとしてのそれと、自己分解に基
ずくそれとがある。エーテルの溶媒としての使用は、そ
の麻酔性と低引火点の故に、これらの欠点を助長し、安
全衛生上好ましくない上に、ペーパーロック等により有
効な対策を阻んでいる。ざらにジアゾメタンの重合によ
る炭化水素生成の制御が必要である。Toxicity manifests itself in the form of irritation to the naked eye, exposed skin, respiratory bronchitis, and asthma. Explosive properties include those as a mixture of ordinary flammable gas and oxygen, and those based on self-decomposition. The use of ether as a solvent, due to its narcotic properties and low flash point, exacerbates these drawbacks, is undesirable from a health and safety standpoint, and prevents effective countermeasures due to paper locks and the like. In general, it is necessary to control the production of hydrocarbons through the polymerization of diazomethane.
本発明者は、かかる現状に鑑み鋭意検討を行なった結果
、これらの問題点を軽減乃至解決する方法を発明するに
至った。As a result of intensive studies in view of the current situation, the inventors of the present invention have come up with a method for alleviating or solving these problems.
く問題点を解決するだめの手段〉
本発明は、酸性物質を含有する微量試料のガスクロマト
グラフ法による分析方法において、ジアゾメタン発生試
薬としてのニトロソ化合物のジオキサンおよび／または
ジメチルホルムアミド溶液を、ジエチレングリコールお
よび／またはそのモノアルキルエーテル（アルキル基の
炭素数＝１〜４）と、触媒としての少量の苛性アルカリ
水溶液の混合溶液の過剰量に滴下させて、ジアゾメタン
を発生させ、それを不活性ガスにより希釈し最大３０体
積％とした後、試料、または揮発性溶媒による希釈試料
に吹込むことを特徴とする、回分式に酸性化合物を含む
微量試料を、安定的に再現性良く安全かつ完全にエステ
ル化する方法に係るものである。以下、本発明を具体的
に説明する。Means for Solving the Problems> The present invention provides a method for analyzing a trace amount of a sample containing an acidic substance by gas chromatography, in which a dioxane and/or dimethylformamide solution of a nitroso compound as a diazomethane generating reagent is mixed with diethylene glycol and/or dimethylformamide. Alternatively, diazomethane is generated by dropping the monoalkyl ether (carbon number of the alkyl group = 1 to 4) into an excess amount of a mixed solution of a small amount of caustic aqueous solution as a catalyst, and diluting it with an inert gas. Stable, reproducible, safe and complete esterification of trace samples containing acidic compounds in a batch manner, characterized by blowing into the sample or diluted sample with a volatile solvent after making up to 30% by volume. It is related to the method. The present invention will be explained in detail below.
本発明においてエステル化の対象とする酸性物質にはジ
アゾメタンによりメチル化され得るすべての有機酸と無
機酸が含まれる。有機酸としては例えばギ酸、酪酸、プ
ロピオン酸、アクリル酸、酪酸、メタアクリル酸、クロ
トン酸、吉草酸、カプロン酸、ニナント酸、カプリル酸
、ノナン酸、カプリン酸、ウンデカン酸、ラウリン酸、
バルミチン酸、ステアリン酸等の脂肪族−塩基性カルポ
ン酸、シュウ酸、マロン酩、＝ハク酸、マレイン酸、グ
ルタル酸、アジピン酸等の脂肪族多塩基性カルボン酸、
安息香酸。Acidic substances to be esterified in the present invention include all organic acids and inorganic acids that can be methylated with diazomethane. Examples of organic acids include formic acid, butyric acid, propionic acid, acrylic acid, butyric acid, methacrylic acid, crotonic acid, valeric acid, caproic acid, ninanthic acid, caprylic acid, nonanoic acid, capric acid, undecanoic acid, lauric acid,
Aliphatic-basic carboxylic acids such as valmitic acid and stearic acid; aliphatic polybasic carboxylic acids such as oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, and adipic acid;
benzoic acid.
フタル酸、ケイ皮酸、ナフトエ酸、ナフタレンジカルボ
ン酸等の芳香族カルボン酸、クエン酸、酒石酸、サルチ
ル酸、没食子酸等のオキシカルボン酸等があげられる。Examples include aromatic carboxylic acids such as phthalic acid, cinnamic acid, naphthoic acid, and naphthalene dicarboxylic acid, and oxycarboxylic acids such as citric acid, tartaric acid, salicylic acid, and gallic acid.
これらの有機酸には無数の異性体、同族体あるいは誘導
体がある。These organic acids exist in countless isomers, homologs, or derivatives.
それらのメチル化とそのエステルが異常を示さない限り
においてそれらが本発明の対象である事はあきらかであ
る。無機酸としては例えばホウ酸、ハロゲン化水素、硝
酸、亜硝酸、硫酸、亜硫酸、リン酸、亜リン酸等があげ
られる。これらの同族体や、多塩基性の場合は部分的エ
ステルももちろん本発明の対象である０本発明は以上の
例示により制約されるものではないのは勿論である。As long as their methylation and their esters do not show abnormalities, they are clearly the subject of the present invention. Examples of inorganic acids include boric acid, hydrogen halide, nitric acid, nitrous acid, sulfuric acid, sulfurous acid, phosphoric acid, and phosphorous acid. Of course, these homologues and partial esters in the case of polybasic compounds are also covered by the present invention.Of course, the present invention is not limited to the above examples.
本発明に係るジアゾメタン発生試薬としてのニトロソ化
合物には、例えば、Ｎ−メチル−Ｎ−二トロン−Ｐ−）
ルエンスルホナミド、Ｎ−メチル−Ｎｏ−二トローＮ−
二トロソグアニジン、Ｎ−（（Ｎ ’−二トロソメチル
アミノ）メチル〕ベンズアミド、Ｎ−（（Ｎ’−ニトロ
ソメチルアミノ）メチル〕カルバミン酸イソプロピルエ
ステル、Ｎ−ニトロソメチルウレアなどが既に世に知ら
れているが、これらに限定されるものではない０本発明
に述べる溶媒に可溶で、苛性アルカリ触媒により接触的
に後述のアルコールと反応してジアゾメタンを発生する
ものであれば、どれでも良い、これらのジアゾメタン発
生試薬の溶媒には、ジオキサンおよび／またはジメチル
ホルムアミドが好適である。これらの溶媒は、上述の化
学的条件を満足させるのと同時に、高沸点かつ適切な低
粘度であるため、高温下でも流量制御に必要な小口径管
による環体連絡配管を可能にする。これらの溶媒を使用
した場合の炭化水素副生反応はほとんどエーテル溶媒と
変らないか、むしろやや抑制気味であることが観察され
た。The nitroso compound as a diazomethane generating reagent according to the present invention includes, for example, N-methyl-N-nitrone-P-)
Luenesulfonamide, N-methyl-No-nitro N-
Nitrosoguanidine, N-((N'-nitrosomethylamino)methyl]benzamide, N-((N'-nitrosomethylamino)methyl)carbamic acid isopropyl ester, N-nitrosomethylurea, etc. are already known to the world. However, the present invention is not limited to any one that is soluble in the solvent described in the present invention and that reacts catalytically with the alcohol described below using a caustic alkali catalyst to generate diazomethane. Dioxane and/or dimethylformamide are suitable as the solvent for the diazomethane generating reagent.These solvents satisfy the above chemical conditions and at the same time have a high boiling point and suitably low viscosity, so that they can be used at high temperatures. However, it is possible to connect the ring with a small-diameter pipe necessary for flow rate control.It has been observed that when these solvents are used, the hydrocarbon by-product reaction is almost the same as with ether solvents, or rather is slightly suppressed. It was done.
次にジアゾメタン発生試薬と反応させるアルコールには
、ジエチレングリー−ルとそのモノアルキルエーテル（
アルキル基の炭素数＝１〜４）の１種またはそれ以上を
混合して用いるのが望ましい、これらは流動性に優れる
ため取扱い容易で、苛性アルカリ水溶液を溶解させ、ジ
アゾメタン発生試薬と容易に反応し、かつその溶液に良
溶媒で、また揮発性が低く、従ってニスチル化試料に不
純物を送り込む可能性が低く、それにジアゾメタン生成
反応で発生する水を良く吸収する。このエステル化反応
において水は一般に有害であるため、水の吸収除去は反
応完結に有利である。Next, the alcohols to be reacted with the diazomethane generating reagent include diethylene glycol and its monoalkyl ether (
It is desirable to use a mixture of one or more alkyl groups (carbon number = 1 to 4).These have excellent fluidity and are easy to handle.They dissolve an aqueous caustic alkali solution and easily react with a diazomethane generating reagent. Moreover, it is a good solvent for the solution and has low volatility, so it is less likely to introduce impurities into the Nistylated sample, and it also absorbs water generated in the diazomethane formation reaction well. Since water is generally harmful in this esterification reaction, absorption and removal of water is advantageous for completing the reaction.
ジアゾメタンの希釈は爆発性の回避とエステル化反応上
の必要性に由来する。ジアゾメタン米
は酸≠のない状態でも自己分解反応で爆発するが、これ
は不活性ガスの同伴により抑制できる、分解反応限界濃
度は厳省には分かっていないが、本発明者は約３０体積
％なら充分安全であることを経験的に知った。一方ジア
ゾメタンは回分式に発生されるので、ニスチル化装こ内
での吹込ガス量は、ジアゾメタンのみでは変化が太き通
る。また反応性吸収性ガスのみでは吹込管を通じて、液
が上昇する恐れがあり、常時監視する必要を生じるため
に、省力化出来ない。The dilution of diazomethane stems from the need to avoid explosiveness and for the esterification reaction. Diazomethane rice explodes due to a self-decomposition reaction even in the absence of acid, but this can be suppressed by entrainment of an inert gas.Although the critical concentration for decomposition reaction is not strictly known, the inventor estimated that it is approximately 30% by volume. I know from experience that it is completely safe. On the other hand, since diazomethane is generated in a batchwise manner, the amount of gas blown into the Nistylation reactor varies greatly if only diazomethane is used. In addition, if only the reactive absorbent gas is used, there is a risk that the liquid will rise through the blowing pipe, and constant monitoring will be required, so labor cannot be saved.
また安全上も避けなければならない現象である、不活性
非吸収性ガスに同伴させてジアゾメタンを送気すれば、
エステル化試料の攪拌および反応が安定し、またそれが
局所的な高濃度域の発生を自然に防止するために、本発
明の目的にきわめて好都合な環境を用意することになる
。In addition, if diazomethane is sent along with an inert non-absorbable gas, which is a phenomenon that must be avoided for safety reasons,
Stirring and reaction of the esterification sample are stable, which naturally prevents the occurrence of localized high concentration areas, thus providing a very favorable environment for the purpose of the present invention.
エステル化を実質上完全に実施するには、吹込みにかな
り安全を見た充分な時間をかけることが大切である。し
かしその一方で、ジアゾメタンに起因する不純物質とし
て既に記述した重合による炭化水素は、温度と試料が同
じならば、ジアゾメタンの平均的および局所的液中濃度
と接触時間に関係する。液中濃度は気相濃度に支配され
ている。この炭化水素の多くはガスクロマトグラムにお
いて低保持時間成分として検出される。したがって、試
料に低保持時間成分を含む際には１分析を妨害する。妨
害を最小限度に抑えるためには吹込み時間を制限せねば
ならない１例えば品質管理のために同室の試料を定期的
に分析する場合などではこの妨害の程度を常に一定に保
つ必要がある。In order to achieve substantially complete esterification, it is important to allow sufficient time for the blowing to be reasonably safe. However, on the other hand, the hydrocarbons due to polymerization, already described as impurities due to diazomethane, are related to the average and local concentration of diazomethane in the liquid and the contact time, given the same temperature and sample. The concentration in the liquid is controlled by the concentration in the gas phase. Many of these hydrocarbons are detected as low retention time components in gas chromatograms. Therefore, when a sample contains low retention time components, it interferes with one analysis. In order to minimize disturbances, the blowing time must be limited. For example, when samples from the same room are analyzed periodically for quality control purposes, it is necessary to keep the degree of this disturbance constant at all times.
安定的に再現性良く安全かつ実質上完全に試料のエステ
ル化を行うには、本発明に係る方法を自動化装置として
具体化することが望ましいことは申すまでもない、その
ためには本発明に係る方法に加えて、装置要素およびシ
ステム制御にも特別の工夫が必要である。工業的に装置
を利用するときは、更に、経済性を配慮しなければなら
ない、中心的問題点はジアゾメタン発生槽（以下反応槽
と言う）の液面検出、注入量測定、反応終点検出器、反
応済み廃液取出しに伴なう要素、反応槽洗浄に伴なう要
素と、エステル化試料管（以下試料管と言う）−・、の
吹１入りと試料管脱着の工夫であろう。It goes without saying that it is desirable to embody the method of the present invention as an automated device in order to esterify a sample reliably, reproducibly, safely, and virtually completely. In addition to the method, equipment elements and system controls also require special consideration. When using the device industrially, economic efficiency must also be taken into consideration.The main issues are liquid level detection in the diazomethane generation tank (hereinafter referred to as reaction tank), injection amount measurement, reaction end point detector, This is likely due to the elements involved in taking out the reacted waste liquid, the elements involved in cleaning the reaction tank, and the installation and removal of the esterification sample tubes (hereinafter referred to as sample tubes).
前段および前々段の、異質の設備的要求に応じる一つの
すぐれた手段は前掲をタイムシーケンス回路により制御
する方法の採用である。以下の実施例は本発明の方法を
タイムシーケンス回路制御方式で具体化した実例である
。前段に例示した装置要素システム制御の問題が、オン
オフ式電磁弁とオートサンプラーにより解決できること
が理解できる。One excellent means of meeting the disparate equipment requirements of the previous stage and the second stage is to adopt a method of controlling the above-mentioned stages using a time sequence circuit. The following embodiment is an example in which the method of the present invention is implemented using a time sequence circuit control system. It can be seen that the problem of device element system control illustrated in the previous section can be solved by using an on-off type solenoid valve and an autosampler.
〈実施例〉
以下に実施例および比較例を述べるが、本発明は勿論こ
れらに限定されるものではない。<Examples> Examples and comparative examples will be described below, but the present invention is of course not limited to these.
実施例１
第１図は本発明の方法を設備化した例の一つである。試
薬槽５，６．７にはそれぞれ水酸化カリウム水溶液（６
０ｇ／１００ｇ水）、Ｎ−メチル−Ｎ−二トロン−ｐ−
１ルニンスルフオンアミド（ＰＴＳＡ）溶液（５０ｇ／
１００ｍ１溶媒、木芙施例では１．４−ジオキサンを溶
媒とした。）カルピトールが入っている。ポンベ１から
出た窒素は３の反応ライン制御計により一定圧力になり
流量測定を受でバッファータンク９の左端の一つへ流れ
ている。この窒素は次に反応槽８へ通る０反応槽の中に
はあらかじめ５．７より水酸化カリウムとカルピトール
が供給されている。オンオフ電磁弁１５を開いて必要量
のＰＴＳＡ溶液を流下させると、ジアゾメタンが発生し
この窒素気流に乗ってエステル化すべき試料が試験管に
いれられ乗っているオートサンプラー１１へ送られる。Example 1 FIG. 1 is an example of equipment in which the method of the present invention is implemented. Potassium hydroxide aqueous solution (6.
0g/100g water), N-methyl-N-nitrone-p-
1 Runinsulfonamide (PTSA) solution (50g/
The solvent was 100 ml, and in the Mokufu example, 1,4-dioxane was used as the solvent. ) Contains calpitol. The nitrogen discharged from the pump 1 is brought to a constant pressure by the reaction line controller 3, and then flows to one of the left ends of the buffer tank 9, where the flow rate is measured. This nitrogen then passes into the reaction tank 8. Potassium hydroxide and calpitol are previously supplied from 5.7 into the reaction tank. When the on/off solenoid valve 15 is opened to allow the required amount of PTSA solution to flow down, diazomethane is generated, and the sample to be esterified is placed in a test tube and sent to the autosampler 11 mounted on the test tube along with the nitrogen stream.
ジアゾメタンは試験管内の試料液を潜った後、除害槽１
３で過剰のジアゾメタンの分解を受け、大気中へ放出さ
れる。オートサンプラーを回転させ次の試験管をセット
するときは、吹込管１２は邪魔であるため、付属のロボ
ットにより支障のない位置まで吊あげておく、吹込管は
そのためフレキシブルチューブ接続になっている。また
このように取外せるように試験管への当りは脱着容易で
かつ機密性保持のできる構造になっている。After dipping into the sample solution in the test tube, the diazomethane is transferred to the abatement tank 1.
In step 3, excess diazomethane is decomposed and released into the atmosphere. When rotating the autosampler and setting the next test tube, the blowing tube 12 is a hindrance, so the attached robot lifts it up to a position where it will not be a hindrance.For this reason, the blowing tube is connected to a flexible tube. In addition, in order to be able to remove it in this manner, the test tube abutment has a structure that allows it to be easily attached and detached and to maintain confidentiality.
試薬槽は加圧できる構造になっていて、８の内圧、試薬
の細管および弁における抵抗に打勝つだけのヘッドをあ
たえれるように作られている、全体を吹込管の手前で二
つに分け、それぞれを透明扉付の密閉箱内に設置した。The reagent tank has a structure that can be pressurized, and is designed to provide enough head to overcome the internal pressure of 8, the reagent tube, and the resistance in the valve. Each was placed in a sealed box with a transparent door.
おのおのの箱には常に一定流量の窒素を流し、万一の漏
れに対する対策とした。シーケンス制御器１４は各種電
磁弁およびオートサンプラーの開閉および駆動を予め定
めたシーケンスに沿って動かすためのシーケンス制御器
である。A constant flow of nitrogen was constantly flowed into each box as a measure against leakage. The sequence controller 14 is a sequence controller for opening/closing and driving various electromagnetic valves and autosamplers according to a predetermined sequence.
本設備を用いて混合脂肪酸のエステル化を行ない、それ
をガスクロマトグラフにより分析した。その結果は第１
表の通りで実質上完全なエステル化が行なわれた０表中
の濃度は重量％である。試料の混合脂肪酸は、リン酸ト
リブチルに既知量の試薬特級脂肪酸を調合したものであ
る。エステルの検出濃度は醜濃度に換算済みである。Mixed fatty acids were esterified using this equipment, and the results were analyzed by gas chromatography. The result is the first
As shown in the table, substantially complete esterification was achieved.The concentrations in the table are in % by weight. The mixed fatty acid sample is a mixture of tributyl phosphate and a known amount of reagent special grade fatty acid. The detected concentration of ester has been converted to the ugliness concentration.
纂１表
酷名称 混合濃度 検出濃度 ニス戸ルｆ）ＺＴ；％
％ ％
ギ敢 １．００ ０．９３ ９３．０酢酸 １．
０１ ０．９９ ９８．０プロピオン酸
１．０１ １．００ ９９．０酪酸 １．
００ １．００ １００．０吉草酸 ０．９８ １．０
０ １０２．０カプロン酸
１．００ １．０１ １０１．０
エナント酸
１．０３ １．００ ９７．１
カプリル酸
１．０２ １．０１ ９９．０
ノナン酸
１．０２ １．０３ １０１．０
カプリン酸
１．０３ １．０３ １００．０
ウンデカン酸
１．００ ０．９８ ９８．０
ラウリン酸
１．０４ １．０２ ９８．１
比較例１
第１図と同じ装置で、ただし試薬槽６のＰＴＳＡの溶媒
にはジニチルエーテルを用いて実施例１の実験を行なっ
た。低温期には異常を生じなかったが、高温の夏期にお
いて、電磁弁内でしばしばペーパーロックを起し操作不
能となった。Summary 1 Table name Mixed concentration Detected concentration Nittor f) ZT;%
% % Giken 1.00 0.93 93.0 Acetic acid 1.
01 0.99 98.0 Propionic acid 1.01 1.00 99.0 Butyric acid 1.
00 1.00 100.0 Valeric acid 0.98 1.0
0 102.0 Caproic acid 1.00 1.01 101.0 Enanthic acid 1.03 1.00 97.1 Caprylic acid 1.02 1.01 99.0 Nonanoic acid 1.02 1.03 101.0 Capric acid 1.03 1.03 100.0 Undecanoic acid 1.00 0.98 98.0 Lauric acid 1.04 1.02 98.1 Comparative Example 1 Using the same apparatus as in Figure 1, except that the PTSA solvent in reagent tank 6 The experiment of Example 1 was conducted using dinityl ether. No abnormalities occurred during the low temperature season, but during the high temperature summer season, paper locks often occurred within the solenoid valve, making it impossible to operate.
実施例２
第１図と同じ装置で、ただし試薬槽６のＰＴＳＡの溶媒
にはジメチルホルムアミド（ＤＭＦ）を用いて実施例１
の実験を行なった。その結果は第１表とほとんど同じで
あった。Example 2 Example 1 was carried out using the same apparatus as in FIG. 1, except that dimethylformamide (DMF) was used as the solvent for PTSA in reagent tank 6.
conducted an experiment. The results were almost the same as in Table 1.
実施例３
実施例１の実験を、ＴＢＰに各種の酸性リン酸エステル
を調合した試料に対し実施した。その結果を第２表に示
す。Example 3 The experiment of Example 1 was carried out on samples prepared by blending various acidic phosphate esters with TBP. The results are shown in Table 2.
第２表
酸名称 混合濃度 検出濃度 エステル化率ＰＰｍ
ＰＰｍ ％
リン酸モノブチル
Ｚｏｏ ９８ ９８．０
リン酸ジブチル
１０６ １０７ １００．９
実施例４
実施例１の実験、を、塩酸処理した不均化ロジン酸石鹸
のへキサン抽出物に対して行なった。Table 2 Acid name Mixed concentration Detected concentration Esterification rate PPm
PPm % Monobutyl phosphate Zoo 98 98.0 Dibutyl phosphate 106 107 100.9 Example 4 The experiment of Example 1 was performed on a hexane extract of a disproportionated rosin acid soap treated with hydrochloric acid.
その結果アビエチン酸が不均化ロジン酸中に０．５１％
含まれることが判った。この分析は同じ不均化ロジン酸
に７ビエチン酸を０．５０％添加した試料の同様の分析
によって正しいことが証明された。As a result, abietic acid was 0.51% in the disproportionated rosin acid.
It was found that it was included. This analysis was confirmed by a similar analysis of the same disproportionated rosin acid sample with 0.50% 7-bietic acid added.
実施例５
実施例１の実験を、植物種子油鹸化物を硫酸酸性に戻し
た後へキサンで抽出した試料について行なった。その結
果リルン酸がこの植物油の中に８．０％含まれているこ
とが判った。この分析はこの植物油処理物にリルン酸を
７゜８５％添加した試料の同様の分析により確かめ
１られた。Example 5 The experiment of Example 1 was conducted on a sample in which the saponified plant seed oil was acidified with sulfuric acid and then extracted with hexane. As a result, it was found that 8.0% of linuric acid was contained in this vegetable oil. This analysis was confirmed by a similar analysis of a sample prepared by adding 7.85% lylunic acid to this processed vegetable oil.
I got 1.
実施例６
第１図と同じ装置で、ただし試薬槽６のＰＴＳＡの溶々
某にはジエチルエーテル
オキサンおよびＤＭＦを用いて、酸性リン酸ブチルを含
むＴＢＰ試料に対してメチル化の実験を行なった．この
ときは溶媒がジエチルエーテルであってもペーパーロッ
クはなかったが，ジエチルエーテルの場合は他の２溶媒
の時に比し、エステル化を完全に行なうためには、ＰＴ
ＳＡ量を第３表に示す通りに，増量させる必要があった
。Example 6 A methylation experiment was carried out on a TBP sample containing acidic butyl phosphate using the same apparatus as in Fig. 1, but using diethyl ether oxane and DMF for the PTSA solution in reagent tank 6. Ta. At this time, there was no paper lock even when the solvent was diethyl ether, but in the case of diethyl ether, compared to the other two solvents, it was necessary to use PT to complete the esterification.
It was necessary to increase the amount of SA as shown in Table 3.
第３表
試料名 溶媒． 吹込時間試料１
ジエチルエーテル ４′３０”１、４−ジオキサン
エ°４５″
ＤＭＦ １“１５′。Table 3 Sample name Solvent. Blowing time sample 1
Diethyl ether 4'30"1,4-dioxane
E°45″DMF 1″15′.
試＃４２ ジエチルエーテル ６°３０°。Trial #42 Diethyl ether 6°30°.
１、４〜ジオキサン ２’００”
ＤＭＦ １ ° ３ ０
″ここに試料１はＴＢＰ中にリン酸モノブチル０、０９
２％、リン酸ジブチルを０．１３８％含む調合試料であ
り、試料２は更に水１％を含む調合試料である．本発明
の場合は従来のジエチルエーテルの場合に比し１／３乃
至１／４の吹込量で済むことが明らかにされた．また試
料１と試料２を比較すると、結果の溶媒による差がジア
ゾメタン中の水含増量による差らしいことを示唆してい
る．エステル化反応の際の不純物の生成はほぼ反応時間
に比例し溶媒種類の影響は二義的であることも明らかと
なった。1,4~Dioxane 2'00” DMF 1° 30
``Here sample 1 contains 0.09 monobutyl phosphate in TBP.
Sample 2 is a blended sample containing 2% dibutyl phosphate and 0.138% dibutyl phosphate, and Sample 2 is a blended sample further containing 1% water. It has been revealed that in the case of the present invention, the amount of injection required is 1/3 to 1/4 compared to the case of conventional diethyl ether. Comparing Sample 1 and Sample 2 suggests that the difference in results due to the solvent is likely due to the increase in water content in diazomethane. It has also become clear that the production of impurities during the esterification reaction is approximately proportional to the reaction time, and that the influence of the type of solvent is secondary.
〈発明の効果〉
ジアゾメタン発生試薬としてのニトロソ化合物のジオキ
サンおよび／またはジメチルホルムアミド溶液を、ジエ
チレングリコールおよび／またはそのモノアル午ルエー
テル（アルキル基の炭素数＝１〜４）と、触媒としての
少量の苛性アルカリ水溶液の混合溶液の過剰量に滴下さ
せて、ジアゾメタンを発生させ、それを不活性ガスによ
り希釈し最大３０体積％とした後、試料、または揮発性
溶媒による希釈試料に吹込むことを特徴とする、回分式
に酸性化合物を含む微量試料のエステル化方法を用いる
ことによって、酸性物質を含有する微量試料のガスクロ
マトグラフ法による分析が安定的に再現性よく安全にか
つ精度よく行われるようになった。<Effect of the invention> A dioxane and/or dimethylformamide solution of a nitroso compound as a diazomethane generating reagent is mixed with diethylene glycol and/or its monoalkaline ether (the number of carbon atoms in the alkyl group = 1 to 4), and a small amount of caustic alkali as a catalyst. Diazomethane is generated by dropping it into an excess amount of a mixed solution of an aqueous solution, diluted with an inert gas to a maximum of 30% by volume, and then blown into a sample or a sample diluted with a volatile solvent. By using a batch esterification method for trace samples containing acidic compounds, gas chromatography analysis of trace samples containing acidic substances can now be performed stably, reproducibly, safely, and accurately. .
第１図は本発明の実施態様を示す流路図である．１は窒
素ボンベ、２は装置箱内部窒素制御計、３は反応ライン
制御計、４は試薬槽圧力制御計、５は水酸化カリウム槽
、６はＰＴＳＡ試薬槽、７はカルピトール槽、８は反応
槽、９はバッファタンク、１０は廃液回収槽、１１はオ
ートサンプラー、１２はアップダウンノズル、１３は除
害槽，１４はシーケンス制御器、１５はオンオフ電磁弁
、１６は三方電磁弁でおる。FIG. 1 is a flow path diagram showing an embodiment of the present invention. 1 is a nitrogen cylinder, 2 is a nitrogen controller inside the equipment box, 3 is a reaction line controller, 4 is a reagent tank pressure controller, 5 is a potassium hydroxide tank, 6 is a PTSA reagent tank, 7 is a calpitol tank, 8 is a reaction tank 9 is a buffer tank, 10 is a waste liquid recovery tank, 11 is an autosampler, 12 is an up-down nozzle, 13 is an abatement tank, 14 is a sequence controller, 15 is an on/off solenoid valve, and 16 is a three-way solenoid valve.
Claims (1)
よる分析方法において、ジアゾメタン発生試薬としての
ニトロソ化合物のジオキサンおよび／またはジメチルホ
ルムアミド溶液を、ジエチレングリコールおよび／また
はそのモノアルキルエーテル（アルキル基の炭素数＝１
〜４）と、触媒としての少量の苛性アルカリ水溶液の混
合溶液の過剰量に滴下させて、ジアゾメタンを発生させ
、それを不活性ガスにより希釈し最大３０体積％とした
後、試料、または揮発性溶媒による希釈試料に吹込むこ
とを特徴とする、回分式に酸性化合物を含む微量試料の
エステル化方法。In a method for analyzing trace samples containing acidic substances using gas chromatography, a dioxane and/or dimethylformamide solution of a nitroso compound as a diazomethane generating reagent is mixed with diethylene glycol and/or its monoalkyl ether (carbon number of alkyl group = 1).
4) and a small amount of aqueous caustic solution as a catalyst to generate diazomethane, dilute it with an inert gas to a maximum of 30% by volume, and then add the sample or volatile A method for esterifying a trace amount of a sample containing an acidic compound in a batch manner, characterized by injecting the diluted sample with a solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23828486A JPS6391559A (en) | 1986-10-07 | 1986-10-07 | Esterification of very small amount of specimen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23828486A JPS6391559A (en) | 1986-10-07 | 1986-10-07 | Esterification of very small amount of specimen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6391559A true JPS6391559A (en) | 1988-04-22 |
Family
ID=17027902
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23828486A Pending JPS6391559A (en) | 1986-10-07 | 1986-10-07 | Esterification of very small amount of specimen |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6391559A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0462794A2 (en) * | 1990-06-21 | 1991-12-27 | Oxford GlycoSystems Limited | Automated process equipment for cleavage of biomolecules |
| US5422079A (en) * | 1990-06-21 | 1995-06-06 | Oxford Glycosystems Limited | Automated process equipment |
-
1986
- 1986-10-07 JP JP23828486A patent/JPS6391559A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0462794A2 (en) * | 1990-06-21 | 1991-12-27 | Oxford GlycoSystems Limited | Automated process equipment for cleavage of biomolecules |
| US5422079A (en) * | 1990-06-21 | 1995-06-06 | Oxford Glycosystems Limited | Automated process equipment |
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