Standard Article

4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium Tetrafluoroborate

  1. James M. Bobbitt1,
  2. Nabyl Merbouh1,2,
  3. Tsutomu Inokuchi3,
  4. Li-Jian Ma3

Published Online: 16 SEP 2013

DOI: 10.1002/047084289X.rn00346.pub3

e-EROS Encyclopedia of Reagents for Organic Synthesis

e-EROS Encyclopedia of Reagents for Organic Synthesis

How to Cite

Bobbitt, J. M., Merbouh, N., Inokuchi, T. and Ma, L.-J. 2013. 4-Acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium Tetrafluoroborate. e-EROS Encyclopedia of Reagents for Organic Synthesis. .

Author Information

  1. 1

    University of Connecticut, Storrs, CT, USA

  2. 2

    Simon Fraser University, Burnaby, Canada

  3. 3

    Okayama University, Okayama, Japan

Publication History

  1. Published Online: 16 SEP 2013

Chemistry Terms

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Abstract

(reagent used to oxidize alcohols to aldehydes or ketones. Of special interest, allyl alcohols can be oxidized without isomerization and phenolic benzyl alcohols can be oxidized without blocking the phenol group; all of these reagents have been used for the oxidation of primary and secondary alcohols to aldehydes or ketones, respectively. They also have a certain number of additional minor oxidation reactions. Many other salts are known1)

Physical Data: mp 195–196 °C dec (Kofler).

1a, mp 193–194 °C (dec.); 1b, mp 177–178 °C (dec.); 10a, mp 162–163 °C; 10b, mp 157–158 °C; 10c, mp 118–119 °C; 10d, mp 76–78 °C; 11a, mp 162–162.5 °C; 11b, mp 121–123 °C; 11c, mp 206–207 °C.

Solubility: partially soluble in water (6 g/100 mL at 0 °C, 8 g/100 mL at 20 °C, and about 100 g/100 mL at 100 °C; reacts very slowly with hot water), slightly soluble in methylene chloride (0.04 g/100 mL at 20 °C). 1a and 1b are slightly soluble in water and methylene chloride, while insoluble in ether; 10a10d are insoluble in ether; 11a11c are insoluble in carbon tetrachloride. Otherwise, solubilities are variable. Most reactions are carried out in methylene chloride, less often in acetonitrile.

Form Supplied in: all of these salts are prepared from the corresponding parent nitroxides, 5, 12, and 13, which are commercially available. None of the salts are commercially available currently.

Preparative Methods: in a slightly modified procedure,3 100 g of 4-acetylamino-2,2,6,6-tetramethyl-1-piperidineoxyl (0.469 mol) is stirred with 50 mL of H2O, and 90 g of 48% aqueous HBF4 (0.492 mol) is added over about 1 h. The mixture is placed in an ice bath, and 332.2 g of commercial bleach (5.25% NaOCl, 0.235 mol) is added over about 2 h. The mixture is allowed to stir in ice for about 3 h and then filtered. The solid bright yellow salt is pressed as dry as possible and washed with two 50-mL portions of ice water and two 100-mL portions of CH2Cl2. The salt is dried at room temperature and in air to constant weight to give 90–95 g (about 65%) of the reagent, mp 195–196 °C. Further drying in a vacuum desiccator reduced the weight only slightly. For recovery of the remainder of the salt, the combined filtrates (water and CH2Cl2) are treated with 20 g of NaHCO3 and 20 mL of 95% ethanol to reduce the oxoammonium salt to the starting nitroxide. The layers are separated and the aqueous phase is extracted with three 50-mL portions of CH2Cl2. The extracts are combined, dried over MgSO4, and evaporated to give 25–30 g of nitroxide, mp 145–147 °C, suitably pure for the preparation of more oxoammonium salt. Oxoammonium salts are prepared from commercially available, nitroxide free radicals, 5, 12, and 13. There are essentially two methods for the preparation of the oxoammonium salts from nitroxides. The first is based on the acid-catalyzed disproportionation of nitroxide in strong acid as shown for 1a in eq 1.14, 20 The method has been used both in water and dry ether for the preparation of many oxoammonium salts. The second is based on the halogens as shown for 11b in eq 2.16, 19 In the halide reactions, the elemental halogens act both as oxidizing agents and the source of the anions.

original image

4-acetylamino-2,2,6,6-tetramethyl-1-piperidineoxyl(4-acetylamino-TEMPO)[14691-89-5]

original image

2,2,6,6-tetramethyl-1-piperidineoxyl(TEMPO)[2564-83-2]

original image

4-methoxy-2,2,6,6-tetramethyl-1-piperidineoxyl(4-methoxy-TEMPO)[95407-69-5]

InChI = 1S/C10H20NO2/c1-9(2)6-8(13-5)7-10(3,4)11(9)12/h8H,6-7H2,1-5H3

InChIKey = SFXHWRCRQNGVLJ-UHFFFAOYSA-N

original image(1)
original image(2)

The preparation of 1a and its applications are described in a tested procedure in Organic Syntheses.20 The procedure involves the use of a second oxidant, bleach, to increase the yield of salt.

Purity: recrystallized, if necessary, from an equal weight of water. Solution heated and cooled as rapidly as possible. The purity of the salt can be assayed using 1-decanol as substrate. It is normally close to 100%.

Handling, Storage, and Precautions:  the salt (tetrafluoroborate) is non-hygroscopic and indefinitely stable. No hazards are known. For anhydrous reactions, the previously dried salt can be dried in a vacuum over P2O5 at 35 °C, although the reduc- tion in weight is slight. The perchlorate salts 1b and 10b have been used extensively,3 but since 1b detonated on drying under vacuum,13 they should both be avoided. Compound 1a appears to be nonhygroscopic, stable indefinitely, and to have ideal solubility properties in methylene chloride. For these reasons, it will be the main theme of this article. The other salts have various degrees of instabilities and some are quite hygroscopic. It should be understood that the other oxoammonium salts have similar properties. Nothing is known about their toxicity.

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Molecular Weight:156.2453
Molecular Formula:C9H18NO
InChIKey:VUZNLSBZRVZGIK-UHFFFAOYSA-N
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Molecular Weight:68.9953
Molecular Formula:NNaO2
InChIKey:LPXPTNMVRIOKMN-UHFFFAOYSA-M
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Molecular Weight:1.00794
Molecular Formula:H
InChIKey:GPRLSGONYQIRFK-UHFFFAOYSA-N
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Molecular Weight:171.22
Molecular Formula:C6H9N3OS
InChIKey:XLVOWGDFXAVSFE-UHFFFAOYSA-N
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Molecular Weight:169.204
Molecular Formula:C6H7N3OS
InChIKey:FGONQMFYFJRAIG-UHFFFAOYSA-N
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Compound Information
Molecular Weight:80.912
Molecular Formula:BrH
InChIKey:CPELXLSAUQHCOX-UHFFFAOYSA-N
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Molecular Weight:103.1198
Molecular Formula:C4H9NO2
InChIKey:IOGXOCVLYRDXLW-UHFFFAOYSA-N
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Compound Information
Molecular Weight:322.368
Molecular Formula:C16H36BrN
InChIKey:Not Available
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Molecular Weight:86.1323
Molecular Formula:C5H10O
InChIKey:Not Available
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Molecular Weight:84.1164
Molecular Formula:C5H8O
InChIKey:SEPQTYODOKLVSB-UHFFFAOYSA-N
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Molecular Weight:159.808
Molecular Formula:Br2
InChIKey:GDTBXPJZTBHREO-UHFFFAOYSA-N
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Compound Information
Molecular Weight:84.933
Molecular Formula:CH2Cl2
InChIKey:YMWUJEATGCHHMB-UHFFFAOYSA-N
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Molecular Weight:136.191
Molecular Formula:C9H12O
InChIKey:VAJVDSVGBWFCLW-UHFFFAOYSA-N
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Molecular Weight:134.1751
Molecular Formula:C9H10O
InChIKey:YGCZTXZTJXYWCO-UHFFFAOYSA-N
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Compound Information
Molecular Weight:33.0299
Molecular Formula:H3NO
InChIKey:AVXURJPOCDRRFD-UHFFFAOYSA-N
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Molecular Weight:98.959
Molecular Formula:C2H4Cl2
InChIKey:WSLDOOZREJYCGB-UHFFFAOYSA-N
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Molecular Weight:Not Available
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Molecular Weight:295.2049
Molecular Formula:C10H16F6NP
InChIKey:XUZKQHMUEBPODI-UHFFFAOYSA-N
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Molecular Weight:72.1057
Molecular Formula:C4H8O
InChIKey:ZSPTYLOMNJNZNG-UHFFFAOYSA-N
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Molecular Weight:70.0898
Molecular Formula:C4H6O
InChIKey:MLUCVPSAIODCQM-NSCUHMNNSA-N
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Compound Information
Molecular Weight:270.2784
Molecular Formula:C13H18O6
InChIKey:Not Available
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Molecular Weight:73.1368
Molecular Formula:C4H11N
InChIKey:Not Available
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Molecular Weight:325.4
Molecular Formula:C17H27NO5
InChIKey:AOKYZMDQACLJGI-VDWCLKJHSA-N
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Compound Information
Molecular Weight:98.999
Molecular Formula:ClCu
InChIKey:OXBLHERUFWYNTN-UHFFFAOYSA-M
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Compound Information
Molecular Weight:73.0938
Molecular Formula:C3H7NO
InChIKey:ZMXDDKWLCZADIW-UHFFFAOYSA-N
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Compound Information
Molecular Weight:211.941
Molecular Formula:C6H10BNaO6
InChIKey:HHYFEYBWNZJVFQ-UHFFFAOYSA-N
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Compound Information
Molecular Weight:210.3556
Molecular Formula:C14H26O
InChIKey:HICDDWYCMJZFHD-UHFFFAOYSA-N
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Molecular Weight:208.3398
Molecular Formula:C14H24O
InChIKey:BTVGBPHQRMNHRN-UHFFFAOYSA-N
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Molecular Weight:241.86
Molecular Formula:FeN3O9
InChIKey:VCJMYUPGQJHHFU-UHFFFAOYSA-N
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Compound Information
Molecular Weight:58.443
Molecular Formula:ClNa
InChIKey:FAPWRFPIFSIZLT-UHFFFAOYSA-M
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Molecular Weight:322.0964
Molecular Formula:C10H11IO4
InChIKey:ZBIKORITPGTTGI-UHFFFAOYSA-N
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Molecular Weight:26.0174
Molecular Formula:CHN
InChIKey:XFXPMWWXUTWYJX-UHFFFAOYSA-N
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Compound Information
Molecular Weight:150.722
Molecular Formula:C6H15ClSi
InChIKey:BCNZYOJHNLTNEZ-UHFFFAOYSA-N
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Molecular Weight:Not Available
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Molecular Weight:209.3079
Molecular Formula:C12H21N2O
InChIKey:ONGFJVQLCPNYTQ-UHFFFAOYSA-N
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Molecular Weight:190.45
Molecular Formula:CuI
InChIKey:LSXDOTMGLUJQCM-UHFFFAOYSA-M
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Molecular Weight:72.1057
Molecular Formula:C4H8O
InChIKey:WYURNTSHIVDZCO-UHFFFAOYSA-N
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Molecular Weight:122.1644
Molecular Formula:C8H10O
InChIKey:WAPNOHKVXSQRPX-UHFFFAOYSA-N
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Molecular Weight:120.1485
Molecular Formula:C8H8O
InChIKey:KWOLFJPFCHCOCG-UHFFFAOYSA-N
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Molecular Weight:74.442
Molecular Formula:ClNaO
InChIKey:Not Available
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Molecular Weight:119.002
Molecular Formula:BrK
InChIKey:IOLCXVTUBQKXJR-UHFFFAOYSA-M
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Molecular Weight:76.0514
Molecular Formula:C2H4O3
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Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:QTBSBXVTEAMEQO-UHFFFAOYSA-N
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Molecular Weight:542.647
Molecular Formula:C27H34N4O6S
InChIKey:HLBWPWATDURSJJ-GBAJDQEWSA-N
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Molecular Weight:540.631
Molecular Formula:C27H32N4O6S
InChIKey:BWYBBMQLUKXECQ-GIVPXCGWSA-N
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Compound Information
Molecular Weight:442.7168
Molecular Formula:C30H50O2
InChIKey:FVWJYYTZTCVBKE-MAIYTPNSSA-N
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Molecular Weight:456.7003
Molecular Formula:C30H48O3
InChIKey:QGJZLNKBHJESQX-KLSVAQHHSA-N
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Compound Information
Molecular Weight:213.2966
Molecular Formula:C11H21N2O2
InChIKey:YYTYIUAYFBFKHX-UHFFFAOYSA-N
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Compound Information
Molecular Weight:90.442
Molecular Formula:ClNaO2
InChIKey:Not Available
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Molecular Weight:164.1565
Molecular Formula:C6H12O5
InChIKey:NALRCAPFICWVAQ-UHFFFAOYSA-N
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Molecular Weight:162.1406
Molecular Formula:C6H10O5
InChIKey:IWJRZZLWGCYUKX-UHFFFAOYSA-N
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Molecular Weight:232.409
Molecular Formula:C3Cl3N3O3
InChIKey:YRIZYWQGELRKNT-UHFFFAOYSA-N
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Compound Information
Molecular Weight:84.0066
Molecular Formula:CHNaO3
InChIKey:UIIMBOGNXHQVGW-UHFFFAOYSA-M
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Compound Information
Molecular Weight:205.2084
Molecular Formula:C8H15NO5
InChIKey:HQEWNHTWZBVBMG-UHFFFAOYSA-N
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Molecular Weight:203.1925
Molecular Formula:C8H13NO5
InChIKey:YLHZEHPLGXGTNS-UHFFFAOYSA-N
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Molecular Weight:194.1825
Molecular Formula:C7H14O6
InChIKey:HOVAGTYPODGVJG-UHFFFAOYSA-N
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Molecular Weight:192.1666
Molecular Formula:C7H12O6
InChIKey:HQELTDCENJWLGH-UHFFFAOYSA-N
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Molecular Weight:235.2344
Molecular Formula:C9H17NO6
InChIKey:ZEVOCXOZYFLVKN-UHFFFAOYSA-N
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Molecular Weight:233.2185
Molecular Formula:C9H15NO6
InChIKey:BVNBJKMXBIWMFT-UHFFFAOYSA-N
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Molecular Weight:359.827
Molecular Formula:C18H14ClNO3S
InChIKey:GHNZUVJGCOWZOQ-UHFFFAOYSA-N
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Molecular Weight:357.811
Molecular Formula:C18H12ClNO3S
InChIKey:CQFZPZLDLNMGAW-UHFFFAOYSA-N
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Molecular Weight:88.1051
Molecular Formula:C4H8O2
InChIKey:XEKOWRVHYACXOJ-UHFFFAOYSA-N
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Molecular Weight:18.0153
Molecular Formula:H2O
InChIKey:XLYOFNOQVPJJNP-UHFFFAOYSA-N
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Molecular Weight:186.2713
Molecular Formula:C10H20NO2
InChIKey:KRNWYBIEWUXCOB-UHFFFAOYSA-N
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Molecular Weight:118.1742
Molecular Formula:C6H14O2
InChIKey:POAOYUHQDCAZBD-UHFFFAOYSA-N
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Molecular Weight:116.1583
Molecular Formula:C6H12O2
InChIKey:RPLPGIHCAYAYKX-UHFFFAOYSA-N
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Molecular Weight:102.894
Molecular Formula:BrNa
InChIKey:JHJLBTNAGRQEKS-UHFFFAOYSA-M
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Molecular Weight:172.2447
Molecular Formula:C9H18NO2
InChIKey:CSGAUKGQUCHWDP-UHFFFAOYSA-N
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Molecular Weight:291.4284
Molecular Formula:C18H29NO2
InChIKey:SWNFBBIWHTVENW-INIZCTEOSA-N
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Molecular Weight:291.4284
Molecular Formula:C18H29NO2
InChIKey:SWNFBBIWHTVENW-MRXNPFEDSA-N
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Molecular Weight:156.1839
Molecular Formula:C10H8N2
InChIKey:ROFVEXUMMXZLPA-UHFFFAOYSA-N
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Compound Information
Molecular Weight:37.833
Molecular Formula:BH4Na
InChIKey:YOQDYZUWIQVZSF-UHFFFAOYSA-N
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Compound Information
Molecular Weight:289.4125
Molecular Formula:C18H27NO2
InChIKey:BKBZZHXWGVVPOX-UHFFFAOYSA-N
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Compound Information
Molecular Weight:325.52
Molecular Formula:C20H27NOSi
InChIKey:Not Available
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Compound Information
Molecular Weight:650
Molecular Formula:C32H72N2O4Ru
InChIKey:XOKNWABDTLDBRC-UHFFFAOYSA-N
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Compound Information
Molecular Weight:192.2112
Molecular Formula:C11H12O3
InChIKey:SLCRPJTYYMMWGN-UHFFFAOYSA-N
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Compound Information
Molecular Weight:190.1953
Molecular Formula:C11H10O3
InChIKey:PMQKSRSJAUZEAW-UHFFFAOYSA-N
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Compound Information
Molecular Weight:192.2112
Molecular Formula:C11H12O3
InChIKey:SLCRPJTYYMMWGN-SNVBAGLBSA-N
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Compound Information
Molecular Weight:92.1384
Molecular Formula:C7H8
InChIKey:YXFVVABEGXRONW-UHFFFAOYSA-N
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