三甲基硅基重氮甲烷：修订间差异

三甲基硅基重氮甲烷
	IUPAC名; (Diazomethyl)trimethylsilane
别名	重氮(三甲基硅基)甲烷
识别
CAS号	18107-18-1
PubChem	167693
ChemSpider	146699
SMILES	C[Si](C)(C)[CH-][N+]#N;
Beilstein	1902903
MeSH	Trimethylsilyldiazomethane
性质
化学式	C4H10N2Si
摩尔质量	114.22 g·mol−1
外观	黄绿色液体
危险性
MSDS	External MSDS[永久失效連結]
	GHS危险性符号;
GHS提示词	Danger
H-术语	H330, H350, H370
P-术语	P201, P202, P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P273
	若非注明，所有数据均出自标准状态（25 ℃，100 kPa）下。

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三甲基硅基重氮甲烷是一种分子式为(CH₃)₃SiCHN₂的重氮化合物，因其相对不易爆炸而被广泛的应用于化学试剂重氮甲烷的替代品。

制备

三甲基硅基重氮甲烷可通过(三甲基硅基)甲基氯化镁与叠氮磷酸二苯酯反应制备^[4]。

应用

三甲基硅基重氮甲烷是一种商业市售试剂，常用于有机化学中的甲基化试剂。它可用于羧酸的甲酯化反应中，以替代较易爆炸的重氮甲烷；它还可与醇类发生反应以制备甲醚，而重氮甲烷则不可^[5]。

它可广泛的应用于氣相色譜法-質譜聯用分析技术，以将多种天然的羧酸化合物衍生化以分析检测。该反应过程迅速且易于操作使得该法被化学家所青睐，然而该反应会形成多种杂质而干扰光谱，杂质通常是因反应中甲醇的不足而产生的三甲基硅基酯化合物RCO₂CH₂SiMe₃。因此酸催化的甲醇解反应对于得到几乎定量的甲酯化产物RCO₂Me很必要^[6]。

三甲基硅基重氮甲烷是硫叶立德[2,3]-σ重排反应（也称为“多伊尔–柯姆斯反应”，Doyle–Kirmse reaction）中制备烯丙基硫化物和烯丙基胺的反应试剂。

安全

虽然三甲基硅基重氮甲烷的爆炸性比重氮甲烷的较弱，但其具有一定的毒性。当三甲基硅烷化重氮甲烷被用于转化羧酸至相应甲酯时，它会经由甲醇解反应在进程中产生重氮甲烷^[6]。当人体吸入三甲基硅烷化重氮甲烷，会与肺部表面的水气发生相似的反应^[7]。所以吸入三甲基硅烷化重氮甲烷可能也会导致与吸入重氮甲烷类似的症状（如肺水肿）^[7]。这使得三甲基硅烷化重氮甲烷吸入后有潜在的致命性，已有至少两人的死亡与吸入三甲基硅烷化重氮甲烷有关联，他们分别是加拿大新斯科舍温莎的制药工人和新泽西的化学家^[8]^[9]。

参考文献

^ Seyferth, Dietmar.; Dow, Alan W.; Menzel, Horst.; Flood, Thomas C. Trimethylsilyldiazomethane and trimethylsilylcarbene. J. Am. Chem. Soc. 1968, 90 (4): 1080–1082. doi:10.1021/ja01006a055.
^ Seyferth, Dietmar; Menzel, Horst; Dow, Alan W.; Flood, Thomas C. Trimethylsilyl-substituted diazoalkanes I. Trimethylsilyldiazomethane. J. Organomet. Chem. 1972, 44 (2): 279–290. doi:10.1016/S0022-328X(00)82916-2.
^ Trimethylsilyldiazomethane. pubchem.ncbi.nlm.nih.gov. [2024-02-06]. （原始内容存档于2024-02-06）（英语）.
^ Takayuki Shioiri, Toyohiko Aoyama, and Shigehiro Mori (1993). "Diazo(trimethylsilyl)methane". Org. Synth.; Coll. Vol. 8: 612.
^ Armin Presser and Antje Hüfner. Diazo(trimethylsilyl)methane – A Mild and Efficient Reagent for the Methylation of Carboxylic Acids and Alcohols in Natural Products. Chemical Monthly. 2004, 135 (8). doi:10.1007/s00706-004-0188-4.
^ ^6.0 ^6.1 Kühnel, E.; Laffan, D. D. P.; Lloyd-Jones, G. C.; Martínez del Campo, T.; Shepperson, I. R.; Slaughter, J. L. Mechanism of Methyl Esterification of Carboxylic Acids by Trimethylsilyldiazomethane. Angew. Chem. Int. Ed. 2007, 46 (37): 7075–7078. doi:10.1002/anie.200702131.
^ ^7.0 ^7.1 Murphy, N. G.; Varney, S. M.; Tallon, J. M.; Thompson, J. R.; Blanc, P. D. Fatal Occupational Exposure to Trimethylsilyl-Diazomethane. Clin. Toxicol. 2009, 47 (7): 712. doi:10.1080/15563650903076924.
^ Family says N.S. pharmaceutical worker named chemical he used before death （页面存档备份，存于互联网档案馆）, The Amherst Daily News, October 20, 2008
^ N.S. probe into pharma worker's death finds vent hoods turned off in lab （页面存档备份，存于互联网档案馆）, canadaeast.com, May 13th, 2009

[1] Seyferth, Dietmar.; Dow, Alan W.; Menzel, Horst.; Flood, Thomas C. Trimethylsilyldiazomethane and trimethylsilylcarbene. J. Am. Chem. Soc. 1968, 90 (4): 1080–1082. doi:10.1021/ja01006a055.

[2] Seyferth, Dietmar; Menzel, Horst; Dow, Alan W.; Flood, Thomas C. Trimethylsilyl-substituted diazoalkanes I. Trimethylsilyldiazomethane. J. Organomet. Chem. 1972, 44 (2): 279–290. doi:10.1016/S0022-328X(00)82916-2.

[3] Trimethylsilyldiazomethane. pubchem.ncbi.nlm.nih.gov. [2024-02-06]. （原始内容存档于2024-02-06）（英语）.

[4] Takayuki Shioiri, Toyohiko Aoyama, and Shigehiro Mori (1993). "Diazo(trimethylsilyl)methane". Org. Synth.; Coll. Vol. 8: 612.

[5] Armin Presser and Antje Hüfner. Diazo(trimethylsilyl)methane – A Mild and Efficient Reagent for the Methylation of Carboxylic Acids and Alcohols in Natural Products. Chemical Monthly. 2004, 135 (8). doi:10.1007/s00706-004-0188-4.

[Lloyd-Jones-6] 6.0 ^6.1 Kühnel, E.; Laffan, D. D. P.; Lloyd-Jones, G. C.; Martínez del Campo, T.; Shepperson, I. R.; Slaughter, J. L. Mechanism of Methyl Esterification of Carboxylic Acids by Trimethylsilyldiazomethane. Angew. Chem. Int. Ed. 2007, 46 (37): 7075–7078. doi:10.1002/anie.200702131.

[Murphy-7] 7.0 ^7.1 Murphy, N. G.; Varney, S. M.; Tallon, J. M.; Thompson, J. R.; Blanc, P. D. Fatal Occupational Exposure to Trimethylsilyl-Diazomethane. Clin. Toxicol. 2009, 47 (7): 712. doi:10.1080/15563650903076924.

[8] Family says N.S. pharmaceutical worker named chemical he used before death （页面存档备份，存于互联网档案馆）, The Amherst Daily News, October 20, 2008

[9] N.S. probe into pharma worker's death finds vent hoods turned off in lab （页面存档备份，存于互联网档案馆）, canadaeast.com, May 13th, 2009

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@@ 第28行： / 第27行： @@
 |  N = 2
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 |Section3={{Chembox Hazards
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+| GHSPictograms = {{GHS02}}{{GHS06}}{{GHS08}}{{GHS09}}<ref>{{cite web |title=Trimethylsilyldiazomethane |url=https://pubchem.ncbi.nlm.nih.gov/compound/167693#section=Safety-and-Hazards |website=pubchem.ncbi.nlm.nih.gov |language=en |access-date=2024-02-06 |archive-date=2024-02-06 |archive-url=https://web.archive.org/web/20240206133923/https://pubchem.ncbi.nlm.nih.gov/compound/167693#section=Safety-and-Hazards |dead-url=no }}</ref>
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-'''三甲基硅烷化重氮甲烷'''，(CH<sub>3</sub>)<sub>3</sub>SiCHN<sub>2</sub>是一种[[重氮化合物]]，被广泛的应用于较易爆炸的化学试剂[[重氮甲烷]]的替代品。
+'''三甲基硅基重氮甲烷'''是一种分子式为(CH<sub>3</sub>)<sub>3</sub>SiCHN<sub>2</sub>的[[重氮化合物]]，因其相对不易爆炸而被广泛的应用于化学试剂[[重氮甲烷]]的替代品。
 ==制备==
-三甲基硅烷化重氮甲烷可通过(三甲基硅基)甲基氯化镁与[[叠氮磷酸二苯酯]]反应制备。
+三甲基硅基重氮甲烷可通过(三甲基硅基)甲基氯化镁与[[叠氮磷酸二苯酯]]反应制备<ref>{{OrgSynth | author = Takayuki Shioiri, Toyohiko Aoyama, and Shigehiro Mori | title = Diazo(trimethylsilyl)methane | prep = cv8p0612 | collvol = 8 | collvolpages = 612 | year = 1993}}</ref>。
-<ref>{{OrgSynth | author = Takayuki Shioiri, Toyohiko Aoyama, and Shigehiro Mori | title = Diazo(trimethylsilyl)methane | prep = cv8p0612 | collvol = 8 | collvolpages = 612 | year = 1993}}</ref>
 ==应用==
-三甲基硅烷化重氮甲烷是一种商业市售[[试剂]]，常用于[[有机化学]]中的[[甲基化试剂]]。它可用于[[羧酸]]的甲酯化中，以替代较易爆炸的[[重氮甲烷]]；它还可与醇类发生反应以制备甲醚，而重氮甲烷则不可。<ref>{{cite journal | author = Armin Presser and Antje Hüfner | journal = [[Chemical Monthly]] | doi = 10.1007/s00706-004-0188-4 | title = Diazo(trimethylsilyl)methane – A Mild and Efficient Reagent for the Methylation of Carboxylic Acids and Alcohols in Natural Products | year = 2004 | volume = 135 | issue = 8}}</ref>
+三甲基硅基重氮甲烷是一种商业市售[[试剂]]，常用于[[有机化学]]中的[[甲基化]]试剂。它可用于[[羧酸]]的甲酯化反应中，以替代较易爆炸的[[重氮甲烷]]；它还可与醇类发生反应以制备甲醚，而重氮甲烷则不可<ref>{{cite journal | author = Armin Presser and Antje Hüfner | journal = [[Chemical Monthly]] | doi = 10.1007/s00706-004-0188-4 | title = Diazo(trimethylsilyl)methane – A Mild and Efficient Reagent for the Methylation of Carboxylic Acids and Alcohols in Natural Products | year = 2004 | volume = 135 | issue = 8}}</ref>。
-它可广泛的应用于[[氣相色譜法-質譜聯用]]分析技术，以将多种天然的羧酸化合物衍生化以分析检测。其反应过程通常快且容易，使得该试剂很常用，然而该反应会形成多种杂质而干扰光谱，杂质通常是不足的[[甲醇]]存在下产生的三甲基硅基酯化合物RCO<sub>2</sub>CH<sub>2</sub>SiMe<sub>3</sub>。因此酸-催化的甲醇化对于得到几乎定量的甲酯化产物RCO<sub>2</sub>Me很必要。<ref name="Lloyd-Jones">{{ cite journal | journal = [[Angewandte Chemie|Angew. Chem. Int. Ed.]] | volume = 46 | issue = 37 | pages = 7075–7078 | year = 2007 | first1 = E. | last1 = Kühnel | first2 = D. D. P. | last2 = Laffan | first3 = G. C. | last3 = Lloyd-Jones | first4 = T. | last4 = Martínez del Campo | first5 = I. R. | last5 = Shepperson | first6 = J. L. | last6 = Slaughter | title = Mechanism of Methyl Esterification of Carboxylic Acids by Trimethylsilyldiazomethane | doi = 10.1002/anie.200702131 }}</ref>
+它可广泛的应用于[[氣相色譜法-質譜聯用]]分析技术，以将多种天然的羧酸化合物衍生化以分析检测。该反应过程迅速且易于操作使得该法被化学家所青睐，然而该反应会形成多种杂质而干扰光谱，杂质通常是因反应中[[甲醇]]的不足而产生的三甲基硅基酯化合物RCO<sub>2</sub>CH<sub>2</sub>SiMe<sub>3</sub>。因此酸催化的甲醇解反应对于得到几乎定量的甲酯化产物RCO<sub>2</sub>Me很必要<ref name="Lloyd-Jones">{{ cite journal | journal = [[Angewandte Chemie|Angew. Chem. Int. Ed.]] | volume = 46 | issue = 37 | pages = 7075–7078 | year = 2007 | first1 = E. | last1 = Kühnel | first2 = D. D. P. | last2 = Laffan | first3 = G. C. | last3 = Lloyd-Jones | first4 = T. | last4 = Martínez del Campo | first5 = I. R. | last5 = Shepperson | first6 = J. L. | last6 = Slaughter | title = Mechanism of Methyl Esterification of Carboxylic Acids by Trimethylsilyldiazomethane | doi = 10.1002/anie.200702131 }}</ref>。
-三甲基硅烷化重氮甲烷是[[Doyle-Kirmse反应]]中制备烯丙基硫化物和烯丙基胺的反应试剂。
+三甲基硅基重氮甲烷是[[硫叶立德2,3-σ重排反应|硫叶立德[2,3]-σ重排反应]]（也称为“多伊尔–柯姆斯反应”，Doyle–Kirmse reaction）中制备烯丙基硫化物和烯丙基胺的反应试剂。
 ==安全==
-虽然三甲基硅烷化重氮甲烷的爆炸性比[[重氮甲烷]]的较弱，但其具有一定的毒性。吸入三甲基硅烷化重氮甲烷可能也会导致与吸入重氮甲烷可能类似的症状（如[[肺水肿]]）。<ref name="Murphy">{{ cite journal | journal = [[Clinical Toxicology|Clin. Toxicol.]] | volume = 47 | issue = 7 | page = 712 | year = 2009 | title = Fatal Occupational Exposure to Trimethylsilyl-Diazomethane | first1 = N. G. | last1 = Murphy | first2 = S. M. | last2 = Varney | first3 = J. M. | last3 = Tallon | first4 = J. R. | last4 = Thompson | first5 = P. D. | last5 = Blanc | doi = 10.1080/15563650903076924 }}</ref>这使得三甲基硅烷化重氮甲烷吸入后有潜在的致命性，已有至少两人的死亡与吸入三甲基硅烷化重氮甲烷有关联，他们分别是[[加拿大]][[新斯科舍]][[温莎]]的配药师和[[新泽西]]的[[化学家]]。<ref>[http://www.amherstdaily.com/index.cfm?sid=181982&sc=508 Family says N.S. pharmaceutical worker named chemical he used before death], ''The Amherst Daily News'', October 20, 2008</ref><ref>[http://www.canadaeast.com/front/article/666039 N.S. probe into pharma worker's death finds vent hoods turned off in lab], canadaeast.com, May 13th, 2009</ref>
+虽然三甲基硅基重氮甲烷的爆炸性比[[重氮甲烷]]的较弱，但其具有一定的毒性。当三甲基硅烷化重氮甲烷被用于转化[[羧酸]]至相应[[甲酯]]时，它会经由[[甲醇解]]反应在进程中产生重氮甲烷<ref name="Lloyd-Jones" />。当人体吸入三甲基硅烷化重氮甲烷，会与肺部表面的水气发生相似的反应<ref name="Murphy" />。所以吸入三甲基硅烷化重氮甲烷可能也会导致与吸入重氮甲烷类似的症状（如[[肺水肿]]）<ref name="Murphy">{{ cite journal | journal = [[Clinical Toxicology|Clin. Toxicol.]] | volume = 47 | issue = 7 | page = 712 | year = 2009 | title = Fatal Occupational Exposure to Trimethylsilyl-Diazomethane | url = https://archive.org/details/sim_clinical-toxicology_2009-08_47_7/page/712 | first1 = N. G. | last1 = Murphy | first2 = S. M. | last2 = Varney | first3 = J. M. | last3 = Tallon | first4 = J. R. | last4 = Thompson | first5 = P. D. | last5 = Blanc | doi = 10.1080/15563650903076924 }}</ref>。这使得三甲基硅烷化重氮甲烷吸入后有潜在的致命性，已有至少两人的死亡与吸入三甲基硅烷化重氮甲烷有关联，他们分别是[[加拿大]][[新斯科舍]][[温莎]]的制药工人和[[新泽西]]的[[化学家]]<ref>[http://www.amherstdaily.com/index.cfm?sid=181982&sc=508 Family says N.S. pharmaceutical worker named chemical he used before death] {{Wayback|url=http://www.amherstdaily.com/index.cfm?sid=181982&sc=508 |date=20081021214644 }}, ''The Amherst Daily News'', October 20, 2008</ref><ref>[http://www.canadaeast.com/front/article/666039 N.S. probe into pharma worker's death finds vent hoods turned off in lab] {{Wayback|url=http://www.canadaeast.com/front/article/666039 |date=20120215144449 }}, canadaeast.com, May 13th, 2009</ref>。
-当三甲基硅烷化重氮甲烷被用于转化[[羧酸]]至相应[[甲酯]]时，它会经由[[甲醇分解作用]]在反应进程中产生重氮甲烷。<ref name="Lloyd-Jones" /> 当人体吸入三甲基硅烷化重氮甲烷，会与肺部表面的水气发生相似的反应。<ref name="Murphy" />
 ==参考文献==
@@ 第59行： / 第56行： @@
 [[Category:重氮化合物]]
 [[Category:有机化学试剂]]
-[[Category:硅烷]]
+[[Category:碳硅烷]]
+[[Category:三甲基硅基化合物]]
-[[en:Trimethylsilyldiazomethane]]
-[[fa:تری‌متیل‌سیلیل‌دی‌آزومتان]]
-[[fr:Triméthylsilyldiazométhane]]
-[[nl:Diazo(trimethylsilyl)methaan]]
-[[ja:トリメチルシリルジアゾメタン]]