脫烷基試劑——三溴化硼
三溴化硼(peng)作為(wei)一種強酸性路易斯酸可以(yi)用于脫烷(wan)基(ji)反(fan)應(ying)(ying),反(fan)應(ying)(ying)機(ji)理如(ru)下圖(tu),首先甲基(ji)醚(mi)中氧原子(zi)的孤對電子(zi)進(jin)攻硼(peng)原子(zi),溴離(li)(li)子(zi)離(li)(li)去,氧原子(zi)為(wei)正電性;然后溴離(li)(li)子(zi)進(jin)攻甲基(ji)碳正中心生成(cheng)甲基(ji)溴;最后烷(wan)氧基(ji)二溴硼(peng)烷(wan)經(jing)過水解得到相應(ying)(ying)的羥基(ji)化合(he)物。一般選擇極性溶(rong)劑促進(jin)反(fan)應(ying)(ying),例如(ru)乙二醇二甲醚(mi)和四氫呋喃。
圖片來源網絡
反應實例:
一(yi)般活性藥物分子都具有手(shou)性中心(xin),2021年(nian)報道的(de)(de)文(wen)獻中嘗試了HBr/AcOH, HCl/iPrOH, AlCl3脫(tuo)(tuo)甲基(ji)(ji)(ji),會(hui)發生消(xiao)旋(xuan)或轉化不(bu)完全;嘗試利用蛋(dan)氨(an)酸(suan)/甲基(ji)(ji)(ji)磺酸(suan)脫(tuo)(tuo)甲基(ji)(ji)(ji)需(xu)要長達(da)3天的(de)(de)時間,并(bing)且長時間反(fan)應會(hui)導(dao)致產物消(xiao)旋(xuan);最后利用三溴化硼可以完全脫(tuo)(tuo)甲基(ji)(ji)(ji)并(bing)順便脫(tuo)(tuo)掉Boc,高(gao)效保護了化合物的(de)(de)手(shou)性。
圖片來源:Org. Process Res. Dev. 2022, 26, 3, 710–729
三溴化硼在半導體中應用
在碳基集成電路制造領域,石墨烯基器件中采用原子層沉積方法生長氮化硼,作為高k柵氧介質。氮化硼基于六邊形層狀結構,具有優異的物理性質和極高的化學穩定性,六方晶型具有寬帶隙(5.5 - 6.0 eV)適用于電子器件的介電層。三溴化硼是一種蒸氣壓較高的前驅體(25℃,70Torr),很容易于氨反應得到氮化硼。在原子層沉積過程中,三溴化硼與基底羥基發生反應,飽和吸附后進行吹掃,然后通入NH3反應,完成后再進行吹掃,往復循環得到氮化硼薄膜,研究表明當沉積溫度為750℃時,可降低氮化硼薄膜對空氣和水份的敏感性。(Thin Solid Films, 2022, 402, 167 - 171)
半導體器件制備工藝中,通常需要在硅襯底中摻雜P型或者N型雜質來形成PN結,擴散和離子注入是半導體摻雜的兩種主要方式。在太陽能電池工業中,長采用擴散的方式向N型晶體摻雜P型雜質,而硼的價格低廉且擴散速度快,常作為摻雜體。行業內大多數都是利用液態三溴化硼作為前驅體,在硅襯底表面沉積三氧化二硼薄膜,然后加熱硅襯底,使之與三氧化二硼發生反應(2B203+3Si=4B+3Si02),生成硼原子,硼原子作為擴散源在高溫下向硅片內部擴散,形成PN結。(CN 104250725 A)
Chemical Name | Boron Tribromide |
Synonym |
BORON TRIBROMIDE, REAGENTPLUS, >=99%
BORON TRIBROMIDE, 99.995%
晶堿石
boron (III) bromide
BORON TRIBROMIDE, REAGENTPLUS, 99.9%
Bortribromid
三溴化硼(0402禁空運)
boronbromide(bbr3)
三溴化硼,1M在二氯甲烷溶劑中
Boron tribromide
tribromoborane
三溴化硼
BORON TRIBROMIDE, 1.0M SOLUTION IN HEPTA NE
tribromo-boran
Boron bromide (BBr3)
BORON TRIBROMIDE SOLUTION, ~1 M IN DICHL OROMETHANE
Borane,tribromo-
Boron,tribromo-
trona
天然堿
BORON TRIBROMIDE
BBr3
三溴化硼 溶液
Borane, tribromo-
BORON TRIBROMIDE, 1.0M SOLUTION IN HEXAN ES
Tribromoboron
tribromuredebore
溴化硼
boron tribromide
三溴硼烷(爆炸,禁止銷售)BORON TRIBROMIDE, 99.9%
三溴硼烷
絲光晶堿石
BORON TRIBROMIDE, 1.0M SOLUTION IN DICHL OROMETHANE
Boron tribromide Solution
BORON BROMIDE
Boron bromide
溴化硼;天然堿
三溴化硼, 99% MIN
碳酸鈉石
tribromoboron
Tribromoborane
天然堿;碳酸鈉石
BBr3 |
PubChem Substance ID | 125307031 |
EC Number | 233-657-9 |
Reaxys-RN | 3903058 |
Merck Number | 1347 |
Beilstein Registry Number | 2384789 |
Chemical Name Translation | 三溴化硼 |
LabNetwork Molecule ID | LN00163667 |
MDL Number | MFCD00011312 |
CAS Number | 10294-33-4 |
GHS Symbol
WGK Germany | 3 |
Hazard Codes |
T+
T+,C
T+;C
T+,C,F,N |
Hazard statements | |
- H290 May be corrosive to metals 可能腐蝕金屬。
- H314 Causes severe skin burns and eye damage 導致嚴重的皮膚灼傷和眼睛損傷
- H330 Fatal if inhaled 吸入致命
- H300 Fatal if swallowed 吞食致命
- H225 Highly flammable liquid and vapour 高度易燃液體和蒸氣
- H300+H330
- H351 Suspected of causing cancer 懷疑致癌
|
Personal Protective Equipment |
Faceshields, full-face respirator (US), Gloves, Goggles, multi-purpose combination respirator cartridge (US), type ABEK (EN14387) respirator filter |
RTECS | ED7400000 |
Precautionary statements | |
- P271 Use only outdoors or in a well-ventilated area.? 只能在室外或通風良好的地方使用。
- P261 Avoid breathing dust/fume/gas/mist/vapours/spray. 避免吸入粉塵/煙/氣體/煙霧/蒸汽/噴霧。
- P305+P351+P338
- P280 Wear protective gloves/protective clothing/eye protection/face protection. 戴防護手套/防護服/眼睛的保護物/面部保護物。
- P304+P340+P310
- P501 Dispose of contents/container to..… 處理內容物/容器.....
- P403+P233
- P305+P351+P338+P310
- P310 Immediately call a POISON CENTER or doctor/physician. 立即呼救解毒中心或醫生/醫師。
- P264 Wash hands thoroughly after handling. 處理后要徹底洗凈雙手。
- P301+P330+P331+P310
- P303+P361+P353
- P284 Wear respiratory protection.? 佩戴呼吸保護裝置。
- P201 Obtain special instructions before use. 使用前獲取專門指示。
- P240 Ground/bond container and receiving equipment. 與地面接觸/連接集裝箱和接受設備。
- P370+P378
- P270 Do not eat, drink or smoke when using this product. 使用本產品時不要吃東西,喝水或吸煙。
- P260 Do not breathe dust/fume/gas/mist/vapours/spray. 不要吸入粉塵/煙/氣體/煙霧/蒸汽/噴霧。
- P202 Do not handle until all safety precautions have been read and understood. 已閱讀并理解所有的安全預防措施之前,切勿操作。
- P301+P310
- P233 Keep container tightly closed. ?保持容器密閉。
- P390 Absorb spillage to prevent material damage. 吸收溢出物,防止重大損害。
- P210 Keep away from heat/sparks/open flames/hot surfaces. — No smoking. 遠離熱源/火花/明火/熱的表面。——禁止吸煙。
- P273 Avoid release to the environment. 避免釋放到環境中。
- P308+P311
|
Signal word |
|
Storage condition |
Moisture Sensitive
2-8℃易吸潮,密封充氬保存。
Poison room
充氬保存
易吸潮,密封充氬保存。
Moisture & Light Sensitive
0-10°C
避光,易吸潮,密封充氬保存。
0-10 |
UN Number |
3390
UN2692
3489
UN3390
UN3384 |
Risk Statements | |
- R35 Causes severe burns 會導致嚴重灼傷
- R14 Reacts violently with water 遇水會猛烈反應
- R26/28 Very toxic by inhalation and if swallowed 吸入及吞食都有劇毒
- R11 Highly flammable 非常易燃
- R50/53
- R65 Harmful: may cause lung damage if swallowed 若吞咽可能傷害肺部器官
- R67 Vapours may cause drowsiness and dizziness 蒸汽可能導致嗜睡和昏厥
- R34 Causes burns 會導致灼傷
- R62 Possible risk of impaired fertility 有削弱生殖能力的危險
- R40 Limited evidence of a carcinogenic effect 有限證據表明其致癌作用
|
Safety Statements | |
- S26 In case of contact with eyes, rinse immediately with plenty of water and seek medical advice 眼睛接觸后,立即用大量水沖洗并征求醫生意見;
- S23 Do not breathe gas/fumes/vapour/spray (appropriate wording to be specified by the manufacturer) 不要吸入氣體/煙霧/蒸汽/噴霧;
- S57 Use appropriate containment to avoid environmental contamination 使用適當容器避免環境污染;
- S45 In case of accident or if you feel unwell seek medical advice immediately (show the label where possible) 發生事故時或感覺不適時,立即求醫(可能時出示標簽);
- S28 After contact with skin, wash immediately with plenty of ... (to be specified by the manufacturer) 皮膚接觸后,立即用大量…(由生產廠家指定)沖洗;
- S36/37/39 Wear suitable protective clothing, gloves and eye/face protection 穿戴適當的防護服、手套和眼睛/面保護;
- S9 Keep container in a well-ventilated place 保持容器在通風良好的場所;
- S16 Keep away from sources of ignition - No smoking 遠離火源,禁止吸煙;
- S33 Take precautionary measures against static discharges 對靜電采取預防措施;
- S62 If swallowed, do not induce vomiting: seek medical advice immediately and show this container or label where possible 吞食后不要催吐:立即求醫并出示該容器或標簽;
- S60 This material and its container must be disposed of as hazardous waste 該物質及其容器必須作為危險廢物處置;
- S61 Avoid release to the environment. Refer to special instructions/safety data sheet 避免釋放到環境中,參考特別指示/安全收據說明書;
|
Packing Group | I |
Hazard Class | 6.1/3, 8 |
Warnings |
危化品目錄(2015) |
Restrict |
危險品 |
⑴.易被水和醇等分解,受熱會爆炸,對人體組織有強烈刺激作用,其蒸氣劇毒,腐蝕性較強,具有強吸水性,見光、遇熱易分解,接觸空氣冒白煙。為強路易式酸,能與堿反應形成絡合物和加成物。
⑵.在干燥空氣中不變化。溶于無機酸并劇烈起泡。天然堿產于不同的鹽湖沉積物中,主要產于堿湖及古代沉積礦床中,常與針碳鈉鈣石、水堿、泡堿、石鹽、芒硝、鈣芒硝、無水芒硝和石膏共生。遇空氣中的濕氣很容易水解。
⑶.重要的工業原料,廣泛用于玻璃、化工、輕工、紡織、漂染、冶金、石油加工、醫藥、食品等方面。
⑷.用作半導體的摻雜材料,有機
用作有機合成的催化劑、中間體和溴化劑,制造高純硼及其它有機硼化合物的原料。
{ALF} Reagent for cleavage of ethers: Synthesis, 249 (1983). Converts alcohols to alkyl bromides under mild conditions: Tetrahedron Lett., 35, 1051 (1994). Cleavage of N-methoxymethyl: Tetrahedron Lett., 42, 8633 (2001), or N-benzyl: Tetrahedron Lett., 45, 4093 (2004) protecting groups can also be achieved under mild conditions. Alkynes undergo bromoboration; the products can be transformed, e.g. to trisubstituted alkenes: Tetrahedron Lett., 29, 1811 (1988), or enyne-allenes: Tetrahedron Lett., 35, 1829 (1994).
{uni_hamburg} Short: II/25A
{ALD} Merck:14,1347
{ALF} Reagent for cleavage of ethers. For a brief feature of uses of the reagent in organic synthesis, see: Synlett, 1636 (2005). See also preceding entry.
{ALF} Reagent for cleavage of ethers: Synthesis, 249 (1983). Converts alcohols to alkyl bromides under mild conditions: Tetrahedron Lett., 35, 1051 (1994). Cl