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三辛基铝 | 1070-00-4

中文名称
三辛基铝
中文别名
三正辛基铝
英文名称
trioctylaluminum
英文别名
tri-n-octylaluminum;trioctylaluminium;TNOAL;tri(n-octyl)aluminium;Al(octyl)3
三辛基铝化学式
CAS
1070-00-4
化学式
C24H51Al
mdl
——
分子量
366.65
InChiKey
LFXVBWRMVZPLFK-UHFFFAOYSA-N
BEILSTEIN
——
EINECS
——
  • 物化性质
  • 计算性质
  • ADMET
  • 安全信息
  • SDS
  • 制备方法与用途
  • 上下游信息
  • 反应信息
  • 文献信息
  • 表征谱图
  • 同类化合物
  • 相关功能分类
  • 相关结构分类

物化性质

  • 沸点:
    361℃[at 101 325 Pa]
  • 密度:
    0.701 g/mL at 25 °C
  • 闪点:
    −6 °F
  • 物理描述:
    Liquid
  • 颜色/状态:
    Colorless liquid
  • 熔点:
    < -40 °C
  • 稳定性/保质期:

    反应强烈,对敏感。

  • 粘度:
    Viscosity: 14.2 cP at 30 °C

计算性质

  • 辛醇/水分配系数(LogP):
    10.23
  • 重原子数:
    25
  • 可旋转键数:
    21
  • 环数:
    0.0
  • sp3杂化的碳原子比例:
    1.0
  • 拓扑面积:
    0
  • 氢给体数:
    0
  • 氢受体数:
    0

ADMET

毒理性
  • 致癌性证据
A4;不可归类为人类致癌物。/铝属和难溶化合物/
A4; Not classifiable as a human carcinogen. /Aluminum metal and insoluble compounds/
来源:Hazardous Substances Data Bank (HSDB)
毒理性
  • 人类毒性摘录
征兆与症状:腐蚀性。能引起严重眼睛和皮肤烧伤。对皮肤、眼睛和呼吸系统有刺激性。如果通过皮肤吸收或吸入,可能有害。吸入含有机铝化合物的烟雾可能导致“属烟雾热”。/安全预防措施:虽然可能发生,但属烟雾热不太可能发生。/有机铝化合物/
/SIGNS AND SYMPTOMS/ Corrosive. Causes severe eye and skin burns. Irritating to skin, eyes, and respiratory system. May be harmful if absorbed through skin or inhaled. "Metal fume fever" may result from inhalation of fumes /from organoaluminum compounds/. /SRP: While possible, metal fume fever is not highly probable./ /Organoaluminum compounds/
来源:Hazardous Substances Data Bank (HSDB)
毒理性
  • 人类毒性摘录
/其他毒性信息/ 热反应性烷基化合物(丁基及以下)的蒸气不具毒性,因为它们会被完全消耗,但是吸入15毫克/立方米或更高浓度的金属氧化物烟雾(Al2O3)可能会导致“属烟雾热”症状。/铝烷基化合物/
/OTHER TOXICITY INFORMATION/ Vapors of the pyrophoric alkyls (butyls and below) are nontoxic because they are completely consumed, but inhalation of the metallic oxide smoke (Al2O3) at 15 mg/cu m or greater can result in symptoms such as "metal fume fever." /Aluminum alkyls/
来源:Hazardous Substances Data Bank (HSDB)

安全信息

  • 危险品标志:
    F,C,N
  • 安全说明:
    S16,S23,S26,S36,S37,S39,S45,S61,S9
  • 危险类别码:
    R11
  • WGK Germany:
    1,2
  • 海关编码:
    2931900090
  • 危险品运输编号:
    UN 2924 3/PG 2
  • 危险标志:
    GHS02,GHS05,GHS07,GHS08,GHS09
  • 危险性描述:
    H225,H260,H304,H314,H336,H361f,H373,H411
  • 危险性防范说明:
    P210,P231 + P232,P280,P370 + P378,P402 + P404,P403 + P235
  • 储存条件:
    密封储存于阴凉、干燥的库房,远离火源、腐蚀区域及易燃易爆区域,并采用氮气进行保护。

SDS

SDS:aa9a1e637a68b358e907086d821bc30b
查看

Section 1. IDENTIFICATION OF THE SUBSTANCE/MIXTURE
Product identifiers
Product name : Trioctylaluminum solution
Relevant identified uses of the substance or mixture and uses advised against
Identified uses : Laboratory chemicals, Manufacture of substances



Section 2. HAZARDS IDENTIFICATION
Classification of the substance or mixture
Classification according to Regulation (EC) No 1272/2008 [EU-GHS/CLP]
Flammable liquids (Category 2)
Substances, which in contact with water, emit flammable gases (Category 1)
Skin corrosion (Category 1B)
Reproductive toxicity (Category 2)
Specific target organ toxicity - single exposure (Category 3)
Specific target organ toxicity - repeated exposure (Category 2)
Aspiration hazard (Category 1)
Chronic aquatic toxicity (Category 2)
Classification according to EU Directives 67/548/EEC or 1999/45/EC
Highly flammable. Contact with water liberates extremely flammable gases. Causes severe burns. Harmful:
may cause lung damage if swallowed. Harmful: danger of serious damage to health by prolonged
exposure through inhalation. Possible risk of impaired fertility. Toxic to aquatic organisms, may cause long-
term adverse effects in the aquatic environment. Vapours may cause drowsiness and dizziness. Reacts
violently with water.
Label elements
Labelling according Regulation (EC) No 1272/2008 [CLP]
Pictogram
Signal word Danger
Hazard statement(s)
H225 Highly flammable liquid and vapour.
H260 In contact with water releases flammable gases which may ignite
spontaneously.
H304 May be fatal if swallowed and enters airways.
H314 Causes severe skin burns and eye damage.
H336 May cause drowsiness or dizziness.
H361f Suspected of damaging fertility.
H373 May cause damage to organs through prolonged or repeated exposure.
H411 Toxic to aquatic life with long lasting effects.
Precautionary statement(s)
P210 Keep away from heat/sparks/open flames/hot surfaces. - No smoking.
P223 Keep away from any possible contact with water, because of violent
reaction and possible flash fire.
P231 + P232 Handle under inert gas. Protect from moisture.
P261 Avoid breathing dust/ fume/ gas/ mist/ vapours/ spray.
P370 + P378 In case of fire: Use dry sand, dry chemical or alcohol-resistant foam for
extinction.
P422 Store contents under inert gas.
Supplemental Hazard information (EU)
EUH014 Reacts violently with water.
According to European Directive 67/548/EEC as amended.
Hazard symbol(s)
R-phrase(s)
R11 Highly flammable.
R14/15 Reacts violently with water, liberating extremely flammable gases.
R35 Causes severe burns.
R48/20 Harmful: danger of serious damage to health by prolonged exposure
through inhalation.
R51/53 Toxic to aquatic organisms, may cause long-term adverse effects in the
aquatic environment.
R62 Possible risk of impaired fertility.
R65 Harmful: may cause lung damage if swallowed.
R67 Vapours may cause drowsiness and dizziness.
S-phrase(s)
S26 In case of contact with eyes, rinse immediately with plenty of water and
seek medical advice.
S36/37/39 Wear suitable protective clothing, gloves and eye/face protection.
S43 In case of fire, use sand, dry chemical or alcohol-resistant foam.
S45 In case of accident or if you feel unwell, seek medical advice immediately
(show the label where possible).
S61 Avoid release to the environment. Refer to special instructions/ Safety
data sheets.
S62 If swallowed, do not induce vomiting: seek medical advice immediately
and show this container or label.
Other hazards - none

Section 3. COMPOSITION/INFORMATION ON INGREDIENTS
Mixtures
Formula : C24H51Al
Molecular Weight : 366,64 g/mol
Component Classification Concentration
n-Hexane
CAS-No. 110-54-3 Flam. Liq. 2; Skin Irrit. 2; Repr. 50 - 100 %
EC-No. 203-777-6 2; STOT SE 3; STOT RE 2;
Index-No. 601-037-00-0 Asp. Tox. 1; Aquatic Chronic
2; H225, H304, H315, H336,
H361f, H373, H411
F, Xn, N, Repr.Cat.3, R11 -
R38 - R48/20 - R62 - R65 -
R67 - R51/53
Trioctylaluminium
CAS-No. 1070-00-4 Pyr. Liq. 1; Water-react. 1; 25 - 50 %
EC-No. 213-964-4 Skin Corr. 1B; H250, H260,
H314, EUH014
F, C, R14/15 - R17 - R35
For the full text of the H-Statements and R-Phrases mentioned in this Section, see Section 16

Section 4. FIRST AID MEASURES
Description of first aid measures
General advice
Consult a physician. Show this safety data sheet to the doctor in attendance.
If inhaled
If breathed in, move person into fresh air. If not breathing, give artificial respiration. Consult a physician.
In case of skin contact
Take off contaminated clothing and shoes immediately. Wash off with soap and plenty of water. Consult a
physician.
In case of eye contact
Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician.
If swallowed
Do NOT induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with
water. Consult a physician.
Most important symptoms and effects, both acute and delayed
Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and
skin., spasm, inflammation and edema of the larynx, spasm, inflammation and edema of the bronchi,
pneumonitis, pulmonary edema, burning sensation, Cough, wheezing, laryngitis, Shortness of breath,
Headache, Nausea
Indication of any immediate medical attention and special treatment needed
no data available

Section 5. FIREFIGHTING MEASURES
Extinguishing media
Suitable extinguishing media
Dry powder
Special hazards arising from the substance or mixture
Carbon oxides, Aluminum oxide
Advice for firefighters
Wear self contained breathing apparatus for fire fighting if necessary.
Further information
no data available

Section 6. ACCIDENTAL RELEASE MEASURES
Personal precautions, protective equipment and emergency procedures
Use personal protective equipment. Avoid breathing vapors, mist or gas. Ensure adequate ventilation.
Remove all sources of ignition. Evacuate personnel to safe areas. Beware of vapours accumulating to
form explosive concentrations. Vapours can accumulate in low areas.
Environmental precautions
Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Discharge into the
environment must be avoided.
Methods and materials for containment and cleaning up
Contain spillage, and then collect with an electrically protected vacuum cleaner or by wet-brushing and
place in container for disposal according to local regulations (see section 13). Do not flush with water.
Reference to other sections
For disposal see section 13.

Section 7. HANDLING AND STORAGE
Precautions for safe handling
Avoid contact with skin and eyes. Avoid inhalation of vapour or mist.
Keep away from sources of ignition - No smoking.Take measures to prevent the build up of electrostatic
charge.
Conditions for safe storage, including any incompatibilities
Store in cool place. Keep container tightly closed in a dry and well-ventilated place. Containers which are
opened must be carefully resealed and kept upright to prevent leakage.
Never allow product to get in contact with water during storage.
Air and moisture sensitive. Handle and store under inert gas.
Specific end use(s)
no data available

Section 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Control parameters
Components with workplace control parameters
Exposure controls
Appropriate engineering controls
Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and
at the end of workday.
Personal protective equipment
Eye/face protection
Tightly fitting safety goggles. Faceshield (8-inch minimum). Use equipment for eye protection
tested and approved under appropriate government standards such as NIOSH (US) or EN
166(EU).
Skin protection
Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique
(without touching glove's outer surface) to avoid skin contact with this product. Dispose of
contaminated gloves after use in accordance with applicable laws and good laboratory practices.
Wash and dry hands.
The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and
the standard EN 374 derived from it.
Body Protection
Complete suit protecting against chemicals, Flame retardant antistatic protective clothing, The type
of protective equipment must be selected according to the concentration and amount of the
dangerous substance at the specific workplace.
Respiratory protection
Where risk assessment shows air-purifying respirators are appropriate use a full-face respirator
with multi-purpose combination (US) or type ABEK (EN 14387) respirator cartridges as a backup
to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air
respirator. Use respirators and components tested and approved under appropriate government
standards such as NIOSH (US) or CEN (EU).

Section 9. PHYSICAL AND CHEMICAL PROPERTIES
Information on basic physical and chemical properties
a) Appearance Form: liquid
b) Odour no data available
c) Odour Threshold no data available
d) pH no data available
e) Melting point/freezing no data available
point
f) Initial boiling point and no data available
boiling range
g) Flash point -21 °C - closed cup
h) Evaporation rate no data available
i) Flammability (solid, gas) no data available
j) Upper/lower no data available
flammability or
explosive limits
k) Vapour pressure no data available
l) Vapour density no data available
m) Relative density 0,701 g/cm3
n) Water solubility no data available
o) Partition coefficient: n- no data available
octanol/water
p) Auto-ignition The substance or mixture is not classified as pyrophoric.
temperature
q) Decomposition no data available
temperature
r) Viscosity no data available
s) Explosive properties no data available
t) Oxidizing properties no data available
Other safety information
no data available

Section 10. STABILITY AND REACTIVITY
Reactivity
no data available
Chemical stability
no data available
Possibility of hazardous reactions
Reacts violently with water.
Conditions to avoid
Heat, flames and sparks. Extremes of temperature and direct sunlight. Exposure to moisture.
Incompatible materials
Water, Oxidizing agents, Strong oxidizing agents, Alcohols, acids, Halogens
Hazardous decomposition products
Other decomposition products - no data available

Section 11. TOXICOLOGICAL INFORMATION
Information on toxicological effects
Acute toxicity
no data available
Skin corrosion/irritation
no data available
Serious eye damage/eye irritation
no data available
Respiratory or skin sensitization
no data available
Germ cell mutagenicity
no data available
Carcinogenicity
IARC: No component of this product present at levels greater than or equal to 0.1% is identified as
probable, possible or confirmed human carcinogen by IARC.
Reproductive toxicity
no data available
Specific target organ toxicity - single exposure
no data available
Specific target organ toxicity - repeated exposure
no data available
Aspiration hazard
no data available
Potential health effects
Inhalation Harmful if inhaled. Material is extremely destructive to the tissue of the
mucous membranes and upper respiratory tract. Vapours may cause
drowsiness and dizziness.
Ingestion Harmful if swallowed. Causes burns. Aspiration hazard if swallowed - can
enter lungs and cause damage.
Skin Harmful if absorbed through skin. Causes skin burns.
Eyes Causes eye burns.
Signs and Symptoms of Exposure
Material is extremely destructive to tissue of the mucous membranes and upper respiratory tract, eyes, and
skin., spasm, inflammation and edema of the larynx, spasm, inflammation and edema of the bronchi,
pneumonitis, pulmonary edema, burning sensation, Cough, wheezing, laryngitis, Shortness of breath,
Headache, Nausea
Additional Information
RTECS: Not available

Section 12. ECOLOGICAL INFORMATION
Toxicity
no data available
Persistence and degradability
no data available
Bioaccumulative potential
no data available
Mobility in soil
no data available
Results of PBT and vPvB assessment
no data available
Other adverse effects
Toxic to aquatic life.

Section 13. DISPOSAL CONSIDERATIONS
Waste treatment methods
Product
Burn in a chemical incinerator equipped with an afterburner and scrubber but exert extra care in igniting
as this material is highly flammable. Offer surplus and non-recyclable solutions to a licensed disposal
company.
Contaminated packaging
Dispose of as unused product.

Section 14. TRANSPORT INFORMATION
UN number
ADR/RID: 3399 IMDG: 3399 IATA: 3399
UN proper shipping name
ADR/RID: ORGANOMETALLIC SUBSTANCE, LIQUID, WATER-REACTIVE, FLAMMABLE
(Trioctylaluminium, n-Hexane)
IMDG: ORGANOMETALLIC SUBSTANCE, LIQUID, WATER-REACTIVE, FLAMMABLE (n-Hexane,
Trioctylaluminium)
IATA: Organometallic substance, liquid, water-reactive, flammable (n-Hexane, Trioctylaluminium)
Transport hazard class(es)
ADR/RID: 4.3 (3) IMDG: 4.3 (3) IATA: 4.3 (3)
Packaging group
ADR/RID: I IMDG: I IATA: I
Environmental hazards
ADR/RID: no IMDG Marine Pollutant: no IATA: no
Special precautions for user
no data available



SECTION 15 - REGULATORY INFORMATION
N/A


SECTION 16 - ADDITIONAL INFORMATION
N/A






制备方法与用途

概述

三辛基铝可用作医药合成中间体。如果吸入三辛基铝,请将患者移到新鲜空气处;若皮肤接触,应脱去污染的衣着,并用肥皂和清彻底冲洗皮肤,如有不适请就医;如眼睛接触到三辛基铝,请分开眼睑,用流动清或生理盐冲洗,并立即就医;如吞食,请立即漱口,禁止催吐,并立即就医。

制备

三辛基铝的制备如下:使用10克TNBA、5.6克1-辛烯和1毫克Co(II)催化剂,在温度为60℃条件下反应20分钟。20分钟后加入5.3毫克Pb(II)杀死催化剂。烷基解产物烷基铝后得到的标准化烷基面积%显示,C4占58%,C6占42%。链增长反应在125℃温度下进行,乙烯压力为2500-3000psig(约17.2-20.7MPa)。

上下游信息

  • 上游原料
    中文名称 英文名称 CAS号 化学式 分子量
  • 下游产品
    中文名称 英文名称 CAS号 化学式 分子量

反应信息

  • 作为反应物:
    描述:
    参考文献:
    名称:
    烷基铝氢化物上烯烃的插入,消除和异构化:一项实验和理论研究†
    摘要:
    插入,消除和异构化与辛烯的二Ñ -octylaluminium氢化[HAL(10月)2 ],三Ñ -octylaluminium [铝(10月)3 ]和秒-octylaluminium种已被研究作为在推定的铝各个步骤基于逆热力学的烯烃异构化方法。尽管从[Al(Oct)3 ]中消除1-辛烯在能量上不利,但该过程是由高温真空蒸馏驱动的,从而导致对1-辛烯的选择性非常高(> 97%)。在高转化率下,如此获得的[HAl(Oct)2 ]主要以氢化物桥接的环状低聚物形式存在,而在低转化率下,混合的烷基/氢化物桥接的二聚体[(Oct)2 Al(μ-H)(μ-Oct)Al(Oct) 2 ]是主要种类。除去烯烃后回收的氢化二正辛基氢化铝可以循环使用,并且对辛烯的重新插入有活性。然而,内部辛烯(顺-和反-2-,3-和4-辛烯)仅部分插入,即使长时间加热后,伯烷基异构化也没有明显的仲烷基。
    DOI:
    10.1039/c5dt00955c
  • 作为产物:
    描述:
    1-碘辛烷 以64%的产率得到
    参考文献:
    名称:
    GAPONIK, L. V.;MARDYKIN, V. P., IZV. VUZOV. XIMIYA I XIM. TEXNOL., 1983, 26, N 1, 30-32
    摘要:
    DOI:
  • 作为试剂:
    描述:
    4-{2-fluoro-6-[((SS)-2-methyl-propane-2-sulfinylimino)-methyl]-phenyl}-piperazine-1-carboxylic acid tert-butyl ester(2-methylpropyl)lithium三辛基铝 作用下, 以 四氢呋喃正己烷正庚烷 为溶剂, 反应 1.0h, 以70%的产率得到4-{2-fluoro-6-[(S)-3-methyl-1-((SS)-2-methyl-propane-2-sulfinylamino)-butyl]-phenyl}-piperazine-1-carboxylic acid tert-butyl ester
    参考文献:
    名称:
    Practical Asymmetric Synthesis of α-Branched 2-Piperazinylbenzylamines by 1,2-Additions of Organometallic Reagents to N-tert-Butanesulfinyl Imines
    摘要:
    2-[4-(tert-Butoxycarbonyl)piperazinyl]benzylidene-tert-butanesulfinamides underwent nucleophilic 1,2-addition with different organometallic reagents to give highly diastereomerically enriched adducts. X-ray crystallography of the resulting alpha-branched N-Boc-2-piperazinylbenzyl-tert-butanesulfinamides confirms different mechanisms depending on the organometallic reagent used. Differential deprotection of the N-Boc and the tert-butanesulfinamides was investigated, and the dehydration byproducts have been identified and characterized. To avoid the formation of byproducts in the acidic deprotection step, the N-tert-butanesulfinamide group was converted to the corresponding N-tert-butanesulfonamide (Bus), which allowed for clean orthogonal deprotection. The efficient synthesis and deprotection of the N-Boc-2-piperazinylbenzyl-tert-butanesulfinamides herein described constitutes an attractive method for extensive structure-activity studies in the search for novel ligands of the human melanocortin 4 receptor.
    DOI:
    10.1021/jo051514p
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文献信息

  • Synthesis of 2-Substituted Propenes by Bidentate Phosphine-Assisted Methylenation of Acyl Fluorides and Acyl Chlorides with AlMe<sub>3</sub>
    作者:Xiu Wang、Zhenhua Wang、Yuya Asanuma、Yasushi Nishihara
    DOI:10.1021/acs.orglett.9b01059
    日期:2019.5.17
    methylenation of acyl fluorides and acyl chlorides with substituted with aryl, alkenyl, and alkyl groups trimethylaluminum afforded an array of 2-substituted propene derivatives. The addition of a catalytic amount of DPPM increased an efficiency of the reactions. Trimethylaluminum as the methylenation reagent not only eliminates the presynthesis of methylene transfer reagent, but provides an efficient method for
    芳基,烯基和烷基三甲基铝取代的酰和酰双膦膦化亚甲基化提供了一系列2取代的丙烯生物。催化量的DPPM的添加提高了反应效率。三甲基铝作为亚甲基化试剂,不仅消除了亚甲基转移试剂的预合成,而且为合成一系列2-取代的丙烯提供了一种有效的方法。
  • Tandem <i>N</i>-Alkylation–Addition Reaction of α-Aldimino Ester and Application to a New Flow System
    作者:Takanori Sano、Isao Mizota、Makoto Shimizu
    DOI:10.1246/cl.130396
    日期:2013.9.5
    N-Alkylation of α-imino ester derived from ethyl glyoxylate proceeded to give an aluminum enolate that reacted with aldehydes to give 1,2-amino alcohols in good yields. This kind of N-alkylation–addition reaction proceeds efficiently by the use of a new flow system consisting of connected two microreactors.
    由乙基乙二醛酯衍生的α-亚基酯经过N-烷基化反应,生成了一个铝烯醇盐,进一步与醛反应得到较高产率的1,2-基醇化合物。这种N-烷基化加成反应通过使用由两个微型反应器相连构成的新型流动系统进行高效进行。
  • Lewis Acid-Promoted Coupling Reactions of Acid Chlorides with Organoaluminum and Organozinc Reagents
    作者:Mitsuhiro Arisawa、Yasuhiro Torisawa、Michiaki Kawahara、Masamichi Yamanaka、Atsushi Nishida、Masako Nakagawa
    DOI:10.1021/jo970244a
    日期:1997.6.1
    An efficient synthesis of alpha,beta-unsaturated ketones by the reaction of acid chlorides with trialkylaluminum (1/3 mole equiv) in the presence of AlCl(3) (1 mol equiv) is described. Dialkylzincs were also useful and are easier to prepare than trialkylaluminum. Reaction of RCOCl with R'AlCl(2) or R'(2)AlCl gave R'COR, without AlCl(3), in high yield.
    描述了在AlCl(3)(1摩尔当量)存在下,酰与三烷基铝(1/3摩尔当量)的反应,可有效合成α,β-不饱和酮。二烷基也是有用的,并且比三烷基铝更容易制备。RCOCl与R'AlCl(2)或R'(2)AlCl的反应以高收率得到了不含AlCl(3)的R'COR。
  • meta-Selective C–H Borylation of Benzamides and Pyridines by an Iridium–Lewis Acid Bifunctional Catalyst
    作者:Lichen Yang、Nao Uemura、Yoshiaki Nakao
    DOI:10.1021/jacs.9b03138
    日期:2019.5.15
    We report herein the iridium-catalyzed meta-selective C-H borylation of benzamides by using a newly designed 2,2'-bipyridine (bpy) ligand bearing an alkylaluminum biphenoxide moiety. We also demonstrate the iridium-catalyzed C3-selective C-H borylation of pyridine with a 1,10-phenanthroline (Phen) ligand bearing an alkylborane moiety. It is proposed that the Lewis acid-base interaction between the
    我们在此报告了通过使用新设计的带有烷基铝联苯氧化物部分的 2,2'-联吡啶 (bpy) 配体催化的苯甲酰胺的间位选择性 CH 硼酸化。我们还展示了吡啶与带有烷基硼烷部分的 1,10-咯啉 (Phen) 配体催化的 C3 选择性 CH 硼酸化。提出路易斯酸部分与基羰基或 sp2 杂化氮原子之间的路易斯酸碱相互作用加速反应并控制位点选择性。
  • Conjugate Addition Routes to 2‐Alkyl‐2,3‐dihydroquinolin‐4(1 <i>H</i> )‐ones and 2‐Alkyl‐4‐hydroxy‐1,2‐dihydroquinoline‐3‐carboxylates
    作者:Alex Kingsbury、Steve Brough、Antonio Pedrina McCarthy、William Lewis、Simon Woodward
    DOI:10.1002/ejic.201901036
    日期:2020.3.27
    quinolin‐4(1H)‐ones to provide 2‐alkyl‐2,3‐dihydroquinolin‐4(1H)‐ones (14 examples, 54–99 % yield). Asymmetric versions require AlEt3 to Boc‐protected ethyl 6‐substituted 4(1H)‐quinolone‐3‐carboxylates (6‐R group = all halogens, n/i/t‐alkyls, CF3) and provide 61–91 % yield, 30–86 % ee; any halogen, Me, or CF3 provide the highest stereoselectivities (76–86 % ee). Additions of AlMe3 or Al(nC8H17)3 provide ≈ 45 and
    在CuBr · SMe2 / PPh3催化下(5/10 mol%)RMgCl(R = Me,Et,n Pr,CH = CH 2,n Bu,i Bu,n C 5 H 11,c C 6 H 11,Bn ,CH 2 Bn,n C 11 H 23)容易地(–78°C)对Cbz或Boc保护的喹啉-4(1 H)-酮进行1,4加成,从而提供2-烷基-2-3,2-二氢喹啉- 4(1 H)-1 (14例,产率54–99%)。非对称版本需要AlEt 3到Boc保护的乙基6取代的4(1 H)-喹诺酮-3-羧酸盐(6-R基团=所有卤素,n / i / t-烷基,CF 3),收率61-91%,ee 30-86%; 任何卤素,Me或CF 3均可提供最高的立体选择性(76–86%ee)。AlMe 3或Al(n C 8 H 17)3的添加在母体中的添加提供≈45和≈75%ee(6-R = H)。配体(S)‐(BINOL)P–N(CHPh
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