Grignard reagent：RX+Mg in ether形成R-Mg-X
反應率：RI>RBr>RCl≥RF
Organolithium reagent:RX+2Li→LiX+RLi
(Solvent不一定是ether，也可用hexane,pentane等alkane)
--------------
以下反應solvent均為 ether
Grignard reagent的R可作為strong nucleophile撞C=O(ketone,aldehyde,formaldehyde)
通常在 ether solvent 進行
When making a tertiary alcohol with two identical alkyl groups,consider using an acid chloride or ester.(用「兩個」Grignard撞ester or acid chloride以做出兩個取代基一樣的三級醇)
Grignard reagent usually do not react with ether, but epoxides are unusually reactive ethers because of their ring strain.(Grignard不與醚反應，但會拆開環氧，接著再加酸，可用於加長醇的長度)
Grignard的缺點是在製作過程中很可能會產生與reagent反應，導致產物不純：
1.RX+Mg→R-Mg-X
2.RMgX+RX→R-R+MgX2(RMgX傾向再與RX反應，因此Grignard產率不高)
If we want to couple two groups together efficiently, we can do it by using an organocopper reagent, a lithium dialkylcuprate, to couple with an alkyl halide.
為了避免上述問題，可使用lithium dialkylcuprate,而lithium dialkylcuprate是從Organolithium做出來ㄉ
2Organolithium+CuI→R2CuLi+LiI
R2CuLi(lithium dialkylcuprate)+R'-X→R-R'+R-Cu+LiX(此方法可用於加長碳鏈)
R2CuLi+R'C=OX→RC=OR'(也可做出ketone)
------------
英文單字：vigorously(活潑的)
Grignard and Organolithium reagents react vigorously and irreversibly with water.Therefore, all reagent and solvents used in these reactions must be dry.
(Grignard and Organolithium 碰到水很容易反應，所以no water很重要)
R-MgX+HOH→R-H+XMgOH
R-Li+HOH→RH+LiOH
However,this is a method for reducing an alkyl halide to an alkane.
也可以用這樣的方式將R-X變回R-H.
而也可使用D(H之isotope)
R-MgX+DOD→R-D+XMgOD
可以順利將D標定上，可用於標定此化合物。作為後續實驗的用途
-----------------
R-Li之間的「R」可替換，與formal charge有關
Li帶正點，傾向與strong nulceophile結合，像是RNH,RC≡CH之酸性物質
R-Li+R'NH→R'N-Li+ + R-H
R-Li+R'C≡CH→R'C≡C-Li+ + R-H
-----------------
Grignard reagents are useful because they add to the electrophilic double bond.However, we must make sure that the only electrophilic double bond in the solution is the one we want the reagent to attack.
We will encounter method for protecting susceptible groups to prevent the reagent from attacking them.(需記憶可能的反應物)
Grignard可與很多物質反應，因此為了盡量與目標物反應，需避免雜質。
Protonate指R-Li or(MgX)遇到會變成R'-Li or (MgX)的意思。
Protonate the Grignard or Organolithium:O-H,N-H,S-H,C≡C-H
Attacked by the Grignard or Organolithium:C=O,C=N,C≡N,S=O,N=O
-------------------
Reduction of the Carbonyl Group:Synthesis of 1° and 2° alcohol
The two most useful hydride reagents, sodium borohydride(NaBH4) and lithium
aluminum hydride(LiAlH4)
「兩者均可以在alcohol,ether,water進行反應」
H anion attack C=O double bond in order to form alkoxide ion.then,adding H+ to form alcohol.
(in ether)
LiAlH4 reduces ketones to secondary alcohols, and it reduces aldehydes, acids, and ester to primary alcohols.
LiAlH4之活性極強就連acid anion(RCOO-)和ester(RCOOR)都能還原成醇(RCOH)
而NaBH4較弱，並不會產生這樣的現象，需注意！！！課本有較詳細之說明。
------------------
Raney Ni
Raney Ni is an effective catalyst for the hydrogenation of ketones conditions, however, so any alkene double bonds in the starting material will also be reduced. In most cases, sodium borohydride is more convenient for reducing simple ketones and aldehydes.
Raney Ni可用於將C=O還原成CHOH，跟上述NaBH4的功能差不多，但是Raney Ni會一併將pi bond都還原，所以如果只想對C=O做加成就使用NaBH4，反之使用Raney Ni
------------------
Thoils
NaH-S+R-X→RSH+NaX
2RSH(in Br2)→RSSR+2HBr
RSSR(in Zn HCl)+2HBr→2RSH
建議看課本
---------------
Oxidation states of alcohols
假如沒有OH group，先把H變成OH，而OH會與「另一個H」脫水，變成C=O，反之沒有「另一個H」的話，終止反應
------------
英文單字：dispose處置
NaOCl,household bleach or sodium hypochloride
NaOCl+RCOOH→HOCl……etc.
HOCl上面的O帶negative，因此遇到-OH group可以產生置換反應，可以加長ROCl
R-OH+HOCl→ROCl(alkyl hypochloride)+H3O plus
RCOO- +ROCl會把Cl搶走，於是形成RCO-→RC=O
mechanism建議看課本
總之(1)NaOCl(2)HOAc→可以將R-OH氧化，一般都是使用二級醇，所以只能做出ketone
---------------------------
(1)Na2Cr2O7 or CrO3(2)H2SO4→氧化
----------------
1.[NaOCl/TEMPO]
2.[PCC,CH2Cl2]
3.Re：DMSO,(COCl)2,
Catalyst:Et3N,CH2Cl2,-60℃
4.Swern oxidation ,Re:DMP under room temp. neutral
可將1級醇氧化停在醛
But 1.之NaOCl過量的話還是會變酸
--------------------
TsOH,TsCl+alcohol→ROTs in pyridine
而TsCl的產率較高
之後使用nucleophile撞ROTs就可以產生產物
--------------------
Reduction of alcohol
1.加濃硫酸進行elimination脫水，再H2 in Pt還原
2.ROTs+LiAlH4→RH
-------------------
Alcohol with Hydrohalic acid
ROH+H正→ROH2 不穩定態
再加X-就能攻擊形成RX
ROH+HBr/H2O → RBr
-----------------
Lucas reagent
ROH + HCl/H2O → (in ZnCl2) RCl
依據不同級數醇有不同情況
1級醇會走Sn2
2.3級醇走Sn1，比較快
所以盡量是3級醇用此方法
-----------------
Alcohol with Phosphorus
3R-OH + PCl3 → 3RCl
3R-OH + PBr3 → 3RBr
R-OH + PCl5 → RCl
R-OH + P/I2 → RI
---------------------
R-OH+SOCl2 加熱→RCl+SO2+HCl
------
醇在180度分子內脫水，變烯
在140分子間脫水，變醚
----------
Esterification of alcohol
1.酸+醇
2.醇+COClR(acid chloride) in pyridine
3.硫酯：ROH+TsOH→ROTs
4.磷脂：磷酸+醇的酯化反應
HIO4可以裂解雙醇
