Organic Chemistry 2 Flashcards
(219 cards)
1
Q
alkene –> markovnikov alkyl halide
A
H-X
2
Q
alkene –> anti-markovnikov alkyl halide
A
H-Br, peroxides
3
Q
alkene –> markovnikov alcohol
A
H20, H+
4
Q
alkene —> anti-markovnikov alcohol
A
1) BH3*THF, 2) H2O2, OH-
5
Q
alkene —> syn addition alkane
A
H2 and Pt, Pd, or Ni
6
Q
alkene –> anti addition alkyl dihalide
A
X2
7
Q
alkene —> anti addition markovnikov halohydrin
A
X2, H20
8
Q
alkene –> epoxide
A
peroxyacid, example: MCPBA
9
Q
epoxide –> anti gycol
A
H+, H2O
10
Q
alkene –> anti glycol
A
1) peroxyacid, 2) H+ H2O
11
Q
alkene —> syn glycol
A
KMnO4 (cold, dilute), OH-, H2O
12
Q
alkene –> syn glycol
A
OsO4 , H2O2
13
Q
Alkene –>ozonide
A
O3
14
Q
ozonide –> ketones and aldehydes
A
(CH3)2S
15
Q
alkene —> ketones and aldehydes
A
1) O3, 2) (CH3)2S
16
Q
alkene –> ketones and acids
A
KMnO4 (warm)
17
Q
acetylide —> acetylide anion
A
NaNH2
18
Q
acetylide anion —>alkyne
A
R-X
19
Q
acetylide anion —> alcohol
A
carbonyl group containing compound (formaldehyde, aldehyde, or ketone)
20
Q
alkyne —> alkane
A
2H2, Pt, Pd, or Ni
21
Q
alkyne –> cis alkene
A
H2, Pd/BaSO4, quinoline (lindlar’s catalyst)
22
Q
alkyne –> trans alkene
A
Na, NH3
23
Q
alkyne –> haloalkane (4 X)
A
2X2
24
Q
alkyne —> geminal haloalkane (markovnikov)
A
2 H-X
25
alkyne ---> (vinyl alcohol ketone), markovnikov
HgSO4, H2SO4
26
alkyne ---> (vinyl alcohol aldehyde), anti-markovnikov
1)SiaBH*THF, 2) H2O2, NaOH
27
alkyne --> alpha-diketone
KMnO4, H2O, Neutral
28
alkyne ---> carboxylic acids
O3, H2O
29
alkene + H-X
markovnikov alkyl halide
30
alkene + H-Br --peroxides->
anti-markovnikov alkyl halide
31
alkene + water --H+->
markovnikov alcohol
32
alkene + 1)BH3*THF, 2)H2O2, OH-
anti-markovnikov alcohol
33
alkene +H2 --Pt,Pd, or Ni->
syn addition alkane
34
alkene + X2
anti addition alkyl dihalide
35
alkene + peroxyacid
syn addition epoxide + carboxylic acid
36
epoxide ---H+, H2O->
anti glycol
37
alkene ---1)peroxyacid, 2)H+, H2O->
anti glycol
38
alkene + KMnO4 (cold, dilute) ---OH-, H2O->
syn glycol
39
alkene + OsO4 ---H2O2 ->
syn glycol
40
alkene + O3
ozonide
41
ozonide --(CH3)2S
ketones and aldehydes
42
alkene + KMnO4(warm)
ketones and acids
43
acetylide + NaNH2
acetylide anion + Na+ + NH3
44
acetylide anion + R-X
alkyne molecule with desired R group
45
acetylide anion + R2C=O
alcohol
46
alkyne + 2H2 --Pt, Pd, or Ni ->
alkane
47
alkyne + H2 ---Pd/BaSO4, quinoline (lindlar's catalyst) -->
cis alkene
48
alkyne -- Na, NH3 -->
trans alkene
49
alkyne + 2X2
haloalkane, 4 halogens
50
alkyne + 2H-X
geminal haloalkane, Markovnikov
51
alkyne -- HgSO4, H2SO4-->
vinyl alcohol ketone , markovnikov
52
alkyne --1) SiaBH*THF, 2) H2O2, NaOH -->
vinyl alcohol aldehyde, anti-markovnikov
53
alkyne + KMnO4 ---H2O, Neutral ->
alpha-diketone
54
alykne --1) KMnO4, OH-, 2) H+ -->
carboxyilic acids
55
alkyne --O3, H2O -->
carboxylic acids
56
What happens when you have a carboxylic acids with a salt?
No REACTION because it already has a negative charge
57
List, in order of decreasing basicity, the charged nucleophiles that are on the table in the blue sheet.
CH3-, NH2-, OH-, OR-, SH-/SR-, -OAc, Cl- (X-)
58
How would you remember the order of the charged nucleophiles?
Come Now Oliver Over Shore Over Clapping
59
What is capable of reacting with a carboxyllic acid? (Which charged nucleophile(s)?
CH3-, NH2-, OH, SH, -OAc
60
What would the LG be in the above case?
The H would bond with the nucleophiles, leaving the carboxylic O with a negative charge
61
How do you know when you can have a reaction with a charged nucleophile?
As long as the LG is MORE stable than the Nucleophile, the reaction WILL happen
62
Is the same true for salts, though?
Yes
63
What is the product of an acyl halides (carboxyllic with a Cl instead of an O at the far right) with a charged nucleophile?
Carboxyllic acid
64
What are the charged nucleophiles that are capable of carrying out this reaction? What is the LG of this reaction?
All of them "Cl"
65
What first happens to the acyl chloride before the reaction takes place (Before it is attacked with the nucleophile?)
It forms a resonance form with a positive charge on the Carbon and negative on oxygen
66
What is the name of the reaction of acyl chlorides with nucleophiles?
Acyl addition elimination (for biochem)
67
What does the reaction of anhydrides and nucleopiles yeild? What is the LG?
Carboxylic acids, LG = "RCOO-"
68
What are the charged nucleophiles that can react with the ESTER? What is the LG??
CH3- and the NH2- LG is the OR-
69
What are the charged nucleophiles that can react with a primary amide? What is the LG?
CH3- LG is NH2
70
What does the reduction of aldehydes and ketones yeild?
Alcohols
71
What are the reagents required for the carbonyls (aldehydes and ketone) reaction?
NaBH4--Sodium boronhydride and LiALH4, LithiumAluminum Hydride
72
What is the first steop of the carbonyl reaction?
The reagent gives a hydride to the central carbon atom, giving the oxygen a negative charge
73
What is the second stop of the carbonyl reaction?
dilute acid gives the negatively charged oxygen an H to stabalize the charge
74
What is the only functional group capable of reacting with a carboxyllic acid to form a salt?
strong base neutral nucleophiles can react to form a salt (O of carb. acid has a negative charge
75
What is fisher esterfication?
It is when a carb. acid reacts with a weak base to form water and an ester or anhydride
76
FE is to what and Salts are to what?
FE is to weak base and salts are to strong base
77
What is the order of reactivity of addition elimination reactions? IN DECREASING REACTIVITY
Acyl halides, anhydrides, esters and amides
78
What do all derivatives yield upon hydrolysis?
Carboxylic acids
79
What is hydrolysis:
Acid/water or base/water followed by acidification
80
PREPARATION SECTION OF TEST
PREPARATION SECTION OF TEST
81
What is needed for the oxidation of aromatic side chains at the benzyl position?
Strong oxidizing agents like hot HNO3 or KMnO4
82
What solvents are needed for oxidation of primary alcohols?
KMnO4 or CrO3, H2SO Chromic Acid
83
Solvent needed for oxidation of aldehydes?
KMnO4
84
How do you know what the product of the preparation of acids is?
It is usually the main compuund, like a benzene ring minus its attachments, but instead of its old attachments, it has the COOH
85
What are the solvents needed for carbonation of grignard reagents?
Make grignard reagent by MG metal, add CO2, then acidify with H+
86
Nitrile hydrolysis requires what?
Nitrile is first formed by Sn2 reaction on an alkyl bromide( from alcohols and HBr combination)
87
Second step?
KCN adds
88
Third step?
Water, dilute acid, or water and OH-
89
What's the product?
R COOH
90
What is needed for the hydrolysis of acyl derivatives?
Hydrolysis with water (plus acid or base)
91
Acid chlorides and water give what products?
carb. acid and HCl
92
Anhydrides and water yeild what?
2 equivalents of carb. acid
93
What do esters need to form carb. acid and alcohol?
Water/acid
94
What is this hydrolysis reaction called in a base?
Saponification
95
What is the last step of saponification?
Forming NEUTRAL acid by acid an acidification step
96
Amides will form RCOOH and an amine with what solvent?
WATER
97
PREPARATION OF CARB ACID DERIVATIVES
PREPARATION OF CARB ACID DERIVATIVES
98
How do you form acid chlorides? What solvents are needed, I mean.
Carb. Acids and Thionyl chloride (SOCL2) and Phosphorus trichloride (PCl3)
99
What solvents are needed to form anhydrides?
Pyridine (with acid chlorides and carb. acids or RCOOH salt) or Heat (with carb. acids and loss of water)
100
What solvents are needed to form esters?
Fisher esterfication (Conc. H+, RCOOH, Alcohol), Acid chlorides and an alcohol, Anhydrides an analcohol
101
How will amides form?
Acid chlorides and an amine
102
How will amides and alcohols form?
Esters and an amine
103
How will salts and amides form?
Anhydrides and an amine
104
REDUCTION OF RCOOH AND DERIVATIVES
REDUCTION OF RCOOH AND DERIVATIVES
105
Esters will be reduced, how?
LAH (LiAlH4), followed by acidification yields two equivalents of alcohol
106
How will amides will be reduced
LAH, neutralization with acid yields an amine
107
Nitriles are also known as what?
Cyanides
108
How will nitriles be reduced
LAH, neutrilization with acid forms an amine
109
How else can amines form by reduction?
reduction with H2 and Pt or Pd
110
How will RCOOH be reduced?
LAH, acidification yeilds a primary alcohol
111
How will all reactions with neutral nucleophiles (Except for what) work?
Except for with amides, all other functional groups, the LG will be the larger group, it will look like a grignard reaction, the LG will be the largest molecules connected together
112
What will the amide reaction with netural nucleophile Water look like?
You will get an NH4 and salt because it's an acid-base reaction
113
A reaction of an amide with another amide will give?
a fifty-fifty mixture
114
FACTORS AFFECTING BASICITY AND ACIDITY
FACTORS AFFECTING BASICITY AND ACIDITY
115
What are the three factors that impact the acid and base properties?
Hybridization, inductance, resonance
116
What type of hybridization makes a strong base?
SP3, less s character
117
What type of inductance makes a strong base?
lower left hand compounds, less electronegative groups, but additing electron donating group
118
What are electron donating groups?
CH3- and other alkyl groups
119
What affect does resonance have on amines?
Aromatic amines have resonance forms and their resonance forms spread electrons around ring, amking e- less available to react=weaker base
120
why are amides even worse bases than aromatic amine?
first order equal to second order
121
To have an amide, you need...
a c double bond O must be directy attached to nitrogen
122
What is the acidity of an amid?
very very acidic. PKA 0
123
What are the steps of saponification?
First, get resonance intermediate by moving double bond, then have nucleophile attack, then get rid of negative charge on O and have leaving group leave, then have the LG grab the H on the molecule....the last step is getting rid of the negative charge
124
Aldehydes are prepared by the oxidation of a
primary alcohol
125
an organic group containing one or more -CHO groups
aldehyde
126
What is the functional group for the aldehydes?
carbonyl group (-CHO)
127
general formula for the aldehydes
R-CHO
128
where is the functional group located on the carbon chain for the aldehydes?
at the end of the carbon chain
129
methyl alcohol oxidizes to form
formaldehyde
130
the molecular formula for formaldehyde
HCHO
131
another name for formaldehyde
methanal
132
a three-carbon chain aldehyde would be called
propanal
133
formaldehyde in water is known as
formalin
134
formalin is what percentage aqueous solution of formaldehyde by weight?
37%
135
formalin is what percentage aqueous solution of formaldehyde by volume?
40%
136
formed by the oxidation of ethanol, a two carbon chain aldehyde
acetaldehyde
137
another name for acetaldehyde
ethanal
138
a benzene derivative in which one of the hydrogens in the ring is replaced with an aldehyde group
benzaldehyde
139
benzaldehyde is known as an
aromatic aldehyde
140
an aldehyde with two aldehyde group (having a carbonyl group at each end of the carbon chain)
dialdehydes
141
the simplest dialdehyde is
glyoxal
142
two examples of dialdehydes
glyoxal and glutaraldehyde
143
the oxidation of a secondary alcohol yields a
ketone
144
the general formula for a ketone is
RCOR
145
a ketone has two ____ groups attached to a ___ group
two alkyl groups attached to a carbonyl group
146
the simplest ketone is
propanone
147
propanone is also known as (2)
acetone, dimethyl ketone
148
the general formula for carboxylic acids
R-COOH
149
the functional group in a carboxylic acid is known as a
carboxyl group
150
two examples of carboxylic acids
methanoic acid, ethanoic acid
151
another name for methanoic acid
formic acid
152
another name for ethanoic acid
acetic acid
153
_____ oxidize for form organic acids
aldehydes
154
_____ oxidizes to form formic acid (also means _____ oxidizes to form ____ acid)
formaldehyde (methanal, methanoic)
155
_____ oxidizes to form acetic acid (also means ____ oxidizes to form ____ acid)
acetaldehyde (ethanal, ethanoic)
156
general formula for esters
R-COO-R
157
two examples of esters
ethyl acetate, methyl salicylate
158
a colorless liquid that has a characteristic smell like certain glues or nail polish removers
ethyl acetate
159
ethyl acetate is derived from ____ and _____
ethanol and acetic acid
160
known as oil of wintergreen, a natural product of many species of plants
methyl salicylate
161
methyl salicylate is derived from _____ and _____
methanol and salicylic acid
162
derived from an alcohol and an organic acid
esters
163
What are two methods of making R-Hals?
1.Alkene + H-Hal -------> R-Hal 2.R-OH + H-Hal -----------> R-Hal + H2O
164
How do you make Alkenes from R-Hals?
R-Hal + Na/KOH ---------> Alkenes + salt + H2O Dissolved In ethanol at high temperatures with High conc of the Na/KOH 2ary or 3ary R-Hals are preferred.
165
How do you make Alcohols from R-Hals?
R-Hal + Na/KOH ---------> Alcohol + salt Dissolved in water at low temperatures with low concentrations of Na/KOH. 1ary or 2ary R-Hal prefered.
166
How do you make amines from R-Hals?
R-Hal + NH3 --------> R-NH2?
167
How can you test for which Hal is on your R-Hal?
R-Hal + Ag+ --> 1.Agcl - Wht ppt(sol In NH3) Very Slow 2.AgBr - Pale Cream ppt(Semi-sol) Slow 3.AgI - Yellow ppt(insoluble) Fast
168
How can you manufacture Grignards Reagent?
R-Hal + Mg ------------> Grignards Reagents: Magnisium metal with trace of iodine. Usually requires cooling. In the presence of ethoxyethane
169
How can you make pure Alkanes with Grignards reagent?
R-MgHal + H2O -----> R + Mg(OH)Hal
170
How can you produce a carbonyl From Grignards reagent?
R-MgHal + CO2 ------> RCOMgHal + H2O -> RCOOH
171
How can you produce Alcohols from Grignards Reagents?
R-MgHal 1.+ methanal -> R-OMgHal + HCl -> R-OH 2.+ ethanal -> 2ary R-OH 3.+ Ketone -> 3ary R-OH
172
How Is ethanol Produced Industrially?
Ethene + H20(g) ---> Ethanol (At 300 C, 60-70 atm and with a phosphurous (v) acid catalyst)
173
What are the conditions at which LDPE is produced? What are its uses?
T: 200 C, P 2000Atm O2 Impurity Uses: for plastic bags
174
What are the conditions at which HDPE is produced? What are its uses?
T: 60 C P: A 2-5Atm Cat: Ziegler-Natta. Uses: milk bottles, plastic pipes and so on.
175
What are the 3 orientations of PP and their uses?
Isotactic: Plastic Crates Atactic: Sealents, Adhesives and Roofing felt SyndioTactic: Medical tubing/bags ect.
176
PCE - uses and full name
Poly(chloroethane) Guttering, plastic windows, cable insulation, sheet meterials footwear, clothing ect.
177
PTFE - uses and full name
Poly(tetrafloroethane) - uses for wrapping foods and chemicals and have a non stick property used in the kitchen.
178
What are the manufacturing conditions of Epoxyethane?
T: 250 C P:15atm Catalyst: Ag
179
What are the Uses of Epoxyethane?
It is used to make long chain alcohols which can be used as: Anti-freeze materials, plasticizers non-ionic surfactants (detergants) and in the manufacture of polyesters.
180
How can you produce Carboxilic acids?
R-COMgHal + H2O ----> R-COOH + Mg(OH)Hal (under acidic conditions)
181
How can you produce Nitriles From R-Hals?
R-hal + KCN -> R-CN + KHal Reagents: Potatsium Cyanide dissolved in aquous ethanol. Conditions: heat under reflux. Doesn't work with 3ary alkanes
182
How can you produce amines from R-Hals?
R-Hal + 2NH3 -> R-NH2 + NH4Hal Reagents ammonia in ethanolic solution
183
What is the equation for Fischer esterification?
R-OH + R-COO ----> Ester Catalyst: H2SO4
184
What are acid anhydrides?
Two carboxlyic acids joint by the same oxygen.
185
What is the Friedal-crafts reaction?
Electrophillic addition of aromatic rings.
186
E.N of the Halogen UP: Strength of the H-hal Bond?
Strength of the H-hal bond UP
187
Examples of nucloephiles
O:Water, Hydroxide, N:Azides Cyanide and Ammonia, Metal Halides,S: Sulfer Thiols.
188
Examples of electrophiles
H+, NO+, HCl, aklyl halides, acyl halides, Carbonyl compounds.
189
What is the Friedal-crafts reaction?
Electrophillic addition of aromatic rings.
190
E.N of the Halogen UP: Strength of the H-hal Bond?
Strength of the H-hal bond UP
191
Examples of nucloephiles
O:Water, Hydroxide, N:Azides Cyanide and Ammonia, Metal Halides,S: Sulfer Thiols.
192
Examples of electrophiles
H+, NO+, HCl, aklyl halides, acyl halides, Carbonyl compounds.
193
General formula for alkynes
CnH2n-2
194
General formula for alkenes
CnH2n
195
General formula for alkanes
CnH2n+2
196
CaC2 + 2H2O ->
->Ca(OH)2 + C2H2 (ethyne/acetylene)
197
Preparing ethyne
Water added to calcium carbide.
198
Preparing ethene in lab
Dehydrate ethanol with concentrated H2SO4 (gives poor yield)
199
Preparing ethene by cracking
Cracking saturated hydrocarbons via steam cracking naptha compounds (C4-C12)
200
Properties alkenes /alkynes
Non polar, insoluble in water, low M.p/B.p but increase with size
201
Sustitution
Alkanes with halogens, halogen atoms swap with hydrogen, hydrogen halide gas as a product, requires UV light
202
C2H6 + Br2 -(UV)>
->C2H5Br + HBr
203
Complete combustion of alkanes
CO2+H2O produced
204
Incomplete combustion
Produce CO and/ or C (soot) instead of CO2
205
Properties of alkanes
Single covalent bonds, Undergo combustion and substituion reactions, nonpolar(insoluble in water) Low MP/BP (increases with size), Less dense than water(float)
206
Isomer
Different form of same molecular formula with a different structural formula
207
Meth-
1 carbon
208
Eth-
2 carbons
209
Prop-
3 carbons
210
But-
4 carbons
211
CH2=CH2 + H2O -(dil. H2SO4/H3PO4)->
->CH3-CH2-OH
212
Functional group
The specific arrangement of atoms and/or bonds responsible for the main physical +chemical properties
213
Homologous series
Family of hydrocarbons with same functional group. Similar chemical + physical properties
214
Hydration
Adding water to alkene, forms alcohols
215
Halogenation
Adding a halogen to alkene, forms halogenoalkanes
216
Testing for unsaturation
Bromine water, decolourises from orange/brown to colourless
217
Hydrogenation
Adding hydrogen to an alkene, forms an alkane
218
CH2=CH2 + H2 -(nickel/platinum)->
->CH3-CH3
219
CH2=CH2 + Br2 ->
CH2BrCH2Br
