Transformations of allyl-substituted and aryl-allyl esters and their corresponding amines

347 Pages·2005·11.213 MB·English

by  Levashova, V. E., Zaikov, G. E

Transformations of
Allyl-Substituted and
Aryl-Allyl Esters and
Their Corresponding Amines
TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
Transformations of
Allyl-Substituted and
Aryl-Allyl Esters and
Their Corresponding Amines
Vera E. Levashova and Gennady E. Zaikov
CRC Press
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Version Date: 20120727
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TThhiiss ppaaggee iinntteennttiioonnaallllyy lleefftt bbllaannkk
ii Vera 1 Levashova and Gennady E. Zaikov
TABLE OF CONTENTS
Page
Preface vii
Part I. Synthesis and properties of alkenyl aryl esters and
N-alkenyl substituted amines
Introduction 2
1.1. Mechanisms of rearrangement 6
1.1.1. Modern state ofrearrangements in alkenyl aryl esters 6
1.1.1.1. Thermal rearrangements 7
1.1.1.2. Catalytic rearrangements 11
1.1.1.3. Factors affecting mechanisms of phenol allyl ester
rearrangements 13
1.1.1.4. Thermal and catalytic rearrangements of allyl esters of
condensed aromatic and heterocyclic compound hydroxy-
derivatives 29
1.1.2. Synthesis and transformations ofN-alkenyl amines. 35
1.2. Modern state of the problem 45
1.2.1. Synthesis and transformations ofa lkenyl-substituted phenol
esters.. . . 45
1.2.1.1. Synthesis of alkenyl-substituted phenol esters 45
1.2.1.2. Thermal transformations 56
1.2.1.2.1. The influence of allyl unit substituents on the
mechanism of alkenyl aryl ester rearrangement 56
,8-Substitution 56
r-and ~r-Substitution 75
y,y- and ~y,y-Substitution 103
1.2.1.2.2. The influence of substituents in the aromatic ring on
the direction of thermal rearrangements for alkenyl-
substituted phenols esters .... . ......... ....... ......... ....... .... 106
Transformations ofA llyl Substituted m
1.2.1.3.1. The influence of substituents in the allyl unit on the
Mechanism of alkenyl-substituted phenol ester
rearrangements 11 0
p.substitution 110
r-
and ~r-Substitution 117
y,y- and ~y,y-Substitution ............................................. 140
1.2.1.3.2. The influence of substituents in aromatic ring on the
rearrangement mechanism of alkenyl-substituted
phenol esters 143
12.2. Synthesis ofN-alkenyl-substituted amines and
N-alkenylammonium salts 149
1.2.2.1. Synthesis ofN-aklenylaniline 149
1.2.2.2. Poly-N-alkenylaminophenylene synthesis and
transformations 153
1.2.2.3. Synthesis of N-alkeny lhexamethy lenetetrammon ium
chlorides 157
1.2.2.3.1. Structure and properties ofN-alkenylhexamethylene-
tetrammonium chlorides 167
1.2.2.4. Synthesis ofN-alkenylpyridinium salts 174
1.2.2.4.1. Structure and properties ofN-alkenylpyridinium
chlorides 185
12.3. The practicality ofO-and N-alkenyl aryl esters, amines and
corresponded transformation products 188
I.2.3 .I. Reagents of predetermined structure 188
1.2.3.2. Inhibitors of sulfate-reducing bacterium growth 188
1.3. Experimental 195
13.1. Analysis methods 195
1.3.1.1. Spectral analysis 195
1.3.1.2. Chromatographic analysis 195
1.3.1.3. Quantum-chemical calculation technique........................... 196
13.2. Initial reagents and techniques for alkenyl aryl ester syntheses
and thermal and catalytic rearrangements 196
1.3.2.1. Production of initial alkenyl chlorides 196
1.3.2.2. Techniques for synthesis of initial esters and
transformation products 200
Vera L Levashova and Gennady E. Zaikov
IV
13. 3. Procedures oft hermal and catalytic rearrangements ofa lkenyl
aryl esters 201
1.3.3.1. Thermal rearrangement of phenol chloroallyl esters 201
1.3 .3 .2. Catalytic rearrangement of phenol chloroallyl esters 203
1.3.3.3. Procedures ofthermal and catalytic rearrangements of
bisaryl allyl esters 203
1.3.3.4. Column chromatography 205
13.4. Procedures ofN-alkenylamines and N-alkenylammonium salt
synthesis 206
1.3.4.1. The production procedure for aniline alkenylation by
2-chloromethyl-3-chloro-1-propene (9) 206
1.3.4.2. Polyaminophenylene alkenylation technique 207
1.3.4.3. Initial compounds for synthesis ofN-alkenylammonium
salts 207
1.3.4.3.1. The production procedure for N-alkenylammonium
salts in chloroform 207
1.3.4.3.2. The production procedure for N-alkenylammonium
salts in aqueous solution 207
1.3.4.3.3. The production procedure for N-alkenulammonium
salts without solvent 208
1.3.4.3.4. N-alkenylammonium salt synthesis from alkenyl
chloride production wastes 208
1.4. Conclusions to Part I 209
References to Part I 211
Part II. Development of waste management technique
for methallyl chloride production and synthesis
of small-tonnage chemical products
Introduction 232
11.1. Compounds suppressing growth of microorganisms, fungi
and algae, and inhibiting corrosion of metals 234
Transformations ofA llyl Substituted v
/11.2. Fungicides 247
/11.3. Inhibitors ofs ulfate-reducing bacterium growth 253
/11.4. Organics-based corrosion inhibitors 256
The adsorption theory 256
The film theory 258
11.2. Modern state of the problem 266
/12.1. The Subject ofi nquiry selection 266
/12.2. Quaternary ammonium salt derivation from hexamethylene-
tetramine (HM/'A) and tertiary butyl chloride (TBC) 268
ll2.3. Reagent derivation from N,N'-tetramethyldiaminomethane 275
ll2.4. Synthesis ofq uaternary ammonium salts derived from
piperidine and morpholine 289
112.5. Tests ofs ynthesized quaternary ammonium salts for
bactericidal and metal corrosion inhibitor properties 295
11.3. Experimental 300
/13.1. Characterization ofi nitial substances 300
/13. 2. Parameters ofs ynthesized compounds 305
/13. 3. Technique for the synthesis ofq uaternary ammonium salts in
aqueous media 309
113.4. Technique for the synthesis ofq uaternary ammonium salts in
chloroform 309
/13.5. Technique for the synthesis ofm ono- and di-(alkyl, alkenyl)-
N,N'-tetramethyl-diaminomethane in acetone ........................... 310
/13. 6. Technique for the synthesis ofq uaternary ammonium salts
from pure piperidine and morpholine (without solvent) 310
/13. 7. Technique for determination ofc hloride-ion weight content in
aqueous solution 311
11.4. Technology and process application 312
1/.4.1. The processfor quaternary ammonium salt synthesis 315
II .4.1.1. Process description 316
11.4.1.1.1. Receipt of initial components 316
11.4.1.1.2. Aqueous N,N' -tetramethyldiaminomethane