RODD'S CHEMISTR Y

OF CARBON COMPOUND S

A modern comprehensive treatis e

SECOND EDITIO N

Edited by

S . COFFE YM .Sc . (London), D .Sc . (Leyden), F .R.I .C .

formerly ofJ.C.I. Dyestuffs Division, Blackley, Mancheste r

VOLUME IV PART A

HETEROCYCLIC COMPOUND SThree-, four- and five-membered heterocyclic compounds with a singl e

hetero-atom in the ring

Heterocyclic Compounds ; Three-, four- and five-membered heterocyclic compound swith a single hetero-atom in the ring

PREFACE VI IOFFICIAL PUBLICATIONS ; SCIENTIFIC JOURNALS AND PERIODICALS XV ILIST OF COMMON ABBREVIATIONS AND SYMBOLS USED xVI I

Chapter 1 . Compounds with Three- and Four-Membered Heterocyclic Ring sby R . LIVINGSTON E

1 . Introduction2 . Three-membered rings containing an oxygen atom 3

a. Oxiranes (ethylene oxides) 3b. Oxirenes (acetylene oxides) 5

3 . Three-membered rings containing one sulphur atom 5a. Thiiranes (ethylene sulphides) 5

(i) Synthesis, 5 - (ii) Properties and reactions, 8 - (iii) Individual thiiranes, 12 -

b. Thiiranium salts (episulphonium salts) 1 2c. Thiirenes (acetylene sulphides) 14

4. Three-membered rings containing one nitrogen atom 1 5a. Aziridines (ethyleneimines) 1 5

(i) Synthesis, 16 - (ii) Reactions of aziridines, 20 - (iii) Properties of individualaziridines, 27 - (iv) Halogenoaziridines, 27 - (v) Cyanoaziridines and aziridin ecarboxylic acids, 30 -

b. Aziridinones (a-lactams) 3 1c. Azirines 3 3

(i) 1-Azirines : synthesis, 33 - (ii) Properties apd reactions of 1-azirines, 35 -(iii) 2-Azirines, 37 -

d. Aziridinium salts 385 . Three-membered rings with more than one hetero-atom 40

a. Oxaziridines (oxaziranes) 40b. Diaziridines and related compounds 42

(i) Diaziridines and diazirines, 42 - (II) Diaziridinones, 44 -

c. Oxadiaziridine 456 . Four-membered rings with one oxygen atom 45

a. Oxetanes (trimethylene oxides) 45(i) Formation, 45 - (ii) Properties and reactions, 46 -

b. Alkoxyoxetanes and oxetanols 48c. Oxetanones 49

(i) Oxetan-2-ones (ß-lactones), 49 - (ii) Oxetan-3-ones, 50 -

d . Oxetes or oxetenes 527 . Four-membered rings with one sulphur atom 5 2

a. Thietanes (trimethylene sulphides) 52

(i) Preparation, 52 _ (ii) Properties and reactions, 53 -b. Thietes or thietenes and their oxides 5 6c. Thietanones 59

8 . Four-membered rings with one selenium atom 6 19 . Four-membered rings containing one nitrogen atom 6 1

a . Azetidines (trimethyleneimines) 6 1

(i) Synthesis, 61- (ii) Properties aid reactions, 63 -

b. Azetidinones ; oxoazetidines

67

(i) Synthesis, 67 - (ii) Reactions, 69 -

c. Azetidine-2,4-diones (malonimides) 701o . Three- and four-membered rings containing other elements 7 1[ 1 . Four-membered rings with two hetero-atoms 7 2

a. Dioxetanes 7 2b. Dithietanes 73c. Oxathietanes 74d. Dithietenes 7 5e. Diazetidines 7 6

(i) 1,2-Diazetidinones, 76 - (ii) 1,3-Diazetidines, 78 -

f. Diazetines (dihydrodiazetes) 79g. Rings containing one nitrogen and one oxygen or sulphur atom 8o

(i) Oxazetidines, 8o - (ii) Thiazetidines, 81 -

Chapter 2 . Compounds Containing a Five-Membered Ring with One Hetero Atomof Group VI Oxygenby R . LIVINGSTON E

1 . The furan group 8 3a. Furan and its substitution products 84

(i) Synthetic methods, 84 - (ii) General properties and reactions, 89 -(iii) Furan, 96 - (iv) Alkyl- and aryl-furans, 97 - (v) Halogenolurans, 102 -(vi) Furansulphonic acids, 103 - (vii) Nitrofurans, 103 - (viii) Amino- an dcyano-furans, 105 - (ix) Oxodihydrofurans ; butenolides (hydroxyfurans), 107- (x) Furfuryl alcohol and related compounds, 109 - (xi) Aldehydes, 112 -(xii) Ketones, 115 - (xiii) Carboxylic acids, 117 -

b. Dihydrofurans

12 ]

(i) 2,3-Dihydrofurans, 123 - (ii) 2,5-Dihydrofurans, 125 --

c. Tetrahydrofurans 12 8

(i) Tetrahydrofuran, 13o - (ii) Halogenotetrahydrofurans, 131 - (iii) Hydroxy -tetrahydrofurans, 132 - (iv) Aminotetrahydrofurans, 132 - (v) Oxotetrahydro -furans, 133 - (vi) Side-chain substituted tetrahydrofurans, 1 33 -

d. Compounds with two or more unfused furan nuclei 13 6e. Polyene derivatives of furan 140

2 . Benzo[b]furans and their hydrogenated products 14 1a. Benzo[b]furans 14 1

(i) General synthetic methods, 141 - (ii) General properties and reactions, 1 45- (iii) Alkyl- and aryl-benzofurans, 148 - (iv) Halogenobenzofurans, 152 -(v) Nitro- and amino-benzofurans, 154 - (vi) Hydroxybenzofurans, 156 -(vii) Alcohols, aldehydes and ketones, 158 - (viii) Benzofurancarboxylicacids, 163 -

b. Hydrobenzofurans 166

(i) 2,3-Dihydrobenzofurans (coumarans), 166 - (ii) Tetrahydrobenzofurans ,176 - (iii) Hexahydrobenzofurans, 178 - (iv) Octahydrobenzofurans, 1 79 -

3 . Isobenzofuran (benzo[c]furan ; 3,4-benzofuran) and its derivatives 18oa. Isobenzofurans 180

(i) Synthetic methods, 181 - (ii) Properties and reactions, 185 - (iii) Individualisobenzofurans, 187 -

b. Hydroisobenzofurans 188

(i) Dihydroisobenzofurans, 188 - (ü) Tetra-, hexa- and octa-hydroisobenzo -furans, 190-

4 . Other bicyclic systems with a furan ring 19 15 . Dibenzofuran or diphenylene oxide and its hydrogenation products 1 94

a. Dibenzofurans 1 94

(1) General synthetic methods . 194 - (ii) Properties and reactions, 196 -(iii) Dibenzofuran and derivatives, 197 -

b. Reduced dibenzofurans 20 3c. Natural products related to dibenzofuran 204

6 . Other tri- and poly-cyclic systems with a furan ring 207a. Condensed systems of benzene rings with one furan nucleus 207b. Systems of benzene rings with more than one furan nucleus 21 5c. Other tri- and poly-cyclic furans 21 7

Chapter 3 . Compounds with Five-Membered Rings Having One Hetero Ato mfrom Group VI ; Sulphur and its Analogues

by R . LIVINGSTON E

t . Monocyclic thiophenes and hydrothiophenes 21 9a. Thiophene and its substitution products 220

(i) Synthetic methods, 220 - (ii) General properties and reactions, 224 -(iii) Thiophene, 229 - (iv) Metal and metalloid derivatives of thiophenes, 231 -(v) Alkyl- and arylthiophenes, 233 - (vi) Halogenothiophenes, 238 - (vii) Nitro -and amino-thiophenes, 241 - (rill) Hydroxythiophenes, 243 - (ix) Sulphoni cacids, thiols and related compounds, 245 - ( .~ ) Thiophene alcohols and relate dcompounds, 247 - (xi) Aldehydes and ketones, 249 - (xii) Thiophenecarboxyli cacids, 252-

b. Thiolenes ; dihydrothiophenes 2 5 5c. Thiolanes, tetrahydrothiophenes 25 7d. Compounds having two or more unfused thiophene rings 26o

2 . Benzo[b]thiophenes (thianaphthenes) and related compounds 265a. Benzo[b]thiophenes 266

(i) Synthetic methods, 266 (ii) General properties and reactions, 270 - -

(iii) Benzo[h]thiophene, 271 - (iv) Alkyl- and aryl-benzothiophenes, 272 -(v) l-lalogenobenzothiophenes, 273 - (vi) Nitrobenzothiophenes, 2 74 -(vii) Aminohenzothiophenes, 275 - (viii) Hydroxybenzothiophencs, 276 -(ix)Sulphonicacids, 277 - (x) Alcohols, aldehydes, ketones, 277- (xi) Carboxyli cacids, 279-

b. Reduced benzothiophenes 28o

(1) Dihydrobenzothiophenes, benzothiolenes, 28o - (ii) Tetrahydrobenzo-thiophenes, 286 - (iii) Hexa- and octa-hydrobenzothiophenes, 287 -

3 . Benzo[c]thiophenes (3,4-benzothiophenes, isobenzothiophenes) and relate dcompounds 28 8a. Benzo[c]thiophenes 28 8b. Hydrobenzo[c]thiophenes 29 1

(1) Dihydrobenzo[c]thiophenes, 291 - (ii) Tetrahydrobenzo[c]thiophenes, 2 9 3- (iii) Hexa- and octa-hydrobenzo[c]thiophenes, 2 93 -

4 . Cycloalkanothiophencs 29 45 . Systems of two fused thiophene rings 29 66 . Dibenzothiophenes 300

a. Dibenzothiophene and its derivatives 30 0

(1) Preparation and synthesis, 300 - (ii) Properties and reactions, 302 -

(iii) Derivatives of dibenzothiophene, 302 -

b. Reduced dibenzothiophenes 30 57 . Other tri- and poly-cyclic systems containing the thiophene ring 30 68 . Compounds with five-membered heterocyclic rings having one selenium

atom 31 3a. Selenophenes and related compounds 31 3

(i) Preparation and properties, 314 - (i1) Selenophenes, 315 - (iii) Selenophen ederivatives, 315 - (iv) Hydroselenophenes, 319 - (v) Biselenienyl (bis-selenophene), 320 - (v1) Metalloid derivatives, 320 -

b. Benzo[b]selenophenes (sclenanaphthenes, 2,3-benzosclenophenes) .

320

c. Dibenzoselenophenes, diphenylene sclenidcs 324d. Systems of two fused selenophene rings 32 5

9 . Heterocyclic five-membered ring compounds having one tellurium atom 32 6a. Tellurophenes 326b. Hydrotellurophenes 327c. Benzotellurophenes 327

Chapter 4 . Compounds Containing a Five-Membered Ring with one Hetero Atomfrom Group V : Nitrogen

by R . LIVINGSTON E

1 . Pyrroles 329a. General synthetic methods 330b. General properties and reactions 335c. Pyrrole and its substitution products 337

(i) Pyrrole, 337 - (ii) N-Derivatives of pyrrole (1-substituted pyrroles), 338 -(iii) Individual N-substituted pyrroles, 340 - (iv) C-Alkyl- and C-aryl-pyrroles ,

34 1 - (v) Halogenopyrroles, 346 - (vi) Nitro-, nitroso-, diazo-, amino- an dcyano-pyrroles, 348 - (vii) Hydroxypyrroles, 351 - (viii) Sulphur derivatives o fpyrroles, 352 - (ix) Pyrrolylalkanols and related compounds, 353 -(x) Aldehydes and ketones, 355 - (xi) Pyrrolecarboxylic acids and theiresters, 359 -

2 . Pyrrolines, dihydropyrroles 36 8a. 1-Pyrrolines 36 8

(i) Synthesis, 369 - (ii) Properties and reactions of 1-pyrrolines, 370 -

b. 1-Pyrroline 1-oxides

37 1

(i) Synthesis, 371 -(ii) Properties and reactions, 372 -

c. 2-Pyrrolines 37 3d. 3-Pyrrolines 374e. Oxopyrrolines ; pyrrolinones 37 5

(i) 5-Oxopyrrolines, 375 - (ii) 4-Oxopyrrolines, 376 - (iii) 3-Oxopyrrolines, 37 7- (iv) Dioxopyrrolines, 378 -

3 . Pyrrolidines ; tetrahydropyrroles 37 9a. Pyrrolidines 37 9

(i) Synthesis, 379 - (ii) Properties and reactions, 38o - (iii) Individualpyrrolidines, 382 -

b. Substituted pyrrolidines 38 3

(i) Hydroxypyrrolidines, 383 - (ii) Oxopyrrolidines, 384 - (iii) Poly-oxopyrrolidines, 387 - (iv) Pyrrolidinecarboxylic acids, 388 -

4, Compounds having two or more independent five-membered rings 39 1a. Bipyrrolyls 39 1b. Compounds having two or more pyrrole rings linked through methylene

or methine groups 393

(i) Dipyrrolylmethanes, 393 - (ii) Pyrromethenes, 395 -

Chapter 5 . Compounds Containing Five-Membered Rings with One Hetero Ato mfrom Group V: Nitrogen; Fused-Ring Compounds

by R. LIVINGSTON E

1 . Indoles (2,3-benzopyrroles) and 3H-indoles 397a. General synthetic methods 398

(i) The Fischer indole synthesis, 398 - (ii) The Bischler synthesis, 401 -(iii) The Madelung synthesis, 402 - (iv) Synthesis from nitro compounds wit hortho side-chains or their reduction products, 402 - (v) Synthesis from benzo -quinones and their derivatives, 403 - (vi) From ketones and isocyanides, 404 -(vii) From pyrroles, 404 - (viii) From o-aminocarbonyl compounds, 404 -(ix) From S-sultams, 405 -

b. General properties and reactions of indoles 40 5

(i) Reduction, 405 - (ii) Addition reactions and polymerisation, 405 -(iii) Substitution reactions, 407 - (iv) Metal compounds, 408 - (v) Oxida-

tion, 408 - (vi) Reaction with benzyne, 410 - (vii) Condensation with nitrosoand carbonyl compounds, 410 - (viii) Alkylation, 411 - (ix) Characterisatio nof indoles, 411 -

c. Indole and its substitution products 41 1

(i) N-Derivatives, 412 - (ir) C-Alkyl-, C-aryl- and related compounds, 414 -(iii) Halogeno-indoles, 418 - (iv) Sulphur compounds, 420 -• (v) Nitro- ,amino- and related indoles, 421 - (vi) Hydroxyindoles, 424 - (vii) Metal an dmetalloid derivatives, 427 - (viii) Indolylcarhinols, aminoalkylindoles an drelated compounds, 428 - (ix) Aldehydes and ketones, 431 (x) Carboxyli cacids. 43 4

d. 3H-Indoles (indolenines) 43 92 . Hydroindoles 445

a . Indolines (dihydroindoles) 445

(i) Synthesis, 445 - (ii) General properties and reactions, 446 (iii) Individua lindolines, 448 -

b . Oxoindolines (indolinones) and hydroxyindoles 448

(i) 2-Oxoindolines (oxindoles), 448 - (ii) 3-Oxoindoline ; indoxyl, 454 -(iii) 3-Hydroxy-2-oxoindolines ; 3-hydroxyoxindoles ; dioxindoles, 456 -(iv) 2,3-Dioxoindolines ; isatins, 458 - (v) Indolines with side-chain carbonylgroups, 464 -

c . Tetra-, hexa-, and octa-hydroindoles 46 5d . Compounds having more than one indole nucleus 46 7

3 . Isoindoles and isoindolines 470a. Isoindoles 470b. Isoindolines 47 4c. Other hydroisoindoles 47 7

(i) Tetrahydroisoindoles, 477 - (ii) Hexa- and octa-hydroisoindoles, 477 -

4 . Other bicyclic pyrrole systems 477a. Spirocyclic systems 477b. Cycloalkenopyrroles 478c. Fused systems of two heterocyclic rings 480

5 . Benzoindoles 4826 . Compounds containing the carbazole nucleus 486

a. Carbazole and its derivatives 486

(i) Synthetic methods, 487 - (ii) General properties and reactions, 490 -(iii) Carbazole, 491- (iv) N-Substituted carbazoles, 492 - (v) C-Alkylcarbazoles ,494 - (vi) Halogenocarbazoles, 495 - (vii) Nitro-, nitroso- and amino-carbazoles, 496 - (viii) Hydroxycarbazoles, 502 - (ix) Sulphonic acids an drelated compounds, 503 - (x) Organometallic derivatives, 503 - (xi) Alcohols ,aldehydes and ketones derived from carbazole, 504 - (xii) Carbazolecarboxylicacids, 506 -

b. Hydrocarbazoles

50 9

(i)-Tetrahydrocarbazoles, 509 - (ii) More fully reduced carbazoles, 514 - .

c. Compounds having more than one singly linked carbazole nucleus 51 7d. Carbazoles with additional fused rings 51 8

(i) Benzocarbazoles, 518 - (ii) More complicated fused ring carbazoles, 524 -

7 . Other tricyclic pyrrole systems 526

Chapter 6 . Other Five-Membered Ring Compounds with One Hetero Atom in the Ringfrom Groups 3, 4 and 5by R . LIVINGSTON E

1 . Phosphorus compounds 53 1a. Mononuclear compounds 53 1

(t) Phospholes, 531 - (ii) Phospholenes and phospholanes, 534 -

b. Polynuclear, fused ring compounds

538

(i) Dibenzophospholes, 538 -

2 . Silicon compounds 539a. Mononuclear compounds 539

(i) Silacyclopentadienes : siloles, 539 - (ii) Silacyclopentenes, 542 -Oil) Silacyclopentanes, 543 -

b. Fused ring compounds 54 33 . Germanium compounds 54 5

a. Five-membered monohuclear compounds 54 5b. Polycyclic compounds with germanium in a five-membered ring 547

4 . Compounds containing aluminium, boron, antimony and tin as the heteroatom 549

AppendixIUPAC Commission on the Nomenclature of Organic Chemistry

B . Fundamental heterocyclic systems 55 1Rule

Extension of the Hantzsch-Widman System 55 1Rule B-2 . Trivial and semi-trivial names 554Rule B-3 . Fused heterocyclic systems 562Rule B-4 . "a" Nomenclature 56 5Rule B-5 . Radicals 567Rule B-6 . Cationic hetero-atoms 568

Heterocyclic Spiro compounds 569Rule B-1o (alternate to Rule B-ti) 569Rule B-1t (alternate to Rule B-1o) 5 6 9

Seniority of ring systems 570Rule C -14 .1 570

Index 575