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30. J. S. Bradshaw, J. Y. K. Hui, J. Heterocycl. Chem., 11, 649 (1974). 31. J. S. Bradshaw, J. Y. K. Hui, B. L. Baymore, R. M. Izatt, J. J. Christensen, J. Heterocycl. Chem., 10, 1 (1973); J. S. Bradshaw, J. Y. K. Hui, J. Y. Chan, B. L. Haymore, J. J. Christensen, R. M. Izatt, J. Heterocycl. Chem., 11, 45 (1974). 32. J. L. Lambert, D. van Ooteghem, E. J. Goethals, J. Polym. Sci. A-I, 9, 3055 (1971). 33. E. J. Goethals, Adv. Polym. Sci., 23, 103 (1977). 34. A. Noshay, C. C. Price, J. Polym. Sci., 54, 533 (1961). 35. W. van Craeynest, E. J. Goethals, Eur. Polym. J., 12,859.9 (1976). 36. J. R. Dann, P. P. Chiesa, J. W. Gates, J. Org. Chem., 26, 1991 (1961). TABLE 8. OLIGOMERS CONTAINING N IN THE MAIN CHAIN

8.1.1.4. Cyclic Oligo(amides) of C-Methyl-$-Alanines |— [NHCHR1CHR2CO]^n

8.1. OLIGO(AMIDES) 8.1.1.

37. F. Vogtle, F. Ley, Chem. Ber., 116, 3000 (1983). 38. F. Vogtle, L. Schunder, Chem. Ber., 102, 2677 (1969). 39. R. H. Mitchell, V. Boekelheide, J. Am. Chem. Soc, 96, 1547 (1974); V. Boekelheide, J. L. Mondt, Tetrahedron Lett., 1203 (1970). 40. K. Galuszko, Rocz. Chem., 49, 1597 (1975). 41. H. J. J.-B. Martel, M. Rasmussen, Tetrahedron Lett., 3843 (1971). 42. B. V. Gorewit, W. K. Musker, J. Coord. Chem., 5, 67 (1976). 43. R. G. GiIUs, A. B. Lacey, Org. Synth., Coll. Vol. IV, 396 (1963). 44. V. Meyer, Chem. Ber., 19, 3259 (1886). 45. J. D. A. Johnson, J. Chem. Soc, 1530 (1933). 46. H. T. Clarke, J. Chem. Soc, 101, 1806 (1912).

Ri

OLIGO(AMIDES) OF p-AMINO ACIDS (NYLON 3)

R2

CH 3

8.1.1.1. Linear Oligo(amides) of (3-Alanine H[NH(CH 2 ) 2 C0] n 0H n

MoI. wt.

m.p. (d) (0C)

Refs.

1 2 3 4 5 6

89.1 160.2 231.2 302.3 373.4 444.5

206 212 >255 >260 >310 >320

1 2,4,96 3,4,96 4,96 5 5

H

H

CH 3

n

MoL wt.

1 3 1 2 3 4 5 6 7 8 9 10 11

85.1 255.3 85.1 170.2 255.3 340.4 425.5 510.6 595.7 680.8 765.9 851.0 936.0

m.p. (0C)

b.p. (°C/mbar) 100/13

300 98-99/20 255 >350 >350 >350 >350 330-335 338-340 327-330 330 325

Refs. 104,105 91 104 84 84,85,87 84 84 84 84 84 84 84 84

8.1.1.5. Linear Oligo(amides) of C-Dimethyl-(3-Alanines H[NHC(R!) 2 C(R 2 ) 2 CO] n OH 8.1.1.2. Cyclic Oligo(amides) of f3-Alanine r [NH(CH 2 ) 2 CO] n -| n 1 2 3 4 5 6 7 8 9 10 11

MoI. wt.

m.p (0C)

Refs.

71.1 142.2 213.2 284.3 355.4 426.5 497.6 568.8 639.7 710.8 781.8

74-74.5 298-299 >360 353 327 360 341 >360 349 >350 >350

6,104,113 4,8,9,72,84,114,116 4,10,84,88,93,101,114,116 4,10,84,114,116 84,114,116 114,116 114,116 114,116 114,116 116 116

Ri

R2

n

MoI. wt.

m.p. (0C)

H

CH 3

CH 3

H

1 3 6 1 3

117.1 315.4 612.8 117.1 315.4

239 209-212 207.5-210.5 217 182-184

R2

n

CH 3

H

1 3

MoI. wt. 103.1 273.3

m.p. (0C) 188-189 240-241

8.1.1.6. Cyclic Oligo(amides) of C-Dimethyl- p-Alanines

Ri

R2

n

MoI. wt.

m.p. (°C)

H

CH 3

1 3 4 5 6 7 8 9 10 11 12 1 3

99.1 297.4 396.5 495.7 594.8 693.9 793.1 892.3 991.3 1090.5 1189.6 99.1 297.4

255-259.5 270 257 310 290 256 315 252 315 245 16-17 257-258

Refs. 102 92

106 94 94 103 95

n [NHC(R 1 ) 2 C(R 2 ) 2 CO]^- ]

8.1.1.3. Linear Oligo(amides) of C-Methyl- $-Alanines H[NHCHR i CHR 2CO] nOH Ri

Refs.

CH 3

H

b.p. (°C/mbar) 70-73/1.1

112/20

Refs. 107 84,91 84 84 84,91 84 84 84 84 84 84 104,105 91

8.1.2. OLIGO(AMIDES) OF y-AMINOBUTYRIC ACID (NYLON 4)

8.1.3. OLIGO(AMIDES) OF-5-AMINOVALERIC ACID (NYLON 5)

8.1.2.1. Linear Oligo(amides) H[NH(CH2)3CO]«OH

8.1.3.1. Linear Oligo(amides) H[NH(CH2)4CO]«OH

n 1 2 3 4 6 8 10 12 16 20

0

MoL wt.

m.p. ( C)

Refs.

103.1 188.2 273.4 358.4 528.6 698.8 869.0 1039.3 1379.6 1719.4

204-205 186 198-199 202-203 196-198 206-208 199-203 208 207-209 206-208

11 4,7,12 4 4 133 133 133 133 133 133

8.1.2.2. Cyclic Oligo(amides) ^[NH(CH2)SCO]n-]

n 1 2 3 4 6 8 10 12 14

MoI. wt.

m.p. (0C)

85.1 170.2 255.3 340.4 510.6 680.9 851.1 1021.3 1191.5

24 283 242-243 255 303 298 312 301 >355

n

MoL wt.

m.p. (0C)

Refs.

1

117.2

160-162

17

2 3 4

216.3 315.4 414.5

178 184-185.5 196.5-198.5

18 18 18

8.1.3.2. Cyclic Oligo(amides) r—[NH(CH2)4CO]/ri n

MoI. wt.

1

98.1

2 3 4

198.3 297.4 396.5

m.p. (0C)

Refs.

39-40

14,17,19

295-296 329-331 266-267

8,18 18 18

Refs. 13,14 4,10,70,71,73 4,10 4,10,70 10,135 135 135 135 135

8.1.3.3. Cationic Oligo(amides)

R

n

MoI. wt.

m.p. ( C )

Refs.

1 0

234.5 216.5

114 93-94

89 89

1

315.5

138

89

8.1.3.4. Amidino-Oligo(aminovaleric Acids)

8.1.2.3. Anionic Oligo(amides)

n

MoI. wt.

m.p. (0C)

0 1

189.2 274.3

92.5 121

Refs. 15 16

n

MoI. wt.

m.p. (0C)

Refs.

1 2 3

198.3 297.4 396.5

166-168 92-94 112

89,118 89 89

8.1.2.4. Cationic Oligo(amides)

R

n

MoI. wt.

1

206.5

m.p. (0C)

Refs.

8.1.4. OLIGO(AMIDES) OF E-AMINOCAPROIC ACID (NYLON 6) 8.1.4.1. Linear Oligo(amides) H[NH(CH2) 5 CO] n OH

181

71,89,118 n

0 1

188.7 273.5

156 162

89,119 89

8.1.2.5. Amidino-Oligo(aminobutyric Acids)

n 1 2 3

MoI. wt. 170.2 255.3 340.4

m.p. (0C)

Refs.

175-177 175 162-163

89,118,121 89 89

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 17

MoI. wt.

m.p. (0C)

131.2 244.3 357.3 470.6 583.8 697.0 810.1 923.3 1036.5 1149.6 1262.8 1375.9 1489.1 1602.3 1715.3 1941.5

206-208 204-205 208-209 220-221 214-215 212-214 210-211 210-211 208-211 212-213 209-212 211-213 210-211 207-208 207-208 209-211

Refs. 20,21 22-24,136 23-25,69,136 23,24,36 23,69,136 23,24,136 23,69,136 23 26,69 26 26,69 26 69 136 69 69

8.1.4.1.

cont'd 8.1.4.5. Anionic Oligo(amides)

n

m.p. ( 0 C)

MoI. wt.

Refs.

18

2054.9

206-209

136

21 22 25 26 30 34 38

2394.5 2507.5 2847.0 2960.2 3412.8 3865.5 4318.1

212-213 209-211 212-213.5 209-211 210-213 211-214 214-217

69 136 69 136 136 136 136

R

n

MoI. wt.

m.p. ( 0 C)

Refs.

H-C 4 H 9

1 2 3 1 2 3

222.8 335.9 449.1 256.8 369.9 483.1

143 176 189 164.5 179 194-195

122 122 122 122 122 122

0 1 2 3

b.p. (°C/mbar)

155.2 268.5 381.5 494.7

nff

123/21

J?f

1.4898 1.4992

0.76 0.67 0.58

Refs.

32 33 33 33

"PC: solvent, tetrahydrofuran/cyclohexane/water (186:14:10).

n

MoI. wt.

m.p. ( 0 C)

1 2 3

226.3 339.5 452.6

168 120 154

8.1.4.4. Amidino-Oligo(aminocaproic

R

n

MoI. wt.

1 2 3 0 1

262.8 375.9 489.1 244.8 357.9

8.1.4.7. End-group Protected

8.1.4.3. Arnidino-Oligo(aminocaproic Acids)

m.p. ( 0 C)

Refs.

112 Oil Oil 137 106-108

120 120 120 89,120 120

Oligo(amides)

C2H5CO-[NH(CH2)SCOL-NHC3H7

Refs. 120,128 120 120

Amides)

0

R

n

MoL wt.

m.p. ( C)

Refs.

M-C4H9

0 1 2 0 1 2

168.3 281.4 394.6 202.3 315.5 428.6

53 129 148-150 76-78 135 157

122 122 122 122 122 122

CH2C6H5

MoI. wt.

8.1.4.6. Cationic Oligo(amides)

8.1.4.2. Oligo(aminocapmic Amides) H+[NH(CH 2 ) 5 CO] n -NHR C L "

CH2C6H5

n

m.p. ( 0 C)

n

MoI. wt.

Refs.

1 2 3 4 5 6 7 8 9 10 11

228.3 341.5 454.7 567.8 681.0 794.2 907.3 1020.5 1133.6 1246.8 1360.0

106 149 172 181 187 191 197 200 201 201 204

31,112 31,112 31,112 31 31,112 31,112 31,112 31,112 31,112 31,112 31

12 13 14 15 16

1473.1 1586.3 1699.3 1812.6 1925.8

202 200 205 206 206

31,112 31 31 31 31

8.1.4.8. Cyclic Oligo(amides) RF

na 1 2 3 4 5 6 7 8 9

MoI. wt.

m.p. ( 0 C)

TCW*

EAWC

113.2 226.3 339.5 452.6 565.8 678.9 792.1 905.3 1018.4

69.5 348 244 256-257 254 260 243 254 245

0.56 0.48 0.34 0.25 0.16 0.10 0.08 0.04 0.02

0.88 0.81 0.77 0.69 0.59 0.49 0.40

Refs. 14,17,27,78 4,24,28,29,45,78,98,110,111,112,148 4,24,28,29,45,78,98,111,112,147 4,24,28,29,45,78,98,111,112 4,24,29,78,98,111,112 4,24,29,60,98,111,112 29,30,60,98,111 29,30,60,98,111 29,30,68,138

8.1.4.8. cont'd RF

na

MoL wt.

10 11 12 13 14 15 16 18 20 21 22 24 25 26 27 28 30 32 33 34 36 38 40 48 50 55 56 60 64 70 72 80 90 100

m.p. (°C)

1131.8 1244.8 1357.9 1471.1 1584.3 1697.4 1810.6 2036.9 2263.2 2376.4 2489.5 2715.9 2829.0 2942.2 3055.3 3168.5 3394.8 3621.2 3734.3 3847.5 4073.8 4300.1 4526.4 5431.7 5658.1 6223.9 6337.0 6789.7 7242.3 7921.3 8147.6 9052.9 10184.5 11316.1

TCW b

EAWc

Refs.

257 249 262 249 263 256 261 263 259 248 250 252 249 246 244 247 255 248 231 231 228 230 235 234 229 226 229 227 226 225 225 224 222 221

117,137 138 117,137 138 117,137 138 117,137 117,137 117,137 138 117,137 117,137 138 137 138 137 117,137 137 138 137 137 137 137 138 138 138 138 138 138 138 138 138 138 138

a

n = 2-40: HPLC (trifluoroethanol/water mixtures), Ref. 117; n = 2-18: FD-MS, Ref. 117; n = 2-100: HPLC (trifluoroethanol/water, gradient elution, Ref. 138. PC, TLC: solvent, tetrahydrofuran/cyclohexane/water (186:14:10). PC, TLC: solvent, ethyl acetate/acetone/water (10:10:2), Refs. 29,134.

b

C

8.1.5. OLIGO(AMIDES) OF HIGHER co-AMINO ACIDS

8.1.5.2. Cyclic Oligo(amides) [— [NH(CH2^CO]n-[

(NYLON 7-12)

x

8.1.5.1. Linear Oligo(amides) H[NH(CH2) ^CO]nOH x 6 7 8 10

11

n 1 2 1 2 1 2 1 2 3 4 5 10 1 2

MoL wt. 145.2 272.4 159.2 300.4 173.3 328.5 201.3 384.6 567.9 751.2 934.5 1850.8 215.3 412.6

0

m.p. ( C) 195 205-208 188 191-192 184 184-186 186-187 189-190 183-184 177-179 177-178 181-182 186-187 192-193

n 6

Refs. 34,35 36 4,37 4,38 4,34 4 34,38,39 4,40,140 5,40,115,140 40,63,115 63 63,67 41 31

6

7

8 9

1 2 3 4 5 6 8 10 1 2 3 4 5 6 1 2 1 2

MoL wt.

m.p. (0C)

Refs.

127.2 254.4 381.6 508.8 636.0 763.2 1017.5 1271.9 141.2 282.4 423.6 564.8 706.0 847.2 155.3 310.5 169.3 338.4

29-30 236-237 259-261 215-216 236 244-245 258-259 262-263 72-73 277 217 219 215 215 138-139 201 162 238

14,17,42 4,10 89 89 89 89 89 89 13,14,34,42 4,10,76,77 89 82,89 89 89 14,42 4,10 14,42 10,144

8.1.5.2. cont'd x

n 10 10

11

14

8.1.6.4. Linear Oligo(amides) of p-Aminobenzoic Acid

m.p. (0C)

MoI. wt.

1 2 4 5 6 7 8 9 3 1 2 3 2

183.3 366.6 741.2 926.6 1111.9 1297.2 1482.5 1667.8 549.9 197.3 394.6 531.9 478.8

155 188-189 203 204 217 205 221 201 184 155 212 175 182

Refs. 42,43,75 4,10,44,75,98 140 140 140 140 140 140 44,60,75,98 13,14,42,75 60,61,75,98,115 31,75 139

R

n

MoI. wt.

m.p. (0C)

H

2 3 2 3 4

256.1 375.4 284.1 403.2 522.2

276 >310 176 >266 >330

C2H5

Refs. 86 86 86 86 86

8.1.6.5. Cyclic Oligo(amides) of 4-Amino-2,3-dihydroquinoline3-Carboxylic Acid

8.1.6. OLIGO(AMIDES) OFAROMATIC AMINO ACIDS 8.1.6.1. Linear Oligo(amides) of o-Aminobenzoic Acid

n

MoI. wt.

m.p. (0C)

Refs.

1 2 3 4

137.1 256.3 375.4 494.5

146 203-204 256 d

46-48 46,123,124,131 46,131 46

R

n

MoI. wt.

m.p. (0C)

H-C3H7 CH 2 C 6 H 5

4 4

857.0 1049.2

198 206

Ref. 97 97

8.1.7. CYCLIC DIAMIDES OF ALIPHATIC DICARBOXYLIC ACIDS AND DIAMINES j — [NH(CH2^NH- CO(CH2)xCO]n-| n

MoI. wt.

m.p. (0C)

6 7 8

1 1 1 1 2 3 4 1 1 1

142.2 170.2 198.3 226.3 452.6 679.0 905.3 254.3 282.4 310.5

201 238 304 337 234 246 244 238 267 209

9 10 11 12

1 1 1 1

338.5 366.6 394.6 422.7

228 195 206 186

x

Refs.

8.1.6.2. Cyclic Oligo(amides) of o-Aminobenzoic Acids 2 3 4 5

Ri H CH 3

R2 H H

C 6 H 5 CH 2

H

CH 3

CH 3 CH 3

n

MoI. wt.

m.p. (0C)

Refs.

2 2 3 4 2 3 3 3

238.2 266.3 399.2 532.2 418.2 627.3 669.3 441.2

335-337 207 >320 >300 158-159 260-263 260-263 >300

47,125-128,131 47 131 130 131 131 129 129

142 49,50,74,139 49,51,139 49,139 143 143 143 49,51,139 49,139 8,49,139,146

49,139,147 8,49,139 139 139

8.1.8. OLIGO(AMIDES) OFADIPIC ACID AND HEXAMETHYLENE DIAMINE (NYLON 6.6) 8.1.8.1. Linear Oligo(amides) H[NH(CH 2 ) 6 NH-CO(CH 2 ) 4 CO] n OH 8.1.6.3. Cyclic Oligo(amides) of m-Aminobenzoic Acids n

R

n

MoI. wt.

CH 3

3

399.2

m.p. (0C) >320

Ref. 132

1 2 3 4 5 10

MoI. wt.

m.p. (0C)

Refs.

244.3 470.7 696.9 923.3 1149.5 2281.1

193 221-222 246-248 247-249 247-250 250-255

52,53 52,53,63 52,53,63 31,63,65 31,63,65 63

8.1.8.2. End-Group Protected

Oligo(amides)

8.1.8.3. Oligomeric Diamines H 2 f [NH(CH 2 )6NH-CO(CH 2 )4CO] w -NH(CH2)6NHj 2Cl"

8.1.8.2.1. OLIGOMERIC DICARBOXYLIC ACID DIPROPYLAMIDES

C3H 7 NH-CO(CH2)4CO-[NH(CH2)6NH-CO(CH2)4CO] n -NHC3H7 0

n

MoI. wt.

m.p. ( C)

Refs.

1 2 3 4 5

454.7 681.0 907.3 1133.6 1359.9

229-230 239-242 248-250 257-260 258-261

64 64 64 64 64

n

MoI. wt.

m.p. ( 0 C)

Refs.

1 2 3 4 5

415.4 641.7 868.0 1094.4 1320.7

248-250 249-251 252-254 251-254 252-255

65 65 65 65 65

8.1.8.4. Oligomeric Dicarboxylic Acids 8.1.8.2.2. OLIGOMERIC DIPROPIONYL DIAMINES

HOOC(CH 2 ) 4 C O - [NH(CH 2 ) 6 NH-CO(CH 2 ) 4 CO] »OH

C2H 5 CO-[NH(CH2)6NH-CO(CH2)4CO] n -NH(CH2)6NH-COC 2 H5 n

MoI. wt.

m.p. ( 0 C)

Refs.

n

MoI. wt.

m.p. ( 0 C)

Refs.

1 2 3

454.7 681.0 907.3

202-203 226-228 229-231

64 64 64

1 2 3 4

372.4 598.7 825.0 1051.3

188-189 200-205 210-211 214-219

56 56,57 56 31

8.1.8.5. Cyclic Oligo(amides) na

MoI. wt.

m.p. ( 0 C)

TCW*

EAW C

1 2 3 4 5 6 7 8 9 10 12 14 16 18 20

226.3 452.6 678.9 905.3 1131.6 1357.9 1584.3 1810.6 2036.9 2263.2 2715.9 3168.5 3621.2 4073.8 4526.4

254 243-244 235 273 279 279 291 282 280 280 280 292 284 275 270

0.47 0.28 0.13 0.06

0.51 0.38 0.23 0.16

a

Refs. 51,53-55,62,80,81,90,98,108 53-55,62,80,81,90,98,109 53,55,62,98 53,60,62,98 149 149 149 149 149 149 149 149 149 149 149

n = 1-20: HPLC (trifluoroethanol/water, gradient elution), Ref. 149. PC, TLC: solvent: tetrahydrofuran/cyclohexane/water (186:14:10). PC, TLC: solvent: ethyl acetate/acetone/water .(10:10:2).

fe C

8.1.9. OLIGO(AMIDES) OF SEBACIC ACID AND HEXAMETHYLENEDIAMINE (NYLON 6.10)

8.1.9.3. Oligomeric Diamines H[NH(CH 2 ) 6 NH-CO(CH 2 ) 8 CO] n -NH(CH 2 ) 6 NH 2

8.1.9.1. Linear Oligo(amides)

H[NH(CH 2 ) 6 NH-CO(CH 2 )8CO] M OH 0

n

MoI. wt.

m.p. ( C)

Refs.

1 2 3

300.4 582.8 865.3

187-188 196-199 208-210

58 63,67 63,67

n

MoI. wt.

m.p. ( 0 C)

Refs.

1 2 3

398.6 681.1 963.5

129-131 177-179 203-210

57,58 58 58

8.1.9.4. Oligomeric Dicarboxylic Acids 8.1.9.2. Cyclic Oligo(amides) f~ [NH(CH 2 ) 6 NH~CO(CH 2 ) 8 CO] n -| HOOC(CH 2 ) 8 CO-[NH(CH 2 ) 6 NH-CO(CH 2 ) 8 CO] WOH n 1 2 3

MoI. wt. 282.4 564.8 847.3

m.p. ( 0 C) 232 222 221

Refs. 51,98,145 58,60,98,145 145

n

MoI. wt.

m.p. ( 0 C)

Refs.

1 2 3

494.6 767.1 1049.5

156-159 182-184 181-185

57,58 57,58 58

8.1.10. OLIGO(AMIDES)OFDECANEDICARBOXYLICACIDAND p,p '-DIAMINO-DICYCLOHEXYLMETHANE (QIANA TYPE)

8.1.13. OLIGO(AMIDES) OF A^-DIALKYLETHYLENEDIAMINE AND DICARBOXYLIC ACIDS 8.1.13.1. Aliphatic Dicarboxylic Acids [-NRCH2CH2NR- CO(CH2)xCO]/n

n 1

Config.

m.p. (0C)

Refs.

trans-trans cis-trans cis-cis

310-314 269-272 254-257

83 83 83

MoI. wt. 404.6

8.1.11. OLIGO(AMIDES) OF OXALIC ACID AND HEXAMETHYLENEDIAMINE [— [NH(CH2)6NH~ COCO]n-^

n

MoI. wt.

1 2 3

170.2 340.4 510.6

m.p. (0C)

Refs.

232 303 345

66 66 66

8.1.12. OLIGO(AMIDES) OF TEREPHTHALIC ACID AND

R

x

C 6 H 5 CH 2

3 5 7

n 2 2 2

MoI. wt.

m.p. (0C)

672.8 729.0 785.1

231-234 199-201 199-204

Refs. 79 79 79

8.1.13.2. Terephthalic Acid

R

n

MoI. wt.

m.p. (0C)

CH 3 C 6 H 5 CH 2

3 3 4 6

654.8 1111.4 1481.8 2222.8

114-123 255-257 143-145 140-144

99 100 100 100

Refs.

Refs.

8.1.13.3. Pyridine-2.5-Dicarboxylic Acid

PENTAMETHYLENEDIAMINE n

MoI. wt.

m.p. (0C)

2

464.3

407

Refs. 59

R

n

MoI. wt.

m.p. (0C)

CH 3

3 4

663.8 885.0

123-129 132-136

99 99

REFERENCES

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77. I. Falgova, J. Kondelikova, J. Kralicek, Angew. Makromol. Chem., 49, 75 (1976). 78. R. Okada, T. Fukumura, H. Tanzawa, J. Polym. ScL, Polym. Lett., 4, 971 (1960). 79. E. Schwartz, A. Shanzer, J. Chem. Soc, Chem. Commun. 634 (1981). 80. P. D. Frayer, J. L. Koenig, J. B. Lando, J. Macromol. ScLPhys. B, 3, 329 (1969). 81. C J . Brown, A. Hill, R. V. Youle, Nature, 177, 128 (1956). 82. Y. Okuno, K. Horita, O. Yonemitsu, Chem. Pharm. Bull., 31, 737 (1983). 83. G. E. Hahn, P. Kusch, V. Rossbach, H. Zahn, Makromol. Chem., 186, 297 (1985). 84. M. Rothe, B. Benz, unpublished data. 85. M. Guaita, L. F. Thomas, Makromol. Chem., 117, 171 (1968). 86. H. Bredereck, H. v. Schuh, Chem. Ber., 81, 715 (1948). 87. L. Trossarelli, M. Guaita, A. Priola, Makromol. Chem., 109, 253 (1967). 88. G. Camino, L. Costa, L. Trossarelli, J. Polym. ScL, Polym. Chem. Ed., 18, 377 (1980). 89. M. Rothe, Ch. Seltenreich, R. HoBbach, H. Emmert, unpublished data. 90. L. E. Alexander, J. Polym. ScL, Polym. Lett. Ed., 10, 759 (1972). 91. J. Lowbridge, E. Mtetwa, R. J. Ridge, C. N. C. Drey, J. Chem. Soc, Perkin Trans. I, 155, (1986). 92. C. N. C. Drey, E. Mtetwa, J. Chem. Soc, Perkin Trans. I, 1587 (1982). 93. D. N. White, C. Morrow, R J. Cox, C. N. C. Drey, J. Lowbridge, J. Chem. Soc, Perkin Trans. II, 239 (1982). 94. C. N. C. Drey, R. J. Ridge, J. Chem. Soc, Perkin Trans. I, 2468 (1981). 95. C. N. C. Drey, J. Lowbridge, R. J. Ridge, J. Chem. Soc, Perkin Trans. I, 2001 (1973). 96. W. Ried, K. Marquardt, Ann. Chem., 642, 141 (1961). 97. H. Berenbold, W-H. Gundel, Ann. Chem., 532 (1978). 98. G. Heidemann, Encycl. Polym. Sci. Technol., 9, 485 (1968). 99. F. Voegtle, W. M. Miiller, Angew. Chem., 96, 711 (1984). 100. F. Behm, W. Simon, W M. Miiller, F. Voegtle, HeIv. Chim. Acta, 68, 940 (1985); F. Voegtle, H. Puff, E. Friedrichs, W. M. Miiller, J. Chem. Soc, Chem. Commun., 1398 (1982). 101. J. L. Van Winkle, J. D. McClure, R H. Williams, J. Org. Chem., 31, 3300 (1966). 102. L. Birkofer, I. Storch, Chem. Ber., 86, 749 (1953). 103. M. D. Slimmer, Chem. Ber., 35, 400 (1902). 104. L. Birkofer, J. Schramm, Ann. Chem., 2195 (1975). 105. R. Graf, Ann. Chem., 661, 111 (1963). 106. D. H. Johnson, J. Chem. Soc. C, 126 (1968). 107. E. Testa, L. Fontanella, Ann. Chem., 625, 95 (1959). 108. M. G. Northolt, L. E. Alexander, J. Phys. Chem., 72, 2838 (1968). 109. M. G. Northolt, Acta Cryst. B, 26, 240 (1970). 110. M. G. Northolt, L. E. Alexander, Acta Cryst. B, 27, 523 (1971). 111. G. Heidemann, H.-J. Nettelbeck, Faserforsch. Textiltechn., 18, 183 (1967).

112. H. Halboth, J. Polym. Sci. C, 729 (1969); H. Halboth, G. Rehage, Faserforsch. Textiltechn., 18, 177 (1967). 113. M. Rothe, A. Haberle, unpublished data. 114. M. Rothe, F. Wehowsky, unpublished data. 115. M. Rothe, W. Fischer, unpublished data. 116. M. Rothe, D. Miihlhausen, unpublished data. 117. M. Rothe, M. Lohmiiller, G. Schmidtberg, unpublished data. 118. M. Rothe, W. Helmling, unpublished data. 119. H. Bredereck, K. Bredereck, Chem. Ber., 94, 2278 (1961). 120. M. Rothe, M. Schlipf, unpublished data. 121. M. Rothe, D. Jacob, unpublished data. 122. M. Rothe, W. Muller, unpublished data. 123. R. P. Staiger, E. B. Miller, J. Org. Chem., 24, 1214 (1959). 124. S. Petersen, E. Tietze, Ann. Chem., 623, 166 (1959). 125. N. S. Dokunikhin, L. A. Galva, J. D. Kraft, Dokl. Akad. Nauk SSSR, 81, 1073 (1951). 126. F. C. Cooper, M. W. Partridge, J. Chem. Soc, 3429 (1954). 127. H. N. Rydon, N. H. P. Smith, D. Williams, J. Chem. Soc, 1900 (1957). 128. D. J. Williams, J. Chem. Soc, Chem. Commun., 170 (1977). 129. S. J. Edge, W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, J. Chem. Soc, Perkin Trans. I, 1701 (1982); S. J. Edge. W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, D. J. Williams, K. A, Woode, Tetrahedron Lett., 2229 (1981). 130. A. Hoorfar, W. D. Ollis, J. F. Stoddart, D. J. Williams, Tetrahedron Lett., 4211 (1980); A. Hoorfar, W. D. Ollis, J. F. Stoddart, J. Chem. Soc, Perkin Trans. I, 1721 (1982). 131. A. Hoorfar, W. D. Oills, J. A. Price, J. S. Stephanatou, J. F. Stoddart, J. Chem. Soc, Perkin Trans. I, 1649 (1982); W. D. Ollis, J. S. Stephanatou, J. F. Stoddart, A. G. Ferrige,

132.

133. 134. 135. 136. 137.

138. 139. 140. 141. 142. 143. 144. 145. 146. 147. 148. 149.

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8.2. OLIGO(PEPTIDES)

8.2.2. OLIGO(PEPTIDES) OF SARCOSINE

8.2.1. OLIGO(PEPTIDES) OF GLYCINE

8.2.2.1. Linear Oligo(peptides) H[N(CH3)CH2CO]nOH

8.2.1.1. Linear Oligo(peptides) H[NHCH2CO]nOH

n

n

MoL wt.

m.p. (0C)

1 2 3 4 5 6

75.1 132.1 189.2 246.2 303.3 360.3

233-236 210-215 235 240 270 >256d

Refs. 1 2,7,75 3,4,75 4,5,75 4,5,75,78 6

1 2

m.p. (0C)

MoI. wt. 89.1 160.2

211-213 190-191

Refs. 1 13,17,21

8.2.2.2. Cyclic Oligo(peptides) |— [N(CH3)CH2CO]^-I 8.2.1.2. Cyclic Oligo(peptides) [-[NHCH2CO]n-] n n 2 4 5 6 7 8 9 10 11

0

MoI. wt.

m.p. ( C)

114.1 228.2 285.3 342.3 399.4 456.4 513.5 570.5 627.6

309 340 >330 >360 >280 >350 290 290 300

MoI. wt.

m.p. (0C)

142.2 213.3 284.4 355.5 426.5 497.7 568.7 639.8 711.0 853.0

147 221 >350 255 315 296 338 >320

Refs.

Refs. 2,7,79,131,174,177,184 8,9,77,79,80,191,205,206 9,77-80,136 4,8,10,11,77,79,80,131 77,79,131 77,79,131,205 77,79,131 77,79,131 77,79,131

2 3 4 5 6 7 8 9 10 12

>320

13,27,51,61,177,187,191,204 51,191,192,197 51,166,191-195,198 51,191-193,199 17,51,163,166,191,193,200 51,191,193,201 51,191,193,196,202 17,163 193,203 17,163

8.2.3. OLIGO(PEPTIDES) OF L - A L A N I N E 8.2.3.1. Linear Oligo(peptides) H[NHCH(CH 3 )CO] nOH Specific rotation n

MoI. wt.

m.p. ( 0 C)

1 2 3 4 5 6 7

89.1 160.2 231.3 302.3 373.4 444.5 515.6

298 257-263 269-272 >320 >320 >320

8.2.3.2. Endgroup Protected Oligo(peptides)

[ai\D +14.5 -38.5 -85.7 -131.0 -150.0 -167.0

( 0 C)

c (%)

25 27 27 27 27 27

10 0.9 0.6 0.6 0.5 0.3

Solvent 6.0 N HCl 0.2 N HCl 0.2 N HCl 0.2 N HCl 0.2 N HCl 0.2 N HCl

Refs. 1 6,12,15,73,85,138,139 14,15,73,85,138,139 15,16,73,85,138,139 15,16,85,138 15,16,85,138 15

R-[NHCH(CH 3 )CO] n -R'

Specific rotation R'

n

MoI. wt.

m.p. ( 0 C)

BOC

OMe

Zb

OEt

2 3 4 5 6 7 2 3 4 5 6 7 10 2 3 4 5 6 7 8 9 3 4 5 6 7 3 5 6 7 8 9

274.3 345.4 416.5 487.6 558.6 629.7 322.4 393.4 464.5 535.6 606.7 677.8 891.0 363.4 434.5 505.6 576.7 647.7 718.8 789.9 861.0 419.5 490.6 561.6 632.7 703.8 460.5 602.7 673.8 744.9 816.0 887.1

110-111 193-194 >240d >240d >240d >240d 116 192 251-253 250 >275d >275d >250d 135-136 198-200 270-271 >275d >275d >275d >275d >275d 138-140 240-241 >250d >250d >250d 110-111 25Od >275d >275d >275d >275d

R

Mo

MEEA

OEt

Mo

[250 >250 95-96

L-VaI

3 4 5 6 7 2

429.5 528.7 627.8 726.9 826.1 330.4

119-120 207-208 220 220 220 166-167

3

429.5

170-171

4

528.7

247-248

5

627.8

>260

6

726.9

>260

7

826.1

>260

2 3 4 5 6 7 2 3 4 5 6 7 2 3 4 5 6 7 8 2

358.5 471.6 584.8 698.0 811.1 924.3 358.5 471.6 584.8 698.0 811.1 924.3 358.5 471.6 584.8 698.0 811.1 924.3 1037.5 358.5

63-64 146-147 214-215 >240 >240 >240 141-142 158-159 208-209 >250 >250 >250 158-159 193-194 245 >250d >250d >240d >240d 133-134

3

471.6

175-176

4

584.8

245

5

698.0

>250d

6

811.1

>250d

7 2 3 4 5 6 7 2

924.3 438.6 591.8 745.1 898.3 1051.5 1204.7 426.5

>250d 117-118 171-172 203-204 >240 >240 >240 121-122

3

573.7

173-174

L-NIe

L-Leu

L-IIe

D-alle

L-Cha

L-Phe

[a]r -23.12 -27.21

Solvent

Refs.

HFIP a HFIP a

-48.3 -40.8 -76.7 -77.4 -91.0 -107.5 -103.6 -126.2 -94.3 193.0 +37.8 -144.5 -3.88 -6.51 -6.42 -7.74 -7.26 -7.51 -46.9 -75.1 -92.6 -101.0 -111.1 -120.0 -44.0 -67.6 -83.4 -87.8 -93.9 +13.9 +24.6 +30.1 + 39.9 +48.1 + 58.3 +58.3 + 73.5

TFE* HFA6 TFE* HFA* TFE* HFA* TFE* HFA* TFE* HFA* TFE* HFA* HFIPC HFIPC HFIPC HFIPC HFIPC HFIPC HFA 235 >235 >235

[a]r

Solvent

-22.2 -16.1 -28.3 - 19.2 -25.0 -21.1 -22.1

Refs.

TFE' DMF' TFE' DMF' TFE' DMF' DMF'

102,107-109,111,112 102,107-109,111,112 102,108,109,111 102,108,109,111 108,109 108,109

a

A = 546nm; T = 200C; c = 5x W-4M; a[(7r/18O) rad x cm 2 /gl; HFIP = hexafluoroisopropanol. ^A = 589 nm; T = 25°C; c = 3 x 10 " 3 M (n = 2-6), 3 x 10 ~4 M (n = 7); TFE = trifluoroethanol; HFA = hexafluoroacetone sesquihydrate. c A = 589 nm; T = 22°C; c = 10 ~3 M; HFIP = hexafluoroisopropanol. ^A = 589 nm; T = 25°C; c = 3 x 10 ~3 M; HFA = hexafluoroacetone sesquihydrate. e A = 589 nm; T = 25°C; c = 0.025-0.2%; TFE = trifluoroethanol. ^A = 589 nm; T = 250C; c = 0.6%; TFE = trifluoroethanol. 8 X = 589 nm; T = 210C; c = 0.1%; hexafluoroacetone sesquihydrate. h A = 589 nm; T = 200C; c = 0.1-0.2%; HFIP = hexafluoroisopropanol. 'A = 589nm; Tin TFE = 23°C, in DMF= 18°C; c = 0.2%; TFE = trifluoroethanol.

8.2.5.3. Endgroup Protected Oligo(peptides) ofTryptophan X-[NHCHRCO]n-OCH3 Specific rotation R

X

n

MoI. wt.

m.p. ( 0 C)

2 3 1 2 3 4 5

538.5 721.8 276.3 428.4 580.6 732.7 884.9

196 85-95 108-109 153-154

151-154

[a]f?

c (%)

Solvent

-13

1

MeOH

-2.4 -47.6 -66.8 -65.6 -65.0

1.0 0.5 0.5 0.5 0.5

MeOH MeOH MeOH MeOH MeOH

Refs. 208,225 208 140 140 140 140 140

a

Z- = Benzyloxycarbonyl-.

8.2.5.4. Cyclic Oligo(peptides) ^ [ N H C H R C O ] ^ Specific rotation R

n

MoI. wt.

m.p. ( 0 C)

L-VaI

2

198.3

269-271

L-Leu

2

226.3

5 2 5 2 5 10 2

565.8 226.3 565.8 294.4 735.9 1471.8 372.4

L-IIe L-Phe

L-Trp

( 0 C)

c (%)

Solvent

-77.5

18-22

1.0

CH 3 COOH

207

277

-46.0

20

0.8

CH3COOH

22,25,177,184,185, 188,207

>300 308 357 315-316 250-254 251.5

-71 -60.0

15 18-22

1.0 1.0

EtOH CH3COOH

-100 -124.3 -142 -14.7

25-28 25 20 20

0.2 1.0 0.4

CH3COOH DMF MeOH CH3COOH

132 131,207 131 177,184,185,188 78 131 230,232

[a] D

Refs.

8.2.5.5. Endgroup Protected Oligo(Dipeptides)

R'[NHCHRiCO-NHCHR 2 CO] n -R"* Specific rotation

R''

Ri

R2

n

MoI. wt.

m.p. ( 0 C)

[a]|?

c (%)

Bocfl

OMe

D-VaI L-CH(CH3)2

L-VaI D-CH(CH3)2

Nps"

OEt

L-Leu -CH 2 CH(CH 3 ) 2

L-AIa -CH3

1 2 3 4 6 8 2 3 4 5 6 8

300.4 528.7 727.0 925.2 1321.8 1718.3 567.6 751.8 936.0 1120.2 1304.4 1672.8

110.7 209.6 232.7 261.1 d d 110-111 203-205 257-26Od >270d >270d >270d

-23.7 -17.8 -21.0 -8.9 -6.2 -11.4 -66.5 -96.9 -101.3 -84.6 -50.0 -52.6

1.02 1.00 1.02 1.00 1.12 1.05 2.0 2.0 2.0 2.0 2.0 2.0

R'

a

Solvent

Refs.

CHCl 3 118 CHCl 3 118 CHCl 3 118 CHCl 3 117,118 CHCl 3 118 CHCl 3 118 HFIP/TFE a (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119 HFIP/TFE (1:2) 119

Boc- — ten. butyloxycarbonyl-; Nps. = 0-nitrophenylsulfenyl-; HFIP = hexafluoroisopropanol; TFE = trifluoroethanol.

8.2.6. OLIGO(PEPTIDES) OF L - A N D D - P R O L I N E

8.2.6.1. Linear Oligo(all-L-peptides) n 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 25 28 30 31 34 37 40

n H[N-CHCO] n OH

MoI. wt.

m.p. ( 0 C)

115.2 212.3 309.4 406.5 503.6 600.7 697.8 794.9 892.0 989.1 1086.2 1183.3 1280.4 1377.5 1474.6 1571.7 1668.8 1765.9 1863.0 1960.1 2057.3 2154.5 2445.7 2737.0 2931.3 3028.5 3320.1 3611.4 3902.7

220-222 144-145 122 170 189 209 228 >280 >280 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300 >300

£ F -Vahies fl 1.00 0.84 0.72 0.60 0.52

1.00 0.91 0.77 0.72 0.66 0.60

1.00 0.92 0.83 0.75 0.70 0.64

1.00 0.95 0.90 0.84 100 0.93

1.00 0.93

1.00 0.92

1.00 0.95 0.93

1.00 0.94 0.90 0.86 0.81

1.00 0.93-530

1.00 0.94

[a]£°*

Refs.

-87 -175 -220 -293 -338 -376 -394 -412 -435 -456 -466 -472 -480 -491 -496 -499 -505 -509 -513 -520 -521 -523 -526 -528 -530 -532 70 -528 -532

1 52,62,69,70,150,171-173 53,62,69,70,150,171-173 62,69,70,150,171-173 62,69,70,150,172,173 62,69,70,150,172,173 62,69,70,150 62,69,70,150 62,69,150 62,69,70,150 62,69,70,150 62,69,70,150 69,70 69 62,69,70 69,70 69 69,70 69 69,70 70 70 70 70 70 70 70 70

a

Paper electrophoresis; buffer; HCOOH/CH3COOH/H2O (1:1:3), 1000-5000V, 40-115mA, 40-240min. *c(%)=l,H2O. 8.2.6.2. Endgroup Protected

Oligo(peptides) n

8.2.6.2.1.tert-BuTYLOXYCARBONYLOLIGO(ALL-L-PROLINES) (CH 3 ) 3 COCO—[N-CHCO] n -OH n 1 2 3 4

MoI. wt. 215.3 312.4 409.5 506.6

m.p. ( 0 C)

R%

[*]$"

Refs.

137-138 191-193 219-220 178

0.84 0.68 0.60 0.53

-105 -153.5 -173 -194

62,72,169,179 62,150,167,179,181 62,150,167,179 62,150,167

8.2.6.2.1. cont'd n

MoI. wt.

m.p. ( 0 C)

R%

5 6 7 8 9 10 11 12 15

603.7 700.8 797.9 894.0 991.1 1088.2 1185.3 1282.4 1573.7

225 247 267 >280 >280 >280 >300 >300 >300

0.47 0.41 0.37 0.33 0.29 0.25 0.23 0.22 0.22

a

[a] Jj**

Refs.

-220 -239 -247 -256 -265 -272 -269 -277 -291

62,150,167 62,150,167 62,150 62,150 62,150 62,150 62,150 62,150 62,150

TLC: solvent, fl-butanol/acetone/acetic acid/ammonia, 1:4/water (9:3:2:2:4). c (%) = 1, CHCl3.

b

8.2.6.2.2. ten-AMYLOXYCARBONYL

OLIGO(ALL-L-PROLINES)

Specific rotation n

MoI. wt.

1 2 3 4 5 6 8

229.3 326.4 423.5 520.6 617.7 714.8 908.0

m.p. ( 0 C)

[300d >310d >250d >280d >250d >250d

158,180,185,186 158 158,159 158 158 158 158

C (%)

Solvent

Refs.

0.5 0.48

H2O CH 3 OH

54,55,180,185 53,154-157,162,163,168,176,189,190

8.2.6.3.3. CYCLIC OLIGO(D,L,L-TRIPROLINES)

Specific rotation n

MoI. wt.

m.p. ( 0 C)

1 2 3 4 5

291.2 582.3 873.5 1164.6 1455.8

181-184 304 23Od 25Od 25Od

[a]|?

c (%)

Solvent

1 1 1 1 0.5

H2O H2O H2O H2O H2O

+70.7 -60.9 -114.5 -72.0 -101.8

Refs. 159-163 159-163 159-163 159-163 159-163

8.2.7. OLIGO(PEPTIDES) OF L - A Z E T I D I N E - 2 - C A R B O X Y L I C ACID I 8.2.7.1. Cyclic Oligo(peptides)

I

r[N-CHCO]nH

n

MoI. wt.

m.p. ( 0 C)

2 3 6

166.2 249.3 498.5

207-212 334-340 339-350

[a]f,78fl

Refs.

+8.2 +20.8 -352.0

175 175 175

«c(%) = 0.5, H 2 O.

8.2.8. OLIGO(PEPTIDES) OF L - H Y D R O X Y AND L-MERCAPTO AMINO ACIDS 8.2.8.1. Linear Oligo(peptides) H[NHCHRCO] n OH Specific rotation

L-Ser -CH 2 OH L-Tyr -CH 2 C 6 H 4 OH L-Cys -CH 2 SH1.5HC1 L-Met -CH 2 CH 2 SCH 3

n

MoI. wt.

1 2 1 2 3 1 2 1 2 3

105.1 192.2 181.2 344.4 507.6 121.1 224.2 149.2 280.4 411.6

m.p. ( 0 C)

285-288 181-182

229-231 219-220

[a] D

( 0 C)

c (%)

Solvent 0

+14.5 +14.2 -7.3 +30.1

25 25 25 19

9.3 7 4 4

NHCl NHCl 6.1 N HCl H 2 O + l e q . HCl

+7.6 +35 +23.4 +27.0 -70.0

26 22 20 24 16

12 1 5 2 1

NHCl 0.2 N HCl 3 N HCl H2O H2O

Refs. 1 28,35,139 1 29-31 31 1 37 1 32-34 33

8.2.8.2. Endgroup Protected Oligo(peptides) (CH 3 )3COCO-[NHCHRCO] n -OCH 3 Specific rotation R

n

MoI. wt.

m.p. ( 0 C)

L-Cys(Me) -CH 2 SCH 3

2 3 4 5 6 7 2 3 4 5 6 7

366.5 483.7 600.8 718.0 835.2 952.3 394.5 525.8 656.9 788.1 919.3 1050.5

94-95 104-105 191-192 211-212 >220 >220 66-67 92-96 191-194 236 d 245 d >275

L-Met -CH 2 CH 2 SCH 3

a

HFIP = hexafluoroisopropanol.

[a] D

-29.6 -37.6 -41.4 -48.1 -50.3 -54.8

c (%)

0.003 M 0.003 M 0.03M 0.003M 0.03M 0.03 M

Solvent*

HFIP a HFIP HFIP HFIP HHP HFIP

Refs. 102,121,122,133 102,121,122,133 102,121,122,133 102,121,122,133 102,121,122,133 102,121,122,133 102,123,124,127-129 102,123,124,127-129 102,123,124,127-129 102,123,124,127-129 102,123,124,126-129 102,123-129

8.2.8J.

Formyl-Oligo(L-Methionines)

HCO-[NHCHRCO]n-OH Specific rotation

R

n

m.p. (0C)

MoI. w t .

[58

8.2.9.3. ai-Oligo(peptides) of y-Unsubstituted L-Glutamic Acid Derivatives

c (%) 3 3 3

+ 2 9 4

3

Solvent

Refs.

MeOH MeOH MeOH

59 59 59

M e 0 H

59

CH 3 CO-[NHCH(CH 2 CH 2 COOH)CO] n -NHC 2 H 5

Specific rotation na

MoI. wt.

[a]|5

c (%)

Solvent

Ref.

1 2 3

216.2 345.4 474.3

-23 -36 -49.5

1 1 1

H2O H2O H2O

226 226 226

a

n = 2-12: ion-exchange chromatography, IR, CD, MS, pK values, Refs. 227,228.

8.2.9.4. 230

[a]f?

c (%)

Solvent 41

Ref.

-29.1 -31.2 -39.3 -34.9 -17.3

0.5-1.5 0.5-1.5 0.5-1.5 0.5-1.5 0.5-1.5

TFE TFE TFE TFE TFE

142 142 142 142 142

TFE, Trifluoroethanol

8.2.9.7. OL-Oligo(peptides) of o-Nitrophenylsulfenyl

L-Glutamic Acid Amides and Esters N p s f l - [ N H C H ( C H 2 C H 2 C O O C H 2 C 6 H 5 ) C O ] n - R Specific rotation

R

n

NHC 2 H 5

1 2 4 6 2 4 8 12

OCH 2 C 6 H 5

a

MoI. wt.

m.p. ( 0 C)

417.5 636.7 1075.2 1513.6 699.7 1138.1 2014.9 2891.7

92-93 147-148 180-182 233-234 65-67 114-115 198-205 236-238

[230 230-270

41 41 41

REFERENCES 1. W. Bachmann, H. T. Clarke, J. Am. Chem. Soc, 49, 2089 (1927). 2. C. F. H. Allen, F. P. Pingert, J. Am. Chem. Soc, 64, 1365 (1942). 3. J. A. Cade, A. Pilbeam, Tetrahedron, 20,519 (1964); J. Chem. Soc, 114(1964). 4. W. S. Rapson, R. G. Shuttleworth, J. N. van Niekerk, J. Chem. Soc, 326 (1943). 5. G. Wittig, G. Lehmann, Chem. Ber., 90,875 (1957); G. Wittig, G. Klar, Ann. Chem., 704, 91 (1967). 6. S. T. Bowden, J. Chem. Soc, 1111 (1931). 7. W. Baker, M. P. V. Boarland, J. F. W. McOmie, J. Chem. Soc, 1476 (1954). 8. W. C. Lothrop, J. Am. Chem. Soc, 63, 1187 (1941). 9. G. Wittig, W. Herwig, Chem. Ber., 87, 1511 (1954). 10. C. Mannich, Chem. Ber., 40, 159 (1907). 11. P G . Copeland, R. E. Dean, D. McNeil, J. Chem. Soc, 1689 (1960). 12. M. Busch, W. Weber, J. Prakt. Chem., 146, 1 (1936). 13. A. E. Gillam, D. H. Hey, J. Chem. Soc, 1170 (1939); H. France, I. M. Heilbron, D. H. Hey, J. Chem. Soc, 1288 (1939); 1364 (1938). 14. G. F. Woods, J. W. Tucker, J. Am. Chem. Soc, 70, 2174 (1948). 15. R. L. Alexander, Jr., J. Org. Chem., 21, 1464 (1956). 16. G. F. Woods, F. T. Reed, J. Am. Chem. Soc, 71, 1348 (1949). 17. M. Bennett, N. B. Sunshine, G. F. Woods, J. Org. Chem., 28, 2514 (1963); W. Davey, D. H. Maass, J. Chem. Soc, 4386 (1963).

18. L. Silverman, W. Houk, Anal. Chem., 27, 1956 (1955). 19. H. A. Staab, F. Binnig, Tetrahedron Lett., 319 (1964); Chem. Ber., 100, 293 (1967); H. Braunling, F. Binnig, H. A. Staab, ibid., 100, 880 (1967). 20. F. Ullmann, G. M. Meyer, O. Loewenthal, E. Gilli, Ann. Chem., 332, 38 (1904). 21. E. Mueller, T. Toepel, Chem. Ber., 72, 273 (1939). 22. G. F. Woods, A. L. Van Artsdale, F. T. Reed, J. Am. Chem. Soc, 72, 3221 (1950). 23. E. A. Johnson, J. Chem. Soc, 4155 (1957). 24. E. Clar, "Polycyclic Hydrocarbons", Academic, New York, Springer, Berlin, 1964. 25. O. Gerngross, M. Dunkel, Chem. Ber., 57, 739 (1924); O. Gerngross, C. Schachnow, R. Jonas, Chem. Ber., 57, 747 (1954). 26. H. O. Wirth, K. H. Goenner, W. Kern, Makromol. Chem., 63, 53 (1963). 27. H. O. Wirth, K. H. Goenner, R. Stueck, W. Kern, Makromol. Chem., 63, 30 (1963). 28. T. W. Campbell, R. N. McDonald, J. Org. Chem., 24, 730 (1959). 29. P. Kovacic, R. M. Lange, J. Org. Chem., 29, 2416 (1964). 30. T. Nozaki, M. Tamura, Y. Harada, K. Saito, Bull. Chem. Soc Japan, 33, 1329 (1960). 31. R. Pummerer, K. Bittner, Chem. Ber., 57, 84 (1924); R. Pummerer, L. Seligsberger, Chem. Ber., 64, 2477 (1931). 32. F. Mayer, K. Freitag, Chem. Ber., 54, 347 (1921). 33. H. O. Wirth, H. Hefner, W. Kern, unpublished results. 34. H. O. Wirth, F. U. Herrmann, W. Kern, Makromol. Chem., 80, 120 (1964).

35. E. Marcus, W. M. Lauer, R. T. Arnold, J. Am. Chem. Soc, 80, 3742 (1958). 36. D. M. Hall, M. S. Lesslie, E. E. Turner, J. Chem. Soc, 711 (1950). 37. W. Kern, M. Seibel, H. O. Wirth, Makromol. Chem., 29, 164 (1959). 38. W. Schlenk, M. Brauns, Chem. Ber., 48, 661 (1914). 39. W. Kern, W. Gruber, H. O. Wirth, Makromol. Chem., 37, 198 (1960).

40. W. Heitz, R. Ullrich, W. Kern, Makromol. Chem., 98, 29 (1966). 41. H. Erdtmann, M. Granath, G. Schultz, Acta Chem. Scand., 8, 1442 (1954). 42. N. Kornblum, Org. Syn. Coll. Vol. Ill, 295 (1962). 43. W. Kern, H. W. Ebersbach, I. Ziegler, Makromol. Chem., 31, 154 (1959).

E. OLrGOMERS CONTAINING HETEROCYCLIC RINGS IN THE MAIN CHAIN

TABLE 22. 22.1.

HETEROCYCLIC OLIGOMERS

OLIGO(FURAN)DERIVATIVES

22.1.1. OLIGO(FURFURYL) ALCOHOLS

n 1 2 3

m.p. (0C)

MoL wt. 98.1 178.2 258.3

-2.5 62-62.5

b.p. (°C/mbar)

nj?

171/1000 141-143/12 192.5-295/8

1.4868 1.5290

Refs. 10,11 10-12,14 10-12,14

22.1.2. OLIGO(FURFURYL) FURANS Ri

R2

n

MoI. wt.

H

H

1 2 3 4 1 2 3 1 2 3 4 5 1 2 3 1 2 3 1 2

148.2 228.2 308.3 388.4 162.2 256.3 350.4 176.2 284.3 392.5 500.6 608.7 190.2 312.4 434.6 204.3 340.4 476.6 216.3 364.5

H

CH3

CH3

CH3

CH3

C2H5

C2H5

C2H5

m.p. (0C)

b.p. (°C/mbar)

df (g/cm3)

nf

78/16 141-146/11

1.102

1.5048 1.5324

91/28 114-116/0.13 165-168/0.04 73-76/7-8 120-123/1.3 163-167/1.3

1.073

1.4993

1.043

1.4966

1.030

1.5172

1.033 1.045 1.046 1.023 1.028 1.034

1.4970 1.5094 1.5173 1.4978 1.5089 1.5199

1.018

1.5221

74-75 99-101

-12 47.0/47.5 Oil 83-85

-9 to-8 13-17 86.8-87.6

68-70/3 143-145/1.3 205-210/1.3 76-77/3 162-163/2 212-215/2 94-95/2 200-205/2

Refs. 10,12,14-15,39 10,12 10,12,14 10,14 16,17 17 16,17 17,18 17,18 17,18 17 17 18 19 19 20 20 20 21 21

22.1.4. FURANOPHANES R' H H CH 3 CH 3 CH 3 C2H5 H

R"

n

CH 3 4 r-2,c-7,c-12,c-17C2H5 4 r-2,c-7,c-12,c-17CH 3 4 CH 3 5 6 C2H5 4 C2H5 4 4

22.1.5. TETRAHYDROFURANOPHANES MoL wt.

m.p. (0C)

376.4

140-142 191.0-192.0 83-88 152.0-153.0 243 Oil 182 174 249-250 268-269

432.5 432.5 540.7 648.8 488.5 544.7 592.8

Refs.

n

16,17,22 22 22 22 18,23,24 17 17,18,24 18,19,22,24 18,20,24 21,24

4

m.p. (0C)

MoI. wt.

448.7 204-209 r-(lS, 3S, 6R, 8S, HR, 13R, 16S, 18R)- 218 r-(lS, 3R, 6S, 8R, HS, 13R, 16S, 18R)- 221 5 560.8 Oil 6 673.0 75-80

Refs. 17,18,20,21,23 25 25 17 17

22.2. OLIGO(THIOPHENE) DERIVATIVES 22.2.1. OLIGO(2.5-THIENYLENES) n

MoI. wt.

m.p. (0C)

b.p. (°C/mbar)

n™

1 2 3 4 5 6 7 8

84.1 166.3 248.4 330.5 412.5 494.8 576.9 659.0

-38.4 33-34 96-97 215-216 257-258 304-305 327-328 364

84.2/1013 125/16

1.5289

22.3.

Refs. 1,27,28,34,41,42,44,49 1,3,26,28,30-33,42,44,47,49 1,3,27-29,41,42,44,46,49 1,3,28,29,42,48 3,27,28,42,44,46 3,29,48 42,46

OLIGO(PYRROLE) DERIVATIVES

22.3.1. OLIGO(PYRROLE) DERIVATIVES

n

MoI. wt.

m.p. (0C)

1

2

214.3

105-106

2

2

174.2

59

3

4 4

428.6 588.8

291 272.0-272.5

No.

Oligomers

R

22.3.2. OLIGO[2,5-(N-METHYL)PYRROLENES]

b.p. (°C/mbar)

Refs. 21,43

125-126/4

35

36,37 21

22.4. OLIGO(PYRIDINE) DERIVATIVES 22.4.1. OLIGO(2,6-PYRIDYLENES)

n

MoI. wt.

1 2 4 5 6 8 16

81.1 160.2 318.4 397.5 476.6 634.8 1267.6

0

m.p. ( C) 14-15 134 145 160 178-182 240-256

b.p. (°C/mbar) 114-115/99.6 77-78/0.5

Refs. 13,42 42 42 42 42 42

n

MoI. wt. m.p. (0C)

1 2 3 4 5 6

79.1 156.2 233.3 310.4 387.5 464.5

-42 70.1 89-90 219-220 265 350

b.p. (°C/mbar)

n$

115.5/1013 273-275/1013 370/1013

1.5095

Refs. 4,5 2,4-6 5 5 5

22.4.2. OLIGO(3,5-PYRIDYLENES)

0

n

MoI. wt.

m.p. ( C)

b.p. (°C/mbar)

nf

1 2 3

79.1 156.2 233.3

-42 68 249-251

115.5 291-292/981

1.5095

3

264.2

233

42,45

4

328.5

255-256

42,45

5

492.7

420

42,45

6

328.5

300-301

42,45

7

528.7

410

45

8

312.3

355-360

45

Refs.

4,9 9

22.4.3. OLIGO(2,6-QUINOLYLENES)

n

MoI. wt.

m.p. (0C)

1 2 3 4

129.2 256.3 383.5 510.6

-15.6 144 267-269 348-350

b.p. (°C/mbar)

nj?

238.1/1013

Refs.

1.6268 7,8 8 8

22.5. CYCLIC OLIGO(HETEROCYCLICS) No.

MoI. wt.

m.p. (0C)

Refs.

1

188.2

189-190

38

2

220.3

194.5-196

38

REFERENCES

1. J. W. Sease, L. Zechmeister, J. Am. Chem. Soc, 69, 270 (1947). 2. Th. Kauffmann, J. Konig, A. Woltermann, Chem. Ber., 109, 3864 (1976). 3. W. Steinkopff, R. Leitsmann, K. H. Hoffmann, Ann. Chem., 546, 180 (1941). 4. G. T. Morgan, F. H. Burstall, J. Chem. Soc, 20 (1932). 5. F. H. Burstall, J. Chem. Soc, 1662 (1938). 6. F. H. Case, W. H. Butte, J. Org. Chem., 26, 4415 (1961). 7. H. Weidel, Monatsh. Chem., 8, 120, 141 (1887). 8. S. G. Waley, J. Chem. Soc, 2008 (1948). 9. M. Busch, W. Weber, J. Prakt. Chem., 146, 1 (1936). 10. J. T. Barr, S. B. Wallon, J. Appl. Polym. ScL, 15,1079 (1971). 11. A. R Dunlop, F. N. Peters, Ind. Eng. Chem., 34, 814 (1942). 12. A. H. Fawcett, W. Dadamba, Makromol. Chem., 183, 2799 (1982). 13. J. Gj0s, S. Gronowitz, Acta Chem. Scand., 25, 2596 (1971). 14. K. Takano, Nippon Kagaku Zasski, 79, 955 (1958); Chem. Abstr., 54,453Oe (1960); ibid., 80, 313 (1959); Chem. Abstr., 55, 5453g (1961).

15. H. Gilman, G. F. Wright, J. Am. Chem. Soc, 55, 3302 (1933). 16. W. H. Brown, H. Sanatzky, Can. J. Chem., 34, 1147 (1956). 17. Y. Kobuke, K. Hanji, K. Horiguchi, M. Asada, Y. Nakayama, J. Furukawa, J. Am. Chem. Soc, 98, 7414 (1976). 18. R. G. Ackman, W. H. Brown, G. F. Wright, J. Org. Chem., 20, 1147(1955). 19. W. H. Brown, W. N. French, Can. J. Chem., 36, 537 (1958). 20. R. E. Beals, W. H. Brown, J. Org. Chem., 21, 447 (1956). 21. W. H. Brown, B. J. Hutchinson, M. H. MacKinnon, Can. J. Chem., 49, 4017 (1971). 22. A. G. S. Hogberg, M. Weber, Acta Chem. Scand. B, 37, 55 (1983). 23. M. Chastrette, F. Chastrette, J. Sabadie, Org. Synth., 57, 74 (1977). 24. M. De Sousa Healy, A. J. Rest, J. Chem. Soc, Chem. Commun., 149 (1981); J. Chem. Soc, Perkin Trans. I, 973 (1985). 25. M. Van Beylen, B. Roland, G. S. D. King, J. Aerts, J. Chem. Res. (S), 388 (1985); (M), 4201 (1985). 26. J. Kagan, S. K. Arora, Heterocycles, 20, 1941 (1983). 27. J. Kagan, S. K. Arora, Heterocycles, 20, 1937 (1983). 28. J. Kagan, S. K. Arora, Tetrahedron Lett., 24, 4043 (1983).

29. J. Kagan, S. K. Arora, J. Org. Chem., 48, 4317 (1983). 30. K. E. Schulte, J. Reisch, L. Homer, Chem. Ber., 95, 1943 (1962). 31. H. J. Kooreman, H. Wynberg, Rec. Trav. Chim. Pays-Bas, 86, 37 (1967). 32. T. Asano, S. Ito, N. Saito, K. Hatakeda, Heterocycles, 6, 317 (1977). 33. J.-P. Beny, S. N. Dhawan, J. Kagan, S. Sundless, J. Org. Chem., 47, 2201 (1982). 34. J.-P. Morizur, Bull. Soc. Chim. France, 1331 (1964); J.-P. Morizur, C. R., Ser. C, 254, 1093 (1962). 35. W. H. Brown, W. N. French, Can. J. Chem., 36, 371 (1958). 36. A. V. Baeyer, Chem. Ber., 19, 2184 (1886). 37. V. V. Chelintzev, B. V. Tronov, S. G. Karmanov, J. Russ. Phys. Chem., 48, 1210 (1916); Chem. Abstr. 11, 1418 (1917). 38. H. E. Winberg, F. S. Fawcett, W. E. Mochel, C. W. Theobald, J. Am. Chem. Soc, 82, 1428 (1960). 39. T. Reichstein, A. Griissner, H. Zschokke, HeIv. Chim. Acta, 15, 1066 (1932). 40. R. Grigg, J. A. Knight, M. V. Sargent, J. Chem. Soc. C, 976 (1966).

41. R. E. Atkinson, R. F. Curtis, G. T. Phillips, J. Chem. Soc. C, 2011 (1967). 42. Th. Kauffmann, Angew. Chem., 91, 1 (1979). Angew. Chem., Int. Ed. Engl., 18, 1 (1979). 43. D. Dolphin, R. Grigg, M. V. Sargent, D. H. Williams, J. A. Knight, Tetrahedron, 21, 3441 (1965). 44. D. D. Cunningham, L. Laguren-Davidson, H. B. Mark Jr., Ch. V. Pham, H. Zimmer, J. Chem. Soc, Chem. Commun., 1021 (1987). 45. Th. Kauffmann, B. Greving, R. Kriegesmann, A. Mitschker, A. Woltermann, Chem. Ber., I l l , 1330 (1978). 46. J. Nakayama, T. Konishi, S. Murabayashi, M. Hoshino, Heterocycles, 26, 1793 (1987). 47. J. Nakayama, Y. Nakamura, T. Tajiri, M. Hoshino, Heterocycles, 24, 637 (1986). 48. J. Nakayama, Y. Nakamura, S. Murabayashi, M. Hoshino, Heterocycles, 26, 939 (1987). 49. K. Tamao, S. Kodama, I. Nakajima, M. Kumada, A. Minato, K. Suzuki, Tetrahedron, 38, 3347 (1982).

TABLE 23. OLIGCKSACCHARIDES) 23.2. OLIGOMERIC HEXOSES 23.1. OLIGOMERIC PENTOSES 23.1.1. OLIGO(p-XYLOPYRANOSES)fl 23.2.1. MALTO-OLIGOfl

0

/I

MoI. wt.

m.p. ( C)

[a]|?inH 2 O

1 2 3 4 5 6 7

150.1 282.2 414.4 546.5 678.6 810.7 942.8

153 186-187 215-216 224-226 240-242 237-242 240-242

19.2 -25.6 -48.1 -61.9 -72.9 -78.5 -74.0

n

MoI. wt.

m.p. (0C)

1 2 3 4 5 6 7

180.2 342.3 504.4 666.6 828.7 990.9 1153.0

146 160-165

a

[a]£f in H 2 O 52.6 136.0 160.0 177.0 180.3 184.7 186.4

Refs. 4-6.

"Refs. 1-3.

23.1.2. OLIGO(p-XYLOPYRANOSE ACETATES)0

23.2.2. CYCLODEXTRINSa n

MoI. wt.

m.p. (0C)

[a] Jf

2 3 4 5 6

534.5 750.7 966.9 1183.1 1399.3

155.5-156 109-110 201-202 249-250 260-261

-74.5 -84.3 -93.7 -97.5 -102.0

fl

Refs. 1-3.

c in CHCl 3 0.9 0.6 0.8 1.1 1.5

n

MoI. wt.

6 7 8

972.8 1135.0 1297.1

a

Refs. 4-6.

[a] D (c = l, H 2 O) 149.0 158.8 170.0

23.2.6. GENTIO-OLIGOSES0

23.2.3. CELLO-OLIGOSES0

n

MoL wt.

m.p. (0C)

[