Refluxing 124.1 g. saligenin in 400 cc. EtOH with 40 g. NaOH in 50 cc. H2O 30 min., adding dropwise 80.5 g. ethylenechlorohydrin, refluxing 3 hrs. longer, filtering, evaporating the EtOH, pouring the residue into 200 cc. H2O, extracting with Et2O, washing the extract with 2% NaOH, drying, evaporating, and distilling at 175-80°/3 mm. gave 115 g. o-(2-hydroxyethoxy)benzyl alc. (I), n25D 1.5535.By the same method propylene chlorohydrin gave 76% o-(2-hydroxypropoxy)benzyl alc. (II), b1.5 170-4°, n25D 1.5418.Adding to 112.1 g. I in 107 g. pyridine and 200 cc. CHCl3 cooled with ice with stirring dropwise 160 g. SOCl2, stirring while allowing the temperature to rise, heating, cooling, pouring into 200 cc. H2O, washing the CHCl3 layer with dilute NaOH, drying, evaporating at 50°, and fractionating in vacuo gave 110 g. o-(2-chloroethoxy)benzyl chloride (III), b1 125-7°.By the same method 121 g. II gave 124 g. o-(2-chloropropoxy)benzyl chloride (IV), b2 125-6°.Dropping 100 cc. 40% MeNH2 solution on 50 g. NaOH pellets, drying the gas with CaCl2, passing it into 100 cc. EtOH at -20°, adding to this at low temperature 41 g. III in 75 cc. EtOH, stirring 1 hr., letting warm to room temperature, keeping another hr. during which an exothermic reaction set in, cooling with water, stirring some hrs. longer, filtering off the crystals of MeNH3Cl, diluting the filtrate with 300 cc. water, separating the oily matter, and washing gave 11 g. methyltris[o-(2-chloroethoxy)benzylammonium chloride (V), m. 170° (H2O).Diluting the filtrate, extracting with Et2O, extracting the Et2O with dilute HCl, adding NaOH, extracting with Et2O, filtering, drying, and evaporating gave an oil, crystallizing during evaporation of the traces of EtOH present to give 26 g. methyl-o-(2-chloroethoxy)benzyl-2,3,4,5-tetrahydro-1,4-benzoxazepinium chloride (VI), m. 122-3° (Me2CO-EtOH, C).Treating 44 g. IV with MeNH2 gave 60% methyltris[o-(2-chloropropoxy)benzyl]ammonium chloride, m. 163-4° (washed with Et2O).No analog of VI was obtained.Dropping into 160 cc. 40% MeNH2 in H2O and 160 cc. Et2O cooled to -15° with stirring 41 g. III, allowing to warm to room temperature, stirring 3 hrs. longer, filtering, separating the Et2O layer, washing, extracting with dilute HCl, adding NaOH with cooling, extracting with Et2O, washing, drying, and evaporating at 40° gave 36 g. crude methyl-o-(2-chloroethoxy)benzylamine (VII).The same method gave from 44 g. IV 40 g. impure Pr analog of VII.Refluxing 30 g. VIII mixed with 11 g. K2CO3 in 40 cc. EtOH 1 hr., evaporating the solvent, dissolving the residue in dilute HCl alkalizing with NaOH, extracting with Et2O by decantation, drying, and fractionating in vacuo gave 3 g. 4-methyl-2,3,4,5-tetrahydro-1,4-benzoxazepine (VIII), b5 104-5°, n25D 1.5422.Heating 32.2 g. Pr analog of VII with 11 g. K2CO3 2 hrs. at 175° and continuing as described for VIII gave 5 g. 3,4-dimethyl-2,3,4,5-tetrahydro-1,4-benzoxazepine (IX), b2 104-11°, n25D 1.5390.Passing HCl gas through 1 g. VIII in 5 cc. EtOH with cooling gave 1 g. VIII.HCl, m. 190° (Me2CO-EtOH).IX (1 g.) gave 0.8 g. IX.HCl, m. 209-10° (Me2CO).VIII.HBr m. 182° (EtOH); VIII picrate m. 154-5°.Passing through 0.5 g. VIII in 5 cc. Et2O a stream of MeBr gave an oil which crystallized on standing to give 0.6 g. 4,4-dimethyl-2,3,4,5-tetrahydro-1,4-benzoxazepinium bromide, m. 170-1° (after rubbing with Et2O); the iodide, prepared by mixing VIII with MeI in Et2O, m. 209°.IX gave 3,4,4-trimethyl-2,3,4,5-tetrahydro-1,4-beuzoxazepinium iodide, m. 224-6°.Dropping into 62 g. saligenin and 20 g. NaOH in 200 cc. Me2CO 62 g. Me2NCH2CH2Cl, refluxing 2 hrs., filtering, concentrating the filtrate, dissolving in Et2O, washing with dilute NaOH, drying, evaporating, and distilling gave 50 g. o-(2-dimethylaminoethoxy)benzyl alc., b2 152°, n25D 1.5282.Adding to 39 g. of this alc. in 150 cc. cooled CHCl3 during 30 min. 24 g. SOCl2, refluxing some hrs., and evaporating gave 30 g. o-(2-dimethylaminoethoxy)benzyl chloride-HCl (X), m. 137-9° (Me2CO-EtOH).Alkalizing 12 g. X in 50 cc. H2O, refrigerating, mixing with 100 cc. Et2O, adding dilute NaOH, extracting the aqueous layer with Et2O, combining with the organic layer, drying, evaporating, adding Me2CO, and evaporating to dryness gave 1.25 g. 4,4-dimethyl-2,3,4,5-tetrahydro-1,4-benzoxazepinium chloride (XI), m. 198-200° (decomposition) (Me2CO-EtOH).Aqueous 25% Me2NH (100 cc.), 100 cc. Et2O, and 10.3 g. III gave at 0° an oily residue which heated 10 min. with EtOH, evaporated to dryness, and rubbed with Et2O gave 2.5 g. XI and 2 g. more from the mother liquors.Melting 2.1 g. XI 10 min. and distilling at 103°/5 mm. gave 0.9 g. VIII.Dropping 205 g. III into 17 g. piperidine in 100 cc. EtOH, keeping 1 hr. at 60°, keeping 1 day at room temperature, pouring into water, extracting with Et2O, and evaporating at 50° gave 24 g. N-[o-(2-chloroethoxy)benzyl] piperidine (XII), used without purification.By the same method, 17.5 g. morpholine gave 24 g. crude N-[o-(2-chloroethoxy)benzyl]morpholine (XIII).Dropping on 37.2 g. saligenin in 300 cc. Me2CO and 12 g. NaOH slowly 59.5 g. N-(2-chloroethyl)piperidine, refluxing hrs., filtering while hot, and evaporating gave 60 g. o-(2-piperidinoethoxy)benzyl alc. (XIV), m. 83-4° (Me2CO-H2O).Adding to 6.9 g. Na dissolved in 200 cc. MeOH 37.2 g. saligenin and then 44.8 g. N-(2-chloroethyl)morpholine, refluxing 5 hrs., concentrating cooling, extracting with Et2O, washing the extract with dilute NaOH, drying, and evaporating to dryness gave 61 g. o-(2-morpholinoethoxy)benzyl alc. (XV), m. 78° (CHCl3).Treating 47 g. XIV with SOCl2 as above gave 40 g. o-(2-piperidinoethoxy)benzyl chloride-HCl (XVI), m. 161-2° (EtOH).XV (47.5 g.) in CHCl3 gave by the same procedure 46 g. o-(2-morpholinoethoxy)benzyl chloride-HCl (XVI), m. 162 (EtOH).Passing a stream of HBr through 29 g. XVI in Et2O gave on standing a solid, giving on rubbing with Me2CO 20 g. 2,3,4,5-tetrahydro-1,4-benzoxazepine-4,1'-spiropiperidinium chloride (XVIII), m. 224-5°.Heating XII with 20 cc. iso-PrOH at 100° gave on evaporation a dark oil which solidified and then treated with Me2CO gave 13 g. XVIII.By the same methods 29.2 g. XVII gave 19 g. 2,3,4,5-tetrahydro-1,4-benzoxazepine-1,4'-spiromorpholine (XIX) (puffing up at 130-40°, decomposing 155-60°) and heating XIII with 20 cc. PhNO2 to boiling and washing the precipitate formed gave 14 g. XIX.Dropping into 61.5 g. III in 60 cc. EtOH with stirring 34.5 g. allylamine, cooling to keep the temperature below 50°, keeping 2 hrs., and extracting the solid with Et2O or C6H6 gave 60.5 g. o-(2-chloroethoxy)benzylallylamine (XX).An analogous procedure gave 96% o-(2-chloropropoxy)benzylallylamine(XXI).Heating without a solvent 14 g. K2CO3 and 46 g. XX 3 hrs. at 130-40°, dissolving in H2O, extracting with Et2O, treating the extract with dilute HCl, decanting, alkalizing, extracting with Et2O, drying, evaporating, and fractionating gave at 105-8°/1 mm. 8.5 g. N-allyl-2,3,4,5-tetrahydro-1,4-benzoxazepine (XXII).XXI (48 g.) gave by the same procedure 7.5 g. 3-methyl-4-allyl-2,3,4,5-tetrahydro-1,4-benzoxazepine (XXIII), b6-7 150-60°.XXII (2 g.) in EtOH gave with HCl in EtOH 2.1 g. XXII.HCl, m. 197°; XXIII.HCl m. 105-8°; XXII.HBr m. 153-6°; XXII picrate m. 137°.