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1、ch3oh的结构rch2oh + narch2ona + 1/2h2(ch3)3coh + k(ch3)3cok + 1/2h2作碱性试剂或亲核试剂作消除反应试剂roh + h2oro- + h3o+6(ch3)2choh + 2al2(ch3)2cho al + 3h23hgcl2ch3oh ch3ch2oh (ch3)2choh (ch3)3cohpka 15.9 16.0 18.0 19.0clch2ch2oh cl3cch2oh hoch2ch2oh hoch2chohch2ohpka 14.5 12.2 14.2 14.1醇的 碳上所连的支链越少,酸性越强多元醇及有较强吸电子基存在,
2、酸性增强rona + h2oroh + naoh介绍乙醇钠的工业制备1o醇 2o醇 3o醇nc4h9oh + h2so4nc4h9oh2so4h+_c2h5oh + bf3c2h5oh+bf3_r oh + hxr x + h2o 醇活性顺序:3o 2o 1o ch3ohhx活性:hi hbr hclhi 酸是强酸,较易反应,不用其它催化剂; hbr较hi弱,需用浓h2so4增强酸性;hcl酸性更弱,需用zncl2作催化剂。3o 醇 、烯丙醇、苄醇 室温下反应液立即混浊、分层; 2o醇 2 5 min. 反应液混浊、分层; 1o醇 加热,反应液混浊、分层;roh + hclrcl + h2ox
3、-cch3ch3ch3oh + hxch3cch3ch3oh2+ch3c+ch3ch3ch3cch3ch3xrohh+roh2+roh2 x r + h2oxx-ch3c-chch3ch3ohhhclch3c-chch3ch3oh2h+-h2och3c-chch3ch3h+重排ch3c-ch2ch3ch3+cl-cl-ch3c-ch2ch3clch3ch3c-chch3ch3h cl3 (ch3)2chch2ohpbr33(ch3)2chch2br + h3po3特点:sn2反应,没有重排。ch3ch2ch2ch2oh + socl2-hclch3ch2ch2ch2osclo-so2ch3ch
4、2ch2ch2clroh + socl2rcl + so2 + hcl rch2oh + br pbr2 rch2opbr2 + hbrbr- + rch2opbr2sn2rch2br + -opbr2ch3ch2cch3ch3oh48%h2so490occh3ch=c(ch3)2+ ch3ch2c=ch2ch384% ohhcch+oh2hcc+-h2ohcc+-h+ccch2ohh+170oc?ch2ohh+ch2oh2+ch2-h2o+重排h+-h+ch2ohh+ch2oh2+ch2-h2o+重排h+-h+al2o3350occh2ohch2ch3chohch3h+ch3choh2ch3
5、+-h2och3ch+ch3ch3chohch3ch3chochch3ch3ch3h+-h+ch3chochch3ch3ch3h+(ch3)3coh(ch3)3coh2-h2o(ch3)3c+ch3ch2oh+(ch3)3coch2ch3h-h+(ch3)3coch2ch3(ar)rona + rxsn2(ar)ror + nax (混合醚)(ch3)3coch2ch3a. (ch3)3cx + ch3ch2onab. (ch3)3cona + ch3ch2xoch2ch3ona + ch3ch2xch3ch2ona + xa.b.cccl ohoh-ccoccocc+ rco3h1). km
6、no4 (h+or oh-)、na2cr2o7-h2so4 、hno31o醇 rch2ohorchoorcooh2o醇 rchohrorc=or3o醇 rcohrro不易被氧化c=c-ch2ohmno2c=c-cho c=c-chohrmno2c=c-c=orhoch2ch2ch=chch2ohmno2hoch2ch2ch=chchoch2ohchocro32c5h5nooohcro32c5h5nooo 1o醇 2o醇 3o醇 cro3-h2so4无反应(3o醇) 橙色变为蓝绿色(1o、2o醇)ch2 ch ch ch2ohohohoh3hio42hcho + 2 hcoohch2ch2nh2
7、oh hio42hcho ch3 c c ch3o ohio42ch3coohch3 c c ch3h3c ch3 ho ohh2so4ch3 c c ch3 ch3 h3c o四甲基乙二醇 (pinacol) 频哪酮 (pinacolone) ch3 c c ch3h3c ch3 ho ohh+ch3 c c ch3h3c ch3 ho +oh2-h2och3 c c ch3h3c ch3+oh重排ch3 c c ch3 ch3 ho ch3+-h+ch3 c c ch3 ch3 o ch3 c c ch3 ho ohch3h+-h2o c c ch3ch3oh+重排-h+ c c ch3
8、h3c o c c ho ohch3h+-h2o+h3c c c ch3h3coh重排-h+ och3 ch3ccc6h5h5c6kmno4(冷)oh-h+abbaphphhohophphoo-oooo_h2co3 h2o rohohpka 5 6.4 10.0 15.7 1619rcoohona+ co2+h2ooh+naco3o_o_g(吸电子基)g(给电子基)电荷分散, 负离子稳定化电荷集中, 负离子去稳定化ohohch3ohclohno2pka 10.0 10.26 9.38 7.15 ohch3ccloor(ch3co)2oococh3+ hcl (ch3cooh)ococh3alc
9、l325oc165ochococh3ohcoch3ocohch3oh+ ch3ch2brnaohh2ooch2ch3 + nabrohclcl+ clch2cooh30%naohreflux 45 h.och2coonaclclh3o+och2coohclclohnaohh2ooch3 + + ch3osoch3ooch3oso-na+oo200ococh2ch=ch2ohch2ch=ch2*oo*ohch2ch=ch2互变异构ohch2ch=ch2*oh br2h2oohbrbrbrbr2cs2ohbroh+ chcl310%naohohchoohcho+香兰素香兰素ohoch3+ chcl
10、3naohohoch3ohcohchooch3+h2oorohhchoohch2ohohch2ohoh + ch3coch32h+cch3ch3ohho-h2ooohooohohooooo+ 2h+ + 2e-ohoho-o-h-oh-o电荷转移络合物电荷转移络合物oonh2ohnohnoh2br2oobrbrbrbr 2 kcnohohcncnoocncnclcl1)hno32)hcl1)hno32)hcl2ooh+3)hno3+ch2chch3h2so4chch3ch3ocoohch3ch3h2so4oh+ch3cch3oso3na+naoh300-320onah+ohc cl lo on
11、 na ao oh hn na ao oh h( (6 6 1 10 0% %) )c cu uh h+ +/350-370clno2naco3130h+ohno2clno2no2no2naco335h+ohno2no2no2醚无 环 醚环 醚脂 肪 醚芳 香 醚环 氧 化 合 物冠 醚oh3ch3csp3ch3ch2och2ch3ch3oc(ch3)3och3och2ch3choch2chchch2chch2ch3clch3ooooooooooch3ch2och2ch3o2ch3choch2ch3oohnch3choch2ch3ooh-ch3ch2ohnch3choochooch3n(ch3
12、ch2)2ncs-na+slewis碱碱 lewis酸酸ror + hclror h+ cl-rorbf3ror + bf3ch3och2ch2ch3hich3-o-ch2ch2ch3h+ i-ch3-o-ch2ch2ch3h+ i-+sn2ch3i + ch3ch2ch2ohch3ch2ch2i + h2o过量hi(ch3)3coch3 + hi(ch3)3coch3 + i- h+(ch3)3coch3 h+sn1(ch3)3c+ + ch3oh(ch3)3cii-过量hich3i + h2och3i + agno3ch3ch2ohagioch3+ hioh + ch3ioch2ch3+
13、hioh+ ch3ch2ihoch3hocoohohch3(ch3)2so4naohoch3ch3kmno4och3cookhbrohcooh1.c6h5-hcnochch22.och3+ ch3ch2o- 3. c6h5ch2mgcl + och2chch31) et2o2) h3o+c6h5chch2ohcno hhh3co c h2c h3c6h5ch2ch2chch3ohooooliooooook+ kcnch3cn25oc 72hch2cl ch2cn (20 % ) + kcnch3cn25oc 0.4 hch2cl ch2cn (100 % ) 18-冠-6kmno418-冠-6hooc(ch2)4cooh 100%ch3sch3+ brch2cooc2h5ch3coch325oc(
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