I
I
1
CHEMICAL E N G I N E E R I N G R E V I E W S
I
UNIT PROCESSES REVIEW
I I
II Friedel-Crafts Reactions I
1
M P O R T A N T developments have been made in specific areas of application and study of the Friedel-Crafts reactions but the most significant advance has come through the greatly increased number and variety of applications. T h e essential features of the pattern established for the 1955 Review have been continued. Discussion has been limited to material that cannot be adequately covered in the tables and bibliography. Space limitations imposed by the large increase in the number of references have dictated necessary changes. T h e tables for openchain acylation and open-chain alkylation have been arranged in the general order of increasing complexity of the substituting reagent, and increasing complexity of the aromatic compound undergoing substitution. T h e tables for ringclosure acylation and ring-closure alkylation have been abbreviated. They have been arranged in the order of increasing size and number of rings. Only pertinent products are included. Because of its frequent use, polyphosphoric acid has been indicated as PPA throughout the tables. Related reactions of less general interest such as the Fries rearrangement olefin acylation, and chloromethylation have been eliminated except for brief consideration of important features in the discussion section and complete lists of references in the bibliography. T h e discussion follows almost the same pattern as the tables. A number of authors have written minor reviews of the modern aspects of Friedel-Crafts reactions (4A, 36A, 65A, 96A). Advantage has been taken of the bulk and easy removal of the tert-butyl group as a means of obtaining several substances in good yield which were obtained with difficulty by direct means ( @ A , 77A). The tert-butyl group blocks the tWo adjacent positions as well as the position it occupies and can be removed readils without disturbing other substituents.
1 670
Acylations hvith phthalic anhydride
(54A) and its tetrachloroanalog (554 provide useful derivatives for characterizing aromatic hydrocarbons. Buu-Hol and his associates (76A) have found zinc chloride to be a good catalyst for benzylation or allylation of polynuclear aromatic hydrocarbons. Polyphosphoric acid continues in popularity for reactions requiring milder conditions. I t does not cleave phenolic ethers ( 3 7 A ) . Antimony pentachloride is generally inferior to aluminum chloride except in the benzoylation of benzene ( 6 9 A ) . I t is presumed that there is less tie-up of the catalyst in this case. Boron trifluoride seems to function better alone a t room temperature than it does with phosphoric acid or ether (770A). Silver perchlorate with magnesium oxide is not so good a catalyst as aluminum chloride, antimony pentachloride, or even ferric chloride (77A). T h e effect of acid concentration, olefin to aromatic ratio, reaction temperature, and reaction time have been investigated for the production of chlorocumene ( 5 6 A ) . Another example of carbon monoxide elimination has been observed in the attempted cyclization of 2.2-dimethyl-5phenylvaleric acid (744). Halogen exchange between aluminum halides and 2,4:6-substituted benzoyl
INDUSTRIAL AND ENGINEERING CHEMISTRY
halides has been explained by postulating a partial ionization to give trace amounts of acylonium ions ( 5 A ) . This evidencc is claimed to indicate that the acylonium ion is the actual acylating agent. Additives which retard, or even suppress, the reactions do so by solvating the acylonium ion as well as tying u p the catalyst. Similar results were obtained using titanium tetrachloride or stannic chloridc. Several kinetic studies have been made which add to mechanistic information (8A, 70A, 77A, 734; ?SA, 39A, 40A, 53‘4, H A , 84ilj93A-95A). Acetylation of tertbutylbenzene gives only 1.5% of the meta isomer and none of the ortho product ( 7 5 A ) . There is continued intrrest in the effects of solvents in modifying the distribution of isomers obtained in alkylations and some acy-lations ( 3 A , 7 A , 72A, 35A, 4 6 d , 4 7 4 72A). Most of these studies have dealt with naphthalene derivatives. Azulene can be acylated without thc use of catalysts ( 3 0 A ) . 10-Alkylphenothiazines undergo substitutions of the Friedel-Crafts type in the 2-position (78A). 2,5 - Diphenyl - 1,4 - dithiadiene suffers desulfurization upon formylation to give a thiophene derivative ( 6 8 A ) . Moed and his associates ( 6 7 A ) found that the Hoesch reaction using amino
K. LEROI NELSON Brigham Young University, Provo, Utah K. LeROl NELSON, associate prafessor o f organic chemistry, Brigham Young University, continues on I&EC’s staff o f review authors after moving from W o y n e University. His research interests include quantitative studies of directive effects in electrophilic aromatic substitution. An interpretive review arlicle on this subject was published b y him in the February 1956 Journal of Organic Chemistry. Nelson graduated from Utah State Agricultural College and obtained his Ph.D., in 1952, from Purdue University. He has had postdoctoral experience in research a t UCLA and taught one year at Purdue before going to W a y n e University. Nelson i s a member of the ACS, British Chemical Society, Sigma Xi, Phi l a m b d a Upsilon, AAAS, AAUP, and Utah Academy of Arts, letters, and Sciences.
FRIEDEL-CRAFTS REACTIONS
OPEN-CHAIN ACYLATION (Aromatics) .4romatzc
1,2,3-(CH30)3CsH3 CsHsN( CHa)? 2;6-(CHjO)?-naphthalene Anthracene Naphthacene Benzene
Product Reugent 1-HCO-2,3,4-( CHIO)J-CBH? CsHjN(CHj)CHO, POCI3 HCON(CH3)3 or C ~ H S ? ; ( C H ~ ) C H O~, - H C O - C ~ H ~ N ( C H 50--170 ~)Z, POCll C6HjN(CH?)CHO, POCIp, C6HsCH3 l-HCO-2,6-(CH3O)?-naphthalene 6344% H C O N ( C H 3 ) ?or C ~ H S N ( C H ~ ) C H O9-HCO-anthracene, , POCI, 5-HCO-naphthacene CsHjN( CHx)CHO, POCI3 .Acetophenone 4-CH3CsHaCOCH3
Toluene t-CaHuCsHS
(721B) (742B, 770B, 777B, 780B) (39B, 98B,
CHsCOCI, AICla, CS2
1.5% ~ - ( ~ - C I H ~ ) C ~ H ~ and COC 98.5% H ~ 4-
(CH,COI,O, ..\IC13 CH3COC1, AIC13, CS: (CHsCO)IO, AICla, C?H?ClI (CH,CO)?O, A1C13, CS? (CHSCO)?O,AlClv, C?H?CI( CeHsCI CsHjOH Anisole
CH3COC1, AlCla CH3CO2H, BF3 or HaPzOi CH3CO?Hor ( C H B C O ) ~PPA, ~ , or (CHACOI?O,.11CIa, CS? CFjCOaCOCH3 CH3CO' C101CHYCO ClodC H J C O - C10,CHjCOCl, AlC13, C S I CHBCOCI, AlC13, CsHbNOz CHjCOCl. .AlCl?, CS? CHXCOF. BF3, CHCla CH3COCI. XlCI3 CHZCOCI, .AlCl$, CS, (CH3CO)ZO. XlC13, C ~ H S N O Z CH3COCl. .AgClOI, M g O CHICOC1, CS? CHSCOC1, .AlCls, (CHzC1)2 CHsCOrH, BF? CH3COCI. AIC13, CSi CHjCOCI, XlC13. CS: CHZCOCl CH3CO?H, PP.4 C H 3 C O ? H ,PPA or BF3 CH3CO2H. PPA CHBCO-H. PPX
( 98B
4-CHaCH:OC,H,COCH,, 21 70 4-CH3COCeHdOCH?CH=CH? Resin Resin 4-(x-C1CjH4O)C6H4COCH3( x = 2, 3 or 4 ) 30ketone 4-CH1COCsHcPiHCOCH3, 85% CHTCOCsH,Si( CH3)3 ~-CH~COC~H~CH?SI(CH~)~ 4-CH?COCsH4CHrChTand 3-CH9COC6HdCH-CN, in nearly equal amounts 4- [( 4-CHaCOCsH4)CH2CH?CH2]CaHdCOzH ~ , ~ - ( C H ~ ) ? C B H ~ C30% OCH~, 2-CH -5-HS-CcHqCOCHq 2-CH,jO-4-C6H-s-CsH3COCH3,48 % Br, C1 or F ) 2 - H 05 - X-C sH 3 C O CH 3 (X yields range from 44-94% 2-CI-4-CH30-CsH1COCHs ~-CH~O-~-F-CBH~COCH, 3-Cl-4-CH3S-CsH3COCHa 3.4-IHO)GH?COCH1 2,4-(HO)aCsH3COCH3, 80-9C I%, (some diacetvlation) 3-CHQO-4-HO-CAH,COCHv 2-CH;O-4-HO-C,H,COCH;, 2-HO-4-CH30-CsH3COCH3 and
( 757Bj (768B) (747B) (755B)
(J5Bi (39B) ( 745H) (74B) (93B'I ( 737R)
(27B) (778B) ( 729B'I ( 7 7 9 B . 729B, 737Bi (729B) ( 729B)
~-HO-~-CH~O-~,~-(CH~CO)JC~H~ I,2-(CH3O),C,H4(also for 1,3-) 2 - 0 2 N C 6 H 4 0 H(also for 4-) 3-CH30CsH4NHCOCH3 ~-(~-C.~H~O)C~H~NHCOCHS 1,3,5-(CH3)3C~H3
CHaCOCI or (CH3CO)?O,.\IC13 CHjCOCI. .UCls. CS? RCOCI, .AlClj, CS?
( 729B J ~.~-(CH~O)LC,~H~COCH~ (896') 3-O-N-4-HO-CcHqCOCHq.4-% j-H0-4-CH3CO-C6H,NHCOCH3 (59B1 (59s) 3-HO-4-CH3CO-C6HpNHCOCH? and 2,4-(CH3CO)?-5-HO-CsH2SH? (478,7278, 2,4,6-(CH3)3C,H2COCH3, 96% 780B) (some diacetylation) 2,6-( C H ~ ) ? - ~ - ( ~ - C ~ H ~ ) C C H ? C O C H ~ (159B) ( 756B) 2-CH,-4-CH,O-5-(i-CeH;)CsHyCOK R Yield, 70 CH, 85 C?HS 62 ~z-C~H; 50 '0 52 71
70
52 61 47 50 57 52
50 44 44 55 30 30
CH3COC1
VOL. 48, NO. 9, P A R T II
SEPTEMBER 1956
1671
UNIT PROCESSES REVIEW OPEN-CHAIN ACYLATION (Aromatics) (Confinued) Aromatic 2-HO-3-02N-CsHaCHj 3- CH 3-4-CI-CGH3oH 2>4-(HO),CsH,COCH. 2-HO-4-CH3O-C&COCH,j 2-CH30-4-HO-CsH3COC:Hj 1,3,5-(H0)3CsH3 3,5-(H0)2C6H,0CH1 3,s-( C H 3 0 ) ? C s H s O H 1,3,5-( CH30 ) 3C6H ,+ 1,2,3-(CH,O)3CaH, 2,5-(C2HjOj~C6H30CH3 3,4,5-(CH30)3CsHnOH
Refmnce (89B)
Reagent CHaCOC1, AICl:; CsHjNO? CHaCOzH, BF, CHQCO7H.PP.4 CH~CO~H PP;\ ; C H ~ C O Z HPPA , CHaCOzH, PPA 01 RF3 CHaCOzH, PP.l CHYCO2H. PP.l CH,CO?H, PP.4 CH3COnH or (CH,CO)?O, PPA CH3COC1, AICI3. CS: CH3COzH,BF3, or CH-COCI, AlC13
(9.3B) ( 729B3
( 1 2 9 j~ ( 729B) (779B, 732B) ( 732B) ( 732B) i1.32B) (66B) (94R) ( 70.?B, 7 79B)
ether
Indan 1-(CpH50?Cj-indan 1-(4-CHsOC6H4)-2-CHl-3-ClHj-6CHaO-indan h-aphthalene CH3COCI or (CHjCO’2O. .41Cla. many solvents CHZCOCI, .41C1,. CtHrSO2 2-C2Hj-naphthalene 1-HO-naphthalme CHaCOgH, PP.4 2-HO-naphthalene l-HO-Z-CH&O-naDhthalene 1,6-(CH3)2-naphthaiene l-HO-Z-HO2C-naphthalene (also for ester) 2-HO-3-HO2C-naphtha1ene (also for ester) 5-CH30-2,3-H2-benzofuran
CHaCOgH, BF3 C H S C O ~ HPP.4 , CHaCOCl
2-(C2H602C)-4,7-( CH, 2-CH30CsH4OH 3-CH3OCsHdOH 1,2-(CH,0)&,H4 (also for 1,3-) 3-CH3-4-Cl-C6H,OH 2,4-(HO)2CsHsCOCH3 2,4-(HO)?CcHjCOC?Hj 2-CH30-4-HO-CtjH3COCzHs 1,2,3-(HO)3CsH1 1,3,5-(HO),C,H3 3,5-(HO)aCsHIOCHB (also for diand tri- ether 2-CHaO-naphthalene 1-HO-naphthalene
2,4,6-(H0)3-1,3,5-(C2HjC0)3-Cs 3,5-(HOl:-2,4,6-(C2HjCO):.C60CHj
(729B) ( 93B (729B) ( 729B) ( 72YB) (23~) (73ZB) ( 732B j
2-CH30-G-C2H6CO-naphthalene l-HO-2-(or 4-)RCO-naphthalene
( 73.5B)
3,4-(CH30)2CsHaCOC2Hj 2-HO-4-CHJ-j-C1-C6H2COCsHj, 46% 2:4-( H O I : - ~ - C H ~ C O - C ~ H ~ C O C ~ H ~ 2,4-(HOjI-1,5-(C2H5C0)2-C6H2 2-CH3O-4-HO-l,j-(C2HjCO)&sH2 ~ , ~ , ~ - ( H O ) , I C ~ H ~'75% COCJ~~, ~
C2HjCOC1,AICla, C6H6XO2 RCOzH, PP.1
'
(85B)
Yield, R C>H,
1-HO-2-CHaCO-naphthalene Chrysene Biphenyl
C:?HjCO?H,PPA C!HjCOCl, .llClz. CS2 RCOCl, .41C1;, CS;
C 6H jS C?Hj CsHjSHCOCH3
3-CH"aO-bipheny1 1,3-(H0)2CsH4 3-CH3-4-CI-CsH3OH 2,4,6-(H0)3CsH2CH3 Filicinic acid (also for 3-CH:: 2-FCsHaOCH3
2-RCO 42
%
4-RCO 1
(735B) I-HO-2-CH3CO-4-CyHjCO-naphthalene 6-CrH5CO-chrysene, 57 ( 24B ) ( 722B) 4-RCO-biphenyl ( R = ~z-C,~H;, n-CiHi;,, Il-C!iH?:.,n-CijH81) (29B) 4-C?HjSC6HaCO-(n-CsH7) 4-RCOCsHaNHCOCH3 ( R = n-C3H;, (8W IZ-CIHg! n-CjHii) 4-RCOCsH4CH2NH2,25-30% ( R = n-CiH;, (84B) n-C?Hg, n-CjHii, i-CsH11, n-CI1H23) (741B) 4-RCOCsH4CH2Si(CH3)3,3 3 4 5 % ( R = n-C.jH7, n-CjHii, n-C;Hlj) (93B) 2-HO-5-C1-CsH3CO-(n-C3H?):86 % ( 93B ) 2-HO-5-F-CsH3CO-(n-C3H;):80% (74B) ~ - H O - ~ - C ~ H ~ - C R H : . C O -6(0~7-, C ~ H ~ ) , (729B) 2,4-(HO)yCcH3CO-(n-CsH7) 2-HO-4-CH3-5-CI-CsH?CO-(n-CsHr) ( 93B 2,4,6-( H O ) ~ - ~ - C H ~ - C ~ H C O - ( ~41 - C70 J H ~ ) , (757B) (152B) 3-(n-C IH7CO)-filicinicacid 3-F-4-CH30-CsHaCOR (JOB) (R = )Z-C4H9,n-CjHii, ~ - C , H I G ) ~ - H O - ~ - C H ~ - ~ - C ~ - C ~ H ~ C O 86 - ( ?%Z - C J H ~()9,3 B ) (2dB) ?,3,4-(HO)3CsHzCOR
so
R
Yield,
Yo
70
70 75-80
Benzene 4-CH3O-biphenyl
CHa( CHr),COCl, AICls C:Hs(CH?),,COCl,AlC13, CsHjNO2
Diphenyl ether h-aphthalene
RCOCl CH3(CH,),,COCI, AlCls, CsHjNO:
Chrysene RCsHj
v - C ~ H ~ ~ C O.UCIa, C I , CsHjNO2 >:-CsHigCOCl,XIC13, CS?
CsHjS( CH 7 1,3-(HO),CsHa 2-HOCsH4COzH 2,4-(H0)2CsH&O?H 1-HO-naphthalene 1,4-(HO)p-naphthaIene 3.j-(CH3)yCsH1-(t-C?Hg~
J : - C S H ~ ~ C OZnClz C~, v-C9H19C02H: ZnCL n-CgHigCOC1, .AlC13, C&j?;O? I -CgHlgCOCI, AICla, CSI ,!-C9H1gCO2H,ZnClz n-CnH,&O?H, ZnCl? RCOCl, AIC13, CS?
4-(C6HjS)CdH&Oa Benzene Benzene
~ I - C ~ ~ H ~ ~ AlCI?, C O C ICsHjNO? , Karite oil, AlCI:. Hydrogenated palm oil, AlCla
CHi(CH?),,COCsHj ( r ~= 4 to 18) ~ - ( ~ - C H ; O C ~ H ~ ) C BCHz),CHj H~CO( i n = 4, 5 %6 ) 4-('C6H,O)C,HgCOR(R = n-C,Hii,n-C:rHij\ 2-CHp(CH2),,CO-naphthalene 4, 6, 8, 10, 1 2 ) (12 Z-(n-CeHI.iCO)-chrysene 4-RCsH,CO-(n-CgHig) ( R = H, HO. CH?, C1. or N H C O C H ] ) ~-(~-CGH!,CO)C,H,N(CH~)~ 2;4-(HO I ? C & H ~ C O - ( ~ ~ - C Y H I ~ ) 2-HO-5-(n-CgHl~CO)C6H3CO~H 2,4-(H0'11-j-(n-C9H19CO)C6HRCOnH 1-HO-4-(n-CgH!9CO)-naphthalene 1,4-(HO).-4-(n-CgHl&O)-naphthalene
2,6-(CH3)?-4-(t-C4Hg)-C8H?COR ( R = n-CgHig, n-Ci7H3j) S o ketone 58% C5H,COR and some C G H ~ R ' 35-39% CsHbCOR
VOL. 48,
NO. 9, P A R T II
( 75B)
(.3ZB)
i?OB) (781B) (37B) (101B)
(707B) (107B) (707B) (707B) (707B) (701B) (759s) ( 767B) (724B) (124B)
SEPTEMBER 1956
1673
UNIT PROCESSES REVIEW OPEN-CHAIN ACYLATION (Aromatics) (Confinued) Aromatic
Redgent
Product Tar 4-CsHjCsH,CO-(i-C3H,), 92% 4-(C6HjO)CBH4CO-(i-CzHi) 2,4,6-(CH,),CsH?CO-(i-C3H7), 75% 2,3,4-(HO j,IC,H?CO-(kC3Hi), 40% 2,4,6-(HO);jC,H?CO-(i-C3H7),20% 4-C6HiCaH,COCH(CH,)C?Hs. 86%
Benzene Biphenyl Diphenyl ether Mesitylene 1,2,3-(H0)3CsH3 1,3,5-(HO)zC6Hs Biphenyl 2,5-(C H ~ O ) ~ C ~ H ~ - ( ~ - C ~ H I ~ Benzene Toluene 1,2-(CHsO)?C6H,(also for Anisole
Reference ( 72 I B ) ( 764B) (30B) ( 70B)
(23B) ( 83B 1 (765B) 2,5-(HOj2-4-(n-C7H;j)-C,H;CO-(i-eiH9), ( 139B) mono ether Cvclonentvl-COCsHi 4-CHjC&CO-cy&ohesy 1 3,4-(CH30)~C~H3CO-cyclohexyl 4-CH,OC~H,COCH~-cyclohexyl
1,3-(HO)GHi Biphenyl Phenol Anisole Anisole 3-CH30-4-HO-CsH3CHO 3-CH30-4-HO-CsH3COzH 3,4,5-(CH30)3CsHzOH Toluene Anisole CsHsCl 4-ClCsHIOH 2-FCsH40CHj 4-FCnHAOCHs 3,4,5--(CH30 ) 3CsHzOH Carbazole N-( CsHbCO)-carbazole
Cyclopentyl-COC1 Cyclohexyl-COC1, AlC13 Cyclohexyl-COC1, .AlCla, C&jNO: Cyclohexyl-CH,COCI, .&lCl?, CsH,NOa Cyclohexyl-(CH?),CO:H, ZnCln CH3CH=CHCOCl, .41C13, (CHCl?), CaH;CH=CHCO,H. PPX C;H;CH=CHCO;H; PPA CsHjCH=CHCOCI, AgClOi CsHjCH=CHCOCl, CsHs CBH,CH=CHCOCl, CsHs CsHjCH=CHCO?H, BF3 CaHjCHgCOCl CsHjCHgCOCl, AlCla, CS? CsHjCHZCOCl CsHjCHICOzH, BF3 CsHjCH2COCl C6H;CHoCOCl. .AlCl-i-C1-CgHsCOCH=CHCOnH Sfaleic anhydride 3,4-(HO)?C6H3COCH=CHCO?H Maleic anhydride Maleic anhydride: AlCls, CH?C1? 3.4-ICH30)pC6H:,COCH=CHCO?H
,,CY-(
Maleic anhydride and 3 . 5 ) 3,5-(CH3)?CsHsOC?Hs 2-Cyclohexyl-C6H40CH3(also for
Product
Reagent
.4romzt1c
Refermce
(72Bj
2-HO-3.j-(CH:~'I.C:~H?COC:H=C:HCO?H
X~H~O-~.~-(CH~)~C:RH~COCH=CHCO~H hfaleic anhydride Maleic anhydride, AICli. CBHLXO? ~-Cyclohesyl-4-CHaO-C6HaCOCH=CHCO~H
A' -- I
I-Cyclohexyl-2,4-( CH?O)a-C&3
Maleic anhydride
2.4-(CH 3 0 I p - 5-cyclohexylC BH pCOCH=CHCO?H
2-CHaO-biphenyl 1,5-( CaH~O)p-2.4-(cyclohexyl)pCsHz Benzene Benzene (also for C:&IjBr) Benzene
Xlaleic anhydride, .41C13: CoHbNO? Maleic anhydride, AlCl?, C:sHjNO?
3-CsHj-4-CH30-CsH3COCH=CHCO?H
Indan Tetralin Benzene CsH5( CHp),COzCrH: 2-CH $0-naphthalene
2.4-( C2HjO)2-5-cyclohexylCsH*COCH=CHCO?H 2-C6H5-maleicanhydride. X1C1, CsHjCOC( CsHs)=CHCO?H, 50 Itaconic anhydride, AlCls, CSr C:sHjCOCH?C(C02H)=CH2: 6370 46c', CsH5COCH(CHs)=CHC02H and 147' Citraconic anhydride. .41Cl3. CSp C6HjCOCH=CHCOaH 1-Cyclopentene-l.2-dicarboxy-lic acid 2-( j-indanylcarbonyl)-l-cyclopentene-1carboxylic acid anhydride, A1CI3: C6HjN02 1 -Cyclopentene-l.2-dicarhox~-lic acid 1-( j:6.7.8-H4-2-naphthylcarhonyl)-lanhvdride. .41C1~CeHJ'JO, cvclouentene-2-carbox~licacid Glutaiic anhydridd: .4iC1, CsH5Cb(CH2)3C02H ' Glutaric anhydride, .41Cls, C?H?C14 4- [C2Hj02C(CH2)4]C6H4C0(CH2)sCOaH Glutaric anhydride, AlCls, CsHjN02 1- and 6- [HOaC(CHz)sCO]-2-CH3O-naphthalene ( 7 0 B ) 3-CHs-glutaric anhydride C ~ H ~ C O C H ~ C H ( C H R ) C H ~90% CO~H> (758B) Sebacic anhydride 3-Cyclohexyl-4-C2H50-C6H sCO(CH2)3C0pH (79B) Glutaric acid, BF3: or bis-chloride. '3.4-(CH3O)?CsH3COCHz]pCH? (738B) .41C13, CSa (762B) ClCOCHaC(CHj)zCHaCOCl. AlCl, ClCO(CHs),COCl. AlCl?. CSa (7B) (182B, 783B) C o c l ; , Arcis, C?Hi2Cl2
( 742B) (39B) (57B, 98B) [ 733B) ( 73B, 66B, 133B)
Benzene Toluene (also for benzene) Toluene Phenol Anisole
:1, I2
CsHsOC?Hj c~,HsCl C6HsCHzCHsNHCOCHs CeHbCH&i( CH3)s CsHsSi(CH 3 1 3 Biphenyl 4-ClCsH4OH 2-FCoH40CH1 (also for 4-) 2-ClCeH4SCHa 4-(t-C4Ho)C6H40CH1 1,2-(CHaO)pCsH4 1,3-(CHaO)zCsH4 [4-CH30CeH4CH(CaH,)]p Mesitvlene 1,2:3-(CH30)aC6Hs 2 >4,6-(i- C 3H i ) 3C sH 2N( CH s ) z 2,4,6-(~ - C ~ H , ) ~ C ~ H ~ N H C ~ H B Naphthalene 2-CHsO-naphthalene 1-CsH5CHz-naphthalene I-HO-2-H0&-naphthalene (also for ester) 2-HO-3-HO2C-naphthalene (also for ester) 7-HO-coumarin 4-CH3-5-HO-coumarin 4-CH 3-5,7-(H O )a-coumarin 8-HO-quinoline 1,4-(CeHs)zCsH4 Phenanthrene Dibenzofuran
1676
4-CiHjOCsH4COCsHs. 83cc 4-ClC6H&OC&Ij. 9-72YG(also some 3-C1) 4-CsHrCOCsH4CHzCHJiHCOCH3
demethylation) 2.4-(C H ~ O ) ~ C ~ H J C O C ~ H ~ 2-CHs0-5- [4-CHzOCsH4CH(CpHj)CH(C~HS)]C~H~COC~H~ 4.6-(CH3)aCsH&OCsHa, 65@0 2:3.4-( 2,3.4-(C H ~ O ) ~ C ~ H P C O C ~ H ~ 2.4.6-(i-C3H;)3-3-HzN-C6HCOCfiHs, 2570 2.4.6-(i-C3H:)3-3-C~Hjr\;H-CsHCOCsHa,69% '0% l-CGHiCO-nauhthaleneand 36% 2-"C6H~CO-naphthalene 1 -C sH5CO-2-CH?O-naphthalene 4-C6HsCH?-1-C6H5CO-naphthalene, 79% 1 -HO-2-HO?C-4-CsHsCO-naphthalene
'
1-CsHiCO-2-HO-3-H02C-naphthalene
CsHjCOCl. AlC13 CsHsCOCl, AlCls CeHsCOCl, AlCls CeHsCOCl CsHsCOCl, AlClc, CSP C B H ~ C O C AlC18 I, CsHjCOC1, AlCla, CsHsSOz
INDUSTRIAL AND ENGINEERING CHEMISTRY
'-HO-8-C~HjCO-coumarin 4-CH3-5-HO-6-C6H~CO-coumarin 4-CH3-5,7-(H0)a-6,8-( C6HjCO)~-coumarin j-CsHBCO-8-HO-quinoline 1-CeH5-4- [4-(CsHjCO)CsH4]CsH( 3.6-(C~HjC0)2-phenanthrene and isomers 2-C6HsCO-dibenzofuran and 1:7-(CsHbC0)2-dibenz~furan
( 98B 1 (777B) (7478) (168B) (97B) (93B) (27B, 3 0 B ) [ 778B) f707B) ( 9 f B , 729B, 150B, 779B) ( 729B) (30~)
FRIEDEL-CRAFTS REACTIONS
OPEN-CHAIN ACYLATION (Aromatics) (Continued) 3-CsHaCO-4,j-cyclopenteno-
(49E)
6,7,8,8a-Ha-acenaphthene l-(RC6HaCO)-2-CHa0-j-(t-C1HS)-C:6H R 4-CH, 2-6" 4-C1 2-Br 3-Br 2-CH30 4-CHa0
1,2,3,4.j-(CH3)&sH Phenanthrene
Reference
Producr
Aromatic 4,5-Cyclopenteno-6,7,8,8a-H~ acenapht hene 4-(t-CcHg)CsHaOCH3
yc
1-(4-CH3C6HaCO)-2,3,4,j,6-(CH3 )&a 3,6-(2-CH3C6H4C0)2-phenanthrenean1 isomers [4-C~Hs-CsHa]zco 2-Br-C&4COC&~
~ - C H ~ C G H ~ C OAlC13, C I , CS: Z-CH3CsHaCOC1, AIC13
CS.
Biphen)-l Benzene Durene Toluene Anisole 2-C1C6HaOCH3 (also for 4Durene Durene Anisole Phenol Benzene (also for toluene Anisole Durene Tetralin [ ~ - C H I O C F H ~ C H ( C ,111 H,
Yield, 76 62 60 68 61 50 60
( 707B)
1-(4-BrCsH4C0)-2,3,5,6-(cH3)a-C6H 4-( 2-ClC 6H 4CO )-C sH aCH 3 4-( 4-ClCsHaCO)-CsHaOCH3 1-( 2-ClC6HaCO)-3-C1-4-CH30-CsH:
1-(2-ClCsHaCO)-2,3,5,6-(CH3)4-CsH (also 4-
or
1
7
1-(2-FC,H4C0)-2,3,5,6-(CH3)a-C6H, 8C 4-( 4-HOCsHaCO)CsH40CHa 4-( 4-HOCsHaCO)CsHaOCHa 2-CH30-CsHaCOC6Hj, 40% I ~ - C H ? O C ~ H I ) ? C84% O. 1 -(4-CH,OC,H;CO)-2,3~5,6-(cH, )4-C&
2-(4-CH30CsH4CO)-5,6,7,8-Ha-naphthalene 2-CHa0-4- [4-CHaOCeHaCH(C?Hj)CH( CzH5)]CsH3COCaH: "--" Z-(i-CoHj)-4-(2-CH30C,jHaCO)-5-CH 3 CGH~O 2-( i- CaHi
2-(i-CaHi)-j-CH&sH3OCHj 2-(i-C?H:)-5-CH3-CsH30CHI A n is ole
Aromatic
Benzene (also for toluene and anisole) Toluene (also for anisole, Toluene (also for anisole Toluene 1:2,3.4.5-(CHa)~,CsH
Refercnct
Reagent
(54B)
2-( ~ - C H ~ C G H ~ S O I N H ) - C G H ~ C O C ~
(17s) (17B) (77B) (757s)
2.4.6-(CH3)sCsH2COC1.hlClj, C S : 2-CH,-4-CH30-5-(i-C3H;iCBHzCOCI, AlC13, CS, 2-CH,-4-CH30-5-(i-C3H;11.3-(CH30)2CsH, C,H,COCI, .41C13, CSI ~ - ( ~ - C ? H ; ) - ~ - C H ~ - C ~ H S O C2-CH,-4-CH30-5-(i-C,H; H iCGH1COC1, .\ICIj, CS: 2,3.6-(CH30)3CsH2COCl 1,4-(CHaO)zCsHa Mesitylene (also for durene 2-CICO-furan, AICls, CS? 4-CICsHaOCHa 2-CICO-furan 2-CICO-thiophene 2-BrCsHaOCH3 (also for 2-Cl 2-CICO-5-CHa-thiophene 2-BrC6HaOCH3 (also for 2-Cl 2-CICO-pyridine, AlCla. C6Hjh-O: CsHjCH*CHzN(CH3)2 Benzene Phthalic acid, SiCla: .41Cl3 1.2-(C1C0)2CsHa. .41C1. 1,4-(CH3)2C~H4(also for 1.3.' Acenap hthene 4-CHaC6HaOCHa
Toluene Benzene and 24 homologs and isomers Phenanthrene
Phthalic anhydride Phthalic anhydride
Benzene and 27 homologs and isomers Anisole CsHjC1 Benzene
3,4.5.6-Cl4-phthalicanhydride
Benzene (also for toluene and biphenyl ) Anisole Anisole
Phthalic anhydride, AlCl?; CrHuClr
(6-IB) ( 756B) ( 756B)
(75fiBj (133B) ( 65B
I;:;[
2-( 3-Br-4-CHaO-C~H3CO)-furan 2-( 3-Br-4-CH30-C6H3CO)-5-CHs-thiophene 2- 14-(CHJ)?NCHtCH&eHaCO]-pyridine 2-HOzCC6HaCOCsHj, 9670 1.4-(CHa)?-2-(2-H02CCsH4Co)c~H~ and 74% 3.3-bis- [2,5-(CHa)z-C~H3]phthalide I-H02C-2-(4-CH3CsH,CO)CsH4 1-HO?C-2-.4rCO-C6H4 3,6-(2-HO:CCsH4C0)2-phenanthrenearid isomers 1-HOrC-2-ArCO-3,4,5,6-Cla-Cs
(30B) (777B) ( 785B ) (3 3 B 1
( 702B) ( 7 7OB)
(2B)
(777s) ( 753B I
9.10-(ClCO)?-anthracene,AlCl: 2,3-(HO?C)?-pyridine!AICI3 CICH?CH(CeHj'lCOC1
(784B) ( 723B)
(77JBl
8-(HO?CCH?)-j-HO-4'.'-(CH30 I?8- [(~-CH~OCGH~)CHI]-~-HO-~',~-(CH~O 12( 730B I
flairone, HaPIO8-(HO CCH,'I-4' ~ . - - ( C H I O- ~ fla\one, HaP-O-
flavone
8-[(4-CH10C5Ha)CH2]-4',5,7-(CH90)3(730Bj flavone
VOL. 48,
NO. 9, P A R T II
SEPTEMBER 1956
1677
UNIT PROCESSES REVIEW ~
~~
OPEN-CHAIN ACYLATION (Pseudoaromatics) Psrudoai oniotic 1,4-(CH3)~-7-(i-CsH;)-azulene Furan 4-HO-coumarin
RCOCI
Pyrrole (also for indole) Pyrrole H
HCOS(CHs)i: POC1; H2NCOC1 H2NCOC1
R4\jN RI--
li
Reaecrii CH3COCl: AlC1:. CS?
) P I
PI oduci 1 .4-(CH1),-3-CHIC:O---(I'-C.,H;:-azulene,18:; 2-CH:,CO-furan 3-RCO-4-HO-coumarin ( R = CHa, n-CjHi1, 12CyH,,. n-CgHis. ClCH,. CfiHjCH?.CoH;CH?CH?, CsC,CH=CH. ChHj) ?-HCO-pyrrole, 8 3 7 ; 2-H2NCO-pyrrole Yields of 60-90 512
CH 3 CH.4 C1H;OnC: CH., CH . j
\R,
1 >2-(CgHj)2-3-CH;-p).rrole Pyridine Pyridine Indole (similarly for 2-CHa. 2-CeH5, 5-CH3CO2, S-CgHjCH20, 5,6(CHaO)?, 6-CHaCO2-7-CHj0, and 1-benz [ g ] ) 2-CHa-pyrrocoline 2,3-( CH3)-pyrrocoline 2-CHs- 4-HO-quinoline Thiophene (also for 2-CI. 2-CHx. 3-CH3, 2-(t-CaHy),2-CHaCONH) 2-(t-C4H9)-thiophene 2-C6Hj-thiophene 2-( 3-C1CsHa)-thiophene 2-( C~H:,CH=CH)-thiopliene 2.44 C6Ha)z-thiophene 2.4-(4-CH,,C~H4)p-thiophene 2,5-( C6Ha)r-I ,4-dithiadiene 2,4-(CgHj)~-selenophene(also for ditolyl and dianisyl j 'Thiophene 2-( t-C4Hy)-thiophenc
HrNCOC1 HCOPL'(CH3)n. POC1.j C6HjN(CH3)CHO;POCI (COCl)?
2-( CGH,CH=CH)-thiopliene
RCOCl. SnCI4. C t H I
2-(3-C1CsH;)-thiopliene 9-( 2-Then)-1ide)fluorene R4\~ /S\,/Rl
CH3COC1. SnCl,. C 5. CHpCOCl
(i.3C. ) ( 7ZC 1 (7c') ( 76C i ( Z2C 1
(22C)
K: R8 K4 H21UCO CH 2 HJCO C2H jOsC CH 3 H&CO CH:3 HrSCO C:H :< HI:NCO H C2HsOrC C: 1.H;O?C H H:NCO 1.24 CBHS)r-3-C.H:,,-j-H.~IC~~-p).rrole I-HCCI-pyridine. lo\\. \ield 2-HCO-p)-ridine. low J ield 3-ClCOCO-indole
K1
/I
Rrferrnri
C6H,S(CHs)CH0.POCI (C:H:Cl):, 2-CH2-3-HCO-pyrrocoline C6H5N(CH1)CH0. POCI.I.( CHrCl)? l-HCO-2,3-(CH~)2-pyrrocolinr CHaCOClor (CHaCO)?O,.\1C17 2-CH3-3-CH~CO-4-HO-quinolinc HCON(CHa)?or C6HjN(CH:>)CH0. 2-HCO-thiophene. 72-77? POC12 C6H,N(CH3)CH0.P O C , , 2-HCO-j-(t-C~E-Iy)-thiophrnr. 81)' 1 C 6 H & ( C H 3 ) C H 0 .POCI.;. C,,HjCH3 2-HCO-5-CeHj-thiophene ~~- - . ?.C!ICSHLi-thiouhenr 2-HC0-5-1 HCON( CH3)?,POCl,. 1 .2-C:lsCcH4 2-HCO-S-{C6H5CH=CHj-thiophene HCON(CH3)?, POCI., 2-HCO-3.5-(C6Hj)n-thiophene: 88% I-HCO-3,5-(4-CH.iCsH()?-thiophene HCOK(CH3)i. POCIi 2-HCO-3.5-(CsHi)2-thiophene. above 32Yc Z-HCO-3,5-(CsHs I?-selenophene
( 2ZC I
i74ci i7 x 1 (7.W)
(77C) i7 J C ) 1177C) ( 7c: ;
).
~
CF3CO2COCH i RCOCI, SnCI4. CS?
(7.50 ( S C . 7t)c:i (8C i
I-CH CO-thiophene. 88' 2-RCO-S-lt-CaHqI-thi~phenr~ iK CH3. CzH,. ~I-C~H-) 2-RCO-5-IChH C H==C.HI - t h i o ~ h e n e( R = CH?. C:?H,. CbH-j1 2-CH ,CO-j.( 3-C!1CtiHi)-thiophene O-iS-CH~CO-2-thenvlidenei-fluorrne
~~
K 3/ ----~~\R ,~ I.5-( CHr )n-thiophene 2,j-(t-C4Hg)?-thiophene 2 5 ( C?H:)2-3-(n-C,3H-)-thiophcne (also for n-C4Hg and n-C,Hll) 2.4-(CsHj)?-thiophene (also for ditolyl) 2.4-(C~Ha)?-sclexio~hene (also for ditolyl and dianhvl) 2.4-(CsWj).-thiophene (also for ditolyl) 2.4-(4-CH3CsHl)?-selenophene 2 . 4 4 CsH j).i-selenophene 2,5-(C2Hj)pthiophene
CH3COC1, \IC1 . ( ' 5 . CH3COC1 CHzCOCl, .\1C11
(somr rrplacement of t-GH9) 7.j-(CHs!p-3-CHaCO-thioplic1i~.T j r 2.5-( t-C4Hy)r-3-CHaCO-thiophcne
2.5-( C2Hi)?-3-CH:jCO-4-(n-C:iH;)-thiophene. 40-5 5; 7-CH1CO-3.5-(CeHj)z-thiophene
2-CH.rCO-3.5-(C,H; )?-selenophene 2-CiHjCO-3,j-(Ci;H5)?-thiophrnr
RCOCI, AlC13. CS?
2-C~HjCO-3.j-(4-CH.,C:hH1)?-sel~nophene 2-( n-C ,H7)-3.5-(CaH 5 ) 3-selenophene 2.S-(C.H5)r-3-RCO-thiophene.yields from 78C?Hj. n-CsH;. ~ - C I Hn-CjHii, ~, n92'C ( R
2-C,Hj-thiophene 2,5-(CH3)2-thiophene Thiophene Thiophene 'Thiophene 2,s-( C*Hj)?-thiophene 2:j-(CzHj)~-thiophene
CH3CH=CHCOCI. AlCl:.. CS, C H 3 0 2 CCH?)aCOC1. ( .\1CI1. CS? C?H:,OnC(CH?)sCOCI
2-(kHaCH=CHCO)-thiophene. -1 5 2.5-( C2Hi)n-3-[CH.,O?C( CHI:)hCO]-thiophene 2:5-( CYH5)2-3[CiH,O,C( CH?).,CO]-thiophene,
C2HjOyC(CH2)RCOC1. .\lCl:, CS? Succinic anhydridr. AlCl:. CsHjNO:
2-(C~HhOpC(CH?):CO]-4.5.6.'-H4-thianaphthene
A7
c
2-(HO?CCH2CH.C:O)-thiophene
Succinic anhydride. .L\IC:l.;, CtiH;NOn 2-(HOaCCH.CHyC:O)-i-(II-C;H,~~i-thiophene
1 678
INDUSTRIAL AND ENGINEERING CHEMISTRY
(7fiC)
(8CI
FRIED EL-CR A FTS REACTIONS OPEN-CHAIN ACYLATION (Pseudoaromatics) (Continued) Reagent
Pwidoaromnt ic
Product
. CtiH,KO,
2-(HOnCCH2CH&O)-5-Br-thiophcne 2 . 5 4 C2Hi)2-3-(HOsCXH.C:H?CO)-thiophene, 60 'C [HO?C(CHJ),CO;-thiophene. 75:);. Glutaric anhydride, .\lCl?. ChH,r\;On 2.5-(CyH5)?-3Glutaric anhydride. AICI;. C 6 H , K 0 , 2- [HO?C(CH2)aCO]-4.5.6.;-H,-thianaphthene.
2-Br-thiophene 2,5-(CH.)?-thiophene(also for diethyl ) 2.5-( CsHj)s-thiophene 4.5.6.T-H4-thianaphthene
Succinic anhydride, .\IC1 Succinic anhydride
2-C1-thiophenc 2-CH.,-j-C,H;-thiophene Thiophene
C6H6COCl.I ? (also 4-CI) CaHjCOCI, AIC1, 4-,YCGHjCOCI
78'; 2-C6HhCO-5-C1-thiophene.34'
2-CHa-3-CsHbCO-5-C6H;-thiophcne 2-(4-XC6H4CO)-thiophene( X = CH.3. CHa0.
and C1) C ~f,H 1 l-CyH60~C-2-C1CO-3-O~S-C:tiH,,,l - C ~ H , ; O ~ C - 2 - t h e n o ~ - 1 - 3 - 0 ~ Y3. -51 SnCI,, C6Hs l-C1CO-2-C~HjOsC-3-Oy".,, l-Thenoyl-2-C2HjO?C-3-0."1. 45 c;; SnCld, C&6 2-ClCO-naphthalene. SnCli 2-Thenoylnaphthalene
Thiophene Thiophrnr Thiophene
OPEN-CHAIN ACYLATION (Aromatics, Gattermann-Koch-Hoesch)
. romatii
Product
Rrazmt
Tetralin 2-C6H:,-6-HO-chroman 2-C6Hj-5-C:H,i-'-HO-chroman 2-C6Hj-6-CH:I-'-HO-chroman 2-CtiHj-5-CH.,0-7-( C,H,CHUO)chroman 2-CsH;,-j-CH.,(>---HO-8-CH ichroman
2-( C:yclohex>-lI-C,H,OCH, 2-C:H (0-hiphenyl 34OCH 3.54 C H s J ? C B H ~ O H 3.4-iCH 4 0 )?CsH?C?Ha 2.6-(HO ).C&Br 2.4-(HO !ICoH ,C:O?H 2-CRH.,-.i-HO---CH..0-ch~oInan 2-CeH;---HO-4-chromanone 1.2.3-(HO ,C:tiHi Hi-j.S-i,CH.O Ir-CbH?OH Hi-'-HO-4-chromanone 2-C6H;,-5-HO-'-CHaO-chroman 2-C6H;-5-C:H,jO---HO-chroman 1 ,3-( H O )?-2.4-(CH s ) 2-C gH. 2.4.6-(HO I:C,H?CH?CH:CH(CHi)? 2.4.6-(HO)iCaH?CHs 1,3-(HO)?CsH( 1.3.5-(HO):iCtiH3 1 .3-(HO)?CsHI 2.4.6-(HO )rCGH?CH,+ (also for 4GHaO 1 1.3.5-(HO I , C ~ H(also :, for I - C H , ) 1
2.4-(H 3-(C~HjCONHCH?CH..)-l-indanone..I\1Cl3 2-C6HS-3-CH3-1-indanone, HrSO, 2-CsH;-3-benzvlidine-l-indanone;HzSO4 2,2-(C&)z-l-indanone, 70yG 3-H02C-5-CH30-l-indanone, HF or .I\lCls (also Y-CHaO, 3-HOpC-6-CzH5-l-indanone,HF or AlC13 3-HO2CCH?-4-0?N-1-indanone: .\IC13 4,5-(CH30)2-1 -indanone, SnCll 2-R2-x-R.-l -indanone, PPA \
K:
X-R?
5-CHsO 40 % 6-CH30 20% 7-CH30 5.6-(CH30\: 30%
CaH;, CaH, CsH3 CtiHs 11 14 pCsHi 2CeHj
H H
H 5,6-(CH,Oi:
Spiro/fluorene-9.2 '-indan-1 '-oncl , 60% 2;2.3-(CeHj)3-1-indanone,50% . 4-CaHj-6,7-(CHy0)2-1-indanone, H,SOa, 84% 3-HO2C-5,6-(CH30):-1-indanone. HF or AICII, 38-10070 3-H07-thianaphthene.H F (enol forrni [also for 5-CH,. 4.--(CH:
-.
Llaj
3-HO-9-Cl-naphtho [ 1:2-b]thiophene, HF, 89 yo 9-Fluorenone, HrSOl 1-H02C-9a-CH3-1,2,4a,9a-HI-9-fluorenone, H ~ S O I cis-1,2,3,4,4a,9a-Hs-9-fluorenone 2-CH30-8a-CH3-4b,5.6:7?8,8a-Hs-9-fluorenonr, SnCl,, 1.5-8 1 3-H0pC-6,7-(CH2),-1-indanone 2-R-4,5-benzindan-l-one, H F ( R = CH3, C?He, n-C,jHi. ir-C 3-R-4,5-benzindan-l-one, HF, low yield ( R = C H I . C?Hj. I: 3 '-CH30-4.5-benzindan-l-one, PP.I\, ALCI, or SnCI, 3-HO?C-6,'-benzindan-l-one, HF, FSOIH or ;UCI 5-Br-l-acenaphthenone, AIC13, 55 70 6-CH30-1-acenaphthenone,PPX or .41C1; 8-CH30-1-acenaphthenone, PPX 5-Aza-2a,3,4,j-H4-1,4-dioxoacenaphthene 1-Ox0-3.4-(CH?)~-indan, PPA, A1C13 or SnCl,, 83-925 1 '-Oxo-4,5-cyclopentenoacenaphthene,SnC14 1 '-Oso-4,5-cyclopenteno-G,7,8,8a-H~-acenaphthen~. SnCl,
INDUSTRIAL AND ENGINEERING CHEMISTRY
i
(JF)
(3F) (JF) ( 3F (2Fi
FRIEDEL-CRAFTS REACTIONS jG A ) . I'he same iiivestigators found that the presence or absence of solvent made little difference. Gerecs and co\corkers (3-7.4-3JA) have accumulated rvidencc that hydrochloric acid plays an imporrant role in the Fries rearrangement. In lubricating oils rich in aromatics, the more reactive aromatics can be rcmoved or rendered harmlrss by prctreatment \\.ith a liquid alkylating catalyst (62.4). The remaining arornatics can br alkylated using a solid catalyst \cith an olefin or alkyl halide. Hydrogen transf'er reactions \\-ith alkanes and olefins pcrmit direct utilization of petroleum fractions to produce alkylbrnzencs derived from the alkanes (50.4: 60.4> 70.4.87.4). l l i x e d cresols react with isobutylcnc io give di-tert-butyl derivatives (27A). Benzyl chloride and alcohol undergo polycondensation to give resins (52'4). Dicarboxylic estrrs have been used as alkylating agents (26.4). Benzene is alkylated in good yield with a complex boron trifluoride-phosphoric acid-water catalyst to give a mixture of mono- and dialkylation (700A). Dodecylbenzrne is obtained from benzene and propylene tetramer in yields u p to 73% (86,4). Excess tctramer leads to side reactions involving fragmentation. hydrogen transfer. polymerization, cyclization. and polyalkylation. Propylene polymrr reacts similarly (67.4). An attempted Friedel-Crafts reaction of anisolc with ethyl chloromaleatc was unsuccessful
RING-CLOSURE ACYLATION (Aromatics) (Confinued) Product om' Rengriit
15H-6,7,16,i T-H4-1j-oxo-c!-clopcnta [ a ]phenanthrene 11H-1 Oa-CHa-l1-0~0-6b,-,8.9,10,1 Oa-He-benzo[a]fluorcnc, SnCl,, 877, 13H-l2-HO~C-13-oso-dibenzo[a,g]fluorene, .41C13 9H-8-HO?C-9-oso-naphtho[2:1-c] fluorene -H-6-HO?C-7-oxo-benzo[g]naphtho[l,2-~]fluorene, HF ~H-6-HO~C-7-oxo-benzo[i]naphtho [1,2-c]fluorene, HF 9H-8-HO:C-9-oso-benzo [i]naphtho[2,1-c]fluorcne~ HF or .-llC:13 1-Tetralone, PP.4 or SnClr380-9070 4-CH~-l-tetralonc..41Cl3, 877, 7-CHs-l-tetralone, PP.1. 88% 2-C~HZ-l-tetralone:nearly quantitdtiw 4-CsHj-l-terralone, :'.lClo, 937, 4-HO2C-l-tetralone. PP.4, 80% 2.7-(CH3):-l-tetralone: .\lC:l 4,6-(CHBi?-l-tetralone. 9 2 7 , j,s-(CH3)?-1-tetralone,PP.\. 937c 3-HOrC-4-CH3-l-tctraione. H:SO( I-(CH3CCl=CHCH?)-5-CH~O-l-tetralonr, PC15, 61 9% 4-CH3-7-CH30-l-tetralone. .4lCll, 447, 5.8-(CH.1O)~l-tetralone, H ? S 0 4 ,68% r2,5,7-(CHs)3-l-tetralone],H 3 P 0 4 ,1.: P 4,5,7-(CH~j~-l-rrtralon 8 8c 7~, 4.6,7-(CH3'i3-l-tetralone. 85y0 5.-,8-(CH3)3-l-tctralone, SnC14, 827, 2.j-(CH3)?-,-[I'-C,,H;I-l-tetralone, .1lC13 2.4-(CH3)2-j-(i-C3H;)-l-tetralone: .\IC13 or [HzPO,, I., PI 3.8-(CH3)~->-(z-C~H;)-i-tetralone, AlC13 i-HO?C-4,4-(CH3):-1-tetralonej HySO4 I.5-(CH3)p-~-CH30-1-tetralone~ .i1Cl3 4.'-(CH3),-5-CH,0-l-trtralone, POCl3 4.7-(CH3)-.-6-CH3O-l-terralone, H:SOI 2-CzHn-5.8-(CH30):-1-tetralone: SnC14,947, 5.8-( HO)y-l.4-naphthoquinone,.41Cla, NaC1 5-HO-8-CI-1.4-na~hthoauinone 2.4,5:7-(CH3);-1-t;-tralon'e,;llCli or HI, P 2.3,5-(CH3)3-8-(i-C3H;)-l-tetralone, AlC13 I.5,8-(CH J3-7-CH30-l-tetralone,H.SO4 3.5,8-(CH3) d - 7 - C H 3 0 --tetralone, l H&Oa 2.5-(CH.;)1-'-CH30-8-(t-C.;H;)-l-tetralone, AlC13 2-CH3-3-C?HaOG6,'-(CHaO)?-l-tetralone, PPA 3-C?H~OGj-Br-'.8-iCHIO)?-l-tetralone. PP.4 [2,314,j-(CH,),-8-(i-C3Hij-l-'letralone], H 3 P 0 4 ,I ? , P 3-HOG-4- [3,4,5-(CH30),CsH~]-6~7-(CH~O~)-l-tetralone, .\1C13 4-Chromanone, PP.4 6-CsHs-4-chromanone, PP.4 7-CH30-4-chromanone, PP.4 6-C1-4-chromanone, H:S04 6-02N-4-chromanone, H ~ S O IPP.4 , or PoC13 4-oxo-1,4-H?-quinoline 1-CeH&oso-l ,2,3,4-H4-quinoline, PPA 1-(4-CHaCsH4SO~)-4-oso-6-Cl-l,2,3,4-H~-quinoline, POC13, low yield (also for 6-Br) 4-Oxo-thiachrolnan: PP.4 8-CH3-4-oso-thiachroman~ HzS04 1-O~o-tmns-3,4-cyclopentano-l,2,3,4-H~-naphthalene, .41C13 l-C6HjCO-j-oxo-l .2.2a,3,4,5-H~-benz[cd]indole, AICI:, (also for l-CH3CO) l-Oso-l,2,3,4.j.6,',8-H~-anthracene,SnC14, 95% ?-CH.,-I-oso-l.2,3,4,5,6,',8-H~-anthracene,80% 1 ,4-(CHi).~-9-[2,~-(CH3)~C~H~]-10-oxo-9,1O-H~-anthracene, ZnCl:, NaCl 1 .3-(CH3):-9-[2.4-(CHj)iC6H3]-10-oxo-9,10-H~-anthracene, ZnCl?, NaCl 1 .j-Dioso-4,8,10-(CH8)~-l,2,3,4~5~6,7,8-H~-anthracene~ PP.4, 63% 9.lO-.hthraquinone-9-C", H2S01 1-Oxo-l,2>3,4,5,6,7,8-H8-phenanthrene 9-Oxo-l,2,3,4,4a,9.1O,trans-lOa-Hs-phenanthrene, H F or HzS04 8-CH.3-1-oxo-l,2,3,4-H4-phenanthrene 1 Oa-H01.C-9-oxo-l,2,4a,9,10,10a-H6-phenanthrene> H?SOI, 100% 9-CHaO-l-oso-l ,2,3,4-H2-H2-henz [cd ]indole. AIClr, 26r; 4-0~0-1.2.3.4-H1-quinoIine, AICI,j. NaC1. 2jC,'; l-(NCCHnCH?i-4-oxo-l.2.3.4-Hl-quinoline. HCl. AlCl:, H~)-4-oxo-~-CHn-l .2,3,4-H4-quinoline,HC1, AICI,?. 295(, H?)-4-oxo-6-Cl-l.2,3,4-H~-quinoline. HCI. .41Cla, 747; H2!-4-oxo-7-C1-1 .2.3.4-H1-quinoline,HCl. AlC1;1, low Tield l-(NCCHzCHr] - 4 - o s o - 6 . ~ - ( C H 1 ).2.3,4-H1-quinoline, ~-l HCl? AlCl 8-CHa-1.7-dioxo-l.2.3.j.6.7-HG-benz [ij Iquinolizine. HCl. AICI:f, 19 8-CI-1.7-dioxo-1.2.3.5.6.7-H6-benzo[ij ]quinolizine. HCI. AlCli 9421-1.?-dioxo-1.2.3..5,6.7-H6-benzo [ij Iquinolizine, HCI. AIC1,i. 7 - j O '
Kc,fermi.p ( ?i I
(7i)
(4;) (2?i (2ij ( - / iI
(2i I
RING-CLOSURE ACYLATION (Aromatics, Sulfonylation) Proditct arid Reagent
2.3-H2-benzo[e]thianaphthene-1.I-dioxide. AICl:+ 54' Benzo [fjthiachroman-1.1 -dioxide. AlCl?. 65 7~ Benzo [g]homothiachroman-1.l-dioxide. .11Cls, 16'-:
RqiPreric.
1
RING-CLOSURE ACYLATION (Complex) Product arid Reagent
,421
Refermcr (7Hi (.3H i
4 , j 8- ( CH .i 1.!- I - t e t r a1on c . .A IC1.i 4,6.7-(CHi)~-l-tetralone.X I C L . PP.l 9-0~0-1,2.3.4.4a,9,10.trans-lOa-Hs-phenanthrene. .%IC.I i 1.8-Diox0-4.5.9.10-(CH
(36.V) ( 7O.V)
2,4-(CH30)?CsHjCH2CbHu (some dialkk lation 1 1- and 2-CsHaCH-naphthalene. \ ields from 70 -
(9.V) (38.V)
80%
Phenolic resin intermcdiatrs
1 684
(7.L.)
(4U.V 1 (67,V)
2-HO-5-(4-ClC,H4CH?I-C,H C O I C H , (4-FCsHd)zCH? 3.4-C1.C gH 3CH ?COHj, 64 '-c,
ArOH (6 examples) Toluene [also for ~ , ~ - ( C H I ) ? C ~ H I . 1,3-(CH3)2CeHir I ,4-(CHa)?C6Hd, and mesitylene] (CaH,j)3CCI,HCI. 1.2-CI2CbHI Phenol (also for 2-CH3) Stvrene. 71 v o HiSO, Benzene Phenol [also for 4-CH3, 4-CI. and CsH,CHClCHj 2,6-(CH3)zI 3,4-(CH3)2CeHaOH
(6h.\. I
( 3 3 N , SON, 8 7 .\?) ( 7 c ) s , J7.V)
CH3COCH?CHzCH=CH:. .\ICle tt-C6HisCH=CH?, H ~ S O I CaH170H, AlClr. HI.SOA 01' H3P04 Diisobutylene, .-\lCld! CeH:.NO?or CH3NOr RCH=CH?, H?SO4
(8S.V)
[ g:;
Benzene [also for toluene. anisole. 1,2-(CH,)zCsH4, 1,3-(CH3)?CsH 1- and 2- [(CH,~).ICHCH.C.H.!-ri~pht~ialene Naphthalene or BFB Toluene (CH3)3CCHsCl. HISO, (CH3)dCCH20H csH jcPH6 Benzene [also for 1,4-(CHjlaCsH1 3 -Valerolactone and 9,iO-H2-phenanthrene] 4-HO-pentane sulfonic acid sultone. CaHjCH(CH3)CH?CH?CH.SO;H:deL'Benzene 1,2-(CH3)2CsH4(also for anisole and tetralin) Benzene (similarly for toluene) ~-CH~C~H~(~-CSH~) Toluene [also for benzene and similarly for 3,4-(CH3),CsHrOHi Benzene
('19.V 1
4-HOC:sHiCH.CH?COCHj, 28-455
Phenolic diphenylmethanes 4-CHaCGH,CH(c6H.j)~ 4-HOCsH,C( CgHj)3 (C6Hj)*CHCH3and more complex products HOC~HICH(CH~)C~H: 2- [CsH5C(CH~)y]-4.5-(CH11?CeHzOH, 7470
( 7U.V) ( 58.V )
(6s)
(12.V, 62.2', 75,V) ( 23'V j (JJ.1') ( 28.1'j (17.V) ( 29.v )
(AV)
FRIEDEL-CRAFTS REACTIONS
OPEN-CHAIN ALKYLATION (Aromatics) (Continued) Reagent
Aromatic
1:2,3-(HO)3CsHa Benzene (also for toluene, anisole, C ~ H ~ B Iand - , CeH5Cl) CsH6C1 .4rH Benzene Benzene (also for toluene; Toluene Benzene Benzene Benzene I,~-(CH~)ZC (also ~ H for ~ 1:4-) Anisole Benzene (also for toluene) Benzene [also for toluene and 1,3-(CH3)zCeH41 1,4-(HO)?-Z-CH3-naphthalene Benzene Benzene Anthracene
(CeH,)*CHCN, 60-82c0 2-HOCsH&H2CH2SOjH sultone, AlCl I
tram-2-HO-cyclohexane-acetic acid lactone, AlC13 1,2-(ClCO)zCsH4, !dC13 1- C H ~ - ~ - C Z H ~ O ? C - ~ - O S O - ~ C?HjO~CCH~-cyclohexene-3, .41C13 (also for methyl ester) 2-( CHz=CHCHz)-l -tetralone, AlC13 2-( CH*=CHCHz)-4-CH3-1 -tetralone, AlC13 Phytol or isophytol, various catalysts
5-hfesitoylacenaphthylene,HCl, AlC13 1-Br-5-mesitoylacenaphthene, A1Clu S-(C1CHz)-phthalimide, .41Cls, CS2 or ZnCl2, C6HsN02
(4-C1CsHn)zCHCC13 S o reaction (CsHa)zCHCHzCO2H, 8770 ( 17N) 178N) (f CcH;iqCHCHoSO?CH . Si0?-;\1?03 CHZ=CHCOZH, BFV(C Z H ~ ) Z O (similarly for corresponding lactone, nitrile, methyl and ethyl esters, and amide)
Product 2-CsH5-thiophene 2-CH3-5-HO2CCH~CH2-pyrrole(corresponding nitrile was obtained only from 2,4-(C11a)zpyrrole ; several failures occurred with the methyl ester)
J-C4H9Br, illCl3, CS2 t-C4HgOH, SnC14, CS? t-C4H9Br, AlC13, C S ? f-C,H&l, SnClr, CSZ
?-CH3-5-(s-C4Hg)-furan (also some t-CaH9) 2 , 5 - ( t-C4H9)2-thiophene 2-CH302C-j-t-C1H9-furan 2- and 3-t-C4Hy-thiophene (also some dialkylation and formation of biaryl tvpe products I 2-CH3-5-t-C4Hg-thiophene,'Z5%, and 2-CH3-3,5(t-C~Hg)z-thiophene, 60 yG 2- [(iYC)XHCH?]-thiophene,65% No reaction 2,5- [C6HjC(CHs)>]-thiophene
3-CH3-thiophene [also for Z-CeHj, t-CdHgCI, FeC13, CS2 2,5-(CH3)2,and 2,5-(CzH5)$] Thiophene CH?=C(CN)?, AlC13, (CHC12)z Thiophene (also for 2-Cl) CsHjCH2C1, I ? Thiophene CsH5C(CH,)?OH;SnClr. CS? [also for ICRH, ) X ( C H A O H 1 Thiophene (CBH~)~COH ' -
Refercnre (74) (6Q)
No reaction
OPEN-CHAIN PSEUDOALKYLATION (Aromatics) Aromatic t-C&I&&5 Tetralin (also for uol\ st\ 1 ene' Benzene Benzene
Kengent
PC13. AlC13 Pc13. .AlCli CH3SC1, XIC
If the phenol is previously saturated with hydrochloric acid, the reaction exhibits simple third-order kinetics. T h e rate of reaction of cyclohexene with benzene in thc presence of aluminum chloride is independent of time or concentration of cyclohexene, but is directly proportional to the concentration of
Reference
Product
4-t-C.iHbCsH4PCl2 f CloPLtetralin
hydrochloric acid (53.4). This is taken to indicate that the actual alkylating agent is RC1 and not olefin. The rate dependence on hydrochloric acid is thus related to the rate of formation of RC1. T h e rate of reaction betTveen phenol and styrene in glacial acetic acid containing perchloric acid is proportional
to the concentration of perchloric acid and independent of initial styrene concentration: although there are batch variations in the effect of initial phenol The acetoxoniurn concentration (29A) ion is considered IO be the effective catalyst. T h e rates of reaction between 3,4-di-
VOL. 48, NO. 9, P A R T II
SEPTEMBER 1956
1685
UNIT PROCESSES REVIEW chlorobenzyl chloride a n d benzene. chlorobenzene, toluene. and m-xylene are third order (70'4). T h e substituents on the ring undergoing substitution havr consistent but rather small influences on the relati\-e rates. Dilution of the nitrobenzene solvent with methylcyclohesanr has onI>-a small diminishins effect o n thc rate. I t is considered that the transition stare involves a nucleophilic displacement by the aromatic on a complex beriveen the benzyl halide a n d aluminum chloride. O d a and Komura ( G 3 - i ) have published a review which includes consideration of the Friedel-Crafts reactions of sulfen) 1 chlorides. ChloromethJ-lationfo1lotvt.d b!. cyclization via aininr displacemenr or. alternacivel)-. l'ormation of a Slannich base fulloived b!- ring-closure alkylation may bt. considered to be the intermediate steps in the synthesis of 3 - a ~ a - l - n i e t h y I - ~ ethyl - 1,2.3,4 - tetrahydrophenanthrene (6A). Added sulfur to inhibir pol) Inerizdtion and the use of aqueous formaldehyde dnd hydrochloric acid permitted the succrssful chlorometh!.la tion of chr sidechain double bond in st!.rene xvithout affecting the benzene ring 170!2.i). Further evidence is advanced in support of the claim that FCH?OH is thc actual intermediate in fluorornethylation (O(i.1). Previously existing kinatic d a t a on chloromethylations haire been shoivn to be in error (77A). Ch1orometh)-lation is a hislily selective reaction and heavily dependent upon the nature of substituents on the ring undergoing substitution a n d reaction conditions. hligration of optically active allyl groups indicates steric control of asymmetric induction in the ortho-Claisen rearrangement (%A). Kinetic and stereochemical evidence suggests that nuclear alkylation of phenols may occur by direct displacement to give CI-alkylation ra ther than through 0-alkylation follo\ved by rearrangrnient ( //.i.J I A ) . Conclusive evidence from several approaches ( 7 9 A : -72.4. -3J.4. 59.4. 77'4, 7.Q.1. 80.4) has confirmed the viriv that thr para-Claisen rearrangement is a twostep process involving a n ortho-dienone intrrmediarr with over-all retention of configuration and structure of the migrating group being due to t\vo successive allylic- rearrangements. T h e literature covered by this period o f review involves only a feiv reactions using (3-1 4 ( 7 1.4. 37.4. 70.1. !13:1) i n
RING-CLOSURE ALKYLATION (Aromatics) Pi oduct uiid Rrngrrii 2-Oxo-intlolinc. . l I ( : l , . S a ( :I 1---( CH, )$-2-oxo-indolinr. AICI NaCl l-Oxo-3-HOyC-4-CH.-7-HO-indan. hlC:l,. XaCI 1- [4-(CH3)2;SC,H4]-i-C:,.Hi-indrne,C H I C O ~ HH?SO, . jsirnilat I! lor 5 ICH')JN, 1.3'- [4-(CH:I!SC:,,H, ~2-indct;c~. (:H C:O>H.HySO, Naphthalene. SnC:l:. 82' 1 ;4-(CH, i$-6-CH40-l.2.3.4-H1-naphthalrne. HIS( 1.4.6,7-(CH &ad. .Vnui; S.S.S.K 97, 839~-42(1954). (53.4) Levedev. N. N.,Zhiir. 0hshciii.i Khini. 24. 1'82-7 11954). (54.4 I Lexvenz. '2' F., SeriJan. K. T.. J . Ani. L'hem. Sac. 75. 4087-9 11053 I . (55.4) Ibid.;pp. 5753-5, ( 56A ) Marnedaliev, Y. G.! Veliev. S.V.. Ijoklady A k a d . .VnuX S.S.S. R . 92, 325-8 (1953 I. (57.1) Ibid., pp. 5--3-5. (58;i) hlarey, .4, F.. Baddar? F. G . , ;\\rad. \ \ , I.. .Va/iirt 172, 1186 -(1953 i .
RING-CLOSURE ALKYLATION (Complex) (Continued) Prodiic/ nrid Rrngerit
(59.ij Sfarvell, I;. S . , Teranishi, R . , J . Am. Chrrri. SOC. 76, 6165-8 (1954 (60.1, Lledcalf. F, C:., L'riens; G. N., C . S. Patent 2 , 6 9 4 , 0 9 ~(Nov. 9, 19541. (61.4j hloed. H . D.. Asscher, XI., others. Rec. trai. chim. 71, 933-44 (1952 I , (62Aj K, V. de Bataafsche Petroleum Maatschappij. Dutch Patent 77,119 (Jan. 15, 1955). (63.1) Oda. K.. Nornura, XI., Kagaku. 8, 70-9 (1933). (64.4) Offutt. N'. C;.~C. S. Patent 2,684,389 (July20. 1954:. (65.11 Ogata, Y., Chemistry arid Chmm. I d ( J a b a n ) 8. 204-7 11955). (66.4) OlAh,' G., Pavlith. ~.4.,Acta Chini. .4cad. Sci. Hune. 3, 425 -9 (1 953 I. (67.4) Paltz. \V. J., Tegge. B. K., C . S. Patent 2,667,519 (Jan. 26, 1954). (68.4) Parham, CY. E.. Traynelis, V. J.. J , l r n . Chem. Soc. 76, 4960 -2 (1954 1. (69.4) Petrova, A. Xf., Zhur. Obshchei Khirn. 24, 491-3 (1954). (70.4) Pines, H., Ipatieff, V. N., U . S. Patent 2,671,815 (&{arch 9. 1954). (71:\) Rhoads. S . J., Raulins, R., Reynolds, R . D., J . A m . Chem. S'oc. 75, 2531-2 (1953). (-2.4) Romadane, I., RodinS, E.. Latcij a s P S R Zincitnu .-tkad. VZstir. 1954, pp. 115-18. ).
Chioman. H J P O ~1.l C , , (,-C?H5-'-HO-coumarin. HsSO, 6-Br-7-HO-coumarin. H&OI .j-HO-6-RSHCO-coumarin. .AlC:l,>. 30 -60' ( ( 6 esamples ) 4.--( C H , 12-5-HO-coumarin.H?SC>, 4-CH:I-6-C2Hj-7-CH30-co~imarin. AICI I or H ~ S O (dlso I for 6-n-C.,H;J 4-C;H.I-6-RSHCO---HO-coumarin, H.SOr. 2-50' ( 5 examples j 4-CH3-5-CH10-8-C2Hj-coumarin. P.0, 4H-3-0~0-4-imino-5-CH.I-'-HO-2.3-Hy-1-benzopyran. HCI, ZnC:l? 4.8-(CH ,~2-5.'-(HO)?-cournarin, HCI. C H i C O r H (similarly for 13 examples 1 4.5-(CH,,)~-~-HO-8-CyHi-coiimari~~, .4lC:l,,. H?SOd or P I O , 2-CH:i-6-CH10-quinoline.HC1 I H-i -CH ,-'-CH,,CO-2,2a,3.4-H4-cyclopent[cd ]indene 2.3-Cyclopentano-2,3-H?-benzo [b /furan 9-H02C-fluorene. .AlCl,g, 7 1 - 8 1 3-HO-2-acenaphthenone 2-CtiHS-naphtho[blthiophene. .\IC1 Anthracene. AlCls 9.10-(CHI):-anthracene, .UCl 9.9.10.10-(CH3)r-9,10-H~-anthracenr. AICI 2.3.6.T-(CH30)1-9.10-Hp-anthracene. HC1 9-H.N-1O-R-phenanthrene. HrSOl ( 5 examples) 9-HO-2,3-H2-1 -benzonaphthenone. .1IC,, 7.8-benzocoumarin, HzSO, 4-CI-benzanthrone, HsSOr (dlso for 9- and 10-1 Naphtho[2.3-e]pyrene, AICI.,. NaCl 4,5,6,6a.6b.7.8.12b-Ha-benzolj Ifluoranthene. PPA Heptaphene. 400 "C. (other products are dibenzo [b,kl]picene and anthracenoj2.1 -a]naphthacene)
(22c-i
(XI
( 1Jl.) (2fL.J
(7L.j (Z-IC-)
(71C-1 (77L.l (2JL?)
(-IC) (16c:j (3C) (27C) (78C) (12C) ( i c -, 23C) (71') (5L.)
MISCELLANEOUS .4romatic .irrSn ( 3 examples) ( CsH ,CH2),Sn
ArSn
4-CH3CsH,0H (similarly for 3 analogs Phenol 4-CH8CgHaOH (similarly for many examples) 4-CHdC6H,0H (similarly for several examples)
Reagerrt CH.jCOCI>.AICls C:H,COCI, .41C13 (similarly for CsHjCOCI) CsHjCHnCI. ;\ICls CCI,, A1Cl3, C S 2 (unsuccessful for a number of similar reagents i C6HjCC13, AIC18, CSy .4rCCla, .41C13 CsHaCC13, AIClj, CS::
Produr/ XrCOCHj, C6HjCHtCOCH3, 78(,c
ArCH 2C g H 1-0u0-4-CH~-4-(31~C-2.5-cyclohexadi1~nr, 60 I ' c 4-HOCsH4COCsHj, 92',, 2-.4rCO-4-CHs-C6HIOHand 2,6-(hrCO )?-4-C:H3C6H?OH 6,12-(CsHj)?-2,8-(CH3)p-6.12-eposv-OH.1 2Hdibenzo [b,f][l,j]dioxocin, 25lrl8
VOL. 48, NO. 9 , P A R T II
SEPTEMBER 1956
1687
UNIT PROCESSES REVIEW (73.4) Rondestvedt, C. S., Jr., Filbev, A. H., J . Org. Chem. 19, 119-28 (1954). Ro~thstein,E., Chemistry c 3 Industry 1954. D. 403. Ruhrc Zbtd., 1954. PD. 2047-52. (38B) Castel, ‘P:, Orza’esi, H., TraLs. soc. pharm. .Montpellier 10,41-2(1950). (39B) Cauquil, G., Barrera, H., Barrera, R., Bull. soc. chim. France 1953, pp. 1111-16. (40B) Cauquil, G., Rouzaud, J., Compt. rend. 237, 1720-2 1’20-2 (1953). (41B) Charlton, J. C., Hughes, E. D., J . Chem. Sac., 11954, 9 5 4 ,pp. ) ~ . 2939-42. /42B) Clar. E.. Kellv. N‘.. J . A m . Chrm. So;. 76. 3502-4 f lb54 i Clar, E..’Stewart, D. G., Ibid., 76, 3504-7 (1955). Cram, D. J., .Allinger, N.L., Ibid.. 76, 726-31 (1954). Cram, D. J . , Allinger, N. L., Steinberg, H., Ibid., 76, 6132-41 (1954). Cram. D. J., Daeniker, H. C . , Ibid., 76, 2743-52 (1954). 14-B) Cromudl, N.H., and Mohrbacher, R. J., Ibid., 75, 6252-6 (1953). (48B) Curtin, D. Y . , Crew, hf. C., Ibid., 76, 3719-22 (1954). (49B) Dannenberg, H., Dannenberg, D., 2..Yaturjorsch. 8b, 165-73 (1953). (50B) Dauben, FV. G., Jiu, J.. J . Am. Chem. SOC. 76, 4426-9 (1954). ( j l B ) Davies, A. G., Kenyon, J., others; J . Chem. Soc. 1954, pp. 3474-9. (52Bj Davies, J. E.: King, F. E., Roberts, J. C., Chemistry & Industry 1954, pp. 1110-11. (53B) Dean, F. If.,Evans, E., Robertson A , , J . Chem. Soc., 1954, pp. 4565-32. (54B) DeTar, D. F., Relyea, D. I.. J . .1m. Chem. Soc. 76, 1680-5 (1954). ( j 5 B ) Dgv; S.: J . Zndian Chem. Soc. 30, 389-800 (1953). (56B) Dreiding, A. S., Tomasewski, A. J., J . Am. Chem. Soc. 76, 540-5 (1954). (5-B) Evans, D. D., Morris, D. S., others, J . Chem. SOL.1954, pp. 1687-90. 58B) Evans, R. F . ?Smith: J. C., Strauss, F. B., J . Inst. Pelroleurn 40, --13 11954). (59Bj rei‘ilman. I. R., Simeonov, .4. X.. Zhur. Obshchei Khim. 23, 2043-6 (1953 I. (GOB) Fuson, K. C . , Emmons, \V. I).. Pnrsliall. G . I$-,, J. :lm. Chem. SUC.76,5466-9 (1954). ( 6 l B ) Furon, K. C.. Friedlander. IV. S., Ibid..76, 4989-91 (1954). (62Bj Fuson, R . C . , Friedlander, \\-. S., Parshall. G. \V.,Ibid., 76, 511921 (1954). (63B) Fuson, R . C., Harnmann, FV. C., Smith, \$-, E., J . Org. Chem. 19, 674-7 (1954). (64B) Fuson, R. C., Lfange, F. E., Zbid., 19, 806-9 (1954). (65Bj Fuson, R. C., T$-allingford, H. P., J . Ani. Chem. Soc. 75, 5950-2 ( 195 3 11.
FRIEDEL-CRAFTS REACTIONS (66B1 Gardner, P. D., Ihid., 76, 453-2 (1954). (67B) Gault, H . , Sclim, Si..Compt. r2vd. 240,630-1 (1955 j. (68B) Ghosal, M., Bagchi. P.? Science atid Culture (India)20, 197-8 (1954’. (69B) Gray, G. tV., Jones. B.. J. Chew SOC.1954, pp. 678-83. (70B) Green, A. L., Hey. D. H.. I b z z , , 1954, pp. 4306-18. (71B i Gupta, S. C. S., Bhattacharjee, A , J . Indian Chem. Soc. 30, 805-8 119543. (72B) Gdpta, S. C. S..Chatterjee. D. s.. Ibid.,29, 438-42 (1952 I , (73B) Gupta, S. C. S.. Chatterjee. D. S . . Ibid., 31, 11-16 (19541. (74B) Ibid., 31, 285-90 (19541. (75B) Gupta, S. C. S.,Chatterjee. D. S . . Science and Cultzo-r (India I 19, 47-8 (1953). (76B) Gupta. ‘ R . C . , lfuthana. Si. S , j . Indian Ins!. Sci. 35A, 259-62 (1953). (77B) Ibid., pp. 263--. (78B) Ibid., pp. 307-9. (79B) Ibtd., pp. 310-14. (80B) Haksar, C. S . : .-lgra ~ ~ r ~ J. i : . Research 2, 233-9 (1953,. (81B) Henze, H . R . , Isbell. A. F.. J..h. Chem. SOC.7 6 , 4152-6 119543. (82B) HoAn, N., Compt. ~ m d 238, . ll36--? (1954). (83B) Howard: G. A , Tatchell, A. R . . Chemistry 3 Industry 1954, p. 5 11. (84B) Ishidate, hf., Nambara. T., Phorrr,. Bull. 1, 290-2 (1953). (85Bj Johnson, LV.. S.. Graber. R . P C. S.Patent 2,683,738 (Julv 13. 1954’1. Johnson, R. G., \Villis, H . B.. Gilman, H., J . .h. Cheni. Sot. 7 6 , 6407-8 (1 954). Johnston, tV. T. G.. Smith. J . C , Staveley, C. SI.. Chrrriistr> 2 Industry 1954, p. 60-. Joshi, G. G., Shah, N. Sf., J . Indian Chem. SOC. 31, 213-30 (1954). Joshi, S. S., Singh, H . . J. A r i n Chem. SOC.76, 4993-4 ( 1 9 5 4 ~ . Kaluszyner, A , , Reuter. S.. Ihid., 75, 5126-7 (1953). Kaye. I. A . , Klein, H . C., Burlant, M’.J., Ibid., 75, 745-6 (1953). Kimoto, S.,.\saki, K., Kishi, S.. J . Pharm. SOC.Japan 74, 358-60 (1954). Kindler, K., Oelschlager, H., Chem. Ber. 87. 194-202 119541. King, F.’E., King,’ T. J., Stokes, P. J., J . Chem. Sac., 1954, pp. 4587-94. King, F. E., King, T. J., Topliss, J. G., Chemistry 3 Industry 1954, pp. 108-9. Kinsley, D. A., Plant, S. G. P., J. Chem. Soc., 1954, pp. 1341-3. Koike, E., Okawa, hl., J. Chem. SOC.Japan, Pure Chem. 74, 9714 (1953). Koike, E., and Okawa, hf., Ihid., 75.83-6 (1954). Koike, E., Okawa: l f . . Kaneko. T.. J . Chem. SOC.Japan. Ind. Chem. 55, 535-8 (1952). Kost: A . N.. Vestnik .ZlosXoc~. I-niz’. 7 , Ser. Fiz. .tfal. i Esterizrn. *L\huk KO.8, 35-‘ (19523. Kosupe. T.. Sato. M..J. Pharm. Socy Japan, Pure Chem. 74, 113941 (1954). 102B) Krimmel, C. P.. U. S. Patent 2,629,737 (Feb. 24, 1953). 103B) Krishnamurti, Sl.,Seshadri, T. R . . Chemistry 3 Industry 1954, pp. 542--3.
(104B) Krishnamurti, hL, Seshadri, T. R.. J . Sci. Ind. Research (India) 13B, 474-5 (1954). (105B) Krishnamurti, hl., Seshadri, T. R., Proc. Indian h a d . Sci. 39A, 1 4 4 52 (1954). (106Bj Kuhn, R., Staab, H. A , , Chem. Ber. 87.266-72 (1954). ( 1 0 7 ~ KulkB, ) RI., J. Am: Chem. SOC.i 6 , 5469-71 (1954). (108B) Lindahl, R . ,G., .-inn. .icad. Sci. Fennzcae 48, :-60 (1953). (109B) Lespagnol. A , . Hallot, J., Bull. soc. pharm. Lille, 1954, pp. 45-6. f l l O B i Lrwenz, G. F., Serijan, K . T . , J . A m . Chem. Sac. 75, 408--9 (1953). (111B) I b i d . , p p . 5753-5. (112B) Loewenthal, H. J. E.: J.Chem. SOL. 1953, pp. 3962-8. (113B) Long, J. P., Schueler, F. \ V . , J . A m . Pharm. Assoc. 43, 79-86 (1954). (114B) Lutz. R . E., Bauer, C. R., J. .im. Chem. Soc. 75, 5997-6002 (1953). (115B) Lutz. R. E., Bailey, P. S., others, Ibid.. 75. 5039-44 11953). (116B) SlacGregor, I. R., Seblett, R . F., Cook, C. H., J. Ory. Chern. 19, 626-30 (1954). (117B) hIacSIillan, J., J . Chem. Soc., 1954, pp. 2585-7. (118B) XfacSfillan, J.. Llulholland, T. P. C.,, others, Ibid.:1954, 429-35. (119B) hiani. R.. Venkataraman. h . Current Sci. (India) 23, 220-1 f1954). (120B) Slarathey. SI.G.. .ithavale, J. LI J . r n i u . Poona. Science an T e c h d . . 1953, pp. 90-3. 1121B) Sfartynoff, Sf.,Compt. rend. 238, 249-51 (1954~1. (122B) hlatsuda, ‘S,,iiatsuda, H.: Kikkawa. S.,J . Chem. SOC.Japan, Ind. Chern. 57, 845-7 (1954). 1123B) Sfatti, J., Perrier, .M.. Bull. soc. chim. France. 1955, pp, 525-30. (124B) Mellier. hf. T.,. OIEaeineuv 9, 167-8 (1954). (125B) Sferck 8r Co., Inc., Brit. Patent 702,012 (Jan. 6, 1954). (126B) Ibid., 713,696 ( h u 5 . 18, 1954). (127B) Morrison, R. T., Il’ishman, Sf., J . Am. Chem. Soc. 76, 1059-61 (1 954). (128B) Motoyanagi, T.. Yamashita, Y . , Ishii, Y . , J. Chern. Soc. Japan, Ind. Chem. 56, 887-90 (1953). (129B) Nakazawa, K., J . Pharm. SOC. Japan 74, 836-9 (1954). (130B) Nakazawa. K . , hfatsuura, S..Ibid., 74,40-2 (1954). (131B) Ibid., pp. 69-72. (132B) Ibid., pp. 1254-5. (133B) Nakazawa, K . , Sfatsuura, S..Baba. S.?Ibid., 74, 498-501 (1954). (134B) Nakazawa, K . . Sfatsuura, S.,Kusuda, K.. Ibid., 74, 495-7 (1954,. (135Bj Nakazawa. K.. Tsubouchi, S., Ibid., 74, 1254-5 (1954,. (136B) Nambara, T.. Ibid., 74, 13-16 (1954). (137B) Oki, Sf.,Bull. Chzm. Sor. Japan 26, 331-6 (19531. (138B) Pailer, hf , Reifschneider. tV.. .tfonatsh. 84, 585-91 (1953 1, (139B) Panizzi, L . , Nicolaus. R., Gar-. chim. ital. 83, 774-81 (1953). (140B) Parikh, R . J . , Thakor: 1’. M.:J. Indian Chem. Soc. 31, 137-40 (1954). (141B) Petrov, A. D.. Chernyshev, E. A , , Kulish, I. .\,, Doklady Akad. :\’aukS.S.S.R. 100,920-32(1955). (142B) Petrova, -4. XI.. Zhur. Obshchei Khim. 24, 491-3 (1954).
(143B) Philbin, E. lf.,Slvirski, J., \\-heeler T. S., C h i i s t r y 3 Industry. 1955, pp. 445-6. (144B) Phillips, D. D., hIcLVhorter, E. J.? J. A m . Chcrn. Soc. 76, 4948-50 (1954). (145B) Profft; E., Chem. Tech. (Berlin) 6 , 366-72 (1954). (146B) Protiva, hf., Exner, O., Chem. List) 47, 736-41 (1953). (147B) Ramage, G. R.! Stead, C. V.. J . Chem. So,:., 1953, pp. 3602-6. (148B) Rastogia, R. P.? Sen. A. B., J . Indian Cherri. SOC. 30, 514-18 (1953). (149B) Reinheimer. J. D.: Taylor, S.. J . Org. Chem. 19, 802-5 (1954). (1jOB) Richtzenhain. H., Alfredsson, B.. Acta Chem. S’cand. 8, 1519-29 (1954). (1j l B ) Riedl, LV., .4rm. 585, 32-7 (1954). (1j2B) Riedl, W., Risse, K. H., Chem. B e l . 87, 865-8 (1954). (153B) Rigaudy, J.. Farthouat. J. Sf,, Buli. SOC. chim. France, 1954, 1261-5. (154B) Robertson, A , , Clarke, J . R . , L‘.S. Patent 2,680,119 (June 1. 1954). ( 1j j B ) Rorig, K . , J . .Im. Cherri. SOC.75, 5381-3 (1953). (156B) Royer, R., Bisaqni, i,,Bull SOL-. chim. France 1954, pp. 486-92. ( 157B) Sallay, I., Fodor, G., d c t a Chin). Acad. Sci. Hung. 2 , 5--60 (1952). (1 5 8 s ) Sato, K . , Sfiyamoto? 0 . .J . Chem. Sac. Japan, Pure Cheni. 7 5 , 225-1 10i4) \ - ~ ‘ -r -
(159B) Schlatter, hl. J.! J . .ini. Chem. Soc. 76,4952-7 (1954). (160B) Simons, J. H., Black, tV. T., Clark. R . F.. Ibid., 7 5 . 5621-2 (1953). (161B) Smith, H . A:. Thompson; R . G.. Ibid.. 77. 1778-83 11955). (162B) Stetter; H:,Krause, H. J , Chem Ber. 87, 209-11 (1954). (163B) Stevens. LV, H . Crobder, D. i . Can. J. Cheni. 32, ’92-801 (1954). (164B) Stevens, C. L., Dykstra. S. J., J. Am. Chem. Soc. 75, 5975-8 (1953). (165B) Ibid., 76, 4402-5 (1954). (166B) Subluskey. L . A , . Sanderson, T. F., J. .im. Chem. Soc. 7 6 . 3512-15 (1954). (16‘B) Szmant, H . H , , Izvitt, G., Ibid., 76, 5459-61 ( 1 954). (168B) Szmant, H. H . , Skendrovich, S.. Ibid., 76, 2282 (1954). (169B) Tadros, W.,Ekladius, L.. Salka, -4.B., J . Chem. SOC. 1954, pp 2351-3. (170B) Takegami, Y ., Azuma, K.. Shingu, H., J Chem. SOC.Japan, Ind. Chem. 55. 630-1 11952 J. (171B) Takegami, Y., Shingu, H . , Ibid.. 5 5 , 717-8 (1952). (172B) Thakor, V. X i . , Shah, R . C.. J . Indian Chem. Soc. 31, 597-9 i\ l- O i 4 i - - ‘ I ’
(1’3B) Thiec, J . , Ann. chim. (Paris) 9, 51-96 (1954). (174B) Thoi, L. V., Belloc. A , , Compt. rend. 239,500-2 (1954). 1175Bi Tomita. M.. Kumaoka. H., Takase, ’ M.,J . Pharm. SOL.. Japan 74, 850-3 (1954). (l76B) Trave, R.. Biachetti, G.! &11 accad. nail. Lincei, Rend., Classe sci. J?S. mat. e nut. 11, 211-18 (1951). ( 1 T B ) Villani, F. J., King, M. S.,others, J. Am. Chem. SOL. 7 6 , 5623-5 (1954). (178B) Vo-thi, T.-T., NquyCn-HoAn. Compt. rend. 237, 1016-18 (1953). (179B) Walker, G. I., J . A m . Chem. SOC.76, 3999-4003 (1954).
VOL. 48, NO. 9, PART II
SEPTEMBER 1956
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UNIT PROCESSES REVIEW jl80B.1 Walker, H . G.: Jr.. Sanderson, J . J., Hauser, C . R . , Ibid., 75, 4109-10 (1953). (181B) 11-ibaut, J . P.. van X e s , K., Stofberg, J., Rec. trac. chim. 73, 501-12 119541. (182B) \V)nn, R.‘\V. Hoch. P. E., U . S. Patent 2,686,812 (Aug. 1’. 1954) [183B) Ibid 2,694,729 (Nov. 16, 1954). (184B) Yokote, hl., Inahata. S., J. Chem. Soc. Japan, Ind. Chem. 56, 796-7 (1953): 1185B) l-ur‘ev. Y, K.. Elvakov. G. B.. BelvakoLa. Z . L7..’ Zhur. Obshchei Khim. 24, 1j68--1 (1954 1.
Open-Chain Acylation (P se udoa ro rna ti c s) (1C) Arakawa. K . , Pharm. Bull. 1, 331-4 (1953). (2C) Badger? G. 51., Rodda, H . J., Sasse, rY. H. F., Chemistry B Industry 1954, p. 308. ( 3 C ) Badger, G. hf., Rodda, H. J., Sasse, \V. H . F.: J . Chem. Sac. 1954, pp. 4162-8. (4C) Bourne, E. J.: Stacey, M., others, Ibid.? 1954, pp. 2006-12. (5C) Cagniant, P., Capniant, P., Bull. soc. chim. France. 1953, pp. 713-25. ( 6 C ) Ibid., 1953, pp. 921-3. (7C) Campaigne: E. E.. .kcher, W. L., J . A m . Chem. SUC. 75, 989-91 (1953). ( 8 C ) Demerseman, P.. Buu-Hoi, S . P., Royer, R., J . ChPm. Soc., 1954, pp:4193-’. (9C) Gol’dfarb. 1’. L.. Korsakova, I . S., Zzzest. d k a d . .Tad S.S.S.R.. Otdel. Khim. .VauL- 1954, pp. 564-9. (10C) Goncalves, R., Brown. E. V., J.Org. Chem. 19, 4-10 (1954). (11C) Hirao, I., hlizunuma, K.: Hayashi, hl., J . Pharm. Soc. Japan 74, 105-6 (1954). (12C) Hurd, C. D., Oliver. G. L.. J. A m . Chem. SOC.76, 50-1 (1954). (13Cj Kaye, I. A , . Klein: H . C., Burlant, LV. J., Ibid., 75, 745-6 (1953). (14Cj Mingoia, Q., Ferreira, P. C., Anais ,fac. farm. e odontol unio. Sa9 Paulo 11,9-16 (1953). (15C) Nam, N. H.. Buu-HoI, N. P., Xuong, N. D., J.Chem. Soc., 1954, pp. 1630-6, (16C) Parham, \Y. E., Traynelis, V. J., J. A m . Chem. Soc. 76. 4960-2 (1954). ( l 7 C ) Rossiter, E. D., Saxton, J. E., J. Chem. Soc., 1953, pp. 3654-9. (18C) Smith, G. F., Zbid., 1954, pp. 3842-6. (19C) Speeter, M. E., Anthony, W. C., J . A m . Chem. Soc. 76, 6208-10 (1954). (20C) Sy, hi., Buu-Hoi, N. P., Xuong, N. D.. J. Chem. Soc., 1954, pp. 1975-8. (21C) Thakor, V. hi., Shah. R . C.,J. Indian Chem. SOC. 31, 597-9 (1354). (22C) Treibs, .4,, Derra, R., .4nn. 589, 174-5 (1955). (23C) Ukita, C., Watanabe, H., Miyazaki, X I . , J . A m . Chem. Soc. 76, 4584-7 (1954).
Open-Chain Acylation (Aromatics, Gattermann-Koc h-Hoesch) (1D) Burtner, R . R., Brown, J. M., J . A m . Chem. Soc. 75,2334-40 (1953). (2D) Davis, C . T., Geissman, T. A , , Ibid., 76, 3507-11 (1954).
1690
( 3 D j Dean. I:. A I . , Evans, E.: Robrrtson, A . J . Chem. Soc., 1954, pp. 4565’2. (4D) Dijkstra. K.. Backer. H. J.. Rec. traz. chim. 73, 695-703 (1954). (5D) Iengar, R.. Mehta. A. C . . others, J . Sci. Ind. Research ( I n d i a ) 13B, 166-74 (1 954). (6Dj Ishii. Y..J . A y . Chem. Soc. Japan 26, 510-1 3 ( 1 952). (7Dj Kuhn. R.. Staab. H . X.. Chem. Brr. 87, 266 -’2 (1954). (8D) Lele, S. S.. Sethna. S., J . Sci. Ind. Rrirarch, (India) 14B, 101-4 (1955). (9D) Linncll. LV. H.. Mathieson, D. LV,. Modi. D. T.. .J. Chem. .Sac., 1953, pp. 3257-61. (10Dj hfehta. A . C., Seshadri, T. R . ? Varadarajan, S.. Proc. Indian .4cad. Sci. 38A, 381-6 (1953). (11D) Xfoed, H . D.. Asscher. hi.. U . S. Patent 2,683,743 (July 13. 1954). (12D) hloed. H . D., Asscher. hf.:others, Rec. /raz. rhim. 71, 933-44 (1952). (13D) Xiurai, J . , Science Rrp/s.: Saitama I.nit,. 1, 23--6 (1952). (14D) Robertson, A , , Venkateswarlu, V.. Whalley. \Y. B., J. Chem. Soc. 1954, pp. 3137-42. (15D) Sernonsk9. hf., KuZik, J., Cern9, .1.. Chem. Listy 47, 1412 (1953). (16D) sorm, F.: Beneiovi, V., others, Ibid., 48, 1823-36 (1954). (17D) \.Vhalley, 11;. B.. J . C h m . Sac. 1953, pp. 3366-71. (18D) 1-oder. L.. Cheng, E. LV.-K., Burroughs, Lj‘., Proc. Iou*a ,4cad. .%. 61, 2-1 -- (1954).
Open-Chain Acylation (Pseudoaromatics, Gattermann-KochHoesch) (1E) Harwy. I). G , . J . Chem. S u r . 1955, p. 2536. (2Ej Klrinspehn. G. G.. Corwin. A . H.. J . .hi. Chrm. .Sw. 7 6 , 5641-6 (1954). ( 3 E ) Plieningcr. H.: Chem. Bpr. 86, 404-12 1195’1)
(4E) \Vhalley. LV, B.. J. Chem. .Sur. 1954, pp. 1651--3. (5E) Ibid., 1953, pp. 34’9~-83.
Open-Chain Acylation (Aromatics, Sulfonylation) Field, L.. Srttlage. P. H.. ,I. .gin. Chem. SOC.7 6 , 1222-5 (1954j. Leandri, G., Maioli, L.. .4nn. chim. 45,3-13 (1955). (3F) Truce, W.E.. Simms. J . A , , Hill, H . E.. J . -4711.Chem. SOC.75, 5411-13 11953). (4F) Truer, i V . E.. Vriesen. C. K.. Ibid.. 75, 5032--6 (1953).
.-lnscll. hi. I:.,Berman. .4. XI.. I t i d . . 1954, 1792-5. .4skam, V.,Linnell. LV. H.; Ibid.. 1954,2435 -8. .1yer, LV. A , , Humber, L. G , . Taylor, \V. I., Zbid., 1954, 3505 -8. Baddeley, G.. Makar. S. 11.. Ivinson, M . G.: Ibid., 1953, 3969-71, Brunner. O . , Hanke, P . . . \ f O ? i O / J h . 85,88-91 (1954). Buchanan, C., Ritchie, A . C . , ,/, Chem. Soc. 1954, 4523-8. Campbell: A . D., Ibid., 1954, 3659-69. Campbell, iV.,Kidd, D.: Ibid.: 1954,2154-5. Carruthers, W., Ibid., 1953, 3486--9. Chatterjea, J. N., J . Indian Cherri. SOC.31, 101-7 (1954). Clar? E., Kelly, W., J. .4ni. C‘lienj. .SOC. 76, 3502-4 (1954). Clar, E., Stewart, D. G.. Zbid.. 7 6 , 3504-7 (1955). Colonge, J . , Sibeud, J., Boisdb, P > Bull. soc. chim. France 1953, 76:70. Corson, B. B.! Dorsky, J . . othrrs. ,J. Org. Chem. 19, 17-26 (19541. Dann, O., Kokorudz, hl., Chem. Be,-. 86,1449-53(19533. Dannenberg, H., Dannenberg-von Dresler. D., Z. ,Vaturforsch. 8b, 165-73 (1953). Dannenberg, H.: Dannenbcrg-von Dresler. D., Ann. 585, 1-15 (1954) Dev. S.,Chemistry 3 Industry 1954, 1021. Dev, S., J . Indian Chrm. SOC.30, ’89--800(1953). Dreiding. A S., Tomasewski, A . .I.. ~ J . Am. Chem. .Soc. 76, 540 -5 (1954). Dufraisse, C.? Etienne, A , : Goffinrt, B.. Campi. rend. 235, 1349-52 i 1952). );vans. R. F.. Smith, J. C., J . C h m . SOC.1954, 798-800. I-vans: K.F., Smith, J . C . , Strauss, F. B.. J. Inst. Petroleum 40, 7-13 11954). Fuson, R. C., Frey, S. E.. J . O I ~ . C h e m 19, 810-16 (1954). Fuson! R. C., Veazey, T . hi., J . -An?. Chem. Soc. 76, 1169-70 (1954). Gensler, I$’, J.: Samour, C . Xl., LVang, S. Y.;Zbid., 76, 3l5--10 (19541. Ginsburg, I)..J . Chem. .Sot. 1954, 2361-4. Green, A. L., Hey, D . H.. I b i d . , 1954,4306-18. Gupta. S. C. S.: Bhattachai-jre, :\.. J . Indian Chem. Soc. 30, 805--8 (1 954). Gupta. P. S., Bhattacharvya, B. K . , Ihtd. 31, 337-45 (19541. Gupta, S. C. S., Chatterjee, D. N., Ibid., 31, 11-16 (1954). Gupta, R . C., Muthana, 51. is.. .J. Indian Inst. Sci. 35A, 259-62. -
( 1 953). Ibcd.. pp. 263-7.
Ring-Closure Acylation (Aromatics) ( l G ) Alder, K., Haydn, J., Kruger, B., Chem. Ber. 86, 1372-80 (1953). (2G) Allison, J . A . C., Braunholtz, J. T., Mann, F. G.: J . Chem. Soc. 1954, 403-8. (3G) .4miel, Y.,Loffler, A , , Ginsburg. D., J . .4m. Chem. SOC.76, 3625-8 (1954). ( 4 G ) Anderson. A . G., Jr., Wang, S. Y., J . Org. Chem. 19, 277-83 (1954). (5G) .4nsell, hl. F., J. Chem. Soc. 1954, 575-7.
INDUSTRIAL AND ENGINEERING CHEMISTRY
Ibid.. pp. 307--9. [bid., pp. 310-14. Ibid.. 36A, 125-7 (1954). Horii. Z., Tamura, Y . ! othcrs, f . Pharm. Soc. Japan 74, 150-3 ( 1 954 ). Horninq, E . C.: LValker, G. S . , J . .4m. Chem. Soc. 76, 1700--2 (1954). Horton, W. J., Johnson, H . \V., Zollinger, J. L., Ibid., 76, 4587~-9 (1954). Huisgen, R., Rapp, W.:others. .4nn. 586, 52-69 (1954).
UNIT PROCESSES REVIEW (42L) Saharia, G. S . : J . Sei. Ind. Researrh ( I n d i a ) 13B, 544-6 (19543. (43L) Sen, A. B., Bhattacharji. S., J . Indian Chem. Soc. 31, 581-2 (19541. (44L) Sen, .A, B., Parmar, S. S., Ibid.: 30, 720-2 (1953'1. (45Lj Setalvad, J. I.: Shah N. SI.,Ihrd., 30.373-8 11953). (46L) Shah, D. N,: Shah: S . SI..J . 01,o. Chem. 19, 1681-5 (1954,. ,\4-L) Thakor, V. h i . , Shah, R . C., J . Indian Chem. SOC.31, 597-9 (19541. (48L) Tiwari, S. S . , Tewar. B. S . . Ibid.. 31, 79-82 (1954). Talk. F., Chenr. Ber. 8 7 , :49L i Treibs. W.. ( j 0 L j VereS, K:: HorAk: V., Chem. List! 48, 1644-7 (1954). (5 1L j Lt'illiams, J. L. R.. J . .41n. Cheni. .So(. 74,6132-3 (1952 I.
Olefin Acylation ,'lhf ) Belov, V. N.! Rudol'fi, T. A . . Sbornik Statei 0 bshchei Ghxni.. A k a d . AVauk S . S . S . R . 1, 266--4 (1953). (?XI) Bergmann, F.: Klein, J., J . .lm. Chem. SOC.75, 4078 (1953 I. (351) Bullock, M. W.,Brockman, J . X.. Jr., others, Ibid., 76, 1828-32 (1954). (-$Si)Burton, H., Praill, P. F. G . . Chemistry t 3 Industry 1954, p. - 5 . ( j h 1 ) Cauquil, G., Barrera, H., Barrera. R., Bull. soc. chim. France 1953, 1111-16. ,651) Chipman, H. R., L' S. Patent 2,690,439 (Sept. 28. 19541 { - I f ) Dermer, 0. C., Sirnpson, D . PIOC.OLlahoma Acad. SCL 34. 160-2 (1953). ,8h1) Ginsburg, D.. J. Chem. S O C . 1954, 216 1-4.. I9SI) Gunstone, F. D., Tulloch, A . P.. J .4ppl. Chem. 4, 291-6 (1954). 110M) Henecka, H.. Ann., 583, 110-28 (1 953). j l l M ) Henne, .A. L., Tedder, J . hf.,J. Chem. SOC.1953,3628-30. (1 231) Hills, P. R.: McQuillin. F. J., Ibid.. 1953. 406-5. (13M) Kosuge, T..'Okeda, H., others, J . Pharm. SOC. Japan 74, 819-20 11954) \ - - - '/.
(14521) Mathieson, D. I\:.! J . Chem. Sac. 1953, 3248-51. (1551) Ibid., pp. 3251-7. (,1651) Reed, L. J., Niu, C.-I., J . .lm. Chem. Soc. 77, 416-19 (1955). (17M) Rosenmund, K . W., Herzberg, H., Chem. Ber. 87. 1575-81 (1954). ,,l85I) Sondheimer, F.; M'oodwaid, R. B.. J . A m . Chem. SOC.75, 5438-9 (1953). (1951) Soper, Q. F., Buting, W. E., others, Ibid., 76, 4109-12 (1954). C7Oli) Wichterle. 0.. Vogel, I.. Chem. Listy 48; 1225-31. ~I
Open-Chain Alkylation (Aromatics) I l N ) Abdurasuleva, A. R., Doklady Akad. Nauk Uzbek.S.S.R. 11,26-8(1953). (2N) Albert, H. E., J . A m . Chem. SOC. 76, 4983-5 (1954). (3N) Bader, A . R., Ibid., 75, 5967-9 (19531. ,(4N) Bartlett, P. D., Roha, M., Stiles, R. M,, Ibid..> . 76. 2349-53 (1954). - , =.., H., Ellwanger, H., (5N) Brintzinper. Chem . Be?. 87, 300-14 (1954). - - I
1 692
Ibid., Brown, H . (3.. Grayson. ?*I.! 75,62 85-92 (1753). F.. U. S. Patent 2,655,547 Bryner, (Oct. 13; 1953). Buhler, D. R... IVang. C. H., Christensen, B. E . . J . ~ n Chern. . ~oc. 75,4336 (1953). Burtner. R. R . . Ibid., 7 5 - 2334--40 11953). (10N) Buu-Hoi. S.P.. Eckcrt, B.. Derncrseman. P.. ,/. O I , , C / W I I I ,19, ' 2 6 - 3 2 ( 1 954 :. ( 1 1 s : Carpenter. .I, 'r.. Hiantrr. K. I'.. J . Cirrin. SOC.1954, 2-31--5. ( 1 2 s ) Carpenter. SI. S.. Easter. LV. hf.. J . 0:s. C h m . 19, 87--1U2 ( 1954 I . (13N) Caiiquil. G.. Barrera. 13.. Barrera. R.. Bull. SOC. cPim. France 1953, 11 11-16. ( 1 4 N ) C l a r . E.. Stextart. D. G., Brit. Patent 718,711 ( S o v . 1'. 19541. ( 1 5 s ) Clar. E.. Steivart. D. G.. J . Ani. Chem. SOC.7 6 , 3504-' (1 055 !. ( l 6 N ) Cook, C. D.. \Voodworth; R . C!.. J . .4m. Chem. SOC. i5, 6242-4 (1953.) ( 1 Y ) Corson B. B.. Dorsk)-. J . . othrrs. J . O r g . Chcm. 19, 17-26 (1954). (18N) Crawford. H . SI.. Glesmann. S'f. C . . J . rlm. Chein. S o p . 76, 1108-9 (1054) ,..-.
( 1 9 s ) Cross. J. XI.. Chiddiu. hf. E.. C . S. Patent 2,694,727 ( N o v . 16. 1954). 120s') Dixon. J. K.. Saundrrs. K . \V.. IND. E N G . C I f E M . 46, 652-60 (1954). ( 2 l N ) Dobrvanskii. .A. F.. Kornilova. 1..I.. Sbo&X- Statri Obshchei Khirn.. .4i;ad. ,VauirS.S.S.R. 1, 315-19 (1953). ( 2 2 5 ) Emr. .\.. Chem. List? 48, 2-9-80 (1954). ( 2 3 s ) Finn, S. R.. James. J. LV.. Standen. C. J . S.:J . AppI. Chem. 4, 296-300 (1954). (24N) Fuson, R. C.; Sfange, F. E.. J. Or?. ChPm. 19,806-9 (1954). (25N) Gardner, P. D.. J . :lm. Chm. S o c . 76, 45.50-2 11954). (26N) GraY,-G. 'M... Jones: B., J . C'hrnr. SOC.1954,6'8-83. (27N) Gupta. P. S.. Bhattacharyya. B. K.. J. Indian Chem. Sac. 31, 33;-45 (1954). (28N) Hart. H., Cassis. F. -4..J . A v . Chem. SOC.i6. 1634-9 (1954). (29N) Hart. H . . Spliethoff, W'. L.. Eleuterio. H. S., Ibid., 76, 4547-50 (1 0 5 4 ) .
(30Ii) He'nkel and Cie. G. m. b. H., Ger. Patent. 816,855 (Oct. 15. 1951 i . (31N) Hirschmann. R . F.. Miller, R . Wendler, N. L.. J . A m . Chem. SOC. 76,4592-4 (19543. (32Ii) Ipatieff, V. N.. Germain, ,J. E.. Pines, H., Ibid., 75, 6056-(1953). (33N) Isler. O., Doebel, K., Heli.. Chin,. Acta 37,225-33 (1954). (34Ii) Jilek, J. 0..Simik, V., Protiva, hf.. Chem. Listy 47, 874-80 (1953). (35N) Jonsaon, K.. d c t a Chem. Scand. 8 , 1203-10 (1954). ( 3 6 s ) Kave. I. A , , Klein, H . C , Burlant, W. J., J . '4m. Chern. Soc. 75, 745-6 (1953). (37N) King, J., Ramage, G. R.! J . Chem. SOC.1954, 936-8. (38N) Koike, E., Okawa, hf., J . Chem. Soc. Japan 74, 971-4 (1953). (39N) Ibid.. 75, 83-6 (1954). (40N) Kornatsu, S . , Japan. Patent 1282 (March 11.1954). (41N) Kosolapoff, G. M., J . A m . Chem. SOC.76,3222 (1954). (42N) Krimmel, C. P.. Thielen, L. E., others, Org. XYnSvntheses 33, 98-100 (1953).
INDUSTRIAL AND ENGINEERING CHEMISTRY
(43K) K u h b a , 6.. I>.>\.IF: 0 . P.: hid.herji, S.5f.>Curreiit J C I . ( I n d i a ) 23, 158-9 (1954 I. (44N) Kundixer. D. G.. Ovist. E. R. L\. .. J . dnr. Chmi. .Sot. 76, 2501- 2 (1354). 1 4 5 s I Lagidze. R. SI.,Potskhverarhvili. B. S.: L S o o b s k h e l r r i o A a d . .Yaui. Gruzinskoi .Y..S.R. 14, 4-3-811 (193). ( 46X 1 Lakhumna. I . C . . Gaind. V . S.. Sfukhei-ji. S. .\I.. L'zritcnt .\I-;. (Irrdiii! 23, 159 &> (1954). '4-s 1 Lenneman, I\., L . . Hites, R. I>.. Komareivsky. 6'. I.. J . Or?. Chrir.. 19,463-8 11954 1 . 148S, Losev. I. P..SniirnoT-a. 0. L7.. 1, 548-51 (19531. ( 4 9 S , hlaki. K.. Ishida. I?..others, ,J. Cheni. SOC.Japan 57, 42-4 (1954,. 1 j O S , Sfamedaliev. Y. G., Vclicv. S. 6-., Llokladv .li.ad. .You/. S.S.S.R . 92,
325-8 (1953). ( 5 1 s ) Ibid.; 96, 531-3 ( 1 9 5 4 1 i j 2 S 1 Xlatti. J.. Perrier. SI..h'i111. Aor. c h t ~ i . France 1955, 523-3rJ. .I. ~ J. 1 5 3 s ) Sfoore. R . F., IVatcrs. I\.. Chrm. Sac. 1954, 243 4 L., ,f,Or:. C'hrm. 19, (54% LIoshy. i\-, 294-304 (1954 I . ( 5 5 s ) hlukherji. S. h f . . Gaind, V. S.. Kao. P. S.. J. Or Rouzier, G.: Bull. sac. chim. France 1954, 316-20. (855) Zagorodnii, 5. V.,Doklady, Ai.ad. ,Vauk S.S.S.R. 97, 257-9 (1954). (86s) Zagorodnii, S.V., Faustova E. hl., Zhur. Obshchei Khim. 23, 1651-4
(1953). (87N) Zagorodnii, S. V.. Gostev, hf. li., Ibid., 24, 2002-6 (1954). (88N) Zaheer, S. H., Singh, B., others. J . Chem. Sac. 1954, 3360-2.
Dealkylation, Disproportionation, and Isomerization Carpenter, .I. T.. Hunter, R . F.. J . Chem. SOC.1954, pp. 2731-5. Bartlett, P. D.: Roha, hl.; Stiles. R . M., J . Am. Chem. Sac. 76,
2349-53( 1954). (3Pj Burtner, R. R.: Ibid.. 75, 2334-40
(19531. (4P) Ddbryanskii: .I.F.. Gavrilov? B. G.. l i h e n ~ r Zopiski Leningrad. Gasudar.rt. 1.1iii. .4. .4. Zhdanoia, S C T . f;hir?i. .YOU/; 11, 261-9 (1952). (5P) Gauilov. B. G.. LIal'tseva. S . X., Ibid.. 13, 203-9 (1953,. (6P) Gavriiov. B. G.. Pushnoi. S. K . . Zbid., 13, 310-19 (1953). (7P) Gavrilov. B. G.. Z h p n . 0 . I.: Zbid..
156-9 ( 1954I . (9P) Hoation. J. K.. Kosenwald. R . H.. L-. ,S. Patent 2,676, 191 (.\pril 2 0 , 19541, (10P) Kinney. I J . Chem. SOC.1954, pp. 4565(7U) Byatnal.
-_I
L.
(1s)Abramovitch.
R. A , . Hev. D. H., J.Cheni. Soc. 1954. 1697-1703.
(1954). (4s) Campbell. -1. D.. Zbid., 1954, 3659-69. f5Sl Cavill. G. \V. K.. Dean. F. 11.. others. J . Chem. SOC.1954, 4573-
81. Clar. F... Kelly, \V..LVriyht. J. L\.,, Ibid.. 1954, 1108-11. Coloqne. J . . Arsac. A , . Bull. sac. chiiri. France 1954, 445-8. Cook. J. \$-., G a i l q R. XI..Loudon: J. D., J . Chem. Sac. 1954, 568-9. Dufraisse: C., E t i h n e ? A . Goffinet, B., Compt. rend. 235, 1349-52
(1952). Faseeh. S. A , . J . Chem. SOC.1953. p. 3708. (11s)Hart, E.P., Ibid., 1954, 4030-1. (125) Koike. E., OkaLva. hi.,Kaneko. T., J. Chem. Sac. Japan 55, 535-8
(1952).
(13s) Kubba, V. P., Vig, 0. P., Mukherji. S. M.,Current Sci. (India) 23, 158-3 (1954). (14s) Lakhumna. I. C.: Gaind, V. S., Mukherji, S. M., Zbid., 23, 159-60 (1954). (15s) hiaitte, P., Ann. chim. 9 , 431-75 (1 954). (16s) hiukherji, S. M., Gaind, V. S.: Rao, P. N., J . Org. Chem. 19, 328-32 (1954). (17s)Scheuer, P. .J., Kimoto, 1%'. I . .
2C J Demerseman, P , Buu-Hoi, l\j P Ro>er. R , Ibzd.. 1954. u u 4193-3U) Evans, K. F.. Smith, J: 'C., Zbid., 1954, pp. 798-800. 4C) Iguchi, S.. Ltsugi, N., J . Pharin. Soc. Japan 73, 1290-4 (1953 I . 5 C j Koelsch, C. F., Masley, P. 'I?., J . A m . Chem. SOC.75, 3596 (1953). (16L-j Lagidze. R . M. Potskhverashvili, B. S.. Soob.rhcheniia ALad. .\hui; CIuziiisLoi S.S.R. 14, 4 7 3 4 0 (1953). (1-L-1 Losev. I . P..SmirnoL-a. 0.\-,, Kyadneva. L. P.. ShwniX .Stotri Obshcliei Kiiiiii.. :I/,ad. .170uk S.S.S.R. 1. 548-51 (1953). Loudon, J . I).. Razdan. R . K.. (18L) J . Chem. SOC.1954, pp. 4299-4303. (19U) Pandit, P. S . , Tilak, B. D.. \'mkataraman. K,. Proc. Z ~ Q rlcnd. I ~ Sci. 38A, 355-60 (1953). (20U) Qielet, R., Hull. snc. chim. I.;or'ci 1953, pp. C46-8. ( 2 1 U ) Richter, H . J., Org. Sjntheses 33, 37-9 (1953). ( 2 2 U ) Shah, D. S . : Shah. N. hl., J . Org. Chem. 19,1681-5 (1954). ( 2 3 U ) Tatsuta, H., Ochii, Y., J.Chein. SOC. Jcficl: 7 5 , 7 1 9 (1954).
VOL. 48, NO. 9, PART II
SEPTEMBER 1956
1693
UNIT PROCESSES REVIEW (24U) Usgaonkar, R . N., Thakor. V. X I . . and Jadhav, G. V., J . Zrrdiuii Chem. Soc. 30, 535-8 (1953). ( 2 5 L - 1 Vig, 0. P., Maheshwary. N. K.. hfukherji. S. b l . , Research Rid/. Enst Punjab L-niu. 34, 10-~-15 !l953).
Baeyer-Type Condensations ( 1 V ) Bradsher, C. K., Jackson, 11'..J.. . T i . . . J . .Im. C h m . Soc. 76, -34 -8 11954 1.
Ibid.. pp. 4140-3. B L I U - H ON. ~ , P.. S u o n q . S 1) , Lavit, D.: J . Or,?. ? h m . 19, 1 562-6 (1954). (4\. I Cologne. J., Arsac. A . . B i d / . ~ O C rhim. Frarice 1954, 445-8. (5\'1 Dannenberg. H., Dannenbrry \'. Dresler, D., A n n . 585, 1 I S (2\') (3\-)
( 1 9 -5 4 ,1. (6L.i Dhingra. D. K.. Kapoor. S. X . . Kacker. P. S . . J . Proc. Irrd/, Chf37nists ( I n d i a ) 25, 171 -3 ( 1 9 5 3 , . \ -
Dison. J. K., Saunders. K. I \ . . I s u . E s c . CHEM. 46, 652 -611 (1954). (8\.) Driver. J . E.. Sousa. J . B.. ~ J Chum. . .)hc. 1954, pp. 985-9. (OV1 Dunbar: R. E.: Gieszler. A 0.. Srimce 122, 241-2 (1955). 1 OV 1 Haarmann and Reimer. Chemischc Fabrik zu Holzminden G. m . b . H . . Grr. Patent 824,939 (Dee. 13. 1951 I. l l \ ' i Ito. Y,,Ohdera, I.. Japan Patrnt 6179 (Nor. 30. 1 9 5 3 ) . 12VI SG. 1954, pp. 936-8. 13\? Lacey,R. N.:Ibid., 1954, pp. 854-60. 14Vi Muller. A , . Lempert-SrCter, XI.. Karcaag-Wilhelms. A . . J . ( I r e . Ch:hrm. 19, 1533-47 (1954). ( l 5 V I Orlando. .A. M., Rei'. f u c . civnc. auim. ( L-iiic. nacl. La Pla/a i 25. $--lo2 (1950). ( 1 h V 1 Quelet. R.: Gavarret, J.. Pineau, K . . Gonip/. rend. 238, 1427-9 (1954 I . ( 1-L.i Kabindran, K., Tilak, B. D.. Proi. Indian Scad. Sci. 38A, 2-1 ~6 (1953). (18V) KirmschnFider, R., .ilonn/rh. 84, 1228-33 (1953). (19V) Riemschneider, K . , J . Chm. Soc. 75, 4853-5 (1953 I . 12OV) Teramura. K.. Itagaki. H.. Oda. R.. J . Chem. SOC.Jupan 57, 126 -(1954). !21V) Csgaonkar, R. N.: Thakor. V. Xf.! others. J . Indian Chrm. Sac. 30, 743-6 (1953). 1 2 2 V ) Ibid.. pp. 765-71. (23Vi Yasue. M.> Kato, Y.. J . Phnini. Soc. Japan 74,116-19 (1954). 124Vi Zaheer. S. H.! Singh. B., others, J . Chem. Soc. 1954, 3360-2. (25\.) Zaugg. H. E., Horrom. B. I V . . J . .4m. Chem. Soc. 76, 581---18 (1954,.
( 5 i V ) Crabb6. P.. Iri:. rhinr. 36, - 5 - R 3 (1954). (6LV) Curtin. D. Y,. .Johnson. H . \\., ,Jr,, J . A m . Chvni. Soc. 7 6 , 22-6 -(1954j. (-LVi Hart, H . , Ibid.. 76, 4033 4 1135-1 , (81V') Hart, H.. Lleuterio. H . S . . I h i d . 76, 516-19 (1954 i . ( 9 \ V I Ibid.. pp. 519-22. (1OIV 1 Hart. H.. M a . K. .I.. / h J . . 7 6 , 3031 --2( 1954 i. ( I l \ \ I Hart, H.. Splirthuff. \\'. I... Eleliteria. H . S..Ihrii.. 76, 454- 50 11954 I . ( 1 2 \ \ I L a u r r . \ Y , 11.. I.uck\\-ood. K. L.. Ibid., 7 6 , 39-4 -6 (l(954 I . ( 1 3 L V i Xlarvcll. I:. K.. Lugan. A. \ - , . others. Ibr'd.. 76, 1 9 2 2 ~ 6(1954 . ( 1 4 \ V ' Xlarvrll. E. ii.. I'eranishi. K.. Ibid.. 76, 616.5 -8 (19541. ( l j \ \ . I Rhoads. S. J . . Kaulins. K.. K v i nolds. K. I>.. / h i d , , 7 5 , 2.5.31 2 (1953 j , I61d.. 7 6 , 3456 63 ( 1 9 5 4 ,. Schmid. K . . Hnrvrlc. I\-.. ichmid. H.. E\/vrivrr/i
